Mmse Journal Vol11

Mechanics, Materials Science & Engineering, July 2017 ISSN 2412-5954
192.168.1.144
MMSE Journal. Open Access www.mmse.xyz

1
Sankt Lorenzen 36, 8715, Sankt Lorenzen, Austria
Mechanics, Materials Science & Engineering Journal
July 2017

2
Mechanics, Materials Sciences & Engineering Journal, Austria, Sankt Lorenzen, 2017
Mechanics, Materials Science & Engineering Journal (MMSE Journal) is journal that deals in peer-
reviewed, open access publishing, focusing on wide range of subject areas, including economics,
business, social sciences, engineering etc.
MMSE Journal is dedicated to knowledge-based products and services for the academic, scientific,
professional, research and student communities worldwide.
Open Access model of the publications promotes research by allowing unrestricted availability of
high quality articles.
All authors bear the personal responsibility for the material they published in the Journal.
The Journal Policy declares the acceptance of the scientific papers worldwide, if they passed the
peer-review procedure. Published by industrial company Magnolithe GmbH
Editor-in-Chief Mr. Peter Zisser
Dr. Zheng Li, University of Bridgeport, USA
Prof. Kravets Victor, National Mining Univerisity, Ukraine
Ph.D., Girish Mukundrao Joshi, VIT University, India
Dr. Yang Yu, University of Technology Sydney, Australia
Prof. Amelia Carolina Sparavigna, Politecnico di Torino, Italy
ISSN 2412-5954 Design and layout: Mechanics, Materials Science &

Engineering Journal (Magnolithe GmbH)
e-ISSN 2414-6935 www.mmse.xyz
Support: hotmail@mmse.xyz
2017, Magnolithe GmbH
Published by Magnolithe GmbH. This is an open

access journal under the CC BY-NC-ND license
http://creativecommons.org/licenses/by-nc-nd/4.0/

3
CONTENT
I. Materials Science MMSE Journal Vol. 11 ................................................................................... 5
Microcapillary Features in Silicon Alloyed High-Strength Cast Iron. R.K. Hasanli,
S.N. Namazov ...................................................................................................................................... 7
Characterization of Aluminium Alloy AA2219 Reinforced with Graphite by Stir Casting
Method. V. Bhuvaneswari, G. Yuvaraj, Dr. A. Saravanakumar, L. Rajesh Kumar, R. Kiruthiha ... 11
Process Optimization of Warm Laser Shock Peening without Coating for Automotive Spring
Steel. S. Prabhakaran, S. Kalainathan ............................................................................................. 18
Studies on 1-Butyl 3-Methylimidazolium Hexafluorophosphate Incorporated PVC-PBMA
Polymer Electrolytes. R. Arunkumar, Ravi Shanker Babu, M. Usha Rani ..................................... 22
Conductivity Enhancement Studies on Poly (Acrylonitrile)-Poly (Vinylidene Fluoride)
Composite Polymer Electrolytes. M. Usha Rani, Ravi Shanker Babu, S. Rajendran,
R. Arunkumar .................................................................................................................................... 28
A Comparative Study on the Dielectric Properties of Lanthanum Copper Titanium Dioxide
(La2/3Cu3Ti4O12) Ceramic with Conventional and Microwave Sintering Routes. Surya Mallick,
Pawan Kumar, M. Malathi ............................................................................................................... 34
Theoretical Investigation on the Structural, Elastic and Mechanical Properties of
Rh3HxNb1-x(x=0.125, 0.875). M. Manjula1, M. Sundareswari ..................................................... 39
Synthesis and Characterization of Monolithic ZnO-SiO2 Nanocomposite Xerogels.
D. Prasanna, P. Elangovan, R. Sheelarani ...................................................................................... 44
DC Conductivity and Dielectric Studies on Fe Concentration Doped LiIAgIB2O3 Glasses.
K. Sreelatha, K. Showrilu, V. Ramesh .............................................................................................. 49
Conductivity, Morphology and Thermal Studies of Polyvinyl Chloride (PVC)-Lithium
Nitrate with Cadmium Oxide (CdO). P. Karthika, R. Gomathy, P.S. Devi Prasadh ................... 55
Electrochemical Detection of Ascorbic Acid Using Pre-treated Graphite Electrode Modified
with PAMAM Dendrimer with Poly (Nile Blue). C. Lakshmi Devi, J. Jayadevi Manoranjitham,
S. Sriman Narayanan ........................................................................................................................ 60
Morphological Investigation of Small Molecule Solution Processed Polymer Solar Cells
Based on Spin Coating Technique. Liyakath Reshma, Kannappan Santhakumar ........................ 65
Analysis on Spectroscopic and Dielectric Study of PBS/PVA Polymer Nanocomposite via
Facile Hydrothermal Process. S. Sharon Tamil Selvi, J. Mary Linet ............................................. 70
Voltammetric Sensing of Dopamine at a Glassy Carbon Electrode Modified with Chromium
(III) Schiff Base Complex. K. Bharathi, S. Praveen Kumar, P. Supriya Prasab, V. Narayanan ... 76
Mechanical and Morphological Characterization of PVA/SA/HNTs Blends and Its
Composites. N. Thayumanavan ........................................................................................................ 81
Mechanical and Thermal Behaviour of Hybrid Filler Reinforced PP/ABS Blend.
S.M.D. Mastan Saheb, P. Tambe, M. Malathi .................................................................................. 86
Effect of Multiple Laser Shock Peening on the Mechanical Properties of ETP Copper. Ayush
Bhattacharya, Siddharth Madan, Chirag Dashora, S. Prabhakaran, V.K. Manupati, S. Kalainathan,
K.P.K. Chakravarthi ......................................................................................................................... 91
Determination of Uric Acid with the Aid of N, N'-Bis (Salicylaldimine)-Benzene-1, 2-Diamine
Cobalt (II) Schiff Base Complex Modified GCE. G.B. Hemalatha, S. Praveen Kumar, S.
Munusamy, S. Muthamizh, A. Padmanaban, T. Dhanasekaran, G. Gnanamoorthy,
V. Narayanan .................................................................................................................................... 97
Electron Distribution in BaTi0.98Zr0.02O3 Piezoceramic Using X-ray Structure Factors.
J. Mangaiyarkkarasi, S.Sasikumar, R. Saravanan .......................................................................... 102
Synthesis, Structural and Optical Studies of Yb Doped CuGaS2 Thin Films Prepared By
Facile Chemical Spray Pyrolysis Technique. S. Kalainathan, N. Ahsan, T. Hoshii, Y. Okada,
T.Logu, K. Sethuraman ................................................................................................................... 110
Performance of SiO2 - TiO2 Thin Films as Protective Layer to Chlorophyll in Medicinal
Plants from UV Radiation: Influence of Dipping Cycles. M. Sankareswari, B. Karunai Selvi,
K. Neyvasagam ................................................................................................................................ 118

4
Structural and Optical Properties of DC Magnetron Sputtered Zirconium Titanate Thin

Films of Varied Film Thickness. D. Jhansi Rani, A. Guru Sampath Kumar, T. Subba Rao ....... 124
Effect of Additives on the Performance of Non-Fullerene Based Organic Solar Cells in Non-
Halogenated Solvents. L. Reshma, V. Sai Saraswathi, P. Induja, M. Shivashankar,
K. Santhakumar ............................................................................................................................... 128
Characterization, Design and Optimization of Industrial Phosphoric Acid Production
Processes by Artificial Neural Network. Gholamhosseion Grivani, Shahriyar Ghammamy, Farzane
Yousefi, Mehdi Ghammamy ............................................................................................................ 133
Microstructure and Supercapacitor Properties of V2O5 Thin Film Prepared by Thermal
Evaporation Method. M. Dhananjaya, N. Guru Prakash, G. Lakshmi Sandhya,
A. Lakshmi Narayana, O.M. Hussain ............................................................................................. 140
Effect of Substrate Temperature on Microstructural and Optical Properties of
Nanostructured ZnTe Thin Films Using Electron Beam Evaporation Technique. M. Shobana,
N. Madhusudhana Rao, S. Kaleemulla, M. Rigana Begam, M. Kuppan ........................................ 147
Textural Enhancement of Hydrothermally Grown TiO2 Nanoparticles and Bilayer-
Nanorods for Better Optical Transport. J. Sahaya Selva Mary, V. Chandrakala, Neena Bachan,
P. Naveen Kumar, K. Pugazhendhi, J. Merline Shyla ..................................................................... 153
Novel and Proficient Organic-Inorganic Lead Bromide Perovskite for Solid-State Solar
Cells. B. Praveen, Tenzin Tenkyong, W. Jothi Jeyarani, J. Sahaya Selva Mary, V.Chandrakala,
Neena Bachan, J. Merline Shyla ..................................................................................................... 160
Stress Stability of Aluminium-Glass Composites. Abodunrin O.W., Alo F.I. ........................ 167
On the Rogue Wave Solution of the Davey-Stewartson Equation. D. Prasanna, S. Selvakumar,
Dr. P. Elangovan ............................................................................................................................ 174
Growth and Characterization of Potassium Di Chromate Doped L-Alanine Crystal.
D. Prasanna, N.Karthikeyan, Dr. P. Elangovan.............................................................................. 180
II. Mechanical Engineering & Physics MMSE Journal Vol. 11 ............................................... 186
Vibration Optimization of a Two-Link Flexible Manipulator with Optimal Input Torques.
Hadi Asadi, Milad Pouya, Pooyan Vahidi Pashaki ........................................................................ 187
Design and Simulation of Capacitive Type Comb-Drive Accelerometer TO Detect Heart Beat
Frequency. P. Ashok Kumar1, G.K.S. Prakash Raaju1, K. Srinivasa Rao ................................... 199
Particular Issues Associated with Performing Meterage Through the Use of Magneto
Therapy Devices. Y.S. Lapchenko, V.Y. Denysiuk, V.V. Krasovski, V.P. Symonyuk ..................... 207
Numerical Simulation of the Shear Resistence Test Proposed by NBR 7190 (1997) for a Wood
of Corymbia Citriodora. Luciano Rossi Bilesky, Claudio De Conti, Priscila Roel de Deus ....... 215
The Influence of Biofuel on the Operational Characteristics of Small Experimental Jet
Engine. K. Ratkovska, M. Hocko, J. Cernan, M. Cuttova .............................................................. 229
Static Analysis of Total Knee Joint Replacement. Vinay Kumar. P, S. Nagakalyan ............ 238
Applying Calculations of Quaternionic Matrices for Formation of the Tables of Directional
Cosines. Victor Kravets, Tamila Kravets, Olexiy Burov ................................................................ 248
Seismic Behaviour of Eccentrically Braced Frame with Vertical Link. Vahid Osat, Ehsan
Darvishan, Morteza Ashoori ........................................................................................................... 260
VII. Environmental Safety MMSE Journal Vol. 11 ................................................................... 269
Understanding the Nature and Characteristics of Dark-Black Stains on Rooftops in Uyo
Metropolis-Nigeria. Ihom A.P., Uko D.K., Markson I.E., Eleghasim O.C. ................................... 270
Prospects to Use Biogas of Refuse Dams of Dnipropetrovsk Region (Ukraine) as Alternative
Energy Carrier. Ye.A. Koroviaka, V.O. Rastsvietaiev, O.O. Dmytruk, V.V. Tykhonenko ............ 289
VI. Information Technologies MMSE Journal Vol. 11 ............................................................. 298
Random Sparse Sampling and Equal Intervals Bregman High-Resolution Signal
Reconstruction. Guojun Qin, Jingfang Wang ............................................................................... 299
VII. Economics & Management MMSE Journal Vol. 11 .......................................................... 308
Methodology of Assessing the Impact of Urban Development Value of the Territory on the
Value of Residential Real Estate by Example of Kiev City, Ukraine. I.M. Ciobanu ............... 309

5
I . M a t e r i a l s S c i e n c e
M M S E J o u r n a l V o l . 1 1

6
Microcapillary Features in Silicon Alloyed High-Strength Cast Iron

1
R.K. Hasanli1,a, S.N. Namazov2,b
1 Associated professor, Dr., Azerbaijan Technical University, Baku, Azerbaijan

2 Professor, Dr., Azerbaijan Technical University, Baku, Azerbaijan
a hasanli_dr@mail.ru
b subhan_namazov@daad-alumni.de
DOI 10.2412/mmse.89.99.501 provided by Seo4U.link
Keywords: alloyed, high-strength cast iron, metal form, segregation, structure.
ABSTRACT. Present study explores features of silicon micro capillary in alloyed high-strength cast iron with nodular
graphite (ductile iron) produced in metal molds. It identified the nature and mechanism of micro liquation of silicon in a
ductile iron alloyed with Nickel and copper, and demonstrated significant change of structural-quality characteristics. It
was concluded that the matrix of alloyed ductile iron has a heterogeneous structure with cross reinforcement and high-
silicon excrement areas.
Introduction. High quality of iron castings depends largely on the structure and properties, including
the nature of the distribution of silicon. However, the structure of high-strength cast iron with nodular
graphite (ductile iron) produced in the metallic form, and the nature of silicon micro liquation in it
has not been studied. Therefore, research in this direction represents both scientific and practical
interest.
Analyses of the Microcapillary Features in Silicon Alloyed High-Strength Cast Irons. Method of
etching in an alkaline solution of sodium picrate was used to study microrespirometry of silicon in
cast iron. The study of micro liquation of silicon in ductile iron, cast in the mold, showed that there
is a significant difference from micro liquation in ductile iron, cast in sand form. Analysis of ductile
iron chill in the cast state showed that the iron acquires the structure of a white cast iron consisting of
perlite and ledeburite (Fig.1).
Fig. 1. The microstructure of unalloyed ductile iron, x300.
1
2017 The Authors. Published by Magnolithe GmbH. This is an open access article under the CC BY-NC-ND license

7
Ductile iron, cast in the mold, unalloyed Nickel and copper are significantly different from unalloyed,
cast in the mold (Fig.2). Introduction of iron Nickel in an amount of from 1.0 to 2.0% increases the
chill cast iron and refines eutectic grains (Fig.3).
Fig. 2. The microstructure of ductile iron, alloyed with 1.0% Ni and 0.5% Cu, x300.
Fig. 3. The microstructure of ductile iron, alloyed with 1.0% Ni, x300.
It is established that the characteristic distribution of silicon in the alloy, chill cast irons due to their
cast structure and has a stable character which does not change after annealing, normalizing and
tempering. The area of metal, representing annealing of cementite, retains their chemical composition
with low content of silicon. It was determined that the copper and Nickel with temperatures of
crystallization increase the activity of carbon (like silicon) and therefore increase its distribution in
the crystal lattice of iron.
The distribution of silicon in the Nickel-copper cast irons, cast into the metal mold and sand mold,
close to equilibrium. Only a small region along the boundaries of austenitic grains has a lower content
of silicon. However, in this case, the contrast in the color of the cone is negligible.
In the Nickel-irons non-uniform distribution of silicon was observed, a reflective cast of austenite -
ledeburite structure. The size of the striped areas (concentration of Si) decreases with increasing
Nickel content in the alloy. However, such heterogeneity does not cause deterioration of properties
that would be expected in accordance with existing views on the impact of micro liquation silicon on
notch toughness (COP) at low temperatures.
It is found that in chill alloyed and unalloyed cast iron with partial chill the most enriched silicon are
at the boundaries of the areas occupied by stable and metastable eutectics. The high concentration of

8
silicon is observed between colonies of plastic ledeburite. Graphite is observed around the highest
concentration of this element.
Unlike half-iron, with the cross-cutting chill, silicon is concentrated mainly in high-silica areas,
namely between the eutectic colonies in complex eutectics, one of the phases in which the
silicocarbide (BCC) or carbide in eutectoid (C+SC), acanthophyllum cementite. In primary and
eutectic austenite (pearlite) content of silicon is lowered.
In works [1], [2], [3], [4], [5] it was proposed that the annealing leads to equalization of chemical
composition upon exposure of the alloy in the austenite region. However, there is another point of
view according to which crystallization occurred when the heterogeneity of the chemical composition
is very stable and fundamentally cannot be eliminated by heat treatment and, in particular, annealing
[6], [7], [8], [9].
When etching of annealed cast iron in picrate of sodium, we found a very peculiar picture of micro
capillary silicon. There is a clear alternation of the areas enriched and depleted in silica, the first of
which are arranged around graphite inclusions, the second - in places where before annealing the
cementite existed.
Mutual arrangement, configuration and size of the combined silicon regions coincide with the
location and shape of the plates of cementite or ledeburite colonies. At the edges of the casting is
observed banded pattern characteristic of directional solidification, and in the center - homogeneous
composition of the zone close to equated.
Thus, it is established that during annealing there is a redistribution of silicon and this is the most
enriched region adjacent to the graphite. However, it is clear that the redistribution occurs only within
a former permitting (austenitic crystallization) regions.
In the locations of the eutectic of cementite, the content of silicon is reduced and after austenitization
of the metal substrate, as well as the final thermal treatment normalization. This result is consistent
with the view stating that when crystallization occurs chemical polarization, caused by different
affinity of the elements to carbon [10], [11], [12].
It is established that carbide-forming elements (Mn, etc.) during the crystallization of the concentrate
in the cementite promote graphitization (Si, Ni, Cu, etc.) in the austenite and this polarization is very
stable. Given the suggested it can be argued that the revealed micro liquation in the picture reflects
an inhomogeneous distribution of not only silicon, but also other elements.
Thus, high-strength cast iron can be considered as a composite material having a heterogeneous
structure with a cross reinforcement consisting of alternating high-silicon regions having a high
hardness and brittleness, and almost excrement, more plastic granules, probably doped with
manganese. Such arrangement of the matrix and reinforcing phases in combination with the presence
of solid lubricants graphite meets the Sharpie rule and may be one of the prospective directions in
creation of wear-resistant cast iron with a heterogeneous structure.
Detected feature in the distribution of silicon can certainly affect the Mechanical properties of
the material. It was established that higher mechanical properties are observed at full, or a significant
chill (exceeding 50%) alloyed cast irons in the cast state. During subsequent thermal treatments
bleached and half-alloy cast irons are mainly pearlite structure with spheroidal graphite.
This structure iron is the most desirable to improve its properties. In addition, the size of the
homogeneous micro regions and graphite inclusions with the increase in the rate of supercoiling of
the alloy crystallizing decreases, which also positively affects the properties of cast iron.
All this makes it possible to express an opinion of the relative influence of micro heterogeneity of
chemical composition on the properties of cast iron. Meanwhile, the generally accepted view that
segregation in cast iron is undesirable as it decreases the ductility of the material. Moreover, even

9
after annealing to achieve complete homogeneity of the cast iron chemical composition is not
possible.
Therefore, in our opinion, one should strive to create such a structure of iron, in which a homogeneous
chemical composition in micro-area would be very fine and brittle and ductile zones efficiently
combined, forming a relatively micro heterogeneous structure. Such a picture is obtained by chill
casting magnesium cast irons subjected to annealing, which increases their properties compared with
the cast irons of similar composition, obtained by casting in sand mold.
Summary. The study of the processes of structure formation in ductile iron casting in the mold
confirms the accuracy of the choice of complex dopants, in an amount of 1.0% Ni and 0.5% Cu that
are responsible for the development of cast metal parts applied in conditions of friction, wear and
elevated mechanical loads. These working conditions are typical for parts of oilfield equipment.
Based on the research of micro capillary silicon and other alloying elements it was proposed that
ductile iron can be considered as a composite material having a heterogeneous structure with
alternation of regions with different silicon content.
References
[1] I.P. Bunin, Y.N. Malinochka, B.P. Taran. Fundamentals of metallography of cast iron. Moscow,
Metallurgy, 1998, 413 p.
[2] V.A. Ilyinsky, A.A. Zhukov and others. New in the theory of graphitization. The relationship
between primary and secondary crystallization graffitists iron-carbon alloys // Metallography and
heat treatment of metals, 2001, No.10. P.10-16
[3] High-strength cast iron with nodular graphite. Theory, production technology, properties and
applications / ed. by M.V. Voloshchenko. Kiev: Sciences. Dumka, 2004, 203 p.
[4] R.K. Hasanli. Structure and properties of ductile iron. Baku, Science, 2013, 252 p.
[5] R.K. Hasanli Peculiarities of structure and phase composition of heat-treated high-strength cast
irons with nodular graphite // Journal of mechanical engineering, 2013, No. 10, pp. 31-33
[6] A.I. Belyakov and others. Production of castings from high-strength nodular cast iron. M.,
Mechanical Engineering, 2010, p. 712
[7] R.K.Hasanli. High-strength cast iron with nodular graphite. Baku: Science, 1998, 203 p.
[8] V.V. Dubrov and others, The use of high-strength cast iron in valve. In proc. High-strength cast
iron with nodular graphite. Kiyev, Naukova Dumka, 1998, pp. 78-81.
[9] E.A. Silva, L.F.V.M. Fernandes, N.A.S. Sampaio, R.B. Ribeiro, J.W.J. Silva, M.S.Pereira (2016),
A Comparison between Dual Phase Steel and Interstitial Free Steel Due To the Springback Effect.
Mechanics, Materials Science & Engineering Journal Vol.4, Magnolithe GmbH, DOI:
10.13140/RG.2.1.3749.7205
[10] L. I. fron, D. A. Litvinenko (1994), Obtaining high-strength weldable steels with bainite
structure using thermomechanical treatment, Metal Science and Heat Treatment, Vol. 36, Is. 10,
Springer, DOI 10.1007/BF01398082
[11] I.N. Bogachev, R.I. Mints Cavitation-erosion fracture of cast iron. Sat. Theory and practice of
foundry production, Ural Polytechnic Institute, vol. 89, 1999, pp. 71-78.
[12] L.P. Ushakov Wear-resistant cast iron with spheroidal graphite. M., Mechanical engineering,
2005, 153 p., DOI 10.1007/BF01398082

10
Characterization of Aluminium Alloy AA2219 Reinforced with Graphite by Stir

Casting Method
2
V. Bhuvaneswari, a, G. Yuvaraj, b, Dr. A. Saravanakumar, c, L. Rajesh Kumar, d, R. Kiruthiha, e
1 KPR Institute of Engineering & Technology, Coimbatore, India

a bhuvaneswari.v@kpriet.ac.in
b yuvarajg75@gmail.com
c saravanakumar.a@kpriet.ac.in
d l.rajeshkumar@kpriet.ac.in
e rkiruthu@gmail.com
Keywords: aluminium alloy, graphite, mechanical properties, stir casting method.
ABSTRACT. Aluminium alloy has been accepted in the world wide for the fabrication of lightweight structures requiring
a high strength to weight ratio, such as aerospace, automotive and structural components resulting in savings of materials
and energy. In this work, mechanical properties like porosity test and surface roughness test of Aluminium Alloy AA2219
is reinforced with graphite powder in the ratio of 1%, 3%, 4.5% (in terms of weight) was done. It is fabricated with
different composition of graphite using stir casting method and maintained at the temperature of 1023 K, and running
speed at 500 rpm. The proposal work is aimed at obtaining a composite material with good surface finish and with less
casting effects. By testing, we obtained the increase in surface roughness values of 3.83 m at 4.5% of graphite and found
porosity is increased up to 0.04%.
Introduction. Nowadays for the light weight applications, aluminium-matrix composites are
extensively used in all mechanical fields for pre-existing structure that have to be retrofitted to make
them seismic resistant, or to repair damage caused by seismic activity. Aaron Lam et al. [1] did the
experimental studies on aluminium alloy 2219 have been formed the creep-aged at 175C for 18 h.
Using the CAF material constants determined for this alloy, corresponding nite element models have
been developed and experimentally validated using the measured proles. Suresh et al., [2]
investigate the Aluminium composites have been produced with copper-coated cenospheres of fly
ash as reinforcement. The results indicate that with increasing percentage of reinforcement, the tensile
strength, impact strength and wear resistance of composites increases up-to 10%. Dunia Abdul Saheb
[3] study the modest attempt has been made to develop aluminium based silicon carbide particulate
MMCs. An increasing of hardness and with increase in weight percentage of ceramic materials has
been observed. The best results (maximum hardness) have been obtained at 25 % weight fraction of
SiC and at 4% weight fraction of graphite. Rajasekaran, & Sampath [4] Aluminium alloy AA2219
was reinforced with TiB particles introduced in-situ by the salt- metal reaction technique and the
results proved that the addition of TiB particles results in increased mechanical properties, such as
0.2%YS, UTS and hardness. Chunlin He et al.,[5] Analysed the corrosion protection from sulphuric
acid anodized coatings on 2024 aluminium and SiC particle reinforced 2024 aluminium metal matrix
composite (SiCp/2024Al MMC) The results show that the anodized coating on 2024Al provides good
corrosion protection to 3.5 wt. % NaCl. Krupinski et al., [6] investigated AlSi7Cu3Mg aluminium
cast alloy was performed for samples cooled with different cooling rate settings. Results observed
2

11
that phase morphology changes increase in relation to the cooling rate for the Al-Si-Cu alloy. The
amount of the pores increases together with the cooling rate. Hashim et al., [7] Combining high
specific strength with good corrosion resistance, metal matrix composites (MMCs) are materials that
are attractive for a large range applications. Vijayaramnath et. al. [8] studied the effect of
reinforcements of aluminium by the addition of different metals. Suryanarayana et. al. [9] studied the
SiC reinforced particles with aluminium for aerospace applications. Rupa Dasgupta [10] investigate
the effect of dispersing SiC in 2014 base alloy adopting the liquid metallurgy route on different wear
modes like sliding, abrasion. P.B. Pawar et.al studied [11] investigate the composite prepared by stir
casting technique, conducted Mechanical tests such as hardness test, microstructure test find out the
properties. Manoj Singla et.al.[12] modest attempt has been made to develop aluminium based silicon
carbide particulate MMCs with an objective to develop a conventional low cost method of producing
MMCs. C. Saravanan et.al. [13] studied the combined effect of reinforcements on Aluminium Metal
Matrix composites with individual and multiple particulate reinforcements like Hybrid Metal matrix
composites are finding increased applications in aerospace. Michael oluwatosin et.al. Reviewed the
different combination of metals along with aluminium alloy and investigate the change in properties.
In the present work, we reinforced the graphite in different percentage that it was not done before in
the previous work and we obtained the good results in surface roughness and porosity.
Properties of aluminium values
Density (g/cc) 2.84
Hardness (BHN) 49.5
Ultimate tensile strength (Mpa) 455
Modulus of elasticity (Gpa) 73.1
Poissons ratio 0.33
Shear strength (Gpa) 285
Thermal conductivity (W/m-K) 120
Melting point (C) 643-750
Table 1. Properties of graphite.

Bulk Density (g/cm3) 1.3-1.95
Porosity (%) 0.7-53
Modulus of Elasticity (GPa) 8-15
Compressive strength (MPa) 20-200
Coefficient of Thermal Expansion (x10-6 C) 1.2-8.2
Thermal conductivity (W/m.K) 25-470
Specific heat capacity (J/kg.K) 710-830

12
Experimental work.
Fabrication of the project
Fabrication of composite bar.
Specimen preparation.
Testing of the specimen
Fabrication of composite bar.
Stir casting. Stir casting is a liquid state method of composite materials fabrication, (is shown in fig.
1) in which a dispersed phase (ceramic particles, short fibres) is mixed with a molten matrix metal by
means of mechanical stirring. The liquid composite material is then cast by conventional casting
methods and may also be processed by conventional metal forming technologies.
Fig. 1. Mechanical stirring machine.
Aluminium Stir Casting Equipment. In a stir casting process, the reinforcing phases are
distributed into molten matrix by mechanical stirring. An interesting recent development in stir
casting is a two-step mixing process. In this process, the matrix material is heated to above its liquids
temperature so that the metal is totally melted.
Adding of Graphite with Melted Aluminium alloy. The melt is then cooled down to a temperature
between the liquids and solidus points and kept in a semi-solid state. At this stage, the preheated
particles are added and mixed. The slurry is again heated to a liquid state and mixed thoroughly. This
two-step mixing process has been used in the fabrication of aluminium.

13
a) B)
Fig. 2. Cast Piece (a) of the Composite Bar (b)
Cast Piece of the Composite Bar. Among all the well-established metal matrix composite fabrication
methods, stir casting is the most economical. The distribution of the particles in the molten matrix
depends on the geometry of the mechanical stirrer in the melt, melting temperature, and the
characteristics of the particles added.
Parameters used in stir casting. There is various process parameters if they properly controlled can
lead to the improved characteristic in composite material.
Stirring speed - 500rpm
Stirring temperature - 1023K
Stirring time - 10min
Preheating time of WC - 30min
Preheating temp of WC - 473K
Composition of the specimen prepared.
Total weight is 750grams required to fabricate the composite bar (100%).
1. Aluminium 738.75gm with 1.5% of WC- 11.25gm.
2. Aluminium 727.5gm with 3% of WC- 22.5gm.
3. Aluminium 716.25gm with 4.5% of WC-33.75gm.
Specimen preparation. Here the specimens are prepared as per the size requirement for the
mechanical testing to be carried out for these materials.
Hardness test. Hardness is defined as the ability of the material to resist plastic deformation, usually
by indentation. Hardness is a measure of how resistant solid matter is to various kinds of permanent
shape change when a compressive force is applied. Some materials, such as metal are harder than
others. Resistance of a material to deformation, indentation, or penetration by means such as abrasion,
drilling, impact, scratching, and/or wear, measured by hardness tests such as Brunel, Knoop,
Rockwell, or Vickers. Since there is no standard hardness scale, each test expresses its results in its
unique measure.
Brunel hardness test. Method of measuring the hardness of a material by pressing a chromium-steel
or tungsten-carbide ball (commonly one centimetre or 0.4 inch in diameter) against the smooth
14
material surface under standard test conditions. The hardness is expressed in Brunel Hardness
Number (BHN) computed by dividing the load in kilograms by the area of indentation made by the
ball measured in square millimetres. American Society for Testing and Materials standard BH test is
ASTM E-10. For measurement up to BHN 500, Brunel hardness is equal to 0.96 times the Vickers
hardness.
Fig. 3. Brunel hardness Equipment.
Table 2. Tests results.

% of Force Intender Trial Trial Trial Average Brunel Hardness
Graphite Applied (dia) mm Number (BHN)
I II III (dia)
(N) mm mm mm mm
1. 250 5.0 2.8 2.8 2.8 2.8 37.14
3. 250 5.0 2.9 2.8 2.9 2.845 34.8
4. 250 5.0 3.1 2.9 2.9 2.965 32.65
Surface roughness test. Surface roughness often shortened to roughness, is a component of surface
texture. It is quantified by the deviations in the direction of the normal vector of a real surface from
its ideal form. If these deviations are large, the surface is rough; if they are small, the surface is
smooth. It is often necessary to know both amplitude and frequency to ensure that a surface is fit for
a purpose.

15
Fig. 4. Surface roughness tester.
Table 3. Rockwell tests results.

Type Spindle Feed Depth of Al Alloy Graphite Trial I Trial II Trial III Average
Insert Speed Rate Cut (%) (%) Surface
Used (rpm) (mm) Roughness
(m)
Triangular 750 0.06 4 98.5 1.5 1.45 1.1 1.2 1.25
Insert
Triangular 750 0.06 4 97.0 3.0 2.5 2.4 2.7 2.53
Insert
Triangular 750 0.06 4 95.5 4.5 3.8 3.9 3.8 3.83
Porosity. Porosity or void fraction is a measure of the void or empty spaces in the material, and is a
fraction of the volume of void over the total volume, between 0 and 1, or as a percentage between 0
and 100%. Strictly speaking, some tests measures the accessible void, the total amount of void
space accessible from the surface.
Table 4. Porosity tests results.

Composition of Volume Mass ( gm) Density(kg/cm) Porosity
Graphite
Before After Before After
1.5 5.4 14.966 14.966 2.77 2.77 -
3.0 5.4 13.731 13.737 2.54217 2.54388 0.02
4.5 5.4 15.267 15.270 2.82722 2.8277 0.04
Summary The following conclusions were drawn from the AA2219 metal matrix composite after
conducting the experiments and analysing the results:

16
Based on hardness test results, the sample A (Al 98.5% & graphite 1.5%) is having maximum
hardness of 37.14 BHN.
Based on the porosity test results, the sample A (Al 98.5% & graphite 1.5%) is having minimum
casting defect.
Based on the surface roughness results, the sample A (Al 98.5% & graphite 1.5%) is having
minimum surface roughness value of 1.25m.
It is concluded, that the minimum amount of graphite percentages (1% to 2%) is preferable for
many applications such as clutches, piston, spoilers, flight controls etc.
References
[1] H. Abdoli, E. Salahi, H. Farnoush, K. Pourazrang, Effect of processing parameters on the
corrosion behaviour of friction stir processed AA2219 aluminium alloy, Solid state sciences, J.
Alloys Compd. 461, 2008, 166172.
[2] Dunia Abdul Saheb Aluminum silicon carbide and aluminum graphite particulate composites
vol. 6 (10) , 2011, 41-46.
[3] S.R. Koteswara Rao, G. Madhusudhan Reddy, K. Prasad Rao Effect of repair welding on
electrochemical corrosion and stress corrosion cracking 202, 2008, 283289.
[4] Koteswara Rao, S.R. Ph.D. Thesis. 2005. Effects of welding processes, thermo mechanical
treatments and scandium additions on the mechanical properties of AA 2219 welds. Indian Institute
of Technology Madras, Chennai, India,
[5] A. Mahamani Procedia Materials Science Effect of In-Situ TiB2 Particle Addition on the
Mechanical Properties of AA 2219 Al Alloy, Composite 6, 2014, 950 960.
[6] N.R. Rajasekaran, V. Sampath, Synthesis behaviour of Nano crystalline AlAl2O3composite
during low time mechanical milling process. Vol. 10 (6), 2011 527-534.
[7] B.Vijayaramnath, C.Elanchezhian, R.M. Annamalai , Aluminium metal matrix composites A
Review, Rev. Adv. Material science. 38, 2014, 55-59.
[8] Surya narayanan, R.Praveen, S.Raghuraman , SiC reinforced Aluminium metal matrix
composites for Aerospace applications, International Journal of Innovative research in science and
Technology, vol 2 (11), 2013, 6336-6339.
[9] Rupa Dasgupta, Aluminium Alloy-Based Metal Matrix Composites: A Potential Material for
Wear Resistant Applications, ISRN Metallurgy, Vol (12), 2015, 253-259.
[10] P.B. Pawar, purushottampawar, Abhay A. Utpat Development of Aluminium Based Silicon
Carbide Particulate Metal Matrix Composite for Spur Gear, Procedia Materials Science ,Volume 6,
2014, 1150-1156.
[11] Manoj Singla, D. Deepak Dwivedi, Lakhvir Singh, Vikas Chawla Development of Aluminium
Based Silicon Carbide Particulate Metal Matrix Composite, Journal of Minerals & Materials
Characterization & Engineering, Vol. 8 (6), 2009, 455-467.
[12] C. Saravanan, Subramanian, V.Ananda Krishnan Effect of Particulate Reinforced Aluminium
Metal Matrix Composite, Review Mechanics and Mechanical Engineering Vol. 19 (1), 2015, 23
30.
[13] Michael oluwatosin, Kenneth kanayo alanine, Lesley heath chown Aluminum metal matrix
Hybrid composites: a review of reinforcement philosophies; mechanical, corrosion and tribological
characteristics vol 2 (11), 2015, 434-444.

17
Process Optimization of Warm Laser Shock Peening without Coating for

Automotive Spring Steel
3
S. Prabhakaran1, S. Kalainathan1,a
1 Centre for Crystal Growth, VIT University, Vellore, India

a spkaran.kmd@gmail.com, s.kalainathan@gmail.com
Keywords: warm laser shock peening (WLSP) without coating, residual stress, hardness, dynamic strain aging, dynamic
precipitations.
ABSTRACT. The current study proposes and optimizes the process parameters for warm laser shock peening without
ablation coating. Warm laser shock peening brings up the advantage of dynamic strain aging and dynamic precipitation
hardening of metallic materials. The low energy Nd: YAG laser at the fundamental wavelength of 1064 nm utilized for
the operation and the borosilicate (BK7) glass was used as a confinement medium. The experiment performed with
different laser pulse densities and the results revealed that the higher pulse densities lead to surface melting due direct
ablation taking place on the pre warmed specimen surface. Also, the process temperature optimization was carried out
and the result indicates that there was a hardness drop during the laser peening at 300 oC, which is due to an excess amount
of precipitation leads to lose the strength of the metal. The microstructural analysis was performed using the field emission
scanning electron microscope (FE-SEM).
Introduction. The post-processing material designing technology in automotive and aerospace

industries is playing a vital role. Most of the fatigue cracks are initiating at the surface and it
propagates throughout the material leading to fatigue fracture. The surface modification technologies
like cold rolling, ball milling, surface attrition treatment, shot peening and laser shock peening (LSP)
are used to modify the surface mechanical properties of metallic materials. Among these, the shot
peening is a mechanical cold working process that can induce compressive residual stress through a
number of successive shots using spherical iron balls, water jet and oil jet. Here, the induced
compressive residual stress (RS) effectively retards the fatigue crack initiation and propagation [1],
[2], [3], [4].
The laser based materials processing techniques are emerging from a decade because of its all round
performance like reliability and consistency in the industries. LSP emerges as a novel cold working
surface modification technique through inducing deep and high compressive residual stress [1], [5],
[6]. The basic phenomena behind this LSP process are the laser matter interaction producing high
pressure ionized gas plasma on the metal surface induces strong compressive shock waves into the
material and this compressive stress production is purely a cold working process [5] ,[6]. Normally
water or glass is utilized as the transparent confinement medium and black paint or PVC tape used as
surface protective ablation medium for LSP process. Ganesh et.al [2] ,[3] introduced the investigation
of LSP on spring steel for automotive applications and LSP has effectively repaired the fatigue life
of partly fatigued SAE 9260 spring steel using poly vinyl chloride (PVC) tape as an ablative medium.
The LSP producing grain refinement induced plastic deformation is liable to the fatigue life
enhancement of metallic materials [1-3]. The ambient condition LSP treatment induced internal RS
relaxation affects the mechanical properties of metal materials under exposure thermal conditions [1],
[4]. The thermal engineering based warm laser shock peening (WLSP) got advantages such as
3

18
dynamic strain aging (DSA), and dynamic precipitations (DP) hardening of low-alloy steel
contributing an extensive improvement in fatigue life cycle [1], [7]. LSPwC method of producing
high compressive RS works effectively with low energy lasers, also it is economical for commercial
applications [1], [4], [5].
Experiments and methods. A high content of Si & Mn medium carbon low alloy steel SAE 9254
hardened (900 0C) and tempered (500 0C) used for the laser surface modification process. The LSPwC
performed at room temperature (25 0C) and pre-warmed (250 15 0 C ) specimens with a low energy
Nd: YAG laser (300 mJ) of pulse duration 10 ns by the fundamental frequency of 1064 nm without
any confinement medium for both the processes. An experiment performed with the optimized
parameters such as laser spot diameter of 0.8 mm. The laser power density used for the current
experimental process is ~ 6 GW cm-2. The borosilicate glass (BK7) is used as the confinement layer
for the experiments. In order to avoid fast cooling of pre-heated specimen the electrical dryers are
used for continues heating of targeting specimen and its surroundings during WLSP experiment.
Subsequently, the WLSP treated specimen slowly cooled from the processing temperature to avoid
RS relaxation by fast cooling [1,7,8]. The mirror polished surface would not act as an opaque medium
but since it is polished transparent surface. An aluminium foil is not an opaque layer and there is an
experimental coating difficulty because of the high-temperature processing. In the case of high energy
laser, an increased thickness of the protective surface needs to be maintained [1].
Results and discussion
Laser pulse density optimization based on the residual stress analysis
Table 1. Residual stress results for the different pulse densities of LSPwC.
Specimen with pulse density Surface residual stress (MPa) Residual stress at 50 m
depth (MPa)
Unpeened 124 196
LSPwC (800 pulses/cm2) -302 -305
LSPwC (1600 pulses/cm2) -330 -397
LSPwC (2500 pulses/cm2) -349 -489
LSPwC (3900 pulses/cm2) -294 -463
The residual stress was measured using to X-ray diffraction sin2 method. The X-ray irradiations at
the diffractive angle (81.920) are measured by Xpert Pro system (PANalytical, Netherlands) using
CuK-radiation. The electrolyte polishing successive layer removal technique adopted for sub-surface
analysis of residual stress. The surface and sub-surface (at 50 m) residual stress values were
considered for the optimization of laser pulse density. The laser pulse density of 800 pulses/cm2 was
induced the compressive residual stress of - 302 MPa and - 305 MPa on the surface and sub-surface
(at 50 m) respectively. Likewise, the laser pulse density of 1600 pulses/cm2 induced -330 MPa and
-397 MPa compressive stress on the surface and sub-surface (at 50 m) respectively. The laser pulse
density of 2500 pulses/cm2 induced -349 MPa and -489 MPa compressive stress on the surface and
sub-surface (at 50 m) respectively and which is the maximum compressive residual stress. Because
the higher pulse density at 3900 pulses/cm2 induced only -294 MPa and -463 MPa compressive
stresses on the surface and sub-surface (at 50 m) respectively due thermal effect producing surface
damage [1], [4].
Process temperature optimization: Vickers microhardness evaluation

19
Fig. 1. Vickers microhardness profile of different temperature war laser shock peening.
The transverse cross-sectional specimens are used to measure Vickers microhardness with a constant
load of 200 g. The excess amount of precipitation will lead to lose the strength of any material.
Likewise, the process temperature optimization is an important task to control the precipitation level
with the study metal SAE 9254 spring steel. The process temperature optimization were carried out
from 100 0C to 300 0C at an interval of 50 0C. The WLSP without coating at 100 0C to 250 0C is
showing the improved hardness drastically. In the case of 300 0C WLSP, the hardness was decreased
due to excess amount precipitaions formed during this process lead lose the strength of the material.
The average microhardness of unpeened specimen is around 343 HV. The WLSP at 250 0C improved
to 427 HV from 343 HV and it shows around 25% of improvement in hardness. Also, the graph
indicates that the hardening effect is more in the sub-surface than the surface for all the temperature
range of process due to direct laser ablation treatment[1,4,5,7,8-10].
Microstructure analysis
(a (b
) )
Fig. 2. SEM of unpeened and FE-SEM of warm laser shock peening without coating specimen surface
morphologies.
The SEM microstructure indicates unpeened specimen microstructure as shown in Fig. 2a. The FE-
SEM shows the precipitations and refined grains produced by WLSP process as shown in Fig. 2b.
The precipitations in the nano range are clearly seen in Fig. 2a. These carbide precipitations are
20
blocking or filling the grain boundaries and increases the dislocation density of the metallic materials.
In such a case excess amount of precipitation will affect the material strength. Due to dynamic strain
aging and dynamic precipitations the material will get hardened and the mechanical properties such
that fatigue life can be improved[1], [4], [9], [10].
Summary. The low energy Nd: YAG laser with the fundamental wavelength was utilized for the
conventional warm laser shock peening process successfully. The higher laser pulse densities
producing thermal effect affect the induction of compressive residual stress and its magnitude. The
laser pulse density of 2500 pulses/cm2 is optimized for the SAE 9254 spring steelfor automotive
applicatons.The process temperature for the warm laser shock peening without coating is optimized
and the higher temperture (above 250 0C) is lead lost the hardness of the metal. So, this indicates that
the excess amount of precipitation may affect the machanical properties of the metallic materials.
References
[1] S. Prabhakaran, S. Kalainathan (2016), Warm laser shock peening without coating induced phase
transformations and pinning effect on fatigue life of low-alloy steel. Materials & Design, pp. 98-107,
DOI 10.1016/j.matdes.2016.06.026
[2] P. Ganesh, et al. (2012), Studies on laser peening of spring steel for automotive
applications. Optics and Lasers in Engineering 50 (5), pp. 678-686, DOI
10.1016/j.optlaseng.2011.11.013
[3] P. Ganesh, et al. Studies on fatigue life enhancement of pre-fatigued spring steel specimens using
laser shock peening, Materials & Design, 54, 2014, pp. 734-741, DOI 10.1016/j.matdes.2013.08.104
[4] S. Prabhakaran, S. Kalainathan. Compound technology of manufacturing and multiple laser
peening on microstructure and fatigue life of dual-phase spring steel. Materials Science and
Engineering: A 674, 2016, pp. 634-645, DOI 10.1016/j.msea.2016.08.031
[5] Kalainathan, S., S. Prabhakaran. Recent development and future perspectives of low energy laser
shock peening. Optics & Laser Technology, 81, 2016, pp.137-144, DOI
10.1016/j.optlastec.2016.02.007
[6] Ramkumar, K. Devendranath, et al. Influence of laser peening on the tensile strength and impact
toughness of dissimilar welds of Inconel 625 and UNS S32205. Materials Science and Engineering:
A 676, 2016, 88-99, DOI 10.1016/j.msea.2016.08.104
[7] Ye, Chang, et al. Fatigue performance improvement in AISI 4140 steel by dynamic strain aging
and dynamic precipitation during warm laser shock peening. Acta materialia 59 (3), 2011, pp. 1014-
1025, DOI 10.1016/j.actamat.2010.10.032
[8] Liao, Yiliang, Chang Ye, Gary J. Cheng. A review: Warm laser shock peening and related laser
processing technique. Optics & Laser Technology 78, 2016, pp.15-24, DOI
10.1016/j.optlastec.2015.09.014
[9] Podgornik, B., Leskovek, V., Godec, M., b. Sencic. Microstructure refinement and its effect on
properties of spring steel. Mater Sci Eng A 599, 2011, pp. 8186.
[10] Scuracchio, B.G., de Lima, N.B., Schon, C.G,. Role of residual stresses induced by double
peening on fatigue durability of automotive leaf springs. Mater Des 47, 2013, pp. 672676, DOI
10.1016/j.matdes.2012.12.066

21
Studies on 1-Butyl 3-Methylimidazolium Hexafluorophosphate Incorporated

PVC-PBMA Polymer Electrolytes
4
R. Arunkumar1, Ravi Shanker Babu1, M. Usha Rani1
1 Department of Physics, School of Advanced Sciences, VIT University, Vellore, Tamilnadu, India
Keywords: ionic liquids, LiPF6, solution casting techniques, impedance analysis, SEM analysis.
ABSTRACT. Polymer electrolytes consisting of polyvinyl chloride (PVC) and poly (butyl methacrylate) (PBMA) as
polymers, lithium hexafluorophosphate (LiPF6) as complex salt and 1-butyl 3-methylimidazolium hexafluorophosphate
(BmImPF6) as plasticizer were prepared by solution casting technique. The effect of ionic liquid (BmImPF 6) on PVC-
PBMA blend polymer electrolytes are investigated by AC impedance, dielectric and SEM analysis to elucidate their
electrical, dielectric and surface morphological assessment. Ionic conductivity of the prepared polymer electrolytes is
found to be in the order of 10-3 S cm-1. Polymer electrolyte with PVC-PBMA-LiPF6-BmImPF6 (17-17-06-60) is found to
be a potential candidate in battery applications.
Introduction. Tremendous research on solid polymer electrolytes with salt/plasticizer/ceramics

replaces liquid electrolytes in lithium batteries because of limitations in liquid electrolytes, like
corrosion, leakage, flammability, degradation etc. Solid polymer electrolytes (SPE) fulfil those
drawbacks and further SPE are highly compatible with electrodes when compare to its counterparts
[1], [2], [3]. Solid polymer electrolytes based lithium batteries are used as power sources (electronic
devices) in laptops, digital cameras, mobile phones, hybrid electric vehicles (HEVs), plug-in hybrid
electric vehicles (PHEVs) and as batteries for electric vehicles (EVs) [4], [5]. The main drawback
with solid polymer electrolyte battery is its poor ionic conductivity at room temperature. To increase
the room temperature ionic conductivity, several methods like addition of plasticizer, blending of
polymers, crosslinking of polymer, incorporation of inorganic fillers and ionic liquids (ILS) are
reported. Among this, the present work focuses on ionic liquid based polymer electrolytes. Ionic
liquid doped polymer electrolytes have good ionic conductivity at low temperature because it can
dissociate the anion and cation easily at lower temperature due to the molten state of ILS is below
373K. Further ionic liquid doped polymer electrolytes have good thermal stability, non-flammability,
non-volatility, non-toxicity and wide electrochemical window [6]. The ionic liquid incorporated
polymer electrolyte batteries are operated at low temperature (313K) [7]. Ionic liquid have the
advantages of the previously mentioned properties when compared to those with organic solvents [8].
The present work reports the investigation on ILS doped polymer electrolytes. Extensively studied
on the variation in ionic conductivity, dielectric behaviour and morphology of polymer electrolytes
with BmImPF6carried out using ac impedance, dielectric and SEM analysis respectively.
Experimental. Polyvinyl chloride with average molecular weight 48000 g/mol, poly (butyl
methacrylate) with average molecular weight 337000 g/mol, lithium hexafluorophosphateand 1-butyl
3-methylimidazolium hexafluorophosphatewere procured from sigma Aldrich, USA.
PVC-PBMA polymer electrolytes with addition of BmImPF6at different ratios were prepared by
solution casting technique. The required amounts of substances were dried at 373K under vacuum at
10-3 millibar for 10h. The dried polymers and salt were treated with pre-distilled tetrahydrofuran and
4

22
left undisturbed. The solution of PVC and PBMA were mixed together for 24h using a magnetic
stirrer followed by the addition of LiPF6 and BmImPF6 after 5h. The homogenous mixture was stirred
at elevated temperature until slurry was formed. The slurry transformed into Teflon coated glass
plate/petridishes and was left in vacuum atmosphere to evaporate the remaining solvent. The resultant
film was subjected to heat treatment toevaporatetheresidual solvent if any.
Conductivity and dielectric measurement of ILS incorporated PVC-PBMA polymer electrolytes were
carried out by using HIOKI 3532-50 LCR Hi TESTER meter in frequency range of 50Hz to 5MHz
with temperature difference 303 to 373K. Surface morphology of PVC-PBMApolymer electrolytes
were analysed by SEM analysis using Carl Zeiss EVO/185H,UK instrument and accelerating voltage
at 10kV.
Conductivity studies
The ionic conductivity of the polymer electrolyte were calculated using the following relation:

= (1)

where L thickness of the sample measured with using peacock meter;

A area of the film (A= r2);
Rb bulk resistance obtained from intercept on X-axis in Cole-Cole plot.
Temperature dependent ionic conductivity of ionic liquid doped PVC-PBMA polymer electrolytes
are depicted in Fig. 1a. Ionic conductivity of the polymer electrolytes increase with increase in
temperature. As the temperature increases polymer electrolyte can expand and produce more free
volume. In free volume, ionic transportation can occur between electrodes, which lead to
enhancement in ionic conductivity. Dependence of ionic conductivity on temperature for polymer
electrolytes doped with ionic liquid exhibited an increase of two orders of magnitude at 373K
(Table.1). Temperature dependent ionic conductivity of polymer electrolytes are found to obeys the
Vogel TammannFulcher (VTF) relation and it confirms the ionic conductivity occurs due to migration
of ions in a viscous matrix [9].
Fig. 1. Ionic conductivity of PVC-PBMA polymer electrolytes depends on (a) temperature and (b)
various concentrations of BmImPF6.

23
Fig. 1 (b) shows the variation of conductivity with the variation of ionic liquid concentration. The
best room temperature ionic conductivity of the polymer electrolytes is found to be 1.284 x 10-3S cm-
1
at 303K for film A5 which is four orders higher than the polymer electrolytes (0.017 x 10-5S cm-1at
303K) without ionic liquid. The increase in ionic conductivity with BmImPF6 concentration is due to
(i) large number of ionic charge carriers provide by ILS since it has cautions (BmIm+) as well as
anions (PF6), further (ii) the low viscosity of BmImPF6 also assist in increasing amorphicity or
reducing crystalinity of the polymer electrolytes which would ensure conformations in polymer chain
leading to segmental motion resulting in higher conductivity [10].
Table 1. Ionic conductivity of PVC-PBMA polymer electrolytes.

Sample PVC:PBMA:LiPF6: Ionic conductivity 10-5 (S cm-1)
code BmImPF6
303K 318K 333K 353K 373K
A1 47:47:06:00 0.017 0.022 0.035 0.108 0.254
A2 37:37:06:20 0.052 0.093 0.162 0.461 1.320
A3 27:27:06:40 0.122 0.230 0.514 2.952 7.371
A4 17:17:06:60 3.912 6.631 8.256 55.06 153.1
A5 07:07:06:80 128.4 228.5 342.0 467.5 961.4
Dielectric studies
The real and imaginary part of dielectric constant (&) of PVC-PBMA polymer electrolytes are
evaluated using the following relation,

= (2)

= (3)
where C capacitance;
d thickness;
A area of the polymer electrolyte membrane;
conductivity;
angular frequency;
o is permittivity of free space (8.854 x 10-12 F/m).
The real () and imaginary part ()of dielectric constant as function of frequency for 60 wt% of
ionic liquid incorporated PVC-PBMA polymer electrolytes at different temperature are depicated in
Fig. 2(a, b). The real and imaginary part of dielectric constant increase with increase in temperature,
which is due to increase in free ions and charge carrier density. The dielectric constants ( and ) of
PVC-PMA polymer electrolytes are high at low frequency and it decrease gradually with increase in
frequency and tends almost to zero at higher frequency denoting the presence of electrode polarization
effect.

24
Fig. 2. Temperature dependent dielectric constant of PVC-PBMA polymer electrolytes (a) real part
and (b) imaginary part.
Dielectric modulus
The dielectric modulus was introduced by Macedo et al and is inversely proportional to the dielectric
constant. The real (M) and imaginary part (M) of dielectric modulus of PVC-PBMA polymer
electrolytes have been calculated by using the following relation:

M =()2 (4)
+()2

M = ()2 +()2 (5)
where , are real and imaginary part of dielectric constant respectively.

Frequency dependent real and imaginary dielectric modulus for 60 wt% of BmImPF6 incorporated
PVC-PBMA polymer electrolytes are depicted in Fig.3a&b respectively. Both real and imaginary
part of dielectric modulus found to decreases at low frequencies, which implies negligible
contribution due to electrode polarization. The peak intensity for both real and imaginary modulus is
high for lower temperature at higher frequency region. The peak intensity of the dielectric modulus
decrease with increase in temperature may be due to the presence of plurality of relaxation
mechanism. The presence of long tail at low frequency is due to large capacitance associated with the
electrodes.

25
Fig. 3. Temperature dependent dielectric modulus of PVC-PBMA polymer electrolytes (a) real part
and (b) imaginary part.
SEM analysis
Fig. 4. SEM image for 60 wt % BmImPF6 incorporated PVC-PBMA polymer electrolytes at

different magnification (a) 3000x and (b) 7000x.
The surface morphology of the PVC-PBMA polymer electrolytes doped with 60 wt%BmImPF6at
different magnifications (3000&7000x) is shown in Fig. 4 (a, b).The presences of smooth and
ununiformed sized pores and further its helps in enhancing the ionic conductivity of the polymer
electrolytes.
Summary. PVC-PBMA blend polymer electrolytes with BmImPF6at different concentration were
prepared by solution casting technique. The temperature dependent ionic conductivity of PVC-PBMA
polymer electrolytes obeys Vogel Tammann Fulcher relation. The detailed frequency dependent
dielectric behaviour (, , M and M) of PVC-PBMA polymer electrolytes are discussed and
reported. These supporting the defence from conductivity studies which proves the high ionic
conductivity of PVC-PBMA polymer electrolyte with 60 wt% of BmImPF6 exhibiting good stability
suitable for battery applications.
References

26
[1] Ramesh, S., Lu, S. C. (2008). Effect of nanosized silica in poly (methyl methacrylate)lithium bis
(trifluoromethanesulfonyl) imide based polymer electrolytes. Journal of Power Sources, 185 (2),
1439-1443.
[2] Armand, M., Tarascon, J. M. (2008). Building better batteries. Nature, 451(7179), 652-657
[3] Tang, C., Hackenberg, K., Fu, Q., Ajayan, P. M., Ardebili, H. (2012). High ion conducting
polymer nanocomposite electrolytes using hybrid nanofillers. Nano letters, 12(3), 1152-1156.
[4] Bernhard, R., Latini, A., Panero, S., Scrosati, B., Hassoun, J. (2013).Poly (ethylenglycol)
dimethyletherlithium bis (trifluoromethanesulfonyl) imide, PEG500DMELiTFSI, as high viscosity
electrolyte for lithium ion batteries. Journal of Power Sources, 226, 329-333.
[5] Barth, W. V., Hueso, A. P., Zhou, L., Lyons, L. J., West, R. (2014). Ionic conductivity studies of
LiBOB-doped silyl solvent blend electrolytes for lithium-ion battery applications. Journal of Power
Sources, 272, 190-195.
[6] Chaurasia, S. K., Singh, R. K., Chandra, S. (2013). Thermal stability, complexing behavior, and
ionic transport of polymeric gel membranes based on polymer PVdF-HFP and ionic liquid,
[BMIM][BF4]. The Journal of Physical Chemistry B, 117(3), 897-906.
[7] Shin, J. H., Henderson, W. A., Scaccia, S., Prosini, P. P., Passerini, S. (2006). Solid-state
Li/LiFePO4 polymer electrolyte batteries incorporating an ionic liquid cycled at 40 C. Journal of
Power Sources, 156(2), 560-566.
[8] Choi, J. A., Kang, Y., Kim, D. W. (2013). Lithium polymer cell assembled by in situ chemical
cross-linking of ionic liquid electrolyte with phosphazene-based cross-linking agent. Electrochimica
Acta, 89, 359-364.
[9] Capiglia, C., Saito, Y., Yamamoto, H., Kageyama, H., Mustarelli, P. (2000). Transport properties
and microstructure of gel polymer electrolytes. Electrochimica Acta, 45(8), 1341-1345.
[10] Singh, P. K., Kim, K. W., Rhee, H. W. (2009). Development and characterization of ionic liquid
doped solid polymer electrolyte membranes for better efficiency. Synthetic Metals, 159(15), 1538-
1541.

27
Conductivity Enhancement Studies on Poly (Acrylonitrile)-Poly (Vinylidene

Fluoride) Composite Polymer Electrolytes
5
M. Usha Rani1, Ravi Shanker Babu1, S. Rajendran2, R. Arunkumar1
1 Department of Physics, School of Advanced Sciences, VIT University, Vellore

2 Department of Physics, Alagappa University, Karaikudi, India
Keywords: polymer electrolyte, composite, inert filler, plasticizer, impedance studies.
ABSTRACT. Composite electrolyte films consisting of poly (acrylonitrile), poly (vinylidene Fluoride), ethylene
carbonate, propylene carbonate, lithium tetra fluoroborate (LiBF4) and also titanium dioxide (TiO2) particles have been
prepared by solution casting technique. The effect of inorganic filler on the conductivity of the blended polymer
electrolyte has been studied. A conductivity of 3.1 x 10 -5 S cm-1 is achieved at room temperature for the composition
PAN-PVdFLiBF4-EC-PC (21-10-8-33.3-27.7), whereas it improves two orders of magnitude (i.e. 5.624 10 3 S cm1)
upon dispersing fine particles of TiO2 as inert filler into the matrix. The role of ceramic phase is to increase the ionic
conductivity and to reduce the melting temperature which is ascertained from conductivity and thermo
gravimetric/differential thermal analysis respectively.
Introduction. Decades ago, Wright and co-workers [1] pioneered the research on solid polymer
electrolytes and later Armand et al. [2] realized the potential applications of these materials in
batteries with high specific energy and other ionic devices. Even though, polymer electrolytes are
advantageous in terms of shape, geometry, mechanical strength and the potential for strong electrode
electrolyte contact, they have some disadvantages like, poor interfacial properties, low ionic
conductivity at ambient temperature [3]. Generally polymer electrolytes show practical ionic
conductivity only at higher temperatures, and their melting points, and at such high temperatures,
they exist in a quasi-liquid state and become very flexible, and therefore show very poor
dimensional stability. A dimensionally polymer electrolyte film easily cause a short circuit between
a cathode and an anode when it is applied to all solid-state lithium battery. Increasing ionic
conductivity by increasing the salt concentration is ruled out because, higher salt content may favour
reduction in crystalline fraction of polymer but causes high ion-pairing interaction, which lead to salt
aggregation [4].
Hitherto several studies have been made primarily on the enhancement of ionic conductivity at
ambient temperature via various approaches such as blends, copolymers, comb-shaped polymers,
cross-linked networks, addition of plasticizers and incorporation of ceramic fillers onto the polymer
matrix [5]. Studies have revealed that plasticized polymer electrolytes lose their mechanical strength
upon addition of plasticizer and lead poor interfacial properties. The mechanical properties of the
polymer electrolytes can be increased either by chemical or physical curing which incurs high
processing cost. Recently, phase-inversion technique has drawn the attention of many researchers,
despite its advantages it suffers from poor rate capability [6]. Very recently, studies reveal that the
composite polymer electrolytes could offer lithium batteries with reliability and improved safety [6].
Many reports are available on the effect of ceramic oxides on polymer electrolytes such as, physical
and electrochemical properties, increase in cation transference number and improvement of
interfacial stability between the composite polymer electrolyte and lithium metal. In this work, novel
5

28
composite polymer electrolyte composed of PAN-PVdF-EC-PC-LiBF4-TiO2 as promising electrolyte

for all solid-state lithium-ion batteries was prepared, and optimization for high ionic conductivity was
carried out by investigating the amount of ceramic filler incorporated.
Experimental. Poly (acrylonitrile) (PAN) (average molecular weight: 94000) and poly (vinylidene
fluoride) (PVdF) (average molecular weight: 534000) bought from Aldrich, USA were dried at 353K
under vacuum for 10 h; lithium tetra fluoroborate (LiBF4) (Aldrich) was dried at 343K under vacuum
for 24h. Plasticizer ethylene carbonate (EC) propylene carbonate (PC) (Aldrich) was used without
further purification. Titanium dioxide (TiO2) procured from Aldrich, USA of particle size <5 m was
used after annealing at 373K for 10 h. All the electrolytes were prepared by solution casting technique.
Appropriate quantities of PAN, PVdF, LiBF4(Table 1) were dissolved by adding in sequence to pre-
distilled DMF (dimethylformamide. E. Merck, Germany). After incorporating the required amount
of plasticizer EC and PC, inorganic filler TiO2was suspended in the solution, stirred for about 48
hours at room temperature, and then at 333K for 4 h before the electrolytes were cast on finely
polished Teflon supports or Teflon covered glass plates. The films were dried in vacuum oven at
333K at a pressure of 103Torr for 24 h. The thus obtained film was visually examined for its dryness
and free-standing nature. The obtained films were characterized by XRD, FTIR, conductivity,
TG/DTA and SEM analysis.
Structural Analysis. The X-ray diffraction method has been used only in a limited perspective to
identify or confirm the amorphicity, complexation of the polymer electrolyte films. The X-ray
diffraction pattern of pure PAN, PVdF, LiBF4, TiO2 and complexes are shown in Fig 1.(I)
respectively. Fig 1 [I. (b), (c) and (d)] reveals the crystalline nature of PVdF (with sharp peaks at 14,
19 & 22 ), LiBF4 and TiO2 respectively. From the diffraction patterns it is obvious that there is a
decrease in relative intensity and broadening of the peak in the complexes. It may be due to the
addition of salt and blending of amorphous PAN, which induces a change in the crystallographic
organization in the crystalline PVdF. This result can be interpreted by considering the Hodge et al.
[7] criterion, which establishes a correlation between the height of the peak and the degree of
crystallinity. The effect of adding TiO2 to the polymer complex is to improve ionic conductivity and
thermal stability. The sharp peaks in the spectrum of polymer complex [Fig.1. I. (g), (h) and (i)] reveal
the presence of undissolved TiO2 in the polymer matrix, Fig 1. I. (e & f) show the effect of Tio2 upon
PVdF which shows the reduction of crystallinity of PVdF. The diffraction peaks are found with lower
intensity till 10 wt% and found to increase on further addition indicating the increase in crystallinity
of the polymer electrolyte which may be responsible for the lowering of ionic conductivity. The
maximum ionic conductivity is found for PAN-PVdF-EC-PC-TiO2 (10 wt %) polymer electrolyte
system which may be due to the higher amorphicity of the polymer electrolyte.
FT-IR spectroscopy is used to establish interaction between the constituents used in the complex. In
the present case, FT-IR is used to establish the interaction between the polymers, salt and plasticizers.
Such interaction can induce changes in vibrational modes of the atoms or molecules in the material.
The FTIR spectra obtained for pure PAN, PVdF, LiBF4, EC, PC, TiO2 and the complexes in the range
of 4000 to 400 cm-1 is shown in Fig. 1 [II (a-k)] respectively. The vibrational bands at 2942, 2245,
1250, 1074 cm-1 in pure PAN is assigned to C-H stretching, CN stretching, C-N stretching, C-C
stretching respectively. The characteristic frequency of PVdF occurring at 1277, 1185, 854 cm- 1 are
assigned to C-F stretching, C-F2 stretching and characteristic frequency of vinylidine compound
respectively. These characteristic frequencies of PAN and PVdF mentioned above are found to be
shifted to 2952, 2243, 1076 and 1174, 881cm-1 for PAN and PVdF respectively. The characteristic
frequency corresponding to C-N and C-F stretching are found to be absent in the complex. Some of
the absorption peaks corresponding to the primary constituents of the polymer complexes were found
to be shifted in the polymer complex. The absorption bands at (1455, 781, 640 cm-1) of PAN, (2996,
1554, 1165 cm-1) of EC, (2933, 1484 cm-1) of PC and 1320 cm-1 of LiBF4 are shifted to (1452, 777,
645 cm-1), (2291, 1556, 1170 cm-1), (2937, 1483 cm-1) and 1313 cm-1 respectively. Apart from the

29
shift in peaks, there are some new peaks obtained at (2980, 2519, 1969, 1570, 974, 717 and 482 cm- 1)
in the complexes. The above analysis establishes the confirmation of complex formation.
Fig. 1. (I). XRD patterns of (a) PAN, (b) PVdF, (c) LiBF4, (d) TiO2 and complexes PAN(21)-
PVdF(10)-LiBF4(8)-EC(33.3)-PC(27.7)-TiO2(X), (e) 0, (f) 5, (g) 10, (h) 15, (i) 20. (II). FTIR Spectra
of (a) PAN (b) PVdF, (c) LiBF4, (d) EC, (e) PC, (f) TiO2 and complexes PAN(21)-PVdF (10)-
LiBF4(8)-EC(33.3)-PC(27.7)-TiO2(X), (g) 0, (h) 5, (i) 10, (j) 15, (k) 20.
Conductivity measurements. Inorganic filler (TiO2) dependent ionic conductivity of PAN-PVdF

composite polymer electrolytes are depicted in Fig.2. Evident from the isotherm (Fig. 2a), that, as the
concentration of ceramic increases, the conductivity is found to increase up to a certain concentration
(10 wt %) and then decrease Table 1. This increase in conductivity due to ceramic addition can be
attributed to (a) the ceramic particles acting as nucleation centres for the formation of minute
crystallites. (b) The ceramic particles aiding in the formation of amorphous phase in the polymer
electrolyte. (c) The formation of a new kinetic path via polymer ceramic boundaries (i.e. mobility of
ions through ceramic rich phase which entraps the residual solvents ensuing ion mobility). The
conductivity is not a linear function of filler concentration, at low concentration levels of TiO2, the
dilution effect which tends to depress the conductivity is efficiently contrasted by the specific
interactions of ceramic surface, which promote fast transport thus the net result is a progressive
enhancement of the conductivity. At higher filler content the dilution effect predominates and the
conductivity decays.
Temperature dependence of ionic conductivity is found to increase with increase in temperature (Fig.
2b) is due to polymer segmental motion. At higher temperature, the segmental motion either permits
the ions to hop from one site to another or provides necessary voids for ions to move in the polymer
matrix. As the temperature increases, polymer chains acquire faster internal modes in which the bond
rotations produce faster segmental motion. This in turn, favours the hoping inter and intra-chain ion
movements and the conductivity of the polymer electrolyte increases accordingly. The temperature

30
dependence of electrical conductivity (log vs. 1/T) indicates that the ionic conductivity obeys VTF
relation, which describes the transport properties in a viscous matrix. However, at lower temperature,
the presence of Li salt lead to salt-polymer or cation-dipole interaction, which increase the cohesive
energy of polymer networks. As the free volume decreases, polymer segmental motion and ionic
mobility are hindered, hence ionic conductivity decreases. It is found that PAN-PVdF-LiBF4-EC-PC
complex with 10 wt. % of TiO2 has got the maximum room temperature conductivity of 5.624 X 10-
3
S/cm which is higher compared to the system bereft of ceramic oxide.
Fig. 2. (a). Conductivity of PAN-PVdF-LiBF4-EC-PC System as a function of TiO2 concentration,

(b). Arrhenius plot of log Vs reciprocal temperature of PAN( 21)-PVdF(10)-LiBF4(8)- PC(27.7)-
EC(33.3)- TiO2(X wt. %) 0 (1), 5 (2), 10 (3), 15 (4), 20 wt. %.
Table 1. Conductivity values of PAN(21)-PVdF(10)-LiBF4(8)-EC(33.3)-PC(27.7) with 5 different

composition of TiO2 at different temperatures.
Films Composition Conductivity values of PAN: PVdF : LiBF4: X TiO2 in x 10-3
of TiO2 S cm-1
303 K 318 K 333 K 353 K 373 K
0 0 0.031 0.076 0.166 0.240 0.372
1 5 0.127 0.240 0.378 0.566 0.831
2 10 5.624 1.413 2.741 4.258 5.505
3 15 0.355 0.933 1.860 3.155 4.168
4 20 0.217 0.644 1.410 2.195 2.792
TG / DTA analysis
Thermal analysis of PAN-PVdF-EC-PC-LiBF4-TiO2 (10 wt. %) system which shows maximum ionic
conductivity was carried out using PERKIN ELMER (Pyris Diamond) USA in the range 32 to 825C
at a heating rate of 10C/min. The TG/DTA spectrum of the sample mentioned above is shown in
Fig. 3.

31
Fig. 3. TG/DTA curve for PAN(21)-PVdF(10)-LiBF4(8)-EC(33.3)-PC(27.7)-TiO2(10).
This shows an endothermic peak in DTA around 49-50C associated with a weight loss of 9% which
may be due to the evaporation of moisture absorbed by the sample during loading. The polymer
electrolyte film is found to be stable till 279C associated with a weight loss of 15% which could be
confirmed by the exothermic peak obtained around 253C-321C with a peak maximum at 290C.
The weight loss of the polymer beyond 290C is heavy which may be due to the decomposition of
the electrolyte constituents indicating the temperature range for efficient usage. Hence it is concluded
that the polymer electrolyte PAN(21)-PVdF(10) EC(33.3)-PC(27.7)-LiBF4(8)-TiO2(10) can be
effectively used in lithium polymer battery applications.
Scanning electron microscopic studies.
The microstructure of polymer blend films plays a vital role for effective use in practical applications.
Fig.4 exhibits the photographs of PAN (21) PVdF (10) LiBF4 (8)- EC (33.3)-PC (27.7) - TiO2
(10) at two different magnification i.e. 200 and 1000. Under these magnifications, it is seen that the
ceramic particles are so closely packed which would offer low unstable interfacial resistance by
reducing the growth of lithium passivation. Moreover the presence of ceramic fillers could
accommodate more amount of plasticizer and polymer matrix in between them (evident from Fig. 4a
and b respectively), which would help in withstanding the stress produced during fabrication and
functioning of this electrolyte in battery applications.

32
Fig. 4. SEM photographs of PAN(21)-PVdF(10)-LiBF4(8)-EC(33.3)-PC(27.7)-TiO2(10) at (a 200

(b) 1000 magnifications.
Summary. Five different polymer electrolyte systems consisting of PANPVdFLiBF4EC- PC-

TiO2 [TiO2=0, 5, 10, 15, 20 wt. %] have been studied. Of the five films, the film 2 is found to be the
best on the basis of conductivity and mechanical stability. The conductivity of the polymer electrolyte
PAN (21)-PVdF (10) EC (33.3)-PC (27.7)-LiBF4 (8)-TiO2 (10) is found to be maximum (5.624 X
10-3 S/cm). The thermal stability of the film is estimated as 280C. Hence, the properties (based on
the studies reported) of PAN (21)-PVdF (10) EC (33.3)-PC (27.7)-LiBF4 (8)-TiO2 (10) polymer
electrolyte look very promising for Li battery applications and could be used effectively.
References
[1] Fenton, D. E., Parker, J. M., Wright, P. V. (1973). Complexes of alkali metal ions with poly
(ethylene oxide). Polymer, Vol. 14(11), 589.
[2] Armand, M. B., Chabagno, J. M., Duclot, N. J., &Vashishta, P. (1979). Mundy, Shenoy (Eds.),
Fast Ion Transport in Solids.
[3] Appetecchi, G. B., Scaccia, S., Passerini, S. (2000). Investigation on the Stability of the Lithium
Polymer Electrolyte Interface. Journal of the Electrochemical Society, Vol. 147(12), 4448-4452, DOI
10.1149/1.1394084
[4] Reddy, M. J., Chu, P. P. (2002). Ion pair formation and its effect in PEO: Mg solid polymer
electrolyte system. Journal of power sources, Vol. 109(2), 340-346.
[5] Marcinek, M., Syzdek, J., Marczewski, M., Piszcz, M., Niedzicki, L., Kalita, M., Kasprzyk, M.
(2015). Electrolytes for Li-ion transportReview. Solid State Ionics, Vol. 276, 107-126.M.
[6] Appetecchi, G. B., Croce, F., Persi, L., Ronci, F., Scrosati, B. (2000). Transport and interfacial
properties of composite polymer electrolytes. Electrochimica Acta, Vol. 45(8), 1481-1490.
[7] Hodge, R. M., Edward, G. H., & Simon, G. P. (1996). Water absorption and states of water in
semi crystalline poly (vinyl alcohol) films. Polymer, Vol. 37(8), 1371-1376.

33
A Comparative Study on the Dielectric Properties of Lanthanum Copper

Titanium Dioxide (La2/3Cu3Ti4O12) Ceramic with Conventional and Microwave
Sintering Routes
6
Surya Mallick1, Pawan Kumar2, M. Malathi1, a
1 Condensed Matter Research Laboratory, Department of Physics, School of Advance Sciences, VIT University,
Vellore, Tamilnadu, India
2 National Institute of Technology, Rourkela, Odisha, India
a mmalathi@vit.ac.in
Keywords: microwave, conventional, dielectric, ceramics.
ABSTRACT. Lanthanum Copper Titanium Dioxide (La2/3Cu3Ti4O12, LCTO) precursor powders were synthesized by a
cost effective solid-state reaction. The material is sintered at two different techniques one is conventional and other one
is microwave. The microstructure and impedance characteristics were found to be strongly dependent on the sintering
conditions. The sintering has been done at 1, 000oC for 4 thin conventional method and for 20, 40and 60 min in microwave
method to compare the effects of two different sintering processes. X-ray powder diffraction study (XRD) analysis,
dielectric constant, dielectric loss and Scanning Electron Microscopy (SEM) results are observed. Structural properties
and phase formation was confirmed through XRD, this confirms Perovskite cubic structure of LCTO ceramics. Density
of the samples determined using Archimedes principle with water as liquid medium. SEM micrographs are taken and
results are being compared. Dielectric constant was investigated for different frequency values (1 kHz, 10 kHz, 100 kHz,
1 MHz) with temperature and the effective dielectric constant and loss as a function of frequency has been studied at
room temperature. Dielectric constant of microwave-sintered sample was found to be higher compared to the conventional
sintered sample at room temperature.
Introduction. Giant dielectric materials have become increasingly important due to the strong
technological needs for the further reduction of dimensional size and the enhancement of performance
in capacitance-based components like capacitors. In recent years a series of Perovskyte- related
structure material, ACu3Ti4O12 (A= Ca1, La2/32, Y2/33, Na1/2Bi1/24, Na1/2La1/25) has been extremely
investigated because of its giant dielectric constant accompanied by low dielectric loss at room
temperature.La2/3Cu3Ti4O12 (LCTO)is a member of the ACu3Ti4O12 family but so far there are limited
literatures reporting LCTO ceramics out of them most studies are focused on preparation,
microstructure and dielectric properties of LCTO ceramics[1-3].LCTO ceramics can be fabricated by
a conventional solid state reaction [4]. However, the solid-state reaction has some disadvantages such
as long processing time, low purity and inhomogeneous grain size, which results in poor dielectric
properties. In general, the improvement of the fabrication methods is an effective way to improve
electrical characteristics of the ceramics. There are many alternative methods have been used to
prepare electronic ceramics which includes Sol-gel method, hydrothermal synthesis, combustion
route, spark plasma sintering , hot pressing, out of which Sol-gel method have been attempted to
prepare LCTO ceramics[1, 4]. However, these methods are complex and expensive which makes it
difficult in industrial application. Microwave sintering for electronic ceramics is superior to
conventional sintering owing to its unique characteristics, such as rapid heating, enhanced
densification rate and improved microstructure. Microwave heating differs significantly from
6

34
conventional heating. In the microwave, sintering process the heat is generated internally within the
material instead of originating from external sources and hence there is an inverse heating profile.
The heating is very rapid as the material is heated by energy conversion rather than by energy transfer,
which occurs in conventional techniques. Microwave sintering ensures considerable time and energy
saving, and therefore considered as one of the most prospective sintering techniques in material
processing. The method has been widely applied in the fabrication of electronic ceramics [5].
In this work, the LCTO ceramics were fabricated by conventional and microwave sintering. The
influence of sintering methods, sintering time on the microstructure and dielectric properties of LCTO
ceramics investigated systematically. The origin of high dielectric constant of LCTO was studied by
impedance analysis. From the XRD peaks, it has been shown that LCTO has a perovskite cubic
structure. LCTO ceramics produced from microwave sintering method giving uniform and dense
grain morphology. Several reports have shown that many factors, such as electrodes, grain boundaries
or domain boundaries are responsible for the high dielectric constant and further improvements in
dielectric properties have been studied [6, 7]. We believe that our present studies would help in
providing more insight and rationalizing the dielectric behaviour of the ceramics at different sintering
routes.
Experimental Methods. Polycrystalline ceramic powders of LCTO were prepared via the
conventional solid-state reaction route using stoichiometric amounts of La2O3, CuO and TiO2. The
raw materials were measured using the high precision balance machine. These were thoroughly mixed
in an acetone medium using a ball mill. Then the mixture was thoroughly grinded for one hour. This
was followed by the calcination of the powder in alumina crucible at 1, 000oC for 4, 6, 8and 12h, at
a heating rate of 5 oC per minute in conventional furnace. During the calcination process, ferroelectric
phase is obtained because of solid phase reaction between the constituents. Single Phase formation
was confirmed through XRD. The XRD patterns of the samples were taken at an angle2(20270)o
with a scanning rate of 2o per minute. The polycrystalline powder was then cold pressed into the
pallets using PVA as a binder. LCTO pallets were sintered in two different methods one is
conventional sintering and other one is microwave sintering. In conventional sintering process, pallets
were fired at one, 000oC for 4h whereas in microwave sintering process pallets were fired at 1,
000oCfor 20, 40 and 60 min, respectively. Pallet densities were measured using Archimedes principle
using water as the liquid medium. The microstructural features and grain size distribution in sintered
pallets were studied by SEM. The grain sizes were found using Average Grain Intercept Method
(AGI) [7]. The dielectric constant measurement was carried out as a function of temperature for
different frequency values (1 kHz, 10 kHz, 100kHz, 1MHz), along with that dielectric constant and
loss as a function of frequency were measured at room temperature using independence gain phase
analyzer. For these purpose surfaces of sintered pallets sputtered with silver. Ideally silver should
adhere strongly to the ceramics, it should be very thin, practically zero resistance and with a good
chemical and physical durability.
Results and Discussions. Fig. 1 shows the XRD patterns of LCTO powders calcined for different
times (4, 6, 8 and 12 h). The XRD patterns are virtually the same and show only single
phaseperovskite (ABX3) structure, without the evidence of the second phase. XRD patterns of LCTO
ceramics are in agreement with the respective joint committee on powder diffraction standards (cubic,
space group- Im3, space group number- 204, JCPDS file no. 75-2188). As the calcination time
increases, the substance begins to melt, these results secondary peaks to the XRD pattern. From the
pattern, it has cleared that cupper and calcium has diffused completely into the LCTO ceramic lattice
to form a solid.

35
Fig. 1. XRD pattern of LCTO calcined at 1, 000C in conventional way for (a) 4h, (b) 6 h, (c) 8 h
and (d) 12h, -Unidentified Phase.
Fig. 2. SEM images of sample Sintered for (a) 4h, (b) 20 min, (c) 40 min and (d) 60 min.
Fig. 2 (a-d) show the surface morphologies of LCTO ceramics sintered at 1, 000oC for 4h in
conventional furnace and for 20, 40and 60minin microwave furnace. We termed conventionally
sintered sample for 4 hours as C-4 and microwave sintered sample for 20, 40, and 60 min as M-20,
M-40, and M-60, respectively. It is clear from the micrographs that the grains have smooth faces
associated with cubic appearance.
From the table 1 it can be shown that the gran size of the conventionally sintered sample (C-4) is less
compared to microwave sintered samples (M-20, M-40 and M-60). Ceramics with larger grain size
have a small volume fraction taken up by Schottky barriers at the grain boundary, which will lead to
the decrease of the effective thickness of charge storage regions. This may corresponds to the thinner
barrier width and consequently leads to larger dielectric constant [8], [9]. As the microwave sintering
time extends LCTO ceramics become uniform, denser and grain size increases. The sample M-20,
M-40 and M-60exhibits relatively homogeneous grain sizes and low porosity. Density of M-40 found
to be 5.06 g /cm3, which is comparatively higher than C-4.

36
Table 1. Calculated grain sizes are listed below.

Sample code Grain size (m)
M-60 2.4
M-40 2.2
M-20 1.4
C-4 1.3
*
M- Microwave, C- conventional
Based on practical application, ceramics with high dielectric constant and low dielectric loss must be
selected firstly. Fig. 3 (a), shows the variation of dielectric constant with temperature at different
frequency values (1 kHz, 10 kHz, 100 kHz, 1 MHz), for M-40. It can be seen that there is a phase
transition from ferroelectric to paraelectric at Curie temperature (Tc) (250 oC, 1 kHz), large value of
Tc can be found at higher frequency range (106 Hz). The Dielectric constants values showing weak
temperature and frequency dependence up to Tc, after that it increases sharply with increase in
temperature which is due to increase in polarization at higher temperature. It is found that there is
weak temperature dependence of dielectric constant at higher frequency range, (106 Hz). Fig. 3 (b),
shows the variation of dielectric constant and dielectric loss of M-40as a function of frequency at
room temperature. Same analysis has been done for M-60, M-20 and C-4, which are not being shown
here. The results indicate that dielectric constant of M-40 is around 1.097, which is comparatively
higher than C-4at room temperature. All the samples reasonably exhibited high dielectric constants
at low frequencies. Furthermore, the dielectric losses of the microwave sintered samples for 20, 40
and 60 min are lower than that of the conventional sintered sample for 4 h at room temperature. The
dielectric loss of M-40 found out to be 1.04 at room temperature.
Fig. 3. (a)Variation of dielectric constant (r) at different frequency values as a function of

temperature, (b) Variation of dielectric constant (r) and dielectric loss (tan ) with frequency at
room temperature forM-40.
Summary. The LCTO ceramics have been successfully prepared by microwave and conventional
sintering route. The effect of sintering process on microstructure and dielectric properties of LCTO
ceramics has been investigated systematically. The sample calcined for 4, 6, 8 and 12 h in
conventional heating are found out to be single phase perovskite cubic structure. SEM analysis

37
showed dense microstructure in the sample with grain size of 1-2m. As the microwave sintering
time extends the grain size and density of LCTO ceramics increases and the sample gradually
becomes denser. The microwave sintered pallets exhibited more homogeneous microstructure, less
porosity as well as comparatively higher value of dielectric constant (M-40, 1, 097) and lower value
of dielectric loss (M-40, 1.04) compared to conventional sintered sample (C-4) at room temperature.
M-40 showed much higher value of dielectric constant (40 x104, at 103Hz), which displays weak
temperature and frequency dependence over a certain temperature range. The Curie temperature (Tc)
found out to be225 oC at 1 kHz, the value increases at higher frequency range.
References
[1] Z. Liu, Z. Yang, X. Chao, Structure dielectric property and impedance spectroscopy of
La2/3Cu3Ti4O12 ceramics by solgel method, Journal of Materials Science: Materials in Electronics,
2016, 8980-8990. DOI 10.1007/s10854-016-4929-z
[2] B.S. Prakash, K.B.R. Varma, Effect of sintering conditions on the microstructural, dielectric,
ferroelectric and varistor properties of CaCu3Ti4O12and La2/3Cu3Ti4O12 ceramics belonging to
the high and low dielectric constant members of ACu3M4O12 (A=alkali, alkaline-earth metal, rare-
earth metal or vacancy, M=transition metal) family of oxides, Physica B: Condensed Matter, 2008,
22462254. DOI 10.1016/j.physb.2007.12.004
[3] B.S. Prakash, K.B.R. Varma, Effect of sintering conditions on the dielectric properties
ofCaCu3Ti4O12 and La2/3Cu3Ti4O12 ceramics: A comparative study, Physica B: Condensed
Matter, 2006, 312-319. DOI 10.1016/j.physb.2006.03.005
[4] Z. Liu, X. Chao, P. Liang, Z. Yang, L. Zhi, Differentiated Electric Behaviors
of La2/3Cu3Ti4O12Ceramics Prepared by Different Methods, Journal of the American Ceramic
Society, 2014, 2154-2163. DOI: 10.1111/jace.12940
[5] W. Cai, C. Fu, G. Chen, X. Deng, K. Liu, R. Gao, Microstructure, dielectric and ferroelectric
properties of barium zirconate titanate ceramics prepared by microwave sintering, Journal of
Materials Science: Materials in Electronics, 2014, 4841-4850. DOI 10.1007/s10854-014-2242-2
[6] L.Singh, U.S. Rai, K.D. Mandal, N.B. Singh, Progress in the growth of CaCu3Ti4O12 and related
functional dielectric perovskites, Progress in Crystal Growth and Characterization of Materials, 2014,
15-62. DOI 10.1016/j.pcrysgrow.2014.04.001
[7] Y. Pu, W. Chen, S. Chen, H.T. Langhammer, Microstructure and dielectric properties of
dysprosium-doped barium titanate ceramics, Ceramica, 2005, 214-218. DOI 10.1590/S0366-
69132005000300007
[8] B.S. Prakash, K.B.R. Varma, Influence of sintering conditions and doping on the dielectric
relaxation originating from the surface layer effects in CaCu3Ti4O12 ceramics, Journal of Physics
and Chemistry of Solids, 2007, 490-502. DOI 10.1016/j.jpcs.2007.01.006
[9] J. liu, R.W. Smith, W.N. Mei, Synthesis of the Giant Dielectric Constant Material CaCu3Ti4O12
by Wet- Chemistry Methods, Chemistry of Materials, 2007, 6020-6024. DOI 10.1021/cm0716553

38
Theoretical Investigation on the Structural, Elastic and Mechanical Properties

of Rh3HxNb1-x(x=0.125, 0.875)
7
M. Manjula1, M. Sundareswari1
1 Department of Physics, Sathyabama University, Chennai, India
Keywords: first-principles theory, density functional theory, electronic properties, mechanical properties, ductility.
ABSTRACT. Electronic, elastic and mechanical properties of Rh3HxNb1-x(x=0.125, 0.87) are investigated from density
functional theory using FP-LAPW method within generalized gradient approximations. The lattice parameters and ground
state properties are calculated by using optimization method. Shear modulus, Youngs modulus, Poissons ratio, G/B ratio
and anisotropy factor are calculated using elastic constants C11, C12 and C44. The calculated results are consistent with
available theoretical and experimental data. Systematic addition of Hf with Rh3Nb shows that the Rh3Hf0.125Nb0.875 and
Rh3Hf0.875Nb0.125 are ductile. Charge density plots assess the results.
Introduction. L12 intermetallic compounds such as rhodium and iridium based compounds are of
great interest in industrial applications [1], [2]. The mechanical and thermal findings on rhodium base
alloys are more convenient for high-temperature structural applications than iridium base alloys.
Rhodium is most frequently used as an alloying agent in other materials such as platinum and
palladium. These alloys are used to make electrodes for aircraft spark plugs, detectors in nuclear
reactors, laboratory crucibles and furnace coils. It has higher thermal conductivity, high temperature
strength, good oxidation resistances and lower thermal expansion coefficient which are beneficial
properties for high temperature applications [3], [4], [5], [6], [7], [8], [9]. The L1 2 crystal structure
offers the possibility of enhanced ductility and workability of these materials. This motivates us to
focus our research on rhodium base alloys. Especially, we focus our attention to design new materials
with enhanced ductility from existing one. Alloying is one of the effective ways to attain our aim. To
our best knowledge no systematic study on Rh3HfxNb1-x ternary alloy system. We have already
reported Rh3HfxNb1-x (x= 0.25.0.75) combinations in our previous work [10]. In the present study, a
first-principles calculation based on the density-functional theory was carried to investigate the
electronic structure and mechanical properties of Rh3HfxNb1-x (x= 0.125.0.875) combinations. The
ductile/brittle nature of these compounds is analysed.
A number of theoretical and experimental structural have been performed for structural, electronic,
elastic and mechanical properties of Rh3Nb. Yamabe et al. investigated the microstructure evolution
and high temperature strength of Rh-based alloys [11]. Rajagopalan and Sundareswari reported
structural and electronic properties of this compound [12]. Chen et al. [13] investigate elastic and
mechanical properties of this compound. The mechanical properties of Rh3Nb are studied by Miura
et al. [14]. Some of the thermal properties were measured by Terada et al. [15]. Their strength
behaviour was discussed by Yamabe-Mitarai et al. [16]
Computational Methods. Our calculations are carried out by means of Full Potential Linearized
Augmented Plane wave (FP-LAPW) method implemented in the WIEN2k code [17]. The basis set is
obtained by dividing the unit cell into non-overlapping spheres surrounding each atom and creating
an interstitial region between the spheres. The exchange and correlation was treated within the
7

39
generalized gradient approximation by Perdew et al [18]. 101010 k-point mesh is used in the
irreducible Brillion Zone. The plane wave expansion is taken as RMT Kmax = 7.0 and lmax=10. Charge
density Fourier expansion are extended up to Gmax=12. The total energies are converged below
0.0001eV and the charges are converged below 0.001mRy.
Result and Discussion. The Rh3Nb alloy has a Cu3Au-type structure with space group 221-Pm3m.
The Rh and Nb atoms are located at the site (0, 0.5, 0.5) and (0,0,0) respectively. The optimized lattice
parameters for Rh3Nb, Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125 are presented in Table 1 and calculated
lattice constant for Rh3Nb agree very well with experimental and theoretical data [12], [13]. For
Rh3Nb, the percentage error between the calculated and the experimental lattice constant is 1.07. The
calculated elastic constants (C11, C12 and C44), Shear modulus (G), Youngs modulus (E), Cauchy
pressure (C12-C44), G/B ratio, Poissons ratio (), and anisotropy factor (A) for Rh3HfxNb1-x (x =0,
0.125, 0.875) combinations are reported in Table1 and these values are used to predict ductile/brittle
nature of the compounds. From Table 1, one can note that the computed B, G, E and C44 values for
Rh3Nb are quantitatively higher than the other two combinations.
For cubic system there are three independent elastic constants namely C11, C12 and C44. The
mechanical stability conditions for cubic crystal are: C11-C12 >0, C11 >0, C44 >0, C11+2C12 >0. The
calculated elastic constants (Table 1) obey the mechanical stability criteria, suggesting that these
compounds are mechanically stable.
Table 1. The optimized lattice parameter, elastic constants and elastic properties of Rh3HfxNb1-x (x=0,
0.125, 0.875).
Parameters Rh3Nb Rh3Hf0.125Nb0.87 Rh3Hf0.875Nb0.12
5 5
Lattice Constant (a.u.)
Present study aexp =7.2887 aoal= 7.3677 acal= 7.4405
acal =7.3668
Other study a aexp=7. 289
acal =7.3625
C11 475.48 374.72 322.10
C12 169.58 186.33 174.16
C44 456.58 211.16 102.88
Cauchy Pressure(C12-C44) -287.00 -24.83 71.28
Bulk Modulus(B), GPa 271.55 249.13 223.47
Shear Modulus(G), GPa 294.81 152.73 90.14
Youngs Modulus(E), GPa 649.42 380.44 238.38
G/B 1.08 0.61 0.40
Poissons Ratio() 0.10 0.25 0.32
B/C44 0.594 1.179 2.172
HV 77.87 25.91 10.68
A 2.27 1.62 1.179
Bulk modulus is a measure of average atomic bond strength of materials [19]. It is strongly correlated
with cohesive energy or binding energy of atoms in crystals. The large value of shear modulus
indicates that the more pronounced directional bonding between atoms [20], [21]. Youngs modulus
(E) indicates the stiffness of the material. Higher its value the material will be stiffer. From Table 1,
the values of B, G and E reveals that the addition of Hf in Rh3Nb can decrease the atomic bond
strength, directional bonding and stiffness of the material.
Ductile/brittle nature of the alloy is investigated to analyse the effect on brittleness of Rh3Nb on
addition of hafnium. The ductility of the compounds investigated based on Cauchy pressure (C12-
C44), G/B ratio and Poissons ratio (). According to Pettifor [22], if C12-C44 is positive, the material
exhibits metallic characteristics and it is negative for non-metallic with directional bonding. Rh3Nb
and Rh3Hf0.125Nb0.875 are brittle having negative Cauchy pressure (-287GPa & -24.83) and
Rh3Hf0.875Nb0.125 is ductile having positive Cauchy pressure (71.28GPa). According to Pugh criterion
40
[23], if G/B < 0.57 the material exhibits ductile behaviour, otherwise, it exhibits brittle behaviour.
This ratio for Rh3Hf0.875Nb0.125 (0.39) is less than 0.57 reveals that ductile nature. Poissons ratio ()
[24] explains about the characteristics of the bonding forces. If >0.26, the material is ductile;
otherwise brittle. The value for Rh3Hf0.875Nb0.125 is 0.33 indicates that the ionic contributions to the
atomic bonding are dominant for these compounds.
Elastic anisotropy factor (A) is an indicator of the degree of anisotropy in the solid structures [25].
For a complete isotropic material A=1, when the value of A is smaller or greater than unity it is a
measure of the degree of elastic anisotropy. From Table 1, it can be seen that the Rh3Nb is and
anisotropy material due to A>1. With the addition of Hf to Rh3Nb, the degree of anisotropy decreases.
The calculated microhardness HV [21] for Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125 is 25.91 GPa and
10.68 GPa respectively (Table 1). From the calculations, it is found that the hardness decreases when
hafnium is added to the parent Rh3Nb alloy. Along with bulk and shear modulus, the elastic constant
C44 is also an important parameter indirectly governing the indentation hardness [26]. Hence,
Rh3Hf0.875Nb0.125 identified as less hard material having low hardness and C44 values than
Rh3Hf0.125Nb0.875.
The results are assessed by plotting charge density plots. Fig. 1 (a-c) shows that the charge density
plots of Rh3Nb, Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125 alloy combinations respectively. In general,
the brittle materials have strong directional characteristic of bonding. From Fig. 1a, one can observe
that the charge density contours encloses Nb-Rh-Nb atoms and this can be attributed to the directional
covalent nature (brittle). Such directionality is decreased in Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125
when Nb is replaced by Hf (Hf-Rh-Nb) shown in Fig. 1b & 1c. In Fig.1c, the electron density contours
enclosing Hf & Rh atoms and Hf & Nb atoms are not observed. This makes the directional bonding
very weak, it may be attributed to the ductile nature of Rh3Hf0.875Nb0.125. Thus, addition of Hf to
Rh3Nb reduces the directional bonding nature present in Rh3Nb, resulting in a transition from brittle
to ductile nature in Rh3Hf0.875Nb0.125.
(a) (b) (c)

Fig. 1. Charge density plot of (a) Rh3Nb (b) Rh3Hf0.125Nb0.875 and (c) Rh3Hf0.875Nb0.125.
Fig. 2 (a-c) represents the DOS curves of Rh3Nb, Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125 alloy
combinations respectively. From DOS histograms, it is observed that the peaks in the total density of
states that lie below the Fermi level are mainly due to the Rh-d states and above the Fermi level are
Nb-d and Hf-d states. In Fig. 2a, one can notice a pseudo gap in Rh3Nb and in Fig. 2 (b-c), there is
no noticeable pseudo gap in Rh3Hf0.125Nb0.875 and Rh3Hf0.875Nb0.125 combinations. The pseudo gap
can directly reflect the strength of covalent bonding.

41
(a) (b) (c)

Fig. 2. DOS histograms of (a) Rh3Nb (b) Rh3Hf0.125Nb0.875and (c) Rh3Hf0.875Nb0.125.
The Debye temperature is one of the important parameter closely related to many physical properties.
It is a measure of thermal conductivity of materials and it can be related to the strength of covalent
bonds [27]. Using the elastic constants, the Debye temperature (D), sound velocities for longitudinal
and shear waves (VL and VS) and Debye average velocity (Vm)[28] are calculated and presented in
Table 2. From Table 2, it can be found that the Debye temperature value for Rh3Hf0.125Nb0.875 (618
K) and Rh3Hf0.875Nb0.125 (448 K) alloy combinations are decreased. Hence, the strength of covalent
bonds decreases in these materials.
Table 2. Calculated mass density (gm/cm3), VL and VS (103m/s), Debye average velocity Vm
(103m/s), and Debye temperature D (K) for Rh3HfxNb1-x(x=0,0.125,0.875)alloys.
Parameters Rh3Nb Rh3Hf0.125Nb0.875 Rh3Hf0.875Nb0.125
45.02 46.21 51.84
3.8422 3.1302 2.5747
VL 2.5589 1.8180 1.3186
VS 2.7970 2.0174 1.4770
Vm 857 618 448
D
Summary. In this work, the structural, elastic and electronic properties of Rh3HfxNb1-x (x =0, 0.125,
0.875) combinations are investigated by means first principles calculations based on DFT with GGA
method. The calculated lattice parameters and bulk modulus are consistent with the literature values.
Youngs modulus, shear modulus, G/B ratio, Poissons ratio and anisotropy factor have been
calculated and discussed. Also in Rh3Nb, a transition from brittle nature to ductile nature is observed
when Hf is added. Rh3Hf0.875Nb0.125 shows ductile nature having highest Cauchy pressure and
Poisson ratio and lowest shear modulus, Youngs modulus and G/B ratio. Charge density plots reveal
decrease in directional bonding nature in Rh3Nb when Hf is added. The sound velocities and Debye
temperatures of the alloys have been calculated.
References
[1] Y. Yamabe-Mitarai, Y. Koizumi, H. Murakami, Y. Ro, T. Maruko, H. Harada, Scr. Metall. Mater.
Vol. 35 (1996) 211.
[2] Y. Yamabe-Mitarai, Y. Ro, T. Maruko, H. Harada, Metall. Mater.Trans. A, Vol. 29 (1998) 537.
[3] R.L. Fleischer, High-strength, high-temperature intermetallic compounds, J. Mater. Sci. Vol. 22
(1987) 2281, DOI 10.1007/BF01082105

42
[5] Y.W. Kim, Intermetallic alloys based on gamma titanium aluminide, J. Met. Vol. 41 (1989), 24,
DOI 10.1007/BF03220267
[6] R. Darolia, NiAl alloys for high-temperature structural applications, J. Met. Vol. 43 (1991) 44,
DOI 10.1007/BF03220163
[7] D.M. Dimiduk, D.B. Miracle, Y.W. Kim, M.G. Mendiratta, ISIJ Int. Vol. 31 (1991), 1223.
[8] M.H. Yoo, S.L. Sass, C.L. Fu, M.J. Mills, D.M. Dimiduk, E.P. George, Acta Metall. Mater. Vol.
41 (1993) 987.
[9] C.T. Liu, J. Stringer, J.N. Mundy, L.L. Horton, P. Angelini, Intermetallics, Vol. 5 (1997) 579.
[10] M. Manjula, M. Sundareswari, J Chem, Pharm Science Special issue, Vol. 11 (2015)15-17.
[11] Y. Yamabe, Y. Koizumi, H. Murakami, Y. Ro, T. Maruko, H. Harada, Scr Metall Mater 1997;
Vol. 36, 393p.
[12] M. Rajagopalan, M. Sundareswari, J Alloy Compds (2004), Vol. 4; 379
[13] K. Chen, L.R. Zhao, J.S. Tse, J.R. Rodgers, Phys. Lett. A, Vol. 331 (2004) 400-403.
[14] S. Miura, K. Honma , Y. Terada , JM Sanchez, T. Mohri, Intermetallics (2000), Vol. 8, 785.
[15] Y. Tetra, K. Ohkubo, S. Miura, J.M. Sanchez, T. Mohri, J. Alloys Comp. (2003), Vol. 354, 202
p.
[16] Y. Yamabe-Mitarai, Y. Ro, S. Nakazawa, Intermetallics, Vol. 9 (2001) pp. 423-429, DOI
10.1080/095008399176715
[17] P Blaha, K. Schwarz, G.K.H. Madsen, D. Kuasnicka, J. Luitz, WIEN2k an augment plane wave
plus local orbitals program for calculating crystal properties, Vienna University of Technology,
Institute of Materials Chemistry, 2001, ISBN 3-9501031-1-2
[18] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made Simple Phys.
Rev. Lett., Vol. 77 (1996) 386, DOI 10.1103/PhysRevLett.77.3865
[19] D.G. Clerc, H.M. Ledbetter, L. Phys. Chem. Solids, Vol. 59 (1998) 1071.
[20] H. Ozisik, E. Deligoz, K. Colakoglu, E. Ateser, The first principles studies of the MgB 7
compound: Hard material, Intermetallics, Vol. 39 (2013) 84-88.
[21] D. Pettifor, Theoretical predictions of structure and related properties of intermetallics, Materials
Science and Technology, Vol. 8 (1992) 345, DOI 10.1179/mst.1992.8.4.345
[22] S.F. Pugh, Relations between the elastic moduli and the plastic properties of polycrystalline pure
metals, Phil. Mag. Vol. 45, (1954), pp. 823-843, DOI 10.1080/14786440808520496
[23] V.V. Bannikov, I.R. Shein, A.L. Ivanovskii, Electronic structure, chemical bonding and elastic
properties of the first thorium-containing nitride perovskite TaThN3, Phys Status Solidi (RRL)
(2007), 89-91, DOI 10.1002/pssr.200600116
[24] S.I. Ranganathan, M. Ostoja-Starzewski, Universal Elastic Anisotropy Index, Phys. Rev. Lett.
Vol. 101 (2008) 055504, DOI 10.1103/PhysRevLett.101.055504
[25] W.J. Zhao, H.B. Xu, Y. X Wang, A hard semiconductor OsN4 with high elastic constant c44,
Phys Status Solidi RRL 3, (2009) 272, DOI 10.1002/pssr.200903252
[26] E. Schreiber, O.L. Anderson, N. Soga, Elastic constants and their measurements, NewYork:
McGraw-Hill; 1973.
[27] J.J. Wang, X.Y. Kuang, Y.Y. Jin, L. Cheng, X.F. Huang, J. Alloys Compd, Vol. 592 (2014), pp.
42-47.

43
Synthesis and Characterization of Monolithic ZnO-SiO2 Nanocomposite

Xerogels
8
D. Prasanna1, P. Elangovan1,a, R. Sheelarani1
1 Dept. of Physics, Pachaiyappas College, Chennai, Tamil Nadu, India

a drelangovanphysics@gmail.com
Keywords: nano composites xerogel, sol gel method.
ABSTRACT. Synthesis and characterization of ZnO doped SiO2 monolithic nano composite xerogels were prepared by
using sol-gel method. In this method prepared samples were observed, that an ageing period of two days is optimum and
a very slow controlled evaporation rate is followed for few days. The prepared ZnO-SiO2 monolithic nano composite
xerogels for various concentrations are characterized by X-ray diffraction, field-emission scanning electron microscope
and Fourier transform-infrared spectroscopy methods.
Introduction: ZnO nano particle embedded into SiO2 composites have attracted extensive research
interests. It has been found that these materials have improved luminescence efficiency compared to bulk
ZnO material. Excellent non-linear optical properties, saturable absorption and optical bistability have
also been reported for these composites various techniques have been employed to prepare nano
ZnO-SiO2 composites, including sol-gel impregnation and magnetron sputtering, etc. Wide varieties
of glass, glass-ceramic monolithics, nanostructural powders etc., are synthesized through sol-gel
technique. In the present work ZnO embedded into SiO2 nanocomposites are synthesized through the
sol-gel process. The steps needed for producing monolithic xerogels are carefully followed.
Experimental.
Materials. Zinc acetate dihydrate (Zn (CH3COO)22H2O), Triethanolamine (TEA) and Sodium
hydroxide (NaOH), Ethanol(C2H6O), Tetraethyl orthosilicate (TEOS) were purchased from s d fine-
chem. limited in Chennai.
Analyses. The starting solution is prepared by mixing TEOS, ethanol and water in the ratio of
10:10:14 respectively. The starting solution is stirred at 40C for few minutes. One drop of
concentrated HCl is diluted in 3 ml of deionized water, is added drop wise in the starting solution.
SAfter 1 hr. of stirring 4 drops of diluted ammonia solution is added to maintain the pH at 4. The
second solution is prepared using 200 g of Zn(CH3COO)22H2O dissolved in deionized water. This
solution is stirred for 1 hrs. at 50C. Finally, the starting and second solutions are mixed and stirred
for 1 hrs. The final sol is poured into the plastic mould and covered with aluminium foil. The sols
are aged at 40C for 48 hrs.
After 2 days, few holes are made in the aluminium foil and kept at 40C for 2-7 days in drying oven.
The number of holes are gradually increased thereafter, and dried for another 10 or 15 days. The
samples are heat treated in PID controlled furnace, with the following scheme of heat treatment.
8

44
In the present work, five samples with different weight fraction of ZnO nanoparticles embedded into
the SiO2 matrix are synthesized by sol-gel process. The concentrations (in wt%) of the different
components zinc acetate dihydrate, ethanol and TEOS for the five samples are present in Table 1.
Table 1. Formulation and proportions of the samples.

Sample Tetraethyl orthosilicate Pure ethanol Zinc acetate dehydrate
ZS1 10 ml 10 ml 0.200 g
ZS2 10 ml 10 ml 0.400 g
ZS3 10 ml 10 ml 0.600 g
ZS4 10 ml 10 ml 0.800 g
ZS5 10 ml 10 ml 1g
500C
Intensity
(a.u.)
300C
120C
10 20 30 40 50 60 70 80
Position [2
Theta]
Fig. 1. XRD patterns of ZS1 xerogel.
Results and discussion. Fig.1 shows the XRD patterns of ZS1 xerogel heat treated at different
temperatures 120, 300 and 500C. In the XRD patterns of ZS1 xerogel, the absence of any sharp peak,
clearly indicates the amorphous nature of the synthesized nanocomposite at all temperatures.
FE-SEM images. The FE-SEM images of ZS1 and ZS4xerogels are provided in Fig. 2 and 4.
respectively. The EDS spectrum of the ZS1 and ZS4 xerogels are presented in Figs. 3 and 5. Fig. 2
shows ZnO nanoparticles are embedded in the SiO2 matrix at only few places due to less (0.200 g)
ZnO in the nanocomposite. When the amount of ZnO is increased, more interstitial gaps are occupied
by ZnO nanoparticles which is clearly evident from the FE-SEM image Fig.4. This fact is supported
by the EDS images 3 and 5 respectively.
45
Fig. 2. FE-SEM of the ZS1. Fig. 3. The EDS spectrum of the ZS1.
Fig. 4. FE-SEM of the ZS4. Fig. 5. The EDS spectrum of the ZS4.
FT-IR spectrum. Fig.6 shows the FT-IR spectrum of ZS1 xerogel samples calcined at 120C, 300C
and 500C. In the FT-IR spectrum the broad bands at 3456 and 1633 cm-1 can be attributed to the
stretching and bending vibrational modes of OH in molecular water and the SiOH stretching of
surface silanols hydrogen-bonded to molecular water respectively [8], [9]. A broad and strong band
is observed at 1086 cm-1 that is assigned to asymmetric stretching vibration of siloxane group
SiOSi. In addition, weak band located at 962 cm-1 is due to ZnOSi stretching vibration
[10]. A medium intensity band is noticed at 801 cm-1 that is due to deformation of SiOSi bond.
A strong peak at 464 cm-1 is caused by the OSiO bending vibration [11].
TG-DTA curves. The TG-DTA curves of ZS1 xerogel recorded in the range of 100 to 1100C are
illustrated in Fig. 7.The TGA curve can be roughly divided into four stages. In stage 1 there is a sharp
decrease in the weight of the sample when it is heated from room temperature up to about 160C and
a weight loss of 17% which corresponds to the loss of physical water. In stage 2 very low weight loss
0.75% is observed between 160 and 360C. Stage 3 occurs between 360 and 600C with weight a
loss of nearly 2%. Stage 4 occurs from 600C up to 1020C and corresponds to a very small weight
loss of about 1.50%. The weight loss of stages 2, 3 and 4 are associated both with the removal of the
organic groups and with evaporation of water formed from polycondensation reactions [12]. The
46
DTA analysis shows a sharp exothermic peak around 530C is the result of progressive
decomposition of organic matter [13]. The sharp endothermic peak around 170C is primarily due to
the removal of physically bound water. The small exothermic peak about 950C can be attributed to
further removal of residual organic matters.
500
C
300
C
%Transmi
120
C
4000 3500 3000 2500 2000 1500 1000 500

Wave
Fig. 6. FT-IR spectrum of ZS1 xerogel samples.
Fig. 7. TG-DTA curves of ZS1 xerogel.
Summary. ZnO doped SiO2 monolithic nanocomposite xerogels are synthesized successfully via sol-
gel method. It has been observed that an ageing period of 2 days are optimum and a very slow
controlled rate of evaporation for the first 7-10 days are the most essential factors in producing crack-
free monolithic xerogels. The amorphous natures of the xerogel are confirmed by XRD patterns. The
FE-SEM images clearly show the ZnO nanoparticles embedded into the SiO2 matrix. The FT-IR
spectrum yields necessary information about the presence of the expected functional groups belonging
47
to the ZnOSiO2nanocomposites. The TGA and DTA analysis provide the details of various stages
of internal changes happening in the xerogels during heat treatment like removal of bound water,
removal of organic matter etc.
References
[1] Fu Z.P., Yang B.F., Li L. An intense ultraviolet photoluminescent in sol-gel ZnO-
SiO2nanocomposites. J. Phys. Condens. Mater., Vol. 15 (2003) 2867-2873.
[2] Mo C.M., Li Y.H., Liu Y.S., Zhang Y. and Zhang L.D. Elemental effect of
photoluminescentinassembliesofnano-ZnO particles/silica aerogels. J. Appl. Phys., Vol. 83 (1998) 4389-
4391.
[3] Chakrabarti, S., Ganguli, D. and Chaudhuri, S. Excitonic and defect related transitions in ZnO-
SiO2nanocomposites synthesized by sol-gel technique. Phys. Status Solidi A, Vol. 201 (2004) 2134-
2142.
[4] Abdullah, M., Shibamoto, S. and Okuyama, K. Synthesis of ZnO/SiO2/nanocomposites emitting
specific luminescence colours.Opt. Mater. Vol. 26 (2004) 95-100.
[5] Mikrajuddin Iskandar, F., Okuyama, K. and Shi, F.G. Stable photoluminescence of zinc oxide
quantum dots in silica nanoparticles matrix prepared by the combined sol-gel and spray drying
method. J. Appl. Lett., Vol. 89 (2001) 6431-6434.
[6] Cannas, C., Mainas, M., Musinu, A. and Piccaluga, G. ZnO-SiO2nanocomposites obtained by
impregnation of mesoporous silica. Compos. Sci. Technol., Vol. 63 (2003) 1187-1191.
[7] Ma, J.G., Liu, Y.C., Xu, C.S., Liu, Y.X., Shao, C.L., Xu, H.Y., Zhang, J.Y.,Lu, Y.M., Shen D.Z. and
Fan, X.W. Preparation and characterization of ZnO particles embedded in SiO2 matrix by reactive
magnetron sputtering. J. Appl. Phys., Vol. 97 (2005) 103509-103515.
[8] Niu, R., Cui, B., Du, F., Chang, Z. and Tang, Z. Synthesis and characterization of Zn-B-Si-O
nano-composites and their doped BaTiO3 ceramics. Mater. Res. Bull., Vol. 45 (2010) 1460-1465.
[9] Hayri, E.A., Greenblatt, M., Tsai, M.T. and Ptsai, P. Ionic conductivity in the M2O-P2O5-SiO2
(M=H, Li, Na, K) system prepared by sol-gel methods. Solid State Ionics, Vol. 37 (1990) 233-277.
[10] Djouadi, D., Chelouche, A., Aksas, A. and Sebais, M. Optical properties of ZnO/silica
nanocomposites prepared by sol-gel method and deposited by dip-coating technique. Phys. Procedia,
Vol. 2 (2009) 701-705.
[11] Xiang, W., Wang, Z., Yang, Q. and Zhao, W. Preparation of sodium borosilicate transport
bulk gel. J. Mater. Sci. Technol., Vol. 12 (1996) 303-307.

48
DC Conductivity and Dielectric Studies on Fe Concentration Doped LiIAgI

B2O3 Glasses
9
K. Sreelatha1,a , K. Showrilu1, V. Ramesh2
1 Dept. of Physics, Ch. S. D. St Theresas (A) College for Women, Eluru, W.G. Dtm. Andhra Pradesh, India
2 Dept. of Physics, Rama Chandra College of Engineering, Vellore, Tamil Nadu, India
a srilatha.prathap@gmail.com
Keywords: DC conductivity, dielectric properties of LiIAgIB2O3 glass system.
ABSTRACT. The conductivity of LiIAgI mixed glasses has been the subject of extensive investigation in recent years
as a quest for new solid electrolytes with super ionic properties due to vast applications. The silver / lithium ions
surrounded by iodide ions diffuse very rapidly and are the main contributors of the conductivity in the glasses. On the
other hand, the silver ions interlocked with the oxide glass network are almost immobile and contribute poorly to the
conductivity. Further, when these glasses are doped with multivalent transition metal ions like iron, mixed electronic and
ionic, pure electronic or pure ionic conduction is expected depending upon the composition of the glass constituents. The
changes in conduction mechanism that take place with the varied oxidation states of iron ions in the glass network and
the role of silver and lithium ions in this process is observed by a systematic study on DC conductivity and dielectric
properties (viz., dielectric constant, loss and AC conductivity over a wide range of frequency and temperature) of LiI
AgIB2O3 glasses mixed with varied concentrations of Fe 2O3 from 0 - 2.0 mol %.
Introduction: A study of the electrical properties of the glasses is of considerable importance because
of the insight it gives into the conduction mechanism process-taking place in them. In fact, the
electrical properties of the glasses are largely controlled by the structure, composition, and the nature
of the bonds of the glasses. The investigation of the changes in the electrical properties of glasses
with controlled variation of chemical composition, doping etc., is of considerable interest in the
application point of view.
Among various transition metal ions, the iron ions are considered as effective and useful dopant ions
in the conducting glass materials owing to the fact that they exist in different valence states with
different coordination simultaneously in the glass network. Hence, the connection between the state
and the position of the iron ion and the electrical properties of the host glass containing highly mobile
ions like Ag+ and Li+ is expected to be highly interesting. Further, dielectric measurements on ionic
materials also give useful information about dynamical processes involving ionic motion and polaron
transfer. It is known that the conductivity of glassy materials is frequency dependent, so that the
diffusivity of the mobile ions is not entirely characterized by the single steady state parameter DC
quantifying DC conductivity.
DC Conductivity. Fig. 1 represents the variation of (DCT) with 1/T for LiIAgIB2O3 glasses doped
with different concentrations of Fe2O3. The plots clearly indicate that DC conductivity obeys
Arrhenius relation. In the concentration range of investigation of Fe2O3, the measured conductivities
are found to vary in the range 106 to103Ohm1 cm1 in the high temperature region. The fig: further
indicates the deviations in linear plots (at T = D/2, i.e., half of the Debye temperature).The activation
energy evaluated from these graphs in the high temperature region is found to decrease with increase
9

49
in the concentration of Fe2O3 up to 0.9 mol % and there after it is found to increase (inset of Fig.1
and Table 1). Fig. 2 presents isotherms of DC conductivity with the concentration of Fe2O3; the
conductivity is increased at faster rates with increase in the concentration of iron ions up to 0.9 mol %
and then it is decreased for further increase of iron ion content.
10-3
F9
F12
10-5
dc T (W-cm) K
-1
F15
0.6
F6
A.E. (eV)
0.4 F20
F3
0.2
0.3 0.8 1.3 1.8
Conc. Fe2O3 (mol%)
10-7
1.55 1.68 1.81 1.94 2.07 2.20

1/T (10-3, K-1)
Fig. 1 Variation of (DCT) with 1/T for LiI-AgI-B2O3:Fe2O3 glasses. Inset represents the variation of
activation energy with the concentration of Fe2O3.
10-3
Zone - II
Zone - I
350 oC
10-5 10-3
-1
280 oC
dc (W-cm)
-1
dc (W-cm)
230 oC
10-6
0.3 0.4 0.5 0.6
A.E. (eV)
-7
10
0.3 0.6 0.9 1.2 1.5 1.8
Conc. Fe2O3 (mol %)
Fig. 2 DC conductivity isotherms of LiI-AgI-B2O3: Fe2O3 glasses Inset shows the variation of
conductivity (at 623 K)with the activation energy.

50
Table 1. Summary of data on conductivity studies of LiIAgIB2O3: Fe2O3 glasses.

N(EF) A.E. for
WDC WH J Wac
Glass ( x 10 20 dipoles
(eV) (eV) (eV) (eV) (eV)
eV-1/cm3)
F3 0.612 0.365 0.091 0.489 1.39 2.77
F6 0.466 0.274 0.069 0.392 1.74 2.31
F9 0.301 0.180 0.045 0.261 3.12 2.28
F12 0.376 0.219 0.055 0.326 2.52 2.57
F15 0.43 0.257 0.064 0.301 2.06 2.74
Dielectric properties. The dielectric constant and loss tan at room temperature (30 oC) of pure
LiIAgIB2O3 glasses at 100 kHz are measured to be 12.4 and 0.005,respectively. The temperature
dependence of of the glasses containing different concentrations of Fe2O3 at 1 kHz is shown in
Fig. 3 and at different frequencies of glass F9 is shown as the inset of the same figure. The value of
is found to exhibit a considerable increase at higher temperatures especially at lower frequencies; the
rate of increase of with temperature is found to be the highest for the glass doped with 0.9 mol %
of Fe2O3. The temperature dependence of tan of all the glasses measured at a frequency of 10 kHz
is presented in Fig. 4. In the inset of the same figure, the variation of tan for one of the glasses (glass
containing 0.9 mol % of Fe2O3), at different frequencies is presented. These curves have exhibited
distinct maxima; with increasing frequency the temperature maximum shifts towards higher
temperature and with increasing temperature the frequency maximum shifts towards higher
frequency, indicating the dielectric relaxation character of dielectric losses of these glasses. From
these curves, the effective activation energy, Wd, for the dipoles is calculated for different
concentrations of Fe2O3 and presented in Table 1; the activation energy is found to be the lowest for
the glass F9 and the highest for the glass F3.
The ac conductivity ac is evaluated at different temperatures from the values of dielectric constant
and loss using the conventional equation and its variation with 1/T for all the glasses at 100 kHz is
presented in Fig. 5.
50
50
1 kHz
F9
40
10 kHz
40 30
e'
100 kHz F12
20
10
30 F15
0 100 200 300
Temparature (oC)
e'
F6
F20
20
F3
10
0 50 100 150 200 250 300 350
o
Temparature ( C)
Fig. A comparison plot of variation of dielectric constant with temperature at 1 kHz for LiI-
AgI-B2O3 glass doped with various concentrations of Fe2O3. Inset shows the variation of
Fig. 3. A comparison plot of variation of dielectric constant with temperature at 1 kHz for LiI-AgI-
dielectric constant with temperature at different frequencies for the glass F9.
B2O3 loss with temperature concentrations of Fe2O3. Inset shows the variation of dielectric constant
with temperature at different frequencies for the glass F9.
51
0.20
1 kHz
0.09
F9
0.16 0.06
10 kHz
Tan d
0.03 F12
0.12
100 kHz
0
Tan d
0 100 200 300 F15
Temperature (oC)
0.08
F6
F20
F3
0.04
0.00
0 50 100 150 200 250 300 350
o
Temperature ( C)
Fig. 4. A comparison plot of variation of dielectric loss with temperature at 10 kHz for LiI-AgI-
B2O3 glasses doped with various concentrations of Fe2O3. Inset (a) shows the variation of
Fig. 4. A comparison plot of variation of dielectric loss with temperature at 10 kHz for LiI-AgI-B2O3
dielectric loss with temperature at different frequencies for the glass F3.
glasses. Inset shows the variation of dielectric loss with temperature at different frequencies for the
glass F9.
Similar to that of DC conductivity, ac is also found to be the highest for the glasses containing 0.9
mol % of Fe2O3 at any temperature. The variation of AC conductivity with temperature exhibited a
plateau up to 110 oC and thereafter (beyond the relaxation region) it is increased rapidly exhibiting
the highest rate of increase for the glass F9. From these plots, the activation energy for the conduction
in the high temperature region over which a near linear dependence of log ac with 1/T could be
observed is evaluated and presented in the Table 1.
Discussion. B2O3 is a well known network former, participates in the network forming with BO3 and
BO4 structural units. AgI and LiI do act as modifiers like any conventional modifiers and create
bonding defects. In some of the recent investigations it has also been reported that Ag+ and Li+ ions
in oxy salt glass matrices experience mixed oxygeniodine coordination and do not induce any
defects in the glass network [1], [2], [3]. According to this model AgI and LiI mainly act to expand
the glass network, which leads to the increase in the accessible volume for the fraction of mobile Ag+
and Li+ ions that act as modifiers. In fact, a general relation between the network expansion and the
conductivity enhancement for a large variety of alkalihalide mixed oxide glasses has been reported
[4]. Iron ions are expected to exist mainly in Fe3+ state in LiIAgIB2O3 glass network. However,
regardless of the original oxidation state of the iron in the starting glass batch, the final glass contains
both Fe3+ and Fe2+ ions [5].
Fe3+ ions are expected to occupy both tetrahedral and octahedral positions in the glass network.
Nevertheless, the fourfold coordination of Fe3+ is observed to be more common than the six fold
coordination in many of the glasses [6]. When a plot is made between log DC vs activation energy
for conduction, a near linear relationship is observed (inset of 2); this observation suggests that the
conductivity enhancement is also related to the thermally stimulated mobility of the charge carriers
in the high temperature region. The maximal effect observed at x = 0.9 mol% in the isotherms of DC
conductivity suggests that there is a changeover of conduction mechanism at this point.
Additionally, as has been mentioned earlier, the conductivity enhancement with temperature for a
given composition of the glass suggests the contribution of ionic transport to the conduction in
addition to the polaron hopping. The decrease in activation energy and increase in conductivity with
iron ion content up to 0.9 mol % (Figs. 1 - 2) may be due to higher rate of polaron hopping
(Fe2+Fe3+) and ionic transport. Though electronic and ionic conductivities are not separated but the
observed trend of increase of conductivity and decrease of activation energy (for the glass containing
Fe2O3 below 0.9 mol %) (zoneI) and decrease of conductivity and increase of activation energy (for

52
the glass containing Fe2O3 beyond 0.9 mol %) (zoneII) indicates different conduction mechanisms
on the two sides of this composition. This type of composition dependence of isothermal conductivity
is quite conventional in the glasses containing mobile monovalent cations (like Li+ and Ag+) and
transition metal ions like iron.
To explore the nature of the hopping conduction in LiIAgIB2O3: Fe2O3 glasses a graph between
log DC (measured at 623 K) and the activation energy WDC is plotted in the inset of Fig. 2. The graph
obtained is a straight line. From the slope of this curve, the value of 1/kT is obtained and the
temperature T is estimated. The value of T is found to be 615 K, which is very close to the actual
temperature. In small polaron hopping model (SPH Model), the polaron bandwidth J for adiabatic
case is given by
J > (2kTWH/)1/4(h0/ )1/2 (1)
The polaron bandwidths are also calculated from the relation:
J = J0 exp(R)
where J0 = WH(min)/4 and are furnished in Table 1.

From this table, it may be noted that J for all the glasses satisfies the Eq.(1) and hence the conduction
may be taken as adiabatic which means there is noncompatibility between the hopping rate of
polaron and phonon frequency. According to a more general polaron hopping model (where WD > 0)
it is the optical multi phonon that determines DC conductivity at high temperatures, while at low
temperatures, charge carrier transport is via an acoustical phononassisted hopping process.
With the gradual increase of Fe2O3 up to 0.9 mol % in the glass network, the values of ', tan and
ac are found to increase at any frequency and temperature and the activation energy for AC
conduction are observed to decrease. This observation indicates an increase in the space charge
polarization owing to the enhanced degree of disorder in the glass network due to the presence larger
proportions of Fe2+ ions that act as modifier. The dielectric relaxation effects exhibited by these
samples can safely be attributed to association of divalent iron with a pair of I or O ions, in analogy
with the mechanismassociation of divalent positive ion with a pair of cationic vacancies in
conventional glasses, glass ceramics and crystals. The increase in the breadth and the intensity of the
relaxation peaks and (for the samples F3 to F9) supports the view point that there is a higher
concentration of divalent iron ions and also Li+ and Ag+ ions in these glasses that acts as modifiers.
The lower values of activation energy for these samples suggest an increasing degree of freedom for
dipoles to orient in the field direction.
The variation of the exponent (obtained by plotting log () vs ) is found to be the highest for the
glass F9 (inset of Fig. 5). Such increase suggests that dimensionality of conduction space is the highest
for this glass [7], [8].
The AC conductivity in the low temperature region (near plateau region) can be understood based on
quantum mechanical tunnelling model. Based on Austin and Motts model (quantum mechanical
tunnelling model) [9], the density of defect energy states near the Fermi level, N(EF), at nearly
temperature independent region of the conductivity (low temperature) is evaluated using:
() = /3 e2KT [N(EF)]2 5 [ ln(o/) ]4 (2)

53
where is the electronic wave function decay constant,

0 is the phonon frequency and presented in table 1.
The value of N(EF) i.e., the density of defect energy, is found to increase gradually from the sample
F3 to F9, indicating a growing degree of disorder with increase in the content of Fe2O3 up to 0.9 mol
% in the glass network.
Summary. LiIAgIB2O3 glasses mixed with different concentrations of Fe2O3 (ranging from 0 to
2.0 mol %) were prepared. DC. conductivity and dielectric properties have been investigated. DC
conductivity is increased up to 0.9 mol % of Fe2O3 and beyond that the conductivity is found to
decrease. The analysis of the DC conductivity results indicated that there is a mixed conduction (both
ionic and electronic) and the ionic conduction seems to prevail over polaron hopping in the glasses
containing Fe2O3 more than 0.9 mol %.
References
[1] K.K. Olsen and J. Zwanziger, Solid State Nucl. Mag. Reson., Vol. 5 (1995), p. 123, DOI
10.1016/0926-2040(95)00035-O
[2] K.K. Olsen, J. Zwanziger, P. Hertmann, C. Jager, J. NonCryst. Solids, Vol. 222 (1997), p. 199,
DOI 10.1016/S0022-3093(97)90114-9
[3] E.I. Kamitsos, J.A. Kaputsis, G.D. Chryssikos, J.M. Hutchinson, A.J. Pappin, M.D. Ingram, J. A.
Duffy, Infrared study of AgI containing superionic glasses, Phys. Chem. Glasses, Vol. 36 (1995), p.
141.
[4] J.D. Wicks, L. Borjesson, G. BushnellWye, W.S. Howells, R.L. McGreevy, Phys. Rev. Lett.,
Vol. 74 (1995), p. 726, DOI 10.1103/PhysRevLett.74.726
[5] G.K. Marasinghe, M. Karabulut, C.S. Ray, D.E. Day, C.H. Booth, P.G. Allen, D.K. Shuh, Ceram.
Trans., Vol. 87 (1998), p. 261.
[6] G.K. Marasinghe, M. Karabulut, C.S. Ray, D.E. Day, C.H. Booth, P.G. Allen, D.K. Shuh, J. Non
Cryst. Solids Vol. 249 (1999), p. 261.
[7] D.L. Sidebottom, Dimensionality Dependence of the Conductivity Dispersion in Ionic Materials,
Phys. Rev. Lett. Vol. 83 (1999), p. 983.
[8] S. Bhattacharya, A. Ghosh, Conductivity spectra in fast ion conducting glasses: Mobile ions
contributing to transport process, Phys. Rev. B, Vol. 70 (2004), 172-203.

54
Conductivity, Morphology and Thermal Studies of Polyvinyl Chloride (PVC)-

Lithium Nitrate with Cadmium Oxide (CdO)
10
P. Karthika1, a, R. Gomathy2, P.S. Devi Prasadh 3, b
1 Department of Physics, SNS College of Engineering, Coimbaore, India

2 Department of Physics, Dr. Mahalingam College of Engineering & Technology, Pollachi, Coimbatore, India
3 School of Advanced Sciences, VIT University, Vellore, Tamilnadu, India
a pkarthikaa@gmail.com
b psdprasadh@gmail.com
Keywords: PVC, LiNO3, CdO, conductivity, SEM, TGA.
ABSTRACT. High ionic conductivity of polymeric system is important in polymer research. Solvent cast technique is
used to formulate the polyvinyl Chloride (PVC) Lithium Nitrate (LiNO3) Cadmium Oxide (CdO) system. Nature of
complexation and concentration of various ionic species are important to understand the conductance mechanism.
Conductivity studies provided with the help of ac impedance analyser. Morphology behaviours of polymer electrolytes
have been studied using SEM. The thermal properties of polyvinyl chloride(PVC) Lithium Nitrate (LiNO3) Cadmium
Oxide (CdO) by Thermo Gravimetric Analysis (TGA) gives rise the information on the thermal stability of polymer
electrolytes.
Introduction. Now a days, researchers have very much interested in studying the ionic conductivity
at ambient temperature due to their unique performance in high power rechargeable lithium battery,
which can be used in laptops and even electric vehicles and other portable electronic equipment. The
preparation of polymer electrolytes with high conductivity, good mechanical strength and thermal
stabilities are interest due to the role of polymer electrolytes in lithium batteries, electro chromic
windows, sensors and fuel cells etc. [1]. In our everyday life, polymers are widely used due to their
fascinating and extraordinary characteristics. To replace the conventional materials in terms of
strength, stability and toughness they are found. Since the beginning of plastic industry, it is observed
that blending yields materials with superior features of the individual components. Blending of
polymers provide new materials which combine the useful property of all constituents.
Technological interest of polymer electrolytes are due to their possible application as solid
electrolytes in various electrochemical devices such as energy conversion units, electro-chromic
display devices, photo chemical solar cells and sensors. The polymer electrolytes in lithium batteries
are most widely studied among the various applications, A polymer electrolyte will function as a
separator as well as an electrolyte in a secondary battery. Studies on polymer electrolytes have great
intention to explain the enhancement mechanism of conductivity. Various ionic species
concentration are important to understand the overall mechanism of conductivity, The structural and
morphological behaviours of polymer electrolytes have been studied by SEM. In this work, polymer
electrolytes are prepared by solution casting technique which contained polyvinyl chloride (PVC) as
a host polymer and lithium nitrate(LiNO3) as a salt. The nano filler CdO added with various
proportion to these polymer electrolytes to get nanocomposite polymer electrolytes (NCPE). Then,
10

55
the thermal characteristics have done by Thermo Gravimetric Analysis (TGA). Conductivity studies
done with the help of ac impedance analyzer.
Experimental Techniques: Chemicals with AR/BDH grade were purchased from Aldrich, Merck
companies and used as such, Tetra Hydro Furan (THF) used after distillation only. Polymer: Poly
(vinyl chloride), Polyelectrolyte: Lithium nitrate(LiNO3) , Solvent: Tetra Hydro Furan (THF), Nano
filler: Cadmium Oxide (CdO). The polymer salt complex prepared by solvent casting technique. It
was very simple and most widely used technique for preparation of thick films. Polymer electrolyte
prepared by solvent casting technique. The appropriate quantity of PVC & LiNO3 dissolved in Tetra
hydro furan. After a complete dissolution of polymer and salt, metallic filler, CdO added and stirred
for 4 5 hours. A homogeneous solution obtained after stirrer and resulting solution poured on to a
glass plate and THF allowed evaporating in air at room temperature in dust free atmosphere. The
films dried for another one day to remove any trace of THF. The concentration of CdO varied and
films were prepared.
Result and Discussion:
AC Impedance Characteristics. PVC composite with LiNO3 studied in order to see the effect of
their addition to polymer electrolyte conductance. This ionic conductivity determined by ac
impedance analysis at room temperature say around 302K. Various combination of the three
components PVC - LiNO3 - CdO were Compared and one of them shown in Fig. 1 (e). The ionic
conductivity of polymer electrolyte can be calculated using the formula given by:
ac = Thickness/(Area)(Resistance) = s/cm.
Ionic conductivity of polymer electrolyte changed due to concentration of conducting species and
their mobility. The conductivity increases against the concentration of CdO, it can be seen that PVC
LiNO3 exhibited the lowest conductivity as 5.27 10- 10 s/cm. The effect of concentration of nanofiller
CdO on the ionic conductivity of the films which showed that the increase in concentration of CdO,
ionic conductivity also increased which may be due to increase in the number of mobile ions in the
solid polymer electrolytes. A highest value 6.33 10-6 s/cm was obtained at 10 Wt % of CdO. The
addition of nanofiller with the polymer electrolyte system made the system be more amorphous and
promoted more free lithium ions from the inorganic salt of LiNO3 [1].
Fig. 1. Impedance Plot for PVC + LiNO3 + CdO (10 Wt ).

56
Increase of CdO content reduced the crystallinity of composite polymer electrolyte. A polymer chain
in the amorphous phase was more flexible which increased segmental motion of polymer. Oxygen
concentration enhanced the conductivity of electrolyte [2]. The lithium (Li +) ion moved like a
gaseous molecule in free volume model where Li+ transferred to coordinating sites in the same
polymer chain. The segmental motion of increased the ionic conductivity. When smaller size
nanofiller added to polymer electrolytes may be promoted amorphous region there by enhancing the
transportation of ions in membrane. Based on Lewis acid base interaction, ceramic filler influenced
the ionic conductivity of polymer electrolyte due to interactions between the surface groups of
ceramic particles and lithium salt [3]. Li+ served as a strong Lewis acid where as polymer and filler
CdO served as a Lewis base centres. Therefore, the polymer Li+ cation and filler Li+ cation
interactions may be widely used to explain the polymer salt complex interaction [4]. This created
structural modification, which may be acted as a cross linking centres for the polymer segment and
the salt anions. The Lewis base interaction centres lowered ionic coupling there by salt dissociation
promoted via a sort of ion ceramic complex formation. The mentioned two effects enhanced the
conductivity of nanocomposites. Oxygen and OH surface groups on CdO grains interacted with
cations and anions based on Lewis acid base and promoted additional site creating favourable high
coordinating pathways in the vicinity of grains for the migrations of ions [5]. It enhanced the mobility
for migrating ions.
SEM Analysis. It is noticed from the figure 2a that the rough surface with streaks. PVC LiNO3
complex with CdO(3 Wt %) showed maximum number of pores of random shapes giving rise to
increase in conductivity of this sample. There are two possible ways for formation, first one was the
evaporation of solvent and second one was the casting of the film. Plasticizer occupied the pores,
which acted as the tunnel for ionic transport. It was observed that pores in 3 Wt % disappeared when
CdO concentration increased to 5 Wt %. This might be occurred due to fill the pores of CdO there by
promoting amorphicity through plasticizing effect of filler. In Fig. 2. (b), it was noticed that the
appearance of number of uniform tracks of few micrometer size along with reduced size which was
responsible for the enhancement o ionic conductivity of PVC- LiNO3 CdO ( 8 Wt %). The distinct
spherules by dark boundaries showed in solid polymer electrolyte with CdO 10 Wt %. This was due
to amorphous phase [10]. Thus, SEM study supported the conclusions drawn through ac conductivity
studies.
a) b)
Fig. 2. (a) SEM Micrograph for PVC + LiNO3, (b) SEM Micrograph for PVC + LiNO3 + CdO
(8 Wt %).

57
TGA/DTA analysis. Based on the TGA graph, the percentage total weight loss of sample can be
calculated through the direct subtraction of the percentage residue from 100 Wt %. Since this graph
was plotted as weight as temperature. In Fig. 3. (a), the TGA/DTA trace of pure PVC, the weight
losses corresponding to various temperature regions were shown . It showed that six stages of
degradation. The first stage of degradation occurred in region 0 C 250 C with weight loss of
1.54 % which ascribed to the removable of unsaturation of PVC [5]. The unbroken double bonds of
vinyl chloride monomers presented in some of PVC macromolecules as a consequences of the
disproportionate chain termination reaction during polymerization and called unsaturation reaction.
These double bonds would be broken at the first stage of degradation and would be led to monomers
evaluation as observed in the case of PMMA [5]. In pure PVC + LiNO3 ,1st degradation occurred at
0 C-150 C with 16.59% weight loss which was very much higher than Pure PVC. There was gradual
then faster degradation around 150 C that indicated the thermal stability of complexes initially lower
than PVC. Around 250 C - 315 C, there was 40.87% weight loss compared with PVC, then the
thermal stability was higher. Around 315 C 445 C, 6.22% weight loss and around 445 C 555 C,
17.95% weight loss occurred , both indicated higher thermal stability. Thermally irreversible state
reached by following degradations such as around 555 C 610 C, 2.86% weight loss, 610 C 770 C,
7.704% weight loss and 770 C 1050 C, 1.85% weight loss. PVC + LiNO3 initially exhibited lower
thermal stability when compared with PVC & then above 150 C showed higher thermal stability.
Fig. 3. (a) TGA DTA plot for pure PVC.
Summary. Using solvent casting technique, the nanocomposite polymer electrolyte prepared and in
order to understand the role of nanofiller on the thermal and electrical properties, the nanofiller of
different concentration of CdO added to PVC - LiNO3. Ionic conductivity of polymer electrolyte
depends on the concentration of conducting species & their mobility .The addition of nano-fillers
enhanced the ionic conductivity. SEM confirmed the plasticizing action of CdO. TG-DTA provided
the information with regard to their thermal stability, crystallinity & other thermal parameters.
References
[1] S. Ramesh and A. K. Arof, Strutural, Thermal and Electrochemical Cell Characteristics of Poly
(Vinyl Chloride)-Based Polymer Electrolytes, Journal of Power Sources, Vol. 99, No. 1-2, 2001, pp.
41-47. DOI 10.1016/S0378-7753(00)00690-X

58
[2] Sejal Shah, Dolly Singh, Anjum Qureshi, N L Singh, V. Shrinet, Dielectric properties and surface
morphology of proton irradiated feuic oxalates dispersed PVC films, Indian J. Pure & Appl. Phys, 46
(2008), 439-442. link: http://hdl.handle.net/123456789/1638
[3] Azizan Ahmad, Mohd.Yusri Abdul Rahman, Siti Aminah Mohd Noor, Mohd Reduan Abu Bakar,
Preparation and characterization of PVC - Al2O3-LiClO4 composite polymeric electrolyte, Sains.
Malays, 38 (4) (2009), 107- 113.
[4] W. Wiec Zorek, J.R. Stevens, Z. Florja Czyk, Composite polyether based solid electrolytes,The
Lewis acid base approach, Solid State Ionics,85(1-4)(1996)67-72. DOI 10.1016/0167-
2738(96)00042-2
[5] F. Croce, L. Persi, F. Ronci, B. Scrosati, Nanocomposite polymer electrolytes and their impact on
the lithium battery technology, Solid State Ionics, 135 (1-4) (2000), 47-52, DOI 10.1038/28818

59
Electrochemical Detection of Ascorbic Acid Using Pre-treated Graphite

Electrode Modified with PAMAM Dendrimer with Poly (Nile Blue)11
C. Lakshmi Devi1, J. Jayadevi Manoranjitham1, S. Sriman Narayanan1, a
1 University of Madras, Department of Analytical Chemistry Guindy Campus, Chennai, Tamil Nadu, India
a sriman55@gmail.com
Keywords: electro polymerization, pre-treated modified electrode, poly (nile blue), poly (amido amine), ascorbic acid.
ABSTRACT. A new type of PAMAM/PNB modified electrode has been prepared for the electro catalytic oxidation of
ascorbic acid. The PAMAM [poly (amido amine)] dendrimer was synthesized based on EDA (ethylenediamine) core in
generation (0.5). The graphite electrode is pre-treated by using H2SO4. The PAMAM (G0.5-NH2) dendrimer is
polymerized on the pre-treated electrode followed by the electrochemical polymerization of nile blue (NB) over the
PAMAM coated electrode. The PAMAM/PNB modified electrode was electrochemically characterized by CV. The cyclic
voltammetry behaviour of PAMAM/PNB modified electrode in 0.1M PBS of pH 7 at scan rate of 50mVs-1 showed a pair
of redox peaks. The utility of the modified electrode towards the electro catalytic oxidation of ascorbic acid was
investigated. It was observed, that the PAMAM/PNB modified electrode showed better electro catalytic oxidation when
compared to bare electrode.
Introduction. Ascorbic acid (AA) is a water-soluble antioxidant and called as vitamin C. Since our
body is unable to synthesize ascorbic acid by its own metabolism, we take the food with rich sources
of AA such as citrus fruits, vegetables, leafy vegetables. The main function of antioxidant is to reduce
the oxidative damage caused by the free radicals, which results in improper functioning of cells as
excess of free radicals results in oxidative stress [1]. Oxidative stress may causes serious health issues
such as damage of normal cells, which leads to cancer, improper protein synthesis, DNA damage etc.
[2]. Insufficient amount of ascorbic acid leads to high blood pressure, stoke cancers, AIDS,
atherosclerosis, gallbladder disease etc. [3]. Therefore, it is very important to detect and quantify AA
in food sources, pharmaceutical compounds. Various methods have been used for determination of
AA among them, electrochemical sensors using conducting polymer dyes have gained much
importance and in the bio analytical science because the polymer consists of more number of
functional groups which helps in enhancing the sensitivity and electro catalytic activity of sensor
device [4]. Some of the early reports where polymer dyes used as sensor for various analyses are poly
nile blue [5], [6], poly neutral red [7], poly brilliant crystal blue [8]. PAMAM dendrimers are
branched three-dimensional macromolecules with covalent micelles, well-defined cavities, high
reactivity and stable compounds used for coating electrodes in order to get physic-chemical properties
[9]. Since dendrimer consists of cavities which helps the dye molecules to adsorb in those cavities
effectively thereby improving the sensitivity of the modified electrode. Here we report a modified
electrode using PAMAM and poly (nile blue) for the determination of AA.
11

60
Fig. 1. Scheme for fabrication of PGE/PAMAM/PNB electrode.
Experimental
Equipment. The electrochemical experiments were carried out using CHI 400A electrochemical
system (CH instruments USA). Cyclic Voltammetry (CV) was performed using conventional three-
electrode setup with the PAMAM/PNB modified electrode as the working electrode, a platinum
electrode as the counter electrode and standard calomel electrode as the reference electrode. The
solutions were made free from oxygen by purging with pure nitrogen. The parameters for the CV
were -0.6 to -1.2V. Scan rate 50mV s-1. pH of the solution was measured using digital pH meter
(Digisun electronics system). All experiments were performed at ambient temperature.
Chemicals and reagents. Graphite electrode (3mm diameter) was purchased from Aldrich.
Ethylenediamine was purchased from Merck. Ascorbic acid and Nile blue were obtained from Cisco
Research Laboratories, India. And all other reagents employed were of analytical grade and used as
received. All the supporting electrolytes (0.1 M) and PBS buffer solution (0.1 M) solution were
prepared in doubly distilled (DD) water.
Poly (amido amine) dendrimer synthesis. Poly (amido amine) dendrimer was synthesized as
reported earlier [10-12]. A round bottom flask (100ml) was taken with the reaction mixture of
Ethylenediamine (0.45 g., 7.49 mmol), methanol (MeOH) (10 mL) and methyl acrylate (5.15 g., 59.8
mmol) and the reaction mixture was stirred for 24 hrs. in nitrogen atmosphere at room temperature.
After 24 hrs. reaction mixture was transferred to rotary evaporator to remove the unreacted methyl
acrylate, which has resulted in an intermediate product bearing four terminal methyl ester groups
(2.98 g., 98.6%). Dissolved 4.93 g. of ethylenediamine in 10 mL methanol was added to the
intermediate product and the reaction mixture was stirred at room temperature for 24 hrs. under
nitrogen, and then the solvent and excess ethylenediamine were removed using rotary evaporator.
This final product G 0.5 PAMAM dendrimer were synthesized by repeating Michael addition and
amidation reaction.
Fabrication of PAMAM/PNB film modified electrode. The base material for preparation of
modified electrode is paraffin impregnated graphite electrode (PIGE). The PIGE was prepared as
reported earlier [13], [14]. The polished end of the PIGE was dipped into 0.5 M H 2SO4 solution and
a potential of 1.6 V was applied for 5min to promote the carboxylic acid on the surface of the PIGE
electrode. This is called as pre-treated graphite electrode (PGE). The PGE was immersed into 0.1 M
NaF solution containing 50L PAMAM dendrimer. The PAMAM dendrimer was electro deposited
to the surface of PGE by applying a potential of 0.6V for 1h. Further, this PGE/PAMAM modified
electrode was dipped into the 0.1M PBS (pH 5) containing 0.5 mM nile blue. The nile blue was electro
polymerized over the surface of PGE/PAMAM modified electrode by applying a potential of -0.6V
to 1.2 V for 20 cycles at a scan rate of 50 mV/s. The resulted PGE/PAMAM-PNB electrode was used
for the electro catalytic oxidation of AA. Fig.1 shows the scheme for fabrication of PGE/PAMAM-
PNB electrode.
Polymerization on nile blue. The electro polymerization of nile blue (NB) over the surface of
PGE/PAMAM electrode was carried out by applying potential a potential of 0.6V to 1.2 V for 20
cycles Fig.2 shows the cyclic voltammograms of electro polymerization of nile blue over the
PEG/PAMAM electrode. The cyclic voltammograms shows two redox couple, the first redox couple

61
around 0.4V is due to the oxidation and reduction of the NB monomers. The second redox peak
around 0.1 V is due to the oxidation and reduction of PNB. The peaks at 0.8 V is due to the monomer.
As the polymerization progresses the peaks at 0.1 increases indicated the formation of the PNB. The
peak current at 0.1V increases for successive cycles due to the growth of the PNB film over the
surface of PGE/PAMAM electrode. Once the polymer film is formed, the PGE/PAMAM-PNB
electrode was dipped into 0.1M PBS of pH 7 solution and scanned at a potential range from 0.6V to
1.2V to conform the formation of polymer film.
Fig. 2. Cyclic voltammograms electropolymerization PNB in 0.1 M PBS (pH 5.3) consists of 0.5
mM NB.
Electrochemical determination of ascorbic acid using PAMAM/PNB modified electrode. Under

optimized condition such as pH, different electrolyte, and scan rate (figures not shown) the
PGE/PAMAM-PNB electrode showed a well defined redox peak in PBS of pH7 at a scan rate of
50mV/s. Thus, PBS of pH7 was used for further studies. In order to investigate the application of
PGE/PAMAM-PNB electrode was used for determination AA. Fig. 3 shows the cyclic
voltammogram of bare and modified in absence and presence of 1.610-4 M AA. The bare PIGE
oxidized AA at 0.3V but the PGE/PAMAM-PNB electrode oxidized at a very lower potential of
around 0.2V. Therefore, the PGE/PAMAM-PNB electrode oxidizes AA at very lower potential and
the peak current is high when comparing with bare PIGE. This is due to the presence of PAMAM and
PNB film, which enhances the electrocatalytic activity of the electrode towards oxidation of AA.
Fig.4 shows the cyclic voltammogram response of PGE/PAMAM-PNB electrode on different
concentration of AA. On increasing the concentration of AA, the oxidation current is also increased
linearly.

62
Fig. 3. CVs of (a) bare, (b) in presence of (1.6X10-4M) Ascorbic acid,(c) PAMAM/PNB film-modified
electrode, and (d) in presence of (1.6X10-4M) Ascorbic acid, in 0.1 M PBS (pH7) solution; scan rate:
50 mV/s.
Summary. A highly stable electro active PGE/PAMAM/PNB film modified electrode was fabricated
successfully by electro polymerization of NB over PGE/PAMAM electrode. The resulted
PGE/PAMAM-PNB electrode was characterized by Cyclic Voltammetry. Further the PGE/PAMAM-
PNB electrode was used for the electrocatalytic oxidation of AA. The modified electrode was found
to be highly stable, selective and sensitive towards the determination of AA. The proposed
PGE/PAMAM-PNB film-modified electrode has shown a high determination range is 1.6M to 1666
M.
Acknowledgements. The authors acknowledge the financial assistance from DST-Inspire fellowship,
New Delhi, India, and Department of Science and Technology for PURSE program in support of this
work.
References
[1] G.H. Wu, Y.F. Wu, X.W. Liu, M.C. Rong, X.M. Chen, X. Chen, An electrochemical ascorbic
acid sensor based on palladium nanoparticles supported on graphene oxide, Analytica Chimica Acta
Vol. 745 (2012), 3337.
[2] J. Sochor, J. Dobes, O. Krystofova, B.R. Nedecky, P. Babula, M. Pohanka, T. Jurikova, O. Zitka,
V. Adam, B. Klejdus, R. Kizek, Electrochemistry as a Tool for Studying Antioxidant Properties, Int.
J. Electrochem. Sci., Vol. 8 (2013), 8464 8489.
[3] Y. Andreu, S. Marcos, J. R. Castillo, J. Galban, sensor film for vitamin C determination based on
absorption properties of polyaniline, Talanta Vol. 65 (2005), 10451051.

63
[4] M. Barsan, E. Ghica, M.A. Brett, Electrochemical sensors and biosensors based on redox
polymer/ carbon nanotube modified electrodes: A review, Analytica Chimica Acta Vol. 881 (2015),
123.
[5] P. Du, S. Liu, P. Wu, C. Cai, Single-walled carbon nanotubes functionalized with poly (nile blue
A) and their application to dehydrogenase-based biosensors, Electrochimica Acta Vol. 53 (2007)
1811-1823. DOI10.1016/j.electacta.2007.08.027.
[6] D. Kul, M.E. Ghica, R. Pauliukaite, C.M.A. Brett, A novel amperometric sensor for ascorbic acid
based on poly(Nile blue A) and functionalised multi-walled carbon nanotube modified electrodes,
Talanta Vol. 111 (2013) 76-84. DOI10.1016/j.talanta.2013.02.043.
[7] A.A. Karyakin, Y.N. Ivanova, E.E. Karyakina, Equilibrium (NAD/NADH) potential on
poly(Neutral Red) modified electrode, Electrochemistry communication Vol. 5 (2003) 677-680. DOI
10.1016/S1388-2481(03)00152-8
[8] M. Chen, J.Q. Xu, S.N. Ding, D. Shan, H.G. Xue, S. Cosnier, M. Holzinger, Poly(brilliant cresyl
blue) electro generated on single-walled carbon nanotubes modified electrode and its application in
mediated bio sensing system, Sensors and Actuators B Vol. 152 (2011) 14-20.
DOI10.1016/j.snb.2010.09.063.
[9] Z. Ningning, Y.Gu, Z. Chang, H. Pingang, Y. Fang, PAMAM Dendrimers-Based DNA
Biosensors for Electrochemical Detection of DNA Hybridization, Electroanalysis Vol. 18 (2006)
2107 2114. DOI 10.1002/elan.200603589.
[10] K. Torigoe, A. Suzuki, K. Esumi, Au(III)PAMAM Interaction and Formation of AuPAMAM
Nanocomposites in Ethyl Acetate, J. Colloid and interface science, Vol. 241 (2001) 346-356.
[11] A.S. Ramrez-Segovia, J.A. Banda-Alemn, S. Gutirrez-Granados, A. Rodrguez,
F.J. Rodrguez, A. Godnez, E. Bustos, J. Manrquez, Glassy carbon electrodes sequentially modified
by cysteamine-capped gold nanoparticles and poly(amidoamine) dendrimers generation 4.5 for
detecting uric acid in human serum without ascorbic acid interference, Analytica Chimica Acta Vol.
812 (2014) 18 25.
[12] Y. Zhang, M. Ying Xu, T. Kun Jiang, Low generational polyamidoamine dendrimers to enhance
the solubility of folic acid: A dendritic effect investigation, Chinese Chemi. Letter, Vol. 25 (2014)
815-818.
[13] H. Cui, G.Z. Zou, X.Q. Lin, Electrochemiluminescence of Luminol in Alkaline Solution at a
Paraffin-Impregnated Graphite Electrode, Anal. Chem. Vol. 75 (2003) 324-331.
DOI 10.1021/ac0201631
[14] F. Scholz, B. Lange, Abrasive stripping voltammetry - an electrochemical solid of wide
applicability, Tr. Anal. Chem, Vol. 11 (1992)359-367.

64
Morphological Investigation of Small Molecule Solution Processed Polymer

Solar Cells Based on Spin Coating Technique
12
Liyakath Reshma 1, Kannappan Santhakumar 2,a
1 School of Electronics Engineering, VIT University, Vellore, Tamil Nadu, India

2 Carbon Dioxide and Green Technologies Centre, VIT University, Vellore, Tamil Nadu, India
a ksanthakumar@vit.ac.in
Keywords: polymer solar cell, small molecule, bulk heterojunction, spin coating, power conversion efficiency.
ABSTRACT. Organic solar cells are one of the best candidates to overcome the traditional energy depletion and energy
pollution, because they use simple processing techniques to fabricate and they are under intense investigation in academic
and industrial laboratories because of their potential to enable mass production of flexible and cost effective devices. Here
we explore an efficient solution-processed polymer bulk heterojunction solar cells based on the combination of a small
molecular donor ((DTS(PTTh2)2) and an acceptor (PC71BM ) by using chlorobenzene as a solvent in order to obtain the
mixing morphology through spin coating. PEDOT: PSS was used as a surface modifier to reduce the work function of
the conductors. The molecular aggregations in chlorobenzene solvent were investigated by means of UVvisible spectra
and photoluminescence measurements. The surface morphology of the active layers deposited was examined using atomic
force microscopy. The current densityvoltage (JV) characteristics of the photovoltaic cells were measured under the
illumination by using Oriel 1000W solar simulator and the maximum power conversion efficiency has been reported for
this polymer combination. These results indicate that the spin coating technique can be a viable alternative to the high-
cost and vacuum-deposited ITO for mass production and low cost roll-to-roll based solar cells.
Introduction. The worlds demand for usable energy increases every year, with an expected increase
from 479 trillion joule (505 quadrillion Btu) in 2008 to 730 trillion joule (770 quadrillion Btu) in
2035, an increase of 52 %. In order to meet this demand, non-renewable fossil fuels, mostly coal,
and renewable sources of useful energy will need to be deployed. As fossil fuels will eventually
run out and their use seems to be as the main contributor to the increase of the global greenhouse
effect, more research done on the development and deployment of alternative technologies for
renewable energy production. Sunlight is an abundant and virtually eternally renewable energy
source, with 174 petawatt of power arriving at the earths atmosphere and about 89 petawatt is
absorbed by land and water. Even using only a fraction of this enormous amount of power may
significantly meet the worlds growing demand for power. Solar cells, which rely on the
photovoltaic effect, transform sunlight into electricity and in order to successfully utilize solar
power, developing well performing and cost-effective photovoltaic devices is paramount. Solar cells
can be categorized into two different kinds, inorganic and organic ones. The former having current
commercial power efficiency between 15 and 20 %, up to 25 % for more refined silicon cells and
top lab-scale efficiencies of more than 40 % reached with lab-scale multi-junction devices consisting
of various inorganic semiconductors and the usage of light concentration techniques. However, the
performance of organic solar cells (or Organic Photovoltaics OPV's) is considerably lower with a
commercial efficiency of about 3 to 5 % and a current top efficiency of 1 0 . 6 %. Organic electron-
donor/electron-acceptor blends are a key ingredient of plastic photovoltaic devices, whose
development raises an ever-increasing scientific interest due to their low cost, easy production process
12

65
and mechanical flexibility. Thus, OPV research has taken a new direction in exploring the uses of
different materials [1]. Over the last two decades, the efficiency of these devices has improved
significantly, in particular through the development of solution-processed bulk heterojunction (BHJ)
OSCs [2,3] based on interpenetrating networks of polymer donors and acceptors that exhibit power
conversion efficiencies (PCEs) over 10% [4] mostly with fullerene-based electron acceptors. Here,
we report a solution-processed small-molecule donor: 5,5 - bisf (4-(7-hexylthiophen 2 - yl)
thiophen 2 yl ) - [1, 2, 5] thiadiazolo [3, 4-c] pyridineg - 3, 3- di - 2-ethylhexylsilylene - 2,2 -
bithiophene, DTS (PTTh2) 2. This small molecule donor exhibits excellent solubility in organic
solvents, strong optical absorption, especially from 600 to 800 nm, and a field-effect hole mobility of
~0.1 cm2 V-1 s-1. The design of DTS (PTTh2) 2 incorporates the [1, 2, 5] thiadiazolo [3, 4-
c]pyridine(PT) unit as a strategic building block. The PT heterocycle has a high electron affinity.
Furthermore, the asymmetric nature of PT allows for mono functionalization, resulting in facile and
high yielding molecular synthesis. In this we investigated the morphologies of active layers deposited
by using a spin coating process instead of spray coating techniques [5] for better morphology and we
studied the effects of the interfacial contact on the device performance and device physics [6] in small
molecule BHJ solar cells based on (DTS (PTTh2) 2) as the electron donor and [6, 6] -phenyl C71-
butyric acid methyl ester (PC71BM) as the acceptor. PEDOT: PSS was utilized as the Hole Transport
Layer [7], [8] because it has an appropriate work function and sufficiently high electrical
conductivity, to be a suitable candidate for a hole transporting material. Chlorobenzene was used as
the solvent, as they are the most attractive processing solvents providing enough solubility and
favourable morphology to improve the performance of the solar cell device and their environmental
accumulation can also be significantly mitigated and ITO was used as the electrode. In this paper, we
report the effect of processing conditions on the performance of DTS (PTTh2) 2: PC71BM based
cells, and the nano-scale morphology of active layers using spin coating technique were
Chlorobenzene (CB) was used as the solvent.
Experimental.
Materials used. DTS(PTTh2)2 and PC71BM were purchased from 1-material. These chemicals act
as an electron donor (D) and acceptor (A) materials, respectively. Chlorobenzene (CB) was purged
with nitrogen to remove residual oxygen prior to use. PEDOT:PSS was purchased from HC Strak
(Newtown, MA Bayer AG) and passed through a 0.20 mm filter before spin-coating.
Fabrication of OSCs. Pre-patterned indium tin oxide (ITO)-coated glass with a sheet resistance of
12 /square were cleaned with detergent, ultrasonicated in acetone and isopropyl alcohol for 15 min,
and dried in an oven at 120C. UV-ozone treatment was then performed for 15 min. A film of PEDOT:
PSS was spin cast (3000 rpm for 30 s) on top of the ITO substrates and was dried for 15 min at 140C.
The active layer solutions were prepared by mixing the polymer and PC71BM in different blend ratios
of 1:1; 1:1.5, 1:2 and 1:3 using CB solution mixed with Dichlorobenzene (DCB) and spin coated on
the top of buffer layer with a speed of 800 rpm for 60 s. Then the samples were transferred into a
vacuum chamber to deposit Al (100 nm) on top of the active layers under a pressure of 2.010-6 Torr.
The active surface area of the device was 0.12 cm2.The design of the solar cell device was in the form
of a sandwich structure of the photoactive polymeric layer between an anode electrode of indium tin
oxide (ITO) and a metal cathode of aluminum (Al). The relative energy level diagram and device
construction of ITO/PEDOT:PSS/ DTS(PTTh2)2:PC71BM/Al were illustrated in Fig. 1. The
thickness of all the active layers thicknesses was well controlled in the range of 120 -125 nm as
measured by Dektak II profilometer. The active surface area of the device was 12mm2.

66
Fig. 1. Relative energy level diagram and Device Architecture.
Device characterization. All absorption measurements were performed using a Cary 5000 UVVis
NIR double-beam spectrophotometer in the two-beam transmission mode. Absorption spectra of
DTS(PTTh2)2 , PC71BM, and DTS(PTTh2)2:PC71BM films were taken near the center of solar cells
lacking the top electrode. PL spectra were measured for DTS(PTTh2)2, PC71BM, and
DTS(PTTh2)2:PC71BM films, which were spin coated onto quartz substrates, using a calibrated
fluorescence spectrophotometer (FP-6500,JASCO). The surface morphology of the blend layers was
examined by atomic force microscopy (AFM) using a Seiko Instruments SPA400-SPI4000 operating
under ambient condition. All AFM images were taken in the dynamic force mode at an optimal force.
Silicon cantilevers (Tip radius: *10 nm; SI-DF20; Seiko Instruments Inc.), with a spring constant of
14 N/m and a resonance frequency of 136 kHz, were used to record AFM images. The current density
(J)-voltage (V) characteristics were measured using a Keithley 2420 m in dark and under illumination
of a sun 2000 solar simulator (Abet) with 100 mw/cm2 AM 1.5 G spectrum. The EQE measurement
was performed using a Jobin-Yvon Triax spectrometer, a Jobin-Yvon xenon light source, a Merlin
lock-in amplifier, a calibrated Si UV detector, and an SR570 low noise current amplifier. The
intensity of the solar simulator was calibrated by standard Si photovoltaic cell. All measurements
were performed under ambient atmosphere at room temperature in open air.
Results and discussion.The absorption spectra of the spin coated DTS(PTTh2)2, PC71BM and
active layers of DTS(PTTh2)2 : PC71BM thin films from 1:1 to 1:4 weight ratios in chlorobenzene
were analyzed. The polymer shows strong absorption from 450 to750 nm. However the absorption
from 300 to 400 nm is relatively weak. To compensate the absorption of DTS(PTTh2)2 , PC71BM,
which has strong absorption in the visible range, is used as the acceptor. The absorption spectra of
blend film prepared in CB: DCB exhibited a stronger absorption extended from 300 to 800 nm than
that of the film prepared in CB solution. This indicates that DCB added into CB modify the absorption
of blend layers and can harvest solar photons more effectively than the film prepared from CB under
the same conditions. Two broad absorption peaks at around 624 and 682 nm are attributed to the -
*transition [9] of the DTS(PTTh2)2 polymer whereas the broad absorption coverage in the range
from 320 to 500 nm is due to absorption of PC71BM. To obtain a deeper insight in the relation
between the morphology and performance of polymer/fullerene bulk heterojunction solar cells,
devices have been characterized via AFM. Altering the blend ratio is one of the common methods of
controlling the morphology of the active layer during device fabrication, and further influencing the
device performance. The AFM topographic images of the DTS(PTTh2)2: PC71BM are shown in Fig.
2. At lower DTS(PTTh2)2 loadings with blend ratio of 1:1, 1:2, the blends showed uneven and larger
number of granular aggregations with a size distribution between 50-100 nm, which were uniformly
dispersed in the DTS(PTTh2)2 matrix. On further increasing the acceptor material concentration to
1:3 and 1:4 ratio, the blend showed such high miscibility that the homogeneous films were obtained

67
with smoother surfaces and for more deeper insights, the devices were characterized via SEM, the
blend ratio of 1:4 showed uniform surface morphology of the blended region as shown in Fig.3. The
current density-voltage (JV) characteristics of photovoltaic cells with various interfacial layers
under AM 1.5G irradiation at 100 mW cm-2 were examined. The observed open circuit voltage is
consistent with the HOMOD LUMOA difference expected from the energy level of DTS(PTTh2)2
and PC71BM. Indeed, according to the typical energy loss in DTS(PTTh2)2-based cells (ca. 0.35 V),
the maximum predictable open circuit voltage is about 0.80V, and it showed a short-circuit current
density of about 12.5 mA cm-2 and a fill factor of 45.20% with a power conversion efficiency of about
4.56%.. In this respect, the DTS(PTTh2)2/PC71BM interface has been shown to be highly efficient
for charge transfer and free carrier generation.
Fig. 2. AFM topographic images for DTS(PTTh2)2:PC71BM blend with different blend ratios: (a)
1:1; (b) 1:2 (c) 1:3; (d) 1:4.
a) b)
Fig. 3. SEM images for DTS(PTTh2) 2:PC71 BM blend a)1:3, b) 1:4.
Summary. BHJ solar cells were fabricated using DTS(PTTh2)2:PC71BM layers prepared in CB with
Dichlorobenzene solvents in an ambient atmosphere. The results clearly indicate that the device
performance is strongly influenced by the solvent additive from which the active layer was prepared.
This result shows that a strong relationship between the device performance and the active layer
morphology that allows efficient exciton dissociation and charge transport pathways in an optimized
polymer and fullerene interface. The choice of the main solvents is equally important in producing
such structure. The addition of co-solvents leads to smoother films, less heterogeneous surface
features, particularly in the distribution of polymer and fullerene phases, and much improved PCE
values in the resulting solar cells. The efficiency of bulk heterojunction solar cells is rapidly
increasing in the current years, so an accurate optimization of each layer and interface composing the

68
device is strictly required in order to avoid loss mechanism and to achieve higher and higher
performances. We anticipate that the device performances could be further improved by varying other
parameters such as solvents and substrate temperatures.
Acknowledgement. This study was supported by DST, New Delhi under Young Scientist Scheme
(Grant No. YSS/2015/001104), CSIR New Delhi under Extramural Research (Grant No.
01(2865)/16/EMR-II) and VIT University under RGEMS Fund.
References
[1] F.C.Krebs, N. Espinosa, M. Hosel, R.R. Sondergaard, M.Jorgensen, Rise to power OPV based
solar parks. Adv. Mater., Vol. 26 (2016), pp. 29-39, DOI 10.1002/adma.201302031.
[2] S. Liu, K. Zhang, J. Lu, J. Zhang, H.L Yip, F. Huang, Y. Cao(2013) High-Efficiency Polymer
Solar Cells via the Incorporation of an Amino-Functionalized Conjugated Metallopolymer as a
Cathode Interlayer. J. Am. Chem. Soc. Vol. 135 (2013), pp. 15326-15329, DOI 10.1021/ja408363c.
[3] S. Kannappan, R. Liyakath, J. Tatsugi, Third-order nonlinear optical characteristics of bulk film
effect on regioregular poly (3-dodecylthiophene) thin films fabricated by the drop-casting method,
Journal of Materials Science: Materials in Electronics, 2016, pp. 1-7, DOI 10.1007/s10854-016-4928-0.
[4] L. Saitoh, R.R. Babu, K. Santhakumar, K. Kojima, T. Mizutani, S. Ochiai, Performance of spray
deposited poly [N-9-hepta-decanyl-2,7- carbazole-alt-5,5-(4,7-di-2-thienyl-2,1, 3-
benzothiadiazole)]/[6,6]-phenyl-C61-butyric acid methyl ester blend active layer based bulk
heterojunction organic solar cell devices, Thin Solid Films, Vol. 520 (2012), pp. 3111-3117, DOI
10.1016/j.tsf.2011.12.022.
[5] V. Krishnakumar, K. Ramamurthi, R. Kumaravel, K. Santhakumar, Preparation of cadmium
stannate films by spray pyrolysis technique, Curr. Appl. Phys., Vol. 9 (2009), pp. 467-471, DOI
10.1016/j.cap.2008.04.006.
[6] S. Ochiai, P. Kumar, K. Santhakumar, P.K. Shin, Examining the effect of additives and
thicknesses of hole transport layer for efficient organic solar cell devices, Electron Mater. Lett., Vol.
9 (2013), pp. 399-403, DOI 0.1007/s13391-013-0013-5.
[7] P. Kumar, K. Santhakumar, J. Tatsugi, P.K. Shin, S. Ochiai, Comparision of properties of
polymer organic solar cells prepared using highly conductive modified PEDOT: PSS films by spin
and spray-coating methods, Jpn. J. Appl. Phys., Vol. 53 (2014) 01AB08.
[8] V.S. Saraswathi, J. Tatsugi, P.K. Shin, K. Santhakumar. Facile biosynthesis, characterization, and
solar assisted photocatalytic effect of ZnO nanoparticles mediated by leaves of L. speciosa. Journal
of Photochemistry and Photobiology B: Biology, Vol. 167 (2016) 89-98. DOI 10.1016
[9] P. Jayavel, J. Kumar, K. Santhakumar, P. Magudapathy, K.G.M. Nair, Investigations on effect
of alpha particle irradiation-induced defects near Pd/n-GaAs interface, Vacuum, Vol. 57 (2000) 51-
59, DOI S0042-207X(99)00211-0.

69
Analysis on Spectroscopic and Dielectric Study of PBS/PVA Polymer

Nanocomposite via Facile Hydrothermal Process
13
S. Sharon Tamil Selvi 1, J. Mary Linet1,a
1 Department of Physics, Loyola College, Chennai, India

a linet.mary@gmail.com
Keywords: lead sulphide, polyvinyl alcohol, hydrothermal technique, electrical property.
ABSTRACT. Lead Sulfide (PbS) nanoparticles have received much attention owing to their attractive nonlinear optical
properties. The present study reports the synthesis of PbS/ Polyvinyl alcohol (PVA) nanocomposite through hydrothermal
technique and characterized byX-ray diffraction (XRD), High Resolution Transmission electron microscopy (HRTEM),
Fourier transform infrared spectroscopy (FT-IR), UV-Visible spectroscopy (UV-Vis) and Dielectric analysis. XRD
spectra revealed the formation of cubic phase of PbS nanoparticles in PVA polymer matrix with average crystallite size
was found to be 28 nm. HRTEM analysis confirmed the formation of cubic particles with the average diameter of 30
2.45 nm. FTIR spectra confirmed the presence of organic molecules on the PbS nanoparticles. The UV-vis absorption
spectra of the PbS/PVA nanocomposite exhibit a significant blue shift from bulk PbS. The electrical property of the
material was studied briefly using dielectric measurements and it reveals that the dielectric constant of PbS in the PVA
matrix is maximum at lower frequency and decreases with increase in frequency. The higher value of dielectric loss at
lower frequency and the decrease of dielectric loss with frequency are due to the free charge motion within the material.
AC conductivity of PbS in polymer matrix increases with increase in frequency.
Introduction. Nanoscience is concerned with the study of the unique properties of matter at its nano
level and it utilizes to craft novel structures, devices and systems. The usage of nanoparticles as
polymer fillers relates to the well-built contemporary interest in progress and application of novel
materials [1]. Polymer nanocomposites are diverse and versatile functional materials in which
nanoscale inorganic particles are dispersed in an organic polymer matrix to enhanced optical,
mechanical, magnetic, and optoelectronic properties [2]. Prologue of stabilizers persuade on the
chemical properties and physical properties of semiconductor materials. Capping agents with strong
binding molecule form dense layer on the particle surface that stabilizes nanoparticles better, while
weak binding molecule consequence fast particle growth leading to large nanoparticles size and
aggregation [3]. Hence, the choice of a pertinent capping agent and its concentration becomes the
requirement for particle size regime, stabilization against aggregation and high quantum yield during
synthesis of nanoparticles [4]. The semiconductor materials have attracted fabulous curiosity owing
to its size and shape dependent optical and electronic properties. Among them, Lead sulphide (PbS)
is an significant IVVI semiconductor owe to its narrow band gap (0.41 eV) and large Bohr excitonic
radius (18 nm), which leads to potential applications in electroluminescence devices, infrared (IR)
detectors, solar absorbers, Pb2+ ion selective sensor and photography [5]. Besides, it has extensive
applications in optical devices such as optical switch due to its non-linear optical properties.
Properties of PVA (polyvinyl alcohol) like the transparency over the whole visible spectrum, good
adhesion to hydrophilic surfaces, formation of oxygen resistant lms and water soluble makes a good
choice for the fabrication of optical devices and colloidal stabilizer [6]. For the materialization of
PVA/PbS nanoparticles facile hydrothermal method was utilized and it is well known that the
hydrothermal technique is an environment affable method for preparation of materials since reactions
13

70
are carried out in a sealed container. Hence, the present work aims at the hydrothermal synthesis of
PbS nanoparticles in PVA matrix. To emphasize the structural, optical morphological and dielectric
properties of PbSPVA nanoparticles, the characterizations like XRD, UV, FTIR, HRTEM and
dielectric studies have been studied and discussed in detail.
Materials and synthesis. All reagents such as Lead (II) acetate trihydrate ((Pb(CH3COO))2* 3H2O),
Thiourea CH4N2S pure (Merk), (C6H15NO3) and PVA (polyvinyl alcohol) were used as received.
Deionized water was used as solvent.
Synthesis of PbS nanoparticles using PVA as capping agent. Initially, 2g of PVA dissolved in 10
ml of deionized water and stirred by a magnetic stirrer at 70 C for 2 hours. (Pb(CH 3COO))2* 3H2O
(0.2 M) was taken together with 30 ml of deionized water, and 0.2M of CH4N2S was also taken and
mixed with another 30 ml of deionized water separately. The above two solutions were then mixed
and followed by the as prepared PVA solution. The final solution was later transferred to the Teflon-
lined autoclave, placed inside a furnace at a temperature of 180C for 10 h and then gradually cooled
to room temperature. The precipitate was then filtered and washed repeatedly with water and ethanol
to remove any non-reacted chemicals or impurities. The final products were then dried in air at 100
C for 4h and collected for characterization.
Results and discussion. X-Ray diffraction studies:The crystallographic phases of the PbS
nanoparticles within the matrices of capping group PVA was shown in Figure 1. The diffractogram
exhibits several peaks pertaining to the (111), (200), (220), (311), (222), (400) and (331) planes of
the cubic phase of PbS according the JCPDS NO 78-1901 [7]. The lattice parameters thereby
calculated was found to the a=b=c 5.931 corresponding to the reported values of PbS. The average
crystallite size of the PVA lead sulphide particle was estimated by the Scherrer equation [8].
D= k/cos (1)
where is the wavelength of the Cu k X-rays (1.5405 ),

is the full width at half maximum (FWHM) of the observed peak.
The crystallite size was found to be 28 nm for the samples prepared with capped PVA.
PVA/PbS
(200)
60
(220)
INTENSITY (COUNTS)
50
(111)
(311)
40
(PVA)
30
(222)
(331)
20
(400)
10
0
10 20 30 40 50 60 70
2 THETA (DEGREE)
Fig. 1. XRD pattern of PVA capped PbS nanoparticles.
Morphological characterization. Fig. 2 (a and b) shows the HRTEM micrographs of the cubic
PbS/PVA nanocomposite, which suggests that the hydrothermal synthesis is a potential method and
71
good uniformity of the particles obtained. The statistical information of the mean particle size of
nanoparticles was determined to be 30 2.45 nm that agrees well with the crystallite size calculated
from XRD. Fig. 2 (c) shows the selected area diffraction pattern of as synthesized PVA capped PbS
NPs. The presence of dark and light spots in the diffraction pattern indicates the formation of small
nanoparticles. Polymer matrix played an important role in the formation of cubic NPs.
a) b) c)
Fig. 2. HRTEM images of PVA capped PbS NPs. (a) 50 nm, (b) 20 nm, (c) SAED pattern.
UV-vis absorption spectroscopy. The visible spectra of the PbS nanoparticles capped with PVA is
shown in Fig. 3. From the UV-vis absorption spectra of the samples were recorded in the wavelength
range of 200 to 800 nm. An optical band gap is obtained by the following equation with the help of
absorption spectra [9].
(h)1/n = A(h - Eg) (2)
To determine the energy band gap, (h)2 vs (h) was plotted. Where is the absorption coefficient,
h is the photon energy, A is a constant, Eg is the band gap and n is for the direct transition. Thus,
a plot of (h)2 vs (h) is a straight line whose intercept on the energy axis gives the energy gap, such
a representation is known as the Tauc Method. The band gap energy of PVA capped PbS
nanoparticles was found to be 4.17 eV. According to the above equation, the energy gap of PVA
capped PbS nanoparticles was shown in Fig. 3 (b). PbS nanoparticles exhibit larger blue-shift due to
the size confinement below of bulk excitonic Bohr radius (18 nm). It is significant shifted towards
blue from its bulk counterparts (0.41 eV) PbS [5]. In the present work, it is clearly seen that the PVA
matrix have played a vital role in the quantum confinement.

72
0.6
80 PbS/PVA= 4.17 eV
Absorbance (a.u) 0.5 70
60
hcm-eV
0.4
50
0.3 40
30
0.2
20
0.1 10

0
200 300 400 500 600 700 800 0 1 2 3 4 5 6 7
Wavelength (nm) hev)
a) b)
Fig. 3. (a) Absorption spectra, (b) Tauc plot of PbS/PVA nanocomposite.
Fourier transform infrared spectroscopy: The Figure 4 shows the FTIR spectrum of PVA capped
PbS nanoparticles. The absorption peak at 1092 cm-1 indicates the presence of lead sulphide (PbS).
Water has been used as solvent in the synthesis process. So that the hydroxyl group (OH) is occurred
predominantly (2400 -3400 cm-1) which indicates the moisture surroundings of nanoparticles. 1412
cm-1 indicates the presence of N-O symmetric stretch and C-N stretch. Br-stretching (Wave number
637.98 cm-1) indicates that mixing of KBr with lead sulphide nanoparticles for making pellet while
FTIR analyses [10], [11].
100
80
Transmittence %
2362
60
637.98
40
1245 2920
20 1092
1412 3369
1609
0
500 1000 1500 2000 2500 3000 3500 4000
Wavelength cm-1
Fig. 4. Shows the FTIR spectrum of PVA capped PbS nanoparticles.
Dielectric Studies.

73
7.0 O 8 50 C
50 C
6.5 O 100 C
100 C 7
6.0 150 C
Dielectric constant (er)
O
150 C
Dielectric Loss (tand)

5.5 200 C
5.0 200 C
O
6
4.5 5
4.0
3.5 4
3.0
2.5 3
2.0
1.5 2
1.0
1
0.5
0.0 0
-0.5
1 2 3 4 5 6 7 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
Log f Log f
a) b)
Fig. 5. (a) Log f versus Dielectric constant, (b) Dielectric Loss with Log f for PVA capped PbS.
0.000018 0
50 C
0
0.000016 100 C
AC conductivity (ac)
0
150 C
0.000014 0
200 C
0.000012
0.000010
0.000008
0.000006
0.000004
0.000002
0.000000
-0.000002
1 2 3 4 5 6 7
Log f
Fig. 6. Log f versus AC conductivity for PVA capped lead sulphide.
The dielectric constant (r) of the material was calculated for different frequencies from the measured
capacitance values. The plot of the dielectric constant versus log f is shown in Fig. 5 (a). It is observed
that the dielectric constant has high value in the low frequency region and thereafter decreases with
the applied frequency. The high value of (r) at low frequencies may be due to the presence of all the
four polarizations namely space charge, orientation and, electronic and ionic polarization and the low
values at higher frequencies may be due to the loss of significance of these polarizations gradually.
The higher value of dielectric loss at lower frequency and the decrease of dielectric loss with
frequency are due to the free charge motion within the material (Fig. 5 (b). The AC electrical
conductivity was determined using the relation:
ac = o r tan ( = 2f, f is the frequency)
With the high AC resistance, it can be mentioned that the space charge polarization plays an important
role in the electrical property of the sample [11].
74
Summary. The PbS/PVA nanocomposites have been successfully synthesized using hydrothermal
method. The structural and microscopic investigations of the sample indicate formation of clustered
cubic PbS nanoparticles with cubic crystal structure. The UV analysis demonstrates that the
nanostructures were blue shifted compared with the bulk PbSs band gap which may be due to exciton
confinement. The measurement of the dielectric properties of PbS NPs provides evidence of
polarization effects.
Acknowledgement Authors are grateful to UGC minor research project [MRP-5666/15
(SERO/UGC)] for providing financial support to undertake this work.
References
[1] Ashok K. Vaseashta, Ion N. Mihailescu, Functionalized Nanoscale Materials, Devices and
Systems, Springer Science & Business Media, 2008. DOI 10.1007/978-1-4020-8903-9
[2] D. Y. Godovsky, Device Applications of Polymer-Nanocomposites, Springer Berlin Heidelberg,
2000. DOI 10.1007/3-540-46414-X_4.
[3] Pallabi Phukan and Dulen Saikia, Optical and Structural Investigation of CdSe Quantum Dots
Dispersed in PVA Matrix and Photovoltaic Applications Pallabi Phukan and Dulen Saikia, Int J
Photoenergy, 2013, DOI 10.1155/2013/728280
[4] D.R. Paul, L.M. Robeson, Polymer nanotechnology: Nanocomposites, Polymer, 49 (2008) 3187
3204, DOI 10.1016/j.polymer.2008.04.017
[5] Masoud Salavati-Niasari, Davood Ghanbari, Hydrothermal synthesis of star-like and dendritic
PbS nanoparticles from new precursors, Partic, 2012. DOI 10.1016/j.partic.2012.02.003
[6] R. Kosti, M. Romevi, D. Markovi, J. Kuljani, M. I. omor,Far-infrared Spectroscopy of a
Nanocomposite of Polyvinyl Alcohol and Lead Sulfide Nanoparticles, Science of Sintering, 2006.
DOI 10.2298/SOS0602191K.
[7] S. Jana, S. Goswami, S. Nandy, K.K. Chattopadhyay, Synthesis of tetrapod like PbS microcrystals
by hydrothermal route and its optical Characterization, Journal of Alloys and Compounds, 2009. DOI
10.1016/j.jallcom.2009.03.110
[8]. Vineet Singh, Pratima Chauhan, Structural and optical characterization of CdS nanoparticles
prepared by chemical precipitation method, Journal of Physics and Chemistry of Solids, 2009. DOI
10.1016/j.jpcs.2009.05.024.
[9] Murugan Saranya, Chella Santhosh, Rajendran Ramachandran, Pratap Kollu, Padmanapan
Saravanan, Mari Vinoba, Soon Kwan Jeong, Andrews Nirmala Grace, Hydrothermal growth of CuS
nanostructures and its photocatalytic properties, Powder Technology, 2014. DOI
10.1016/j.powtec.2013.10.031.
[10] Talaat M.Hammad, Jamil K.Salem, S.Kuhn, Nadia M. Abu Shanab, R. Hempelmann, Surface
morphology and optical properties of PVA/PbS nanoparticles, Journal of Luminescence 2015. DOI
10.1016/j.jlumin.2014.07.009.
[11] S. Jana, R. Thapa, R. Maity, K.K. Chattopadhyay, Optical and dielectric properties of PVA
capped nanocrystalline PbS thin films synthesized by chemical bath deposition, Physica E, 2008. DOI
10.1016/j.physe.2008.04.015.

75
Voltammetric Sensing of Dopamine at a Glassy Carbon Electrode Modified with

Chromium (III) Schiff Base Complex14
K. Bharathi1, S. Praveen Kumar2, P. Supriya Prasab1, V. Narayanan2,a
1 Department of Chemistry, DKM College for Women, Vellore, India

2 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India
a vnnara@yahoo.co.in
Keywords: dopamine, chromium (III) Schiff base complex, microwave irradiation, electrochemical polymerization,
differential pulse voltammetry.
ABSTRACT. Dopamine is one of the most important neurotransmitters, which belongs the catecholamine family. It is
widely distributed in brain and nervous system of mammals. It involves a crucial role in the function of central nervous,
hormonal, renal and cardiovascular systems. It is also controlling brain activity, human metabolism and persistence of
addiction. Due to the more functions in several organs are related with dopamine, such as brain, immune system, kidneys,
and pancreas. The abnormal level of dopamine has numerous significant in health problems, it may cause Parkinsons
disease, drug addiction, psychosis and attention deficit hyperactivity disorder. Hence, it is very important to develop a
selective and sensitive method for the determination of dopamine. Dopamine has good electrochemical activity, it can be
determined electrochemically with better detection limit. In the present work chromium (III) Schiff base complex
modified GCE was utilized for the detection of dopamine. Chromium (III) is an essential biological element and it is less
toxic to human cell. The chromium (III) has better electrochemical activity and it can be an efficient electrocatalytic
sensor for the dopamine detection. The chromium (III) Schiff base complex modified GCE shows the oxidation potential
at 0.196 V and the peak current is 6.74 A. The bare GCE exhibits the oxidation peak for dopamine at 0.316 V and the
peak current is 5.79 A. The chromium (III) Schiff base complex modified GCE shows better electroctalytic sensing
activity for dopamine detection than bare GCE. Based on the above result the chromium (III) Schiff base complex can be
used for the determination of dopamine in real samples.
Introduction. It is necessary to develop a simple, accurate, selective and sensitive analytical method
for the determination of dopamine, that has great impact on clinical process. Since, dopamine (DA)
is an important neurotransmitter in central nervous system of the mammals and it affects brain
processes that control movement, emotional response, and the ability to experience pleasure and pain.
The DA deficiency caused Parkinsons disease, it is one of the most common diseases in the brain. A
DA imbalance in the prefrontal cortex will lead to eating and sleeping disorders [1], [2]. DA is a
simple organic molecule in catecholamine family and it has significant role in human metabolism.
Up to date, several analytical methodologies with different principles are available for the DA
quantification, such as titrimetry, spectrophotometry, chromatography, capillary electrophoresis,
chemiluminescence, FTIR and Raman spectrometry, ow-injection analysis, thermo gravimetric
analysis and Electrochemical methods [3]. But the electrochemical techniques was widely used for
the determination of DA, due to its advantages of high sensitivity, better selectivity, faster response
and low costs over other analytical methods. The DA also exhibits high electrochemical redox
activity. However, at the bare electrode surface, DA exhibits sluggish electrocatalytic redox activity.
Thus, to increase the detection quality considerable efforts have been develop with the aid of modied
electrodes. The modified electrodes enhance the voltammetric response of bare GCE and exhibits
better performance for DA detection. There are several methods have been used for the electrode
14

76
modification chemical modification, spin coating method and electrochemical polymerization etc.
Based on the above factors in the present work we employed the electrochemically polymerization
process for the bare glassy carbon electrode surface modification. The chromium (III) Schiff base
complex were used for the substrate to modified the GCE surface. Electrochemical polymerization
of redox-active species like symmetrical metal complexes, is an effective tool for the modification of
the surface of bare glassy carbon electrode. The Schiff base metal complexes forms polymer-coated
electrodes via anodic oxidation, for different types of applications in the electrochemical elds such
as electrochemical catalysis and electrochemical analysis [4]. The chromium (III) Schiff base
complex was synthesized by microwave irradiation method. It is one of the best synthetic method, it
gives better yield and purity than other synthetic methods. It required minimum quantity of solvents,
less amount of energy consumption and very short time duration. This microwave irradiation method
is one of the green chemical synthetic method [5]. Chromium (III) forms stable metal complex with
Schiff base ligands, +3 oxidation state is more stable due its d3 electronic conguration under
physiological conditions. Chromium (III) complex is less cytotoxic than chromium (VI) complexes
to human cells and it is an essential nutrient in the glucose tolerance factor (GTF) to maintain the
normal level of glucose in carbohydrate and lipid metabolism. Insucient of chromium (III) in take
may cause the Type II diabetes and cardiovascular diseases. Chromium coordination polymers have
great interest in biological, clinical, analytical and pharmacological fields because of its multifunction
importance. Chromium (III) metal complexes are having combined photochemistry, electromagnetic
property and electrochemical properties. The chromium Schiff base complex polymer are connected
covalently through carbon-carbon linkage between the ligands and it has efcient energy transfer.
The chromium (III) Schiff base complex has good electrochemical redox behaviour it can be an
efficient electrocatakytic sensor for the determination of DA. The chromium (III) Schiff base complex
modified GCE shows better linearity form 110-5 to 110-3 and good detection limit 110 nM with the
sensitivity of 2.369810-6 A/M. The chromium (III) Schiff base complex modified GCE has better
electrocatalytic sensing activity for the detection of DA than bare GCE it reveals from the results.
From the result the chromium (III) Schiff base complex can be used for the analysis of dopamine in
real samples.
Experimental procedure.
Fig. 1. Synthesis of chromium (III) Schiff base complex.
The Schiff base ligand was synthesied by the following procedure, 1 mM [0.1462 g] of
Triethylenetetramine was added with 2 mM [0.2242 g.] of salicylaldehyde, gradually under stirred
condition. An yellow colour solution was obtained and it was irradiated in the microwave oven at 320
W for 2-3 minutes. After the irradiation, the mixture was cooled to room temperature and then it was
kept for 12 hr. at 100C. The obtained coloured solid product was ltered, washed with cold ethanol
and dried overnight in a desiccator. The Schiff bases were recrystallized using 1:1 methanol and

77
dichloromethane as solvent. 1:1 ratio of Schiff base ligand and chromium (III) chloride was mixed
under stirring condition and it was employed for microwave irradiation at 320 W for 5 min, a brown
colour solution was obtained and it was cooled to room temperature for 24 hrs., brown colour solid
was obtained. The brown colour solid was recrystallized by 1:1 methanol and dichloromethane. The
synthetic scheme was shown in Fig. 1.
Result and Discussion
FT-IR spectral analysis. The FT-IR spectrum of chromium (III) Schiff base complex was recorded
in the range of 4000400 cm-1 using KBr pellet. The FT-IR spectrum shows an important
characteristic band at 1633 cm-1, which corresponds to the stretching vibration of imine group (C=N).
A peak appeared at 610 cm-1 due to the bond formation of chromium and nitrogen [ (Cr-N)]. The
chromium and oxygen [ (Cr-O)] bond shows a peak at 540 cm-1. This peak conforms the complex
formation between Schiff base ligand and chromium (III) metal ion. A peak at 3425 cm -1 is exhibit
due to the presence of O-H stretching vibrational bands, it shows that water molecules were
solvated/coordinated in the metal complex. Other characteristic peaks also observed in the spectrum.
The spectrum is shown in Fig. 2a.
UV-Visible spectral analysis. The electronic spectrum of chromium (III) Schiff base complex was
show in Fig. 2b, which is recorded in methanol solution at room temperature in the range of 200-
800 nm. The electronic spectrum shows an absorption at 225 nm for the * transition in ligand.
A peak at 286 nm explains the n* transition. The d-d transition of chromium (III) metal ion
exhibits at 357 nm and 645 nm. The d-d transitions were observed due to 4T2g 4A2g (1) and 4T1g
4A2g (2) electron transitions in chromium (III) metal ion. It conforms the octahedral geometry of
Cr (III) Schiff base complex and the magnetic momentum is 3.17 BM.
Fluorescence spectral analysis. The fluorescence spectrum of chromium (III) Schiff base complex
was recorded using methanol solution in ambient temperature and it was given in Fig. 2c. The
chromium (III) Schiff base complex shows an emission peak at 600 nm, when it was excited at 475
nm. The emission band at 600 nm is attributed due to 4T1g 4A2g electronic. It is both Laporte and
spin forbidden in octahedral (Oh) symmetry.
Electrochemical Studies. The electrochemical redox activity of the chromium (III) Schiff base
complex was examined by using three electrode system. The glassy carbon electrode was working
electrode, silver and silver chloride (Ag/AgCl) was reference electrode and platinum wire used as
counter electrode. Voltammetry measurements was carried in the acetonitrile solution, in presence of
tetrabutylammonium perchlorate (TBAP) as supporting electrolyte. The chromium (III) complex
exhibits only a reduction peak at -0.85 V. It indicates that chromium (III) Schiff base complex has
good electrochemical activity. The reduction behaviour of the chromium (III) metal complex
attributed to electrons transfer from Cr (II) to electrode, it is one electron transfer, which can be
calculated by using ip = nFQ/4RT [4].
Electrochemical polymerization. The glassy carbon electrode (GCE) was modified by the
electrochemical polymerization of 0.1 M chromium (III) Schiff base complex in acetonitrile solution.
It was shown in the Fig. 3a. The Cr (III) Schiff base complex shows a oxidation peak at -0.085 V.
There is no considerable changes at the number of cycles increase for the polymerization. The
polymerized Cr(III) Schiff base complex (poly-Cr-SBC) were deposited on the electrode surface. The
modified surface coverage concentration was determined by using =Q/nFA. The calculated
modified electrode surface coverage concentration is 0.0234 10-11 mol cm-2. The poly-Cr-SBC/GCE
was used for the sensing of dopamine (DA). The Cr complex modified GCE (poly-Cr-SBC/GCE)
was dried and stored at 10 0C when it was not used.

78
Fig. 2. a) FT-IR spectrum, b) UV-Visible spectrum, c) Fluorescence spectrum, d) Cyclic

voltammogram in 0.1 M TBAP at the scan rate of 50 mVs-1 of chromium (III) complex.
Fig. 3. a) Cyclic voltammogram of chromium (III) complex polymerization in 0.1 M TBAP, b)

Cyclic voltammogram of Electrocatalytic sensing of dopamine in PBS at the scan rate of 50 mVs-1.
Electrocatalytic Sensing of dopamine. The electrochemical behaviour of dopamine (DA) at GCE

and poly-Cr-SBC/GCE were investigated by cyclic voltammetry (CV) in phosphate buffer as
background electrolyte. Cyclic voltammograms of DA using GCE and poly-Cr-SBC/GCE as working
electrodes are shown in Fig. 3b. In the voltammogram the oxidation peak of DA at pH 7 was appears
at 0.317 V (vs SCE) for bare GCE and for modified electrode it exhibits at 0.194 V, which is about
123 mV more negative than that of GCE. A broad peak at bare GCE indicates that a slow electron
transfer reaction was occurred for the DA oxidation. However, the modified GCE shows a sharp
oxidation peak with 123 mV negative shift, it indicates that electron transfer rate was enhanced at

79
modified GCE. It must be pointed out that the oxidation peak current of DA observed on modified
GCE has increased than that of bare GCE. At modified GCE oxidation peak of DA is well defined
sharp peak, enhanced peak current and more negative shift, it reveals that the modified GCE has
better electrocatalytic active than bare GCE. The chromium (III) Schiff base complex enhanced the
electrocatalytic sensing activity of dopamine. The fig. 4 explains the electrochemical reaction of DA
at working electrode [6].
Fig. 4. Electrocatalytic redox mechanism of dopamine (DA).
Summary. In this present work, we synthesized chromium Schiff base complex using microwave
irradiation method. The synthesized complex was characterized by FT-IR, UV-Vis and Fluorescence
spectral techniques. The electrochemical redox property of Cr (III) Schiff base complexes by using
cyclic voltammetry. The chromium Schiff base complex was electrochemically polymerized on the
GCE surface and the modified electrode was successfully used for the detection of dopamine. The
modified electrode shows a better result than bare GCE.
References
[1] Y. L. Xie, J. Yuan, H. L. Ye, P. Song, S. Q. Hu, J. Electroanal. Chem., 749 (2015) 2630. DOI
10.1016/j.jelechem.2015.04.035.
[2] J. Chou, T. J. Ilgen, S. Gordon, A. D. Ranasinghe, E. W. McFarland, H. Metiu, S. K. Buratto, J.
Electroanal. Chem., 632 (2009) 97101. DOI 10.1016/j.jelechem.2009.04.002.
[3] H. Yao, Y. Sun, X. Lin, Y. Tang, L. Huang, Electrochim. Acta, 52 (2007) 61656171, DOI
10.1016/j.electacta.2007.04.013.
[4] S. P. Kumar, R. Suresh, K. Giribabu, R. Manigandan, S. Munusamy, S. Muthamizh, V.
Narayanan, Spectrochim. Acta A, 139 (2015) 431441. DOI 10.1016/j.saa.2014.12.012.
[5]N. Fahmi, S. Shrivastava, R. Meena, S.C. Joshi, R.V. Singh, New J. Chem. 37(2013) 14451453.
DOI 10.1039/C3NJ40907D.
[6] F. Zhu, J. Yan, C. Sun, X. Zhang, B. Mao, J. Electroanal. Chem., 640 (2010) 5155. DOI
10.1016/j.jelechem.2010.01.006.

80
Mechanical and Morphological Characterization of PVA/SA/HNTs Blends and

Its Composites15
N. Thayumanavan1
1 Jawaharlal College of Engineering and Technology, Palakkad, Kerala, India
Keywords: polyvinyl alcohol (PVA), sodium alginate (SA), halloysite nanotube (HNTs).
ABSTRACT. Halloysite nanotube (HNTs) filled polyvinyl alcohol (PVA)/sodium alginate (SA) blend and its composites
films were prepared by solution casting. It was found out, that SA a biopolymer act as a modifier that improves the
dispersion of HNTs in composites by establishing the interaction between the HNTs and SA established through FTIR
and solution experiments. Morphological observation indicates the improved dispersion of HNTs in presence of SA for
PVA/SA/HNTs composite film as compared with PVA/HNTs composite film, which results in a remarkable improvement
in mechanical properties.
Introduction. Halloysite nanotubes (HNTs) filled polymer blends and its composites are under
intense investigations for various applications [1], [2]. The incorporation of small concentration of
HNTs in polymer blend matric result in an enhancement in mechanical and thermal properties [1],
[2]. HNTs as a reinforcing material is more attractive as compared to carbon nanotubes due to its
lower cost [3], [4]. In this work, polyvinyl alcohol (PVA) as a matrix material is used and HNTs as a
filler material. PVA is a biodegradable polymer used in biomedical, coatings and fuel cells
applications [5], [6]. Filler material is added to improve mechanical and thermal properties of PVA
composites. The properties of PVA composites depends on the dispersion of filler in PVA matrix.
Sodium alginate (SA) has been utilized which will intercalate into interlayer space of HNTs to
overcome the aggregation of HNTs in polymer matrix. The aim of this paper is to develop
PVA/HSA/NTs blends and its composites by solution processing route with an aim to achieve
improved mechanical properties which can be exploited for several potential applications.
Materials and Experimental procedure. Halloysite nanotube (HNTs) were received from Imerys
Tableware and PVA (99% hydrolyzed, Mw ~ 89,000~98,000) purchased from Aldrich. The procedure
for preparing PVA/SA/HNTs nanocomposite films are as follows. HNTs was dissolved in 10 mL of
water and treated with ultrasound for 45 min to make a homogeneous dispersion (1 mg/mL). PVA
powder was dissolved in distilled water at 90oC and the solution was subsequently cooled to room
temperature. The HNTs aqueous dispersion was gradually added to the PVA solution, sonicated at
room temperature for 15 min, and stirred to obtain homogeneous PVA/HNTs solutions. Finally, the
above solutions were cast into polystyrene petri dishes at room temperature for film formation until
its weight equilibrated. The weight contents of HNTs in the nanocomposite films described above
were controlled to be 0.5, 2.5, 5 and 10 wt%. In addition SA powder was dissolved in distilled water
at room temperature and subsequently added to PVA solution and aqueous dispersion of HNTs for
the preparation of PVA/SA blend film and PVA/SA/HNTs nanocomposite blend film.
Characterization. Mechanical properties of films were tested using Tensiometer (Kudale
Instrument, India) at 10 mm/min having sample size of 60x10x1 mm for at least 10 samples. The data
reported here are average of 5 tests for each composition; the standard deviation is less than 5%.
15

81
Fourier transform infrared spectroscopic analysis (FTIR) was performed on the samples with Mettler
Taldeo FTIR in the scanning range of 4004000 cm-1. Optical microscopy was performed on film
using Karl Zeiss optical microscope.
Results and discussion.
a) b) c)
Fig. 1. Optical micrograph of PVA/HNTs composites having concentration of (a) 5 wt% HNTs, (b)
10 wt% HNTs, (c) PVA/SA/HNTs composites having 5 wt% of 1:1 ratio of HNTs and SA.
a) b) c)
Fig .2. Optical micrograph of PVA/SA/HNTs composites having fixed concentration of HNTs with
varying SA content (a) 10 wt%, (b) 20 wt%, (c) 30 wt% of SA.
a) b)
Fig. 3. Photograph of PVA/HNTs and PVA/SA/HNTs solution.
PVA/HNTs nanocomposite optical micrograph is shown in Figure 1a,b. It is to be noted that HNTs
has been dispersed in the form of granules all over the matrix which suggests the aggregation of HNTs
(Figure 1a,b). In order to reduce the aggregate nature of HNTs in PVA matrix, SA a biopolymer has
been utilized. It can be clearly seen that SA helps in HNT to disperse in the PVA/SA matrix (Figure
1c). With an increase in SA concentration from 5 to 10 wt% result in the formation of matrix-droplet
morphology in case of PVA/SA/HNTs composites (Figure 2). In addition, SA phase consist of less
aggregates of HNTs as compare to PVA phase as shown in Figure 2a,b,c, which is due the possible

82
interaction between the HNTs and SA which is confirmed with the help of solution experiments and
FTIR spectroscopy.
To check the solubility of HNTs in PVA and PVA/SA blend, aqueous solution of HNTs has been
mixed with PVA solution and PVA/SA solution followed by 1 hour sonication and kept for seven
days at room temperature without disturbance. Figure 3a shows the addition of HNT in PVA solution
result in sedimentation of HNTs occurs at the bottom of the mixture after seven days of mixing. This
is due to the aggregated nature of HNTs in PVA solution suspended at bottom of the mixture. While
the addition of HNT in PVA/SA solution exhibit translucent, dense solution without any
sedimentation at the bottom of the mixture suggesting the formation of stable solution (Figure 3b)
which is possibly due to establishment of an interaction between HNTs and SA. Similar strategies
were employed for the dispersion of carbon based nanoparticle like carbon nanotube (CNT) and
graphene in polymer matrix by covalent grafting of a suitable polymer with CNT and utilizing the -
electron cloud of CNT for improved dispersion by establishing - interaction or cation- iterations
[7], [8].
Figure 4 shows the FT-IR spectroscopy of PVA/SA and PVA/SA/HNT composite films. The
PVA/SA films exhibit characteristic peak at 1740 cm-1 that is formed due to the formation of hydrogen
bonding, as reported in the literature [9]. In the other case, PVA/SA/HNT films exhibit complete
absence of a characteristic peak as seen in case of the PVA/SA film, which shows the appearance of
peak, is due to the HNTs. This shows that there is an interaction between HNTs and PVA/SA phase.
a)
b)
Fig. 4. FT-IR graph comparisons of PVA/SA and PVA/SA/HNT composite films (a) PVA/SA, (b)
PVA/SA/HNT.

83
a) 9
Modulus (GPa)
7
0 2 4 6 8 10
Weight % of HNTs
50
b) 45
Tensile Strength (MPa)
40
35
30
25
20
0 2 4 6 8 10
Weight % of HNTs
Fig. 5. Mechanical properties of PVA and PVA/HNTs composites (a) Modulus, (b) Tensile strength.
10
80
a) PVA/SA/HNTs b)
9 PVA/SA/HNTs
PVA/SA 70
Modulus (GPa)
PVA/SA
8
60
7
50
6
40
5
30
4
20
0 10 20 30 0 10 20 30
Weight % of SA Weight % of SA
Fig. 6. Mechanical properties of PVA/SA films and PVA/SA/HNTs composites films (a) Modulus,
(b) Tensile strength.
Tensile testing was performed on the PVA, PVA/SA and PVA/SA/HNTs composite films.
Mechanical properties of the PVA, PVA/SA, PVA/HNTs and PVA/SA/HNTs composites were
calculated using stress strain curves. With an addition of HNTs in PVA matrix results in an increase
in tensile properties of PVA/HNTs composite film as shown in Figure 5. It has been observed that
with an increase in HNTs concentration in PVA result in an increase in tensile strength and tensile
modulus of PVA/HNTs composites (Figure 5 a, b). In addition, by addition of SA in PVA results in
an increase in tensile properties of PVA/SA blend film (Figure 6,b). However tensile modulus and
the tensile strength of the PVA/SA blend films increases considerably till 20 wt % of SA. With further
increase the concentration of SA in the PVA/SA blend films to 30 wt %, there is a drop both in the
tensile modulus as well as the tensile strength of the PVA/SA blend. This drop is due to the brittle
84
nature of SA [9]. By addition of SA and HNTs in PVA matrix results in a remarkable improvement
in tensile properties of PVA/SA/HNTs composites. This remarkable increase in the tensile modulus
(GPa) and tensile strength (MPa) in case of the PVA/SA/HNTs composite films is due to the
interaction between the matrix and the HNTs (as established by FTIR spectroscopy) as well as due to
the better dispersion of HNTs in the PVA/SA matrix (as established by the solution experiment).
Here, mechanical properties increases in case PVA/SA/HNTs composite up to the SA concentration
of 20 wt% of SA and when SA concentration increases more than 20 wt% result in a decrease in
mechanical properties as expected due to the brittle nature of SA.
Summary. PVA, PVA/SA, PVA/HNTs and PVA/SA/HNTs composites has been prepared by solvent
processing method. It was observed that with an addition of SA and HNTs result in an increase in
mechanical properties of blend and composites respectively. However, remarkable increase in
mechanical properties was observed in case of PVA/SA/HNTs composites due to the interaction
between the matrix and the HNTs as well as due to the better dispersion of HNTs in the PVA/SA
matrix.
References
[1] Kubade P, Tambe P. Influence of halloysite nanotubes (HNTs) on morphology, crystallization,
mechanical and thermal behaviour of PP/ABS blend and their composites in presence and absence of
dual compatibilizer. Compos Interfaces 2016; 5: 433451. DOI 10.1080/09276440.2016.1144392
[2] Kubade P, Tambe P. Influence of surface modification of halloysite nanotubes and its localization
in PP phase on mechanical and thermal properties of PP/ABS blends. Compo Interfaces 2017; 24(5):
469487. DOI 10.1080/09276440.2016.1235442
[3] Tambe PB, Bhattacharyya AR, Kamath S. Structure property relationship studies in amine
functionalized multiwall carbon nanotubes filled polypropylene composite fiber. Polym Eng Sci
2012; 52: 11831194. DOI 10.1002/pen.22186
[4] N. Thayumanavan, P. B. Tambe, G. M. Joshi and M. Shukla, Effect of sodium alginate
modification of graphene (by anion- type of interaction) on the mechanical and thermal properties
of polyvinyl alcohol (PVA) nanocomposites. Compos Interface. 2014;21:487-506.
[6] N. Thayumanavan, P. B. Tambe and G. M. Joshi, Effect of surfactant and sodium alginate
modification of graphene on the mechanical and thermal properties of polyvinyl alcohol (PVA)
nanocomposites. Cellulose Chem Tech. 2015; 49: 69-80
[7] P. V. Kodgire, A. R. Bhattacharya, S. Bose, N. Gupta, A. R. Kulkarni, A. Misra, Control of
multiwall carbon nanotubes dispersion in polyamide6 matrix: An assessment through electrical
conductivity, Chem. Phy. Lett. Vol. 432, 2006, 480-485.
[8] P. M. Ajayan, L. S. Schadler, C. Giannaris, A. Rubio, Single-Walled Carbon NanotubePolymer
Composites: Strength and Weakness, Adv. Mater. 12, 2000, 750.
[9] C. Tuncer and D. Serkan, Preparation and Characterization of Blend Films of Poly(Vinyl Alcohol)
and Sodium Alginate, J. of Macromolecular Science Vol. 43, 2006, 1113-1121, DOI
10.1080/10601320600740389 Vol 9.

85
Mechanical and Thermal Behaviour of Hybrid Filler Reinforced PP/ABS Blend

16
S.M.D. Mastan Saheb1, P. Tambe2, M. Malathi1
1 School of Advanced Sciences, VIT University, Vellore, India

2 School of Mechanical Engineering, VIT University, Vellore, India
Keywords: polypropylene (PP), blends, composites, fillers.
ABSTRACT. In this study, the influence of Halloysite nanotubes (HNTs) and intercalated graphite (IG) on the
mechanical and thermal properties of polypropylene (PP)/acrylonitrile butadiene styrene (ABS) blend were studied.
Hybrid fillers reinforced PP/ABS blends were processed using twin screw extruder followed by injection moulding. The
addition of hybrid fillers increases the crystallinity of PP phase of PP/ABS blends and its composites. In addition, hybrid
fillers increase the thermal stability of PP/ABS blends. Transmission electron microscopy (TEM) studies and solution
experiments show the selective localization of hybrid fillers in PP phase of PP/ABS blend and its composites. Further,
scanning electron microscopy (SEM) studies of cryo-fractures and etched PP/ABS blends and its composites samples
show the formation of matrix-droplet morphology. Due to increase on crystallinity of PP phase, selective localization of
hybrid fillers and an interaction between hybrid filler and PP phase results in an enhancement in tensile modulus and
impact strength of hybrid filler reinforced PP/ABS blend. The increase in tensile modulus and tensile strength are and
respectively.
Introduction. Polymer blend of polypropylene (PP) and acrylonitrile butadiene styrene (ABS) are of
commercial interest [1], [2]. PP is attractive commodity plastics due to its low cost, and addition of
ABS overcomes the low impact properties of PP, as ABS has good impact properties [3], [4], [5], [6].
PP/ABS blends are compatible using various compatibilizers [5], [6], [7]. Recently, Kubade et.al [1]
reported that the compatibilizer influences mechanical and thermal properties of PP/ABS blends
significantly, because compatibilizer refines PP/ABS blend morphology. They used polypropylene
grafted maleic anhydride (PP-g-MA) and styrene-ethylene, butylene-styrene triblock copolymer
grafted with maleic anhydrite (SEBS-g-MA). In polymer blend, filler material are added to improve
the properties and process ability of polymer blends. The various fillers added in PP/ABS blends are
carbon black (CB), Halloysite nanotubes (HNTs) and multiwall carbon nanotubes (MWNT) [1, 2, 8,
9]. Hom et.al [8] shows the electrically conducting behaviour in case of 10 wt.% of CB in 55/45
PP/ABS blend, due to formation of co-continuous morphology. Khare et. al. [9] demonstrate that non-
covalently modified MWNT in PP/ABS blend show enhanced electrical conductivity at low
concentration of MWNT. In addition, Kubade et.al. [2] shows that surface modified HNTs helps on
achieving better dispersion of HNTs in PP/ABS blends, and subsequently enhanced the mechanical
properties significantly. So far, there are no reports regarding the use of dual filler in PP/ABS blends.
In this regard we are attempting to study the use of dual fillers in PP/ABS blends in presence of dual
compatibilizer. The filler materials used were HNTs and intercalated graphite (IG). Compatibilizers
used were PP-g-MA and SEBS-g-MA. PP/ABS blends and its composites were prepared using twin
screw extruder followed by injection moulding. The prepared samples were characterized using
various characterization techniques.
Materials and experimental procedure. PP of trade name REPOL 110MA was supplied by
Reliance Industries, Ltd, India. PP-g-MA was supplied by Pluss Polymer Ltd, India. SEBS-g-MA
16

86
was supplied by Karton, India. ABS of Terluran GP-22 was supplied by Strylotion, India. Halloysite
nanotubes were kindly supplied by Imerys Tableware, New Zealand. Melamine and graphite powder
was supplied by Sakshi Dies and Chemicals, India. PP/ABS blends in a ratio of 80/20 and its
composites were processed using twin screw extruder of S. C. Dey & Co., India, which was operated
at 155-210-240oC with a rotational speed of 10 rpm. In addition, pure blend sample was also prepared.
Extruded strand was injection moulded using injection moulding machine of S. C. Dey & Co., India,
operated at 235 oC and applied pressure of 7 bar. The concentration of HNTs was 1 wt.%. and IG was
4 wt.%. IG was prepared by mixing melamine and graphite in 3: 1 ratio in a ball mill for 6 hours.
Characterization. HNTs and IG were characterized using transmission electron microscopy (TEM)
of JEOL JEM 2100. The tensile testing of samples were tested on universal testing machine, Instron
(8801) according to ASTM D638; and impact testing of samples were tested on CEAST (Instron)
pendulum impact tester according to ASTM D256. Thermo gravimetric analysis (TGA) of samples
were performed on Q500 from TA instruments in the heating rate of 10oC/min in temperature range
of 25 to 900oC. Scanning electron microscopy (SEM) of samples were performed over Hitachi SU
3500. Differential scanning calorimetric (DSC) measurements of samples were carried out using a
DSC Q200 from TA instruments in the temperature range from 25 C to 235 C at a scan rate of
10 C/min under nitrogen atmosphere. The degree of crystallinity (Xc) of PP phase was calculated
from the ratio of normalized heat of fusion (Hm, norm) of second heating run to the heat of fusion of
normalized 100% crystalline PP, (Hm)100%, which was calculates as 207 J/g [1].
Results and discussion.
Fig. 1. TEM images of (a) HNTs, (b) IG (c) & (d) PP/ABS blends and its composites, (e) SEM
image of PP/ABS blends and its composites, (f) Solution experiments.
The Fig. 1 (a-b) shows TEM image of HNTs and IG respectively. It depict HNTs have hollow tubular
structure, while IG having two-dimensional platelets. The measured HTTs diameter is 60-80nm,

87
while IG size is in microns. HNTs and IG are mixed with PP/ABS blends in presence of compatabilier
using twin screw extruder. The extrude strand was microtome and TEM image was taken. Fig. 1c
show the TEM image of PP/ABS blends and its composites. It shows the dispersion of HNTs and IG
in PP/ABS matrix. The size of IG particles in several hundred nanometers, as seen in Fig. 1d. In
addition, HNTs is localized near ABS phase. The interfacial calculation of PP-HNTs pair and ABS-
HNTs pair suggest the affinity of ABS towards ABS phase [2]. But, due to the formation of layer of
SEBS-g-MA around ABS phase, SEBS-g-MA restricts the HNTs in PP phase [1], [2]. It was noted
that interfacial tension of SEBS-g-MA-HNTs pair is higher than HNTs-PP pair. The SEM image of
cryo-fractured morphology of hybrid filler reinforced PP/ABS blend show the formation of matrix-
droplet morphology (Fig. 1e). It was found that hybrid filler reinforced PP/ABS blends has refined
morphology as compared to PP/ABS blend (not shown here). Further, solution experiments were
carried out to probe the dispersion of HNTs and IG in PP/ABS matrix. PP/ABS blend and its
composites was dissolved in terrahydrofurane and xylene respectively to dissolve ABS and PP phase.
Fig. 1 (f) show the dark colour solution of PP phase dissolved in xylene, depicting localization of
fillers in PP phase, while other glass vial of ABS dissolved in THF shows no trace of fillers.
100
(a) 6
PA (b)
PA1H1G
80
Heat Flow (W/g)
Weight (%)
4
60
40
exo
20 PA
PA1H1G
0 0
100 110 120 130 200 300 400 500 600 700
Temperature (oC) Temperature (oC)
Fig. 2. (a) Crystallization exotherm and (b) TG curves of PP/ABS blends and its composites.
The influence of HNTs and IG on the crystalline behaviours was characterized using DSC. Fig. 2a
shows the crystalline exothermal of PP/ABS blends and its composites. The crystallization
temperature (Tc) of PA/ABS blend is 121.3 oC, while Tc of PP/ABS blends and its composites is 120.3
o
C depicting dereaase in crystallization rate. The decrease in crystallization is due to interaction of
filler and matrix. Similar study was observed by various researcher earlier [10], [11]. Melting
temperature (Tm) of blends were recorded from the melting endotherms of PP/ABS blends and its
composites. The Tm of hybrid filler reinforced PP/ABS blend is higher as compare to PP/ABS blend,
as noted from melting endotherms. Percent crystallinity (Xc) of PP/ABS blends and its composites
was calculated. Xc value of hybrid filler reinforced PP/ABS blends and its composites is 39.1 %, while
Xc value of PP/ABS blends is 46.2%. This observation depict interaction between filler and matrix
helps in formation of more PP crystals.
The influence of HNTs and IG on the thermal behaviour of PP/ABS blends was characterized using
TGA. Fig. 2 b) shows the TG curve of PP/ABS blends and its composites. TG curve of hybrid filler
reinforced PP/ABS blends is shifted towards higher temperature as compare to PP/ABS blend. This
observation confirm the enhancement in thermal stability of polymer with an incorporation of HNTs
and IG. The differential of TG curve were carried out and maximum degradation temperature (Tdeg)
was noted. Tdeg value of hybrid filler reinforced PP/ABS blends and its composites is 466 oC, while
Tdeg value of PP/ABS blends is 485 oC. The increase in thermal stability is due to the interaction
between fillers and polymer.

88
(a) 960 (b) 32

Tensile Modulus (MPa)

PA
PA 28 PA1H1G
930
PA1H1G
24
900
20
870
16
840
12
810
(c) 200
PA
Impact Strength (KJ/m2)
PA1H1G
(d)
150
100
50
Fig. 3. (a) Tensile modulus, (b) Tensile strength, (c) Impact strength of PP/ABS blends and its
composites (d).
The extruded stands were injection moulded as per ASTM standard for tensile and impact testing.
Fig. 3a-b shows the histogram of tensile modules and tensile strength of PP/ABS blends and its
composites. Tensile modulus of hybrid filler reinforced PP/ABS blend is higher as compare to
PP/ABS blend. The increase in tensile modulus is due to refinement in morphology of hybrid filler
reinforced PP/ABS blend, increase in crystallinity of PP phase, selective localization of fillers in PP
phase, and interaction between HNTs and IG with polymers. There exist an interaction between nitrile
group of ABS and maleic anhydride group of SEBS-g-MAH [12], which restrict the deformation of
ABS droplets result in an enhanced stress transfer from PP phase to ABS phase. The combined effect
of these observation enhance the tensile modulus of hybrid filler reinforced PP/ABS blend. Tensile
strength of hybrid filler reinforced PP/ABS blend is lower as compare to PP/ABS blend. The decrease
is due decrease in modulus of rigidity of hybrid filler reinforced PP/ABS blend. Impact strength of
hybrid filler reinforced PP/ABS blend is higher as compare to PP/ABS blend. Due to interaction
between hybrid filler and polymer, it results in restricting delamination of fillers and prevent the
catastrophic crack propagation. Fig. 3 (c) shows the pull out of ABS from the blend matrix. This
observation depicts that droplet pull out occur due void growth at PP/ABS interface or cavitation,
which resulted in enhanced energy absorption. These are the reason responsible for the remarkable
enhancement in impact strength of hybrid filler reinforced PP/ABS blend.
Summary. Hybrid fillers reinforced PP/ABS blends in presence of compatibilizer were successfully
prepared using twin-screw extruder followed by injection moulding. TEM observation reveals HNTs
is localized near the ABS phase, while the IG is in PP phase. Solution experiments also confirm the
localization of hybrid fillers in PP phase. The localization of hybrid fillers influences the crystallinity
of PP phase. Percent crystallinity of PP phase is higher by an addition of hybrid fillers in PP/ABS
blend. Thermal stability of PP/ABS blend increases due to addition of hybrid fillers. Due to increase
on crystallinity of PP phase, selective localization of hybrid fillers and an interaction between hybrid
filler and PP phase results in an enhancement in tensile modulus and impact strength of hybrid filler
89
reinforced PP/ABS blend. The mechanism of increase in impact strength is due to void growth or
cavitation.
References
[1] Kubade P, Tambe P. Influence of halloysite nanotubes (HNTs) on morphology, crystallization,
mechanical and thermal behaviour of PP/ABS blend and their composites in presence and absence of
dual compatibilizer. Compos Interfaces 2016; 5: 433451. DOI 10.1080/09276440.2016.1144392
[2] Kubade P, Tambe P. Influence of surface modification of halloysite nanotubes and its localization
in PP phase on mechanical and thermal properties of PP/ABS blends. Compo Interfaces 2017; 24(5):
469487. DOI 10.1080/09276440.2016.1235442
[3] Tambe PB, Bhattacharyya AR, Kamath S. Structure property relationship studies in amine
functionalized multiwall carbon nanotubes filled polypropylene composite fiber. Polym Eng Sci
2012; 52: 11831194. DOI 10.1002/pen.22186
[4] P. B. Tambe, A. R. Bhattacharyya, and A. R. Kulkarni, Journal of Applied Polymer Science 127,
2013, 1017.
[5] A.C. Patel, R.B. Brahmbhatt, B.D. Sarawade and S. Devi, Morphological and mechanical
properties of PP/ABS blends compatibilized with PP-g-acrylic acid, Journal of Applied Polymer
Science Vol. 81, 2001, 1731-1741.
[6] A.C. Patel, R.B. Brahmbhatt, and S. Devi,. Journal of Applied Polymer Science 88, 2003,72.
[7] P. Eskandari, M. M. Mazidi, and K. R. Aghjeh, The Polymer Society of Korea and Springer 24,
2016, 14.
[8] S. Hom, A. R. Bhattacharyya, R. A. Khare, A.R. Kulkarni, M. Saroop, and A. Biswas, Journal of
Applied Polymer Science 112, 2009, 998.
[9] Khare, R.A., A.R. Bhattacharyya and A.R. Kulkarni, Polymer Engineering and Science 120, 2011,
2663.
[10] N. Thayumanavan, P. B. Tambe, G. M. Joshi and M. Shukla, Effect of sodium alginate
modification of graphene (by anion- type of interaction) on the mechanical and thermal properties
of polyvinyl alcohol (PVA) nanocomposites. Compos Interface. 2014; 21:487-506
[11] N. Thayumanavan, P. B. Tambe and G. M. Joshi, Effect of surfactant and sodium alginate
modification of graphene on the mechanical and thermal properties of polyvinyl alcohol (PVA)
nanocomposites. Cellulose Chem Tech. 2015; 49: 69-80
[12] S. Bonda, S. Mohanty and S. K. Nayak, S. Bonda, S. Mohanty and S. K. Nayak, Iran Polym. J.
23, 2014, 415, Iran Polym. J. Vol. 23, 2014, 415, DOI 10.1007/s13726-014-0236-9

90
Effect of Multiple Laser Shock Peening on the Mechanical Properties of ETP

Copper
17
Ayush Bhattacharya1, Siddharth Madan1, Chirag Dashora1, S. Prabhakaran2, V.K. Manupati1,a,

S. Kalainathan2, K.P.K. Chakravarthi3
1 School of Mechanical Engineering, VIT University, Vellore, Tamil Nadu, India

2 Centre for Crystal Growth, VIT University, Vellore, Tamil Nadu, India
3 Indian Institute of Technology Kharagpur, Kharagpur, West Bengal, India
a manupativijay@gmail.com
Keywords: laser shock peening, ETP copper, mechanical properties, ultimate tensile strength, elongation.
ABSTRACT. The study conducted proposes the effect of multiple laser shock peening (LSP) on ETP copper alloy plates,
with a low energy laser to investigate the changes in the mechanical properties of the material. In this paper, a study of
the microstructure, micro hardness and surface morphology has been conducted on the parent sample, and the laser peened
sample. The aim of this current research work is to investigate the changes in the mechanical properties of ETP Copper
after LSP and to study the changes in the microstructure, micro hardness, tensile strength, elongation and surface
morphology of the laser peened sample, and comparing it with the parent sample.
Introduction. Electrolytic Tough Pitch (ETP) copper has long been the standard type of commercial
wrought copper used in the production of sheet, plate, bar, strip, and wire. It is widely used in the
automotive and aerospace sectors, due to its engineering material, owing to its excellent corrosion
resistance, good ductility as well as high thermal and electrical conductivity. The motivation of this
research work drawn from the fact that this material has its potential to be used for the fabrication of
heat sinks in International Thermonuclear Experimental Reactor (ITER) applications. Although ETP
copper is not 100% oxygen free, it is considered OFC (oxygen free copper) because it has a minimum
conductivity rating of 100% IACS (International Annealed Copper Standard) while the minimum
rating to consider OFC is 99.9% pure.
Laser shock Peening (LSP) is a surface enhancement process used to enhance the properties of a
material surface. The basic mechanism involved in this process is to create compressive residual
stresses to a certain depth in the material which helps delay the premature failures. These deep, high
magnitude compressive residual stresses modify the surface hardness and microstructure, therefore,
improving different properties of the material such as strength and wear, corrosion and fatigue
resistances. The principle involved in laser peening involves a laser pulse with a duration of several
nano-seconds is focused on a material surface. The material surface evaporates instantly by ablative
interaction. The evaporating material is limited by water, and the resulting high-density metallic vapor
is ionized to form a plasma by inverse bremsstrahlung. The absorbed laser energy, in the plasma,
generates a heat-sustained shock wave and impinges on the material with an intensity of several giga-
pascals, far higher than the yield strength of most materials. The shock wave propagates through the
material losing energy thus creating a permanent strain. Once after propagation of the shock wave,
17

91
the strained region is elastically constrained to form compressive residual stresses on the surface.
However, conventionally, LSP works with protective coatings applied to the metal surface, such as
black paint or Al foils or vinyl tape. These coatings protect the surface from the thermal effects
causing surface damage. The laser peening without protective coating (LPwC) has been proposed [3]
for the advantages:
(a) It is applicable for direct treatment of nuclear plant components during maintenance with low laser
pulse energies (< 1 Joule) that can be sent through optical bers;
(b) Surface chemistry of the treated material is not altered.
The study [2] effects of single shot Laser Shock Peening on ETP Copper in both room temperature
(RT-LSP) as well as cryogenic conditions (CLSP). They concluded that nanotwins were observed in
copper after CLSP and not RT-LSP. In addition to this, they found that more energy was stored in the
material as defects (dislocations), unique microstructure changes and higher material strength when
LSP was done in cryogenic conditions.
In [5] stated that LSP improved the micro-hardness, surface roughness whereas [4] and [6] had stated
that the compressive forces produced by the LSP process resulted in a decrease of the Fatigue Crack
Growth Rate as well as Fatigue Crack Initiation Life, thereby highly increasing the fatigue life of Ti
alloys.
The aim of this current research work is to investigate the changes in the mechanical properties of
ETP Copper after LSP, and to study the changes in the microstructure, micro hardness, tensile
strength and surface morphology of the laser peened sample, and comparing it with the parent sample.
Experiments and Characteristics
Specimen Preparation. Specimens of dimensions 15 X 15 X 5 mm3 (length X breadth X thickness)
were prepared by electric discharge machine (EDM) wire cutting. Mechanical Polishing was carried
out with SiC abrasive sheets with grit sizes of 800, 1000, 1200, 1500, 2000. The specimen was then
mirror polished in a disc polisher, with alumina powder and then rinsed in acetone. The polished
sample was then etched for 15 secs, with an etching solution with the following concentrations: FeCl3
(2.5 gm) + HCl (25 mL) (38% cons) + water (50 mL). An optical microscope (ZEISS, Germany) was
used to study the microstructures, before and after the LPwC Operation. Micro-hardness as a function
of depth was measured using a Vickers Hardness Tester (Mitutoyo, Japan) with an indent load of
50gf and an indent time of 15 secs. Surface roughness was measured with a stylus profilometer
(Marsurf, Germany) operated with roughness filter cut-off of 0.8 mm over a range of 5.00 mm. The
tensile test was carried out using the universal material testing servo-hydraulic machine (INSTRON
8801).
LPwC Process
Fig. 1. Schematic representation of LPwC processing setup.

92
Table 1. Experimental parameters for conducting laser peening process.

Parameter Magnitude
Laser Wavelength 1064 nm
Pulse Repetition Rate 10 Hz
Pulse Duration 10 ns
Laser Energy 300 mJ
Number of Shots 5
Spot Diameter 0.8 mm
Pulse Power Density 6 GW/cm^2
Shock Wave Pressure 8.41 GPa
Pulse Density 1600 Pulses/cm^2
A Nd:YAG laser (Litron, UK) with operating fundamental wavelength of 1064 nm was used for the
LPwC process. The experiment was carried out in ambient conditions (25 degrees C), one can find
the detailed process as shown in Fig. 1.
The energy utilized was 300 mJ with a pulse duration of 10 ns. Multiple shocks were given with a
repetition rate of 10 Hz. In general LPwC process, the target metal surface is mirror polished, and a
confinement medium like water or a transparent glass is used. No protecting coating was pre-owned
for the material being used. Hence direct laser-matter interaction was made to take place on the
decarburized surface that could behave as an ablation medium as well as an opaque medium (colour
of decarburized surface was black). The decarburized layer was partially removed by grinding it until
getting a thin film (100 150 micro m) [7], [8]. This was done to avoid effects of impedance mismatch
for the full ablation and to form a full plasma for LPwC operation. A smooth and uniform surface
was prepared for the multiple shock LPwC operation. Water was used as the confinement layer, with
a thickness of 1-2 mm. For maintaining uniformity in the application of water, a water jet setup was
used. The LSP parameters, which have been shown in Table 1, tuned to get a match of shock
impedance between the water and the decarburized copper surface to attain peak pressure. A 2D XY
translation motorized stage (SVP Lasers, India) was employed to perform LPwC experiments in
transverse and longitudinal directions. The overlapping rate (75%) was fixed at 90% in the
longitudinal direction and at 40% in the transverse direction.
For tensile testing, transverse specimens were prepared according to ASTM: E8/E8M Standard test
methods and tested for a nominal strain rate of 0.5 mm/min under ambient conditions. Double sided
LSP was performed for this study, and these are shown in Fig. 2 (b), (c), and (d).
Results and Discussion
Fig. 3 shows the microstructures of the sample that is without laser shock processing and with laser
shock peening (Fig. 3 (a-b) as observed by optical microscopy images. The grains were almost
equated having micron-sized precipitates distributed throughout the matrix apart from the presence
of annealing twins in Fig. 3 (a), and almost circular inclusions in Fig. 3 (b). A very few large grains
are present in both the samples, with no signs of abnormal grain growth observed.

93
a) ` b)
c)
d)
Fig. 2. Laser peened specimen (a), (b) tensile test specimen dimensions, (c) unpeened tensile test
specimen, (d) LPWC tensile test specimen.
a) b)
Fig. 3. (a) Without laser peened microstructure at 20X, (b) laser shock peened microstructure at 20X.
The micro-hardness as a function of depth was measured performing the Vickers Hardness Test. The
average hardness of the untreated specimen was 76.5 HV. Average Hardness of LPwC specimen was
found to be increased at 104 HV. The results indicated an approximately 36% increase in hardness
after LPwC process. The hardness at 50 micro meters was observed to be highest at 141.2 HV and
then gradually started decreasing with increasing depth Fig. 4 (a), (b) till it showed similar hardness
values as the untreated sample at 700 micro meter depth. This effect can be explained due to the
reduction in intensity of the shock wave, during its propagation into the material and the strain
hardening effect of the LPwC process.

94
The tensile results showed an increase of 3% in UTS values accompanied with decrease of 6% in
elongation values. This can be attributed due to higher material strength and increased brittleness
character in the material due to the coherent precipitates, which are dispersed at the sub-grain
boundaries and inside the grains.
Table 2. Tensile test results.

Tensile Sample UTS (GPa) Elongation (mm)
Unpeened 0.236 41.340
LPwC 0.243 38.825
Fig. 4. (a) Variation of hardness as a function of depth, (b) tensile stress-strain curves for unpeened
and LSP samples.
Summary. In this study, the effect of LPwC was studied on ETP copper specimens, with a laser
wavelength o 1064nm, laser energy of 300mJ and a power density of 6 GW cm. Some of the
observations after the analysis were, microstructure was observed both before and after LPwC on
ETP Copper specimens. Annealing twins were found to occur in the LPwC microstructure, due to
lowering of stacking fault energy (SFE). Higher values of hardness, surface roughness and UTS were
recorded with decrease in ductility of the material, after LPwC Operation. The increase in hardness
and UTS is caused by coherent precipitates or the second phase particles, which are dispersed at the
sub-grain boundaries and inside the grains. The precipitates obstruct the movement of dislocations
giving rise to higher UTS and strength in the material.
References
[1] Ye.C. Suslov, S. Lin, D. Liao, Y. Fei, X., Cheng G. J. Microstructure and mechanical properties
of copper subjected to cryogenic laser shock peening. Journal of Applied Physics, 110(8), 2011,
083504, DOI 10.1063/1.3651508
[2] Cakir O., Temel H., Kiyak M. Chemical etching of Cu-ETP copper. Journal of Materials
Processing Technology, 162, 2005, 275-279.
[3] N. Mukai, N. Aoki, M. Obata, A. Ito, Y. Sano and C. Konagai: Proc. 3rd JSME/ASME Int. Conf.
on Nuclear Engineering (ICONE-3), Kyoto, 1995 p.III-1489.
[4] Sokol D.W., Clauer A.H., Dulaney J.L., Lahrman D. W. Applications of laser peening to titanium
alloys. In Photonic Applications Systems Technologies Conference (p. PTuB4). Optical Society of
America. 2005.
[5] Qiao H., Zhao J., Gao Y. Experimental investigation of laser peening on TiAl alloy microstructure
and properties. Chinese Journal of Aeronautics, 28(2), 2015, 609-616.
95
[6] Zhou J.Z., Huang S., Zuo L.D., Meng X.K., Sheng J., Tian Q., Zhu W. L. Effects of laser peening
on residual stresses and fatigue crack growth properties of Ti6Al4V titanium alloy. Optics and
Lasers in Engineering, 52, 2014, 189-194.
[7] S. Prabhakaran, S. Kalainathan. Compound technology of manufacturing and multiple laser
peening on microstructure and fatigue life of dual-phase spring steel. Materials Science &
Engineering A, 2016, 634645
[8] S. Prabhakaran, S. Kalainathan. Warm laser shock peening without coating induced phase
transformations and pinning effect on fatigue life of low-alloy steel. Materials and Design 107, 2016,
98107.

96
Determination of Uric Acid with the Aid of N, N'-Bis (Salicylaldimine)-Benzene-

1, 2-Diamine Cobalt (II) Schiff Base Complex Modified GCE
18
G.B. Hemalatha1, S. Praveen Kumar1, S. Munusamy1, S. Muthamizh1, A. Padmanaban1,

T. Dhanasekaran1, G. Gnanamoorthy1, V. Narayanan1,a
1 Department of Inorganic Chemistry, University of Madras, Guindy Campus, Chennai, India

a vnnara@yahoo.co.in
Keywords: cobalt (II) Schiff base complex, microwave irradiation, uric acid, electrochemical polymerization, differential
pulse voltammetry.
ABSTRACT. Uric acid (UA) is the principal end product of purine metabolism and it is biologically important oxypurine
present in body fluids such as blood or urine. The abnormal level of uric acid is associated with several disorders such as
gout, LeschNyhan syndrome and Hyperuricemia. The elevation of uric acid concentrations may indicate other medical
conditions such as kidney injury, leukemia and pneumonia. The determination of UA is an essential topic in clinical
research because it is related with several diseases. A selective and sensitive accurate method should be developed for the
uric acid determination with reliable concentration. Uric acid has good electrochemical activity, which under goes
irreversibly oxidized in an aqueous solution and forms allantoin as the major product. Among the various methods which
are available for the determination uric acid, electrochemical method gives fast response, high selectivity and sensitivity
with low detection limits. It is one of the cost effective methods for uric acid determination in human fluids. In the present
work we utilized cobalt(II) Schiff base complex as an effective electrocatalytic sensor for uric acid determination. The
cobalt(II) Schiff base complex was deposited on the glassy carbon electrode by electrochemical polymerization process.
The modified GCE shows better electrocatalytic sensing activity for uric acid determination. The cobalt(II) Schiff base
complex modified GCE exhibits an irreversible anodic peak at 0.48 V with peak current 7.03 A and the bare GCE shows
the uric acid oxidation potential at 0.556 V with peak current 6.59 A. The result reveals that cobalt(II) Schiff base
complex modified GCE has better electrocatalytic activity than bare GCE. So that the cobalt(II) Schiff base complex can
be used as efficient electrocatalytic sensor for uric acid determination in real samples.
Introduction. The Schiff base ligands are having wide range of applications in several biological,
chemical and pharmacological activities. These Schiff base ligands have simple synthetic process and
better stability in complex formation they have more interest in research field. The Schiff base metal
complexes were widely used in analytical chemistry, biochemistry, medicinal chemistry and
electrochemistry. The Schiff base complex activities were mostly depends on the nature of the ligands
[1]. The Schiff base structural arrangements and their coordination sites may attribute variety of
functions in the metal complexes. The structure and function relationships play major role in Schiff
base and their metal complex synthesis and its studies in research field. The synthesis of Schiff base
ligands and their metal complexes in various kinds of structural arrangements was getting great
interest. It has variety of applications in different fields like electrochemical sensors, ionic
ferroelectrics, highly efcient catalysts in different synthetic chemical reactions, and biologically
active compounds. The salen type tetradentate Schiff base ligands have more attention among the
various types of Schiff ligands. It forms stable complexes through the coordination of transition metal
imine nitrogen and phenolic oxygen. The salen type Schiff base ligands provides planar coordination
sites for better stability of metal complexes. Cobalt metal is an important trace element in human and
living things, which is present in many enzymes and vitamin B12 complex. The cobalt metal complex
plays a major role in biological function, chemical processes and it also been used in various
18

97
analytical measurements. The cobalt metal has two stable oxidation states +2 and +3, due to variable
oxidation states these cobalt complexes have better catalytic and electrochemical activity [2]. In the
present work cobalt(II) Schiff base complex was synthesized by microwave irradiation method [3].
In this method reaction completed in a very short period and it gives more yields when compared
with other synthetic methods. The microwave irradiation method requires minimum quantity of
solvents and less energy consumption. It is one of the green chemical synthetic routes in the synthetic
chemistry. The cobalt(II) Schiff base complex was utilized for the electrocatalytic sensing of uric acid
(UA). Uric acid is the final end product of purine metabolism, it is necessity to maintain constant
level in human body. The abnormal level of uric acid may lead to some diseases in human. The
excesses urinary elimination is leads to hyperuricemia. The high level uric acid in human blood serum
is leads to diabetes, hypertension, LeschNyhan syndrome and gout. The level of UA in human
fulides indicates various diseases in clinical process. Hence there is a necessity for the determination
of UA in human physiological fluids. There are several methods available and reported for the UA
determination such as, enzymatic, high-performance liquid chromatography (HPLC), capillary
electrophoresis (CE), colorimetric and electrochemical methods. Among the available determination
methods, the electrochemical method better than other determine methods of UA. This
electrochemical method has high sensitivity, selectivity, low detection limit, inexpensive, faster
response and simple procedure. Therefore electrochemical method has been chosen for the
determination of UA [4].
Experimental procedure. An absolute methanol solution of 2 mmol of salicylaldehyde (0.123 g)
was taken in a beaker and subjected to stirring and then 1 mmol o-phenylenediamine (0.108 g) in
methanol was added to aldehyde solution under stirring. The stirring was continued for 1 hr. and
employed for microwave irradiation at 320 W for 2-3 min. A yellow colour solution was obtained it
was collected and recrystallized by ethanol. Then 1 mmol of Schiff base ligand was taken and 1 mmol
of cobalt(II) chloride (0.238 g) was added in the Schiff base ligand. It was continuously stirred for
about 2 h and it was subjected for the microwave irradiation at 320 W, for 5 min. A brown colour
precipitate was obtained, it was collected and recrystallized by using hot ethanol. The cobalt(II) Schiff
base complex synthetic procedure was given in Scheme-1.
Instrumentation. UV-Visible spectrum was recorded in PerkinElmer lambda 35 UV-visible
spectrophotometer, FT-IR spectral data was recorded on a Perkin-Elmer FT-IR 8300 using KBr pellet
disk and electrochemical studies were obtained using CHI-1103A electrochemical analyser with
three-electrode cell. Glassy carbon electrode was used as working electrode, silver and silver chloride
electrode and saturated calomel electrode were used as reference electrode, platinum wire was used
as counter electrode. Tetrabutylammonium perchlorate (TBAP) used as supporting electrolyte in
complex studies. The phosphate buffer solution pH 7.4 (PBS) was used as back ground electrolyte
for uric acid sensing.
Fig. 1. Synthesis of Cobalt (II) Schiff base complex.

Result and Discussion

98
FT-IR analysis. The FT-IR spectrum of cobalt (II) Schiff base complex was recorded using KBr disk
in the IR range of 4000400 cm-1 and the spectrum was given in Fig. 2 (a). The IR spectrum explains
valuable characteristic information about the cobalt (II) Schiff base complex. In the IR spectrum a
peak shows at 3536 cm-1 due to the solvated water molecules in the complex [ (Co. . . .OH2)]. The
imine group [ (C=N)] exhibit its vibrational frequency, in the spectrum at 1610 cm -1. This C=N
vibrational band has been shifted towards the lower region in the spectrum, due to coordination of
cobalt metal ion with the imine nitrogen. The lone pair electrons presented in imine nitrogen was
involved in the bond formation, so that bond order was decreased. The [ (C=N)] normally observed
in free Schiff base ligand at above 1650 cm-1. It has blue shift in the IR spectrum, when compare with
free Schiff base ligand C=N stretching frequency. The complex formation between Schiff base ligand
and cobalt (II) metal ion was further confirmed by two major peaks in the region of 400-600 cm-1,
the metal nitrogen and metal oxygen bonds. The metal nitrogen [ (Co-N)] bond exhibits at 570 cm- 1
and the metal oxygen bond [ (Co-O)] was appeared at 480 cm-1. The FT-IR spectrum clearly
indicates that the complex formation between cobalt (II) metal ion and Schiff base ligand. The other
characteristic peaks also observed in the spectrum [5].
UV-Visible analysis. The UV-Visible spectrum of the cobalt (II) Schiff base complex was recorded
in methanol solution, in the range of 200-800 nm at room temperature and the spectrum was shown
in Fig. 2 (b). The electronic spectrum of cobalt(II) Schiff base complex shows three absorption bands,
a peak at 248 nm is due to * transition in the phenyl ring. The second absorption band appeared
at 305 nm was assigned to n * transition. This n * transition appeared due to the C=C in the
aromatic ring in ligand field. The d d transitions of cobalt (II) metal ion shows two absorption
peaks at visible region. The d-d transition exhibits its absorption peaks at 400 nm and 605 nm. The
electronic transitions in the cobalt (II) Schiff base complex was explains the geometry and magnetic
momentum of the complex. The UV-Visible spectrum of cobalt (II) Schiff base complex confirm the
octahedral geometry and the magnetic moment value is 3.78 BM.
Electrochemical studies
The electrochemical redox behaviour of the cobalt (II) Schiff base complex was examined in 0.1 M
acetonitrile solution with the aid of cyclic voltammetry (CV) technique. The cyclic voltammetry
technique has three electrodes, such as glassy carbon electrode (GCE), silver- silver chloride
(Ag/AgCl) and platinum wire were used as working, reference and counter electrodes respectively.
In the electrochemical studies of cobalt (II) Schiff base complex tetrabutylammonium perchlorate
(TBAP) as supporting electrolyte. The cyclic voltammogram of cobalt (II) Schiff base complex was
shown in Fig. 2 (c). In the CV cobalt (II) Schiff base complex exhibits an oxidation peaks due to
electronic transition from Co (II) state to Co (III) state. The anodic peak observed at 1.294 V
corresponds to the oxidation of Co (II)/Co (III). The number of electron transfer in the electrochemical
redox process of cobalt (II) Schiff base complex was calculated using equation:
ip = nFQ/4RT
It shows that cobalt (II) Schiff base complex has good electrochemical activity, it is an one electron
transfer electrochemical redox behaviour.
Electrochemical polymerization. The cobalt (II) Schiff base complex was electrochemically
polymerized for the modification of glassy carbon electrode (GCE). The modified GCE was utilized
for UA electrocatalytic sensing. The electrochemical polymerization was carried out in 0.1 M
acetonitrile solution of cobalt (II) Schiff base complex, in the potential range of 0 to 1.6 V working
potential. The electrochemical polymerization of cobalt (II) Schiff base complex also shows the same
kind of electrochemical redox process. The electrochemical polymerization was carried at 50 mVS -1
scan rate for 20 cycles. The polymerized cobalt (II) Schiff base complex was deposited on the surface
of GCE, the cyclic voltammogram of electrochemical polymerization was shown in the Fig. 2 (d).
99
The poly cobalt (II) Schiff base complex modified GCE [ploy-Co-SBC/GCE] was utilized for the
determination of UA.
Fig. 2. (a) FT-IR spectrum, (b) UV-Visible spectrum, (c) Cyclic voltammogram in 0.1 M TBAP at
the scan rate of 50 mVs-1 of cobalt(II) complex and (d) Cyclic voltammogram of cobalt(II) Schiff
base complex polymerization in 0.1 M TBAP.
Electrocatalytic Sensing of Uric Acid. The electrocatalytic sensing of UA at both bare GCE and
poly-Co-SBC/CE were investigated with the aid of cyclic voltammetry (CV) in phosphate buffer
(pH = 7.4). The Cyclic voltammograms of UA sensing at bare and poly-Co-SBC/GCE modified
electrodes were shown in Fig. 3 (a). In cyclic voltammogram the UA exhibits only an oxidation peak
for both the electrodes. The bare GCE shows the UA anodic peak at 0.552 V (vs SCE), with the
anodic peak current of 6.59 A. The cobalt (II) Schiff base complex modified GCE shows the UA
anodic peak at 0.483 V with the peak current of 7.15 A. The modified GCE shows the anodic peak
of UA at low potential and higher peak current than the bare GCE. The increasing electrocatalytic
sensing activity of modified GCE is due to the polymerized cobalt (II) Schiff base complex on the
working electrode surface. The UA oxidation was facile by the cobalt (II) redox activity. The
modified GCE exhibits 69 mV negative shift with higher anodic peak current. The UA oxidation was
exhibits as a broad peak at bare GCE, it explains that a slow electron transfer, but the modified GCE
shows a sharp peak it indicates faster electron transfer reaction. The electrocatalytic oxidation of UA
at modified GCE has well defined sharp peak, enhanced peak current and more negative shift, it
clearly shows that modified GCE has better electrochemical active than bare GCE. The scan rate
effect was also studied for the UA sensing [6], [7]. The different scan rate shows the UA sensing
process is adsorption process. The scan rate effect was shown in Fig. 3 (b).

100
Fig. 3. (a) Cyclic voltammogram of electrocatalytic sensing of UA in PBS at the scan rate of 50
mVs-1, (b) scan rate effect of UA sensing at poly-Co-SBC/GCE in PBS.
Summary. The microwave irradiation method was successfully used for the synthesis of cobalt (II)
Schiff base complex. The synthesized cobalt (II) Schiff base complex was characterized by FT-IR
and UV-Vis. spectral techniques. These spectral techniques confirm the cobalt (II) Schiff base
complex. The electrochemical redox activity of cobalt (II) Schiff base complex was examined in
acetonitrile solution with the aid of cyclic voltammetry. The CV gives additional information about
the cobalt (II) metal ion, it confirms the cobalt at +2 oxidation state. The cobalt (II) Schiff base
complex was electrochemically polymerized on GCE surface and fabricated for electrocatalytic
sensing of UA. The cobalt(II) Schiff base complex was successfully utilized for the electrochemical
determination of UA. The poly-Co-SBC/GCE shows better electrocatalytic activity for determination
of UA. Hence, it can be utilized for the UA determination in real sample analysis.
References
[1] S.P. Kumar, R. Suresh, K. Giribabu, R. Manigandan, S. Munusamy, S. Muthamizh, V. Narayanan,
Spectrochim. Acta A, 139, 2015, 431441, DOI: 10.1016/j.saa.2014.12.012
[2] B.S. Rana, S.L. Jain, B. Singh, A. Bhaumik, B. Sain, A.K. Sinha, Dalton Trans., 39, 2010, 7760
7767, DOI: 10.1039/c0dt00208a.
[3] N. Fahmi, S. Shrivastava, R. Meena, S.C. Joshi, R.V. Singh, New J. Chem., 37, 2013, 14451453,
DOI: 10.1039/C3NJ40907D.
[4] R.N. Goyal, V.K. Gupta, A. Sangal, N. Bachheti, Electroanalysis, 17, 2005, 2217-2223, DOI:
10.1002/elan.200503353.
[5] P.K. Khatri, S.L. Jain, L.N. Sivakumar, B. Sain, Org. Biomol. Chem., 9, 2011, 3370- 3374. DOI:
10.1039/c0ob01163k.
[6] S.M. Ghoreishi, M. Behpoura, F. Saeidinejada, Anal. Methods, 4, 2012, 2447-2453, DOI:
10.1039/C2AY00017B.
[7] N. Lavanya, E. Fazio, F. Neri, A. Bonavita, S.G. Leonardi, G. Neri, C. Sekar, Sensor. Actuator.
B, 22, 2015, 14121422, DOI: 10.1016/j.snb.2015.08.020.

101
Electron Distribution in BaTi0.98Zr0.02O3 Piezoceramic Using X-ray Structure

Factors
19
J. Mangaiyarkkarasi1, S.Sasikumar2, R. Saravanan2
1 PG and Research Department of Physics, NMSSVN College, Nagamalai, Madurai, India

2 Research centre and PG Department of Physics, The Madura College, Madurai, India
Keywords: barium titanate, X-ray diffraction, structure factor, maximum entropy method, charge density.
ABSTRACT. Single phased BaTi0.98Zr0.02O3 piezo ceramic has been synthesized by conventional high temperature solid
state reaction technique at 1450 oC for 10 hrs. and characterized. Precise electronic structure and charge density
distributions of BaTi0.98Zr0.02O3 have been completely analyzed through powder X-ray diffraction data (PXRD). Powder
profile refinement clearly evidenced that, the prepared ceramic has been crystallized in cubic perovskite structure with
space group symmetry Pm 3 m. Average grain size is calculated by Scherer formulation. The bonding nature and electron
distribution around Ba and O and Ti and O are examined by adapting maximum entropy method (MEM). The predominant
ionic nature of Ba-O bond and the partial covalent nature of Ti-O bond are revealed by MEM qualitatively as well as
quantitatively. The optical band gap energy has been estimated as 3.11 eV from UV-vis absorption spectroscopy. Surface
morphology and microstructure are also analyzed by scanning electron microscopy (SEM). Particles with irregular shapes
are observed from SEM image. Atomic percentages of chemical compositions of the synthesized ceramic are further
confirmed by energy dispersive X-ray spectroscopy (EDS).
Introduction. Recently, the interest towards lead-free piezoelectric ceramic materials has been
increasing for electromechanical transducer devices [1]. Among them, barium zirconium titanate
(BZT) ceramic has attracted great attention for its potential applications in the fabrication of
microwave devices and piezoelectric transducers due to its high dielectric constant, low dielectric
loss and large tunability [2]. BZT has been particularly used for multilayer ceramic capacitors
(MLCCs). The addition of Zr at the lattice sites of Ti is known to be effectively changes the Curie
temperature (TC) and also presents many interesting features in the dielectric and ferroelectric
properties of BaTiO3 [3]. Moreover, Zr4+ ion is comparatively more stable than Ti4+ ion, hence the Ti
doping at the lattice sites of Zr would depress the conduction, thereby reducing the leakage current in
the BaTiO3 structure [4]. BZT ceramic materials exhibit promising infrared and optical properties
which are highly essential for designing pyroelectric and electro-optical devices [5]. Microwave
dielectric properties of these Zr doped BaTiO3 materials also find applications in storage capacitors
for the next DRAM generation, FeRAMs and non-volatile random access memories [6]. Even though
many researchers have reported the structural and dielectric related investigations, the precise
electronic structure, chemical bonding and charge density distribution studies are lacking in literature.
The detailed knowledge of the internal electronic structure of a material is extremely beneficial to
understand the properties more clearly [7]. In this aspect, the present study focuses more on the
bonding interactions between the constituent atoms of the BZT ceramic system. The accurate
electronic structure of any crystalline material can be successfully elucidated by constructing the
electron density from the X-ray structure factors using less biased mathematical tool such as
maximum entropy method (MEM) [8].
19

102
Experimental. BaTi0.98Zr0.02O3 ceramic has been synthesized by conventional high temperature solid
state reaction technique. The stoichiometric mixtures of high purity starting materials BaCO3 (Alfa
aesar, 99.997%), ZrO2 (Alfa aesar, 99.99%) and TiO2 (Alfa aesar, 99.99%) were thoroughly mixed
using agate mortar and pestle. The mixed powder compound was calcined at 1200 oC for 2 hrs. in
alumina crucibles using tubular furnace. Then the calcined powder was ground well using ball mill
at 200 rpm for 5 h and compressed into dense pellets. These pellets were sintered to a high temperature
of 1450oC with a dwell time of 10 h at a heating rate of 5o C/min in air and then they were slowly
cooled at a normal cooling rate. The resultant sintered sample was finally ground well as smooth
powder for characterization studies.
The synthesized sample has been structurally characterized by powder X-ray diffraction (PXRD) data
sets collected at Sophisticated Analytical Instrument Facility (SAIF), Cochin University, Cochin,
India using X-ray diffractometer (Bruker AXS D8 advance) with monochromatic CuK radiation
(=1.54056 ), in the 2 range of 10-120 with the step size of 0.02. Optical band gap has been
evaluated from the UV-vis data obtained in the range of 200 nm-2000 nm using UV-vis spectrometer
(Cary 5000, Varian, Germany). SEM image was recorded using scanning electron microscope (Carl
Zeiss Evo 18) to analyze the surface morphology and microstructure. EDS results were also obtained
using Energy dispersive X-ray spectrometer (Quantax 200 with X-flash-Bruker) to confirm the
elemental compositions at International Research Centre, Kalasalingam University, Krishnankoil.
Result and discussions.
Powder X-ray diffraction analysis and structure refinement. The raw powder XRD pattern for
the synthesized ceramic BaTi0.98Zr0.02O3 is shown in the figure 1. The sharp, well defined Bragg peaks
indicated that the synthesized ceramic possess long range of crystalline nature. The prepared ceramic
presents the cubic perovskite structure with the space group of Pm 3 m (space group number: 221) in
agreement with the corresponding Joint Committee on Powder Diffraction Standards (JCPDS) data
base (PDF# 31-0174).
Fig. 1. Raw XRD profile of BaTi0.98Zr0.02O3.

103
Fig. 2. Fitted XRD profile of BaTi0.98Zr0.02O3.
The structural studies has been carried out using the Rietveld refinement technique [9] using the
software JANA 2006 [10]. The position coordinates (x, y, z) were taken as (0, 0, 0) for barium, (0.5,
0.5, 0.5) for titanium and (0.5, 0.5, 0) for oxygen from standard Wyckoff position table [11].
Structural parameters along with the profile parameters, asymmetry, background and some other
correction parameters related to the XRD pattern were also refined to minimize the error between
experimentally observed and theoretically built profiles. Figure 2 represents fitted profile of
BaTi0.98Zr0.02O3 using Rietveld [9] method. Refined profile confirms the better fitting between the
experimental and calculated profiles.
Table 1. Refined parameters from Rietveld refinement of BaTi0.98Zr0.02O3.

Parameters Values
a=b=c () 4.0102(10)
== () 90
Volume (3) 64.49(1)
Density (gm/cc) 6.02(1)
Profile reliability factor, RP (%) 6.94
Observed profile reliability factor, Robs (%) 3.19
Goodness of fit, GOF 1.27
Number of electrons in the unit cell, F(000) 102
The refinement provides satisfactory agreement factors and the structural parameters which are listed
in table 1. The lattice parameter value is 4.0102 and cell volume is 64.49 . The average grain size
of the prepared ceramic was calculated through Scherer formula [12]:
t = 0.9 / cos,
where t is grain size;

is wavelength of X-ray;
is the full width at half maximum (FWHM);
is the Bragg angle.
The average grain size is calculated as 26 nm.

104
Electron density and bonding investigations using MEM method. The precise electronic structure
analysis can be done effectively by maximum entropy method (MEM) [10], which provides a more
clear understanding and visualization of bonding features. The X-ray structure factors retrieved from
Rietveld [9] method were utilized for MEM [10] refinement. Since the prepared system is crystallized
in cubic structure, the unit cell was divided into 646464 pixels. The prior charge density assigned
to each pixel is F000/a3. The software package PRIMA [13] was employed for the numerical MEM
computations and then the electron density maps are plotted using VESTA [14].
Fig. 3. (a) 3D unit cell with (100) plane shaded, (b) 2D electron density distributions of
BaTi0.98Zr0.02O3 on the (100) plane, (c) enlarged view of bonding between Ba and O atom.
To understand the nature of bonds along Ba-O and Ti-O bond paths, 2-dimensional charge density
contour maps are constructed for two different miller planes (100) & (200) with the contour range of
0 e/3 to 1 e/3, and the contour interval of 0.04 e/3. Figure 4(a) shows the 3D unit cell with shaded
(100) plane. The positions of the constituent atoms Ba, Ti and O are distinctly visualized, in which
Ba atoms are at the corners of the cube, Ti atom is at the body center, and the O atoms are at the face
centers. Figure 3 (b) and 3 (c) demonstrate the 2D contour maps upon (100) plane and enlarged
bonding portion between Ba and O atoms respectively. Figure 4 (a) shows the 3D unit cell with
shaded (200) plane. There is no sharing of valence charges are seen between Ba and O atoms, which
indicates the ionic nature of Ba-O band. Figure 4 (b) and 4 (c) demonstrate the 2D contour map upon
(200) plane and enlarged bonding portion between Ti and O atoms respectively. The charge density
contours between the Ti and O atoms are overlapping which authenticates the covalent nature of Ti-
O bond.

105
Fig. 4. (a) 3D unit cell with (200) plane shaded, (b) 2D electron density distributions of
BaTi0.98Zr0.02O3 on the (200) plane, (c) enlarged view of bonding between Ti and O atoms.
The accurate values of bond lengths and numerical values of electron densities for Ba-O and Ti-O
bonds are calculated by drawing one dimensional line profiles. Figure 5 and 6 represent the one
dimensional line profiles for Ba-O and Ti-O respectively. The bond length of Ba-O bond is 2.8357
and the bond length for Ti-O bond is 2.0051 . The electron density at bond critical point (BCP)
between Ba and O is 0.2509 e/3. The minimum electron density value confirms the ionic nature
between Ba and O ions. The electron density at bond critical point (BCP) between Ti and O is 0.6197
e/3, which confirms the covalent nature between Ti and O ions.
Fig. 5. 1D line profile for Ba-O bond.
Fig. 6. 1D line profile for Ti-O bond.

106
Band gap evaluation. Band gap energy of BaTi0.98Zr0.02O3 has been evaluated by the procedure
proposed by Tauc et al., [15] using UV-Vis data. A graph was drawn by taking energy values (h) in
X-axis and (h)2 in the Y-axis shown in figure 7. The band gap energy has been evaluated by
extrapolating the linear portion of the curve to X-axis. The band gap energy for the synthesized
sample is 3.11 eV.
Fig. 7. UV-Visible plot of BaTi0.98Zr0.02O3.
SEM/EDS studies. Surface morphology and the microstructure of the prepared sample have been
investigated by scanning electron microscopy (SEM). SEM micrograph corresponding to 25000
magnifications is shown in figure 8.
Fig. 8 SEM image of BaTi0.98Zr0.02O3.
Fig.9 EDS spectrum of BaTi0.98Zr0.02O3.

107
Particles with non-uniform and irregular shapes and sizes are clearly visualized from this figure. The
EDS spectrum is given in figure 9 confirms the presence of Ba, Ti, Zr and O atoms and no other
additional peaks are seen. The stoichiometry of the prepared sample is given in table 2.
Table 2. Elemental compositions from EDS

Element Atom(%) Weight(%)
Ba 34.49 77.32
Zr 10.07 7.87
Ti 0.27 0.40
O 55.17 14.41
Summary. BaTi0.98Zr0.02O3 ceramic material has been synthesized through high temperature solid
state reaction method and analysed. Powder profile refinement confirms that the sample has been
crystallized in cubic perovskite structure with single phase. The precise electronic structure, bonding
interactions and electron distribution around Ba and O and Ti and O have been investigated through
maximum entropy method (MEM). The predominant ionic nature of Ba-O bond and the partial
covalent nature of Ti-O bond are revealed by MEM calculations. The optical band gap energy has
been evaluated as 3.11 eV from UV-vis absorption spectroscopy. Particles with irregular shapes and
sizes are clearly visualized from SEM image. Atomic percentages of chemical compositions of the
synthesized ceramic are further confirmed by EDS spectrum.
References
[1] A. Dixit, Majumder S. B, A. Savvinov, R. S. Katiyar, R. Guo, A. S. Bhalla, Investigations on the
sol-gel-derived barium zirconium titanate thin films, J. Mater. Lett., 56, 933 (2002),
DOI: 10.4236/wjcmp.2015.54035.
[2] S. Sarangi, T. Badapanda, B. Behera, S. Anwar, Frequency and temperature dependence dielectric
behavior of barium zirconate titanate nanocrystalline powder obtained by mechanochemical synthesis
J Mater Sci: Mater Electron., 24, 4033 (2013), DOI 10.1007/s10854-013-1358-0.
[3] M. Aghayan, A.Khorsand Zak, M.Behdani, A.Manaf Hashim Solgel combustion synthesis of
Zr-doped BaTiO3 nanopowders and ceramics: Dielectric and ferroelectric studies, Ceram. Int., 40,
16141 (2014). DOI: 10.1016/j.ceramint.2014.07.045.
[4] N. Nanakorn, P. Jalupoom, N. Vaneesorn, A. Thanaboonsombut, Dielectric and ferroelectric
properties of Ba(ZrxTi1-x)O3 ceramics, Ceram. Int 34, 779 (2008),
DOI:10.1016/j.ceramint.2007.09.024
[5] A. Liu, J. Xue, X. Meng, J. Sun, Z. Huang, J. Chu, Infrared optical properties of Ba(Zr0.20Ti0.80)O3
and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method, Applied Surface Science 254, 5660
(2008) DOI:10.1016/j.apsusc.2008.03.178.
[6] L.S. Cavalcante, J. C. Sczancoski, F. S. De Vicente, M. T. Frabbro, M. Siu Li, J. A. Varela, E.
Longo, Microstructure, dielectric properties and optical band gap control on the photoluminescence
behavior of Ba[Zr0.25Ti0.75]O3 thin films, J Sol-Gel Sci Technol. 49, 35 (2009). DOI: 10.1007/s10971-
008-1841-x.
[7] R. Saravanan, Practical application of maximum entropy method in electron density and bonding
studies, Phys. Scr. 79 048303 (2009), DOI:10.1088/0031-8949/79/04/048303.
[8] D.M. Collins, Electron density images from imperfect data by iterative entropy maximization,
Nature. 49, 298 (1982). DOI:10.1038 298049a0.

108
[9] H.M. Rietveld, A profile refinement method for nuclear and magnetic structures, J. Appl.
Crystallogr. 2, 65 (1969) DOI: 10.1107/S002 1889869006558.
[10] V. Petricek, M. Dusek L. Palatinus (2006), Jana 2006. The crystallographic computing system,
Institute of Physics, Praha, Czech Republic.
[11] B. D Cullity, S. R Stock, Elements of X-ray diffraction, Pearson education. 3rd edn. Prentice
Hall, Upper Saddle River, 558 (2001).
[12] R.W.G. Wyckoff, Crystal structures. Vol.2, Inter-space publishers, London, (1963).
[13] F. Izumi, R. A Dilanien, Recent Research Developments in Physics, Part II, Vol. 3. Trivandrum:
Transworld Research Network; 2002. 699.
[14] K. Momma, F. Izumi, VESTA: A three-dimensional visualization system for electronic and
structural analysis, J Appl Crystallogr, 41, 653 (2008) DOI: 10.1107 S0021889808012016.
[15] J. Tauc, R. Grigorvici, A.Vancu, Optical properties and electronic structure of amorphous
germanium, J. Phys. Stat. Solidi(b) 15, 627 (1966). DOI: 10.1002/pssb.19660150224.

109
Synthesis, Structural and Optical Studies of Yb Doped CuGaS2 Thin Films

Prepared By Facile Chemical Spray Pyrolysis Technique 20
S. Kalainathan1,2, N. Ahsan2, T. Hoshii2, Y. Okada2, T. Logu3, K. Sethuraman3
1 Centre for Crystal Growth, School of Advanced Sciences, VIT University, Vellore, India
2 Research Center for Advanced Science and Technology (RCAST), The University of Tokyo, Japan
3 School of Physics, Madurai Kamaraj University, Madurai, Tamil Nadu, India
Keywords: thin films, intermediate band solar cells, spray pyrolysis, CuGaS2, optical properties.
ABSTRACT. Pristine and Ytterbium (Yb) doped (1-4%) chalcopyrite CuGaS2 (CGS) thin films were successfully
prepared by facile homebuilt chemical spray pyrolysis technique and annealed in vacuum, nitrogen and argon
atmospheres. X-ray diffraction characterization confirmed that all the prepared films are in tetragonal chalcopyrite
structure with polycrystalline nature. The structural characterization of the thin films confirmed the formation of CGS
without any presence of secondary phases in X-ray diffraction analysis. The optical band gaps of pristine and Yb doped
CGS thin films were obtained from UV absorption spectra. The pristine CGS film shows a band gap of 2.40 eV. It is
found that the band gap values decreases from 2.40 to 2.20 and 2.10 eV for 1 and 2 wt% Yb doping, and further widen
from 2.4 to 2.2.47 and 2.61 eV for 3 and 4wt% of Yb. Fascinatingly, 1 and 2wt% Yb doped CGS thin films gives two
band gaps 2.2- 1.1 eV and 2.1-1.0 eV, and this can be due to the formation of sub-band gap below the conduction band
after doping. The presence of Yb in the host CGS thin film was confirmed by X-ray photoelectron spectroscopy studies.
The photoelectric response of the sample has also been studied which shows significant photo current for the 1 wt% Yb
doped CGS thin films.
Introduction. The incorporation of an impurity band within the semiconductor band gap can allow
the absorption of low energy photons and thus can increase the efficiency of intermediate band (IB)
solar cells [1], [2], [3]. For a traditional photovoltaic semiconductor the electrons are excited directly
from the valence band (VB) to the conduction band (CB) by absorbing photons, whereas in the case
of IB semiconductors three photon transitions from VB to IB, IB to CB and VB to CB occurs due to
the insertion of partially filled IB into the forbidden band gap which results in the enhancement of
photocurrent without affecting the photo voltage. The percentage of upper limit efficiency was
calculated to be 65.1% which was greater than the conventional Schokley-Queisser single junction
solar cell whose efficiency was about 40.7%, and by increasing more the number of IBs will result in
the increase of efficiency upto 80% [1], [2], [3]. Various IB materials such as thin films of highly
mismatched alloys III-V dilute nitrides [4, 5], deep impurity doped hosts [6], and nanostructures using
quantum dots [7], quantum rings [8], quantum wells [9], etc. makes the IB material to be easily
fabricated and also its high density enhances absorption [6].
Ternary chalcopyrite semiconductor copper gallium sulphide (CuGaS2/CGS) attracts research
interests for the optoelectronic and photovoltaic solar cell device applications due to the direct band
gap of 2.49eV in the green region of the visible spectrum at room temperature [10]. Doping of
transition metals in CGS has been found to be a potential candidate for IB solar cells [6, 11]. Earlier
reports for doping of transition metals such as Fe [12], [13], [14], V [15], Mn [16], [17], [18], Cr [19-
21], Zn [22], [23], Ti [24] to the CGS hosts have been predicted for the creation of IB. Theoretical
insights and experimental verifications have also been reported for transition metals doped CGS [21].
20

110
The valency match and the less distortion in lattice make the transition and rare earth elements to a
suitable dopant for a chalcopyrite lattice. This motivated us to dope rare earth element Ytterbium
(Yb) in our chalcopyrite CGS and to study the influence of Yb on the structure and optical properties
of CGS. In this paper we report the preparation of Yb doped CGS by spray pyrolysis method which
seems to be better method due to its cost effectiveness and large scale production.
Experimental details
In archetypal synthesis of Pristine and Yb doped chalcopyrite CGS thin films, 0.1 M of copper acetate,
gallium chloride and of thiourea were dissolved using deionised water and excess thiourea was added
then stirred for a 30 minutes at ambient temperature to obtain a homogeneous transparent solution.
For the synthesis of Yb doped CGS thin films, the concentrations of dopant of ytterbium chloride
were varied between (1-4 wt%). The follow-on mixture solution was then used for the deposition of
CGS thin films by the chemical spray pyrolysis technique. In each deposition, the nozzle to substrate
distance maintained at 23 cm and 45 mL of precursor solution sprayed at a rate of 3 mL/min on
ultrasonically cleaned glass substrate maintained at an optimized substrate temperature of 250 C.
These CGS thin films were annealed in vacuum, nitrogen and argon atmosphere. Obtained thin films
thickness is in the range of ~ 650 nm. The final films were characterized by X-ray diffractometer
(Bruker D8 Advance model, Germany), optical absorption studies were carried out using UV-Vis
instrument (Hamamatsu, Japan).The band-gap of the samples was estimated using the Tauc plot.
Scanning electron microscope (JEOL, JCM-6000) was used to examine particle size and the surface
morphology. X-ray Photoelectron Spectroscopy analysis (XPS, Shimadzu ESCA 3400) was
performed to investigate the elemental states of prepared samples. The electrical properties of the
films were studied using the Hall measurement setup in Vander Pauw configuration (Ecopia HMS-
3000).
Results and discussions
X-ray Diffraction (XRD) studies
Fig. 1. XRD patterns of (a) as deposited CGS and (1-4% Yb doped) CGS thin films (b) annealed in
vacuum atmosphere, (c) annealed in nitrogen atmosphere, (d) annealed in argon atmosphere.
111
The XRD patterns were recorded using Powder X-ray Diffractometer (Bruker, Germany) D8
Advance model in the 2 angle range of 10-80o. The XRD patterns of the CGS thin films for prisitine
and various Yb doping concentrations annealed in vacuum, nitrogen and argon are shown in figures
1(a-d). The formation of chalcopyrite structure of CGS (JCPDS Card No.:65-1571) is confirmed by
XRD. No secondary phases were observed in all doping concentrations. This proved the presence of
single phase CGS in the prepared thin films. The average crystallite size is calculated using Scherrer
equation and dislocation density obtained using Williamson and Smallmans formula and tabulated
in Table 1.
Optical Properties
Optical absorption properties of the prepared pristine and doped CGS thin films were analyzed by
UV-Vis-NIR absorption spectroscopy in the wavelength range between 300-1500nm. The absorption
spectra for pristine and Ytterbium doped CGS thin films are shown in Fig. 2(a), there is a strong
absorption in the visible region between 400 to 500 nm for the pristine and ytterbium doped CGS thin
films. The fluctuation in the film thickness may be the origin for the oscillation in the absorption
spectra [25].
Fig. 2. (a) Absorption spectra and (b) Tauc Plot of pristine and Yb doped (1, 2, 3 & 4 wt%) CGS
thin films annealed in argon atmosphere.
Ytterbium doping has influenced the absorbance value in the visible region, and the absorbance value
increased for the increase in ytterbium concentration. The direct optical band gap of the prepared thin
films can be determined by extrapolation of the linear region to the photon energy (h) axis vs. (h)2.
The Taucs plot is shown in Fig.2 (b).The pristine CGS film shows a band gap of 2.41 eV. It is found
that the band gap values decreases from 2.40 to 2.20 and 2.10 eV for 1 and 2 wt% Yb doping, and
further widen from 2.4 to 2.47 and 2.61 eV for 3 and 4wt% of Yb. Fascinatingly (Fig. 3), 1 and 2wt%
Yb doped thin films gives two band gaps 2.2- 1.1 eV and 2.1-1.0 eV, and this can be due to the
formation of sub-band gap below the conduction band after doping [38, 39]. The change of optical
band gap values of the CGS film for increasing Yb doping levels can be explained by the Burstein
Moss effect [40].

112
Fig. 3. Schematic diagram of bandgap and IB bandgap of pristine and Yb doped (1& 2 wt%) CGS
thin films annealed in argon atmosphere.
X-ray photoelectron spectroscopy (XPS) Studies

XPS studies were carried out for prisitine and Yb (1% and 4%) doped CGS thin films in order to
evaluate the presence of elements in the thin films. The wide scan XPS spectra is shown in Fig. 4(a)
which shows the presence of Ga, S, C and Cu ions in different states within the prepared thin films.
The clear distinction of peaks with a separation of around 27eV for Ga2p1/2 and Ga2p3/2 proves that
Ga exists in trivalent state [29]. As shown in Fig.4 (b), the XPS spectra for the thin film with 4% of
Yb clarify the presence of Yb4d state, and prove the existence of Yb ions in the prepared CGS thin
films [30].
Fig. 4. (a) Wide range XPS and (b) selective region spectra of pristine, Yb (1% doped) and Yb (4%
doped) CGS thin films.
Hall measurements
The electrical property is an essential parameter for high-quality absorber material. The electrical
properties of pristine and Yb doped CGS thin films were characterized by Hall Effect measurements.
The progression of Yb doped CGS thin film resistivity, conductivity, carrier concentration and
mobility as a function of doping concentration is shown in fig.5 and in table 1.

113
Fig. 5. The dependence of resistivity, Hall mobility, carrier concentration on Yb doping level in
CGS thin films.
Table 1. The dependence of average crystallite size, average dislocation density band gap, type of
conduction, carrier concentration, Hall mobility and resistivity on Yb doping level in CGS films.
Avg.
Dislocation Carrier
Avg.
Sample density Bandgap Concentrati Mobility Resistivity
Crystallite Type
Name (eV) on 1016 (cm2/Vs) ( cm)
size (nm) 1015 (cm-3)
lines/m2
CGS 12 6.944 2.40 p 1.102 188.2 2.792
CGS: 1Yb 17 3.460 2.20, 1.10 p 5.498 309.2 0.253
CGS: 2Yb 16 3.906 2.10, 1.00 p 5.601 161.3 0.681
CGS: 3Yb 9 12.345 2.47 n 6.435 305.8 1.193
CGS: 4Yb 6 27.777 2.61 n 423.0 78.2 2.251
It is found that samples up to 2 wt% have p-type conductivity then it changed to n type. There is a
decrease in resistivity for 1 wt% of Yb doped CGS from 2.792 W cm to 0.253 W cm with respect to
pristine CGS thin film. The variation in the electrical resistivity is attributed to the change in carrier
concentration which is 5.4981016(cm-3). As expected, electron mobility drops significantly with the
increase in Yb doping concentration. This is primarily due to the rise in the ionized impurity scattering
with increasing Yb doping in the CGS thin films. Introducing Yb increases free electron density by
substituting host Ga ions with Yb ions thereby giving free electron. The carrier concentration has
risen with increasing Yb dopant concentration. This has caused higher amount of formation of
conduction electrons. The resistivity then started increasing with doping concentration to 2.251 cm
at 4wt% doping. The 1 wt% of Yb is a suitable donor dopant for the fabrication of low resistance P
type CGS thin films.
Photo-response study
The photo response property was investigated for the pristine and 1 wt % Yb doped CGS thin films.
As shown in the fig.6, it was observed that the photo response property was improved for 1 wt% of
Yb dopant CGS film compared to pristine CGS thin film.

114
Fig. 6. Photo response for (b) Pristine and (b) 1 wt% Yb doped CGS thin films.
From absorption spectra, we could observe the absorption edge and absorption area increases as we
increase the dopant concentration. Intermediated band is also predominant for 1 wt of Yb doped CGS
film. Consequently, the large absorption area and the presence of intermediate band in 1wt% Yb
doped CGS thin films have a direct correlation with the photo response. Here the visible light photons
produce excitation of the electrons from the valence band to the conduction band with the help of
intermediate band, thus the generation of majority carriers in the presence of light enhances the film
conductivity. This property may be employed for the generation of photocurrent and potential
application of Yb doped CGS thin film in solar energy conversion devices.
Summary. Pristine and Yb doped CGS thin films were prepared by facile chemical spray pyrolysis
technique. Then the films were annealed in vacuum, nitrogen and argon atmospheres. The single
phase formation of CGS was confirmed by XRD and XPS techniques. The absorption in the visible
region was found to be increasing as the concentration of Yb is increased which is likely due to the
presence of intermediate bands due to the Yb species, which absorbs the photon energy. The
absorbance due to the intermediate bands could be controlled by changing the doping concentration
of Yb. Elemental analysis and presence of Yb ions were proved by X-ray photoelectron spectroscopy.
The doping of Yb is found to decrease the film resistivity and increase the electron carrier
concentration in the films. The photoelectric response of the sample has also been studied which
shows significant photo current for the 1 wt% Yb doped CGS thin films. By considering above
reports, we suggest that 1 wt% Yb is the superior choice for use as a donor dopant to formulate CGS
based solar cells.
Acknowledgement. The authors would like to thank VIT University for their constant support and
encouragement. This work was performed under the JSPS fellowship for research program in Japan.
References
[1] Y.Okada, N.J.Ekins-Daukes, T.Kita, R.Tamaki, M.Yoshida, A.Pusch,O.Hess,C.C.Phillips,
D.J.Farrell, K.Yoshida, N.Ahsan, Y.Shoji, T.Sogabe and J.F.Guillemoles, Intermediate band solar
cells: Recent progress and future directions, Appl. Phys Rev 2,21-302 (2015).
[2] Ping Chen, Mingsheng Qin, Haijie Chen, Chongying Yang, Yaoming Wang, and Fuqiang Huang,
Cr incorporation in CuGaS2 chalcopyrite: A new intermediate-band photovoltaic material with wide-
spectrum solar absorption, Phys. Status Solidi A, 210 (2013), 1098-1102.
[3] Miaomiao Han, Xiaoli Zhang and Z. Zeng, The investigation of transition metal doped CuGaS2 for
promising intermediate band materials, RSC Adv., 4 (2014), 62380-62386.
[4] N. Ahsan, N. Miyashita, M. M. Islam, K. M. Yu, W. Walukiewicz, and Y. Okada, Two-photon
excitation in an intermediate band solar cell structure, Appl. Phys. Lett. 100 (2012), 72-111.

115
[5] N. Lpez, A. Reichertz, K. M. Yu, K. Campman, and W. Walukiewicz, Phys. Rev. Lett.,
Engineering the Electronic Band Structure for Multiband Solar Cells, 106, (2011), 028701.
[6] J. Wu, D. Shao, Zh. Li, M. O. Manasreh, V. P. Kunets, Zh. M. Wang, and G. J. Salamo,
Intermediate-band material based on GaAs quantum rings for solar cells,
Appl. Phys. Lett. 95 (2009), 071-908.
[7] Q. Shao, A. A. Balandin, A. I. Fedoseyev, and M. Turowski, Intermediate-band solar cells based
on quantum dot supracrystals, Appl. Phys. Lett. 91, (2007), 163503-163503-3.
[8] D. C. Johnson, I. M. Ballard, K. W. J. Barnham, J. P.Connolly, M. Mazzer, A. Bessie`re, C.
Calder, G. Hill, and J. S. Roberts, Observation of photon recycling in strain-balanced quantum well
solar cells Appl. Phys. Lett. 90 (2007), 213-505.
[9] Antonio Mart, David Fuertes Marrn and Antonio Luque, Evaluation of the efficiency potential
of intermediate band solar cells based on thin-film chalcopyrite materials, Journal of Applied Physics
103 (2008), 073706.
[10] Woon-Jo Jeong, Gye-Choon Park, Structural and electrical properties of CuGaS2 thin films by
electron beam evaporation, Solar Energy Materials & Solar Cells 75 (2003) 93100.
[11] Zhao Zongyan, Zhou Dacheng, and Yi Juan, Journal of Semiconductors, Analysis of the
electronic structures of 3d transition metals doped CuGaS2 based on DFT calculations, 35 (2014), 1.
[12] Teranishi T, Sato K, Kondo K, Optical Properties of a Magnetic Semiconductor: Chalcopyrite
CuFeS2: I. Absorption Spectra of CuFeS2 and Fe-Doped CuAlS2 and CuGaS2, J Phys Soc Japan, 36
(1974), 1618-1624.
[13] Von Bardeleben H J, Goltzene A, Meyer B, Effects of iron content and stoichiometry on the
coloration of CuGaS2, Phys Status Solidi A, 48 (1978), 145.
[14] Sato K, Teranishi T. Effect of delocalization of d-electrons on the optical reflectivity spectra of
CuGa1-xFexS2 and CuAl1-xFexS2 systems. Jpn J Appl Phys, 19S3 (1980) (Supplement 19-3), 101.
[15] Palacios P, Snchez K, Conesa J C, Theoretical modelling of intermediate band solar cell
materials based on metal-doped chalcopyrite compounds, Thin Solid Films, 515 (2007), 6280-6284.
[16] Zhao Y J, Zunger A, Electronic structure and ferromagnetism of Mn substituted CuAlS2,
CuGaS2, CuInS2, CuGaSe2, and CuGaTe2, Phy. Rev B, 69 (2004) 104-422.
[17] Zhao Y J, Zunger A, Site preference for Mn substitution in spintronic CuMIIIX2VIchalcopyrite
semiconductors, Phys Rev B, 69 (2004), 075208
[18] Picozzi S, Zhao Y J, Freeman A J, Mn-doped CuGaS2 chalcopyrites: An ab initio study of
ferromagnetic semiconductors, Phys Rev B, 66(2002), 205-206.
[19] Palacios P, Aguilera I, Wahnon P, et al. Thermodynamics of the Formation of Ti- and Cr-doped
CuGaS2 Intermediate-band Photovoltaic Materials, J Phys Chem C, 112 (25) (2008), 9525-9529.
[20] Palacios P, Aguilera I, Wahnn P, Ab-initio vibrational properties of transition metal
chalcopyrite alloys determined as high-efficiency intermediate-band photovoltaic materials, Thin
Solid Films, 516 (2008) 7070-7074.
[21] Aguilera I, Palacios P, Wahnn P, Optical properties of chalcopyrite-type intermediate transition
metal band materials from first principles, Thin Solid Films, 516 ( 2008), 7055-7059.
[22] Seminvski Y, Palacios P, Wahnn P, Intermediate band position modulated by Zn addition in
Ti doped CuGaS2, Thin Solid Films, 519(2011) 7517-7521.
[23] Seminvski Y, Palacios P, Conesa J C, Thermodynamics of zinc insertion in CuGaS2:Ti, used
as a modulator agent in an intermediate-band photovoltaic material, Computational and Theoretical
Chemistry, 975(2011) 134-137.

116
[24] W-J Jeong, G-C Park, Structural and electrical properties of CuGaS2 thin films by electron beam
evaporation, Sol Energ Mat Sol C 75 (2003), 93-100.
[25] Dong C, PowderX: Windows-95-based program for powder X-ray diffraction data processing,
Journal of Applied Crystallography 32 (1999) 4.
[26] Arham S. Ahmed, Shafeeq M. Muhameda , M.L. Singla, SartajTabassum , Alim H. Naqvi ,
Ameer Azam, Band gap narrowing and fluorescence properties of nickel doped SnO2 nanoparticles,
Journal of Luminescence 131 (2011) 16.
[27] K. Sankarasubramanian, P. Soundarrajan, T. Logu, S. Kiruthika, K. Sethuraman, R. Ramesh
Babu, K. Ramamurthi, Influence of Mn doping on structural, optical and electrical properties of CdO
thin films prepared by cost effective spray pyrolysis method Materials Science in Semiconductor
Processing 26 (2014) 346353.
[28] V.R. Shinde, T.P. Gujar, C.D. Lokhande, R.S. Mane, S.H. Han, Mn doped and undoped ZnO
films: A comparative structural, optical and electrical properties study, Mater. Chem. Phys. 96 (2006)
326.
[29] Zhongping Liu, Qiaoyan Hao, Rui Tang, Linlin Wang and Kaibin Tang, Facile one-pot synthesis
of polytypic CuGaS2 Nanoplates, Nanoscale Research Letters 8, (2013) 524.
[30] Youichi Ohno, XPS studies of the intermediate valence state of Yb in (YbS)1.25CrS2, Journal of
Electron Spectroscopy and Related Phenomena 165 (2008) 14.

117
Performance of SiO2 - TiO2 Thin Films as Protective Layer to Chlorophyll in

Medicinal Plants from UV Radiation: Influence of Dipping Cycles 21
M. Sankareswari1, B. Karunai Selvi1, K. Neyvasagam2
1 V.V. Vanniaperumal College for Women, Virudhunagar, Tamilnadu, India

2 PG and Research Department of Physics, The Madura College, Madurai, Tamilnadu, India
Keywords: SiO2 - TiO2 thin films, XRD, UV radiation, chlorophyll, S.trilobatum, S.nigrum.
ABSTRACT. Titanium dioxide (TiO2) is a wide band gap semiconductor and efficient light harvester. SiO2 doped TiO2
(SiO2 - TiO2) thin films of different dipping cycles were prepared on glass substrate using sol gel method and annealed
at 400C for 3 hours. Thin films were characterized by various techniques such as X - ray diffraction (XRD), UV - visible
spectroscopy and Scanning Electron Microscopy (SEM) with elemental analysis (EDAX). Ultraviolet rays constitute a
very small fraction in solar spectrum but it influences much in all living organisms and their metabolisms. Plants use
chlorophyll to trap light energy needed for photosynthesis. Increased exposure of UV light reduces the total chlorophyll
in medicinal plants. TiO2 has strong Ultra Violet (UV) light absorbing capability because of its advantages like non
toxicity, chemical stability at high temperature and permanent stability under UV exposure. In the present study, the
performance of SiO2 - TiO2 thin films as a protective layer to the chlorophyll contents present in the medicinal plants of
Solanum trilobatum (Thuthuvaalai) and Solanum nigrum (Manathakkali) under UV radiation has been investigated. The
results revealed that SiO2 - TiO2 thin films are good UV absorbers and chlorophyll content increases with the increase in
number of dipping cycles.
Introduction. Transparent conducting oxide (TCO) materials are of great interest due to their
distinctive physical, chemical, optical and opto electronic properties. Among the various TCO
materials ZnO, CdO, SnO, SnO2 and TiO2 etc., TiO2 plays a promising role in several areas of
research because of its high efficient photo catalytic activity, high refractive index, resistance to
photo corrosion, chemical stability, low cost and non toxicity [1]. Another importance of TiO2 is
its implementation in self sterilizing surfaces and its usage in hospitals because of its reliable and
stable characters under irradiation [2]. The phase structure and semiconducting properties of TiO2
thin films can be strongly modified by doping with impurities like Ag, Fe, Cu, SiO2, ZnO etc., [3].
SiO2 doped in TiO2 enlarges surface area and enhances the thermal stability and visible light photo
activity of TiO2 [4]. Plants use chlorophyll to trap light energy needed for photosynthesis. Chlorophyll
is more beneficial to human body in a numerous unique and distinct ways. It has anti-mutagenic and
anti-carcinogenic properties. A recommended intake of chlorophyll keeps the circulatory and
digestive systems healthier [5]. Increased exposure of UV light reduces total chlorophyll in medicinal
plants.
Medicinal plants like S.trilobatum and S.nigrum belongs to the family of Solanaceae that are well
known for their medicinal properties across the world. S.trilobatum is an important plant in Siddha
medicine, which has anti-bacterial, anti-fungal and anti-tumor activities. It is a rejuvenator and has
also been traditionally used to treat respiratory diseases.
S.nigrum is an important ingredient in traditional Indian medicine. Infusions are used in dysentery,
stomach complaints and fever. The juice of this plant is used to treat on ulcers and other skin diseases.
Traditionally the plant has been used to treat tuberculosis. Since SiO2 - TiO2 thin films efficiently
21

118
transform destructive UV light energy into heat, it can be used to protect chlorophyll content in
S.trilobatum and S.nigrum medicinal plants from UV radiation. In our present work, the properties of
SiO2-TiO2 thin films prepared at various dipping cycles (4, 6 and 8) by sol-gel dip coating method
have been studied elaborately. The effect of SiO2 - TiO2 thin films as a protective layer against UV
radiation in medicinal plant is also reported.
Experimental. SiO2 - TiO2 thin films of various dipping cycles were prepared by using sol-gel dip
coating technique. Titanium - tetra -iso -propoxide (TTIP) and Tetra- ethyl- ortho -silicate (TEOS)
were used as starting materials. Ethanol was used as a solvent with acetic acid as a stabilizer. 4ml of
TTIP was dissolved in 30 ml of ethanol. Then, 1 ml of acetic acid was added to stabilize the solution.
Finally, 1 mol % of TEOS was added to the solution and stirred for an hour. Obtained solution was
deposited on microscopic glass slide by dip coating machine with a speed of 50 mm for 30 seconds.
The deposited film was pre annealed at 100 C for 10 min. This procedure was repeated to obtain
films of 4, 6 and 8 dipping cycles. Finally, the obtained films were post annealed at 400C for 3
hours. The annealed films were characterized by x-ray diffraction (XRD), UV visible spectroscopy
and Scanning Electron Microscopy (SEM) with elemental analysis (EDAX) studies. The thickness of
the film was measured using stylus profilometer.
The chlorophyll content of S.trilobatum and S.nigrum leaves were determined under UV exposed
condition. 1g of finely cut healthy fresh green leaves of S.trilobatum and S.nigrum were taken in 100
ml conical flasks. The control flasks containing S.trilobatum and S.nigrum leaves were completely
unexposed to UV light i.e. they were maintained under room condition. Two flasks of S.trilobatum
and S.nigrum were completely exposed to UV light and the other flasks were covered with thin films
as prepared with 4, 6 and 8 dipping cycles. Then, they were exposed for 10 minutes with UV light of
wavelength 260 nm at a distance of 40 cm. Chlorophyll was estimated using the method described by
Arnon [6] on the UV exposed and unexposed leaves for both the plants.
1g of finely cut fresh leaves of S.trilobatum and S.nigrum was grounded to get a fine pulp with the
addition of 20 ml of 80 % acetone using mortar and pestle. This solution was then centrifuged for 5
min at 5000 rpm. The supernatant was transferred to a volumetric flask. The residue was then
grounded with 20 ml of 80 % acetone, and then centrifuged for 5 min at
5000 rpm. Finally, the supernatant was transferred to the same volumetric flask. This process was
repeated for 4 times till the residues became almost colorless. The volume was made up to 100 ml
with 80 % acetone. This procedure was repeated for all samples. The absorbance of the solution was
observed at 663 and 645 nm by (systronics) UV spectrophotometer. 80% acetone is used as a blank
for this experiment. The amount of chlorophyll which is present in the extract (i.e.mg of chlorophyll
present per gram of tissue) was calculated using the following equations.
mg chlorophyll a/g tissue = [12.7(A663) 2.69(A645)] V/(1000 W)

mg chlorophyll b/g tissue = [22.9(A645) 4.68(A663)] V/(1000 W)
mg total chlorophyll /g tissue = [20.2(A645) + 8.02(A663)] V/(1000 W)
where A is the absorbance at specific wavelength;

V is the final volume of chlorophyll extract in 80 % acetone which in this case is 100 ml;
W is the fresh weight of tissue extracted which is 1g.
Thus,
V / (1000 W) = 100 / (1000 1) = 0.1.

119
The experiments were repeated thrice. The statistical software SPSS version 17.0 was used for
analysis.
Results and Discussion. The XRD pattern of SiO2 - TiO2 thin films of different dipping cycles are
shown in Fig.1.
Fig. 1. XRD pattern of SiO2 - TiO2 thin films.
The dominant peak is observed at 25.25 for films of 4, 6 and 8 dip cycles. The films have tetragonal
(101) crystal structure and anatase phase which are in agreement with standard JCPDs data (File
No.89-4203).
The crystallite sizes of the films were determined using the well known Debye-Scherer formula
k
D (1)
Cos
The crystallite sizes are found to be 22.11 nm, 53.95 nm and 65.46 nm for different dipping cycles
such as 4, 6 and 8 respectively, which imply that the crystallinity of the films improves with increase
in dipping cycles.
EDAX spectra and SEM analysis of 6 dipping cycles of SiO2 - TiO2 thin film annealed at 400 C is
shown in Figure 2 (a) and (b). EDAX spectrum indicated the main peaks of Ti, Si and O elements.
The SEM micrograph of the SiO2 - TiO2 thin film indicated fractured structure. During drying and
annealing process of the films, crack formation takes place as a result of contraction stress and
different thermal coefficient of expansion of the over layer and substrate [7].

120
(a) (b)
Fig. 2. (a) SEM and (b) EDAX spectra of SiO2 - TiO2 thin film of 6 dipping cycles.
Figure 3 shows the UV - visible transmittance spectra of SiO2 - TiO2 thin films of different dipping
cycles. The transmittance spectra lie in the wavelength range 140 nm - 740 nm. Transmittance is
mainly dependent on thickness and surface structure of the thin films [8]. The optical transmittance
of the deposited film is low. It is observed that as the dipping cycle increases, the transmittance of the
film decreases which is due to the increase in film thickness and the scattering effect originating from
increased crystallite size [9]. The average transmittance values at 500 nm are 48 %, 35 % and 30 %
for 4, 6 and 8 dipping cycles respectively.
Fig. 3. Transmittance spectra of SiO2 - TiO2 thin film.
In fresh S.trilobatum and S.nigrum leaves (unexposed to UV), total chlorophyll content is high
whereas in the UV treated samples, the total chlorophyll content gradually increases as the dipping
cycle increases due to increase in film thickness. In the UV completely exposed treatment the total
chlorophyll content is minimum as shown in Fig. 4.

121
Fig. 4. Comparison of total chlorophyll (%) a) S.trilobatum, b) S.nigrum plants for different number
of dipping cycles.
From Fig. 4, it can be observed that in S.nigrum, with thin film of 8 dipping cycles, the total
chlorophyll content (99.3 8.5 %) is equal to the control treatment (100 8.6 %). Similarly, in
S.trilobatum also with film of 8 dipping cycles, the chlorophyll content is maximum (72.6 5.9 %).
Films of highest (8) dipping cycles absorb maximum UV light since increased thickness protects the
leaves from UV damage leading to increase in chlorophyll content.
Summary. SiO2 - TiO2 thin films of various dipping cycles have been deposited on glass substrate
using dip coating technique resulting in highly efficient UV absorbing film. The thin films exhibit
anatase phase with tetragonal structure having a preferential orientation along (1 0 1) plane. SEM
image reveals that the film has fractured structure. The presence of Si, Ti and O has been confirmed
from EDAX spectra. XRD study reveals that crystallite size increases as the dipping cycle increases.
This study showed that SiO2 - TiO2 thin films are good absorber of UV light that protects total
chlorophyll content in medicinal plants S.trilobatum and S.nigrum act as protective layer against UV
radiation.
References
[1] P. Malliga, J. PandiaRajan, N. PrithiviKumaran, K. Neyvasagam. Influence of film thickness on
structural and optical properties of sol gel spin coated TiO2 thin film. IOSR Journal of Applied
physics, 2014, 6, 22-28 http://iosrjournals.org/iosr-jap/papers/Vol6-issue1/Version-
1/D06112228.pdf
[2] T.S. Senthil, N. Muthukumarsamy, S. Agilan, M. Thambidurai and R. Balasundaraprabu.
Preparation and characterization of monocrystalline TiO2 thin films. Journal of Materials Science and
Engineering:B, 2010, 174:102-104. DOI 10.1016/j.mseb.2010.04.009
[3] Sen. S. Mahantys, Roys, Heintzo, Bourgeos, D.Chaumont. Investigation on sol- gel synthesized
Ag-doped TiO2 cermet thin films. Thin solid films. 2005, 474:245-249, DOI
10.1016/j.tsf.2004.04.004
[4] A.A. Ismail and N.H. Matsunaga. Influence of Vanadium content onto TiO2:SiO2 matrix for
photocatalytic oxidation of trichloroethylene. Journal of Chemical Physics Letters. 2007,447,74-78.
DOI 10.1016/j.cplett.2007.08.075
[5] M. Durgadevi and N. Banu. Study of antioxidant activity of chlorophyll from some medicinal
plants. Indian journal of research. 2015, Volume 4(2), 6-8. DOI 10.15373/2249555X.
[6] D.I Arnon. Copper enzymes isolated chloroplasts, polyphenoloxidase in Beta vulgeries. Plant
physiology. 1949. 24:1 15.

122
[7] E. Rahmani, A. Ahamadpour, M. Zebarjid. Enhancing the photocatalytic activity of TiO2 nano
crystalline thin film by doping with SiO2.Journal of Chemical Engineering, 2011, 174: 709 713.
DOI: 10.1016/j.cej.2011.09.073.
[8] Hemraj M. Yadav and Jung Sik Kim. Fabrication of SiO2/TiO2 double layer thin films with
self - cleaning and photocatalytic properties. Journal of Materials science: Materials in Electronics,
2016, Volume 27 (10), 10082 10088. DOI 10.1007/s10854-016-5082-4
[9] P. Malliga, B. Karunai Selvi, J. Pandia Rajan, N. Prithivikumaran and K. Neyvasagam. Studies
on the performance of TiO2 thin films as a protective layer in Ocimum tenuiflorum from UV radiation.
2015, AIP conference proceeding. DOI 10.1063/1.4917951.

123
Structural and Optical Properties of DC Magnetron Sputtered Zirconium

Titanate Thin Films of Varied Film Thickness22
D. Jhansi Rani1,a, A. Guru Sampath Kumar1, T. Subba Rao1
1 Materials research laboratory, Dept. of Physics, Sri Krishnadevaraya University, Anantapuramu, India
a jhansiranidvr@gmail.com
Keywords: zirconium titanate thin films, film thickness, DC magnetron reactive sputtering, wave guides.
ABSTRACT. Zirconium titanate thin films with thickness in the range of 245 to 715 nm were deposited by employing
direct current magnetron reactive sputtering technique and the film properties have been studied as a function of film
thickness. The films exhibited high transmittance of 80-91% and the band gap energy decreased from 3.4 to 3.1 eV with
increase in thickness while the packing density of the films increased with film thickness. The crystallinity of the films
improved with increase in thickness. The X-ray diffractograms showed a predominant peak in (111) orientation
corresponding to the scattering angle of 30o. The surface morphology demonstrated that the denser is the film the smoother
is the surface.
Introduction. The high-k dielectric materials, ZrO2, TiO2, Ta2O5, ZrTiO4 and Zr (Sn, Ti) O4 act as
potential candidates for gate dielectrics, dynamic random access memory (DRAM) and microwave
communications. Besides high dielectric constant, high quality factor, good thermal, chemical
stabilities [1] and high permittivity zirconium titanate (ZTO) exhibits good optical properties. It has
high transmittance over a wide range of wave length and high refractive index [2] as well. Hence it
finds application as wave guides in microwave frequency regions. In this paper, we demonstrated the
fabrication, characterization and the effect of thickness on the properties of nano crystalline ZTO thin
films deposited on glass substrates by DC magnetron reactive sputtering technique.
Experimental details. Initially, the vacuum chamber was evacuated to a base pressure of 1 X 10-5
mbar by the combination of diffusion and rotary pumps. The sputtering powers of 155 watt and 175
watt were applied to Zr and Ti targets respectively. Thickness has been measured by Brukers step
profilometer as 245, 325, 545, 620 and 715nm.
Results and discussion:
XRD. Thickness had a pronounced effect on structural properties and is illustrated by the
diffractograms shown in Fig.1.The films with thickness of 245 and 325 nm were not well crystallized
but, for the films with thickness from 545nm onwards crystallinity improved gradually. The denser
film (715 nm) is characterized by more crystallization and orientation, with a high intense peak in
(111) direction at 30.15o and minor peaks in (120), (311) directions appeared with less intensities at
50.35o and 59.82o respectively. The grain sizes were estimated from Debye Scherrers formula [3]:
k
D (1)
cos b
22

124
where D is size of the crystallite;

k is the Scherers constant;
o
is the X-ray wave length 1.54 A ;
is the full width at half maximum;
b is the Braggs angle.
The crystallite size varied from 1.71 nm to 13.14 nm, confirming the nano structure of the deposited
films. The thickness vs. crystallite size is shown in Fig. 1.
Fig. 1. (a) X-ray diffractograms and (b) crystallite size.
SEM. The surface morphology has been studied from SEM micrographs obtained by using FESEM-
SUPRA 55. Fig. 2 (a)-(e) illustrates that the films were pin hole and crack free. The images revealed
the evolution and thickness dependence of the grain size.
Fig. 2. SEM micrographs of the films with thickness (a) 245 nm, (b) 325 nm, (c) 545 nm, (d) 620 nm
and (e) 715 nm.

125
EDXS. The spectra shown in Fig. 4 also conveyed the presence of only the elements Zr, Ti and O at
the corresponding binding energies of 0.7 keV (O), 2 keV (Zr) and 4.5 and 5 keV (Ti). This ensures
the purity of the films.
Fig. 3. EDAS spectra of the films with thickness (a) 245 nm, (b) 325 nm, (c) 545 nm, (d) 620 nm and
(e) 715 nm.
Optical properties. The transmittance spectra of ZTO thin films have been recorded in the ultra
violet visible near IR (UV-VIS-NIR) region by Hitachi U-3400 spectrophotometer within a wave
length range from 200 to 900 nm. From the spectra, transmittance varied as 91, 87, 86, 83 and 80%
for films with thickness 245, 325, 545, 620 and 715 nm respectively.
Fig. 4. Transmittance spectra of films deposited at distinct thicknesses.
The optical packing density of the deposited films could be obtained by [4]:

126
n f - 1 nb 2 2
2
p 2 2 % (2)
n f 2 nb - 1
where nb is the bulk refractive index;

nf is the refractive index of the thin films.
The packing density increased from 81 to 98% with thickness.
Fig. 5. Variation of packing density with film thickness.
Summary Nano crystalline zirconium titanate thin films were deposited on to glass substrates using
DC magnetron sputtering, by varying the deposition time, which in turn varies film thickness.
Thickness has a considerable effect on the film properties. The films showed higher transmittance.
The films have high optical packing density of 81 to 98%. Optical transmittance spectra revealed that
all the films have high transmittance in the visible region above 300nm of wavelength.
Acknowledgements. The author, D. Jhansi Rani, gratefully acknowledges Department of Science
and Technology (DST), New Delhi for financial aid under INSPIRE Fellowship (IF120615).
References
[1] Y. Kim, Jeongmin oh, T.G. Kim, B.W. Park, Jpn. J. Appl. Phys 40, 4599-4603 (2001).
[2] A.P. Huang, P.K. Chu, H. Yan, M.K. Zhu, J. Vac. Sci.Technol. B 23, 566 (2005).
[3] B.D. Cullity, Elements of XRD,Addison Wesley publishing company, Massachusetts, 170,
(1967).
[4] D. Pamu, K. Sudheendran, M.G. Krishna, K.C.J. Raju, J. Mat. Sci. Engg. B 168, 208-213, (2010).

127
Effect of Additives on the Performance of Non-Fullerene Based Organic Solar

Cells in Non-Halogenated Solvents23
L. Reshma1, V. Sai Saraswathi2, P. Induja3, M. Shivashankar4, K.Santhakumar1,a
1 School of Electronics Engineering, VIT University, Vellore, Tamil Nadu, India

2 School of Bio Science & Technology, VIT University, Vellore, Tamil Nadu, India
3 School of Advanced Sciences, VIT University, Vellore, Tamil Nadu, India
4 Carbon Dioxide and Green Technologies Centre, VIT University, Vellore, Tamil Nadu, India
a jhansiranidvr@gmail.com
Keywords: polymer solar cell, non-fullerene acceptor, spray coating, power conversion efficiency, air stability.
ABSTRACT. Achieving highly stable and reliable organic solar cells relies on the advancement of good performance
and enthusiastically reasonable hole transporting buffer layers tuned in to the anode and the photoactive materials of the
solar cell stack. We explore the photophysics of all polymer solar cells based on the blends of the low band gap polymers
poly(3-hexylthiophene) (P3HT) as a donor and poly {[N,N-9-bis(2-octyldodecyl)-naphthalene-1,4,5,8-
bis(dicarboximide)-2,6-diyl]-alt-5,59-(2,29-bithiophene)} (P(NDI2OD-T2)) as an acceptor blend active layer in 2-methyl
anisole with 2% 1,8 diiodooctane (DIO) using air brush spray coating method. Polyethyleneimine ethoxylated (PEIE) is
used as a surface modifier and SnO2 was used as an anode to minimize chemical damage of the transparent conducting
electrode. The fabricated films were characterized and the solar cell performance was evaluated. An efficiency of 5.6 %
was achieved and the devices are highly stable, retaining 75% of its original efficiency after being stored in air even
without encapsulation.
Introduction. Solar cells are one of the best candidates to overcome traditional energy depletion and
environmental pollution. Especially, organic solar cells (OSCs) represent an exciting class of
renewable energy technology; they are lightweight, flexible and have a low production cost with a
scalable approach for solar energy conversion [1]. Over the last two decades, the efficiency of these
devices has improved significantly, in particular through the development of solution-processed bulk
heterojunction (BHJ) OSCs [2,3] based on interpenetrating networks of polymer donors and
acceptors that exhibit power conversion efficiencies (PCEs) over 10% mostly with fullerene-based
electron acceptors [4]. Very recently, however, highly efficient solution-processable non-fullerene
acceptors have been discovered and their performance is more or less comparable to that of
conventional fullerene-based acceptors. The low-band-gap polymers of P3HT and P(NDI2OD-T2)
were used as an electron-rich donor and as an electron-deficient acceptor respectively. 2-Methyl
anisole, a halogen free greener organic solvent was selected as they are the most attractive processing
solvents providing enough solubility and favourable morphology to improve the performance of
P3HT: P(NDI2OD-T2) solar cell device and their environmental accumulation can also be
significantly mitigated. In this paper, we report the effect of processing conditions on the performance
of P3HT: P(NDI2OD-T2) based cells, and the nano-scale morphology of active layers using spray-
coating technique [5] were 2-methyl anisole was used as the solvent [6,7]. The parameters such as
spraying time and substrate-nozzle distance were varied and the coated active layers of P3HT:
P(NDI2OD-T2) were investigated.
23

128
Experimental
Materials used. P3HT (Sigma Aldrich, 87 kg mol1 ), regioregularity 98%, polydispersity < 2)
and P(NDI2OD-T2) from polyera corporation . P3HT had a molecular weight (MW) of average Mn
54,000 75,000, whereas P(NDI2OD-T2) had a MW of 96.6 kg mol1 and poly diversity index of
about 4.0. 2-Methyl anisole purchased from sigma Aldrich was used as the solvent. The molecular
structures of P3HT, P(NDI2OD-T2) are shown in the Fig. 1(a).
a) b) c)
Fig. 1. (a) molecular structure of P3HT and P(NDI2OD-T2), (b) Device Architecture, (c) relative
energy level diagram.
Fabrication of OSCs and device characterization. Photovoltaic devices used an

ITO/PEIE/P3HT:P(NDI2OD-T2)/Al architecture, with Polyethyleneimine ethoxylated ( PEIE ) (5
nm) coated on indium tin oxide (ITO) glass substrates were used as the transparent substrate and
aluminium as the top electrode. Commercially available pre-patterned 12 W/h sheet resistance ITO
substrates were cleaned with detergent, ultrasonicated in acetone and isopropyl alcohol for 15 min,
and dried in an oven at 120 C. UV-ozone treatment was then performed for 15 min and plasma
etched prior to coating with a 5 nm layer of PEIE. Each PEIE solution was spin coated on the ITO
substrate at 5000 rpm for 40s and then thermally annealed at 110 C for 10 min. Fig. 1 (b) illustrate
the configurations of OSCs in the form of a sandwich structure of the photoactive polymeric layer
between an anode electrode of indium tin oxide (ITO) and a metal cathode of aluminium (Al), which
has a structure of ITO(180nm)/SnO2 (xnm)/PEIE(5nm)/P3HT:P(NDI2OD-T2) (120nm)/Al(100nm).
The relative energy level diagram is illustrated in the Fig. 1 (c). Polymer blends were spin-coated
from P3HT:P (NDI2OD-T2) solutions of varying concentration of 1:1; 1:2, 1:3, and 1:4 using 2-
methyl anisole solvent. In each case, the initial solution was prepared in a glovebox with the measured
P (NDI2OD-T2) and P3HT polymers allowed to dissolve in a hot solution for at least an hour. By
introducing the nitrogen gas with the pressure of 8.5 x 10-4 Pa into the spray apparatus, the solution
of P3HT: P (NDI2OD-T2) were spray cast onto the PEIE film to form the active layer with the
thickness ranging from 120 125 nm. The blend films were prepared with different time periods from
10 40 s and the substrate-nozzle distances were varied from 10 to 30 cm. Once the active layer has
been deposited, the MoO3 hole transporting layer (HTL) and 100 nm aluminium top electrode were
deposited via thermal evaporation for a final thickness of ~5 nm and ~100nm, respectively.
Completed devices were annealed at 130 C for 10 minutes inside a glove box and then encapsulated
with epoxy resin and soda-lime cap. SnO2 buffer layers with different thicknesses of 515 nm were
deposited onto ITO transparent anodes by RF magnetron sputtering. All absorption measurements
were performed using a Cary 5000 UVVisNIR double-beam spectrophotometer in the two-beam
transmission mode. Absorption spectra of P3HT, P(NDI2OD-T2), and P3HT:P(NDI2OD-T2) films
were taken near the centre of solar cells lacking the top electrode. The surface morphology of the
blend layers was examined by atomic force microscopy (AFM) using a Seiko Instruments SPA400-
SPI4000 operating under ambient condition. The current density (J)-voltage (V) characteristics were
measured using a Keithley 2420 m in dark and under illumination of a sun 2000 solar simulator (Abet)

129
with 100 mw/cm2 AM 1.5 G spectrum. All measurements were performed under ambient atmosphere
at room temperature in open air.
Results and Discussion. The absorption spectra of spray coated P3HT, P(NDI2OD-T2) and active
layers of P3HT: P(NDI2OD-T2) thin films from 1:1 to 1:4 weight ratios in 2-methyl anisole with 2%
1,8 diiodooctane (DIO) are shown in Fig. 2 (a). For the absorption spectra of P3HT film fabricated
from 2-methyl anisole, wavelength of the absorption peak (max) is at 526 nm. The pure P (NDI2OD-
T2) film has a broad near-IR absorption band extending from 550 nm to 850 nm and a -* absorption
feature at 390 nm. The extinction coefficient (eabs) were calculated by using Beer-Lambert Law from
the absorption spectra of both films and solution of P3HT: P(NDI2OD-T2) For the films, the values
of eabs were 5320, 2710, 1860, 1564 and 1610 for P3HT: P(NDI2OD-T2) concentration of 1:0, 1:3,
1:2, 1:1, 1:4, respectively. However, for the solutions, the values of eabs were 40, 44, 42, 45 and 47
for similar concentration of P3HT: P(NDI2OD-T2). The extinction coefficients of the solution were
lower than that of the films by about two orders of magnitude. Hence, the inter-chain interaction
among the P3HT chains results into more delocalized conjugated electrons, the lowering of the
bandgap between -* transition [8], [9].
To evaluate the role of the blend morphology, the topography of the thin films was investigated by
atomic force microscopy (AFM). The tendency of the polymerpolymer blends to phase separate is
generally described to low entropy of mixing and is governed by a spinodal decomposition of the
blend. The properties of the spray solution not only affect the thickness optimization by a proper
choice of nozzle-substrate distance, but also play an important role on morphology of the films. The
topography and surface roughness of the films were investigated by atomic force microscopy (AFM).
AFM topographic images for P3HT: P (NDI2OD-T2) films with different blend ratios: 1:1(a); 1:2(b);
1:3(c); 1:4(d) are shown in the Fig. 2 (b). At lower P(NDI2OD-T2) loadings with blend ratio of 1:1,
1:2, the blends showed uneven and larger number of granular aggregations with a size distribution
between 50-100 nm, which were uniformly dispersed in the P3HT matrix. On further increasing the
acceptor material concentration to 1:3 ratio, the blend showed such high miscibility that the
homogeneous films were obtained with smoother surfaces and this improved the device efficiency to
a greater extent. For the ratio of 1:4, the surfaces of the blend films become increasingly uneven and
large P(NDI2OD-T2) aggregations were observed, this results in lower absorption when compared to
other blend ratio. The SnO2 film is composed of nano-sized particles with root mean square (RMS)
roughness of ~3 nm. The PEIE film itself is very smooth with RMS roughness of 0.369 nm, which
was determined independently by spray coating a relatively thick film on ITO (180 nm). However,
for the ultra-thin layer of PEIE used in our device fabrication, the roughness of the PEIE film is
predominantly influenced by the under layer. Hence, the RMS roughness of the PEIE coated SnO 2
film is similar to that of SnO2 (3.112 nm). The current density-voltage (JV) characteristics of
photovoltaic cells with various interfacial layers under AM 1.5G irradiation at 100 mW cm-2 were
examined. The effect of the D/A weight ratio along with the influence of the solvent on the
photovoltaic behaviour of the PSC is summarized in Table 1. The observed open circuit voltage is
consistent with the HOMOD LUMOA difference expected from the energy level of P3HT and
P (NDI2OD-T2). Indeed, according to the typical energy loss in P3HT-based cells (ca. 0.35 V), the
maximum predictable open circuit voltage is about 0.69V, and it showed a short-circuit current
density of about 12.4 mA cm-2 and a fill factor of 54.93%. In this respect, the P3HT/P (NDI2OD-T2)
interface has been shown to be highly efficient for charge transfer and free carrier generation.
Specifically, for 20 cm 30 s when the substrate-to-nozzle distance was increased to 20 cm the layers
with uniform thickness were observed and it showed maximum efficiency of about 5.6% for 1:3 blend
ratio with Voc of 0.68, Jsc of 12.9 mA/cm2. And FF of 63.84 % and reduced at the ratio of 1:1, 1:2 and
1:4 for P3HT: P (NDI2OD-T2) blend because of its less uniformity and thickness and similarly for
SnO2 concentration. When the thickness is around 20cm, it showed maximum efficiency of about
5.6% with Voc of 0.68, Jsc of 12.9mA/cm2, and FF of 63.84 % and reduced at the other thickness level
as shown in the Table 2. It can be explained by the fact that, with decreasing P(NDI2OD-T2) loading,
a large number of P(NDI2OD-T2) clusters with size above 100 nm dispersed in the film not only
130
reduce the P3HT: P (NDI2OD-T2) interface but also act as charge traps resulting in a strong
deterioration of photovoltaic performance.
Fig. 2. (a) Absorption spectra for P3HT: P(NDI2OD-T2) blends, (b) AFM topographic images for
P3HT: P(NDI2OD-T2) blend with different blend ratios: (a) 1:1, (b) 1:2 (c)1:3, (d)1:4
Table 1. Photovoltaic Performance of the BHJ Polymer Solar Cells Composed of ITO/PEIE/P3HT:
P (ND12OD-T2)/MoO3/Al fabricated with different weight ratios under AM 1.5G illumination of
100 mWcm-2.
P3HT:P(ND12OD-T2), Active layer Voc, (V) Jsc, (mA cm-2) FF, (%) PCEavg, (%)
weight ratio (nm)
1:1 130 0.68 0.1 9.2 0.3 43.16 0.2 2.7 0.1
1:2 127 0.67 0.3 10.8 0.2 48.37 0.3 3.5 0.1
1:3 123 0.69 0.2 12.4 0.3 54.93 0.2 4.7 0.2
1:4 125 0.67 0.1 10.1 0.2 44.33 0.3 3.0 0.3
Summary. We have explored the photovoltaic properties of the P(NDI2ODT2) in the blend with the
P3HT using 2-methyl anisole solvent with 2% 1,8 diiodooctane (DIO) by varying spray time in
ambient atmosphere. High fill factor in all-polymer solar cells have been demonstrated for the first
time with values of nearly 64%, suggesting a highly balanced mobility into the polymer-blend thin
films. Thus, using high mobility electron transporting polymers such as P (NDI2OD-T2) enables FF
values comparable with those reported for fullerene-based devices. Spectral and morphological
investigation of P3HT: P (NDI2OD-T2) blends reveals that these low band gap polymers exhibited
uniform surface morphology and thickness for 1:3 blend ratio with 5% SnO2 concentration and
attained a maximum power conversion efficiency of about 5.6%. Thus the morphological properties
and the device efficiency achieved indicates that the P3HT:P (NDI2OD-T2) system is a promising
all-polymer system for further device optimization and for practical use of non-fullerene OSCs.
However, several limiting factors still hinder to reach high efficiencies as for instance the photoactive
blend morphology, thus further optimizations are necessary. The use of additive molecules may
eventually lead to a better morphology and to an overall improvement of the device performance. In
addition, the electronic structure of the blend could play an important role on the ultimate efficiency.
Adjusting the D and A, HOMO and LUMO levels by combining P(NDI2OD-T2) with new high-
performing p-type polymers would allow us to minimize the energy loss due to the LUMO offset.
Acknowledgement. This study was supported by DST, New Delhi under Young Scientist Scheme
(Grant No. YSS/2015/001104), CSIR New Delhi under Extramural Research (Grant No.
01(2865)/16/EMR-II) and VIT University under RGEMS Fund.
References

131
[1] F.C. Krebs, N. Espinosa, M. Hosel, R.R. Sondergaard, M. Jorgensen, Rise to power OPV- based
solar parks. Adv Mater., 26(2016) 29-39. DOI 10.1002/adma.201302031.
[2] S. Liu, K. Zhang, J. Lu, J. Zhang, H.L Yip, F. Huang, Y. Cao(2013) High-Efficiency Polymer
Solar Cells via the Incorporation of an Amino-Functionalized Conjugated Metallopolymer as a
Cathode Interlayer. J Am Chem Soc 135 (2013):15326-29. DOI 10.1021/ja408363c.
[3] S. Kannappan, R. Liyakath, J. Tatsugi, Third-order nonlinear optical characteristics of bulk film
effect on regioregular poly (3-dodecylthiophene) thin films fabricated by the drop-casting method,
Journal of Materials Science: Materials in Electronics. 2016:1-7. DOI 10.1007/s10854-016-4928-0.
[4] L. Saitoh, R.R. Babu, K. Santhakumar, K. Kojima, T. Mizutani, S. Ochiai, Performance of spray
deposited poly [N-9-hepta-decanyl-2,7- carbazole-alt-5,5-(4,7-di-2-thienyl-2,1, 3-
benzothiadiazole)]/[6,6]-phenyl-C61-butyric acid methyl ester blend active layer based bulk
heterojunction organic solar cell devices, Thin Solid Films, 520 (2012) 3111-3117. DOI
10.1016/j.tsf.2011.12.022.
[5] V. Krishnakumar, K. Ramamurthi, R. Kumaravel, K. Santhakumar, Preparation of cadmium
stannate films by spray pyrolysis technique, Curr. Appl. Phys., 9 (2009): 467-471. DOI
10.1016/j.cap.2008.04.006.
[6] S. Ochiai, P. Kumar, K. Santhakumar, P.K. Shin, Examining the effect of additives and
thicknesses of hole transport layer for efficient organic solar cell devices, Electron Mater. Lett., 9
(2013): 399-403. DOI 10.1007/s13391-013-0013-5.
[7] P. Kumar, K. Santhakumar, J.Tatsugi, P.K. Shin, S. Ochiai, Comparision of properties of
polymer organic solar cells prepared using highly conductive modified PEDOT: PSS films by spin
and spray-coating methods, Jpn. J. Appl. Phys., 53 (2014) 01AB08.
[8] V.S.Saraswathi, J.Tatsugi, P.K.Shin, K.Santhakumar. Facile biosynthesis, characterization, and
solar assisted photocatalytic effect of ZnO nanoparticles mediated by leaves of L. speciosa. Journal
of Photochemistry and Photobiology B: Biology.167 (2016) 89-98. DOI 10.1016
[9] P. Jayavel, J. Kumar, K. Santhakumar, P. Magudapathy, K.G.M. Nair, Investigations on effect
of alpha particle irradiation-induced defects near Pd/n-GaAs interface, Vacuum, 57 (2000) 51-59.
DOI S0042-207X(99)00211-0.

132
Characterization, Design and Optimization of Industrial Phosphoric Acid

Production Processes by Artificial Neural Network 24
Gholamhosseion Grivani1,a, Shahriyar Ghammamy2,b, Farzane Yousefi1,c, Mehdi Ghammamy3,d
1 Department of Chemistry, Faculty of Science, Damghan University, Semnan, Damghan, Iran

2 Department of Chemistry, Faculty of Science, Imam Khomeini International University, Qazvin, Iran
3 Department of Mechanical Engineering, Faculty of Engineering, Tehran University, Tehran, Iran
a grivani@du.ac.ir
b shghamami@yahoo.com
c f4380110672@gmail.com
d Mghamazi@alumni.ut.ac.ir
Keywords: phosphoric acid, optimisation, modelling and simulation, genetic algorithm.
ABSTRACT. In this paper we optimized industrial scale phosphoric acid production processes by genetic algorithm and
Artificial Neural Network. In this work an efficient method is suggested to design an optimized cast in order to increase
the rate of phosphoric acid and purity percent in manufacturing process. The predicted results are in very good agreement
with the experimental data with an error of less than 4.88%. The simulation model has been examined with real
experimental data obtained from the Phosphate Mines. A parametric study has been made to find the optimum operating
conditions of the pilot plant for a given phosphate rock. The effect of varying reactor(s) time, sulphuric acid rate, water
rate, soil rate agitatorimpeller speed has been investigated. More than 160 samples were made in laboratory and the
results are derived by changing the parameters and using the limited component software. We also hope to gain feedback
that will improve the modeling to better meet the needs of the phosphate industry. Finally, using the Pareto front extracted
from optimization algorithms, optimum template selection and remodeling results have been examined with finite element
software. Studies have confirmed that using the developed method is an effective tool to achieve the proper format in
order to restructure and reduce the strain based on improving the convergence rate and the applied force.
Introduction. Phosphoric acid is an important intermediate chemical product. It is added to foods as

a preservative, acidifying agent, flavour enhancer, and clarifying agent. Phosphoric acid is also used
in processes such as the coagulation of rubber latex, electro polishing, soil stabilization, and as a
catalyst in the production of propylene and butene polymers, ethylbenzene, and cumene. Eightly
percent of the acid is used in the production of agricultural fertilizers. Production capacity for
phosphoric acid yielded about 33 million tons of P2O5. It is mainly obtained through the attack of
phosphate rock with sulphuric acid. Its quality depends greatly on the P2O5 rock content and nature
of the present impurities, among which some can be recovered like uranium, rare earth, etc. . Almost
all phosphoric acid needed for the fertilizer industry is produced by wet processes. In many of these
processes, the raw phosphate ore is converted into phosphoric acid and calcium sulphate di-hydrate
(gypsum) by adding a mixed solution of sulphuric and phosphoric acids to the reactor. genetic
algorithm is one of the random optimizing methods invented in 1995 by Kennedy & Eberhart . multi
objective particle swarm algorithm (MOPSO) simultaneously searches different spaces of design and
optimizing points for the complex problems such as non-convex and discrete problems. In MOPSO
method, selecting the best local guide (the global best particle) for each particle of the population
24

133
from a set of Pareto-optimal solutions has a great impact on the convergence and diversity of
solutions, especially when optimizing problems with high number of objectives. In this paper an
efficient method is suggested to design an optimized cast in order to increase the homogeneity of the
microstructure material and to reduce the applied force required in the manufacturing process. In this
work, we develop a design framework that is able to transparently capture the process phenomena
involved regardless of the modelled process task. Reactions of phosphoric acid production display
below [1-8 ]:
3Ca3(PO4)2.CaF2+ 14H2SO4 10 Ca( H2PO4)2 +2HF (1)

Ca( H2PO4)2+ H2SO4 + nH2O 2H3PO4+ 10 CaSO4. nH2O (2)
Chemicals and reagents. In laboratory, we mixed different rate of water, soil and Sulphuric acid by
different time. After several minutes, reaction completed. Table 1 shows the values of input
parameters and their output objective functions.
Table 1. Values of input parameters and their output objective functions.

1 400 40 210 540 425 0.6938
2 350 60 150 480 287 0.64134
3 300 60 180 540 330 0.7087
4 300 60 210 540 359 0.7584
5 450 60 90 360 174 0.6991
6 500 60 60 300 371 0.3372
7 500 60 30 300 297 0.2621
8 450 50 120 360 125 0.6964
9 500 40 120 300 407 0.4697
10 350 70 120 480 275 0.5387
11 300 80 120 540 159 0.5773
12 350 70 90 480 198 0.4653
13 300 80 60 540 88 0.3873
14 300 80 30 540 153 0.309
15 450 50 150 360 317 0.5806
16 500 40 180 300 494 0.5977
17 500 40 210 300 428 0.6583
18 450 50 150 480 370 0.54029
19 500 40 180 540 443 0.608
20 500 40 210 540 480 0.6409
21 350 70 90 360 165 0.461
22 300 80 60 300 101 0.50008
Modelling with artificial neural network

Artificial neural network (ANNs) are non-linear mapping structures based on the function of the
human brain. They are powerful tools for modelling, especially when the underlying data relationship
is unknown. ANNs can identify and learn correlated patterns between input data sets and
corresponding target values. An artificial neuron is a computational model inspired in the natural
neurons. Natural neurons receive signals through synapses located on the dendrites or membrane of
the neuron. When the signals received are strong enough (surpass a certain threshold), the neuron is
134
activated and emits a signal though the axon. This signal might be sent to another synapse, and might
activate other neurons. Each neuron in our brain accepts input from many other neurons and then
provides a resulting output. This is precisely what we will be replicating in code. Each neuron class
will have a structure where there is a body of attributes and one output [9-10].
Fig. 1. Neural network training.
Considering four effective parameters in cast design includes water rate, acid rate, soil rate, and time,
which have more effects on sulphuric acid rate and purity percent, in order to recognize the first
objective function (sulphuric acid rate), artificial neural network is designed with four entrance
neuron layers, two middle layer with 12 and 1 neurons and external layer with one neuron.
Furthermore, in order to recognize the second objective function (purity percent), another neural
network is designed with four entering neuron layers, middle layers, two middle layer with 14 and 1
neurons and external layer with one neuron. Figures 2 and 3 shows the Modelling of artificial neural
network for first and second objective functions
Fig. 2. Modeling of artificial neural network for first objective function (sulphuric acid rate)

135
Fig. 3. Modeling of artificial neural network for second objective function (purity percent).
The physical topology of a network refers to the configuration of cables, computers, and other
peripherals. Physical topology should not be confused with logical topology which is the method used
to pass information between workstations. Logical topology was discussed in the Protocol chapter.
In order to train and test the neural network in order to forecast the homogeneity coefficient and
amount of applied force in the cast, precise data are needed, so some models are produced by finite
element software and changing the cast design parameters to diagnose the search space related to the
neural network and calculate and save the objective functions. Produced data in pervious stage include
corner and curving angles, radius ration, friction coefficient, strain homogeneity coefficient and
applied force. Around 85 percent of the data are considered for training and others for testing the
predictability of the network for new data. Squared error of the network for training is 0.0079 and in
testing is 0.0096. Squared errors of the testing shows that the network is not affected by over training
and maximum error of the neural network is 4.88 %. Neural network estimated the homogeneity
coefficient with 95.12precision. Neural network output is compared to laboratory data in figure 4.
MSEtr =0.0198
MSEts =0.0198
Ans =7
Fig. 4. (a) Squared error of the network for testing, (b) The output of the artificial neural network
(ANN) model for data test.
Training process of the second neural network is done same as the previous network, in order to
predict the purity percent needed for the process based on the effective casting parameters. Using the
136
extracted functions from the above neural network, we can begins the optimization process. Created
functions by this neural network acts for cost functions in optimization process.
Optimizing the multi-objective problems
Multi-objective optimization is a class of problems with solutions that can be evaluated along two or
more incomparable or conflicting objectives. Most optimization problems naturally have several
objectives to be achieved (normally conflicting with each other), but in order to simplify their
solution, they are treated as if they had only one (the remaining objectives are normally handled as
constraints). The Multiobjective Optimization Problem (MOP) (also called multicriteria optimization,
multiperformance or vector optimization problem) can be defined (in words) as the problem of
finding: a vector of decision variables which satisfies constraints and optimizes a vector function
whose elements represent the objective functions. These functions form a mathematical description
of performance criteria which are usually in conflict with each other. Hence, the term optimize
means finding such a solution which would give the values of all the objective functions acceptable
to the decision maker. These types of problems differ from standard optimization problems in that
the end result is not a single best solution but rather a set of alternatives, where for each member
of the set, no other solution is completely better (the Pareto set). Multi-objective opti mization
problems occur in many different real-world domains, such as architecture (stability vs. cost), and
automobile design and as such are a very important problem domain. In solving the multi-objective
problem, objective functions usually contradict with each other. It means that improving one function
results in decline of the other function. so, all the functions cannot be seen in the best mode. In order
to optimize all the objective functions at the same time optimized points are used. Improper points
are the points that no other point is dominant over them. Proximate algorithms can find good answers
(near optimization) in short time for hard optimized problems. Table 2 shows the design variables
and their changes domain. This limit is considered as the limit of the problem. The homogeneity
coefficient and maximum applied force are considered as object function [11-15].
Table 2. Design variables and their changes limit.

Time Sulphuric acid rate Soil rate Water rate
}300,540{ }30,210{ }30,80{ }300,500{
Pareto front shows the objective function toward each other. Optimized points can be considered
where two objective functions are satisfied. As it was said, horizontal axis is phosphoric acid rate and
vertical axis is purity percent. This chart is composed of discrete points each of which shows the
optimized points for both objective functions. After repeating the optimizing algorithms, the optimal
points (optimized area) are shown as the figure 6. The parts shown in figure 6 indicate a proper limit
for choosing the proper optimizing point since both functions in this limit are satisfied and so several
proper points are chosen form this limit. Table 3 shows the values of input parameters and their output
objective functions.

137
Fig. 5. Desired range for the optimal point in Pareto.
Table 3. Optimal point extracted from the Pareto frontunctions.

Objective 1 Objective 2 Time(min) sulphuric Soil rate(g) Water rate
acid
rate(ml)
Optimal 413 0.52876 360 68.2 67.5 486
cast
Summary. Genetic Algorithms are a family of computational models inspired by evolution. These
algorithms encode a potential solution to a specific problem on a simple chromosome like the one
data structure information of Genetic algorithms are often viewed as function optimizers. Although
the range and apply recombination operators to these structures so as to preserve critical of problems
to which genetic algorithms have been applied is quite broad. During each successive generation, a
portion of the existing population is selected to breed a new generation. Individual solutions are
selected through a fitness-based process, where fitter solutions (as measured by a fitness function)
are typically more likely to be selected. Certain selection methods rate the fitness of each solution
and preferentially select the best solutions. This work proposes a way that facilitates the modelling,
design and optimization of phosphoric acid production processes. As we have demonstrated modern
process simulators such as genetic algorithm can be of considerable value for the design, operation
and management of phosphoric acid production speed. Optimizing methods taken form nature, which
are normally expressed by random qualities and start the research performance from several points.
As this is ongoing work, we intend to further investigate the insights generated through the proposed
designs from an industrial user perspective as well as to explore more design cases with respect to
phosphogypsum utilization.
Acknowledgment
We gratefully acknowledge the financial support from the Research Council of Imam Khoemieni
International University by Grant No, 751387-91.
References
[1] Papadopoulos, A.I., Seferlis, P., & Theodosiadis, K. (2007). Modeling, Design and Optimisation
of Industrial Phosphoric Acid Production Processes.
138
[2] Mohamed Azaroual, Christophe Kervevan, Arnault Lassin, Laurent Andr, Mohamed Amalhay,
Lhachmi Khamar, Mohamed EL Guendouzi, Thermo-kinetic and Physico-Chemical Modeling of
Processes Generating Scaling Problems in Phosphoric Acid and Fertilizers Production Industries,
Procedia Engineering, 2012, Vol. 46, 68-75, DOI 10.1016/j.proeng.2012.09.447
[3] N. Boulkroune, A.H. Meniai, Modeling purification of phosphoric acid contaminated with
cadmium by liquid-liquid extraction, Energy Procedia, 2012, Vol. 18, 1189-1198, DOI
10.1016/j.egypro.2012.05.134
[4] Ms.G. Bharathi kannamma, Dr.D. Prabhakaran, Dr.T. Kannadasan, Analysis and Simulation of
Dihydrate Process for the Production of Phosphoric Acid (Reactor Section), American Journal of
Engineering Research (AJER), 2013, Vol. 02, Iss. 07, 01-08
[5] John E. Cameron, Phosphoric Acid by Wet Process: Pond Water Management.
[6] Samir I. Abu-Eishah,Nizar M. Abu-Jabal, Parametric study on the production of phosphoric acid
by the dihydrate process, Chemical Engineering Journal 81 (2001) 231250
[7] Gan, C., V. Limsombunchai, M. Clemes, A. Weng (2007), Consumer choice prediction : artificial
neural networks versus logistic models, Lincoln University. Commerce Division.
[8] Carlos A. Coello Coello, Nareli Cruz Cortes, Solving Multiobjective Optimization Problems
Using an Artificial Immune System, Genet Program Evolvable Mach (2005) 6: 163. DOI
10.1007/s10710-005-6164-x
[9] Mahdi Ghamami, Masoud Shariat Panahi, Maryam Rezaei, Optimization of locomotive body
structures by using imperialist competitive algorithm, Journal of Computational and Applied
Research in mechanical engineering (JCARME), 2014, 3(2): 105-113.
[10] Rao, S.S, Engineering Optimization: Theory and Practice, Fourth Edition, 2009 by John Wiley
& Sons, Inc.
[11] Kennedy, J, Eberhart, R, Particle Swarm Optimization, Proceedings of IEEE International
Conference on Neural Networks, Perth, Australia, 1942-1948. 1995
[12] Zitzler E., Laumanns M., Bleuler S. (2004) A Tutorial on Evolutionary Multiobjective
Optimization. In: Gandibleux X., Sevaux M., Srensen K., Tkindt V. (eds) Metaheuristics for
Multiobjective Optimisation. Lecture Notes in Economics and Mathematical Systems, vol 535.
Springer, Berlin, Heidelberg.

139
Microstructure and Supercapacitor Properties of V2O5 Thin Film Prepared by

Thermal Evaporation Method 25
M. Dhananjaya1, N. Guru Prakash1, G. Lakshmi Sandhya1, A. Lakshmi Narayana1, O.M. Hussain1
1 Thin Film Laboratory, Dept. of Physics, Sri Venkateswara University, Tirupati, India
a hussainsvu@gmail.com
Keywords: Vanadium pentoxide thin films, thermal evaporation, structure and electrochemical properties.
ABSTRACT. Transition metal oxide based supercapacitors perform excellent charge storage capability and long life
time stability. Among transition metal oxides, vanadium pentoxide is one of the best suited materials for supercapacitve
applications, because it has wide range of oxidation states, layered structure, high energy density (theoretical capacity of
440 mAhg1), and low cost. The nano structured vanadium pentoxide thin films are deposited onto Ni substrates at
various substrate temperature by thermal evaporation technique. The prepared V2O5 films at TS = 300 C exhibited
characteristic peaks with predominant (0 0 1) orientation signifying orthorhombic V2O5 phase with space group of Pmmn
(59), and the calculated crystallite size is 25 nm. Raman studies confirmed the formation of V2O5 phase. The average
grain size of the deposited film is about 148 nm. The films deposited at TS = 300 C exhibited a high rate pseudo
capacitance of 730 mFcm-2 at 1mAcm-2 of current density. The electrochemical impedance analysis revealed the films
have a lower charge transfer resistance, resulting better capacitance.
Introduction. In recent decades, electrochemical capacitors have been considered as one of the prime
candidate for the next generation energy storage devices due to their higher power densities (5 kW
kg-1) with longer cycling life (105 cycles) than the batteries and higher energy density (100-200 W
h kg-1) than conventional dielectric capacitors [1] . These outstanding properties made them as
excellent candidates for hybrid electric vehicles, computers, electric mobile devices, camera-flash
equipment, navigational devices and other applications. According to the charge storage mechanism,
the electrochemical capacitors are classified into two types, viz electric double-layer capacitors
(EDLCs) and pseudo capacitors. In EDLCs no electron transfer takes place between the electrode-
electrolyte interface during charge storage process (non-faradic), while in pseudo capacitors, charge
storage process involve a reversible faradaic redox reaction at the electrode-electrolyte interface. Till
to date, most extensively used electrode materials for super capacitors are carbon materials such as
activated carbon fiber cloth, CNTs, carbon aerogels, conducting polymers, and transition metal oxides
or hydroxides. One major disadvantage of carbon based EDLC is lower specific energy storage. Most
of the available commercial products have a specific energy below 10 Wh/kg, whereas the lowest
numeral for batteries is 35-40 Wh/kg. Transition metal oxides present an attractive alternative
electrode materials because of high specific capacitance at low resistance, probably making it easier
to construct high energy, high power super capacitors. Recently, oxide materials such as CuO, MnO2,
NiO2, TiO2, V2O5, SnO2 etc which have been studied as electrode material for super capacitor. Among
transition metal oxides, vanadium pentoxide (V2O5) has been studied as the active material for
electrochemical pseudo capacitor applications because of its broad range of oxidation states, layered
structure, high energy density, low cost and capability of fast response during charge-discharge
process . Especially, V2O5 is interesting in the form of thin film for the possibility of integration into
micro-electronic circuitry and its applications in electrochromic devices. The V2O5 thin films can be
25

140
prepared by various types of techniques including RF/DC magnetron sputtering [2], pulsed laser
ablation [3], e-beam evaporation [4]-[5], plasma-enhanced chemical vapor deposition [6],
electrodeposition [7]-[8], hydrothermal [9], sol-gel deposition [10] etc. Hence in present work
vanadium oxide thin films were deposited by using thermal evaporation technique (12" vacuum
coating unit model-12A4D), and studied the effect of the substrate temperature on electrochemical
behavior for supercapacitor applications.
Experimental details. Thin films of V2O5 were prepared by thermal evaporation technique using 12"
vacuum coating unit model-12A4D. Target material such as commercially available V2O5 powder,
of purity 99.995% was subjected to a pressure of 8MPa in air at room temperature to make pellets 12
mm diameter and 2 mm thickness with specific gravity of 2.2116 g cm-3. Nickel substrates were used
for the formation of vanadium oxide thin films at ambient temperature. Initially the system is
evacuated to a base pressure of 1x 10 -6 mbar with a diffusion pumping system backed by rotary
pump. The source material has been thermally evaporated from a molybdenum boat while keeping
the deposition pressure at 1x 10 -4 mbar and the source-substrate distance at 13 cm. The depositions
were carried out by varying substrate temperature from 100 C to 400 C. The microstructural
properties of the as-deposited films have been ascertained by X-ray diffraction (XRD), and was
performed in a Siefert X-ray diffractometer (model 3003TT) with Cu K radiation source(1.54 A ).
The angular (2) range was studied from 10 to 70 . The Raman spectra were recorded at room
temperature with a Horiba Jobin Yvon LabRAM HR800UV Raman spectrometer using a 532 nm as
an excitation wavelength from He-Ne laser. The surface topology of the films were observed by
Scanning Electron Microscopy (SEM), (Carl Zeiss EVO50 Scanning Electron Microscope). The
elemental composition have been analyzed with Energy Dispersive Spectrometer (INCA, Oxford
instrumental EDS).The effects of stoichiometry on the electrochemical properties of vanadium oxide
thin films were investigated using a three-electrode cell with V2O5 thin films on Ni-substrate as
working electrode, platinum foil as a counter electrode and Ag/AgCl electrode as reference electrode.
The electrochemical properties were carried out using a CHI 600C electrochemical analyzer.
Surface Morphology. The physical properties of materials are strongly dependent on the
microstructure such as grain size, grain boundaries, and orientation distribution of grains. Figure 1
illustrates the SEM images of V2O5 thin films deposited at various substrate temperatures. The surface
topography shows the uniform distribution of nano grains. The grain size of the prepared films
increased with increase in the substrate temperature. The average grain size of the prepared samples
at substrate temperature of 200,250 and 300 C are 100 nm, 106 nm and 148 nm respectively.
(a) (b) (c)
Fig. 1. SEM images of V2O5 thin films at various substrate temperatures (a) 200 (b) 250 (c) 300 C.
X-ray diffraction studies. The X-ray diffraction (XRD) spectra of the vanadium oxide thin films
deposited at substrate temperatures of 200, 250, and 300 C is shown in Figure 2. The films prepared

141
at 200 C and 250 C exhibited (2 0 1) orientation. However at 300 C, a predominant (0 0 1)

orientation is observed to be predominant at 300 C, which indicates a c-axis oriented structure. The
XRD pattern of the films prepared at 300 C can be indexed as V2O5 phase with orthorhombic
structure and is in good agreement with JCPDS no: 772418 [11]. The average crystallite size
calculated using Scherrers equation for films deposited at 300 C is 25.34 nm.
Fig. 2. The X-ray diffraction spectra of V2O5 thin films with various substrate temperatures.
Raman studies. The prepared V2O5 thin films are characterized by Raman spectra in the wavelength
range from 100-1200 cm-1 , as shown in figure 3. Raman spectroscopic measurements can be
discussed using the shape and frequency of the 21 ( = 7Ag+3B1g+7B2g+4B3g ) allowed modes located
in the high- and low-wavenumber regions corresponding to the internal and external modes,
respectively [12]. The internal modes consists of V-O stretching vibrations in the range of 500-1000
cm-1 and external modes includes V-O-V bending vibrations in the range of 200-500 cm-1 [10] .The
prepared samples were exhibited eight raman active modes and one raman inactive (infraredactive)
mode (=4Ag(R)+2B1g(R)+B2g(R)+B3g(R)+B3u(IR)), corresponding nine obvious peaks that are
located at 147, 200, 284, 310, 403, 532, 700, 837, 980 cm-1 respectively [13], [14]. In internal
modes, the high-frequency Raman peak around 1000 cm-1 corresponds to vanadyl oxygen streching
mode (V=OV ). The peaks exhibited at 977 and 980 cm-1 correspond to the terminal oxygen stretching
mode which consequences from the unshared oxygen. The second peak at 700 cm-1 is corresponds to
doubly coordinated oxygen (V2-OB) stretching mode which results from corner oxygen, which is
common to two pyramids. The third peak at 532 cm-1 is associated with the triply coordinated
oxygen (V3-OC). In external modes, the predominant low-wavenumber peak at 147 cm-1
corresponds to the skeleton bent vibration, which is a characteristics of the layer-type structure of
V2O5. The peaks at 200 and 284 cm-1 are associated to the bending vibrations of the OC-V-OB bond.
The peak located at 310, and 403 cm-1 are assigned to the triply coordinated oxygen (V3-OC) and
the bending vibration of the V-OB-V bonds respectively [13], [14].

142
Fig. 3. Raman spectra of V2O5 thin films with various substrate temperatures.
Electrochemical studies. The electrochemical measurements of V2O5 are carried using three-
electrode cell. Figure 4 shows a characteristic CV curves of deposited V 2O5 thin films at various
substrate temperature within the potential range from -0.6 to 0 V in 1M of LiSO4 solution at a scan
rate of 10 mV s-1. The electrochemical Li+ ion insertion into and extraction from the layered
framework of V2O5 can be expressed as follows:
V2O5xLi+xe-LixV2O5 (1)
where x is the mole fraction of inserted Li+ ions.

The specific capacitance of these films can be derived from the CV curves by following equation:

CS = (2)
where I represent the applied working current;

is the potential difference;
w is the total electrode area;
is potential window;
is scan rate [15].
The film deposited on Ni substrates exhibited specific capacitance of 95.3, 205.9 mF cm -2, and 241
mF cm-2 at substrate temperature of 200, 250, and 300 C respectively. The process of intercalation
and de-intercalation of the Li+ ions into V2O5 nano structured frames increased with increase the
substrate temperature for prepared films , due to the presence of large number of ( 0 0 1) orientation
planes and good crystallinity offered by the electrode. The galvanostatic charge-discharge (GCD)
studies are also used to study the specific capacitance of V2O5 thin films. The CD profiles collected
in 1M LiSO4 of electrolyte at current density of 1 mAcm-2 as shown in figure 5. These nonlinear
charge/discharge curves indicate a significant contribution of pseudo capacitance from vanadium
oxides. The potential drop is decreases for the films prepared at 300C due to the presence of large
143
number of ( 0 0 1) orientation planes and good crystallinity offered by the electrode. These results
reveals that the films prepared at 300C have much lower internal resistance, which is of great interest
in fabricating higher specific capacitance super capacitors. The specific capacitance of the prepared
films can be derived based on the following equation:

C = (3)
where I represent the applied working current;

dV is the potential range,
dt is the discharging time
A represents active area of the electrode material.
The specific capacitance of these films obtained at current density of 1 mAcm-2 are 388, 244 mFcm - 2
and 730 mFcm-2 at substrate temperature of 200,250 and 300 C. The electrochemical impedance
spectroscopic (EIS) measurements of V2O5 thin films are studied in the frequency range from 1 Hz
to 0.1 M Hz in Li2SO4 solution, and corresponding Nyquist plots are shown in figure 6. The Nyquist
plots of the prepared films presented semicircle in high frequency region from electrochemical
reaction impedance of the electrodes. The charge transfer resistance of the films were 8.4, 8.1, 7.5
ohms acquired from the Nyquist plots of the prepared sample at substrate temperature of 200, 250
and 300 C. The series resistance assessed from the Nyquist plot is found to be decreased as the
substrate temperature increases. Hence, the electrochemical impedance analysis revealed the films
deposited at 300 0C have a lower charge transfer resistance, resulting better discharge capacity.
Fig. 4. CV curves of the prepared V2O5 thin films at different substrate temperature

144
Fig. 5. CP curves of the prepared V2O5 thin films at different substrate temperature.
Fig. 6. Nyquist plots of the prepared V2O5 thin films at different substrate temperature.
Summary. The nano structured vanadium pentoxide thin films have been deposited onto Ni
substrates at maintained 1 104 m.bar of base pressure with different substrate temperature by
thermal evaporation technique. The XRD, Raman Spectroscopy and SEM analysis revealed the films
prepared at 300 C have orthorhombic structure, increased crystallainity and increased average grain
size with increase the substrate temperature. The electrochemical studies such as cyclic voltammetry,
Galvanostatic Charge-Discharge, electrochemical impedance spectroscopic revealed the
electrochemical performance of the prepared electrode films increased with increase the substrate
temperature. Among all conditions the optimized was 300 C substrate temperature, which have (0 0
1) orientation peak of orthorhombic structure, average crystallite size is 25 nm from XRD, average
grain size is 148 nm from SEM. And also the charge transfer resistance is 7.5 ohms and resulting
better specific capacitance is 730 mFcm-2 at 1 mA cm-2 of current density.
References
[1] B. Saravanakumar, Kamatchi K. Purushothaman and G.Muralidharan, Interconnected V2O5
Nanoporous Network for High-Performance Supercapacitors, ACS Appl. Mater. Interfaces 2012, 4
(9), pp 44844490, DOI 10.1021/am301162p.

145
[2] X.J. Wang, H.D. Li, Y.J. Fei, X. Wang, Y.Y. Xiong, Y.X. Nie, K.A. Feng, XRD and Raman study
of vanadium oxide thin films deposited on fused silica substrates by RF magnetron sputtering,
Applied surface science, Vol. 177 (2001), 8-14, DOI 10.1016/s0169-4332(00)00918-1.
[3] Wang YL, Li MC, Chen XK, Wu G, Yang JP, Wang R, Zhao LC, Removal of Metal Catalyst in
Multi-Walled Carbon Nanotubes with Combination of Air and Hydrogen Annealing Followed by
Acid Treatment, Journal of Nanoscience and Nanotechnology, Vol. 8, Num.r 5, 2008, pp. 5807-
5812(6), DOI 10.1166/jnn.2008.232.
[4] R.T. Rajendra Kumar, B. Karunagaran, V. Senthil Kumar, Y.L. Jeyachandran,D. Mangalaraj,
Sa.K. Narayandass, Structural properties of V2O5 thin films prepared by vacuum evaporation,
Materials Science in Semiconductor Processing; Vol. 6, Iss. 56, OctoberDecember 2003, 543-546,
DOI 10.1016/j.mssp.2003.08.017.
[5] Ramana. C, Hussain.O, Naidu. B, Reddy. P. Spectroscopic characterization of electron-beam
evaporated V2O5 thin films, Thin Solid Films 1997, Vol. 305, 219-226 DOI 10.1016/S0040-
6090(97)00141-7.
[6] Davide Barreca , Lidia Armelao , Federico Caccavale , Vito Di Noto , Andrea Gregori, Gian
Andrea Rizzi , and Eugenio Tondello, Chem. Mater. 2000, Vol. 12, 98-103.
[7] Arunabha Ghosh, Eun Ju Ra, Meihua Jin, Hae-Kyung Jeong, Tae Hyung Kim, Chandan Biswas
and Young Hee Lee, High Pseudocapacitance from Ultrathin V2O5 Films Electrodeposited on Self-
Standing Carbon-Nanofiber Paper, Advanced functional Materials (2001), Volume 21, Issue 13, July
8, 25412547, DOI 10.1002/adfm.201002603.
[8] Katsunori Takahashi , Steven J. Limmer , Ying Wang, Guozhong Cao, Synthesis and
Electrochemical Properties of Single-Crystal V2O5 Nanorod Arrays by Template-Based
Electrodeposition, J. Phys. Chem. B, 2004, 108 (28), pp. 97959800.
[9] Q.T. Qu, L.L. Liu, Y.P. Wu, R. Holze, Electrochemical behaviour of V2O50.6H2O nanoribbons
in neutral aqueous electrolyte solution, Electrochimica Acta, Vol. 96, 2013, 8-12, DOI
10.1016/j.electacta.2013.02.078..
[10] Z. Ghorannevis, M. T. Hosseinnejad, M. Habibi, P. Golmahdi, Effect of substrate temperature
on structural, morphological and optical properties of deposited Al/ZnO films, J Theor. Appl. Phys.
(2015) 9:33-38, DOI 10.1007/s40094-014-0157-1
[11] C. V. Ramana, R. J. Smith, O. M. Hussain, M. Massotand, C. M. Julien, Surface analysis of
pulsed laser-deposited V2O5 thin films and their lithium intercalated products studied by Raman
spectroscopy, Surf. Interface Anal. 2005, 406411, DOI 10.1002/sia.2018.
[12] Bo Zhou, Deyan He, Raman spectrum of vanadium pentoxide from density-functional
perturbation theory, J. Raman Spectrosc. 2008; 39: 14751481.
[13] Se-Hee Lee, Hyeonsik M. Cheong, Maeng Je Seong, Ping Liu, C. Edwin Tracy, Angelo
Mascarenhas, J. Roland Pitts and Satyen K. Deb, Microstructure study of amorphous vanadium oxide
thin films using Raman spectroscopy, J. Appl. Phys., Vol. 92, No. 4, 15 August 2002.
[14] J.Y. Chou, J.L. Lensch-Falk, E.R. Hemesath, L.J. Lauhon, Vanadium oxide nanowire phase and
orientation analysed by Raman spectroscopy, J. Appl. Phys. 105, 2009.

146
Effect of Substrate Temperature on Microstructural and Optical Properties of

Nanostructured ZnTe Thin Films Using Electron Beam Evaporation Technique
26
M. Shobana1, N. Madhusudhana Rao1,a, S. Kaleemulla1, M. Rigana Begam2, M. Kuppan1
1 Centre for Crystal Growth, Thin Films Research Laboratory, School of Advanced Sciences, VIT University, Vellore,
Tamil Nadu, India
2 Department of Science and Humanities, Indira Gandhi College of Engineering and Technology for Women,
Chengalpattu, Kanchipuram, Tamil Nadu, India
a drnmrao@gmail.com
Keywords: thin films, physical vapour deposition, II-VI semiconductors, Zinctelluride/ZnTe, substrate temperature,
optoelectronic devices.
ABSTRACT. Single phase ZnTe nanostructured thin films were deposited on glass substrates using electron beam
evaporation at various substrate temperatures (Ts like 423 K, 523 K and 623 K) under high vacuum of 2 x 10 -4 Pa. Effect
of substrate temperature Ts on the structural, optical and morphological properties of prepared films have been
investigated using powder X-ray diffractometer, UV-Vis-NIR spectroscopy, Scanning Electron Microscopy (SEM) and
Atomic Force Microscopy (AFM) analysis. Powder X-ray diffraction (PXRD) studies revealed that all the coated samples
crystallized well in polycrystalline zinc blende structure along preferential <111> orientation. Optical transmission spectra
exhibited an interference fringes, which confirms the formation of smooth and uniform films. SEM micrograph showed
that the particles were spherical in shape with average size of 25nm. AFM images proved that densely packed columnar
grain growth with evidence of nanostructure topography. Further the estimated lattice constant (a), average grain size (D)
increased and average lattice strain () decreased and also optical band gap energy (Eg) decreased with increase of Ts.
Introduction. Currently, there has been substantial interest among scientific research community in
the field of semiconductor device thin film technology i.e. (i) to develop high-performance functional
materials by different existed/novel techniques and (ii) Good quality/robust adhesion for a long
time/uniform layer, defect free, homogeneous and stoichiometric with nanosized structures. One of
the most important factor that in the growth of thin film is, optimisation of deposition parameters for
attaining controlled size as well as shape of grains. ZnTe belongs to a class of AII-BVI inorganic
chalcogenide semiconductor with direct transition wide optical band gap (2.26 eV at room
temperature, 547 nm) and native P-type electrical conduction due to Te excess and Zn vacancy
nonstoichiometry, which is also called as Self-Compensation effect [1], [2], [3]. Due to these unique
properties, ZnTe is an exemplary candidate for optoelectronic device application, Also an imperative
source for stable window and contacting material in CdTe, CdS, HgCdTe, etc. based multi-layer solar
cells to achieve higher efficiency [4], [5], [6], [7]. Till date, numerous deposition processes: thermal
evaporation [8], pulsed laser deposition [9], rf magnetron sputtering [10], closed space sublimation
and electron beam evaporation [11], [12] etc. had been employed by many other researchers for the
growth of ZnTe thin films but each of these techniques has its own merits and demerits. Electron
beam evaporation (EBE) is a conventional, well known, most suitable and cost-effective
comparatively with other physical vapour deposition (PVD) methods. To the best of authors
knowledge very few studies have reported on thickness dependence [13]-[14] and substrate
temperature dependence [15] ZnTe thin films by EBE method. In the present work, an attempt has
been made to investigate the influence of Ts on major physical properties of E-beam evaporated thin
26

147
films under identical deposition conditions. The nucleation growth kinetics and surface morphology
of films can be affected by thermodynamic conditions mainly substrate/growth temperature,
annealing temperature, deposition rate and also the thickness of a film.
Experimental
Synthesis. Device-grade ZnTe films have been grown on a microscopic glass substrates size of 75x
22x1.35mm3 using EBE method (Instrument: Hind Hivac 12A4D coating unit) by varying growth
temperature (Ts) viz 423 K, 523 K and 623 K. Commercial ZnTe powder 150mg (99.99% purity,
Sigma-Aldrich Chemicals Company, USA) weighed accurately, taken in a graphite crucible and used
as a source material. Prior to deposition: (a) the substrates were chemically well-cleaned followed by
ultrasonic technique and then dried in hot air oven at 100C (b) The chamber (12 inches) thoroughly
cleaned to attain high vacuum and avoid impurity (c) Substrates were fixed with a resistive heater
assembly and were mounted over a vertical platform above the evaporation target. The Thickness of
the films was found using a digital quartz crystal thickness monitor (Model: "Hind Hivac" DTM-101)
attachment during the deposition. After deposition, the films were allowed cool slowly to room
temperature. The films obtained were uniform, pinhole free and had good adhesion to the surface of
the substrate. ZnTe films were grown by optimizing other deposition parameters.
Characterization. Structural analysis was carried out using P-XRD on a high-resolution X-ray
Bruker D8 Advance diffractometer having CuK1 (=1.5406) X-ray source at the scan rate of 4C
per min. Optical transmission spectra of the all films were recorded using UV-Vis-NIR JASCO V-
670 double beam spectrophotometer in the wavelength range of 200nm to 2500nm. Microstructural
analysis were performed with HR-SEM (Model: FEI Quanta 200 FEG) and AFM (Model: Nanosurf
Easyscan 2) in static force operating mode with silicon tip CONTOR cantilever type. All these
measurements reported in our research were taken at room temperature.
Structural study. From Fig. 1 (a) powder X-ray diffraction patterns, all the films were identified to
be single-phase polycrystalline with zinc blende (space group F 43m No.216) structure. It can be seen
that preferential diffraction peaks at 2 values 25.27, 41.86 and 49.48 which corresponds to <111>,
<220> and <311> planes respectively are in good agreement with the standard JCPDS file no.# 15-
0746. In the case of elevated temperature, slight shift towards higher angle in diffraction peaks, the
intensity of predominant <111> orientation gradually decreased simultaneously <220> and <311>
orientations increased (clear proof for <111> plane from Fig. 1 (b)). Scherers and Williamson- Hall
formulae were employed to calculate the average grain size (D) and lattice strain (). From Table 1,
it can be manifested that lattice constant (a) and average crystallite size (D) increased whereas lattice
strain () decreased with increase of substrate temperature Ts.
Optical study. Fig.2 (a) shows optical transmission spectra of all the samples as a function of
wavelength occur an interference fringes in the Vis-NIR range which suggested that homogeneity,
uniform thickness and surface smoothness of thin films. It can be found that sharp fall of transmission
at absorption band edge that consider the good crystallinity of deposited films and also transmittance
percentage increaseses concurrently blue shift in absorption wavelength. Fig.2 (b) depicts that Taucs
plot of (h)2 versus energy (Eg=h) of incident photon radiation. The optical band gap energy can
be evaluated by extrapolating linear portion of the respective Taucs plot curve to =0 (x-axis). As
Ts increases the band gap decreases which is attributed to well-known quantum confinement effect.
The absorption coefficient () can be calculated using the below equation:
1
- ln(T )
t (1)

148
where t and T film thickness (m) and transmittance (a.u) respectively.

The value of the band gap (Eg) are given in Table 1.
a)
b)
Fig. 1. (a) P-XRD patterns of ZnTe thin films deposited at various Ts, (b) Enlarged P-XRD patterns
of ZnTe thin films in the 2 range of 24.8-25.6 for <111> reflection.

149
a)
b)
Fig. 2. a) Transmission spectra of ZnTe thin films deposited at different Ts, b) (h)2 Vs h plots of
ZnTe films deposited at different T.
Table 1. Lattice parameter, grain size, micro-strain and energy band gap for ZnTe thin films
deposited at different Ts.
Lattice Constant a () Average Mean Lattice Band Gap
Ts (K) Grain Size D Strain Energy Eg
Standard Calculated (nm) (eV)
()
423 K 6.102 6.103 12 0.009 2.24
523 K 6.105 13 0.008 2.20
623 K 6.113 14 0.007 2.18
Microstructural study Surface morphology/topography. Surface morphology of as-grown ZnTe

thin film sample was shown in Fig. 3 (a) with magnification of 100000x. It can be obviously seen
that uniform, spherical shape grains are distributed over 500nm scale scanning surface with mean
particle size of 25.6nm. Fig.3 (b) & (c) illustrates two and three dimensional AFM images of ZnTe
thin films deposited at 423 K. It is confirmed that compact, nearly porous-free and columnar growth
pattern. These obtained results do agree the formation of nanocrystalline ZnTe thin films.

150
a) b) c)
Fig. 3. (a) SEM micrograph, (b) 2D AFM, (c) 3D AFM images of ZnTe thin films at Ts- 423 K.
Summary. Good quality nonostructured ZnTe thin films were deposited by EBE method at different
substrate temperature with fixed optimum growth environment. Above-mentioned results exactly
stated that defect-free, high degree crystallinity with nanoscale size grains harvested in all the
samples. Hence, our research emphasized as Ts is one of the major factors for thin film sample
coating, which tailors microstructural and optical properties.
Acknowledgements. One of the authors (MS) gratefully acknowledges VIT University, Vellore for
providing huge support, financial assistance and excellent research facilities. All authors thank SAIF,
IIT Madras for SEM examination.
References
[1] Olusola, O. I., Madugu, M. L., Abdul-Manaf, N. A., & Dharmadasa, I. M. (2016). Growth and
characterisation of n-and p-type ZnTe thin films for applications in electronic devices. Current
Applied Physics, 16(2), 120-130. DOI 10.1016/j.cap.2015.11.008
[2] Ersching, K., Campos, C. E. M., De Lima, J. C., Grandi, T. A., Souza, S. M., da Silva, D. L., &
Pizani, P. S. (2009). X-ray diffraction, Raman, and photoacoustic studies of ZnTe
nanocrystals. Journal of Applied Physics, 105(12), 123532. DOI 10.1063/1.3155887
[3] Rakhshani, A. E. (2013). Effect of growth temperature, thermal annealing and nitrogen doping on
optoelectronic properties of sputter-deposited ZnTe films. Thin Solid Films, 536, 88-93. DOI
10.1016/j.tsf.2013.03.136
[4] Lovergine, N., Longo, M., Prete, P., Gerardi, C., Calcagnile, L., Cingolani, R., & Mancini, A. M.
(1997). Growth of ZnTe by metalorganic vapor phase epitaxy: Surface adsorption reactions, precursor
stoichiometry effects, and optical studies. Journal of applied physics, 81(2), 685-692. DOI
10.1063/1.364208
[5] Fauzi, F., Diso, D. G., Echendu, O. K., Patel, V., Purandare, Y., Burton, R., & Dharmadasa, I. M.
(2013). Development of ZnTe layers using an electrochemical technique for applications in thin-film
solar cells. Semiconductor Science and Technology, 28(4), 045005. DOI 10.1088/0268-
1242/28/4/045005
[6] Shan, C. X., Fan, X. W., Zhang, J. Y., Zhang, Z. Z., Wang, X. H., Ma, J. G., Zhong, G. Z. (2002).
Structural and luminescent properties of ZnTe film grown on silicon by metalorganic chemical vapour
deposition. Journal of Vacuum Science & Technology A, 20(6), 1886-1890. DOI 10.1116/1.1507344
[7] Chang, J. H., Takai, T., Godo, K., Song, J. S., Koo, B. H., Hanada, T., & Yao, T. (2002). ZnTe
Based LightEmittingDiodes Grown on ZnTe Substrates by Molecular Beam Epitaxy. Physica status
solidi (b), 229(2), 995-999. DOI 10.1002/1521-3951
151
[8] Bacaksiz, E., Aksu, S., Ozer, N., Tomakin, M., & zelik, A. (2009). The influence of substrate
temperature on the morphology, optical and electrical properties of thermal-evaporated ZnTe Thin
Films. Applied Surface Science, 256(5), 1566-1572. DOI 10.1016/j.apsusc.2009.09.023
[9] Xu, M., Gao, K., Wu, J., Cai, H., Yuan, Y., Prucnal, S., ... & Zhou, S. (2016). Polycrystalline
ZnTe thin film on silicon synthesized by pulsed laser deposition and subsequent pulsed laser
melting. Materials Research Express, 3(3), 036403. DOI 10.1088/2053-1591/3/3/036403
[10] Bellakhder, H., Outzourhit, A., & Ameziane, E. L. (2001). Study of ZnTe thin films deposited
by rf sputtering. Thin Solid Films, 382(1), 30-33. DOI 10.1016/S0040-6090(00)01697-7
[11] Farooq, M. U., Khan, M., Faraz, A., Maqsood, A., Ahmad, W., Li, L. (2014). Comparative study
of ZnTe thin films prepared using close space sublimation (CSS) and electron beam evaporation
(EBE) thin film fabrication techniques for optoelectronic applications. Materials Technology, 29(1),
29-35. DOI 10.1179/1753555713Y.0000000101
[12] Zia, R., Saleemi, F., Riaz, M., & Nassem, S. (2016). Structural and Optoelectrical Properties of
ZnTe Thin Films Prepared by E-Beam Evaporation. Journal of Electronic Materials, 45(10), 4762-
4768. DOI 10.1007/s11664-016-4761-5
[13] Salem, A. M., Dahy, T. M., & El-Gendy, Y. A. (2008). Thickness dependence of optical
parameters for ZnTe thin films deposited by electron beam gun evaporation technique. Physica B:
Condensed Matter, 403(18), 3027-3033. DOI 10.1016/j.physb.2008.03.005
[14] Balu, A. R., Nagarethinam, V. S., Thayumanavan, A., Murali, K. R., Sanjeeviraja, C., &
Jayachandran, M. (2010). Effect of thickness on the microstructural, optoelectronic and
morphological properties of electron beam evaporated ZnTe films. Journal of Alloys and
Compounds, 502(2), 434-438. DOI 10.1016/j.jallcom.2010.04.191
[15] Ahamed, M. S. B., Nagarethinam, V. S., Thayumanavan, A., Murali, K. R., Sanjeeviraja, C., &
Jayachandran, M. (2010). Structural, optical, electrical and morphological properties of ZnTe films
deposited by electron beam evaporation. Journal of Materials Science: Materials in
Electronics, 21(12), 1229-1234. DOI 10.1007/s10854-009-0051-9

152
Textural Enhancement of Hydrothermally Grown TiO2 Nanoparticles and

Bilayer-Nanorods for Better Optical Transport
27
J. Sahaya Selva Mary1, V. Chandrakala, Neena Bachan1, P. Naveen Kumar1, K. Pugazhendhi1,

J. Merline Shyla1,a
1 Department of Physics, Energy NanoTechnology Centre (ENTeC), Loyola Institute of Frontier Energy (LIFE),
Loyola College, Chennai, India
a jmshyla@gmail.com
Keywords: bilayer-nanorods, nanoparticles, hydrothermal, photoconductivity.
ABSTRACT. TiO2 nanostructures have been studied as photoanode materials via improvement of their textural and
electronic properties for Dye Sensitized Solar Cells (DSSCs). They have exhibited appreciable photovoltaic performance
owing to their excellent electron transport and high specific surface area. We report herein, the comparative analysis of
TiO2 nanoparticles (TPs) and Bilayer-TiO2 nanorods (B-TRs) prepared by hydrothermal method at 200 C for 12 h and
120 C for 12 h respectively using an autoclave unit. The as-synthesized samples were characterized using High
Resolution Scanning Electron Microscopy (HR-SEM), Energy Dispersive X-ray (EDAX), Fourier Transform Infrared
(FT-IR) spectroscopy, Ultra Violet -Visible Spectroscopy (UV-Vis) and Photoconductivity techniques. The
morphological results showed that the TPs are spherical in shape with diameter in the range of 18-29 nm and the B-TRs
revealed the formation of hierarchical nanostructures on top of aligned nanorod trunks possessing porous nature and
dimensions of ~ 262 nm diameter and ~ 660 nm length. FTIR spectra confirmed the presence of Ti-O-Ti vibrations in
both the cases. The optical properties of TPs and B-TRs showed a strong absorption edge in the UV region.
Photoconductivity techniques revealed the ohmic nature of the samples with a linear increase in both dark and
photocurrent with corresponding increase in the applied field. However, in B-TRs there is a significant increase in
photocurrent than TPs which suggests a strong capability of absorbing light. Thus we can conclude that the bilayer
nanostructure with better photoresponse, can be used as a promising photo anode material for DSSCs.
Introduction. In the past decade, extensive research has been done in the development of technology
for efficient utilizing of renewable energy. Among them, photovoltaic is considered as the most
promising technology due to its availability, sustainability and reliability [1-2]. Although
photovoltaic devices built on silicon or compound semiconductors have achieved high efficiency for
practical use, they still require major breakthrough to meet the long-term goal of very-low cost
production [3]. Among the various semiconducting metal oxides, TiO2 has attracted considerable
attention in the field of energy conversion and environmental protection [4] due to its cost
effectiveness, non-toxic nature, accessibility, stability [5] and unique photoelectric conversion
capability [6]. Functional properties of TiO2 are influenced by many factors such as crystallinity,
particle size, surface area, and synthesis techniques [7]. TiO2 nanostructures have been studied as
photoanode materials for DSSCs and they have exhibited appreciable photovoltaic performance
owing to their excellent electron transport and high specific surface area [8]. Synthesis methods such
as hydrothermal, solvothermal, sol-gel, direct oxidation, chemical vapour deposition (CVD), electro
deposition, and microwave methods have been used for the synthesis of TiO2 nanostructures [9].
Among these, hydrothermal technique is the most important and promising fabrication method for
nanoscale materials [10]. In this study, a comparative analysis of TiO2 nanostructures (TPs and B-
TRs), prepared by hydrothermal method using Teflon-lined stainless steel autoclave was investigated.
27

153
Experimental Procedure. Synthesis of TPs. The TiO2 nanoparticles were obtained by the
hydrothermal reaction of Titanium (IV) butoxide, ethanol, acetic acid, and deionized water in
autoclave at 200 C for 12h. The obtained sample was dried at 100 C for 2h and finally calcined at
550 C for 1.30h.
Synthesis of B-TRs. Titanium (IV) butoxide (TBOT) was mixed with deionized water and
hydrochloric acid. The mixture solution was stirred well for 30 mins at room temperature. Then the
cleaned FTO substrates were placed into an autoclave filled with the solution and kept inside the
furnace. The hydrothermal treatment was done at 120C for 12h. The obtained product was washed
thoroughly several times with deionized water. The resultant samples were calcined at 450 C for 2h.
Characterization Techniques. The morphology and microstructure of the samples were examined by
a High Resolution Scanning Electron Microscope (HITACHI S-4800) with Energy Dispersive X-ray
spectrometry (EDX). Fourier transformed infrared (FTIR) spectra of the samples were recorded using
a Perkin Elmer R1 spectrometer ranging from 4000 to 400 cm-1, respectively. The optical absorption
properties were measured in the range 200-600 nm using CARY 5E UVVisNIR spectrophotometer.
The field dependent dark and photo conductivity tests were recorded by using a Kiethley
Picoammeter 6485 and the constant voltage source.
Textural Properties. The surface morphology was analyzed using HR-SEM. Fig.1a show the HR-
SEM image of the as-synthesized TPs. The TPs exhibit good spherical morphology [11] with diameter
ranging from 18-29 nm. HR-SEM image Fig. 1b which clearly shows the arrangement of vertically
oriented dense B-TRs, with flower bunch at the top of nanorods surface [12]. Diameters of the
nanorods are found to be ~262 nm and the length around 660 nm. It is observed that the nanorods
were formed in a hierarchical order and are highly porous in nature. The morphology and porous
nature of the TiO2 layer could possess high internal surface area for efficient dye adsorption which
plays an important role in the improved photoelectric conversion efficiency of DSSCs [6]. Hence we
could conclude that for enhancing electron transport in DSSCs it is important to supplant the straight
nanorods or nanoparticles by bilayer nanorods which give an immediate conduction pathway for fast
gathering of photogenerated electrons [13] thereby reducing charge recombination [14].
Fig. 1. HR-SEM image (a) TPs and (b) B-TRs.
Compositional analysis. Energy Dispersive X-ray spectrometry (EDX) analysis of B-TRs and TPs
shows the presence of Titanium and Oxygen elements as shown in Fig. 2 a)-b). Sn and F elements
were originated from FTO substrate Fig. 2 (b) [15].

154
Fig. 2. EDAX image of (a) TPs and (b) B-TRs.
Spectroscopic Analysis. Fig. 3 a)-b) represent the Fourier Transform Infrared (FTIR) spectrum of
B-TRs and TPs. The broad spectrum shows the asymmetrical and symmetrical stretching vibration
of hydroxyl group (-OH) at 3365 cm-1 (33503450 cm-1) and 1625 cm-1 (16201630 cm-1) [16]. The
band centred at around 450, 563, 645, 704, 761 cm-1 (450800 cm-1) is characteristic of a Ti-O
stretching and TiOTi distortion vibration [17].
Fig. 3. FTIR image of (a) TPs and (b) B-TRs.
Optical analysis. The optical properties of TPs and B-TRs were studied by UVVis diffuse
reflectance spectroscopy, which is shown in Fig. 4 a)-b).The absorption spectra of the TPs and B-TRs
show an enhanced absorption in the UV region (353 nm and 370 nm). When compared to TPs a slight
blue shift is observed in the case of B-TRs, which could be due to the hierarchical nanostructure [18].

155
Fig. 4. UVVis diffuse absorption spectra image of (a) TPs and (b) B-TRs.
The optical band gap of the sample was calculated by Kubelka-Munk function [F(R) h]2 versus
photon energy (h) as shown in Fig. 5 a)-b) [28]. From the optical absorption edge, the band gap of
TPs and B-TRs nanomaterials have been found to be 2.4 eV and 3.3 eV respectively suggesting an
enhanced surface area in the latter.
Fig. 5. K-M plot image of (a) TPs and (b) B-TRs.
Electro-optical analysis. The field-dependent dark and photoconductive behaviour of TPs and B-
TRs are depicted in Fig. 6 a)-b). The plots indicate a linear increase of current in the dark and visible
light-illuminated TPs and B-TRs samples with increase in the applied field [19]. It is observed that
the photocurrent (IP) is significantly greater than the dark current (ID) in B-TRs. This is due to the
hierarchical structure of B-TRs, which has a strong capability of absorbing light in the near visible
region [20]. Thus, we could conclude from the results that B-TRs, which revealed better photo
response than TPs qualify as appropriate candidates for photovoltaic applications.

156
Fig. 6. Electro-optical image of (a) TPs and (b) B-TRs.
Summary. Semiconductor TiO2 with different nanostructures, such as bilayer nanorods and
nanoparticles were synthesized via hydrothermal process. The morphological results showed that the
TPs are spherical in shape and the B-TRs display bilayer nanorods formation with flower bunch on
the top of aligned nanorod trunks. The as-synthesized B-TRs which were composed of longer
nanorods could effectively increase electron recombination lifetime and direct electron transport rate
than that of TPs. FTIR spectra confirmed the presence of Ti-O-Ti vibrations in both the cases. The
optical properties of TPs and B-TRs showed a strong absorption in the UV region. The band gap
calculated from KM-plot was found to be 3.3 eV for B-TRs and 2.4 eV for TPs. The field-dependent
dark and photoconductivity behaviour of B-TRs and TPs are observed, that the photocurrent (IP) is
found to be greater than the dark current (ID). But in B-TRs there is a significant increase in
photocurrent than TPs suggesting strong light absorbing capability consequential to the increase in
surface area. Thus we can conclude the bilayer nanostructure with better photo response is a
promising photo anode material for DSSCs.
Acknowledgement. The funding extended by the Loyola College - Times of India Research Grants
(6LCTOI1421F002) towards this work is gratefully acknowledged.
References
[1] Yaoguang Rong, Zhiliang Ku, Anyi Mei, Tongfa Liu, Mi Xu, Songguk Ko, Xiong Li, Hongwei
Han, Hole-Conductor-Free Mesoscopic TiO2/CH3NH3PbI3 Heterojunction Solar Cells Based on
Anatase Nanosheets and Carbon Counter Electrodes, Journal of Physical Chemistry Letters, 2014, 5,
21602164, DOI 10.1021/jz500833z.
[2] M. Malekshahi Byranvand, A. Nemati Kharat, M. H. Bazargan, Titania Nanostructures for Dye-
sensitized Solar Cells, Nano-Micro Letters, 2012, 4 (4), 253-266, DOI 10.3786/nml.v4i4.p253-266.
[3] Qifeng Zhang, Christopher S. Dandeneau, Xiaoyuan Zhou, and Guozhong Cao, ZnO
Nanostructures for Dye-Sensitized Solar Cells, Advanced Materials, 2009, 21, 40874108, DOI
10.1002/adma.200803827.
[4] Yang Lu, Guozhong Wang, Haimin Zhang,Yunxia Zhang, Shenghong Kang, Huijun Zhao,
Photoelectrochemical manifestation of intrinsic photoelectron transport properties of vertically
aligned {001} faceted single crystal TiO2 nanosheet films RSC Adv., 2015, 5, 55438- 55444, DOI
10.1039/C5RA08571C.
157
[5] Guolei Xiang, Di Wu, Jie He and Xun Wang, Chem. Commun., 2011, 47, 1145611458, DOI
10.1039/C1CC90151F.
[6] Xu Song, Yun Hu, Mengmeng Zheng, Chaohai Wei, Applied Catalysis B: Environmental, 2016,
182, 587597.
[7] Muneer M. Ba-Abbad, Abdul Amir H. Kadhum, Abu Bakar Mohamad, Mohd S. Takriff,
Kamaruzzaman Sopian, Synthesis and catalytic activity of TiO 2 nanoparticles for photochemical
oxidation of concentrated chlorophenols under direct solar radiation, International Journal of
Electrochemical Science, 2012, 7, 4871 4888.
[8] Qifeng Zhang, Guozhong Cao, Nanostructured photoelectrodes for dye-sensitized solar cells,
Nano Today, 2011, 6, 91109, DOI 10.1016/j.nantod.2010.12.007
[9] J.Sahaya Selva Mary, P. Princy, J.Annai Joseph Steffy, P. Naveen Kumar, Neena Bachan and J.
Merline Shyla, Morphological impact of TIO2 nanostructures on transport properties, International
Journal of Technical Research and Applications, 2016, 37, 60-64, e-ISSN: 2320-8163.
[10] Akila Yuvapragasam, Muthukumarasamy.N, Agilan.S, Dhayalan Velauthapillai, Senthil.T.S,
Senthilarasu Sundaram, Natural dye sensitized TiO2 nanorods assembly of broccoli shape based solar
cells, Journal of Photochemistry and Photobiology. B, 2015, DOI 10.1016/j.jphotobiol.2015.04.017.
[11] F.Kamil, K.A. Hubiter, T.K. Abed, A.A. Al-Amiery, Synthesis of Aluminum and Titanium
Oxides Nanoparticles via Sol-Gel Method: Optimization for the Minimum Size Journal of
Nanoscience and Technology, 2016, 2(1), 37-39, ISSN: 2455-0191.
[12] Bin Liu and Eray S. Aydi, Growth of Oriented Single-Crystalline Rutile TiO2 Nanorods on
Transparent Conducting Substrates for Dye-Sensitized Solar Cells, Journal of American Chemical
Society, 2009, 131, 39853990, DOI 10.1021/ja8078972.
[13] Hao Lu, Kaimo Deng, Zhiwei Shi, Qiong Liu, Guobin Zhu, Hongtao Fan and Liang Li, Novel
ZnO microflowers on nanorod arrays: local dissolution-driven growth and enhanced light harvesting
in dye-sensitized solar cells, Nanoscale Research Letters, 2014, 9, 183, DOI 10.1186/1556-276X-9-
183.
[14] Xudong Wang, Zhaodong Li, Jian Shi, and Yanhao Yu, One-Dimensional Titanium Dioxide
Nanomaterials: Nanowires, Nanorods, and Nanobelts, Chemical Reviews, 2014, 114 (19), pp 9346
9384, DOI 10.1021/cr400633s.
[15] Quanjun Li, Bingbing Liu, Lin Wang, Dongmei Li, Ran Liu, Bo Zou, Tian Cui, Guangtian Zou,
Pressure-Induced Amorphization and Polyamorphism in One-Dimensional Single-Crystal TiO2
Nanomaterials, J. Phys. Chem. Lett., 2010, 1, 309314, DOI 10.1021/jz9001828.
[16] G. M. Herrera-Sandoval, D. B. Baez-Angarita, S. N. Correa-Torres, O. M. Primera-Pedrozo, S.
P. Hernndez-Rivera, Novel EPS/TiO2 Nanocomposite Prepared from Recycled Polystyrene,
Materials Sciences and Applications, 2013, 4 (3), DOI 10.4236/msa.2013.43021
[17] Xu Song, Yun Hu, Mengmeng Zheng, Chaohai Wei, Solvent-free in situ synthesis of g-C3N4/{0
0 1}TiO2 composite with enhanced UV- and visible-light photocatalytic activity for NO oxidation,
Applied Catalysis B: Environmental, 2016, 182 587597, DOI 10.1016/j.apcatb.2015.10.007.
[18] Wei Li, Cheng Li, Bo Chen, Xiuling Jiao, Dairong Chenab, Facile synthesis of sheet-like N
TiO2/g-C3N4 heterojunctions with highly enhanced and stable visible-light photocatalytic activities,
RSC Adv., 2015, 5, 34281, DOI 10.1039/C5RA04100G.
[19] Tenzin Tenkyong, Neena Bachan, J. Raja, P. Naveen Kumar, J. Merline Shyla, Investigation of
sol-gel processed CuO/SiO2 nanocomposite as a potential photoanode material, Materials Science-
Poland, 2015, 33 (4), 826-834, DOI 10.1515/msp-2015-0097.
[20] J. Annai Joseph Steffy, P. Naveen Kumar, J. Sahaya Selva Mary, W. Jothi Jeyarani, Tenzin
Tenkyong, K. Pugazhendhi, V. Chandrakala and J. Merline Shyla, Hierarchical rutile TiO2
158
heterostructures and plasmon impregnated TiO2/SnO2-Ag bilayer nanocomposites as proficient

photoanode systems, Surface & Coatings Technology, 2016, Vol. 310, 113121 DOI
10.1016/j.surfcoat.2016.12.071.

159
Novel and Proficient Organic-Inorganic Lead Bromide Perovskite for Solid-

State Solar Cells
28
B. Praveen1, Tenzin Tenkyong1, W. Jothi Jeyarani1, J. Sahaya Selva Mary1, V.Chandrakala1,

Neena Bachan1, J. Merline Shyla1,a
1 Department of Physics, Energy NanoTechnology Centre (ENTeC), Loyola Institute of Frontier Energy (LIFE),
Loyola College, Chennai, India
a jmshyla@gmail.com
Keywords: perovskite, spin coating, photoconductivity, solid-state solar cells.
ABSTRACT. Efficient solar cells based on organic/inorganic lead halide perovskite absorbers which are emerging
recently, assure the renovation in the fields of dye sensitized, organic and thin film solar cells, whose performance are
reported to have exceeded ~ 24% power conversion efficiency. Here, we report the synthesis and fabrication of a novel
and proficient perovskite material prepared by spin coating technique using methyl ammonium lead bromide
(CH3NH3PbBr3). Several characterization techniques such as UltravioletVisible Diffuse Reflectance Spectroscopy (UV-
DRS), Fourier Transformer Infra-Red (FTIR) analysis, X-Ray Diffraction (XRD) analysis and Field dependent dark and
photoconductivity are to be done to analyze the behavior of the perovskite material. The X-ray diffraction pattern reveals
the composition of the materials present in the sample. UV-visible analysis showed an enhanced absorption of the
perovskite material and the photoconductivity techniques revealed the ohmic nature of the samples with a linear increase
in both dark and photocurrent with corresponding increase in the applied field. Thus, these novel and proficient perovskite
materials could overcome the limitations of existing perovskites and lead to higher performance in solid-state solar cells.
Introduction. Efficient and economical energy harvesting by solar cells is a great challenge for the
21st century in the field of key technology for sustainable energy supply. Most recently, inorganic
organic hybrid perovskite materials have been widely fabricated and rapidly demonstrated in the most
promising emerging photovoltaic devices with respect to increase in efficiency[1-2]. Perovskite is a
material with a specific crystal structure named after the Russian mineralogist L. A. Perovski [3].
Inorganic-organic perovskite materials taking the form ABX3 (A = CH3NH3+; B = Pb+; and X=Cl,
I, Br) has with in the past 4 years been used to fabricate high-performance hybrid solar cells, with
reported power conversion efficiencies () >25 % [4]. An organo-lead halide perovskite based solar
cell which requires charge separation (electrons and holes) and less recombination in a light absorbing
material to transmit electricity for photovoltaic applications [5].
In the present work, the CH3NH3PbBr3 perovskite material has been synthesized and fabricated by
using the spin coating method. The perovskite sensitizer has high light absorption coefficient [6], [7]
which would aid in increasing the light harvesting ability of the sensitized material.
Experimental Section
Perovskite (CH3NH3PbBr3) synthesis. The perovskite solution was synthesised as described in the
Fig 1. Initially Methylammonium Bromide (CH3NH3Br) precursor solution was synthesized by
reacting 30 mL of hydrobromide acid and 23 mL of methylamine at 0oC for 2 h with continuous
stirring. The precipitate was recovered by evaporating at 50C for 1 h. The product is washed (using
funnel and filter paper) three times with di-ethyl ether or one time with ethanol and finally dried at
28

160
60C for 24 h. An amount of 0.369g of prepared CH3NH3Br solution was added to 1.157g of PbBr2
(lead bromide) in 2 mL of dimethyl formamide and was kept at 60C for 12 h to obtain the final
solution [8].
Fig. 1. Schematic representation for CH3NH3PbBr3 Perovskite.
Fabrication of perovskite material. The final process involved in the completion of the procedure
is the fabrication of the perovskite solution onto the ITO substrate by spin coating at 3000 rpm for 30
sec. It is followed by drying the perovskite coated substrate by placing it on hot plate at 100 oC for 5
min to complete the fabrication process [9].
Characterization. To investigate the crystallinity of the film, X-Ray Diffraction (XRD) technique
was adopted employing Rigaku (Japan) diffractometer using Cu K as a radiation source at 9 kW
having wavelength of 1.5405 . The optical absorption properties were measured in the range 200-
600 nm using CARY 5E UVVisNIR spectrophotometer. The Fourier Transform Infrared spectra
of the samples were studied using Perkin-Elmer infrared spectrophotometer and the spectrum was
recorded in the wavenumber range of 500 to 4000 cm-1.The field dependent dark and
photoconductivity of the material was done using a Keithley pico-ammeter 6485 and constant voltage
source.
XRD analysis

161
Fig. 2. The XRD diffraction pattern of the CH3NH3PbBr3perovskite.
Figure 2 represents the phase structure of the perovskite materials. The plane values in the XRD
pattern represented by (001), (011), (022), (012), (112), (022), (122), (013) (PDF#01-076-2758) [10]
and intense peaks at 14.96, 21.20, 30.21, 33.84, 37.12, 43.24, 45.96 and 48.64 could be
correlated to the crystalline nature of the perovskite sample [11].
UV-Vis Absorption Spectroscopy.
a)

162
b)
Fig. 3. (a)The UV-Vis absorption spectra and (b) the diffuse reflectance spectra of the
CH3NH3PbBr3 perovskite.
Fig. 4. The Kubelka-Munk plot of CH3NH3PbBr3 perovskite.
Figure 3 (a) showing the absorption spectrum obtained through diffuse reflectance technique
indicated a red shift in the range of 300-600 nm for the CH3NH3PbBr3 perovskite confirming its photo
response in the visible region [10], [13]. Figure 3(b) showed the UVVis diffuse reflectance spectrum
of the CH3NH3PbBr3 perovskite and evidenced its light scattering ability. The enhanced light
scattering could confine the incident light in CH3NH3PbBr3 perovskite and thus play a significant role
in improving the light-harvesting efficiency. Therefore the determined higher photocurrent of
CH3NH3PbBr3 perovskite can be partially attributed to the enhanced light scattering effect in the long-
wavelength region [14].
Figure 4 shows that the Kubelka-Munk (K-M) plot [h-(R)2] vs h (eV) of CH3NH3PbBr3 perovskite
was used to estimate its direct bandgap energy as 2.2 eV [15].
FTIR Analysis. Figure 5 shows the Fourier transform infrared spectrum of theCH3NH3PbBr3
perovskite sample. The normal modes with frequencies between 500 and 4000 cm-1 are exclusively
163
internal vibrations of the MA cations, i.e., torsion, stretching, and bending modes of the C H, NH,
and CN bonds [16].
Fig. 5.The FTIR spectrum of CH3NH3PbBr3 perovskite.
The three strong bands observed at 3483, 2422 and 1679 cm-1 were associated with degeneracy and
symmetric NH3+ stretching vibrations [17]. The characteristic absorption peaks at 1523, 1132 and
619 cm-1 confirmed the CH3, C-C symmetric stretching and (C-Br) strong stretching vibrations
respectively [18].
Field Dependent Dark and Photocurrent
Fig. 6. The field dependent dark and photocurrent ofCH3NH3PbBr3perovskite.
The plots indicated a linear increase of current in both dark and visible light-illuminated conditions
[19]. Further, photocurrent was found to be significantly higher than the dark current thereby
suggesting a strong photoresponse in the CH3NH3PbBr3 perovskite material [20].
164
Summary Perovskite-type CH3NH3PbBr3 compounds possessing cubic and tetragonal crystal

structures were synthesized and characterized with X-ray diffraction parameters. UV-visible analysis
showed an enhanced absorption of the perovskite material and the photoconductivity studies
suggested the ohmic nature of the samples with a linear increase in both dark and photocurrent with
corresponding increase in the applied field. Reectance measurements using integrating sphere
provide the absorption coeffcient of the hybrid structures that assist in calculating the band gap of 2.2
eV. Therefore, high-efficiency CH3NH3PbBr3 perovskite material with several advantages such as
lower cost, long-term stability, and simple structure would lead to improved performance in solar
cells.
Acknowledgement. This work was partially funded by the Loyola College Times of India Research
Grants (6LCTOI1421F002) and the authors acknowledge the same.
References
[1] Seungchan Ryu, Jun Hong Noh, Nam Joong Jeon, Young Chan Kim, Woon Seok Yang, Jang won
Seo, Sang Il Seok, Voltage output of efficient perovskite solar cells with high open-circuit voltage
and fill factor, Energy Environ. Sci., 2614, 7, 2014. DOI 10.1039/c4ee00762j
[2] Takeo Oku, Crystal Structures of CH3NH3PbI3 and Related Perovskite Compounds Used for Solar
Cells, Solar Cells - New Approaches and Reviews, 2015. DOI 10.5772/59284
[3] Yingzhuang Ma, Shufeng Wang, Lingling Zheng, Zelin Lu, Danfei Zhang, Zuqiang Bian,
Chunhui Huang, and Lixin Xiao, Chin. J. Chem. 32, 957963, 2014. DOI 10.1002/cjoc.20140043
[4] Zong-Liang Tseng, Chien-Hung Chiang, and Chun-Guey Wu, Surface Engineering of ZnO Thin
Film for High Efficiency Planar Perovskite Solar Cells, Scientific Reports, 5,13211, 2015. DOI
10.1038/srep13211
[5] Sigalit Aharon, Bat El Cohen and Lioz Etgar, Hybrid Lead Halide Iodide and Lead Halide
Bromide in Efficient Hole Conductor Free Perovskite Solar Cell, J. Phys. Chem. C, Special Issue:
Michael Gratzel Festschrift, 2014, 118 (30), pp 1716017165, DOI 10.1021/jp5023407
[6] Tanja Ivanovska, Zoran Saponjic, Marija Radoicic, Luca Ortolani, Vittorio Morandi, Giampiero
Ruani (2014), Improvement of Dye Solar Cell Efficiency by Photoanode Posttreatment, International
Journal of Photoenergy, Vol. 2014, 1-10, DOI 10.1155/2014/835760
[7] Liu, Bin and Aydil, Eray S., Growth of Oriented Single-Crystalline Rutile TiO2 Nanorods on
Transparent Conducting Substrates for Dye-Sensitized Solar Cells, Journal of the American Chemical
Society, 131, 11, 3985-3990, 2009. DOI 10.1021/ja8078972
[8] Jin Hyuck Heo, Dae Ho Song, and Sang Hyuk Im, Planar CH3NH3PbBr3 Hybrid Solar Cells with
10.4% Power Conversion Efficiency, Fabricated by Controlled Crystallization in the Spin-Coating
Process, Adv. Mater, 2014, Vol. 26, 81798183, DOI 10.1002/adma.201403140
[9] Haralds Abolins, Sarah Brittman, Forrest Bradbury, Erik Garnett, Controlling the Morphology of
CH3NH3PbBr3Perovskite Films on Planar Substrates, Student Undergraduate Research E-journal,
2015.
[10] Eran Edri, Saar Kirmayer, David Cahen, and Gary Hodes, High Open-Circuit Voltage Solar
Cells Based on OrganicInorganic Lead Bromide Perovskite, J. Phys. Chem. Lett. 4, 897902, 2013,
DOI 10.1021/jz400348q
[11] Pengjun Zhao, Jinbao Xu, Xiaoyu Dong, Lei Wang, Wei Ren, Liang Bian, Aimin Chang, Large-
Size CH3NH3PbBr3 Single Crystal: Growth and In Situ Characterization of the Photophysics
Properties, J. Phys. Chem. Lett. 6, 26222628, 2015. DOI 10.1021/acs.jpclett.5b01017
[12] Andrew Barnabas Wong, Minliang Lai, Samuel Wilson Eaton, Yi Yu, Elbert Lin, Letian Dou,
Anthony Fu, Peidong Yang, Growth and Anion Exchange Conversion of CH3NH3PbX3 Nanorod
Arrays for Light-Emitting Diodes, Nano Lett. 15, 55195524, 2015. DOI

165
10.1021/acs.nanolett.5b02082
[13] Jun Hong Noh, Sang Hyuk Im, Jin Hyuck Heo, Tarak N. Mandal, Sang Il Seok, Chemical
Management for Colorful, Efficient, and Stable InorganicOrganic Hybrid Nanostructured Solar
Cells , Nano Lett, DOI 10.1021/nl400349b
[14] Bing Cai, Yedi Xing, Zhou Yang, Wen-Hua Zhang, Jieshan Qiu, High performance hybrid solar
cells sensitized by organolead halide perovskites, Energy & Environmental Science, 2013. DOI
10.1039/c3ee40343b
[15] Ye Yang, Mengjin Yang, Zhen Li, Ryan Crisp, Kai Zhu, Matthew C. Beard, Comparison of
Recombination Dynamics in CH3NH3PbBr3 and CH3NH3PbI3 Perovskite Films: Influence of
Exciton Binding Energy, J. Phys. Chem. Lett. 6, 46884692, 2015. DOI 10.1021/acs.jpclett.5b02290
[16] Miguel A. Prez-Osorio, Rebecca L. Milot, Marina R. Filip, Jay B. Patel, Laura M. Herz,
Michael B. Johnston, Feliciano Giustino, Vibrational Properties of the OrganicInorganic Halide
Perovskite CH3NH3PbI3 from Theory and Experiment: Factor Group Analysis, First-Principles
Calculations, and Low-Temperature Infrared Spectra, J. Phys. Chem. C 119, 2570325718, 2015.
DOI 10.1021/acs.jpcc.5b07432
[17] Tobias Glaser, Christian Mller, Michael Sendner, Christian Krekeler, Octavi Escala Semonin,
Trevor D Hull, Omer Yaffe, Jonathan S. Owen, Wolfgang Kowalsky, Annemarie Pucci, Robert
Lovrincic, Infrared Spectroscopic Study of Vibrational Modes in Methylammonium Lead Halide
Perovskites, J. Phys. Chem. Lett., 2015, 6 (15), pp 29132918. DOI 10.1021/acs.jpclett.5b01309
[18] Aure lien M. A. Leguy, Alejandro R. Gon Anuradha Pallipurath, M. Isabel Alonso, Mariano
Campoy-Quiles, Mark T. Weller, Jenny Nelson, Aron Walshd and Piers R. F. Barnes, Dynamic
disorder, phonon lifetimes, and the assignment of modes to the vibrational spectra of
methylammonium lead halide perovskites, Phys. Chem., 2016, 18, 27051-27066, DOI
10.1039/c6cp03474h
[19] V. Chandrakala, J. Annai Joseph Steffy, Neena Bachan, W. Jothi Jeyarani, Tenzin Tenkyong,
and J. Merline Shyla, A Comparative Investigation of Dye-Sensitized Titanium Dioxide (TiO2)
Nanorods Grown on Indium Tin Oxide (ITO) Substrates by Direct and Seed-Mediated Hydrothermal
Methods, Acta Metall. Sin. (Engl. Lett.), 2016, Volume 29, Issue 5, pp 457463, DOI
10.1007/s40195-016-0409-y
[20] Y. Kawamura, H. Mashiyama, K. Hasebe, Structural Study on CubicTetragonal Transition of
CH3NH3PbI3 J. Phys. Soc. Jpn., 71, 7, 1694-1697, 2002. DOI 10.1143/JPSJ.71.169

166
Stress Stability of Aluminium-Glass Composites 29
Abodunrin O.W.1, Alo F.I.2
1 Department of Physics, Joseph Ayo Babalola University, Osun State, Nigeria

2 Department of Material Science and Engineering, O.A.U, Ife, Osun state, Nigeria
a tayoabodunrin@yahoo.com
b iretispecial2005@yahoo.com
Keywords: pressure, particle size, ductility, fracture toughness, stable stress, max. compressive stress, yield point and
structural stability.
ABSTRACT. The effects of compaction pressure and particle size on the mechanical property of Aluminium-Glass based
samples are reported in this study. The samples were of cross sectional area 34.0 x35.0 mm2 with varying thickness 20.8 -
22.10 mm. Particle size of 26.5nm was used for both Aluminium and Glass. The samples were made into solids by
pressing the materials together at constant pressure of 300bars. Results showed that composition of Aluminium in Glass,
compaction pressure and particle size greatly influenced the stress/time relationship of the samples. With the particle size,
it was revealed that samples were found with stress stability between 5 - 70% weights of Aluminium in the composites.
The sample was noted to have maximum strength for 30 % weight of Aluminium in composites in the compression test
analyses.
Introduction. Stress stability is the ability of a body or system to return to a previously established
steady state, after being perturbed. Besides, it is also the ability of a body to regain balance at the
moment of giving it any distortion. Stress stability of a molded material could also imply an increase
in stress which corresponds to an equal increase in time. In such compacted material, the stress / time
relationship did not accommodate points of fracture and rupture up to the yield point [1, 2]. Stress
stability is a mechanical quantity which was usually measured from compressive strength of the
material. It was determined from observation of the stress time relationship of a material. The higher
the stress a material could withstand, the higher was its resistance to fracture. The fracture toughness
was thus improved from contribution of stress stability and the maximum compressive strength of the
material. A fracture is the propagation of micro cracks / cracks within certain regions of the material
under the action of high / residual stress developed in the sample. A point of fracture of the material
is a point on the stress-time curve where the sample experiences separation into parts as a result of
close and diverse fractures within certain regions of the material under the action of increasing load
in compression test. The yield point is a point on stress-time curve above the proportionality region
where sudden increase of a unit stress does not have corresponding unit increase in time.
The toughness of a material signifies the ability of a material to absorb energy without causing
breakage. This implies that Metallic-Glass had the capability to absorb much energy before or at point
of breakage of the samples up to the yield point [3]. The choice of Aluminium is as a result of its
ductility and strength used in diverse areas. Fracture toughness is the ability of the material to resist
crack propagation in the material. Ductility is defined as the ability of a material to undergo
appreciable plastic deformation before fracture. Glass had low ductility [4, 5] and the need for
29

167
reinforcement of a material of high ductility, structural stability was considered to increase the level
at which breakage may be experienced during impact or compression test [6, 7].
Much is yet to be done in the direction of stress stability by combining metallic elements with Glass
to form composites.
Therefore, attention in this study is geared towards determining the stress stability at constant pressure
and same particle sizes. Moreover, Aluminium-Glass composites were proposed for industrial and
domestic purposes.
Experimental procedure
The materials used for the study include Aluminium powder of purity of 95.50% purity, sodium
silicate powder of purity 99.50% both of particle sizes of 26.5nm obtained from British drug House
(BDH), England. The specimen slide was boiled in cromic acid and agitated in trioxoethelene for 20
minutes to remove unwanted attachment on the surface of slides. Glass powder of particle size of
26.5nm which had earlier been crushed and pulverized before sieving with a mechanical mesh from
mechanical section at Centre for Energy Research and Development (CERD) in Obafemi Awolowo
University, Ile-Ife, Nigeria was used. Weighing was done with digital weighing balance (Model, BT
200) of sensitivity 0.001g. Sodium silicate liquid was prepared by mixing distilled warm water at
800C with sodium silicate powder in ratio 1:3.
A manually operated press capable of producing one composite at a time with an average thickness
of 21.5mm and cross sectional area of 1156mm2 was used for molding the samples at Engineering
Geology Laboratory at Federal University of Technology, Akure. Formula for mixing in percentage
is AlxGlass100-x x= 5.0, 10.0, 15.0, 20.0100.0.The Aluminium and Glass powders in grams were
mixed together in 20 different ratios at 300 bars. Sodium silicate liquid added was between 12.5-14.5
% of Al-Glass Mixture. The mixing was carried out manually in a closed container.
The samples were subjected to same moisture condition for four weeks in an open atmosphere in the
laboratory. Samples were measured with compressive test machine from CERD.
Results
Discussion
Compressive Stress of the Samples of Al-Glass. In Table 1 the stress has highest value for 30 %
weights of Aluminium in the composites of 300 bars. As for the lowest values, stress was noted at
100 % weight of Aluminium in the composites.
Compressive Stress with Thickness of the Samples of Al-Glass. The stress with % weight of
Aluminium was in reverse direction to that of stress-thickness relationship in Figures 1 and 2. The
thickness and stress have maxima at 0 and 30 % weight of Aluminium.
Stress, Time, Strength and Stress Stability of Al-Glass Composites. Figures 3 6 displayed a
pressure value of 300 bars and 26.5 nm particle size whereby the stress time relationships were
found to be stable over specified ranges which are indications that the material has the tendency of
being stress stable.
Figure 3 displayed the variation of stress time for Al5Glass95, Al10Glass90, Al15Glass85, Al20Glass80
and Al25Glass75 of 26.5 nm particle sizes. The results showed that as the time increases the stress
increased gradually without rupture along each of the curves. The increase in strain - time became
noticeable for these composites without fracture along the curves. All these samples were classified
as being stress stable.
The variation of stress - time for samples Al30Glass70, Al35Glass65, Al40Glass60 and Al45Glass55 at 26.5
nm particle sizes are shown in Figure 4. The results depicted gradual increase in stress - time along
the curve with no ruptures up to the point of breakage. These are indications of stress stability of the
materials just before the point of breakage.

168
Table 1. Compressive test values of samples at room temperature (27C), 300 bars, 26.5 nm
particle size and area of 1190 mm2.
% wt Thickness Maximum Compressive stress(MPa)
(Al/Glass) (mm)
0.00/100.0 22.10 32.12
5.00/95.0 21.90 40.24
10.0/90.0 21.70 43.94
15.0/85.0 21.50 45.53
20.0/80.0 21.40 47.86
25.0/75.0 21.30 48.77
30.0/70.0 21.25 57.03
35.0/65.0 21.20 42.27
40.0/60.0 21.20 41.45
45.0/55.0 21.15 40.98
50.0/50.0 21.10 36.09
55.0/45.0 20.95 35.46
60.0/40.0 20.80 30.01
65.0/35.0 20.75 28.54
70.0/30.0 20.73 26.56
75.0/25.0 20.73 22.60
80.0/20.0 20.60 9.17
85.0/15.0 20.60 6.60
90.0/10.0 20.50 5.60
95.0/5.00 20.35 5.06
100.0/0.00 20.28 4.06

169
60
50
40
stress ( Mpa)
30
20
10
0
0 20 40 60 80 100 120
% weight of Al
Fig. 1. Variation of Stress with % Weight of Al at 300 bars and 26.5nm.
60
50
Compress Stress (MPa)
40
30
20
10
0
20 20.5 21 21.5 22 22.5
Thickness (mm)
Fig. 2. Variation of Compressive Stress with Thickness at 300 bars and 26.5 nm.

170
60
m
Maximum compressive Stress(Mpa) 50 m
m
m b
40
b
30
20
10
0
0 20 40 60 80 100 120 140 160 180
-10
Time (seconds)
Al5Glass95 Al10Glass90 Al15Glass85 Al20Glass80 Al25Glass75
Fig. 3. Compressive Stress versus Time from 5 to 25 % wt. of Al for 300 bars and 26.5 nm, m is the
point of maximum compressive stress.
60
m
Maximum Compressive Stress (Mpa)
50
m b m
40
b
30 b
20
10
0
0 20 40 60 80 100 120
-10
Time(seconds)
Al30Glass70 Al40Glass60 Al45Glass55
Fig. 4. Compressive Stress versus Time from 30 to 45 % wt. of Al for 300 bars and 26.5 nm,
m = max compressive stress, b = point of breakage.

171
40
Maximum Compressive Stress (Mpa)

35
30
25
20
15
10
5
0
0 0.5 1 1.5 2 2.5 3 3.5 4 4.5
-5
Time (seconds
Al50Glass50 Al55Glass45 Al60Glass40 Al65Glass35 Al70Glass30
Fig. 5. Compressive Stress with Time for samples from 50 to 70 % wt. of Al, pressure of 300 bars
and 26.5 nm particle size (m = max compressive stress, b = point of breakage).
25
Maximum Compressive Stress(MPa)
20
15
10
0
0 5 10 15 20 25 30
-5
Time (seconds)
Al75Glass25 Al80Glass20 Al85Glass15

Al90Glass10 Al100Glass0
Fig. 6. Compressive Stress versus Time (from 75 to 100 % wt. of Al for 300 bars and 26.5 nm).
It should be noted that samples that contain points of rupture and fracture did not have stress stability.
For a sample to have stress stability, it must not exhibit the above mentioned flaws. In other words,
the sample with stress stability must display gradual increase in stress with corresponding equal
increase in time. The point of breakage did not necessarily coincide with the maximum compressive
stress which was found in the samples observed. Stress stabilities were observed in Figure 5 for
samples Al50Glass50 Al55Glass45Al60Glass740Al65Glass35 and Al70Glass30 as an increase in stress
corresponds to equal increase in time. The figure also revealed that the samples at 26.5 nm have no
point of fracture or rupture over the entire range. The stress-time curves for the samples increased
gradually from the origin to maximum values up to the yield point. The samples have different ranges
of values for stability in the region of stress stability.

172
There was an improvement in the composites considered from ordinary glass, whose maximum
compressive stress was 30.32 MPa to Al-Glass composite which maximum compressive stress was
57.03 MPa at particle size 26.5 nm. The implication of this was that a new composite that could with
stand stress up to 57.03 MPa was obtained. The sample that could with stand minimum stress was
Al100Glass0 while that for maximum stress it was Al30Glass70.
Figure 6 reflected the variation of compressive stress versus time for samples Al75Glass25,
Al80Glass20, Al85Glass15, Al90Glass10 and Al100Glass0 at 26.5 nm particle sizes. The results revealed
that all of these samples have points of fracture or rupture along the curves which implied they are
not candidates of stress stability. In addition, Al75Glass25 has a zig-zag nature of stress - time which
was an indication that the sample was also without stress stability.
Summary. The combination of Al with other metal had been noted to generate improve
performance in various device applications and utilization. Therefore, the mechanical properties of
Glass could be adjusted for suitable application and utilization with appropriate reinforcement of Al
in Glass.
Improved compressive strength of Glass to 57.03 MPa was obtained while stress stabilities were
observed from 5-70 % weight of Aluminium in composites at 26.5 nm particle size.
The material could also be useful for decoration and other house hold aesthetics. Having examined
the improved strength of the material, it is recommended the Al-Glass be used as pharmaceutical
packaging material, aerospace and automobile industries.
References
[1] David, R. (2001). Stress-Strain Curves, Department of Materials Science and Engineering
Massachusetts Institute of Technology, Cambridge, 1-14.
[2] Nicholas, J. H. (2010). Dynamic Stability of Structures, proceedings of International Conference,
7-41.
[3] Shantanu, V. M. (2015). Toughness of Bulk Metallic Glasses, Journal of Metals, Review, 5, 1279-
1305.
[4] Yoldas, B. E. (1975). Monolithic Glass Formation by Chemical Polymerization, Journal of
Material Science, 10, 1856.
[5] Chantikul, P., Anstis, G.R., Lawn, B.R. and Marshall, D.B. (1981). A Critical Evaluation of
Indentation Techniques for Measuring Fracture Toughness II Strength Method.J. Am. Ceram. Soc.,
64(9): 539-543.
[6]Wachtman. J. B. (1996). Mechanical and Optical Properties of Ceramics. John Wiley & Sons.
[7] Abodunrin O.W. and Oluyamo S.S. (2017). Structural Stability of Nano Crystalline Al-Glass
Composites. International Organization of Scientific Research (IOSR) Journal of Applied Physics, 9
(1), 96-99.

173
On the Rogue Wave Solution of the Davey-Stewartson Equation 30
D. Prasanna1, S. Selvakumar2, Dr. P. Elangovan1
1 PG & Research Dept. of Physics, Pachaiyappas College, Chennai, Tamilnadu, India

2 PG & Research Department of Physics, Government Arts College, Ariyalur, Tamilnadu, India
a dprasanna85@gmail.com
Keywords: Rogue wave, mathematical physics, nonlinear.
ABSTRACT. Constructing Rogue wave solution for the nonlinear evolution equations is the one of the challenging tasks
for nonlinear community. Rogue wave is the deepest trough (hole) before or after the largest crest and it appears from
nowhere and disappears without a trace. Benjamin-Feir Instability or Modulation Instability is responsible for the Rogue
wave formation in both ocean and optics. The Mathematical model for the rogue waves is the nonlinear Schrodinger
(NLS) equation. Rogue wave is one of the peculiar nonlinear waves which arises suddenly and swallow many ocean liner.
Introduction. Rogue wave is an isolated huge wave with amplitude much larger than the average
wave crests around it. First observed in the ocean. Later in optics, BEC, Multi-component Plasmas
and so on. Rogue wave is first recorded in 1990s at Draupner oil platform in North Sea. Optical
rogue waves are observed in nonlinear optical fibers by Solli et.al in 2007 [7].
Wave motion is a mode of transmission of energy through a medium in the form of disturbance, so
wave is a disturbance which travels through space and time. Waves are important in all branches of
physical and biological science. Indeed the wave concept is one of the most important unifying
threads running through the entire fabric of the natural sciences. There are two broad category of
waves (i). linear waves and (ii). nonlinear waves. Linear waves are governed by linear evolution
equations which are linear partial differential equations (PDEs) and hence the superposition principle
is valid. Wave travels with constant velocity is known as phase velocity (vp) and is independent of
wave number vp vp(k) vp = k (1.1) and the wave group travel with the velocity (vg) which is known
as group velocity which is given by, vg = d / dk. If the group velocity is not same as the phase
velocity then each component of the wave group travel with its own velocity and after certain time
each component dies down in due course which is due to the dispersion phenomenon, such type waves
are called as dispersive waves. This type of waves has less permanent life because of dispersion. The
causes of formation of this types of waves due to earthquake, storms, and so on. Some examples for
the nonlinear waves are: cyclonic waves, tsunami waves, tidal waves, electromagnetic waves in
nonlinear optical fibres, solitary waves on shallow water surface and rogue waves [1].
Definition of the Rogue Wave: Rogue wave - it has deepest trough (hole) before or after the largest
crest and it appears from nowhere and disappears without a trace. Soliton - localized wave, which
propagate large distance without change of its size.
Causes of the Rogue wave formation: Earthquakes Ocean plates moving the quakes and the
vibrations make ripples, some of which are large enough to form a rogue wave. Storms When strong
winds from a storm happen to blow in the opposing direction of the ocean current the forces might
be strong enough to randomly generate rogue wave.

174
Mathematical model for the Rogue waves:

(1 + 1)-dimensional Nonlinear Schrodinger equation is:
iqt + qxx 2|q|2q = 0
Rogue wave solution of the NLS equation:
q = [14( 1 + 2ix \1 + 4x2 + 4t2)]eix
Mechanisms of Rogue wave formation: Breathers 1. Ma breathers, 2. Akhmediev breathers. Ma

breathers are periodic in time and Akhmediev breathers are periodic along space. If we increase the
modulation parameter, the temporal separation between adjacent peaks increases. When this
parameter reaches to the particular critical value, the rogue wave arises.
Two soliton solution: Taylor series expansion of two-soliton solution of the DS equation.
Ma breather solution:
a) b) c) d)
Fig. 1. Rogue wave solution arises from the Ma breather solution with the modulation parameter
value (a) = 0:9; (b) = 0:8; (c) = 0:6; (d) = 0:1.

175
Akhmedive breather solution.
a) b) c) d)
Fig. 2. Rogue wave solution arises from the Akhmedive breather solution with the modulation
parameter (a) a= 0.1; (b) a= 0.2; (c) a=0.3; (d) a=0.4.
Rogue wave solution of the DS Equation:

(2+1)-dimensional NLS equation or Davey-stewartson equation
iqt + aqxx + qyy + b|q|2 q 2qp = 0 (1)
apxx pyy ab(|q|2 )xx = 0 (2)
where a= 1;
b constant;
q complex field;
p real field
Two-soliton solution of the DS Equation:
The bilinear transformation is:
q = g/ f, p = 2a (log f)xx (3)
Boundary condition is:
|q|2 qo2
substituting the equation (3) into the equation (1) and (2) We get the bilinear form of the DS
equation
(iDt + aDx2 + Dy2 bqo2) g .f = 0 (4)

176
(aDx2 Dy2 bqo2) f .f = bgg (5)
We introduce Hirota expansion for the function g and f as,
f = (1 + 1 f1 + 2 f2 + 3 f3 + ...) (6)
g = g0 (1 + g1 + g2+ g3 + ...)
1 2 3
(7)
Substituting g and f in the bilinear equation (4) and (5) we have,
0: (it + a2x + 2y bq02) (g0.1) = 0 (8a)

(ax2 y2 bq02)(1.1) = bg0g 0* (8b)
1: [i(Dt + 2kDx + 2lDy) + aDx2 + Dy2] (1.f1 + g1.1) = 0 (9a)
[(aDx2 Dy2 bq02)] (1.f1 + f1.1) = bq02 (1.g1* + g1.1) (9b)
2: [i(Dt + 2kDx + 2lDy ) + aDx2 + Dy2] + (1.f2 + g2.1 + g1.f1) = 0 (10a)
[aDx2 Dy2 bq02)] (1.f2 + f2.1 + f1.f1) = bq02 (1.g2* + g1.g1* + g2.1) (10b)
From the equation (8b) we get
g0 = q0e i = kx + ly t + (0)
Substituting g0 in the equation (8a) we get the dispersion relation is
= ak2 + l2 bq02 (11)
for the one soliton solution from the equation (9a) and (9b) we choose
f1 = e 1 g1 = e1+i1
For the two soliton solution by assuming:
f1 = e1 + e2 g1 = e1+i1 + e2+i2
Substituting the above equation into the equations (10a) and (10b) we get,
f2 = De1+2 g2 = De1+2+i(1+2)
Therefore
f = 1 + e1 + e2 + De1+2 (12)
177
g = q0ei (1 + e1+i1 + e2+i2 + De1+2+i(1+2) (13)

where,
j = Kjx + Ljy jt + j0
j = 2akKj + 2lLj (aK j2 + Lj2 ) cot j /2 (14)
sin (j/ 2) = aKj
2 2
Lj2/ 2
2bq0 ; j = 1, 2. (15)
D = [ (2bq02 sin(1 /2 ) cos(12/ 2) + aK1K2 + L1L2) / (2bq02 sin(1 /2 ) cos(1+2/ 2) + aK1K2 +

L1L2)] (16)
Rogue wave solution of the DS equation:

Putting K1 = K2* = ic , L1 = L2* = id and 10 = 20* = (i ) + i.
1 = 2 = 2 d2 ac2 /2bq02 (17)

= [ + (ac + d ) 2bq0 d ac
2 2 2 2 2]
(18)

= (2akc + 2ld) = (19)
D = 1 + 2 (d2 ac2 2bq02) + o(3 ) = 1 + 22 + o(3) (20)
g = q0e i(kx+lyt)[ 2( 2 + 2 + 2 4( i) + o(3) (21)
f = 2 (2 + 2+ 2) + o (3) (22)
where
= cx + dy t + = t + 2 = d2 ac2 /2bq02
Rogue wave solutions:

Substituting the equation (21) and (22) into the equation (3).
q = q0e i(kx+lyt) [1 (4( i)) /(2 + 2 + 2)] (23)

4ac2 [(2 + 2 2) / (2 + 2 + 2)2] (24)

178
a) (b)
Fig. 3. The Rogue waves solution of the Davey-Stewartson equation with the parameter values a =
1, r = 1; k = 1, l = 1, c = 1 2, and d = 1/ 2. (a) t= - 0.05; (b) t=-0.2.
Summary. We have obtained two-soliton solution of the DS equation through bilinear method. By
choosing wave number as pure imaginary and by making Taylor expansion of two-soliton solution
we obtained first order Rogue wave solution of the DS equation.
References
[1] C. Kharif, E. Pelinovsky, A. Slunyaev, Rogue wave in the Ocean, Springer-Verky Berlin
Heidelberg, 2009.
[2] M. Tajiri, T. Arai, Growing-and-decaying mode solution to the Davey-Stewartson equation, Phys.
Rev E 60 (1999).
[3] J. Satsuma, M.J. Ablowitz, Twodimensional lumps in nonlinear dispersive systems, J.Math. Phys
20 (1979), DOI 10.1063/1.524208
[4] R. Hirota, The Direct Method in Soliton Theory, Cambridge University Press, Cambridge, 2004
[5] N. Akhmedive, A.Ankiewicz, N. Akhmedive, A.Ankiewicz, Phys. Rev E 80 (2009), Phys. Rev E
80 (2009), DOI 10.1103/PhysRevE.80.026601
[6] M. Lakshmanan, S. Rajasekar, Nonlinear Dynamics, Integrability, Chaos and Pattertns, Springer-
Verlag, Berlin 2003
[7] D. R.Solli, C. Ropers, P. Koonath & B. Jalali, Optical Rogue Waves, Nature 450, 1054-1057
(2007), DOI 10.1038/nature06402

179
Growth and Characterization of Potassium Di Chromate Doped L-Alanine

Crystal 31
D. Prasanna1, N.Karthikeyan2, Dr. P. Elangovan 1
1 PG & Research Department of Physics, Pachaiyappas College, Chennai, Tamil Nadu, India
2 Department of Physics, Prist University, Thanjavur, India
Keywords: L-alanine, amino acid, potassium, single crystal.
ABSTRACT. L-alanine is a neutral, genetically coded amino acid. Single crystals of L-alanine have been grown from
buffered aqueous solutions and characterized as to their optical quality via waveforms distortion analysis, electro optical
response and harmonic generation efficiency. L-alanine was first crystallized by BERNAL and later by SIMPSON et al.
DESTRO et al. who refined the structure. By using slow evaporation method to prepare seed crystal and the preparation
methods, properties and characteristic reactions of amino acids were discussed. A brief study of L-lysine
monohydrochloride has been made. And various properties and uses of L-alanine have been studied.
Introduction. Crystals are ordered arrangements of atoms (or molecules). A material in crystalline
form has special optical and electrical properties, in many cases improved properties over materials
with randomly arranged atoms or molecules (also said to be amorphous or glassy). Crystal growth is
a controlled phase transformation to solid phase, either from solid or liquid or gaseous phase. The
growth units, namely the atoms, or molecules, diffuse to the growth site from the mother phase, when
given sufficient time to get orderly arranged on the lattice Since crystal growth has a vital and
fundamental part of materials science and engineering, crystals of suitable size and perfection are
required for fundamental data acquisition and for practical devices such as detectors, integrated
circuits and for other millions and millions of applications.
Experimental
Synthesis of L-Alanine. Potassium phthalimide reacts with l-bromo-l-methyl propyl ester which
gives an esterified phthalimide. Then hydrolysis takes place formine an acid. For release of amino
acid, aqueous HCl is added. Thus, the acid is released forming L-alanine (P. Chattopadhyay).

180
Fig. 1. Formation of L-alanine
Seed preparation. Preparation of LAKDC: LAKDC synthesis at room temperature with known
solubility is prepared as follows:

L-alanine + Pottasium dichromate LAKDC
Amount of LAKDC Required:
X = (P/P+Q) x
Solubility of the compound at particular temperature

Prepration of Mixed Salt (LAKDC):
here x = 0.2
L-Alanine Molecular weight in grams x Molar ratio = P
Pottasium di chromate Molecular weight in grams x Molar ratio = Q

Total Molecular weight = P+Q
Preparation of Seed. Slow evaporation method was employed in preparing the seed. In this method,
4.084 grams of ADP which is in crystal form is powdered and doped with 45.91568 grams of TGS
which is in powder form is taken in 200ml beaker. This has been dissolved in 125ml of doubly
distilled water and poured into a Pettidish. The Petri dish is covered with a plastic paper with few
small holes to enable evaporation of solvents and kept in an undisturbed place. After a week seeds
are produced in the Pettidish and the fine seeds of good morphology were selected for crystal growth.
Preparing the Solution. Making up the solution is the most time consuming step. There appear to
cut for obtaining a solution precisely equilibrated at a desired temperature, but it may be helpful to
mention some common pitfalls. A precisely saturated solution can never be make simply by
181
combining the necessary amount of water and salts as determined by solubility curves, 1.Because an
astonishingly larger amount of published solubility date is not accurate.2.heating to complete
dissolution introduces gross errors.
Growth of Crystal by Slow Evaporation. The prepared saturated solution (salt about 200ml) is
taken in a 500ml beaker. A precisely fine seed crystal tied in a nylon thread is inserted in the solution.
It is seen carefully that the crystal seed is centered in the solution. So that the crystal growth takes is
covered by a thin plastic paper with fine holes for evaporation of the solvent and the whole apparatus
is placed undisturbed periodic to ensure the growth of the crystal.
Harvesting the Grown Crystal. Crystals grown of suitable size are harvested carefully from the
beaker. Crystal obtained from mixed crystals is shown below (Fig. 2):
Fig. 2. Pottasium di chromate doped L-Alanine.
Characterization Studies.
Powder X-Ray Diffraction Analysis: The aim of the study is to determine the cell parameters of
ferroelectric L-Alanine doped TGS crystals grown from solution. The grown crystal was powdered
and the powder was distributed uniformly on a glass plate. The glass plate with powder was mounted
on the sample holder. Monochromatic intense X-ray of wavelength 1.540598 (CuK) was used. The
powder specimen of the crystal can be considered to be a collection of randomly oriented tiny crystals.
The diffracted rays from the powder are detected by means of a detector and it is amplified.The d
values were calculated from the observed 2 values corresponding to the peaks using Bragg's
equation. The observed `d' values were then compared with the d values of the JCPDS data.
Table 1. Structure of L-alanine.

Compound a B c Structure
Pure l- 6.032 12.343 5.784 90 90 90 Orthorhomic
alanine
l-alanine 5.382 6.211 12.213 90 90 90 Orthorhomic
doprd
K2Cr2O7
Fourier Transform Infrared (FTIR) Spectral Studies: The stretching and bending modes of vibrations
exhibited by the L-Alanine doped TGS compound was analysed using FTIR. The FTIR spectrum was
recorded between 400-4000 cm-1 and show in Fig.2.The observed mode are found to be as follows,
182
the peak observed at about 3165 cm-1 due to NH3 asymmetric stretching is clearly indicates the
presence of NH3 group in amine functionality. The broad band observed at about 1708 cm-1 in L-
Alanine is C = O stretching the medium strong band in 1628 cm-1 is more available group of C = C
stretching vibration. The strong NH3d(NH3) vibration was observed at the wave number 1505 cm1.
The peak observed at about 1425 cm-1 is CH2 scissoring. The peak observed at about 1307 cm-1 is
assigned as CH2 wagging, and the peak at 1126 cm-1 is due to CH2twisting. The peak 906 cm-1 is
assigned to C-O-C stretching and the peak 865 cm-1 in assigned as SO4 symmetric stretching. The
rocking of O-C-O bending mode of band is assigned at wave number 645 cm-1.
l-alanine doped K2Cr2O7
ll
100.0
95 LA+K2Cr2O7 456
90
1959
85
80 2031
2291 486
75 2248
70
65
60 772
918
55 2111
1151 649
50
%T
45
2505 1235
849
40
35 1013
1113
30 1518
1508
25 2853 2601 539
2811 1455
20 2782
2936
15 2730
2987 1594 1411 1306
10 3083 1618 1361
0.0
4000.0 3600 3200 2800 2400 2000 1800 1600 1400 1200 1000 800 600 450.0
cm-1
Fig. 3. FTIR Spectrum L-Alanine doped K2Cr2O7.
UV-VIS-NIR Spectral Studies. The band gap energy value of 4.76 eV indicates that the material is
a high band gap energy dielectric compound. The grown crystalline material is found to be optically
transparent from UV to near IR.
Fig. 4. UV-VIS-NIR absorbance spectrum of L-Alanine doped K2Cr2O7.

183
Thermal Analysis. Thermal properties of the LAKDC were revealed from the TG/DTA analysis.
The above figures show the TG/DTA curve of the sample. Both the curves show the melting point of
LAKDC is 213C. The TGA curve shows that the material has high thermal stability; it is stable up
to300.1C. The TGA curve shows that the major decomposition takes place after 397.1C. The DTA
line shows two exothermic peaks 300C and 400C. Around 99.4% of the material decomposes at
397C.Finally the pyridine moiety goes out from the material and only .6% remains as residue at
800C.
30.00
120.0
20.00
100.0
102.8%
10.00 507.5Cel
5.52uV
80.0
0.00
60.0
DTA uV
TG %
-10.00
40.0
-20.00
-30.00 20.0
-40.00
0.0
300.4Cel
-47.00uV
-50.00
100.0 200.0 300.0 400.0 500.0 600.0 700.0 800.0
Temp Cel
Fig. 5. Thermal analysis of L-Alanine doped K2Cr2O7.
Summary. Slow evaporation method was employed in preparing the seed. The preparation methods,
properties and characteristic reactions of amino acids were discussed.
A brief study of L-lysine monohydrochloride have been made. And various properties and uses of L-
alanine have been studied. Some of the properties of L-alanine are: colourless crystal; soluble in
water; slightly soluble in alcohol; insoluble in ether; optically active and it is nontoxic.
The fundamental requirement for infrared activity, leading to absorption of infrared radiation, is that
there must be a net change in dipole moment during the vibration for the molecule or the functional
group under study. The FT-IR spectrum confirms the presence of molecules in grown crystals and
the frequency bonding between them. The UV-VIS-NIR spectrum recorded for the grown L-Alanine
doped K2Cr2O7 crystalline material. The fundamental absorption peak cut off wavelength occur at
260 nm. This indicates that the crystal is transparent from near UV to near IR including complete
visible portion of Electromagnetic spectrum. Thermal properties of the LAKDC were revealed from
the TG/DTA analysis.
References
[1] Crystals and Crystal Growing, Alan Holden and Phylis Singer, Anchor Books-Doubleday, New
York, 1960
[2] The Growth of Single Crystals, R. A. Laudise, Solid State Physical Electronics Series, Nick
Holonyak, Jr. Editor, Prentice-Hall, Inc., 1970
[3] X-ray Structure Determination A Practical Guide, 2nd edition, George H. Stout and Lyle H.
Jensen, John Wiliey & Sons, New York, 1989.
184
[4] Fundamentals of Analytical Chemistry, 3rd. edition, Saunders Golden Sunburst Series, Holt,
Rinehart and Winston, Philadelphia, 1976.
[5] Mohd. Shkir, I.S. Yahia, A.M.A. Al-Qahtani, Bulk monocrystal growth, optical, dielectric, third
order nonlinear, thermal and mechanical studies on HCl added L-alanine: An organic NLO material,
Mater. Chem. Phys. 184 (2016), 12-22, DOI 10.1016/j.matchemphys.2016.07.052
[6] P.P.Sahay, R.K.Nath and S.Tiwari, Optical properties of thermally evaporated CdS thin films,
Crystal. Res. Technology, vol.42 (3), pp. 275-280, 2007.
[7] D. Rayan Babu, D. Jayaraman R. Mohan Kumar R. Jayavel, Growth and characterization of non-
linear optical L-alanine tetrafluoroborate (L-AlFB) single crystals, Journal of Crystal Growth, 245,
2002, 121-125, DOI 10.1016/S0022-0248(02)01708-6

185
I I. M ec hanic al Engi neeri ng & Physic s


186
Vibration Optimization of a Two-Link Flexible Manipulator with Optimal Input

Torques32
Hadi Asadi1,a, Milad Pouya2, b, Pooyan Vahidi Pashaki3, c
1 School of Mechanical Engineering, Yazd University, Yazd, Iran

2 School of Mechanical Engineering, International Pardis, University of Guilan, Rasht, Iran
3 Department of Mechanical Engineering, Islamic Azad University, Science and Research Branch, Tehran, Iran
a asadihadi26@gmail.com
b Miladpouya5@gmail.com
c Pooyan.vahidi66@gmail.com
Keywords: optimization, two-link flexible manipulator, path planning, vibration, genetic algorithm (GA), Broyden-
Fletcher-Goldfarb-Shanno (BFGS) algorithm.
ABSTRACT. This paper is concerned with the optimal path planning for reduction in residual vibration of two- flexible
manipulator. Therefore, after presenting the model of a two-link flexible manipulator, the dynamic equations of motion
were derived using the assumed modes method. Assuming a desired path for the end effector, the robot was then optimized
by considering multiple objective functions. The objective functions should be defined such that in addition to
guaranteeing the end effector to travel on the desired path, they can prevent the undesirable extra vibrations of the flexible
components. Moreover, in order to assure a complete stop of the robot at the end of the path, the velocity of the end
effector at the final point in the path should also reach zero. Securing these two objectives, a time-optimal control may
then be applied in order for the robot to travel the path in the minimum duration possible. In all the scenarios, the input
motor torques applied to the Two-Link are determined as the optimization variables in a given range. The optimization
procedures were carried out based on the Genetic algorithm and BroydenFletcherGoldfarbShanno algorithms, and the
results are then compared. It is observe that the BFGS algorithm was able to achieve better results compared to GA
running a lower number of iterations. Then the final value of the objective function after optimization indicates the
decrease in the vibrations of the end effector at the tip of the flexible link.
Introduction. Path planning of a robot between two given states is considered among the important
topics in designing industrial robots. Generally, the problem involves using an optimization algorithm
in order to find the optimal input torques, by application of which to the system, the end effector of
the robot travels the desired path with an acceptable accuracy. Due to the effects of flexibility in
flexible robots, achieving an acceptable accuracy has always been a difficulty. Multiple contradictory
objective functions such as high stiffness and damping, low-mass, and high accuracy should be
considered simultaneously in the optimization process of these robots. Hence, the selection of
appropriate objective functions is of great importance in this regard.
Optimization of flexible manipulators is far more difficult than rigid manipulators since multiple
objectives such as high stiffness, high damping capacity, low link weight, and high accuracy must be
met in order to achieve a high performance. The concept of optimization calls for objective
function(s), which may be used as a performance criterion for the design. In the optimization
procedure of robots, weight, workspace, supplied energy, etc. may be considered as the objective
32

187
functions of the design process, while each of which is dependent on several other design variables.
The optimization objectives in designing flexible manipulators include increasing stiffness, reducing
weight, increasing accuracy coefficient, reducing the end effector deviation from the considered
point, and maximizing the operation speed and acceleration. For the accuracy to increase, the
deviation of the end effector at high speeds should be reduced. Furthermore, increases in speed and
accuracy result in increased efficiency.
Most research on optimization has been conducted using specific algorithms such as genetic and
gradient descent algorithms. Hiroyoki and Tetsoji [1] and Kojima [2] used GA to reduce the
remaining vibrations in a two-link rigid-flexible manipulator and to optimize the motion trajectory.
In [1], the angular velocity of the joints was determined by a third degree polynomial with three
parameters and a fitness function with four parameters. In [2], the joint angles were described using
a fourth degree polynomial. Using GA, Anderson [3] optimized the system and investigated the effect
of different design parameters on the objective function. In the present study, the control error and
the energy were first minimized, and then, the effect of different parameters on the objective function
was determined. Optimization of Diamond robot is considered for the future work. Lee [4], first,
derived the equilibrium equations of the robot using the Euler-Lagrange method, and then
investigated the effect of optimization on different parameters such as natural frequency and
dynamical stress. Rahman [5] carried out an optimal design of a 3-DOF planar robot with parallel
links. He first described the kinematic model of the manipulator and derived the equations of motion
as well as the matrices of mass, stiffness, and damping. He then considered two objective functions
based on mass and workspace so that the former is minimized and the latter is maximized. Hegde [6]
used the EulerBernoulli beam theory and the finite element method (FEM) to derive the dynamic
equations for the optimization process, for which the intermediate method was utilized. Neto [7]
proposed an optimization procedure for finding the optimized design structure of a composite fiber
in order to be used in flexible systems. The elastic energy of the flexible bar, which itself is dependent
on the layer orientations, was considered as the objective function in this procedure. The purpose of
this optimization was to reduce the elastic deformation of the plane, hence raising the need for planes
with higher stiffness [12].
In this study, after presenting the model of a two-link flexible manipulator, the dynamic equations of
motion were derived using the assumed modes method. Assuming a desired path for the end effector,
the robot was then optimized by taking into account multiple objective functions. The objective
functions were defined such that in addition to guaranteeing the end effector to travel on the desired
path, they could prevent the undesirable extra vibrations of the flexible components. Moreover, in
order to assure a complete stop of the robot at the end of the path, the velocity of the end effector at
the final point in the path should also reach zero. After securing these two objectives, a time-optimal
control may then be applied in order for the robot to travel the path in the minimum duration possible.
In all the scenarios, the input motor torques applied to the Two-Link were determined as the
optimization variables in a given range such that all the considered objectives are achieved [13].
As compared to the studies reviewed in the literature on the same subject, the main differences and
contributions of the paper lie in the following points: the considered objective function, application
of BFGS algorithm, optimization variables in order to identify the most influential optimal parameter.
2. Equations of motion for the two-link rigid-flexible manipulator. The considered system in this
section includes two members which, as demonstrated in Fig. 1, are connected to each other by a
revolute joint and are only capable of planar motions. The first member is considered rigid, while the
second is flexible and is modeled as a flexible narrow beam. Longitudinal deformations are neglected
in the second member. It is assumed that the second member may freely bend in the horizontal plane
but can resist vertical bending as well as torsion. Hence, the Euler-Bernoulli theory may appropriately
be used to describe the bending motions of the flexible member. In addition, the Lagrange equation
can be used to derive the dynamic model of the two-link manipulator.

188
Fig. 1. The schematic diagram of a two-link rigid-flexible manipulator.
According to Fig. 1, X 0OY0 is the fixed coordinate system, and X1OY1 and X 2OY2 are the moving
coordinate systems attached to the joints corresponding to the rigid and flexible links, respectively.
In addition, 1 and 2 are the rotation angles of each of the links with respect to the X axis of their
previous coordinate system, and w( x, t ) is the elastic transverse displacement of the flexible member.
Since the bending motions of a beam do not impose significant axial vibrations, axial deformations
were not included in our study. Two perpendicular pairs of unit vectors (i , j ) and (i , j ) attached
1 1 2 2
to the moving coordinates of the links are shown in Fig. 1. The position vectors of the points on the
Two-Link are R1 and R2, which are obtained according to the following relations( Eq. (1) and Eq.
(2)):
x r cos 1
R1 1 1
y1 r1 sin 1 (1)
x l cos 1 r2 cos(1 2 ) - w sin(1 2 )
R2 2 1
y2 l1 sin 1 r2 sin(1 2 ) w cos(1 2 ) (2)
where r1 and r2 are the distances of the points on links 1 and 2 to the origin of their corresponding
coordinate systems.
Moreover, l1 and l2 are the lengths of link 1 and 2, respectively. The total kinetic energy of the
system is calculated as follows (Eq. (3)):
l
1 1 1 12
T J112 J h (1 2 )2 M hl1212 RT2 R 2 AL dr2
2 2 2 20
(3)

189
where J1 is the moment of inertia of the first link around its rotational axis;
J h and M h are the moment of inertia and the mass of the driving motor acting on the second
link at point O2 , respectively;
AL is the mass linear density of the second link, and the elastic potential energy is obtained
as Eq. (4):
l
12 (4)
2 0
U EI ( w( x, t )) 2 dx
where EI is the flexural rigidity of the flexible link,

(, ) is the second derivative of the transverse elastic displacement with respect to the
variable x .
Since the flexible link is considered as a fixed support beam, the following boundary conditions hold
true at the two ends of this member:
2 3 )5(
w(0, t ) 0, w(0, t ) 0, w(l2 , t ) 0, w(l2 , t ) 0
x x 2 x3
The general form of the equations of motions for the two-link rigid-flexible system is obtained as
follows according to Lagrange equations:
d L L
- i - i i (i 1, 2) )6(
dt i i
d L L )7(
- 0 ( j 1, 2)
dt w j w j
where L is the Lagrangian function defined as L T - U ;

i are the generalized torques applied to the system;
ii are the damping torques at the th joint.

Substituting the equations of kinetic and potential energies in the above relations, the dynamic
equations of motion are concluded [8], [9]. Selecting the n first modes as the assumed-modes for the
discretization procedure, the following centralized model is acquired for the system (Eq. (8)):
MX + KX = F(X, X) + Bu )8(

190
Where X 1 , 2 , 1 , 2 ,...n T X 1 ,2 , w1 , w2 ,..., wn is the vector of generalized coordinates,

T
M and K are the mass and stiffness matrices, respectively, the vector F contains the nonlinear
expressions associated with the Coriolis and centripetal forces, and Bu represents the inputs to the
system.
3. The employed optimization algorithm.
3.1 BroydenFletcherGoldfarbShanno algorithm.
As a conventional gradient search method in nonlinear optimization, Hessian matrix is used as the
gradient coefficient to update the weights. The algorithms based on this method are known as Newton
and quasi-Newton methods, hence sharing similar fundamentals. Similar to conjugate gradient
method, these algorithms converge at a high rate. The BFGS method is one of the most well-known
and widely used quasi-Newton methods [10]. This algorithm is generally used for optimization of
multivariable functions, the basis of which is an approximation of the Hessian matrix. The order of
convergence in algorithms based on BFGS is high. Issues such as motion path planning optimization
can be addressed using this algorithm. In this method, after making an initial guess x (0) , the gradient
vector c is calculated according to the objective function f (x) .
c(0) f (x (0) ) )9(
If the norm of the gradient is smaller than the suggested convergence value, the program stops
iterating, otherwise, iteration continues. Then, similar to all quasi-Newton methods, the Hessian
matrix is calculated. The initial value of the Hessian matrix is selected as H(0) I , and then the search
direction for the th iteration is determined as Eq. (10):
d( k ) -H-1c( k ) (10)
Then, the optimal step k is selected such that f (x k k d k ) is minimized. After correcting the
optimal solution according to the following relation (Eq. (11)) :
x( k 1) x( k ) k d( k ) (11)
And correcting the Hessian matrix based on the proposed relation in [8], the iteration number is set
to k=k+1, and we return to the beginning of the algorithm. Generally, the optimization stops based
on the norm of the gradient of the objective function and/or the allowed maximum number of
iterations so that in case the given tolerance for the norm of the gradient vector is not achieved, the
algorithm does not get stuck in the optimization loop.
3.2 Genetic algorithm.
Genetic algorithm (GA) is an efficient method for searching large, extensive spaces to eventually get
directed towards finding one optimal solution, the achievement of which may not be possible during
the lifetime of a person if manually searched for [10]. In this method, using a series of coded variables,
191
the design space is transformed into the genetic space. The advantage of working with coded variables
lies in the ability of codes to transform a continuous space into a discrete one. GA is significantly
different than the traditional optimization algorithms. For instance, GA deals with a population or a
set of points at a given time while traditional optimization methods can only be applied to a single
specific point. What this feature means is that GA processes a large number of designs at a time.
Another interesting feature is concerned with the basics of this method which, in fact, is built upon a
guided random search process. Hence, random operators adaptively inspect the search space.
Essentially, the three following concepts need to be clarified before using GA:
Defining the objective or cost function,
Defining and implementing the genetic space,
Defining and implementing the genetic operators.
If the above items are defined correctly, we can make sure the algorithm performs well and its
performance can be increased by applying some alterations.
4. Numerical optimization
In this section, by introducing the objective function and performing the optimization procedure, the
optimal torques to the manipulator are determined such that the end effector starts moving from its
stationary state, and after traveling the desired path, reduce its speed to zero at the end of the path.
When optimal torques are applied, the end effector travels the path with the least vibrations possible.
Optimal control is needed to be used in order to achieve these objectives. However, since the
application of optimal control to such a nonlinear, complex system is a highly difficult task, usually
optimization methods are used instead. The aforementioned objective function is considered as Eq.
(12):
f k1 (( x - X )2 ( y - Y ))2 k2 ( xd 2 yd 2 ) )21(
Where x and y are the components of the points of the traveled path in the fixed coordinate system by
the end effector attached to the tip of the flexible link;
X and Y are the points of the desired path;

x d and y d are the velocity components of the end effector at the end of the path.
k1 and k2 are the weight coefficients of the objective function.

The first expression, which is the difference of the points obtained from the execution of the plan and
those of the desired path, was considered for correct traveling of the path, and the second expression
for reducing the velocity to zero at the end of the path. The specifications of the links and driving
motor of the flexible link are given in Table 1. The empty cells in the table indicate the parameters,
which are not present in the equations of motion.

192
Table 1. The specifications of the links and the driving motor of the flexible link.
Moment of Inertia Mass Length
(Kgm2 )
Damping Ratio (Nms) (Kg) (m)
Rigid Link 16.1 --- --- 1662

Flexible Link --- --- 1617 1651
Motors 1611 1627 161. ---
In the first part of this section, the values of the objective function in the GA and BFGS is investigated
and compared. The optimization process is first performed on the rigid manipulator and then on the
flexible-rigid manipulator by both algorithms. It should be noted that the coefficients of the objective
function for both algorithms were 1 = 10000 and 2 = 100.
In order to run the optimization procedure, the considered total duration is divided into smaller
intervals. The manipulator is supposed to travel the path in 0.5 s with 11 steps. The path is considered
an inclined straight line and the error is the deviation from the desired path. The lower the error while
traveling the path, the more successful the optimization procedure and the less the vibrations of the
end effector on the flexible link. The torques at the first and second joints are the inputs to the
equations of the motion of the manipulator. After transforming the equations of motion to the state-
space form and substituting the initial input torques (the guessed values), by running the direct
dynamics and numerically integrating the equations of motion, the position and velocity of the end
effector on the second link is calculated at different consecutive moments. The objective function is
calculated based on these values. In the main stage, by applying the optimization algorithm, the input
torques are changed to minimize the objective function and reduce the vibrations of the manipulator.
This procedure continues until the desired accuracy is achieved and the optimization algorithm is
terminated. the initial population in the proposed algorithm is randomly selected using the roulette
wheel selection. Two-point crossover occurs with a rate of 0.8 and point mutation with a rate of 0.5.
The diversity operator makes modifications to all genes with a probability of 0.8. The selection
operator is considered comparative, meaning that between two chromosomes, the one with the better
fitness makes it to the next stage. The new population is sorted based on their fitness values and the
n chromosomes with the least fitness values are determined, where n is the number of the initial
population. Determination of the n chromosomes with the best fitness values results in elitism and
increases the convergence rate to the optimal solution. The number of population and iterations were
considered 20 and 400, respectively, as given in Table 2.
The value of the objective function with respect to the number of iterations is given in Fig. 2 for both
algorithms. The objective function reaches the maximum allowed iterations (400) in the GA
algorithm before achieving the optimal solution while the BFGS achieves the desired tolerance after
19 iterations. It can be concluded that the BFGS algorithm converges to the optimal solution at a
higher rate than the GA. The value of the objective function is considerably high for the initial input
torques. The slope of changes in the values of the objective function is high but gradually decreases
as it converges to the optimal solution. The final value of the objective function after the optimization
process indicates a reduction of vibrations at the end effector installed on the flexible link.

193
Table 2. The values considered for the parameters of GA.

Variable name Value Symbol
Initial population 11 Npop

Mutation type Point mutation ---
Mutation rate 165 Pm
Mutation intensity Dependent on the objective function fm
Crossover type Two-point crossover ---
Crossover rate 168 Pc
Crossover intensity . 57 .57 r fc
Diversity rate 168 Pd
Diversity intensity fm fd
Number of iterations. 011 igen
Fig. 2. The value of the objective function with respect to the number of iterations in the BFGS and
genetic algorithms.
The path traveled by the end effector after optimization is shown in Fig. 3 for both algorithms. It is
obviously observed that the vibrations of the end effector after optimization using BFGS algorithm
are fewer than GA, and hence, the manipulator travels the path with fewer errors. In the BFGS
algorithm, the manipulator tracks the desired path roughly adjacent to it. Regarding the GA, it should
be noted that the traveled path may be improved by increasing the number of iterations, but the
convergence rate would significantly be slow. The desired path and the travel duration for both
algorithms were similar.

194
Fig. 3. Comparison between the traveled path by the manipulator and the desired path using the
BFGS and the genetic algorithms.
The torques applied by the first and second joints before and after optimization using the two
algorithms are shown in the diagrams of Figs. 4 and 5. As shown, many changes were made to the
initial torques in order to achieve the optimal solution. These changes are due to the random selection
of the initial torques. The closer the initial guesses to the optimal values, the faster the convergence
rate in achieving the optimal solution. Regarding the initial torques, it should be noted that their values
in both algorithms were selected such that the convergence rate increased according to their
corresponding algorithms.
a) BFGS algorithm b) Genetic algorithm

Fig. 4. The torque in the first joint before and after optimization.
a) BFGS algorithm b) Genetic algorithm

Fig. 5. The torque in the second joint before and after optimization.

195
In order to illustrate the effect of optimization on the velocities at the beginning and end of the
manipulator path, the zero-velocity condition at these two points should be met. Table 3 demonstrates
these changes before and after optimization, and as shown, the velocity roughly decreases to zero.
Table 3. The effect of the optimization in velocities at the beginning and end of the manipulator
path.
Velocity in the end of the Velocity in the beginning of the
path (m/s) path (m/s)
Before optimization -0.8433 0.5235
After optimization 0.0626 0.0446
4.1 Effect of initial population in the genetic algorithm.

Since the objective function in the genetic algorithm is dependent on many parameters, efforts are
focused on employing the best parameters possible. Obviously, larger sizes for the initial population
results in better results in the end, however, on the other hand, it also causes longer durations to
achieve the desired solution. Table 4 demonstrates the advantages and weaknesses of selecting large
population sizes.
Table 4. The effect of initial population in optimization with genetic algorithm.

Value of the optimal Algorithm Number of iterations Size of the initial
function runtime (s) igen population Npop
27611 669660 011 21

22609 215.616 011 11
961. 28756.1 011 .1
7605 1689621 011 01
4.2 Effect of number of iterations in the genetic algorithm on the optimization of two-link rigid-
flexible manipulator
The number of iterations is another parameter that highly affects the final solution. As the number of
iterations increases, better solutions are achieved, however, on the other hand, longer runtimes are
required for the calculations. In Table 5, the algorithm was run for different numbers of iterations.
Table 5. The effect of the number of iterations in optimization using genetic algorithm.
Value of optimal Algorithm runtime Number of initial Number of iterations
function (s) population Npop igen
11629 .906. 21 .11
27611 669660 21 011
20675 809618 21 511

196
21659 21106.6 21 611

86.7 2106609 21 711
5. Performance improvement of the genetic algorithm for a rigid-flexible manipulator

Efforts were made to increase the convergence rate of the employed GA as well as its accuracy. The
number of steps for traveling the desired path is one of the factors affecting the convergence rate of
the algorithm. For instance, assuming 400 iterations for the algorithm, if the number of steps is
decreased from 11 to 6, the algorithm runtime is reduced by half while the value of the objective
function is doubled.
Increasing the mutation rate in low values of the optimal function is another effort to increase the
converging rate in the GA. Although in the beginning of the optimization process, usually the values
of the optimal function quickly decrease, this value rarely decreases as we approach the end of the
process. Hence, we may multiply the mutation rate by a factor to increase the chromosome mutations
for lower values of the optimal function.
As it was mentioned in the previous sections, the BFGS algorithm outperforms the GA. However, the
advantage of GA over BFGS algorithm is that its different parameters can freely be adjusted by the
users. Hence, the performance of GA can be further improved than that of the BFGS algorithm by
changing its parameters or presenting new operators. To this end, in order to improve the convergence
rate and decrease the value of the objective function in GA, a novel heuristic algorithm is presented
and integrated with the algorithm, the details of which are given in the following section.
Summary. In this study, after presenting a model of a two-link flexible manipulator, the dynamic
equations of motion were derived using the assumed modes method. Then, considering the desired
path for the end effector of the manipulator, the manipulator was optimized by utilizing a
multivariable objective function. The objective functions were selected such that in addition to
guaranteeing the end effector to travel on the desired path, they can prevent the undesirable extra
vibrations of the flexible components. Moreover, in order to assure a complete stop of the robot at
the end of the path, the velocity of the end effector at the final point in the path should also reach
zero. In order to validate the results, the optimization process was carried out using the BFGS
algorithm and the genetic algorithm. In all the scenarios, the input motor torques applied to the Two-
Link are determined as the optimization variables in a given range such that all the considered
objectives are achieved. According to the results, it was observed that the BFGS algorithm was faster
than GA in converging to the optimal solution. The slope of changes in the values of the objective
function is high but gradually decreases as it converges to the optimal solution. The BFGS algorithm
was able to achieve better results compared to GA running a lower number of iterations. Since the
final value of the objective function after optimization indicates the decrease in the vibrations of the
end effector at the tip of the flexible link, the efficiency of optimization results in the reduction of
vibration.
References
[1] Kojima H, Kibe T. Residual Vibration Reduction Control of a Two-Link Flexible Robot Arm
Using Optimal Trajectory Planning based on Genetic Algorithm. Journal of the Robotics Society of
Japan. 2001, No. 19, 905-912, DOI 10.7210/jrsj.19.905
[2] Kojima H, Kibe T. Optimal trajectory planning of a two-link flexible robot arm based on genetic
algorithm for residual vibration reduction. Proceedings 2001 IEEE/RSJ International Conference on
Intelligent Robots and Systems Expanding the Societal Role of Robotics in the Next Millennium (Cat
No01CH37180)2001. p. 2276-2281 vol.4, DOI 10.1109/IROS.2001.976409
197
[3] Andersson J. Sensitivity analysis in Pareto optimal design.

[https://www.semanticscholar.org/paper/Sensitivity-Analysis-in-Pareto-Optimal-Design-
Andersson/4e11cc0a5beac33d6ab50623ce512b71e709de28]
[4] Li H, Yang Z, Huang T. Dynamics and elasto-dynamics optimization of a 2-DOF planar parallel
pick-and-place robot with flexible links. Structural and Multidisciplinary Optimization. 2009, Vol.38,
195-204, DOI 10.1007/s00158-008-0276-x
[5] Caro S, Chablat D, Ur-Rehman R, Wenger P. Multiobjective Design Optimization of 3PRR
Planar Parallel Manipulators. In: Bernard A, editor. Global Product Development: Proceedings of the
20th CIRP Design Conference, Ecole Centrale de Nantes, Nantes, France, 19th-21st April 2010.
Springer Berlin Heidelberg, Berlin, Heidelberg, 2011. p. 373-83.
[6] Hegde GS, Vinod MS, Shankar A. Optimum dynamic design of flexible robotic manipulator.
International Journal of Mechanics and Materials in Design. 2009, 5, 315-25.
[7] Neto MA, Ambrsio JAC, Leal RP. Sensitivity analysis of flexible multibody systems using
composite materials components. International Journal for Numerical Methods in Engineering. 2009,
77, 386-413.
[8] Zhang X, Xu W, Nair SS. Comparison of some modeling and control issues for a flexible two link
manipulator. ISA Transactions. 2004, 43, 509-25.
[9] Dubay R, Hassan M, Li C, Charest M. Finite element based model predictive control for active
vibration suppression of a one-link flexible manipulator. ISA Transactions. 2014, 53, 1609-19.
[10] Arora JS. Chapter 1 - Introduction to Design Optimization. Introduction to Optimum Design
(Third Edition). Academic Press, Boston, 2012. p. 1-15.
[11] Gennert MA, Yuille AL. Determining the optimal weights in multiple objective function
optimization. ICCV1988. p. 87-9.
[12] Pashaki, Pooyan Vahidi, and Milad Pouya. "Volumetric error compensation in five-axis CNC
machining center through kinematics modeling of geometric error." Advances in Science and
Technology Research Journal 10.30 (2016).
[13] Pashaki, Pouyan Vahidi, and Milad Pouya. "Investigation of High-Speed Cryogenic Machining
Based on Finite Element Approach." Latin American Journal of Solids and Structures 14.4 (2017):
629-642.

198
Design and Simulation of Capacitive Type Comb-Drive Accelerometer TO

Detect Heart Beat Frequency33
P. Ashok Kumar1, G.K.S. Prakash Raaju1, K. Srinivasa Rao2,a
1 Department of ECE, KL University, Green Fields, Andhra Pradesh, India

2 Professor and Head of Micro Electronic Research Group, Department of ECE, KL University, Green Fields, Andhra
Pradesh, India
a ashok09411@gmail.com, drksrao@kluniversity.in
Keywords: inertial sensors, MEMS accelerometer, sensitivity capacitive comb drive, proof mass.
ABSTRACT. MEMS Accelerometers are one of the most common inertial sensors, a dynamic sensor capable of a vast
range of sensing. The basic principle of operation behind the MEMS accelerometer is the displacement of a small proof
mass etched into the silicon surface of the integrated circuit and suspended by small beams. MEMS accelerometers in
Structural Health Monitoring systems can be able to measure the range of acceleration 4g with increasing sensitivity
and decreasing cross sensitivity. In this paper, we have designed and simulated the MEMS capacitive comb drive
accelerometer with respect to the vibrational frequency of the chest wall. The design consists of a proof mass
(4000m6200m) with movable electrodes (2500m200m), fixed beam of electrodes (2500m200m) and a
cantilever beam as a spring (1000m2000m). The Device operates in dynamic mode and simulated using COMSOL
MULTIPHYSICS 5.2 version software. The output total displacement at 20 Hz is 1.52E-10 m and at 40 Hz is 1.45E-
9m, acceleration at 20 Hz is 9.63E-7 m/s2 and at 40 Hz is 9.19E-6 m/s2 is measured. The simulated results are correlated
to the modeling results at the range of frequency 20 Hz 40 Hz.
Introduction. According to the survey of World Health Organization on 22 September 2016 Global
Hearts, a new initiative from the World Health Organization (WHO) and partners launched on the
margins of the UN General Assembly, aims to beat back the global threat of cardiovascular disease,
including heart attacks and strokes - the worlds leading cause of death. The cardiovascular diseases
generally have no symptoms and it can be identified by chest pain or shortness of breath. The
diagnosis of heart diseases is often done by observing the heart beats. These heart beats can be
monitored by different structural health monitoring systems. Structural Health Monitoring (SHM)
systems collect and analyze information about a civil structure so that indications of a structure
distress can be identified early. The existing SHMs Electrocardiogram (ECG), Ballistocardiogram
(BCG) Phonocardiogram (PCG), Ultrasound cardiogram (UCG) are costly devices, contains more
number of components and is difficult to handle for long time ambulatory monitoring of heart
functions and its motions.
Miniaturization of Bio-medical sensors has increased importance of Microsystems technology in
medical applications. Bio-MEMS sensors play an important role in heart rate monitoring. The optical
sensors [1] based on the blood flow, the pressure sensors [2] which transform the vibrations (due to
pumping of blood by heart) into electrical signals and body worn sensors using mechanical
transducers [3] are the existing designs for monitoring the heart rate. Recent research has shown that
accelerometer sensors can be used to reliably detect some physical activity types when tested on small
datasets. The physical mechanisms underlying MEMS accelerometer include piezoelectric,
piezoresistive, electromagnetic, electrostatic, ferroelectric, optical, tunneling, thermal and capacitive.
33

199
The advantages of the MEMS capacitive accelerometer are high sensitivity, low temperature
sensitivity, good DC response and noise performance, low power dissipation, low drift and reduced
parasitic due to single integration chip
In this paper, the MEMS inertial sensor called capacitive type comb-drive accelerometer is designed
to monitor heart beat frequency with increasing sensitivity (4g) and decreasing cross-sensitivity.
The accelerometer is placed on the chest wall a slight variation on the chest surface due to heart beat
allows visualizing the heart motion for assisting and understanding heart function. The device
produces linearity at the heart beat frequency range.
Theory. MEMS accelerometers are the electromechanical devices used to measure acceleration
forces, such forces may be static like continuous force of gravity or dynamic to sense movement of
vibrations. The proposed MEMS capacitive comb-drive accelerometer has the sensitivity range 4g.
Initially the proposed accelerometer has the nominal capacitance when there is no acceleration (a=0).
The device senses the acceleration when it is placed on the chest wall which is transferred to the proof
mass through the flexible elements such as springs. The Proof mass and movable comb fingers move
along the direction of body force while fixed comb fingers remains stationary. The movement
develops the small parallel plate capacitors which are added up to get effective capacitance.
Proposed Design Structure. Figure.1 illustrates the MEMS comb drive capacitive accelerometer
that can be used prototype design of Multiphysics model. The comb drive structure consists of proof
mass with interdigitated fingers extending from the frame. The proof mass is suspended from the
fixed beams with two cantilever springs. The capacitor plates are arranged such that there are two
types of plates: fixed and movable plates as shown in Fig.1. When the proof mass vibrates with the
input vibrations then the movable plates are also moves developing a capacitance with the given
voltage of 5V across the plates.
Fig. 1. 3D view of MEMS comb-drive accelerometer structure.

200
Table 1. Geometries of the Design.

S.No Component Dimensions
1 Proof mass 6200m 4000m 500m
2 Electrodes (fixed and moving) 2500m 200m 500m
3 No.fo electrodes 6
4 Overlapping area of electrodes 1m
5 Cantilever spring 200 m 30 m 500 m
The proof mass can be derived from is =h= 9.8710-5 , where the total area is obtained
from the structure layout, h is the structural thickness and is the density of Silicon
2.33103/3. The spring values calculated from cantilever beams and the spring approximated
constant =1.557 / .
The resonance frequency value is 20Hz obtained from the equation.
1
= 2 (1)
Other important parameters Area moment of Inertia and estimating the damping effect of the system
are the most important steps in the analysis and design process of the proposed design.
Table 2. Premilinary parameters to design the comb drive accelerometer.
S. No Parameters Value
1. Youngs modulus of silicon (E) 160GPa
2. Proof mass (ms) 9.8710-5 kg
3 Spring constant (K) 1.557
4. Frequency of heart vibrations 20 Hz
5. Natural frequency () 125.6 rad/sec
6. Area moment of inertia (I) 1.0410-14 m4
7. Damping coefficient (B) 1.5910-9 N-s/m
8. Damping ratio () 6.410-8

201
Principle of operation. Accelerometer measures the vibrations on the chest wall driven at the
resonant frequency by the inplane and Outplane sensing. The vast majority of accelerometers have in
common a mechanical sensing element consisting of a proof mass attached by a mechanical
suspension system to a reference frame. The accelerometer can thus be modeled by a second order
mass-Damper-spring system as shown in Fig. 2.
Fig. 2. Mass-Damper-Spring system.
According to Newtons second law any external inertial forces due to acceleration displace the
supporting frame relative to the proof mass. This in turn applies a force F = ma on the spring with m
being the mass of the proof mass and a being the acceleration. The spring is deflected until its elastic
force equals the forced produced by the acceleration. In the first order force acting on the spring is
proportional to its displacement F=kx.
Hence,

= (2)

where a is the acceleration produced by force;

m is proof mass;
k is the spring constant;
x is the displacement of the proof mass.
Initially when there is no acceleration i.e, a = 0, then there is no displacement of the proof mass and
electrodes attached to it hence there will be the nominal capacitance about 5.1 pF. When the device
is placed on the chest wall and senses any external acceleration changes the displacement of proof
mass the changes can be monitored along each axis and then analyzed to provide the information of
the heart motion occurring.
Simulation. The accelerometer is modeled in 3D using COMSOL Multiphysics, the simulation and
results are carried out in this software. The simulations are necessary to find the variation of the comb
drive capacitance with respect to the displacement with given input acceleration. The simulations are

202
carried out using the physics Electrostatics and solid mechanics in MEMS module. Stationary and
frequency domain analysis is done for capacitance and displacement results.
Results and Analysis.
Displacement analysis. When the device is placed on chest wall, the input acceleration is produced
due to vibrations of the chest wall. The total displacement at different frequencies is observed.
Fig. 5. Maximum and minimum displacement with input acceleration.
Table 3. The total displacement at different heart beat frequencies.

Acceleration (m/s2) Frequency Displacement
9.63e-7 20 1.52e-10
2.36e-6 25 3.73e-10
4.95e-6 30 7.82e-10
7.61e-6 35 1.20e-9
9.19e-6 40 1.45e-9
The values of displacement at the frequency range of 20Hz 40Hz is obtained and plotted against
the acceleration.

203
1.60E-09
1.40E-09
1.20E-09
Displacement (m)
1.00E-09
8.00E-10
6.00E-10
4.00E-10
2.00E-10
0.00E+00
0.00E+00 2.00E-06 4.00E-06 6.00E-06 8.00E-06 1.00E-05
acceleration (m/s^2)
Fig. 6. Acceleration vs Displacement.
The graph illustrates the displacement of the electrodes is directly proportional to the applied
acceleration at the range of 20Hz to 40Hz frequency.
Capacitance analysis. Theoretically, the capacitance can be calculated with equation
C = (2NsLsHx)/d02 (3)
where = 0r (Permittivity of medium);

Ns No. of sensing electrodes;
Ls length of the sensing electrode;
H thickness of the sensing electrode;
X displacement of the electrodes;
d0 nominal distance between electrodes.
The practical capacitance can be calculated using the following energy relation
1
= 2 2 (4)
The capacitance can be easily measured when the electrostatic energy is known with given 5V
potential difference between moving and fixed electrodes.

204
Fig. 7. Capacitance 20 Hz and 40 Hz frequencies respectively.
Table 5. The total Capacitance at different heart beat frequencies.

Acceleration Frequency Theoretical capacitance Capacitance (pF)
(pF)
(m/s2) (Hz)
9.63e-7 20 0.51 0.12
2.36e-6 25 1.26 0.91
4.95e-6 30 2.65 2.01
7.61e-6 35 4.08 3.63
9.19e-6 40 4.93 4.13
The values of capacitance with change in displacement is obtained and plotted against the
acceleration.
5
Practical
Capacitance
capacitance (pF)
4 (pF)
3
Theortical
capacitance
2
(pF)
1
0
0.00E+00 2.00E-06 4.00E-06 6.00E-06 8.00E-06 1.00E-05
acceleration (m/s^2)
Fig. 8. Acceleration vs Capacitance.

205
The graph illustrates the linear increase of capacitance from 20Hz to 40Hz with the input
accelerations. The increase in capacitance is due to decrease of distance between parallel plates of
electrodes.
Summary. In this paper proposed design of comb-drive accelerometer is carried out with suitable
capacitive sensing technique. Hence the accelerometer is capacitive type comb-drive accelerometer.
The mathematical modeling is done for to find the mass, spring constant and other preliminary
parameters. The device is modeled at the resonant frequency 20Hz hence the device senses the
acceleration only between 20Hz 40Hz (maximum frequency of heart under stationary condition).
The displacement and capacitance values are obtained by simulating the accelerometer in COMSOL
Multiphysics software. By obtaining the simulated results it is concluded that when the displacement
is in between 1.52e-10 to 1.45e-9 range then the person is in normal heart beat frequency range 20Hz
40Hz otherwise the person is affected with Tachycardia or Bardycardia.
Acknowledgement. The authors would like to thank National MEMS Designing Center (NMDC)
supported by NPMASS, IISc Bangalore.
References
[1] P. Ake Oberg, Optical sensors for heart-and respiratory rate measurements, Engineering in
medicine and biology society, 1996. Bridging disciplines for Biomedicine. Proceedings of the 18th
Annual international Conference of the IEEE.
[2] Xu Wang, Jingjing Jin and Shilong Li, Measurement and analysis of Heart Signal Based on the
Pressure Sensor, 2008 6th IEEE international conference on Industrial Informatics Year:2008.
[3] Domenico Zito, Domenico Pepe, Bruno Neri, Werable System-on-a-chip pulse radar sensors for
Health Care: System Overview, Advanced Information Networking and Applications Workshops,
2007, AINAW '07. 21st International Conference on Year: 2007, Volume: 2.
[4] Siram Sai Krishna, Nuti Venkata Subrahmanya Ayyappa Sai, Dr.K.Srinivasa Rao Alain
Beliveau, (1999) Design and Simulation of MEMS-based Piezoelectric Accelerometer.. Evaluation
of MEMS Capacitive Accelerometers. IEEE Explore, 1-9.
[5] B. S.Kavitha, S. B. (n.d.). Capacitive Accelerometer Characteristics Study. IEEE Explore, 1.
[6] Ndu Osonwanne, J. V. (2010). MEMS Comb Drive Reduction Deyond Minimum Feature Size:
A Computational Study. IEEE Explore, 1-5.
[7] Senturia, S. D. (2001). Microsystem Design. Dordrecht: Kluwer Academic Publishers.
[8] Shefali Gupta, T. P. (2005). Optimizing the Performance of MEMS Electrostatic Comb Drive
Actuator with Different Flexure Springs. IEEE Explore, 1-6.

206
Particular Issues Associated with Performing Meterage Through the Use of

Magneto Therapy Devices 34
Y.S. Lapchenko1,a, V.Y. Denysiuk1,b, V.V. Krasovski1,c, V.P. Symonyuk1,d
1 Lutsk National Technical University, Lutsk, Ukraine

a y.lapchenko@lntu.edu.ua
b v.denysiuk@lntu.edu.ua
c vlkras@i.ua
d v.symonyuk@lntu.edu.ua
Keywords: magneto therapy, inductor, magnetic induction, electronic oscillograph, electromotive force, transducer.
ABSTRACT. This article describes the features of the measurement of magnetic parameters of magneto therapy devices.
The following measurement of magnetic induction of a continuous magnetic field, the magnetic induction of the
sinusoidal magnetic field. Also describes the inductive method of measuring a variable magnetic induction of the
sinusoidal and non-sinusoidal of the magnetic field.
Introduction. Magnetic fields which are used in magneto therapy and magneto biology, generally
are inhomogeneous and limited in volume, they are distinct in the variety of parameters. Thus, the
magnitude of magnetic induction can range from fractions to hundreds milliteslas; the fields can be
continuous and variable/alternating (sinusoidal, rippled, pulsed), they are characterized by various
frequencies and waveform of the currency that goes through the inductor. At this variety of
parameters, relevant industrial metering devices can scarcely ever be found. However, even if they
are available, the process of measurement and obtaining a result is quite time-consuming. Firstly, it
is related to the fact that key parameters of the magnetic field, magnetic induction and its gradient,
are vector quantities and must be estimated not only in magnitude (module), but also in orientation.
Transducers, which respond to the direction of a vector, are used for metering quantities. That kind
of transducer must be compact, much smaller than the field action area, because the induction
aggregates throughout the transducer [1].
Research results. For the convenience of use and the increase of mechanical performance, the
transducer along with the connected wires are usually mounted in an applicator which is a thin plastic
plate considerably more long than wide, and is sufficient for manipulating.
Using a step-by-step approaching during the process of metering, a place where a vector of magnetic
induction vertical to the surface of the transducer is found, which is shown by a maximum value of a
device attached to it. In the process of magnetic induction metering on the surface of the magnetic
field source, an applicator is attached against this surface. Taking into account that magnetic field is
inhomogeneous, when magnetic induction and its gradients are in nearly, yet surrounding points, they
can fundamentally differ depending on the type of source (constant magnet, solenoid, electromagnet),
its configuration (the form of section, correlation of crosswise size and longitudinal size), and
dimensions, metering result is valid only to the point at which it is received. In other words, the results
of metering parameters of the field must be snapped to coordinate grid.

207
When it comes to commercialization, as the identity of magneto therapy devices design is provided
with a set of production documents, for the purpose of electrics and background data control, it is
sufficient to check magnetic induction in one pre-selected point, usually near the poles or at the axis
of symmetry. However, this value, which is usually brought in the device configuration, is not only
deficient for the characterization of inhomogeneous magnetic field intensity, but in fact it does not
let assess the field and cannot be used in describing an operative factor or while attempting to
reproduce it. In order to characterize inhomogeneous field (while the homogeneous field in magneto
therapy devices should be considered as an exception), it is needed to snap an image of magnetic
field in the coordinate grid, which makes possible to assess the value of magnetic induction, its
gradient and the direction in the centre of an action or in other studies area. The metering can be done
once at any moment before or after treatment or experimentation, without a patient, in the air, and
they will stay the same in the volume of biological object placed into the field, because living tissues
are transparent for low-frequency magnetic field. So simplifies the metrological assurance in magneto
therapy and magneto biology.
Getting started metering in variable magnetic field, it is necessary to know the current waveform that
supplies the inductor. Industrial gauges are usually designed for continuous field or a field that varies
in accordance with the law and approaches sinusoidal. Upon these and other laws of field alteration,
different methods of metering are used, one of which is inductive.
In magneto therapy and magneto biology the intensity of variable field is usual to characterize by
peak value of magnetic induction and its gradient. But industrial teslameters are standardized at the
average (half-period average) or effective values (root-mean-square). The relation between amplitude
(m), average (av), and effective (e) values for some curves (fig. 1). They are in line in sinusoidal
and pulsating double-wave curves, for which:
Bam 1,414Be 1,571Bav , (1)
and differ in pulsating half-wave curve:
Bam 2Be 3,142Bav . (2)
Fig. 1. The relation between amplitude (m), average (av), and effective (e) values for sinusoidal
wave (a), pulsating double-wave curve (b), and pulsating half-wave curve (c): period of
variation; 0 length of half wave.

208
In the general case, but with the increase of the correlation of the period of variation () to the length
of the half wave (0), the average and effective values decrease. Consequently, the result of pulsed
magnetic field metering depends on the selection of value even more. Depicting magnetic induction
of variable field, it should be necessarily indicated which value is the question, amplitude, effective
or average.
Background noise (induction) affects the magnetic measurements significantly. If the source of
magnetic field is absent, or at the long distance from it, and the devices figures on the chosen scale
differ from zero, the time of metering is changed, performs in another room or shielded cabin.
Industrial Magnetometers and the Scope of Their Use. General Characteristic. Our country does
not produce devices that are intended for metering the intensity of non-sinusoidal variable fields,
including pulsing and pulsed, and does not have industrial gauges for metering the gradient of
magnetic induction at all. The major measure of inaccuracy is introduced, consequently, it belongs to
the bounds of metering. For this reason, the measure of inaccuracy rises greatly at the distance from
the end of the scale, and the first third of pointer-and-scale instruments is not in use generally.
Additional gauging errors are connected not only with the influence of the environment (temperature
change, irrelevant magnetic fields etc.), but in many ways with the procedure of metering: with final
dimensions of the transducer, inexactness of defining its place in the applicator, and, therefore, on the
coordinate grid in the effective magnetic field action area, the aberration of the surface from the point
which is perpendicular to the vector of magnetic induction, instability of the devices figures, and, of
course, the operators qualification. They can by many times exceed the main inaccuracies that are
specified in the devices description.
Magnetic Induction of Continuous Field Detectors. Magnetic field intensity is defined through the
use of any magnetic induction detector which has a suitable scale, or using webermeters completed
with metering coils. The limits of magnetic induction detecting through the use of webermeter are
calculated according to a formula:
B (10 ) / S K , mT
where is a limit of webermeters detection, Wb;

Sk is a constant of metering coil, sm2.
Constant can not be increased randomly:
S K wS , sm2, (3)
It is explained by the fact that, on one side, the square S of the coils form of the section is limited, as
a transducer should be compact, and, on the other side, for each webermeter there is a higher limit of
coil resistance, so, the number of coils w cannot be arbitrarily large. It is well to bear in mind that the
work with the webermeter puts some trouble, because the counting is carried out taking into account
the difference of devices figures, and the indicator drags.
Thus, the most casal and the least time-consuming is metering the magnetic field intensity using
industrial magnetic field detectors. The intensity of continuous field can be defined through the use
of industrial webermeters completed with the produced by the consumer, and those that have been
metrologically checked with measuring coils.
Magnetic Induction of Sinusoidal Fields Detectors. To select the most appropriate teslameter
which is intended to define variable field magnetic induction, inductors power current waveform and

209
its frequency must be acquainted, and in some cases a harmonic factor. An oscilloscope, a frequency
meter and a distortion-factor meter are used to determine them [2].
Teslameters which are designed to work in a variable magnetic field, within all borders are suitable
to measure induction of a sinusoidal field of 50 Hz. Allowable frequencies different from 50 Hz, as
well as inaccuracies depend on the chosen metering borders. Thus, for example, through the use of
milliteslameter 4356 within 0,1 and 0,3 mT it is possible to determine induction with 10%
inaccuracy in the whole audio-frequency range, and on other borders the metering inaccuracy
decreases, but the allowable frequency range is remarkably narrowed down.
Teslameter conforming to the waveform and current frequency, may also need limits of metering,
which can be finalized when the value, wherein the scale is graduated average, effective or
amplitude is known, because according to this, the limits of metering may change by a factor of
1,5. Thus, the scales of 4356 are graduated upon the average values. For the purpose of enumeration
into normally used amplitude values, it is necessary to multiply the devices readings by a coefficient
of 1,57 according to the formula (1), and in this way in amplitude values the limits of measurement
of this device will be from 0,157 to 157 mT rather than nominal 0,1-100 mT. Unlike the device
4356, microteslameter 79 shows true values which can be enumerated into amplitude by
multiplying according to the formula (1) by a coefficient 1,41. So, within amplitude values the limits
of metering of the device are 0,14 T-1,4 mT instead of nominal 0,1 T-1 mT.
Thuswise, industrial devices allow to define an amplitude value of the intensity of sinusoidal field
approximately from fractions of T to 150 mT with the frequency 400 Hz, and to 1,4 T in audio-
frequency range.
Inductive Method of Metering Variable Magnetic Induction. Particular Issues Associated with
Induction Method, and Major Connections. Owing to the lack of industrial devices, it is often
necessary to use specific methods of metering. The intensity of variable magnetic field can be defined
in two different ways: ferroprobe, which is based on the Hall Effect of Faraday Effect, inductive, etc.
Ferroprobe transducers, as a rule, are designed for magnetic field metering up to 10 mT, they are
unappropriated to define the intensity of the field different from sinusoidal. Hall probe needs special
power sources, and their parameters are very temperature-dependent. Implementation of Faraday
method is associated with complex hardware, and is advantageous for studying magnetic fields, the
intensity of which exceeds the intensity used in medicine greatly. Besides, corresponding Hall and
Faraday probes are not always available [3].
Inductive method can be comparatively easy implemented at metering the intensity of variable field
in the wide range of magnetic induction values and frequency. The method is based on using the law
of electromagnetic induction: electromotive force that appears in the coil when put into the variable
magnetic field is analyzed. Thus, metering coil is used as a transducer of magnetic values into
electrical. The benefits of inductive method are stipulated by the ability to make a metering coil with
the necessary dimensions and constant Sk in the laboratory, as well as operational comfort, high
overload ability, and no temperature dependence. For the implementation of inductive method, there
is no need in additional power sources, and metrological examination is limited by the definition of
constant Sk.
Metering coil and its outputs which at the process of metering are connected with the input of an
electronic voltmeter or integrating circuit, are usually mounted on a flat applicator. Maximum values
of the voltmeter are received providing that magnetic induction vector is parallel to its axis and,
consequently, is perpendicular to the surface of the applicator.
If such a coil is put into a variable field in induction B, electromotive force
E (t ) S K Bn / t , (4)

210
is proportional to derivative Bn / t and, therefore, magnetic induction can be determined by the

result of integration E (t ) .
Sometimes when the law of variation is known as, for example, in sinusoidal field, magnetic induction
is derived from differentiation operator, and with the purpose of its definition, it is sufficient to
determine E (t ) .
Magnetic Induction of Sinusoidal Field Metering. In the sinusoidal magnetic field the amplitude
of magnetic induction in accordance with the expression (3) is counted on formula:
Bam Eam / 2fS K .
With the purpose of metering sinusoidal electromotive force, any electronic voltmeter is attached to
the ends of the metering coil (fig. 2, ). As the scale of the voltmeter is normally graduated in effective
values, we change the amplitude value of electromotive force into the effective value. Then, taking
into account the expression (1), we get
Bam Ee 10 4 / 4,44 fS K 2250 Ee /( fS K ) , mT, (5)
and with frequency of 50 Hz
Bam 45 Ee / S K , mT, (5)
where Sk is a constant of metering coil, sm2;

f is a frequency, Hz;
E e is an effective value of electromotive force, mV.
If the scale of being used voltmeter is graduated in amplitude or average values, which is rare, for the
purpose of the evaluation by formula (5) they are changed into effective value:
Ea 0,707 Eam or Ea 1,11 Eav . (6)

211
Fig. 2. Variable magnetic induction measurement in sinusoidal field by inductive method (); in
non-sinusoidal field using capacitive integrator (b), V voltmeter.
As a consequence of the formula (5), the responsiveness of the device which is defined by the
capacitive integrator (the ratio of induction effective electromotive force to the amplitude value of
the defined magnetic induction), can be in general introduced as fSk/2250 mV/mT, and with the
frequency of 50 Hz Sk/45 mV/mT. It is evident that when magnetic induction B and frequency f are
unchangeable and the constant of measuring coil Sk rises, the responsiveness of the device and
electromotive force value undergoes a rise. Consequently, under a weak magnetic field of low
frequency metering, there is a need of a coil with a quite large constant. Thus, if to consider that the
least positive reference of electronic millivoltmeter is 20 mV (the reference at which the urban
laboratory can ignore background noise), so based upon formulas (5) and (5, a), it comes out that for
the purpose of metering 10 mT field with the frequency 50 Hz, the constant of the coil must be not
less than 90 sm2, and with 5 Hz frequency not less than 900 sm2.
Magnetic Induction of Non-Sinusoidal Variable Magnetic Field Metering. When it comes to
metering a non-sinusoidal variable field through the use of magnetic induction method, and
electromotive force is related to the derivative of magnetic induction according to formula (4), and
for the purpose of magnetic induction measurement a capacitive integrator with capacity (C) on the
output is used (fig. 2, b). In the effect that integration is being performed with relatively small
distortion, active resistance R should be much more than reactive resistance I / C , and for pulsed
signal, the time constant RC should be much more than pulse duration , so it is necessary that
RC 1 or RC im (7)
In these conditions, the amplitude of the magnetic induction can be calculated by the following
formula:

212
Bam RCU a 10 4 / S K ,
where R active resistance, kOhm;

capacity, F;
Sk coil constant, sm2;
Ua peak output voltage, mV.
If capacitive integrator is correct according to (7), valid waveform of magnetic field alteration that
was distorted by differentiating on the metering coil, is restored on the output. To control the form of
integrated electromotive force, electron oscillograph is used, upon that its vertical plates are
connected to the capacity in parallel (fig. 2, b). The comparison of the form of an integrated
waveform with the form of inductor current waveform is convenient to make using dual beam
oscilloscope.
Strict observance of the condition (7) includes in a substantial decrease of output voltage, so it can be
comparatively inconsiderable against noise which is sensibly detectable on the scale of 10 mV. In
some instances to increase electric potential Ua coils with constant Sk are used, which go far beyond
1000 sm2.
Example. If the frequency of pulsation is 50 Hz, time length of pulsating impulse is 1/(502)=0,01 s
and RC0,01 s is necessary. This condition is fulfilled, for instance, when =10 F and R=30 kOhm
(RC=0,3 s). If in such case the constant of measuring coil Sk=600 sm2, then
Bam=0,3Ua104/600=5Ua, mT, with calibration constant 0,2 mV/mT. Then at magnetic induction
measurement 40 mT Ua is only 8 mV, which does not provide accurate results. If the coil is changed
to the one with constant Sk=1500 sm2, then Bam=0,3Ua104/1500=2Ua, mT, with calibration constant
0,5 mV/mT, and with the same magnetic induction Ua=20 mV, which is allowable.
Measurement of no-sinusoidal alternating current is done through the use of electronic oscillograph.
The Use of Electronic Oscillograph. If in the context of studying the magnetic field there is a need
to determine the variation of its intensity or the amplitude of non-sinusoidal signal, low-frequency or
impulse (when the pulsing field is studied) electronic oscillograph is used. Working with oscillograph,
a horizontal scan is usually in the position when two-three periods of the studied waveform are on
the screen, and with the aid of vertical scan and base-line drift it is necessary that the maximal range
of the image covers the largest screen area, but is within the working area, its lineal part (it is about
80-90% of the vertical scale of electron-beam tube).
To control the form of the current waveform, voltage power supply is connected to vertical plates of
the oscillograph. To control the form of current waveform or when powered by direct current, within
the aim of defining pulsation coefficient, the circuit of the inductor is interrupted (the power supply
should be turned off in advance!), low-value resistor with resistance r is switched in steps with the
inductor, and its ends are connected to vertical plates of electronic oscillograph. Resistance r (usually
1-2 Ohm) must be much less than the inductors resistance, so that the parameters of the circuit would
change less when the inductor is taken off. The power dissipated by this resistor should not exceed
the limit.
The method for determining the amplitude of the studied waveform depends on its shape. For
sinusoidal waveform, as a rule, any electronic voltmeter is suitable, but it is necessary to get
acquainted with its description in order to find out in which values the scale is graduated. Usually,
these are effective values with scales are set out in average or straightly in amplitude values. The
necessary recalculation is easy to be made in accordance with the formula (1):

213
U am 1,414U e 1,571U av .
When the waveform is non-sinusoidal, for example, pulsed or impulsive, it is not easy to find a
suitable voltmeter for its metering, so an oscillograph is used. First of all, vertical extension is fixed,
wherein the maximal range of the studied signal is within working part of the screen. In this position
the responsiveness of oscillograph in vertical direction is determined with the use of an acquainted
external sinusoidal
q 2,8U ra / hr , mV/line
where effective value of sinusoidal voltage defined with voltmeter, mV;

the range of sinusoid image according to oscillograph screen scale or using internal
calibrator.
Then, leaving unchanged vertical extension of the oscillograph, the studies signal is applied onto
vertical plates, and its range h is determined within indications on the screen. Then, if the irregular
signal is monopolar, amplitude value of its current is Uam=qh, m, and if the signal is symmetrically
bipolar, so Uam=qh/2, and if the coefficient of pulsation is being determined, then:
k p gh / I av r 100 , %,
where I av power in inductor circuit metered by magnetoelectric device, m, and r, Ohm.

Summary. In magnetic therapy and magneto biology magnetic fields are characterized by a large
variety of options for measurement, which are used for measuring the parameters of the magnetic
field. The choice of instrument for measuring parameters of magnetic field depends on the current
form that feeds the inductor and method of measurement of parameters of the magnetic field.
The intensity of the variable magnetic field is characterized by amplitude values of magnetic
induction and its gradient. Because of research established ties of amplitude, average and current
values of the sine wave, pulsating double-wave and half-wave curves. Found that as the relevant
period changes to duration of half-wave the average and current values.
Substantiation of the features of the application of instruments for measuring magnetic induction
direct current and sinusoidal magnetic fields. Inductive measurement technique of the variable
magnetic induction confirmed their effectiveness in measuring sinusoidal and non-sinusoidal
magnetic fields using electronic an oscilloscope to determine the law of change of the non-sinusoidal
magnetic field.
References
[1] K.J.H. Buschow, F.R. de Boer (2004), Physics of Magnetism and Magnetic Materials, Springer
US, P. 182, DOI 10.1007/b100503
[2] Y. Lapchenko (2015). Justification of the choice of material for magnetic core inductors-
electromagnets magnetotherapy devices. Perspective technologies and devices: collected scientific
papers. P. 21-24.
[3] V. Stasyuk (2014). Basics of creating money measuring the magnetic field of the Earth. Existing
solutions. Scientific proceeding of Ukrainian research institute of communication, 1, P. 87-92.

214
Numerical Simulation of the Shear Resistence Test Proposed by NBR 7190

(1997) for a Wood of Corymbia Citriodora
35
Luciano Rossi Bilesky1, a, Cludio De Conti2,b, Priscila Roel de Deus1,c
1 Fatec, Capo Bonito, Brazil

2 Unesp, Rosana, Brazil
a luciano.bilesky@fatec.sp.gov.br
b conti@rosana.unesp.br
c priscila.roel@fatec.sp.gov.br
Keywords: MEF, specimens, eucalyptus, shear block test.
ABSTRACT. The mechanical tests are fundamental for the study of the mechanical behaviour of the materials. In Brazil,
the tests for the verification of the mechanical behaviour of the wood are normalized by the norm NBR 7190 (1997).
These tests seek to provide the necessary conditions to obtain these properties, which is not always achieved with wood,
because it is an anisotropic material and with great variability in its radial and longitudinal constitution. The objective of
this work was to study the tensile and deformation fields present in the specimen of the test of shear strength for wood
proposed by the Brazilian standard NBR 7190 (1997) through numerical simulation using the finite element method with
the aid of commercial software ANSYS 11. In carrying out the test it is assumed that the stress fields in the shear region
are homogeneous, as well as the strain fields are uniform, different from that verified by this present study, in which the
stress fields were heterogeneous and the strain fields were not uniform, which shows that the values predicted by this test
can be underestimated, since the rupture of the test body will occur in a region where the stress concentration is of greater
intensity.
Introduction. Wood is one of the most present materials in the life of man, his biological origin and
abundance in the beginnings of civilization, contributed to that it was one of the first materials to be
manipulated by the man in the making of diverse utensils. In modern life one can find it with the most
varied applications, such as in civil construction, furniture and objects essential to modern life, due
to their natural characteristics such as density, strength and appearance.
Wood is an anisotropic material, however, it may have its simplified behaviour for an orthotropic
model [1]. In this model, three symmetry planes are defined orthogonal to each other, taking into
account their anatomy, that is, the longitudinal direction to the fibres, the direction of the ray cells,
which is radial the direction of the fibres and the direction that tangents the Growth rings as shown
in Fig. 1.
Other simplifications must be considered in order to apply the orthotropic model to the wood, such
as admitting that the trunk has a homogeneous cylindrical geometry, absent from us and other defects
and linear growth rings.
35

215
Fig. 1. Relative reference directions for wood material [2].
For the proper use of the wood it is necessary to know its physical and mechanical behavior, for that,
they are realized through tests that try to provide the conditions necessary to obtain the properties.
However many of these conditions are not obtained through the experimental investigation due to the
heterogeneity, variability and anisotropy of the wood material.
For the characterization of the shear behavior of the wood, some tests are proposed by technical
standards, such as COPANT 30: 1-007, ASTM D143-94 (1994), EN 408 (2002) and NBR 7190
(1997). Although they are widely used and indicated by the technical norms, these tests present
limitations in the characterization of the behavior of the wood to the shear, since they are tests initially
developed for composite materials with isotropic or orthotropic behavior, which were adapted for
wood material without considering Its real behavior due to the heterogeneity of its constitution.
Among the difficulties encountered in the use of the tests in the literature, it is possible to consider
the absence of a global test to characterize all the mechanical properties of the wood, simultaneously
in all planes of symmetry (LR, RL and RT) of the wood. Another difficulty found is that not all tests
are applicable to all planes of symmetry of the wood material, that is, certain tests are specific to
certain planes of orthotropic.
In Brazil, the standard test proposed for the determination of shear strength is NBR 7190 (1997),
which consists of a prismatic test specimen previously prepared, so that when subjected to a stress
with the aid of a mechanism coupled to Universal testing machine, provides a shear stress in a specific
region of the test body.
A similar test to NBR 7190 (1997) is proposed by the ASTM D143-94 (1994) standard, known as a
"shear block test", which differs only by the dimensions of the specimen and the loading rate of the
overall load applied by the test machine universal.
The test proposed by NBR 7190 (1997) admits that the critical plane of the test body has a
homogeneous and uniform distribution of stresses, promoting a pure shear state in this region [3].
The shear block test ASTM D143-94 (1994) demonstrated a similarity to NBR 7190 (1997), and it
can present values of shear strength, underestimated by up to 30% when compared to the results with
other types of tests [4].
Values of the shear strength obtained by ASTM D143-94 (1994) are lower because the ratio of stress
state in the critical plane of the specimen is not homogeneous as intended with said test [5].

216
This work aims to investigate by numerical simulation by the finite element method the verification
of the behavior of the tensile fields and the deformation fields of said test specimen for Corymbia
citriodora wood.
Materials and Methods: In order to obtain the shear stress parallel to the wood fibers according to
NBR 7190 (1997), a test piece with the geometry and dimensions shown in Fig. 2 is used, the
precision of the dimensions being 0.1 mm. The region of the specimen, where the shear will actually
occur, is called a critical section plane (Av), in which the arrangement of this plane is configured
parallel to the radial direction of the wood.
The tension is requested from the test body with the aid of the mechanism shown in Fig. 3. To provide
a shearing tension, the coupling device is moved vertically downwards with a monotonic loading
increasing at a rate of 2.5 MPa / min.
Fig. 2. Dimensions of the specimens for the shear strength test proposed by NBR 7190 (1997).
Fig. 3. Mechanism of aid for the solicitation of force in the specimens.
For the numerical simulation by the finite element method the commercial software ANSYS 11 .
The model was constructed using the geometry and dimensions shown in Fig. 2.
In the construction of the model, the element selected for the analysis was the SOLID 64 of the
ANSYS 11 software element library, because it shows good behavior for structural analysis, since
it allows the entry of all engineering constants related to the study, as well as allowing accurate
reading of the results of this simulation.

217
The engineering constants used for numerical simulation are experimentally determined and are
presented in Table 1 [6].
Table 1. Engineering constants of Corymbia citriodora.

Corymbia citriodora
EL 16981 MPa GLR 861 MPa
ER 1825 MPa S11 0,058.10-12
LR 0,23 S12 0,014.10-12
LT 0,48 S22 0,548.10-12
RT 0,70 S66 1,161.10-12
The engineering constants ET, GLT and GRT are not found in the literature, so they were determined
analytically by the conversion factors of Equation 1 [1].
E L 20 ET 1,6 E L 20

ET 1,6 ER 1 ER 1
(1)
G LR 10 G LT 9,4 G LR 10

G LT 9,4 G RT 1 G RT 1
For the construction of the mesh of the model under study, a convergence analysis was performed
using as a criterion the stabilization of the data found in the center of line 4 indicated in Fig. 4, because
it is a region present in the critical shear plane.
Fig. 4. Reference lines for analysis of strain and strain fields.

218
To obtain the mesh, the number of elements at each interaction was increased, the data were obtained
with the relation xicenter/ximaximum, where xicenter is the value of the greatness x (deformation or tension)
in study in the center of line 4 in the reference x, y or z of the model and ximaxmum is the largest value
of the magnitude in line 4.
The criterion used for the choice of the mesh was the comparison with the stabilization of the variation
of the normalized values of the quantities x, y, z, xy, xz, yz, x, y, z, xy, xz and yz, and thus the
option for the mesh that presents the convergence of these data with less number of nodes used.
The boundary conditions imposed on the model were the fixation of the areas A1 and A2 indicated in
Fig. 5 in the x, y and z directions; and the application of a stress in the downward direction y, with an
intensity of 16.3 MPa in area A3, referring to the shear modulus of Corymbia citriodora wood [7].
Fig. 5. Contour conditions imposed on the specimen model. Regions A1, A2 and A3 that will be
considered in this study.
Results. The graphs of Figs. 6 and 7 show the values obtained by the grid convergence analysis using
the ratio xijcenter / xijmaximum as a function of the number of nodes generated.

219
Fig. 6. Analysis of the convergence of the meshes of the test specimens by the stabilization of the
stresses ij.
Fig. 7. Analysis of the convergence of the meshes of the test specimens by the stabilization of the
deformation ij.
The mesh determined by the convergence analysis for the numerical simulation consists of 14813
nodes and 9759 elements and can be seen in Fig. 8.

220
Fig. 8. Specimen mesh.
For the verification of the stress fields x generated in the test specimen, Fig. 9 is presented, composed
of the model generated by the FEM, accompanied by the graphs of the normalized stress along the
lines representing the shear area.
(a)
(b) (c)
Fig. 9. (a) Stress fields x with unit of measurement in Pa. (b) Graph of stress x normalized along
reference lines 1 and 3; (c) Graph of stress x normalized along reference lines 2 and 4.
221
It can be seen from Fig. 9 that a homogeneous stress state does not occur for the stress x, because
along the reference line 1 and 3 the stress do not show homogeneity. In lines 2 and 4 the
homogenization of the stresses occurs in a considerably large region, but in its extremities, an
accentuation of tensions x is undesirable, due to the strains x in the test body are not uniform, as
shown in Fig. 10.
Fig. 10. Strain fields x in the test body model proposed by NBR 7190 (1997) with unit of measure in
m.
Fig. 11 shows the strain fields y in the specimen model. As can be seen, the strains y occurring in
the region of the shear area can be considered uniform in a large region. However when taken as
reference lines 2 and 4, it is found that the strain fields near the lower support base are shown without
uniformity.
Fig. 11. Strain fields y in the model of the test body proposed by NBR 7190 (1997) with unit of
measurement in m.
Fig. 12 shows the stress fields y obtained by the numerical simulation by MEF, together with the
graphs of stress y normalized along the reference lines of the shear area.

222
The stress fields y can not be considered homogeneous, it is possible to verify through Fig. 12 the
absence of a region with y homogeneous voltages along the reference lines 1, 2 3 and 4 due to the
deformations found not to be uniform nature. In lines 2 and 4, the stress modulus y is accentuated at
the ends of the specimen.
(a)
(b) (c)
Fig. 12. (a) Stress fields y with unit of measurement in Pa. (b) Graph of stress y normalized along
reference lines 1 and 3. (c) Graph of stress y normalized along reference lines 2 and 4.
Fig. 13 shows the stress fields z, obtained in the test body model, along with the graph of the stress
z normalized along the reference lines around the shear area.
The stress fields z, present in Fig. 13, can not be considered homogeneous. In reference lines 1 and
3 of the shear area the stresses are not homogeneous over the entire length of these lines, due to the
non-uniform deformation of the specimen. In the reference lines 2 and 4, the tensions z can be
considered homogeneous in a great extension of these lines, however, the stresses at the extremities
of the test body occur, due to the deformation due to the poisson effect found in the junctions of lines
1 and 2, 2 and 4, 3 and 4, and 3 and 2.

223
(a)
(b) (c)
Fig. 13. (b) Stress fields z. (b) Graph of stress z normalized along reference lines 1 and 3. (c) Graph
of the stress z normalized along the reference lines 2 and 4. (Unit of measurement of in Pa).
The deformations z can be observed in Fig. 14.
Fig. 14. Strain fields z in the model of the specims proposed by NBR 7190 (1997) with unit of measure
in m.

224
(a)
(b) (c)
Fig. 15. (a) Stress fields xy; (b) Graph of stress xy normalized along reference lines 1 and 3; (c)
Graph of stress xy normalized along reference lines 2 and 4. (Unit of measurement of in Pa).
When analyzed in Fig.s 15, 16 and 17, corresponding to the stress fields xy, xz and yz, a behavior
trend is observed close to the stress fields of x and y, these stress fields being non-uniform and with
accentuation in its module at the ends of the reference lines. This intensification of the stresses can
be attributed to the non-uniform deformations occurring in the specimen.

225
(a)
(b) (c)
Fig. 16. (a) Stress fields xz; (b) Graph of stress xz normalized along reference lines 1 and 3; (c)
Graph of stress xz normalized along reference lines 2 and 4. (Unit of measurement of in Pa).
With the observation of the data obtained by the MEF analysis of the test to determine the shear
behavior proposed by NBR 7190 (1997), it can be verified that the fields of stresses x, y, z, xy, xz
and yz are not homogeneous, as well as the strain fields x, y and z, are not found uniform, thus
concluding that a homogeneous stress state is not found in the shear region Av, data obtained by this
assay assuming a state of stress that does not occur are not accurate because shearing accompanied
by rupture of the test specimen occurs first in isolated regions.

226
(a)
(b) (c)
Fig. 17. (a) Stress fields yz; (b) Graph of stress yz normalized along reference lines 1 and 3; (c)
Graph of stress yz normalized along reference lines 2 and 4. (Unit of measurement of in Pa).
Summary. Through the numerical analysis performed using the finite element method, it was
possible to observe the non-existence of a uniform tensile and strain field in the shear area of the test
shear strength test proposed by NBR 7190 (1997) due to the shear strength homogeneity it is possible
to conclude that the values determined by the respective assay can be underestimated.
References
[1] Bodig, J., Jayne, B. A. Mechanics of Wood and Wood Composites. 2. ed., Florida. Krieger
Publishing Company, 1993, 712p.
[2] Calil Junior, C., Lahr, F. A. R., Dias, A. A. Dimensionamento de Elementos Estruturais de
madeira. Barueri: Manole, 2003. 152 p.
[3] Moreschi, J. C. Propriedades Tecnolgicas da Madeira. Curitiba: UFPR, 2007. 168p.
[4] Rammer, D. R., Soltis L. A. Experimental Shear Strength of Glued-laminated Beams. Madison,
U.S. Department of Agriculture, Forest product Laboratory, 1994. 527p.

227
[5] Liu, J.Y., Ross R.J., Rammer D. R.. Improved Arcan Shear Test for Wood. New Orleans: Gopu,
1996.
[6] Ballarin, A. W., Nogueira, M. Caracterizao elstica da madeira de Eucalyptus Citriodora.
Revista Cerne, 9(1): 66-80, 2003.
[7] Instituto de Pesquisas Tecnolgicas do Estado de So Paulo. IPT. Madeira: Uso Sustentvel na
Construo Civil. So Paulo, 2009. 103p.
[6] I. Kolin, S. Koscak-Kolin, M. Golub, Geothermal Electricity Production by means of the Low
Temperature Difference Stirling Engine, Proceedings World Geothermal Congress 2000, Kyushu -
Tohoku, Japan, May 28 - June 10, 2000, 3199-3203
[7] J. Selwin Rajadurai, Thermodynamics and Thermal Engineering, New Age International, 2003,
Heat engineering, 1102 p.
[8] P. Mazzoldi, M. Nigro, C. Voci. (1991), Meccanica, Napoli, S.E.S., 314 p

228
The Influence of Biofuel on the Operational Characteristics of Small

Experimental Jet Engine 36
K. Ratkovska1, a, M. Hocko2, b, J. Cernan3, c, M. Cuttova3, d
1 Department of Power System Engineering, Pilsen, 306 14, Czech Republic

2 Department of Aviation Engineering, Kosice, 041 21, Slovakia
3 Department of Aviation Technical Studies, Kosice, 041 21, Slovakia
a ratkovsk@zcu.kke.cz
b marian.hocko@tuke.sk
c jozef.cernan@tuke.sk
d miroslava.cuttova@tuke.sk
Keywords: Fatty Acid Methyl Esters, jet engine, alternate fuel.
ABSTRACT. This paper investigates the results from experimental measurements made on a small experimental jet
engine designated as MPM-20. The aim of these measurements is to evaluate the possibility of using a blend of the Fatty
Acid Methyl Ester biofuel and Aviation turbine fuel for driving aircraft turbocompressor engines. The experiments were
focused on evaluating the influence of different concentrations of mixtures both fuel types on fuel flow rate, change to
revolutions and the thrust of the turbocompressor engine. A significant influence of the composition of the mixture on the
process of the engine ignition was recorded. As the percentages of biofuel increased in the blend with aviation turbine
fuel, the time taken to reach the engine operation mode was prolonged. More accurate data and results obtained from the
measurements on the small jet engine are discussed in detail in this article.
Introduction. Since the introduction of jet engine aircraft in the early 1950s, world air transportation
revenue traffic volume has experienced unprecedented growth. Today, air transportation accounts for
about 10% of the passenger kilometres travelled by all major motorized modes, and for around 40%
of the interregional transport of goods by value [1].
The historical growth in air transportation was entirely fuelled with petroleum-derived jet fuel. Unlike
any other sector, air transportation heavily depends on this high-energy-density fuel. For nearly 100
years, the perennial fear of peak oil point of time when half of the worlds oil resources will have
been depleted and prices therefore will arise to maximum has also contributed to the search for
alternatives to petroleum [2]. It follows that the aviation industry needs to find new organic
alternatives to conventional fuels, which should be a full substitute for kerosene and jet fuel. The
main reasons are the dependency of aviation fuels on petroleum and the increasing impact of air
transport on the earth's atmosphere [3].
According to numerous studies [4, 5, 6] it is believed that some specific Fatty Acid Methyl Ester
(FAME) blends, such as low carbon number saturated fatty acid esters, could be reconsidered as a
possible aviation fuel blend component. However, at the present moment FAME is not approved as
a jet fuel additive. The maximum allowable level is 50 ppm, which is the officially accepted functional
definition of Identified Incidental Material [7]. All the accepted alternative jet fuels have a common
drawback: they do not have any oxygen in their molecular structures since FAME are not approved
additives. However, the presence of oxygen in a fuel has two main advantages: it reduces the carbon

229
content of the fuel, which in turn reduces its carbon footprint and reduces the soot formation
(emission) of the fuel. Llamas et al. [8] make the point that based on smoke point testing, jet fuel
containing oxygenates should give lower total particulate matter (PM) emissions than conventional
jet fuel. According to numerous studies, emissions from planes at large airports are significant sources
of local air pollution, including fine PM that can increase peoples risk of heart disease and asthma
[9].
At present, there are many studies in progress with varying results. In one such study focused on
alternatives to conventional diesel fuels it has been found that tall oil methyl esterdiesel fuel blends
had the advantages of decreasing CO emissions (up to 38.9%), low sulphur content and higher cetane
number [10]. However, the literature on the production and use of biodiesel for the aviation sector is
still scarce and in some cases, contradictory. Dunn [11] studied the properties of a fuels obtained by
blending 10-30% vol. of soybean FAME with JP-8 and JP-8+100. Dagaut and Gail [12] examined
the oxidation behaviour of a blend of 20% vol. Rapeseed FAME with Jet-A1. This blend is important
also for our research.
Experimental.
Experiments were carried out for examination of how different concentrations of blends of Fatty Acid
Methyl Ester (FAME) biofuels and aviation turbine fuel - Jet A-1 affect the operational characteristics
of small jet engine. The concentration of FAME biofuel was varied from 0% to 40%. The methyl
fatty acid esters of rapeseed are a biofuel, and the fuel is nontoxic, as it does not contain any heavy
metals or any harmful substances. For experiments was used small experimental jet engine designated
as MPM-20 shown on Fig. 1.
Fig. 1. Experimental jet engine MPM-20.
Small experimental jet engine marked as MPM-20 was made by constructional modification of the
TS-20/21 turbo starter. The MPM-20 jet engine is made up of following main components: a mixed
(axial-radial) air intake system, a centrifugal compressor with a single sided impeller, an annular
combustion chamber, a single stage axial uncooled gas turbine of the reaction type, an output system
with the fixed outlet nozzle. Detailed constructional description has been already mentioned in our
previous work [13].
An MPM-20 jet engine is equipped with sensors that continuously monitor the basic thermodynamic
parameters of the engine and other selected parameters describing its activity. Principal schematics
230
of such system, providing controlling and monitoring function, is shown on Fig. 2. In the measuring
chain were used analog and digital sensors, which are connected to the bus system of SCXI 1000 with
transduction SCXI cards 1102 and 1303. The system was connected to a PC, where with the help of
the program LabView environment is processed and displayed as a virtual dashboard for immediate
endpoint all the measured parameters of the engine MPM20.
This system allows the monitoring of the engine during operation and also recording these parameters
for the purpose of subsequent diagnosis of correct operation of the engine and its systems. Electronic
management of engine MPM 20 improved characteristics of the engine and also the possibility of its
regulation within the prescribed limits. The monitoring of conditions in real time allows safer
operation of the engine and the protection of the parts before exceeding the safe operating temperature
and pressure [17].
Fig. 2. Schematics of MPM-20 controlling and monitoring system.
During experiment the MPM-20 was set to the reduced operation mode (n = 46 700 min-1). The
length of measurement cycles ranged from 45 5 seconds. The short time operation cycles is
necessary because the original Turbo-starter was constructed only for short operation suited for
starting up more powerful jet engine. The long-term operation of the MPM-20 small turbojet engine
231
causes an increase of the thermal stress of the hot engine parts, in particular the combustor liner,
turbine stator vanes and rotor blades, turbine rotor disc, and the engine can be easily damaged. Most
importantly, the turbine rotor disc dangerously changes its outer radius at high temperatures there
is a danger of destruction of the rotor blades by collision with the outer turbine ring [13].
Fatty Acid Methyl Ester in rapeseed.
The fatty acid methyl esters of rapeseed are a biofuel. Biofuels can be defined as liquid fuels produced
from biomass for either transport or burning purposes. They can be produced from agricultural and
forest products, and the biodegradable portion of industrial and municipal waste [14, 15]. Methyl
esters must meet the requirements of standard EN 14214, which strictly applies only to methyl esters
made from rapeseed oil (FAME).
Although it is chemically different from petroleum products, its density, viscosity, calorific value and
process of burning is very close to diesel fuel. In comparison with diesel fuel, it is characterized by
much better parameters for CO2 and SO2 emissions, and has only slightly higher NOX emissions.
FAME is nontoxic, as it does not contain any heavy metals or any harmful substances [16]. When
examining the possibility of blends of FAME biofuel and A-1 jet fuel, it was found that at all
concentrations (from 0% to 90%) there was a homogeneous blend, without the formation of deposits
or coagulants. The density of blends depended on the increasing proportion of FAME biofuel in the
blend
The physical properties of FAME (Fig. 3b) biofuel and fuel Jet A-1 (Fig. 3a) are shown in Table 1.
a) b)
Fig. 3. a) Jet A -1, b) FAME [15].
Table 1. The physical properties of FAME biofuel and Jet A-1.

Parameter Unit Jet A11 FAME2 Parameter
Density (15 C) kg.m-3 810 882 Density (15 C)
Acid number mgKOH/g 0.003 0.23 Acid number
Flashpoint C 64 168 Flashpoint
Sulphur content mg.kg-1 0.01 0.1 Sulphur content

1
based on the standards STN 050100
2
based on the standards TSHV 08-001 a EN14214

232
Operational parameters of MPM-20

The experimental measurements were conducted on the MPM-20 jet engine operating in the reduced
mode for 45 5 seconds and the concentration of FAME biofuel was varied from 0% to 40% [17].
Measured values of the basic parameters (0% FAME) of the MPM-20, as the thermodynamic
parameters, engine revolutions, fuel flow rate and thrust is given in Table 2. Comparing with these
values it is possible to analyse the influence of a particular concentration of a blend FAME biofuel
and Jet A-1 fuel on the operational characteristics in steady state mode and the transition modes of
the engine. For each concentration of biofuel blends of FAME and Jet A-1 were performed at least
three measurements, which have been selected for the evaluation of a representative graph.
Table 2. Change in MPM20 basic parameters and the operational characteristics.

Parameter 20 sec. 30 sec. 40 sec. 45 sec.
T0 [C] 25.5 25.5 25.5 29.1
T2t [C] 107.1 123.5 105.4 70.5
T3t [C] 943.1 992.8 1007.9 456.9
T4t [C] 620.8 652.8 666.6 361.6
p2t [Pa] 263645.8 262923.1 260784.9 -
p3t [Pa] 192083.9 190688.5 188005.8 -
Qf[l.min-1] 1.233 1.221 1.204 -
n [RPM] 46 808.7 46 820.9 46 424.9 15 068.9
FN [N] 448.7 451.3 444.9 4.18
Engine revolutions. The change in engine revolutions of MPM-20 Fig. 4 during its operation is
controlled by a regulatory management system of the engine, which is set to maintain a constant speed
on the operating mode n = nmax. The aforementioned regulating law depends on the needs of the
original turbine starter TS-20, from which the MPM-20 was created. For this reason, the flow rate of
fuel mixture Qf was changed. To maintain constant revolutions of the operating mode it was necessary
for the individual blend of FAME biofuel and fuel Jet A-1 to ensure the required energy value, which
required increased delivery of the blend of FAME biofuel, and fuel Jet A-1. In the range of operation
of the MPM-20 from 25 seconds to 40 seconds, the maximum revolutions difference is nmax = 60.6
RPM which represents a deviation of 0.129% relative to the maximum engine revolutions.

233
Fig. 1. Behavior of engine revolutions.
Table 3. Change of engine revolutions n [RPM x103].

Blend Jet
20 sec. 25 sec. 30 sec. 35 sec. 40 sec.
A1/FAME
100 % 46.8 46.81 46.82 46.83 46.42
90 % / 10% 46.82 46.8 46.77 46.7 46.71
80 % / 20% 42.22 46.77 46.7 46.79 46.65
70 % / 30% 46.96 46.85 46.68 46.66 46.58
60 % / 40% 46.94 46.82 46.82 46.72 46.67
Fuel flow rate. The course of changes in the supply of different blends of FAME biofuels and fuel
Jet A-1 at startup of the engine corresponds to the startup of the MPM-20. After reaching the operating
mode of MPM-20, the flow rate of the fuel blend stabilizes and it only minimally falls by about 0.002
l.min.-1 (60% Jet A-1 and 40% FAME) to 0.052 l.min.-1 (80% Jet A-1 and 20% FAME). The biggest
difference in the rate of flow of fuel Qf = 0.071 l.min.-1 between fuel Jet A-1 (1.204 l.min.-1) and a
blend of 60% of fuel Jet A-1 and 40% FAME biofuel (1.277 l.min.-1) occurred in the 40th second.

234
Fig. 2. Behavior of fuel flow rate.
Table 4. Change of fuel flow rate - Qf [l.min-1].

20 30 40
Blend Jet A1/FAME 25 sec. 35 sec.
sec. sec. sec.
100 % 1.233 1.218 1.221 1.218 1.204
90 % / 10% 1.245 1.226 1.230 1.225 1.221
80 % / 20% 1.164 1.299 1.264 1.261 1.247
70 % / 30% 1.288 1.273 1.259 1.271 1.255
60 % / 40% 1.288 1.277 1.278 1.278 1.275
Thrust. The change in the thrust of the experimental engine MPM-20 depends on the composition of
the blend of the fuel Jet A-1 and FAME biofuel. In operation mode, the change is relatively low and
is not proportional to the proportion of the FAME biofuel in the fuel blend. The MPM-20 achieves
the highest thrust with a blend containing 20% FAME biofuel. From 20 seconds to 35 seconds the
maximum deviation of thrust is 37.5 N (20 seconds) and the minimum deviation of thrust is 15.8 N
(35 seconds), which is a deviation of 8.3%. The measured values of the thrust from the MPM-20
correspond to the calculated value.

235
Fig. 3. Behavior of thrust.
Table 5. Change of thrust FN [N].

Blend Jet
20 sec. 25 sec. 30 sec. 35 sec. 40 sec.
A1/FAME
100 % 448.7 444.9 451.3 451.3 444.9
90 % / 10% 441.3 440.5 444.8 438.9 438.8
80 % / 20% 418.7 460.9 460.8 454.7 456.4
70 % / 30% 456.2 448.9 448.8 448.9 442.8
60 % / 40% 450.1 446.1 441.9 439.9 439.9
Summary. The measurements confirmed that due to small differences in the calorific values of Jet
A-1 fuel and FAME biofuel, different concentrations of the blends have only a small effect on the
measured parameters (thrust, engine revolutions, fuel flow rate) of the MPM-20 experimental engine.
The operating mode of the engine control law had a major impact, which ensures maintain constant
revolutions nmax. = const.
The composition of the mixture of Jet A-1 and FAME biofuel has a substantial effect on the startup
of the MPM-20. Increasing the percentages of FAME biofuel in Jet A-1 fuel prolonged the time taken
to reach operating mode. After exceeding 40% of FAME biofuel mixed with Jet A-1 fuel the startup
process failed. The reason for the unsuccessful ignition of the mixture was the evaporation of an
insufficient amount of atomizing fuel mixture in the fuel nozzle, which was designed to dispense Jet
A-1 fuel. The ignitor for the fuel-air mixture is only an electric discharge spark plug, which is not
enough to ignite a mixture with a composition different from pure Jet A-1 fuel. When re-starting the
heated MPM-20 engine after the previous operation, startup was successful with a mixture of 60%
Jet A-1 and 40% biofuel. The evaporation of this mixture was caused by heat radiating from the
heated parts of the MPM-20. The delayed start of the MPM-20 using a blend of 80% Jet A-1 and 20%
biofuels was atypical. The largest deviation was measured with this composition. But this deviation
was determined mainly by different temperature of the engine at the beginning of the test.
Acknowledgments
The authors would like to take this opportunity to thank the staff of the Laboratory of Intelligent
Control Systems of Jet Engine. The presented work was financially supported by the Ministry of
Education, Youth and Sport Czech Republic Project LQ1603 (Research for SUSEN). This work has

236
been realized within the SUSEN Project (established in the framework of the European Regional
Development Fund (ERDF) in project CZ.1.05/2.1.00/03.0108).
References
[1] Shafer, A. et al. Transportation in a Climate-Constrained World, MIT Press, Cambridge MA, 2009
[2] Chuck, Ch. Biofuels for Aviation: Feedstocks, Technology and Implementation, Academic Press,
ISBN: 9780128032152, pp. 390.
[3] Altin, R. An experimental investigation on use of vegetable oils as diesel engine fuels, Ph.D.
Thesis, Ankara Gazi University, 1998
[4] Blakey, S. et al. Aviation gas turbine alternative fuels: a review, Proc. Combust. Inst. 3 (2011),
pp. 2863-2885.
[5] Chuck, Ch. Et al. The compatibility of potential bioderived fuels with Jet A-1 aviation Kerosene,
Appl. Energy 118 (2014), pp. 83-91.
[6] Wilson, G.R. et al. Certification of alternative aviation fuels and blend components, Energy Fuels
27 (2013), pp. 962-966, DOI 10.1021/ef301888b
[7] Llamas, A. et al. Oxygen extended sooting index of FAME blends with aviation kerosene, Energy
Fuels 27 (11) (2013), pp. 6815-6822, DOI 10.1021/ef401623t
[8] ASTM International, ASTM D 1322-15el: Standard Test Method for Smoke Point of Kerosine
and Aviation Turbine Fuel, ASTM International, West Conshohocken, PA, 2015.
[9] Duran, A. et al. Alternative fuel properties of tall oil fatty acid methyl esterdiesel fuel blends,
Bioresource Technology Vol. 98 Issue 2 (2007), pp. 241246
[10] Dunn, R.O. et al. Low-temperature properties of triglyceride-based diesel fuels: transesterified
methyl esters and petroleum middle distilate/ester blends, J. American. Oil Chem. Soc. 72 (8) 1995,
pp. 895-904.
[11] Dagaut P., Gail S. Kinetics of gas turbine liquid fuels combustion: jet A1 and biokerosene,
Proceedings of ASME Turbo Expo Vol. 2 (2007), pp. 93-101
[12] Ratkovsk K., eran, J., Cttov, M. Semrd, K.: The Analyses for the Casing Improvements
of the MPM-20 Engine, In: Proceeding of ASME TurboExpo Vol. 8. (2015)., pp. 1-9. ISBN: 978-0-
7918-5679-6
[13] Jiricek I., Rabl V. Energy from Biomass / Energie z biomasy, (AZE 04/2005) Available on:
http://www.vscht.cz/ktt/zdrene/5.0_Energie_z_biomasy.pdf
[14] Ratkovsk, K. Hocko, M.: The influence of the blend of FAME biofuel and jet fuel on the
thermodynamic parameters of an MPM 20 engine, Experimental fluid mechanics 2016, Marinske
Lzne, Czech Republic
[15] A. Dufey, Biofuels production, trade and sustainable development: emerging issues (2006)
ISBN: 978-1-84369-643-8 Available on: http://pubs.iied.org/pdfs/15504IIED.pdf
[16] Fz L., Andoga R., Madarsz L. Mathematical model of a small Turbojet Engine MPM-20. In:
Studies in Computational Intelligence. Vol. 313 (2010), pp. 313-322. - ISSN 1860-949X.

237
Static Analysis of Total Knee Joint Replacement 37
Vinay Kumar. P1, 2, S. Nagakalyan2, b
1 Department of Mechanical & Aerospace Engineering, Indian Institute of Technology Hyderabad, TS, India
2 Department of Mechanical Engineering, Kommuri Pratap Reddy Institute of Technology, Hyderabad, TS, India
Keywords: tibial component, femoral component, tibial insert, contact stresses, wear.
ABSTRACT. Knee joint is important joint in human. This joint is also called as weight bearing joint and stabilizes the
body movements. The disease caused to knee joint due to Rheumatoid arthritis, Osteo-arthritis and Traumatic arthritis is
called Knee joint failure. The failure knee joint is replaced by artificial components either partially or totally. 3-
Dimensional assembly in different orientations of knee joint components are modelled in SolidWorks V6. Analysis in
different orientations is performed using Ansys14 software. The early failure (wear and tear) of knee joint implant
components is found out by evaluating contact stresses between the Femoral component and UHMWPE. The metallic
implant material used in this project is TNTZ (titanium alloy) and compared with CoCr, Ti6Al4V. It is observed, the
contact stresses are less in UHMWPE with TNTZ material is used as compared to other materials.
Introduction. The contact stresses of knee prosthetic depend on the amount of load applied and the
contact area between the femoral and tibial components [1]. It also depends on the angle of flexion
and extension. If the load on the knee prosthetic increases, the life of the knee prosthetic decreases.
The meniscus in the knee joint is multifunctional component; it plays a major role in load
transmission, shock absorption and lubrication [2]. The failure of meniscus is the meniscal tear, it
causes severe pain in the knee joint. The contact stresses are high in the articular cartilage after
meniscectomy as compared to that of a knee joint. Failure knee joint is replaced by metallic implants
[3]. After knee surgery, the stress shielding increases at the knee joint leading to gradual bone loss
and knee joint failure. FEA analysis is done to obtain the stresses at the knee joint between the femoral
bone and the implant. In the hybrid implant the stresses produced are less when compared to
commercial implant, providing better stress shielding as compared to the conventional implant. Total
knee replacement failure is due to loosening of femoral component, tibial-femoral instability, and
fatigue failure of tibial tray [4]. These are due to over weight of the body and mal-alignment of the
knee joint. The dynamic and finite element models of fixed and mobile implants are developed and
demonstrated the performance of knee joint and contact pressure distribution in the tibio-femoral
contact surfaces at different orientations. Ma-alignment indicate severe stress shielding in the knee
joint leads to bone resorption. This will result in more chance to failure of knee joint, induces more
pain to the patient. Surgical repair of patella-femoral joint is known as Patella-femoral arthroplasty
where the patella and femoral parts are replaced by artificial components [5]. The implant designs are
Richards type II patello-femoral prosthesis, Physiological model of knee, Journey patello-femoral
joint prosthesis, Genesis II total knee prosthesis and Journey patello-femoral joint prosthesis. The von
misses stresses are evaluated during 1200 flexion of knee joint and the effect of stress shielding is
found. The FEA results are compared with the experimental results. From the results it indicates that
during flexion, the Richards II patello-femoral prosthesis has higher stress compared with the other
patella-femoral prosthesis, and in Genisis II total knee prosthesis the stress shielding is high compared
to physiological model of knee joint. The materials used in knee replacement surgery must be bio-
compatible, light weight and should have high strength to weight ratio [6]. Most commonly used

238
materials in knee replacement surgery are titanium alloys, cobolt chromium alloys, steel alloy, etc.
These materials are having high strength but more weight. Stress shielding causes bone resorption
and leads to failure of total knee replacement surgery. The patient experiences more pain than before
surgery. The implant youngs modulus and bone youngs modulus is different which increases effect
of stress shielding [7]. To reduce the stress shielding between the bone and the implant, alternate
materials are introduced which are having low youngs modulus and high strength. Titanium- alloy
is a suitable bio-compatible material with low youngs modulus. The strength of the alloy is increased,
maintaining low youngs modulus by different strengthening mechanism such as strain hardening,
grain modification, etc. Wear of TKR is due to more contact area and high contact stresses in the knee
joint [8]. Wear analysis is performed experimentally and numerically and compared the results. The
results show very near values. Author predicted that it taken 2 months to conduct experiment and 2
hours to find computational wear. The contact stresses are depend on the sagittal radius of knee joint
and lower contact stresses are seen in polyethylene chopped fiber composite artificial joint compared
to polyethylene [9]. Jasper Harris [10] studied the mechanical properties of UHMWP in order gain a
better understanding of wear. Depending upon material treating, the strength of the material can vary
in different directions. 3 Dimensional CAD model of knee joint implants can be done by tomographic
data and MIMICS software [11]. Brandi C Kar et al. [12] studied various knee implants, materials,
wear analysis of knee joint implants and its biomechanics.
3D CAD Model of Knee Joint Implant. Three-dimensional CAD model is developed in SolidWorks
V6 software according to ISO standards ISO 7207 - 1: 2007. The generated CAD models are imported
to Ansys 14.0 for static analysis of the knee joint implants to evaluate the contact stresses between
the femoral and tibial insert components at the different flexion angles such as 150, 450 and 600. The
geometrical 3D model of femoral component, tibial component and UHMWPE is shown in the Fig.
1.
(a) Femoral Component (b) Tibial Component (c) Tibial Insert

Fig. 1. Knee joint components.
During the knee motion, the knee flexions and extends from 00 to 900 shown in the Fig. 2. At this
instant, loads are acted at the contact regions of femur bone, meniscus normal to the thigh- bone.
a) 0-degrees b) 30-degrees c) 60-degrees d) 90-degrees

Fig. 2. Knee motion from 00 to 900.
239
The assembly of knee joint implant comprises of femoral component (fixed to femur bone), tibial
insert (UHMWPE in between femur & shin bone) and tibial baseplate (fixed to shin bone).
Considering the knee joint kinematics, various geometric orientations of the knee joint implant are
modelled shown in the Fig. 3.
(a) 150 Flexion Angle (b) 450 Flexion Angle
(c) 600 Flexion Angle

Fig. 3. Knee joint implant at different flexion angles.
FE Analysis
Assumptions in the model:
The following assumptions are made in solving the problem numerically
1. The knee implant is made of linear, elastic, isotropic, homogeneous material;
2. The contact surfaces are perfectly bonded together;
3. The load applied on femoral component is equal for magnitude and direction;
4. The tibial tray is fixed and constrained in all degrees of freedom;
5. In the fixed implants, polyethylene insert is fixed to the tibial tray, and there is no movement
with the femoral component.
Materials and their properties:
Materials. The materials which are used in knee joint replacement surgery must have certain
properties as per ISO standards.
Anti-allergic;
Biocompatible;
Non-corrosive;

240
Non-toxic.
The following are some materials which used in knee joint implants:
1. Cobalt chromium alloy (CoCrMo);
2. Stainless steel 316L;
3. Titanium alloys;
4. Ti-6Al-4V;
5. Ti-29Nb-13Ta-4.6Zr also known as TNTZ etc.;
6. Porous Tantalum;
7. Ultra High Molecular Weight Polyethylene (UHMWPE).
Properties.
Table 1. Mechanical properties of materials.

Density Youngs Poissons Tensile yield Ultimate tensile
Material
(Kg/m3) modulus (GPa) ratio strength (MPa) strength (MPa)
CoCr 7990 200 0.3 560 1000
Ti6Al4V 4430 113.8 0.36 880 950
TNTZ 6075 35 0.36 800 820
SS 316L 7990 193 0.3 290 558
UHMWPE 926 0.69 0.45 21 48
Porous
2490 3.5 0.34 51 110
Tantalum
Model validation with Experimental results. The failure of knee joint implant replacement is
because of wear between Femoral component, PE insert and Tibial Tray. The early detection of
contact stresses in the contact areas of implant components prevents wear and increases the life of
knee joint implant replacement. Tomaso et al. [1] conducted experiments on knee joint component to
find the contact stresses at different stages of gait cycle between Femoral component, Tibial Tray and
PE insert. The femoral component (implant to femur bone) and tibial tray (implant to shin bone) is
made of Cobalt chromium and tibial insert(bearing component) is prepared of UHMWPE (Ultra High
Molecular Weight Polyethylene). The CAD model of knee joint components is validated by the
experimental results. Vertical load is applied on the model at various flexion angles from 150 600
as follows.
Table 2. Loads at various flexion angles.

Flexion angle (0) Load applied (N)
15 2200
45 3200
60 2800

241
The maximum pressure is calculated at the contact regions between Femoral component, PE insert,
and Tibial Tray tabulated in Table 3.
Table 3. Validation of results: Superior surface.

Flexion Load Experiment[1] FEM[1]
FEM (MPa)
angle (Deg) applied (N) (MPa) (MPa)
15 2200 14.5 15 15.61
45 3200 25 27.7 27.86
60 2800 22 24.6 24.89
Fig. 4 shows model validation for maximum pressures at the contact regions of knee implant between
Experimental results and FEM simulations.
From the model validation results, the FEM simulations are conducted on the knee joint implant using
different materials on designed knee joint implant.
Author FEM Experiment Results CoCr

27.86
27.7
24.89
24.6
25
22
15.616
14.5
15
15 DEG 45 DEG 60 DEG
Fig. 4. Validation results.
Results and Discussion. The total knee joint implant components are designed in SolidWorks V6
and Finite Element Analysis is performed at various flexion angles (150, 450, 600 ), to determine the
contact stresses between Femoral component & PE insert.
Case 1: Titanium alloy (Ti-6Al-4V) is used.
Case 2: Titanium -alloy (TNTZ) is used.
The contact stresses between Femur component and Polyethylene insert for above two cases are
obtained at different flexion angles and are compared with the experimental results [1] and tabulated
in Table 4. From the results it is found that, the contact stresses are less with TNTZ material compared
with Ti-6Al-4V, Co-Cr and to the experimental results. This proves that the knee joint model is best
suitable and increases life of the knee joint implant replacement.

242
Table 4. Contact stresses between FC and PE insert for case 1 & 2 respectively
Flexion Load Experiment[1] FEM[1] FEM Case 1 FEM Case 2
angle (Deg) applied (N) (MPa) (MPa) (MPa) (MPa)
15 2200 14.5 15 18.38 10.6
45 3200 25 27.7 30.79 21.7
60 2800 22 24.6 34.65 20.2
Author FEM Experiment Results Ti6Al4V Author FEM Experiment Results TNTZ
30.795
27.7
28.651
24.6
21.719
27.7
25
20.212
24.6
22
25
22
16.386
14.5
15
10.616
14.5
15
15 DEG 45 DEG 60 DEG 15 DEG 45 DEG 60 DEG
(a) Ti6Al4V (b) TNTZ

Fig. 5. Comparison of contact stresses between FE and TB insert.
The contact stresses on PE insert for different materials at various flexion angles and at different
loading conditions are shown in the Fig. 6 to Fig. 8.
The following figures are the stresses in the UHMWPE components at flexion angle 150 with Co-Cr,
Ti-6Al-4V and TNTZ alloys.
(a) Co-Cr alloy (b) Ti-6Al-4V alloy

243
(c) TNTZ
20
15
Co-Cr
10 TNTZ
Ti-6Al-4V
Ti-6Al-4V
5
TNTZ
0 Co-Cr
15 Deg Flexion
Angle at 2200 N
Load
(d) Comparison of contact stresses between FE and TB insert with Co-Cr, Ti-6Al-4V & TNTZ
Fig. 6. 150 Flexion Angle UHMWPE @ 2200N Load.
The following figures are the stresses in the UHMWPE component at flexion angle 45 0 with Co-Cr,
Ti-6Al-4V and TNTZ alloys respectively.
(a) Co-Cr Material (b) Ti-6Al-4V alloy

244
(c) TNTZ alloy
35
30
25
Co-Cr
20
Ti-6Al-4V
15 TNTZ
TNTZ
10 Ti-6Al-4V
5
0 Co-Cr
45 Deg Flexion Angle

at 3200 N Load
(d) Comparison of contact stresses between FE and TB insert with Co-Cr, Ti-6Al-4V
& TNTZ alloys respectively.
The following figures are the stresses in the UHMWPE component at flexion angle 600 with Co-Cr,
Ti-6Al-4V and TNTZ alloys respectively.

245
(a) Co-Cr alloy (b) Ti-6Al-4V alloy
(c) TNTZ alloy
30
25
20
Co-Cr
15
Ti-6Al-4V
10 TNTZ
Ti-6Al-4V TNTZ
5
0 Co-Cr
60 Deg Flexion
Angle at 2800 N
Load
(d) Comparison of contact stresses between FE and TB insert with Co-Cr, Ti-6Al-4V &
TNTZ alloys respectively
Summary. From the comparison of FEA results with experimental results Fig. 4, it was observed
that the contact stresses are more in the Ti-6Al-4V material knee joint implant compared to the CoCr

246
material. This increase in the contact stresses results in increase in wear between the Femoral
component and PE insert and increases the life of the knee joint implant.
From the comparison of FEA results with experimental Fig. 5, it was observed that the contact stresses
are 33% less in the TNTZ material knee joint implant compared to the CoCr material. This reduction
in the contact stresses proves reduction in wear between the Femoral component and PE insert and
increases the life of the knee joint implant.
By using TNTZ material for knee joint implant, the overall weight of the knee joint implant is reduced
by 23.96 % compared to the implant used by Tomaso et al [1].
Acknowledge. Authors express deep sense of gratitude to IIT Hyderabad & special thanks to KPRIT.
References
[1] Tomaso Villa, Francesco Migliavacca, Dario Gastaldi, Maurizio Colombo, Riccardo Pietrabissa.
Contact stresses and fatigue life in a knee prosthesis: Comparison between in vitro measurements and
computational simulations. J. of Biomechanics. 2004 37, 45-53. DOI 10.1016/S0021-
9290(03)00255-0
[2] E. Pena, B. Calvo, M.A. Martinez, D. Palanca, M.Doblare. Finite element analysis of the effect
of meniscal tears and meniscectomies on human knee biomechanics. Clinical Biomechanics. 2005,
20, 498-507. DOI 10.1016/ j.clinbio mech.2005.01.009
[3] Habiba B, Ziauddin M, Milan M, Md. Youssef. Finite element investigation of hybrid and
conventional knee implants. International J. of Engineering 2009, 3. 257-264.
[4] M. Sivasankar, V. Mugendiran, S. Venkatesan, A. Velu. Failure analysis of knee prosthesis.
Recent Research in Science and Technology. 2010, 2(6), 100-106.
[5] Bernardo I, Hans-Peter W. van J, Luc L and Nico V. Periprosthetic stress shielding in patella-
femoral arthroplasty: A numerical analysis. SIMULIA Customer Conference. 2011, 1-12.
[6] Y.Kalyana, Suneel. D and Lingaraju. D. Alternate materials for modeling and analysis of
prosthetic knee joint. International Journal of Science and Advanced Technology. 2011, 1(5). 262-
266.
[7] M. Niinomi and M. Nakai. Titanium-based biomaterials for preventing stress shielding between
implant devices and bone. International Journal of Biomaterials. 2011, 10.1155, 1-10. DOI
10.1155/2011/836587
[8] Lucy A. Knight, Saikat P, John C. Coleman, Fred B, Hani H, Danny L. Levine, Mark T, and Paul
J. R. Comparison of long-term numerical and experimental total knee replacement wear during
simulated gait loading. Journal of Biomechanics. 2007, 40, 1550-1558. DOI 10.1016/j.jbio
mech.2006.07.027
[9] C. Shashishekar, C.S. Ramesh. Finite element analysis of prosthetic knee joint using ansys. WIT
press. 2007, 12, 1-8. DOI 10.2495/BIO070071
[10] Jasper H. A study of the mechanical properties of Ultra High Molecular Weight Polyethylene.
University of PitsBurgh. Available at http://www.phyast.pitt.edu/~reupfom/Jasper.pdf
[11] Piotr Borkowski, Tomasz Sowinski, Krzysztof Kwiatkowski, Konstanty Skalski, Magdalena
Zabicka, Mark Polczynski. Geometric Modeling of knee Joint including Anatomical Properties.
Biomechanica, Vol. 9, 2006.
[12] Brandi C. Carr, Tarun G. Knee Implants, Review of models and Bio-mechanics. Elsevier,
Materials and Design. 2009, 30. 398413. DOI 10.1016/j.matdes.2008.03.032

247
Applying Calculations of Quaternionic Matrices for Formation of the Tables of

Directional Cosines38
Victor Kravets1,a, Tamila Kravets1, Olexiy Burov2
1 National Mining University, Dnipro, Ukraine

2 Jack Baskin School of Engineering, University of California-Santa Cruz, CA, USA
a prof.w.kravets@gmail.com
Keywords: monomial (1,0,-1)-matrices-(4x4), quaternionic matrices, parameters of Rodrigues-Hamilton, finite turn,

matrices of directional cosines.
ABSTRACT. The mathematical apparatus of monomial (1,0,-1)-matrices-(4x4) is applied to the description of the turn
in space in the moving (bound) and fixed (inertial) frames of reference. A general algorithm for the formation of
transformation matrices of the sequence of three independent turns with repetition and in opposite directions is proposed.
A finite set of systems of three independent turns is constructed, consisting of 96 variants and including known systems
of angles. The algorithm is approved for the formation of tables of directing cosines of the Euler-Krylov angles systems,
aircraft angles, Euler angles, nautical angles. The proposed algorithm for generating directional cosine tables meets both
the aesthetic criteria, expressed in orderliness, laconism, convenience of analytical transformations, and the utilitarian
needs of computer technologies, providing a mathematically elegant, compact, universal matrix algorithm that, on whole,
increases the productivity of intellectual labor.
Introduction. In the dynamics of the navigated moving systems [1-4], traditionally or due to the
specific character of particular technical problems, it has become common to represent the solid body
turn by three independent angles: plane angles and relative bearings, Euler angles, Euler-Krylov
angles [5], etc.
The finite turn matrices corresponding to these angles have a drawback: the turn formulas which they
represent, are lacking symmetry. They are lengthy and difficult to observe [6]. The traditional
methods to deduct these matrices cannot be considered simple and concise. What is more, getting the
exact results is time consuming and requires much concentration [7].
Thus, it is considered appropriate to develop a common algorithm on the ground of the obtained
results [8] for building the matrices of directional cosines corresponding to any independent turns.
The set of systems of three independent turns in space
Sequences of three independent turns in space are built on combinatory basis and make turns systems
set.
Turns systems set is considered as element groups: differing in turn order around three axes ( ey1 , ey 2 ,
ey 3 ) with repetition in two opposite directions.
Clockwise turn towards unit vector ey1 (right propeller) is considered positive and marked as ;
in opposite direction: - .
Accordingly, for basis vectors ey 2 : and ey 3 : . Then systems set of three independent turns

248
is defined by coil diagrams, given on Fig. 1.
Fig. 1. Coil diagrams of three independent turns with repetition.

249
Here the following turns correspond to turn S1 system:
- first positive turn about ey1 axis to angle, that is (ey1 , );
- second positive turn about ey 2 axis to angle, that is (ey 2 , );
- third positive turn about ey 3 axis to angle, that is (ey 3 , ) or in an abridged form
S1 ( , , ) , which constitutes Euler-Krylov angles system.
We shall also note, that at body axes corresponding orientation, the turn system S33 ( , , )
constitutes aircraft axes turn axes about aircraft principal axes. An aircraft in flight is free to rotate
in three dimensions: pitch, nose up or down about an axis running from wing to wing; yaw, nose left
or right about an axis running up and down; and roll, turn about an axis running from nose to tail,
where - yaw angle, - pitch angle, - roll (the bank angle).
Turn system S67 ( , , ) constitutes Euler angles, where - precession angle, -

nutation angle, - intrinsic turn angle. Turn system S41 ( , , ) constitutes nautical
angles, where - hull angle (angle of trim), - angle of heel (angle of roll), -
yaw angle of ship and so on for other angle systems, constituting turns set: S1 , S2 , S3 ,...,
S32 , S33 , S34 ,..., S64 , S65 , S66 ,..., S96 .
Algorithm for building the matrices of directional cosines
The offered algorithm implies the following single sequence of simple operations:
1. Addition of Rodrigues-Hamilton parameters set according to the accepted turn sequence of the
bound reference system regarding the stable one:
- first turn ai ;
- second turn bi ;
- third turn i ( j 0,1, 2,3).

2. Forming four unified quaternionic matrices for each preset turn:
- first turn A, t A, At , t At ;
- second turn B, t B, Bt , t Bt ;
- third turn C, tC, C t , tC t .

3. Defining four quaternionic matrices of the resulting turn, as a product of the respective formed
quaternionic matrices:
- R A B C; t R t A t B t C;
- Rt C t At Bt ; t Rt tC t t Bt t At .
- forming sought direct and inverse matrices for the directional cosines as a kernel of the product of,
respectively, two unified matrices equivalent to the quaternion for the direct matrix and two unified
matrices equivalent to the conjugate quaternion for the conjugate matrix:
R t R or t R R

250
Rt t Rt or t Rt Rt .
The offered algorithm, unlike other known ones, has no geometrical constructions and in general
reduces the error probability during the process of calculation, owing to the symmetry of calculation
formulas and quaternionic matrices properties [8].
Matrix of directional cosines for the angles of aircrafts flight direction
In the dynamics of the flight, the orientation of the plane or rocket (body axes) in the inertial space
(initial launch reference system) is defined by three angles , , , which respectively are called yaw
attitude (angle of yaw), pitch attitude (angle of pitch) and angle of bank (or roll) (Fig. 2).
ey 2
ey 3 e y1
Fig. 2. The sequence of turns for the set of angles of the aircrafts direction.
ey 2 , ; 2. ey 3 , ; 3. ey1 , .
The sequence of turn which accomplishes the transition from the initial launch reference system to
the fixed one corresponds to the following Rodrigues-Hamilton parameters set:

a0 cos , a1 0, a2 sin , a3 0 ; (1)
2 2

b0 cos , b1 0 , b2 0 , b3 sin ; (2)
2 2

251

c0 cos , c1 sin , c2 0 , c3 0 . (3)
2 2
For each of three turns, there are respective quaternionic matrices:

cos 0 sin 0 cos 0 0 sin
2 2 2 2

0 cos 0 sin 0 cos - sin 0
A 2 2 , B 2 2 ,

- sin 0 cos 0 0 sin cos 0
2 2 2 2

0 - sin 0 cos - sin 0 0 cos
2 2 2 2

cos sin 0 0
2 2

- sin cos 0 0
C 2 2 .

0 0 cos - sin
2 2

0 0 sin cos
2 2
Quaternionic matrix of the resulting turn is found as:
R A B C , t
R tA tB tC .
In a similar way, for the resulting turn we find the matrices equivalent to the conjugate quaternion:
t
R t tC t tBt tAt , R t C t B t At .
Specifically, Rodrigues-Hamilton parameters of the resulting turn are defined by formula:
r tC t tB t a
or, in an extended form:

252

cos - sin 0 0 cos 0 0 - sin
2 2 2 2
r0 cos
2
r1 sin cos 0 0 0 cos sin 0
2 2 2 2 0
r2 ,
0 0 cos sin 0 - sin cos 0 sin
r3 2 2 2 2 2
0
0 0 - sin cos sin 0 0 cos
2 2 2 2
which after transformations takes the form [1]:

cos cos cos - sin sin sin
r0 2 2 2 2 2 2

r1 sin cos cos cos sin sin
2 2 2 2 2 2 .
r2
cos cos sin sin sin cos
r3 2 2 2 2 2 2

- sin cos sin cos sin cos
2 2 2 2 2 2
The sought matrix of directional cosines is found by the following formula expansion:
Rt R A B C tA tB tC .
According to the commutative property of the examined matrices, this formula takes the form:
R tR A tA B tB C tC .
The inverse matrix of directional cosines is found in a similar way:
Rt tRt C t Bt At tC t tBt tAt
or
Rt t Rt C t tC t Bt t Bt At t At .
Obtaining the product of matrices R t tR t and accomplishing simple trigonometric transformations,

we obtain in the kernel of the resulting matrix the matrix of directional cosines:

253
cos cos sin - sin cos

sin sin - cos cos sin cos cos sin cos cos sin sin ,
cos sin sin cos sin - cos sin cos cos - sin sin sin
which corresponds to the known matrix form for the directional cosines of the angles of aircrafts
flight direction [6] and, thus, the correctness of the offered algorithm is confirmed.
Matrix of directional cosines for Euler-Krylov angles
When Euler-Krylov angles are used, three successive turns of the moving system regarding a fixed
one are accomplished via independent angles which are denoted respectively , , [6] (Fig. 3).
ey 3
e y1 e y 2
Fig. 3. Sequence for turns of Euler-Krylov angles system.
ey1 , ; 2. ey 2 , ; 3. ey 3 , .
To the provided turns sequence, the following set of Rodrigues-Hamilton corresponds:

a0 cos , a1 sin , a2 0, a3 0 ; (4)
2 2

b0 cos , b1 0, b2 sin , b3 0 ; (5)
2 2

c0 cos , c1 0, c2 0, c3 sin . (6)
2 2
According to the set sequence of three turns, the quaternion equivalent matrices are formed. Then,
the resulting turns parameters are found as:

254

cos 0 0 - sin cos 0 - sin 0
r0 2 2 2 2 cos
2
r1 0 cos sin 0 0 cos 0 - sin
2 2 2 2 sin .
r2 2
0 - sin cos 0 sin 0 cos 0 0
r3 2 2 2 2
0
sin 0 0 cos 0 sin 0 cos
2 2 2 2
Hence, we find the sought Rodrigues-Hamilton parameters for the resulting turn [1]:

cos cos cos - sin sin sin
r0 2 2 2 2 2 2

r1 cos cos sin sin sin cos
2 2 2 2 2 2 .
r2
- sin cos sin cos sin cos
r3 2 2 2 2 2 2

sin cos cos cos sin sin
2 2 2 2 2 2
After simple trigonometric transformations, taking into consideration the found Rodrigues-Hamilton
parameters, the kernel of the resulting matrix takes the following form:
cos cos sin sin cos cos sin - cos sin cos sin sin
- cos sin - sin sin sin cos cos cos sin sin sin cos ,
sin - sin cos cos cos
which corresponds to the known result [6].

Hence, for the first column and the third row of the finite turn matrix, a simple connection is found
in form of:
r1
cos cos r1 r0 r3 - r2
r0
- cos sin r2 - r3 r0 r1 ,
- r3
sin r3 r2 - r1 r0
r2
r1 r2 r3
r0 r3 -r2
sin - sin cos cos cos r3 r2 -r1 r0 .
-r3 r0 r1
r2 -r1 r0
The found correspondence may be useful for the inverse problem solution the search of Euler-
255
Krylov angles by the known Rodrigues-Hamilton parameters of the resulting turn [1].
Matrix of the directional cosines for Euler angles
Let us assume that the movement (turn) of the moving axes from the initial position to the final
position is accomplished with a help of set sequence of three turns with the predefined angles. The
angles , , of these turns, Euler angles, are three independent values and are nominated,
respectively, precession angle, nutation angle and intrinsic turn angle, i.e., the sequence of turns for
system of Euler angles is the following: ey 3 , ; 2. ey1 ,; 3. ey 3 , .
The provided turns sequence is characterized by the following set of Rodrigues-Hamilton
parameters:

a0 cos , a1 0, a2 0, a3 sin ; (7)
2 2

b0 cos , b1 sin , b2 0, b3 0; (8)
2 2

c0 cos , c1 0, c2 0, c3 sin . (9)
2 2
The resulting turns parameters are found with the formula:

cos 0 0 - sin cos - sin 0 0
r0 2 2 2 2 cos
2
r1 0 cos sin 0 sin cos 0 0 0
2 2 2 2 ,
r2 0
0 - sin cos 0 0 0 cos sin
r3 2 2 2 2
sin
sin 0 0 cos 0 0 - sin cos 2
2 2 2 2
which is transformed to the form of:

cos cos cos - sin cos sin
r0 2 2 2 2 2 2

r1 cos sin cos sin sin sin
2 2 2 2 2 2
r2
- sin sin cos cos sin sin
r3 2 2 2 2 2 2

sin cos cos cos cos sin
2 2 2 2 2 2
or

256

cos cos
r0 2 2
-
r1 sin cos
2 2 .
r2 -
sin sin
r3 2 2

cos sin
2 2
It is easy to check that for Euler angles the matrix of directional cosines R t t R t acquires the known
form:
cos cos - sin sin cos cos sin sin cos cos sin sin
- sin cos - cos sin cos - sin sin cos cos cos cos sin
sin sin - sin cos cos
and constitutes the kernel of the resulting matrix Rt t Rt .

In particular, the following equations are correct
r3
sin sin r1 r0 r3 - r2
- r2
cos sin r2 - r3 r0 r1 ,
r1
cos r3 r2 - r1 r0
r0
r1 r2 r3
r0 r3 - r2
sin sin - sin cos cos r3 r2 - r1 r0 .
- r3 r0 r1
r2 - r1 r0
This equation is used for inverse problem solving: finding Euler angles , , the known
Rodrigues-Hamilton parameters of the resulting turn.
Matrix for directional cosines of relative bearing
The matrix for directional cosines of relative bearings, used by Aleksey Krylov in ship oscillation
theory, is found on the ground of the system of angles , , , which define respectively pitch, list
and yaw of the ship.
For the turn sequence offered by Aleksey Krylov, we obtain:
ey 2 , ; 2. ey1 ,; 3. ey 3 , .
Then, Rodrigus-Hamilton parameters have respectively the form:

257

a0 cos , a1 0, a2 sin , a3 0 ; (10)
2 2

b0 cos , b1 sin , b2 o, b3 0 ; (11)
2 2

c0 cos , c1 0, c2 0, c3 sin . (12)
2 2
The resulting turn which can be found via relative bearing is characterized by Rodrigues-Hamilton
parameters which can be found with the following formula:

cos 0 0 - sin cos - sin 0 0
2 2 2 2
r0 cos
2
r1 0 cos sin 0 sin cos 0 0
2 2 2 2 0 ,
r2
0 - sin cos 0 0 0 cos sin sin
r3 2 2 2 2 2
0
sin 0 0 cos 0 0 - sin cos
2 2 2 2
or, in an expanded form

cos cos cos sin sin sin
r0 2 2 2 2 2 2

r1 cos sin cos sin cos sin
2 2 2 2 2 2 .
r2
- sin sin cos cos cos sin
r3 2 2 2 2 2 2

sin cos cos - cos sin sin
2 2 2 2 2 2
The found matrix for directional cosines, which constitutes the matrix kernel Rt t Rt , which
corresponds to the defined Rodrigues-Hamilton parameters of the resulting turn, can be reduced to
the known form:
cos cos sin sin sin sin cos - cos sin sin cos sin
- cos sin sin cos sin cos cos sin sin cos cos sin
cos sin - sin cos cos
It is to mention that the inverse problem finding the relative bearings by the known Rodrigues-
Hamilton parameters of resulting turn, is easily solved with the following equations:

258
r1 r2 r3
r0 r3 - r2
cos sin - sin cos cos r3 r2 - r1 r0 ;
- r3 r0 r1
r2 - r1 r0
r2
sin cos r1 r0 r3 - r2
r3
cos cos r2 - r3 r0 r1 .
r0
- sin r3 r2 - r1 r0
- r1
The provided algorithm is applied to other systems of independent turns in a similar way.
Summary. The methods were developed to represent the theory of solid body finite turn by
quaternionic matrices. With a help of Rodrigues-Hamilton parameters, the formulas are obtained for
forward and backward transformations of the moving reference system regarding a fixed one. The
concise formulas are provided for adding the sequence of finite turns of the solid body in three-
dimensional space.
The algorithm is offered for composing the matrices of directional cosines. This algorithm was tested
on the examples of plane angles, Euler-Krylov angles, relative bearings and Euler angles. In contrast
to other known methods, the offered algorithm is based on the mathematical apparatus of quaternionic
matrices, and the lengthy transformations and geometrical construction are not necessary. Due to the
properties of quaternionic matrices, the algorithm contains a calculation formula distinguished by an
ordered record, which reduces the error rate during calculation and provide the ability to build
effective computational algorithms.
References
[1] Ishlinskij, A.Yu. Orientatsiya, giroskopy i inertsial'naya navigatsiya [Orientation, gyroscopes and
inertial navigation], Nauka Publ., Moscow, 1976, 672 p. (in Russian).
[2] Raushenbax, B.V., Tokar', E.N. Upravlenie orientatsiej kosmicheskix apparatov [The orientation
of the spacecraft management], Nauka Publ., Moscow, 1974, 600 p. (in Russian).
[3] Lysenko, L.N. Navedenie i navigatsiya ballisticheskix raket [Guidance and navigation of ballistic
missiles], Bauman university Publ., Moscow, 2007, 672 p. (in Russian).
[4] Igdalov, I.M., Kuchma, L.D., Polyakov, N.V., Sheptun, Yu.D. Raketa kak ob"ekt upravleniya
[The missile as an object of control], Art-Press Publ., Dnipro, 2004, 544 p. (in Russian). ISBN: 966-
7985-81-4.
[5] Korn, G., Korn, T. Spravochnik po matematike dlya nauchnyh rabotnikov i inzhenerov
[Mathematical Handbook for Scientists and Engineers], Nauka Publ., Moscow, 1984, 832 p. (in
Russian).
[6] Lur'e, A.I., Analytical mechanics, Springer Science & Business Media Publ., 2002, 824 p.
[7] Pavlovskij, M.A. Teoretichna mexanika [Theoretical Mechanics], Technika Publ., Kyiv, 2002,
512 p. [in Ukrainian]
[8] Kravets, V., Kravets, T., Burov, O. Monomial (1, 0, -1)-matrices-(44). Part 1. Application to the
transfer in space. Lap Lambert Academic Publishing, Omni Scriptum GmbH&Co. KG., 2016, 137 p.
ISBN: 978-3-330-01784-9.

259
Seismic Behaviour of Eccentrically Braced Frame with Vertical Link

39
Vahid Osat1, Ehsan Darvishan2,a, Morteza Ashoori3
1 M. Sc., Department of Civil Engineering, College of engineering, Roudehen Branch, Islamic Azad university,
Roudehen, Iran
2 Assistant Professor, Department of Civil Engineering, College of engineering, Roudehen Branch, Islamic Azad
university, Roudehen, Iran
3 M. Sc., Department of Civil Engineering, Sharif University of Technology, Tehran, Iran
a Darvishan@riau.ac.ir
Keywords: steel, eccentrically braced frame, vertical link, time history, seismic performance, nonlinear analysis.
ABSTRACT. The design of an eccentrically braced frame is based on providing a weak section in frame which will
remain essentially elastic outside a well define link. Eccentrically braced frames combine stiffness of centrically braced
frame with ductility and capability to dissipate seismic energy of moment resistant frame. In this paper the seismic
behavior of eccentrically braced frame with vertical link is presented. Three regular frame with vertical link which its
length is correlated to the capability to dissipate seismic energy are considered. The analytical models used to simulate
the test through inelastic time history analyses that is performed in OpenSees software and simulation results were
obtained. The results indicated that by reducing the vertical link length in EBFs, the maximum lateral displacements of
roofs have been reduced for all frames due to 5 real earthquake records. Reducing the vertical link length decreases the
maximum base shear of the structure. Therefore, it can be said that vertical link length improved the seismic performance
of the EBFs.
Introduction. Eccentrically braced frames (EBF) which are used in seismic design and seismic
rehabilitation of structure in seismic areas constitute a suitable compromise between seismic resistant
moment resistant frames and concentrically braced frames. In EBF frames, a horizontal or vertical
eccentricity (e) forms at the end of brace members that is called link or fuse. There are two type
eccentrically braced frame, eccentrically braced frame with vertical and horizontal link that are shown
in Fig. 1. One of the advantages of vertical links over their horizontal counterparts is the exclusion of
plastic deformation from the main structure result on no damage in the roof of the structures under
severe earthquake; easy and simple rehabilitation; and the replacement of link after earthquake. using
the vertical links for seismic rehabilitation of the existing buildings is possible with minor changes in
the main structure; however, in large or tall building and also in strengthening of the existing
structures, due to limitation of dimensions of the existing components of the structures, the
application of the single vertical link has lots of obstacles. The transferred shear from the vertical
links, especially in concrete structures, can limit the application of big vertical links. In such case,
using double vertical links is recommended[1].
39

260
Fig. 1. Geometrical configuration of eccentrically braced frames [2].
The length and section property of vertical links and the bracing configuration affect the linear and
nonlinear behaviour of EBFs. If the length of vertical link is long enough, flexural yielding will occur
prior to shear yielding. AISC-2005 recommends Eq.1 to ensure formation of shear hinges prior to
flexural hinges [3].
MP
e , (1)
VP
where e, M P and V P are link length, nominal plastic moment and shear capacities, respectively.
Kasai et al. suggested using of the factor 1.4 in lieu of 1.6 in order to ensure shear behavior. As
mentioned in the test setup for vertical links, the end moments of the link will not be equal, Figure.
5. Thus, Eq. 1 will be modified to Eq. 2 for such links [4], [5]:
MP
e 0.8(1 ) (2)
VP
where
M2
, (3)
M1
where M 1 and M 2 are internal bending moments along the link.
In 1998, Vetr applied the Eq.4 to design maximum length of vertical shear links of specimens based
on reports of Kasai et al. about weld rupture at connection of horizontal links to column[6]:
MP
e 0.35(1 ) (4)
VP

261
Description of case study frames and analysis. Four regular EBFs with four bays are considered
which their configurations are shown in Figure 2. The frames are designed based on Iranian code of
practice for seismic resistant design of building (Standard 2800) [7]. Once the frames are designed,
to evaluate their seismic response of frame, they are modelled with program OpenSees. Section
property of structural member are listed in Table 1.
Fig. 2. Frames configuration.
Table 1. Section properties of structural members for 4-story frame.

Story Columns Beams Bracing Fuse
1 IPB360 IPE330 2UNP120 IPE280


262

10 IPB360 IPE330 2UNP120 IPE360
11 IPB300 IPE330 2UNP120 IPE360
12 IPB300 IPE330 2UNP120 IPE360
Time history analysis. 5 real earthquake records were registered in Soil type II according to Iranian
Code (Standard 2800) that is listed in Table 2. The spectral acceleration of ground motion records is
scaled and matched to the target spectrum that is obtained Standard 2800. Comparison earthquake
records and target spectrum is indicated in Fig. 2 [8].
Table 4. Specification of earthquake records
ID Earthquake Recording Station

NO. M Year Name Name Owner
1 6.5 1979 Imperial Valley Elcentro Array USGS
2 6.9 1995 Kobe, Japan Nishi Akashi CUE
3 7.4 1990 Mnjil, Iran Abbar BHRC
4 7.3 1992 Tabas, Iran Tabas USGS
5 7.3 1952 Tast, USA California alluvium

263
1.8
1.6
1.4
1.2
Sa [g]
1
0.8
0.6
0.4
0.2
0
0 1 2 3 4 5
Time [sec]
Fig. 3. Comparison mean spectrum and target spectrum.
Result and discussion. The nonlinear dynamic analyses were conducted on EBFs subjected to the
earthquake excitations by using OpenSees program. Fig. 4 indicates the displacement response of the
EBFs. As it is seen from Fig. 4, by reducing the vertical link length in EBFs, the maximum lateral
displacements of roofs have been reduced for all frames due to 5 real earthquake records. For example,
the maximum lateral displacements of roofs for 4-story EBFs by vertical link length equal to 60 cm
due to Imperial Valley earthquake is 11.7 cm, while it was observed the maximum lateral
displacements of roofs for 4-story EBFs by vertical link length equal to 40 cm due to Imperial Valley
earthquake is 7.0 cm.
15
Vertical link length= 60cm
10
Displacement [cm]

5
-5
-10
-15
0 5 10 15 20 25 30 35 40 45
Time [sec]
Fig. 4. Comparison lateral displacement of roofs time histories for 4-story EB frames due to
Imperial Valley earthquake.
30
20
Displacement [cm]
10
-10
Vertical Link lenngth=40cm
-20
Vertical Link lenngth=60cm
-30
0 5 10 15 20 25 30 35 40 45
Time [sec]

264
40
Vertical Link length= 40cm
20
Displacement [cm] Vertical Link length= 60cm
0
-20
-40
-60
-80
0 5 10 15 20 25 30 35 40 45
Time [sec]
The maximum lateral displacement of roofs for frames subjected to five different earthquakes in
two cases with different vertical link length, i.e., 40cm and 60 cm, are shown in Tables 5.
Table 5. The maximum lateral displacement of roofs for four, eight and twelve stories frames.
The maximum lateral displacement (cm)
Records El centro Kobe Manjil Tabas Tast
Vertical link length=40
7.0 4.9 1.8 4.9 1.9
cm
4-Story
11.7 4.9 1.9 5.0 2.5
cm
28.4 9.3 10.1 8.3 8.1
cm
8-Story
cm 29.2 10.5 11.6 8.4 9.2
20.5 19.0 25.8 14.2 14.2
cm
12-Story
24.1 25.1 25.9 14.8 20.6
cm
The time histories of seismic base shear of four, eight and twelve-story frames due to Imperial Valley
earthquake are given in Fig. 7, 8 and 9.

265
3000
2000 Vertical length=40 cm

Vertical length=60 cm
Base Shear [kN]
1000
-1000
-2000
-3000
-4000
0 5 10 15 20 25 30 35 40 45
Time [sec]
Fig. 7. Comparison base shear time histories for 4-story EB frames due to Imperial Valley
earthquake.
4000
Base Shear [kN]
2000
-2000
-4000
0 5 10 15 20 25 30 35 40 45
Time [sec]
earthquake.
4000
Vertical link length=40cm
2000
Vertical link length=60cm
Base Shear [kN]
-2000
-4000
-6000
0 5 10 15 20 25 30 35 40 45
Time [sec]
earthquake.
The maximum base shear for frames subjected to five different earthquakes in two cases with different
vertical link length, i.e., 40 cm and 60 cm, are shown in Tables 6.

266
Table 6. The maximum base shear for four, eight and twelve stories frames.
Base shear (KN)
Records El centro Kobe Manjil Tabas Tast
2802.5 2303.5 2311.3 2223.6 2387.9
cm
4-Story
2319.3 1612 1736.9 1633.6 1897.6
cm
3333 2568.9 2701.7 2300.5 2895.9
cm
8-Story
2783.2 1851.2 1798.5 1772.4 2049.2
cm
3306.3 2934.7 2494 3046.9 2984.2
cm
12-Story
3150 2892.6 2717.8 3001 2770.2
cm
Summary. The main goal of this study was to evaluate the seismic performance of eccentrically
braced frame. Structural model used in this paper, are two dimensional steel eccentrically braced
frames with vertical link. The vertical links were located between the top of inverted V-bracing and
the beam. Four, eight and twelve-story frames were selected were each having four bays 5m length.
The structural members were designed based on Standard 2800 and AISC-2005. IPE cross-section,
and Box cross-section were used in designing of frames. Once the frames are designed, to evaluate
their seismic response of frame, they are modelled with program OpenSees. In this approach the
earthquake ground motion can be applied to the model simultaneously, the time history of
displacement can be considered. The results indicated that by reducing the vertical link length in
EBFs, the maximum lateral displacements of roofs have been reduced for all frames due to 5 real
earthquake records. In all models due to five different earthquakes, maximum base shear were
reduced by increasing the vertical link length.
References
[1] M.-R. Shayanfar and A.-T. Sina, "Assessment of the seismic behavior of eccentrically braced
frame with double vertical link (DV-EBF)," The, vol. 14, pp. 12-17, (2008).
[2] R. Montuori, E. Nastri, and V. Piluso, "Theory of Plastic Mechanism Control for MRFEBF dual
systems: Closed form solution," Engineering Structures, vol. 118, pp. 287-306, (2016), DOI
10.1016/j.engstruct.2016.03.050.
[3] AISC, Seismic Provision for structural steel Building, (2005), http://aec.ihs.com/news/2006/aisc-
seismicprovisions.htm.
[4] K. Kasai and X. Han, "Refined design and analysis of eccentrically braced frames," Journal of
Structural Engineering, ASCE, (1997).
[5] K. Kasai and E. P. Popov, "General behavior of WF steel shear link beams," Journal of Structural
Engineering, vol. 112, pp. 362-382, (1986), DOI 10.1061/(ASCE)0733-9445(1986)112:2(362).

267
[6] M. Vetr, "Seismic behavior, analysis and design of eccentrically braced frames with vertical shear
links," Ph.. D. Thesis. University Tech. Darmstadt W. Germany, (1998), http://www. tudarmstadt.
de.
[7] I. S. Code, "Iranian code of practice for seismic resistant design of buildings," ed: Standard,
(2005).
[8] H. Mostafaei, M. Sohrabi Gilani, and M. Ghaemian, "Stability analysis of arch dam abutments
due to seismic loading," Scientia Iranica A, vol. 24, pp. 467-475, (2017).

268
VII. Environmental Safety


269
Understanding the Nature and Characteristics of Dark-Black Stains on Rooftops

in Uyo Metropolis-Nigeria
40
Ihom A.P.1, Uko D.K. 1, Markson I.E. 1, Eleghasim O.C. 1
1 Department of Mechanical Engineering, University of Uyo, Uyo, PMB, Uyo, Nigeria

a ihom@uniuyo.edu.ng
Keywords: understanding, environmental pollution, nature, characterization, dark black stains, Uyo.
ABSTRACT. Understanding the Nature and Characteristics of Dark-Black Stains on Roof-Tops in Uyo Metropolis-
Nigeria; a study aimed at knowing the nature and characteristics of dark black stains on rooftops in Uyo metropolis has
been undertaken. The study which covered key areas of the town, involved taking samples from rooftops, these samples
were sent out for tests using Energy Dispersive X-Ray Fluorescence (ED-XRF), Optical Emission Spectrometer (OES),
X -Ray Diffractometer (XRD) and Scanning Electron Microscope (SEM). The tests were carried out on the dark black
stains which were scrapped from the rooftops. Tests were also carried out on the sheets, which were directly cut from the
roofs. The work was able to establish that the dark black stains on the roofs can be cleaned using soft brush and water.
The results of the work equally provided the nature and characteristics of the dark black stains on the surface of roofs in
Uyo metropolis. The major components of the dark black stains are alumina (16%), silica (43.80%), carbonaceous and
volatile organic matter (16.59%), iron oxide (heamatite) (10.55%), potassium oxide (3.20%), titanium oxide (2.93%) and
sulphite (SO3) (2.71%). The SEM micrographs gave the structure of the dark black stains which were scrapped from the
roofs, the structure revealed small shinny white particles, amorphous molecular structure similar to that of polymers and
a crystal structure which resembles that formed by carbon and silica. The SEM micrographs also show how the stains are
formed on aluminium and zinc substrate. The nature and characteristics of the dark black stains have indicated that using
water from these rooftops for direct consumption purpose may have some health implications, and relevant government
agencies are requested to investigate the health implications.
Introduction. In an address presented by the governor of Akwa Ibom State, Mr Udom Emmanuel
Gabriel at the environment summit organized by the state government at Le Meridien Hotel and Golf
Resort, Uyo. The governor lamented the adverse effects of environmental pollution caused by oil
flaring and fossil fuels combustion on humans and the environment, he specifically mentioned
darkening rooftops in Uyo metropolis which has taken away the aesthetics of many buildings in the
state. According to the governor, the problem is so serious that many people are now using dark and
black coloured roofing sheets to conceal the black deposits on their roof-tops. The nature of this black
deposit is not understood, it is only assumed that it is from gas flaring and combustion of fossil fuels
from generators and automobiles. Olajire [13] and Nkwocha [11] also in their respective studies have
linked the dark black stains on the roofs to pollution from gas flaring and other industrial activities.
Fig. 1-5 clearly captures the menace.
40

270
Fig. 1. Building in Uyo Metropolis: The Roof is Completely Covered with Dark-Black Deposit.
Fig. 2. Building Roof Completely Covered with Dark-Black Coating/Deposit.
Fig. 3. Building Roof Completely Covered with Dark-Black Deposit.

271
Fig. 4. The Roof Top of the Building in the Front is covered with Dark-Black Deposit, the Storey
Buildings Behind are Roofed with Dark-colour Roofing Sheets to Conceal the Effect of the Dark-
Black Deposit.
Fig. 5. Dark-Black Deposit on Colour Roofs in a Housing Estate in Uyo Town.
Environment means the surroundings in which we live. It is a life-sustaining system in which various
living beings like animals, including man, birds, insects, micro-organisms like algae, fungi, protozoa,
amoeba and non-living beings like air, water, and soil are inter-related. From time immemorial, the
biosphere is discharging faithfully its duty of recycling waste products to make good the loss so that
every generation finds it the same as the one before it. According to [2] this self-cleaning and
equilibrium maintenance of the biosphere is disastrously disturbed, if waste products released into it
exceed its capacity to purify herself. Of late, this is what is happening. We load it with enormous
amounts of waste product that the biosphere is becoming more and more poisonous and soon a day
will be reached when it becomes inhabitable. When air is polluted, it carries the pollutant with it along
the way some of the pollutants are deposited on things with which it comes into contact with. Living
things also inhales the polluted air. When it rains the rain washes the pollutants unto roof-tops and
272
down to the soil this explains the interrelationship mentioned above by [2]. Tice [15], Okedere and
Elehinafe in their respective works have addressed the effect of air pollution from various sources
and associated side effects on structures and living things.
Primitive man ate uncooked food available from plants, birds or animals within his reach. He ate the
raw meat. He drank the water from the rivers. He lived in caves or huts made of mud, wood and
leaves of some trees. This sort of living never polluted the environment. When Promethenes stole
fire, mans travails began. He used it not only to cook food but also as a weapon to destroy the
neighbour-hood. With fire, smoke issuing out was polluting the atmosphere; there was stink. It was
in the beginning of the first century that the Roman philosopher Sceneca complained about air
pollution. This went on increasing until in the 20th century the Ganges became a death bed for all
aquatic animals and the series of air pollution disasters affected millions all over the world [2].
Buildings in Uyo metropolis shortly on completion, the roof gets covered up with dark-black deposits.
For reflective roofing sheets they cease to be reflective as a result of this deposits. Jordan Woods [18]
of the Berkeley Laboratory notes that reflective roofs are needed for cool buildings [18]. Aesthetics
is very important in building structures; aesthetics is now being taken away in most structures shortly
after completion by this menace, which requires thorough investigation in order to be able to tackle
it. The menace may even have health implication in which case the findings may be of value to the
Federal Ministry of Health. In a recent publication by Ihom [5] and [6] the authors observed that
WHO has released a report which said that air pollution has become worse in many cities around the
world in recent years, especially in Africa and South-East Asia. The UN agencys report showed that
nearly 90 per cent of the world population breathes air that is markedly above the limits recommended
by the WHO. Experts from the agency identified car traffic, the burning of coal, oil and gas as well
as badly insulated houses as the main culprits. The UN agency had said in April, 2012 that polluted
air killed 3.7 million people under the age of 60 in 2012 [17]. Similarly in a publication by Ola [12]
the authors observed after their work, which was aimed at indexing pollution in Jos Metropolis that
the levels of H2S, Carbon monoxide and particulate matter were above specified limits for quality air
and therefore had some health implications on humans. Understanding the nature of this deposit,
which obviously is from the air is therefore very important.
The preceding forms the objective of this work, which is to understand the nature of the dark-black
deposits on the surface of roof-tops in Uyo metropolis. The project is part of an Institutional Based
Research Work sponsored by Tertiary Education Trust Fund (TETFUND) and it is ongoing.
Materials and method
Materials and Equipment. The materials used for this work included; samples of the dark-black
deposits scrapped from roof-tops, samples of test specimens taken from zinc-plated roofing sheet
covered with the deposit, samples of test specimens taken from aluminium roofing sheet, and water.
The equipment used included; sample cutting scissors, test specimen plastic containers, roof climbing
ladder, scrapping tools, Energy Dispersive X-Ray Fluorescence (ED-XRF), Scanning Electron
Microscope (SEM), Shimadzu X-ray Diffractometer (XRD) and Optical Emission Spectrometer
(OES). Others included, bucket, soft brush and imaging device.
The Study Area. The study area of this research work is Uyo metropolis. Uyo is the Capital of Akwa
Ibom state. It is a major oil producing state in Nigeria, with a lot of gas flaring activities going on
from the oil exploiting companies. The population of Uyo according to the 2006 Nigerian census
which comprises Uyo and Itu is 436,606. The metropolitan area covers an estimated area of 168 km 2
(65sq.mi). Uyo is a fast-growing city and has witnessed some infrastructural growth in recent years.
It is located on coordinates 502`N and 7056E.

273
The average annual rainfall in the study area is between 2000-4000mm with the period of fall usually
between April and October. The rainfall reaches its peak in the months of June and September, while
the dry period falls between November to March. The relative humidity of the area varies between
75% and 95% with mean annual temperatures of about 26 to 36oC. Fig. 6 is the map of the study area.
The samples for the work were taken in different areas of the metropolis covering, Use Offot on
Nwanniba road, University of Uyo, main campus on Nwanniba road, Ikot-Okubo on Abak road and
Mbaibong on Oron road. The town is characterized by high usage of generators as a result of incessant
power failure from the national grid and high vehicular traffic typical of a growing metropolis.
Fig. 6. The Map of Uyo Metropolis the Study Area.
Method. Sample test specimens were taken from roof tops of buildings in different parts of Uyo
metropolis as indicated in the study area above. The samples which were taken included the dark-
black coating on top of roofs, which was scrapped from the roof and labeled No1, dark-black coating
on zinc coated roofing sheet, labeled No2, and dark-black coating on aluminium base roofing sheet,
labeled No3. The last two were cut directly from the roof, see Fig. 9-10. These specimens were sent
to National Steel Raw Materials Exploration Agency, Kaduna, Defence Industries Corporation of
Nigeria (DICON), and National Metallurgical Development Centre, Jos for analysis. To determine
the nature of the dark-black deposit on roof-tops in Uyo-metropolis. Compositional tests were carried
out using Shimadzu X-ray Diffractometer (XRD) made in Japan, mini Pal4 ED-XRF (Energy
Dispersive X-ray Fluorescence) and Optical Emission Spectrometer (OES). The microstructure of the
deposits on the surface of the roof-tops was carried out using Scanning Electron Microscope (SEM).
Critical examinations of the roofs were also carried out using visual examination to ascertain the
nature of the deposit and also to establish whether it was living things growing on the roof. Remedial
steps were taken to remove the dark-black coating from the roof by cleaning with water and soft brush
(See fig. 7-8. No chemical was used for the cleaning, since there was no chemical reaction between
the deposits and the roof base. The dark-black deposit was stuck to the roof purely by adsorption,
274
which upon cleaning revealed a clean-shining surface of the roof. See fig.7. Only few growths were
seen on the roofs and where they existed the zinc coating was eroded and accompanied by corrosion.
The colour of the growth was also different from that of the dark-black deposit.
Fig. 7. Field work and sample taking in progress.
Fig. 8. Roofs showing Reflective Surfaces where test specimens were scrapped from the roofs.

275
Fig. 9. Transferring test samples to plastic containers.
a) b)
Fig. 10. Dark-Black material scrapped in (a), test specimens cut from the roofs in (b).

Results. The result of the work is as presented below:
Scanning Electron Microscope (SEM) Micrographs

276
Fig. 11. Scanning Electron Microscope (SEM) Micrographs of the Scrapped Coatings on the
Rooftops of Buildings at different magnifications (1000X, 1500X, 2000X).
The micrograph on the Fig. 11 shows that the dark-black material is not a uniform material; small
white particles are there, amorphous-like structure like that of the polymer material can be seen and
crystal-like structure similar to that seen in some carbon forms can be seen.

277
Fig. 12. Scanning Electron Microscope (SEM) Micrographs of dark-black Deposit on Aluminium-
base roofing sheet at different Magnifications (400X, 1000X, 1500X). The light shining areas are
where the deposit of the material is low and the dark areas are where the deposit has covered the
aluminium sheet completely.

278
Fig. 13. Scanning Electron Microscope (SEM) Micrographs of dark-black Deposit on Zinc-Coated
base roofing sheet at different Magnifications (400X, 500X, 1000X). The light areas have low deposit
of the material; the substrate is still shining and the dark areas have large deposit of the material;
the substrate is covered.
Chemical Analysis Using ED-XRF

279
Table 1. Chemical Composition of Dark-Black Material Scrapped from Roof-Tops (Analysed at

DICON). Parameters (in %).
S Sample Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 V2O5
/No
1 Blackish 24.10 46.00 1.5 3.16 2.81 1.5 2.48 0.11
powder
from
rooftop
Cr2O3 MnO Fe2O3 NiO CuO ZnO Yb2O3 Re2O7 Ag2O Eu2O3
0.034 0.15 14.49 0.02 0.11 0.15 0.06 0.19 2.87 0.23
Table 2. Chemical Composition of Dark-Black Material Scrapped from Roof-Tops (Analysed at

NMDC Jos). Parameters (in %).
S/No Sample Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 V2O5
1 Blackish 16.00 43.80 1.20 2.71 3.20 1.62 2.93 0.11
powder
from
roof-top
Cr2O3 MnO Fe2O3 NiO Co2O3 CuO ZnO Br Rb2O SrO

0.10 0.31 10.55 0.05 ND 0.09 0.22 0.07 0.03 0.05
ZrO2 Yb2O3 Re2O7 PbO Carbonaceous and volatile

matter
0.20 0.001 0.06 0.11 16.59
X-Ray Diffractometer (XRD) Analysis Result on Dark-Black Material Scrapped from Roof-Tops
(Analysed at NSRMEA, Kaduna)

280
Fig. 14. X-Ray Diffractometer Plot of Intensity against Theta-2Theta for the Dark-Black Material
from the Roof-Tops.

281
Fig. 15. X-Ray Diffractometer (XRD) Analysis Result on Zinc Coated Roofing sheet Covered with
Dark-Black Material (Analysed at NSRMEA, Kaduna).

282
Fig. 16. X-Ray Diffractometer Plot of Intensity against Theta-2Theta for the Zinc Coated Sheet
Covered with Dark-Black Material.
Fig. 17. X-Ray Diffractometer (XRD) Analysis Result on Aluminium Alloy Roofing Sheet Covered
with Dark-Black Material (Analysed at NSRMEA, Kaduna).

283
Fig. 18. X-Ray Diffractometer Plot of Intensity against Theta-2Theta for the Aluminium Roofing
Sheet Covered with Dark-Black Material.
Fig. 19. X-Ray Diffractometer (XRD) Analysis Result.

284
Table 3. Optical Emission Spectrometer (OES) Analysis Result of the Aluminium Alloy Roofing Sheet
Covered with Dark-Black Material (Analysed at DICON, Kaduna). Parameter (in %)
Element Cu Si Mg Zn Fe Mn Ni Ti Cr
% 1.9924 16.182 5.6218 7.5650 0.75939 1.0102 3.0453 0.11968 0.50535
Sn Pb V P Al Ba
0.16975 0.11760 0.10747 - 59.24 3.46
Discussion. The method and the results of this work have been well presented and from the method
it was established that the attachment of the dark-black material onto roof-tops is more of a physical
thing than chemical. The deposits can be scrapped and it can also be cleaned with water and a soft
brush without affecting the surface of the roofing sheets. The few growth of living things sighted
occurred where the zinc coating on the roofing sheet had cracks. In such areas corrosion was also
noticed. Other growths noticed on top of the deposits had no effect on the zinc coated roofing or the
aluminium roofing sheets. This observation is in complete agreement with previous studies which
had said that the presence of zinc, copper granules and aluminium salts discourages algae, fungal,
moss and lichens growth [1], [4], [18]. According to InspectApedia.com [7], dark black or brown roof
shingle stains are often caused by black algae, bleed-through or extractive bleeding of asphalt, dirt,
soot, or organic debris. However, there are other roof stain colors and causes. Dangelo [4] said: Just
like wearing lighter colored clothing, a lighter colored shingle can reduce roof temperatures by 50
degrees or more. An added benefit is that white or light colored roofs benefit the environment as
well. Dark-black stained roofs reduce the reflectiveness of roofs thereby making buildings to be hot
requiring the use of air-conditioning systems.
The objective of this work is to understand the nature and characteristics of the dark-black stains on
rooftops in Uyo metropolis. Water harvesting from rooftops is a common practice in Nigeria and
therefore establishing the nature of this dark-black stains, which mixes with the water, is imperative.
On this premise SEM micrographs were taken of the dark-black stains scrapped from the roof tops,
dark-black stains on aluminium roofing sheet and dark-black stains on zinc coated roofing sheets (see
Fig. 11-13). The micrographs (Fig. 11) which were taken at different magnifications revealed that the
dark-black stains were not of uniform composition, but consisted of small white particles, amorphous-
like molecular structure like that of the polymer material and a crystal-like structure similar to that
seen in some carbon forms [8].
Chemical analysis using ED-XRF was carried out on the dark-black stains scrapped from the rooftops.
The samples were sent to two different institutions for comparison so as to establish reliable result
(see Tables 1-2). The dark-black stains from visual observation were sooty in nature. The two results
have some compounds that are usually found in soot. The dark-black deposit is from the particulates
in the air as well as the soot particles in the air. Gas flaring, the use of generators, and vehicular traffic
releases emissions in the surrounding under study. The result from DICON Kaduna is higher than
that from NMDC Jos in some of the parameters measured this may be because the analysis from
DICON Kaduna did not take cognizance of organic, carbonaceous and volatile matter. The result
from NMDC Jos however, assigned a total of 16.59% to this components. The result from NMDC
Jos is therefore more reliable. In the two results the highest components of the dark-black stain
powder scrapped from the roofs are SiO2, Al2O3, Fe2O3, Carbonaceous and volatile organic matter,
K2O, TiO2 and SO3 see Tables 1-2 for detail percentages. Dara [3] said, that owing to particulates
large surface areas, particulates provide excellent sites for absorption of various organic and inorganic
species which encourage heterogeneous phase reactions in the atmosphere. Particulates include

285
Fe2O3, V2O3, CaO, PbCl2, PbBr2, fly ash, aerosols, soot etc. polycyclic aromatic hydrocarbons (PAH)
are important constituents of several organic particulates which are carcinogenic. Soot is a highly
condensed product of PAH compounds and can itself adsorb many PAH compounds and toxic trace
metals e.g Be, Cd, V, Ni, and Mn as well as carcinogenic organics such as benzo--pyrenes [3]. The
last sentence agrees with the analysis results in Tables 1-2.
X-Ray Diffractometer (XRD) Analysis was also carried out on the dark black stains scrapped from
the roof, dark-black stains on zinc substrate and dark-black stains on aluminium substrate, which
were taken directly from the roofs (see Figs. 14-16). The X-Ray Diffractometer analysis of the
scrapped dark black stains showed that in addition to the composition given by ED-XRF; the dark-
black stains contained polytetrafluoroethylene, Calcium Fluoride, zinc phosphate hydrate, carbon
(graphite) and magnesium. This result explains the structure seen in the SEM micrographs for the
dark-black stains; the polytetrafluoroethylene may be responsible for the amorphous polymer
structure seen and the carbon may be responsible for the carbon structure sighted in the SEM. The
Zinc phosphate hydrate was scrapped along with the dark-black stains when samples were taken. This
compound is normally at the surface of zinc coated roofing sheets. The XRD identification of
components present in the dark black stains scrapped from roof-tops agreed with composition of soot
and particulate as stated by [3].
The only new compounds in the analysis of the dark-black stains on zinc and aluminium substrate are
chromium nitride, molybdenum carbide, and barium oxide. The chromium nitride indicate the
presence of nitrogen. The molybdenum carbide indicate the presence of molybdenum on the substrate.
The barium oxide indicate the presence of barium on the substrate. Table 3 which is the result of
chemical analysis of the aluminium alloy roofing sheet using Optical Emission Spectrometer,
confirms the presence of barium.
The above discussion have shown that the deposits on rooftops in Uyo metropolis are from
particulates and soot. The health implications of these pollutants have been highlighted in the work
by Okedere and Elehinafe who worked on the effect of suspended particulate matter from diesel
generators. Other authors like Kirby [9], Mendez [10], Person and Kucera [14] have discussed rooftop
stains and quality of water from the rooftops in their respective works. Of concern from the present
study to health is SO3, and polytetraflouroethylene which have health implications as shown by Dara
[3], the other metals which are present in the dark black stains and also known to be associated with
toxicity are actually in small quantities and may only cause problem over an extended period of
exposure or usage of water from the roof tops.
Summary. The study titled Understanding the Nature and Characteristics of Dark-Black Stains on
Roof-Tops in Uyo Metropolis-Nigeria was extensively and elaborately undertaken and considered
to truly understand the true nature and characteristics of these dark black stains which have become
an eye saw on rooftops in Uyo metropolis. The following findings and conclusions were drawn from
the work:
1. The dark black stain/ covering on the rooftops is as a result of polluted atmosphere which is
polluted with particulates, aerosols and soot these gets deposited on rooftops
2. The dark black stains are physically adsorbed or adhered to the roof and can be cleaned using
water and soft brush.
3. The major components of the dark black stain are alumina, silica, carbonaceous and volatile
organic matter, iron oxide (heamatite), potassium oxide, titanium oxide and sulphite (SO3 ).
4. The dark black color is from the soot which contains carbon and other organic compounds and
normally absorbs other particulates too. This explains the large compounds present in the dark black
stain.
286
5. Finally, the wide range of tests carried out on the dark black stain on the rooftops have
established that the components of health concern are SO3 and the polytetrafluoroethylene. The
other metallic components are in small quantities and may have health implication only after
extended use of water from these rooftops.
Acknowledgement. The authors of this work want to acknowledge the management of University of
Uyo for approving this research work for TETFUND Institutional Research Grant without which this
work would not have been possible. Our unreserved appreciation goes to the sponsors of this research
work Tertiary Education Trust Fund, Abuja. We equally acknowledge institutions where this research
work was carried out time will fail us to mention you by names again, since you have been earlier on
mentioned in the work.
References
[1] Asanusung, K.E. (2014) Investigation of the possible causes of Aluminium Roofing Sheet
Discolouration and its remedy: A Case Study of the University of Uyo Male Hostel Roof, Permanent
Site, PGD Project, Department of Mechanical Engineering University of Uyo, Uyo, Nigeria.
[2] Bhatia, S.C.(2008) Environmental Chemistry, 4th Edition Reprint, published by Satish Kumar Jain
for CBS Publishers & Distributors, Darya Ganj, New Delhi (India) p. 1-20.
[3] Dara, S.S. (2007) A Text book of Environmental Chemistry and Pollution Control, Seventh
Reprint, S.Chand and Company Ltd, Ram Nagar New Delhi, p. 24-31.
[4] Dangelo, S. (2016), How White Roofs Can Help Your Home Cool, assessed at
http//www.dangeloandson.com.
[5] Ihom, A.P. (2014) Environmental Pollution Prevention and Control: The Current Perspective (A
Review), Journal of Multidisciplinary Engineering Science and Technology (JMEST), Vol. 1 Issue
5, 93-99.
[6] Ihom, A.P. and Offiong, A. (2014) Zinc-Plated Roofing Sheets and the Effect of Atmospheric
Pollution on the Durability of the Sheets, Journal of Multidisciplinary Engineering Science and
Technology (JMEST), Vol. 1, Issue 4, 125-132.
[7] Inspect Apedia (2017) Accessed at www.InspectApedia.com
[8] Katsnelson, I.M. (2007) Graphene: Carbon in Two Dimensions, Materials Today, vol. 10, No.1- 2,
20-27.
[9] Kirby, J.R. (1996) Cleaning, Preventing algae on asphalt shingles, National Rooting Contractors
Association p.45, available at www.nrca.net accessed 2015.
[10] Mendez C.B., Afshar B.R., Kinney K., Barret M.E., Kirisits, M.J. (2010) Effect of Root Material
on Water Quality for rainwater harvesting Systems. Texas Water Development board Report.
[11] Nkwocha, C.O. (2010) Environmental Impact of Oil and Gas Production in Nigeria, Journal of
energy and power engineering, vol. 6, pp. 70-75.
[12] Ola, S.A., Salami, S.J., Ihom, P.A.(2013) The Levels of Toxic Gases; Carbon Monoxide,
Hydrogen Sulphide and Particulate Matter to Index Pollution in Jos Metropolis, Nigeria, Journal of
Atmospheric Pollution, Vol. 1, No. 1, 8-11.
[13] Olajire, A.A., Ayodele, E.T., Onyedirdan, G.O., Olugbemi, E.A. (2003) Levels and Specification
of Heavy Metals in Soils of Industrial Southern Nigeria, Environmental Monitoring Assessment, Vol.
82(2), 135-155.

287
[14] Person, D. and Kucera, V. (2001) Release of Metals from Buildings, Constructions and Products
during Atmospheric Exposure in Stockholm, Water, Air, and Solid Pollution Focus, 1(3), 133-150.
[15] E. A. Tice (1962) Effects of Air Pollution on the Atmospheric Corrosion Behavior of Some
Metals and Alloys, Journal of the Air Pollution Control Association, 12:12, 553-559, DOI
10.1080/00022470.1962.10468127
[17] WHO (2014), WHO Report Worsening Air Quality in Cities. The Guardian Mobile, 7 May, 2014
[18] Woods, J. (2017) Reflective Surfaces (Geoengineering) Accessed at http//en.wikipedia.org/

288
Prospects to Use Biogas of Refuse Dams of Dnipropetrovsk Region (Ukraine) as

Alternative Energy Carrier
41
Ye.A. Koroviaka 1,a, V.O. Rastsvietaiev 1,b, O.O. Dmytruk 1,c, V.V. Tykhonenko 1,d
1 State Higher Educational Institution "National Mining University", Dnipro, Ukraine

a koroviakaye@gmail.com
b 717ras@gmail.com
c vasilenkoelena20@ukr.net
d lerita8888@gmail.com
Keywords: biogas, solid domestic waste landfills, regeneration, a well, recovery, use of methane, environmental safety.
ABSTRACT. Prospects for recovery and use of biogas from solid domestic waste landfills in Dnipropetrovsk region
have been considered. Scientific sources have been analyzed. The world practices to use biogas from solid domestic waste
landfills have been estimated. Gas volume released has been studied. Methane released by solid domestic waste landfills
may be used effectively as automobile fuel, electric powers and heat depending upon location of the landfills as for
business infrastructure. Methane utilization will make it possible to solve a problem of improving the safety of solid
domestic waste landfills in terms of environment. Scientific substantiation of technological solutions concerning recovery
of methane from solid domestic waste landfills is impossible without involving dependences which determine total
volume of landfill gas being released. That will help perform feasibility evaluation as for projects to use landfill gas.
Practical proposals concerning the selection and substantiation of priorities to use methane released by solid domestic
waste landfills have been made. In particular, operation schedule for specific conditions of Ihren landfill located in
Dnipropetrovsk region has been proposed.
Introduction. Methane is basic component of gas released by solid domestic waste landfills. Release
of methane into the atmosphere transforms it into the main culprit of green house effect. Reduction
of methane release, its recovery and use as energy carrier may result in the generation of substantial
amount of energy as well as positive economic and ecological effects. Implementation of projects
aimed at regeneration of landfill gas energy favours the reduction of green house gases and air
polluting substances. Moreover, that improves air quality and reduces potential health risk.
Furthermore, gas-recovery projects decrease dependence on certain energy carriers, create jobs, and
help the growth of local economy. There are considerable international capabilities for the extension
of landfill gas energy use [1].
Thousands of tons of urban solid domestic waste get into Ukrainian landfills every day. As a
consequence of natural process of breakdown of such organic substances as foods and paper buried
at the landfills, gas being a side-product of decomposition, is released. Almost 50 % of the gas is
methane (4) being a basic component of natural gas; carbon dioxide (2) is other 50 % added by
negligible quantity of organic substances being out of methane group.
All over the world, landfills are third largest anthropogenic source of waste making up almost 12 %
of global waste. It is known that during two last decades, Ukrainian population experienced next to
41

289
5 mln decrease (or 10 %) from its number in 1990 (51 mln) to 42 mln in 2015. However, quantity of
daily waste experiences its accumulation and enlargement rather than its decrease. During the last
decade, volume of daily waste being products of life of each Ukrainian experienced its 45 % increase.
The Department of Environmental Safety of the Ministry of Environmental Protection estimates
concentration of all types of waste in Ukraine at the level of 35 billion tons; moreover, 2.6 bln ton of
them are highly toxic.
On the data by environmentalists, every Ukrainian annually produces about 220-250 kg of solid
domestic waste; in the context of cities the figures are 330-380 kg. The volume experiences constant
increase. More than 90 % of solid domestic wastes in Ukraine are transported to landfills. Burial of
the waste within landfills involves transfer of vast sites and their costly development. As the National
Ecological Centre of Ukraine informs, more than a billion cubic meters of biowaste has been
accumulated within landfills. According to data by the State Statistics Committee of Ukraine only
3.5 % of it is reprocessed. The waste occupies more than 7 thousand hectares of land. The waste is a
filtrate polluting soil, poisoning ground water, and overwhelming human health. Moreover, that is
biogas being formed in the process of organics burning; methane (4) and carbon dioxide (2) are
their macrocomponents. Fig.1 explains approximate distribution of 4 outburst from landfills in the
context of industrial areas of Ukraine.
Fig. 1. Total volume of methane outburst from landfills in industrial areas of Ukraine in the context
of the year of 2011.
As early as 2007 Dnipropetrovsk region was announced as a zone of severe ecological catastrophe.
However, over the last years the situation did not improve; it worsens. Annually, 300-350 thousand
tons of solid domestic waste and up to 400 thousand tons of construction waste are produced in the
city. Two landfills are used to bury it: small share is transported to a landfill in the neighbourhood of
Novomoskovsk town; almost 140-150 thousand tons are transported to waste disposal works; all other
wastes (that is 50 %) remain at unauthorized landfills within the city.

290
There are several alternatives to use landfill gas in Dnipropetrovsk region:

electrical energy generation with the use of engines, turbines, microturbines, and other techniques;
gas processing to produce alternative fuel for local industrial enterprises or other organizations
having need of constant deliveries of fuel (direct use of biogas is reliable involving minimum
processing and minor modifications of available burning equipment);
use of landfill gas to produce gas of gas-line quality or alternative fuel for motor transport.
Vertical wells are applied to extract gas within solid domestic waste landfills. As a rule, they are
located uniformly at the territory of a landfill body; spacing between neighbouring wells is 200-
600 m [2]. Their diameter varies in the interval 200 to 600 m and their depth depends on the landfill
body thickness; thus, it may be several tens of meters.
Auger drilling is considered as the most expedient technique while well making in waste mass in the
context of Dnipropetrovsk region.
A process of gas flaring is reasonable from the viewpoint that gas-forming calculation error is not
less than 30 %. If there are no reliable data concerning morphological composition of solid domestic
waste and registration of its amount being delivered then the error may experience several-time
increase. If it is planned to use the biogas for power generation sector such an error is inadmissible.
There is a technology for landfill gas recovery basing upon anoxic fermentation of solid domestic
waste. Constriction stage one involves receiving volume excavation (a pit) meant for 10-20 years of
operation. The pit bottom is laid with 1-m thickness clay (or polyethylene film) to prevent polluted
water from getting into water-bearing levels. In the process of a landfill formation, waste is put into
special reservoirs of the pit corresponding to daily norms waste delivered to the landfill. Each
reservoir having 2 to 4 meters height is isolated by means of clay [2].
According to the world practice, a waste-filled landfill is roofed with clay, film, soil. Grass is
planted at the top. The pit is equipped with engineering structures to remove liquid and gaseous
products of waste decomposition. Wells and pipes are laid within the pit body; pumping equipment
is mounted. The gas obtained is piped to electric power stations, boiler stations, annealing furnaces,
microturbines etc. [3, 4].
During the first 2-3 months, mainly CO2 seepages from the covered pit. Then high-grade gas starts
its emission. The period lasts up to 30-70 years. After 25 years, volume of methane production
decreases slowly. After the gas stopped to be produced, the territory occupied by the pit, may be
reused for municipal waste processing.
Gas-collecting station (station for landfill gas collection) is meant for forced methane recovery from
landfill mass. To do that, special electrical fan is applied to produce insignificant discharge (about
100 mbar) within the network of gas-transmission pipelines.
The technique for landfill gas collection and disposal may be applied in the process of solid domestic
and industrial waste deintoxication by means of their burying within landfills. A method of landfill
gas collection and disposal within a landfill involves: preparation of support, installation of a system
of vertical gas drainage from wells with perforated walls, layer-by-layer placement of waste,
installation of horizontal gas drainage system at the surface of each completed waste layer in the form
of drains isolating surface coverage of the shaped landfill, and disposal of gas form the wells. In this
context, wells of vertical gas drainage are engineered at certain height. To do that, understructures
located within the landfill area are used. Then internal cavity of each well is backfilled as well as its
gravel packing. Perforated wells are built up to certain height. Gravel packing height should be equal
291
to the height of following layer of waste; it is covered by draining material. During the last
heightening cycle, the wells are equipped with nonperforated walls to be higher than the surface of
the formed landfill and without gravel packing by means of draining material.
Generally, direct burning of biogas in gas boilers of centralized heat supply system and in industrial
boilers within a 10-kilometer radius of the landfill is the most efficient technique of its utilization.
Availability of relatively uniform biogas consumption for a full year is that important factor effecting
economic indices of the project. However, the technique is rather time-consuming as it involves
redesign of centralized heat supply system.
As a rule, modern home and industrial gas boilers are not meant for the use low-calorific biogas. The
situation is also complicated by the fact that biogas may contain strong concentration of carbon
dioxide and other gases.
Specifically developed slot burners for biogas are one of the problem solutions. Development of the
burners has taken into consideration peculiarities of biogas burning (i.e. insignificant limits of flame
stability etc.). They can function within a wide range of modes of a boiler operation from 160 to
318 cubic meters per hour. The burners are made of special steel having dismountable cones; they
are not susceptible to hydrogen sulfide corrosion; moreover, they are equipped with special devices
for flame stabilization. To decrease excess air factor, their design provides specific bands directing
air to each cone preventing accumulation of excessive air.
It should also be noted that in the process of active stage of a landfill degasification, gas is extracted
from a landfill substrate. Then the gas is accumulated within gas receiver through a system of water
vapour condensate removal. From the gas receiver, landfill gas is delivered to consumers through the
system of such contaminants as water, sulphur, and carbon dioxide removal. The purified gas may be
delivered to heating boilers, to cogeneration plants to produce electricity, to absorption or combined
chillers to produce cold etc.
The majority of the abovementioned techniques have a number of disadvantages; the most important
of them is significant capital cost to implement all measures connected with utilization of gas from
waste landfills. Despite the fact, use of biogas as automobile fuel is the most acceptable in the context
of Dnipropetrovsk region.
Purpose. The paper considers prospects to utilize biogas from waste landfills in Dnipropetrovsk
region (Ukraine) in terms of municipal Ihren landfill which area is 14.9 hectares. The landfill is
located in the neighbourhood of residential area Ihren not far from Synelnykove highway (Fig.2).
Materials and Methods. Average distance from Dnipro centre is 22 km. The landfill operated from
1947 to 2007 [5].
Generally, following idea is implemented to extract landfill gas: networks of vertical gas-drainage
wells are connected with the help of pipelines in which compressor plants develop dilution required
for biogas transportation to its place of use. Plants to collect gas and utilize it are mounted within
special site out of the landfill body. It is anticipated that biogas to be extracted within Ihren landfill
can be used as automobile fuel. Fig. 2 shows rational place for the fuel station location.
Fig. 3 demonstrates principal technique for landfill gas recovery and utilization [6].
According to a structure shown in Fig. 3, after transportation with the use of a pipeline, biogas is
delivered to a compression unit. Within it the gas is purified and prepared for further processing in
the system of gas preparation.

292
After the process of biogas purification and preparation, 4 content may arrive at 95 % and sulphur
content drops down to almost zero. It should be noted that separation of 2 and S is performed using
specific devices with the help of water (namely washing). Then, small special compressor gas
pressure is boosted up to 10 bar. It is worth of mentioning that within the absorber excessive pressure
of carbon dioxide is absorbed by water. Methane concentration in the biogas increases form 60 % up
to acceptable level to be used as automobile fuel (98 %). After that, gas is transported to a receiver
where liquid extrudes gas with its further compression up to 270 bar; the operation involves specific
high-pressure water pump.
Fig. 2. Ihren landfill. 1 is territory of Ihren landfill; 2 is possible location for compression unit;
3is the main gas pipeline with the length of 180 200 m; 4 is possible location of fuel station; 5
is Synelnykove highway.

293
Fig. 3. A plant unit for biogas recovery and utilization.
When the technological operations are being performed, moisture may reach 100 %. To use the biogas
as automobile fuel, it is dried up at final stage; the operation is effected with the help of adsorption
two-column dehumidifier. If it is required, the columns may be alternatively switched from drainage-
regeneration mode.
When the abovementioned operations are completed, the gas is delivered to storage of compressed
gas. Pressure within the storage is 270 bar. Hydraulic volume of the storage is determined with the
help of calculations depending upon parameters of gas recovery and consumption. Trilinear classic
compressed gas storage system with a panel of compressed air priority cascade distribution is used
under standard conditions. To be used as automobile fuel, the biogas is delivered under pressure of
almost 100 bar. It is expected that manometer for pressure measurement is equipped with temperature
compensation.
Determination of placement of wells within Ihren landfill should involve geometry of vehicles to be
used while biogas recovering. As a rule, distance between wells is 30-40 m [7]. Consequently,
estimated number of production wells within 15 hectares of Ihren landfill is 135.
To determine yield of wells constructed within solid domestic waste landfill it is required to identify
intensity rate of biogas production. The procedure is impossible without the availability of parameters
of rate of microorganism generation and growth. Thus, the intensity can be calculated with the help
of dependence proposed by Jacques Lucien Monod [8]:
S S
(1)
kS S
where microorganism growth rate, days 1;

s relative growth rate, days 1;
S concentration of substrate, kg/m3;
kS kinetic parameter (half-saturated constant).

294
Following functional dependence is applicable to explain internal state of solid domestic waste
film biomasses:
S f (Tw , d , , ts , Len ) (2)
where w fermentation temperature, ;

thickness of biomass layer, m;
biomass density, kg/m3;
ts period of a well operation for biogas recovery, days;
Len biological consumption of oxygen (almost complete oxidation) by initial raw material.
Steady process of biomass fermentation in such systems and in terms of anaerobic environment is
possible if only following conditions are met:
Tw , d , Len const (3)
Hence, kinetic model of Conto applied for wider range of solid domestic waste fractions can become
theoretical basis for the development of mathematical model to immobilize methane-forming
microorganisms. It describes intensity of biogas formation (V, m3/day) depending upon technological
parameters of anaerobic fermentation process [8]:
BO S kS

VC 1- (4)
k S - 1
where boundary output of biogas from a unit of solid domestic waste organic matter when their
composition is specified in the context of permanent exposure time, m3/kg;
S initial concentration of organic matter in the substrate, kg/m3;
maximum rate of microorganism growth within the specified fermentation process of solid
domestic waste components, days 1;
kS kinetic parameter (a constant of half-saturation).
Results. Theoretical dependences of rates concerning generation and recovery of biogas in terms of
time have been built (Fig.4)

295
Fig. 4. Theoretical indices of biogas generation and recovery volume in the context of Ihren
landfill.
According to the dependences, shown in Fig. 5, the most rational interval for biogas application as
automobile fuel coincides with the greatest intensity of its generation. The period falls at 2019 2023.
This very time is the most rational for the construction of all required wells, communications and
additional equipment for fuel filling station (Fig. 2). According to [9], return period of such a station
is less than 6 months.
However, a number of various techniques to calculate efficiency indices of fuel filling stations are
available and proposed including those using landfill gas (biogas).
While estimating projects (in particular for fuel filling stations) and selecting them, payback ratio acts
as the known being determined using the equation of cash flows received during the whole period of
the project operation and capital investment involved in its implementation [10].
T -r t T
Kt e P dt Dt e -rP t dt (5)
0 0
where rP coefficient of capital investment return, algebraic value;

T service life of the project (so called time horizon), years;
Dt cash received as a result of the project implementation (the cash is considered as a result
of advance capital functioning), year t;
Kt capital expenditure during t year.
In the context of the specific case, return ratio is the ratio specified by a certain project frame; its
importance does not cover other projects. Moreover, it is a ratio of maximum level of capital
investment profitability for a certain project, namely fuel filling station.
It should also be noted that critical discount rate (rk) is minimum return coefficient that is a project
which calculations meet rP > rk requirements is considered as efficient; thus it may be accepted for
implementation. In terms of Ihren landfill it has been determined that the rated return coefficients
meet the abovementioned requirements.
296
Summary. Landfills of solid domestic waste are sources of high-energy gas containing up to 70 %
of methane which may by used effectively to produce automobile fuel (in particular, as exemplified
by Ihren landfill) depending upon landfills as for the business infrastructure.
The modeling results help determine that in the context of Ihren landfill located in Dnipropetrovsk
region (Ukraine) total maximum rate of biogas recovery may achieve 386 m3/year.
According to the results of economic expediency substantiation and theoretical calculations it has
been determined that values of rated ratio coefficient, demonstrated as an example to construct fuel
filling station, is considered to be reasonable and the offer itself may be acceptable for
implementation.
Biogas utilization will make it possible to improve ecological situation in Dnipropetrovsk region
preventing emissions of greenhouse gases and toxic substances.
Acknowledgement. The development of technological basis for environmentally safe extraction of
minerals in the context of technologically loaded mining regions of Ukraine.
References
[1] Design documentation, process plan, environmental protection, and electrics to manufacture
concrete products developed by Lennox Enterprise MME, Kyiv, 2012 (Director L.I. Diachuk)
[2] Bondarenko, V.I. Problems of solid domestic waste utilization and disposal of hazardous waste
in Ukraine; from the project concept to the state scientific and technical programme / Bondarenko,
V.I., Zhovtianski, V.A. // Power Technologies and Resource Conservation 2008. # 4. Pp. 63-
69
[3] Piatnichko, A.I. Utilization of biogas from closed SDW landfills// Piatnichko, A.I., Bannov,
V.E.:// Ekologia Plus. 2009. # 4 Pp. 12-14.
[4] Heletukha, H.H. Prospects to produce and use biomethane in Ukraine [Text] / H.H. Heletukha,
P.P. Kucheruk, Yu.B. Matveiev // Analytical note of BAU. Bioenergetic Association of Ukraine:
2014. # 11. 43 pp.
[5] Official site of Dnipropetrovsk Regional State Administration Dnipropetrovsk region, Regional
News [E-resource] Access mode: http://adm.dp.ua/OBLADM/obl
dp.nsf/archive/3E2AEC730D59F164C225730E00473948?opendocument
[6] Koroviaka, E.A. Regeneration of methane educed by landfills and possibilities for its utilization
in Dnipropetrovsk region / E.A. Koroviaka, E.A. Vassylenko, Ye.S. Manukian // Geotechnical
Mechanics: Interdepartmental collection of scientific papers / M.C. Poliakov Institute of Rock
Mechanics of NAS of Ukraine. Dnipropetrovsk, 2014. Issue 117. Pp. 215-224.
[7] Carry out research; develop techniques and operation parameters to collect biogas from solid
domestic waste landfills: Research report / K.D. Pamfilov ACF; # 02880/019106. Moscow, 1998.
[8] Badmaev, Yu.Ts. Intensive technique for anaerobic processing of pig husbandry manure in the
context of Republic of Buryatia: abstract of thesis for a Degree of Cand.Sc. {Engineering}: 05.20.01/
Yu.Ts. Badmaev; ASRIEA RAA and Baikal Institute of Natural Resource Use of S RAS Ulan-
Ude, 2006. 22 pp.
[9] We and cogeneration [E-resource]: article / 2G Bio-Energietechnik. E-journal 2009. Access
mode: http://www.2g.rusbusi ness.com/index.php
[10] Science in the context of modern capitalist economy/ Under the editorship of S.M. Nikitin. M.,
Nauka, 1987. 240 pp.

297
VI. Information Technologies


298
Random Sparse Sampling and Equal Intervals Bregman High-Resolution Signal

Reconstruction42
Guojun Qin1, Jingfang Wang2
1 School of Mechanical Engineering, Hunan International Economics University, Changsha, China

2 School of Electrical & Information Engineering, Hunan International Economics University, Changsha, China
Keywords: compressed sensing, random sampling, incoherent measurement matrix, sparse sampling, Bregman
reconstruction.
ABSTRACT. Compressed sensing (CS) is a new signal processing methods, signal sampling and reconstruction are
processed to take full advantage of the signal sparse knowledge structure in the transform domain. It consists of three
elements: the sparse matrix, incoherent measurement matrix and reconstruction algorithm. In the framework of
compressed sensing theory, the sampling rate is no longer decided in the bandwidth of the signal, but it depends on the
structure and content of the information in the signal. In this paper, a complex domain random observation matrix is
designed and interval samples are projected to any set of random sample, ie, sparse random sampling. The signal is
successfully restored by the use of Bregman algorithm. The signal is described in the transform space, and a theoretical
framework is established with a new signal descriptions and processing. By making the case to ensure that the information
loss, signal is sampled at much lower than the Nyquist sampling theorem requiring rate, but also the signal is completely
restored in high probability. The sparse signal is simulated in sampling and reconstruction of time domain and frequency
domain, and the signal length, the measured value, the signal sparse level and SNR influence are analyzed in the
reconstruction error.
Introduction. Sampling theorem was the law which is followed in a sampling process, it described
the relationship between the sampling frequency and the frequency spectrum of the signal. Sampling
theorem was first proposed by Nyquist in 1928, who is the American telecommunications engineer,
this theorem was clearly stated and formally incorporated theorem in 1948 by the founder Shannon
of information theory , so it is called Shannon sampling theorem in many references. The theory
dominates almost all of the signals / images acquisition, processing, storage, transmission, etc., that
is: when the highest frequency of a signal is m ,
The sampling rate as long as the 2 m is sampled to this signal, signal can be perfectly reconstructed.
This is a problem with sufficient but not necessarily, if two samples are taken to a waveform with the
highest frequency, they are with necessary and sufficient, then the other one cycle of all frequency
waves gather more than two samples - adequate but not necessary. As can be seen, Shannon sampling
theorem is not the best, it does not make use of the structural characteristics of the signal itself
sparsity (with respect to the signal length, only a very few non-zero coefficients, and the remaining
coefficients are zero), only a small part of the collected data is our actual useful work. They want to
keep, but most of the rest will have to give up and thus waste a lot of storage space.
Nyquist theory codec is that encoding end of the signal is sampled first, and then the samples were
all converted and encoded for amplitude and position of one important factor, and finally the coded
value were stored or transmitted; decoding of the signal is only the reverse process of encoding, the
signal is restored by the de-compression, inverse transform.

299
There are two shortcomings in Nyquist theory:

(1) Since the sampling rate of the signal can not be lower two times than the signal bandwidth
(frequency difference between the highest and the lowest signal frequency), which makes the
hardware system is facing great pressure in the sampling rate;
(2) In the compression encoding process, in order to reduce the cost of storage, processing and
transmission, of a large number of conversion calculated small coefficients are discarded, it results in
a waste of data computing and memory resources. This high-speed sampling re-compressing process
wastes a lot of sampling resources, so it naturally raises a question: Can other transform space is used
to describe signal? A new theoretical framework is created for describing and processing signal, so
that the information is not loss case, the required sampling rate is used with far lower than the Shannon
sampling theorem to sample signal, while the signal can be fully restored? Whether can the signal
sample be transformed into the sampling information?
Signal sampling, compression encoding occur in one step in compressed sensing (Compressive
sensing / sampling, CS) [1, 2], sparse signals are used, it is far below the Nyquist sampling rate of the
signal, non-adaptive measurement is encoded. Measured values are not signal itself, but it is
projection value from the high dimension to low-dimensional space, from a mathematical point view,
each measurement value is the combination function of on each sample signal under the traditional
theory, a measured value already contains the small amount of information in all the sample signal.
Decoding process is not simple reverse process of encoding, but under the inverse thought in the blind
source separation, the signal sparse decomposition is used in conventional reconstruction methods to
achieve accurate reconstruction of a signal in the sense of probability or do approximate weight
structure under certain error. The required number of measurements for decoding is much smaller
than the number of samples of Nyquist theory. Correspondence between the Nyquist sampling theory
and CS as shown in Table 1 [3], [4].
Table 1. Correspondence between Nyquist sampling and CS Theory.

Nyquist sampling CS Theory
Prerequisites Signal bandwidth Sparsity signal
Local uniform
Sampling Method Global,Randomly
intervals
Key point Nyquist sampling rule Non-correlation measurement matrix
Means of the
Fourier transform Nonlinear optimization
reconstructed signal
Complexity Sampling Computing
If you want to capture a small part of the data and expect to "decompress" a lot of information from
these few data, it is necessary to ensure that:
1) The amount of collected data contains global information of the original signal;
2) There is an algorithm which the original information can be restored from a small amount of data.
In this study, a compressed sensing sparse random sampling method is researched with high-
resolution signal reconstruction. A complex domain measurement matrix is devised in the method,
the non-uniform sampling is limit from the sampling frequency, there are frequency advantage of
high resolution and anti-aliasing [5], at a low sampling frequency, the separate Bregman method is
used to reduce spectral noise which is caused by non-uniform sampling, the even spaced signals are
reconstructed with the high-resolution [6, 7].

300
Compressed sensing principle

Compressed Sensing statements. The main idea of compressive Sensing (Compressive Sensing CS)
theory is that: Suppose the coefficients of a signal x with length N are sparse (that is, only a small
number of non-zero coefficient) on orthogonal basis or on a tight frame , if the coefficients are
projected to another observation group : M N M N , which is not related to the transform
group , the observation set y:M 1 is obtained. Then the signal x can rely on these observations
to solve an optimization problem and accurate recovery. CS theory is the theoretical framework with
a new sampling while achieving the compression purpose, its compressive sampling procedure is
shown in Figure 1.
Fig. 1. Compression sampling process.
First, if the signal x R N is compressible on an orthogonal base or tight frame , the transform
coefficients T x are obtained, is equivalent x or approximation sparse representation; The
second step, a smooth measurement matrix is designed, which is irrelevant to the transform base
with M N dimension, the observation x is projected to M-dimensional space to give the set of
observations y x , the sampling process is compressed, i.e. drawing sample [8]. Finally, the
optimization problem solving x approach x exactly or approximately.
When the observations with noise z,
y x +z (1)
It can be converted for the sake:
min || T x ||1 s.t. || y - x || 2 e (2)

x
1
or x arg min || y - x || 2 || T x ||1 (3)
x 2
Recovery signals separable Bregman iterative algorithm.

Question (3) solving is first converted to sparse vector (4) solving, A , then

301

arg min || y - A || 22 || ||1 (4)
2
Specific steps of Bregman algorithm are as follows [9, 10]:

-1
Step 1: to calculate B (A A I N ) , I N is the N-order unit matrix, F A y ; b0 , d 0 are N-
T T
dimensional zero vector;
Step 2: ( 10) is given, the iteration terminated conditions d ( 0.001) the number of iterations
n 1;
Step 3: to calculate n B( F d n-1 - bn-1 ) ,

d n sign( n bn-1 ) max(| n bn-1 | -1,0)
bn bn-1 n - d n ;
Step 4: if || n - n-1 || d n n 1 , go to step 3; otherwise, the iteration stops, n ;

Step 5: x .
Sparse random sampling design
Signal sparse representation. Transform based of adaptive signal is , the signal expression should
be sparse at the base[11]. Transform coefficient vector of signal X is under the transform base , if
1
0 <P <2 and R> 0, these coefficients satisfy: || || p ( | i | ) R , the coefficient vector is sparse
p p
i
[12]. If the support domain {i : i 0} of the transform coefficients i X , i is equal or less K,
namely there is K nonzero entries only in R N . The number K of non-zero entries reflect the signal
inherent freedom. Or sparseness is a measure of non-zero coefficients, and it constitutes a number of
scales of the signal component. Typically, sparse representation of the signal can be measured by the
0-norm of the representing vector. A vector 0-norm is the number of non-zero elements in the vector.
Fourier transform is our common one [13], [14].
Irrelevant and Isometric properties. The adaptive M N -dimensional measurement matrix is
designed which is not related to transformation base . Observation matrix design goal is to
restore the original signal as little as possible from the observation values. In the specific design, it is
need to consider the following two aspects:
1) the relationship between the observation matrix and the base matrix ;
2) the relationship between the matrix A and K- sparse signals .
First, the observation matrix and the base matrix have incoherence. Coherent between
observation matrix and the base matrix is defined as formula (5):
(, ) N max 1k m | k , j | (5)
1 j N

302
The degree of coherence gives the maximum coherence between any two vectors in and .
When and contain coherent vectors, their coherence degree is coherence. The compressed
sampling of the signal makes for each observation contains the different information of the original
signal as much as possible, which requires orthogonal between the vectors of and , that degree
of coherence is as small as possible, which is the reason of incoherence between the measurement
matrix and base matrix [15]. Just to satisfy the following formula, signal can be reconstructed high
probability [16].
M C 2 (, ) K log N (6)
Second, the relationship between the matrix A and the K- sparse signals is about Restricted
Isometry Property (RIP) [17], the matrix "equidistance constant": any K = 1, 2, , the matrix A
isometric constant d K is defined to satisfy the minimum value of the following formula (7), which
is optionally K- sparse vector:
(1 - d K ) || || 2 || A || 2 (1 d K ) || || 2
2 2 2
(7)
If d K <1, Matrix A is called to satisfy the K-order RIP, matrix A is approximately to ensure in this
time that the Euclidean distance of K- sparse signal remains unchanged, which means that is
impossible in null space of A (otherwise there will be infinitely many solutions for ). In practice,
random matrix is commonly used as observation, common are Gaussian measurement matrix, binary
measurement matrix, Fourier observation matrix and irrelevant observation matrix . Random
observations provide an effective way to achieve the compressed samples
Low-rate signal sampling and measurement matrix design. In fact, the design of the observation
partis is to design an efficient observation matrix, that is to design efficient observation (ie, sampling)
agreement of useful information to capture a sparse signals, whereby the signal is compressed into a
small number of sparse data. The agreement is non-adaptive, it requires only a small amount of link
between the fixed waveform and the original signal, the fixed waveform is irrelevant to signal
compact represented base. In addition, the observation process is independent of the signal itself. the
reconstructed signal can be collected by optimization methods in a small number of observations.
Measurement matrix is determined by the measured waveform and sampling methods. Measured
waveform generally includes a Gaussian random waveform with independent and identically
distribution, Bonu Li random waveform and orthogonal functions; sampling methods include a
uniform sampling, random sampling and jitter sampling.
Sampling interval is [0, T], M points were collected randomly in this interval,
ti rand (0,1)T , i 1,2,, M , rand (0,1) is random point in interval (0,1];
x [ x(t ), x(t ),, x(t )] , y ~
~
1 2 M
T
x R , N-dimensional complex frequency domain vector
M
C , M N is reconstructed at equal intervals.

N
Random measurement matrix is designed:
1 N /2 l t
(m, n) exp( 2i ( m - n)), m 1,2,, M ; n 1,2,, N , (8)
N l - N / 21 N Ts

303
where Ts is the equivalent sampling interval in the time domain which is used to reconstruct N points
uniformly, is Fourier base, j (tn ) N -1/ 2ei 2jt n , j, n 1,2,, N , t m belongs to domain collections
of the reconstructed signal including a random collection. Such design of and meet incoherence
in formula (5) and Restricted Isometry Property (RIP) in formula (7). A This random
extraction makes each observation with random uncorrelated characteristics. The irrelevant feature
between Stochastic Observation Matrix is a sufficient condition for proper signal recovery, if
observation matrix is highly irrelevant with the signal, it can ensure to restore the effective signal.
N points x* [ x(Ts ), x(2Ts ),, x( NTs )]T are sampled in the sampling space Ts in interval [0, T], then
is a mapping: : x* R N ~ x R M , it is proven below by discrete Fourier transform formula
and inverse Fourier transform formula:
N 1 N /2 N l tm
(m, n) x* (n) [ x* (n) exp( 2i ( - n))]
n 1 N l - N / 21 n 1 N Ts
1 N /2 N l lt
[ x* (n) exp( -2i n)] exp( 2i m ) (9)
N l - N / 21 n 1 N NTs
1 N /2 lt m t
X (l ) exp( 2i )~
x ( m ) x(tm )
N l - N / 21 NTs Ts
The compressed sensing harmonic detection is to find a way of the reversed mapping :
F : R M C N (frequency domain), or further mapping: F : R M R N (time domain).
Compressed sensing sampling signal recovery implementation steps
1) In the given interval (0, T) of the time domain, the maximum number of samples M is set based
on the maximum frequency of reference signal contained in this interval, this point sequence is the
observation vector; the range of reconstruction points N (> M) is determined to decide the equivalent
sampling interval Ts;
2) N points are reconstructed at equal interval Ts in this section, thereby a frequency domain
1
resolution f Hz is given;
NTs
3) From formula (8), M N -dimension observation matrix is designed, N N - dimension
inverse Fourier transform matrix is designed;
x [ x(t1 ), x(t2 ),, x(tM )]T are randomly sampled n the given interval (0, T);
4) M points ~
5) Bregman algorithm is used to reconstruct N-points in complex frequency domain,

arg min || y - A || 22 || ||1 , y= ~
x;
2
6) Inverse Fourier transform is used to obtain N-point signals x real ( ) at equal intervals in time
domain.
7) Real-time processing of the next frame, go to step 4.
Experimental testing and evaluation
Experimental select signal function is
304
2
x(t ) 2 cos(40t ) cos(140t ) cos(300t ) (10)
6 5 4
The highest frequency of the signal is f max 150Hz , M = 128 points are sampled randomly within 1
second, that is, its random equivalent sampling frequency is f s 128Hz f max , random equivalent
sampling frequency is much less than twice the highest frequency of signal, it does not meet the
Nyquist sampling theorem. In terms of such a uniform sampling frequency, then there must be a
Fourier transform spectrum aliasing and disclosure, it is impossible to detect the signal harmonics. M
= 256 points are sampled, and N = 4 128 512 points are reconstructed in frequency domain by this
method, its resolution is 1 Hz, the signal contained frequency in the original signal is same as the
measured frequency of the reconstructed signal, they were 20,70,150. The original corresponding
amplitudes were 2, 1, 0.5, while the results of our method were 1.9823,0.9798,0.4830; the original
corresponding phase were 30 , 72 , 45 , and the results of method were 29.9256 , 71.9750 ,
45.2006 ; the detection results are shown in Figure 2. Each harmonic frequency, amplitude and
initial phase of the true values and the detected values were plotted on the same graph, the result is
very accurate.
Fig. 2. Compressed sensing sparse sampling and signal reconstruction n
The above picture of figure 2 shows the original signal, the sampling points and the reconstruct time
domain signal, the middle picture of figure 2 shows the amplitude-frequency diagram of the original
signal and the reconstructed signal, the below picture of figure 2 shows the phase-frequency diagram
of the original signal and the reconstructed signal. The relative error of time-domain reconstructed
signal is:

305
|| x - x || 2
Relative error = || x || 2 = 0. 0139.
Summary. Random sampling technique is as a non-uniform sampling method, it can effectively

improve the sampling rate in sampling system. In a random sampling, the non-uniform distribution
characteristics of the sampling interval is not need to collect enough samples to signal reconstruction.
In this study, the sparsity of signal is used in the Fourier transform, complex random measurement
matrix is designed, namely it is random sparse sampling; Bregman iterative algorithm is used
successfully to restore signal. This method does not increase the costs on the basis of any hardware,
and it is able to reconstruct the original signal by the limited random samples. Experimental results
show that the frequency domain sparse signals are sampling far below the Nyquist frequency signal
sampling rate, the original signal is accurately reconstructed by compressing the sensor signal
reconstruction algorithms.
Compression sensing basic idea is to extract much information as little as possible from the data [18-
22], there is no doubt that it has a great theory and promising idea. Compressed sensing is an extension
of the traditional information theory, but it is beyond the traditional compression theory, it has become
a new sub-branch. When the signal has a sparse feature, compressed sensing can accurately
reconstruct the source signal by a small number of observations which is much smaller than the length
of signal. Compressed sensing theory is that sampling and compressed signal are combined into a
single step, the signal is encoded, it breaks the traditional Nyquist sampling theorem limit in a certain
extent, the burden is reduced on the hardware processing.
In the framework of the compressed sensing theory, the sampling rate is no longer determined by the
bandwidth of the signal, but depending on the structure and content of the information in the signal.
It uses transform space to describe signal, a new theoretical framework is established for describing
and signal processing, so that in the case to ensure that information is not lost, with far lower than
signal sampling rate which the Nyquist sampling theorem requires, but also recovery signal is
completed in high probability. Compared with conventional Nyquist sampling, Compression sensing
reduces hardware requirements and saves resources.
Acknowledgements : This work is sponsored by the National Natural Science Foundation project
(51375484) of China.
References
[1] D.L. Donoho, Compressed sensing. IEEE Trans. Information Theory, 2006 , 52 (4 ) :1289-1306.
[2] Baraniuk R G. Compressive sensing. IEEE Signal Processing Magaz ine , 2007, 24(4 ) : 118 -121.
[3] Donoho D,Tsaig Y. Extensions of compressed sensing. Signal Processing,2006,86 ( 3 ):533-48.
[4] Shi G M , Liu D H , Gao D H ,Liu Z , Lin J, Wang L J . Advances in theory and application of
compressed sensin. Chinese joum al of Eleetronics, 2009 , 37 (5 ) :1070-1081. (in Chinese )
[5] Shapiro H SSilverman R AAlias-free sampling of random noiseJournal of the Society for
Industrial and Applied Mathematics, 19608(2) 225-248
[6] S. Osher, Y. Mao, B. Dong, and W. Yin, Fast Linearized Bregman Iteration for Compressed
Sensing and Sparse Denoising, UCLA CAM Report (08-37), 2008.
[7] W. Yin, S. Osher, D. Goldfarb, and J. Darbon, Bregman iterative algorithms for 1-minimization
with applications to compressed sensing, SIAM J. Imaging Sci., 1 (2008),pp. 143168.
[8] E.J. Cande`s, J. Romberg, and T. Tao, Robust uncertainty principles: Exact signal reconstruction
from highly incomplete frequency information, IEEE Trans. Inform. Theory, vol. 52, no. 2, pp. 489
509, Feb. 2006.

306
[9] J.-F. Cai, S. Osher, and Z. Shen,, Linearized Bregman iterations for compressed sensing, Math.
Comp. 78 (2009), 1515-1536.
[10] J.-F. Cai, S. Osher, and Z. Shen, Convergence of the Linearized Bregman Iteration for 1-norm
Minimization, Math. Comp. 78 (2009), 2127-2136.
[11] E J Candes,J Romberg. Sparsity and incoherence in compressive sampling. Inverse Problems .
2007 ,23 (3) :969-985.
[12] E.J. Cande`s and T. Tao, Near-optimal signal recovery from random projections: Universal
encoding strategies? IEEE Trans. Inform. Theory, vol. 52, no. 12, pp.54065425, Dec. 2006.
[13] S. Chen, D. L. Donoho, M. Saunders. Atomic Decomposition by Basis Pursuit. SIAM Journal
on Scientific Computing, 1999, 20 (1): 33-61
[14] Candes E J and Tao T. Decoding by linear programming, IEEE Transactions on Information
Theory, 2005, 51(12):4203-4215.
[15] Candes E J. The restricted isometry property and its implications for compressed sensing.
Comptes rendus del Cademie des Sciences, Serie1, 2008, 346(9-10): 589-592.
[16] Baraniuk R G, Davenport M A, DeVore R, and Wakin M B. A simple proof of the restricted
isometry property for random matrices. Constructive Approximation, 2008, 28(3):253-263.
[17]Haupt J and Nowak RA generalized restricted isometry propertyUnivemity of Wisconsin
Madison Technical Report ECB-07-1May 2007
[18] Liu Zhaoting, He Jin, Liu Zhong, High Resolution Frequency Estimation with Compressed
Sensing, Signal Processing, 2009, 25 (8),1252-1256
[19] HE Ya-peng, LI Hong-tao, WANG Ke-rang, ZHU Xiao-hua, Compressive Sensing Based High
Resolution DOA Estimation, Journal of Astronautics, 2011, 32(6),1344-1349
[20] Jin Jian, Gu Yuan-tao, Mei Shun-liang, An Introduction to Compressive Sampling and Its
Applications, Journal of Electronics & Information Technology, 2010, 32(2), 470-475
[21] L. M. Brgman, A relaxation method of finding a common point of convex sets and its
application to the solution of problems in convex programming, Z. Vyisl. Mat. i Mat. Fiz. 7 (1967),
620-631.
[22] E. Cands, J. Romberg, and T. Tao, Stable signal recovery from incomplete and inaccurate
measurements,Comm. Pure Appl. Math., vol. 59, no. 8, pp. 12071223, Aug. 2006.

307
VIII. Economics & Management


308
Methodology of Assessing the Impact of Urban Development Value of the

Territory on the Value of Residential Real Estate by Example of Kiev City,
Ukraine
43
I.M. Ciobanu1,a
1 Candidate of engineering sciences, Kyiv, Ukraine

a jdoroshenko@ukr.net
Keywords: residential real estate, urban development value, methodology, zonal coefficient of location, correlation
connection, least squares method, economic and planning zoning.
ABSTRACT. The paper proposes a methodology for assessing the impact of the urban development value of the territory
on the value of various types of residential real estate and it is proved that the urban development value of the territory,
which is displayed through the value of the zonal coefficient of the location CL2 , is observed (laid) in the cost of housing
and it is not the same for different types of multistory residential real estate objects.
Introduction. Ukraine is a country with a high level of urbanization (about 68% of the population
lives in cities). Housing construction by area occupies the first place among other built-up land in
cities, which plays an important role in the formation and development of cities. It occupies 15.3%
of the built-up areas in the Balance Sheet of Kyiv City.
The urban value of the territory has a direct impact on the spatial distribution and density of residential
property in the city plan and is a factor influencing the value of residential property. Therefore, we
investigate the dependence between the cost of different types of residential development and the
degree of urban development value of the territory, expressed by the magnitude of the zonal
coefficient CL2 in order to determine the role of the land component in the structure of the value of
residential real estate.
Scientific researches of Yu. Bocharova, O. Gutnova, V. Davydovych, M. Diomin,
Ye. Kliushnichenko, O. Kudriavtsev, H. Lavryk, A. Ositniank, T. Panchenko, I. Prybitkova,
B. Solucha, O. Khorhota, G.Filvarova, I.Fomin, T. Ustenko, Z. Yarhyna and others are devoted to the
optimization of the functional use of territories and spatial organization of cities; they were conducted
in conditions of universal ownership of land and real estate and the planned implementation of all
city-planning measures. The issue of spatial organization of housing development was considered
without taking into account the influence of legal categories and economic interest of land owners.
Based on the comparison method, according to which the value of land is measured by the proportion
that it brings to the value of the property and increases with increasing degree of urban development
value of the territory, to develop a methodology for assessing the impact of the urban development
value of the territory on the cost of various types of residential real estate and prove that the urban
development value of the territory, which is displayed through the value of the zonal coefficient C L2
is observed (laid) in the cost of residential development and it is not the same for different types of
objects of the residential real estate, depending on their location.

309
The main material. Residential real estate most clearly reflects the urban construction value of the
territory, because it provides social and consumer functions. Since commercial real estate objects can
be presented on the market as a single business or as a common property, the difference between
these indicators is almost impossible to analyze without statistical data. The presence of a business
component is laid at the level of developer's profit in residential real estate.
The value of land can be defined as normative or expert. From the point of view of expert assessment,
the market mechanisms operate only, and the final value already takes into account the entire set of
features of the property itself and the features of its location.
Unlike expert evaluation of the normative monetary assessment, various factors affecting the
regional, zonal and local levels are taken into account. Thus, the calculation of 1 m2 of the land
settlement is made on the basis of the base cost, depending on the level of development and
arrangement of its territory, as well as its place in the national, regional and local systems of
production and resettlement and is determined by the formula (1):
Ex Np
BCs CL1 , (1)
Nc
where BCs base cost of 1 m2 of settlements (UAH);

Ex expenses for the development and arrangement of the territory of the settlement;
Np norm of profit (6%);
Nc norm of capitalization(3%);
The coefficient, which characterizes the functional use of the land, takes into account the relative
profitability of the types of economic activity within its boundaries and for the residential land
Cf = 1.0. Taking into account that the objects of the unified functional use are analyzed in the work,
the influence of the indicated coefficient is not taken into account at all. The coefficient that
characterizes the dependence of rental income on the location of the locality in the national, regional
and local systems of production and resettlement (CL1) is taken into account in the value of the base
value. The coefficient, which reflects the features of the local location of the land plot and its
environment (CL3), is not considered, as real estate objects are analyzed in a concentrated urban space
with maximally approximate values. Proceeding from this, it is assumed that the unique coefficient
of location that reflects the urban development value of the territory is the zonal coefficient C L2.
The method of comparison or transfer was used to confirm this assumption. It consists of the principle
of contribution according to which, the value of land is measured by the component (share) that it
brings into the value of the property and increases as the degree of urban development value of the
territory increases.
According to [1], the constituent components of the zonal value of the territories (CL2) are:
1) Transport and functional convenience;
2) The ecological quality of the territory;
3) Engineering and infrastructure support;
4) Social and urban-friendly attractiveness of the environment;
5) The level of social and economic development of the territory.
The research was conducted on the example of Kyiv City. According to [2], there are 741 economic-
planning zones within the boundaries of Kyiv City, depending on the heterogeneity of the functional
and planning qualities of the territory that affect the size of the rental income; the difference in

310
accessibility at the level of engineering provision and improvement of the territory, development of
the service sector of the population; the ecological quality of the territory and the attractiveness of the
environment.
According to [3], there are seven planning zones: the Central, Southern, Urban Area of Vyshgorod,
Western, Northern, Northern Left Bank and Eastern on the territory of the city.
The author studied the location of residential real estate on the territory of Kiev City. According to
the results of research, it was found that housing development is dispersed in 432 economic and
planning zones, of which 17 are residential buildings. The range of values for K 2 in Kiev City is
from 0.5 to 6.95. It is established that despite one of the main principles of the allocation of economic-
planning regions as a functional homogeneity. We also observe a significant number of areas of mixed
functional use. It does not refer to small intersections in the general homogeneous functional space
of other functions, but to the principle combination of functions.
Yu.F. Dehtiarenko, Yu.M. Palekha, Yu.M. Mantsevych, A.V. Tarnopolskyi [4] were performed
zoning of the territory of Kyiv City on the distribution of the values of the zonal coefficient C L2 into
4 zones with the corresponding ranges: 0.1-0.99; 1-1.99; 2-3.49; 3.5-6.96, but such a grouping does
not reflect with sufficient accuracy impact of the urban development value of the territory on
residential real estate.
Based on studies of dispersal residential development of Kyiv City [5] and zoning of its territory
according to the scale values of 0.5, it was established that zoning the territory of Kyiv City at the
value of the coefficient CL2 > 3.0 is concentrated in the downtown. Therefore, in order to avoid
significant fragmentation of the territory, it was proposed to perform zone zoning on the scale of
value 1.0 within the values of the coefficient CL2 from 3.0 to 6.95.
Due to the above, the method proposed the entire territory of Kyiv City that are under residential
development to merge into 8 zones of urban development value of the territory, with the following
ranges of values of the zonal coefficient CL2 (Table 1, Fig. 1.):
Table 1. Zones of urban development value in Kiev, Ukraine for the residential buildings
Value Value
No Quantity of No Quantity of
of the zonal economic- of the zonal economic-
zone coefficient planning zones zone coefficient planning zones
L2 L2
1 6,00 - 6,95 3 5 2,0 - 2,99 60
2 5,0 5,99 5 6 1,5 - 1,99 140
3 4,0 - 4,99 13 7 1- 1,49 113
4 3,0 3,99 16 8 0,5 - 0,99 41
Analyzing the dispersion of these zones, it should be noted that their greatest integrity is observed for
the range of the value L2 from 3.00 to 6.95, the smallest: from 0.50 to 2.99, respectively.
Further work also suggests that the urban development value of the territory displayed by the value
of the zonal coefficient L2, is observed (laid) in the cost of residential development. It is not the same
for different types of objects of multi-storied residential real estate, depending on their location.
In order to identify this unevenness, the analysis of the cost of multistoried residential real estate
objects of different periods of development (of different types) in the areas of different urban
development values was performed.

311
Based on the sale data of residential real estate, a sample of 1,500 objects was created for the research.
Public resources like the Internet portals on real estate agencies and periodicals were used as sources
of information. Residential real estate is differentiated according to the types, which are based on the
period of their construction: the 'Pre-revolutionary', the 'Pre-war', 'Stalin's' and 'Khrushchevs' periods
construction, Panel Construction and New Buildings in each of the 8 zones of urban construction
value of the territory. The number of analogues for comparison is substantiated by the method of
analogues in the expert monetary assessment of the real estate object. In particular, it is considered
that a comparison of at least 5 analog objects is sufficient to establish the predictive estate prices.
Therefore, not less than 5 analogues were analyzed in zones with the greatest integrity of the range
CL2 and 20 proposals for the sale of different types of housing were analyzed in zones with the least
integrity. The peculiarity of the analysis was the selection of completely unified by area, the size of
the objects of housing like apartments, according to the type of residential development, storey, etc.
Fig. 1. Economic planning zoning of the territory of Kiev City under residential buildings.
In addition, in order to identify the absolutely clear value of the urban development value of the
territory under different types of residential buildings, all the houses in which the investigated
apartments located, are located on plots of land the ownership of which is not formalized. The above
analysis was performed using data from the automated system of the Software Complex Cadastre

312
of the Main Department of Land Resources of the Kyiv City State Administration (KCSA). The
buildings are on the balance of the relevant housing maintenance offices, associations of co-owners
of multi-apartment buildings (condominiums). In this case, the ownership of residential any buildings
have not been acquired, and have not been issued, concerning that apartments were used for analysis,
but also the land was not invented by the relevant housing-service offices. New buildings were
seemed like exceptions, because they have built on designated land areas, since 2000.
Analysis of the statistical data of the value of various objects of residential real estate in the same area
of urban development value has shown that the cost of 1m2 of residential real estate is the most
expensive in the 'Pre-revolutionary' and the 'Pre-war' periods and 'Stalin's' period buildings in central
areas. It was also interesting fact that the value of 'Khrushchev's' period, the 'Pre-war' and the 'Pre-
revolutionary' periods buildings in the indicated zones, is practically identical.
The problem of dispersal of housing becomes very relevant, with the rise of prices for residential real
estate, approaching, and sometimes equals to the level of developed European countries.
Analysis of the dispersal of residential buildings, depending on the period of development, allowed
revealing the interesting facts. In particular, the 'Pre-revolutionary' and the 'Pre-war' period buildings
and buildings of 'Stalin's' period are concentrated in the central zones. There are not any objects of
'pane' construction in the years 1990-1995 practically, but somewhat smaller quantity of
'Khrushchev's' period buildings, but there are also 'impregnations' of new buildings (new housing
development).
The method of least squares was applied for testing the hypothesis of the correlation of the zonal
coefficient of the location CL2 with the cost of residential properties.
The correlation dependence is represented as:
Mx(Y)=(x), (2)
where (x) const.

The best estimate of the regression function in terms of the Least Squares Method is the selective
regression curve of y for x.
yx= (x, b0, b1, bp), (3)
where yx is conventional selective medium variable y at a fixed value variable x= x;

b0, b1, ... bp are the parameters of the curve.
Statistical relationships between variables can be studied using correlation methods (establishing the
relationship between two random variables and assessing its constraints) and regression (establishing
the type of dependence between them) of analyzes.
Assumed that x is a coefficient of urban planning value of the territory CL2;
y is the average price for n-type residential area in the relevant territory values of urban development
CL2.
Data on statistical dependence is conveniently set in the form of a correlation table (x i and yi are the
middle of the corresponding intervals, ni and nj are the corresponding frequencies). If we depict the
obtained dependence graphically by points on the coordinate plane, then we obtain the so-called
correlation field (Fig. 2).

313
We can make assumptions about the existence of a linear correlation relationship between x and y,
based on the form of the correlation field. Therefore, the regression equation will be built the formulas
(4):
yx b0 b1 x , (4)
For each value (=1,2,,l), that is, for each row of the correlation table we calculate group averages.
yx b0 b1 x , (5)
We use the Least Squares Method, according to which unknown parameters are chosen in such a way
that the sum of the squares of deviations of the empirical group average of the values (found by the
regression equation) would be minimal for this purpose.
(b0 b1 x - y)2 min (6)
Considering this amount as a function b0 and b1, we differentiate it according to these parameters and
equate the derivatives to zero (7):

2(b0 b1 x - y ) 0,
b 0 (7)

2(b0 b1 x - y ) 0.
b1
And then we obtain a system of normal equations for determining linear regression parameters (8),
after some simple transformations:
b0 n b1 x y,
, (8)
b0 x b1 x xy ,
2
where n is a number of population units (given values of x and y). This is a system of normal equations
of the least squares method for a linear function ( yx ).
Dividing both sides of the two equations in n, we obtain (9):
b0 b1 x y,
, (9)
b0 x b 2 x 2 xy.

314
where the corresponding averages are determined by the formulas (10):
m l l m m
yjnj
j 1
xini
i 1
xiyjnij
j 1
x i
2
ni
y ,x i 1
, xy ,x
2 i 1
, (10)
n n n n
Now we rewrite the regression equation as follows (11):
yx - y byx ( x - x) (11)
The regression coefficient shows how many units the variable y changes in average with an increment
of x per unit.
The coefficients byx and 1/bxy determine the angle coefficients to the axis Ox of the corresponding
regression lines that intersect at the point ( x, y ) .
Let's turn to the estimation of the correlation dependence density. However, you can see that byx
depends on the unit of measurement of the variables. The value of r is an indicator of the density of
the connection and it is called the sample correlation coefficient. If r>0 (byx>0, bxy>0), then the
correlation dependence between the variables is called direct, if r<0 (byx<0, bxy<0) is inverse.
That is, the coefficient of correlation r for x and y is a geometric average of the regression coefficients
r byxbxy . We use the formula (12) for practical calculations:
n xy - x y
r
n x - ( x) n y
(12)
2 2 2
- ( xy ) 2
Determination coefficient (R2) shows the share of the changes (variation) of the resultant
characteristic under the influence of the factor characteristic. It is calculated using the formula (13):
R 2
1-
(y - y ) j j
2
(13)
y - n
2
( y) 2 j
j
It can vary from 0 to 1. If it is closer to 1, the tendency is established more adequate, and, accordingly,
the connection of the chosen trend and the dynamic range are closer. Based on the value of the
determination coefficient, in statistical practice, it is accepted to apply the following gradation of
trend matching to the dynamic series: R2 = 0 means a lack of connection; R2 < 0.3 means weak
connection; R2 = 0.3 to 0.6 means middle connection; R2 = from 0.7 to 0.9 means a high connection;
R2 = from 0.9 to 1 shows that the selected trend fully corresponds to the dynamic range.

315
Fig. 2. Dependence of the value of residential real estate on the urban development value of the
territory.
Based on this algorithm, there were designed and constructed regression equations for different types
of housing and graphically represented the data for correlation analysis in the correlation field, i.e.
points in the plane, each of which has coordinates (Fig.2).
The equation of a linear function is:
- for the 'Pre-revolutionary' period buildings: y = 2837,6 x + 9839,2; R = 0,7469;
-for the 'Pre-war' period buildings: y = 2601 x + 9435,1; R = 0,662;
- for the 'Stalin's' period buildings: y = 5313,7 x + 5969,1; R = 0,9556;
- for the 'Khrushchevs' period buildings: y = 4168,6 x + 8181,2; R = 0,732;
- for panel construction: y = 1408 x + 16363; R = 0,6386;
- for the new buildings: y = 3821,5 x + 9665,2; R = 0,7432.
The conducted analysis allowed establishing that among the urban value of the territory (the values
of the zonal coefficient location CL2) and the value of different types of housing there is a close
correlation, which is in functional connection values of the average values of these characteristics.
Since, the regression coefficient (b1, which denote the byx) shows how many units on average will
change the variable y with increasing variable x per unit. It follows from this that due to increment of
urban values of the area per unit, the cost of a particular type of real estate will increase to a
corresponding value byx. This statement can be specified by formula (14):
CL 2 1 Vr(CL 2 ) byx (14)
where Vr(CL2) - the value of residential real estate

316
Equation (14) will be as follows:

- for the 'Pre-revolutionary' period buildings: CL2 + 1 = VrevR(CL2)+ 2837,6;
-for the 'Pre-war' period buildings: CL2 + 1 = Vwar R(CL2)+ 2601;
- for the 'Stalin's' period buildings: CL2+ 1 = VstalR(CL2)+ 5313,7;
- for the 'Khrushchevs' period buildings: CL2+ 1 = VKhrushR(CL2)+ 4168,6;
- for panel construction: CL2 + 1 = VpanR(CL2)+ 1408;
- for the new buildings: CL2+ 1 = VnewR(CL2)+ 3821,5.
If the regression equation and correlation fields had been analyzed, then the clear linear dependence
appeared between the cost of different types of residential development and the degree of urban
development value of the territory, as evidenced by the value of R2, which is the determination
coefficient and reflects the density index of connection. Since, in all cases, R2 > 0 varies from 0.6386
to 0.9556 and, accordingly, byx> 0 , the correlation dependence between the variables is sufficiently
large and is called direct. So, the hypothesis had been proven.
Hence the regression equation can be written as a straight line equation = kx+b, the coefficient k is
called the angular coefficient of the straight line.
The angular coefficient with the precision to the sign is equal to the tangent of the acute angle formed
by the straight line with the abscissa (or is equal to the tangent of the angle between the direct and
positive direction of the axis Ox). The value of the angle between the straight lines characterizes the
tightness of the connection between the random variables: if the angle is smaller, the connection is
closer.
We calculate the value of the angular coefficient for different types of housing using the following
formula:
k tg (c/d) (15)
k1 = 0,3255; k2 = 0,1340; k3 = 0,4550; k4 = 0,3398; k5 = 0,2089; k6 = 0,3098;

where k1 the value of the angular coefficient for the 'Pre-revolutionary' period buildings;
k2 the value of the angular coefficient for the 'Pre-war' period buildings;
k3 the value of the angular coefficient for the 'Stalin's' period buildings;
k4 the value of the angular coefficient for the 'Khrushchevs' period buildings;
k5 the value of the angular coefficient for panel construction;
k6 the value of the angular coefficient for the new buildings.
Therefore, the value of the angular coefficient of the linear equation for different types of housing
varies from 0.13 to 0.46, which actually reflects the difference in the quality of housing within the
same type of development, taking into account physical and moral deterioration, the quality of
building materials, etc.
Summary. Based on the results of research, conducted by us, the methodology for assessing impact
of the urban development of the territory on the cost of various types of residential real estate had
been developed.
Based on this of this methodology, there were established:

317
- The dependence of the value of residential real estate on the urban development value of the territory
is different for different types of development (buildings);
- The indicator of the integral coefficient of value of different types of residential development varies
directly in proportion to the growth of urban development value of the territory;
- Between the urban development value of the territory and the cost of housing there is a close
correlation, which is reflected by the determination coefficient that varies from 0.6 to 0.9, which
characterizes different types of housing;
- Therefore, the value of the angular coefficient of the linear equation for different types of housing
varies from 0.13 to 0.46, which actually reflects the difference in the quality of housing within the
same type of development, taking into account physical and moral deterioration, the quality of
building materials, etc.
References
[1] On approval of the technical documentation on the normative monetary estimation of land in Kiev
and Procedure of estimation (2007) Decision of Kiev city council 2007 43/1877. Available at:
http://search.ligazakon.ua/l_doc2.nsf/link1/MR071188.html
[2] Tkachenko R.O., 2008. Organizational and economic development of regional real estate market
of habitation (on the base of mortgage crediting), Abstract of Cand. Sci. (Tech.) dissertation,
08.00.05, NAS Ukrainian Rada of Productive Forces study, Kyiv, Ukraine [in Ukrainian].
[3] On the approval of the General Plan of Kiev and its planning projects for the suburban until 2020
(2002). Decision of Kiev ity ouncil 2002 370/1804. Available at:
http://kmr.ligazakon.ua/SITE2/l_docki2.nsf/alldocWWW/56E1D135DED9D0B0C22573C00053FC
A6?OpenDocument
[4] Dehtiarenko Yu.F., Mantsevich Yu.M., Palekha Y.M., Tarnopolskyi A.V., 2008. Impact of
monetary valuation on the land market in Kyiv: state, problems and prospects of disintegration .
Scientific and Production Magazine "Land Management and Cadastre", 1. - K., "CROP" p.
59-68.
[5] Doroshenko I.M., 2012. Regularities of formation and development of residential real estate
market in Ukraine. Abstract of Cand. Sci. (Tech.) dissertation, 05.24.04, KNUCA, Kyiv, Ukraine
p.160 [in Ukrainian].

318
Mechanics, Materials Science & Engineering Journal
e-ISSN 2414-6935
ISSN 2412-5954
Regarding advertisement, please contact hotmail@mmse.xyz
Powered by Magnolithe GmbH, Austria http://magnolithe.at
See more at: https://mmse.xyz/

319

Mmse Journal Vol11

Enviado por

Dados do documento

Direitos autorais

Formatos disponíveis

Compartilhar este documento

Compartilhar ou incorporar documento

Opções de compartilhamento

Você considera este documento útil?

Este conteúdo é inapropriado?

Direitos autorais:

Formatos disponíveis

Mmse Journal Vol11

Enviado por

Direitos autorais:

Formatos disponíveis

Mechanics, Materials Science & Engineering, July 2017 ISSN 2412-5954

MMSE Journal. Open Access www.mmse.xyz

Sankt Lorenzen 36, 8715, Sankt Lorenzen, Austria

Mechanics, Materials Science & Engineering Journal

MMSE Journal. Open Access www.mmse.xyz

Editor-in-Chief Mr. Peter Zisser

Dr. Zheng Li, University of Bridgeport, USA

Prof. Kravets Victor, National Mining Univerisity, Ukraine

Ph.D., Girish Mukundrao Joshi, VIT University, India

Dr. Yang Yu, University of Technology Sydney, Australia

Prof. Amelia Carolina Sparavigna, Politecnico di Torino, Italy

ISSN 2412-5954 Design and layout: Mechanics, Materials Science &

2017, Magnolithe GmbH

Published by Magnolithe GmbH. This is an open

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

Structural and Optical Properties of DC Magnetron Sputtered Zirconium Titanate Thin

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

Microcapillary Features in Silicon Alloyed High-Strength Cast Iron

R.K. Hasanli1,a, S.N. Namazov2,b

1 Associated professor, Dr., Azerbaijan Technical University, Baku, Azerbaijan

DOI 10.2412/mmse.89.99.501 provided by Seo4U.link

Keywords: alloyed, high-strength cast iron, metal form, segregation, structure.

Fig. 1. The microstructure of unalloyed ductile iron, x300.

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

Characterization of Aluminium Alloy AA2219 Reinforced with Graphite by Stir

V. Bhuvaneswari, a, G. Yuvaraj, b, Dr. A. Saravanakumar, c, L. Rajesh Kumar, d, R. Kiruthiha, e

1 KPR Institute of Engineering & Technology, Coimbatore, India

DOI 10.2412/mmse.79.48.932 provided by Seo4U.link

Keywords: aluminium alloy, graphite, mechanical properties, stir casting method.

MMSE Journal. Open Access www.mmse.xyz

Table 1. Properties of graphite.

Porosity (%) 0.7-53

Modulus of Elasticity (GPa) 8-15

Compressive strength (MPa) 20-200

Coefficient of Thermal Expansion (x10-6 C) 1.2-8.2

Thermal conductivity (W/m.K) 25-470

Specific heat capacity (J/kg.K) 710-830

MMSE Journal. Open Access www.mmse.xyz

Fig. 1. Mechanical stirring machine.

MMSE Journal. Open Access www.mmse.xyz

Fig. 3. Brunel hardness Equipment.

Table 2. Tests results.

MMSE Journal. Open Access www.mmse.xyz

Fig. 4. Surface roughness tester.

Table 3. Rockwell tests results.

Table 4. Porosity tests results.

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

Process Optimization of Warm Laser Shock Peening without Coating for

1 Centre for Crystal Growth, VIT University, Vellore, India

DOI 10.2412/mmse.91.76.916 provided by Seo4U.link

Introduction. The post-processing material designing technology in automotive and aerospace

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

MMSE Journal. Open Access www.mmse.xyz

Studies on 1-Butyl 3-Methylimidazolium Hexafluorophosphate Incorporated

R. Arunkumar1, Ravi Shanker Babu1, M. Usha Rani1

DOI 10.2412/mmse.59.9.873 provided by Seo4U.link

Introduction. Tremendous research on solid polymer electrolytes with salt/plasticizer/ceramics