Property Improvements of an Epoxy Resin by Nanosilica

Particle Reinforcement for Tribological Applications

SUBMISSION OF MINOR PROJECT FOR THE DEGREE OF

BACHELOR OF TECHNOLOGY

in

Mechanical Engineering

By

SACHIN CHAINTHA (06305) AMAN CHANDEL (06318)

SAURABH GUPTA (06315) ASHWANI THAKUR (06317)

Under the Guidance of

Dr. AMAR PATNAIK

Department of Mechanical Engineering

Department of Mechanical Engineering

National Institute of Technology
Hamirpur
April. 2009

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 Property Improvements of an Epoxy Resin by Nanosilica Particle
Reinforcement for Tribological Applications

1. Introduction
Fibre reinforced polymer composites have many applications as a class of structural
materials because of their ease of fabrication, relatively low cost and superior mechanical
properties compared to polymer resins. A pre-requisite of most structural/engineering
materials is that they have good stiffness and strength along with adequate toughness.
Composites reinforced with man-made fibers like glass fibers usually fulfill this
requirement, especially since they exhibit crack-stopping capability which makes them
very attractive for structural or semi-structural applications. However, natural fiber
reinforced materials have inferior mechanical and wear-resistance properties than
conventional glass-fibre reinforced composites. In order to overcome these
disadvantages, several treatments have been proposed in the literature [1–4]. In spite of
this, in recent years, there is an increasing interest in natural fibers as substitutes for glass
fibers mainly because of their low specific gravity, low cost, as well as their renewable
and biodegradable nature [5]. Among the naturally available fibers again, there has been
a growing demand, more specifically, for the use of ligno-cellulosic fibers (derived from
plant leaf or bark) as reinforcing elements in polymeric matrix [6-10]. Several types of
natural fibres which are abundantly available like sisal, jute, coir, oil palm, bamboo,
wheat and flax straw, waste silk, banana have proved to be good and effective
reinforcement in the thermoset and thermoplastic matrices [11-19]. Sugarcane fibres are
long plant fibres, like hemp, flax [20-22], and bamboo [16,17] that have considerable
potential in the manufacture of composite materials. Natural fibre-reinforced polymers
exhibit very different wear properties, mechanical performances and environmental aging
resistances depending on their inter-phase properties, but most studies available in the
existing literature have been dedicated to fibre surface treatment [1-5]. And although
reinforcement of these natural fibers has long been an attractive option in composite
making, the potential of pine bark, as a reinforcing fiber has not been explored so far.
Hence the present work is undertaken to investigate exclusively the tensile, flexural as
well as the wear behaviour of this plant fibre (pine bark) reinforced composite. The

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Himalayan subtropical pine forests are renowned for being the largest in the whole of
Indo-Pacific areas. Various types of pine trees are found in this region; especially in
Himachal Pradesh, wide ranging tracts of Chir Pine are seen. The scientific name of Chir
Pine is Pinus roxburghii. Over the years these forests have faced several threats from the
modern day society. Overgrazing, cultivation, exploitation for fuel woods etc have
brought about degradation of this eco region. Hence, there is an urgent need for
plantation, preservation of this natural wealth and its utilization with great care and
sensibility.
Surprisingly, publications concerning the tribological behaviour of natural fiber
reinforced polymers are rare in the tribology literature. Only few articles were
concentrated on the use of sugarcane bagasse to reinforce low cost composites [23], and
to reinforce cement composite [24]. Furthermore, a series of researches was focused on
the study of abrasive wear behaviour of bamboo fibres [16-17, 25-28]. The work by El-
Tayeb [29] reports the adhesive behaviour of sugarcane reinforced polymer composites
as compared to that of glass reinforced polymer composites. It is strange that despite the
interest and environmental appeal of plant fibres, their use has been limited mostly to
non-tribological applications. It may be due to their lower strength and stiffness
compared with synthetic fiber reinforced polymer composites. However, the stiffness and
strength shortcomings of bio-composites can be overcome by structural configurations
and better arrangement in a sense of placing fibers in specific locations for highest
strength performance and also by hybridization of the composites. Composites having
two or more fillers contained in the same matrix are called hybrid composites [30,31].
Recently there is a growing interest in hybridizing different natural fibers in order to
produce high performance composite materials.
Against this background, the present investigation is undertaken to develop a new kind of
hybrid composite consisting of pine-bark fibers as the reinforcement, cement-kiln-dust as
the particulate filler and polyester as the matrix. Short fibers in the form of flakes of pine
tree barks, which are abundantly available in the Himalayan valley in northern India are
reinforced in polyester resin filled with a fixed quantity of cement kiln dust to prepare the
composites. The cement kiln dust is a by-product of the manufacture of Portland cement.
It is generated during the calcining process in the kiln. Apart from CaO, that constitutes

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roughly 60 % of the dust, other compounds present in it include SiO2, Al2O3, Fe2O3, K2O,
Na2O, Cl–, etc. The present work thus involves the development of this new class of
particle filled plant fiber reinforced composites and reports on their sliding wear
characteristics. Such multi-component hybrid composites form complex systems and
there is inadequate research reported on their wear characteristics. To study the
correlation between the wear properties and the characteristic parameters, e.g., the
composition of the composite and the operating conditions is of prime importance for
designing proper composites in order to satisfy various functional requirements. But
visualization of impact of any individual control factor in an interacting environment
really becomes difficult. To this end, an attempt has been made in this study to analyze
the impact of more than one parameter on abrasive wear behavior of the epoxy based
nanosilica filled composites. It is important as in actual practice the resultant wear rate is
the combined effect of more than one interacting variable. An inexpensive and easy-to-
operate experimental strategy based on Taguchi’s parameter design has been adopted to
study the effect of various parameters and their interactions. This experimental procedure
has been successfully applied for parametric appraisal in the wire electrical discharge
machining (WEDM) process, drilling of metal matrix composites, and erosion behavior
of polymer–matrix composites [32-37].
2. Identified Research Gaps
At present, the incorporation of the SiO2, particles in a polymer matrix on a nanoscale
level is a major challenge in this field. The formation of agglomerates which is observed
in composites prepared by conventional techniques can deteriorate the final properties of
the product. To overcome this problem, the sol-gel process for incorporating nanosilica
particles into a reactive epoxy resin may try in the works presented here. By this process,
inorganic or inorganic-organic materials can be produced from liquid starting materials
via a low temperature process. By employing chemical methods, nanoparticles can be
produced elegantly and free of agglomerates.
The major challenge is to transfer these nanosilica particles from the aqueous medium
into the prepolymer of a reactive epoxy resin without affecting the particle distribution. In
the liquid process, toxicological problems during handling of the pure nanoparticle
substances do not exist or can be eliminated at the initial stage. The incorporation of

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nanosilica particles also aims at a low shrinkage upon curing because this improves the
toughness and ductility of the cured products and also prevents debonding of the casting
compound from the matrix. The special nano-scaled design of the particles is the key to a
property enhancement. The silica phase consists of surface-modified, synthetic SiO2,
nanospheres with diameter of less than 50 nm and extremely narrow size distribution.
3. Specific objectives of this project work up to eight semesters
Keeping in view of the magnitude of the problem, current status of research and
preliminary findings based on some of the commercial composites the following
objectives are set in the scope of the present project work.
• Development of methods for the efficient fabrication of the SiO2 particles in a
polymer matrix on a nanoscale level.
• The formation of agglomerates which is observed in composites prepared by
conventional techniques can deteriorate the final properties of the product or not.
• To overcome this problem, the sol-gel process for incorporating nanosilica particles
into a reactive epoxy resin may try in the works presented here.
• By this process, inorganic or inorganic-organic materials can be produced from
liquid starting materials via a low temperature process. By employing chemical
methods, nanoparticles can be produced elegantly and free of agglomerates.
• Study on Structural and Mechanical Analysis of the composites. Structural
properties such as: Microstructure, Viscosity Studies of the Unfilled and Filled
Resin and Mechanical Properties like Three-Point Bending, Micro-hardness,
Fracture Toughness.
• Study on the tribological properties of the prepared composites and their failure
analysis (fracture surface).
4. Proposed Methodology
1. The raw materials needed for this work are epoxy resin, E-glass fibers and
incorporation of SiO2 particle under different weight percentage. These are to be
procured from different firms.
2. Composite slabs will be fabricated using injection molding technique following
prescribed norms for loading and curing. Specimens for various characterization
tests will be made as per required dimensions using a diamond cutter.

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 3. Friction and dry wear test will be carried out using abrasive wear test rig. Wear rate
will be calculated on ‘mass loss’ basis under different operating conditions. Real
time wear situations will be simulated by varying the control factors such as: sliding
velocity, normal load, erodent size, sliding distance etc. The influence of each
factor on the material loss will be studied in an interacting environment. For this,
the experimental schedule will be designed as per Taguchi’s methodology. This will
lead to identify significant factors and the relative significance of their interactions.
4. The eroded samples will be examined under scanning electron microscope to get an
insight to the damage mechanism as a result of solid particle impact.
5. Experimental details

5.1. Specimen preparation

Glass fiber are reinforced epoxy resin composite mixed with nano-silica powder with
different weight percentage. The composites are cast by conventional hand-lay-up
technique so as to get square specimens (120x120 mm2). Composites of five different
compositions (0 wt%, 4 wt%, 8 wt% and 12 wt% of nanoSiO2) are made with the weight
fraction of glass fiber kept fixed (50 wt%) for all samples. Its common name is
Bisphenol-A-Diglycidyl-Ether and it chemically belongs to the ‘epoxide’ family. The
epoxy resin and the hardener are supplied by Ciba Geigy India Ltd. E-glass fiber and
epoxy resin have modulus of 72.5 GPa and 3.42GPa respectively and possess density of
2590 kg/m3 and 1100 kg/m3 respectively. The composite slabs are made by conventional
hand-lay-up technique followed by light compression moulding technique. A stainless
steel mould having dimensions of 210 × 210 × 40 mm3 is used. A releasing agent (Silicon
spray) is used to facilitate easy removal of the composite from the mould after curing.
The low temperature curing epoxy resin and corresponding hardener (HY951) are mixed
in a ratio of 10:1 by weight as recommended. The mix is stirred manually to disperse the
fibres in the matrix. Care is taken to ensure a uniform sample since fibres have a
tendency to clump and tangle together when mixed. The cast of each composite is cured
under a load of about 50kg for 24 h before it removed from the mould. Then this cast is
post cured in the air for another 24 h after removing out of the mould. Specimens of
suitable dimension are cut using a diamond cutter for physical characterization and

6
mechanical testing. Utmost care has been taken to maintain uniformity and homogeneity
of the composite.
5.2. Abrasive wear test

The schematic representation of rubber wheel test set up is shown in Figure 1. In the
present study, silica sand (density 2.6 g/cm3) is used as the abrasive. The abrasive
particles of AFS 60 grade silica sand were angular in shape with sharp edges. The shape
of the silica sand used for abrasive wear study is shown in Figure 2. The abrasive is fed at
the contacting face between the rotating rubber wheel and the test sample. The tests were
conducted at a rotational speed of 100 rpm. The rate of feeding the abrasive is 255±5
g/min. The sample is cleaned with acetone and then dried. Its initial weight is determined
in a high precision digital balance (0.1mg accuracy) before it is mounted in the sample
holder. The abrasives were introduced between the test specimen and rotating abrasive
wheel composed of chlorobutyl rubber tyre (hardness: Durometer-A 58-62). The
diameter of the rubber wheel used is 228 mm. The test specimen is pressed against the
rotating wheel at a specified force by means of lever arm while a controlled flow of
abrasives abrades the test surface. The rotation of the abrasive wheel is such that its
contacting face moves in the direction of sand flow. The pivot axis of the lever arm lies
within a plane, which is approximately tangent to the rubber wheel surface and normal to
the horizontal diameter along which the load is applied. At the end of a set test duration,
the specimen is removed, thoroughly cleaned and again weighed (final weight). The
difference in weight before and after abrasion is determined. At least three tests were
performed and the average values so obtained were used in this study. The wear rate is
measured by the loss in weight, which is then converted into specific wear rate using the
measured density data. The specific wear rate (WS) is calculated from the equation:
WS = Δm/ρt VS.FN (1)
where
Δm is the mass loss in the test duration (gm)
ρ is the density of the composite (gm/mm3)
t is the test duration (sec).
Vs is the sliding velocity (m/sec)
FN is the average normal load (N).

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 The specific wear rate is defined as the volume loss of the specimen per unit sliding
distance per unit applied normal load.
Abrasive hopper

. .. . .. . . .. . . Abrasive particles
. . .. . .
..
.
.
.
.
.
Nozzle .
.
..
..
. Normal load
..
.
Rubber wheel Sample holder
Steel disc ..
.. Composite sample
..
..
..
. .. .
. .. .. .
. . . .. .
. .. .
..
.... ..
Particle collecting bag
.. ..
.. ..

Figure 1. Schematic diagram of abrasive jet machine

5.3. Experimental design

Taguchi experimental design is a powerful analysis tool for modeling and analyzing the
influence of control factors on performance output. This method achieves the integration
of design of experiments (DOE) with the parametric optimization of the process yielding
the desired results. The orthogonal array (OA) requires a set of well-balanced (minimum
experimental runs) experiments. Taguchi’s method uses a statistical measure of
performance called signal-to-noise ratio (S/N), which is logarithmic function of desired
output to serve as objective functions for optimization. The S/N ratio considers both the
mean and the variability into account. It is defined as the ratio of the mean (signal) to the
standard deviation (noise). The ratio depends on the quality characteristics of the
product/process to be optimized. The three categories of S/N ratios are used: lower the-
better (LB), higher-the-better (HB) and nominal-the best (NB). The experimental
observations are transformed into a signal-to-noise (S/N) ratio. There are several S/N

8
ratios available depending on the type of characteristics. The S/N ratio for minimum
erosion rate coming under smaller is better characteristic can be calculated as logarithmic
transformation of the loss function as shown below

Smaller is the better characteristic: (2)

where ‘n’ the number of observations, and y the observed data.

The most important stage in the design of experiment lies in the selection of the control
factors. Exhaustive literature review on erosion behavior of polymer composites reveal
that factors viz., impact velocity, filler content, erodent temperature, impingement angle,
stand-off distance and erodent size etc largely influence the erosion rate of polymer
composites [18]. Hence in the present work the impact of these five parameters are
studied using L16 (45) orthogonal design. In conventional full factorial experiment design,
it would require 45 = 1024 runs to study five factors each at four levels whereas,
Taguchi’s factorial experiment approach reduces it to only 16 runs offering a great
advantage in terms of experimental time and cost. The operating conditions under which
erosion tests are carried out are given in Table 1. The tests are conducted as per
experimental design given in Table 2 in which each column represents a test parameter
whereas a row stands for a treatment or test condition which is nothing but combination
of parameter levels [19].
The plan of the experiments is as follows: the first column is assigned to sliding velocity
(A), the second column to normal load (B), the third column to nano-silica content (C),
the fourth column to sliding distance (D) and the fifth column to erodent size (E),
respectively to estimate specific wear rate.
Table 1. Levels of the variables used in the experiment
Control factor Level
I II III IV Units
A: Sliding velocity 60 120 180 240 cm/sec
B: Normal load 10 20 30 40 N
C: Fly ash content 75 70 65 60 %
D: Sliding distance 500 1000 1500 2000 m
E: Erodent size 200 300 400 500 µm

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Table 2. Orthogonal array for L16 (45) Taguchi Design
Expt. No. A B C D E
1 1 1 1 1 1
2 1 2 2 2 2
3 1 3 3 3 3
4 1 4 4 4 4
5 2 1 2 3 4
6 2 2 1 4 3
7 2 3 4 1 2
8 2 4 3 2 1
9 3 1 3 4 2
10 3 2 4 3 1
11 3 3 1 2 4
12 3 4 2 1 3
13 4 1 4 2 3
14 4 2 3 1 4
15 4 3 2 4 1
16 4 4 1 3 2

6. Expected out come of this project work as:

The most important benefits expected from the nanosilica reinforcement are the
following: (i) lower viscosity of the resin formulation compared to common reinforcing
fillers and a complete suppression of sedimentation, (ii) increased fracture toughness,
impact strength, and modulus, (iii) improved scratch- and abrasion-resistance, (iv)
reduced shrinkage upon curing and reduction of the coefficient of thermal expansion, (v)
improved dielectric properties, (vi) improvement of heat distortion, chemical resistance,
glass transition temperature, durability and weathering stability, (vii) no adverse
influence on the processing characteristics of the basic resin The following section deals
with the exact description of the preparation of nanosilica-reinforced epoxies by the sol-
gel technique, and of the relation of their structure to various rheological, mechanical,
and tribological properties.

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 7. Road Map for project Work:
Time period Up-to Sixth Sem. Up-to Seventh Sem. Up-to Eight Sem.
Jan-Mar-2009 May-2009 Jun-sept-09 Oct-09 Nov-Dec-09 Jan-Mar-09 Up to end
Sem
Literature Survey:
Sample preparation
Results and Analysis:
Calculation of erosion rate and
exposure towards SEM.
Microstructure
Observations/Aspects: will be
done for all the three samples
in order to asses the rate of
erosion and type of fracture.
Mechanical Properties study
Computer Simulation of
thermal properties by Ansys-
8 software and compare with
experimental results.
Report writing and
presentation

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