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1 B.

Tech Project | Department of Textile Technology | IIT Delhi



MID TERM REPORT
TTD411

Development of Porous Nano-Fibres using
Electrospinning


UNDER THE GUIDANCE OF
Dr. Bhanu Nandan




Shivam Verma Rupak Kumar
(2011TT10965) (2011TT10956)

2 B. Tech Project | Department of Textile Technology | IIT Delhi

ACKNOWLEDGEMENT--




I am thankful to Dr. Bhanu Nandan (Department of Textile
Technology), for giving me an opportunity to take up this project
which shall be beneficial to us and also for providing all the help and
guidance whenever required.

I am highly thankful to my project guide Mr Thangapandey for his
constant support and guidance. He has been source of motivation and
encouragement at time of difficulties, providing me all the necessary
help towards successful completion of this project.








Shivam Verma Rupak Kumar
(2011TT10965) (2011TT10956)





3 B. Tech Project | Department of Textile Technology | IIT Delhi



INDEX
1. Introduction 4
2. Literature Review 5
3. Objective 8
4. Plan of work 9
5. Experimental Approach 10
6. Conclusion 12
7. Future Work 13
8. References 14














4 B. Tech Project | Department of Textile Technology | IIT Delhi


INTRODUCTION


Nano-fibres are defined as fibres with diameters less than 1000 nm. They can be
produced by various methods such as: interfacial polymerization, electrospinning, and
force spinning.
Nano-fibres exhibit special properties mainly due to extremely high surface to weight
ratio compared to conventional nonwovens. Low density, large surface area to mass,
high pore volume, and tight pore size make the nano-fibre nonwoven appropriate for a
wide range of applications- from medical to consumer products and industrial to high-
tech applications for aerospace, capacitors, transistors, drug delivery systems, battery
separators, energy storage, fuel cells, and information technology.
Nano-fibres having a porous structure which ranges from a few tens of a nanometres to
1 micron on its surface are porous nano-fibres and is influenced by the type of polymers,
solvent used, and elctrospinning conditions.
When electrospinning of a polymer solution is done convective evaporation of the
solvent occurs. During the event of solvent evaporation, the solution becomes
thermodynamically unstable, this leads to the occurrence of phase separation into 2
phases: a polymer rich phase and a polymer deficient phase.
Porous nanofibres have a wide range of application potentials in the repair and
reconstruction of tissues such as blood vessels, bone, muscle, nerves, ligament and liver,
as well as in the delivery and controlled release of antibiotics, anticancer drugs, proteins,
DNA and live cells and other biomedical applications


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LITERATURE REVIEW

Electrospinning was first patented in the US in 1902[5]; however, the process was largely
forgotten until the 1990s. With interest in the field of nanoscience and nanotechnology,
researchers began new investigations of nanofibre production using electrospinning [6]
the ability to form porous fibers through electrospinning means that the surface area of
the fiber mesh can be increased tremendously. A number of processing techniques such
as drawing [7], template synthesis [8, 9], phase separation [10], self-assembly [11, 12],
electrospinning [13, 14], etc. have been used to prepare polymer nanofibres.
Electrospinning is a simple, convenient and unique process for producing ultrafine fibers
with diameter range of 100 nm to 5m. In electrospinning an electric field draws a
polymer melt or polymer solution from the tip of a capillary to a collector. A voltage is
applied to the polymer, which causes a jet of the solution to be drawn toward a
grounded collector, while the liquid jet is drawn to the collector, rapid evaporation of
solvent serves to solidify the fiber and prevent varicose breakup. Recently there has
been much interest to produce nanofibers with some exceptional structures such as
core/shell composite fibers, multichannel tubular structure and porous fibers. Porous
materials have much potential for applications in fuel cell membranes, tissue
engineering, catalysis, sensors, separations, electrochemical cells, drug delivery,
chemical filtration, etc. Many applications of electrospun nanofibers could be greatly
improved by increasing the surface area and porosity of the fibers. So producing porous
nanofibers in a versatile and inexpensive way was tried by a number of researchers.
Different methods for producing porous nanofibers.

1) Thermally induced phase separation:
A method for producing porous nanofibre is developed by Xia et al (15). In his work
thermally induced phase separation happen between the solvent rich and solvent poor
regions in the fibres during electrospinning by immersing the collector in a bath of liquid
nitrogen. Finally with removing the solvent in vacuum, porous polystyrene nanofibres
are produced. In this method phase separation into solvent rich and solvent poor
regions is induced when the remaining solvent is frozen in nitrogen bath before reaching
the collector. These porous fibres are promising for use in the encapsulation of active
substances, as supports of catalysts, lightweight reinforcement, and hydrophobic
coatings. The electrospinning setup with the modified collector used in this method is
shown in figure 3, and SEM images of polystyrene porous fibres prepared by
electrospinning into liquid nitrogen, followed by drying in vacuum is shown in figure
6 B. Tech Project | Department of Textile Technology | IIT Delhi

4.Nanofibers produced by this method have larger diameters than those collected
without the use of a liquid nitrogen bath, since the fibres are drawn in shorter distance.
The SEM image shows that the fibres are not interconnected, and that the morphology
of individual fibres is not degraded by this method. This method can be readily used with
non-volatile solvents and does not require selective dissolution of phase-separated
polymers.




2) Selective Dissolution:
A facile method for the preparation of porous ultrafine nanofibres is selective
dissolution technique that was used by number of groups. Ma et al(15), produced highly
porous PAN nanofibers, via this technique, PAN/NaHC03 composite nanofibers were
electrospun, and then NaHC03 was removed by a selective
Dissolution and reaction with the solution of hydrochloric acid, Different content of
NaHC03 had significant effect on the morphology of the final porous fibres. The SEM
image of the final porous nanofibre is shown in figure 5. In the other work, You et al
used this technique to produce porous ultrafine poly (glycolic acid)
(PGA) fibres, thus ultrafine PGA/poly (L-lactic acid) (PLA) blend fibres were electrospun
and then the PLA was removed by dissolving with chloroform. The resulting PGA fibres
had three dimensionally interconnected pores with a circular shape and the very narrow
pore size distribution. Ultra-fine porous PGA fibres are shown in figure 6.

7 B. Tech Project | Department of Textile Technology | IIT Delhi




3) Selective pyrolyzate composite formation(15):
Peng et al used a facile method to obtain carbon nanofibers with a nanoporous structure
using selective pyrolyzate composite formation. A blend of polyacrylonitrile and a
copolymer of acrylonitrile and methyl methacrylate in dimethylformamide was
electrospun into nano fibres with a micro phase-separated structure. With pyrolyzing
the copolymer domains in oxidation process, nanoporous structure was obtained, and
preserved after carbonization.
Rapid solvent evaporation and solidification of the electrospun fibres during
electrospinning, decreases the domain coarsening, so there are fine and stretched phase
domains in the nanofibers, and carbon nanofibers with a large amount of nanopores
throughout the surface and the interior of the fibres were obtained. The nanopores in
the fibres at about several tens of nanometres in widths are continuous. A resulted
porous fibre is shown in figure7
8 B. Tech Project | Department of Textile Technology | IIT Delhi




OBJECTIVE

The main goal of the present work is to develop a porous nanofibre using
electrospinning technique. The nanofibres produced through electrospinning should be
bead free and possess uniform structure. Optimization of different properties of
nanofibres can be done by varying different process parameters.
Specific Objectives of the project includes:
FTIR characterization to confirm the hydrogen bonding between hydroxyl groups
of resorcinol and the pyridine units of the core-forming P4VP block.
Optimization and Preparation of poly 4-vinylpyridine nanofibres using
electrospinning.

9 B. Tech Project | Department of Textile Technology | IIT Delhi

PLAN OF WORK

TIME
Jul'12 Aug'12 Sep'12 Oct'12 Nov'12
TASK
Literature Review
Material procurement
Conducted FTIR Spectroscopy
Mid-term presentation and report
Sample preparation
Final presentation and report

10 B. Tech Project | Department of Textile Technology | IIT Delhi

EXPERIMENTAL APPROACH

Material- Poly-4-vinyl Pyridine (P4VP), Resorcinol, Dimethyl Formamide (DMF)
Techniques- Electrospinning, FTIR Spectroscopy
Experimentation Done-
FTIR spectroscopy for confirming the bonding of solvent (Resorcinol) and P4VP
Solution for electrospinning was prepared by preparing 2 different solutions of P4VP in
DMF and Resorcinol in DMF. Finally we need a 1:1 molar ratio of P4VP and Resorcinol, so
for this we prepared a 2% weight by volume polymer solution by dissolving 0.1g of P4VP
in 2.5 ml of DMF and corresponding to that we prepared a 0.105g resorcinol solution in
2.5 ml DMF (the calculation is shown below as)
Molecular weight of P4VP = 1, 60, 000 gm
Molecular weight of 1 repeating unit = 105 gm
Degree of polymerization = 160000/105 = 1523.80
Molecular weight of Resorcinol = 110 gm
For 1 pyridine unit we require 1 unit of resorcinol so,
Weight required for 1 mole of P4VP = 110*1532.80 = 167619.1 gm
So if we take 0.1gm of P4VP we require [(167619.1/160000)*0.1] gm of
resorcinol which is = 0.105 gm
The resorcinol solution was then added drop-wise to the stirring polymer solution with
the help of a micro-pipette to obtain final solution of p4vp and resorcinol.
The solutions was stirred for more than 24 hours with a magnetic stirrer to obtain a
homogenous solution.
Testing for FTIR spectroscopy-
5 drops of the homogenous solution prepared was added to a glass slide and
flattened out to develop film
The solution on the slide was dried at room temperature for 24 hours and then
dried in vacuum oven to completely remove DMF
A little dried solution was scratched from the slide and mixed and grinded with
KBr (used only for referencing) to form a powder solution
A pellet was formed and put in front of laser for detecting % change in
transmission due to different functional groups present
11 B. Tech Project | Department of Textile Technology | IIT Delhi

RESULTS & DISCUSSION

The results obtained from FTIR are shown below:





12 B. Tech Project | Department of Textile Technology | IIT Delhi

Understanding FTIR Spectroscopy--
Fourier transform infrared spectroscopy (FTIR) is a technique which is used to obtain an
infrared spectrum of absorption, emission, photoconductivity scattering of a solid, liquid
or gas. An FTIR spectrometer simultaneously collects spectral data in a wide spectral
range.

Infrared spectroscopy gives information on the vibrational and rotational modes of
motion of a molecule and hence an important technique for identification and
characterisation of a substance. The infrared spectrum of an organic compound provides
a unique fingerprint, which is readily distinguished from the absorption patterns of other
compounds; only optical isomers absorb in exactly the same way. Hence FTIR is an
important technique for identification and characterization of a substance.
FTIR characterization to confirm the hydrogen bonding between hydroxyl groups of
resorcinol and the pyridine units of the core-forming P4VP block:
From FTIR spectrum of P4VP and one can see a strong peak appearing at 1600 cm-1 that
is assigned to the stretching vibration of hydroxyl groups of resorcinol. After the mixing
with P4VP in DMF, a shoulder peak appears at 1597 cm-1, indicating the formation of
hydrogen bonding between the hydroxyl groups on the surfaces of resorcinol and the
pyridine groups of the copolymer. The hydrogen bonding results in a decrease in the
strength of the H-O bonds and consequent decrease in the wavenumber of their
stretching vibration. It is reasonable that the hydroxyl groups largely exist in the crystal
lattice (or within the wall) of resorcinol and only a small portion of them are located on
the surface to possibly form hydrogen bonding with the pyridine groups, hence the
signal intensity of hydrogen bonded hydroxyl groups at 1597 cm-1 is relatively low.

13 B. Tech Project | Department of Textile Technology | IIT Delhi

REFERENCES

1.
2.
3.
4.
5. Morton, W. J., Method of Dispersing Fluids, US Patent 705,691, (1902)
6. Doshi, J., and Reneker, D. H., J. Electrostat. (1995) 35, 151
7. Ondarcuhu, T, Joachim, C. Drawing a single nanofibre over hundreds of microns.
Europhys Lett, 1998, 42, 2, page 215
8. Feng, L et al. Super- Hydrophobic Surface of Aligned Polyacrylonitrile Nanofibers.
Angew Chem Int, 2004, 41, 7, page 1221
9. Martin, C . Membrane-based synthesis of nanomaterials. Chem Mater, 1996, 8,
page1739
10. Ma, P, Zhang, R . Synthetic nano-scale fibrous extracellular matrix. J Biomed Mat
Res,1999, 46, page 60
11. Liu, G et al. Polystyrene-block-poly (2-cinnamoylethyl methacrylate) nanofibers-
Preparation, characterization, and liquid crystalline properties. Chem-A European
J, 1999, 5, page 2740
12. Whitesides, GM, Grzybowski, B. Self-assembly at all scales. Science, 2002, 295,
page 2418
13. Deitzel, J, et al. Controlled deposition of electrospun poly(ethylene oxide) fibers.
Polymer, 2001, 42, page 8163
14. Fong, H, Reneker, DH. Electrospinning and formation of nanofibers. In: Salem DR,
editor. Structure formation in polymeric fibers. Munich, Hanse, 2001, Page 225
15. PRODUCING POROUS NANOFIBERS M.Salehi Esfandarani, M.Safar Johari Textile
Engineering Department, Amirkabir University of Technology, Tehran, Iran

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