Nano-fibres exhibit special properties mainly due to extremely high surface to weight ratio compared to conventional nonwovens. Porous nano-fibers have a porous structure which ranges from a few tens of a nanometres to 1 micron on its surface. Electrospinning can be used to produce porous nano fibres.
Nano-fibres exhibit special properties mainly due to extremely high surface to weight ratio compared to conventional nonwovens. Porous nano-fibers have a porous structure which ranges from a few tens of a nanometres to 1 micron on its surface. Electrospinning can be used to produce porous nano fibres.
Nano-fibres exhibit special properties mainly due to extremely high surface to weight ratio compared to conventional nonwovens. Porous nano-fibers have a porous structure which ranges from a few tens of a nanometres to 1 micron on its surface. Electrospinning can be used to produce porous nano fibres.
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.
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
5 B. Tech Project | Department of Textile Technology | IIT Delhi
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.
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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:
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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