A study in the optimization of manufacture of Nano-fibres




1 2 3







PSG College of Technology
jayanth.psgtech@gmail.com aran_swmech@yahoo.com

PSG College of Technology PSG College of Technology PSG IAS

dilipswmechpsg@gmail.com 4Nanotechnology Research Facility, pvn@ias.psgtech.ac.in

Nanotechnology Research Facility, PSG IAS

Abstract: - Nanofibres find applications in several fields like bio-medical engineering, sensor technology, filtration etc. Manufacture of nanofibres is therefore of considerable interest and the present investigation is focussed on nanofibres of Polyvinyl Alcohol, were produced using electrospinning equipment. The fibres were characterised using High Resolution Transmission Electron Microscope(HRTEM). Parameters that govern the formation and size of fibres are concentration, voltage, collector distance, feed rate and nozzle diameter. A set of experiments based on Taguchi’s Design of Experiments were conducted to study the influence of the process parameters. It was found that increase in concentration increases the fibre size whereas increase in voltage and collector distance has the opposite effect. From the results obtained the percentage of contribution of each factor over the fibre diameter was determined.

Keywords: Electrospinning, Nanofibre, PVA,Optimisation.

1. INTRODUCTION Nanotechnology is emerging to be a very significant technology with considerable potential for application in engineering, electronics, material science, textiles, medicine etc. The coming decades will see a metamorphosis from micro level to nano level materials, revolutionising the human experience of comfort, performance, entertainment, communications etc. Polymeric nano fibres have high functional and high performance capabilities that is already revolutionising the world of material science. The properties of the nanometre scale materials have been found to be significantly superior to that of the bulk materials. Polymeric nanofibres can be manufactured by a number of techniques such as drawing, template synthesis, phase separation, self-assembly and electrospinningi. Out of these approaches to fabricate nanofibres, electrospinning has proved itself to be a very versatile method. Electrospun polymeric nanofibres have been found to be

promising for various applications due to a very large surface area to volume ratio, flexibility in surface functionalities, and superior mechanical performance. Electrospinning process can be applied to a wide range of materials such as synthetic and natural polymers, metals as well as ceramics and composite systems at a low costii. Also electrospinning can be carried out from polymer solutions or from polymer melts. The criterion of using the term ‘nano’ is still different between academic and commercial sector. While the academic community uses <100nm criterion as the benchmark for the nanotechnology classification, the commercial sector has allowed broader flexibility - even up to 500 nmi. 2. LITERATURE REVIEW 2.1 Electrospinning In conventional melt or solution spinning, the fibre is subject to tensile, rheological, gravitational, inertial, and aerodynamic forces. There are various limitations like dependence of fibre diameter on the orifice diameter, instability of the liquid column and mechanical


It was found that the concentration of the polymer in the solution. textiles. drug carriers etc. it is usually dissolved in water at an elevated temperature. loses its surface tension gradually so that it narrows to form a Taylor’s cone (founded by Taylor) and it occurs when the electrostatic forces equals the surface tension force. antibacterial bandages. electrospun PVA fibres exhibited a broad diameter distribution. hydrophilicity. There is also a need to develop mathematical model of the electrospinning process.fracture of the fibres. The liquid droplet at the nozzle opening. which normally is the collector. 3. This necessitates comprehensive experimentation as there is still lack of a clear understanding on the influence of process parameters on fibre formation. But gravitational stretching is limited to a shorter range due to capillary instability and aerodynamic forces. The PVA properties can be improved or modified by importing other compositev.2 Mechanism In electrospinning process. lack of toxicity. As the molten polymer or polymer solution leaves the orifice.3 Suitability of PVA PVA is well known as a semi-crystalline hydrophilic polymer with properties such as excellent film forming ability. solute permeability. EXPERIMENTATION Though electrospinning has been around for many years. The molecular weight of the polymer also was found to influence the fibre diameterviii. So stretching the jets is the only option. Since there are a large number of variables involved. PVA fibers can be readily cross linked to improve mechanical properties and make it insoluble in watervi. it rapidly hardens due to heat or mass transfer to the environment or due to chemical reactions. The final fibre. 2. When the electrostatic force exceeds the surface tension. With increasing solution concentration. water solubility and gas permeability. builds up on the target to form a non-woven fabriciii. medical devices. And fibres with uniform diameter and narrower distribution were obtained at lower spinning voltagex. it is necessary to limit the number of experiments carried out. and the flow becomes unstable. applied electric potential. Spirally they coil over the collector as fibres. with a diameter of as low as 10 nm.1 Selection of polymer: As discussed in literature review. METHODOLOGY 3. whereas the solvent evaporates.4 Electrospinning of PVA PVA has been electrospun extensively considering its utility in many of the applications. The jet will travel towards the region of a lower potential. good mechanical properties. good chemical stability. Nanospun PVA fibre has found several applications in filtration. the surface tension of the polymer solution is overcome and a fluid jet will emerge from the tip of the orifice. pharmaceutical. Thinner fibres were received on the target with lower voltage applied on the nozzle. Since it is a water soluble polymer. sensors. the distance between the nozzle and the collector. The tensile force. and good thermal stability. and food additives. the morphology changed from beaded fibre to uniform fibre and the average fibre diameter increased from 87 nm to 246 nmix. creating a “whipping” mechanism that further significantly reduces the diameter. nozzle tip to collector distance and the voltage largely determine the final diameter of the PVA fibrevii. 2. PVA has a very good film forming ability leading to an 2 . biodegradability. PVA is also widely used as a controlled-releasing carrier of drugs and proteins because of its good tissue compatibility. ease of manipulation under swelling conditions. it has been the subject of applied research only recently because of the demand for nanofibres for several engineering applications. is generated by the interaction of an applied electric field with the electrical charge carried by the jetiv. that overcomes the surface tension and elongates the emerging jet. Today. Electrospinning is a straightforward method to produce polymer nanofibres from polymer solutions. when applied very high voltage. This study was therefore undertaken as a first step in our efforts to arrive at a quantitative understanding of the influence of process parameters on the diameter of fibre produced. At voltages above 10 kV. These advantages have led to its broad industrial use including chemical engineering. 2. Very thin jets cannot be directly generated due to surface tension and interfacial forces at the orifice. the polymer flow rate and the ambient conditions such as temperature and humidity1. a thin film jet is ejected with very high elongation ratios of the order of 10000. a high voltage is applied to an orifice holding the polymeric fluid and when the charges reach a critical limit. The parameters that affect the electrospinning process and fibre morphology are polymer solution characteristics such as viscosity and concentration.

bead like structures (Fig 2) were present. we used polymer solution of poly vinyl alcohol (PVOH or PVA) as precursor for fibre formation. Concentration (C) of the spinning solution 7% to 12% iii. ii. nozzles of different diameter and a collector plate. -1 ------------.0.1 Electrospinning Equipment 3. the fibres were found to be uniform. 3.5 TAGUCHI’S ORTHOGONAL ARRAY: The experimental design proposed by Taguchi involves using orthogonal arrays to organize the parameters affecting the process 4. Voltage (V) range in which the fibres were satisfactory . 8%.20 and 18 gauges Based on the Taguchi’s design of experiments. The Taguchi method is best used when there are an intermediate number of variables (3 to 50). collector distance and at lower flow rate. thus saving time and resourcesxi. The PVA of molecular weight 1. The distance between the nozzle tip and the collector was altered between 8 cm to 20 cm. The polymer feed rate was tried between 0. Out of the spinning variables for the electrospinning experiment. The two levels are 1.1 Characterization of electrospun PVA Nanofibers The nanofibres were characterized using transmission electron microscopy (HRTEM). as PVA is easily soluble in water.5 ml/hr. but the diameter of the fibres increased considerably. The solubility of Poly vinyl alcohol (PVA) increases significantly above 80 C. and the levels at which they should be varied. few interactions between variables. It was found that for all the experiments carried out at lower polymer concentrations.High Level 4. The measured mean diameter of the fibres in for the eight experiments is shown in Table-1. 20 and 21 gauges. Collector Distance (D) . The nozzle sizes chosen were 18. 2 levels and L8 experiment design was used i.0 ml/hr iv. This allows for the collection of the necessary data to determine which factors most affect product quality with a minimum amount of experimentation. The voltage was varied from 0 to 27 KV.1 ml to 1. using the smaller nozzle diameter. +1 ------------. Instead of having to test all possible combinations like the factorial design. At the higher polymer concentration. Solutions of concentration of 4%.4 Preliminary Experimentation: Preliminary experiments were carried out to determine the range of the parameters within which the nanofibres are produced. Finest diameter was spun when the voltage and collector distance are the highest. The polymer solution was also sonicated for at least one hour and the polymer solution was found to be uniform after the sonication. In this study. RESULTS AND DISCUSSION Fig. Feed rate (FR) . it was found that satisfactory electrospinning was possible only between the following ranges of conditions. The equipment is housed in a glass enclosure as shown in the photograph. 6%. The electrospinning equipment consists of a high voltage supply. The stirring speed was reduced for higher concentrations as the pellet started wobbling.16 to 27 KV. the Taguchi method tests pairs of combinations. 3 .000 g/mol was used for the study.3 Equipments used: The set up used for the study is shown in Figure 1.e. Nozzle diameter(ND) . i.excellent electro-spinnability and hence it is one of the widely used polymers used in electrospinning. a feed pump. 3. 3. The PVA solution was prepared using distilled water (DW) and stirred until complete dissolution of polymer occurred. The solutions were prepared under constant stirring using magnetic stirrer at 80 C for 2 hours. the solvent used was distilled water.2 Preparation of spinning solution: For preparation of the spinning solution. The beads were found to decrease in number at higher voltage. and when only a few variables contribute significantly. the lower and higher levels in which the satisfactory spinning was possible formed the two levels.10 cm to 20 cm v.Low Level 2.4 ml to 1. 10% and 12% by weight were prepared. two limits and 8 experiments. 25.

6 1.767 55.47 0 0. Table 2: ANOVA.4 45.7 55.9 0 0.Based on Signal/Noise Ratio Factor Sum of squares DO F Varianc e F calc ulat ed 1.21 0 Infe renc e NS S NS NS NS V C FR D ND ERR TOTAL 2. voltage vs. In the interactions.2 4 0. which is a tool designed especially for Taguchi’s design of experiments. CONCLUSIONS Fig 3Diameter of fibres from L8 experiments 4. collector distance. Col. both graphically and numerically.8 3 320. we can appreciate the contribution of the individual parameters.99 0. 04 4.0 7 0. These factors need to be identified and analysed carefully. the above inference cannot be arrived at. all the variables show good influence on fibre diameter.99 78. It is only at the lower concentration that maximum changes are apparent. flow rate vs.06 0.3 1. flow rate. when ANOVA analysis is done for the whole set of experiments together.61 0.Based on Averages Factor Sum of squares DO F Varianc e F calc ulat ed 10.14 0 Infe renc e NS S NS NS NS V -1 -1 -1 -1 1 1 1 1 C -1 -1 1 1 -1 -1 1 1 1 2 3 4 5 6 7 8 F R -1 -1 1 1 1 1 -1 -1 η1 η2 η3 η4 η5 η6 η7 η8 = = = = = = = = 186 135 239 267 135 123 260 231 V C FR D ND ERR TOTAL 22234 657098 9152 15617 1252 480447 1185800 1 1 1 1 1 234 239 22234 657098 9152 15617 1252 2053 Fig.3 1. The software is quite powerful in analysing the experimental data and presenting the results in the desired form. ANOVA analysis identified presence of external factors that influenced the fibre diameter. At lower polymer concentrations.02 Pure sum of squares 0.114 0 % cont ribu tion 0. 5. the fibre diameter decreases for the larger nozzle diameter and also at the higher flow rate (contrary to the expectations) indicating that electrospinning is a complex process that entails careful experimentation in identifying the variable interactions in order to optimise the spinning parameters. it can be confidently concluded that Taguchi’s design is a 4 .3 Further analysis: When the data is analysed taking the concentration as the primary parameter and its interaction with other parameters at both levels. No. 2 Beaded and smooth fibres The data were evaluated using Qualitek-4 software. It can be observed from the table that the changes in fibre diameters are insignificant at the higher concentration (12%). Number & Factor Assigned Mean Fibre Dia (Η) in nm D -1 1 -1 1 -1 1 -1 1 N D -1 1 -1 1 1 -1 1 -1 distance & voltage vs.Table 1 TAGUCHI’S ORTHOGONAL ARRAY Expt. the following inferences were arrived at: Polymer concentration is the single most contributing factor to effect a change in the fibre diameter.5 1.99 0.078 1 1 1 1 1 2 7 2. Annexure 1 shows the interaction between other variables and concentration.61 Pure sum of squares 201809 6550451 70992 135635 0 % cont ribu tion 1.4 45.883 4. By analysing the data.81 1.004 3.5 1. At lower concentration. However. collector Based on the above results. flow rate. contributing to nearly 55% (78% based on S/N) of the total contribution (all parameters put together).46 7.29 24.55 43. nozzle diameter showed higher level interactions.2 The ANOVA analysis: ANOVA analysis for averages and S/N ratio (signal to noise ratio) carried out using the software is presented in Tables 2 and 3. Table 3: ANOVA.004 1. A generalised ANOVA test does not lead to this conclusion.

5 128.good starting point for the optimisation of electrospinning of polymers.engin. In the interactions. 2004. x 6. 1983. 2 0. New York.php/Design_of_experiments. 2131. Carraher and J.7 32 12 249. The conclusions arrived at in the present investigation are listed below. “Study on morphology of electrospun poly(vinyl alcohol) mats”. voltage and collector distance also exhibited higher level interactions with nozzle diameter. REFERENCES iSeeram iiiWebsite:http://www. “Preparation of Polymer Nanofibers Containing Silver Nanoparticles by using Poly(N-vinylpyrrolidone)”. xiWebsite:http://controls. Proceedings on the International Conference on Solid Dielectrics.4 129 FLOW RATE (ml/hr) LEVEL 1 0. “Modification of Polymers”.6 Ramakrishna et al. It was possible to produce finer fibres of 123 nm (Experiment 6) by adopting Taguchi design. Biji Manoj and Mr.0 Change in dia (nm) 7% % 160. Plenum. 7. 41(3).2 Hai-Sheng Wang et al. “Nanometre diameter fibres of polymer. 9 263. 3 (2). Nanotechnology. “Preparation and Characterization of Nanoscaled Poly(vinyl alcohol)Fibers via Electrospinning”. 9 7 COLLECTOR DISTANCE (CM) LEVEL 1 10 LEVEL 2 20 Change in dia (nm) 7% % 160. 7. 2005. Little interaction was observed between voltage and collector distance. European Polymer Journal. 2005.as px iv Darrel H Reneker and Iskoo Chun. 5 249. time and associated costs can be reduced. 2005. vii 3. 1. 493-497. Voltage and collector distance are also important factors influencing the fibre diameter.edu/wiki/ index.4 LEVEL 2 1.4 117 Chan ge In Dia (nm) 88. K. 8 245.5 13 4. Similarly. UK. L. 2002.4 124 5 . Chunxue Zhang et al. Bin Ding et al.com/technicalser vices/technicalbulletins/technicalnewsletters. “Preparation and Properties of Poly (vinyl alcohol) Nanofibers by Electrospinning”. collector distance and nozzle diameter.zeusinc. flow rate showed higher level interactions with voltage. NEEDLE DIA (G) LEVEL 2 1 1 LEVEL 1 2 8 Change in dia (nm) 7% 15 4.8 120. this means the amount of experimental work. 8 28.6 128. Polymer concentration was found to be the most significant parameter influencing the diameter of the nanofibres. Acknowledgements: The authors wish to acknowledge the help of Dr.K. Karthikeyan in carrying out the experimental work and for the useful inputs in planning the experimental work. voltage and concentration and also concentration with collector distance. Our next set of experiments would focus on optimising the concentration in order to eliminate bead formation and optimising the factors like needle diameter and collector distance.8 31. Recent Patents on Nanotechnology. Obviously. vi C. Moore.9 Chan ge In Dia (nm) 80. 7 12 % 234.umich. ii VOLTAGE (KV) LEVEL 1 1 6 LEVEL 2 2 7 Change in dia (nm) 7% 160 . 3. Macromolecular Rapid Communications. 1996. Singapore. 8 7 Chan ge In Dia (nm) 85.5 12 245. viii 4. Materials Letters. produced by electrospinning”. An introduction to electrospinning. 2009.8 19. 2007. Qiang Li et al.5 128 . pages 1903–1907. 73-79. “Functional Polymeric Nanofibres from Electrospinning”. 423-432. E. 215-218. Higher voltage and higher collector distance resulted in finer fibres.8 31.Koski et al. 216–223. “Effect of molecular weight on fibrous PVA produced by electrospinning”. 6 12 % 252. The influence of nozzle diameter and the polymer flow rate show a complex interaction in determining the diameter of fibres and require further experimentation. _ Annexure 1: Interaction of other parameters with concentration change INTERACTION OF OTHER PARAMETERS WITH CONCENTRATION Chan ge In Dia (nm) 92. Issue 24. Fibers and Polymers. ix 5.. v Wen Ji Jin et al. These two observations are in agreement with the findings of the previous study on PVA electrospinning viii. 9 252. World Scientific Publish Co. 2. 58 (3-4). A. Volume 26.

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