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A study in the optimization of manufacture of Nano-fibres


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PSG College of Technology

PSG College of Technology PSG College of Technology PSG IAS 4Nanotechnology Research Facility,


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 Taguchis 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

fracture of the fibres. Very thin jets cannot be directly generated due to surface tension and interfacial forces at the orifice. So stretching the jets is the only option. But gravitational stretching is limited to a shorter range due to capillary instability and aerodynamic forces. Electrospinning is a straightforward method to produce polymer nanofibres from polymer solutions. 2.2 Mechanism In electrospinning process, a high voltage is applied to an orifice holding the polymeric fluid and when the charges reach a critical limit, the surface tension of the polymer solution is overcome and a fluid jet will emerge from the tip of the orifice. The jet will travel towards the region of a lower potential, which normally is the collector. As the molten polymer or polymer solution leaves the orifice, it rapidly hardens due to heat or mass transfer to the environment or due to chemical reactions. The liquid droplet at the nozzle opening, when applied very high voltage, loses its surface tension gradually so that it narrows to form a Taylors cone (founded by Taylor) and it occurs when the electrostatic forces equals the surface tension force. When the electrostatic force exceeds the surface tension, a thin film jet is ejected with very high elongation ratios of the order of 10000, and the flow becomes unstable, creating a whipping mechanism that further significantly reduces the diameter. Spirally they coil over the collector as fibres, whereas the solvent evaporates. The final fibre, with a diameter of as low as 10 nm, builds up on the target to form a non-woven fabriciii. The tensile force, that overcomes the surface tension and elongates the emerging jet, is generated by the interaction of an applied electric field with the electrical charge carried by the jetiv. The parameters that affect the electrospinning process and fibre morphology are polymer solution characteristics such as viscosity and concentration, applied electric potential, the distance between the nozzle and the collector, the polymer flow rate and the ambient conditions such as temperature and humidity1. 2.3 Suitability of PVA PVA is well known as a semi-crystalline hydrophilic polymer with properties such as excellent film forming ability, good mechanical properties, hydrophilicity, good chemical stability, and good thermal stability. The PVA properties can be improved or modified by importing other compositev. Today, PVA is also widely used as a controlled-releasing carrier of

drugs and proteins because of its good tissue compatibility, lack of toxicity, biodegradability, ease of manipulation under swelling conditions, solute permeability, water solubility and gas permeability. PVA fibers can be readily cross linked to improve mechanical properties and make it insoluble in watervi. These advantages have led to its broad industrial use including chemical engineering, pharmaceutical, textiles, medical devices, and food additives. Nanospun PVA fibre has found several applications in filtration, sensors, antibacterial bandages, drug carriers etc. 2.4 Electrospinning of PVA PVA has been electrospun extensively considering its utility in many of the applications. Since it is a water soluble polymer, it is usually dissolved in water at an elevated temperature. It was found that the concentration of the polymer in the solution, nozzle tip to collector distance and the voltage largely determine the final diameter of the PVA fibrevii. The molecular weight of the polymer also was found to influence the fibre diameterviii. With increasing solution concentration, the morphology changed from beaded fibre to uniform fibre and the average fibre diameter increased from 87 nm to 246 nmix. At voltages above 10 kV, electrospun PVA fibres exhibited a broad diameter distribution. Thinner fibres were received on the target with lower voltage applied on the nozzle. And fibres with uniform diameter and narrower distribution were obtained at lower spinning voltagex. 3. EXPERIMENTATION Though electrospinning has been around for many years, it has been the subject of applied research only recently because of the demand for nanofibres for several engineering applications. This necessitates comprehensive experimentation as there is still lack of a clear understanding on the influence of process parameters on fibre formation. Since there are a large number of variables involved, it is necessary to limit the number of experiments carried out. There is also a need to develop mathematical model of the electrospinning process. 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. METHODOLOGY 3.1 Selection of polymer: As discussed in literature review, PVA has a very good film forming ability leading to an

excellent electro-spinnability and hence it is one of the widely used polymers used in electrospinning. In this study, we used polymer solution of poly vinyl alcohol (PVOH or PVA) as precursor for fibre formation. The PVA of molecular weight 1, 25,000 g/mol was used for the study. 3.2 Preparation of spinning solution: For preparation of the spinning solution, the solvent used was distilled water, as PVA is easily soluble in water. The solubility of Poly vinyl alcohol (PVA) increases significantly above 80 C. The solutions were prepared under constant stirring using magnetic stirrer at 80 C for 2 hours. The stirring speed was reduced for higher concentrations as the pellet started wobbling. The PVA solution was prepared using distilled water (DW) and stirred until complete dissolution of polymer occurred. The polymer solution was also sonicated for at least one hour and the polymer solution was found to be uniform after the sonication. 3.3 Equipments used: The set up used for the study is shown in Figure 1. The electrospinning equipment consists of a high voltage supply, a feed pump, nozzles of different diameter and a collector plate. The equipment is housed in a glass enclosure as shown in the photograph.

and the levels at which they should be varied. Instead of having to test all possible combinations like the factorial design, the Taguchi method tests pairs of combinations. This allows for the collection of the necessary data to determine which factors most affect product quality with a minimum amount of experimentation, thus saving time and resourcesxi. The Taguchi method is best used when there are an intermediate number of variables (3 to 50), few interactions between variables, and when only a few variables contribute significantly. Out of the spinning variables for the electrospinning experiment, it was found that satisfactory electrospinning was possible only between the following ranges of conditions. i. Voltage (V) range in which the fibres were satisfactory - 16 to 27 KV. ii. Concentration (C) of the spinning solution 7% to 12% iii. Feed rate (FR) - 0.4 ml to 1.0 ml/hr iv. Collector Distance (D) - 10 cm to 20 cm v. Nozzle diameter(ND) - 20 and 18 gauges

Based on the Taguchis design of experiments, the lower and higher levels in which the satisfactory spinning was possible formed the two levels. 2 levels and L8 experiment design was used i.e. two limits and 8 experiments. The two levels are 1. -1 ------------- Low Level 2. +1 ------------- High Level 4. RESULTS AND DISCUSSION

Fig.1 Electrospinning Equipment 3.4 Preliminary Experimentation: Preliminary experiments were carried out to determine the range of the parameters within which the nanofibres are produced. Solutions of concentration of 4%, 6%, 8%, 10% and 12% by weight were prepared. The nozzle sizes chosen were 18, 20 and 21 gauges. The polymer feed rate was tried between 0.1 ml to 1.5 ml/hr. The distance between the nozzle tip and the collector was altered between 8 cm to 20 cm. The voltage was varied from 0 to 27 KV. 3.5 TAGUCHIS ORTHOGONAL ARRAY: The experimental design proposed by Taguchi involves using orthogonal arrays to organize the parameters affecting the process

4.1 Characterization of electrospun PVA Nanofibers The nanofibres were characterized using transmission electron microscopy (HRTEM). The measured mean diameter of the fibres in for the eight experiments is shown in Table-1. It was found that for all the experiments carried out at lower polymer concentrations, bead like structures (Fig 2) were present. The beads were found to decrease in number at higher voltage, collector distance and at lower flow rate. At the higher polymer concentration, the fibres were found to be uniform, but the diameter of the fibres increased considerably. Finest diameter was spun when the voltage and collector distance are the highest, using the smaller nozzle diameter.


Expt. No. Col. Number & Factor Assigned Mean Fibre Dia () in nm D -1 1 -1 1 -1 1 -1 1 N D -1 1 -1 1 1 -1 1 -1

distance & voltage vs. nozzle diameter showed higher level interactions. ANOVA analysis identified presence of external factors that influenced the fibre diameter. These factors need to be identified and analysed carefully. At lower polymer concentrations, all the variables show good influence on fibre diameter. However, when ANOVA analysis is done for the whole set of experiments together; the above inference cannot be arrived at. Table 2: ANOVA- Based on Averages
Factor Sum of squares DO F Varianc e F calc ulat ed 10.8 3 320. 04 4.46 7.61 0.61 Pure sum of squares 201809 6550451 70992 135635 0 % cont ribu tion 1.7 55.2 4 0.6 1.14 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

1 2 3 4 5 6 7 8

= = = = = = = =

186 135 239 267 135 123 260 231


22234 657098 9152 15617 1252 480447 1185800

1 1 1 1 1 234 239

22234 657098 9152 15617 1252 2053

Fig. 2 Beaded and smooth fibres The data were evaluated using Qualitek-4 software, which is a tool designed especially for Taguchis design of experiments. The software is quite powerful in analysing the experimental data and presenting the results in the desired form, both graphically and numerically.

Table 3: ANOVA- Based on Signal/Noise Ratio

Factor Sum of squares DO F Varianc e F calc ulat ed 1.29 24.0 7 0.81 1.06 0.02 Pure sum of squares 0.55 43.47 0 0.114 0 % cont ribu tion 0.99 78.9 0 0.21 0 Infe renc e NS S NS NS NS


2.4 45.3 1.5 1.99 0.004 3.767 55.078

1 1 1 1 1 2 7

2.4 45.3 1.5 1.99 0.004 1.883

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, we can appreciate the contribution of the individual parameters. Annexure 1 shows the interaction between other variables and concentration. It can be observed from the table that the changes in fibre diameters are insignificant at the higher concentration (12%). It is only at the lower concentration that maximum changes are apparent. A generalised ANOVA test does not lead to this conclusion. At lower concentration, 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. 5. CONCLUSIONS

Fig 3Diameter of fibres from L8 experiments 4.2 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. By analysing the data, the following inferences were arrived at: Polymer concentration is the single most contributing factor to effect a change in the fibre diameter, contributing to nearly 55% (78% based on S/N) of the total contribution (all parameters put together). In the interactions, voltage vs. flow rate, flow rate vs. collector distance, flow rate, collector

Based on the above results, it can be confidently concluded that Taguchis design is a

good starting point for the optimisation of electrospinning of polymers. Obviously, this means the amount of experimental work, time and associated costs can be reduced. The conclusions arrived at in the present investigation are listed below. 1. Polymer concentration was found to be the most significant parameter influencing the diameter of the nanofibres. Voltage and collector distance are also important factors influencing the fibre diameter. Higher voltage and higher collector distance resulted in finer fibres. These two observations are in agreement with the findings of the previous study on PVA electrospinning viii. The influence of nozzle diameter and the polymer flow rate show a complex interaction in determining the diameter of fibres and require further experimentation. In the interactions, flow rate showed higher level interactions with voltage, collector distance and nozzle diameter. Similarly, voltage and collector distance also exhibited higher level interactions with nozzle diameter. Little interaction was observed between voltage and collector distance, voltage and concentration and also concentration with collector distance. It was possible to produce finer fibres of 123 nm (Experiment 6) by adopting Taguchi design. 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. Acknowledgements: The authors wish to acknowledge the help of Dr. Biji Manoj and Mr. K.K. Karthikeyan in carrying out the experimental work and for the useful inputs in planning the experimental work. 7. REFERENCES

iiiWebsite: vices/technicalbulletins/ px iv

Darrel H Reneker and Iskoo Chun. Nanometre diameter fibres of polymer, produced by electrospinning, Nanotechnology, 1996, 7, 216223.


v Wen Ji Jin et al. Preparation of Polymer Nanofibers Containing Silver Nanoparticles by using Poly(N-vinylpyrrolidone), Macromolecular Rapid Communications, 2005, Volume 26, Issue 24, pages 19031907. vi

C. L. E. Carraher and J. Moore, Modification of Polymers, Plenum, New York, 1983.



Bin Ding et al. Preparation and Characterization of Nanoscaled Poly(vinyl alcohol)Fibers via Electrospinning, Fibers and Polymers, 2002, 3 (2), 73-79.


A.Koski et al. Effect of molecular weight on fibrous PVA produced by electrospinning, Materials Letters, 2004, 58 (3-4), 493-497.


Chunxue Zhang et al. Study on morphology of electrospun poly(vinyl alcohol) mats, European Polymer Journal, 2005, 41(3), 423-432.


Qiang Li et al. Preparation and Properties of Poly (vinyl alcohol) Nanofibers by Electrospinning, Proceedings on the International Conference on Solid Dielectrics, UK, 2007, 215-218.

index.php/Design_of_experiments. _

Annexure 1: Interaction of other parameters with concentration change

INTERACTION OF OTHER PARAMETERS WITH CONCENTRATION Chan ge In Dia (nm) 92.4 117 Chan ge In Dia (nm) 88.8 120.6

Ramakrishna et al. An introduction to electrospinning, 2005, World Scientific Publish Co, Singapore.

VOLTAGE (KV) LEVEL 1 1 6 LEVEL 2 2 7 Change in dia (nm)

7% 160 .5 128 .8 31. 6

12 % 252. 8 245. 9 7

COLLECTOR DISTANCE (CM) LEVEL 1 10 LEVEL 2 20 Change in dia (nm)

7% % 160.6 128.7 32

12 249. 5 249. 2 0.2

Hai-Sheng Wang et al., Functional Polymeric Nanofibres from Electrospinning, Recent Patents on Nanotechnology, 2009, 3, 2131.

NEEDLE DIA (G) LEVEL 2 1 1 LEVEL 1 2 8 Change in dia (nm)

7% 15 4.5 13 4.8 19. 7

12 % 234. 9 263. 8 28.9

Chan ge In Dia (nm) 80.4 129

FLOW RATE (ml/hr) LEVEL 1 0.4 LEVEL 2 1.0 Change in dia (nm)

7% % 160.5 128.8 31.5

12 245. 9 252. 8 7

Chan ge In Dia (nm) 85.4 124