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A study in the optimization of manufacture of Nano-fibres




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 electrospinning
i
.

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
cost
ii
. 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 nm
i
.

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
2
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 fabric
iii
.

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 jet
iv
. 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
humidity
1
.

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 composite
v
. Today, PVA is also
widely used as a controlled-releasing carrier of
drugs and proteins because of its good tissue
compatibility, lack of toxicity, bio-
degradability, 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 water
vi
.

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 fibre
vii
.
The molecular weight of the polymer also was
found to influence the fibre diameter
viii
. With
increasing solution concentration, the
morphology changed from beaded fibre to
uniform fibre and the average fibre diameter
increased from 87 nm to 246 nm
ix
. 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 voltage
x
.

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
3
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.











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
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
resources
xi
. 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

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.
Table 1 TAGUCHIS ORTHOGONAL ARRAY
E
x
p
t
.

N
o
.


Col. Number &
Factor Assigned

Mean
Fibre Dia ()
in nm

V C F
R
D N
D

1 - 1 - 1 - 1 - 1 - 1 1 = 1 8 6
2 - 1 - 1 - 1 1 1 2 = 1 3 5
3 - 1 1 1 - 1 - 1 3 = 2 3 9
4 - 1 1 1 1 1 4 = 2 6 7
5 1 - 1 1 - 1 1 5 = 1 3 5
6 1 - 1 1 1 - 1 6 = 1 2 3
7 1 1 - 1 - 1 1 7 = 2 6 0
8 1 1 - 1 1 - 1 8 = 2 3 1










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
Fig.1 Electrospinning Equipment
4
is quite powerful in analysing the experimental
data and presenting the results in the desired
form, both graphically and numerically.


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
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
Pure
sum of
squares
%
cont
ribu
tion
Infe
renc
e
V 22234 1 22234 10.8
3
201809 1.7 NS
C 657098 1 657098 320.
04
6550451 55.2
4
S
FR 9152 1 9152 4.46 70992 0.6 NS
D 15617 1 15617 7.61 135635 1.14 NS
ND 1252 1 1252 0.61 0 0 NS
ERR 480447 234 2053
TOTAL 1185800 239







Table 3: ANOVA- Based on Signal/Noise Ratio
Factor Sum of
squares
DO
F
Varianc
e
F
calc
ulat
ed
Pure
sum of
squares
%
cont
ribu
tion
Infe
renc
e
V 2.4 1 2.4 1.29 0.55 0.99 NS
C 45.3 1 45.3 24.0
7
43.47 78.9 S
FR 1.5 1 1.5 0.81 0 0 NS
D 1.99 1 1.99 1.06 0.114 0.21 NS
ND 0.004 1 0.004 0.02 0 0 NS
ERR 3.767 2 1.883
TOTAL 55.078 7

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

Based on the above results, it can be
confidently concluded that Taguchis design is a
5
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.

2. 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
.

3. The influence of nozzle diameter and the
polymer flow rate show a complex interaction in
determining the diameter of fibres and require
further experimentation.

4. 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.

5. Little interaction was observed between voltage
and collector distance, voltage and concentration
and also concentration with collector distance.

6. 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

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

ii
Hai-Sheng Wang et al., Functional
Polymeric Nanofibres from Electrospinning,
Recent Patents on Nanotechnology, 2009, 3, 21-
31.


iii
Website:http://www.zeusinc.com/technicalser
vices/technicalbulletins/technicalnewsletters.as
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.

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

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

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

x
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.

xi
Website:http://controls.engin.umich.edu/wiki/
index.php/Design_of_experiments. _

Annexure 1: Interaction of other
parameters with concentration change
INTERACTION OF OTHER PARAMETERS WITH CONCENTRATION
VOLTAGE
(KV) 7 % 12 %

COLLECTOR
DISTANCE
(CM)
7 % 12
%
Chan
ge
In
Dia
(nm)
Chan
ge
In
Dia
(nm)
LEVEL
1
1
6
160
.5
252.
8 92.4
LEVEL
1 10 160.6
249.
5 88.8
LEVEL
2
2
7
128
.8
245.
9 117
LEVEL
2 20 128.7
249.
2 120.6
Change in dia
(nm)
31.
6 7

Change in dia
(nm) 32 0.2


NEEDLE
DIA (G) 7 % 12 %
Chan
ge
In
Dia
(nm)
FLOW
RATE
(ml/hr)

7 % 12
%
Chan
ge
In
Dia
(nm)
LEVEL
1
2
1
15
4.5
234.
9 80.4
LEVEL
1 0.4 160.5
245.
9 85.4
LEVEL
2
1
8
13
4.8
263.
8 129
LEVEL
2 1.0 128.8
252.
8 124
Change in dia
(nm)
19.
7 28.9

Change in dia
(nm) 31.5 7