Characterization of Starchpoly (Vinyl Alcohol) Clay Nanocomposite F

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Original Article
Characterization of
starch/poly(vinyl alcohol)/
clay nanocomposite films
prepared in twin-screw
extruder for food
packaging application
Journal of Plastic Film & Sheeting

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The Author(s) 2015
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DOI: 10.1177/8756087914568904
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Amir H Navarchian, Mehdi Jalalian and

Majid Pirooz
Abstract
Starch/poly(vinyl alcohol)/montmorillonite (MMT) nanocomposites were prepared in a twin-screw extruder for food packaging film application. In order to
obtain a better compatibility between starch and silicate layers, MMT modification
was performed using citric acid. X-ray diffraction (XRD) analysis was used to
characterize the expanded microstructure of citric acid-modified MMT
(CMMT). The effects of some compositional and operational factors including
poly(vinyl alcohol) content, CMMT content, screw speed, and temperature profile
in the extruder, on the tensile strength parameter of resulted films were investigated by using Taguchi experimental design. It was found that PVA content, CMMT
percentage and screw speed were the most important factors, respectively, affecting the tensile strength property; while the temperature profile was insignificant
factor, in the range of examined levels. The best levels of examined factors that
could lead to the maximum tensile strength were obtained. The optimum sample
was further characterized by XRD, transmission electron microscopy (TEM),
Fourier transform infrared (FTIR), thermogravimetric analysis (TGA), water
uptake, biodegradability, oxygen permeability, and overall migration test.
Department of Chemical Engineering, Faculty of Engineering, University of Isfahan, Isfahan, Islamic

Republic of Iran
Corresponding author:
Amir H Navarchian, Department of Chemical Engineering, Faculty of Engineering, University of Isfahan,
P.O. Box 81746-73441 Isfahan, Islamic Republic of Iran.
Email: Navarchian@eng.ui.ac.ir
Downloaded from jpf.sagepub.com at GEORGIAN COURT UNIV on March 28, 2015
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Journal of Plastic Film & Sheeting 0(0)
Keywords
Nanocomposite, starch, poly(vinyl alcohol), clay, packaging film
Introduction
Synthetic polymers have long been utilized for packaging applications. Their
synthesis involves production of hazardous waste and the products made by
these plastics are not easily degradable, causing environmental problems.1
Therefore, the biodegradable materials, derived from renewable resources,
have been carried into the center of public interest for environmental protection and sustainable development.2 Biodegradable polymers have become
important materials tailored to new environmental friendly products, especially in the packaging industry.3
Starch is a natural polymer that is known to be completely biodegradable
in soil and water.4 In the food packaging sector, starch-based material has
received great attention owing to its biodegradability, wide availability, and
low cost.5 It is produced in plants and is mainly a mixture of linear amylose
(poly-a-1,4-D-glucopyranoside) and branched amylopectin (poly-a-1,4-D-glucopyranoside and a-1,6-D-glucopyranoside). The ratio of amylose to amylopectin varies with the starch source. Amylose is the minor component
(approximately 20%) of the starch and forms the amorphous regions,
whereas the short branching chains of the amylopectin are predominantly
responsible for crystalline properties of the starch due to its helical form
that can be packed together.6,7 This crystalline property of amylopectin
leads to its poor process capability, and therefore plasticizers are often introduced to make the starch ow when processed.
Thermoplastic starch (TPS) or plasticized starch is obtained after disruption and plasticization of native starch macromolecules, by temperature and
in presence of water and/or another plasticizer, such as glycerol. However, the
TPS has some limitations: it is mostly water-soluble and has low mechanical
strength.8 These properties may be improved by adding certain synthetic
polymers, inorganic materials, or lignin (Table 1). Poly(vinyl alcohol)
(PVA), has been used previously in TPS to improve properties such as elongation, reduce brittleness, and facilitate processability.9 On the other hand,
with development of nanotechnology, polymer/layered silicate (PLS) nanocomposites have attracted great attention because of their remarkably
improved mechanical, thermal, and barrier properties compared with the original polymers. Montmorillonite (MMT), as an environmentally-friendly
layered silicate, has been successfully used to prepare TPS/clay composites
by melt intercalation. Experimental results have already revealed that MMT
can be dispersed in the TPS matrix and the TPS/clay composites exhibited
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higher tensile strength, thermal stability, and moisture barrier properties than
TPS itself.10 Our previous work proved that citric acid-modied montmorillonite (CMMT) clay represented even better mechanical properties in comparison with MMT in the starch. The interactions between citric acid and
starch chains were responsible for this improvement.4
TPS and TPS/clay lms can be made by various techniques such as solution casting and thermoplastic extrusion processing. Compared with solution
casting, thermoplastic extrusion is a green and facile process.11 Melt extrusion is an attractive route for cost eective polymer processing, which
enhances the commercial viability and cost-competitiveness of these materials.12 Various compositional factors and processing parameters may inuence the nal properties of TPS-based packaging lms. Many authors have
investigated just the eects of material composition including clay and/or
PVA content8,9,1316 on physical and mechanical properties of these lms.
There are also some limited reports available on the eects of processing
conditions such as screw speed and extruder temperature prole.1720
Although there are many papers recently published on the starch-based
nanocomposite lms as shown in Table 1, there are few reports that apply
experimental design to analyze the eects of both material and process parameters on the physical and mechanical properties of starch/clay nanocomposites produced in extruder.
In this study, the inuence of clay content, PVA percentage, screw speed,
and temperature prole on the tensile stress of starch/PVA/clay nanocomposite lms prepared in a twin-screw extruder (followed by thermo-pressing) has
been statistically investigated by using a Taguchi experimental design
approach. The optimum conditions to attain the maximum tensile stress
have been obtained for above factors and the optimum sample has been
characterized by X-ray diraction (XRD), transmission electron microscopy
(TEM), Fourier transform infrared (FTIR), and thermogravimetric analysis
(TGA). The water absorption, oxygen permeability, biodegradability, and
overall migrated materials of the lms were also examined.
27
26
25
24
PVA
(40%)
Carboxymethylcellulose
(10%)
PVA
(0%, 40%, 50%, 60%,
100%)
Natural rubber (0%, 10%

and 20%)
Second polymer
MMT
(0%, 2.5%, 5%)
Nano-TiO2
(0.5%, 1%, 2%)
Talc
(0%, 1.7%, 5.2%, 8.7%)
MMT
(0%, 1%, 3%, 5%, 7%)
Nano-TiO2
(0%, 2.5%, 5%)
Beta Zeolite
Na-Beidellite
(1%, 2%, 4%)
MMT
(0%, 3%, 6%)
MMT
Filler type and content
Compression molding
Solution casting
Solution casting
Solution casting
Solution casting
Melt extrusion in twinscrew extruder
Solution casting
Melt extrusion in twinscrew extruder
Film preparation
method
Filler content
Filler content
Filler content
PVA content
Filler content
(continued)
Natural rubber type

Filler content
Glycerol content
Natural rubber content
Filler content
Water content
Clay content
PVA content
Clay content
Filler type
Filler content
Investigated factors
23
22
21
13
Ref.
Table 1. Summary of some recent works on starch-based nanocomposite films.
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32
31
30
29
28
Ref.
PVA
(20%, 33%, 50%, 67%,
80%)
Poly(lactic acid)
(58%)
PVA
(0%, 10%, 30%)
Second polymer
Table 1. Continued
MMT
(0, 5, 10, 15, 20)
MMT
OMMT (Cloisite 30B)
(3%, 5%)
MMT
(2%, 4%, 6%, 8%)
MMT
(3%, 5%)
MMT
(0%, 1%, 3%, 5%, 7%, 10%)
Filler type and content
Solution casting
Extrusion/thermopressing
Thermo-pressing
Extrusion/thermopressing
Solution casting
Film preparation
method
Filler content
Glycerol content
PVA content
PVA content
Filler content
PVA type
Filler content
Filler content
Film preparation
methodology
Filler type
Investigated factors
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Experimental
Material
Cornstarch with 28% amylose and 10.1% moisture was obtained from
Glucozan Ghazvin Company (Ghazvin, Iran). PVA with molecular weight
of 145,000 g/mol, 98% hydrolyzed and 1.3 g/cm3 density was supplied by
Merck (KGaA, Darmstadt, Germany). Sulfuric acid (98% w/w), citric acid
(C6H8O7) with 1.665 g/cm3 density, and glycerol (about 87% purity) were also
obtained from the same company. Cloisite Na (MMT) as untreated MMT
was purchased from Southern Clay Products (USA).
Design of experiments
The Taguchi experimental design approach was used as an eective technique
to reduce the number of experiments while retaining quality of data collection. The rst important step in designing an experiment is the proper selection of factors and their levels. In this study, the following main factors were
considered each at three levels (Table 2):
. clay content
. PVA content
. screw rotation speed
. extruder temperature prole.
The factors and their levels have been selected according to our literature
review on previous publications4,9,17,18,20,3336 and some screening experiments in this work. CMMT and PVA percentages were reported based on
a xed weight of starch. Three extruder temperature proles were used in
order to investigate thermal processing conditions on the extruded composites. Each temperature prole included four temperature zones from the feed
section to the die exit. The three temperature proles were:
. Low: 8090100110 ( C)
. Mid: 90100110120 ( C)
. High: 100110120130 ( C)
For a Taguchi-designed experiment with four factors all in three levels, a
standard L9 orthogonal array was employed as shown in Table 3.36 This
saturated design yields the main eects and is suitable for the experiments
for which it is assumed that there is no signicant interaction among the
selected factors. In order to avoid the systematic bias, the sequence in which
these runs were carried out was randomized.37 The statistical analysis of the
results was carried out using Qualitek-4 (Nutek Inc., USA) software. The
signal-to-noise ratio (S/N) is used as a transformed response in the Taguchi
method to indicate the magnitude of changes in response due to variations
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of controlled factors respect to that of errors. In this work, the tensile

properties were used as the response in calculations. In order to maximize
the tensile properties, the following S/N formulation was used:37
2

1=y1 1=y22 1=y2n
S=N 10 log
1
n
Table 2. Selected factors and their respective levels.

Factor
Unit
Level 1
Level 2
Level 3
CMMT content
PVA content
Screw speed
Extruder temperature profile
wt.%
wt.%
r/min

C
3
0
12
Low
5
5
24
Mid
7
10
36
High
Table 3. Designed experiments with coded variables based on the Taguchi method.
Factors
Trial no.
CMMT%
PVA%
Screw speed
Temperature
1
2
3
4
5
6
7
8
9
1
1
1
2
2
2
3
3
3
1
2
3
1
2
3
1
2
3
1
2
3
2
3
1
3
1
2
1
2
3
3
1
2
2
3
1
Preparation of modified MMT with citric acid

In order to provide more compatibility between silicate layers and starch
macromolecules, MMT was modied by citric acid according to our previous
work.4 About 5.04 g citric acid (26.25 mmol) and 2.4 ml sulfuric acid (98%)
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were added subsequently to 700 ml water at 80 C in a 1000 cm3 beaker. This
solution was gradually added to clay suspension containing 20 g MMT in
500 ml water. The mixture was stirred at 80 C for 3 h, and then cooled to
room temperature. The resulted suspension was subsequently ltered, and the
cake was washed with distilled water and centrifuged for 30 min. The modied
clays were dried at 60 C for 24 h, and nally ground into a ne powder. The
CMMT was obtained after screening.4,14
Preparation of TPS/PVA/clay nanocomposite films

Dried CMMT was dispersed in distilled water (with CMMT/water:1/5 weight
ratio) at room temperature by subsequent mechanical and ultrasonic mixing,
each for 1 h. Specied amount of cornstarch, PVA, and glycerol were completely premixed and then added to clay dispersion. The mixture was heated
at 80 C for 30 min with continuous stirring to gelatinize the starch granules
and then was retained in the tightly sealed plastic bags for 24 h to swell the
granular cornstarch molecules. In all experiments, the amount of glycerol was
constant at 30% of starch weight.
In the next step, the swollen mixtures were transferred into a 26:1 L/D
counter-rotating twin-screw extruder (BPM, Iran) with screw diameter of
46 mm. The screw speed and the extruder temperature prole were set at
specied conditions as given in Table 2. The round cross-section extrudate
was cooled and pelletized. Finally, the lms were prepared by hot press molding at 200 C for 2 min. The lms thickness was 0.25 0.02 mm.
Characterization
X-ray diffraction. XRD analysis was carried out on a BrukerD8-Advance X-ray
diractometer (Bruker, Germany) using CuKa radiation (40 kV, 40 mA and
l 0.154 nm). Samples were scanned at 1 /min in the range of 2 210 .
The basal spacing of the silicate layer, d(001), was calculated using Braggs
equation (nl 2d sin ), where is the diraction angle and l is the
wavelength.
Tensile strength measurement. Tensile tests were performed according to ASTM
D882-02 by using H25KS tester (Hounseld, England). The crosshead speed
was 50 mm/min. Rectangular specimens were conditioned at 50 5% relative
humidity (RH) and 23 2 C for one week before testing. Two samples were
tested for tensile strength at each run.
Fourier-transformed infrared. FTIR spectra of nanocomposite lms were measured by Nicolet 400D Impact spectrometer (Nicolet Instrument
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Corporation, USA) in the range of 4504000 cm1 and with a resolution of

16 cm1.
Transmission electron microscopy. TEM was used to study the nanocomposite
lm morphology. An EM900 microscope model (Zeiss, Jena, Germany),
operating at an accelerating voltage of 80 kV, was used.
Thermogravimetric analysis. TGA of composites (about 10 mg) was carried out
using a TG 50-METTLER model TGA instrument (USA) under nitrogen
atmosphere at a heating rate of 10 C/min. The scanning temperature was
between 25 C and 500 C.
Water absorption. The samples were cut into small pieces (60 20 0.25 mm),
put into oven, and dried at 110 C for 24 h. Then, they were taken out,
weighted, and stored at 75% RH for a period of time and weighted every
day. The water content (K) was calculated from the following equation:
K
w2 w1
100
w1
where
w1 dried sample weight (g)
w2 humidified sample weight (g)
Biodegradation. Biodegradation of nanocomposites was studied by soil burial

test under laboratory conditions (average temperature of 25 C). Local soil
was enriched with 20 wt.% bovine manure. The soil pH was 7.7. Samples were
cut into pieces with 25 25 0.25 mm dimensions, weighted (0.20 0.05 g),
and buried in separate plastic containers (10 l) lled with soil, previously
passed through a 2 mm sieve. Every seven days for a period of 28 days, samples were cleaned with a smooth brush and weighted. Periodically, the soil
moisture content was measured; an average value of 7 wt. % was maintained
during the test. The weight reduction with time was used to evaluate
degradation.
Permeability test. In this study, the constant-volume method is used to measure
oxygen permeability through starch-based nanocomposite lms. This method
is based on pressure measurement at a constant volume when subjecting pressure dierence on the sides of a thin layer. A NM1391 model apparatus
(designed at University of Isfahan, Iran) was used and the tests were carried
out according to ASTM D1434.
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Overall migration test. Overall migration test was performed according to

Iranian National Standard Test Number 1-13737. Fourteen nanocomposite
specimens (11 mm diameter disks) were threaded onto a stainless steel wire
with alternating glass bead spacers and placed in a 23 ml glass vial. Vial was
lled with 22 ml of water and then was capped and maintained at 40 C for 10
days. The blank sample was prepared by water poured in a vial (without
sample) containing the support stand with glass bead spacers. Blank vial
was placed in the same temperature-controlled oven. Test result in milligrams
of migrant (s) per square meter of sample exposed, E, was expressed as
follows:
E
WB
2R2 CTN
where
W total weight of migrant (s) in the liquid (mg)
B
weight of migrant (s) in the blank (mg)
radius of the disk (m)
circumference of disk (m)
thickness of disk (m)
number of disks per cell
Results and discussions

Microstructure of films
The XRD analysis was used to investigate the silicate layer dispersion in the
starch/PVA matrix. Table 4 shows the XRD results for all nanocomposite
lms prepared in accordance with the designed experiment (Table 3). In this
table, the distance between the silicate layers in nanocomposites (dnc) minus
that of intact clay (d0) is shown by d:
d dnc d0
According to Majdzadeh et al.,4 the initial distances between the layers (d0)
in MMT and CMMT used in our lab are 1.11 and 1.48 nm, respectively. As
observed in Figure 1, the XRD peak displacement toward the smaller angles
indicates the intercalation morphology for all nine samples. The d values
can be considered as a quantitative criterion for the degree of intercalation of
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polymer chains within the silicate layers. In this work, d variation among
various samples is 0.30 0.02 nm, representing a rather similar expansion of
silicate layer galleries in the polymer matrix for all nanocomposite lms.
The XRD patterns from trial numbers 2, 5, 6, and 7 (as representatives of
dierent values of d) are illustrated in Figure 1.
Table 4. XRD results and tensile strength of the starch/PVA/CMMT nanocomposite
films.
Tensile strength (MPa)
Trial No.
2 ( )
dnc (nm)
d (nm)
Replication 1
Replication 1
1
2
3
4
5
6
7
8
9
4.98
4.90
5.02
4.94
4.94
5.02
4.98
4.94
4.98
1.77
1.80
1.76
1.79
1.79
1.76
1.77
1.79
1.77
0.29
0.32
0.28
0.31
0.31
0.28
0.29
0.31
0.29
9.7
17.7
9.0
16.7
14.7
10.7
11.3
14.0
10.0
10.0
17.3
8.7
15.3
16.3
9.3
10.7
12.0
11.7
Figure 1. XRD patterns of some nanocomposite films as illustrations.
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Tensile strength property

The replicated tensile strength results are given in last columns of Table 4.
This property is usually selected as representative for tensile properties.37
Figure 2 indicates that the average values of tensile strength for nanocomposite lms prepared in dierent experimental runs is essentially proportional to
the silicate layer gallery expansion (d) obtained from XRD analysis.
Increasing the silicate layer spacing in nanocomposite lms linearly increases
the tensile strength. A same behavior was also observed by other authors.4
The relation between silicate layer gallery expansion and tensile property is
ascribed to the better contact area between the polymer chains and the silicate
layers for samples with greater d. This conrms the strong dependency of
the mechanical properties to the nanocomposite morphology.
Figure 2. Correlation between tensile strength (average value for each run) and corresponding gallery spacing expansion (d) of nanocomposites.
Analysis of variance for mechanical properties

Analysis of variance (ANOVA) is a powerful technique in Taguchi method
that explores the percent contribution of factors aecting the response. The
strategy of ANOVA is to evaluate the variations that each factor cause relative to the total variation observed in the results.37
In this work, the target is to maximize the tensile strength (or Bigger is
better for this response in Taguchi terminology), as this is the main mechanical property for packaging lms. There are several statistical terms in
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ANOVA table, among them the F-ratio is the most meaningful one.
As observed, the F-ratio values of some factors are greater than critical
value (9.00), with 90% condence level, indicating the signicance of these
factors on the response. According to ANOVA table, three factors namely
PVA percentage, screw speed, and clay percentage have the highest eects,
respectively, on the tensile strength of nanocomposite lms. The extruder
temperature prole however has a minor eect on the response. As the inuence contribution of this factor is less than 10% of the most important factor
(PVA wt.%), its eect can be pooled in the error term.37
The last column of the ANOVA table represents the percent contribution
of variability resulted from each factor after pooling the insignicant factor
with error term. The other/error term is therefore consisted of the eects of
three sources of variability:
. the uncontrollable factors,
. the pooled factors and/or those that are not considered in the experiments, and
. the experimental error.37
In the following, the eects of each factor on the tensile strength are
investigated as shown in some bar charts. Each data on these main eect
graphs is an average of replicated results obtained at each level of the corresponding factor according to Table 3. Thus, each graph is plotted based on 18
(9 2) experimental data. It should be noted that the interpretation of
ANOVA information (Table 5) is valid just in the range of examined levels
for the factors. That is why the level selection is very important in any experimental design approach.
Table 5. ANOVA table for tensile strength after pooling the effect of extruder temperature profile with the error term (confidence level of 90%).
Factors
CMMT content
PVA content
Screw speed
Extruder temperature
profile
Other/error
Total
DOF
Sum of
squares
Variance
2
2
2
(2)
3.756
21.445
10.603
(0.317)
1.878
10.722
5.301
2
8
0.316
36.122
0.158
F-ratio
Pure sum
11.842
3.439
67.609
21.128
33.427
10.286
Pooled (CI 90%)
Percent
contribution
9.520
58.491
28.476
3.513
100.000
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Figure 3. Effect of PVA content on S/N of tensile strength for nanocomposite samples
(the data label on each point is the corresponding actual tensile strength (MPa)).
Effect of PVA content

Figure 3 shows the main-eect plot of PVA content. Tensile strength of
starch/PVA/clay nanocomposite lms increased with added PVA content
from 0% to 5% by weight. The positive eect of PVA percentage in this
range is probably due to the fact that all components in the nanocomposite
lms including starch, PVA, citric acid, and silicate layers have hydroxyl
groups (OH) in their chemical structure. Thus, all components may tend
to form inter-molecular and intra-molecular hydrogen bonds together
which improve the integrity of the lms.38,39
With increasing PVA from 5% to 10% the tensile strength drops. It is
supposed that at higher PVA content, some of the excess PVA macromolecules probably encapsulate the CMMT particles leading to agglomerates
that reduce tensile strength.9
Effect of screw speed

Mixing intensity as a function of screw speed and screw geometry (length and
shape of mixing elements) aects the stress subjected on clay layers and polymeric chains. Screw speed is therefore the most important mixing factor in a
twin-screw extruder for delaminating and dispersing clay layers.18
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ANOVA analysis of the results showed that screw speed at its mid-level
(24 r/min) led to the highest tensile strength for the nanocomposite lms
(Figure 4). When the screw speed is very high (say 36 r/min), the stress applied
to nanocomposite increases, while the residence time for material in the extruder decreases. In other words, there is not enough time for macromolecules to
migrate into the silicate layers. On the other hand, if the screw speed is very
low (12 r/min), materials suer lower stress which cannot force polymer into
clay galleries and as result cannot lead to well-intercalated morphology with
increased mechanical strength. Therefore, there will be an optimum point for
screw rotational velocity. The stressstrain behaviors of some nanocomposite
lms are illustrated in Figure 5.
Figure 4. Effect of screw speed on S/N of tensile strength for nanocomposite samples
(the data label on each point is the corresponding actual tensile strength (MPa)).
Effect of clay content

Addition of a proper amount of clay to TPS increases the tensile strength of
resulted lms. This could be justied by structural reasons such as:
. the homogeneous dispersion of silicate layers with very high Young
modulus (170 GPa8) in the starch matrix,
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. the strong interactions (typically by hydrogen bonding) between the

nanoller and matrix, and
. the high aspect (width-to-thickness) ratio and thus the vast exposed
surface of the nanoller.40
According to main-eect plot of clay content (Figure 6), clay content at its
mid-level (5 wt.%) provides the highest tensile strength. In other words, there
is an optimum level for the clay content. A higher CMMT content might
contribute to aggregates and CMMT stacks in a starch matrix and also to
lower starch phase plasticization.11,40,41
Figure 5. Stressstrain curves of some illustrated nanocomposite films.
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Figure 6. Effect of CMMT content on S/N of tensile strength for nanocomposite samples (the data label on each point is the corresponding actual tensile strength (MPa)).
Optimum conditions
The optimum conditions to attain a starch/PVA/clay nanocomposite with
maximum tensile strength can be determined from maximum points in
main-eect plots (Figures 3, 4, 6). The nanocomposite with optimum properties is therefore obtained with 5% by weight CMMT, 5% by weight PVA, and
at 24 r/min screw speed for the current extruder. Since the extruder temperature prole was found to be an insignicant factor, it can be xed arbitrarily
for example on its mid-level. Applying the optimum condition, the contribution of each factor on improvement of response above the current grand
average of results can be found using Taguchi approach.36
CMMT content: 1.11 MPa (0.913 in S/N unit),

PVA content: 1.25 MPa (1.936 in S/N unit),
screw rotation speed: 1.19 MPa (1.506 in S/N unit), and
extruder temperature prole: 1.02 MPa (0.196 in S/N unit).
The expected result (tensile strength) at optimum condition is therefore

predicted to be about 20.02 MPa (26.029 in S/N unit). This result is the
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sum of factor contributions plus the average value, that shows even 24.3%
improvement in tensile strength over the best result (i.e. run #2) in Table 4.
Characterization of nanocomposite film

Chemical structure. Figure 7 shows the FTIR spectra for CMMT, starch, TPS,
and optimum nanocomposite lm. One can see that the characteristic OH
stretching peak for hydroxyl groups in the starch at 3389 cm1 shifts to
3328 cm1 for the TPS. Primary hydroxyl inter-molecular and intra-molecular
interactions in starch are weakened due to new strong hydrogen bond formation between starch and glycerol.13 In other words, glycerol is able to create a
more stable hydrogen bond with hydroxyl groups, which decreases the frequency of stretching in corresponding OH bond in the TPS.4
Formation of nanocomposite shifts the peak of OH group in TPS to lower
wavenumbers even more (3308 cm1) which indicates formation of strong
bonds among PVA, silicate layers, and starch. Tensile properties enhancement of samples containing optimum amount of PVA and CMMT can be
ascribed to disruption of the crystallites by breaking inter-molecular hydrogen
bonds in starch molecules themselves and formation of new hydrogen bonds
between PVA, CMMT, and starch molecules.9
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Figure 7. FTIR spectra of (a) CMMT, (b) starch, (c) TPS, and (d) optimum nanocomposite film.
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Morphology. Figure 8 indicates the XRD pattern of nanocomposite lm prepared at optimum condition. The peak position for this sample is slightly
shifted to the left showing a d-spacing of 1.88 nm (d 0.4 nm). Thus, the
XRD result represents an intercalated morphology for the optimum sample.
Generally, TEM is combined with XRD to arm the nanocomposite
microstructure. Figure 9 shows the TEM micrographs of optimum starch/
PVA/CMMT nanocomposite lm. As seen, most of the CMMT layers are
dispersed throughout the polymer matrix. It is very interesting that in this
image some exfoliation is also observed. The intercalation morphology is
however more cautioning remark as it corresponds better with XRD results.
The mechanism of this dispersion level can most probably be suggested by
the CMMT compatibility with starch and PVA chains. Citric acid in MMT
gallery space can make desirable hydrogen binding and, accordingly, it can
improve the intercalation of polymer chains within the gallery. This micrograph also justies the good mechanical behaviors of optimum nanocomposite lms, as the silicate layers can play the role of reinforcing action into the
matrix.4
Figure 8. XRD pattern of optimum sample.
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Figure 9. TEM micrograph of optimum sample.
Water absorption. Low water uptake property is an important parameter for a

packaging lm as it aects the food conservation. Figure 10 shows the water
uptake behavior of some nanocomposite lms including the optimum.
Comparing samples made in runs 1, 4, and 7 and looking at their corresponding preparation conditions (Table 3), one can understand that all have no
PVA content, but with dierent clay content (3%, 5% and 10%, respectively)
as well as mixing extent (12, 24 and 36 r/min, respectively). The water uptake
decreases with simultaneous increasing of both CMMT content and screw
speed. Generally, this means that the eect of silicate layers content with
better distribution throughout the matrix (most probably due to the higher
r/min) should be important for reducing water absorption. Increasing the clay
percentage decreases the water absorption as a result of:
. introducing tortuous and thus longer pathways through the matrix for
the diusion of water molecules and
. strong interactions between the polymer matrix and clay silicate layer
interface that decrease the tendency of the polymer chains hydroxyl
groups to interact with water.15,40,42,43
On the other hand, as observed from these curves, in the initial testing
days, the water absorption rate is higher than those in the later days due to
driving force reduction.
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A comparison between samples 9 and 7 indicates that PVA content is a

signicant factor also for water uptake. Increasing the PVA percentage
decreases water absorption which is probably due to lower sensitivity of
PVA to humidity than starch and/or better distribution of clay layers in
presence of PVA. Furthermore, hydroxyl groups in PVA react most probably
with starch which decreases free hydroxyl groups in the resulted nanocomposite to create hydrogen bonds with water and moisture absorption.42
As mentioned, for a food packaging application, a lower water uptake is
desired for starch-based nanocomposite lms. The water uptake curve of
sample prepared at optimum condition (the best tensile property) is the
lowest one among the examined samples. This sample was prepared at midlevels of all factors and so it is implied from the experimental design point of
view, that the factors have probably synergetic and compatible interactions
for water absorption so that their setting at mid-levels results in a comparatively lower water uptake.
Figure 10. Water absorption behavior of some illustrated nanocomposite films and the
optimum one.
Thermogravimetric analysis. It is important to investigate the thermal behavior

of food packaging lm, as it is exposed to heat when food is warmed up inside
the package by a microwave or other devices.44
TGA and dynamic task graphs of optimum nanocomposite lm are shown
in Figure 11. Three weight losses are obvious on the thermograph. The rst
one occurs between 50 C and 130 C, most possibly corresponding to water
loss; the second one is observed between 110 C and 210 C due to plasticizer
(glycerol) volatilization; and the third one around 300 C is ascribed to the
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starch decomposition. The decomposition mechanism begins with hydroxyl

groups eliminating accompanied by depolymerization, decomposition, and
nally carbon production.45
It should be noted that the maximum temperature used in our extrusion
experiments performed in this study was about 130 C. For starch/clay/PVA
system, the maximum increase in temperature due to the viscous dissipation is
about 46 C.46 This means that there is no possibility for degradation of
components during the extrusion process.
Figure 11. Thermo gravimetric curves of nanocomposite prepared at optimum

condition.
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Biodegradation. Gradual variation in the color, thickness, surface roughness,

and increasing erosion indicates the progress of degradation.36 Figure 12
shows the biodegradation progress for nanocomposite lm prepared at optimum condition. The photos include the sample at:
. initial state (a),
. after 14 days (b), and
. after one month (c).
Figure 13 plots the weight loss (Wt/W0 100) for optimum sample versus
time (in days). Sample decomposition rate is low initially due to adaption of
the microorganism population to the new polymeric environment.36 During
surface erosion, a-amylase molecules agglomerate and scission of a (1-4) glucose units occurs, while in the second stage bulk diusion takes place, causing
complete decomposition.47
Figure 12. Photographs for nanocomposite films; before soil burial (a); after soil burial
for 14 days (b), and for 30 days (c).
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Figure 13. Weight loss versus time for optimum nanocomposite film.
Permeability test. One of the most important characteristics of a food packaging lm is its barrier property against oxygen. Table 6 illustrates the oxygen
permeability values for sample 6 and for the optimal one. These two samples
contain same amounts of CMMT. The optimum sample however contains
silicate layers with slightly greater gallery distance (1.88 nm vs. 1.76 nm) and
therefore has probably better clay dispersion than sample 6. The optimum
sample has a lower diusivity and better barrier against oxygen molecules,
though the clay content is the same. The dierence can be ascribed to the
more intercalated microstructure that leads to more tortuous and longer diffusion pathways for oxygen molecules.40
Overall migration test. The total amount of migrated species from packaging
lms into the food is vital for preventing any hygienic problem. The migration
test showed that the average overall migration of components in the starch
nanocomposite lm into the water was 6.417 mg/dm2. According to Iranian
National Standard Test Number 1-13737, the total migration of a food
packaging lm should not exceed 10 mg/dm2. Thus the optimum nanocomposite sample has appropriate migration value as a food packaging lm. The
migrant materials most probably contain starch molecules, PVA, glycerol and
clay. The barrier properties of clay layers and the tortuous pathway for
migrant to exit from lm decelerate this migration process. Furthermore,
hydrogen bonds between nanocomposite components prevent them to be
released into the solution and result in a low migration value.42
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Table 6. Oxygen permeability values for sample 6 and optimum sample.

O2 permeability
Sample
Optimum
sample
Sample 6
Preparation condition
Screw
PVA
CMMT
cm3(STP)
Temperature speed content content
d-spacing
cm/cm2 S cmHg (Barrer) distribution (r/min)
(%)
(%)
(nm)
1.86
0.11 1010
0.11
Mid
24
1.76
0.24 1010
0.24
Mid
12
10
Conclusions
Plasticized starch/PVA/clay nanocomposites were prepared by melt extrusion
and the inuences of various factors on the microstructure, mechanical, and
physical properties of these nanocomposites were statistically analyzed using
a Taguchi experimental approach. The main conclusions in the range of considered levels can be listed as follows:
. The tensile strength is strongly inuenced by PVA content, screw
speed, and clay content. The temperature prole (in the range of examined levels in this study) was found to be an insignicant factor for
tensile property improvement.
. The optimum conditions for prepared starch/PVA/clay nanocomposites were obtained as follow: screw speed and temperature prole in
their mid-levels, PVA and clay content were 5 wt. % for both.
. The optimum sample indicated an intercalated/exfoliated morphology
with very low water uptake and oxygen permeability, sucient thermal
stability, and excellent biodegradability. The lms also passed the
migration test. This means that the starch/PVA/clay nanocomposites
have potential to be used as food packaging lm.
Conflict of interest
None declared.
Funding
This work was nancially supported by Iranian Nanotechnology Initiative.
References
1. Chung Y-L, Ansari S, Estevez L, et al. Preparation and properties of biodegradable
starchclay nanocomposites. Carbohydr Polym 2010; 79: 391396.
XML Template (2015)

[10.2.20151:02pm]
[130]
(JPF)
[PREPRINTER stage]
Navarchian et al.
27
2. Barikani M and Mohammadi M. Synthesis and characterization of starch-modified polyurethane. Carbohydr Polym 2007; 68: 773780.
3. Mondragon M, Mancilla JE and Rodr guez-Gonzalez FJ. Nanocomposites from
plasticized high-amylopectin, normal and high-amylose maize starches. Polym
Eng Sci 2008; 48: 12611267.
4. Majdzadeh-Ardakani K, Navarchian AH and Sadeghi F. Optimization of mechanical properties of thermoplastic starch/clay nanocomposites. Carbohydr Polym
2010; 79: 547554.
5. Avella M, De Vlieger JJ, Errico ME, et al. Biodegradable starch/clay nanocomposite films for food packaging applications. Food Chem 2005; 93: 467474.
6. Dean K, Yu L and Wu DY. Preparation and characterization of melt-extruded
thermoplastic starch/clay nanocomposites. Compos Sci Technol 2007; 67: 413421.
7. Ghanbarzade B, Almasi H and Entezami A. Studying morphological and moisture barrier properties of starch-CMC-nanoclay biodegradable bionanocomposite
film. J Innov Food Sci Technol 2013; 5: Pe83Pe92. (En117).
8. Cyras VP, Manfredi LB, Ton-That M-T, et al. Physical and mechanical properties
of thermoplastic starch/montmorillonite nanocomposite films. Carbohydr Polym
2008; 73: 5563.
9. Dean KM, Do MD, Petinakis E, et al. Key interactions in biodegradable thermoplastic starch/poly (vinyl alcohol)/montmorillonite micro- and nanocomposites.
Compos Sci Technol 2008; 68: 14531462.
10. Qiao X, Jiang W and Sun K. Reinforced thermoplastic acetylated starch with
layered silicates. Starch-Starke 2005; 57: 581586.
11. Wang N, Zhang X, Han N, et al. Effect of citric acid and processing on the
performance of thermoplastic starch/montmorillonite nanocomposites.
Carbohydr Polym 2009; 76: 6873.
12. Raquez JM, Narayan R and Dubois P. Recent Advances in reactive extrusion
processing of biodegradable polymer-based compositions. Macromol Mater Eng
2008; 293: 447470.
13. Majdzadeh-Ardakani K and Nazari B. Improving the mechanical properties of
thermoplastic starch/poly (vinyl alcohol)/clay nanocomposites. Compos Sci
Technol 2010; 70: 15571563.
14. Huang M, Yu J and Ma X. High mechanical performance MMT-urea and formamide-plasticized thermoplastic cornstarch biodegradable nanocomposites.
Carbohydr Polym 2006; 63: 393399.
15. Huang M-F, Yu J-G and Ma X-F. Studies on the properties of montmorillonitereinforced thermoplastic starch composites. Polymer 2004; 45: 70177023.
16. Wilhelm H-M, Sierakowski M-R, Souza G, et al. Starch films reinforced with
mineral clay. Carbohydr Polym 2003; 52: 101110.
17. Di Y, Iannace S, Di Maio E, et al. Nanocomposites by melt intercalation
based on polycaprolactone and organoclay. J Polym Sci B Polym Phys 2003;
41: 670678.
18. Incarnato L, Scarfato P, Russo G, et al. Preparation and characterization
of new melt compounded copolyamide nanocomposites. Polymer 2003; 44:
46254634.
XML Template (2015)

[10.2.20151:02pm]
[130]
(JPF)
[PREPRINTER stage]
28
19. Sauceau M, Fages J, Common A, et al. New challenges in polymer foaming: A

review of extrusion processes assisted by supercritical carbon dioxide. Prog Polym
Sci 2011; 36: 749766.
20. Kumar P, Sandeep K, Alavi S, et al. Preparation and characterization of bionanocomposite films based on soy protein isolate and montmorillonite using melt
extrusion. J Food Eng 2010; 100: 480489.
21. Belibi PC, Daou TJ, Ndjaka J-MB, et al. Tensile and water barrier properties of
cassava starch composite films reinforced by synthetic zeolite and beidellite.
J Food Eng 2013; 115: 339346.
22. Majdzadeh-Ardakani K and Sadeghi-Ardakani S. Experimental investigation of
mechanical properties of Starch/natural rubber/clay nanocomposites. Dig J
Nanometer Biosys 2010; 10: 20.
23. Almasi H, Ghanbarzadeh B and Entezami AA. Physicochemical properties of
starchCMCnanoclay biodegradable films. Int J Biol Macromol 2010; 46: 15.
24. Hejri Z, Ahmadpour A, Seifkordi AA and Zebarjad SM. Role of nano-sized TiO2
on mechanical and thermal behavior of starch/Poly(vinyl alcohol) blend films. Int
J Nano Sci Nanotechnol 2012; 8: 215226.
25. Heydari A, Alemzadeh I and Vossoughi M. Functional properties of biodegradable corn starch nanocomposites for food packaging applications. Mater Des
2013; 50: 954961.
26. Sreekumar P, Al-Harthi MA and De S. Reinforcement of starch/poly(vinyl alcohol) blend using nano-titanium dioxide. J Compos Mater 2012; 46: 31813187.
27. Castillo L, Lopez O, Lopez C, et al. Thermoplastic starch films reinforced with
talc nanoparticles. Carbohydr Polym 2013; 95: 664674.
28. Slavutsky AM, Bertuzzi MA and Armada M. Water barrier properties of starchclay nanocomposite films. Brazilian J Food Technol 2012; 15: 208218.
29. Muller CM, Laurindo JB and Yamashita F. Composites of thermoplastic starch
and nanoclays produced by extrusion and thermopressing. Carbohydr Polym 2012;
89: 504510.
30. Jalalvandi E, Majid R, Ghanbari T, et al. Effects of montmorillonite (MMT) on
morphological, tensile, physical barrier properties and biodegradability of
poly(lactic acid)/starch/MMT nanocomposites. J Thermoplast Compos Mater.
Epub ahead of print 2013. DOI: 10.1177/0892705713486129.
31. Katerinopoulou K, Giannakas A, Grigoriadi K, et al. Preparation and characterization of acetylated corn starch(PVA)/clay nanocomposite films. Carbohydr
Polym 2014; 102: 216222.
32. Ali SS, Tang X, Alavi S, et al. Structure and physical properties of starch/poly
vinyl alcohol/sodium montmorillonite nanocomposite films. J Agric Food Chem
2011; 59: 1238412395.
33. Mao L, Imam S, Gordon S, et al. Extruded cornstarch-glycerol-polyvinyl alcohol
blends: Mechanical properties, morphology, and biodegradability. J Polym
Environ 2000; 8: 205211.
34. NurHanani Z, Beatty E, Roos Y, et al. Manufacture and characterization of
gelatin films derived from beef, pork and fish sources using twin screw extrusion.
J Food Eng 2012; 113: 606614.
XML Template (2015)

[10.2.20151:02pm]
[130]
(JPF)
[PREPRINTER stage]
Navarchian et al.
29
35. Xie F, Halley PJ and Averous L. Rheology to understand and optimize processibility, structures and properties of starch polymeric materials. Prog Polym Sci
2012; 37: 595623.
36. Magalhaes N and Andrade C. Thermoplastic corn starch/clay hybrids: Effect of
clay type and content on physical properties. Carbohydr Polym 2009; 75: 712718.
37. Roy RK. Design of experiments using the Taguchi approach: 16 steps to product
and process improvement. New York: John Wiley & Sons, 2001.
38. Tang X, Alavi S and Herald TJ. Effects of plasticizers on the structure and properties of starchclay nanocomposite films. Carbohydr Polym 2008; 74: 552558.
39. Chen C-H and Lai L-S. Mechanical and water vapor barrier properties of tapioca
starch/decolorized hsian-tsao leaf gum films in the presence of plasticizer. Food
Hydrocoll 2008; 22: 15841595.
40. Xie F, Pollet E, Halley PJ, et al. Starch-based nano-biocomposites. Prog Polym
Sci 2013; 38: 15901628.
41. Kampeerapappun P, Aht-ong D, Pentrakoon D, et al. Preparation of cassava
starch/montmorillonite composite film. Carbohydr Polym 2007; 67: 155163.
42. Chen B and Evans JR. Thermoplastic starchclay nanocomposites and their characteristics. Carbohydr Polym 2005; 61: 455463.
43. Dai H, Chang PR, Geng F, et al. Preparation and properties of thermoplastic
starch/montmorillonite nanocomposite using N-(2-hydroxyethyl) formamide as a
new additive. J Polym Environ 2009; 17: 225232.
44. Tunc S and Duman O. Preparation of active antimicrobial methylcellulose/carvacrol/montmorillonite nanocomposite films and investigation of carvacrol release.
LWT-Food Sci Technol 2011; 44: 465472.
45. Masclaux C, Gouanve F and Espuche E. Experimental and modelling studies of
transport in starch nanocomposite films as affected by relative humidity. J Membr
Sci 2010; 363: 221231.
46. Martin O, Averous L and Della Valle G. In-line determination of plasticized
wheat starch viscoelastic behavior: Impact of processing. Carbohydr Polym
2003; 53: 169182.
47. Spiridon I, Popescu MC, Bodarlau R, et al. Enzymatic degradation of some
nanocomposites of poly(vinyl alcohol) with starch. Polym Degrad Stab 2008; 93:
18841890.
Biographies
Amir H Navarchian received his PhD in chemical engineering from Tarbiat
Modares University, Tehran, Iran, in 2003. He is currently an associate professor of chemical engineering at the University of Isfahan, Isfahan, Iran,
where he is also the Head of Oce for University-Industry Collaborations.
His research interests cover polymer/clay nanocomposites, starch-based
packaging lms, polymer gas sensors, polymer membranes and emulsion
polymerization.
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Mehdi Jalalian received his MSc in chemical engineering from the University
of Isfahan, Isfahan, Iran, in 2012. His research was focused on starch/clay
nanocomposites and packaging lms. He is currently a process engineer in
National Iranian Gas Company (NIGC).
Majid Pirooz received his MSc in chemical engineering from the University of
Isfahan, Isfahan, Iran, in 2014. His research is focused on starch/clay nanocomposites and packaging lms.

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Journal of Plastic Film & Sheeting

Amir H Navarchian, Mehdi Jalalian and

Department of Chemical Engineering, Faculty of Engineering, University of Isfahan, Isfahan, Islamic

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Natural rubber (0%, 10%

Filler type and content

Melt extrusion in twinscrew extruder

Melt extrusion in twinscrew extruder

Natural rubber type

Table 1. Summary of some recent works on starch-based nanocomposite films.

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Filler type and content

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of controlled factors respect to that of errors. In this work, the tensile

Table 2. Selected factors and their respective levels.

Preparation of modified MMT with citric acid

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Preparation of TPS/PVA/clay nanocomposite films

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Corporation, USA) in the range of 4504000 cm1 and with a resolution of

Biodegradation. Biodegradation of nanocomposites was studied by soil burial

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Overall migration test. Overall migration test was performed according to

weight of migrant (s) in the blank (mg)

radius of the disk (m)

circumference of disk (m)

thickness of disk (m)

number of disks per cell

Results and discussions

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Figure 1. XRD patterns of some nanocomposite films as illustrations.

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Tensile strength property

Analysis of variance for mechanical properties

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Effect of PVA content

Effect of screw speed

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