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Characterization of starch/poly(vinyl alcohol)/clay nanocomposite films

prepared in twin-screw extruder for food packaging application

Article  in  Journal of Plastic Film and Sheeting · July 2015

DOI: 10.1177/8756087914568904

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Original Article
Journal of Plastic Film & Sheeting
2015, Vol. 31(3) 309–336
Characterization of ß The Author(s) 2015
Reprints and permissions:
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DOI: 10.1177/8756087914568904
clay nanocomposite films jpf.sagepub.com

prepared in twin-screw
extruder for food
packaging application

Amir H Navarchian, Mehdi Jalalian and

Majid Pirooz

Abstract
Starch/poly(vinyl alcohol)/montmorillonite (MMT) nanocomposites were pre-
pared 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 investi-
gated by using Taguchi experimental design. It was found that PVA content, CMMT
percentage and screw speed were the most important factors, respectively, affect-
ing 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

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310 Journal of Plastic Film & Sheeting 31(3)

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 protec-
tion and sustainable development.2 Biodegradable polymers have become
important materials tailored to new environmental friendly products, espe-
cially 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-glu-
copyranoside and a-1,6-D-glucopyranoside). The ratio of amylose to amylo-
pectin 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 intro-
duced to make the starch flow when processed.
Thermoplastic starch (TPS) or plasticized starch is obtained after disrup-
tion 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 elong-
ation, reduce brittleness, and facilitate processability.9 On the other hand,
with development of nanotechnology, polymer/layered silicate (PLS) nano-
composites have attracted great attention because of their remarkably
improved mechanical, thermal, and barrier properties compared with the ori-
ginal 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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Navarchian et al. 311

higher tensile strength, thermal stability, and moisture barrier properties than
TPS itself.10 Our previous work proved that citric acid-modified montmoril-
lonite (CMMT) clay represented even better mechanical properties in com-
parison with MMT in the starch. The interactions between citric acid and
starch chains were responsible for this improvement.4
TPS and TPS/clay films can be made by various techniques such as solu-
tion casting and thermoplastic extrusion processing. Compared with solution
casting, thermoplastic extrusion is a ‘‘green’’ and facile process.11 Melt extru-
sion is an attractive route for cost effective polymer processing, which
enhances the commercial viability and cost-competitiveness of these mater-
ials.12 Various compositional factors and processing parameters may influ-
ence the final properties of TPS-based packaging films. Many authors have
investigated just the effects of material composition including clay and/or
PVA content8,9,13–16 on physical and mechanical properties of these films.
There are also some limited reports available on the effects of processing
conditions such as screw speed and extruder temperature profile.17–20
Although there are many papers recently published on the starch-based
nanocomposite films as shown in Table 1, there are few reports that apply
experimental design to analyze the effects of both material and process par-
ameters on the physical and mechanical properties of starch/clay nanocom-
posites produced in extruder.
In this study, the influence of clay content, PVA percentage, screw speed,
and temperature profile on the tensile stress of starch/PVA/clay nanocompo-
site films 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 diffraction (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 films were also examined.

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 Table 1. Summary of some recent works on starch-based nanocomposite films.
312

Film preparation
Ref. Second polymer Filler type and content method Investigated factors
13
– MMT Melt extrusion in twin- Water content
screw extruder Clay content
PVA content
Clay content
21
– Beta Zeolite Solution casting Filler type
Na-Beidellite Filler content
(1%, 2%, 4%)
22
Natural rubber (0%, 10% MMT Melt extrusion in twin- Natural rubber type
and 20%) (0%, 3%, 6%) screw extruder Filler content
Glycerol content
Natural rubber content
23
Carboxymethylcellulose MMT Solution casting Filler content
(10%) (0%, 1%, 3%, 5%, 7%)
24
PVA Nano-TiO2 Solution casting PVA content
(0%, 40%, 50%, 60%, (0%, 2.5%, 5%) Filler content
100%)

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25
– MMT Solution casting Filler content
(0%, 2.5%, 5%)
26
PVA Nano-TiO2 Solution casting Filler content
(40%) (0.5%, 1%, 2%)
27
– Talc Compression molding Filler content
(0%, 1.7%, 5.2%, 8.7%)
(continued)
Journal of Plastic Film & Sheeting 31(3)
 Table 1. Continued

Film preparation
Ref. Second polymer Filler type and content method Investigated factors
28
– MMT Solution casting Filler content
Navarchian et al.

(0%, 1%, 3%, 5%, 7%, 10%) Film preparation

methodology
29
– MMT Extrusion/thermo- Filler type
OMMT (Cloisite 30B) pressing
(3%, 5%)
30
Poly(lactic acid) MMT Extrusion/thermo- Filler content
(58%) (2%, 4%, 6%, 8%) pressing
31
PVA MMT Thermo-pressing Filler content
(0%, 10%, 30%) (3%, 5%) Glycerol content
PVA content
32
PVA MMT Solution casting PVA content
(20%, 33%, 50%, 67%, (0, 5, 10, 15, 20) Filler content
80%) PVA type

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313
314 Journal of Plastic Film & Sheeting 31(3)

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 Naþ (MMT) as untreated MMT
was purchased from Southern Clay Products (USA).

Design of experiments
The Taguchi experimental design approach was used as an effective technique
to reduce the number of experiments while retaining quality of data collec-
tion. The first important step in designing an experiment is the proper selec-
tion 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 profile.
The factors and their levels have been selected according to our literature
review on previous publications4,9,17,18,20,33–36 and some screening experi-
ments in this work. CMMT and PVA percentages were reported based on
a fixed weight of starch. Three extruder temperature profiles were used in
order to investigate thermal processing conditions on the extruded compos-
ites. Each temperature profile included four temperature zones from the feed
section to the die exit. The three temperature profiles were:
. Low: 80–90–100–110 ( C)
. Mid: 90–100–110–120 ( C)
. High: 100–110–120–130 ( 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 effects and is suitable for the experiments
for which it is assumed that there is no significant 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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Navarchian et al. 315

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 þ 1=y22 þ    þ 1=y2n
S=N ¼ 10  log ð1Þ
n

Table 2. Selected factors and their respective levels.

Factor Unit Level 1 Level 2 Level 3

CMMT content wt.% 3 5 7

PVA content wt.% 0 5 10
Screw speed r/min 12 24 36

Extruder temperature profile C Low Mid High

Table 3. Designed experiments with coded variables based on the Taguchi method.

Factors

Trial no. CMMT% PVA% Screw speed Temperature

1 1 1 1 1
2 1 2 2 2
3 1 3 3 3
4 2 1 2 3
5 2 2 3 1
6 2 3 1 2
7 3 1 3 2
8 3 2 1 3
9 3 3 2 1

Preparation of modified MMT with citric acid

In order to provide more compatibility between silicate layers and starch
macromolecules, MMT was modified 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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316 Journal of Plastic Film & Sheeting 31(3)

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 filtered, and the
cake was washed with distilled water and centrifuged for 30 min. The modified
clays were dried at 60 C for 24 h, and finally ground into a fine 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. Specified amount of cornstarch, PVA, and glycerol were com-
pletely 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 profile were set at
specified conditions as given in Table 2. The round cross-section extrudate
was cooled and pelletized. Finally, the films were prepared by hot press mold-
ing at 200 C for 2 min. The films thickness was 0.25  0.02 mm.

Characterization
X-ray diffraction. XRD analysis was carried out on a BrukerD8-Advance X-ray
diffractometer (Bruker, Germany) using CuKa radiation (40 kV, 40 mA and
l ¼ 0.154 nm). Samples were scanned at 1 /min in the range of 2 ¼ 2–10 .
The basal spacing of the silicate layer, d(001), was calculated using Bragg’s
equation (nl ¼ 2d sin ), where  is the diffraction angle and l is the
wavelength.

Tensile strength measurement. Tensile tests were performed according to ASTM

D882-02 by using H25KS tester (Hounsfield, 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 films were mea-

sured by Nicolet 400D Impact spectrometer (Nicolet Instrument

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Navarchian et al. 317

Corporation, USA) in the range of 450–4000 cm1 and with a resolution of

16 cm1.

Transmission electron microscopy. TEM was used to study the nanocomposite

film 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:
w2  w1
K¼  100 ð2Þ
w1
where

w1 ¼ dried sample weight (g)

w2 ¼ 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) filled with soil, previously
passed through a 2 mm sieve. Every seven days for a period of 28 days, sam-
ples 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 films. This method
is based on pressure measurement at a constant volume when subjecting pres-
sure difference 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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318 Journal of Plastic Film & Sheeting 31(3)

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
filled 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:
WB
E¼ ð3Þ
ð2R2 þ CTÞN

where

W ¼ total weight of migrant (s) in the liquid (mg)

B ¼ weight of migrant (s) in the blank (mg)
R ¼ radius of the disk (m)
C ¼ circumference of disk (m)
T ¼ thickness of disk (m)
N ¼ 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
films 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 ¼ dnc  d0 ð4Þ

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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Navarchian et al. 319

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 films.
The XRD patterns from trial numbers 2, 5, 6, and 7 (as representatives of
different 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 4.98 1.77 0.29 9.7 10.0

2 4.90 1.80 0.32 17.7 17.3
3 5.02 1.76 0.28 9.0 8.7
4 4.94 1.79 0.31 16.7 15.3
5 4.94 1.79 0.31 14.7 16.3
6 5.02 1.76 0.28 10.7 9.3
7 4.98 1.77 0.29 11.3 10.7
8 4.94 1.79 0.31 14.0 12.0
9 4.98 1.77 0.29 10.0 11.7

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

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320 Journal of Plastic Film & Sheeting 31(3)

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 nanocompo-
site films prepared in different experimental runs is essentially proportional to
the silicate layer gallery expansion (
d) obtained from XRD analysis.
Increasing the silicate layer spacing in nanocomposite films 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 confirms the strong dependency of
the mechanical properties to the nanocomposite morphology.

Figure 2. Correlation between tensile strength (average value for each run) and cor-
responding 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 affecting the response. The
strategy of ANOVA is to evaluate the variations that each factor cause rela-
tive 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 mech-
anical property for packaging films. There are several statistical terms in
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% confidence level, indicating the significance of these

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Navarchian et al. 321

factors on the response. According to ANOVA table, three factors namely

PVA percentage, screw speed, and clay percentage have the highest effects,
respectively, on the tensile strength of nanocomposite films. The extruder
temperature profile however has a minor effect on the response. As the influ-
ence contribution of this factor is less than 10% of the most important factor
(PVA wt.%), its effect 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 insignificant factor
with error term. The other/error term is therefore consisted of the effects of
three sources of variability:
. the uncontrollable factors,
. the pooled factors and/or those that are not considered in the experi-
ments, and
. the experimental error.37
In the following, the effects of each factor on the tensile strength are
investigated as shown in some bar charts. Each data on these main effect
graphs is an average of replicated results obtained at each level of the corres-
ponding 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 experi-
mental design approach.

Table 5. ANOVA table for tensile strength after pooling the effect of extruder tem-
perature profile with the error term (confidence level of 90%).

Sum of Percent
Factors DOF squares Variance F-ratio Pure sum contribution

CMMT content 2 3.756 1.878 11.842 3.439 9.520

PVA content 2 21.445 10.722 67.609 21.128 58.491
Screw speed 2 10.603 5.301 33.427 10.286 28.476
Extruder temperature (2) (0.317) – Pooled (CI ¼ 90%) –
profile
Other/error 2 0.316 0.158 – – 3.513
Total 8 36.122 – – – 100.000

Effect of PVA content

Figure 3 shows the main-effect plot of PVA content. Tensile strength of
starch/PVA/clay nanocomposite films increased with added PVA content

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322 Journal of Plastic Film & Sheeting 31(3)

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)).

from 0% to 5% by weight. The positive effect of PVA percentage in this range

is probably due to the fact that all components in the nanocomposite films
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 films.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 macromol-
ecules 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) affects the stress subjected on clay layers and poly-
meric chains. Screw speed is therefore the most important mixing factor in a
twin-screw extruder for delaminating and dispersing clay layers.18
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 films
(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

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Navarchian et al. 323

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)).

Figure 5. Stress–strain curves of some illustrated nanocomposite films.

extruder decreases. In other words, there is not enough time for macromol-
ecules to migrate into the silicate layers. On the other hand, if the screw speed
is very low (12 r/min), materials suffer lower stress which cannot force poly-
mer into clay galleries and as result cannot lead to well-intercalated morph-
ology with increased mechanical strength. Therefore, there will be an
optimum point for screw rotational velocity. The stress–strain behaviors of
some nanocomposite films are illustrated in Figure 5.

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324 Journal of Plastic Film & Sheeting 31(3)

Effect of clay content

Addition of a proper amount of clay to TPS increases the tensile strength of
resulted films. This could be justified by structural reasons such as:
. the homogeneous dispersion of silicate layers with very high Young
modulus (170 GPa8) in the starch matrix,
. the strong interactions (typically by hydrogen bonding) between the
nanofiller and matrix, and
. the high aspect (width-to-thickness) ratio and thus the vast exposed
surface of the nanofiller.40
According to main-effect 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 6. Effect of CMMT content on S/N of tensile strength for nanocomposite sam-
ples (the data label on each point is the corresponding actual tensile strength (MPa)).

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Navarchian et al. 325

Optimum conditions
The optimum conditions to attain a starch/PVA/clay nanocomposite with
maximum tensile strength can be determined from maximum points in
main-effect plots (Figures 3, 4, 6). The nanocomposite with optimum proper-
ties 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 tempera-
ture profile was found to be an insignificant factor, it can be fixed arbitrarily
for example on its mid-level. Applying the optimum condition, the contribu-
tion 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 profile: 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
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 film. One can see that the characteristic O–H
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 forma-
tion between starch and glycerol.13 In other words, glycerol is able to create a
more stable hydrogen bond with hydroxyl groups, which decreases the fre-
quency of stretching in corresponding O–H 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 enhance-
ment 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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326 Journal of Plastic Film & Sheeting 31(3)

Figure 7. FTIR spectra of (a) CMMT, (b) starch, (c) TPS, and (d) optimum nanocompo-
site film.

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Navarchian et al. 327

Morphology. Figure 8 indicates the XRD pattern of nanocomposite film pre-

pared at optimum condition. The peak position for this sample is slightly
shifted to the left showing a d-spacing of 1.88 nm (
d ¼ 0.4 nm). Thus, the
XRD result represents an intercalated morphology for the optimum sample.
Generally, TEM is combined with XRD to affirm the nanocomposite
microstructure. Figure 9 shows the TEM micrographs of optimum starch/
PVA/CMMT nanocomposite film. 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 micro-
graph also justifies the good mechanical behaviors of optimum nanocompo-
site films, 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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328 Journal of Plastic Film & Sheeting 31(3)

Figure 9. TEM micrograph of optimum sample.

Water absorption. Low water uptake property is an important parameter for a

packaging film as it affects the food conservation. Figure 10 shows the water
uptake behavior of some nanocomposite films including the optimum.
Comparing samples made in runs 1, 4, and 7 and looking at their correspond-
ing preparation conditions (Table 3), one can understand that all have no
PVA content, but with different 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 effect 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 diffusion 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.
A comparison between samples 9 and 7 indicates that PVA content is a
significant factor also for water uptake. Increasing the PVA percentage
decreases water absorption which is probably due to lower sensitivity of

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Navarchian et al. 329

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 nanocompo-
site 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 films. 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 mid-
levels 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 film, 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 film are shown
in Figure 11. Three weight losses are obvious on the thermograph. The first
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
starch decomposition. The decomposition mechanism begins with hydroxyl

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330 Journal of Plastic Film & Sheeting 31(3)

groups eliminating accompanied by depolymerization, decomposition, and

finally 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 4–6 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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Navarchian et al. 331

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 film prepared at opti-
mum 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

Figure 12. Photographs for nanocomposite films; before soil burial (a); after soil burial
for 14 days (b), and for 30 days (c).

Figure 13. Weight loss versus time for optimum nanocomposite film.

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332 Journal of Plastic Film & Sheeting 31(3)

the microorganism population to the new polymeric environment.36 During

surface erosion, a-amylase molecules agglomerate and scission of a (1-4) glu-
cose units occurs, while in the second stage bulk diffusion takes place, causing
complete decomposition.47

Permeability test. One of the most important characteristics of a food packa-

ging film 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 diffusivity and better barrier against oxygen molecules,
though the clay content is the same. The difference can be ascribed to the
more intercalated microstructure that leads to more tortuous and longer dif-
fusion pathways for oxygen molecules.40

Table 6. Oxygen permeability values for sample 6 and optimum sample.

O2 permeability Preparation condition

Screw PVA CMMT

d-spacing cm3(STP) Temperature speed content content
Sample (nm) cm/cm2 S cmHg (Barrer) distribution (r/min) (%) (%)

Optimum 1.86 0.11  1010 0.11 Mid 24 5 5

sample
Sample 6 1.76 0.24  1010 0.24 Mid 12 10 5

Overall migration test. The total amount of migrated species from packaging
films 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 film into the water was 6.417 mg/dm2. According to Iranian
National Standard Test Number 1-13737, the total migration of a food
packaging film should not exceed 10 mg/dm2. Thus the optimum nanocom-
posite sample has appropriate migration value as a food packaging film. 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 film 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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Navarchian et al. 333

Conclusions
Plasticized starch/PVA/clay nanocomposites were prepared by melt extrusion
and the influences 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 con-
sidered levels can be listed as follows:
. The tensile strength is strongly influenced by PVA content, screw
speed, and clay content. The temperature profile (in the range of exam-
ined levels in this study) was found to be an insignificant factor for
tensile property improvement.
. The optimum conditions for prepared starch/PVA/clay nanocompo-
sites were obtained as follow: screw speed and temperature profile 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, sufficient thermal
stability, and excellent biodegradability. The films also passed the
migration test. This means that the starch/PVA/clay nanocomposites
have potential to be used as food packaging film.

Conflict of interest
None declared.

Funding
This work was financially supported by Iranian Nanotechnology Initiative.

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Biographies
Amir H Navarchian received his PhD in chemical engineering from Tarbiat
Modares University, Tehran, Iran, in 2003. He is currently an associate pro-
fessor of chemical engineering at the University of Isfahan, Isfahan, Iran,
where he is also the Head of Office for University-Industry Collaborations.
His research interests cover polymer/clay nanocomposites, starch-based
packaging films, polymer gas sensors, polymer membranes and emulsion
polymerization.

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 films. 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 nano-
composites and packaging films.

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