Accepted Manuscript

Title: Preparation of ecofriendly UV-protective food

packaging material by starch/TiO2 bio-nanocomposite:
characterization

Author: Vahid Goudarzi Iman Shahabi-Ghahfarrokhia Amin

Babaei-Qazvini

PII: S0141-8130(16)31856-6
DOI: http://dx.doi.org/doi:10.1016/j.ijbiomac.2016.11.065
Reference: BIOMAC 6757

To appear in: International Journal of Biological Macromolecules

Received date: 2-10-2016

Revised date: 12-11-2016
Accepted date: 17-11-2016

Please cite this article as: Vahid Goudarzi, Iman Shahabi-Ghahfarrokhia, Amin
Babaei-Qazvini, Preparation of ecofriendly UV-protective food packaging material by
starch/TiO2 bio-nanocomposite: characterization, International Journal of Biological
Macromolecules http://dx.doi.org/10.1016/j.ijbiomac.2016.11.065

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Preparation of ecofriendly UV-protective food packaging material
by starch/TiO2 bio-nanocomposite: characterization

Vahid Goudarzia, Iman Shahabi- Ghahfarrokhia*, Amin Babaei-Qazvinib

a) Department of Food Science and Technology, Faculty of Agriculture, University

of Zanjan, 45371-38791, Zanjan, Iran, Vahid.goudarzi@znu.ac.ir

b) Department of Food Science and Technology, Faculty of Agriculture, Islamic

Azad University, North Tehran Branch, Tehran, Iran, Amin_babaei@ut.ac.ir

*Corresponding author: i.shahabi@znu.ac.ir, Tel.: +98 24 3305 4380, Fax: +98 24

3305 2348

1
Highlights
 Physical and mechanical properties of starch/TiO2 nanocomposites were

investigated.

 TiO2 improved approximately all the drawbacks of starch film as packaging

material.

 TiO2 improved thermal properties of starch/TiO2 nanocomposite.

 Starch/TiO2 nanocomposites were protected foods against UV-A, UV-B, and

UV-C region

2
 Abstract
In this study, ecofriendly starch/TiO2 bio-nanocomposites were produced using with different
nano-TiO2 (TiO2) content (1, 3, and 5 (wt %)). Physical, mechanical, thermal, water-vapor
permeability (WVP) properties and UV transmittance were investigated. Our results showed that
the increasing TiO2 content increased the hydrophobicity of starch/TiO2 films. WVP of the bio-
nanocomposites was reduced, simultaneously. With increasing TiO2 content, tensile strength and
Young’s modulus of the film specimens were reduced while elongation at break and tensile
energy to break were increased. The thermal properties of specimens showed that glass transition
temperature of the films increased but melting point of the specimen films was decreased by
increasing TiO2 content. Scanning electron microscopy observations demonstrated, the most of
films’ physical properties were in relation to their microstructures. The starch/TiO2
nanocomposites effectively protect goods against UV light, and could potentially be applied as
UV-shielding packaging materials.

Keywords: Starch; TiO2 nanoparticles; Ecofriendly;

1. Introduction
Despite chemically synthesized polymeric films have long been used in the food packaging,
but they have led to serious ecological problems due to their nonbiodegradability. Hence, during
the two past decades, biodegradable polymers have been considered as the alternative to
synthetic polymers, mainly because of environmental concerns, finitude of petroleum resources,
and increasing the oil price [1, 2]. Carbohydrate based polymers i.e. starch [3], pullulan [4],
cellulose [1] and kefiran [2]; protein based polymers i.e. whey protein [4], soy protein [5], have
been considered as a potential environmentally-friendly substitute for the use of petroleum based
polymers.
Despite the advantages of biopolymers, some obstacles such as weak barrier properties,
sensitivity to water and low mechanical properties were limited the use of biopolymers as
packaging material [6]. Therefore, several papers were published in this field in recent years [2-
5, 7]. Many researchers tried to overcome these drawbacks through chemical modification by
changing the pH [8], the plasticizer [9], develop chemical cross-linking [10], composition with
different biopolymers or nanoparticles [2, 7] and using ionizing rays i.e. UV irradiation [11] and
γ-irradiation [6].
Among the natural polymers, starch has been considered as one of the most promising
candidates for this regard because of it is a cheap, world-wide availability, abundant, renewable
and biodegradable biopolymer [12, 13]. Starch structure is constituted by two macromolecules,

3
amylose and amylopectin. Amylose is a linear polysaccharide, poly (α -1, 4-glucopyronosyl),
while amylopectin is poly (α -1, 4-glucopyronosyl) with many α -1, 6-glucopyronosyl branches
[14-16]. Recently, a new class of materials represented by bio-nanocomposites with different
barrier, mechanical, and thermal properties has been considered as a promising option in
modifying the properties of these biopolymer-based packaging materials [17]. Some nanofillers
possess good interfacial interactions with some of polymers and sometimes improve the
properties of the nanocomposite. The capability is due to the large specific surface area and the
high surface energy of nanofillers. Nanoparticles could improve the mechanical and physical
properties [7] filtering UV [2], anti-microbial [18], and antioxidant [17]. Bio-nanocomposites
consist of a biopolymer matrix reinforced with nanoparticles possess at least one dimension in
the nanometer range (1–100 nm) [17, 19]. Different nanoparticles have been mixed with
biopolymers to give them more strength and barrier properties [2, 20-22].
Titanium dioxide (TiO2) is an inert, nontoxic, ecofriendly [22, 23] and inexpensive material
with potential activity against a wide variety of microbes due to its photocatalytic activity [7].
The anti-microbial activity of TiO2 is related to reactive oxygen species production. The formed
hydroxyl free radicals and peroxide under UV irradiation disturb cell membrane [24]. TiO2
possess some unique properties among the various metal oxides which used to modifying the
packaging properties of biopolymers i.e. UV protective and anti-microbial activities,
simultaneously [7, 21, 22]. TiO2 exists in three different crystalline shapes: Rutile (the most
stable phase), anatase and brookite. Anatase is the most photolytic crystalline shape of TiO2
[25].The incorporation of TiO2 nanoparticles into biopolymer films such as kefiran-whey
protein isolate [7], soy protein isolate [5], poly(L-lactic acid) [26] have been reported to
modify some physicochemical properties of packaging materials.
UV light can adversely foods by generating free radicals in products by a wide variety of
organic photochemical reactions [2]. Singlet oxygen, produce by UV irradiation from sun light,
is the fastest cause of lipid oxidation, destruction of antioxidants and damage of vitamins and
proteins [2]. Oxidation reactions alters the flavor, color, decreases the nutritional quality of foods
and produces toxic compounds [2]. All of them can make foods less acceptable or unacceptable
to consumers [2]. Hence, the inorganic UV absorbers, such as titanium dioxide (TiO2) [27], zinc
oxide (ZnO) [2] have been attracted great attention in recent years. Among the mentioned nano
particles, TiO2 was interested as UV filter due to the optical and electrical properties, low cost,
high photocatalytic activity, chemical stability and biocompatibility [27, 28].
The main purpose of this study was preparation of an ecofriendly UV-protective food
packaging material. Furthermore, the effects of TiO2 on packaging properties of starch based
biopolymer as a food packaging material were investigated.
2. Materials and methods
2.1. Materials
Wheat starch (11-13 % moisture) was obtained from Khosheh-Zarin starch Industry (Bojnord,
Iran). Anatase TiO2 nanoparticles were supplied by Nanoshel LLC (New York, USA).
According producer data sheet the average diameter of the particles was about 20 nm. The
analytical grade chemicals including Magnesium nitrite and glycerol were purchased from
Merck Co., (Darmstadt, Germany). Sodium chloride and calcium chloride were also provided
from Dr. Mojalali Co., (Tehran, Iran).
4
2.2. Preparation of the film
A starch solution 5% (wt %) in distilled water was prepared. This solution was mixed and
heated until the starch gelatinized (80 ˚C for 60 min). Thus, plasticizer (glycerol, 40% wt% of
dry base) was incorporated into the solution to achieve more-flexible films. The suspensions of
TiO2 nanoparticles were prepared in water so that the final TiO2 content in film specimens were
1%, 3%, and 5%; (wt % of dry base). The suspensions were stirred for 15 min, and then
sonicated by ultrasonic homogenizer (Dr. Hielscher, Teltow, Germany) for 30 min. The TiO2
suspension were added to starch solution gradually and mixed for 10 min. Film forming
solutions were casted onto flat, leveled, non-stick disposable polystyrene plates with 15 cm
internal diameter and dried at room temperature. The dried films were peeled off the casting
surface. Before every analysis, the film specimens were conditioned inside desiccators
containing saturated magnesium nitrite solution to ensure a relative humidity (RH) of 50-55 % at
25 ˚C for at least 48h.
2.3. Physical characteristics
2.3.1. Film Thickness
The thickness of specimens was measured by a hand-held micrometer with an accuracy of
0.01 mm. The thickness of ten randomly selected points was measured for each specimen and the
mean value was reported for all experiments.
2.3.2. Moisture content
The moisture content (MC) of specimens was determined by measuring the weight loss of
films before and after drying in a laboratory oven (Pars Azma Co., Iran) at 105±1 ˚C until
constant weight. MC was calculated with Eq. (1) in triplicate.
W1 - W2
MC = ×100 (1)
W1
Where W1 was initial weight of specimen and W2 was weight of specimen after oven drying
2.3.3. Moisture absorption
The moisture absorption (MA) was determined (three replicates) according to the difference
weight of films before and after conditioning at relative humidity of 50-55 %. The test specimens
were prepared with the dimensions of 20 mm × 20 mm. They were first conditioned at 0% RH
(prepared by dried calcium chloride) to constant weight. After weighing (m1), they were
conditioned in a desiccator containing magnesium nitrite saturated solution at 25 ˚C to ensure a
RH of 55%. The sample was weighed at desired intervals until the equilibrium state was reached
(m2). The moisture absorption of the specimen was calculated with Eq. (2)
m2 - m1
MA = 100 (2)
m1
2.3.4. Film solubility in water
Solubility in water (SW) was defined as the percentage of the total soluble matter of film that
is solubilized after immersion in distilled water. Film specimens (20 mm × 20 mm) were dried at

5
105 ± 1 ˚C to constant weight (m3). The dried films were immersed in 50 ml of distilled water
with periodic stirring for 6 h at 25 ˚C. After that, the remaining pieces of films were removed and
dried at 105 ± 1 ˚C until constant weight (m4). The SW of the specimens was calculated using Eq
(3) in triplicate.

m3 - m4
SW = ×100 (3)
m3
2.4. Colorimetric measurements
A portable colorimeter (RGB-1002, Lutron Electronic Enterprise Co., Taiwan) was employed
to measure the color value of the film. Film specimens were placed on a black standard plate
(L*= 1, a*=0, b*=0) and the lightness (L) and chromaticity parameters a (red-green) and b
(yellow-blue) were measured. All colors can be described by L values ranging from 0 (black) to
100 (white); negative values of a (greenness) to positive values (redness); and negative values of
b (blueness) to positive values (yellowness). All Measurements were performed in four
replicates. The total color difference (ΔE) and whiteness index (WI) were calculated using Eqs
(4,5), respectively[2].

WI =100- (100- L)2 + a2 + b2 (4)

ΔE = ( L* - L)2 + (a* - a)2 + (b* - b)2 (5)

2.5. Water Vapor Permeability (WVP)

ASTM E96 standard was used for measuring the WVP of specimens films [29]. Special glass
vials with the diameter of 13 mm and the height of 45 mm, containing calcium chloride desiccant
(0% RH, assay vial) or nothing (control cup), were used to determine WVP of the films. The
vials were covered with film specimens and sealed to the vial mouths using with double side
tape. Each vial was placed in a desiccator maintained at 75% RH with a saturated solution of
sodium chloride (Dr Mojallali Co., Tehran, Iran). The difference in RH corresponds to a driving
force of 1753.55 Pa, expressed as water vapor partial pressure. After that the films were attached,
the weight gain of the whole assembly was periodically recorded (with an accuracy of 0.0001 g)
every 1 h during the first 12 h and continued up to stationary phase (after 96 h). The slope (S) of
the linear region of weight vs. time plot (R2≥ 0.986) was divided by the effective film area (A) to
obtain the water vapor transmission rate (WVTR) Eq. (6). This was multiplied by the thickness
of the film and divided by the pressure difference between the inner and outer surfaces to obtain
the WVP Eq (7). Three replicates of each film treatment were tested for WVP measurement.

S
WVTR = (6)
A
WVTR×X
WVP = (7)
ΔP

6
 Where A is the effective film area, X is the average film thickness (m) and ΔP is the driving
force (1753.55 Pa).
2.6. Mechanical properties
According to ASTM standard method D882-02 [30] with a slight modification by a
mechanical evaluation device (STM-250, Santam Co., Iran) was used to measure tensile strength
(TS), elongation at break (EB), tensile energy to break (TEB), and Young’s modulus (YM) of the
preconditioned films. Films were cut in rectangular strips of 100 mm length and 10 mm wide.
All film strips were conditioned at 55% RH for at least 48 h in a desiccator using saturated
magnesium nitrate solution. The films were mount with an initial grip separation of 50 mm and
stretched at a cross-head speed of 10 mm/min. In contrast to ASTM standard method, three
replicates were run for each film specimen. TS, EB and TEB were calculated by Eqs (8-10),
respectively.
FMax
TS = (8)
AMin

LMax
EB = ×100 (9)
L0

TEB = AStress-Strain (10)

Where FMax is maximum load, AMin is minimum cross section area, LMax is extension at the
moment of rupture, L0 is initial length of specimen, AStress-Strain area under stress–strain curve.

YM was calculated by drawing a tangent to the initial linear portion of the force extension
curve, selecting any point on this tangent and dividing the tensile stress by the corresponding
strain, Eq (11).

stress
YM = (11)
strain
2.7. Microstructural
The morphology of the surface area and cross sections of the specimen films were observed
by field emission scanning electron microscope (FE-SEM, Hitachi, S4160; Japan) with the
accelerating beam at a voltage of 30 kV. The cross sections were prepared by breaking the films
in liquid nitrogen and mounted on aluminum stubs using a double-sided tape. Then, the film
specimens were sputtered with gold using a KYKY-SBC-12 sputter coater.
2.8. Thermal properties
The thermal properties of the composite films were measured using differential scanning
calorimetry (DSC) equipment (DS1, Mettler Toledo; Switzerland) according to ASTM standard
method D3418-08 [31] . Nearly 5 mg film sample was cut and sealed into a sample pan of DSC
equipment, using a sealed empty aluminum pan as reference sample. All samples were scanned
at a heating rate of 10 ˚C /min between temperatures ranging from -50 ˚C to 220 ˚C. The

7
nitrogen gas was used as the purge gas at a flow rate of 20 ml/min. The glass transition
temperatures (Tg) of the film specimens were determined as the midpoint temperature of a step-
down shift in baseline thermograms. The melting point (Tm) was determined as the temperature
where the peak of the endotherm occurs.
2.9. Contact angle
Sessile drop method used for Contact angle measurements. A 5 µl droplet of water was placed
on the film surface. The image of the drop was captured using a digital camera (AM2111, Dino-
Light, Taiwan). The contact angle is defined as the angle between the baseline of the drop and
the tangent line at the point of contact of the water droplet with the surface [32]. Image J
software (version Java 1.6.0_05) was used to estimate the contact angle.

2.10. UV-Vis spectroscopy

The UV–visible spectra of the starch and starch/TiO2 nanocomposites were recorded using a
UV-2600 spectrophotometer (SPECORD 250 UV/ VIS, Germany) from 200 to 800 nm.
2.11. Statistical analysis
The results obtained from all experiments were analyzed on a completely randomized design
with the analysis of variance (ANOVA) procedure using SPSS software (Version 16; SPSS Inc.,
USA). Duncan’s multiple range tests were used to compare the difference among mean values of
film specimens’ properties at P<0.05.
3. Results and discussion
3.1. Microstructure
Figure 1 shows the surface and cross-section of the starch film and starch nanocomposites. AS
be shown, the surface of starch film was smooth and homogenous. There was no significant
difference between starch and starch/TiO2 (1%) nanocomposite. After that the aggregated nano
TiO2 was appeared on surface of starch/TiO2 nanocomposite (Figure 1-S). It confirmed that there
was no good affinity between starch matrix and TiO2 nanoparticles at high content of nano
particles (3%, 5%). The aggregation of TiO2 was increased with increasing TiO2 content. The
surface appearance of nanocomposites become rougher with increased TiO2 content,
consequently. This is due to the high surface energy of nano particles[2]. Such an occurrence
was observed at cross-section of the specimens. It is agree with previous researches [7, 21].

8
Figure 1. Scanning electron micrographs of the surface (S) and cross-section (C) of: 1) starch, 2)
starch/TiO2 (1%), 3) starch/TiO2 (3%), 4) starch/TiO2 (5%)

3.2. Color
Table 1 presents haunter color parameters (L, a, and b), ∆E, and WI of the starch and
starch/TiO2 nanocomposites films. All color values were depend on TiO2 content, except a value.
L value, ∆E, and WI were increased with increasing TiO2 content. But b value was decreased,
simultaneously. It is clear from the photos taken from the samples (Figure 2) and the colorimeter
data (Table 1) with increasing TiO2 content, the color of the films was tended to be white and
simultaneously L value of the films was increased. Our result was contradictory with the
observations of Teymourpour et al [33], who reported that the incorporation of TiO2
nanoparticles in the soluble soybean polysaccharide film was led to the decrease of L and
increase of a and b. On the other hand, Zolfi et al [34], reported that the presence of TiO2
nanoparticles in the film prepared with kefiran/whey protein led to the increase of WI and
decrease of ∆E. It seem different results in color of the biopolymer film may be due to the

9
difference in the type of biopolymer, the crystallite type of nano TiO2, the preparation method,
the thickness of film and the size of TiO2.
Table 1. Hunter color values (L, a, and b), total color difference (∆E), and whiteness
index (WI) of starch and starch/TiO2 nanocomposite films ‡,*
TiO2 content
L a b ΔE WI
(%)
0 7.93±1.17d -0.80±0.40a 0.25±0.07a 6.90±1.20d 7.93±1.17d

1 57.55±1.27c -0.69±0.50a -1.46±0.48c 56.49±1.27c 57.52±1.26c

3 73.38±1.52b -0.68±0.31a 1.01±0.22bc 72.30±1.52b 73.35±1.52b

5 84.12±0.87a -0.90±0.72a 0.33±0.02ab 83.03±0.86a 84.06±0.91a

‡
Means within each column with the same letters are not significantly different (P<0.05)
* Data are means ± SD

Figure 2. Photo taken from the of the a) starch, b) starch/TiO2 (1%), c) starch/TiO2 (3%), d)
starch/TiO2 (5%) with backlight

3.3. UV-Vis spectroscopy

10
 The visual properties of starch and starch/TiO2 bionanocomposites are shown in Figure 2. As
shown, the transparency of film specimens against visible light was decreased with increasing
TiO2 content.
UV-Vis spectra of the film specimens were shown in Figure 3. There was drastically
difference between the absorption of starch and the bionanocomposites in visible and UV region.
It confirmed the visual properties of the film specimens (Figure 2) and UV protective properties
of the starch/TiO2 bionanocomposites. TiO2 is a direct wide-band-gap semiconductor with a
band gap of 3.05 eV [35]. An absorption peak was found at 340 nm for the nanocomposite
polymers, and the intensity of the peak increased with increasing TiO2 content. However the
absorption of bionanocomposites was increased with increasing TiO2 content from 200 nm to
800 nm. But this difference was highly depend on TiO2 content in UV-B region (280 nm to 315
nm). The free radical formation under the UV light can be reduced the quality of food by
destruction of antioxidants, oxidation of lipids, destruction of nutrients, changes in color, and
formation of off-flavors [36, 37].

Figure 3. UV-visible absorption spectra of Starch and Starch/TiO2 nanocomposite films

3.4. Contact angle

Contact angle measurements can be a good way to determine hydrophilic and hydrophobic of
the surface. A high water contact angle indicates higher hydrophobicity of the surface and vice
versa Figure 1 (S1-S4) and Table 2 shows the water droplet and the contact angle of the
specimens, respectively. As shown at Table 2, the contact angle of starch based nanocomposite
was increased at low TiO2 content (1%), significantly. Subsequently, it was decreased with

11
increasing TiO2 content to 3%. After that, there was no significant difference between contact
angles of starch/TiO2 (3% and 5%) bionanocomposite. As shown at Figure 1 (S1-S4), the
aggregated TiO2 nanoparticles were appeared on the surface. It seems, the aggregated particles
were decreased the contact angles at high level of TiO2 (3%, and 5%). Whereas at 1% of TiO2,
homogenous dispersion of nano particles in matrix of polymer (Figure 1) and good interaction
between hydrophilic substituent of starch and TiO2 nano particles were increased the contact
angle, drastically. Similar findings were reported by El-Wail et al [38].

Table 2. Physical properties and Contact angle of starch and starch/TiO2 nanocomposites
incorporated with various TiO2 content‡,*
TiO2 Moisture Moisture Solubility in Contact
Thickness
content Content absorption water angle
(mm)
(%) (%) (%) (%) (degree)
0 0.14±0.00a 18.16±1.29a 13.94±0.24a 18.84±0.43a 87.67±2.52b
1 0.13±0.00a 16.39±1.17a 11.71±0.40b 18.70±0.85a 111.23±5.57a
3 0.12±0.01b 17.35±0.77a 11.55±0.30b 17.21±0.19b 85.67±3.06b
5 0.11±0.01b 17.74±0.80a 11.51±0.70b 16.88±.020b 84.67±3.06b
‡ Means within each column with the same letters are not significantly different (P<0.05)
* Data are means ± SD

3.5. Thickness, moisture content, water-absorption, and solubility

A great drawback to the use of biopolymer materials is moisture sensitivity; thus, any increase
in water resistance of biopolymers was the main purpose of several studies [1, 6, 7, 39].Table 2
shows the thickness, MC, MA, and SW of film specimens.
The thickness of starch film was about 0.14 mm. The thickness of film specimens was
decreased with increasing nano TiO2 content. As regards, the change was not significant at low
TiO2 content (1%). After that there was a significant difference between starch/TiO2 (1%) and
other starch/TiO2 (3% and 5%) bionanocomposites. But the difference was not significantly
between starch/TiO2 (3%) and starch/TiO2 (5%) films. There were several inconsistency in
dependence of the thickness of nano composite films to nano filer content in previous studies [2,
7, 26] . It seems, it was related to incorporation of nano filer and polymer matrix. Nevertheless,
nano filer content was an effective parameter on the thickness of nano composites in current
study.
However MC of film specimens was independent from TiO2 content. But MA, and SW was
depend on TiO2 content. Some researchers believed that MC is related to the total void volume

12
of water molecules in the microstructure of the film [40]. Furthermore, it seems the created
interaction between matrix of polymer and nano filler, were hindered diffusion of water
molecules in the composites [22]. Consequently, MA of starch/ TiO2 films was decreased.
SW of the film specimens was independent from TiO2 content at low amount of nano filler
(1%). After that SW of the film specimens was decreased at high TiO2 content (3% and 5%),
significantly. But the difference was not significantly between starch/TiO2 (3%) and starch/TiO2
(5%) films. It was reported in previous studies [2, 7]. It seems the formation of a network
structure between TiO2 and starch could be increased the interaction among the polymer chains,
and inhibited the scission of these chains in water solutions [22].
There was some inconsistency between the effects of nano fillers on water resistance of
bionanocomposites [2, 4, 7, 22]. It seems nano filler content, and the type of nano filler and
biopolymers were effective parameters in sensitivity of bionanocomposite to water. The
mentioned result was agree with the contact angle of film specimens (Table 2).
3.6. Water vapor permeability
One of the most important packaging property is often to avoid or at least to decrease the
moisture transfer between food and the surrounding atmosphere. Therefore, the WVP of the
packaging material should be as low as possible [21]. During WVP measurement no lag phase
before steady-state rate was observed. It seems, it was due to the hydrophilic properties of starch film and
the long step times (1h) (data was not shown).

Figure 4 shows the change of WVP at different nanoparticles content. WVP of starch/TiO2
nanocomposites was decreased with increasing TiO2 content from 0% to 1% and 3%,
significantly. Then by increasing TiO2 content (5%), WVP of specimens was increased.
Nevertheless, WVP of starch/TiO2 nanocomposites (5%) was lower than starch film. The
previous studies showed the reducing effect of TiO2 nanoparticles on water vapor barrier of some
biopolymers [7, 21, 41]. It seems, the formation of hydrogen bonds between Ti–O and hydroxyl
groups of starch was the main reason in decreasing of WVP with increasing TiO2 content [21].
But at the high TiO2 content (5%), aggregated nano particles destroyed the structure of
nanocomposite (Figure 1). Consequently, the WVP of the specimen was increased.

13
 Figure 4. Effect of TiO2 content on water vapor permeability (WVP) of starch film and
Starch/TiO2 nanocomposites. Mean values with different letter are significantly different
(P<0.05).

3.7. Mechanical properties

Packaging materials may be subjected to various type of mechanical stress during use,
therefore determination of mechanical properties is necessary. The amounts of TS, EB, YM and
TEB of starch and starch/TiO2 nanocomposites films are shown in Table 3. TS of starch/TiO2
nanocomposite was independent from TiO2 content. With increasing TiO2 content, the EB and
the TEB of the nano- composites were increased. But, YM was decreased, simultaneously.
Despite of increasing EB and decreasing YM with increasing TiO2 content, there was no
significant difference between the EB and the YM of starch/TiO2 nanocomposites. With
increasing TiO2 content from 1% to 3%, there was no significant difference between the TEB of
starch and starch/TiO2 nanocomposites. Afterward TEB of starch/TiO2 nanocomposites (5%)
was increased. However, there was no significant difference between the TEB of starch/TiO2
nanocomposites. But, it was significantly more than starch film. This could be attributed to
reducing crosslinking in the matrix of nanocomposites and increasing mobility of chains and the
preventative effect of nanoparticles on strain hardening of the polymer chains after cold
drawing [42]. Furthermore, some researchers believed, the weak affinity between nano filler and
matrix of polymer were led to lubricant surface between polymer chains like a ball bearing. It
was increased the mobility of polymer chains and make the movement of nanocomposite chains
easier than that for virgin polymer chains [2]. It seems, the mechanical properties of
nanocomposites depend on the polymers and nano filers type [2, 7, 20].

14
Table 3. Effect of TiO2 content on the mechanical properties of starch and starch/TiO2
nanocomposite films‡,*
TiO2 Tensile Tensile
Elongation at Young’s
content strength energy to
Break (%) modulus (MPa)
(%) (MPa) break (MJ)
0 5.74±0.22a 35.84±2.39b 120.22±8.27a 1.01±0.20b
1 5.51±0.47a 40.44±3.28a 92.30±8.19b 1.80±0.29ab
3 5.34±0.71a 42.50±4.05a 81.07±7.16b 1.78±0.58ab
5 5.27±0.49a 50.94±3.56a 86.91±3.12b 1.95±0.28a
‡
Means within each column with the same letters are not significantly different (P<0.05)
* Data are means ± SD

3.8. Thermal properties

Thermograms of starch and starch/TiO2 nanocomposite films are shown in Figure 5. Tg is the
temperature at which the material undergoes a structural transition from an amorphous
solid state (glassy state) to a more viscous rubbery state. Below Tg, films are rigid and
brittle, whereas above Tg they become flexible and pliable [43]. Tm shows the requirement
energy to disrupt the crystal lattice of a polymer [44]. Starch is a semi-crystalline polymer that
does not melt in the traditional sense to form a liquid; its melting does mean loss of crystallinity
due to disruption of hydrogen bonds [20].
Tg of the film specimens was increased with increasing TiO2 content. It may be due to the
fact that TiO2 could be form chemical bonds with hydroxyl group substituent of starch chains
[45]. On the other hand, Tm of film specimens was reduced with increasing TiO2 content. The
Tm of starch film was 186.67 ◦C, by increasing the TiO2 content from 0% to 3%, the Tm was
decreased to 172.33 ◦C. Our results were inconsistent with previous studies [2, 4, 7]. It may be
due to the size and type of the nanofiller, the type of polymer, and homogeneity of nanofiller in
polymer matrix.

15
 Figure 5. DSC thermograms of starch and starch/TiO2 nanocomposite films

4. Conclusion
The main purpose of the current study was develop an ecofriendly UV-protective bio-
nanocomposite. TiO2 content was an effective parameter on decreasing the sensitivity of starch
based nanocomposites to water (MA, WS, and WVP). Furthermore, UV-Vis spectrum of the film
specimens confirmed UV-protective properties of starch/TiO2 against UV-A, UV-B, and UV-C
region. As well as the mechanical and thermal properties of starch based nanocomposite was
depend on TiO2 content. Therefore, the starch/TiO2 bionanocomposites can be candidate as a
UV-shielding food packaging material. Ecofriendly ingredients of starch/TiO2
bionanocomposites rectified the environmental pollution of this packaging material.
Acknowledgment
The authors are grateful to the University of Zanjan and the Iranian Nanotechnology Council
for providing financial aid for this research. We would like to acknowledge the extraordinary
suggestions Dr. Mehrnaz Zargham.

16
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