International Journal of Biological Macromolecules 120 (2018) 2007–2016

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Effect of film constituents and different processing conditions on the

properties of starch based thermoplastic films
C. Chandra Mohan, K. Harini, S. Karthikeyan, K. Sudharsan, M. Sukumar ⁎
Centre for Food Technology, Anna University, Sardar Patel road, Guindy, Chennai 600025, Tamilnadu, India

a r t i c l e i n f o a b s t r a c t

Article history: The main aim of this study is to examine the different film preparation methods (Hot air oven method, Micro-
Received 27 August 2018 wave oven method, and UV irradiation method) for development of Bio-thermoplastic films from agro waste
Received in revised form 4 September 2018 polysaccharides. The rheological properties were also studied for different combinations of tamarind seed starch
Accepted 25 September 2018
(T), okra mucilage polysaccharide (OK), Residual rice bran starch (R) and sugarcane bagasse cellulose (C). In-
Available online 26 September 2018
crease in concentration of okra mucilage polysaccharide and sugarcane bagasse cellulose found to highly influ-
Keywords:
ence the rheological viscous properties of tamarind starch solution. Increase in concentration of okra mucilage
Polysaccharides (above 1.5%) in tamarind film matrix solution significantly increased the elongation properties of starch films. In-
Tamarind seed starch crease in concentration of cellulose (above 1%) in tamarind film matrix solution significantly increased the tensile
Bio-thermoplastic films strength of starch films. The microwave oven method was found to be the quickest method (~10 to 20 min) for
Microwave treatment biopolymer film preparation. SEM and AFM analysis revealed that UV – irradiation method produces stable bio-
Ultraviolet treatment thermoplastic films with low surface roughness and high barrier properties. The interaction of starch molecules
Surface properties with other natural polysaccharide produces stable thermoplastic biopolymer films, that can be developed under
different processing conditions to eradicate environmental pollution caused by petrochemical plastics.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction -D‑xylopyranose linked (1-6) to glucose residues. Mucilage of okra con-

Accumulation of synthetic petrochemical-based plastics has been a
huge concern for environmental welfare. To eradicate this concern,
many researchers have worked on the development of different biolog-
ical based natural polymers [1–4]. Environmentally abundant polymers
such as starch and cellulose have been under rigorous study to replace
the existing synthetic polymers [2,3,5]. Potential starch and cellulose-
based polymers were found to have high thermal properties, thus
they were called as Bio-thermoplastics. Bio-thermoplastics are environ-
mental friendly plastics, composed of naturally existing polymers or bi-
ologically produced polymers. These Bio-thermoplastics can be
disintegrated into their simple forms of monomers by soil and atmo-
spheric microbes, thus they preserve the environment from pollution.
Starch-based biopolymer films are produced, mainly depending on
the gelatinization properties of the starch molecules. After gelatiniza-
tion, rheological properties of starch matrix solution play a major role
in film casting and formation [1,6]. Rheological properties are also im-
portant for scale-up operation in pilot and industrial level production
of starch-based bio-thermoplastic films [7,8]. The tamarind starch mol-
ecules composed of (1‑4)‑β‑D‑glucan backbone substituted with side
chains of α‑D‑xylopyranose and β‑D‑galactopyranosyl (1‑2)- α
⁎ Corresponding author.
E-mail address: sukumar@annauniv.edu (M. Sukumar).
tains polysaccharide with repeating units of α - (1‑2)‑rhamnose and α -
(1-4)‑galacturonic acid residues. Cellulose is high molecular weight
homopolysaccharide composed of β‑1, 4‑anhydro‑D‑glucopyranose
units. The interaction between these natural polymers can significantly
influence the overall rheological properties of starch film matrix.
The difference in processing and preparation methods, highly influ-
ence the characteristics of Bio-thermoplastic films. Gelatinization,
crosslinkers, plasticizers, gelling and gumming agents are some of the
processing and preparation methods which have been studied and val-
idated by many researchers. Hot air oven is the drying method, which
can be employed to remove moisture, from the film matrix to produce
biopolymer films [1,9]. Microwaves are high energy waves, which disso-
ciates the bond between hydrogen and oxygen to release a large
amount of heat. This, in turn, facilitates the evaporation of water mole-
cules from the film. UV irradiation is the most important non-thermal
method to facilitate the interaction between different molecules in the
reaction [10]. Thus, all three above mentioned, film preparation
methods should be studied in detail for commercialization and industri-
alization of Bio-thermoplastics production. The interaction between
polysaccharides can vary depending on the processing conditions,
which in turn may affect the overall properties of Bio-thermoplastic
films. In this study, hot air oven, microwave, and UV irradiation
methods have been investigated to improve the characteristics of
starch-based bio-thermoplastic films.

https://doi.org/10.1016/j.ijbiomac.2018.09.161
0141-8130/© 2018 Elsevier B.V. All rights reserved.
2008 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016
Mechanical properties and gas permeability are the two most im-
portant parameters of any packaging film [1,9]. Especially bio-
thermoplastic films have to be produced and modified in such a way
to meet the standards of existing synthetic polymers, for replacing
them. Optimization study on combination of different polysaccharides
may be the ideal solution to match the existing synthetic polymer stan-
dards. Surface properties of bioplastic films play a major role in defining
its mechanical and gas permeability properties. Smooth surfaces tend
to provide a barrier for diffusion of gases and moisture through
the Bio-thermoplastic films. Thus surface roughness studies of Bio-
thermoplastic films gains its importance [11]. Processing conditions
for production of Bio-thermoplastics can influence its surface rough-
ness, mechanical and gas permeability properties.
The main aim of this study is to examine the rheological properties
of different polysaccharide combinations for Bio-thermoplastic film
preparation. It is also the aim of this study to investigate the effect of dif-
ferent processing conditions on the Mechanical property, Gas perme-
ability and Surface roughness property of Bio-thermoplastic films.
2. Materials and methods
2.1. Overview of our initial study
Different agro-industrial waste materials were subjected to extrac-
tion of polysaccharides. The extracted polysaccharides were character-
ized thoroughly for its bio thermoplastic ability through morphology,
thermal stability, crystallinity and chemical composition analyses [12].
2.2. Work elaborated in this manuscript
This manuscript is the continuation of our initial work. This work
was carried out in three parts, First: Preparation of film matrix solutions
in different concentrations and combinations from extracted polysac-
charides. Second: Study on rheological properties of film matrix solu-
tion. Third: Study on the effect of different processing conditions (Hot
air oven, Microwave oven, and Ultraviolet irradiation) on the different
properties of Bio-thermoplastic films.
2.3. Preparation and characterization of bio-polymer film solution
2.3.1. Preparation of film casting solutions
Tamarind seed starch at varying concentrations (2, 4 & 6 g/100 mL)
was taken as a major matrix for preparation of biopolymer films. Resid-
ual rice bran starch at varying concentrations (2, 4 & 6 g/100 mL), Okra
mucilage polysaccharide at varying concentrations (1, 1.5 & 2 g/100 mL)
and sugarcane bagasse cellulose at varying concentrations (1, 1.5 &
2 g/100 mL) were added as a supplement, gumming and reinforcing
agents, respectively, for production of biopolymer films. Thus, each
starch concentration of T was mixed with three different concentrations
of R, OK and C. Prepared film matrix solutions were subjected to gelati-
nization at 95 °C for 30 min.
2.3.2. Measurement of film casting solution visco-pasting properties
Pasting viscosities of Bio-thermoplastic film solutions was estimated
using DVII+ Pro Brookfield Viscometer (Brookfield Viscometers Ltd.,
Harlow, UK). S60 spindle was used to measure the viscosity. The sus-
pension was equilibrated to 50 °C at 100 rpm stirring for 10 s, heated
to 95 °C at the rate of 15 °C/min and held at 95 °C for 23 min. The sus-
pension was cooled to 50 °C at the same rate and held for 9 min. The vis-
cosity was measured in cP (centipoise). [13,14]
2.3.3. Spreadability analysis
Spreadability profile of film casting solutions was analyzed using TA-
XT plus (Stable Micro Systems, Surrey, UK), texture analyzer. Spread-
ability was measured with a conical spreadability rig (Model HDP/SR,
Stable Micro Systems, Ltd.) at room temperature (25 ± 2 °C). Samples
were filled into female cones to avoid air pockets and leveled to
obtain a uniform surface. Each sample was penetrated with a corre-
sponding male cone to a distance 2 mm from the bottom of the sample
holder. The instrument was operated at test speed = 3 mm/s, post-test
speed = l0 mm/s, and distance = 30 mm with automatic detection of
the force with a 50 kg load cell (trigger force = 5 g force). Spreadability
parameters such as firmness and adhesiveness were evaluated. [15]
2.4. Film preparation
100 mL of gelatinized film matrix solutions were mixed with 1.5 mL
of glycerol (plasticizer). These solutions were made to cast over glass
Petri dishes (15 cm dia). Hot air oven method: Film matrix solutions
were incubated at different temperature conditions (40, 60 & 80 °C)
for 3–4 h. Ultraviolet irradiation method: The Petri-dishes were incu-
bated at room temperature in UV-Chamber (Heber Scientific, India) at
365 nm (Intensity of 1000 ± 35 mW/cm−2) for 24–36 h. Microwave
method: The Petri-dishes were subjected to microwave treatment
using a microwave oven (Whirlpool Corporation, US) at different
power ranges (175 W, 350 W & 525 W) for 15–20 min.
2.5. Characterization of biopolymer films
All the film samples were conditioned at constant 50% humidity for
10–15 days, before performing characterization analyses. This condi-
tioning was done to avoid any errors in characterization parameters,
due to moisture sorption capacity of starch films.
2.5.1. Oxygen transfer rate
The oxygen transmission rate was determined using an Ox-Tran
Modular System at 23 °C and 50 ± 1% RH. The samples were equili-
brated at 50 ± 1% RH (23 ± 1 °C) for a period of 48 h before analysis.
Film samples were placed on a stainless-steel mask with an open test
area of 5 cm2. On one side of the film, 100% oxygen gas was flowing
with nitrogen gas (98% N2 and 2% H2) on the other side. Nitrogen gas
was conducted with the colorimetric sensor and measurements were
obtained when a steady state was reached. The relative humidity of
both gases was controlled by a humidifier and varied from 50 to 90%.
The permeability analysis was not performed below RH 50% because
the starch films began cracking at these lower RH levels. Oxygen perme-
ability was calculated by dividing O2 transmission rate by the difference
in O2 partial pressure between both sides of the film (101 kPa) and mul-
tiplying by the average thickness of the film (μm). [11]
2.5.2. Mechanical properties
Tensile strength (TS) (Mpa) and elongation at break (EB) (%) param-
eters (mechanical properties) were measured using the Universal Test-
ing Machine (DL 10000) (Thechnosys Instruments) according to the
standard testing method ASTM D882-97. [1]
TS (Mpa) was calculated by the following equation:
Fmax
TS ¼ ð1Þ
A
where, Fmax is maximum load (N) needed to pull the sample apart; A is a
cross-sectional area (m2) of the samples.
EB (%) was calculated by the following equation:
 
L
EB ¼  100 ð2Þ
25
where, L is film elongation at the moment of rupture (mm); 25 is initial
grip length (mm) of samples.
 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016
2.5.3. Swelling properties
Swelling capacity was evaluated by immersing pre-weighed dry
films (wti) of 1 × 1 cm into 100 mL of Phosphate buffer saline solution
at 4 °C under shaking. The weight gain of swollen films (wtf) was mea-
sured after 30 min, by gently blotting the surface with Whatman paper.
The average of three determinations is reported. The degree of swelling
(% Sw) was evaluated using the following equation [16,17]:
 
wt f −wti
%Sw ¼  100
wti
2.5.4. Water vapor permeability test
Water vapor permeability of films was estimated according to the
method described in our previous study [4]. Film samples were used
to seal a hole on the top of a plastic cell. The plastic cell, containing dis-
tilled water, was loaded into a desiccator. The desiccator was placed into
a chamber at 25 °C for 24 h. At least three weights of the cell were taken
during the 24 h of storage. Water vapor permeability was calculated
with Eq. (4).
Δm:l
WVP ¼
A:Δt:Δp
where, Δm/Δt - the weight of moisture loss per unit of time (g s−1), A –
film area exposed to moisture transfer (m2), l – film thickness (μm), p –
water vapor pressure difference between the two sides of the film (Pa).
ΔRH
Δp ¼ p ð5Þ
100 vap:sat
Linear regression was used to estimate the slope of the g s−1 plot. p
was calculated according to Eq. (5), where p vap sat was the saturated
vapor pressure of pure water and equals to 3160 Pa at 25 °C. RH was
the relative humidity gradient between the cell and the surroundings.
2.5.5. Fourier transforms infrared spectroscopy
Fourier transform infrared spectroscopy (FTIR) was used to deter-
mine the chemical bonds, present in produced Bio-thermoplastic
films. The FTIR analysis was performed using Carry 660 (Agilent Tech-
nologies, USA) model FTIR with film samples dispersed in the pellet of
KBr. The dried film samples (0.3–0.5 mg) were ground in about 80 mg
of spectral grade KBr (Sigma) and pressed into pellets using a hydraulic
press. The spectral measurements were carried out in an absorbance
range of 400–4000 cm−1 with plain KBr pellet as the background refer-
ence [4].
2.5.6. Scanning electron spectroscopy
The surface micrographs of starch films were obtained through a
scanning electron microscope (HITACHI-S3400N, Japan). The films
were placed on the surface of a double-sided tape which is attached to
a stub. The images were taken at an accelerating potential of 15 kV in
different magnifications [4].
2.5.7. Atomic force microscopy
Atomic force micrographs of Bio-thermoplastic films were taken
using Park XE-100 AFM (Park systems, Korea) at contact mode. Several
measurements were taken for (50 μm × 50 μm) area over film surface.
Statistical parameters: Average maximum height of roughness (Rtm),
Average maximum roughness valley depth (Rvm), average roughness
(Ra) and root mean square roughness (Rq) were calculated to estimate
the roughness of films quantitatively. [11]
3. Results and discussions
In this study, Tamarind seed starch, Okra mucilage polysaccharide,
Residual rice bran starch and Sugarcane bagasse cellulose extracted in
2009
our previous study [12], was used for Bio-thermoplastic film prepara-
tion. Average particle size and crystallinity index of Tamarind seed
starch, Okra mucilage polysaccharide, Residual rice bran starch and Sug-
arcane bagasse cellulose was estimated to be (55 μm, 31.07%), (115 μm,
28.95%), (70 μm, 28.55%), and (120 μm, 73.21%), respectively [12].
3.1. Pasting viscous properties of biopolymer film solutions
Different polysaccharides extracted from agro-industrial wastes in
ð3Þ
our previous study [12], were subjected to film matrix production.
Thus produced film matrix solutions were examined for its rheological
properties through analysis of viscosity and spreadability. Pasting vis-
cosity properties of different polysaccharide film matrix solutions are
tabulated in Table 1. Starch undergoes gelatinization on heating with
water, thus releases linear amylose chains from complex starch struc-
ture [18]. The interaction between these amylose molecules plays a
vital role in the production of stable Bio-thermoplastic films [1,4].
Among extracted polysaccharides, both tamarind and residual rice
bran were found to have a high amount of starch thus, they were inves-
tigated for potential film-forming properties. Generally, starch mole-
cules exhibit three states of viscosity during gelatinization (on
ð4Þ increase in temperature), namely peak viscosity, setback viscosity and
final viscosity. Initial peak viscosity is due to sudden increase of viscosity
during absorption of water molecules in the solution by starch mole-
cules [8]. Set back viscosity corresponds to the retrogradation of starch
molecules which releases the absorbed water molecules, which in
turn reduces the viscosity [7,19]. Final viscosity is the permanent viscos-
ity of the starch solution after retrogradation [8,19]. Among investigated
starch film matrix solutions, tamarind seed starch was found to have a
high peak, setback and final viscosities (P b 0.05) in all three investi-
gated concentrations. Especially high setback viscosity values of tama-
rind seed starch directly implicate high amount of amylose content
[7,8]. Thus tamarind seed starch was selected as potential Bio-
thermoplastic film matrix solution, and rice bran starch was taken as a
supplement for the film matrix solution. Pasting properties of Okra mu-
cilage polysaccharide mixed tamarind starch solutions showed signifi-
cant (P b 0.05) increase in peak viscosity. This may attribute to the
high amount of water absorbing fibers in okra mucilage polysaccharides
[13]. These high water absorbing fibers present in okra mucilage takes
up the free water molecules present in T + OK solution, which reduces
its free-flowing nature. Thus, an increase in the concentration of okra
polysaccharides in tamarind starch solution, significantly (P b 0.05) in-
creased the peak viscosity. Hassan [20], has studied the interaction be-
tween okra mucilage and starch and reported that okra mucilage
alters the conformation of amylose and amylopectin chains in starch.
Setback viscosity and final viscosity of T + OK solution showed signifi-
cant (P b 0.05) increase only in higher concentrations of tamarind
seed starch. This implies that SV and FV of T + OK solution highly
depended on amylose content of tamarind seed starch, rather than
okra mucilage. Sugarcane bagasse cellulose is highly crystalline in na-
ture, and they are not water soluble. But even then amorphous regions
of cellulose (containing hemicellulose) interacts with water molecules
[21] and which may facilitate the increase in pasting properties of T
+ C solutions. Sugarcane bagasse cellulose mixed tamarind seed starch
solution showed significant (P b 0.05) increase in peak and final viscos-
ities, which may attribute to the increase of total dispersed solids in so-
lution. Averous et al. [22] studied the interaction between cellulose and
starch in composite and reported that there is a strong interaction be-
tween cellulose fibers and starch molecules which in turn may even in-
crease the thermal stability of the cellulose starch composite. Residual
rice bran starch was found to be rich in starch and fiber [12]. Even
though the amylose content of rice bran starch was examined to
be low, these starch molecules may influence the pasting properties of
T + R solutions. Like cellulose, residual rice bran starch mixed tamarind
seed starch solutions also showed significant (P b 0.05) increase in peak
and final viscosities, this may attribute to increase in amylose content
2010 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016

Table 1
Pasting viscosity properties and spreadability (Firmness & Adhesiveness) of polysaccharide solutions in different combinations.

Constituents Concentrations Peak viscosity Setback viscosity Final viscosity Firmness Adhesiveness

Unit Centipoise (cp) Fmax (N) N.s

T 2% 2503.22 ± 74.21a 2157.33 ± 49.28a,c 2748.47 ± 84.27a,c 0.68 ± 0.11 1.36 ± 0.43
4% 2857.64 ± 49.32a 2511.74 ± 52.49a,c 2987.54 ± 47.85a,c 1.06 ± 0.24 2.46 ± 0.54
6% 3148.76 ± 85.47a 2746.55 ± 48.76a,c 3347.48 ± 73.57a,c 1.85 ± 0.34 3.44 ± 0.58
OK mixed 2% T 1% 3847.94 ± 63.47b 2214.74 ± 38.41d 2849.26 ± 43.52d 1.24 ± 0.76 2.29 ± 0.27
1.5% 3986.24 ± 54.77b 2349.71 ± 45.63d 2895.77 ± 61.49d 1.68 ± 0.28 3.11 ± 0.38
2% 4124.63 ± 57.64b 2485.67 ± 34.74b 2947.28 ± 54.33d 1.94 ± 0.31 3.99 ± 0.19
OK mixed 4% T 1% 4596.37 ± 61.47b 2698.74 ± 51.27d 3274.76 ± 37.49b 1.89 ± 0.61 3.76 ± 0.24
1.5% 4873.85 ± 73.49b 2847.67 ± 73.28b 3541.27 ± 47.11b 2.06 ± 0.22 4.13 ± 0.37
2% 5760.69 ± 54.63b 3147.67 ± 39.99b 3974.76 ± 49.67b 2.38 ± 0.41 4.87 ± 0.41
OK mixed 6% T 1% 5874.49 ± 44.76b 3268.46 ± 75.35b 4132.25 ± 71.36b 3.11 ± 0.62 5.37 ± 0.57
1.5% 6147.65 ± 52.19b 3495.85 ± 47.85b 4674.73 ± 65.85b 3.86 ± 0.71 6.19 ± 0.43
2% 6735.94 ± 61.84b 3749.67 ± 75.69b 4936.41 ± 57.67b 4.27 ± 0.47 7.24 ± 0.68
C mixed 2% T 1% 2849.74 ± 63.51b 2199.35 ± 47.35d 2947.61 ± 43.27d 0.90 ± 0.57 2.13 ± 0.34
1.5% 3085.47 ± 49.22b 2298.74 ± 59.68d 3149.21 ± 29.47b 1.11 ± 0.28 2.59 ± 0.47
2% 3197.41 ± 61.34b 2386.41 ± 49.67b 3317.63 ± 44.28b 1.31 ± 0.37 2.95 ± 0.27
C mixed 4% T 1% 3114.57 ± 62.87b 2668.48 ± 57.95d 3242.54 ± 64.35b 1.23 ± 0.41 2.27 ± 0.56
1.5% 3297.11 ± 49.33b 2887.45 ± 41.38b 3426.47 ± 28.64b 1.46 ± 0.52 2.73 ± 0.32
2% 3476.58 ± 57.19b 3164.19 ± 53.61b 3671.16 ± 36.74b 1.69 ± 0.54 2.99 ± 0.49
C mixed 6% T 1% 3216.47 ± 28.49b 2816.75 ± 46.25d 3567.39 ± 67.22b 2.13 ± 0.38 4.26 ± 0.57
1.5% 3316.49 ± 49.72b 2974.26 ± 49.26b 3746.28 ± 49.24b 2.31 ± 0.29 4.68 ± 0.43
2% 3516.76 ± 72.85b 3126.41 ± 36.49b 3974.67 ± 53.69b 2.52 ± 0.53 5.09 ± 0.19
R 2% 1853.68 ± 57.64 1376.41 ± 49.76 2058.74 ± 57.66 0.51 ± 0.28 1.22 ± 0.35
4% 2138.45 ± 72.55 1876.74 ± 64.87 2346.24 ± 61.68 0.83 ± 0.57 1.58 ± 0.47
6% 2573.99 ± 48.52 2079.67 ± 73.58 2811.71 ± 59.22 1.02 ± 0.63 2.34 ± 0.59
R mixed 2% T 2% 2764.11 ± 67.26b 2347.67 ± 57.61b 3147.67 ± 49.27b 0.98 ± 0.51 1.57 ± 0.74
4% 3147.36 ± 43.87b 2798.64 ± 64.19d 3319.49 ± 67.71b 1.16 ± 0.28 2.09 ± 0.33
6% 3367.82 ± 84.26b 3094.11 ± 73.34b 3571.97 ± 47.29b 1.35 ± 0.56 2.59 ± 0.24
R mixed 4% T 2% 3047.37 ± 53.19b 2847.67 ± 43.14b 3276.14 ± 37.69b 1.21 ± 0.58 2.18 ± 0.37
4% 3517.49 ± 47.64b 3147.41 ± 47.43b 3417.57 ± 67.16b 1.39 ± 0.46 2.82 ± 0.48
6% 3798.61 ± 66.73b 3297.85 ± 76.53b 3649.97 ± 51.44b 1.51 ± 0.37 3.09 ± 0.51
R mixed 6% T 2% 3489.46 ± 53.17b 3011.73 ± 37.67b 3674.19 ± 46.25b 2.01 ± 0.22 4.08 ± 0.61
4% 3674.42 ± 46.33b 3298.74 ± 45.36b 3841.96 ± 67.49b 2.19 ± 0.31 4.29 ± 0.35
6% 3947.76 ± 65.28b 3571.29 ± 61.17b 4167.39 ± 48.95b 2.28 ± 0.47 4.47 ± 0.52

Results are given in the form of Mean ± S.D. of triplicate analyses; T – Tamarind seed starch; OK – Okra mucilage polysaccharides; C – Sugarcane bagasse cellulose; R – Rice bran starch;
Bold values in the table, indicates the physical properties of optimized tamarind seed starch concentration, selected for development of biothermoplastic films.
a - b, represents significant differences (P b 0.05) between values.
c - d, represents insignificance (P N 0.05) between the values.

due to the addition of residual rice bran starch. Set back viscosity of both
T + C and T + R solutions didn't show a significant difference (P N 0.05)
at low concentrations of cellulose and residual rice bran starch, respec-
tively. This insignificance in setback viscosities may be attributed to the
release of free water molecules from starch globules during retrograda-
tion, which reduces the viscosity of starch solutions significantly at this
stage [23].
Pasting studies only gave the viscosity parameters of the potential
Bio-thermoplastic film solutions. Apart from viscos parameters, spread-
ability of Bio-thermoplastic film solutions becomes vital, due to the pro-
cess of casting involved in film preparation procedure. Spreadability
studies gain its importance also for its need in scaleup of the process
to an industrial level. Spreadability depends on to parameters, namely
hardness, and adhesiveness. Firmness or hardness is the measure of
the maximum force required to spread the matrix solution over an
area with a vertical push. Adhesiveness is the measure of the force re-
quired to separate the matrix solution from the surface [15]. Generally,
adhesiveness of film solution reduces after incubation (for removal of
solvent from the solution matrix), this facilitates the peeling of films
from the casting surface. Firmness and adhesiveness were measured
for gelatinized film matrix solutions after pasting studies and the results
were tabulated in Table 1. Spreadability of tamarind starch solution was
found to be high with corresponding low firmness values at different
concentration. Firmness value was found to be increasing with an in-
crease in the concentration of tamarind starch in solution. This was
found to be in agreement to increase in final viscosity of the tamarind
starch solution. Addition of Okra, cellulose and residual rice bran poly-
saccharides in tamarind starch solution was found to increase its firm-
ness, thus reduces the spreadability of film matrix solutions
significantly. Since, spreadability is directly proportional to viscosity
[1,15], this reduction in spreadability may be due to the high final vis-
cosity of film matrix solutions. Spreadability directly influences the
thickness of the Bio-thermoplastic films [1], which inturn may influence
all mechanical and physical properties [4,24]. Low concentration of tam-
arind seed starch may reduce the characteristics of films by several
folds. Thus, 4% tamarind seed starch solution (with the firmness of
1.06 ± 0.24 N) and its combinations were taken for further film produc-
tion and characterization studies. 2% tamarind starch solution was also
studied but they were only used for initial visual observation studies.
High concentration (6%) of tamarind starch was not used for combina-
tion studies as it had a high reduction in spreadability property, which
makes it difficult to cast film solutions over casting surface.
3.2. General visual observations on the effects of film preparation tech-
niques on bio-thermoplastic films
Many important visual observations were made for the preparation
of Bio-thermoplastic films under different film preparation conditions.
Initial trials on individual polysaccharides for film preparation revealed
that okra mucilage and sugarcane bagasse cellulose are not suitable for
individual film preparations. This may be due to lack of amylose and
amylopectin linkages in both okra [7,13] and sugarcane bagasse poly-
saccharides [5]. Especially, sugarcane bagasse crystalline cellulose is in-
soluble due to lack of interactions with water. Therefore, both okra and
cellulose polysaccharides can only be added as supplementing agents
for the production of starch-based film matrix solutions. Trial films pro-
duced from residual rice bran starch were found to be brittle in nature
on comparison with tamarind starch films, this may attribute to fewer
 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016 2011

interactions between amylose molecules in rice bran starch (which also

contains a high amount of fiber). Hot air oven method is one of the in-
vestigated thermal methods for film preparation, in this study. The tem-
perature inside the hot air oven chamber is increased to facilitate the
phase transition of water from liquid to vapor state. Consecutively, in-
ternal water molecules diffuse to the surface of the film in the event of
evaporation of water. This evaporation facilitates the solidification of
retrogradated amylose molecules present in the starch film solution,
which inturn gives the amorphous starch-based films [25]. The UV irra-
diation is the non-thermal film preparation method, it is mainly known
for its application in photografting [10]. Ultraviolet irradiation has been
known to influence chemical bonds between molecules. In UV irradia-
tion, diffusion of solvent molecules with air to attain equilibrium serves
as a major driving force for drying of film solution matrix. In both hot air
oven and UV irradiation method, it was found to be possible to make
films of all investigated combinations. Therefore, from initial trials,
both hot air oven and UV irradiation method were examined to be suit-
able for preparation of Bio-thermoplastic films. But these methods of
film preparation are time consuming in nature (3–4 h for hot air oven
method at 60 °C and 24–36 h for the UV irradiation method at room Fig. 2. Mechanical properties of tamarind starch-based films produced in Microwave oven
temperature). Difference in time (3–4 h) for hot air oven and method (T – Tamarind seed starch; OK – Okra mucilage polysaccharides; C – Sugarcane
(24–36 h) UV irradiation methods, were mainly due to different compo- bagasse cellulose; R – Residual rice bran starch).
sitions of films produced in these processes. Since there is a difference in
the interaction of solvent molecules with different polysaccharides. evaporation. 25–30 mL matrix solution (in 15 cm dia Petri dish) was
Level of bound, unbound and free solvent present in film matrix also dif- found to be optimum for film preparation at 350 W microwave. At
fers [26]. This inturn results in incubation time variations within the sin- 525 W, only 2% tamarind starch film was able to be made. Other inves-
gle process. In the optimization of Hot air oven method, 60 °C provides tigated combinations were found not to be suitable for film preparation
the ideal condition for film preparation without charring the film matrix in 525 W microwave method. Low power range (175 W) microwave
solution. The microwave is the electromagnetic wave, which creates a was examined to be suitable for film preparation with 2 and 4% tama-
chemical bond oscillation in dipolar molecules, which breaks them to rind seed starch including their all investigated combinations. 6% tama-
release a high amount of energy. The energy released from the mole- rind seed starch and its combinations were not found to be suitable for
cules will facilitate localized heating of molecules in a highly efficient film preparation even at a low power range of 175 W, this is due to
manner [27]. In film preparation, microwave acts on dipolar solvents shrinkage of films during processing.
to facilitate localized heating and evaporation, thus the time require-
ment for energy transfer is less in microwave wave method. This re- 3.3. Characterization of produced biopolymer films
sulted in low time requirement (15–30 min), for film preparation,
which provides the remedy for the time consumption problem, in the 3.3.1. Mechanical and physical properties of bio-thermoplastic films
other two investigated methods. On the optimization of power ranges Mechanical and physical properties of bio-thermoplastic films are
in a microwave oven, high power range of 350 W only produced combi- studied to match the existing standards of synthetic polymers. The in-
nations of 2% tamarind starch films. During microwave processing, high teraction between the monomeric content of the biopolymer matrix so-
concentration films started to shrink; this shrinkage may be due to ir- lution highly influences the mechanical and physical properties of
regular solidification of polysaccharides during localized heating and biopolymer films. Combinations of biopolymers with distinct individual

Fig. 1. Mechanical properties of tamarind starch-based films produced in Hot air oven Fig. 3. Mechanical properties of tamarind starch-based films produced in UV irradiation
method (T – Tamarind seed starch; OK – Okra mucilage polysaccharides; C – Sugarcane method (T – Tamarind seed starch; OK – Okra mucilage polysaccharides; C – Sugarcane
bagasse cellulose; R – Residual rice bran starch). bagasse cellulose; R – Residual rice bran starch).
2012 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016

Table 2
Mechanical properties, Oxygen transfer rate and percentage swelling index of Bio-thermoplastic films.

Casting methods Concentrations Oxygen transfer rate Water vapor permeability Swelling index

cm3 μmm−2 d−1 kPa−1 g s−1 m−1 Pa−1 %

HAO (60 °C) 4% T 16.11 ± 1.49a,c 0.92 ± 0.05a,c 60.14 ± 4.25a,c

4%T + 1%OK 15.41 ± 1.27d 0.73 ± 0.07b 76.29 ± 3.46b
4%T + 1.5%OK 14.34 ± 1.66b 0.67 ± 0.04b 79.43 ± 4.65b
4%T + 2%OK 13.75 ± 1.34b 0.54 ± 0.06b 82.47 ± 5.21b
4%T + 1%C 14.21 ± 2.47b 0.71 ± 0.03b 58.24 ± 2.49d
4%T + 1.5%C 12.11 ± 1.62b 0.64 ± 0.04b 55.76 ± 2.77b
4%T + 2%C 10.32 ± 1.58b 0.48 ± 0.07b 50.34 ± 3.11b
4%T + 2%R 15.11 ± 1.34d 0.82 ± 0.12d 60.11 ± 2.11d
4%T + 4%R 14.56 ± 2.11b 0.76 ± 0.05b 58.41 ± 3.41d
4%T + 6%R 13.62 ± 2.47b 0.65 ± 0.02b 55.37 ± 2.13b
T + OK + C 14.11 ± 4.71b 0.61 ± 0.09b 62.41 ± 3.14b
T + OK + R 14.57 ± 3.19b 0.75 ± 0.11b 80.49 ± 4.34b
T + OK + C + R 10.11 ± 4.76b 0.45 ± 0.13b 58.16 ± 4.74d
MWO (175 W) 4% T 18.56 ± 2.15a,c 1.12 ± 0.13a,c 70.04 ± 3.12a,c
4%T + 1%OK 17.41 ± 1.16d 0.95 ± 0.03d 78.11 ± 2.15b
4%T + 1.5%OK 16.14 ± 1.34b 0.74 ± 0.11b 80.12 ± 2.13b
4%T + 2%OK 14.31 ± 1.24b 0.69 ± 0.06b 83.11 ± 4.34b
4%T + 1%C 15.62 ± 1.31b 0.86 ± 0.12b 60.12 ± 1.16b
4%T + 1.5%C 13.34 ± 2.16b 0.77 ± 0.14b 56.17 ± 3.41b
4%T + 2%C 11.15 ± 2.41b 0.59 ± 0.16b 51.13 ± 2.32b
4%T + 2%R 16.91 ± 2.63b 0.96 ± 0.02d 62.13 ± 1.23b
4%T + 4%R 15.37 ± 1.41b 0.84 ± 0.14b 59.24 ± 2.54b
4%T + 6%R 14.62 ± 1.67b 0.77 ± 0.11b 56.16 ± 1.34b
T + OK + C 15.37 ± 3.26b 0.73 ± 0.07b 63.27 ± 2.31b
T + OK + R 15.16 ± 3.19b 0.86 ± 0.08b 82.48 ± 2.16b
T + OK + C + R 12.11 ± 3.14b 0.57 ± 0.11b 60.59 ± 3.15b
UV-RT (1000 mWcm−2) 4% T 13.28 ± 1.32a,c 0.81 ± 0.12a,c 57.26 ± 3.47a,c
4%T + 1%OK 12.94 ± 1.34d 0.62 ± 0.02b 72.16 ± 2.76b
4%T + 1.5%OK 11.84 ± 1.42b 0.53 ± 0.11b 75.59 ± 1.63b
4%T + 2%OK 10.46 ± 2.15b 0.47 ± 0.04b 80.11 ± 2.35b
4%T + 1%C 13.41 ± 1.22d 0.60 ± 0.12b 56.51 ± 1.34d
4%T + 1.5%C 11.23 ± 2.41b 0.55 ± 0.02b 53.74 ± 1.29b
4%T + 2%C 9.11 ± 2.13b 0.36 ± 0.09b 47.18 ± 2.67b
4%T + 2%R 14.22 ± 1.16b 0.70 ± 0.13b 58.32 ± 1.49d
4%T + 4%R 13.16 ± 1.34d 0.62 ± 0.09b 56.46 ± 1.87d
4%T + 6%R 12.24 ± 1.51b 0.56 ± 0.10b 53.18 ± 1.98b
T + OK + C 12.42 ± 2.61b 0.54 ± 0.04b 59.36 ± 2.98b
T + OK + R 12.34 ± 2.85b 0.63 ± 0.12b 76.74 ± 2.56b
T + OK + C + R 9.28 ± 3.48b 0.38 ± 0.15b 55.84 ± 2.74b

Results are given in the form of Mean ± S.D. of triplicate analyses; HAO – Hot Air Oven; MWO – Microwave Oven; UV-RT – Ultraviolet irradiation at room temperature; T – Tamarind seed
starch; OK – Okra mucilage polysaccharides; C – Sugarcane bagasse cellulose; R – Residual rice bran starch.
a - b, represents significant differences (P b 0.05) between values.
c - d, represents insignificance (P N 0.05) between the values.

properties can also influence the overall properties of Bio-thermoplastic
films. Mechanical properties of tamarind starch film and its combina-
tions were depicted in Figs. 1–3. Figs. 1, 2 & 3 correspond to different
film preparation methods of hot air oven, microwave oven and UV irra-
diation methods, respectively. Physical properties of 4% tamarind starch
film and its combinations with other investigated polysaccharides for
different preparation conditions were tabulated in Table 2.
In Hot air oven method, Addition of Okra mucilage with tamarind
starch was found to significantly (P b 0.05) increases the elongation
property and reduces the tensile strength of the Bio-thermoplastic

Fig. 4. Scanning electron & atomic force micrographs of tamarind starch film produced by Hot Air Oven (HAO) method (Other film combination images are given in supplementary data
[Fig. S4]).
C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016 2013

starch films. Low concentrations of Okra mucilage were not found to in-
fluence the oxygen transfer rate (OTR) significantly (P N 0.05). But in
higher concentrations, it had reduced the OTR, which may be due to
the interaction between okra mucilage and starch [7]. Okra mucilage
moderately influenced the water vapor permeability (WVP) of tama-
rind starch films. Increase in swelling index was also noted for okra
polysaccharide infused tamarind starch films, this may attribute to
high water holding capacity of okra polysaccharides [13]. Addition of
Cellulose with tamarind starch was found to have exact opposite effect
on comparison with okra mucilage addition. Cellulose has increased the
tensile strength and decreased the elongation of bio-thermoplastic
starch films significantly (P b 0.05). Similar results of cellulose effect
were observed by other researchers [4,5,9]. Averous et al. [22], reported
that a decrease in elongation property of starch-cellulose composite
may be due to the strong interaction between the cellulose fibers and
gelatinized starch molecules. Cellulose addition with tamarind starch
film significantly (P b 0.05) reduced both OTR and WVP properties,
which may be attributed to the high crystallinity index of sugarcane ba-
gasse cellulose [12]. Rice bran starch addition with tamarind starch was
not found to influence the mechanical, OTR, WVP and swelling proper-
ties of bio-thermoplastic films on lower concentrations. At higher con-
centrations, they were found to influence the mechanical and physical
properties with moderate significance (P b 0.05). From the above results
2% okra (for an increase in elongation), 2% cellulose (for an increase in
tensile strength) and 2% rice bran starch (for a moderate increase in ten-
sile strength without affecting elongation values) were selected for fur-
ther combination studies. T + OK + C, which is the combination of
tamarind starch, okra and cellulose was found to retain good tensile
strength (attributed to cellulose) with improved elongation (attributed
to okra mucilage). T + OK + C, films were also found to have signifi-
cantly reduced OTR and WVP properties. Compared to T + OK+ C
films, T + OK + R films showed minimal influence on mechanical and
physical properties. Combination of four polysaccharides (T + OK + C
+ R) films showed a significant reduction in OTR and WVP properties
in comparison with all investigated combinations. Similar observations
were also noted in the other two investigated preparation methods (Mi-
crowave oven (MWO) method and UV- irradiation method), with dif-
ferences in intensity of significance.
On comparing the different methods, films prepared using the MWO
method showed a high reduction in mechanical parameters and in-
crease in OTR, WVP and swelling index. This may be due to the sudden
removal of moisture from the film matrix solution in a microwave oven,
which may impart micropores in the film structure. These micropores
may affect the overall properties of the film. Films produced by UV – ir-
radiation method showed much improved mechanical, OTR, WVP and
swelling index properties than the other two investigated methods.
This may be due to proper solidification (Both crystalline and amor-
phous solidification are possible in combinational films) of molecules
at room temperature. The crystalline nature of films may be attributed
to the spontaneous recrystallization of amylose molecules after gelatini-
zation [28]. This process occurs mainly during film drying when the
chain mobility is still high due to the water content [25]. Rindlav-
Westling et al. [29], reported that drying conditions at high relative hu-
midity, or long drying times, greatly promote amylose crystallization,
whereas amylopectin shows a retarded crystallization and may attri-
bute to amorphous solidification. Okra polysaccharide may also attri-
bute to amorphous solidification of Bio-thermoplastic films. The

Fig. 5. Roughness parameters of tamarind starch-based Bio-thermoplastic films obtained

from the Atomic force microscopic analysis (Fig. A – Hot Air Oven; Fig. B – Microwave
Oven; Fig. C – Ultraviolet irradiation at room temperature; T – Tamarind seed starch;
OK – Okra mucilage polysaccharides; C – Sugarcane bagasse cellulose; R – Rice bran
starch; Red bar - Average maximum height of roughness (Rtm); Blue bar - Average
maximum roughness valley depth (Rvm); Green bar - Average roughness (Ra); Brown
bar - Root mean square roughness (Rq)).
2014 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016
Fig. 6. Scanning electron & atomic force micrographs of tamarind starch films produced by Microwave oven (MWO) method (Other combination film images are given in supplementary
data [Fig. S5]).
improved film characteristics in the UV irradiation method may also be
attributed to the interaction between molecules at UV – irradiation.
3.3.2. Chemical interactions between polysaccharides in bio-thermoplastic
films
Fourier transform infrared spectroscopy (FTIR) is an analysis, which
can give the chemical nature and functional groups present in Bio-
thermoplastic films. Interactions between polysaccharides in films can
be studied extensively using FTIR analysis. FTIR analysis was performed
for all investigated Bio-thermoplastic polymer films and their band pat-
terns were depicted in Figs. S1–3. Figs. S1, S2, and S3 correspond to bio-
thermoplastic films produced using hot air oven, microwave oven, and
UV – irradiation methods, respectively. Band assignments were given
according to IR interpretation given by Coates, [30]. In all the FTIR
band patterns only five prominent peaks were able to be observed
clearly. Broad high-intensity band between 3720 and 3083 cm−1,
which corresponds to polymeric OH stretch [2]. Peaks at 2887 and
2309 cm−1 attributes to C\\H Asym./Sym. stretch and carbon skeletal
vibrations, respectively [31]. Prominent peaks at 2103 cm−1 and
1663 cm−1, represents terminal alkyne binding bands between poly-
mers and primary amine N\\H stretch, respectively [4]. Other bonds
of characteristic C\\O\\C, C\\O\\H, and C\\O between 1525 and
400 cm−1 were found to be in overlap with each other to give single
broad high-intensity band. These patterns were found to be same for
all investigated combinations of Bio-thermoplastic films and they
were also found to be the same for all three investigated film prepara-
tion techniques. There were only intensity variations were observed in
the FTIR patterns of Bio-thermoplastic films. This similarity in spectral
bands may be due to the complex nature of natural polysaccharides in
combinations. Even in tamarind starch films after gelatinization,
Fig. 7. Scanning electron & Atomic force micrographs of tamarind seed starch films produced by Ultraviolet irradiation (UV) method (Other composition film images are given in
supplementary data [Fig. S6]).
reformation of bonding between amylose, amylopectin, and plasticizer
occurs in a random way, thus it becomes harder to predict the binding
nature of natural polysaccharides.
3.3.3. Morphological and surface characteristics of bio-thermoplastic films
Surface morphology of Bio-thermoplastic films was studied using
both scanning electron microscope and atomic force microscope. Scan-
ning electron micrographs and corresponding atomic force micrographs
were depicted in Figs. 4–6. Surface micrographs of bio-thermoplastic
films produced in HAO, MWO and UV – irradiation methods were
given in Figs. 4, 5 and 6, respectively.
On comparing the scanning electron micrographs (Fig. 4) of films
produced in hot air oven method, T + R film showed visual smoothness
on its surface compared to other investigated films. This smooth surface
of T + R films may be due to amylose content of both tamarind and re-
sidual rice bran starch. Both the starch molecules gelatinized during ma-
trix preparation, which disintegrates coarse starch globules to form a
smooth film matrix solution. Scanning electron micrographs of other in-
vestigated films showed rough surfaces compared to T + R film. This vi-
sual roughness on the film micrograph surfaces may be attributed to a
combination of other polysaccharides (OK and C). Sugarcane bagasse
cellulose is insoluble in water and it was also found to have a high crys-
tallinity index of 73.21% [12]. Statistical roughness parameters (Fig. 5A),
confirmed the observed visual smoothness on SEM micrographs of T
+ R film, with significantly (P b 0.05) low values for Average roughness
(Ra) and Root mean square roughness (Rq), on comparison with other
investigated films. T + OK + C films were found to be having high aver-
age and root mean square roughness compared to other film samples
produced using the hot air oven method.
 C. Chandra Mohan et al. / International Journal of Biological Macromolecules 120 (2018) 2007–2016
On comparing the films produced in a microwave oven method, T
and T + R films showed visual smooth surface compared to other
films (Fig. 6). Since both films didn't have OK and C, this may only attri-
bute to the amylose molecules present in starch globules of both T and
R. Statistical roughness parameters (Fig. 5B), confirmed the visual
smoothness of T and T + R films, with low Ra and Rq values. The T
+ OK + C film was examined to be having the roughest surface
among all combinations of thermoplastic films, produced using the mi-
crowave oven method.
On comparing the films produced by UV- irradiation method, T, T
+ OK and T + R films showed smooth surfaces compared to other
films (Fig. 7). The smoothness of T and T + R film may attribute only
to amylose molecules (starch globules) present in film matrix. Statistical
parameters of roughness (Fig. 5C), confirmed the visual smoothness of
T, T + OK, and T + R with low Ra and Rq values. The T + C film sample
was examined to be having the roughest surface, with significantly (P b
0.05) high Ra and Rq values, among other investigated films produced
using UV – irradiation method.
Surface roughness parameter (Fig. 5), comparison of different film
production methods showed that UV – irradiation method produces
films with significantly (P b 0.05) low surface roughness. This may be
due to the increased drying time of films in the UV irradiation method,
at which recrystallization of amylose is stable after gelatinization [29].
Surface roughness parameters of Bio-thermoplastic films produced in
Hot air oven and microwave oven methods are found not to be signifi-
cantly (P N 0.05) different. Cellulose infused tamarind starch films was
found to have the highest surface roughness among all three investi-
gated methods. Having a high crystallinity index and average particle
size [12], sugarcane bagasse cellulose interaction with water is minimal,
thus it dosen't exhibit even distribution in film matrix. Gelatinized
starch molecules facilitate the even distribution of cellulose molecules
in film matrix, with high pasting viscosity. On drying, water molecules
evaporate and the amylose molecules start to recrystallize [28], since
the interaction between the amylose molecules are high they tend to
crystallize as a thin layer, at which evenly distributed cellulose mole-
cules are trapped. Thus the surface of films becomes rough because of
cellulose molecules. Cano et al. [25], reported the same phenomenon
on the incorporation of bran filler in starch films, leads to the appear-
ance of a great number of hard particles on the film surface.
4. Conclusions
The tamarind seed starch solution was found to have high pasting
viscosities on comparison with residual rice bran starch solution. In-
crease in concentration of okra mucilage in tamarind starch increased
the peak and final viscosities of the film matrix solution. The low
power (175 W) microwave oven method was found to be the quickest
method for production of Bio-thermoplastic starch films, but it was
noted to have a positive effect only in lower concentrations of film ma-
trix solution. The MWO and HAO methods had more or less the same ef-
fect on mechanical and physical properties of tamarind starch films. The
interaction of okra mucilage and cellulose affects the elongation and
tensile strength of tamarind starch films, respectively. The interaction
between cellulose and starch in the film matrix solution improves the
OTR and WVTR properties of tamarind starch films. Cellulose infused
tamarind starch films showed higher surface roughness compared to
okra infused Bio-thermoplastic films. UV irradiation method was
examined to be producing stable bio-plastic films with low surface
roughness. The tamarind starch in combination with other natural poly-
saccharides can produce stable biothermoplastic films, that can be a po-
tential substitute for existing petrochemical plastics.
Acknowledgments
The authors would like to acknowledge funding from the University
Grants Commission (UGC), New Delhi (UGC/MRP/MAJOR/BIOT/2013/
2015
19727). The first author would like to express his sincere thanks to
Council of scientific and industrial research – CSIR for the award of a se-
nior research fellowship (No.:09/468/0500/2016/EMR-I).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.ijbiomac.2018.09.161.
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