Journal of Reinforced Plastics and Composites

http://jrp.sagepub.com/

Bioplastic based on starch and cellulose nanocrystals from rice straw

Melissa B Agustin, Bashir Ahmmad, Shanna Marie M Alonzo and Famille M Patriana
Journal of Reinforced Plastics and Composites published online 5 November 2014
DOI: 10.1177/0731684414558325

The online version of this article can be found at:

http://jrp.sagepub.com/content/early/2014/11/05/0731684414558325

Published by:

http://www.sagepublications.com

Additional services and information for Journal of Reinforced Plastics and Composites can be found at:

Email Alerts: http://jrp.sagepub.com/cgi/alerts

Subscriptions: http://jrp.sagepub.com/subscriptions

Reprints: http://www.sagepub.com/journalsReprints.nav

Permissions: http://www.sagepub.com/journalsPermissions.nav

Citations: http://jrp.sagepub.com/content/early/2014/11/05/0731684414558325.refs.html

>> OnlineFirst Version of Record - Nov 5, 2014

What is This?

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:46am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

Original Article
Journal of Reinforced Plastics
and Composites

Bioplastic based on starch and cellulose 0(0) 1–9

! The Author(s) 2014
Reprints and permissions:
nanocrystals from rice straw sagepub.co.uk/journalsPermissions.nav
DOI: 10.1177/0731684414558325
jrp.sagepub.com

Melissa B Agustin1, Bashir Ahmmad2, Shanna Marie M Alonzo1

and Famille M Patriana1

Abstract
Bioplastic based on starch as the matrix and cellulose nanocrystals from rice straw as reinforcing filler were prepared in
this study. The isolation of cellulose nanocrystal (CNC) followed a series of steps: delignification, sulfuric acid hydrolysis,
and sonication. The process afforded short, rod-like CNCs with particle diameter ranging from 10 to 12 nm and
crystallinity index of 76.1%. Fourier transform infrared analysis of the CNCs also confirmed absorption patterns typical
of cellulose and the removal of silica. Bioplastic with different starch-to-CNC ratios were prepared by solution casting
and evaporation method. Scanning electron micrographs of the films showed uniform dispersion of CNC in the starch
matrix. Mechanical tests revealed that both tensile strength and modulus significantly increased with increasing CNC load
while percent elongation decreased. The moisture uptake of the films reinforced with CNC also decreased an indication
of improvement in water resistance. However, the thermal stability of the films decreased by the addition of CNC.

Keywords
Rice straw, cellulose nanocrystals, starch-based bioplastic

Introduction others.3 The large contribution of starch-based plastics

The demand for the production of environment- in the market can be accounted for its several cited
friendly material is increasing. The rising concern advantages such as high abundance, low cost, and
towards environmental problems brought by petro- renewability.
leum-based products inspired the development of the However, starch alone is not a true thermoplastic. It
so called ‘‘green’’ materials. The guiding principles for has to be processed in the presence of heat and mech-
the production of these materials are sustainability, anical treatment together with a plasticizer, most often
industrial ecology, eco-efficiency, and green chemis- glycerol. This process produces thermoplastic starch
try.1,2 One of the ‘‘green’’ materials emerging in the (TPS). Pure TPS cannot meet the different properties
market nowadays is biodegradable plastics or bioplas- needed for a particular application. It has to be com-
tics. Bioplastics are derived from agricultural resources bined with other materials often a filler to modify
and biomass feedstock that are renewable and therefore its properties. Generally, reinforcement with filler
comply with materials that are eco-efficient and sustain-
able. It has been reported that the worldwide produc-
tion capacity of bioplastics will increase from 0.36 Mt
in 2007 to 3.45 Mt in 2020.3 1
Department of Chemistry, College of Arts and Sciences, Central Luzon
Among the biopolymer matrices being utilized for State University, Science City of Muñoz, Nueva Ecija, Philippines
2
the production of bioplastics, starch is considered the Graduate School of Science and Engineering, Yamagata University,
most widely used material. Starch-based plastics have Yonezawa, Japan
been projected to comprise the largest production cap-
Corresponding author:
acity amounting to 1.3 Mt in 2020 while the remaining Bashir Ahmmad, Graduate School of Science and Engineering, Yamagata
production is based on polylactic acid (PLA), polyhy- University, 4-3-16 Jonan, Yonezawa 992-8510, Japan.
droxyalkanoates (PHA), bio-based polyethylene, and Email: arima@yz.yamagata-u.ac.jp

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:46am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

2 Journal of Reinforced Plastics and Composites 0(0)

enhances the mechanical properties of starch and Preparation of cellulose fibers by delignification
reduces the hydrophilic character.4
In recent years, the use of bio-based and nano-sized
and bleaching
fillers has attracted substantial research interest. Several The method described by Elanthikkal et al.14 with slight
advantages of using nano-sized fillers from natural modification was employed in the preparation of cellu-
resources have already been cited in different works lose fibers. Fifty grams of the cut rice straws was trans-
and these include low density, renewable character, ferred into a 2-L beaker and treated with 700 mL of
great abundance, high specific resistance, excellent 10% w/v NaOH solution. The mixture was heated
mechanical properties, biodegradability, low-cost, low with occasional stirring for 2 h at a temperature range
abrasive nature, and reactive surface for easy modifica- of 60–65 C removing the lignin, hemicellulose and
tion.5–8 Moreover, it was also noted that the nanoscale other pectic substances. After heating, the mixture
dimensions of the filler keeps the transparency of the was filtered and washed several times to separate the
material if inherent for the neat matrix.9 insoluble pulp and remove the excess NaOH. The insol-
One of the most investigated bio-based fillers is cel- uble pulps which constitute the cellulose fibers were
lulose nanocrystals (CNCs); cellulose crystallites with bleached with 500 mL of 1% v/v sodium hypochlorite
at least one dimension equal or less than 100 nm. solution buffered to a pH of 5 by an acetate buffer. The
CNCs can be isolated from the native cellulose by bleached fibers were washed at least thrice with distilled
acid hydrolysis. The amorphous portion of the cellulose water or until the pH of the washing becomes neutral.
can be easily hydrolyzed in strong acidic condition leav- The cellulose fibers were air dried and weighed.
ing the individual crystallites. Sulfuric acid is com-
monly used because the introduction of sulfate esters
Isolation of cellulose nanocrystals by acid hydrolysis
on the surface of the individual crystallites stabilizes the
resulting suspension of CNCs by electrostatic repul- Ten grams of the bleached fibers were hydrolyzed in
sion.10 Depending on the source and reaction condition 100 mL 50% v/v H2SO4 at 30 C for 3 h with constant
during hydrolysis, the size and properties of the isolated stirring. Hydrolysis was stopped by the addition of
CNCs also vary.11 100 mL cold 20% NaOH solution. The suspension
In the present paper, our group reports the isolation was then centrifugated at 8500 r/min for 10 min obtain-
and characterization of CNCs from rice straw and its ing the coagulated CNC. The coagulated CNC was sus-
application as reinforcing filler in starch-based bioplas- pended again in cold distilled water, and the
tic. Rice straw is one of the most abundant agricultural centrifugation process was repeated until the pH of
residues in the Philippines. The Philippine Rice supernatant reaches around 2–3. The resulting suspen-
Research Institute cited that 11.3 million tons of rice sion was dialyzed against distilled water to remove the
straw every year is being left on the field during rice excess sulfuric acid by using SpectraPor 4 dialysis mem-
production.12 This study therefore seeks to find a novel branes (12–14 kDa MWCO). When the pH of the water
application for rice straw. Although isolation of CNC outside the membrane reaches around 6–7, the suspen-
from rice straw was reported by Lu et al.13 using tolu- sion was collected. Every 200 mL of the CNC suspen-
ene solution and high concentration of sulfuric acid sion underwent sonication using Cole Palmer 4710
at high temperature, this work employed relatively series ultrasonic homogenizer for 10 min in an ice
milder condition, i.e. lower acid concentration and bath at atmospheric condition. The collected suspen-
temperature. sion was stored in a refrigerator and a portion of it
was freeze dried for analysis that required dry samples.
The percent CNC in the suspension was determined
Materials and methods using gravimetric method.
Materials
Characterization of the isolated CNCs
Rice straws (R216 variety) were obtained from a farm
in Science City of Muñoz, Nueva Ecija, Philippines. The FTIR spectrum of the isolated CNC was recorded
Technical grade sodium hydroxide and sodium hypo- from 4000 to 400 cm1 on a Perkin-Elmer Spectrum
chlorite for the delignification and bleaching process One spectrometer equipped with attenuated total
were purchased from Alyson’s Chemical Enterprise. reflectance (ATR) accessory. The spectrum was col-
Analytical grade glycerol, sulfuric acid and acetic acid lected from a total of 16 scans at a resolution of 4 cm1.
were obtained from Ajax Chemicals. Food-grade corn- A JEOL JEM 1010 transmission electron micro-
starch with an amylose content of 31% supplied by scope (TEM) was used to determine the shape and
Food Industries Inc. was used for the bioplastic size of the CNCs. The CNC suspension was prepared
preparation. in methanol at 100 mg/mL concentration and was

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:46am]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d
Agustin et al.
diluted 5-fold. A drop of suspension was placed onto
carbon-coated grid at room temperature and then
examined using TEM operating at 100 kV. The diam-
eter of the isolated CNCs was determined by using the
software, SemAfore. For comparison, scanning elec-
tron micrographs of raw and delignified rice straw
were also taken.
The x-ray diffraction patterns of the untreated and
delignified rice straw, and the isolated CNC were
measured using the Rigaku (ultimate VII) X-ray dif-
fraction instrument operated at a target voltage of
40 kV and current of 40 mA. All samples were scanned
at 2y ranging from 4 to 80 at a rate of 10 /min. The
crystallinity index was obtained using the following
equation15
Imax  Iam
Crystallinity index ¼
Imax
where Imax is the maximum intensity, Iam is the min-
imum intensity that lies between the two most well-
defined peaks.
Preparation of starch-CNC bioplastic film
by solution casting
Ten grams corn starch was dissolved in 200 mL distilled
water and heated at 60 C for 15 min with constant stir-
ring. CNC was then added in the form of a suspension
to avoid agglomeration. The amount of CNC per 100 g
(dry weight) starch was varied to identify the optimum
starch to CNC ratio. Glycerol (3 g) was then added
and the mixture was stirred for two h at a constant
temperature of 70 C. The mixture was casted and
cooled on glass plates and then dried at room tem-
perature. Overall, bioplastic films with starch to CNC
ratios of 100:0, 100:2.5, 100:5, 100:10, and 100:15 were
prepared.
Characterization of starch–CNC bioplastic film
The morphology of the fracture surface (cross-sectional
surface) of the starch-CNC films were visualized using a
scanning electron microscope (SEM, JSM 5800). The
films were frozen in liquid nitrogen and cut into small
portions which were then mounted vertically using a
small metal support on the sample holder. The samples
were sputter coated with gold using a sputter-coater
and viewed under the scanning electron microscope.
Tensile strength and modulus were determined using
the ASTM D882-02 method. Samples with dimensions
of 10 cm in length, 1.5 cm in width, and 0.20  0.04 mm
in thickness were cut manually and conditioned at a
relative humidity of 50  5% and temperature of
23  2 C for 24 h. Films were then stretched by
Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014
[1–9]
(JRP) [PREPRINTER stage]
3
Instron 5585H tensometer using 50 N load cell at a
crosshead speed of 12.5 mm/min. The average values
from five measurements were obtained and statistical
significance of differences in means was evaluated
using the least significance difference analysis at 95%
confidence level.
Moisture uptake test was determined at conditions
with two different relative humidity values: 40% and
70%. Films were cut into 2  2 cm2 sheets, weighed,
and oven dried at 50 C for 24 h. Then, these were
placed inside a desiccator with silica gel. The humidity
was kept constant at 40% and monitored using a
hygrometer. The films were re-weighed and placed
back in the desiccator and this process was repeated
until a constant weight that agrees within 0.0005 g is
achieved (Wo). The silica gel was replaced by a satu-
rated solution of sodium chloride to increase the
x100%
humidity to 70%. The films were weighed again and
placed back in the desiccator and this was repeated
until a constant weight that agrees within 0.0005 g
was reached (Wh). The moisture uptake was reported
as percentage and was calculated using the equation
Wh  Wo
% Moisture uptake ¼ x 100:
Wo
Thermogravimetric analysis (TGA) was carried out
using TA Instrument Q50. The weight loss of the bio-
plastic films due to thermal degradation was monitored
as a function of temperature. Five milligrams of the
film placed in a platinum pan was heated initially to
110 C for 10 min to remove bound moisture. The tem-
perature was then ramped to 600 C at a heating rate of
20 C/min under the flow of nitrogen gas.
Results and discussions
CNC yield
The suspension of CNCs produced after acid hydrolysis
had a density of 1.58 g/mL and a concentration of
2.66% CNC by mass. Figure 1 shows the untreated
rice straw, delignified rice straw and the CNC suspen-
sion. The delignified rice straw appears as white cottony
fibers and this consequently produced a white suspen-
sion of CNCs. The percent yield of CNC based from
the raw rice straws was found to be 6.6%.
Characterization of the isolated CNC
Chemical characteristics. FTIR analysis was carried out to
determine the chemical characteristics of the raw rice
straw (RRS), the delignified rice straw (DRS), and the
isolated CNC. The FTIR spectra are shown in Figure 2.
All spectra show the presence of hydroxyl group
XML Template (2014) [30.10.2014–9:46am]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d
4 Journal of Reinforced Plastics and Composites 0(0)
Figure 1. The raw rice straw sample before chemical treatment (a), the cellulose fibers after alkali delignification (b), and the CNC
suspension at varying concentrations (c) after acid hydrolysis.
CNC
DRS
Intensity / a.u.
RRS
2897
3338
4000 3500 3000 2500
Wave number / cm -1
Figure 2. FTIR spectra of the raw rice straw (RRS), the
delignified rice straw (DRS), and the isolated CNCs.
corresponding to the broad band at 3338 cm1. The
–CH stretching was also observed at 2897 cm1. The
signal for the aliphatic ester of lignin or hemicellulose
which can be seen at 1740 cm1 on the other hand was
not clearly evident in all of the spectra. The absorption
band at 1640 cm1 is attributed to hydroxyl bending of
adsorbed water. It can be seen that this peak weakened
after chemical treatment. It was reported that the
decrease in the intensity of this peak can be due to
partial removal of hemicelluloses.16 The peak at
1428 cm1 can be due to –CH deformation both for
lignin and cellulose.17 Since the intensity of this peak
increased after delignification relative to the raw rice
straw, it can be deduced that this peak is more due to
cellulose than lignin. However, it cannot still be con-
cluded that the isolated CNC is free of lignin. Wagging
of –CH2 groups was observed at 1315 cm1. The peak
at 1160 cm1 can be ascribed to C–O–C asymmetric
stretching of hemicellulose, lignin, and cellulose.
Similar with the 1428 cm1 peak, the intensity of this
peak increases after delignification. The ether linkages
[1–9]
(JRP) [PREPRINTER stage]
of the cellulose or the C–O–C group stretching caused
the prominent peak in the region 1030 cm1. The shoul-
der peak at 1109 cm1 and the peak at 898 cm1 are
associated to glucose ring stretching. The removal of
silica from the raw rice straw can also be observed
after delignification due to the disappearance of peak
at 798 cm1. The Si–O symmetric stretching of silica is
798
observed in this region.13
664
556
898
1640
1428
1315
1160
Morphological structure. Changes in the morphological
1109
1030
structure of rice straw are shown in Figure 3. The
2000 1500 1000 500 untreated rice straw (Figure 3(a)) shows the cellulose
fibers embedded in hemicelluloses and lignin. These
substances are removed during delignification as seen
in the image for the delignified rice straw (Figure 3(b)),
which shows smaller and more defined cellulose fibers
with an average diameter of 4.98 mm. These fibers are
further separated into much smaller crystalline cellulose
as seen in the TEM micrographs of the isolated CNC
(Figure 3(c) and (d)). Short, rod-like cellulose nano-
crystals were obtained. Despite the dilution done
during sample preparation, it can be seen that agglom-
eration still occurred. The strong hydrogen bonds
between individual crystals hold the particles together
because the steric stabilization which keeps the CNCs
suspended in a liquid medium becomes inactive in the
dry phase.18 The negative sulfate groups on the surface
of CNCs are responsible for the stability of the CNC
suspension due to electrostatic repulsion.19
The particle size distribution of the isolated CNCs
revealed almost uniform width in a range of 10–12 nm.
The CNC isolated by Lu et al.13 also from rice straw,
however, gave a wider width range of 4–26 nm with an
average of 11.2 nm. Their method employed higher sul-
furic acid concentration and temperature but shorter
hydrolysis time.
Crystallinity. The changes in crystallinity of rice straw
before and after chemical treatment can be seen from
the diffraction patterns presented in Figure 4. All three
Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014
XML Template (2014) [30.10.2014–9:47am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

Agustin et al. 5

Figure 3. SEM micrographs of the (a) raw rice straw and (b) the delignified rice straw and (c and d) TEM micrographs at different
magnifications of a dilute suspension of the isolated CNCs.

diffractograms display two well-defined peaks

around 2y ¼ 15 and 22 , characteristic of cellulose.
200

The appearance of a singlet peak at 2 ¼ 22 for the

isolated CNC confirmed that the isolated CNC was
Cellulose I.13
The 22 peak of the CNCs is the sharpest, indicating
110
Intensity

the higher perfection of the crystal lattice than that of

the raw and delignified rice straw. This is further sup-
ported by the computed crystallinity indices of the raw,
004

CNC untreated rice straw, delignified rice straw, and CNC

which are found to be 42.6%, 64.4%, and 76.1%,
DRS respectively. The higher crystallinity of delignified rice
RRS straw relative to the raw rice straw can be attributed to
the removal of the amorphous lignin and hemicelluloses
10 20 30 40 50
during delignification. Crystallinity index further
Diffraction angle, 2θ/deg
increased after acid hydrolysis due to the removal of
the amorphous cellulose. The hydronium ions penetrate
Figure 4. X-ray diffraction patterns of the raw rice straw in these amorphous zones, promoting the hydrolytic
(RRS), the delignified rice straw (DRS), and the isolated CNCs. cleavage of the glycosidic bonds releasing individual

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:47am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

6 Journal of Reinforced Plastics and Composites 0(0)

Figure 5. SEM micrographs showing the cross-sectional morphology of the bioplastic films with varying starch to CNC ratios.

crystallites,20 whereas the crystalline zones are more Mechanical properties. The mechanical properties of the
resistant to chemical attack.17 bioplastic film which include the tensile strength, per-
The calculated crystallinity index of the isolated cent elongation at break, and modulus are presented in
CNC on the other hand is lower than those reported Table 1. In general, significant improvement in tensile
from other sources. The CNC from sugarcane baggase strength and modulus was observed for films reinforced
hydrolyzed by 6 M H2SO4 for 30 min gave higher crys- with CNC while elongation at break decreased.
tallinity index of 87.5%.21 Rice straw hydrolyzed by Tensile strength is the maximum tensile stress sus-
64% H2SO4 for 45 min yielded CNC with crystallinity tained by the film when tested under tension. High ten-
index of 91.2%.13 The lower crystallinity could be sile strength is generally required, but usually values
attributed to the longer hydrolysis time. Despite the were adjusted according to the proposed application
milder acid condition and temperature, the 3-h expos- of the film.23 The tensile strength of CNC-reinforced
ure of the fibers to acid may have destroyed not films increased with increasing starch: CNC ratio. The
only the amorphous parts but also some portion of highest tensile strength was observed in film with starch
the crystalline region. Similar effect of longer hydrolysis to CNC ratio of 100: 10 and showed 167% improve-
time was also observed for garlic stalks hydrolyzed ment relative to nonreinforced film (100:0). Increasing
for 5 h.22 the ratio to 100:15 also showed no significant difference
in tensile strength with that of 100:10. This could
imply that the starch to CNC ratio of 100:10 may
Characterization of the starch–CNC bioplastic films
have been optimum for improving the tensile strength
Cross-sectional morphology. The cross-sectional morph- of the film.
ology of the bioplastic films with varying starch to Crystalline materials are known to have high stiff-
CNC ratios are presented in Figure 5. The cross section ness. It is expected then that addition of cellulose nano-
of the films revealed uniform dispersion of CNCs in the crystals to thermoplastic materials will increase its
starch matrix even at higher CNC load. CNC agglom- modulus. Indeed, significant increase in modulus was
eration and unplasticized starch, which are often seen observed for reinforced films even at very low CNC
as white spots were not seen in the micrographs. The content. Similar with the trend in tensile strength, the
homogeneous dispersion of CNC in the starch matrix modulus of 100:2.5 and 100:5 ratios of starch to CNC
can be ascribed to the relatively small size of the crys- are not significantly different. Also, 100:5 and 100:15
tals and the strong H-bonding interaction between cel- ratios gave the highest modulus resulting to 175%
lulose and starch. improvement.

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:47am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

Agustin et al. 7

Table 1. Mechanical properties and moisture uptake of the bioplastic films with varying starch to CNC
ratios.

Tensile Young’s Percent elongation % Moisture

Starch: CNC ratio strength (MPa) modulus (MPa) at break (%) uptake

100:0 10.0  0.5a 327  52a 33.1  2.6a 13.8  0.3

100:2.5 13.9  0.9b 531  44b 20.9  2.8b 11.0  0.5
100:5 14.0  1.5b 504  26b 23.1  2.4b 9.5  0.2
100:10 26.8  0.8c 898  50c 4.2  0.2c 10.0  0.6
100:15 26.0  1.2c 896  51c 3.6  0.4c 10.1  0.1
Treatments with same letter superscript are not significantly different at 95% confidence level.

The increase in stiffness of the film on the other hand

decreased its elasticity evident from the significant 120
100:0
decrease in percent elongation at break (%EB) of 100:2.5
CNC-reinforced films. In contrast to the trend in tensile 100 100:5
strength and modulus, %EB decreased with increasing 100:10

% weight loss
80 100:15
concentration of CNC in the films.
The reinforcing effect of CNC in TPS could be
attributed to strong filler-matrix compatibility and 60

good filler dispersion. The compatibility of cellulose

with starch has been widely acknowledged due to the 40

hydroxyl groups that can form hydrogen-bonds. CNCs

and starch forming hydrogen bonds can form a rigid 20

network that reinforced the resulting bioplastic film.20

Good dispersion of filler in the matrix also account for 0
100 200 300 400 500 600
better reinforcement. Filler aggregation results to a het- Temperature / C
o

erogeneous phase, featuring discontinuities thereby

resulting to decrease in mechanical properties.23 The
Figure 6. Thermogravimetric curves of the bioplastic films with
increase in mechanical properties of the film even at
varying starch to CNC ratios.
higher concentration could therefore confirm the uni-
form dispersion of CNC in the starch matrix as seen in
the SEM. However, the nonsignificant difference
between the mechanical properties of 100:10 and Table 2. Thermal characteristics of the bioplastic films with
100:15 starch-to-CNC ratios may imply that there varying starch to CNC ratios.
may have been CNC aggregation at 100:15 ratio,
Starch: % Residue
which may not be visible in the SEM micrographs. CNC ratio T5%WL Tmax ( C) at 500 C
The small difference in the amount of CNC between
the two ratios may also be the reason for their similar 100: 0 171.6 323.75 7.742
mechanical properties. 100: 2.5 222.8 318.42 11.38
100: 5 214.0 314.2 13.35
Moisture uptake. One of the weak points of starch-based 100: 10 209.7 306.87 17.13
bioplastics is its poor resistance to moisture. Therefore, 100: 15 210.9 277.36 20.37
filler addition does not only aim to enhance mechanical
properties but also to improve the water resistance of T5%WL: temperature at 5% weight loss; Tmax: temperature at maximum
weight loss rate.
starch-based materials. The moisture uptake of the
films (Table 1) decreased with the addition of CNC.
The decrease can be attributed to the formation of
hydrogen bonding between the CNCs and the hydroxyl Thermal stability. This is one of the important properties
functional group of the starch matrix.24 The resulting of a material that determines its usability at high tem-
hydrogen-bonded network of cellulose with the starch perature applications. The thermogravimetric curves of
in the composite could have prevented the formation of each film are shown in Figure 6. The thermal data
voids where water molecules can pass through. obtained from these curves are given in Table 2.

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:47am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

8 Journal of Reinforced Plastics and Composites 0(0)

After the removal of adsorbed moisture by isother- Conflict of interest

mal heating at 110 C, the loss in weight of the films None declared.
varied with the addition of CNC. Nonreinforced film
(100:0) showed 5% weight loss at temperatures lower Funding
than 200 C while CNC-reinforced films are relatively
This research was supported by the International Foundation
stable at this low temperature. All CNC-reinforced
for Science through a grant (F/4928-1) for M. B. Agustin and
films had had 5% weight loss temperatures above by the Grants-in-Aid for Young Scientists (B) (No. 26810117,
200oC. As the temperature was increased to 400 C, all 2014–2015) from the Japanese Society for the Promotion of
films underwent rapid thermal decomposition as Science.
reflected in the abrupt downward inflection of the
curve in Figure 6. All films have maximum weight-
References
loss rate temperatures (Tmax) in the range of
277–323 C and this coincided with the widely accepted 1. Khalil HPSA, Tehrani MA, Davoudpour Y, et al.
Natural fiber reinforced poly(vinyl chloride) composites:
primary thermal decomposition of cellulosic materials
A review. J Reinf Plast Compos 2013; 32: 330–356.
which lies between 200 C and 400 C. However, add-
2. La Mantia FP and Morreale M. Green composites: A
ition of CNCs shifted Tmax to lower temperatures. As brief review. Compos Part A: Appl Sci Manuf 2011; 42:
the amount of CNC increases, the Tmax decreases, indi- 579–588.
cative of decreasing thermal stability. The decrease in 3. Shen L, Haufe J and Patel MK. Product overview and
thermal stability of the film reinforced with CNC can market projection of emerging bio-based plastics. Report,
be ascribed to the inherent low thermal stability of Utrecht University, The Netherlands, June 2009.
CNCs obtained by sulfuric acid hydrolysis. According 4. Dogossy G and Czigany T. Thermoplastic starch com-
to Julien et al.25 less energy is required to remove sul- posites reinforced by agricultural by-products: Properties,
furic acid in sulfated anhydroglucose units of cellulose. biodegradability, and application. J Reinf Plast Compos
The sulfuric acid released is reported to catalyze the 2011; 30: 1819–1825.
removal of ring hydroxyl groups by dehydration or 5. HabibiY, Lucia LA and Rojas OJ. Cellulose nanocrys-
tals: Chemistry, self-assembly, and applications. Chem
esterification.26 Beyond 400 C, the loss in weight yield-
Rev 2010; 110: 3479–3500.
ing the char residue was relatively constant. 6. Sathiskumar TP, Naveen J and Satheeshkumar S. Hybrid
Nonreinforced films gave the lowest char residue fiber reinforced polymer composites - a review. J Reinf
while CNC-reinforced films showed increasing char Plast Compos 2014; 33: 454–471.
residue with increasing CNC content. Sulfate groups 7. Nunna S, Chandra PR, Shrivastava S, et al. A review on
on the surface of the CNC are known to act as mechanical behavior of natural fiber based hybrid com-
flame retardant increasing the char residue during posites. J Reinf Plast Compos 2012; 31: 759–769.
pyrolysis.26 8. Bhatnagar A and Sain M. Processing of cellulose nano-
fiber-reinforced composites. J Reinf Plast Compos 2005;
24: 1259–1268.
9. Pasquini D, Teixeira EDM, Curvelo AADS, et al.
Conclusions Extraction of cellulose whiskers from cassava bagasse
and their applications as reinforcing agent in natural
Short, rod-like cellulose nanocrystals with a narrow
rubber. Ind Crop Prod 2010; 32: 486–490.
width distribution of 10–12 nm and crystallinity of 10. Fleming K, Gray DG and Matthews S. Cellulose crystal-
76.1% can be isolated from rice straw at a relatively lites. Chem Eur J 2001; 7: 1831–1835.
milder condition (30 C and 50% H2SO4) but longer 11. Azizi Samir MAS, Alloin F and Dufresne A. Review
hydrolysis time (3 h). The isolated CNCs can be used of recent research into cellulosic whiskers, their
as reinforcing filler for starch-based bioplastics. Tensile properties and their application in nanocomposite field.
strength and modulus significantly increased with Biomacromolecules 2005; 6: 612–626.
increasing CNC load. Elongation at break, however, 12. Philippine Rice Research Institute. PhilRice to study rice
decreased. The moisture resistance of the starch-based straw as power source, http://www.philrice.gov.ph (2012,
bioplastics can also be enhanced by CNC addition, accessed April 2013).
which can be related to the rigid network of crystalline 13. Lu P and Hsieh YL. Preparation and characterization of
cellulose nanocrystals from rice straw. Carbohydr Polym
cellulose that hinders the absorption of water.
2012; 87: 564–573.
However, the inherent low thermal stability of sulfuric 14. Elanthikkal S, Gopalakrishnapanicker U, Varghese S,
acid-hydrolyzed CNC decreased the thermal stability et al. Cellulose microfibres produced from banana plant
of the bioplastic. If aiming for thermally stable CNC- wastes: Isolation and characterization. Carbohydr Polym
reinforced bioplastic, thermal stabilization of sulfuric- 2010; 80: 852–859.
acid hydrolyzed CNC should be considered for future 15. Segal L, Creely JJ, Martin AE, et al. An empirical
work. method for estimating the degree of crystallinity of

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014

XML Template (2014) [30.10.2014–9:47am] [1–9]
//blrnas3.glyph.com/cenpro/ApplicationFiles/Journals/SAGE/3B2/JRPJ/Vol00000/140109/APPFile/SG-JRPJ140109.3d (JRP) [PREPRINTER stage]

Agustin et al. 9

native cellulose using the X-ray diffractometer. Tex Res J 21. Teixeira EDM, Bondancia TJ, Teodoro KBR, et al.
1959; 29: 786–794. Sugarcane bagasse whiskers: Extraction and characteriza-
16. Chen X, Yu J, Zhang Z, et al. Study on struc- tions. Ind Crop Prod 2011; 33: 63–66.
ture and thermal stability properties of cellulose 22. Agustin MB, Ahmmad B, De Leon ERP, et al. Starch-
fibers from rice straw. Carbohydr Polym 2011; 85(1): based biocomposite films reinforced with cellulose nano-
245–250. crystalsfrom garlic stalks. Polym Compos 2013; 34:
17. Rosa MF, Medeiros ES, Malmonge JA, et al. Cellulose 1325–1332.
nanowhiskers from coconut husk fibers: Effect of prep- 23. Wittaya T. Microcomposites of rice starch film reinforced
aration conditions on their thermal and morphological with microcrystalline cellulose from palm pressed fiber.
behavior. Carbohydr Polym 2010; 81: 83–92. Intl Food Res J 2009; 500: 493–500.
18. Lee J and Cheng Y. Critical freezing rate in freeze drying 24. Cañigueral N, Vilaseca F, Méndez JA, et al. Behavior
nanocrystal dispersions. J Control Release 2006; 111: of biocomposite materials from flax strands and
185–192. starch-based biopolymer. Chem Eng Sci 2009; 64:
19. Teixeira EDM, Pasquini D, Curvelo AAS, et al. 2651–2658.
Cassava bagasse cellulose nanofibrils reinforced thermo- 25. Julien S, Chornet E and Overend RP. Influence of acid
plastic cassava starch. Carbohydr Polym 2009; 78: pretreatment (H2SO4, HCl, HNO3) on reaction selectivity
422–431. in the vacuum pyrolysis of cellulose. J Appl Pyro 1993;
20. Siqueira G, Bras J and Dufresne A. Cellulose whiskers 21: 25–43.
versus microfibrils: Influence of the nature of the nano- 26. Roman M and Winter TW. Effect of sulfate groups from
particle and its surface functionalization on the thermal sulfuric acid hydrolysis on the thermal degradation
and mechanical properties of nanocomposites. behavior of bacterial cellulose. Biomacromolecules 2004;
Biomacromolecules 2009; 10: 425–432. 5: 1671–1677.

Downloaded from jrp.sagepub.com at Northeastern University on November 27, 2014