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What is This?
Original Article
Journal of Reinforced Plastics
and Composites
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
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
Agustin et al. 3
diluted 5-fold. A drop of suspension was placed onto Instron 5585H tensometer using 50 N load cell at a
carbon-coated grid at room temperature and then crosshead speed of 12.5 mm/min. The average values
examined using TEM operating at 100 kV. The diam- from five measurements were obtained and statistical
eter of the isolated CNCs was determined by using the significance of differences in means was evaluated
software, SemAfore. For comparison, scanning elec- using the least significance difference analysis at 95%
tron micrographs of raw and delignified rice straw confidence level.
were also taken. Moisture uptake test was determined at conditions
The x-ray diffraction patterns of the untreated and with two different relative humidity values: 40% and
delignified rice straw, and the isolated CNC were 70%. Films were cut into 2 2 cm2 sheets, weighed,
measured using the Rigaku (ultimate VII) X-ray dif- and oven dried at 50 C for 24 h. Then, these were
fraction instrument operated at a target voltage of placed inside a desiccator with silica gel. The humidity
40 kV and current of 40 mA. All samples were scanned was kept constant at 40% and monitored using a
at 2y ranging from 4 to 80 at a rate of 10 /min. The hygrometer. The films were re-weighed and placed
crystallinity index was obtained using the following back in the desiccator and this process was repeated
equation15 until a constant weight that agrees within 0.0005 g is
achieved (Wo). The silica gel was replaced by a satu-
Imax Iam rated solution of sodium chloride to increase the
Crystallinity index ¼ x100%
Imax humidity to 70%. The films were weighed again and
placed back in the desiccator and this was repeated
where Imax is the maximum intensity, Iam is the min- until a constant weight that agrees within 0.0005 g
imum intensity that lies between the two most well- was reached (Wh). The moisture uptake was reported
defined peaks. as percentage and was calculated using the equation
Wh Wo
Preparation of starch-CNC bioplastic film % Moisture uptake ¼ x 100:
Wo
by solution casting
Ten grams corn starch was dissolved in 200 mL distilled Thermogravimetric analysis (TGA) was carried out
water and heated at 60 C for 15 min with constant stir- using TA Instrument Q50. The weight loss of the bio-
ring. CNC was then added in the form of a suspension plastic films due to thermal degradation was monitored
to avoid agglomeration. The amount of CNC per 100 g as a function of temperature. Five milligrams of the
(dry weight) starch was varied to identify the optimum film placed in a platinum pan was heated initially to
starch to CNC ratio. Glycerol (3 g) was then added 110 C for 10 min to remove bound moisture. The tem-
and the mixture was stirred for two h at a constant perature was then ramped to 600 C at a heating rate of
temperature of 70 C. The mixture was casted and 20 C/min under the flow of nitrogen gas.
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 Results and discussions
prepared.
CNC yield
The suspension of CNCs produced after acid hydrolysis
Characterization of starch–CNC bioplastic film had a density of 1.58 g/mL and a concentration of
The morphology of the fracture surface (cross-sectional 2.66% CNC by mass. Figure 1 shows the untreated
surface) of the starch-CNC films were visualized using a rice straw, delignified rice straw and the CNC suspen-
scanning electron microscope (SEM, JSM 5800). The sion. The delignified rice straw appears as white cottony
films were frozen in liquid nitrogen and cut into small fibers and this consequently produced a white suspen-
portions which were then mounted vertically using a sion of CNCs. The percent yield of CNC based from
small metal support on the sample holder. The samples the raw rice straws was found to be 6.6%.
were sputter coated with gold using a sputter-coater
and viewed under the scanning electron microscope.
Tensile strength and modulus were determined using
Characterization of the isolated CNC
the ASTM D882-02 method. Samples with dimensions Chemical characteristics. FTIR analysis was carried out to
of 10 cm in length, 1.5 cm in width, and 0.20 0.04 mm determine the chemical characteristics of the raw rice
in thickness were cut manually and conditioned at a straw (RRS), the delignified rice straw (DRS), and the
relative humidity of 50 5% and temperature of isolated CNC. The FTIR spectra are shown in Figure 2.
23 2 C for 24 h. Films were then stretched by All spectra show the presence of hydroxyl group
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.
1160
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.
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.
Agustin et al. 7
Table 1. Mechanical properties and moisture uptake of the bioplastic films with varying starch to CNC
ratios.
% 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
Agustin et al. 9
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