Extraction of microcrystalline cellulose from rice straw and its effect on polyvinyl

alcohol biocomposites film

Kwok-Mern Chin, Sam Sung Ting, Ong Hui Lin, and Wei Tieng Owi

Citation: AIP Conference Proceedings 1865, 040006 (2017); doi: 10.1063/1.4993348

View online: http://dx.doi.org/10.1063/1.4993348
View Table of Contents: http://aip.scitation.org/toc/apc/1865/1
Published by the American Institute of Physics

Articles you may be interested in

A comparative study of green composites based on tapioca starch and celluloses
AIP Conference Proceedings 1865, 040019 (2017); 10.1063/1.4993361
 Extraction of Microcrystalline Cellulose from Rice Straw
and Its Effect on Polyvinyl Alcohol Biocomposites Film
Kwok-Mern Chin1, Sam Sung Ting1, Ong Hui Lin2, Wei Tieng Owi2
1
School of Bioprocess Engineering, Universiti Malaysia Perlis (UniMAP), 02600 Arau, Perlis, Malaysia
2
School of Materials Engineering, Universiti Malaysia Perlis (UniMAP), 02600 Arau, Perlis, Malaysia.

Abstract. The poor management and underutilization of agricultural wastes had proliferated interest of researchers around the
world to find alternatives to utilize them as potential value-added products. One of the green alternatives is by extracting cellulose
from these waste materials and incorporating them in polymer as reinforcement fillers. The surging amount of plastic waste also
posed major issues to the environment due to its recalcitrance to degrade. Microcrystalline cellulose (MCC-RS) was extracted from
rice straw through cyclic alkaline and bleaching treatment to remove hemicellulose and lignin respectively. Polyvinyl alcohol
(PVOH) was chosen as the matrix and different ratios of PVOH / MCC-RS films were prepared (2.5, 5.0, 7.5 and 10.0wt% of
MCC) through solution casting method and its tensile, thermal and morphological properties were studied. X-ray powder diffraction
(XRD) results showed increased crystallinity of MCC-RS after chemical treatment (from 44.5% to 60.8%) due to the successful
removal of lignin and hemicellulose, which was then confirmed with Fourier transform infrared spectroscopy (FTIR) results. For
the biocomposites, both tensile strength and Young’s modulus of the films increased with increasing MCC-RS content up until
7.5wt%, supported with scanning electron microscopy (SEM) results which depicted improvement in the interfacial adhesion
between MCC-RS and PVOH. From the overall results, the improvement in properties of biocomposite from cellulose-based
microfiller had shown promising future in application of the water soluble plastic packaging industry.

Keywords: microcrystalline cellulose (MCC), rice straw, polyvinyl alcohol (PVOH), biocomposite

INTRODUCTION

The vast development of plastic based industries had led to uncontrollable uses of this petrochemical based
product in many different areas and industries around the world. Polymers, which can occur in different forms and
properties, had undoubtedly play a vital role in our daily lives [1]. However, polymers such as polypropylene (PP),
polyethylene (PE) and polyvinyl chloride (PVC) are non-biodegradable, thereby causing serious environmental issues
such as water pollution, greenhouse effects and increase in dumpsites and landfills. Researches on blending non-
degradable polymer such as PE and PP with nature based materials to stimulate biodegradation had proven to be
successful but this approach is not entirely sustainable [2]. As such, these problems have stipulated the increase in
researches on environmental friendly and fully biodegradable polymers for the past few decades [3-5]. Biodegradable
polymers are completely biodegradable in the natural environment and can be made from renewable natural materials
or biodegradable petrochemical polymers. Polyvinyl alcohol (PVOH), a biodegradable synthetic petrochemical
polymer, is currently being widely used in various fields such as medicine, health, packaging and adhesive industry
due to its mediocre mechanical properties, non-toxic, inert and excellent biocompatibility nature [6]. Therefore, further
improvements in terms of mechanical properties can be made through the introduction of reinforcement fillers into
the system. Cellulose, which occurs in abundance around the world and is fully biodegradable, can be utilized as
reinforcement fillers in polymer composites [7-8]. Microcrystalline cellulose (MCC), which is the filler of interest,
can be produced through a series of mechanical grinding and chemical treatments. Due to their remarkable tensile
strength of approximately 6GPa, MCC can address the discrepancies posed by PVOH. In the present study, thin films
of MCC reinforced biodegradable composite with different ratio of MCC content were prepared and characterized.

EXPERIMENTAL CONDITION
Materials
Polyvinyl alcohol was purchased from Sigma Aldrich (Mw 89,000-98,000, 99+% hydrolyzed). Dry rice straw
was collected from paddy field in Arau, Perlis (6°25'58.0"N+100°13'56.8"E). All other reagents and solvents are
sodium hydroxide (NaOH) sodium chlorite (NaClO2) and acetic acid glacial (CH3COOH) purchased from Merck,
Acros and HmbG respectively.

Proceeding of the 3rd International Conference of Global Network for Innovative Technology 2016 (3rd IGNITE-2016)
AIP Conf. Proc. 1865, 040006-1–040006-6; doi: 10.1063/1.4993348
Published by AIP Publishing. 978-0-7354-1545-4/$30.00

040006-1
 Sample Preparation
Initially, dry rice straw was washed thoroughly with running water to remove impurities such as sand and dirt and
left to dry outdoors for 48 hours. The dried and cleaned rice straw was milled with a grinder to pass through a 150-
mesh screen. After that, the rice straw fiber was treated with a sodium hydroxide aqueous solution of 4% (w/w) for 2
hours at 80oC under mechanical stirring. The rice straw fiber was then washed several times with distilled water until
the alkali was completely removed or pH reached 7. After this treatment, the rice straw fiber was bleached with a
solution made up of equal parts (v:v) of acetate buffer (40 g NaOH and 75 mL glacial acetic acid, diluted to 1 L of
distilled water) and aqueous chlorite (1.7 wt.% NaClO2 in water). This bleaching treatment was also performed at
80oC for 2 hours under mechanical stirring. Then, rice straw fiber was washed again with distilled water until pH
reached 7. Both these treatments was repeated for 4 cycles with a 1:20 fiber to liquid ratio until a white colored
microcrystalline cellulose (MCC-RS) pulp was obtained. The MCC pulp was dried in an oven at 40oC for 24 hours
prior to biocomposites preparation. PVOH solution was prepared by dissolving free-flowing granules of PVOH in
distilled water to a predetermined concentration of 5 wt% at 80oC for 30 minutes under mechanical stirring. Varying
proportions of MCC-RS will be added to the prepared PVOH solution to adjust the MCC concentration to 0, 2.5, 5.0,
7.5 and 10.0 wt% (of the weight of the solid PVOH content) respectively. The final suspension will then be casted in
an acrylic plate and dried in an oven at 35oC for 24 hours. The films obtained will be kept in a drying cabinet to
equilibrate for 24 hours before characterization.

Characterization
Infrared spectra of rice straw fiber, MCC-RS and PVOH/MCC-RS biocomposite films were obtained in the
range of 4000–650 cm-1 wavenumber with 32 scans and at a resolution of 4 cm-1 by using a FTIR spectrophotometer
of model PerkinElmer Spectrum 10 in attenuated total reflection (ATR) mode. The crystallinity of the rice straw fiber
and MCC-RS was analyzed by Bruker D2 Phaser X-ray diffractometer with a monochromatic CuKα radiation source.
The measurements were performed at a step size of 0.02o in a 2θ angle range of 10o to 40o. The crystallinity index
(CrI) was calculated by using peak area method. In order to study the fractured morphology of the biocomposite films
and the structure of rice straw fiber and cellulose, all samples were first coated with platinum through JEOL JFC-1600
Auto Fine Coater. Then, SEM micrographs of the samples were taken by using scanning electron microscopy (SEM)
of model JEOL JSM-6460 LA. Tensile test was performed on five specimens with 10mm x 1mm dimension at a strain
rate of 50mm/min. A total of ten measurements of tensile strength, elongation at break and Young’s modulus were
performed for each formulation and the average results were obtained.

RESULTS AND DISCUSSION

Microcrystalline Cellulose from Rice Straw (MCC-RS)

Figure 1 shows the FTIR spectra of cellulose and untreated rice straw fiber respectively. The peak at
wavenumber 1739 cm-1 and 1514 cm-1 which constitutes the vibration of lignin and 789 cm -1 which constitutes the
vibration of hemicellulose disappeared after MCC-RS was obtained after alkaline and bleaching treatment of rice
straw [9-10] . Moreover, the intensity of the peak at 1061 cm-1 of MCC-RS which is attributed to cellulose is much
higher than untreated rice straw. Interestingly, there are no new peaks which can be observed in between MCC-RS
and untreated rice straw. This finding revealed the fact that there is no chemical reaction occurred during the alkaline
and bleaching treatment of rice straw to obtain MCC-RS, which then proved the success of the chemical treatments
employed to obtain MCC-RS from rice straw.

040006-2
 Figure 1: FTIR spectra of (a) MCC-RS and (b) untreated Figure 2: X-ray diffraction of (a) MCC-RS
rice straw fiber and (b) untreated rice straw fiber

The crystalline type of cellulose and its crystallinity degree can be determined from the interpretation of XRD
diffraction patterns of untreated rice straw and MCC-RS in Figure 2. The characteristic peaks which occur around
16.1o and 22.4o is ascribed to a typical cellulose I crystal lattice structure [10]. A narrower and more intense peak was
shown at 22.4o in the diffraction pattern of MCC-RS indicate that the removal of hemicellulose and lignin through
chemical treatments had caused a significant improvement in the crystallinity index of MCC-RS as compared to
untreated rice straw (from 44.5% to 60.8%). This will directly improve the tensile strength of the MCC-RS fibers itself
[11]. Therefore, it is expected that the mechanical properties of the biocomposites will improve as well through the
addition of MCC-RS fibers which was shown in Figure 6 in the later section [10, 12]. In addition, this phenomenon
also implies that MCC-RS was able to form better and more organized structure at the crystalline interfaces which
have surpassed the original crystalline order of the untreated rice straw. Next, SEM images of the untreated rice straw
fiber and MCC-RS are shown in Figure 3. It can be clearly seen that the morphology of the untreated rice straw fiber
was contrastive with the morphology of the MCC-RS. This is due to the success of the removal of amorphous
hemicellulose and lignin which enveloped the untreated rice straw fiber through chemical treatments, leaving only
cellulose behind. The smoother, web-like appearance of MCC-RS and the reduction in average diameter of the MCC-
RS to approximately 3μm will provide a larger surface area for hydrogen bonding with PVOH.

Figure 3: SEM images of (a)-(b) untreated rice straw fiber and (c)-(d) MCC-RS

040006-3
 Polyvinyl Alcohol / Microcrystalline Cellulose Biocomposites (PVOH/MCC-RS)
Figure 4 shows the FTIR spectra of PVOH/7.5MCC-RS, PVOH/2.5MCC-RS 2.5 and neat PVOH,
respectively. As for the case of neat PVOH, the spectrum portrayed characteristic PVOH absorption bands which
consist of -OH stretching at 3298 cm-1, asymmetric –CH2 stretching at 2938 cm-1, symmetric -CH2 stretching at 2920
cm-1, stretching of C=O at 1660 cm-1, bending of CH2 at 1420 cm-1 and stretching of C-O at 1088 cm-1 [13-14]. From
the observed differences in the –OH region (3200-3500cm-1) of the Figure 4(a) - 4(c), it can be inferred that the
addition of MCC-RS into the PVOH matrix had reduced the intensity of -OH stretching region. This phenomenon was
to be expected due to decreasing concentration of PVOH in respect to the increasing filler content in the biocomposites
[15]. Similar reduction in the C=O absorption band at 1660cm -1 can be seen that is related to the decrease in the
amount of unreacted acetate group of PVOH in the biocomposites, which then signified that there is increase in amount
of hydrogen bonding interaction between MCC-RS and PVOH. SEM images of the fractured surface of neat PVOH
and PVOH/7.5MCC-RS are shown in Figure 5. As for neat PVOH, the fractured surface appears to be smooth while
for PVOH/7.5MCC-RS, protruding MCC-RS fibrils were seen on the fractured surface which demonstrated the strong
bonding between the MCC-RS with PVOH [16].

Figure 4: FTIR spectra of PVOH with (a) 7.5wt% (b) 2.5wt% of MCC-RS content and (c) neat PVOH

Figure 5: SEM images of (a) fractured surface of neat PVOH and (b) fractured surface of PVOH/7.5MCC-RS

Figure 6 shows the tensile strength and Young’s modulus of PVOH as a function of MCC-RS content. The
Young’s modulus increases with increasing filler content up until 7.5wt% MCC-RS, then level off at higher filler

040006-4
loading. It is interesting to note that the Young’s modulus of PVOH with 7.5wt% MCC-RS approximately doubled
the Young’s modulus of neat PVOH, reaching up to 2.26GPa from 1.06GPa of neat PVOH which the increase is much
higher than PVOH with commercial microfbrillated cellulose [17]. This increase in Young’s modulus can be ascribed
to several reasons, one of which the improvement is due to the dense and extensive intermolecular and intramolecular
of MCC-RS, coupled with its web-like structure with intrinsic rigidity and stiffness. Next, the high surface area of
MCC-RS, excellent compatibility of MCC-RS with PVOH and the homogeneous, uniform distribution of MCC-RS
in PVOH had led to this occurrence as well. At 10wt% MCC-RS content, the drop in Young’s modulus is mainly due
to the oversaturation and agglomeration of MCC-RS. In terms of tensile strength, the trend is similar to that of Young’s
modulus. There is an approximate 38.3% increase in the tensile strength of PVOH with 7.5wt% MCC-RS as compared
to the neat PVOH. Efficient stress transfer of between chains of PVOH and MCC-RS are mainly responsible for this
phenomenon [18-19]. Again, aggregation of MCC-RS at 10wt% MCC-RS content had influenced the sharp drop in
tensile strength. On the other hand, Figure 7 illustrates the elongation at break of PVOH as a function of MCC-RS
content. It can be observed that the elongation at break decreases with increasing MCC-RS content. This is probably
attributed to the “hardening” effect of highly crystalline and rigid MCC-RS on the soft chains of the PVOH matrix,
thereby substantially reduced the overall chain mobility of all biocomposites with MCC-RS content.

70

35 2.50
Tensile 60
Strength
30 Young's

Elongation at break (%)

Modulus 2.00 50
Young's Modulus (GPa)
Tensile Strength (MPa)

25
40
20 1.50
30
15 1.00
20
10
0.50
5 10

0 0.00 0
0 2.5 5.0 7.5 10.0 0 2.5 5.0 7.5 10.0
MCC-RS Content (wt%) MCC-RS Content (wt%)

Figure 6: Tensile strength and Young’s modulus of Figure 7: Elongation at break of PVOH as a function of
PVOH as a function of MCC-RS content MCC-RS content

CONCLUSION

Microcrystalline cellulose (MCC-RS) was successfully extracted from rice straw fiber. The crystallinity of
MCC-RS was found to be much higher than of rice straw fiber. PVOH with 7.5wt% of MCC-RS showed the best
tensile strength and Young’s modulus, reaching up to 30.6MPa and 2.26GPa respectively. Such biocomposites showed
promising applications in food and biomedical packaging industry. All in all, the incorporation of MCC-RS into
PVOH matrix had proved its capability to act as a reinforcement filler in the biocomposite.

040006-5
 REFERENCES
1. R.J. Young and P.A Lovell, Introduction to polymers (3rd ed.), Boca Raton, Fla: CRC (2012).
2. T. Fakhrul and M. Islam, Procedia Engineering 56, 795-800 (2013).
3. A.N. Nakagaito and H. Yano, Cellulose 15, 555–559 (2008).
4. A.N. Nakagaito, A. Fujimura, T. Sakai, Y. Hama and H. Yano, Composites Science & Technology 69,
1293-1297 (2009).
5. X. Huang and A.N. Netravali, Composites Science & Technology 69, 1009–1015 (2009).
6. M.P.D. Paula, T.M. Lacerda and E. Frollini, eXPRESS Polymer Letters 2(6), 423-428 (2008).
7. M. Jawaid and H.P.S. Abdul Khalil, Cellulosic/synthetic fibre reinforced polymer hybrid composites: A
review. Carbohydrate Polymers 86, 1–18 (2011).
8. S. Kalia, A. Dufresne, B.M. Cherian, B.S Kaith, L. Avérous, J. Njuguna, and E. Nassiopoulos,
International Journal of Polymer Science, 1-35 (2011).
9. F. Xu, J.X. Sun, R.C. Sun, P. Fowler and M.S. Baird, Industrial Crops and Products 23, 180–193 (2006).
10. G. Fan, M. Wang, C. Liao, T. Fang, J. Li, J. and R. Zhou, Carbohydrate Polymers 94, 71– 76 (2013).
11. X. Chen, J. Yu, Z. Zhang and C. Lu, Carbohydrate Polymers 85, 245–250 (2011).
12. E.S. Mohamed and L.H. Mohammad, Carbohydrate Polymers 67, 1–10 (2007).
13. D. Edgren, P.C. Zhu, E. Struble, R. Frame and Y. Zhang, Journal of Macromolecular Science A 47, 545–
551 (2010).
14. S. Guzman-Puyol, L. Ceseracciu, J. Heredia-Guerrero, G.C. Anyfantis, R. Cingolani, A. Athanassiou, and
I.S. Bayer, Chemical Engineering Journal 277, 242–251 (2015).
15. M. Karimi and F. Asadi, Journal of Textiles and Polymers 1(1), 1-8 (2013).
16. K. Qiu and A.N. Netravali, Composites Science and Technology 72, 1588–1594 (2012).
17. J. Lu, T. Wang, and L.T. Drzal, Composites: Part A 39, 738–746 (2007).
18. A.L.S. Pereira, D.M. do Nascimento, M.M.S. Filhoc, J.P.S. Morais, N.F. Vasconcelos, J.P.A. Feitosa,
A.I.S. Brígida and M.F. Rosa, Carbohydrate Polymers 112, 165–172 (2014).
19. Y.M. Zhou, S.Y. Fu, L.M. Zheng and H.Y. Zhan, eXPRESS Polymer Letters 6, 794–804 (2012).

040006-6