Materials Science Forum Vol 695 (2011) pp 170-173 Online: 2011-07-27

© (2011) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/MSF.695.170

Effect of Microcrystalline Cellulose from Banana Stem Fiber on

Mechanical Properties and Cystallinity of PLA Composite Films
Voravadee Suchaiya1,2,a, Duangdao Aht-Ong1,2,b*
1
Department of Materials Science, Faculty of Science, Chulalongkorn University,
Bangkok, 10330 Thailand
2
National Center for Petroleum, Petrochemicals, and Advanced Materials, Chulalongkorn University,
Bangkok, 10330 Thailand
a
Voravadee_aung@yahoo.com, bduangdao.a@chula.ac.th

Keywords: biocomposite film, microcrystalline cellulose, polylactic acid, agricultural waste, cellulose
powder

Abstract. This work focused on the preparation of the biocomposite films of polylactic acid (PLA)
reinforced with microcrystalline cellulose (MCC) prepared from agricultural waste, banana stem
fiber, and commercial microcrystalline cellulose, Avicel PH 101. Banana stem microcrystalline
cellulose (BS MCC) was prepared by three steps, delignification, bleaching, and acid hydrolysis. PLA
and two types of MCC were processed using twin screw extruder and fabricated into film by a
compression molding. The mechanical and crystalline behaviors of the biocomopsite films were
investigated as a function of type and amount of MCC. The tensile strength and Young’s modulus of
PLA composites were increased when concentration of MCC increased. Particularly, banana stem
(BS MCC) can enhance tensile strength and Young’s modulus of PLA composites than the
commercial MCC (Avicel PH 101) because BS MCC had better dispersion in PLA matrix than Avicel
PH 101. This result was confirmed by SEM image of fractured surface of PLA composites. In
addition, XRD patterns of BS MCC/PLA composites exhibited higher crystalline peak than that of
Avicel PH 101/PLA composites
Introduction
Polylactic acid (PLA) is the most popular biodegradable polymer because of its good mechanical
properties, i.e. high tensile strength and high Young's modulus [1]. Nevertheless, PLA is rather
expensive. Mixing of PLA and natural polymers such as starch or microcrystalline cellulose is one
of the ways for reducing cost of PLA. Microcrystalline cellulose (MCC) is popular filler of polymer
because it has a high Young's modulus, biodegradability, and low cost [1]. The cooperation of PLA
and MCC to prepare fully-biodegradable polymer is aimed to lower PLA price. Therefore, the
objective of this study is to prepare biocomposite films of PLA reinforced with MCC prepared from
banana stem fiber, one of the agricultural wastes in Thailand and commercial MCC, Avicel PH 101.
The PLA and MCC were mixed in a twin screw extruder and fabricated by a compression molding.
The effects of types and amount of MCC on mechanical properties and crystalline behaviors of the
PLA composites were studied. The average particle size of BS MCC and Avicel PH 101 was
measured by laser particle size analyzer. The morphology of composites was investigated by
scanning electron microscope (SEM). The mechanical properties of biocomposite films were
evaluated by tensile testing. Crystalline behavior of biocomposite films was characterized by X-ray
difractometer.
Experiment
Materials. Polylactic acid (PLA 2002D) was supplied from NatureWork LLC. An analytical grade of
37% hydrochloric acid, HCl, and 35% hydrogen peroxide, H2O2, were obtained from Qrec chemical
Manufacture. Commercial microcrystalline cellulose, Avicel PH101 obtained from Fluka. Dried
banana stem was used as raw material for microcrystalline cellulose preparation.

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 Materials Science Forum Vol. 695 171

Microcellulose preparation. 1,000 g of dried banana stem was heated and stirred in 1 M of NaOH
for 4 hr and then bleached with 8 % of H2O2 in 15% of NaOH for 45 min at 90 °C. Next, bleached
pulp was hydrolyzed and stirred vigorously with 2.5 N of HCl solution for 2.5 hr. The ratio of fiber
and solvent was 1:10. Then, the suspension was filtered and washed with distilled water until the pH
reached to neutral. Subsequently, obtained microcrystalline cellulose was dried in an oven at 60°C
over night, and ground to decrease its agglomeration.
Biocomposite preparation. MCC and PLA were physically pre-mixed prior to feeding into a twin
screw extruder (PRISM TSE 16 TC, Thermo Electron Corporation, UK) at various ratios of
reinforcement (i.e., 10, 20, 30, and 40 wt%). The mixtures were fed into the twin screw extruder
which had a screw diameter of 17.8 and L/D ratio of 40. The temperature profiles for four heating
zones of the twin screw extruder were set as 130, 150, 180, and 180 °C and a screw speed was fixed at
32 rpm. Then PLA compound pellet was fabricated into films by compression molding. Dried
compound pellet was preheated for 7.5 min by, hot compressed into films at 180 °C for 7 min, and
then cooled down in the mold for 20 min, respectively.
Characterization and Testing. The morphology of MCC and biocomposite films was studied using
scanning electron microscope (SEM; JSM 6480, JOEL, Tokyo, Japan) with accelerating voltage of 15
kV. The surfaces of samples were coated with thin layer of gold before being scanned to improve
quality of SEM image. Average particle size of MCC was determined by the laser particle size
analyzer (Matersizer 2000, Malvern, Worcestershire, UK). The mechanical properties of the
biocomposite films were measured by tensile test following ASTM D638 using a universal testing
machine (LR100k, LLOYD, Fareham, UK) with a crosshead speed of 50 mm/min and a gauge length
of 10 cm. Crystallinity behavior of biocomposite films was investigated by Philips X-ray
diffractometer (PW3710) with a scan scpoe between 2º and 50º
Results and discussion
The average particle sizes of BS MCC and Avicel PH 101 determined by laser particle size
analyzer were 27 µm and 50 µm, respectively. Fig 1 showed SEM micrographs of BS MCC and
Avicel PH 101. BS MCC (Fig. 1a.) presented the mixture between flake and pellet shape with smooth
surface; whereas, Avicel PH 101 (Fig. 1b.) displayed short fiber with rough surface. The particle size
of Avicel PH 101 seemed to be larger when compared with BS MCC. This result was in good
agreement with the average particle size measured by the laser particle size analyzer.

(a) (b)
Fig.1. SEM micrograph of (a) BS MCC and (b) Avicel PH 101
The tensile strength and Young’s modulus of PLA biocomposites were shown in Fig. 2(a)
and 2(b), respectively. As presented in Fig. 2(a) and 2(b), PLA rienforced with MCC shown better
tensile strength and Young’s modulus values than that of neat PLA. Moreover, the tensile strength
and Young’s modulus values of PLA composites was increased when the concentration of MCC
increased. The improvement of tensile strength and Young’s modulus indicated that the applied
stress can be efficiently transfer from matrix to stronger reinforcement [1]. As shown in Fig. 2(a)
and 2(b), the BS MCC displayed greater efficiency to enhance the tensile strength and Young’s
modulus of PLA than Avicel PH 101, probably because of the difference in the particle size of
reinforcement. Due to the smaller particle size of BS MCC comparing to Avicel PH 101, BS MCC
had better dispersion in PLA matrix than Avicel PH 101 in accordance with SEM micrograph of
172 Eco-Materials Processing and Design XII

fractured surface of PLA composites. The highest tensile strength and Young’s modulus of PLA
composites presented at 40%wt of BS MCC and 30 wt% in case of Avicel PH 101. This is because
the addition of 40 wt% of Avicel PH 101 tended to agglomerate in PLA matrix. Fig. 2(c). showed
the elongation at break of neat PLA and PLA composites. Unlike tensile strength and Young’s
modulus, the elongation at break of PLA decreased when the amount of MCC increased.
Furthermore, the elongation at break of PLA composites was dramatically decreased in case of PLA
reinforced with Avicel PH 101. Because of the poor compatibility and between hydrophilic MCC
and hydrophobic PLA, their interfacial adhesion was not good leading to poor elongation at break.

(a) (b) (c)

Fig. 2. Tensile properties of Neat PLA and PLA composite: (a) tensile strength, (b) Young’s modulus, and (c) elongation
at break
The morphology of fractured surface of PLA composites was studied by SEM as shown in
Fig. 3. The fractured surface of the composites can clarify the failure mechanisms and the
interaction between reinforcement and matrix [1]. As seen, gray area presented the PLA matrix;
whereas, holes in the PLA matrix were believed to be imprints of MCC, which indicated that the
composites had poor interfacial adhesion between matrix and reinforcement. However, the SEM
images in Fig. 3(a) and 3(b) confirmed that BS MCC had better dispersion in PLA matrix than that
of Avicel PH 101 although some agglomeration of BS MCC seemed to appear in the matrix at high
concentration. The evidence of holes of MCC in PLA composite with the lack of interfacial
adhesion was responsible for the cause of failure in the composite; particularly for the decrease in
the elongation at break.
The crystallinity of reinforcements, BS MCC and Avicel PH101, and neat PLA was studied by
X-ray diffractometer. Moreover, the effects of type and amount of the reinforcement on crystalline
behavior of PLA composites were also investigated by X-ray diffractometer. Fig. 4 (a) showed the
X-ray diffraction(XRD) patterns of BS MCC, Avicel PH101,and neat PLA. As shown, neat PLA
displayed a broad peak around 2θ=10 to 25. XRD patterns of Avicel PH 101 and BS MCC are similar
to work of Dobircau and co-workers (2009), their XRD patterns showed mainly sharp peak of
α-cellulose in cellulose I structure at 2θ= 22.7 [2]. In this work, the main sharp peak and shoulder of
Avicel PH101 and BS MCC were presented at 2θ= 22.5 and at 2θ=15, respectively. From the
observation, both reinforcements displayed higher crystallinity than neat PLA. In addition, although
the main peak at 2θ=22.5 of Avicel PH 101 seemed to be narrow than BS MCC, its intensity and peak
area of Avicel PH101 seemed to be lower than BS MCC. It can be implied that BS MCC had high
crystallinity than Avicel PH101.
Fig. 4 (b) and (c) presented the XRD patterns of PLA composite reinforced with BS MCC and
Avicel PH101, respectively. As shown in these figures, PLA composites shown broad amorphous
peak and sharp crystalline peak at 2θ= 16 and 22.5 which referred to PLA amorphous and cellulose
crystalline peak, respectively. Mathew and co-worker (2004) have reported the same results of XRD
pattern for PLA reinforced with MCC and wood powder (WP) [1]. They have described that all
MCC/PLA composites presented high amorphous and weak crystalline band owing to the fast cooling
during composite fabrication. In the present work, Avicel PH 101/PLA composites shown higher
broad peak and lower sharp peark than that of BS MCC/PLA composites as shown in Fig. 4 (b) and
 Materials Science Forum Vol. 695 173

(c). It can be implied that BS MCC/PLA composites had higher crystallinity than Avicel PH 101/PLA
composites. Because of high crystallinity, BS MCC/PLA composites had good mechanical properties
such as tensile strength, Young’s modulus, and elongation at break. However, future study is
necessary to confirm this effect. This result is in agreement with tensile testing results.

(a) (b)
Fig. 3. SEM micrographs of fractured surface of (a) 30 wt% BS MCC/PLA, (b) 30 wt% Avicel PH 101/PLA

(a) (b) (c)

Fig. 4. XRD patterns of (a) reinforcement and neat PLA, (b) Avicel PH101/PLA composite and (c) BS MCC/PLA
composite.

Conclusions. The biocmposite films of PLA reinforced with MCC (0-40 wt%) prepared from banana
stem fiber or Avicel PH 101 were prepared. The results showed that the obtained MCC had smaller
average particle size than Avicel PH 101. Tensile strength and Young’s modulus of PLA composites
were increased when concentration of MCC was increased. However, the elongation at break of PLA
composites was decreased when the amount of reinforcement increased. This is because the main key
of reinforcement was to induce stiffness and strength of composite. Comparing to commercial MCC,
BS MCC had significantly enhanced tensile strength and Young’s modulus more than Avicel PH 101
due to its higher surface area and good dispersion in PLA matrix. SEM analysis suggested that future
studies should be focused on the improvement of interfacial adhesion between PLA and MCC
because the improvement of interfacial bond between reinforcement and matrix is one of the ways to
enhance the toughness, elongation, and thermal stability of PLA biocomposites. XRD patterns of BS
MCC/PLA composites presented higher crystallinity than those of Avicel PH101/PLA composites,
supporting the tensile properties results.

Acknowledgments. The authors would like to acknowledge the research scholarship from the
National Innovation Agency (NIA) through grant no. D4-52 and the National Research University
Project of CHE and the Ratchadaphiseksomphot Endowment Fund (AM001I and AM1027A) for
providing the financial support on this research. In addition, the authors would like to thank another
partial financial support from The National Center for Petroleum, Petrochemicals, and Advanced
Materials, Chulalongkorn University.

References
[1] A. P. Mathew, K. Oksaman and M. Sain. J. Appl. Polym. Sci. Vol.97 (2005), p. 2014-2025.
[2] L. Dobircau, P.A. Sreekumar, R. Saiah, N. Leblanc, C. Terrié, R. Gattin and J.M. Saiter.
Composite: Part A. Vol. 40 (2009), p.329–334.
Eco-Materials Processing and Design XII
10.4028/www.scientific.net/MSF.695

Effect of Microcrystalline Cellulose from Banana Stem Fiber on Mechanical Properties and
Crystallinity of PLA Composite Films
10.4028/www.scientific.net/MSF.695.170

DOI References
[2] L. Dobircau, P.A. Sreekumar, R. Saiah, N. Leblanc, C. Terrié, R. Gattin and J.M. Saiter. Composite: Part
A. Vol. 40 (2009), p.329–334.
doi:10.1016/j.compositesa.2008.11.004