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Improvement of Biocomposite Properties Based Tapioca Starch and Sugarcane

Bagasse Cellulose Nanofibers

Article  in  Key Engineering Materials · June 2020

DOI: 10.4028/www.scientific.net/KEM.849.96

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Key Engineering Materials Submitted: 2019-10-11
ISSN: 1662-9795, Vol. 849, pp 96-101 Revised: 2020-01-15
doi:10.4028/www.scientific.net/KEM.849.96 Accepted: 2020-01-15
© 2020 Trans Tech Publications Ltd, Switzerland Online: 2020-06-24

Improvement of Biocomposite Properties Based Tapioca Starch and

Sugarcane Bagasse Cellulose Nanofibers
MOCHAMAD Asrofi1,a*, SUJITO2,b, EDI Syafri3,c, S.M. Sapuan4,d
and R.A. Ilyas4,e
1
Laboratory of Material Testing, Department of Mechanical Engineering, University of Jember,
Kampus Tegalboto, Jember 68121, East Java, Indonesia
2
Department of Physics, University of Jember, Jl. Kalimantan No. 37, Jember, 68121, East Java,
Indonesia
3
Department of Agricultural Technology, Agricultural Polytechnic, Payakumbuh, West Sumatra
26271, Indonesia
4
Advanced Engineering Materials and Composites Research Centre, Department of Mechanical
and Manufacturing Engineering, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor,
Malaysia
a
asrofi.teknik@unej.ac.id, bsujito.fmipa@unej.ac.id, cedisyafri11@gmail.com,
d
sapuan@upm.edu.my, eahmadilyasrushdan@yahoo.com

Keywords: Sugarcane Bagasse Fiber, Cellulose Nanofibers, Tapioca Starch, Biocomposite,

Tensile Properties.

Abstract. Biocomposite based tapioca starch (TS) and sugarcane bagasse cellulose nanofibers
(SBCN) was made through casting method. SBCN was prepared by chemical and ultrasonication
process. It was successfully displayed by transmission electron microscope (TEM) in range 20 -
45 nm. Meanwhile, particle size analysis (PSA) also supported the distribution diameter of SBCN
for 59.75 ± 10.84 nm. SBCN and glycerol were used as reinforcement and plasticizer, respectively.
The amount concentration of SBCN was varied from 0 to 8 wt%. Biocomposite was characterized
by using scanning electron microscopy (SEM) and tensile test. SEM image displays SBCN is in
good interfacial bonding with the matrix. The highest tensile strength of biocomposite was in
TS/4SBCN sample for 20.84 MPa. These results showed that SBCN fiber become potential
candidate as reinforcement in biocomposite application.

Introduction
The development of biodegradable materials from renewable sources is increasing due to
environmental awareness. Among of natural polymers, starch is considered as one of the most
promising candidates because its advantages such as, availability, low cost and good performance
[1,2]. Tapioca (Manihot esculenta) is an important source of starch in several countries such as
Thailand, Malaysia, Indonesia and some African regions. In addition, using of tapioca starch for
bioplastics composite has been developed by many previous researchers [3-5]. In its application,
starch has several limitations such as low tensile strength and moisture resistance. One solution to
overcome this limitation is the addition of with organic and inorganic fillers in starch matrix [6, 7].
Cellulose nano fibers (CNF) is a new type of filler which shows high efficiency in improving the
physical and mechanical properties of starch-based biocomposite. Nano particle-sized fillers have
good compatibility with matrix due to the high contact surface area [8]. One of the fiber plants
which has a high cellulose content is sugarcane bagasse. Sugarcane bagasse fiber has high α-
cellulose content approximately 85%. Other advantages are good mechanical properties, low
density, low cost and abundant in earth. Therefore, sugarcane bagasse fiber has potential to
reinforce starch biocomposite [9].
Several previous studies have explained that sugarcane bagasse cellulose has a good bond with
the starch matrix [9, 10]. This is indicated by the hydroxyl bond formation between cellulose and
starch resulting in improvement of mechanical properties [11]. Meanwhile, the fiber size of

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 Key Engineering Materials Vol. 849 97

sugarcane bagasse is also play important factor due to its function in filling the void fraction in
starch matrix. Previous studies reported that nano-sized cellulose sugarcane bagasse was effective
in increasing the properties of biocomposite. Nano size fiber can spread evenly into the starch
matrix. Even distribution makes less voids formation [8, 12].
In this study, the synthesis of SBCN was carried out by the chemical-ultrasonic method. The
SBCN was added into tapioca starch matrix as reinforcement. The addition of SBCN to the matrix
is expected to improve the tensile properties of biocomposite. According to the best our review,
there is no research reported about SBCN reinforced tapioca starch matrix. We state that the
research about sugarcane bagasse cellulose fiber in nanoscale is limited information. The synthesis
of SBCN was produced by chemical and ultrasonication method namely pulping, bleaching, sulfuric
acid hydrolysis and ultrasonication. The characterization of SBCN was carried out by using particle
size analyzer (PSA) and transmission electron microscopy (TEM), while biocomposites were
characterized by using scanning electron microscopy (SEM) and tensile test.

Materials and Methods

Materials. Sugarcane bagasse was obtained from local sugarcane ice seller at Jember, Indonesia.
Sodium hydroxide (98% NaOH), potassium hydroxide (KOH), sodium chlorite (NaClO2), acetic
acid (CH3COOH), sulfuric acid (H2SO4) and glycerol were purchased from CV. Aneka Kimia
located at Jember, Indonesia. Tapioca starch was supplied by Laboratory of Material Testing,
Department of Mechanical Engineering, University of Jember, Jember, Indonesia.
Preparation of sugarcane bagasse cellulose nanofibers (SBCN). The overall isolation of
SBCN was in accordance previous method and modified in hydrolysis process [13, 14]. Hydrolysis
was carried out before the ultrasonication process. Hydrolysis process used 30% H2SO4 for 60 min
with ratio fiber and solution (1 : 8.75). After hydrolysis, sugar cane bagasse fiber was washed by
distilled water until neutral pH. Then, it was ultrasonicated by using sonicator (Ultrasonic 750W) at
70 oC for 150 min to obtain SBCN.
Fabrication TS/SBCN biocomposites. The composition of biocomposite from SBCN and
tapioca starch was presented in Table 1. Tapioca starch was dissolved in distilled water (% w/v) and
SBCN (% w/w based tapioca starch) with different concentrations. Glycerol as a plasticizer (30%
w/w from tapioca starch) was added in mixing solution. Then, the biocomposite solution was heated
at 65-75oC with constant stirring (200 rpm) until gelatinized, poured into an acrylic mold (11 cm x
9.5 cm x 0.3 cm). To remove air bubbles, the mold was placed in an ultrasonic batch for 15 min [15,
16]. After that, it was dried in drying oven at 40oC for 17 h. Biocomposite was stored in the
desiccator for 24 h before characterization.
Table 1. The composition of the biocomposite from tapioca starch reinforced SBCN
Biocomposites code Glycerol TS, w/40 ml SBCN
(w/w dry starch basis) aqudest (% dry starch basis)
TS (Control) 0.3 2 0
TS/2SBCN 0.3 2 2
TS/4SBCN 0.3 2 4
TS/8SBCN 0.3 2 8
*This composition is similar with previous report but difference in the addition of % fiber content
and glycerol volume [17].
SEM and TEM. The surface morphology of biocomposite was observed using SEM (Model
JSM 6510 LA from JEOL) with a voltage and flow at probe for 15 kV and 8 mA, respectively. The
tested sample was placed on the SEM stub sample. The preparation sample was previously coated
with carbon followed by coating with gold to reduce electron charge. SEM images were enlarged to
98 Waste and Biomass Application

get image clarity. Furthermore, the morphology of SBCN was observed using TEM-Tecnai T20 at
200 kV for microstructure observation. The suspension of SBCN after ultrasonication process was
dripped a few drops over the holley carbon grid and dried at room temperature for 4 h. The dried
SBCN solution was directly observed by TEM instrument.
Tensile strength. The tensile strength of biocomposite sample was determined using a tensile
machine at room temperature conditions of 25oC. Tensile specimen was formed according to the
American Standard Testing Material (ASTM) D-638 type IV. The test was maintained on crosshead
speed of 2 mm/min using a load cell of 5 kN load. Five samples were tested for each biocomposite
variation as stated in previous report [17].

Results and Discussions

Morphological of SBCN. PSA and TEM images of SBCN suspension are shown in Figures 1a
and 1b, respectively. The average size of SBCN produced by the chemical-ultrasonication method
is 59.75 ± 10.84 nm. This SBCN diameter is smaller in size compared to the hydrolysis-
homogenization process which carried out by previous report about isolation of nanocellulose from
sugarcane bagasse for 95 nm [18]. This proved that the hydrolysis treatment with H2SO4 and
ultrasonication had successfully broken the hydrogen bonds between cellulose [13,14]. This is
supported by the SBCN morphology by TEM (Figure 1b) which shows SBCN are disintegrated and
spread evenly.

Size Distribution by Number

Number (Percent)

Size (d.nm)

Fig. 1. SBCN distribution by different characterization: a) PSA and b) TEM

According to previous researchers, the ultrasonication process was very effective for breaking
the hydrogen cellulose chain in the liquid medium. The ultrasonication emits ultrasonic waves and
form cavitation in a liquid medium. The cavitation formed will collide with each other to break the
bond. However, this process has a disadvantage such as high-power electricity consumption
[15,19].

Morphology SEM of TS/SBCN Biocomposite. Fig. 2 shows the fracture surface morphology of
a TS/SBCN biocomposite. Figure 2a displays the control sample (pure TS film). It can be seen that
fracture surface looks smoother than biocomposite samples. This phenomenon is caused by good
mixing between glycerol and tapioca starch during gelatinization process [8]. Good mixing and
dispersion able to make homogeneous film. A similar phenomenon was also reported by previous
studies of films from yam bean starch [6, 12]. The addition of SBCN in the tapioca starch matrix
displays a rougher surface. The addition of 2%SBCN into TS matrix (Fig. 2b) showed less
dispersion of SBCN particles than 4% and 8% SBCN in TS matrix. This fracture is also
accompanied by cracks in various parts. This is due to the bad preparation of biocomposite samples
[20].
 Key Engineering Materials Vol. 849 99

Fig. 2. Fracture morphology by SEM image: a) 0% (control), b) 2%, c) 4%, d) 8% of SBCN

Meanwhile, the addition of 4% SBCN in TS matrix (Fig. 2c) shows a more homogeneous surface
and it has denser structure. The SBCN particles looks evenly dispersed in various parts of the
matrix. This results in a good bond between the fiber and matrix resulting in higher tensile strength
[16]. Different phenomena are shown by 8% SBCN in the TS matrix (Fig. 2d). This sample shows
porosity in several parts. In addition, clot formations are formed in these samples. This is due to the
ineffective transfer of stress from fiber to matrix [15, 21]. This factor affected in decreasing
mechanical properties. This result is also supported by the tensile strength which shows a
decreasing up to 200% compared to the addition of 4% SBCN in TS matrix.

Tensile strength and strain of TS/SBCN biocomposites. The tensile strength and tensile strain
of TS/SBCN biomposites are shown by Fig. 3a and 3b, respectively.

Fig. 3. Tensile properties of all samples tested: a) tensile strength and b) tensile strain of all
biocomposites tested
It can be seen that the tensile strength increased significantly from 2.37 ± 0.34 MPa to 20.51 ±
1.37 MPa with the addition of 4% SBCN in starch matrix (Figure 3a). This tensile strength is higher
than the previous research as conducted by previous report for 6.68 MPa (10% fiber in starch
matrix) [22]. Conversely, there was a decrease in tensile strain 4%SBCN biocomposites from
55.27% (control) to 2.37% (Fig. 3b). This indicates that the SBCN particles are distributed evenly
100 Waste and Biomass Application

in tapioca starch matrix for 4% SBCN samples. In addition, good adhesion bonding between matrix
and fiber is also become supporting factor in increasing tensile strength [12, 22]. This result was
supported by SEM imaging (Fig. 2c). The addition of SBCN to the TS matrix makes the sample
become brittle (strain reduced). It is affected by the present of SBCN in TS matrix which results in
the prevention mobility of starch chain. Similar results were reported by previous studies [15].

Conclusion
SBCN was successfully synthesized by chemical-ultrasonication method with a diameter of
59.75 ± 10.84 nm. This SBCN has potential used as reinforcement in biocomposite based starch due
to its nanosized fiber. The SBCN was found in good dispersion in biocomposite based tapioca
matrix. Beside that, the mixing SBCN and tapioca starch resulting in good adhesion bonding. This
is affected in highest tensile strength of 4% SBCN in TS matrix for 20.84 MPa. This improvement
in biocomposite properties proves that SBCN might have potential as a reinforcement in
biopolymer matrix-based packaging material.

Acknowledgements
This research was funded and supported by Institute of Research and Community Service,
University of Jember for beginner lecturer research scheme with project number:
3107/UN25.3.1/LT/2019.

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