Production of bioplastic from cassava peel

with different concentrations of glycerol and

CaCO3 as filler
Cite as: AIP Conference Proceedings 2332, 020004 (2021); https://doi.org/10.1063/5.0043482
Published Online: 26 February 2021

Nur Diyana Zainol Abidin, Nur Syahirah Azhar, Muhammad Naiman Sarip, et al.

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AIP Conference Proceedings 2332, 020004 (2021); https://doi.org/10.1063/5.0043482 2332, 020004

© 2021 Author(s).
 Production of Bioplastic from Cassava Peel with Different
Concentrations of Glycerol and CaCO3 as Filler

Nur Diyana Zainol Abidin1, Nur Syahirah Azhar1, Muhammad Naiman Sarip2,
Huzaifah A. Hamid3 and Nor Atikah Husna Ahmad Nasir1, a)

1
Department of Biology, Faculty of Applied Sciences,
Universiti Teknologi MARA Perlis Branch, Arau Campus, 02600 Arau, Perlis, Malaysia.
2
Department of Polymer Technology Faculty of Applied Sciences,
Universiti Teknologi MARA Perlis Branch, Arau Campus, 02600 Arau, Perlis, Malaysia.
3
Department of English and Linguistic, Academy of Language Studies,
Universiti Teknologi MARA Perlis Branch, Arau Campus, 02600 Arau, Perlis, Malaysia.
a)
Corresponding author: [email protected]

Abstract. Bioplastic is created to overcome plastic contamination while maintaining the characteristics of plastics which
are flexible, cost effective and durable. In this study, bioplastic was formulated by using agriculture waste from cassava
peel. Three different concentration of glycerol were set up at 20%, 30% and 40% with constant amount of CaCO3 (filler)
were used for the optimization. The characterization of the bioplastic was carried out using FTIR analysis. Each sample
shows similarities in spectra, indicating similar chemical composition of functional group present - which are hydroxyl
group in alcohol and phenol (O-H), aliphatic saturated hydrocarbon chain (C-H) and ester, ether, carboxylic acid as well
as anhydride group (C-O). In mechanical tests, the bioplastics are divided into tensile test, water absorption test and soil
burial degradation test. Through tensile test, the bioplastic with 20% of glycerol shows the highest strength up to 5.82 ±
1.00 MPa, with Young’s modulus at 99.79 ± 42.03 MPa and tensile strain at 10.34 ± 2.43%. Through water absorption
test, the highest level of water absorbance was found to be at 40% glycerol addition at 28.64 ± 0.16% meanwhile the
lowest level of absorption was at 20% which is 24.49 ± 0.21%. Even though the 40% glycerol shows the highest
degradation rate, it was found that the 20% glycerol yielded higher mechanical properties and could maintain the
characteristics of plastics better than the 40% glycerol.

INTRODUCTION
270 million tons of plastics were produced worldwide with an estimation of 10-100,000 tonnes floating on the
ocean surface, whereby 80% of it is derived from land-based sources and 20% from marine [1]. At this rate, plastic
waste could harm environment and affect living organisms including human, plants and animals [2]. This is because
most plastics are petrochemical-based polymer derived, which are non-biodegradable. Due to concern on economic,
environment and safety, scientists have invented a biodegradable polymer (bioplastic) as an alternative [3].
Bioplastics are claimed to be more convenient because they are degradable and environmentally friendly [4].
Unfortunately, the bioplastic development depends on cost and process, which need additives such as filler, colorant
and plasticizers. In South East Asia, the abundance of agriculture waste such as cassava peel is deemed as a brilliant
alternative to replace the synthetic plastic. This is because cassava peel is rich in starch, which contains high amount
of amylopectin. This can contribute to a greater binding for the plastics [5]. However, bioplastic poses several
problems such as poor mechanical properties and high level of moisture content [3]. In enhancing the properties of
bioplastic, the addition of plasticizer and filler is necessary. Thus, reinforcing fillers such as calcium carbonate

4th International Sciences, Technology & Engineering Conference (ISTEC) 2020

AIP Conf. Proc. 2332, 020004-1–020004-8; https://doi.org/10.1063/5.0043482
Published by AIP Publishing. 978-0-7354-4076-0/$30.00

020004-1
(CaCO3) and optimising the amount of glycerol (plasticizer), are likely to solve this problem. Fillers such as CaCO 3
could enhance the strength, durability and working properties of bioplastic. Meanwhile, glycerol as plasticizer offers
flexibility in the polymer structure by decreasing intermolecular forces and glass transition of the material, thus
increasing the mobility rate of the polymer chains in the starch films [6].
In most research, the role of these two elements were studied separately or only the concentration of filler was
studied [7]. Thus, the aim of our study is to examine the effect of glycerol on bioplastic with constant amount of
CaCO3. The optimised plasticizer is very important because it can increase the flexibility and softness of plastic that
will help in the degradation of the plastics [8]. Furthermore, this study was also conducted to reduce the amount of
discarded agriculture waste in Malaysia and ultimately contribute to a waste-to-wealth industry [9].

MATERIALS AND METHODS

Preparation of the Cassava Peel Starch

100 g of small pieces of cassava peels were mixed with 100 mL of distilled water and filtered with muslin cloth.
Starch was settled down at the bottom of the beaker after 30 minutes, and separated from the slurry before being
washed with distilled water and dried in the oven at 70 °C for 40 minutes, until a fine powder was obtained [3].

Preparation of Bioplastic Film

5 g of cassava starch was added with 0.2 g of CaCO3 and the mixture was stirred before adding 70 mL of
distilled water and was heated at 60 °C for 1 hour. Different amount of glycerol as in Table 1 were added into the
mixture before being poured into the 8.5 cm x 2 cm x 0.3 cm petri dish and dried in oven at 60 °C [10].
TABLE 1. Formulation of bioplastic from different concentration of glycerol with CaCO3.
Composition (g/70 mL) Distilled Water
Sample (%) Calcium Carbonate
Cassava Starch Glycerol
(CaCO3)
20 5 0.2 0.8
30 5 0.2 1.2
40 5 0.2 1.6

FTIR Analysis of Bioplastic

FTIR analysis was conducted before and after the production of bioplastic. 0.05 g of raw materials and small
pieces of bioplastic film were placed onto the germanium plate. The spectra were measured between 400 and 4000
cm-1 using Spectrum 100 Perkin Elmer FTIR [9].

Tensile Test
Using Instron Testing Instrument, tensile strength consisting of tensile stress (MPa), Young's modulus (MPa)
and elongation at break (%) was evaluated. The sample from each mixture was cut into 1 cm × 6.0 cm and the 5
mm/min cross-speed was used according to ASTM D638 [3].

Water Absorption Test

Water absorption test was carried out according to ASTM D570. Sample size of 1 cm x 3 cm with 0.028 cm
thickness was prepared for the water absorption test and dried in oven at 50 °C for 2 hours. Bioplastic humidity
absorption capacity was acquired by soaking the sample for 24 hours in water. Next, the sample was instantly dried
using cloth and weight. Bioplastic water absorption capacity can be calculated as in Equation 1.

Water Absorption (%) = x 100 (1)

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 Soil Burial Degradation Test
The sample was cut at 1.5 cm x 1.5 cm and buried for a month at a depth of 5 cm in the dumping soil. The loss
weight of bioplastic was measured every 7 days [11]. The degradation of the test sample was studied before and
after soil burial as in Equation 2.

Degradation (%) = x 100 (2)

Statistical Analysis
Using descriptive analysis, the data obtained were analyzed using Statistical Package for Social Science (SPSS)
software ver. 20.0. The p value of Moisture Absorption Test and Biodegradability Test were analyzed and p< 0.05
was considered as significant. The information is represented in mean ± standard deviation.

RESULTS AND DISCUSSION

FTIR Analysis on Cassava Peel, CaCO3 and Glycerol

Table 2 represents the comparison of the wavelength range of FTIR on cassava peel, CaCO3 and glycerol.
TABLE 2. Wavelength range FTIR analysis of cassava peel, CaCO3 and glycerol.
Wavenumber (cm-1) Wavelength range
Functional Group
Cassava Peel CaCO3 Glycerol (cm-1)
Hydroxyl groups in
3302.08 - 3408.46 3450 – 3200 alcohol and phenols
(O-H)
Aliphatic saturated
2942.00 - 2529.38 3000 – 2500
hydrocarbon chain (C-H)
- - 1563.19 2000 - 1500 Carboxyl group
- 1747.90 - 2540 - 1000 Carbonyl group (C=O)
1641.08 - - 1950 – 1600 Alkene (C=C)
Ester, ether, carboxylic
1001.82 1403.27 1117.50 1450 – 1000
acid, anhydrides (C-O)
871.90
- - 950 - 700 Ca-O
711.90
Sources: [7, 12]

In Table 2, the broad absorption of FTIR analysis on cassava peel is at wavenumber of 3302.08 cm-1 while for
glycerol the wavelength is 3408.46 cm-1 in which the range is of 3400 – 3200 cm-1. Therefore, this indicates the
presence of O-H groups of free hydroxyl groups and bonded O-H in polymeric compounds such as alcohol and
phenols. Wavenumber of 2942.00 cm-1 in cassava peel and 2529.38 cm-1 in glycerol in which the range was 3000 –
2500 cm-1 shows the presence of aliphatic saturated hydrocarbon chain (C-H). Carbonyl group and Ca-O were only
present in CaCO3 at wavenumber of 1747.90 cm-1 and 711.90 cm-1 in which the range was of 2540 – 1000 cm-1 and
950 – 700 cm-1 respectively. While functional group of alkenes was only present in cassava peel at wavenumber of
1641.08 cm-1 in which the range was at 1950 – 1600 cm-1 and carboxyl group was only present in glycerol at
wavenumber of 1563.19 cm-1 in which the range was of 2000 – 1500 cm-1. Lastly, at wavenumber of 1001.82 cm-1
in cassava peel, 1403.27 cm-1 in calcium carbonate and 1117.50 cm-1 in glycerol indicate presence of functional
group ester, ether, carboxylic acid and anhydrides (C-O) which was in the range of 1450-1000 cm-1.

020004-3
 Presence of hydroxyl group (O-H) in cassava peels indicates the formation of a hydrogen bond as there was an
interaction between hydrogen atoms with an electronegative atom either oxygen, fluorine or nitrogen [13].
Hydrogen atoms have partial positive charge while oxygen atoms have partial negative charge in which they are
attracted to each other and thus form a hydrogen bond. As hydroxyl groups have hydrophilic properties which lead
to the formation of hydrogen bond, it enhances solubility of the sample in water. Therefore, the production of
bioplastic from cassava peel can absorb some water as it contains hydroxyl group that increases solubility in water
[14]. In addition, hydrocarbon chain (C-H) was found to be present in cassava and glycerol while alkene (C=C) was
present in CaCO3. Hydrocarbon chain is a basic unit in the production of plastic in which the carbon atom in
hydrocarbon chain acts as backbone for every organic material in polymer while alkene group is reactive and
commonly used in production of polymer or plastics such as polyethene, which is produced from polymerizing the
simplest alkene, ethane (C2H4). Other than that, calcium oxide (Ca-O) acts as desiccant in polymer in order to
prevent dryness and known as hydroscopic substance.

FTIR Analysis on Bioplastic from Cassava Peel with Different Concentration of Glycerol
with Addition of CaCO3
Figure 1 shows a comparison between FTIR spectra of bioplastic on different concentration of glycerol.

O-H C-H

FIGURE 1. FTIR analysis on bioplastic with different concentration of glycerol

In Figure 1, bioplastics on 20%, 30% and 40% of glycerol contain the same functional groups which are O-H, C-
H and C-O. The wavelength of O-H and C-O for all three types of bioplastics decreased when the concentration of
glycerol increased. However, for C-H, the number of wavelengths at 40% of glycerol (2925.22 cm-1) was slightly
higher than 30% of glycerol (2921.77 cm-1). Bioplastic with 20% of glycerol shows the highest number of
wavelengths in every functional group present, indicating higher mechanical properties compared to bioplastic with
30% and 40% of glycerol. This is due to the existence of covalent and hydrogen bond that occurred during the
interaction between those functional groups.

020004-4
 Tensile Test
The tensile test of the bioplastics of cassava peel were evaluated using Tensile Strength, Young’s Modulus and
Tensile Strain (Elongation at Break) as in Fig. 2 (a) and (b).

FIGURE 2(a). Tensile strength and Young’s Modulus of cassava peel bioplastic with different concentration of glycerol
Note: All data are presented in mean ± standard deviation, n=3. MPa is a unit for tensile strength as well as Young’s modulus
which is denoted as mega pascal.

FIGURE 2(b). Tensile strain of cassava peel bioplastic with different concentration of glycerol

In Fig. 2(a) and 2(b), the percentage of tensile strength, Young’s Modulus, and tensile strains of the bioplastic
decreased when glycerol concentration increased. In tensile strength, the increasing amount of glycerol in the
bioplastic led to reducing the strength because of glycerol and starch that is hydrophilic. These are due to the
cassava having a hydroxyl group, which is hydrophilic, leading to hydrogen bond formation. It thus enhances water
solubility and reduces the mechanical properties of the bioplastics [14].
Meanwhile, for the tensile strain, the decreasing rate happened when an increased amount of glycerol was added,
caused by the reduction in interaction between the starch chains. These caused an expansion of distance between

020004-5
starch molecules that allow glycerol to embed between glycerol and starch [15]. Thus, based on the comparison of
the effect of glycerol in the bioplastic, it is recommended that the optimum amount for the tensile strength, Young’s
Modulus, and tensile strain is 20% of glycerol. At this rate, the bioplastic produced is stronger, has a greater material
hardness, and requires more force or stress to stretch the sample as it is not easily breakable.

Water Absorption Test

The percentage of water absorption is shown on Fig. 3.

FIGURE 3. Water absorption of cassava peel bioplastic with different concentration of glycerol
Note: All data are presented in mean ± standard deviation, n=3. * The mean different is significant at P < 0.05 by one- way
ANOVA.

In Figure 3, the rate of water absorption increased when the concentration of glycerol in the bioplastic increased.
This is due to the hydrophilic properties of both glycerol and starch. These properties increased the affinity between
glycerol and water, hence increased the water absorption [11]. The fact that cassava starch contains a hydroxyl
(OH), carbonyl (CO), and ester (COOH) shows that the concentration of hydrophilic properties in the bioplastics is
high. Hence, with high concentration of hydrophilic starch and glycerol cause more rapid degradation in the soil.
Moreover, the properties of the CaCO3 that is hydrophobic, causing the sample to repel the water. Therefore, the
presence of the CaCO3 can increase the strength of the mechanical properties of the bioplastic. Thus, bioplastic at
20% which contains the lowest capacity of water absorption is the most suitable material because the small amount
of water it absorbed will not reduce the mechanical properties of the bioplastic.

Soil Burial Degradation Test

Bioplastics with different concentration of glycerol were buried in dumping soil with time interval within four
weeks and the changes in weight loss of the bioplastics were observed weekly. The findings of soil burial
degradation test on the bioplastics with different concentration of glycerol are presented in Fig. 4.

020004-6
 FIGURE 4. Soil burial degradation of cassava peel bioplastic with different concentration of glycerol
Note: All data are presented in mean ± standard deviation, n=3. *The mean different is significant at P < 0.05 by one-way
ANOVA.

Based on Fig. 4, all the bioplastics are fully degraded at 100 ± 0.00% within four weeks. However, the fastest
degradations were achieved on 40% glycerol and 30% glycerol which was at Week 3. The higher level of glycerol
concentration increases the rate of the bioplastic degradation. This is due to glycerol characteristic which is
hydrophilic towards water. Other than that, hydroxyl group in cassava starch absorbs the water in the soil to initiate
hydrolysis reaction to degrade the bioplastic into a small piece [11]. The degradation also depends on the
environmental condition which are temperature, humidity and presence of the microorganism in the soil. Examples
of soil bacteria are Pseudomonas sp., Streptococcus sp., and Bacillus sp. that help in the degradation of the
bioplastic [16]. These bacteria could break the hydroxyl (OH), carbonyl (CO) and also ester (COOH) in the cassava
starch [17]. Moreover, glycerol has the ability to absorb water easily as water is the medium for most bacteria in the
soil. Therefore, the higher amount of glycerol increases the amount of water to penetrate through the structure of the
bioplastic. Thus, the bioplastics becomes easier to degrade. However, the addition of CaCO 3 could decrease the rate
of the degradation. This is due to the properties of the CaCO3 which is hydrophobic, that will repel the water
absorption. Therefore, by adding the CaCO3 as a filler, the rate of bioplastic degradation will slow down compared
to the bioplastic of cassava without filler [11]. In short, the degradation of bioplastic is influenced by factors such as
temperature, humidity and presence of suitable microorganism.

CONCLUSIONS
The different concentration of glycerol will lead to different physical characteristics of bioplastics in terms of
texture, appearance and characteristic. However, the functional groups of the bioplastics are not affected. The tensile
properties will be decreased with the increasing amount of the glycerol. The higher amount of glycerol will also
accelerate the bioplastic degradation, however, the addition of CaCO 3 (filler) could slow down the degradation.
Thus, the addition of 20% of glycerol in the bioplastic proves to be the most effective compared to other
concentration and has the potential to be used to replace current synthetic plastic.

ACKNOWLEDGMENTS
The researchers would like to express their deep appreciation to Faculty of Applied Sciences, Universiti
Teknologi MARA Perlis Branch.

020004-7
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