Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

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Synthesis and characterization of biodegradable plastic from

watermelon rind starch and chitosan by using glycerol as plasticizer
Syaubari, Abubakar, Teku Muhammad Asnawi, Muhammad Zaki, M. Khadafi, Intan Harmanita
Chemical Engineering Department, Engineering Faculty of Syiah Kuala University – Darussalam, Banda Aceh, Indonesia

a r t i c l e i n f o a b s t r a c t

Article history: Watermelon rind is a part of the watermelon that is rarely used, less application of polymer materials
Available online xxxx which has the potential to produce starch. In case of increasing the tensile strength characteristic of
the bioplastic film, chitosan and lemongrass oil additives are obtained from biomass and used for the
Keywords: anti-microbial agent. Chitosan and lemongrass oil additives were chosen to combine with watermelon
Synthesis rind starch. Glycerol was used as a plasticizing agent because it could be fully dissolved in starch solu-
Biodegradable tions and other organic materials. For this case of study in watermelon, rind starch was produced by
Watermelon skin starch
the extraction method, the yield makes up to 0.07%. Bioplastic films can be obtained by adding plasticiz-
Glycerol
Chitosan
ing agent and amylose/amylopectin, but this study is evaluating the differences between each combina-
Lemongrass oil tion of additives with different compositions. Therefore, conducted some analysis of Tensile Strength,
FTIR, Scanning Electron Microscopy, and Biodegradation for this study. Sample starch +0.5 ml glycerol
+0.75 g chitosan, has the highest tensile strength value of 52 MPa, and the highest elongation value
was found in the starch + glycerol 0.5 ml sample which was 14.2%. The effect of combined lemongrass
oil influences the degradation process, resulting in a long time in the degradation process than the other
samples.
Ó 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND
license (https://creativecommons.org/licenses/by-nc-nd/4.0) Selection and peer-review under responsi-
bility of the scientific committee of the 2nd International Conference on Chemical Engineering and
Applied Sciences.

1. Introduction often chosen as a raw material for making bio-plastics because of

the abundant availability of starch in nature [3,4]. One of the plants
Nowadays in the modern industrial use of synthetic polymers that contain starch is watermelon rind (Citrullus lanatus). Water-
such as plastics have an important role in the local economy. How- melon is a popular fruit, known and much loved by the public. Just
ever, the use of synthetic polymers has deficiencies that hurt the like other fruit peels, watermelon skins are always trash. As a food
environment because they cannot be degraded biologically, expen- ingredient, watermelon rind (albedo) is rarely consumed because
sive in recycling, and are contaminated with foodstuffs packed of its sour taste. Watermelon albedo still has several useful sub-
because of the specific substances that migrate into the packaged stances such as vitamin C, citrulline, minerals, and enzymes and
material.Table 1 contains starch that can be used for the manufacture of bioplastics.
This poses a huge problem for the environment and public Watermelon has a carbohydrate content of 7.55 g in 100 g of
health, it is necessary for the assessment and control of the manu- watermelon (Source: USDA.gov Agricultural Research Services).
facturing technology of new materials that can and biodegradable. These carbohydrates are saccharide polymers formed from many
One alternative solution is the use of biodegradable plastic. monomers with glossic bonds which contain amylose and amy-
Biodegradable plastic is plastic that can decompose naturally by lopectin which are the materials to be extracted and used to make
microorganisms. Biodegradable plastics can be made from various bio-plastic films [5,6].
raw materials which have a fairly high starch composition [1,2]. Starch is the main ingredient needed in the manufacture of
Bio-plastics can be made from renewable materials, namely biodegradable plastics that affect the physical properties of plas-
compounds found in plants, such as starch, pectin, cellulose, colla- tics, then polymers, namely chitosan which functions as a bio-
gen, casein, proteins, or lipids found in animals. Starch is more plastic reinforcement, plasticizers in the form of glycerol to

https://doi.org/10.1016/j.matpr.2022.04.535
2214-7853/Ó 2022 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (https://creativecommons.org/licenses/by-nc-nd/4.0)
Selection and peer-review under responsibility of the scientific committee of the 2nd International Conference on Chemical Engineering and Applied Sciences.

Please cite this article as: Syaubari, Abubakar, Teku Muhammad Asnawi et al., Synthesis and characterization of biodegradable plastic from watermelon
rind starch and chitosan by using glycerol as plasticizer, Materials Today: Proceedings, https://doi.org/10.1016/j.matpr.2022.04.535
Syaubari, Abubakar, Teku Muhammad Asnawi et al. Materials Today: Proceedings xxx (xxxx) xxx

Table 1
Picture of Visual Biodegradable Plastic Decomposition.

improve the mechanical properties of plastics, and the addition of more water resistance (swelling) is added. The glycerol plasticizer
citronella oil as an antioxidant in plastics. added in the process of making biodegradable plastic is superior
Chitosan in this study was used as a reinforcement and as an because the glycerol does not evaporate when added so that the
edible coating to prevent contamination of bio-plastic films when plastic product produced with glycerol plasticizer is better than
used for food. This additive is a biopolymer that can be obtained plastic using other plasticizers which makes the mechanical prop-
from shrimp or crab shells. erties of the plastic stronger. Glycerol is an effective plasticizer
Glycerol is suitable for use as a plasticizer in the process of mak- because it can reduce internal hydrogen bonds in intermolecular
ing starch-based plastics. The more plasticizers are added, the bonds [7,8].

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Syaubari, Abubakar, Teku Muhammad Asnawi et al. Materials Today: Proceedings xxx (xxxx) xxx

2. Materials and methods ter plastic based on mechanical tests in a glycerol starch solution,
chitosan was added and a study was also made on the effect of
The watermelon rind size was reduced to obtain a fine water- adding antioxidants.
melon rind starch powder. Separate the watermelon rind and the
watermelon filling done with a knife. Watermelon rind weighs 3.1. Tensile strength analysis
about 30% of the weight of a watermelon. All watermelon skins
were washed and measured for the green outer skin so that all Fig. 1 it can be seen from the data that the average tensile
the skins were white, then crushed with a grater and pressed/- strength value produced is 25 MPa and the highest tensile strength
mashed. After that, blended with a ratio of watermelon rind and value is found in the sample of Starch + Glycerol 0.5 ml + Chitosan
water 3:1 (w/w). Watermelon rind pulp is soaked for 24 h and sep- 0.75 gr, which is 52 MPa. Samples of Starch + Glycerol + Chitosan
arated by water and sediment. The precipitate was dried at room had a significantly increasing trend than the samples of Starch
temperature with air circulation which was sprinkled on a long- + Glycerol and Starch + Glycerol + Chitosan + Lemongrass because
board for 24 h. they used chitosan with variations in the concentration of chitosan,
namely 0.25; 0.5 and 0.75 gr so that the tensile strength value also
increases. This is because chitosan is a polymer material that has
2.1. Preparation of chitosan solution
reinforcing properties. Plastics that have a large concentration of
chitosan components make the hydrogen bonds contained in the
Before making a chitosan solution, acetic acid is diluted from a
concentration of 100% to 1% by a dilution process. After obtaining plastic more and more so that the chemical bonds will be stronger
and difficult to break because it requires a large amount of energy
1% acetic acid, then chitosan with each composition variation
(0.25gr; 0.5gr 0.75gr) was added to 50 ml of 1% acetic acid and stir- to break these bonds [9,10].
The tensile strength value in the starch + glycerol sample has a
red until dissolved at 50 °C.
decreasing trend as the amount of glycerol composition increases,
namely 0.3; 0.5, and 0.7 ml. The cause of the decrease in the tensile
2.2. Biodegradable plastic manufacturing strength value is the increase in the amount of glycerol composi-
tion in which glycerol is generally a small hydrophilic molecule,
1. The manufacture of biodegradable plastic from banana weevil which can be bound between nearby polymer chains, reducing
starch is carried out as follows: molecular attraction and increasing molecular mobility, making
2. Five grams of watermelon rind starch was dissolved with 60 ml water vapor molecules move (Souza, et. al. 2013). Glycerol mixed
of distilled water in a beaker and stirred using a magnetic stirrer with polymer solution will form hydrogen bonds between polymer
and heated on a hot plate for 10 min at 70 °C and at constant molecules to be reduced or tenuous to facilitate the movement of
speed until homogeneous. polymer molecules, increasing polymer flexibility affects the film
3. In the starch + glycerol sample, only glycerol plasticizer was tends to be flexible and can reduce the value of tensile strength
added to the starch solution, stirred at a constant speed for [9,10].
10 min and the temperature was raised at 80–85 °C until The addition of essential oils to bio-plastic films can reduce
thickened. intermolecular interactions between polymer chains, which results
4. In the starch + glycerol + chitosan sample, glycerol plasticizer in lower tensile strength values [11]. In Fig. 1 the tensile strength
and chitosan solution were added to the starch solution, stirred of the starch + glycerol + chitosan + citronella oil sample is lower
at a constant speed for 10 min and the temperature was raised than the other samples with the lowest tensile strength value of
at 80–85 °C until thickened. 9 MPa in the sample of starch + glycerol 0.5 ml + chitosan 0.5 g
5. In the sample of Starch + Glycerol + Chitosan + Lemongrass Oil, + citronella oil 0.2 ml. This is due to the addition of citronella oil
glycerol plasticizer was added, a solution of chitosan and to the bio-plastic film.
lemongrass oil into the starch solution was stirred at a constant
speed for 10 min and the temperature was raised at 80–85 °C 3.2. Elongation of break analysis
until thickened.
6. Printing is done by pouring a thick solution on acrylic glass that Elongation is the elongation at break which is defined as the
has been given duct tape to hold the liquid from spilling and percentage change in the bio-plastic film when it is pulled to break
control the thickness of the plastic. [9,10]. In Fig. 2 it can be seen that the starch + glycerol sample has
7. Then dried at room temperature for 72 h. a fairly large elongation with an elongation value of 14.2% in the
8. A thin layer of dry plastic is removed from the plate with the 0.5 ml starch + glycerol sample and increases with the addition of
help of the flat end of the spatula slowly. glycerol composition, but slightly decreases in the starch + glycerol
9. The results obtained are transferred to a place that is protected sample with a glycerol composition of 0.7 ml. Glycerol is a plasti-
from the sun and prepared for sample analysis. cizer that makes a material flexible because reduced hydrogen
bonds affect the reduction of molecular attraction and increase
3. Results and discussion intermolecular mobility.Fig. 3
The addition of chitosan to starch + glycerol + chitosan samples
Watermelon rind weighs about 30% of the weight of a water- reduced the elongation value because chitosan acts as a reinforce-
melon. All watermelon skins were washed and measured for the ment in bio-plastic films so that the elasticity decreases. The struc-
green outer skin so that all the skins were white, then crushed with ture of chitosan has more hydrogen bonds which make the bio-
a grater and pressed/mashed. After that, blended with a ratio of plastic film stronger but more likely to be inelastic.
watermelon rind and water 3:1 (w/w). Watermelon rind pulp is Samples of Starch + Glycerol + Chitosan + Lemongrass Oil are
soaked for 24 h and separated by water and sediment. The precip- samples with the addition of complex additives. The percent elon-
itate was dried at room temperature with air circulation which was gation value of this sample is quite small compared to other sam-
sprinkled on a longboard for 24 h. After that, it was sieved with a ples with an elongation value of 1% in the sample of Starch
size of 120 mesh. Yield in the form of flour after drying obtained + Glycerol 0.5 ml + Chitosan 0.5 g + Lemongrass Oil 0.2 ml. This is
26% which is ready to be used for the manufacture of biodegrad- because the addition of these additives makes the bio-plastic film
able plastic using glycerol as a plasticizer. Besides that, to get a bet- excess of hydrogen molecules which makes the mobility bonds
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Syaubari, Abubakar, Teku Muhammad Asnawi et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 1. Tensile Strength Analysis.

Fig. 2. Elongation of Break Analysis.

By using a Scanning Electron Microscope, we can identify the

surface of the bioplastic film morphologically using the EVO HD
15 Scanning Electron Microscope from Carl Zeiss. From Fig. 4 it
can be seen that there are no cavities or cracks in the starch + glyc-
erol sample. However, there is still starch in the sample that is not
completely homogeneous, so there are still a few white dots. The
starch + glycerol + chitosan sample in Fig. 4 looks a little cracked,

Fig. 3. Micrograph Surface of Bioplastic Film on Starch + Glycerol Sample with

10,000x. Magnification.

between small molecules less elastic. However, there was a small

increase in the percent elongation value along with the addition
of citronella oil composition.

3.3. SEM analysis

This analysis was carried out from one sample of Starch + Glyc-
erol, Starch + Glycerol + Chitosan, and Starch + Glycerol + Chitosan Fig. 4. Micrograph Surface of Bioplastic Film on Starch + Glycerol + Chitosan
+ Lemongrass to see the morphology of the bioplastic film formed. Sample with 10,000. Magnification.

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Syaubari, Abubakar, Teku Muhammad Asnawi et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 5. FTIR Spectrum of Starch + Glycerol Samples.

the environment by following environmental indications includ-

ing; temperature, humidity, biomass, and soil type. In the follow-
ing biodegradation test, compost soil was used. Samples that
have been cut to size are then buried in the ground and evaluated
every 5 days starting from the first day of burial. The visual evalu-
ation was carried out in this test due to the inaccessibility of digital
scales with an accuracy of up to 2 decimal places or more.
Based on the length of time of decomposition, it can be seen
that some samples have different times in the decomposition per-
iod to the environment with normal compost soil conditions. Sam-
ples A1, A2, and A3 can decompose within 15 days which is faster
than other samples. Then the B3 sample experienced a change in
Fig. 6. FTIR Spectrum of Starch + Glycerol + Chitosan Samples.
the decomposition time of the environment, namely B3 with a time
of 20 days. This is because the addition of chitosan in the sample is
this is because this sample is given the addition of chitosan so that quite significant. The biodegradation time that can be achieved by
it makes the sample less elastic when exposed to excessive pres- samples C1, C2, and C3 is longer than samples A and B, the addition
sure or friction from the outside. However, the sample is already of citronella oil to the sample as an antioxidant and antimicrobial
a bit more even. agent can slow down the degradation time. However, it is not very
significant because the composition of the addition of citronella oil
3.4. Test of functional groups is still small in the bio-plastic film so that the sample does not
degrade longer to the environment.
Functional group analysis was performed using the IRAffinity-
1S FTIR Spectrophotometer from Shimadzu with a wavelength of 4. Conclusions
4000–400 cm 1. The FTIR spectrum obtained can be seen in Fig. 5.
Fig. 5 shows the spectrum of the starch + glycerol sample giving Based on the results of experiments that have been carried out,
a complex frequency range associated with the type of hydroxyl several conclusions can be drawn as follows:
molecule, it can be seen in the spectrum at a wavelength of
3637 cm 1 that there is an OAH stretch group with a hydroxyl/al- 1. Watermelon rind is successful in producing starch to make
cohol molecule type. This group is found in glycerol which func- biodegradable plastic with a yield value of 26%
tions as a plasticizer in bio-plastic films. The carbon chain bonds 2. The results of the tensile strength analysis showed that the
are shown to be quite complex in the spectrum, at a wavelength sample of Starch + Glycerol 0.5 ml + Chitosan 0.5 gr had a high
of 3300–2837 cm 1. Changes in the FTIR spectrum are influenced tensile strength value of 52 MPa due to the high addition of chi-
by the addition of several different components that can affect dif- tosan, but had a low percent elongation value. While the starch
ferences in chemical interactions between molecules [12]. + glycerol 0.5 ml sample had a high percent elongation value of
It can be seen in Fig. 6 functional group OAH stretch with 14.2% and a low tensile strength of 21 MPa because there was
hydroxyl/alcohol molecule type at a wavelength of 3637 cm 1. This no addition of chitosan and lemongrass oil.
functional group is found in glycerol. At a wavelength of 3. The biodegradable plastic samples obtained no longer have cav-
2835 cm 1, it shows the NAH stretch functional group which ities and only a few cracks, but there are still some fine grains of
belongs to the type of amine salt, the functional group is found starch that are not completely homogeneous.
in chitosan which has an NAH functional group. The complex 4. Analysis of the functional groups obtained in the starch + glyc-
CAH carbon chain bonds in the spectrum are shown at wave- erol sample has an OAH stretch group at a wavelength of 3637
lengths 3300–2837 cm 1. cm 1. Samples of Starch + Glycerol + Chitosan contained NAH
stretch groups at a wavelength of 2835 cm 1 obtained from
3.5. Test of biodegradation the addition of chitosan. While the samples of starch + glycerol
+ chitosan + citronella oil contained C@O groups at a wave-
Biodegradation tests were carried out on bio-plastic films to length of 1680 cm1 and C@C at 1648–1638 cm 1 which were
determine the time required for the material to decompose into found in citronella oil additives.

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Syaubari, Abubakar, Teku Muhammad Asnawi et al. Materials Today: Proceedings xxx (xxxx) xxx

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