The Concentration Of Sorbitol On Bioplastic Cellulose Based Carrageenan

Waste On Biodegradability And Mechanical Properties Bioplastic

M D Arief1, A S Mubarak2,3 and D Y Pujiastuti2

1
Fisheries Product Technology, Faculty of Fisheries and Marine, Universitas Airlangga,
Kampus C Unair, Jl. Mulyorejo Surabaya 60115, East Java, Indonesia
2
Department of Marine, Faculty of Fisheries and Marine, Universitas Airlangga, Kampus C
Unair, Jl. Mulyorejo Surabaya 60115, East Java, Indonesia
3
Corresponding author: [email protected]

Abstract. Synthetic plastic waste is the cause of environmental pollution. Therefore, there is a need for
innovation in the manufacture of plastics using renewable raw materials, namely the manufacture of
bioplastics. Bioplastics can be made from carrageenan industrial waste because they have a high
cellulose content of 71.38%. In the manufacture of bioplastics it is necessary to add sorbitol plasticizer,
sorbitol can reduce internal hydrogen in the intermolecular bonds which affect the biodegradability and
mechanical properties of the bioplastic. The purpose of this study was to determine the effect of
sorbitol concentration on bioplastics cellulose based from carrageenan waste on biodegradability and to
determine the best sorbitol concentration in the manufacture of bioplastics cellulose to meet
biodegradation standards and mechanical properties based on literature reviews. This research is
experimental in testing the biodegradability of bioplastics cellulose based from carrageenan waste with
the addition of sorbitol (0, 3, 6, 9, 12 ml) and a literature study on the mechanical properties of
bioplastics and the content of waste cellulose. The experimental study used ANOVA data analysis and
continued with DMRT. The results of this study indicated that the effect of sorbitol concentration had
an effect on the biodegradability of bioplastics (P <0.05) with the highest value of 58.68 ± 0.90% for 7
days at a sorbitol concentration of 12 ml. Based on the literature review, the sorbitol concentration in
cellulosic bioplastics that meets biodegradation standards and the mechanical properties of bioplastics
is 3 ml.

Keywords: Bioplastic, Carrageenan Waste, Plasticizer, Sorbitol

1. Introduction
Synthetic plastic or non-degradable plastic is a cause of waste and triggers for
environmental pollution [7]. Therefore, there needs to be innovation in making plastics using
renewable raw materials, by making bioplastics. Bioplastic is a type of plastic that is almost
entirely made of materials that are easily renewable and can be decomposed by microorganisms. One
of the materials that can be used as a basis for making bioplastics is cellulose derived from
carrageenan waste. In the process of making carrageenan, waste produced between 65-70% of the
weight of seaweed and still contains 71.38% cellulose [4]. The high cellulose content in carrageenan
waste can be used as a raw material for making bioplastics.
Bioplastics based cellulose are easily degraded but have weak hydrogen bonds due to the distance
between the tenuous molecules, which causes bioplastics to be less strong and flexible. Therefore, it is
necessary to add cellulose adhesives, one of which is chitosan. Chitosan has a role to reduce the
distance between cellulose molecules due to weak hydrogen bonds .The addition of chitosan causes
bioplastics to be fragile, rigid and inelastic, therefore in the process of making bioplastics it is
necessary to have an additional material namely sorbitol
Sorbitol is a material that can reduce internal hydrogen bonds in intermolecular bonds [3].The
addition of sorbitol is directly proportional to the percentage of strain or elongation, meaning that the
greater the concentration of addition of sorbitol, the greater the value of the percentage of strain or
elongation. High sorbitol concentration also causes a decrease in tensile strength in bioplastics [23].
Sorbitol concentration can also affect the degradation ability of bioplastics. The higher the sorbitol
concentration will accelerate the process of bioplastic degradation [5]. Degradation is the ability of
biodegradable films to decompose microbes, moisture and chemical factors present in the soil [5]so
that the addition of sorbitol will affect whether or not the bioplastic is degraded.
The purpose of this study are (1) to determine the effect of sorbitol concentration on cellulose
based bioplastics from carrageenan waste on biodegradation ability ;(2) determine the best sorbitol
concentration in making bioplasticscellulose to meet biodegradation standards and mechanical
properties based on literature review.

2. Methods
The method used was experimental and literature review. Experimental research was conducted at
the Chemical Analysis Laboratory of the Faculty of Fisheries and Maritime,UniversitasAirlangga,
Surabaya in February-March 2020 and literatures study in March-April 2020.

2.1 Bioplastic manufacturing

The process of making bioplastics starts from the process of separating cellulose in carrageenan
waste. Waste sample powder is immersed in a 6% H2O2 solution which is heated for 1 hour at 700C in
a water bath shaker at a ratio of 1: 3 w / v. Then washing with water to neutral pH and dried for 2-5
days. The cellulose obtained was weighed 50 grams and added 1 gram of chitosan, then given the
treatment of the addition of glycerol (0; 3; 6; 9; and 12 ml)and 2.5 grams CMC for each treatment.
The mixture is heated in 100 ml of distilled water and stirred for 30 minutes at 700C. Then printed on
a petri dish with a diameter of 9 cm and dried in an oven at 600C for 1 hour. The formulation for
making bioplastics is in Table 1.

Table 1.Bioplastic Formulation

Treatment
No. Materials Unit
P0 P1 P2 P3 P4
1. Carrageenan Waste Gram 50 50 50 50 50
2. Aquades ml 100 100 100 100 100
3. Sorbitol ml 0 3 6 9 12
4. Chitosan Gram 1 1 1 1 1
5. CMC Gram 2,5 2,5 2,5 2,5 2,5

2.2 Biodegradation test

The biodegradation test is indicated by the degree of damage to bioplastics.The biodegradation
test is chosen by using the soil as an aid to the degradation process or so-called soil burial test
technique [28]. The sample is placed and planted in a soil-filled pot, the sample is left exposed to air.
Previously, the sample was weighed first as the initial mass (m0). After that, burial was carried out in
the soil for a period of7 days. Bioplastic samples that have been buried are then dried and weighed.
Then the re-weighing process is carried out as the value of m1[25]. The percentage value of average
mass reduction from buried bioplastics is obtained through the following equation:
𝑚1 − 𝑚0
m (%) = x 100%
𝑚0
2.3 Data analysis
The experimental method includes a biodegradation test using a Completely Randomized Design
(CRD) and continued by Duncan’s Multiple Range Test. The statistical analysis was performed using
the IBM SPSS statistics version 23.0 software. The reviews related to parameters that are not possible
to obtain due to the existence of a pandemic were conducted a literature review using qualitative
descriptive analysis.
3. Results and discussion
3.1 Results
This research produced bioplastics from carrageenan waste cellulose. The resulting bioplastics are
circular with a diameter of 9 cm (Figure 1).

(a) (b) (c) (d) (e)

Figure 1.Bioplastic Carrageenan Waste Cellulose with Addition of Sorbitol

Note: Letter notation (a) sorbitol concentration 0 ml; (b) sorbitol concentration of 3 ml; (c) sorbitol
concentration of 6 ml; (d) sorbitol concentration of 9 ml; (e) sorbitol concentration of 12 ml

80
Biodegradation (%)

d e
60
c
40 b

20 a

0
0 3 6 9 12
Sorbitol Concentration (ml)

Figure 2.Comparison Graph of Bioplastic Percentage of Biodegradation with Different Sorbitol

Concentrations.
Note: Different superscript letter notations in the same column show comparisons between treatments
are very significant differences (P <0.05).

The results of the Analyze of Variance (ANOVA) test showed that the addition of sorbitol
concentration (0, 3, 6, 9, 12 ml) significantly affected biodegradability of bioplastics. Meanwhile, in
the DMRT follow-up test, it was found that best bioplastic biodegradation capability obtained is in
making bioplastics with the addition of 12 ml sorbitol, the value is 58.68 ± 0.90% for 7 days,

3.2 Discussion
The results of the analysis show that the concentration of sorbitol on cellulose based bioplastics
from carrageenan waste significantly affects on biodegradation ability in the bioplastic, so increasing
the sorbitol concentration will further accelerate the process of bioplastic degradation. Based on the
results of this study, the degradation of cellulose based bioplastics from carrageenan waste with the
addition of 12 ml sorbitol obtained the highest value of 58.68 ± 0.90% for 7 days. These results
indicate that the degradation time of carrageenan waste cellulose bioplastic with the addition of
sorbitol is faster than the ASTM D-6002 standard which explains that 60 days is the time required to
degrade 100% bioplastics [22]. Furthermore, when compared to LDPE and HDPE packets whose
degradation ability only reached 75.3% for 120 days [19], the carrageenan waste cellulose bioplastic
with the addition of sorbitol has a much higher degradation ability because of the fast degradation
time. The addition of plasticizer to cellulose bioplastics can reduce the degree of crystallinity in
cellulose which will result in decreased bioplastic density [29], so that the addition of sorbitol to
bioplastics can accelerate the process of biodegradation [36].
Sorbitol is a hydrophilic material that can to bind water. Water is a growing medium for most bacteria
and microbes, so the high water content causes bioplastics to be more easily degraded [1]. Plastic
surfaces that are hydrophilic will make it easier for decomposing bacteria to colonize [33]. The
bacterial colony will stick to the surface of the plastic and form a biofilm, then the bacteria break
down complex polymers into simple ones thus accelerating the degradation process [3]. Furthermore,
according to Sumartono et al. [29], the length of time a material's biodegradation is affected by the
polymer structure contained in a material.
Bioplastics cellulose is easily degraded because they contain hydroxyl (OH) and carbonyl (CO)
groups [34]. According to Pratomo and Rohaeti [16] the process of biodegradation of biodegradable
films occurs because of the bond breaking reaction in the β-1,4-glycosidic bond so that the cellulose
molecule decomposes back into glucose molecules gradually. Chemical degradation reactions in
linear polymers cause a decrease in molecular weight or shortening of chain length [31]. The addition
of sorbitol to bioplastic manufacturing can also affect the mechanical properties of bioplastics such as
tensile strength, percent elongation, and water resistance.
Tensile Strength is the maximum tensile strength that a plastic sheet can withstand during
measurement. Tensile strength values indicate the tensile strength of plastics produced when under
load [15]. The resulting bioplastics are not fragile, this is because the addition of sorbitol as a
plasticizer serves to reduce intermolecular forces and increase film flexibility and weaken the polymer
chain hydrogen bonds [13] so that it can affect the tensile strength of bioplastics.
Research on the effect of sorbitol on bioplastic manufacturing has been carried out several times.
In the research of Hidayati et al. [5] using nata de cassava and sorbitol showed tensile strength values
on the addition of 0 ml sorbitol that was 62.22 MPa, 3 ml sorbitol was 35.28 MPa, 6 ml sorbitol was
16.66 MPa, 9 ml sorbitol was 11, 76 MPa, the results of the study indicate that the addition of sorbitol
3 ml in bioplastic manufacturing has produced tensile strength under SNI standards of packaging
materials which range from 24.7-302 MPa[12].
According to Putra et al. [18] the higher the concentration of sorbitol used in making bioplastics,
the lower the tensile strength value of bioplastics produced. Sorbitol can reduce the molecular internal
hydrogen bonds and cause the intermolecular pull of adjacent polymer chains to reduce the tensile
strength [2]. Sorbitol is a hydrophilic material (capable of binding water) and can make the bioplastic
surface-soft which causes a reduction in strength between adjacent molecules so that the tensile
strength is lower [27].
The addition of sorbitol to bioplastic manufacturing also influences cellulose will reduce
intermolecular interactions and increase polymer mobility [21]. Increasing the concentration of
plasticizer in this case sorbitol will reduce hydrogen bonds to increase flexibility so that the tensile
strength decreases [8]. According to research Hidayati et al. [6], the addition of chitosan and CMC in
bioplastic production also affects the tensile strength value, CMC concentration> 3.5% and chitosan>
3.5% can reduce the tensile strength of biodegradable films, this is caused by the formation of
intermolecular hydrogen bonds between NH4 + from chitosan and OH- from CMC. The addition of
sorbitol to bioplastic manufacturing can also affect the percent elongation in bioplastics.
Percent of elongation is the amount of length increase caused by the load pulling at the time of
breaking up. The addition of plasticizers can affect the percentage of elongation because plasticizers
can cause bonds to be reduced so that the plastic is more elastic [17]. Cellulose in seaweed itself has
high flexibility so that it affect the percent elongation, because the addition of plasticizer gives a more
elastic properties to the plastic [30].
Several studies have been conducted to determine the effect of sorbitol addition on bioplastics on
percent elongation. The results of Sitompul et al. [26] in making bioplastics with the addition of 3 ml
sorbitol, bioplastics have an elongation percent of 44.65%, so according to the results of the study are
in under SNI standard packaging materials with an elongation percent value of 21-220% [12].
According to Afif et al. [1] sorbitol will disrupt hydrogen bonds between adjacent polymer
molecules so that the tensile strength of polymer chain intermolecular is reduced, causing bioplastics
to become more elastic. The mechanism of sorbitol insertion between amylose-amylopectin-chitosan
molecules is presented in Figure 3
 Figure 3.Hydrogen Interaction between Starch-Sorbitol-Chitosan [1]

The increased concentration of sorbitol in bioplastics also affects the nature of water resistance.
The nature of the bioplastic's resistance to water is determined by the swelling test that is the
percentage of plastic condensation by the presence of water [35]. In the study of Afif et al. [1],the
addition of sorbitol 1 ml, 2 ml, 3 ml, and 4 ml in the making of bioplastics resulted in a bloating result
of 71.04%; 73.78%; 87.39%; and 88.03%, this shows that the addition of sorbitol influences on the
percent of distension so that the greater the sorbitol added, the greater the percent of distension in
bioplastics.
The increase in percent distension is due to the increased concentration of sorbitol because
sorbitol has hydrophilic properties [5]. Sorbitol has many -OH groups so that it can bind to water
through hydrogen interactions which causes an increase in water absorption in bioplastics.
Based on the results of the study, the degradation of cellulose bioplastics from waste making
carrageenan with the addition of 12 ml sorbitol gets the highest value of 58.68 ± 0.90% for 7 days.
Based on the literature review of previous studies on the mechanical properties of bioplastic based
cellulose with the addition of sorbitol, it is known that the concentration of 3 ml sorbitol can meet the
SNI mechanical properties standards namely the tensile strength value of 24.7-302 MPa, elongation
percent 21 -220%, and 99% hydrophobicity [12].

4. Conclusion
The concentration of sorbitol on cellulose based bioplastics from carrageenan waste affects on
biodegradation ability in the bioplastic. The highest degradation rates were at sorbitol concentrations
of 12 ml with a value of 58.68 ± 0.90% for 7 days. Based on the literature review the best sorbitol
concentration is 3 ml, which is based on the effect of sorbitol on the ability of biodegradation and
mechanical properties of bioplastics based on the literature study conducted.

5. References

[1] Afif, M., Wijayati, N., and Mursiti, S. 2018. Pembuatan dan Karakterisasi Bioplastik dari Pati
Biji Alpukat-Kitosan denganPlasticizer Sorbitol. Indonesian Journal of Chemical Science.
7(2) : 102-109.
[2] Cheng, L.H., Abdkarim, A.,Norziah, M.H., Fazilah ,A., Seow ,C.C. 2006. Modification of the
microstructural and physical properties of konjacglucomannan-based films by alkali and
sodium carboxyl methyl cellulose.Journal of Food Science.2(2) : 62-71.
[3] Das, M.P and Kumar S. 2013. Influence of Cell Surface Hydrophobicity in Colonization and
Biofilm Formation on LDPE Biodegradation. Journal of Pharmacy and Pharmaceutical
Science. 5(4).
[4] Fithriani, D., Rodiah, N., and Bakti, B.S. 2007. Ekstraksi Selulosa dari Limbah Pembuatan
Karagenan. Jurnal Pascapanen and Bioteknologi Kelautan and Perikanan .2(2) :91-97.
[5] Hidayati, S., Zuidar, A.S., and Ardiani, A. 2015. Aplikasi Sorbitol Pada Produksi
Biodegradable Film dari Nata De Cassava. Reaktor. 15(3): 195-203.
[6] Hidayati, S., Zulferiyenni, and Satyajaya, W. 2019. Optimasi Pembuatan Biodegradable Film
dari Selulosa Limbah Padat Rumput Laut Eucheuma cottonii dengan Penambahan Gliserol,
Kitosan, CMC dan Tapioka. Jurnal Pengolahan Hasil Perikanan Indonesia. 22(2) : 30-354.
[7] Joshi P.A., and Jaysawal S.R. 2010. Isolation and Characterization of poly-β hydroxyl
alkanoate Producing Bacteria from Sewage Sample.J of Cell and Tissue Research.10 : 2165-
2168.
[8] Krochta and D.M. Johnston. 1997. Edible and Biodegradable Polymers Film: Challenges and
Opportunities. J. Food Technologi. 51(2) : 61-74.
[9] Laohakunjit, N. and Noomhorm, A. 2004. Effect of Plasticizers on Mechanical and Barrier
Properties of Rice Starch Film.Starch.56 : 348-356.
[10] Lazuardi, G. P. and Cahyaningrum S.E. 2013. Pembuatan dan Karakteristik Bioplastik
Berbahan Dasar Kitosan and Pati Singkong dengan Plasticizer Gliserol (Universitas Negeri
Surabaya)
[11] Lehninger, A.L. 1993. Dasar-dasar biokimia. Jilid 1, 2, 3.Erlangga, Jakarta.
[12] Melani, A., Herawati, N., and Kurniawan, A.F. 2017. Bioplastik Pati Umbi Talas Melalui
Proses Melt Interaction (Kajian PengaruhJ enis Filler, Konsentrasi Filler dan Jenis
Plasticizer).JurnalDistilasi. 2(2) :53-67.
[13] Nurfauzi, S., Sultan, S.M., Argo, B.D., and Djoyowasito, G. 2018. Pengaruh Konsentrasi
CMC and Suhu Pengeringan Terhadap Sifat Mekanik dan Sifat Degradasi pada Plastik
Biodegradable Berbasis Tepung Jagung. Jurnal Keteknikan Pertanian Tropis dan Biosistem.
6(1) : 90-99.
[14] Nuriah, L., Iswarin, S.J., and Wiyono. 2011. Karakteristik Sifat Mekanik Bioplastik dari Pati
Ubi Kayu Dengan Pemlastis Gliserol dan Sorbitol.Jurnal Natural. 1(1).
[15] Pratiwi, R., Driyanti, R., & Melisa, I.B. 2016. Pemanfaatan Selulosa dari Limbah Jerami Padi
(Oryza sativa) sebagai Bahan Bioplastik. IJPST, 3(3) : 83-91.
[16] Pratomo, H. and Rohaeti, E. 2011. BioplastikNata De Cassava Sebagai Bahan Edible Film
Ramah Lingkungan. Jurnal Penelitian Saintek. 16 (2) : 172-190.
[17] Purwanti, A. 2010. Analisis Kuat Tarik dan Elongasi Plastik Kitosan Terplastisasi Sorbitol.
Jurna lTeknologi. 3(2): 99-106.
[18] Putra, A.D., Johan, V.S., and Efendi, R. 2017. Penambahan Sorbitol Sebagai Plasticizer
dalam pembuatan Edible Film Pati Sukun. JOM Fakultas Pertanian. 4(2) : 1-15.
[19] Razhiyafathima M., Praseetha P.K. and Rimal Isaac R.S 2016. Journal Pharmacy Chemical
Biology Science 4(2).
[20] Rimadianti, N. 2007. Karakteristik EdibleFilm dari Isinglass dengan Penambahan Sorbitol
Sebagai Plasticizer.Skripsi. Fakultas Perikanan dan Ilmu Kelautan. Institut Pertanian Bogor.
Bogor.
[21] Rodriguez, M., Oses, J., Ziani, K., and Mate, J.I.2006. Combined Effect Of Plasticizer and
Surfactants On The Physical Properties Of Starch Based Edible Films, Journal of Food
Research International, 39, pp. 840-846.
[22] Rohman, M. A. 2016. Pengaruh Penambahan Glutaraldehida terhadap Karakteristik Film
Bioplastik Kitosan Terplastis Carboxy Methyl Cellulose (CMC) (Fakultas Perikanan dan
Kelautan Universitas Airlangga)
[23] Sanyang, M.L., Sapuan, S.M., Jawaid, M., Ishak, M.R., and Sahari, J.2015. Effect of
Plasticizer Type and Concentration on Tensile, Thermal and Barrier Properties of
BiodegradableFilms Based on Sugar Palm (Arengapinnata) Starch, Polymers, 7(6), pp. 1106-
1124.
[24] Selpiana, Patricia, Cindy P.A. 2016. Pengaruh Penambahan Kitosan dan Gliserol pada
Pembuatan Bioplastik dari Ampas Tebu dan Ampas Tahu. Jurnal Teknik Kimia. 22 (1) : 57-
64.
[25] Singh TP, Chatli ML, Sahoo J 2014 Journal of Food Science and Technology 52(5) 2530-
2543.
[26] Sitompul, A.J., Sagita, W., and Zubaidah, E. 2017. Pengaruh Jenis dan Konsentrasi Plasticizer
terhadap Sifat Fisik Edible Film Kolang Kaling (Arenga pinnata). Jurnal Pangan dan
Agroindustri 5(1) : 13-25)
[27] Sobral,`P.J.A., Menegalli ,F.C., Hubinger ,M.D., Roques ,M.A. 2001. Mechanical, water
vapor marrier and thermal properties of gelatin based edible films. Food Hydrocolloid.15(6) :
423-432.
[28] Subowo, W.S and Pujiastuti, S. 2003. Plastik Yang Terdegradasi Secara Alami
(Biodegradable) Terbuat Dari LDPE dan Pati Jagung Terlapis. Prosiding Simposium Nasional
Polimer IV. Bandung. Pusat Penelitian Informatika-LIPI. hal 203-208.
[29] Sumartono, N.W., Fitri H., Reni D., Wulan N., and Dea S.H 2015. Jurnal Pelita 10 (2)
(Universitas Negeri Yogyakarta)
[30] Sulityo, H.W., and Ismiyati. 2012. Pengaruh Formulasi Pati Singkong-Selulosa terhadap Sifat
Mekanik dan Hidrofobisitas pada Pembuatan Bioplastik. Konversi.1 (2).
[31] Surdia, N.M. 2000. Degradasi Polimer. Majalah Polimer Indonesia 3 (1) : 20-21.
[32] Susanti, Jasruddin, Subaer. 2015. Sintesis Komposit Bioplastik Berbahan Dasar Tepung
Tapioka dengan Penguat Serat Bambu. Jurnal Sains dan Pendidikan Fisika. 11(2):179–184.
[33] Usha, R., SangeethaT., and Palaniswamy M. 2011. Screening of Polyethylene Degrading
Microorganisms from Garbage Soil.Libyan Agriculture Research Center Journal International
Vol. 2.
[34] Utami, M.R., Latifah, and N. Widiarti. 2014. Sintesis Plastik Biodegradable dari Kulit Pisang
dengan Penambahan Kitosan dan Plasticizer Gliserol. Indonesian Journal of Chemical
Science.3(2): 163-167.
[35] Utomo, A. W., B. D. Argo., dan M. B. Hermanto.2013. Pengaruh Suhu dan Lama
PengeringanTerhadap Karakteristik Fisikokimiawi Plastik Biodegradable dari Komposit Pati
Lidah Buaya (Aloe vera)-kitosan. Jurnal Fakultas Teknologi Pertanian. Universitas Brawijaya.
1(1):73-79.
[36] Widyaningsih, S., Kartika,D., and Nurhayati, Y.T. 2012. Pengaruh Penambahan Sorbitol dan
Kalsium Karbonat Terhadap Karakteristik dan Sifat Biodegradasi Film dari Pati Kulit Pisang.
Molekul. 7(1) : 69-81.