The effect of glycerol from biodiesel production waste

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... Faculty of Fisheries and Marine, Universitas Airlangga, Surabaya 60115 ... Human dependence on the use of plastic as the packaging of food products pose ... The chitosan edible film has the disadvantage that it is rigid and less flexible.
The effect of glycerol from biodiesel production waste as a plasticizer on physical character edible film of chitosan Fajar Abdul Rosyid, Rr. Juni Triastuti, and Sapto Andriyono

Citation: AIP Conference Proceedings 1813, 020015 (2017); doi: 10.1063/1.4975953 View online: http://dx.doi.org/10.1063/1.4975953 View Table of Contents: http://aip.scitation.org/toc/apc/1813/1 Published by the American Institute of Physics

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The Effect of Glycerol from Biodiesel Production Waste as a Plasticizer on Physical Character Edible Film of Chitosan Fajar Abdul Rosyid1, Rr. Juni Triastuti2*, Sapto Andriyono3 1

Aquaculture Department, Faculty of Fisheries and Marine, Universitas Airlangga, Surabaya 60115 2,3 Marine Department, Faculty of Fisheries and Marine, Universitas Airlangga, Surabaya 60115 *)

Corresponding author: [email protected]

Abstract.Chitosan edible film is a thin layer of clear packaging made from chitosan edible and biodegradable. Edible chitosan films are stiffer and less elastic, so it should be added plasticizer glycerol. One source of glycerol is inexpensive and easily obtained is crude glycerol from biodiesel production. The purpose of this study was to determine the effect of various concentrations of crude glycerol plasticizer on the physical characteristics of chitosan edible film and determine the best concentration of crude glycerol plasticizer. This study used a completely randomized design (CRD) with five treatments and four replications. The Edible film using the g chitosan and some plasticizers concentration of crude glycerol (0.2, 0.4, 0.8, and 1 mL) and a control treatment that used 0.4 mL of pure glycerol was made. The results showed that the use of crude glycerol plasticizer had effect to the physical character of chitosan edible film. Increasing concentrations of crude glycerol plasticizer exhibits the lowers value of the thickness and tensile strength, however, can increase the value of percent elongation. The best concentration of this research is the treatment of B (0.2 ml crude glycerol) which resulted in 0.55 mm thickness, the tensile strength of 95.38 kgf/cm2 and a percent elongation of 2.13%.

INTRODUCTION Human dependence on the use of plastic as the packaging of food products pose problems of an increase in the amount of waste on the environment. Garbage plastic used for food packaging is difficult broken down by organisms in the soil [1]. In addition to causing environmental problems in the use of plastic will increase the potential for harmful particulate contamination of plastic on the packed food products. Plastic particle contamination in food products causes health problems such as cancer, hormonal changes, and other health disorders [2].Edible films are one solution that can solve the problems of dependence and dangers in the use of plastic. The edible film is a thin layer of clear packaging made from hydrocolloid or lipids which is edible and biodegradable. One type of edible film is a chitosan edible film. The chitosan edible film has the disadvantage that it is rigid and less flexible. The plasticizer is a component that is added to the manufacturing process of edible film to improve the properties of rigid and less flexible [3]. Glycerol is a plasticizer that can improve the nature of the rigid and less flexible than chitosan edible film. One source of glycerol is not used much of the waste is the production of biodiesel in the form of crude glycerol.The crude glycerol has almost the same capabilities and price much cheaper than pure glycerol. The present study aimed to determine the effect of using crude glycerol on the physical characteristics of chitosan edible film.

MATERIAL AND METHOD The first stage is a crude glycerol preparation by removal of the methanol contained in crude glycerol using evaporation method. The level of purity of crude glycerol was tested by using a gas chromatography. Chitosan edible film was made by dissolving chitosan with 1% acetic acid solvent 100mL stirrer heated above 60°C with a velocity of 6000 rpm for 15 minutes [4]. Once the chitosan solution was formed, glycerol plasticizer was added, corresponding to each treatment and homogenized back for 15 minutes.That solution was then allowed at a cool

The 1st International Conference on Mathematics, Science, and Computer Science (ICMSC) 2016 AIP Conf. Proc. 1813, 020015-1–020015-6; doi: 10.1063/1.4975953 Published by AIP Publishing. 978-0-7354-1481-5/$30.00

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condition for 15 minutes before it was poured into the mold. Pouring was done by shaking evenly on all sides. The mold containing a solution of edible film was put in the oven at 100°C for 3 hours. The final stage was the removal of a layer of chitosan edible film of mold. Chitosan edible film was tested for value of thickness, tensile strength and percent elongation. Thickness testing was conducted according to [4]. Thickness testing was measured by means of calipers while the tensile strength and percent elongation was tested by using Autograph according to ASTM. Having obtained the three parameter values on the physical character of the data processing was done in order to obtain conclusions about the effect of crude glycerol to the edible film chitosan and treatment with the best physical characteristics. The microscopic structure of the edible film with the best treatment and control then was viewed using Scanning Electron Microscope (SEM) to determine the changes in the microscopic structure of an edible film that was formed.

RESULTS AND DISCUSSION Thickness Value Edible film thickness measurements indicated that the value of edible film thickness ranged from 0.05 to 0.099 mm. Results of analysis of variance showed a highly significant difference (p ≤ 0.05) between an edible film that uses plasticizer pure glycerol (Treatment A) and crude glycerol (Treatment B, C, D, and E). Increasing concentrations of crude glycerol did not make a difference in the value of the thickness between 0.0550 and 0.0500 mm. The highest of thickness was in treatment A (control) with a thickness of 0.099 mm. The thickness of each treatment is figure out in FIGURE 1. 0.12

0.1

[VALUE]0 ± 0,0077

mm

0.08

0.06

0.055

0.0545

0.0525

0.05

0.04

0.02

0 A

B

C

D

E

FIGURE 1. The thickness of the edible film with different concentrations of crude glycerol.

The thickness difference between the control treatment that uses pure glycerol and four treatments that use crude glycerol due to the differences in purity glycerol is used. The purity of crude glycerol is obtained by transesterification in biodiesel production approximately 70-80% [3]. Pure glycerol used in this study had a purity of 98%, while crude glycerol has only a purity of 9.32%. The thickness of the edible film is determined by the amount

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of solids dissolved in a solution of the edible film that was made. The greater amount of dissolved solids makes the edible film is thicker [3]. Glycerol plasticizer is a form of dissolved solid in an edible film [4]. The purity of pure glycerol increased the number of dissolved solids is greater than crude glycerol. The film of pure glycerol is thicker than crude glycerol due to the differences in the amount of dissolved solids. Impairment thickness occurs along with increased concentrations of crude glycerol were added. The decline in crude glycerol concentration difference of this nature did not give a significant effect (p ≤ 0.05) on edible film thickness as evidenced by Duncan's Multiple Range Test. A significant decrease in the thickness was not due to the impurities in crude glycerol molecules such as water, salt, and soap. Glycerol is a polyhydric alcohol compound, having three hydrogen molecules that have a hydrophilic nature so easily bind with water and soap [5]. One of the stages in the manufacture of an edible film is the drying process by heating. Warming make a glycerol molecule that binds with soapy water evaporate, so that the number of dissolved solids will be reduced (6). Decreasing the number of solids is due to the evaporation of water and soap down the value of edible film thickness [2].

Tensile Strength Test Results of testing the tensile strength of chitosan edible film with the addition of plasticizers crude glycerol in the treatment of A to E were 51.43 kgf/cm2, 9538 kgf/cm2, 54.64 kgf/cm2, 47.92 kgf/cm2, and 41.54 kgf/cm2. Results of analysis of variance showed that the addition of crude glycerol had significant effect (p ≤ 0.05) in the value of tensile strength chitosan edible film. Duncan's multiple range test results showed that all treatments that used crude glycerol plasticizer showed significantly different. Treatment with pure glycerol plasticizer that has a tensile strength values were not significantly different with treatment C and D. The highest of tensile strength value was showed in treatment B which was equal to 95,38kgf/cm2. The tensile strength in each treatment can be seen in FIGURE 2.

Tensile Strenght 120.00

a

95.38 ± 5.0

100.00

Kgf/cm2

80.00 60.00

b

bc

54.64 ± 4.59

51.43 ± 2.21

c

47.92 ± 2,26

40.00

d

41.54 ± 3.36

20.00 0.00

A

B

C

D

E

Treatment FIGURE 2. Tensile strength of edible film with different concentrations of crude glycerol.

The results of tensile strength values indicated that the decline in value of tensile strength occurs along with the addition of glycerol content is used. The more glycerol contained then the resulting tensile strength would be lower. Control treatment with a purity level of 98% glycerol and added of 0.4 mL have a tensile strength value lower than the addition of 0.2 mL of crude glycerol with a purity level 9.32%. Values for tensile strength chitosan edible film is closely related to chitosan structure hollow and rigid. Glycerol molecule that enters the cavity chitosan change the nature rigid and become more elastic. The greater the concentration of glycerol is added, the smaller the value of the tensile strength and more elastic the film will be [7]. Decreasing of tensile strength values as weused the concentration of glycerol plasticizer caused by reducing intermolecular forces between the molecules of chitosan polysaccharide chain. The more the concentration of plasticizer added to the bond of cohesion between the polymer will be less [8]. The decrease of the intermolecular

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force stretchs the distance between molecules so that the edible film to be more easily broken. Glycerol is a small hydrophilic molecule that can easily enter to fill the space between the chain polysaccharide molecules chitosan and hydrogen bonds form thereby increasing the flexibility of the film [1].

Percent Elongation Percent elongation chitosan edible film produced in this study ranged from 1.95 to 4.04%. Analysis of variance (p ≤ 0.05) showed a marked influence on the addition of crude glycerol in percent elongation value. Duncan's multiple range test results showed treatment with the addition of 0.8 mL of crude glycerol plasticizer produces the highest percent elongation at 4.04%, but not significantly different with the control. Meanwhile treatment B, C, and E did not show a significant difference to the value of percent elongation. Edible films with percent elongation value were lowest for the treatment with the addition of 1 mL of crude glycerol with a value of 1.95% percent elongation. Graph percent elongation value chitosan edible film on this research can be seen in FIGURE 3. 4.50

4.04

4.00 3.50

[VALUE] ± 0,61

(%)

3.00 2.50

2.55 2.13

1.95

2.00 1.50 1.00 0.50 0.00 A

B

C

D

E

FIGURE 3. Percent elongation edible film with the addition of different crude glycerol

Percent elongation of an edible film is closely related to the flexibility of the film. The higher the percent elongation of an edible film the more elastic the film. Glycerol as plasticizer serves to lower bond mechanical cohesion between molecules and changes the nature of stiff, so the film will be more elastic. Mobility between chains of polymer molecules increases as the reduced intermolecular forces of the polymer chitosan in it filled with glycerol [4]. Value percent elongation obtained by an edible film with crude glycerol plasticizer increases as more glycerol molecules that go between the polymer chitosan and lowering the intermolecular forces of the polymer. Percent elongation is impaired in the addition of 1 mL of crude glycerol allegedly due to the saturation in edible form. The number of chitosan particles, estimated at less than crude glycerol so that the film formed impressed soft and easily broken.

The Microscopic Structure Edible film the microscopic structure of the sample control treatment (pure glycerol) and treated with crude glycerol observed using Scanning Electron Microscope (SEM). Observation of the microscopic structure aimed to see changes in the microscopic structure of chitosan. Microscopic structure of chitosan, edible film various treatments with crude glycerol can be seen in FIGURE 4.

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(a)

(b)

FIGURE 4. (a) Edible Film with pure glycerol plasticizer (b) Edible film with crude glycerol plasticizer

The microscopic structure through a scanning electron microscope (SEM) showed significant differences among edible film which was formed by plasticizer pure glycerol and crude glycerol. Capturing images in a transverse section of the film showed that the edible film was filled by pure glycerol and orderly, while the crude glycerol tend to be irregular and there were still many empty spaces unfilled. The microscopic structure of the edible film exhibits that glycerol molecules are small and hydrophilic into the cleft is owned by the polymer chitosan. The number of pure glycerol molecules that go into the polymer chitosan chains more when compared with the crude glycerol. On the control looks more compact compare to crude glycerol movie that looks fragile with some parts that look empty. Sections empty pores of the polymer chitosan is location of the moisture will get into the layer edible film. The more the empty pores in the polymer layer edible film, the greater the water vapor transmission rate that can extend beyond the edible film [9]. Chitosan edible film with plasticizer crude glycerol has empty pores so that the value of the rate of water vapor transmits believed to be large. The value of the water vapor transmission rate that is greatest in an edible film and it was supported by a low thickness value. The lower the value of the thickness of a film of the moisture will be easier to penetrate the layers of the film so that the water vapor transmission rate value will increase [10].

CONCLUSION The conclusion of this study is crude glycerol plasticizer has some effects on the physical character of chitosan edible film. Increasing concentrations of crude glycerol plasticizer decreased the value of the thickness and tensile strength but increased the value of percent elongation. The best treatment for an edible film with plasticizer crude glycerol is treatment B (0.2 mL) which resulted in 0.55 mm thickness, 95.38 kgf/cm2 of tensile strength, and 2.13% percent elongation.

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