Accepted Manuscript

A simple method for improving the properties of the sago starch films prepared by
using ultrasonication treatment

Hairul Abral, Azmi Basri, Faris Muhammad, Yuzalmi Fernando, Fadli Hafizulhaq,
Melbi Mahardika, Eni Sugiarti, M.S. Sapuan, R.A. Ilyas, Ilfa Stephane

PII: S0268-005X(18)31539-X
DOI: https://doi.org/10.1016/j.foodhyd.2019.02.012
Reference: FOOHYD 4938

To appear in: Food Hydrocolloids

Received Date: 14 August 2018

Revised Date: 24 January 2019
Accepted Date: 6 February 2019

Please cite this article as: Abral, H., Basri, A., Muhammad, F., Fernando, Y., Hafizulhaq, F., Mahardika,
M., Sugiarti, E., Sapuan, M.S., Ilyas, R.A., Stephane, I., A simple method for improving the properties
of the sago starch films prepared by using ultrasonication treatment, Food Hydrocolloids (2019), doi:
https://doi.org/10.1016/j.foodhyd.2019.02.012.

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 ACCEPTED MANUSCRIPT

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FESEM fracture surface before ultrasonication Moisture absoption of film before
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shows more insoluble starch granules ultrasonication (S-0) is higher than after
ultrasonication for 5 min (S-5)
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FESEM fracture surface after ultrasonication 5 min sonicated film (S-5) has higher thermal
shows more homogeneous structures stability than non-sonicated film (S-0)
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 ACCEPTED MANUSCRIPT
1 A simple method for improving the properties of the sago starch films prepared by using

2 ultrasonication treatment

4 Hairul Abrala*, Azmi Basria, Faris Muhammada, Yuzalmi Fernandoa, Fadli Hafizulhaqa,

5 Melbi Mahardikaa, Eni Sugiartib, MS Sapuanc, RA Ilyasc, Ilfa Stephaned.

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6
a

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7 Department of Mechanical Engineering, Andalas University, 25163 Padang, Sumatera Barat,

8 Indonesia

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b
9 High-Temperature Coating Laboratory, Research Center for Physics, Indonesian Institute of

10 Sciences (LIPI) Serpong, Indonesia

11 c)

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Department of Mechanical and Manufacturing Engineering, Faculty of Engineering,
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12 Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia
d)
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13 Department of Information System, STMIK Indonesia Padang, Indonesia

*
14 Corresponding author. Tel.: +62-75172566
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15 E-mail address: abral@ft.unand.ac.id

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16

17 Abstract
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18 Starch granules containing amylopectin-rich fractions like sago starch may remain insoluble
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19 and undamaged decreasing properties of the film. The aim of this study is to characterize
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20 native sago starch films prepared using ultrasonication. An ultrasonication probe was used

21 during gelatinization for 2.5, 5, and 10 min respectively. Ultrasonication decreases the

22 incomplete gelatinized granules resulting in a film with a more compact structure, and lower

23 moisture vapor permeability than non-treated film. The longest duration resulted in a film

24 with the highest transparency, and the highest thermal resistance. The duration for 5 min

25 increased tensile strength of the film by 227%, and its moisture absorption decreased by
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26 27.39% compared to non-sonicated film. After ultrasonication for 10 min, melting

27 temperature increased by 7% in comparison to non-sonicated film. This work promotes a

28 simple method to improve the tensile and physical properties of starch based film.

29

30 Keywords: Starch film; transparency; ultrasonication; ghost.

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31

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32 1. Introduction

33 Development of starch-based bioplastics has been given considerable attention as an

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34 environmentally friendly biodegradable alternative to hydrocarbon-based plastics (Abral,

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35 Dalimunthe, et al., 2018). When starch films are used for food packaging it is required to
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36 have good transparency, sufficient strength and low moisture absorption so as be able to

37 improve the shelf life of food. Solution casting is one of common method for preparing starch
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38 film, especially at the laboratory level. During this preparation, some defects resulting in

39 inhomogeneous structures may occur. These inhomogeneous structure result from

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40 incompletely soluble starch granules often called ghosts (Abral, Anugrah, et al., 2018). This
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41 can decrease the transparency of starch film (Garcia-Hernandez, Vernon-Carter, & Alvarez-
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42 Ramirez, 2017). Ghost formation is a result of cross-linking of polysaccharide chains within

43 swollen granules (Debet & Gidley, 2007). Previous studies found that ultrasonication is
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44 effective in reducing insoluble and agglomerated starch granules (Abral, Putra, Asrofi, Park,
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45 & Kim, 2018; Lima & Andrade, 2010). This is because sound energy from ultrasonication

46 produces acoustic cavitation: the formation, growth, and collapse of starch granules within

47 the liquid matrix (Asrofi, Abral, Kasim, Pratoto, Mahardika, et al., 2018b; Mahardika, Abral,

48 Kasim, Arief, & Asrofi, 2018). The violent collapse of the bubbles results in microjets and

49 shock waves which shatter the aggregations of the agglomerated granules suspended (E.

50 Syafri, Kasim, Abral, & Asben, 2018).

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51 Physical and mechanical properties of a maize starch film after ultrasonication of the

52 starch gel improve due to an increase in homogeneity of the structural starch film resulting in

53 increased transparency and tensile strength of the film along disappearance of the ghosts

54 (Abral, Anugrah, et al., 2018; Cheng, Chen, Liu, Ye, & Ke, 2010). In contrast, another

55 previous study claimed that a high ghost phase fraction enhanced the tensile (elongation at

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56 break and tensile stress) properties of corn starch film (Garcia-Hernandez et al., 2017). These

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57 dissimilarities in results could be due to differences in the starch sources used for preparing

58 starch films.

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59 This present study used sago starch granules from Metroxylon Sagu palm. This material

60 is abundantly available in tropical country like Indonesia and has a very low cost compared

61
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with other common starches (Abral, Kasmianto, & Mastariyanto Perdana, 2012; Nouri &
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62 Mohammadi Nafchi, 2014). Sago palm contains a large amount of starch in its trunk and its
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63 productivity was about 4 times that of paddy rice (Karim, Tie, Manan, & Zaidul, 2008). Sago

64 starch has unique characteristics and some of its physicochemical properties similar to
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65 common starch like cassava and potato (Mohammadi Nafchi, Cheng, & Karim, 2011). It is a
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66 potential source for bioplastics with high amylopectin content leading to better tensile

67 properties (Hanafi Ismail & Nur Fasihah Zaaba, 2012). However, starch films from granules
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68 with high amylopectin may have incompletely soluble and agglomerated starch granules
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69 decreasing film properties (Debet & Gidley, 2007).

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70 Many studies have been reported on the properties of starch-based films made from

71 various starches including high amylopectin corn, jicama, and wheat (Abral, Anugrah, et al.,

72 2018; Debet & Gidley, 2007; Garcia-Hernandez et al., 2017; Hafizulhaq, Abral, Kasim,

73 Arief, & Affi, 2018). However, as far as the authors are aware no work has been reported on

74 sago starch film prepared using an ultrasonic probe. Therefore, the objective of the present

75 study was to determine the properties of the sago starch prepared by a simple and
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76 environmentally friendly method using ultrasonication further. The main motivation was to

77 obtain the optimum ultrasonic duration of the sago starch gel to maximize several properties

78 of the film. Morphology of the fracture surface of the plasticized sago film was observed

79 using a field-emission scanning electron microscopy (FESEM). X-ray diffraction (XRD) and

80 Fourier transform infrared (FTIR) of films were characterized. Other properties measured are

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81 viscosity, transparency, tensile strength and modulus, fracture strain, moisture absorption,

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82 water vapor permeability, and thermal resistance.

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83 2. Materials and Experiment

84 2.1 Material

85
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Sago starch was obtained from local small-scale industry in Padang, Indonesia. For
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86 purification, the starch (1000 g) was mixed with distilled water (3000 mL). The solution was

87 stirred manually for a 1 min. After 15 h, the liquid fraction containing purities was decanted
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88 off leaving purer sediment of starch. This was repeated three more times. The resulting wet
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89 pure starch was poured into a Teflon plate to be dried in a drying oven (Universal Oven
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90 Memmert UN-55) for 20 h at 50 oC. A small electrical blender was used to refine dried starch

91 bundles for 5 min. Chemical analysis indicated that the purified sago starch contained 21%
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92 amylose, and 79% amylopectin indicating it was a high amylopectin content starch (Al-

93 Hassan & Norziah, 2012).

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94
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95 2.2. Preparation of the bioplastic

96 The purified sago starch, distilled water, and glycerol were weighed for 15, 150, and 7.5

97 g respectively using a precision balance to the nearest 0.1 mg (Kenko). These materials were

98 mixed and gelatinized using a hot plate magnetic stirrer (Daihan MSH-20D) at 500 rpm, 70
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99 C for 45 min. This gelatinization temperature of sago gel was determined by using a temperature

100 probe integrated with the hot plate magnetic stirrer. When the solution started to gelatinize that was
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101 the temperature chosen for this process and susequent ultrasonication. During gelatinization, four

102 gel samples were treated; one without and three with ultrasonication for 2.5, 5, and 10 min

103 respectively using a 20 mm diameter SJIA 1200W ultrasonic probe at 600 watts at 100%

104 amplitude and 20 kHz. Ultrasonication times longer than 10 minutes were initially trailed but

105 because the of films from these proved too brittle for further testing so were not used in this

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106 study. Ultrasonic warming was limited so the gel temperature did not exceed 70 oC. Viscosity

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107 of four non- and sonicated gel samples was measured using an NDJ-8S digital rotary

108 viscometer at 50 oC with rotor #2 at 6 rpm about 10 s. The sample was cast in a petri dish

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109 (140 mm diameter). The petri dish was vibrated using an ultrasonic bath (PS-70AL, 420

110 watts, 40 kHz, 100% amplitude) for 15 min to remove trapped air bubbles and ensure

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homogeneity of the gel. A film formed after drying in a drying oven (Universal Oven
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112 Memmert UN-55) at 50 oC for 21 h. All the tested samples were labelled with the letter S
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113 (starch film), and a number corresponding to the ultrasonic duration used. Thus the

114 abbreviation S-2.5 represents starch film ultrasonicated for 2.5 min.
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115
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116 2.3 Characterization

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117 2.3.1. Opacity

118 The opacity of the film was measured using UV-vis spectrophotometer (Shimadzu
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119 UV 1800, Japan) between wavelengths of 400-800 nm according to ASTM D 1003-00

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120 (Standard Test Method for Haze and Luminous Transmittance of Transparent Plastics). Films

121 of 0.34 mm thickness were cut into 9 x 35 mm rectangles. The opacity measurement was

122 carried out in triplicate.

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124 2.3.2. FESEM observation

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125 The fracture surface of the sample after tensile testing was observed using FESEM.

126 The film samples were placed on the FESEM sample stub. They were coated with carbon and

127 gold to reduce the static charge. The surface morphology of the sample was observed using a

128 model JFIB 4610 SEM from JEOL with 10 kV and 8 mA.

129

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130 2.3.3. FTIR

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131 FTIR spectra of the non- and sonicated film (S-0, S-2.5, S-5, and S-10) were recorded

132 using an IR spectrometer (PerkinElmer Frontier equipment) to compare the functional groups

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133 and molecular bond structure of the film. Before the characterization, all samples were dried

134 using a drying oven (Universal Oven Memmert UN-55 at 50 oC) until constant weight. The

135
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dried samples were cut (approximately 10 x 10 mm) with steel scissor, formed into a sheet
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136 film and scanned at a frequency range of 4000–600 cm-1 at 4 cm-1 resolution. Three different
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137 locations for each sample per treatment were tested.

138
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139 2.3.4. X-Ray Diffraction

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140 PANalyticalXpert PRO at 25 oC, 40 kV and 30 mA was used to perform X-ray

141 diffraction testing. The samples were scanned from 2θ = 3o to 40o. The crystallinity index
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142 (CI) percentage was measured using an Eq. 1 (Segal, Creely, Martin, & Conrad, 1958):

−
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% = 100 1
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143 where I200 is the intensity of the peak at 22.6o which is associated with the crystalline region

144 of cellulose, and Iam is the intensity taken at 2θ = 18o in the diffraction pattern as

145 characteristic of the amorphous regions in the cellulose.

146

147 2.3.5. Tensile Properties

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148 A testing machine (Com-Ten testing machine 95T) was used to characterize the tensile

149 properties of films including tensile strength (TS), tensile modulus (TM) and fracture strain

150 (FS). All samples were prepared with ASTM D882-12 standard and conditioned for 48 h with

151 50±5% relative humidity at 25°C. Tensile tests were performed with tensile speed for 3

152 mm/min at room temperature and repeated five times for each sample.

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153

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154 2.3.6. Thermogravimetry analysis (TGA) and derivative (DTG), differential thermal analysis

155 (DTA), and differential scanning calorimetry (DSC)

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156 Thermal gravimetric analysis is a method to measure the thermal characteristics of

157 materials such as the starch based film (Abral, Hartono, et al., 2018). TGA, DTG and DTA of

158
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samples were performed by using a thermal analysis instrument DTG-60 from Shimadzu.
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159 The samples were weighed between 4 and 5 mg and input into the instrument which was set

up with a nitrogen flow rate of 50 ml/min and the heating rate of 20 oC/min. DSC was
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161 measured using TA Instrument (Model Q20) from room temperature up to 280 ◦C at 10
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162 ◦C/min with nitrogen flow rate of 50 ml/min. The weight of each sample was 5–10 mg.
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163

164 2.3.7. Moisture absorption and water vapor permeability

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165 Moisture absorption (MA): Both non-sonicated and sonicated films were dried in a
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166 drying oven (Universal Oven Memmert UN-55) until constant weight then stored in a closed
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167 chamber with 99% relative humidity (RH) for 9 h. The samples were taken out and weighed

168 on a precision balance to the nearest 0.1 mg (Kenko). Percentage of MA in the sample was

169 calculated using Eq. 2 (Edi Syafri, Kasim, Abral, & Asben, 2017):

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% = 100 2

170 where:

171 wh is final weight and wo initial weight of sample.

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172

173 Water vapor permeability (WVP): Film with diameter of about 45 mm was stored in a

174 desiccator at RH 50±5% and 25 oC for seven days. This film was sealed on top of a plastic

175 bottle (45 mm diameter) containing distilled water of 30 mL (100% RH). Sealing the film

176 uses Vaseline for preventing the leakage of moisture through seals. The bottle was weighed

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177 to get initial mass and stored in a closed desiccator (1000 g silica gel) at 25oC. A Kenko

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178 precision balance to the nearest 0.1 mg was used to weigh the bottles for each three hours

179 during 24 h. Average WVP value was determined using the Eq. 3:

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180

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! " #
181 WVP = (3)
$ " % " &
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182
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183 where dW = weight loss of the plastic bottle (g), L = film thickness (m), A = the exposed area

184 of film sealing top of a plastic bottle (m2), dt = the time under the partial water vapor pressure
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185 gradient (dP=2533 Pa). Three samples per treatment were tested.
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186

187 2.3.8 Statistical analysis

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188 IBM SPSS Statistics 25.0 (IBM Corporation, Chicago, USA) was used to conduct statistical
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189 analysis. The effect of non-sonicated and sonicated treatments on opacity, tensile properties,
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190 water vapor permeability, and moisture absorption of the films at the 5% significance level

191 was identified using analysis of variance (ANOVA) and P-test. The measurements were

192 replicated at least three times for each film tested.

193

194 3. Results and discussions

195 3.1. Viscosity

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196 Table 1 displays viscosity of the starch gel before and after ultrasonication. Two and a

197 half minutes of ultrasonication reduces viscosity dramatically from 4999 to 125 MPa.s.

198 However longer ultrasonication increases viscosity that may be due to lower temperature of

199 the gel. The drastic decrease in viscosity can be attributed to the high mobility of the

200 sonicated gel due to the kinetic energy of the jets of liquid from acoustic cavitation scissoring

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201 the sago starch long polymer chain into shorter lengths, thus increasing the fraction of free

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202 mobile starch molecules (Cheng et al., 2010). Ultrasonication also breaks cross-links between

203 polymers, resulting in an increase in the number of mobile polymer molecules. It also

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204 destroys the granular starch agglomerations hindering mobility of the polymer chains in the

205 gel which will result in lowering the viscosity. Similar decreases in viscosity of the starch gel

206
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have been observed in previous studies due to ultrasonic treatment (Cheng et al., 2010; Iida,
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207 Tuziuti, Yasui, Towata, & Kozuka, 2008).
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208

209 3.2 FESEM morphology

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210 Fig. 1 shows the FESEM fracture surface of tensile samples before and after
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211 ultrasonication in cross-section. The non-sonicated film (Fig. 1a) displays a rougher surface

212 than the sonicated film (Fig. 1b, 1c, 1d). The rough surface is attributed to the presence of
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213 partially gelatinized starch that impedes crack propagation. Smoother and more homogeneous
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214 fracture surface are observed for longer ultrasonic duration. As shown in Fig. 1a, micro and
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215 nano cracks appear at boundaries between the complete and incomplete gelatinized sections

216 (marked with i). These two sections had different molecular structures resulting in a weak

217 bonding in the boundary. As a result of this weakness, initial crack may propagate along this

218 boundary. Furthermore, where clumps of starch agglomerations occur micro and nano-sized

219 porosities will exist between the starch agglomerations. This may result in more spaces for

220 water molecules to diffuse. Homogeneous and non-homogeneous gelatinized starch structures
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221 may experience slippage at boundary surfaces due to poor interface bonding, thus reducing

222 tensile properties of the film. Ultrasonication eliminates these defects resulting in better

223 properties.

224

225 3.3. Opacity

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226 Fig. 2 displays the absorbance curve as function of wavelength for the plasticized film

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227 without and with ultrasonication for 2.5, 5 and 10 min. There is a significant increase of the

228 transparency for longer duration (p ≤ 0.05). The S-0 film had the highest opacity (385.9 ±

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229 0.73 AUnm) as shown in Table 2. This opacity decreases to lowest value (192.5 ± 0.06

230 AUnm) after 10 min ultrasonication. This lower transparency of the S-0 film is because some

231
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defects such as agglomerations of incompletely gelatinized starch hinder light transmission
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232 (Li et al., 2015). When these are eliminated by ultrasonication, transmission increases. The
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233 more homogeneous and compact structures of the sonicated film are supported by FESEM

234 results as shown in Fig. 1d. This result is in agreement with a last study (Fu, Wang, Li, Wei,
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235 & Adhikari, 2011).

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236

237 3.4 FTIR Spectra

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238 Fig. 3 displays average FTIR curve of three different locations of each sago starch film

for various ultrasonic treatment. Bands in range of 3500-3200, 2927, 1647 cm-1 correspond to
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239
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240 O-H stretching, C-H stretching, O-H of absorbed water, respectively (Al-Hassan & Norziah,

241 2017; Hanafi Ismail & Nur Fasihah Zaaba, 2012). According to a previous study, FTIR

242 spectra in the range of about 3500-3200 cm-1 can be used to measure the hydrophilicity of the

243 biopolymer (Asrofi, Abral, Kasim, Pratoto, & Mahardika, 2018; Matějková & Šimon, 2012).

244 In this case, transmittance (T) values in the peak at about 3300 cm-1 became higher for longer

245 ultrasonic duration. For example, average T of O-H stretching for non-sonicated film shifts
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246 from 9.9±0.64 to 13.0±2.29% after 10 min ultrasonication (Table 2). This increasing T value

247 can be attributed to the higher hydrophobicity of the film after ultrasonication (Goyat, Ray, &

248 Ghosh, 2011). The increasing hydrophobicity is consistent with S-10 film having the highest

249 moisture resistance as shown in Fig. 6. Results of the FTIR study are in agreement with

250 previous work which has reported increasing hydrophobicity of biocomposites after

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251 ultrasonication (Asrofi, Abral, Kurnia, Sapuan, & Kim, 2018).

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252

253 3.5 X-ray diffraction

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254 Fig. 4 displays X-ray diffraction patterns for the film before and after ultrasonication. All

255 samples show three main sharp peaks at about 18o, 19o, and 23o; a typical diffraction pattern

256
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of starch bioplastics as semi-crystalline materials (Abral et al., 2019; Duy, Rashid, & Ismail,
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257 2012). After various ultrasonic treatments, the three main peaks change that can be related to
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258 polymer mobility and orientation of the polymer crystal lattice (Cheng et al., 2010; Kaith,

259 Jindal, & Maiti, 2009). Table 2 displays the crystallinity index (CI) of each film. CI for S-0
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260 was lowest (13%), which indicated that S-0 had the largest number of amorphous structures.
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261 After 2.5 min ultrasonication, CI of S-2.5 increased slightly to 16%. However, further

262 ultrasonication makes insignificant changes in CI of the film. The slight increase in CI may
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263 be due to the more homogeneous polymer structure after ultrasonication (Asrofi, Abral,
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264 Kasim, Pratoto, Mahardika, et al., 2018a). Disappearance of ghosts releasing amylopectin or
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265 amylose to the matrix modifies the diffraction pattern (Garcia-Hernandez et al., 2017). This

266 result is consistent with FESEM morphology (Fig. 1b) which showed sonicated film was

267 more compact and homogeneous. The fact that CI peaks after 2.5 minutes of sonication

268 suggests this duration is sufficient to achieve a homogeneous polymer structure. The slight

269 reduction in intensity and narrowing of the three main peaks in Fig. 4 indicates that longer

270 sonication destroys the polymer structure (Abral, Lawrensius, Handayani, & Sugiarti, 2018).
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271

272 3.6 Tensile Properties

273 Average value of tensile strength (TS), tensile modulus (TM), and fracture strain (FS)

274 were shown in Table 2. There was a slight increase in both TS and TM and decrease in FS

275 with ultrasonication. For example, TS, TM, and FS increase to 227, 221, and 66% after 5 min

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276 ultrasonication. These results are in contrast to the last findings (Garcia-Hernandez et al.,

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277 2017). The disappearance of defects, such as micro- and nano-sized cracks, ghosts (see Fig.

278 1a) and increased amylopectin in the sago starch matrix as amylopectin-rich ghosts were

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279 destroyed appeared to improve tensile properties (Cheng et al., 2010). However, film strength

280 increases may also be a result of compaction of the polymer structure resulting in a more

281
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effective resistance against external load (Asrofi, Abral, Kasim, Pratoto, Mahardika, et al.,
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282 2018b). This compactness is a result of the restructuring of the polymers in the matrix to fill
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283 micro- and nano-sized porosities as more active short chains are created by the ultrasonic

284 kinetic energy (Abral, Anugrah, et al., 2018). Similar results have also been reported in a
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285 previous study (Cheng et al., 2010).

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286

287 3.7 Thermal properties

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288 Fig. 5 shows effect of ultrasonication duration on thermal properties of the film. Thermal
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289 resistance of the film increases with a higher ultrasonic duration. Fig. 5a shows the type of
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290 three steps of weight loss as temperature increases is observed for all films. The first step of

291 the weight loss from 60-180 °C corresponds to evaporation of absorbed water (Ilyas, Sapuan,

292 & Ishak, 2018). As temperature increases to 180-360 °C, a second large weight loss appeared

293 due to the volatile decomposition of the starch film (Abral, Anugrah, et al., 2018). As shown

294 in Fig. 5b, the maximum decomposition rate and the temperature of the maximum

295 decomposition for S-0 are -0.327 mg/°C, and 342.76 °C respectively, but -0.275 mg/°C, and
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296 357.4 °C for S-10. This result is also in agreement with DTA curve (Fig. 5c) which displays

297 higher activation energy for the decomposition of S-10 in comparison to S-0, as the second

298 endothermic DTA peak shifts from -192.25 µV at 317.89 °C for S-0 to -210.34 µV at 333.80

299 °C for S-10. These results confirm thermal resistance of the film increased after

300 ultrasonication. The more homogeneous structure and lower number of defects (Fig. 1d)

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301 result in a more compact structure which restricts the movement of the bioplastic molecular

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302 chains which increases resistance to decomposition (Liu & Zhang, 2006). This result is also

303 in agreement with a previous study (El-Shekeil, Sapuan, Jawaid, & Al-Shuja’a, 2014). In the

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304 temperature range 360-570 °C, a third weight loss represents a final decomposition to ash

305 (Abral, Dalimunthe, et al., 2018). DSC curve also confirms the enhancement of the thermal

306
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resistance as shown in Fig. 5d. The glass transition (Tg) and melting temperature (Tm) of
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307 sample without ulrasonication was lower than that with ultasonication. For example, Tm for
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308 S-0 is 187.02 ◦C that is lower (7%) than Tm for S-10 (200.06 ◦C).

309
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310 3.8 Moisture absorption and water vapor permeability

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311 Fig. 6a and 6b show average MA and WVP before and after ultrasonication. Non-

312 sonicated sago starch film displayed higher MA than sonicated, and required a longer time
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313 (greater than 6 h) to reach steady state than sonicated film. The sample that reached steady
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314 state fastest was S-10, with MA of about 29.24% (a 27.39% decrease compared to S-0). This
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315 is because the S-0 film contains more nano and/or micro-sized porosities for water to diffuse

316 into (Maneerung, Tokura, & Rujiravanit, 2008). Sonication reduced the viscosity of the sago

317 starch gel resulting in the more active depolymerized chains filling the porosities. Both

318 dimension and number of porosities decreased causing a decrease in diffusion of water

319 molecules. The decrease in MA of the film is also confirmed by the FTIR curve which shows

320 a weaker intensity of the hydrophilic functional group band at 3500-3200 cm-1
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321 (corresponding to O-H stretching) and 1647 cm-1 (O-H of absorbed water). The enhancement

322 of the moisture resistance was also confirmed in WVP curve as shown in Fig. 6b. WVP value

323 of the sample after ultrasonication is lower than that before ultrasonication. This is because

324 the greater compactness in the polymer structure of the sonicated film leads to greater

325 resistance to the diffusion of the water molecules (Fu et al., 2011; Ilyas, Sapuan, Ishak, &

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326 Zainudin, 2018). Consequently, it results in lower WVP values.

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327

328 4. Conclusions

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329 Sago starch gel was sonicated for 0, 2.5, 5 or 10 min using an ultrasonic probe sonicator,

330 then the non- and sonicated gel were treated using an ultrasonic bath. Ultrasonication

331
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duration for 10 min at 600 watts resulted in the best properties of sago starch film including
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332 highest thermal resistance, the lowest water vapor permeability, the highest transparency, and
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333 the lowest moisture absorption. The sonicated film showed a more compact and

334 homogeneous structure, and had higher thermal resistance, and tensile strength than the non-
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335 sonicated film. Permeability to water vapor, opacity, and water absorption capacity of the
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336 films significantly decreased after ultrasonication. This present study provides further

337 evidence that ultrasonication could become one simple, environmentally friendly process in
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338 the fabrication of sago starch film to improve its properties.

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339
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340 Acknowledgment

341 Acknowledgment is addressed to Directorate General of Higher Education for supporting

342 research funding with project name Fundamental Research (grant number

343 06/UN.16.17/PP.PKLN.MM/LPPM/2019).

344

345 References:
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346 Abral, H., Anugrah, A. S., Hafizulhaq, F., Handayani, D., Sugiarti, E., & Muslimin, A. N.

347 (2018). Effect of nanofibers fraction on properties of the starch based biocomposite

348 prepared in various ultrasonic powers. International Journal of Biological

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378 Nanocellulose from Water Hyacinth Fiber (WHF) Produced via Digester-Sonication and

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380 https://doi.org/10.1007/s12221-018-7953-1

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382 Characterization of the Sonicated Yam Bean Starch Bionanocomposites Reinforced By
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383 Nanocellulose Water Hyacinth Fiber (Whf): the Effect of Various Fiber Loading.

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397 Journal of Agricultural and Food Chemistry, 55, 4752–4760.

398 Duy, N. Q., Rashid, A. A., & Ismail, H. (2012). Effects of filler loading and different

399 preparation methods on properties of cassava starch/natural rubber composites. Polymer-

400 Plastics Technology and Engineering, 51, 938–942. https://doi.org/Doi

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403 content on mechanical, morphological and thermal properties of kenaf fibers reinforced

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416 Opacity of Starch-Based Biocomposites Reinforced with Cellulose Fiber from

417 Bengkoang. Fibers, 6(3), 62. https://doi.org/10.3390/fib6030062

418 Hanafi Ismail, & Nur Fasihah Zaaba. (2012). The mechanical properties, water resistance and

419 degradation behaviour of silica-filled sago starch/PVA plastic films. Journal of

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422 starch and polysaccharide solutions with ultrasound after gelatinization. Innovative Food

423 Science and Emerging Technologies, 9, 140–146.

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446 Acetamide. Macromolecular Materials and Engineering, 291, 820–828.

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457 thermal properties and heat sealability of sago starch films. Food Hydrocolloids, 25(1),
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471 characterization from ramie using a chemical-ultrasonic treatment. Journal of Natural

472 Fibers. https://doi.org/10.1080/15440478.2018.1455073

473

474 Figure captions

475 Fig. 1. FESEM fracture surface photographs of the film a) before and b) after ultrasonication.

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476 Crack (i) is observed in the boundary between homogeneous (ii) and inhomogeneous

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477 structures (iii).

478 Fig. 2. Opacity of the starch film after various treatments.

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479 Fig. 3. FTIR curves before and after ultrasound treatment.

480 Fig. 4. XRD patterns of the non-sonicated and sonicated films

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482 figure for glass transition (Tg) and melting temperature (Tm).
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483 Fig. 6. MA (a) and WVP (b) of non-sonicated and sonicated film. The mean difference is

484 significant at p ≤ 0.05. Different letters indicate significant difference among treatment.
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Table 1. Viscosity of the starch gel before and after ultrasonication.

Rotation speed
Sample Viscosity (MPa.s)
(rpm)/T (oC)
S-0 4999

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6/50
S-5 164
S-10 465

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Table 2. Tensile properties, opacity, and crystallinity index (CI), T of O-H stretching in the peak at
about 3300 cm-1 of the films before and after ultrasonication

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CI T (%)* Opacity
Sample TS (MPa) TM (MPa) FS (%) (AUnm)*
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a a a,b a,b
S-0 0.59 ± 0.21 36.96 ± 5.91 8.07 ± 3.91 12.9 9.9 ± 0.64 385.9 ± 0.73a
a a a a
S-2.5 0.81 ± 0.27 60.46 ± 9.74 5.99 ± 2.49 15.6 9.7 ± 0.22 325.5 ± 0.72b
b b b a,b
S-5 1.93 ± 0.82 118.71 ± 50.55 13.36 ± 2.9 15.0 10.2 ± 0.61 283.3 ± 0.15c
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S-10 1.17 ± 0.17a,b 80.97 ± 9.53a,b 7.85 ± 2.05a 15.4 13.0 ± 2.29b 192.5 ± 0.06d
Values are mean ± SD. Different letters in each column explain significant difference at 5% level of
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Highlights
• Ultrasonication of starch gel increases tensile properties of starch film.
• Thermal, and moisture resistance of the sonicated film was higher than non-sonicated
film.
• XRD, FTIR, and FESEM were used to characterize the film.
• Smoother and more compact fracture surface of the film were observed after

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ultrasonication.
• These simply fabricated starch bioplastics have commercial potential.

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