Accepted Manuscript

Title: BIODEGRADABLE POLYMER BLENDS BASED

ON CORNSTARCH AND THERMOPLASTIC CHITOSAN
PROCESSED BY EXTRUSION

Author: J.F. Mendes R.T Paschoalin V.B. Carmona Alfredo R

Sena Neto A.C.P. Marques J.M. Marconcini L.H.C. Mattoso
E.S. Medeiros J.E. Oliveira

PII: S0144-8617(15)01073-5
DOI: http://dx.doi.org/doi:10.1016/j.carbpol.2015.10.093
Reference: CARP 10510

To appear in:

Received date: 5-8-2015

Revised date: 17-10-2015
Accepted date: 29-10-2015

Please cite this article as: Mendes, J. F., Paschoalin, R. T., Carmona, V. B., Sena Neto, A.
R., Marques, A. C. P., Marconcini, J. M., Mattoso, L. H. C., Medeiros, E. S., and Oliveira,
J. E.,BIODEGRADABLE POLYMER BLENDS BASED ON CORNSTARCH AND
THERMOPLASTIC CHITOSAN PROCESSED BY EXTRUSION, Carbohydrate
Polymers (2015), http://dx.doi.org/10.1016/j.carbpol.2015.10.093

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*Manuscript

1 BIODEGRADABLE POLYMER BLENDS BASED ON

2 CORNSTARCH AND THERMOPLASTIC CHITOSAN
3 PROCESSED BY EXTRUSION

4 Mendes, J.F. 1; Paschoalin, R.T.2; Carmona, V.B.2; Sena Neto, Alfredo R.2; Marques,
5 A.C.P.3; Marconcini, J.M.2; Mattoso, L.H.C.2 ; Medeiros, E.S.4, Oliveira, J.E.*5
1
6 Programa de Pós-Graduação em Engenheira de Biomateriais, Universidade Federal de
7 Lavras, Lavras-MG, 37.200-000, Brazil.

t
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2
8 Laboratório de Nanotecnologia Nacional de Agricultura (LNNA), Embrapa
9 Instrumentação, São Carlos, SP 13.560-970, Brasil.

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10 Departamento de Ciências dos Alimentos, Universidade Federal de Lavras, Lavras-
11 MG, 37.200-000, Brazil.

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12 Laboratório de Materiais e Biossistemas (LAMAB), Departamento de Engenharia de
13 Materiais, Universidade Federal da Paraíba, João Pessoa-PB, 58.100-100, Brazil.

14
15
5
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Departamento de Engenharia, Universidade Federal de Lavras, Lavras-MG,
37.200-000, Brasil.

16
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17 ABSTRACT
18 Blends of thermoplastic cornstarch (TPS) and chitosan (TPC) were obtained by
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19 melt extrusion. The effect of TPC incorporation in TPS matrix and polymer interaction
20 on morphology and thermal and mechanical properties were investigated. Possible
21 interactions between the starch molecules and thermoplastic chitosan were assessed by
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22 XRD and FTIR techniques. Scanning Electron Microscopy (SEM) analyses showed a
23 homogeneous fracture surface without the presence of starch granules or chitosan
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24 aggregates. Although the incorporation of thermoplastic chitosan caused a decrease in

25 both tensile strength and stiffness, films with better extensibility and thermal stability
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26 were produced.

27 Keywords: thermoplastic starch; thermoplastic chitosan; extrusion; biodegradable

28 polymers.
29

30

31

32

33

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34 1. INTRODUCTION

35 In recent decades, the growing environmental awareness has encouraged the

36 development of biodegradable materials from renewable resources to replace
37 conventional non-biodegradable materials in many applications. Among them,
38 polysaccharides such as starches offer several advantages for the replacement of
39 synthetic polymers in plastics industries due to their low cost, non-toxicity,

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40 biodegradability and availability(Fajardo et al., 2010; Simkovic, 2013). Corn has been

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41 the main source of starch commercially available . Other minor sources include rice,
42 wheat, potato and cassava and starchy foods such as yams, peas and lentils(Bergthaller,

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43 2005).

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44 Starch is composed of amylose and amylopectin with relative amounts of each
45 component varying according to its plant source As an example, cornstarch has about
46 28wt.% amylose as compared to cassava starch with 17wt.%. Film-forming, barrier and
47
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mechanical properties, as well as processing conditions, are dependent on amylose to
48 amylopectin ratio. In general, an increasing amount of amylose improves the
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49 abovementioned properties(Forssell, Lahtinen, Lahelin, & Myllärinen, 2002; Raquez et
50 al., 2008; Rindlava, Hulleman, & Gatenholma, 1997).
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51 Starch-based films, however, are brittle and hydrophilic, therefore limiting their
52 processing and application. In order to overcome these drawbacks, starch can be mixed
53 with various synthetic and natural polymers. These approaches are: multilayer structures
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54 with aliphatic polyesters (Martin, Schwach, Avérous, & Couturier, 2001), blends with
55 natural rubber(Carmona, De Campos, Marconcini, & Mattoso, 2014a) or
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56 zein(Corradini, De Medeiros, Carvalho, Curvelo, & Mattoso, 2006) and composites

57 with fibers(Rosa et al., 2009). Another widely used approach to improve mechanical
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58 properties and processability of starch films is the addition of chitosan.

59 Chitosan, which is obtained by partial or total deacetylation of chitin, is one of the most
60 abundant polysaccharides in nature, and a promising material for the production of
61 packaging materials due to the attractive combination of price, abundance and
62 thermoplastic behavior, apart from its more hydrophobic nature as compared to starch.
63 Moreover, chitosan is non-toxic, biodegradable, and has antimicrobial activity(Matet,
64 Heuzey, & Ajji, 2014).

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65 Several studies investigated the use of starch and chitosan in the production of
66 biofilms(Bourtoom & Chinnan, 2008; Dang & Yoksan, 2014; Fajardo et al., 2010;
67 Kittur, Harish Prashanth, Udaya Sankar, & Tharanathan, 2002; Lopez et al., 2014;
68 Pelissari, Grossmann, Yamashita, & Pineda, 2009; Pelissari, Yamashita, & Grossmann,
69 2011; Tuhin et al., 2012; Xu, Kim, Hanna, & Nag, 2005). However, since chitosan films
70 are fragile and require plasticizers to reduce the frictional forces between the polymer
71 chains to improve mechanical properties and flexibility, addition of polyols such as

t
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72 glycerol may reduce this drawback (Leceta, Guerrero, & Caba, 2013; Park, Marsh, &
73 Rhim, 2002)(Srinivasa, Ramesh, & Tharanathan, 2007)(Garry Kerch; Vadim Korkhov,

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74 2011; Leceta et al., 2013). Furthermore, chitosan hydrophobic nature and mechanical
75 properties can also be modified and improved through blends with poly(ethylene

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76 glycol), poly(vinyl alcohol), polyamides, poly(acrylic acid), gelatin, starch and
77 cellulose(Arvanitoyannis, I.; Psomiadou, E.; Nakayama, A.; Aiba, S.; Yamamoto, 1997;
78
79
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Kuzmina, O.; Heinze, T.; Wawro, 2012; Lee, Kim, Kim, Lee, & Lee, 1998; Zhai, Zhao,
Yoshii, & Kume, 2004).
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80 Most works related to the production of biodegradable films based on starch and
81 chitosan are obtained by casting (Ibrahim, Aziz, Osman, Refaat, & El-sayed, 2010;
82 Leceta, Peñalba, Arana, Guerrero, & Caba, 2015; Sindhu Mathew, 2008; Xu et al.,
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83 2005). In most of these studies, starch is pre-gelatinized prior to chitosan addition and
84 pouring into a mold. Such methods are not adequate to large-scale production of films,
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85 therefore limiting their industrial application. On the other hand, processing of starch-
86 chitosan by methods such as extrusion and injection molding have been relatively
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87 neglected.

88 In this work, cornstarch-chitosan blends were produced by extrusion so as to evaluate

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89 the effect of chitosan addition on blend morphology, and mechanical and thermal
90 properties, envisioning a large scale, mass production material, for industrial packaging
91 application.

92

93 2. EXPERIMENTAL
94 2.1 Materials

95 Chitosan with a molecular weight of 90-310kDa and a degree of deacetylation of 75-

96 85% was purchased from Polymar (Foratelza-CE, Brazil). Cornstarch, containing 70%

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 97 amylose and 30% amylopectin (Amidex® 3001), was supplied by Corn Products Brasil
98 (Balsa Nova - PR, Brazil). Glycerol, and citric and stearic acid were purchased from
99 Synth (Rio de Janeiro, Brazil).

100 2.2. Starch-chitosan blending by extrusion

101 Thermoplastic starch (TPS) was prepared from native corn starch:glycerol:water
102 (60:24:15 wt.%). The thermoplastic chitosan (TPC) was obtained from the physical

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103 mixture of chitosan powder, acetic acid, glycerol and water at the following proportions:

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104 17, 2, 33 and 50 wt.%, respectively. Glycerol was first added to chitosan and a 2wt.%

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105 acetic acid solution was subsequently added to form a paste following the procedure
106 described by Epure, Griffon, Pollet, & Avérous, (2011) in order to obtain the TPC.

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107 Additionally, 1 wt.% of stearic acid and 1 wt.% citric acid were added to both
108 compositions as processing aid.

109
110
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Each of these mixtures was pre-mixed manually and then extruded using a model
ZSK18 co-rotating twin-screw extruder (Coperion Ltd., SP, Brazil), with L/D=40, screw
111 diameter (D)=18 mm equipped with seven heating zones. The temperature profile (from
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112 the feeder to the matrix) and screw speed were: 120/125/130/135/135/140/140°C and
113 300rpm for TPS, and 108/90/90/100/100/110°C and 200 rpm for TPC. The TPS/TPC
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114 blends were prepared using 5 (TC5) and 10 (TC10) wt.% in the abovementioned
115 extruder with the following temperature profile and screw speed:
116 101/104/109/109/107/106/107ºC and 350 rpm. These conditions were established based
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117 on previous works reported by our group (Carmona, Corrêa, Marconcini, & Mattoso,
118 2015)(Carmona, De Campos, Marconcini, & Mattoso, 2014b) (Sengupta et al., 2007)
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119 (Giroto et al., 2015)(de Campos et al., 2013).

120 Extruded polymers and blends were pelletized using an automatic pelletizer (Coperion
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121 Ltd., SP, Brazil), do produce 2-mm pellets that were subsequently extruded in a single
122 screw extruder (AX Plasticos Ltda., São Paulo, Brazil) operating at 120rpm and a
123 temperature profile of 80/90/100oC. This extruder is equipped with a slit die to produce
124 sheets that were then hot-pressed into films of about 800 µm in thickness.

125 2.3. Characterization

126 2.3.1 Fourier Transform Infrared Spectroscopy (FTIR)

127 Fourier Transform Infrared Spectroscopy measurements were obtained using a FTIR
128 model Vertex 70 Bruker spectrophotometer (Bruker, Germany). Spectra were recorded

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129 at a spectral range between 3500 and 6000cm-1 at a scan rate of 180 scans and spectral
130 resolution of 2 cm-1. The FTIR spectrum was employed in the transmittance mode.
131 FTIR analyses were performed to study the effect of the addition of thermoplastic
132 chitosan in thermoplastic starch, to verify possible interactions among starch, chitosan
133 and glycerol.

134 2.3.2. X-ray diffraction (XRD)

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135 The crystal structures of TPS and blends with TPC were analyzed from diffraction

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136 patterns obtained on a model XRD-6000 Shimadzu X-ray diffractometer (Shimadzu,
137 Kyoto, Japan). Samples were scanned from 5 to 40 (2Ө) using a scan rate of 1º.min-1.

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138 The diffraction patterns were fitted using Gaussian curves, after peak deconvolution
using a dedicated software (Origin 8.0TM). Crystallinity index (CI) of TPC and blends

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139
140 were estimated based on areas under the crystalline and amorphous peaks after baseline
141 correction. The IC of TPS was estimated as a function of the B and Vh crystal form
142
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according to Hulleman et al.(Hulleman, Kalisvaart, Janssen, Feil, & Vliegenthart, 1999)

143 2.3.3. Scanning Electron Microscopy (SEM) analyses

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144 Qualitative evaluation of the degree of mixture (distribution and dispersion of the TPC
145 phase in TPS) was performed by using a model JSM 6510 JEOL SEM, operating at a
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146 5kV. Samples were mounted with carbon tape on aluminum stubs. Cross-sections of
147 fractured samples were mounted with the cross-section positioned upward on the stubs.
148 All specimens were sputter-coated with gold in a sputter (Balzer, SCD 050).
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149 2.3.4. Thermogravimetric measurements

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150 TG/DTG analyzes of the copolymers and blends were performed on a TGA Q500 TA
151 Instruments TG (TA Instruments, USA). Thermogravimetric curves were performed
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152 under synthetic air atmosphere. Approximately 6 mg samples were loaded to a platinum
153 crucible heated at a heating rate of 10ºC.min-1 from 25 to 600°C.

154 2.3.5. Film thickness

155 Film thickness was measured using a digital micrometer (IP65 Mitutoyo) at five random
156 positions. The mean values were used to calculate barrier and mechanical properties.

157 2.3.6. Mechanical properties

158 Tensile strength, maximum elongation at break and elastic modulus were measured
159 using a model DL3000 universal testing machine (EMIC, São Paulo, Brazil). Tests were

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160 carried out according to ASTM D882-09. Test samples of mid-section 15mm wide; 100
161 mm long and 0.8 mm in thickness were cut from the extruded films. At least six
162 samples were tested for each composition. Clamp-to-clamp distance, test speed and load
163 cell were 50 mm, 25mm.min-1 and 50 kgf, respectively. The tensile strength (σmax) was
164 calculated by dividing the maximum force on the cross-sectional area and the percent
165 elongation () was calculated as follows:

d - d0

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166 e (%) = ´100 (1)

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d0

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167 Where d is the final displacement, d0 is the initial displacement (clamp-to-clamp
168 distance). The elastic modulus (ε) was determined from the linear slope of the stress

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169 versus strain curves.
170
171

172
2.4. Statistical analysis an
Data were subjected to analysis of variance (ANOVA) to determine statistical
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173 differences. Multiple comparisons were performed by the Tukey test using the Sisvar®
174 statistical software (Version 5.4). Statistical differences were declared at p < 0.05.
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175 3. RESULTS AND DISCUSSION

176 3.1. FTIR characterization

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177 Fig. 1 shows the FTIR spectra corresponding to TPS and TPC as well as to TPS / TPC
178 blends.
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179
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180 Fig. 1. FTIR spectra of thermoplastic cornstarch (TPS), thermoplastic chitosan (TPC) and TPS
181 blends with 5 e 10 wt.% TPC (TC5 e TC10).

182
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183 The FTIR spectrum of TPS film featured absorption bands corresponding to the
184 functional groups of starch and glycerol, i.e., bands at 920, 1022 and 1148 cm-1 (CO
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185 stretching), 1648 cm-1 (bound water), 3277 cm-1 (-OH groups), 2914 cm-1 (CH
186 stretching) and 1423 cm-1 (glycerol ). These results are similar to the ones observed in
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187 the literature(RAMAZAN KIZIL, JOSEPH IRUDAYARAJ, 2002).

188 Similarly, TPC spectrum was similar to previous studies (Lopez et al., 2014; Pranoto,
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189 Rakshit, & Salokhe, 2005; Xu et al., 2005), in which the band at 3300 cm-1, due to - OH
190 stretching, overlaps the - NH stretching band, in the same region. A small peak at 1647
191 cm-1 shows attributed to C = O (amide I) stretching, a peak at 1717 cm-1, indicating the
192 presence of carbonyl groups, and peaks at 2875, 1415 and 1150-1014 cm-1 which
193 correspond to stretching of –CH, carboxyl (-COO-) and CO groups, respectively.

194 The FTIR spectra of TPS / TPC blends resembled the pure TPS film (Fig. 1). This is
195 somewhat understandable since a small amount of thermoplastic chitosan was added to
196 TPS. A similar behavior was observed in the literature with starch films plasticized with
197 0.37-1.45 wt.% chitosan(Dang & Yoksan, 2014).

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198 Despite the FTIR spectra of the blends show typical signals for both components, i.e.,
199 starch and plasticized chitosan, these interactions were not significant enough to cause
200 peak shifts, as seen in Figure 1.

201 3.2 X-ray diffraction (XRD) analyzes

202 X-ray diffraction patterns of TPS, TPC and TPS/TPC blends are shown in Fig.2.

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203

204 Fig.2. X-ray diffraction patterns of thermoplastic cornstarch (TPS), thermoplastic chitosan
205 (PTC) and TPS blends with 5 e 10 wt.% TPC (TC5 e TC10).
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206 TPS films showed diffraction peaks and broad amorphous halo, a typical behavior of a
207 semi-crystalline polymer with low degree of crystallinity. TPS films showed diffraction
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208 peaks (2Ө) at 13.7, 17.7, 20.4, 21.1 and 29.9º (Fig. 2). Peaks at 13.7 and 21.1º are
209 assigned to the Vh-type crystals of amylose complexed with glycerol(Teixeira E.M.,
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210 Lotti C., Ana C. Corre, Kelcilene B. R. Teodoro, José M. Marconcini, 2010), while the
211 peaks at 17.7 and 29.9 belong to B-type crystals, which may have been formed during
212 storage(Dang & Yoksan, 2014). Additionally, the absence of A-type crystals, which is
213 characteristic of the cereal starches granules, evidences that the native cornstarch
214 structure was completely destructurized during extrusion(Shi et al., 2006), as can also
215 be observed in SEM characterization.

216 Mikus et al. (Mikus, P.Y.; Alix, S.; Soulestin, J.; Lacrampe, M. F.; Krawczak, P.;
217 Coqueret, X.; Dole, 2014) stressed that the Vh-type crystallinity is induced by heat
218 treatment, where the interaction between the hydroxyl groups of the starch molecules
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219 are replaced by hydrogen bonds formed between the plasticizer and starch during
220 processing.

221 XDR diffraction patterns of PS/TPC blends are similar to the TPS matrix. However, it
222 can be observed that with increasing TPC amounts in TPS matrix, the V-type
223 crystallinity peaks become wider, which is due to the decrease in formation of glycerol-
224 amylose complex because of the limited mobility of amylose molecules. The same

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225 behavior was observed by Lopez et al.

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226 3.2 SEM characterization

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227 SEM micrographs of the surface and fracture surface of TPS films and blends with TPC
228 are shown in Fig. 3.

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229
230 Fig. 3: SEM micrographs of (A) TPS-Fracture surface; (B) TPC- Fracture surface; , (C) TC5-
231 Fracture surface; (D) TC10- Fracture surface; (E) TC5-Film surface; (F) TC10- Film surface.
232
233 The pure starch film (Figure 3A) showed the cross-section showed the absence of starch
234 granules after processing, demonstrating the extrusion process completely
235 destructurized the native cornstarch granules. These observations are consistent with the
236 results of X-ray diffraction. The same behavior was observed to thermoplastic chitosan

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237 (Fig.B). However, there are small surface cracks, which may have been formed during
238 the compression-molding step after the extruded films were formed as a consequence of
239 the brittle nature of chitosan.
240 On the other hand, TPS/TPS blends (Fig. 3C, D, E and F) had a homogeneous surface
241 without cracks and with good structural integrity. In certain localized positions of the
242 films there were slight surface irregularities that may be formed during extrusion, at the
243 die/polymer contact surface, a defect somewhat similar to some surface defects known

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244 to happen during processing of certain polymers(Tadmor & Gogos, 2006).
245 In Figs 3 C and D (fracture surface) show the presence of TPC particles dispersed

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246 within the starch matrix. No disruption of the TPS/SPC interface was observed. This
247 shows that there is a relatively good interfacial adhesion between the two components.

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248 Similar results were reported by Salleh et al.(Salleh, Muhamad, & Khairuddin, 2009) to
249 starch-chitosan films obtained by casting, in which chitosan particles dispersed within
250

251
the starch-chitosan matrix were observed.

3.4 Thermogravimetric analyzes

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252 TG curves and their first derivative (DTG) curves for TPS, TPC and TPC/TPC blends
253 are shown in Fig. 4 (a and b). From TG (Figure 4, a), and DTG (Figure 4,b) curves the
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254 onset (Tonset) and endset (Tendset) temperatures for degradation of TPS and blends are
255 shown in Table 1.
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256

257 (A)

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258

259 (B)

260
261
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Fig.4. TG (a) and DTG(c) of thermoplastic cornstarch (TPS), thermoplastic chitosan
(PTC) and TPS blends with 5 e 10 wt.% TPC (TC5 e TC10).
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262

263 The TG curve of TPS clearly shows a degradation to take place in three steps, ranging
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264 from 25-160ºC, 160-500ºC and 500-600, respectively due to the evaporation of free
265 water(Pelissari et al., 2009), evaporation of water(Cyras, Manfredi, Ton-That, &
266 Vázquez, 2008) and decomposition of the starch of the previously formed residue since
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267 an oxidative atmosphere (Pelissari et al., 2009) (Figure 4). Some gases such as CO2,
268 CO, H2O, and other small volatile compounds are released during this stage along with
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269 carbonaceous residue formation(Zhang, Golding, & Burgar, 2002).

270 TPS exhibited a steady weight loss from room temperature to about 250°C. This is due
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271 to release of adsorbed water during its combustion and glycerol evaporation. Such
272 phenomenon prevents the distinction between the first and second TPS degradation
273 phase and causes higher weight loss in the first degradation phase.

274 The TG curve of TPC presents a weight loss in two steps: the first weight loss at 140-
275 350°C, with a reduction of about 4%, and the second loss at 350-500°C, with a 93%
276 weight loss. A similar behavior was observed by Neto et al. (Neto et al., 2005).
277 Furthermore, as shown in Table 1, the addition of chitosan did not significantly change
278 the thermal stability of blends as compared to thermoplastic starch alone.

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279 TPS/TPC blends (Fig.4) showed a mass loss in the temperature ranges of 25-160ºC,
280 160-500ºC and 500-600oC, respectively due to free water evaporation, water and
281 glycerol(Cyras et al., 2008) volatilization, and decomposition of starch and
282 chitosan(Pelissari et al., 2009).

283 Table 1. Thermal properties (obtained by TG and DTG analyses) of the TPS and
284 blends.
Tonset Tonset Tendset Residue at 600ºC

t
Formulation (ºC) (ºC) (ºC) (%)

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TPS 277 335 447 0.1

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TC5 285 333 457 0.2

TC10 276 330 461 0.2

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TPC 252 297 495 0.2

285

286 3.5. Mechanical properties

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287 The tensile strength, elongation at break and elastic modulus of pure thermoplastic
288 polymers and are shown in Table 2. Figure 6 shows representative stress-strain curves
289 of these polymers and blends. These curves display the typical stress-strain behavior of
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290 plasticized starch-based polymers and blends in which the lowest part of the curve
291 displays a plastic behavior at deformations lower than 1%, followed by a plastic zone
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292 until sample rupture.

293
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294 Table 2. Mechanical properties of TPS, TPC and TPS/TPC blends with 5 and 10wt.%TPC.

Tensile Elongation Elastic

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Film Thickness
Strength at break Modulus
Formulation (µm)
(MPa) (%) (MPa)

TPS 755 2.1±0.3(a) 69±16 (a) 39.00±0.01(a)

TC5 757 1.5±0.2(b) 108±15(b) 16.10±0.06(b)

TC10 838 1.1±0.2(c) 93±3(b) 8.40±0.01(b)

295 Values correspond to average and standard deviations of the mechanical properties.
296 Two consecutive letters of the same type show that the values are not statistically
297 significant (p<0.05) using Turkey test. Different letters indicate that the averaged values
298 are statistically different at the same level of significance (p<0.05).

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299 According to Table 2, the tensile strength of the biofilms was significantly affected by
300 the addition of thermoplastic chitosan. The presence of TPC reduced tensile strength of
301 the blends, which was probably due to their plasticizing capability. Results in Table 2
302 also show that the addition of chitosan led to a significant reduction in elastic modulus
303 (p <0.05), corroborating the abovementioned discussion in which chitosan acts as a
304 plasticizer to TPS, thus forming less rigid films.

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305
306 Fig.6: Representative stress-strain curves of TPS, TPC and TPS/TPC blends with 5 and
307
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10wt.%TPC.

308 The addition of thermoplastic chitosan significantly affected the elongation at break, as
309 compared to TPS (Figure 6). This elongation at break indicates that the flexibility and
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310 stretching of the films increased with the addition of chitosan. The addition of TPC at
311 concentrations between 5 and 10wt.% to TPS matrix did not significantly differ.
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312 However, this represents an increase in elongation at break of 56 and 35%, respectively,
313 when compared to pure TPS. A similar behavior was reported in the literature(Pelissari
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314 et al., 2009), in which the physical-chemical properties and the antimicrobial activity of
315 starch-chitosan films with oregano essential oil were studied.

316 Several studies(Alves, V.D.; Mali, S.; Beléia, A.; Grossmann, 2007; Mali, S.; Karam,
317 L.B.; Ramos, L.P.; Grossmann, 2004; Sobral, P.J.A.; Menegalli, F.C.; Hubinger, M.D.;
318 Roques, 2001) reported that the addition of chitosan decreases the elastic modulus of
319 the TPS/TPC blends. These authors reported that the addition of the plasticizer help the
320 TPS matrix to become less dense, thus facilitating the movement of the polymer chains
321 and improving the flexibility of the films. These results are consistent with the literature
322 because this increase in elastic modulus of the blends with respect to TPS is due to the
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323 presence of hydrogen bonds between the plasticizer and starch molecules as well as due
324 to the presence of Vh-type crystals as also pointed out by Mikus et al. (Mikus, P.Y.;
325 Alix, S.; Soulestin, J.; Lacrampe, M. F.; Krawczak, P.; Coqueret, X.; Dole, 2014)

326
327 4. CONCLUSIONS
328
329 Results show that it was possible to successfully produce cornstarch-chitosan blends by

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330 extrusion with a high dispersion and distribution degree of the TPC phase in TPS as

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331 observed by scanning electron microscopy analyzes. SEM micrographs showed blends
332 with homogeneous surface, and the criofractured samples displayed no agglomeration

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333 of chitosan within a completely destructurized starch matrix. These blends also had
334 good thermal stability in which the addition of chitosan produced more thermally stable

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335 films. Moreover, addition of 5 and 10wt.% chitosan acted as a plasticizer to TPS matrix,
336 increasing the elongation at break (elongation at break increased by 56 to 35%,
337
338
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respectively) and decreasing tensile strength and elastic modulus. Therefore, the
obtained blends have potential for applications in packaging, especially where a high
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339 output of processed polymer is required as compared to batch processing such as
340 casting.
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341
342 Acknowledgments
343
344 The authors are grateful to Empresa Brasileira de Pesquisa Agropecuária (EMBRAPA)
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345 for the facilities and equipment.

346
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347 5. REFERENCES
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348 Alves, V.D.; Mali, S.; Beléia, A.; Grossmann, M. V. E. (2007). Effect of glycerol and
349 amylose enrichment on cassava starch film properties. Journal of Food
350 Engineering, 78, 941–946. http://doi.org/10.1016/j.jfoodeng.2005.12.007

351 Arvanitoyannis, I.; Psomiadou, E.; Nakayama, A.; Aiba, S.; Yamamoto, N. (1997).
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