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JF 4024855
JF 4024855
Article
Crosslinked potato starch-based blend
films using ascorbic acid as a plasticizer
Hun-Soo Byun, and Soon-Do Yoon
J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/jf4024855 • Publication Date (Web): 02 Aug 2013
Downloaded from http://pubs.acs.org on August 11, 2013
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2 acid as a plasticizer
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16 e-mail: yunsd03@chonnam.ac.kr
17 ABSTRACT
18 The main object of this study is to prepare the crosslinked potato starch
19 (PS)/PVA blend films added ascorbic acid (AsA) as a plasticizer with/without heat
21 swelling, solubility, water vapor absorption, thermal analysis, optical properties, and
22 biodegradability. Specific surface area, pore volume, and topography of the films
23 with/without heat curing are also investigated in the nitrogen adsorption and desorption
24 isotherms and atomic force microscopy (AFM) analysis. The results indicate that the
25 cured films possess higher mechanical, thermal, and optical properties compared to that
26 of non-cured films. The mechanical and water barrier properties of AsA-added film are
27 also found to be superior to other films with polyol plasticizers (glycerol and xylitol).
28 The biodegradability test revealed that the prepared films are degraded by about 35-80%
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32 KEYWORDS: Potato starch/PVA blend films, Ascorbic acid, Heat curing, Mechanical
33 properties, Biodegradability
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35 INTRODUCTION
36 The same durable properties which make plastics ideal for many applications
39 these materials are not readily biodegradable, and because of their resistance to
40 microbial degradation, they accumulate in the environment. Research into the synthesis
41 of materials from natural sources such as starch, protein, and cellulose has been
43 much research is devoted to starch, because it is very cheap and abundant. Starch has
44 been used as a replacement for synthetic polymeric plastics in the food, textile, and
49 applications. Starch/PVA blend polymers are one of the most popular biodegradable
50 plastics and are widely used in packaging and agricultural field.9-12 Generally, when
52 high rigidity and low workability. The conventional plasticizer used for starch/PVA
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53 blend polymers is glycerol, water,13,14 and ethylene glycol15 that increases the flexibility
54 and workability, but several other chemicals like sorbitol,16,17 urea,18 malic acid, tartaric
55 acid, citric acid,19,20 and glycerol-urea complex plasticizers21 have also been
56 successfully employed.
57 The type of plasticizer plays a key role in determining the physical properties of
59 elongation at break, and water resistance of starch/PVA blend films added polyols i.e.,
60 glycerol and sorbitol and organic acid i.e., malic acid, tartaric acid, and citric acid have
62 that the strength and flexibility of the films added organic acid are superior to those of
63 the films added polyols because they contain carboxyl groups as a functional group. In
65 groups as functional groups has been used as a new synthesized plasticizer for the
66 starch-based films.22,23 The results showed that BHF forms more stable and stronger
67 hydrogen bonds between the components of films than glycerol. Physical properties of
68 the starch-based films with BHF have been improved, thus demonstrating that the type
70 also very important to search for a cheap and nontoxic plasticizer, which gives desirable
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71 properties to starch-based blend films. In this study, starch/PVA blend films were
73 occurring organic compound with antioxidant properties which widely exists in many
74 biological liquids, medicines, vegetables, and fruits. It is one of the most important
75 soluble vitamins which play a significant role in the biological functioning, such as the
77 of common cold, mental illness, and infertility.24 It is also widely used in foods and
79 groups, 1 ether group, and 1 ketone group as functional groups which are well
80 combined with starch and PVA molecules. It is relative cheap and abundant compound
81 in nature. As above mentioned, various raw and synthetic materials are used as
83 plasticizer, and applied various fields such as packaging, agricultural, and edible films.
84 The object of this work is to prepare the biodegradable films using potato starch,
85 PVA, and AsA as a plasticizer and a casting method. We also evaluated the effect of AsA
86 content and heat curing time and temperature on optical properties and physical
87 properties of the prepared films such as tensile strength, elongation at break, water
88 resistance, and water vapor absorption, thermal properties, and biodegradability in soil.
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89 EXPERIMENT
90 Materials
91 Potato starch (PS) was purchased from Samyang Genex Co., Korea. Polyvinyl
92 alcohol (PVA), ascorbic acid (AsA), glycerol (GL), and xylitol (XL) were purchased
93 from Aldrich Chemical Company, Inc. (Milwaukee, WI). PVA was 99% hydrolyzed
94 with an average molecular weight of 89,000-98,000. Distilled water (DW) was used in
95 all experiments.
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98 Crosslinked PS/PVA blend films were obtained by the casting method. At first,
99 PVA solution was prepared by dissolving PVA in hot water (90 ℃). PS and plasticizers
100 (GL, XL, and AsA) were mixed together with water using a Kitchenaid mixer (Anymix,
101 Hyun-woo Star, Seoul, Korea) for 15 minute. Formulations contained 10, 20, 30, 40 and
102 50 wt.% GL, XL, and AsA (weight basis). PVA solution and mixed PS/ plasticizers were
103 kept at 95 ℃ for 10 minutes. Then, the mixture was blended to form homogeneously
104 gel-like solution with a mechanical stirrer (600 rpm) at room temperature for 60 minutes.
105 Bubbles, the by-product of preparation, were removed by using an aspirator. The mixing
106 composition is shown in Table 1. The gel-like solution thus prepared was poured on a
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107 pre-warmed (60 ℃) teflon mould (200 × 200 × 1 mm). Water was evaporated from the
108 moulds in a ventilated oven at 50 ℃ for 24 hours. Dried films were put in open
109 polyethylene bags and stored at 25 ℃ and at 53% RH for one week. The prepared films
110 were then cured in a vacuum oven at 95±2, 120±2, 140±2, or 160±2 ℃ for 30, 60, 90,
111 120, 180, 240, and 300 min under the atmospheric pressure. After heat curing, films
112 were conditioned again at 53% RH and 25 ℃ for one week before the measurements
113 were performed. The surfaces of the prepared films with/without the heat curing were
114 investigated with scanning electron microscopy (SEM, S-4700, Hitachi, Japan),
116
118 Tensile strength (TS) and elongation at break (%E) were evaluated for each film
119 using an Instron 6012 testing machine (USA). Five dumbbell shaped specimens with a
120 width of 15 mm (ASTM D-421) were cut from each film. Each piece was measured for
121 thickness in three places along the test length using a mechanical scanner (Digital
122 thickness gauge ‘Mitutoyo’ Tokyo, Japan) at 15 random positions around the film. The
123 specimen’s average thickness was about 0.12±0.003 mm. Both gauge length and grip
124 distance were 50.0 mm. Crosshead speed was 20 mm/min and load cell was 250 kgf.
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125 The tests were carried out at 25 ℃ and 53% RH in a constant temperature and humid
126 room.
127
129 The FTIR spectra of the non cured films and cured films with/without AsA
130 were recorded on an FT-IR spectrometer (JASCO FT/IR-430, Japan). The samples were
131 thoroughly dried in a vacuum oven at 50 ℃ and 16 scans were collected for each
132 sample.
133
137 environment (flow rate, 20 mL/min) at a heating rate of 10 °C/min. The sample size was
139
141 Each film specimen was cut into a rectangle piece and placed directly in a UV–
142 Vis. spectrophotometer (Optizen 2120UV, Mecasys Co., Ltd, Korea) test cell. All
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143 measurements were performed using air as the reference. A spectrum of each film was
144 obtained at wavelengths between 200 and 800 nm. The transparency at 600 nm (T600)
146
148
150 The opacity of the films was obtained using the following eq. (2) according to
152
154
156 The degree of swelling (DS) and solubility (S) of the films were measured
157 applying the following method. The dried films were immersed in distilled water at
158 room temperature (25 ℃). After the equilibrium (24 h), moisture on the surface of the
159 film was removed, and the weight of the films was measured. DS in films was
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161 DS =
(W e− W0 )
(3)
W0
162
163 where We is the weight of the film at the adsorbing equilibrium, and W0 is the first dry
165 The swollen films were dried again for 24 h at 60 ℃, and its solubility (S) was
167
168 S=
(W 0 − Wd )
(4)
Wd
169
170 where W0 is the first dry weight of the film and Wd is the dry weight of the swelled film.
171
173 The pieces of prepared films were cut into small pieces (5 cm × 5 cm) and the
174 weight of pieces was measured immediately. They were then dried in an oven at 60 ℃
175 overnight and weighed. The water content (k) of starch/PVA composite films was
177
178 k=
(W f − W0 )
(5)
W0
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179 where W0 is the mass of the dried sample and Wf is the mass of the sample before
180 drying.
181 The nitrogen adsorption and desorption isotherms at 77 K was measured in the
182 relative pressure range of 10-5 to 0.99, using the volumetric adsorption analyzer
183 (Micromeritics, ASAP 2020) to characterize the geometrical structures of the films
184 with/without heat curing. Prior to the measurement, about 0.2 g of the sample was
185 outgassed at 373 K under vacuum for 24 h to remove the moisture contents as well as
186 the impurities. The textural properties such as the specific surface area (Brunauer–
187 Emmett–Teller, BET), pore volume (total pore volume at P/P0 = 0.99 and Barrett-
188 Joyner-Halenda, BJH, for mesopore size distribution) were calculated from the nitrogen
189 adsorption isotherm data. Atomic force microscopy (AFM) was also employed to assess
190 the topography and roughness value of the surface of the films. AFM imaging was
191 performed with a Multimode IV (Veeco, USA) and the images were scanned in tapping
192 mode (Non-contact mode) using silicon cantilevers. All measurements were conducted
194
196 Soil burial degradation was carried out as described by Devi et. al.29 and our
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197 previous work30 with a slight modification. Garden pots with an approximate capacity
198 of 10 L were filled with soil taken from a culture field in Gangjin Gun (Korea). The
199 samples were cut into 3 cm × 3 cm pieces and buried in the soil at the depth of 10 cm.
200 The pots were placed in an uncovered gazebo. The soil was kept moist by sprinkling
201 water at a regular time interval to maintain 30-50% humidity. The excess water was
202 drained through the hole at the bottom of the pot. The degradation of the specimen was
203 determined at a regular time interval (15 days) by taking the specimen carefully from
204 the soil and washing it gently with distilled water to remove the soil. The specimen was
205 dried in an oven until a constant weight was obtained. Weight loss of the specimen with
206 time was used to indicate the degradation rate in the soil burial test.
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209 The measurement of mechanical properties such as tensile strength (TS) and
210 elongation at break (%E) on biodegradable films plays an important role in various
211 fields for application and modification. In addition, the treatment of curing has a
212 significant effect on mechanical properties. The methods of curing are gamma and
213 electron beam irradiation,31,32 UV irradiation,33-35 and heat curing.36,37 The mechanical
214 properties and water resistance for the films are improved by the treatments of these
215 methods.
216 Figure 1a shows the FT-IR spectra obtained for non cured films and cured films
217 with/without AsA at different curing times. The strong peaks observed at 990-998,
218 1015-1020 and 1080 cm-1 are characteristic of the anhydroglucose ring such as found in
219 starch. The broad band at 3265-3280 cm-1 was due to hydrogen-bonded hydroxyl groups
220 (O–H). This band is of great importance since it indicates the presence of hydrogen
221 bonding in the polymer. Higher frequencies shift were observed when the heat curing
222 time increased (about 3280 cm-1). This result is closely related with an increase in
223 hydrogen bonding between PS, PVA, and AsA hydroxyl groups, provoking an
224 improvement in the mechanical properties and a decrease of water solubility of the
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225 blended films.38 AsA is easily hydrolyzed by heat or light. To verify hydrolysis of
226 AsA, the AsA was boiled in the DW at 90 ℃, which was the same preparation condition
227 of the films. Figure 1b clearly shows the results of the FT-IR spectra before and after the
228 treatment of AsA. The results indicate that the hydrolysis of AsA did not occur to the
229 synthesis condition of the films. As shown in Figure 2b for the typical FT-IR spectrum
230 of AsA, the spectra of C=O, C-O-C, and O-H appeared at 1757, 1678, and 2920-3525
232 Figure 2 shows the effect of heat curing time and temperature on TS and %E of
233 non-plasticizer film and AsA-added film. As shown in Figure 2a, TS slightly increased
234 with increasing heat curing time whereas %E decreased until 120 min. However, when
235 the curing time exceeded 150 min, TS increased and %E decreased rapidly because the
236 films were discolored and oxidized. TS and %E of films with heat curing temperature
237 are shown in Figure 2b. TS slightly increased whereas %E drastically decreased with
238 increasing curing temperature. In case of being heat curing process at 120 ℃, the
239 phenomenon of discoloration of films occurred when heat curing lasted more than 150
240 min. When heat curing was performed for 120 min, the film discoloration occurred after
241 the temperature reached 140 ℃ or higher. Taking these results into consideration, the
242 crosslinked PS/PVA blend films were prepared by heat curing at 120 ℃ for 120 min
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243 using glycerol (GL), xylitol (XL), and AsA as plasticizers. In addition, the results of the
244 effects on heat curing revealed that TS of cured films was improved about 1.5 times
246 Figure 3a and b show the results of TS and %E for cured films with plasticizers
247 (GL, XL, and AsA) contents. Each plasticizer is added from 0 to 50 wt.% as mass
248 percent ratio to total CS and PVA weight basis. As the content of GL, XL, and AsA
250 plasticizers indicated that TS of film added XL having 5 hydroxyl groups was higher
251 than film added GL which has 3 hydroxyl groups. However, TS of the film added AsA
252 which has 4 hydroxyl groups was highest of all the films because AsA not only has 4
253 hydroxyl groups but also 1 ether and ketone groups. In other words, TS of AsA-added
254 film was improved because of the existence of the functional groups, i.e., hydroxyl,
255 ether, and ketone groups, which can combine with starch and PVA molecules. In
256 addition, the results of %E indicated that GL-added films have higher values than XL-
257 added films or AsA-added films. The %E values of XL-added films were higher than
258 those of AsA-added films when less than 30 wt.% of plasticizers were added. However,
259 when more than 30 wt.% plasticizers was added, the %E values of AsA-added films
260 were higher than XL-added films. A possible explanation of this phenomenon is that
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261 when AsA was added more than 30 wt%, the effect of inter-intramolecular reaction of 1
262 ether and ketone groups as functional groups of AsA takes place between the
264 Figure 4 presents the effect of heat curing on the SEM images of the surface of
265 films to which 40 wt.% plasticizers are added. The surface of non-cured film without
266 plasticizers appeared quite homogeneous and smooth (Figure 4a). However, as shown in
267 Figure 4c, e, and g, the non-cured films to which 40 wt.% plasticizers (GL, XL, and
268 AsA) were added appeared somewhat slightly rough and agglomerated due to the
269 combination of PS, PVA, and plasticizers for blended films formation. SEM images of
270 the surface of the cured films with/without added plasticizers showed no phenomenon
272
275 and cured films with/without plasticizers. The effects of the heat curing on the film
276 without plasticizer and the AsA-added film is shown in Figure 5a. The physical
277 properties such as tensile properties, water resistance, and thermal stability are generally
278 improved by the treatment of heat curing.32 As shown in Figure 5a, the TGA curve of
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279 the cured films with/without AsA shifted toward the high temperature region. It means
280 that the thermal properties of cured films are improved by heat curing which increased
281 the mutual reaction of inter-intramolecular combinations. In other words, heat curing
282 treatment of the film was slightly decreased the degree of thermal decomposition. This
283 may be due to the crosslinking of the films, which increases the resistance to thermal
284 decomposition. The thermal properties have a close relation with mechanical properties.
285 Comparison of the non-cured films and cured films showed that the TS value of the film
286 without plasticizer increased from 55.6 MPa to 69.2 MPa, and at the same time the
287 thermal stability was also improved. The TS value of the non-cured AsA-added film
288 increased from 15.6 MPa to 20.1 MPa when treated with heat curing. The degree of
289 thermal decomposition of the cured film without AsA was higher than that of the cured
290 AsA-added films because the strong interaction between PS and PVA was weakened by
291 addition of AsA as the plasticizer. Since PS and plasticizers (GL, XL, and AsA) are
293 PS/PVA blend film intensifies its thermal decomposition. Figure 5b and c show the TGA
294 curves for the cured films added with 20, 40, and 50 wt.% AsA and the cured films
295 added with 40 wt.% GL, XL, and AsA. As shown in Figure 5b, the degree of thermal
296 decomposition increased but TS decreased (see Figure 3a) because the mobility between
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297 the components of films is increased by the addition of AsA as the plasticizer.
298 Furthermore, the flexibility of AsA-added films is also increased. Figure 5c shows the
299 TGA curves of the cured films added with the same ratio of GL, XL, and AsA (40 wt.%).
300 The changes in the rate of thermal decomposition in the cured films indicate that the
302 addition, the reason for reversed phenomenon at the region more than 350 ℃ is that the
303 strong interactions between PS, PVA, and plasticizer are formed by the heat curing
305
307 Evaluation of the degree of swelling (DS) and solubility (S) of the prepared
308 films plays an important role in the characterizing the degree of incorporation and
309 crosslinking between the constituents of films as well as water resistance.39 Figure 6
310 shows the effect of heat curing time and temperature on the DS and S of the film
311 without plasticizer and that of the AsA-added film. As shown in Figure 6a, with
312 increasing heat curing time, DS values of the film without plasticizer gradually
313 decreased for 300 min until to the end of experiment but the S values drastically
314 decreased until 120 min and increased again when the film was cured longer than 150
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315 min. In the AsA-added film, DS and S values decreased rapidly until 120 min of curing
316 time, but when curing continued for 150 min or longer, DS values slowly decreased
317 whereas S values increased. These results indicate that the inter-intramolecular
318 interaction between PS, PVA, and plasticizer is improved up to 120 min of heat curing,
319 but when heat curing continued for longer than 150 min, the film properties was
320 markedly deteriorated with the film’s discoloration and oxidation. As for the effects of
321 heat curing temperature, DS values gradually decreased until the final heat curing stage
322 of 160 ℃ but S values decreased rapidly up to 120 ℃ and then increased up to 160 ℃
323 of heat curing (Figure 6b). These results suggest that these combinations between the
324 constituents of films were destroyed by high temperature. From the results, the changes
325 in DS and S indicate that the water resistance was improved by heat curing.
326 Table 2 lists DS and S values of cured films to which various plasticizers (GL,
327 XL, and AsA) were added. As the content of plasticizers increased, DS values decreased,
328 but S values increased. DS values increased in the order of GL-added film < XL-added
329 film < AsA-added film. S values increased in the order of AsA-added film < XL-added
330 film < GL-added film. The GL-added films had the lowest DS value and the highest S
331 value. It means that GL-added film has relatively weak bond strength. In contrast, the
332 AsA-added films showed the highest DS value and the lowest S value, which indicates
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333 that the degree of combination between PS, PVA and AsA is stronger than in the films
335
338 packing materials is that it should protect materials from the effects of light, i.e.,
339 ultraviolet radiation. Figure 7 shows the light transmission characterization of non cured
340 and cured films added various plasticizers. Cured films had lower transmittance (%)
341 compared with non cured films suggesting that cured films are improved the light
342 barrier properties by heat curing. In addition, films added AsA had the lowest
343 transmittance (%) when compared with the films added GL, XL, and AsA. It means that
344 AsA-added films have good barrier to ultraviolet light. The opacity and transparency of
345 non-cured and cured films with GL, XL, and AsA are shown in Table 4. The results
346 indicated that the opacity and transparency values had a tendency to increase due to the
348 heat curing. It could confirm that the opacity and transparency values of prepared films
349 in this study have lower compared with their values of synthetic films reported. The
350 results obtained seem to indicate that the AsA-added films are clear enough to be used
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351 as packaging or coating materials when compared with reported values by Shiku et.al.40
352
355 defects. Enhancement of water resistance is also an important issue. Therefore, this
356 investigated the water contents of the non-cured films and cured films to which GL, XL,
357 and AsA are added as plasticizer. The influence of humidity on the prepared films was
358 also evaluated because PS/PVA blend films are highly sensitive to humidity. Figure 8
359 shows the effect of water contents on non-cured films and cured films to which 40 wt.%
360 plasticizers were added. The measurement of water contents for the non-cured films and
361 the cured films with/without various plasticizers were carried out at the same 55% RH.
362 The water contents are highly dependent on the plasticizers regardless of their treatment
363 conditions. The equilibrium water content of non-cured films appeared in the order of
365 film without an plasticizer (0.0714) (Figure 8a). However, as shown in Figure 8b, the
366 water content of the cured films, which was greater than the non-cured films, recorded
367 0.1222 (GL-added film), 0.1147 (XL-added film), 0.0903 (AsA-added film), and 0.0990
368 (none plasticizer), respectively. The water content of the cured films was higher than
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369 that of non-cured films. The hydrophilic properties of plasticizers are closely connected
370 to the water resistance of starch-based blend films.20 From these results, the water
371 content of the GL-added film and the XL-added film was higher than that of the AsA-
372 added film, which shows that GL and XL are more hydrophilic than AsA. The results of
373 water vapor absorption in the prepared films indicated that the water resistance of the
374 AsA-added film was better than that of GL-added film and XL-added film.
375 It is important to note that the water content of the cured films is higher than
376 that of non-cured films. In order to confirm this phenomenon, we conducted BET
377 experiment and AFM analysis on the specific surface area, pore volume, and topography
378 of both the non-cured film and the cured films which 40 wt.% AsA was added. Figure 9
379 shows the results of the nitrogen adsorption and desorption isotherms and AFM image
380 on the films. The nitrogen adsorption and desorption isotherms of the prepared films
381 seemed to belong to type Ⅴ according to the IUPAC classification. The adsorption
382 behaviors of the prepared films were similar to each other. However, the adsorbed
383 amount of the cured film was larger than that of the non-cured film. The detailed
384 properties of the films such as the surface area, pore volume, and average pore size are
385 listed in Table 3. The results of AFM analysis also confirmed that the surface roughness
386 of the cured film is decreased by heat curing, and pores are formed which can absorb
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388
390 The biodegradability of the non-cured films and the cured films to which 40
391 wt.% GL, XL, and AsA was added as plasticizers was estimated by using a soil burial
392 method. As shown in Figure. 10a and b, the degree of biodegradation of the films was
393 investigated by weight loss of the films with time. In the all films, a rapid degradation
394 occurred in the initial 60 days, followed by a slow degradation until the end of the
395 experiment (165 days). Biodegradation of the cured films was slightly lower than that of
396 the non-cured films due to the influence of cross-linking by the treatment of heat curing.
398 degree of biodegradation of the AsA-added films was higher than that of the GL-added
399 films and XL-added films. The biodegradability of the GL-added films and XL-added
400 films is low because GL and XL as used for plasticizers play a role as antibacterial
401 agents.
402
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403 CONCLUSIONS
404 Biodegradable films were successfully prepared by using potato starch, PVA,
405 and ascorbic acid (AsA) as a plasticizer and by heat curing treatment. The tensile
406 strength (TS), elongation at break (%E), degree of swelling (DS), solubility (S), optical
407 properties, water vapor absorption, thermal analysis, and biodegradability for the
408 prepared films were investigated. The results of the evaluation of physical properties for
409 non-cured films and cured films indicated that TS, %E, thermal properties and water
410 resistance of cured films were improved up to 65-295% by the treatment of heat curing.
411 In addition, the results of the optical properties illustrated that cured films had lower
412 than that of non-cared films. Especially, the optical properties of AsA-added films was
413 superior to that of the other films. The water vapor absorption of cured films was
414 slightly higher than that of non-cured films. In order to verify this phenomenon, specific
415 surface area, pore volume, and topography of films with/without the heat curing were
416 investigated by using BET experiment and AFM analysis. The results indicated that the
417 nitrogen adsorption-desorption behavior of the prepared films was similar to each other.
418 However, the adsorbed amount of cured film was larger than that of non-cured film. The
419 results of AFM analysis verified that the surface roughness of cured film was decreased
420 by heat curing process, and that pores are formed which can absorb H2O molecules.
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421 Compared to the properties of the films with various plasticizers (GL, XL, and AsA),
422 the mechanical, thermal and water barrier properties of film added AsA having 4
423 hydroxyl, 1 ether, and ketone groups were superior to the other films added GL and XL
425 The soil burial biodegradation test showed that the prepared films were
426 degraded by about 35-80% after 165 days. The degree of biodegradation of cured films,
427 however, was lower than that of non-cured films. In addition, the biodegradability
428 showed different results with different plasticizers. The degree of biodegradation of
429 AsA-added films was higher than that of GL-added films and XL-added films.
430 According to the results of this study, it could be found that AsA was used as an
432
433
434
435 ACKNOWLEDGMENTS
436 This study was financially supported by Chonnam Nation University, 2012
437
438
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439 REFERENCES
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444 (2) Chaudhary, A. L.; Miler, M.; Torley, P. J.; Sopade, P. A.; Halley, P. J. Amylose
445 content and chemical modification effects on the extrusion of thermoplastic starch
447 (3) Zhang, J. F.; Sun, X. Mechanical properties of poly(lactic acid)/starch composites
449 (4) Funke, U.; Bergthaller, W.; Lindhauer, M. G. Processing and characterization of
450 biodegradable products based on starch. Polym Degrad Stabil 1998, 59, 293-296.
451 (5) Angellier, H.; Molina-Boisseau, S.; Dole, P.; Dufresne, A. Thermoplastic starch-
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456 (7) van Soest, J. J. G.; Benes, K.; De Wit, D. The influence of starch molecular mass on
457 the properties of extruded thermoplastic starch. Polym 1996, 37, 3543-3552.
458 (8) Ma, X.; Jian, R.; Chang, P. R.; Yu, J. Fabrication and characterization of citric acid-
461 (9) Liao, H. T.; Wu, C. S. Preparation and characterization of ternary blends composed
462 of polylactide, poly(e-caprolactone) and starch. Mat Sci Eng A, 2009, 515, 207-214.
463 (10) Guana, J.; Eskridgeb, K. M.; Hannaa, M. A. Acetylated starch-polylactic acid
464 loose-fill packaging materials. Ind Crop Prod 2005, 22, 109-123.
467 (12) Ren, J.; Fu, H.; Ren, T.; Yuan, W. Preparation, characterization and properties of
468 binary and ternary blends with thermoplastic starch, poly(lactic acid) and
470 (13) Lawton, J. W.; Fanta, G. F. Glycerol-plasticized films prepared from poly(vinyl
471 alcohol) mixtures: Effect of poly (ethylene-co-acrylic acid). Carbohyd Polym 1994,
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473 (14) Liu, Z. Q.; Feng, Y.; Yi, X. S. Thermoplastic starch/PVAI compounds: Preparation,
474 processing and properties. J Appl Polym Sci 1999, 74, 2667-2673.
475 (15) Lourdin, D.; Coignard, L.; Bizot, H.; Colonna, P. Influence of equilibrium relative
476 humidity and plasticizer concentration on the water content and glass transition of
478 (16) Park, H. R.; Chough, S. H.; Yun Y. H.; Yoon, S. D. Properties of starch/PVA blend
479 films containing citric acid as additive. J Polym Environ 2005, 13, 375-382.
480 (17) Westhoff, R. P.; Kwolek, W. F.; Otey, F. H. Starch-polyvinyl alcohol films effect
482 (18) Tudorachi, N.; Cascaval, C. N.; Rusu, M.; Pruteanu, M. Testing of polyvinyl
483 alcohol and starch mixtures as biodegradable polymeric materials. Polym Test 2000,
485 (19) Yoon, S. D.; Chough, S. H.; Park, H. R. Effects of additives with different
486 functional groups on the physical properties of starch/PVA blend film. J Appl Polym
488 (20) Zou, G. X.; Jin, P. Q.; Xin, L. Z. Extruded starch/PVA composites: Water
489 resistance, thermal properties, and morphology. J Elastom Plast 2008, 40, 303-316.
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490 (21) Zhou, X. Y.; Cu, Y.F.; Jia, D. M.; Xie, D. Effect of a complex plasticizer on the
491 structure and properties of the thermoplastic PVA/starch blends. Polym-Plast Technol
493 (22) Dai, H.; Chang, P. R.; Geng, F.; Yu, J.; Ma, X. Preparation and properties of
496 (23) Dai, H.; Chang, P. R.; Yu, J.; Ma, X. N,N-bis(2-hydroxyethyl)formamide as a new
498 (24) Thiagarajan, S.; Chen, S. M. Preparation and characterization of PtAu hybrid film
500 ascorbic acid and uric acid. Talanta 2007, 74, 212-222.
501 (25) Arrigoni, O.; De Tullio, M. C. Ascorbic acid: much more than just an antioxidant.
503 (26) Han, J. H.; Floros, J. D. Casting antimicrobial packaging films and measuring their
504 physical properties and antimicrobial activity. J Plast Film Sheet 1997, 13, 287-298.
505 (27) Gontard, N.; Guilbert, S. Biopackaging: Technology and properties of edible
507 packaging and preservation (pp. 159–181). Food packaging and preservation, New
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509 (28) Labuza, T. P.; Kaanane, A.; Chen, J. Y. Effect of temperature on the moisture
510 sorption isotherms and water activity shift of two dehydrated foods. J Food Sci 1985,
512 (29) Thakore, I. M.; Desai, S.; Sarawade, B. D.; Devi, S. Studies on biodegradability,
515 (30) Yun, Y. H.; Wee, Y. J.; Byun, H. S.; Yoon, S. D. Biodegradability of Chemically
516 Modified Starch (RS4)/PVA Blend Films: Part 2. J Polym Environ 2008, 16, 12-18.
517 (31) Zhai, M. L.; Yoshii, F.; Kume, T.; Hashim, K. Syntheses of PVA/starch grafted
519 (32) Zhai, M. L.; Yoshii, F.; Kume, T. Radiation modification of starch-based plastic
521 (33) Rhim, J. W.; Gennadios, A.; Handa, A.; Weller, C. L.; Hanna, M. A. Solubility,
522 tensile, and color properties of modified soy protein isolate films. J Agr Food Chem
524 (34) Kaczmarek, H.; Podgorski, A. The effect of UV-irradiation on poly (vinyl alcohol)
525 composites with montmorillonite. J Photoch Photobio A: Chem 2007, 191, 209–215.
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528 (36) Miller, K. S.; Chiang, M. T.; Krochta, J. M. Heat curing of whey protein films. J
530 (37) Kim, K. M.; Weller, C. L.; Hanna, M. A.; Gennadios, A. Heat curing of soy protein
531 films at selected temperatures and pressures. LWT-Food Sci Technol 2002, 35, 140–
532 145.
533 (38) Elizondo, N. J.; Sobral, P. J. A.; Menegalli, F. C. Development of films based on
534 blends of Amaranthus cruentus flour and poly(vinyl alcohol). Carbohyd Polym 2009,
536 (39) Chen, L.; Remondetto, G.; Rouabhia, M.; Subirade, M. Kinetics of the breakdown
537 of cross-linked soy protein films for drug delivery. Biomaterials 2008, 29, 3750–
538 3756.
539 (40) Shiku, Y.; Hamaguchi, P. Y.; Benjakul, S.; Visessanguan, W.; Munehiko, T. Effect
540 of surimi quality on properties of edible films based on Alaska Pollack. Food Chem
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543
544 Figure 1. (a) FT-IR spectra of non-cured and cured films with/without ascorbic acid
545 (AsA). (b) FT-IR spectra of AsA and heat curing treated AsA.
546
547 Figure 2. Tensile strength (TS) and elongation at break (%E) for non-plasticizer film
548 and AsA-added film with heat curing time and temperature. (a) TS and %E for
549 non- plasticizer film and AsA-added film with heat curing time. (b) TS and %E
550 for non- plasticizer film and AsA-added film with heat curing temperature.
551
552 Figure 3. Tensile strength (TS) and elongation at break (%E) for cured film glycerol
553 (GL), xylitol (XL), and ascorbic acid (AsA) content. (a) TS for cured film GL,
554 XL, and AsA contents. (b) %E for cured film GL, XL, and AsA contents.
555
556 Figure 4. Scanning electron microscope (SEM) image of the surface of PS/PVA blend
557 films added 40 wt.% GL, XL, and AsA with/without heat curing. (a) Non-cured
558 film without added plasticizer. (b) Cured film without added plasticizer. (c) Non-
559 cured film with added 40 wt.% GL. (d) Cured film with added 40 wt.% GL. (e)
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560 Non-cured film with added 40 wt.% XL. (f) Cured film with added 40 wt.% XL.
561 (g) Non-cured film with added 40 wt.% AsA. (h) Non-cured film with added 40
562 wt.% AsA. Non-cured films represent PSP, PSPG4, PSPX4, and PSPA4, and
563 cured films represent PSP-C, PSPG4-C, PSPX4-C, and PSPA4-C, respectively.
564
566 with/without plasticizers. (a) TGA curves of non-cured and cured films
567 with/without added AsA. (b) TGA curves of cured films with 20, 40, and 50
568 wt.% AsA. (c) TGA curves of cured films with added with 40 wt.% GL, XL, and
569 AsA.
570
571 Figure 6. Degree of swelling (DS) and solubility (S) for non- plasticizer film and AsA-
572 added film with heat curing time and temperature. (a) DS and S for non-
573 plasticizer film and AsA-added film with heat curing time. (b) DS and S for non-
574 plasticizer film and AsA-added film with heat curing temperature.
575
576 Figure 7. Transmittance (%) of non-cued and cured films added various plasticizers. (a)
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578 (b) Transmittance (%) of cured films with/without added 40 wt.% plasticizers.
579 Figure 8. Water contents of non-cured and cured PS/PVA blend films with/without
580 added 40 wt.% GL, XL, and AsA. (a) Water contents of non-cured films
581 with/without added 40 wt.% GL, XL, and AsA in terms of adsorption time (hr).
582 (b) Water contents of cured films with/without added 40 wt.% GL, XL, and AsA
584
585 Figure 9. Nitrogen adsorption and desorption isotherms and atomic force microscopy
586 (AFM) images of non-cured and cured films with added 40 wt.% AsA.
587
588 Fig. 10. Biodegradation of non-cured and cured films with/without added 40 wt.% GL,
589 XL, and AsA. (a) Biodegradation of non-cured films with/without added 40
590 wt.% GL, XL, and AsA. (b) Biodegradation of cured films with/without added
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592 Table 1. Composition of gel-like solutions used to prepare PS/PVA blend films.
PSP 5 5 - - - 100
PSPG1 5 5 10 - - 100
PSPG2 5 5 20 - - 100
PSPG3 5 5 30 - - 100
PSPG4 5 5 40 - - 100
PSPG5 5 5 50 - - 100
PSPX1 5 5 - 10 - 100
PSPX2 5 5 - 20 - 100
PSPX3 5 5 - 30 - 100
PSPX4 5 5 - 40 - 100
PSPX5 5 5 - 50 - 100
PSPA1 5 5 - - 10 100
PSPA2 5 5 - - 20 100
PSPA3 5 5 - - 30 100
PSPA4 5 5 - - 40 100
PSPA5 5 5 - - 50 100
593
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594 Table 2. Degree of swelling and solubility of cured PS/PVA blend films in terms of
596
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597 Table 3. Comparison specific surface area, pore volume, and pore diameter among heat
599
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600 Table 4. Opacity and transparency of non-cured and cured PS/PVA blend films with
602
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603 Figure 1
604
605
606
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607 Figure 2
608
609
610
611
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612 Figure 3
613
614
615
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616 Figure 4
617
618
619
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620 Figure 5
621
622
623
624
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625 Figure 6
626
627
628
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629 Figure 7
630
631
632
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633 Figure 8
634
635
636
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637 Figure 9
638
639
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640 Figure 10
641
642
643
644
645
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648
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