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Green composite ﬁlms prepared from cellulose, starch and lignin in room-temperature ionic liquid
Rong-Lan Wu a,b, Xiu-Li Wang a, Fang Li a, Hui-Zhang Li a, Yu-Zhong Wang a,*
Center for Degradable and Flame-Retardant Polymeric Materials, College of Chemistry, State Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu 610064, China b Key Lab of Oil and Gas Fine Chemicals, Ministry of Education, Xinjiang University, Urumqi, Xinjiang, 830046, China
a r t i c l e
i n f o
a b s t r a c t
A series of novel biobased composite ﬁlms derived from cellulose, starch and lignin were prepared from an ionic liquid (IL), 1-allyl-3-methylimidazolium chloride (AmimCl) by coagulating in a nonsolvent condition. The ionic liquid can be recycled with a high yield and purity after the green ﬁlm was prepared. The uniform design method was applied to investigate mechanical properties of the biobased composite ﬁlms. The effect of each component and their associated interactive effects were investigated. The experimental results showed that contents of cellulose, lignin and starch had a signiﬁcant inﬂuence on the mechanical properties of composite ﬁlms. The composite ﬁlms showed relatively excellent mechanical properties in dry and wet states owing to the mutual property supplement of different components. The composite ﬁlms were characterized via FT-IR, X-ray diffraction (XRD) and scanning electron microscope (SEM). Their thermal stability and gas permeability were also investigated, and the results showed that the composite ﬁlms had good thermal stability and high gas barrier capacity and give a CO2:O2 permeability ratio close to 1. Ó 2008 Elsevier Ltd. All rights reserved.
Article history: Received 2 September 2008 Received in revised form 15 November 2008 Accepted 18 November 2008 Available online 24 January 2009 Keywords: Cellulose Starch Lignin Ionic liquid Homogenous blends
1. Introduction Synthetic polymers have provided undeniable beneﬁts for the development of the society. However, non-biodegradable petroleum-based plastics have become a threat to the environment and the diminishing petrochemical resources. Therefore, an increasing attention has been paid on the development of environmentally benign natural biobased materials, which is a solution not only to burgeoning environmental threats but also to the uncertainty of petroleum supply (Cakmakli et al., 2004). Cellulose, starch and lignin are three kinds of abundant biopolymers in the nature, The potential advantages of such biobased materials, apart from their environmental gains, are low cost, not depending on petroleum sources, available from renewable resources, and enabling to replace some synthetic polymers, etc. However, their inherent disadvantages such as the relatively low tensile property and high water absorbency of starch, the poor solubility and processability of cellulose, have limited their wider applications. Furthermore, all of them cannot melt, and cannot be processed like thermoplastic polymers. This makes the process much different from the synthetic polymer. Traditionally, the three
* Corresponding author. Address: Center for Degradable and Flame-Retardant Polymeric Materials, College of Chemistry, Sichuan University, Chengdu 610064, China. Fax: +86 28 85410259. E-mail address: firstname.lastname@example.org (Y.-Z. Wang). 0960-8524/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2008.11.044
biobased polymers have been incorporated into other polymeric materials as lower cost and biodegradable ﬁllers, respectively. Many systems based on these natural polymers have been investigated recently, such as PCL/starch (Ikeo et al., 2006), PHB/lignin (Kai et al., 2004), PCL/cellulose (Sanchez-Garcia et al., 2008), etc. However, these synthetic biodegradable polymers are expensive and/or rely on the petroleum resources. In addition, because of the poor compatibility between hydrophobic polymers and natural polymers, reactive compatibilizers or coupling agents are often used to improve interfacial interactions of these composites. Recently, many attentions had been paid on preparing the totally biodegradable blends with the natural polymers and their derivatives, such as cellulose diacetate/starch (Lee et al., 2006), starch acetate/native starch (Guan and Hanna, 2004), cationic starch/cellulose (Bratskaya et al., 2006) and chitosan/cellulose acetate (Liu and Bai, 2005), etc. These blends present good compatibility and retain biodegradability. However, compared with the preparation of environmental friendly materials based on pure natural polymers, using their derivatives will increase the cost and complicacy. To preserve biodegradability, low cost and to improve the mechanical resistance of ﬁnal products, associations between cellulose and plasticized starch have been tested. It is well known that cellulose ﬁbers can reinforce plasticized starch (Kumar and Singh, 2008; Averous et al., 2001) but only little attention has been paid
respectively) and Y3. the recovery of AmimCl was also discussed. which were named. and the cellulose solution was coagulated in the distilled water to obtain a regenerated biopolymer gel. This equipment was operated according to Standard Method D3985-81 (ASTM. another study reported the dissolution of starch in BmimCl (Stevenson et al. Gas permeability Oxygen permeability and carbon dioxide permeability were measured using differential-pressure method with a VAC-VBS gas permeability tester (Labthink Inc. USA) under nitrogen atmosphere. Ltd. However..4.1..1. it has been found that lignin can be dissolved directly in AmimCl with heating. 2. lignin can be used as a plasticizer of starch. 2. Ltd. Wu et al..3... Liang et al. A series of cellulose/starch/lignin blend ﬁlms (CSL ﬁlms) with different weight ratios were . 2. Shenzhen SANS Test Machine Co. 2. The complete dissolution procedure of the materials was conﬁrmed by an optical microscopy. Thermal analysis Thermogravimetric analysis was carried out using a SDT Q600 (TA Co. which allocates experimental points uniformly scattered on the domain. 1-Methylimidazole was purchased from Kaile Chemical Reagent Co.2. 30–85 wt%). Y4 (the elonga- 2.3. Fortunately. amylose and amylopectin contents are 25% and 75%. 2007). Corn starch was obtained from Langfang Starch Company (technical grade.3. Y2 (the tensile strength of dry and wet ﬁlms. a reinforcing agent of cellulose and a compatibilizer of cellulose and starch. The uniform design method was applied to investigate the effect of each component and their interactive effects on the mechanical properties of the ﬁlms.. Oxygen and carbon dioxide transmission rates were obtained in cm3/m2 day atm. heated to 80 °C with continuous stirring. the obtained transparent membranes were washed with running water and dried in the air. 2. Materials The IL. respectively. The wet ﬁlms were measured immediately after immersed in water for 30 min.4. 2007). because of the poor solubility and processability of them.3. 2007) For example. Lignin was purchased from Wuhan East China Chemical Co. Therefore. X-ray diffraction studies The X-ray diffraction patterns with Cu Ka radiation at 40 kV and 30 mA were recorded in the range of 2h = 5–50° with an X-ray diffractometer (X0 pert. chemical engineering and biotechnology (Ban et al. Subsequently. The relationship between the structure and properties of the composite ﬁlms were investigated using FT-IR. starch (S. obtained from Leshan Beiya Yasong Paper Company (Chengdu. Testing was performed at 25 °C under dry environment (0% RH). The rb and eb values are the averages of ﬁve measurements. According to the supplier. Multiplying these values by ﬁlm thickness provided the diffusion coefﬁcients of oxygen and carbon dioxide. 1994. Langfang. to prepare natural biopolymer composites composed of cellulose. and can form a cementing material for cellulose ﬁbrils. Preparation of composite ﬁlms All the materials were dried at 80 °C under vacuum for 24 h before used. after which air bubble was taken off in a vacuum oven. The composite ﬁlms were ground into powder and dried under vacuum for 24 h before the infrared (IR) measurement. Allyl chloride (analytical grade P 99. 2005). XRD. China). they became transparent solution in which biopolymer concentration is about 6 wt%. Uniform design method Uniform design is an experimental design. Ltd. Furthermore..5%) was purchased from Sinopharm Chemical Reagent Co. The composite ﬁlms were cut into powder for the measurement of X-ray diffraction. IL can be recovered by evaporating water from the coagulated liquid. 2004). Mechanical properties measurement The tensile strength (rb) and elongation at break (eb) of the ﬁlms in both dry and wet states were measured on a universal testing machine (CMT6503. Methods 2. Philips).. China). Microscopic analysis The dry ﬁlms were frozen in liquid nitrogen.5. and X3. 2001). it is difﬁcult to dissolve the three biopolymers in a common solvent or process them in melt state. It is one powerful tool in studying the interaction of mixtures has been widely used in chemistry. China). AmimCl as solvent. TG analyses and gas permeability. 2. (Shanghai. The experimental program used three independent variables. 1996). Natural cellulose (bamboo pulp) with a degree of polymerization of 650. To obtain novel natural biopolymer composite materials. Hebei. at a tensile rate of 10 mm minÀ1. which can improve the mechanical properties of the composite material of lignin/cellulose (Rohella et al.. 10–65 wt%). cellulose (C. starch and lignin are given in Tables 1 and 2. 2006.5–10 wt%). The following functions were considered as dependent variables: Y1. 2005. China). lignin (L. proposed by Fang and Wang in 1980s. (Linhai. starch and lignin on the mechanical properties in this study. obtained by this method. in this work. based on quasi-Monte Carlo method or number–theoretic method (NTM) (Fang. The free surface (side in direct contact with the coagulant) and the fracture surface of the ﬁlms were sputtered with gold and observed using a scanning Electron Microscope Philips XL-3 (FEI Company. The whole procedure was described as follows: all materials were dispersed into AmimCl. FT-IR spectroscopy analysis The IR spectra were recorded with a Fourier transform IR (FT-IR) spectrometer (6700. room-temperature ionic liquids having the imidazolium structure have been found to be nonderivatizing solvents for cellulose and starch (Seoud et al.. 2.3.6. Ltd. starch and lignin. Characterization 2. / Bioresource Technology 100 (2009) 2569–2574 to the plasticized starch toughening cellulose (Dufresne and Vignon. (Wuhan.5 mm. Furthermore.) according to ISO6239. 1998). respectively. The weight ratios of cellulose.2570 R. it has been reported that lignin can increase the plasticity of starch matrix due to its lower molecular weight fraction (Morais et al. USA). The mixed solution was cast onto a glass plate with thickness of about 0.3.2.. 2005).. The uniform design was performed to study the effects of cellulose. X2. China).3. Three samples were measured for each test. 1989). 0. 1-allyl-3-methylimidazolium chloride (AmimCl) was synthesized according to the literature (Zhang et al. Pouteau et al. it has been demonstrated that 1-allyl-3-methylimidazolium chloride (AmimCl) could dissolved cellulose in high concentrations (Zhang et al.. we attempted to prepare cellulose/starch/lignin composite ﬁlms (CSL ﬁlms) using the ionic liquid. snapped immediately and vacuum-dried. Samples (about 10 mg) were heated from room-temperature to 500 °C at a heating rate of 10 °C/min. X1. Oregon. Recently.). NICOLET).. 2.-L.3. and used in the experiment without further puriﬁcation.
This result indicates that the synergistic interactions among cellulose.6 ± 2.8 ± 2.1 ± 1.3 ± 1. starch and lignin demonstrate that optimal strength can be achieved by higher cellulose and lignin contents with lower level of starch content. It can be observed that cellulose can greatly enhance the ﬂexibility of dry and wet ﬁlms especially at high starch contents.2 ± 0. In this multiple biopolymer system. interactions among cellulose.2.0 ± 2.0 Wet 91.6 83.2 8.1 16. Regarding eb values of the CSL ﬁlms in dry and wet states. the components of cellulose. Content of cellulose (wt%) 1 2 3 4 5 6 7 8 85.0 ± 3.5 ± 1.5 17.1 72. These results suggest that a proper proportion among cellulose.6 ± 1.7 ± 4. As the starch and lignin contents increase. which mainly depend on components in CSL ﬁlms. each biopolymer not only contributes to the properties of composite ﬁlms alone but also engages in biopolymer– biopolymer interactions which affect the mechanical properties of overall systems.9 43. Wu et al. Results and discussion 3.8 2571 Elongation (eb) of the composite ﬁlms (%) Dry 92.8 64.5 ± 2. starch and lignin levels can enhance the strength of ﬁlms.8 3.0 23.1 41.8 ± 2.5 5.9 34.1 ± 2. Fig.3 Wet 16. The results indicate that the synergistic interactions among cellulose. Table 3 gives the summary of stepwise regression equations which described the contributions of each component and their inﬂuence on mechanical properties of the ﬁlms.1 Wet 91.8 29.0 60.2 ± 3.0 ± 2. Fig.6 4. 2007).2 62.0 ± 0.98 ± 1. of expt.1 28. In summary.0 19.6 7. Thus.2 ± 2.R.0 24.0 ± 2.2 Wet 16.6 15. 3.2 ± 2.3 34. Table 2 shows the rb and eb values of binary and ternary composite ﬁlms consisted of cellulose.3 ± 2.6 69.0. indicating that starch has a negative effect on strength at high cellulose content.9 16. More speciﬁcally.3 14.9 ± 0. Effect of component on the mechanical properties Tensile strength (rb) and elongation at break (eb) are important mechanical properties of the CSL ﬁlms.1 Elongation (eb) of the composite ﬁlms (%) Dry 92.8 ± 0.7 ± 4.2 ± 1. starch and lignin contents on the strength of dry and wet ﬁlms.7 4.9 ± 2.2 31. respectively.5 40. there is an almost similar dependence on the starch and lignin. respectively) were also sued. starch and lignin have good afﬁnity to each other and obtain Table 2 Mechanical properties of binary and ternary composite ﬁlms. The solubilization efﬁciency of them in IL was found in an order of starch > lignin P cellulose. Therefore.7 ± 1.1 44.3 51.5 94.6 59.5 65.2 ± 2. the inﬂuence of lignin on strength is signiﬁcant at a high cellulose content compared to low cellulose content. starch and lignin show a signiﬁcant effect on rb and eb of CSL ﬁlms in wet and dry states.9 ± 2.2 91.9 8. It is found that in dry state rb values of CSL ﬁlms decrease monotonically with the increase of the starch content.1 25.5 ± 1. and the higher the content of cellulose. Similar to the addition of cellulose..0 15.2 ± 1.8 3. 3.6 75.0 2.8 ± 1.5 94.8 15. It was also observed that the viscosity of the solution mainly depends on the content of cellulose.61 ± 1.4 7.4 ± 2.1 ± 3.9 62.3 65.3 ± 1.9 ± 3. Cellulose/starch/lignin composite ﬁlms Tensile strength (rb) of the composite ﬁlms (Mpa) Dry 85/10/5 85/15/0 85/0/15 95/1/4 95/5/0 95/0/5 35.0 27.0 61. However.2 ± 1. starch and lignin contents on the elongation at break of dry and wet composite ﬁlms. eb values of ﬁlms increase at ﬁrst. the strength of dry ﬁlms will not increase with the increase of cellulose content. Dissolution of biopolymer into ionic liquid The dissolving process of cellulose. lignin also plays an important role in reinforcing dry and wet composite ﬁlms.5 ± 3.9 ± 1. then decrease.1 tion at break of dry and wet ﬁlms.6 ± 2.0 40.5 Content of lignin (wt%) 5.1 Tensile strength (rb) of the composite ﬁlms (MPa) Dry 35.3 60. It is probably due to the high crystallinity of cellulose and the aromatic character of lignin (Kilpelainen et al.9 ± 2. The generalized regression models of the wet and dry composite ﬁlms were obtained.9 ± 0.0 ± 3. Furthermore. It was very interesting to observe that the mixed biopolymers without being pretreated or activated can be dissolved in AmimCl within 30 min.3 62.1 ± 1.4 33.0 78.4 Content of starch (wt%) 10. rb values of wet and dry CSL ﬁlms increase.4 4. The values of rb and eb of the CSL ﬁlms are better than those of cellulose/starch and cellulose/lignin blended ﬁlms.2 44.0 15.8 ± 0.9 ± 1. / Bioresource Technology 100 (2009) 2569–2574 Table 1 Uniform design data for the composite ﬁlms.7 0.2 6.7 ± 2. the CSL ﬁlms with different components were prepared and the uniform design method was used to conduct the statistical analyses for mechanical properties of the composite ﬁlms.3 81.7 . cellulose. However.9 34.2 ± 2.-L.9 9.9 ± 1.3 ± 2. It can be seen that with the increase of cellulose concentration.6 84.5 ± 1.9 6. 1 and 2). starch and lignin. when starch content goes up to a high level (>35 wt%).1. the higher the viscosity of the solution. No. 2 shows the effects of cellulose. 1 shows the effects of cellulose. The experimental data were analysed using the Data Processing Software of Uniform Design 3. starch and lignin show different dependence on rb and eb of CSL ﬁlms in different states.1 ± 1.1 55. The design of the experiments and corresponding results obtained are listed in Table 1. starch and lignin in AmimCl at 80 °C was real time monitored using a hot stage optical microscopy.1 69.3 1.9 72.0 28. starch and lignin reinforce the composites.2 13.5 ± 0.1 ± 1. These results suggest that the optimal ﬂexibility can be achieved at higher cellulose content with middle level of lignin and starch contents. and in wet state rb values at ﬁrst increase slightly then decrease.2 34.9 ± 3. the corresponding surface diagrams can be derived from regression model by holding one variable ﬁxed (shown in Figs.
The original materials are bamboo pulp. corn starch and lignin.0°.2°.992 0. the intra. During the dissolution in AmimCl. However. which shows ﬁve diffraction peaks of A-type starch at 15. respectively.8°. A broad peak appears in the pattern of regenerated starch (RS). Wu et al. which is also broadened and shifted to 1150 and 1151 cmÀ1 in the composites ﬁlms.. starch and lignin.3. respectively.0466X1X2 À 0. 2008).3° and 22.56X 2 3 R2 0.2°.0185X2X3 2 Y2 = 3. The regenerated samples were obtained through dissolving these original materials in AmimCl and then coagulated with distilled water. Kadla and Kubo.2572 R. 19. rb–S–L (c). IL can break down the inter. Effects of content of cellulose (C). 2003). 17. .1° and 21. indicating that regenerated starch has lost its crystallization. (2005). This phenomenon shows that.. rb–C–L (d). which are moved to a lower wave numbers(around 1114 and 1012 cmÀ1) in the composite ﬁlms. 3.197X2X3 À 3.1° (Liu et al. The absorption peaks at 3431. rb–C–S (b). 1998). The characteristic peaks of corn starch and the –C–O bond stretching of –C–O–H group appear at about 1156 and 1081 cmÀ1. The bamboo pulp has the typical diffraction peaks of cellulose I at 2h = 14.-L. Eq. Peaks at 1120 and 1040 cmÀ1 for lignin are characteristic bands of the primary and secondary –OH groups (Nada et al. which was also testiﬁed from the results of Zhang et al.000726X 2 À 0. 1070 and 1012 cmÀ1.and inter-molecular hydrogen bonds of each component were destroyed and the three components were dispersed uniformly in the IL.997 0. Compared the spectrum of CSL ﬁlms to those of cellulose. starch and lignin. respectively. respectively) in composite ﬁlms and become broader. Corn starch is a semi-crystalline material.00265X 2 + 0. The peak at 1160 cmÀ1 belongs to the C–O stretching of cellulose (Kataoka and Kondo. no.. Therefore.995 mutual property supplement.and intra-molecular hydrogen bonds rapidly and destroy Fig. which can achieve the excellent tensile strength without sacriﬁcing the extensibility of ﬁlms. 1998.6° (Zhang et al. a corresponding effect is shown in the asymmetric C–O–C stretching region (1020–1160 cmÀ1) of the composite ﬁlms with different contents of cellulose. 2008). which combined the three components compactly. we suggest that starch and lignin can also be dispersed molecularly in AmimCl.35X 2 2 3 2 Y4 = 18.313X 2 2 3 Y3 = À18. and these peaks shift to lower wave numbers (around 1150.178X2 + 0. 3440 and 3427 cmÀ1 attribute to the –OH groups on cellulose.1X3 + 0. starch and lignin. starch (S) and lignin (L) on tensile strength (rb) of the dry and wet ﬁlms: rb–C–L (a). starch and lignin could be dissolved in AmimCl easily compared with cellulose. The XRD patterns of the original and regenerated materials reveal that the intensity of diffraction peaks of these regenerated materials is reduced signiﬁcantly. Reddy and Yang.2 + 33. This transformation from cellulose I to cellulose II occurred. / Bioresource Technology 100 (2009) 2569–2574 Table 3 Relationship between ﬁlm mechanical property and content of biopolymers.00828X 1 + 0.462X1X3 + 0. the –C–O bond stretching of –C–O–C group in the anhydroglucose ring appears at about 1020 cmÀ1 (Wang et al. In this work. respectively. 1 2 3 4 Multiple regression model Y1 = 31. These results suggest that strong hydrogen bonds have been formed among the cellulose. 2008). it exhibits the typical diffraction patterns of cellulose II at 2h = 20. 1.7 + 0. 18.00817X1X2 + 0.9° and 23. Furthermore. in the dissolution process. rb–C–S (e) and rb–L–S (f). 2008). 16. after dissolved and regenerated.976 0. Furthermore.. The crystallinity of regenerated cellulose (RC) decreases greatly in comparison with the original cellulose. Structure and morphology of composite ﬁlms FT-IR measurements were carried out to identify the possible interactions among cellulose. starch and lignin.0357X2X3 À 2.08 À 0.0219X 2 À 0.0269X1X3 À 0. 2005. which are broadened and shifted to around 3421 cmÀ1 in composite ﬁlms. starch and lignin in composite ﬁlms.3 À 0.2°. and it had been reported that cellulose could be dispersed molecularly in AmimCl (Wan et al. the rapid coagulation process was favorable to the formation of hydrogen bonds between the hydroxyl groups of three biopolymers.. it can be found that the spectrum of CSL ﬁlms is similar to that of cellulose because the molecular structure of CSL ﬁlm is mainly based on cellulose.0526X1X3 + 0.
20 ± 0. a dense and homogeneous texture. eb–L–C (d).64 ± 0. 2006). which hinders the crystallization of cellulose and starch.65 12. The maximum decomposition temperatures of the composite ﬁlms (Tmax = 331–335 °C) are slightly lower than that of pure cellulose.53 11.R. 3.88 Carbon dioxide permeability (Â10À3cm3/ m day atm) 13.4.67 1. so as to reduce respiration and prevent changes (Yun et al. it can be seen that the free and fracture surfaces of all ﬁlms display uniformity from the interior to the surface.5. Effects of content of cellulose (C).87 21. The X-ray diffraction pattern of the regenerated lignin (RL) is very similar with that of original lignin due to its amorphous and highly cross-linked morphology (Rohella et al..65 1. Moreover.2 Permeability evaluated at 25 °C and 0% relative humidity.and inter-molecular hydrogen bonds of cellulose were partially broken by IL during the solution process. but higher than that of starch (Tmax = 309 °C). It is different from the structure of the cellulose regenerated from NaOH/H2O (Zhang et al.98 13.49 ± 0. / Bioresource Technology 100 (2009) 2569–2574 2573 Fig. and the molecular chains are aggregated in rapid coagulation process. .08 ± 0. which provides one promising applications as fresh food packaging.95 ± 1. eb–C–S (b). such as reducing oxygen and elevating carbon dioxide concentrations.08 ± 0. CSL ﬁlms can create and maintain a suitable atmosphere. with the addition of starch and lignin to cellulose.84 ± 0. A small weight loss of about 2–5% below 100 °C is assigned to the release of moisture from the samples.05 1. which is probably due to its complex structure. Wu et al. 2002). showing relatively high thermal stability because of the enhancement of inter-molecular hydrogen bonds among biopolymers in the blend ﬁlms. 3.. The maximum decomposition temperature of the RC (Tmax = 326 °C) is lower than that of pure cellulose (Tmax = 345 °C). Gas permeability of composite ﬁlms Table 4 Gas permeability of RC and composite ﬁlms. These results further prove the excellent compatibility and a higher homogeneity in the ternary blend system.05–1.95 21.79 Permeability ratio (PCO2:PO2) 1. The three biopolymers can be dispersed molecularly in AmimCl. 2.16 ± 0..01 13. Furthermore.13 15.37 ± 1. By observing the surface morphologies of the regenerated cellulose and composite ﬁlms. all of the composite ﬁlms become quite amorphous after dissolved and blended in IL. eb–L–S (c).67.77 13. which is coincident with the result of the X-ray diffraction. 1996). the original crystalline forms of cellulose and starch. This result suggested that the strong intra. that is. starch and lignin.-L. no porous structure can be observed. Thermal properties of composite ﬁlms Samples for thermogravimetric analysis were the same as those of FT-IR spectroscopy tests. no obvious phase separation can be seen and there is not any phase interfaces among these three kinds of biopolymers.a Cellulose/starch/ lignin composite ﬁlms 50/40/10 73/25/2 80/15/5 90/1/9 RC a Oxygen permeability (Â10À3cm3/ m day atm) 12.30 ± 0. eb–C–S (e) and eb–L–S (f). the coagulation process is so transitory that it is unfavorable to the crystallization of cellulose and starch. lignin and RC. starch (S) and lignin (L) on elongation at break (eb) of the dry and wet ﬁlms: eb–C–L (a). CSL ﬁlms have higher gas permeability values than RC ﬁlm and give a wide range of CO2:O2 permeation ratios in the range of 1.19 1. Different from the regenerated materials. All of the samples show one-stage degradation within the range of 240–400 °C except lignin. Oxygen and carbon dioxide permeability values of RC ﬁlm and CSL composite ﬁlms have been presented in Table 4. 2001. Thus. The lignin sample exhibits a multi-step degradation process and the major weight loss started at 241 °C. probably due to the strong dissolving effect of AmimCl and the formation of inter-molecular hydrogen bond among cellulose. The residual weights of the composite ﬁlms beyond 500 °C increase slightly with increasing cellulose and lignin content in the composite ﬁlms.
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