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Composites: Part A 37 (2006) 8091 www.elsevier.

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Biodegradable polymers/bamboo ber biocomposite with bio-based coupling agent


Seung-Hwan Lee*, Siqun Wang
Tennessee Forest Product Center, 2506 Jacob Drive, University of Tennessee, Knoxville, TN 37996-4563, USA Received 9 December 2004; revised 28 March 2005; accepted 20 April 2005

Abstract Effects of lysine-based diisocyanate (LDI) as a coupling agent on the properties of biocomposite from poly (lactic acid) (PLA), poly (butylene succinate) (PBS) and bamboo ber (BF) were investigated. Tensile properties, water resistance, and interfacial adhesion of both PLA/BF and PBS/BF composites were improved by the addition of LDI, whereas thermal ow became somewhat difcult due to crosslinking between polymer matrix and BF. Crystallization temperature and enthalpy in both composites were increased and decreased with increasing LDI content, respectively. The heat of fusion in both composites was decreased by addition of LDI, whereas there was no signicant change in melting temperature. Thermal degradation temperature of both composites was lower than those of pure polymer matrix, but the composites with LDI showed higher degradation temperature than those without LDI. Enzymatic biodegradability of PLA/BF and PBS/BF composites was investigated by Proteinase K and Lipase PS, respectively. Both composites could be quickly decomposed by enzyme and the addition of LDI delayed the degradation. q 2005 Elsevier Ltd. All rights reserved.
Keywords: Biocomposite; Poly (lactic acid); Poly (butylene succinate); Bamboo ber; Lysine diisocyanate; Coupling agent

1. Introduction In recent years, the development of biocomposites from biodegradable polymers and natural bers have attracted great interests in the composite science, because they could allow complete degradation in soil or by composting process and do not emit any toxic or noxious components [116]. Among the biodegradable polymers, in particular, poly (lactic acid) (PLA) and poly (butylene succinate) (PBS) are of increasing commercial interest. PLA can be synthesized by the condensation polymerization of the lactic acid or ring opening polymerization of the cyclic lactide dimer. Advanced industrial technologies of polymerization have been developed to obtain high molecular weight PLA that leads to a potential for structural materials with enough lifetime to maintain mechanical properties without rapid hydrolysis even under humid environment, as well as good
* Corresponding author. Tel.: C1 865 974 4965; fax: C1 865 946 1109. E-mail address: lshyhk@hotmail.com (S.-H. Lee).

1359-835X/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.compositesa.2005.04.015

compostability. PLA is transparent and crystalline polymer with relatively high melting point and has brittle properties, i.e. high strength and low elongation at break [17]. PBS is a white crystalline thermoplastic with melting point of about 90120 8C (similar to LDPE), glass transition temperature of about K45 to K10 8C (between PE and PP), tensile strength between PE and PP, and stiffness between LDPE and HDPE. PBS has excellent processing capabilities and can be processed on polyolen processing machines at temperatures of 160200 8C, into various products, such as infected, extruded and blown ones [1]. Furthermore, its raw materials, butanediol and succinic acid, may be soon available from bio-based renewable resources [1823]. Natural bers can be a renewable and cheaper substitute for synthetic bers, such as glass and carbon and have numerous advantages, such as low cost, low density, high toughness, acceptable specic strength properties, ease of separation and biodegradability. So, there is much research on natural ber-reinforced composites [2433]. However, the main drawback of natural ber may be their hydrophilic nature, which decreases the compatibility with hydrophobic polymeric matrix. In these composite elds, therefore, most of the research has focused on improving interfacial

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properties between the polymer matrices and natural llers in order to enhance the physical and mechanical properties of the end products. The purpose of this study was to develop the biocomposites with designable interfacial properties from biodegradable polymers, PLA and PBS, and bamboo ber by using lysine-diisocyanate as a bio-based coupling agent. So far, several conventional isocyanates, such as methylene diisocyanate (MDI), toluene diisocyanate (TDI), 4-4 0 -methylenedicyclohexyl diisocyanate (hydrogenated MDI), and hexamethylene diisocyanate have been used as a coupling agent [3438]. For example, Wang et al. reported the effect of MDI on the properties of PLA/starch blend. The addition of MDI resulted in an enhancement of mechanical properties and water resistance [3940]. However, these isocyanates have found limited use as a biocompatible material because their ultimate hydrolysis products, i.e. their corresponding diamines, such as 4,4 0 methylenedianiline and 2,4-diaminotoluene have been found to be a cancer suspect agent or produce hepatitis in man. So, the use of nontoxic materials should be expected as a coupling agent, in order to synthesize fully biodegradable biocomposites without emitting toxic or noxious components. Lysine-diisocyanate (LDI) is based on lysine with two amino groups and one carboxyl group, which is one of natural amino acids. LDI can react with hydroxyl or carboxyl groups in PLA or PBS, producing urethane bonds that can be easily and completely hydrolyzed into raw materials [4145]. For example, the polyurethane that synthesized from LDI, glycerol, and ascorbic acid can be completely degraded in aqueous solution and yield the nontoxic breakdown products of lysine, glycerol, and ascorbic acid [46]. In fact, our interest in LDI as a bio-based coupling agent stems from these facts, because ecotoxicity is currently a key point in biocomposites.

(Kyoto, Japan). All other chemicals were purchased from commercial sources. 2.2. Compounding and compression molding The polymers and BF were rst mixed as dry solids. The mixture was placed into a batch mixer (Labo Prostomill, Toyo Seiki, Japan) rotating at a speed of 30 rpm. After the addition, the rotation speed was increased to 70 rpm and kneading was conducted for 5 min. Then LDI was added to the mixture and kneading was further carried out for 10 min. The amount of LDI added was expressed by NCO content as following equation NCO content ZWeight of NCO group=Weight of composite ! 100 % 1

The kneading temperatures were 180 8C and 140 8C in the cases of PLA and PBS, respectively. The kneaded samples were compression-molded into sheets under a pressure of 150 kgf cmK2 at 180 8C (PLA/BF composite) and 140 8C (PBS/BF composite). 2.3. Tensile properties and water absorption test Dog-bone-shaped samples (5!0.4!50 mm) were cut from compression-molded sheets and tensile measurements were made with a Shimadzu Autograph AG-1 (5kN) (Kyoto, Japan) machine at a cross head speed of 5 mm minK1. The samples with dimensions 50!50!0.5 mm were used to examine water absorption behavior after vacuum drying at 45 8C for 24 h. The samples were immersed in deionized water (25 8C) and periodically taken out of the water. Then, the excess water on the surface was removed by blotting with tissue paper and specimens were weighed. The amount of water absorbed (Mt) was calculated as follows Mt % Z Wt K Wo =Wo ! 100 (2)

2. Experimental 2.1. Materials PLA (LACEA H-100J) and PBS (Enpol G5300) were purchased from Mitsui Chemical, Inc. (Tokyo, Japan) and Ire Chemical Ltd (Wonju, Korea), respectively. Average length and diameter of bamboo ber (BF) used in this study were approximately 500 and 70 mm, respectively. L-lysine-diisocyanate (LDI) was kindly supplied by Kyowa Hakko Co., Ltd (Tokyo, Japan). The BF was oven-dried at 105 8C for 6 h, whereas PLA and PBS were vacuum-dried at 40 8C for 24 h prior to use. Proteinase K and Lipase PS were purchased from Nacalai Tesque, INC.

where Wt and Wo, are the weights of the specimen before and after immersion in water respectively. 2.4. Differential scanning calorimeter (DSC) and thermal gravity analysis (TGA) DSC measurement was performed on a Perkin-Elmer Diamond DSC. The samples (about 7 mg) were heated to 200 and 150 8C at 20 8C minK1 in PLA and PBS/BF composites, respectively, and kept for 5 min to remove the thermal history. Then, the samples were cooled to 40 8C at the rate of 2 and 10 8C minK1 in PLA and PBS/BF composites, respectively, and heated again to 200 and 150 8C at the rate of 20 8C minK1 in PLA and PBS/BF composites, respectively. The endothermic and exothermic

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Table 1 Activation energy for ow of the PLA and PBS/BF (70/30) composites NCO content (%) 0 0.11 0.33 0.65 1.30 Activation energy for ow (kJ/mol) PLA/BF composite 193.9 195.1 195.3 197.0 211.9 PBS/BF composite 63.4 76.5 91.5 114.1

2.6. Enzymatic hydrolysis The vacuum-dried samples (10!10!0.4 mm3) were weighed and dipped in a test tube of 5 ml of the Proteinase K solution (50 mM TrisHCL buffer, pH 8.6) and Lipase PS solution (0.1 M phosphate buffer, pH 6.0) in the case of PLA and PBS/BF composites, respectively. The test tube was sealed and kept at 38 8C for a predetermined time and replaced every 48 h (Proteinase K) and 1 week (Lipase PS), so that enzyme activity remained at a desired level throughout the experiment duration. The sample was then removed from the solution, washed thoroughly with distilled water and ethanol, and then dried in vacuum at 38 8C. The time-course of the weight loss was evaluated and the remaining samples were observed by SEM. 2.7. Scanning electron microscopy The morphology of the fractured samples after tensile testing was examined using a JEOL JSM-5900LV scanning microscope.

peaks were termed as crystallization temperature (Tc) and melting temperature (Tm), respectively. The crystallization enthalpy (DHc) and the heat of fusion (DHm) were also determined from the area of crystallization and melting peaks, respectively. These values in the composite were divided by the weight proportion of polymer and the obtained values were parenthesized in Table 1. Thermal degradation temperature was measured by a Perkin-Elmer Pyris 1 TGA. Samples of about 7 mg were heated from 50 to 600 8C at a rate of 10 8C minK1 under nitrogen ow (20 mL/min). 2.5. Thermal ow properties

3. Results and discussion Apparent melt viscosity of composites was measured at various temperatures with a ow tester (Shimadzu CFT500D). The shear stress applied was 2.452!104 Pa and the orice diameter and length of die were 1 and 10 mm, respectively. 3.1. Interfacial morphology Many of properties in composite materials would be affected by their morphology. Fig. 1 shows SEM

Fig. 1. SEM micrographs of interface between matrix and BF in PLA/BF (70/30) composite without (A), or with LDI (NCO content, 0.65%) (B), and PBS/BF (70/30) composite without (C), or with LDI (NCO content, 0.65%) (D).

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micrographs of the tensile fractured surface of PLA and PBS/BF composite with or without LDI. In the PLA/BF composite without LDI, two phases can be clearly seen and many BFs were pulled out from the matrix in the fracture process, with large voids thereby being created. Also, gaps between PBS and BF in the PBS/BF composite without LDI were visible. These ndings suggest that the interaction between matrix and ller was very weak, resulting in less interfacial adhesion. These features are typical of incompatible polymer composites. On the other hand, the micrographs of both composites after compounding with LDI of 0.65% showed that BF appeared to be coated with matrix polymer. This improved interfacial adhesion may be due to the compatible effect of graft copolymer with LDI intermediates, which could be produced through a chemical reaction between the hydroxyl groups of polymer and BF under kneading conditions of higher temperatures and pressure [39,40]. In our previous paper, it was conrmed that isocyanate groups react with terminal hydroxyl or carboxyl groups of PLA and the hydroxyl groups of corn starch, producing a graft copolymer of PLA and CS with urethane linkage that is conrmed by NMR measurement [15]. The morphology results support the improvement of tensile properties and water resistance by adding LDI, which will be discussed below. 3.2. Tensile properties Fig. 2 shows the effect of isocyanate group (NCO) content on the tensile properties of the PLA and PBS/BF (70/30 by wt.) composites. In the case of PLA/BF composite, as NCO content increased to 0.33%, tensile strength and Youngs modulus increased rapidly from 29 to 42 MPa and from 2666 to 2964 MPa, respectively, and then leveled-off. However, there was no signicant effect of LDI addition on the elongation at break, showing the value of less than 5%. Similarly, the tensile strength of PBS/BF composites increased steeply from 21 to 34 MPa with NCO contents of 0.33%, respectively, and then leveled-off. However, Youngs modulus was not much changed by the addition of LDI. Elongation at break increased slightly by addition of LDI, but still showed the value less than 10%. The NCO group content at which the value of tensile strength plateaued could be considered the critical interfacial concentration, which is the minimum value of interfacial saturation for a coupling agent in the dispersed phase, because the average size of the dispersed BF will not be changed with the addition of the coupling agent [15,4749]. Figs. 3 and 4 show the effect of BF content on the tensile properties of PLA and PBS/BF composites with or without LDI. The NCO content was set at 0.65%. In both composites without LDI, the tensile strength gradually decreased with the increase of BF content. This may be due to poor interfacial adhesion between the polymer matrix and BF ller. This is a general phenomenon in incompatible

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Fig. 2. Effect of NCO content on the tensile properties of PLA or PBS/BF (70/30) composites. C, Tensile strength; &, Youngs modulus; :, Elongation at break.

composites with different characteristics, such as hydrophobicity of the polymer matrix and hydrophilicity of the ller [5053]. However, the tensile strength of the PLA/ BF composite with LDI kept the value of about 45 MPa by increasing BF content up to 30% and then decreased. These values were higher than those of the composites without LDI. Furthermore, the tensile strength of PBS/BF composite with LDI increased by increasing BF content and this improvement was more pronounced at higher BF contents. This may be attributed to enhanced interfacial adhesion between the polymer matrix and BF ller by adding LDI. All composites showed the increase of Youngs modulus as BF content increased. This is common in composites reinforced with a hard ller. On the other hand, the composites with LDI showed higher values than the composite without, indicating that the composite was further hardened by the addition of LDI. Elongation at break decreased with increasing BF content in all composites. This may be due to the increase in the discontinuity of the polymer matrix with the increase in the dispersed phase (BF). However, the composites with LDI showed slightly higher elongation at break than the composite without LDI.

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Fig. 4. Effect of BF content and the addition of LDI on the tensile properties of PBS/BF composites. White, with LDI (NCO content, 0.65%); black, without LDI.

BF content (%)
Fig. 3. Effect of BF content and the addition of LDI on the tensile properties of PLA/BF composites. White, with LDI (NCO content 0.65%); black, without LDI.

3.3. Water absorption BF is hydrophilic because it contains an abundance of hydroxyl groups, but PLA and PBS are hydrophobic polymers. The effect of the addition of LDI and BF content on the water absorption behavior of the composites was investigated and indicated in Fig. 5. The water absorption for all composites increased greatly during the rst 20 h and then leveled-off. When compared to the composite with and without LDI, absorption amount and time to reach the plateau were smaller and longer, respectively, for all composites with LDI than

without, indicating that the addition of LDI makes the absorption of water difcult. This can be explained by the improvement in interfacial adhesion between the polymer matrix and BF ller due to the coupling effect of LDI and the reaction of LDI with the hydroxyl groups of polymers and BF resulting in less hydrophilicity. It was also found that the absorption amount increased in all composites as BF content increased. Because PLA and PBS can absorb only the water of about 1%, BF content will be the major factor affecting the water absorption of the composites. The increase of BF content caused

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Fig. 5. Effect of BF content and the addition of LDI on water absorption of PLA or PBS/BF composites. CB, 90/10; &,, 80/20; :6, 70/30; %, 60/40; *C, 50/50; white and *, (solid line) with LDI (NCO content, 0.65%); black and C, (dash line) without LDI.

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Fig. 6. Relationship of logarithm apparent melt viscosity (Ln h) and reciprocal temperature (1/T) in PLA/BF composite. NCO content: C, 0%; &, 0.11%; :, 0.33%; %, 0.65%; *, 1.30%.

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the absorption rate to quicken, because of its strong hydrophilicity. 3.4. Thermal ow properties Figs. 6 and 7 show the relationship of logarithm apparent melt viscosity (Ln h) and reciprocal temperature (1/T) in PLA and PBS/BF composites, respectively. Under the given shear stress (4.9!104 Pa), the apparent viscosity of all composites decreased with increasing temperature. The relationship between Ln h and 1/T is linear, indicating that the dependence of h on temperature obeys the Arrhenius equation: h Z A expE=RT (3)

Fig. 7. Relationship of logarithm apparent melt viscosity (Ln h) and reciprocal temperature (1/T) in PBS/BF composite. NCO content: C, 0%; &, 0.11%; :, 0.33%; %, 0.65%.

Table 2 Effect of LDI on crystallization and melting behavior of the PLA and PBS/BF (70/30) composites Sample NCO content (%) 0 0.11 0.33 0.65 1.30 0 0.11 0.33 0.65 1.30 Tc (8C) DHc (J/g) Tm (8C) DHm (J/g)

PLA PLA/BF composite

where A is a constant that is related to material properties; E, the activation energy for ow; R, the universal gas constant; and T, the absolute temperature. According to the Arrhenius equation, the activation energy for ow was calculated and the values are summarized in Table 1. The composites with LDI in both composites require higher activation energy for ow compared to the composite without LDI, showing larger values than the composite without LDI. It was also found

PBS PBS/BF composite

112.8 115.2 118.4 118.7 119.4 120.2 68.1 74.6 78.0 80.2 82.2 82.6

33.2 23.5 (33.6) 21.5 (30.7) 20.2 (28.9) 16.4 (23.4) 14.5 (20.7) 60.1 40.8 (58.2) 37.8 (54.0) 38.1 (54.4) 37.3 (53.3) 31.2 (44.6)

165.3 162.3 162.7 161.8 162.2 161.6 112.1 112.0 112.1 112.3 112.9 112.1

41.1 27.4 (39.1) 23.5 (33.6) 23.6 (33.7) 23.1 (33.0) 22.8 (32.6) 65.3 42.3 (60.4) 35.8 (51.1) 29.4 (42.0) 24.5 (35.0) 21.7 (31.0)

( ) Values divided by the weight proportion of polymers.

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Fig. 8. TGA thermograms of PLA, PBS, BF and PLA or PBS/BF composites with different NCO content.

that the activation energy increased as LDI content increased. This suggests that the addition of LDI leads to an increase in hindrance of molecular motions of polymer matrix due to crosslinks with BF, making thermal ow difcult. 3.5. Crystallization and melting behavior Thermal properties were investigated by DSC and the obtained results are summarized in Table 2. Pure PLA and PBS had a crystallization temperature (Tc) of 112.8 8C and 68.1 8C, respectively. In both PLA and PBS/BF composites, the Tc shifted to high temperature by adding either BF or LDI, and further increased as LDI content increases. These higher Tc values of the composites than the pure polymers indicate that the crystallization rate than the composites

becomes more rapid in nonisothermal processes. The increase in Tc could be considered to be due to the nucleation effect of the BF and LDI. In particular, the urethane linkage between polymer matrix and BF produced by the addition of LDI might further enhance nucleation of polymer matrix. In both composites, however, crystallization enthalpy (DHc) was decreased by increasing LDI content. The molecular motion of the polymer matrix could be restricted by the addition of LDI, resulting in a decrease of crystallization enthalpy. Melting temperatures (Tm) of pure PLA and PBS were 165.3 and 112.1 8C, respectively. These Tms were not signicantly affected by the addition of either BF or LDI. However, the heat of fusion (DHc) in both composites was decreased by addition of BF and LDI. This may be also attributed to the strong interfacial interaction between

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Fig. 9. DTG thermograms of PLA, PBS, BF and PLA or PBS/BF composites with different NCO content.

polymer matrix and BF, conning polymer chain orientation.


Weight remaining/%

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3.6. Thermal degradation Figs. 8 and 9 show the TGA curves and derivative thermograms (DTG) for PLA, PBS, BF, and the PLA and PBS/BF composite with different LDI content. Thermal degradation of PLA and PBS showed completely in a single stage and occurred at 376 and 405 8C, respectively. In the case of BF, main three-stage loss of mass was observed. The rst stage with a small hump in the temperature range from 250 to 300 8C is characteristic of low molecular weight components, such as hemicellulose and the second one, appearing at higher temperatures in the range of 300 and 400 8C, is corresponded to the thermal degradation of cellulose. And the third one near 420 8C is due to lignin decomposition.

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Fig. 10. Weight remaining for pure PLA and PLA/BF composites with and without LDI plotted as a function of enzymatic degradation time. C, PLA; &, PLA/BF composite without LDI; :, with LDI (NCO content, 0.33%); %, (0.65%).

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Fig. 11. Weight remaining for pure PBS and PBS/BF composites with and without LDI plotted as a function of enzymatic degradation time. C, PBS; &, PBS/BF composite without LDI; :, with LDI (NCO content, 0.33%); %, (0.65%).

In the case of PLA/BF composites, the incorporation of BF in PLA matrix has signicantly affected the thermal degradation temperature. The composites showed a lower degradation temperature (more than 50 8C) than that of PLA and a two-stage loss of mass was mainly observed for all composites. That is, the degradation in the range of 280 340 8C is due to PLA degradation and the small hump near 350 8C is due to BF degradation. These lower degradation temperatures may be attributed to the decrease of molecular weight of PLA by high kneading temperatures (180 8C). In the composites, however, thermal degradation temperature was increased by increasing LDI content. It can be generally said that the increase of molecular weight by cross-linking reaction between matrix and BF, or molecular chain-extension of the matrix itself, could increase the thermal degradation temperature [5456]. PBS/BF composites showed an intermediate thermal stability between those of PBS and BF and the addition of

Fig. 12. SEM micrographs of PLA or PBS/BF composites with LDI (NCO content, 0.65%) after different enzymatic degradation time. (A) control of PLA/BF composite, (B) after 7 days, (C) 9 days, (D) control of PBS/BF composite, (E) after 2 days, (F) 4 days.

Weight remaining/%

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Fig. 13. SEM micrographs of PLA/BF (after 7 days) and PBS/BF (after 7 days) composites with or without LDI after enzymatic degradation. (A) PLA/BF composite without LDI, (B) with LDI (NCO content, 0.33%), (C) (0.65%), (D) PBS/BF composite without LDI, (E) with (NCO content, 0.33%), (F) (0.65%).

LDI also improved the thermal stability of the composite, showing higher thermal degradation temperature in the composite with LDI. 3.7. Enzymatic degradation The effect of the addition of LDI on biodegradability of the composites was investigated by enzymatic degradation using Proteinase K and Lipase PS, which are well known to degrade easily PLA and PBS, respectively [5759]. Figs. 10 and 11 show the weight remaining for PLA and/or PBS/ BF composites with and without LDI along with pure PLA and PBS as a function of elapsing time, respectively. It was observed that the weight remaining of all samples decreased almost linearly with elapsing time. The degradation of pure PLA and PBS was slower than that of all composites, indicating that BF improved the degradation of both polymers. As compared between the composites with and without LDI, all composites with LDI were more difcult to be degraded than those without. By increasing LDI content, degradation rate became much slower. The improved interfacial adhesion between

polymer matrix and BF by coupling effect of LDI will make the area exposed to enzyme hydrolysis smaller, resulting in decreasing degradation rate. Fig. 12 shows the SEM micrographs of PLA or PBS/BF (70/30) composites with LDI degraded for different degradation time. It can be clearly seen that the matrix of both composites became reduced as enzymatic degradation proceeded. Fig. 13 shows the effect of LDI content on the degradation at the same period. In the case of the composites without LDI (A and D), the majority of matrix was degraded even though degradation time is short. However, the loss of matrix occurred slower in the composites with LDI than without LDI and lots of parts remained in the composites with more LDI content. As mentioned above, stronger interfacial adhesion will reduce the area exposed to enzyme hydrolysis and this would result in a longer degradation time.

4. Conclusions A low concentration of LDI as bio-based coupling agent was added to environmental-friendly biocomposite during

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kneading process. Particularly, tensile properties and water resistance were appreciably improved by this mechanochemical reactive processing, which will be of merit for industrial applications. These improvements were due to the enhanced interfacial adhesion between the polymer matrix and BF. Furthermore, the results of enzymatic degradation showed that biodegradability could be adjusted by controlling the degree of interfacial adhesion using LDI. In areas, where biocompatibility and environmentally responsible design and construction are required, these biocomposites have potential for dramatic growth with a green concept. Primary applications for biocomposites include toys for children, furniture, ooring, hardware for electronic products, especially one-way disposable products, and so on.

Acknowledgements This work was supported by the USDA Wood Utilization Research Grant and the Tennessee Agricultural Experiment Station, Project #83.

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