Biodegradable green composites reinforced by the fiber recycling from disposable chopsticks

Yeng-Fong Shih, Chien-Chung Huang, Po-Wei Chen

Department of Applied Chemistry, Chaoyang University of Technology, Wufong Township,
Taichung County 41349, Taiwan
ABSTRACT
The use of disposable chopsticks is very popular in chopsticks-using countries, such as Taiwan,
China and Japan, and is one of the major sources of waste in these countries. In this study, the fiber
recycling from disposable chopsticks was chemically modified by coupling agents. Furthermore, the
modified fiber was added to the biodegradable polymer (polylactic acid, PLA), to form novel
fiber-reinforced green composites. These composites prepared by melt-mixing method, were
examined by scanning electron microscopy, differential scanning calorimetry, thermogravimetric
analysis, and mechanical tests. The results indicated that the Tg of PLA was increased by the addition
of fiber, which may improve the heat resistance of PLA. The thermogravimetric analysis of the
composites showed that the degradation process of fiber-filled systems started earlier than that of
plain PLA, but possessed a higher char yield. Mechanical tests showed that the tensile strength of the
composites markedly increased with the fiber content, reaching 115 MPa in the case of being
reinforced with 40 phr fiber, which is about 3 times higher as compared to the pristine PLA.
Furthermore, this type of reinforced PLA would be more environmental friendly than the artificial
additive-reinforced one, and could effectively reduce and reuse the waste of disposable chopsticks.
Keywords: polylactic acid, disposable chopsticks, green composites
1

1. Introduction
Disposable chopsticks are common everyday implements used in restaurants and for eating
takeaway lunches bought at convenience stores and supermarkets, and are generally made from
bamboo. According to research by the Taiwan Environmental Protection Administration, the annual
average consumption of disposable chopsticks between 1999 and 2005 was around 6.2 billion pairs
(about 50,000 tons) in Taiwan. Although the government forbids the use of disposable chopsticks in
government organizations and school restaurants since 2006, the annual consumption of disposable
chopsticks was still around 4.8 billion pairs (about 38,000 tons) in 2007. This amount of disposable
chopsticks equals to about 3 million of cut down bamboo plants. For this reason, how to recycle and
reuse these disposable chopsticks becomes an urgent research topic in chopsticks-using countries or
areas [1-3]. Moreover, natural fibers have attracted a great deal of interests for reinforcing plastics
recently, because they are green or eco-friendly. Advantages of such fibers over man-made fibers
include low density, low cost, recyclability, and biodegradability [46]. Moreover, the mechanical
properties of natural fibers, especially flax, hemp, jute, and sisal, are very good and may compete
with glass fiber in specific strength and modulus [79]. These advantages make natural fibers a
potential replacement for glass fibers in composite materials, and various researchers investigated the
strengthening effects on the natural fillers reinforced polymer composites [10-17].
Recently, increasing awareness of the environmental damage caused by plastic materials over
the last few decades has led to research aimed at producing eco-friendly versions of biodegradable
polymers. The development of those polymers has been a subject of great interest in materials
science for both ecological and biomedical perspectives [18]. Poly(lactic acid) (PLA) is well known
for its degradability to natural products in a short period of time (0.52 years) in contrast to
conventional plastics like PS, PE, etc. which need 5001000 years [19, 20]. PLA has a renewable
source [21], with the lactic acid monomers used to produce it coming from the fermentation of corn,
potato, sugar beat, and sugar cane [22, 23]. Moreover, PLA is a thermoplastic, high-strength, high
2

modulus polymer that can be used in either the industrial packaging field or medical applications.
However, the high brittleness and the quite high price of PLA currently limit its applications and
considerable efforts have been made to improve these characteristics of the polymer [2431].
Incorporating the plant fibers into biodegradable polymers can not only enhance the mechanical
properties, but also reduce the cost of the materials, and form a totally natural green composite.
PLA/plant fiber green composites were widely investigated and one property of these composites
was increased fiber reinforcement [32-36].
Furthermore, the recycled cellulose fibers attract a great interest due to the continually reduced
amount of resources. Chen et al. incorporated sugar beet pulp (SBP, the residue from the sugar
extraction process) into PLA to form the composites. But the tensile strength of the PLA/SBP
composite was not enhanced by the addition of the SBP [37]. Bhardwaj et al. incorporated recycled
cellulose fiber (RCF) into Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) to form a renewable
resource-based green composite. It was found that the tensile and storage moduli of the PHBV-based
composites were improved by 220% and 190%, respectively, by reinforcement with 40 wt % RCF.
The heat deflection temperature (HDT) of the PHBV-based composites was increased from 105 to
131C [38]. Chopped glass fiber- and recycled newspaper cellulose fiber (RNCF)-reinforced PLA
composites were prepared by Huda et al., the results confirmed that the storage and loss moduli of
the PLA/RNCF composites increased with respect to the pure polymer. The heat defection
temperature of PLA/RNCF was found to be comparable to that of the glass fiber-reinforced PLA
composites [39]. Huda et al. also found that RNCF reinforced PLA biocomposites possess similar
mechanical properties to talc-filled composites. The results illustrate that RNCF possesses good
thermal properties, compares favorably with talc filler in mechanical properties, and could be a good
alternative reinforcement fiber for biopolymer composites [40]. In our previous researches, it was
also found that the mechanical and thermal properties of polybutylene succinate [41], poly(lactic acid)
[42] and epoxy [43] were all promoted by the addition of water bamboo husk. In this study, due to
3

the high strength of bamboo fiber [11, 44], and the reuse of the disposable chopsticks, the bamboo
fiber recycling from disposable chopsticks was incorporated into PLA, in order to enhance the
mechanical and thermal properties of the plastics. Furthermore, the production of such green
composites will reduce the amount of waste, and lead to a cost reduction of PLA products.

2. Experimental
2.1 Materials
The poly(lactic acid) (PLA, PLA2002D T M ) was supplied by Nature-WorksLLC. The
recycled disposable chopsticks (RDCs) were first forced between two rollers, of which one was fixed
and the other was rotating, in order to accelerate the separation of fiber and lignin. Subsequently,
these RDCs were subjected to various surface chemical modifications like washing, alkali and
coupling agent treatment. The procedures for surface chemical modifications were as follows: The
RDCs were washed with 2% detergent solution at 60C for 1 h, then washed with distilled water and
finally dried in a vacuum oven at 80C. The washed fibers were treated with 25% NaOH solution for
2 hr at 50C, washed in running tap water and then with distilled water until the pH value reached 7.0,
followed by oven drying to obtain alkali treated fibers. These fibers were then chopped and screened
to obtain an average fiber diameter of 20 m and 1 cm length, and were subsequently treated by
silane coupling agent. The coupling agent (Triethoxy-vinylsilane) was supplied by Dow Corning Co.
Surface treatment of dried fiber was carried out in the acetone solution of silane. Fiber (5g) and
silane (0.5g) were put in a flask with the proper volume of acetone. After agitation for half an hour,
the flask was sealed with a polytetrafluoroethylene film and then kept for 12 h at room temperature.
4

Then the samples were washed with acetone to remove compounds not covalently bonded to the
fiber, and then dried at 80C in an oven to constant weight.

2.2 Preparation of the composites

The PLA, surface chemically modified RDCs fiber (MRDCF) were dried in an air oven at
100C for 4 hours under reduced pressure, until the moisture content was below 1.0 wt %.
Immediately after drying, the PLA was melt blended with fiber in a counter-rotating internal mixer
(Brabender PL2000, Duisburg, Germany) with a rotation speed of 60 rpm for 15 min at 170C. The
amount of fiber was 20, 40, 60 phr which was based on the weight of PLA. The formulations of the
samples are shown in Table 1. Samples for the investigations were prepared by compression molding
(0.5 mm thick) at 185C and then solidification by quenching to ambient temperature. The annealed
samples were prepared from the quenched samples by annealing at 130C for 1.5 h in order to allow
the crystallization to complete.

2.3 Instruments
The infrared spectra were obtained by a FTIR spectrometer (PERKIN ELMER Paragon 500)
with a resolution of 2 cm-1 by scanning 50 times from 300 to 4000 cm-1 at room temperature. All film
samples were carried out with the conventional NaCl disk method. Phase transition behavior was
analyzed by differential scanning calorimeter (DSC; TA Instruments DSC Q20). Thermal behavior
5

was investigated using a TA Instruments TGA Q50 thermogravimetry analysis (TGA). All
experiments were carried out under a nitrogen atmosphere at a purge rate of 100 ml/min. Samples of
approximately 5 mg were heated to 500C at a heating rate of 10C/min. A mechanical testing
machine, Hung TA HT9102, was used to measure the tensile properties, according to ASTM D 638
standard. All results were taken as the average value of five samples. A JEOL scanning electron
microscope (SEM; model JSM-5200) was used to evaluate the morphologies of fractured surfaces of
pure PLA and the composites. The samples were sputter-coated with gold particles up to a thickness
of about 10 nm before the surface characterization. Transmission electron microscopy (TEM)
observation of the morphology was carried on JEOL JEM-1200CX.

3. Results and discussion

3.1. FTIR spectrum
As shown in Figure 1, a peak at 1598 cm-1 was found for the coupling agent. This is the
characteristic absorption peak of C=C resulting from the coupling agent. The characteristic
absorption peaks of silane were also found at 1168, 962, and 1106, 1082 cm-1. This could be
attributed to the presence of the asymmetric stretching of Si-O-Si- and/or to the -Si-O-C- bonds [45,
46]. It is important to note that the peaks found at 1162, 1104, 1058 cm-1 for the MRCDF indicate
the existence of polysiloxanes deposited on the fiber and the occurrence of a condensation reaction
between the silane coupling agent and the fiber.

3.2. DSC analysis

Figure 2 and Table 2 show the DSC results for samples recorded during heating scan at the
rate of 10C/min. The thermograms reveal the following: the glass transition (Tg), and the main
melting process characterized by two, more or less separated, endotherms (at Tm1 and Tm2). The
results show that Tgs (57.9, 59.5 and 56.3C) of MRDCF reinforced composites (PLA20, PLA40 and
PLA60) are slightly larger than that (54.2C) of pristine PLA. This result reveals that the fiber may
restrict the mobility of the polymer chain, and lead to the higher transition temperature. However, the
Tg of PLA60 is smaller than that of PLA40 indicating that the adhesion of fiber/matrix in PLA60
composite became poor. This is confirmed by the SEM analysis (Figure 8). Botev et al. found that
the incorporation of untreated short basalt fibers in a matrix of PP decreased its Tg because of the
poor fiber/matrix adhesion [47]. In addition, Sandi et al. reported that a higher glass transition
temperature for lower fiber contents was obtained due to better adhesion [48].
Moreover, two Tms were found for the composites in the thermograms. The temperatures of
first Tm (Tm1) (139.3-145.9, 137.1-144.3 and 144.2C) for the composites (PLA20, PLA40 and
PLA60) are much lower than that (154.5C) of pristine PLA. Most probably they are connected with
a minute fraction of thinner and/or less perfect crystals formed during quenching of the films to room
temperature after cold crystallization [49]. The temperatures of second Tm (Tm2) (152.7, 149.6 and
147.5C) for the MRDCF reinforced composites are similar to that (154.5C) of pristine PLA, and is
more probable to refer to the melting point of the originally crystallized parts. It is important to note
7

that the peak of Tm2 is more significant than that of Tm1 for PLA20 and PLA40, but PLA60 was on
the contrary. Tm1 for PLA60 was 144.2C specifically, whereas broad-ranged Tm1s for PLA20 and
PLA40 were about 139.3~145.9 and 137.1~144.3C, respectively. This indicates that a higher content
of MRDCF would greatly influence the crystallite formation of PLA, and lead to a significant
amount of less ordered crystals of the composites. This is consistent with the results of Tg
measurement, namely that higher content of MRDCF will change the main crystal type and lead to
the difference effect on thermal transition temperature. Moreover, the values of Hf were decreased
with the addition of the MRDCF. This indicates that the MRDCF may disrupt the crystallite
formation of PLA, and lead to less ordered crystals and smaller crystallinity of the composites as
compared with the pristine PLA [50].

3.3. TGA analysis

TGA thermograms of various samples under nitrogen are shown in Figure 3. The
decomposition temperatures (T5, T25, T50 and T75) of MRDCF reinforced composites at different
weight-loss (5, 25, 50 and 75%) are all smaller than those of pristine PLA due to the nature of the
plant. Plant fibers would release of absorbed moisture at about 40-1400C, and proceed the
degradation process of cellulosic substances such as hemicelluloses and cellulose at about 140-3700C
[51]. However, the char yields of MRDCF reinforced composites (Table 3) are all larger than those
of pristine PLA. Especially, the char yield of PLA60 is more than 20%. These results reveal that the
addition of MRDCF to PLA would effectively raise the char yields of the samples. As reported
8

previously [52-54], the char yield is directly correlated to the potency of flame retardation for the
polymers. Increasing char formation can limit the production of combustible gases, decrease the
exothermicity of the pyrolysis reaction, and inhibit the thermal conductivity of the burning materials
[55].

3.4. Mechanical properties

Figure 4 shows that the tensile strengths of MRDCF reinforced PLA composites are all larger
than that of pristine PLA. Especially PLA40, whose tensile strength (115 MPa) is almost 3 times
higher than that of neat PLA (38MPa). However, the tensile strength of PLA60 is somewhat smaller
than that of PLA40. From the analysis of DSC, it is found that the crystallization behavior of PLA60
was quite different from those of other samples. So this particular morphology or the aggregation
resulting from the high content of fibers may subsequently influence the mechanical properties of the
composites.

3.5. SEM and TEM analysis

The SEM photograph of the fracture surface of PLA is shown in Figure 5, whereas the SEM
photograph of the untreated fiber reinforced PLA matrix is shown in Figure 6. The compatibility
between the untreated fiber and PLA matrix is poor as evidenced by the presence of pull-out fiber on
the fracture surface. Furthermore, the compatibility between fiber and PLA matrix is improved when
the fiber is treated by silane coupling agents as seen in Figure 7. This is shown by the densely knitted
9

texture. This implies that the coupling agents play an important role as compatibilizer between the
fiber and polymer matrix. However, the adhesion between fiber and polymer matrix would
deteriorate when the content of silane-treated fiber was as large as 60 phr. Due to the lower content
of polymer matrix, the exposed fibers, aggregated fibers and void caused from the pulled-out fibers
were found in Figure 8. This corroborates with the results of Tg and mechanical analysis that the poor
adhesion of fiber/matrix decreased the Tg and tensile strength of the composite.
Figure 9 shows that two distinct features were present in the micrograph. The fibers
distributed uniformly in the most part of polymer matrix, whereas aggregates were also found in
certain areas. This is consistent with the results of SEM analysis (Figure 8).

4. Conclusions
For the biodegradable plastics (PLA), the addition of MRDCF provides improvement on the
mechanical or thermal properties of the reinforced materials. Moreover, because of the innate
biodegradability of MRDCF, this type of reinforced plastics would be more environmental friendly
than the traditional ones. Furthermore, the waste from disposable chopsticks could be reduced and
reused, and the cost of PLA composites would be effectively reduced.

Acknowledgements
The author thanks the National Science Council of Taiwan for financial support (NSC
97-2221-E-324-001).
10

References
1. http://www.ibpcosaka.or.jp/network/e_trade_japanesemarket/household_products/disposable
_chopsticks03.html: Disposable Chopsticks 2003, Japanese Market News.
2. http://www.japanfs.org/en/mailmagazine/newsletter/pages/027818.html: Giving Disposable
Chopsticks a Life Cycle, JFS Newsletter.
3. http://www.gadling.com/2007/08/27/big-in-japan-making-biofuel-out-of-used-chopsticks:
Big in Japan: Making Biofuel Out of Used Chopsticks.
4. A. K. Mohanty, A. Wibowo A, M. Misra, L. T. Drzal, Composites: Part A 35 (2003) 363-370.
5. C. Baley, Composites: Part A 33 (2002) 939-948.
6. B. van Voorn, H. H. G. Smit, R. J. Sinke, B. de Klerk, Composites: Part A 32 (2001) 1271-1279.
7. L. Xue, G. T. Lope, P. Satyanarayan, J. Polym. Environ. 15 (2007) 25-37.
8. K. van de Velde, P. Kiekens, J. Appl. Polym. Sci. 83 (2002) 2634-2643.
9. T. W. Frederick, W. Norman, Natural fibers plastics and composites, Kluwer Academic Publishers,
New York (2004).
10. C. A. S. Hill, H. P. S. Khalil, J. Appl. Polym. Sci. 78 (2000) 1685-1697.
11. A. P. Deshpande, M. B. Rao, C. L. Rao, J. Appl. Polym. Sci. 76 (2000) 83-92.
12. K. L. Oksman, W. L. A. Berglund, J. Appl. Polym. Sci. 84 (2002) 2358-2365.
13. M. M. Thwe, K. Liao, Composites: Part A 33 (2002) 43-52.
14. G. C. Stael, M. I. B. Tavares, Polym. Test. 19 (2000) 251-259.
15. L. A. Pothan, Z. Oommen, S. Thomas, Comp. Sci. Technol. 63 (2003) 283-293.
16. L. A. Pothan, S. Thomas, Comp. Sci. Technol. 63 (2003) 1231-1240.
11

17. M. Z. Rong, M. Q. Zhang, Y. Liu, G. C. Yang, H. M. Zeng, Comp. Sci. Technol. 61 (2001)
1437-1447.
18. Y. Ikada, H. Tsuji, Macromol. Rapid Commun. 21 (2000) 117-132.
19. H. Urayama, T. Kanamori, Y. Kimura, Macromol. Mater. Eng. 287 (2002) 116-121.
20. R. G. Sinclair, Pure Appl. Chem. A33(5) (1966) 585-588.
21. H Tsuji, Y. Ikada, J. Appl. Polym. Sci. 67 (1998) 405-415.
22. G. B. Kharas, F. Sanchez-Riera, D. K. Severson, Plastics from microbes, Hanser Publishers, New
York (1994).
23. O. Martin, L. Averous, Polymer 42 (2001) 6209-6219.
24. T. M. Wu, C. Y. Wu, Polym. Degrad. Stab. 91 (2006) 2198-2204.
25. C. S. Wu, Macromol. Biosci. 5 (2005) 352-361.
26. M. Pluta, Polymer 45 (2004) 8239-8251.
27. Z. Kulinski, E. Piorkowska, Polymer 46 (2005) 10290-10300.
28. M. Pluta, M. A. Paul, M. Alexandre, P. Dubois, A. Galeski, J. Appl. Polym. Sci. 86 (2002)
1497-1506.
29. S. S. Ray, K. Yamada, A. Ogami, M. Okamoto, K. Ueda, Macromol. Rapid Commun. 23 (2002)
943-947.
30. S. S. Ray, K. Yamada, M. Okamoto, K. Ueda, Nano Letters 2 (2002) 1093-1096.
31. S. S. Ray, K. Yamada, M. Okamoto, K. Ueda, Polymer 44 (2003) 845-857.
12

32. D. Plackett, T. L. Andersen, W. B. Pedersen, L. Nielsen, Comp. Sci. Technol. 63 (2003)

1287-1296.
33. M. Shibata, K. Ozawa, N. Teramoto, R. Yosomiya, H. Takeishi, Macromol. Mater. Eng. 288
(2003) 35-43.
34. P. Pan, B. Zhu, W. Kai, S. Serizawa, M. Iji, Y. Inoue, J. Appl. Polym. Sci. 105 (2007)
1511-1520.
35. M. S. Huda, L. T. Drzal, A. K. Mohanty, M. Misra, Comp. Sci. Technol. 68 (2008) 424-432.
36. R. Masirek, Z. Kulinski, D. Chionna, E. Piorkowska, M. Pracella, J. Appl. Polym. Sci. 105 (2007)
255-268.
37. F. Chen, L. Liu, P. H. Cooke, K. B. Hicks, J. Zhang, Ind. Eng. Chem. Res. 47 (22) (2008)
8667-8675.
38. R. Bhardwaj, A. K. Mohanty, L. T. Drzal, F. Pourboghrat, M. Misra, Biomacromolecules 7 (2006)
2044-2051.
39. M. S. Huda, L. T. Drzal, A. K. Mohanty, M. Misra, Comp. Sci. Technol. 66 (2006) 18131824.
40. M. S. Huda, L. T. Drzal, M. Misra, A. K. Mohanty, K. Williams, D. F. Mielewski, Ind. Eng.
Chem. Res. 44 (15) (2005) 5593-5601.
41. Y. F. Shih, W. C. Lee, R. J. Jeng, C. M. Huang, J. Appl. Polym. Sci. 99 (2006) 188-199.
42. K. H. Wang, T. M. Wu, Y. F. Shih C. M. Huang, Polym. Eng. Sci. 48 (2008) 1833-1839.
43. Y. F. Shih, Mater. Sci. Eng. A 445446 (2007) 289-295.
13

44. K. Okubo, T. Fujii, Y. Yamamoto, Composites: Part A 35 (2004) 377383.

45. L. Britcher, D. Kehoe, J. Matisons, G. Swincer, Macromolecules 28 (1995) 3110-3118.
46. C. J. Pouchert, (Ed.) The Aldrich Library of Infrared spectra, 3rd ed; Aldrich Chemical Company,
Milwaukee, 1985. p. 62, 123, 1535.
47. M. Botev, H. Betchev, D. Bikiaris, C. Panayiotou, J. Appl. Polym. Sci. 74 (1999) 523531.
48. A. R. Sandi, D. F. Caulfield, N. M. Stark, C. C. Clemons, In Proceedings of Fifth International
Conference on Wood Fiber-Plastic Composites. Forest products Society: Madison, WI, 1999.
49. Z. Kulinski, E. Piorkowska, Polymer 46 (2005) 10290-10300.
50. T. D. Fornes, D. R. Paul, Polymer 44 (2003) 3945-3961.
51. P. Pan, B, Zhu, W. Kai, S. Serizawa, M. Iji, Y. Inoue, J. Appl. Polym. Sci. 105 (2007)1511-1520.
52. Y. F. Shih, R. J. Jeng, J. Appl. Polym. Sci. 86 (2002) 1904-1910.
53. C. S. Wu, Y. L. Liu, K. L. Hsu, Polymer 44 (2003) 565-573.
54. Y. F. Shih, Y. T. Wang, R. J. Jeng, K. M. Wei, Polym. Degrad. Stab. 86 (2004) 339-348.
55. E. M. Pearce, R. Leipins, Environ. Health Perspect 11 (1975) 59- 69.

14

Figure captions
Figure 1

FT-IR analysis

Figure 2

DSC thermograms of samples (a)Tg (b)Tm

Figure 3 TGA curves of (a)neat PLA (b)PLA20 (c)PLA40 (d)PLA60

Figure 4 Tensile strength of MRDCF reinforced PLA as a function of fiber content
Figure 5

SEM micrograph of the fracture surface of pristine PLA

Figure 6

SEM micrograph of the fracture surface of untreated RDCs fiber (40 phr) containing
sample

Figure 7

SEM micrograph of the fracture surface of MRDCF-containing sample (PLA40)

Figure 8

SEM micrograph of the fracture surface of MRDCF-containing sample (PLA60)

Figure 9 TEM micrograph of MRDCF-containing sample (PLA60)

15

Table captions
Table 1

Formulations of samples (wt.)

Table 2 The results of DSC analysis

Table 3 TGA Characterization of Neat PLA and PLA/MRDCF Composites

16