Effect of Starch and Plasticizer Types and Fiber Content on Properties of Polylactic Acid/Thermoplastic Starch Blend

Polylactic acid (PLA) is the most commercially available bio-based and biodegradable plastic at present. PLA has been used in plastic related industries including single-used containers, disposable and environmentally friendly packaging owing to its renewability, compostability, biodegradability, and safety. Although PLA demonstrates reasonably good optical, physical, mechanical and barrier properties comparable to the existing petroleum-based plastics, its brittleness and mold shrinkage as well as its price are the points to be concerned for the production of rigid and semi-rigid packaging. Blending PLA with other bio-based polymers including thermoplastic starch (TPS) is an alternative not only to achieve a complete bio-based plastic, but also to reduce the brittleness, shrinkage during molding and production cost of the PLA-based products. TPS is a material produced mainly from starch which is cheap, renewable, biodegradable, compostable, and nontoxic. It is commonly prepared by a plasticization of starch under applying heat and shear force. Although glycerol has been reported as one of the most plasticizers used for preparing TPS, its migration caused the surface stickiness of the TPS products. In some cases, mixed plasticizers or natural fibers have been applied to impede the retrogradation of starch or reduce the migration of glycerol. The introduction of fibers into TPS-based materials could reinforce the polymer matrix as well. Therefore, the objective of the present research is to study the effect of starch type (i.e. native starch and phosphate starch), plasticizer type (i.e. glycerol and xylitol with a weight ratio of glycerol to xylitol of 100:0, 75:25, 50:50, 25:75 and 0:100) and fiber content (i.e. in the range of 1-25 %wt) on properties of PLA/TPS blend and composite. PLA/TPS blends and composites were prepared using a twin-screw extruder and then converted into dumbbell-shaped specimens using an injection molding machine. The PLA/TPS blends prepared by using phosphate starch showed higher tensile strength and stiffness than the blends prepared by using native one. In contrast, the blends from native starch exhibited higher extensibility and heat distortion temperature (HDT) than those from the modified starch. Increasing xylitol content resulted in enhanced tensile strength, stiffness and water resistance, but decreased extensibility and HDT of the PLA/TPS blend. Tensile properties and hydrophobicity of the blend could be improved by incorporating silane treated-jute fibers.




References:
[1] D. Garlotta, “A literature review of poly(lactic acid),” J. Polym.
Environ., vol. 9, 2001, pp. 63-84.
[2] O. Martin and L. Averous, “Poly(lactic acid): Plasticization and
properties of biodegradable multiphase system,” Polymer, vol. 42, 2001,
pp. 6209-6219.
[3] M. S. Huda, L. T. Drzal, A. K. Mohanty, and M. Misra, “Chopped glass
and recycled newspaper as reinforcement in injection mold poly(lactic
acid)(PLA) composite: A comparative studies,” Compos. Sci. Technol.,
vol. 66, 2006, pp. 1813-1824.
[4] M. A. Shirai, M. V. E. Grossmann, S. Mali, F. Yamashita, P. S. Garcia
and C. M. O. Muller, “Development of biodegradable flexible films of
starch and poly(lactic acid) plasticized with adipate or citrate esters,”
Carbohyd. Polym., vol. 92, 2013, pp. 19-22.
[5] M. A. Huneault and H. Li, “Morphology and properties of
compatibilized polylactide/thermoplastic starch blends,” Polymer, vol.
48, 2007, pp. 270-280.
Contact angle (Degree)
(a)
(f)
(e)
(d)
(b)
(c)
115
100
85
70
55
40
25
0 170 345 518 690 865
Absorption time (sec)
58
57
56
55
54
53
52
51
50
HDT (C)
100:0 25:75 50:50 75:25 0:100
Glycerol:xylitol (w/w)
a (a) ab ab abc
bcde
d de cde
e
f
57
56
55
54
53
52
51
50
ab a (b)
ab
ab
bc
HDT (C)
c
0 2.3 3.9 6.5 12.5 25
Silane-treated jute fiber content (% wt)
[6] O. V. López, E. Z. Noemí, M .V. E. Grossmann and M. A. García,
“Acetylated and native corn starch blend films produced by blown
extrusion,” J. Food Eng., vol. 116, 2013, pp. 286–297.
[7] J. Girones , J. P. Lopez, P. Mutje , A. J. F. Carvalho, A. A. S. Curvelo ,
and F. Vilaseca, “Natural fiber-reinforced thermoplastic starch
composites obtained by melt processing,” Compos. Sci. Technol., vol.
72, 2012, pp. 858–863.
[8] X. F. Ma, J. G. Yu, and Y. B. Ma, “Urea and formamide as a mixed
plasticizer for thermoplastic wheat flour,” Carbohyd. Polym., vol. 60,
2005, pp. 111–116.
[9] A. H. Li and M. A. Huneault, “Comparison of sorbitol and glycerol as
plasticizers for thermoplastic starch in TPS/PLA blends,” J. Appl.
Polym. Sci., 2011, vol. 119, pp. 2439-2448.
[10] A. H. Liu, D. Chaudhary, G. Ingram and J. John, “Interactions of
hydrophilic plasticizer molecules with amorphous starch biopolymeran
investigation into the glass transition and the water activity behavior,” J.
Polym. Sci. Pol. Phys., 2011, vol. 49, pp. 1041–1049.
[11] D. Plackett, T. L. Andersen, W. B. Pedersen and L. Nielsen,
“Biodegradable composites based on l-polylactide and jute fibres,”
Compos. Sci. Technol., vol. 63, 2003, pp. 1287–1296.
[12] D. Cho, J. M. Seo, W. H. Park, S. O. Han, T. W. Hwang, C. H. Choi,
and S. J. Jung, “Improvement of the interfacial, flexural, and thermal
properties of jute/poly(lactic acid) biocomposites by fiber surface
treatments,” J. Biobased Mater. Bio., vol. 1, 2007, pp. 331–340.
[13] A. Le Duigou, P. Davies and C. Baley, “Interfacial bonding of flax
fibre/poly(l-lactide) bio-composites,” Compos. Sci. Technol., vol. 70,
2010, pp. 231–239.
[14] Q. F. Shi, H. Y. Mou, Q. Y. Li, J. K. Wang and W. H. Guo, “Influence
of heat treatment on the heat distortion temperature of poly(lactic
acid)/bamboo fiber/talc hybrid biocomposites,” J. Appl. Polym. Sci., vol.
123, 2012, p. 2828-2836.
[15] R. Auras, L. T. Lim, S. E. M. Selke and H. Tsuji, Poly(lactic acid):
synthesis, structures, properties, processing, and applications. New
Jersey: John Wiley & Sons, Inc., 2010, pp. 303.
[16] O. Faruka, A. K. Bledzki, H. P. Fink, M. Sain, “Biocomposites
reinforced with natural fibers: 2000–2010,” Prog. Mater. Sci., vol. 37,
2012, pp. 1552–1596.
[17] X. Qiao, Z. Tang and K. Sun. “Plasticization of corn starch by polyol
mixtures,” Carbohydr. Polym., vol. 83, 2011, pp. 659–664.
[18] M. S. Huda, L. T. Drzal, A. K. Mohanty and M. Misra, “Effect of fiber
surface-treatments on the properties of laminated biocomposites from
poly(lactic acid) (pla) and kenaf fibers,” Composites Science and
Technology, vol. 68, 2008, pp. 424-432.