Abstract
The crystallization and degradation behaviors of poly(l-lactic acid) (PLLA) and its blends with poly(ethylene oxide) (PEO) were investigated by depolarized light intensity (DLI). It was found that DLI is sensitive to study the degree of order in polymer thin film samples. The growth rate of the PLLA spherulites was increased by blending up to 80 % PEO, as it increased the chain mobility in the blend melts. At larger PEO compositions (i.e., 90 % PEO), the dilution effect dominates and the PLLA growth rate was retarded. Three distinct blend groups with respect to the blend composition were proposed: (1) 10–20 wt% PEO in which the PEO is not able to form any ordered structure in the binary blend; (2) 30–50 wt% PEO in which the PEO is able to form some order but not enough to develop spherulitic crystals; (3) 60–90 wt% PEO in which the PEO forms a network of spherulites throughout the pre-crystallized PLLA.
Similar content being viewed by others
References
Magill JH (1962) A new technique for following rapid rates of crystallization II Isotactic polypropylene. Polymer 3:35
Al-Raheil IA, Qudah AA (1995) On the triple melting behaviour of poly(ethylene succinate). Polym Int 37(4):249
Muchova M, Lednicky F (1995) Induction time as a measure for heterogeneous spherulite nucleation: quantitative evaluation of early-stage growth kinetics. J Macromol Sci B 34(1–2):55
Miyata T, Masuko T (1998) Crystallization behaviour of poly(l-lactide). Polymer 39(22):5515
Ghanem A (1999) On the validity of crystallization kinetics parameters derived from the depolarized light intensity (DLI) technique: an experimental study of polyvinylidene fluoride. J Polym Sci Pol Phys 37(10):997
Wang C, Chen CC, Cheng YW, Liao WP, Wang ML (2002) Simultaneous presence of positive and negative spherulites in syndiotactic polystyrene and its blends with atactic polystyrene. Polymer 43(19):5271
Xu Y, Shang S, Huang J (2010) Crystallization behavior of poly(trimethylene terephthalate)–poly(ethylene glycol) segmented copolyesters/multi-walled carbon nanotube. Polym Test 29(8):1007
Cai Y, Yan S, Yin J, Fan Y, Chen X (2011) Crystallization behavior of biodegradable poly(l-lactic acid) filled with a powerful nucleating agent: N, N′-bis(benzoyl) suberic acid dihydrazide. J Appl Polym Sci 121(3):1408
Ziabicki A, Misztal-Faraj B (2005) Applicability of light depolarization technique to crystallization studies. Polymer 46:2395
Barrall EM II, Sweeney MA (1969) Depolarized light intensity and optical microscopy of some mesophase-forming materials. Molecular Crystals 5(3):257
Huang S, Li H, Jiang S, Chen X, An L (2011) Morphologies and structures in poly(l-lactide-b-ethylene oxide) copolymers determined by crystallization, microphase separation, and vitrification. Polym Bull 67(5):885
Xiong ZJ, Zhang XQ, Liu GM, Zhao Y, Wang R, Wang DJ (2013) Crystallization and tensile behavior of poly(l-lactide)/poly(ethylene oxide) blend. Chem J Chinese U 34(5):1288
Choi K-M, Lim S-W, Choi M-C, Kim Y-M, Han D-H, Ha C-S (2014) Thermal and mechanical properties of poly(lactic acid) modified by poly(ethylene glycol) acrylate through reactive blending. Polym Bull 71(12):3305
Xue F, Chen X, An L, Funari S, Jiang S (2014) Crystallization induced layer-to-layer transitions in symmetric PEO-b-PLLA block copolymer with synchrotron simultaneous SAXS/WAXS. RSC Adv 4(99):56346
Woo EM, Lugito G, Tsai JH (2015) Effects of top confinement and diluents on morphology in crystallization of poly(l-lactic acid) interacting with poly(ethylene oxide). J Polym Sci Part B Polym Phys 53(16):1160
Adamski P, Dylik-Gromiec LA, Wojciechowski M (1981) Investigation of spherulite growth rate and activation energy of cholesteryl nonanoate and cholesteryl decanoate mixtures. J Crys Growth 52(1):332
Agari Y, Sakai K, Kano Y, Nomura R (2007) Preparation and properties of the biodegradable graded blend of poly(l-lactic acid) and poly(ethylene oxide). J Polym Sci Pol Phys 45(21):2972
Nijenhuis AJ, Colstee E, Grijpma DW, Pennings AJ (1996) High molecular weight poly(l-lactide) and poly(ethylene oxide) blends: thermal characterization and physical properties. Polymer 37(26):5849
Lai WC, Liau WB, Yang LY (2008) The effect of ionic interaction on the miscibility and crystallization behaviors of poly(ethylene glycol)/poly(l-lactic acid) blends. J Appl Polym Sci 110(6):3616
Wang C, Fan K, Hsiue G (2005) Enzymatic degradation of PLLA-PEOz-PLLA triblock copolymers. Biomaterials 26(16):2803
Lee J, Jeong ED, Cho EJ, Gardella JA, Hicks W, Hard R, Bright FV (2008) Surface-phase separation of PEO-containing biodegradable PLLA blends and block copolymers. Appl Surf Sci 255(5):2360
Hsieh YT, Woo EM (2013) Lamellar assembly and orientation-induced internal micro-voids by cross-sectional dissection of poly(ethylene oxide)/poly(l-lactic acid) blend. Express Polym Lett 7(4):396
Li JZ, Schultz JM, Chan CM (2015) The relationship between morphology and impact toughness of poly(l-lactic acid)/poly(ethylene oxide) blends. Polymer 63:179
Younes H, Cohn D (1988) Phase separation in poly(ethylene glycol)/poly(lactic acid) blends. Eur Polym J 24(8):765
Acknowledgments
The project is partially sponsored by Science Foundation of China University of Petroleum, Beijing (No. YJRC-2013-34) and the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry.
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Zhang, X., Singfield, K.L. & Ye, H. Using depolarized light intensity to study the crystallization and degradation behavior of poly(l-lactic acid) and its blends with poly(ethylene oxide). Polym. Bull. 73, 3437–3451 (2016). https://doi.org/10.1007/s00289-016-1665-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00289-016-1665-8