Abstract
A thermal study of poly(l-lactide) under nitrogen atmosphere has been carried out through thermogravimetric (TG) analysis and differential thermal analysis (DTA) measurements. The experimental data were collected with the heating rates of 2.5 to 30 K min−1 and from ambient temperature up to 750 K. The thermal features were obtained from resultant TG and DTA curves. The results show that the thermal decomposition was mainly in the temperature range of 550–660 K. Kinetic analyses of the mass loss versus temperature data have been performed with four different temperature integral models, including the distributed activation energy model (DAEM), Flynn–Wall–Ozawa, Coats–Redfern, and Tang models. Through the DAEM model, the activation energy distribution function and the relationship between activation energy and pre-exponential factor have been obtained. The activation energy thus obtained at different conversion levels ranges from 91.34 to 107.44 kJ mol−1, and similar results have been produced using the other three models. With these kinetic parameters, the TG curves have been simulated with the above four models by assuming the first-order reaction mechanism, resulting in satisfactory simulation results.
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References
Garlotta D. A literature review of poly(lactic acid). J Polym Environ. 2001;9(2):63–84.
Auras R, Harte B, Selke S. An overview of polylactides as packaging materials. Macromol Biosci. 2004;4:835–64.
McNeill IC, Leiper HA. Degradation studies of some polyesters and polycarbonates-1. Polylactide: general features of the degradation under programmed heating conditions. Polym Degrad Stab. 1985;11:267–85.
Leiper HA, McNeill IC. Degradation studies of some polyesters and polycarbonates-2. Polylactide: degradation under isothermal conditions, thermal degradation mechanism and photolysis of the polymer. Polym Degrad Stab. 1985;11:309–26.
Babanalbandi A, Hill DJT, Hunter DS, Kettle L. Thermal stability of poly(lactic acid) before and after γ-radiolysis. Polym Int. 1999;48:980–4.
Aoyagi Y, Yamashita K, Doi Y. Thermal degradation of poly[(R)-3-hydroxybutyrate], poly[ε-caprolactone], and poly[(S)-lactide]. Polym Degrad Stab. 2002;76:53–9.
Cam D, Marucci M. Influence of residual monomers and metals on poly(l-lactide) thermal stability. Polymer. 1997;38:1879–84.
Noda M, Okuyama H. Thermal catalytic depolymerization of poly(l-lactic acid) oligomer into L, l-lactide: effects of Al, Ti, Zn, and Zr compounds as catalysts. Chem Pharm Bull. 1999;47:467–71.
Fan Y, Nishida H, Hoshihara S, Shirai Y, Tokiwa Y, Endo T. Pyrolysis kinetics of poly(l-lactide) with carboxyl and calcium salt end structures. Polym Degrad Stab. 2003;79:547–62.
Nishida H, Moria T, Hoshihara S, Fan Y, Shirai Y, Endo T. Effect of tin on poly(l-lactic acid) pyrolysis. Polym Degrad Stab. 2003;81:515–23.
Fan Y, Nishida H, Mori T, Shirai Y, Endo T. Thermal degradation of poly(l-lactide): effect of alkali earth metal oxides for selective l, L-lactide formation. Polymer. 2004;45:1197–205.
Fan Y, Nishida H, Shirai Y, Endo T. Thermal stability of poly(l-lactide): influence of end protection by acetyl group. Polym Degrad Stab. 2004;84:143–9.
Mori T, Nishida H, Shirai Y, Endo T. Effects of chain end structures on pyrolysis of poly(l-lactic acid) containing tin atoms. Polym Degrad Stab. 2004;84:243–51.
Fan Y, Nishida H, Shirai Y, Tokiwa Y, Endo T. Thermal degradation behaviour of poly(lactic acid) stereocomplex. Polym Degrad Stab. 2004;86:197–208.
Chrissafis K. Detail kinetic analysis of the thermal decomposition of PLA with oxidized multi-walled carbon nanotubes. Thermochim Acta. 2010;511:163–7.
Kim H-S, Chae YS, Kwon HI, Yoon J-S. Thermal degradation behaviour of multi-walled carbon nanotube-reinforced poly(l-lactide) nanocomposites. Polym Int. 2009;58:826–31.
Zhou Q, Xanthos M. Nanosize and microsize clay effects on the kinetics of the thermal degradation of polylactides. Polym Degrad Stab. 2009;94:327–38.
Carrasco F, Gámez-Pérez J, Santana OO, Maspoch ML. Processing of poly(lactic acid)/organomontmorillonite nanocomposites: microstructure, thermal stability and kinetics of the thermal decomposition. Chem Eng J. 2011;178:451–60.
Motoyama T, Tsukegi T, Shirai Y, Nishida H, Endo T. Effects of MgO catalyst on depolymerization of poly-l-lactic acid to l,l-lactide. Polym Degrad Stab. 2007;92:1350–8.
Weng Y-X, Jin Y-J, Meng Q-Y, Wang L, Zhang M, Wang Y-Z. Biodegradation behavior of poly(butylene adipate-co-terephthalate) (PBAT), poly(lactic acid) (PLA), and their blend under soil conditions. Polym Test. 2013;32:918–26.
Zeng C, Zhang N-W, Feng S-Q, Ren J. Thermal stability of copolymer derived from l-lactic acid and poly(tetramethylene) glycol through direct polycondensation. J Therm Anal Calorim. 2013;111:633–46.
Blanco I, Siracusa V. Kinetic study of the thermal and thermo-oxidative degradations of polylactide-modified films for food packaging. J Therm Anal Calorim. 2013;112:1171–7.
Dai L, Wang L-Y, Yuan T-Q, He J. Study on thermal degradation kinetics of cellulose-graft-poly(l-lactic acid) by thermogravimetric analysis. Polym Degrad Stab. 2014;99:233–9.
Perinović S, Andričić B, Erceg M. Thermal properties of poly(l-lactide)/olive stone flour composites. Thermochim Acta. 2010;510:97–102.
Vyazovkin S. Model-free kinetics—staying free of multiplying entities without necessity. J Therm Anal Calorim. 2006;83(1):45–51.
Reverte C, Dirion JL, Cabassud M. Kinetic model identification and parameters estimation from TGA experiments. J Anal Appl Pyrolysis. 2007;79(1–2):297–305.
Budrugeac P, Segal E. Application of isoconversional and multivariate non-linear regression methods for evaluation of the degradation mechanism and kinetic parameters of an epoxy resin. Polym Degrad Stab. 2008;93(6):1073–80.
Carrasco F, Pagès P, Gámez-Pérez J, Santana OO, Maspoch ML. Processing of poly(lactic acid): characterization of chemical structure, thermal stability and mechanical properties. Polym Degrad Stab. 2010;95(2):116–25.
Cai JM, Liu RH. Parametric study of the nonisothermal nth-order distributed activation energy model involved the Weibull distribution for biomass pyrolysis. J Therm Anal Calorim. 2007;89:971–5.
Li Z, Liu C, Chen Z, Qian J, Zhao W, Zhu Q. Analysis coals and biomass pyrolysis using the distributed activation energy model. Bioresour Technol. 2009;100:948–52.
Sonobe T, Worasuwannarak N. Kinetic analyses of biomass pyrolysis using the distributed activation energy model. Fuel. 2008;87:414–21.
Mani T, Murugan P, Mahinpey N. Determination of distributed activation energy model kinetic parameters using annealing optimization method for nonisothermal pyrolysis of lignin. Ind Eng Chem Res. 2009;48:1464–7.
Miura K, Mae K, Shimada M, Minami H. Analysis of formation rates of sulfur-containing gases during the pyrolysis of various coals. Energy Fuel. 2001;15:629–36.
Miura K, Maki T. A simple method for estimating f(E) and k0(E) in the distributed activation energy model. Energy Fuel. 1998;12:864–9.
Tang W, Liu Y, Zhang H, Wang C. New approximate formula for Arrhenius temperature integral. Thermochim Acta. 2003;408:39–43.
Šesták J, Berggren G. Study of the kinetics of the mechanism of solid-state reactions at increasing temperatures. Thermochim Acta. 1971;3:1–12.
Georgieva V, Zvezdova D, Vlaev L. Non-isothermal kinetics of thermal degradation of chitin. J Therm Anal Calorim. 2013;111(1):763–71.
Flynn JH, Wall LA. General treatment of thermogravimetry of polymers. J Res Natl Bur Stand Sect A. 1966;70A(6):487–523.
Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc Jpn. 1965;38:1881–6.
Coats AW, Redfern JP. Kinetic parameters from thermogravimetric data. Nature. 1964;201:68–9.
He W, Deng F, Liao G-X, Lin W, Jiang Y-Y, Jian X-G. Kinetics of thermal degradation of poly(aryl ether) containing phthalazinone and life estimation. J Therm Anal Calorim. 2010;100:1055–62.
Turmanova SC, Genieva SD, Dimitrova AS, Vlaev LT. Nonisothermal degradation kinetics of filled with rice husk ash polypropene composites. Express Polym Lett. 2008;2:133–46.
Madhysudanan PM, Krishnan K, Ninan KN. New equations for kinetic analysis of non-isothermal reactions. Thermochim Acta. 1993;221:13–21.
Tudorachi N, Lipsa R, Mustata FR. Thermal degradation of carboxymethyl starch–g-poly(lactic acid) copolymer by TG–FTIR–MS analysis. Ind Eng Chem Res. 2012;51(48):15537–45.
Seo DK, Park SS, Hwang JH, Yu T. Study of the pyrolysis of biomass using thermo-gravimetric analysis (TGA) and concentration measurements of the evolved species. J Anal Appl Pyrolysis. 2010;89:66–73.
Willium PT, Besler S. The influence of temperature and heating rate on the slow pyrolysis of biomass. Renew Energy. 1996;7(3):233–50.
Brown ME, Maciejewski M, Vyazovkin S, Nomen R, Sempere J, Burnham A, Opfermann J, Strey R, Anderson HL, Kemmler A, Keuleers R, Janssens J, Desseyn HO, Li C-R, Tang TB, Roduit B, Malek J, Mitsuhashi T. Computational aspects of kinetic analysis Part A: the ICTAC kinetics project-data, methods and results. Thermochim Acta. 2000;355:125–43.
Vyazovkin S, Burnham AK, Criado JM, Pérez-Maqueda LA, Popescud C, Sbirrazzuoli N. ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta. 2011;520:1–19.
Cai J, Li T, Liu R. A critical study of the Miura-Maki integral method for the estimation of the kinetic parameters of the distributed activation energy model. Bioresour Technol. 2011;102:3894–9.
Carrasco F, Pagès P, Gámez-Pérez J, Santana OO, Maspoch ML. Kinetics of the thermal decomposition of processed poly(lactic acid). Polym Degrad Stab. 2010;95:2508–14.
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The authors would like to thank Tianjin University of Commerce (TJUC–080015) for partially funding this project.
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Huang, Z., Ye, Qq. & Teng, Lj. A comparison study on thermal decomposition behavior of poly(l-lactide) with different kinetic models. J Therm Anal Calorim 119, 2015–2027 (2015). https://doi.org/10.1007/s10973-014-4311-4
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DOI: https://doi.org/10.1007/s10973-014-4311-4