Abstract
In this paper, the isothermal crystallization of polycaprolactone (PCL)/modified clay nanocomposites, at several temperatures, was studied. The effects of clay type (organo-modified bentonite B-TBHP and organo-modified montmorillonite C20A) and also the clay content were analysed. Bulk crystallization was studied by differential scanning calorimetry and modelled by the Avrami equation. Special effort was made to correlate the crystallization parameters with the clay dispersion degree inside the polymer matrix. The lowest induction time and fastest overall crystallization rate were obtained with the B-TBHP nanocomposites, which showed the lowest clay dispersion degree. In contrast, C20A nanocomposites showed higher clay dispersion degree inside the PCL matrix and higher induction times and lower overall crystallization rate than B-TBHP ones, even retarding the formation of the equilibrium nucleus with critical dimensions in comparison with neat PCL.
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References
Xu W, Ge M, He P. Nonisothermal crystallization kinetics of polyoxymethylene/montmorillonite nanocomposite. J Appl Polym Sci. 2001;82(9):2281–9.
Ke Y, Long C, Qi Z. Crystallization, properties, and crystal and nanoscale morphology of PET–clay nanocomposites. J Appl Polym Sci. 1999;71(7):1139–46.
Liu X, Wu Q. PP/clay nanocomposites prepared by grafting-melt intercalation. Polymer. 2001;42(25):10013–9.
Alexandre M, Dubois P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mat Sci Eng R Rep. 2000;28(1):1–63.
Messersmith PB, Giannelis EP. Synthesis and barrier properties of poly (ε-caprolactone)-layered silicate nanocomposites. J Polym Sci Part A Polym Chem. 1995;33(7):1047–57.
Kojima Y, Usuki A, Kawasumi M, Okada A, Fukushima Y, Kurauchi T, et al. Mechanical properties of nylon 6-clay hybrid. J Mat Res. 1993;8(05):1185–9.
Gilman JW, Jackson CL, Morgan AB, Harris R Jr, Manias E, Giannelis EP, et al. Flammability properties of polymer-layered-silicate nanocomposites. Polypropylene and polystyrene nanocomposites. Chem Mat. 2000;12(7):1866–73.
Gorrasi G, Tortora M, Vittoria V, Pollet E, Lepoittevin B, Alexandre M, et al. Vapor barrier properties of polycaprolactone montmorillonite nanocomposites: effect of clay dispersion. Polymer. 2003;44(8):2271–9.
Di Maio E, Iannace S, Sorrentino L, Nicolais L. Isothermal crystallization in PCL/clay nanocomposites investigated with thermal and rheometric methods. Polymer. 2004;45(26):8893–900.
Homminga D, Goderis B, Dolbnya I, Groeninckx G. Crystallization behavior of polymer/montmorillonite nanocomposites. Part II. Intercalated poly (ε-caprolactone)/montmorillonite nanocomposites. Polymer. 2006;47(5):1620–9.
Krikorian V, Pochan DJ. Unusual crystallization behavior of organoclay reinforced poly (l-lactic acid) nanocomposites. Macromolecules. 2004;37(17):6480–91.
Kennedy M, Turturro G, Brown G, St-Pierre L. Silica retards radial growth of spherulites in isotactic polystyrene. Nature. 1980;287:316–17.
Jain S, Goossens H, van Duin M, Lemstra P. Effect of in situ prepared silica nano-particles on non-isothermal crystallization of polypropylene. Polymer. 2005;46(20):8805–18.
Yuan Q, Awate S, Misra R. Nonisothermal crystallization behavior of polypropylene–clay nanocomposites. Eur Polym J. 2006;42(9):1994–2003.
Papageorgiou GZ, Achilias DS, Bikiaris DN. Crystallization kinetics of biodegradable poly (butylene succinate) under isothermal and non-isothermal conditions. Macromol Chem Phys. 2007;208(12):1250–64.
Medellin-Rodriguez F, Mata-Padilla J, Hsiao B, Waldo-Mendoza M, Ramirez-Vargas E, Sanchez-Valdes S. The effect of nanoclays on the nucleation, crystallization, and melting mechanisms of isotactic polypropylene. Polym Eng Sci. 2007;47(11):1889.
Xu W, Ge M, He P. Nonisothermal crystallization kinetics of polypropylene/montmorillonite nanocomposites. J Polym Sci Part B Polym Phys. 2002;40(5):408–14.
Xu W, Liang G, Zhai H, Tang S, Hang G, Pan W-P. Preparation and crystallization behaviour of PP/PP-g-MAH/Org-MMT nanocomposite. Eur Polym J. 2003;39(7):1467–74.
Birgersson E, Li H, Wu S. Transient analysis of temperature-sensitive neutral hydrogels. J Mech Phys Sol. 2008;56(2):444–66.
Ollier R, Vázquez A, Alvarez V. Biodegradable nanocomposites based on modified bentonite and polycaprolactone. In: Advances in nanotechnology. New York: Nova Publishers; 2011. p. 281–301.
Wagener R, Reisinger TJ. A rheological method to compare the degree of exfoliation of nanocomposites. Polymer. 2003;44(24):7513–8.
Ollier R, Lanfranconi M, Ludueña L, Alvarez V (eds.) Preparation and characterization of PCL/modified-clay biodegradable nanocomposites Euporean polymer conference EPF 2013 2013 2013; Pisa.
Kelnar I, Kratochvíl J, Kaprálková L. Crystallization and thermal properties of melt-drawn PCL/PLA microfibrillar composites. J Therm Anal Calorim. 2016;124:799–805.
Ludueña LN, Vazquez A, Alvarez VA. Crystallization of polycaprolactone–clay nanocomposites. J Appl Polym Sci. 2008;109(5):3148–56.
Olewnik E, Garman K. Thermal properties of nanocomposites based on polyethylene and n-heptaquinolinum modified montmorillonite. J Therm Anal Calorim. 2012;110:479–84.
Jimenez G, Ogata N, Kawai H, Ogihara T. Structure and thermal/mechanical properties of poly (ϵ-caprolactone)-clay blend. J Appl Polym Sci. 1997;64(11):2211–20.
Luduena L, Kenny J, Vázquez A, Alvarez V. Effect of clay organic modifier on the final performance of PCL/clay nanocomposites. Mat Sci Eng A. 2011;529:215–23.
Ludueña L, Vázquez A, Alvarez V. Effect of the type of clay organo-modifier on the morphology, thermal/mechanical/impact/barrier properties and biodegradation in soil of polycaprolactone/clay nanocomposites. J Appl Polym Sci. 2013;128(5):2648–57.
Díaz A, Franco L, Casas M, del Valle L, Aymamí J, Olmo C, Puiggalí J. Preparation of micro-molded exfoliated clay nanocomposites by means of ultrasonic technology. J Polym Res. 2014;21:584.
Gupta Y, Abbas S, Sharma R, Setua D. Crystallization kinetics of polyurethane nanocomposites. J Therm Anal Calorim. 2015;119:1393–405.
Chen J, Xu J, Xu H, Li Z, Zhong G, Lei J. The crystallization behavior of biodegradable poly(butylene succinate) in the presence of organically modified clay with a wide range of loadings. Chin J Polym Sci. 2015;33(4):576–86.
Desio GP, Rebenfeld L. Crystallization of fiber-reinforced poly (phenylene sulfide) composites II Modeling the crystallization kinetics. J Appl Polym Sci. 1992;45(11):2005–20.
Acknowledgements
This work was supported by the National Agency of Science and Technology (ANPCyT) [Fonarsec FSNano004] and the National University of Mar del Plata (UNMdP) [15G327].
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Lanfranconi, M., Alvarez, V.A. & Ludueña, L.N. Isothermal crystallization of polycaprolactone/modified clay biodegradable nanocomposites. J Therm Anal Calorim 126, 1273–1280 (2016). https://doi.org/10.1007/s10973-016-5734-x
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DOI: https://doi.org/10.1007/s10973-016-5734-x