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Kinetics of thermal degradation applied to biocomposites with TPS, PCL and sisal fibers by non-isothermal procedures

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Abstract

The thermal degradation behavior of the biocomposite with thermoplastic starch (TPS), poly(ε-caprolactone) (PCL) and bleached sisal fibers were investigated by thermogravimetry analysis (TG/DTG) under synthetic air atmosphere, differential scanning calorimetry, and their crystal structure by X-ray diffraction. Applying the non-isothermal Ozawa method, the TG/DTG curves average activation energy could be obtained for thermal degradation of the biocomposites with 5, 10, and 20 % of bleached sisal fibers. The apparent activation energy values for the biocomposites decreased when compared with the TPS/PCL blend, requiring lower energy to recycle this material. However, continuous addition of sisal fibers increased the activation energy of composites.

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References

  1. Cyras VP, Martucci JF, Iannace S, Vazquez A. Influence of the fiber content and the processing conditions on the flexural creep behavior of sisal–PCL–starch composites. J Thermoplast Compos. 2000;15:253–65.

    Article  Google Scholar 

  2. Whisler RL, Memiller JN, Paschall EF. Starch chemistry and technology. New York: Academic Press; 1984.

    Google Scholar 

  3. Peanasky JS, Long JM, Wool RP. Percolation effects in degradable polyethylene–starch blends. J Polym Sci. 1991;29:565–79.

    Article  CAS  Google Scholar 

  4. George ER, Sullivan TM, Park EH. Thermoplastic starch blends with a poly(ethylene-co-vinyl alcohol): processability and physical properties. Polym Eng Sci. 1994;34:17–23.

    Article  CAS  Google Scholar 

  5. Swanson CL, Shogren RL, Fanta GF, Iman SH. Starch–plastic materials—preparation, physical properties, and biodegradability (a review of recent USDA research). J Environ Polym Degrad. 1993;1:155–66.

    Article  CAS  Google Scholar 

  6. Raghavan D, Emekalan A. Characterization of starch/polyethylene and starch/polyethylene/poly(lactic acid) composites. Polym Degrad Stab. 2001;72:509–17.

    Article  CAS  Google Scholar 

  7. Griffith LG. Polymeric biomaterials. Acta Mater. 2000;48:263–77.

    Article  CAS  Google Scholar 

  8. Chandra R, Rustgi R. Biodegradable polymers. Prog Polym Sci. 1998;23:1273–335.

    Article  CAS  Google Scholar 

  9. Darwis D, Mitomo H, Enjoji T, Yoshii F, Makuuchi K. Enzymatic degradation of radiation crosslinked poly(3-caprolactone). Polym Degrad Stab. 1998;62:259–65.

    Article  CAS  Google Scholar 

  10. Yu L, Dean K, Li L. Polymer blends and composites from renewable resources. Prog Polym Sci. 2006;31:576–602.

    Article  CAS  Google Scholar 

  11. Bledzki AK, Gassan J. Composites reinforced with cellulose based fibres. Prog Polym Sci. 1999;24:221–74.

    Article  CAS  Google Scholar 

  12. Mohanty AK, Misra M, Hinrichsen G. Biofibres, biodegradable polymers and biocomposites: an overview. Macromol Mater Eng. 2000;276(277):1–24.

    Article  Google Scholar 

  13. Nishino T, Hirao K, Kotera M, Nakamae K, Inagaki H. Kenaf reinforced biodegradable composite. Compos Sci Technol. 2003;63:1281–6.

    Article  CAS  Google Scholar 

  14. Wong S, Shanks R, Hodzic A. Properties of poly (3-hydroxybutyric acid) composites with flax fibers modified by plasticiser absorption. Macromol Mater Eng. 2002;287:647–55.

    CAS  Google Scholar 

  15. Alvarez V, Vázquez A. Thermal degradation of cellulose derivatives/starch blends and sisal fibre biocomposites. Polym Degrad Stab. 2004;84:13–21.

    Article  CAS  Google Scholar 

  16. Campos A, Teixeira EM, Marconcini JM, Chiou B-S, Orts WJ, Wood D, Mattoso LHC, Imam SH. Starch/polycaprolactone-containing composites reinforced with pre-treated sisal fibers. Trends Polym Sci. 2011;15:89–99.

    CAS  Google Scholar 

  17. Sivalingam G, Karthik R, Madras G. Kinetics of thermal degradation of poly (ε-caprolactone). J Anal Appl Pyrolysis. 2003;70:631–47.

    Article  CAS  Google Scholar 

  18. Yao F, Wu Q, Lei Y, Guo W, Xu Y. Thermal decomposition kinetics of natural fibers: activation energy with dynamic thermogravimetric analysis. Polym Degrad Stab. 2008;93:90–8.

    Article  CAS  Google Scholar 

  19. Sathasivam K, Haris MRHM. Thermal properties of modified banana trunk fibers. J Therm Anal Calorim. 2012;108:9–17.

    Article  CAS  Google Scholar 

  20. Sun JX, Sun XF, Zhao H, Sun RC. Isolation and characterization of cellulose from sugarcane bagasse. Polym Degrad Stab. 2004;84(2):331–9.

    Article  CAS  Google Scholar 

  21. Ozawa T. A new method of analyzing thermogravimetric data. Bull Chem Soc.;65(38):1881–6.

  22. Carmona VB, Oliveira RM, Silva WTL, Mattoso LHC, Marconcini JM. Nanosilica from rice husk: extraction and characterization. Ind Crop Prod. 2013;43:291–6.

    Article  CAS  Google Scholar 

  23. Vertuccio L, Gorrasi G, Sorrentino A, Vittoria V. Nano clay reinforced PCL/starch blends obtained by high energy ball milling. Carbohydr Polym. 2009;75:172–9.

    Article  CAS  Google Scholar 

  24. Kesel CD, Lefevre C, Nagry JB, David C. Blends of polycaprolactone with polyvinylalcohol: a DSC, optical microscopy and solid state NMR study. Polymer. 1999;40:1969–78.

    Article  Google Scholar 

  25. Borysiak S, Garbaczyk J. Applying the WAXS method to estimate the supermolecular structure of cellulose fibres after mercerisation. Fibres Text East Eur. 2003;11:104–7.

    Google Scholar 

  26. Hulleman SHD, Kalisvaart MG, Jansen FHP, Feil H, Vliegenthart JFG. Origins of B-type crystallinity in glycerol-plasticised, compression-molded potato starches. Carbohyd Polym. 1999;39:351–60.

    Article  CAS  Google Scholar 

  27. Tomczak F, Satyanarayana KG, Sydenstricker THD. Studies on lignocellulosic fibers of Brazil: part III—morphology and properties of Brazilian curaua fibers. Compos Part A. 2007;38:2227–36.

    Article  Google Scholar 

  28. Guinesi LS, da Róz AL, Corradini E, Teixeira EM, Curvelo AAS. Kinetics of thermal degradation applied to starches from different botanical origins by non-isothermal procedures. Thermochim Acta. 2006;447:190–6.

    Article  CAS  Google Scholar 

  29. Draye A, Persenaire O, Brozek O, Roda J, Kosek T, Dubois Ph. Thermogravimetric analysis of poly(ε-caprolactam) and poly[(ε-caprolactam)-co-(ε-caprolactone)] polymers. Polymer. 2001;42:8325–32.

    Article  CAS  Google Scholar 

  30. 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.

    Article  CAS  Google Scholar 

  31. Di Franco CR, Cyras VP, Busalmen JP, Ruseckaite RA, Vásquez A. Degradation of polycaprolactone/starch blends and composites with sisal fibre. Polym Degrad Stab. 2004;86:95–103.

    Article  Google Scholar 

  32. Yang H, Yan R, Chen H, Lee DH. Zheng C. Characteristics of hemicellulose, cellulose and lignin pyrolysis fuel. 2007;86:1781–8.

    CAS  Google Scholar 

  33. Martin AR, Alice M, Odilon RRF, Mattoso LHC. Studies on the thermal properties of sisal fiber and its constituents. Thermochim Acta. 2010;506:14–9.

    Article  CAS  Google Scholar 

  34. Ruseckaite R, Jiménez A. Thermal degradation of mixtures of polycaprolactone with cellulose derivatives. Polym Degrad Stab. 2003;81:353–8.

    Article  CAS  Google Scholar 

  35. Avérous L, Le Digabel F. Properties of biocomposites based on lignocellulosic fillers. Carbohyd Polym. 2006;66:480–93.

    Article  Google Scholar 

  36. Shuttleworth PS, Budarin V, Clark JH. Thermal investigation of “molten starch”. J Therm Anal Calorim. 2011;105:577–81.

    Article  CAS  Google Scholar 

  37. Mansaray KG, Ghaly AE. Determination of kinetic parameters of rice husks in oxygen using thermogravimetric analysis. Biomass Bioenerg. 1999;17:19–31.

    Article  CAS  Google Scholar 

  38. Sonobe T, Worasuwannarak N. Kinetic analyses of biomass pyrolysis using the distributed activation energy model. Fuel. 2008;87:414–21.

    Article  CAS  Google Scholar 

  39. Borysiak S. Supermolecular structure of wood/polypropylene composites: I. The influence of processing parameters and chemical treatment of the filler. Polym Bull. 2009;64:275–90.

    Article  Google Scholar 

  40. He Y, Inoue Y. Novel FTIR method for determining the crystallinity of poly (3-caprolactone). Polym Int. 2000;49:623–6.

    Article  CAS  Google Scholar 

  41. Siqueira G, Bras J, Dufresne A. Cellulose whiskers versus microfibrils: influence of the nature of the nanoparticle and its surface functionalization on the thermal and mechanical properties of nanocomposites. Biomacromolecules 2009;10:425–32.

    Article  CAS  Google Scholar 

  42. Borysiak S. Influence of wood mercerization on the crystallization of polypropylene in wood/PP composites. J Therm Anal Calorim. 2012;109:595–603.

    Article  CAS  Google Scholar 

  43. Di Y, Iannace S, Maio ED, Nicolais L. Nanocomposites by melt intercalation based on polycaprolactone and organoclay. J Polym Sci. 2003;41:670–8.

    Article  CAS  Google Scholar 

  44. Chen E, Wu T. Isothermal crystallization kinetics and thermal behavior of poly(3-caprolactone)/multi-walled carbon nanotube composites. Polym Degrad Stab. 2007;92:1009–15.

    Article  CAS  Google Scholar 

  45. Ahmed J, Auras R, Kijchavengkul T, Varshney SK. Rheological, thermal and structural behavior of poly(ε-caprolactone) and nanoclay blended films. J Food Eng. 2012;111:580–9.

    Article  CAS  Google Scholar 

  46. Campos A, Tonoli GHD, Marconcini JM, Mattoso LHC, Klamczynski A, Gregorski KS, Wood D, Williams T, Chiou B-S, Imam SH. TPS/PCL composite reinforced with treated sisal fibers: property, biodegradation and water-absorption. J Polym Environ. 2012; doi:10.1007/s10924-012-0512-8.

    Google Scholar 

  47. Cheng HKF, Sahoo NG, Lu X, Li L. Thermal kinetics of montmorillonite nanoclay/maleic anhydride-modified polypropylene nanocomposites. J Therm Anal Calorim. 2012;109:17–25.

    Article  CAS  Google Scholar 

  48. Shanks RA, Gunaratne LMWK. Gelatinization and retrogradation of thermoplastic starch characterized using modulated temperature differential scanning calorimetry. J Therm Anal Calorim. 2011;106:93–9.

    Article  CAS  Google Scholar 

  49. Magalhaes NF, Andrade CT. Thermoplastic corn starch/clay hybrids: effect of clay type and content on physical properties. Carbohydr Polym. 2009;75:712–8.

    Article  CAS  Google Scholar 

  50. Xing Z, Yang G. Crystallization, melting behavior, and wettability of poly(ε-caprolactone) and poly(ε-caprolactone)/poly(N-vinylpyrrolidone) blends. J Appl Polym Sci. 2010;115:2747–55.

    Article  CAS  Google Scholar 

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Acknowledgments

The authors are grateful for the financial support of the projects granted by FAPESP (2008/08264-9), Capes, CNPq, FINEP, and Embrapa.

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Authors and Affiliations

  1. Materials Science and Engineering Department (PPG-CEM), Federal University of São Carlos, São Carlos, SP, 13565-905, Brazil

    Vitor Brait Carmona

  2. National Nanotechnology Laboratory for Agriculture (LNNA), Embrapa Instrumentation, São Carlos, SP, 13560-970, Brazil

    Vitor Brait Carmona, Adriana de Campos, José Manoel Marconcini & Luiz Henrique Capparelli Mattoso

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  1. Vitor Brait Carmona
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  2. Adriana de Campos
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  3. José Manoel Marconcini
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  4. Luiz Henrique Capparelli Mattoso
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Correspondence to José Manoel Marconcini.

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Carmona, V.B., de Campos, A., Marconcini, J.M. et al. Kinetics of thermal degradation applied to biocomposites with TPS, PCL and sisal fibers by non-isothermal procedures. J Therm Anal Calorim 115, 153–160 (2014). https://doi.org/10.1007/s10973-013-3259-0

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  • DOI: https://doi.org/10.1007/s10973-013-3259-0

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