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Isothermal crystallization kinetics and melting behavior of poly(l-lactic acid)/WS2 inorganic nanotube nanocomposites

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Abstract

Environmentally friendly and biocompatible tungsten disulphide inorganic nanotubes (INT-WS2) were introduced into a poly(l-lactic acid) biopolymer matrix to generate novel nanocomposite materials through an advantageous melt-processing route. The effects of INT-WS2 on isothermal crystallization and melting behaviour of PLLA have been investigated. INT-WS2 has excellent acceleration effectiveness on the melt-crystallization of PLLA better than the promising nano-sized fillers reported in the literature (e.g. carbon nanotubes, graphene oxide, cellulose nanocrystals). In particular, the addition of INT-WS2 remarkably influences the energetics and kinetics of nucleation and growth of PLLA, reducing the fold surface free energy by up to 18 %. In the same way, the final crystallinity and subsequent melting behaviour of PLLA were controlled by both the incorporation INT-WS2 and variation of the crystallization temperature. These observations will enable the development of novel melt-processable PLLA/INT-WS2 nanocomposites with improved crystallization behaviour for many eco-friendly and biomedical applications.

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References

  1. Sodergard A, Stolt M (2002) Properties of lactic acid based polymers and their correlation with composition. Prog Polym Sci 27:1123–1163

    Article  Google Scholar 

  2. Rasal RM, Janrkor AV, Hirt DE (2010) Poly(lactic acid) modifications. Prog Polym Sci 35:338–356

    Article  Google Scholar 

  3. Lim LT, Auras R, Rubino M (2008) Processing technologies for poly(lactic acid). Prog Polym Sci 33:820–882

    Article  Google Scholar 

  4. Tian H, Tang Z, Zhuang X, Chen X, Jing Z (2012) Biodegradable synthetic polymers: preparation, functionalization and biomedical application. Prog Polym Sci 37:237–280

    Article  Google Scholar 

  5. Saeidou S, Huneault MA, Li H, Park CB (2012) Poly(lactic acid) crystallization. Prog Polym Sci 37:1657–1677

    Article  Google Scholar 

  6. Kulinski Z, Piorkowska E (2005) Crystallization, structure and properties of plasticized poly(l-lactide). Polymer 46:10290–10300

    Article  Google Scholar 

  7. Lemmouchi Y, Murariu M, Santos AMD, Amass AJ, Schacht E, Dubois P (2009) Plasticization of poly(lactide) with blends of tributyl citrate and low molecular weight poly(d, l-lactide)-b-poly(ethylene glycol) copolymers. Eur Polym J 45:2839–2848

    Article  Google Scholar 

  8. Libster D, Aserin A, Garti N (2007) Advanced nucleating agents for polypropylene. Polym Adv Technol 18:685–695

    Article  Google Scholar 

  9. Pan P, Liang Z, Cao A, Inoue Y (2009) Layered metal phosphonate reinforced poly(l-lactide) composites with a highly enhanced crystallization rate. ACS Appl Mater Interfaces 1:402–411

    Article  Google Scholar 

  10. Liang W, Zhong X (2010) Effect of a novel nucleating agent on isothermal crystallization of poly(l-lactic acid). Chin J Chem Eng 18:899–904

    Article  Google Scholar 

  11. Harris AM, Lee EC (2008) Improving mechanical performance of injection molded PLA by controlling crystallinity. J Appl Polym Sci 107:2246–2255

    Article  Google Scholar 

  12. Pan P, Yang J, Shan G, Bao Y, Weng Z, Inoue Y (2012) Nucleation effects of nucleobases on the crystallization kinetics of poly(l-lactide). Macromol Mater Eng 297:670–679

    Article  Google Scholar 

  13. 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 121:1408–1416

    Article  Google Scholar 

  14. Pei A, Zhou Q, Berglund LA (2010) Functionalized cellulose nanocrystals as biobased nucleation agents in poly(l-lactide) (PLLA)–crystallization and mechanical effects. Comp Sci Technol 70:815–821

    Article  Google Scholar 

  15. Li Y, Chen C, Li J, Sun XS (2012) Isothermal crystallization and melting behaviors of bionanocomposites from poly(lactic acid) and TiO2 nanowires. J Appl Polym Sci 124:2968–2977

    Article  Google Scholar 

  16. Pan H, Qiu Z (2010) Biodegradable poly(l-lactide)/polyhedral oligomeric silsesquioxanes nanocomposites: enhanced crystallization, mechanical properties, and hydrolytic degradation. Macromolecules 43:1499–1506

    Article  Google Scholar 

  17. Yu J, Qiu Z (2011) Effect of low octavinyl-polyhedral oligomeric silsesquioxanes loadings on the melt crystallization and morphology of biodegradable poly(l-lactide). Thermochim Acta 519:90–95

    Article  Google Scholar 

  18. Ublekov F, Baldrian J, Kratochvil J, Steinhart M, Nedkov E (2012) Influence of clay content on the melting behavior and crystal structure of nonisothermal crystallized poly(l-lactic acid)/nanocomposites. J Appl Polym Sci 124:1643–1648

    Article  Google Scholar 

  19. Shieh YT, Twu YK, Su CC, Lin RH, Liu GL (2010) Crystallization kinetics study of poly(l-lactic acid)/carbon nanotubes nanocomposites. J Polym Sci, Part B: Polym Phys 48:983–989

    Article  Google Scholar 

  20. Han L, Han C, Bian J, Bian Y, Lin H, Wang X, Zhang H, Dong L (2012) Preparation and characteristics of a novel nano-sized calcium carbonate (nano-CaCo3)-supported nucleating agent of poly(l-lactide). Polym Eng Sci 52:1474–1484

    Article  Google Scholar 

  21. Song P, Chen G, Wei Z, Chang Y, Zhang W, Liang J (2012) Rapid crystallization of poly(l-lactic acid) induced by a nanoscaled zinc citrate complex as nucleating agent. Polymer 53:4300–4309

    Article  Google Scholar 

  22. Wang H, Qiu Z (2012) Crystallization kinetics and morphology of biodegradable poly(l-lactic acid)/graphene oxide nanocomposites: influences of graphene oxide loading and crystallization temperature. Thermochim Acta 527:40–46

    Article  Google Scholar 

  23. Tsuji H, Kawashima Y, Takikawa H, Tanaka S (2007) Poly(l-lactide)/nano-structured carbon composites: conductivity, thermal properties, crystallization, and biodegradation. Polymer 48:4213–4225

    Article  Google Scholar 

  24. Naffakh M, Díez-Pascual AM, Marco C, Ellis G, Gómez-Fatou MA (2013) Opportunities and challenges in the use of inorganic fullerene-like nanoparticles to produce advanced polymer nanocomposites. Prog Polym Sci 38:1163–1231

    Article  Google Scholar 

  25. Tenne R, Margulis L, Genut M, Hodes G (1992) Polyhedral and cylindrical structures of tungsten disulphide. Nature 360:444–445

    Article  Google Scholar 

  26. Margulis L, Salitra G, Tenne R, Talianker M (1993) Nested fullerene-like structures. Nature 365:113–114

    Article  Google Scholar 

  27. Zak A, Sallacan Ecker L, Fleischer N, Tenne R (2011) Large-scale synthesis of WS2 multiwall nanotubes and their dispersion, an update. Sens Transducers J 12:1–10

    Google Scholar 

  28. Pardo M, Shuster-Meiseles T, Levin-Zaidman S, Rudich A, Rudich Y (2014) Low cytotoxicity of inorganic nanotubes and fullerene-like nanostructures in human bronchial epithelial cells: relation to inflammatory gene induction and antioxidant response. Environ Sci Technol 48:3457–3466

    Article  Google Scholar 

  29. Goldman EB, Zak A, Tenne R, Kartvelishvily E, Levin-Zaidman S, Neumann Y, Stiubea-Cohen R, Palmon A, Hovav AH, Aframian DJ (2015) Tissue Eng Part A 21:1013–1023

    Article  Google Scholar 

  30. Naffakh M, Marco C, Ellis G (2013) Development of novel melt-processable biopolymer nanocomposites based on poly(l-lactic acid) and WS2 inorganic nanotubes. Cryst Eng Comm 16:5062–5072

    Article  Google Scholar 

  31. Fischer EW, Sterzel HJ, Wegner G (1973) Investigation of the structure of solution grown crystals of lactide copolymers by means of chemical reactions. Kolloid. Z Z Polym 251:980–990

    Article  Google Scholar 

  32. Hay JN (1971) Application of the modified Avrami equations to polymer crystallisation kinetics. Br Polym J 3:74–82

    Article  Google Scholar 

  33. Yasuniwa MS, Tsubakihara Y, Sugimoto Y, Nakafuku C (2004) Thermal analysis of the double-melting behavior of poly(l-lactic acid). J Polym Sci Part B 42:25–32

    Article  Google Scholar 

  34. He Y, Fan Z, Hu Y, Wu T, Wei J, Li S (2007) DSC analysis of isothermal melt-crystallization, glass transition and melting behavior of poly(l-lactide) with different molecular weights. Eur Polym J 43:4431–4439

    Article  Google Scholar 

  35. Pan PJ, Kai WH, Zhu B, Dong T, Inoue Y (2007) Polymorphous crystallization and multiple melting behavior of poly(l-lactide): molecular weight dependence. Macromolecules 40:6898–6905

    Article  Google Scholar 

  36. Pan PJ, Kai WH, Zhu B, Dong T, Inoue Y (2008) Polymorphic transition in disordered poly(l-lactide) crystals induced by annealing at elevated temperatures. Macromolecules 41:4296–4304

    Article  Google Scholar 

  37. Song P, Chen G, Wei Z, Zhang W, Liang J (2013) Calorimetric analysis of the multiple melting behavior of melt-crystallized poly(l-lactic acid) with a low optical purity. J Therm Anal Calorim 111:1507–1514

    Article  Google Scholar 

  38. Hoffman JD, Weeks JJ (1962) Melting process and the equilibrium melting temperature of polychlorotrifluoroethylene. J Res Natl Bur Stand A66:13–28

    Article  Google Scholar 

  39. Lauritzen JL, Hoffman JD (1973) Extension of theory of growth of chain-folded polymer crystals to large undercoolings. J Appl Phys 44:4340–4352

    Article  Google Scholar 

  40. Hoffman JD, Davies GT, Lauritzen JJ (1976) In: Hannay NB (ed) Treatise on solid state chemistry, vol 3. Plenum Press, New York

    Google Scholar 

  41. Vasanthakumari R, Pennings AJ (1983) Crystallization kinetics of poly(lactic acid). Polymer 24:175–178

    Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Spanish Ministry Economy and Competitivity (MINECO), Project MAT2013-41021-P. MN would also like to acknowledge the MINECO for a ‘Ramón y Cajal’ Senior Research Fellowship. Very special thanks and appreciation go to Dr. Alla Zak for providing the WS2 inorganic nanotubes that made this research possible.

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Authors and Affiliations

  1. Escuela Técnica Superior de Ingenieros Industriales, Universidad Politécnica de Madrid (ETSII-UPM), José Gutiérrez Abascal 2, 28006, Madrid, Spain

    Mohammed Naffakh

  2. Instituto de Ciencia y Tecnología de Polímeros (ICTP-CSIC), Juan de la Cierva 3, 28006, Madrid, Spain

    Carlos Marco

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  1. Mohammed Naffakh
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  2. Carlos Marco
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Correspondence to Mohammed Naffakh.

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Naffakh, M., Marco, C. Isothermal crystallization kinetics and melting behavior of poly(l-lactic acid)/WS2 inorganic nanotube nanocomposites. J Mater Sci 50, 6066–6074 (2015). https://doi.org/10.1007/s10853-015-9156-0

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  • DOI: https://doi.org/10.1007/s10853-015-9156-0

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