Advertisement

Journal of Materials Science

, Volume 54, Issue 5, pp 3863–3877 | Cite as

Transition from microcellular to nanocellular chain extended poly(lactic acid)/hydroxyl-functionalized graphene foams by supercritical CO2

  • Xianzeng Wang
  • Jianguo Mi
  • Hongfu Zhou
  • Xiangdong Wang
Composites
  • 74 Downloads

Abstract

Currently, preparing nanocellular semi-crystalline polymer foams by supercritical CO2 is a big and newly developing challenge. In this paper, chain extender (CE) and hydroxyl-functionalized graphene (HG) were introduced into poly(lactic acid) (PLA) through melt blending method to improve the crystallization behaviors, rheological properties and foaming behaviors of PLA. Differential scanning calorimetry results showed that the cold crystallization temperature of chain extended PLA (CPLA)/HG was higher 8.2 °C than that of CPLA, due to the introduction of HG and the strong interaction between CPLA and HG. The viscoelasticity of PLA was improved by the addition of CE and HG, due to the formation of branching structure and the interaction between CPLA and HG. Compared with that in PLA/HG, HG aggregation in CPLA/HG became many but small, indicating that the aggregation of HG in the matrix released. A facile batch foaming method with constant foaming temperature slightly lower than melting temperature was employed to fabricate nanocellular PLA foams in the presence of supercritical CO2. The transition temperature from microcells to nanocells in various PLA foams was confirmed. The effect of chain extension, foaming temperature and the introduction of HG on cell size, cell density, cell size distribution and volume expansion ratio (VER) was studied systematically. For the CPLA/HG foam prepared at 130 °C, its cell size could reach 350 ± 247 nm as well as its cell density and VER were 1.76 × 1013 cells/cm3 and 3.71 ± 0.16 times, respectively. Finally, the foaming mechanism for the nanocell formation was proposed and explained by schematic diagram.

Notes

Funding

This study was funded by the National Natural Science Foundation of China (51673004 and 51703004), the Natural Science Foundation of Beijing Municipality (2162012) and Top Young Innovative Talents Program of Beijing Municipal University (CIT&TCD201704041).

Compliance with ethical standards

Conflict of interest

The authors declare that they have no competing interests.

References

  1. 1.
    Okolieocha C, Raps D, Subramaniam K, Altstadt V (2015) Microcellular to nanocellular polymer foams: progress (2004–2015) and future directions—a review. Eur Polym J 73:500–519CrossRefGoogle Scholar
  2. 2.
    Muanchan P, Ito H (2018) Nanocellular foams confined within PS microfibers obtained by CO2 batch foaming process. Microsyst Technol 24:655–662CrossRefGoogle Scholar
  3. 3.
    Nofar M, Park CB (2014) Poly(lactic acid) foaming. Prog Polym Sci 39:1721–1741CrossRefGoogle Scholar
  4. 4.
    Yeh SK, Chen YR, Kang TW et al (2018) Different approaches for creating nanocellular TPU foams by supercritical CO2 foaming. J Polym Res 25:30CrossRefGoogle Scholar
  5. 5.
    Leon MD, Bernardo V, Rodriguez-Perez MA (2017) Key production parameters to obtain transparent nanocellular PMMA. Macromol Mater Eng 302:1700343CrossRefGoogle Scholar
  6. 6.
    Luo Y, Ye C (2012) Using nanocapsules as building blocks to fabricate organic polymer nanofoam with ultra low thermal conductivity and high mechanical strength. Polymer 53:5699–5705CrossRefGoogle Scholar
  7. 7.
    Forest C, Chaumont P, Cassagnau P, Swoboda B, Sonntag P (2015) Polymer nano-foams for insulating applications prepared from CO2 foaming. Prog Polym Sci 41:122–145CrossRefGoogle Scholar
  8. 8.
    Ling J, Zhai W, Feng W, Shen B, Zhang J, Zheng WG (2013) A facile preparation of lightweight microcellular polyetherimide/graphene composites foams for electromagnetic interference (EMI) shielding. Acs Appl Mater Interfaces 5:2677–2684CrossRefGoogle Scholar
  9. 9.
    Gaspard S, Oujja M, Nalda RD, Castillejo M, Banares L, Lazare S, Bonneau R (2008) Nanofoaming dynamics in biopolymers by femtosecond laser irradiation. Appl Phys A 93:209–213CrossRefGoogle Scholar
  10. 10.
    Reignier J, Huneault MA (2006) Preparation of interconnected poly(3-caprolactone) porous scaffolds by a combination of polymer and salt particulate leaching. Polymer 47:4703–4717CrossRefGoogle Scholar
  11. 11.
    Hong SM, Hwang SS (2006) A nanofoaming process and dielectric properties of polymethylphenylsilsesquioxane-based nanofoams. J Appl Polym Sci 100:4964–4971CrossRefGoogle Scholar
  12. 12.
    Costeux S (2014) CO2-blown nanocellular foams. J Appl Polym Sci 41293:1–16Google Scholar
  13. 13.
    Costeux S, Zhu L (2013) Low density thermoplastic nanofoams nucleated by nanoparticles. Polymer 54:2785–2795CrossRefGoogle Scholar
  14. 14.
    Guo H, Kumar V (2015) Some thermodynamic and kinetic low-temperature properties of the PC-CO2 system and morphological characteristics of solid-state PC nanofoams produced with liquid CO2. Polymer 56:46–56CrossRefGoogle Scholar
  15. 15.
    Tiwary P, Park CB, Kontopoulou M (2017) Transition from microcellular to nanocellular PLA foams by controlling viscosity, branching and crystallization. Eur Polym J 91:283–296CrossRefGoogle Scholar
  16. 16.
    Yi XJO, Lai YL, Davoodi P, Wang CH (2018) Production of drug-releasing biodegradable microporous scaffold using a two-step micro-encapsulation/supercritical foaming process. J Supercrit Fluid 133:263–269CrossRefGoogle Scholar
  17. 17.
    Lee ST (2004) Thermoplastic foam processing: Principles and development. CRC Press, Boca RatonGoogle Scholar
  18. 18.
    Zhao H, Cui Z, Wang X, Turng LS, Peng X (2013) Processing and characterization of solid and microcellular poly(lactic acid)/polyhydroxybutyrate-valerate (PLA/PHBV) blends and PLA/PHBV/Clay nanocomposites. Compos Part B Eng 51:79–91CrossRefGoogle Scholar
  19. 19.
    Wang X, Liu W, Zhou H, Liu B, Li H, Du Z, Zhang C (2013) Study on the effect of dispersion phase morphology on porous structure of poly(lactic acid)/poly(ethylene terephthalate glycol-modified) blending foams. Polymer 54:5839–5851CrossRefGoogle Scholar
  20. 20.
    Lu X, Tang L, Wang L, Zhao J, Li D, Wu Z, Xiao P (2016) Morphology and properties of bio-based poly(lactic acid)/high-density polyethylene blends and their glass fiber reinforced composites. Polym Test 54:90–97CrossRefGoogle Scholar
  21. 21.
    Wang Z, Ding X, Zhao M, Wang X, Xu G, Xiang A, Zhou H (2017) A cooling and two-step depressurization foaming approach for the preparation of modified HDPE foam with complex cellular structure. J Supercrit Fluid 125:22–30CrossRefGoogle Scholar
  22. 22.
    Mihai M, Huneault MA, Favis BD, Li H (2007) Extrusion foaming of semi-crystalline PLA and PLA/thermoplastic starch blends. Macromol Biosci 7:907–920CrossRefGoogle Scholar
  23. 23.
    Chen P, Zhou H, Liu W, Zhang M, Du Z, Wang X (2015) The synergistic effect of zinc oxide and phenylphosphonic acid zinc salt on the crystallization behavior of poly(lactic acid). Polym Degrad Stab 122:25–35CrossRefGoogle Scholar
  24. 24.
    Liu W, Chen P, Wang X, Wang F, Wu Y (2017) Effects of poly(butyleneadipate-co-terephthalate) as a macromolecular nucleating agent on the crystallization and foaming behavior of biodegradable poly(lactic acid). Cell Polym 36:75–96CrossRefGoogle Scholar
  25. 25.
    Nerkar M, Ramsay JA, Ramsay BA, Kontopoulou M (2015) Dramatic improvements in strain hardening and crystallization kinetics of PLA by simple reactive modification in the melt state. Macromol Mater Eng 299:1419–1424CrossRefGoogle Scholar
  26. 26.
    Bouakaz BS, Habi A, Grohens Y, Pillin I (2017) Organomontmorillonite/graphene-PLA/PCL nanofilled blends: new strategy to enhance the functional properties of PLA/PCL blend. Appl Clay Sci 139:81–91CrossRefGoogle Scholar
  27. 27.
    Zhao JC, Du FP, Zhou XP et al (2011) Thermal conductive and electrical properties of polyurethane/hyperbranched poly(urea-urethane)-grafted multi-walled carbon nanotube composites. Compos Part B Eng 42:2111–2116CrossRefGoogle Scholar
  28. 28.
    Zhou H, Wang X, Du Z, Li H, Yu K (2015) Preparation and characterization of chain extended poly(butylene succinate) foams. Polym Eng Sci 55:988–994CrossRefGoogle Scholar
  29. 29.
    Wang X, Zhang Y, Liu B, Du Z, Li H (2008) Crystallization behavior and crystal morphology of linear/long chain branching polypropylene blends. Polym J 40:450–454CrossRefGoogle Scholar
  30. 30.
    Sullivan EM, Yun JO, Gerhardt RA, Wang B, Kalaitzidou K (2014) Understanding the effect of polymer crystallinity on the electrical conductivity of exfoliated graphite nanoplatelet/polylactic acid composite films. J Polym Res 21:563CrossRefGoogle Scholar
  31. 31.
    Qi F, Tang M, Chen X, Chen M, Guo G, Zhang Z (2015) Morphological structure, thermal and mechanical properties of tough poly(lactic acid) upon stereocomplexes. Eur Polym J 71:314–324CrossRefGoogle Scholar
  32. 32.
    Pantani R, Santis FD, Sorrentino A, Maio FD, Titomanlio G (2010) Crystallization kinetics of virgin and processed poly(lactic acid). Polym Degrad Stabil 95:1148–1159CrossRefGoogle Scholar
  33. 33.
    Zhao M, Ding X, Mi J, Zhou H, Wang X (2017) Role of high-density polyethylene in the crystallization behaviors, rheological property, and supercritical CO2 foaming of poly(lactic acid). Polym Degrad Stab 146:277–286CrossRefGoogle Scholar
  34. 34.
    Kuang TR, Mi HY, Fu DJ, Jing X, Chen BY, Mou WJ, Peng XF (2015) Fabrication of poly(lactic acid)/graphene oxide foams with highly oriented and elongated cell structure via unidirectional foaming using supercritical carbon dioxide. Ind Eng Chem Res 54:758–768CrossRefGoogle Scholar
  35. 35.
    Wang X, Zhou H, Liu B, Du Z, Li H (2015) Chain extension and foaming behavior of poly(lactic acid) by functionalized multiwalled carbon nanotubes and chain extender. Adv Polym Technol 33:21444Google Scholar
  36. 36.
    Chen L, Rende D, Schadler LS, Ozisik R (2013) Polymer nanocomposite foams. J Mater Chem A 1:3837–3850CrossRefGoogle Scholar
  37. 37.
    Mihai M, Huneault MA, Favis BD (2010) Rheology and extrusion foaming of chain-branched poly(lactic acid). Polym Eng Sci 50:629–642CrossRefGoogle Scholar
  38. 38.
    Kolodka E, Wang W, Zhu S, Hamielec AE (2004) Rheological and thermomechanical properties of long-chain-branched polyethylene prepared by slurry polymerization with metallocene catalysts. J Appl Polym Sci 92:307–316CrossRefGoogle Scholar
  39. 39.
    Rajagopalan G, Immordino KM Jr, Gillespie JW, Mcknight SH (2000) Diffusion and reaction of epoxy and amine in polysulfone studied using fourier transform infrared spectroscopy: experimental results. Polymer 41:2591–2602CrossRefGoogle Scholar
  40. 40.
    Liu C, Ye S, Feng J (2017) Promoting the dispersion of graphene and crystallization of poly(lactic acid) with a freezing-dried graphene/PEG masterbatch. Compos Sci Technol 144:215–222CrossRefGoogle Scholar
  41. 41.
    Li K, Cui Z, Sun X, Turng LS, Huang H (2011) Effects of nanoclay on the morphology and physical properties of solid and microcellular injection molded polyactide/poly(butylenes adipate-co-terephthalate) (PLA/PBAT) nanocomposites and blends. J Biobased Mater Bioenergy 5:442–451CrossRefGoogle Scholar
  42. 42.
    Najafi N, Heuzey MC, Carreau PJ, Therriault D, Park CB (2014) Rheological and foaming behavior of linear and branched polylactides. Rheol Acta 53:779–790CrossRefGoogle Scholar
  43. 43.
    Zhang Y, Tiwary P, Parent JS, Kontopoulou M, Park CB (2013) Crystallization and foaming of coagent-modified polypropylene: nucleation effects of cross-linked nanoparticles. Polymer 54:4814–4819CrossRefGoogle Scholar
  44. 44.
    Nofar M, Guo Y, Park CB (2013) Double crystal melting peak generation for expanded polypropylene bead foam manufacturing. Ind Eng Chem Res 52:2297–2303CrossRefGoogle Scholar
  45. 45.
    Nofar M, Zhu W, Park CB (2012) Effect of dissolved CO2 on the crystallization behavior of linear and branched PLA. Polymer 53:3341–3353CrossRefGoogle Scholar
  46. 46.
    Liu H, Wang X, Zhou H, Liu W, Liu B (2015) The Preparation and characterization of branching poly(ethylene terephthalate) and its foaming behavior. Cell Polym 34:63–94CrossRefGoogle Scholar
  47. 47.
    Colton JS, Suh NP (1987) Nucleation of microcellular foam: theory and practice. Polym Eng Sci 27:500–503CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.School of Materials and Mechanical EngineeringBeijing Technology and Business UniversityBeijingPeople’s Republic of China
  2. 2.Beijing Key Laboratory of Quality Evaluation Technology for Hygiene and Safety of PlasticsBeijingPeople’s Republic of China
  3. 3.State Key Laboratory of Organic-Inorganic CompositesBeijing University of Chemical TechnologyBeijingPeople’s Republic of China

Personalised recommendations