Effects of cooling process on the solid–liquid phase separation process in ultra-high-molecular-weight polyethylene/liquid paraffin blends

  • Lei Sheng
  • Yanqiu Du
  • Hui Zhang
  • Zhihui Chen
  • Junjie Pan
  • Tao Wang
  • Xianli Huang
  • Jianping HeEmail author
Original Paper


Ultra-high-molecular-weight polyethylene (UHMWPE) microporous membrane is generally prepared by thermally induced phase separation process. The phase separation process is closely related to the cooling process in practical production. In this paper, the phase separation temperature of UHMWPE/liquid paraffin blends was explored by the hot-stage-optical device and differential scanning calorimeter (DSC), and the result showed that the temperature was about 105–125 °C. The effects of cooling condition and crystallization ability of UHMWPE on the separation process of the blends were also investigated by DSC. The results showed that the phase separation was affected by the cooling rates rather than the initial cooling temperature. And the crystallization of UHMWPE was mainly limited by the nucleating at a low cooling rate, which could form larger porous structure. In a word, it should be inspirational for the actual production of the UHMWPE microporous membrane.

Graphical abstract

The solid–liquid phase separation will occur in the cooling process of UHMWPE/LP blends, which is driven by the external temperature difference. It is significant to understand the phase separation process. In this paper, the effects of the melting properties and cooling condition on phase separation process were investigated, the S–L phase separation range is at 105–125 °C, and the speed of phase separation is mainly related to the external temperature difference and the UHMWPE content. It could be inspirational for actual production of the UHMWPE membrane with more uniform pore structure.


Keywords Cooling process Phase separation process Porous structure 



This author was grateful for the financial support from the National Natural Science Foundation of China (11575084 and 51602153), the Natural Science Foundation of Jiangsu Province (BK20160795) and A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).


  1. 1.
    Jeong G, Kim YU, Kim H, Kim YJ, Sohn HJ (2011) Prospective materials and applications for Li secondary batteries. Energy Environ Sci 4:1986–2002CrossRefGoogle Scholar
  2. 2.
    Li H, Wang Z, Chen L, Huang X (2010) Research on advanced materials for Li+ ion batteries. Adv Mater 21:4593–4607CrossRefGoogle Scholar
  3. 3.
    Palacín MR (2009) Recent advances in rechargeable battery materials: a chemist’s perspective. Chem Soc Rev 38:2565–2575CrossRefGoogle Scholar
  4. 4.
    Arora P, Zhang ZJ (2004) Battery separators. Chem Rev 35:4419–4462CrossRefGoogle Scholar
  5. 5.
    Huang XS (2011) Separator technologies for lithium-ion batteries. J Solid State Electrochem 15:649–662CrossRefGoogle Scholar
  6. 6.
    Huang X, Hitt J (2013) Lithium ion battery separators: development and performance characterization of a composite membrane. J Membr Sci 425–426:163–168CrossRefGoogle Scholar
  7. 7.
    Hofmann A, Kaufmann C, Müller M, Hanemann T (2015) Interaction of high flash point electrolytes and pe-based separators for li-ion batteries. Int J Mol Sci 16:20258–20276CrossRefGoogle Scholar
  8. 8.
    Yan S, Xiao X, Huang X, Li X, Qi Y (2014) Unveiling the environment-dependent mechanical properties of porous polypropylene separators. Polymer 55:6282–6292CrossRefGoogle Scholar
  9. 9.
    Bierenbaum HS (1974) Microporous polymeric films. Ind. Eng. Chem. Res. Dev. 13:2–9CrossRefGoogle Scholar
  10. 10.
    Castro AJ (1981) Methods for making microporous products. Patent US4247498Google Scholar
  11. 11.
    Lloyd DR, Kim SS, Kinzer KE (1988) Microporous membrane formation via thermally-induced phase separation. ii. liquid—liquid phase separation. J Membr Sci 64:239–261Google Scholar
  12. 12.
    Kim SS, Lloyd DR (1992) Thermodynamics of polymer/diluent systems for thermally induced phase separation: 2. solid-liquid phase separation systems. Polymer 33:1036–1046CrossRefGoogle Scholar
  13. 13.
    Gu M, Zhang J, Wang X, Ma W (2006) Crystallization behavior of PVDF in PVDF-DMP system via thermally induced phase separation. J Appl Polym Sci 102:3714–3719CrossRefGoogle Scholar
  14. 14.
    Matsuyama H, Okafuji H, Maki T, Teramoto M, Tsujioka N (2010) Membrane formation via thermally induced phase separation in polypropylene/polybutene/diluent system. J Appl Polym Sci 84:1701–1708CrossRefGoogle Scholar
  15. 15.
    Zhou B, Tang Y, Li Q, Lin Y, Yu M, Xiong Y (2015) Preparation of polypropylene microfiltration membranes via thermally induced (solid–liquid or liquid–liquid) phase separation method. J Appl Polym, Sci, p 132Google Scholar
  16. 16.
    Yang Z, Li P, Xie L, Wang Z, Wang SC (2006) Preparation of iPP hollow-fiber microporous membranes via thermally induced phase separation with co-solvents of DBP and DOP. Desalination 192:168–181CrossRefGoogle Scholar
  17. 17.
    Liu M, Liu S, Xu Z, Wei Y, Yang H (2016) Formation of microporous polymeric membranes via thermally induced phase separation: a review. Front Chem Sci Eng 10:57–75CrossRefGoogle Scholar
  18. 18.
    Kim SS, Lloyd DR (1991) Microporous membrane formation via thermally-induced phase separation. iii. effect of thermodynamic interactions on the structure of isotactic polypropylene membranes. J Membr Sci 64:13–29CrossRefGoogle Scholar
  19. 19.
    Laxminarayan A, Mcguire KS, Kim SS, Lloyd DR (1994) Effect of initial composition, phase separation temperature and polymer crystallization on the formation of microcellular structures via thermally induced phase separation. Polymer 35:3060–3068CrossRefGoogle Scholar
  20. 20.
    Matsuyama H, Yuasa M, Kitamura Y, Teramoto M, Lloyd DR (2000) Structure control of anisotropic and asymmetric polypropylene membrane prepared by thermally induced phase separation. J Membr Sci 179:91–100CrossRefGoogle Scholar
  21. 21.
    Kim SS, Lim G, Alwattari AA, Wang YF, Lloyd DR (1991) Microporous membrane formation via thermally-induced phase separation. v. effect of diluent mobility and crystallization on the structure of isotactic polypropylene membranes. J Membr Sci 64:41–53CrossRefGoogle Scholar
  22. 22.
    Matsuyama H, Okafuji H, Maki T, Teramoto M, Kubota N (2003) Preparation of polyethylene hollow fiber membrane via thermally induced phase separation. J Membr Sci 223:119–126CrossRefGoogle Scholar
  23. 23.
    Cui AH, Liu Z, Xiao CF, Zhang YF (2010) Effect of micro-sized SiO2 -particle on the performance of PVDF blend membranes via TIPS. J Membr Sci 360:259–264CrossRefGoogle Scholar
  24. 24.
    Jeon MY, Kim CK (2007) Phase behavior of polymer/diluent/diluent mixtures and their application to control microporous membrane structure. J Membr Sci 300:172–181CrossRefGoogle Scholar
  25. 25.
    Mo G, Zhang R, Wang Y, Yan Q (2016) Rheological and optical investigation of the gelation with and without phase separation in PAN/DMSO/H2O ternary blends. Polymer 84:243–253CrossRefGoogle Scholar
  26. 26.
    Mcguire KS, Laxminarayan A, Martula DS, Lloyd DR (1996) Kinetics of droplet growth in liquid–liquid phase separation of polymer–diluent systems: model development. J Colloid Interface Sci 182:46–58CrossRefGoogle Scholar
  27. 27.
    Hanks PL, Lloyd DR (2007) Deterministic model for matrix solidification in liquid–liquid thermally induced phase separation. J Membr Sci 306:125–133CrossRefGoogle Scholar
  28. 28.
    Hu W, Frenkel D, Mathot VBF (2003) Lattice-model study of the thermodynamic interplay of polymer crystallization and liquid–liquid demixing. J Chem Phys 118:10343–10348CrossRefGoogle Scholar
  29. 29.
    Li D, Krantz WB, Greenberg AR, Sani RL (2006) Membrane formation via thermally induced phase separation (TIPS): model development and validation. J Membr Sci 279:50–60CrossRefGoogle Scholar
  30. 30.
    Stephens CP, Benson RS, Martinez-Pardo ME, Barker ED, Walker JB, Stephens TP (2005) The effect of dose rate on the crystalline lamellar thickness distribution in gamma-radiation of UHMWPE. Nucl Instrum Methods Phys Res 236:540–545CrossRefGoogle Scholar
  31. 31.
    Park JH, Rutledge GC (2018) Ultrafine high performance polyethylene fibers. J Mater Sci 53:3049–3063CrossRefGoogle Scholar
  32. 32.
    Jiang H, Dou N, Fan G, Yang Z, Zhang X (2013) Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend. J Chem Phys 139:357Google Scholar
  33. 33.
    Jiang H, Dou N, Fan G, Zhang X, Yang Z (2014) Orientational phase-separated domains in a polyolefin blend under a temperature gradient field. Polymer 55:2271–2278CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  1. 1.College of Material Science and TechnologyNanjing University of Aeronautics and AstronauticsNanjingPeople’s Republic of China

Personalised recommendations