화학공학소재연구정보센터
홈 로그인 로그아웃 연락처 사이트맵
Journal of Industrial and Engineering Chemistry, Vol.107, 444-455, March, 2022
DOI10.1016/j.jiec.2021.12.016  Export Citation
Enhanced morphology and hydrophilicity of PVDF flat membrane with modified CaCO3@SMA additive via thermally induced phase separation method
Zhichao Zhang†, Wei Wang1, †, Xin Xu1, Xi Liu1, Yuanling Li, and Peng Zhang1
  • College of Environmental Science and Engineering, Nankai University, No. 38 Tongyan Road, Jinnan District, Tianjin 300350, PR China
  • 1State Key Laboratory of Separation Membranes and Membrane Processes, School of Materials Science and Engineering, Tiangong University, No. 399 BinShuiXi Road, XiQing District, Tianjin 300387, PR China, Korea
E-mail:,
Modified CaCO3@SMA nanoparticles obtained by coordination reaction between poly(styrene-co-maleic anhydride) (SMA) and calcium carbonate (CaCO3) nanoparticles were adopted as additive to prepare polyvinylidene fluoride (PVDF) flat membrane via thermally induced phase separation (TIPS) method with dioctyl phthalate (DOP) and dibutyl phthalate (DBP) as mixed diluent. The CaCO3 nanoparticles modified by SMA effectively reduced the adverse agglomeration of nanoparticles and made the additive disperse evenly in PVDF matrix. The presence of modified CaCO3@SMA changed the membrane morphology from dispersed spherulites with large pores to fuzzy dendrite structures with uniform pore sizes. The membrane pore sizes, pore size distribution and tensile strength were significantly improved compared to both virgin membranes and those containing unmodified CaCO3 nanoparticles. After the CaCO3 was pickled, the porosity and the connectivity between membrane pores were greatly enhanced, resulting in a significant increase in pure water flux. At the same time, the amphiphilic SMA fixed in and on the membrane surface improved the hydrophilic and anti-fouling properties demonstrated in a three-cycle test. The present study provided a potential TIPS method for the fabrication of PVDF membrane combined with a simple strategy of modified inorganic particle additive.
Keywords:Polyvinylidene fluoride membrane;Thermally induced phase separation;Modified calcium carbonate;Poly (styrene-co-maleic anhydride)
  1. Fan S, Aghajani M, Wang M, Martinez J, Ding Y, J. Membr. Sci., 616(May) (2020)
  2. Drioli E, Stankiewicz AI, Macedonio F, J. Membr. Sci., 380(44563), 1 (2011)
  3. Kim JF, Kim JH, Lee YM, Drioli E, AIChE J., 62(2), 461 (2016)
  4. Kim JF, Jung JT, Wang HH, Lee SY, Moore T, Sanguineti A, Drioli E, Lee YM, J. Membr. Sci., 509, 94 (2016)
  5. Wu Y, Gao R, Gao S, Li M, J. Appl. Polym. Sci., 135(15), 1 (2018)
  6. Cui Z, Hassankiadeh NT, Lee SY, Lee JM, Woo KT, Sanguineti A, Arcella V, Lee YM, Drioli E, J. Membr. Sci., 444, 223 (2013)
  7. Liu F, Hashim NA, Liu Y, Abed MRM, Li K, J. Membr. Sci., 375(44563), 1 (2011)
  8. Wu Z, Cui Z, Li T, Qin S, He B, Han N, Li J, Appl. Surf. Sci., 419, 429 (2017)
  9. Zuo JH, Li ZK, Wei C, Yan X, Chen Y, Lang WZ, J. Membr. Sci., 577(43435), 79 (2019)
  10. Liu F, Tao MM, Xue LX, Desalination, 298, 99 (2012)
  11. Gu M, Zhang J, Wang X, Tao H, Ge L, Desalination, 192(44564), 160 (2006)
  12. Xiang S, Guo Z, Wang Y, Liu H, Zhang J, Cui Z, Wang H, Li J, Eur. Polym. J., 126 (2020)
  13. Zhou Q, Wang Z, Shen H, Zhu Z, Liu L, Yang L, Cheng L, J. Chem. Technol. Biotechnol., 91(6), 1697 (2016)
  14. Ji GL, Zhu LP, Zhu BK, Zhang CF, Xu YY, J. Membr. Sci., 319(44563), 264 (2008)
  15. Hashim NA, Liu Y, Li K, Ind. Eng. Chem. Res., 50(5), 3035 (2011)
  16. Doi IY, Moriyama; Haruo Matsumura. U.S. Pat. 5022990, Jun 11,1991 (n.d.)
  17. Pan B, Zhu L, Li X, Polym. Compos., 34(7), 1204 (2013)
  18. Zhuravlev LT, Colloids Surf. A: Physicochem. Eng. Asp., 173(44564), 1 (2000)
  19. Domka L, Colloid Polym. Sci., 271(11), 1091 (1933)
  20. Liang HQ, Wu QY, Wan LS, Huang XJ, Xu ZK, J. Membr. Sci., 465, 56 (2014)
  21. Kang GD, Cao YM, J. Membr. Sci., 463, 145 (2014)
  22. Zhang J, Cao P, Cui Z, Wang Q, Fan F, Qiu M, Wang X, Wang Z, Wang Y, AIP Adv., 9, 1 (2019)
  23. Fang C, Zhang P, Rajabzadeh S, Kato N, Matsuyama H, Colloids Surf. A: Physicochem. Eng. Asp., 611 (2021)
  24. Sukitpaneenit P, Chung TS, J. Membr. Sci., 340(44563), 192 (2009)
  25. Ma W, Zhang J, Wang X, Wang S, Appl. Surf. Sci., 253(20), 8377 (2007)
  26. Wang H, Zhao X, He C, Sep. Purif. Technol., 166, 1 (2016)
  27. Rana D, Matsuura T, Chem. Rev., 110(4), 2448 (2010)
  28. Sun J, Wu L, Hu F, RSC Adv., 5(51), 40753 (2015)
  29. Jiang JH, Zhu LP, Zhang HT, Zhu BK, Xu YY, J. Membr. Sci., 457, 73 (2014)
  30. Nishigochi S, Ishigami T, Maruyama T, Hao Y, Ohmukai Y, Iwasaki Y, Matsuyama H, Ind. Eng. Chem. Res., 53(6), 2491 (2014)
  31. Jin Y, Hu D, Lin Y, Polym. Adv. Technol. (July), 1-10, (2018).
  32. Zhi S, Wan L, Xu Z, J. Membr. Sci., 454, 144 (2014)
  33. Rajabzadeh S, Liang C, Ohmukai Y, Maruyama T, Matsuyama H, J. Membr. Sci., 423-424, 189 (2012)
  34. Cha BJ, Yang JM, Macromol. Res., 14(6), 596 (2006)
  35. Rajabzadeh S, Maruyama T, Ohmukai Y, Sotani T, Matsuyama H, Sep. Purif. Technol., 66, 76 (2009)
  36. Hassankiadeh NT, Cui Z, Sanguineti A, Arcella V, Moo Y, Drioli E, J. Memb. Sci., (2015).
  37. Chen Q, Yang B, Ding M, Pan Y, Qian J, Zheng Z, Eur. Polym. J., 140(Sep.) (2020)
  38. Zuo JH, Cheng P, Chen XF, Yan X, Guo YJ, Lang WZ, Sep. Purif. Technol., 192(43009), 348 (2018)
  39. Wu L, Sun J, Appl. Surf. Sci., 322, 101 (2014)
  40. Cui Z, J. Mater. Sci., 54(7), 5971 (2019)
  41. Song Y, Wang Z, Wang Q, Li B, Zhong B, J. Appl. Polym. Sci., 2, 1 (2016)
  42. Li X, Lu X, J. Appl. Polym. Sci., 3, 1 (2005)
  43. Wei D, Zhou S, Li M, Xue A, Zhang Y, Zhao Y, Appl. Clay Sci., 181(June) (2019)
  44. Cui A, Liu Z, Xiao C, Zhang Y, J. Membr. Sci., 360(44563), 259 (2010)
  45. Qin A, Wu X, Ma B, J. Mater. Sci., 49(22), 7797 (2014)
  46. Mun J, Park HM, Koh E, Lee YT, J. Ind. Eng. Chem., (2018).
  47. Xi Z, Xu Y, Zhu L, Wang Y, Zhu B, J. Membr. Sci., 327, 244 (2009)
  48. Boributh S, Chanachai A, Jiraratananon R, J. Membr. Sci., 342, 97 (2009)
  49. Du JR, Peldszus S, Huck PM, Feng X, Water Res., 43(18), 4559 (2009)
  50. Shen C, Yang J, Cui Z, Qin S, Qin Q, J. Taiwan Inst. Chem. Eng., 1 (2020)
  51. Zuo G, Wang R, J. Membr. Sci., 447, 26 (2013)
  52. Fu W, Pei T, Mao Y, Li G, J. Membr. Sci., 572, 453 (2019)
  53. Xiang S, Yang J, Cui Z, Qin S, Qin Q, Mater. Lett., 285 (2021)
  54. Zhu X, Loo H, Bai R, J. Membr. Sci., 436, 47 (2013)
  55. Zhu L, Zhang X, Xu L, Du C, Zhu B, Xu Y, Colloids Surf. B: Biointerfaces, 57(2), 189 (2007)
  56. Godard BJJ, Bomal PY, J. Mater. Sci., 28, 6605 (1993)
  57. Zheng XJGFM, J. Dispers. Sci. Technol., 1003-1010, (2016).
  58. RashmiV, Isloor AM, Bhat UK, Ismail AF, Desalination, 351, 220 (2014)
  59. Zhao J, Yi J, Shi L, Wang R, J. Memb. Sci., (November), 118914, (2020).
  60. Xiang T, Tang M, Liu Y, Li H, Li L, Cao W, Sun S, Zhao C, Desalination, 295, 26 (2012)
  61. Aerts P, Genne I, Kuypers S, Leysen R, Vankelecom IFJ, Jacobs PA, J. Membr. Sci., 178, 1 (2000)
  62. Li X, Xu G, Lu X, Xiao C, J. Appl. Polym. Sci., 107(6), 3630 (2008)
  63. Kato BT, Sugawara A, Hosoda N, Adv. Mater., 14(12), 869 (2002)