Enhancing the Performances of Polymeric PVDF Membranes for Oil/Water Separation by Hydrophilic and Underwater Oleophobic Surfaces Modification


Faraziehan Senusi(1), Benjamin Ballinger(2), Suzylawati Ismail(3*)

(1) School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Pulau Pinang, Malaysia; Faculty of Chemical Engineering, Universiti Teknologi MARA (UiTM) Pulau Pinang, Permatang Pauh 13500 Pulau Pinang, Malaysia
(2) School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Pulau Pinang, Malaysia
(3) School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, 14300 Pulau Pinang, Malaysia
(*) Corresponding Author


This paper investigates the permeability and separation performance of polyphenolic-amine coated PVDF membrane with hydrophilic (26.9 ± 5.6°) and underwater oleophobic (162.1 ± 5.1°) surface modification. Surface chemical structures, surface compositions and hydrophilicity of membranes were investigated by Attenuated Total Reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and contact angle analyses, respectively. The separation of emulsion oil solutions was evaluated using cross-flow filtration mode in term of high permeation flux and excellent oil resistance. Then, the flux recovery ratio of filtration process was calculated at different transmembrane pressures (TMP) and initial concentrations of emulsion feed solutions. The results showed a decrease in the flux recovery ratio at higher pressures and initial oil concentrations. By applying Hermia’s blocking model, formation of cake layer shows dominant fouling mechanism for the emulsion oil separation process.


polyphenolic coating; hydrophilicity; underwater oleophobic; polymeric membrane; emulsion oil

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[1] Zhu, Y., Wang, D., Jiang, L., and Jin, J., 2014, Recent progress in developing advanced membranes for emulsified oil/water separation, NPG Asia Mater., 6, e101.

[2] Genc, A., and Bakirci, B., 2015, Treatment of emulsified oils by electrocoagulation: Pulsed voltage applications, Water Sci. Technol., 71 (8), 1196–1202.

[3] Tripathi, B.P., Dubey, N.C., Subair, R., Choudhury, S., and Stamm, M., 2016, Enhanced hydrophilic and antifouling polyacrylonitrile membrane with polydopamine modified silica nanoparticles, RSC Adv., 6 (6), 4448–4457.

[4] Yin, J., Fan, H., and Zhou, J., 2016, Cellulose acetate/poly(vinyl alcohol) and cellulose acetate/crosslinked poly(vinyl alcohol) blend membranes: preparation, characterization, and antifouling properties, Desalin. Water Treat., 57 (23), 10572–10584.

[5] Fang, L.F., Zhou, M.Y., Wang, N.C., Zhu, B.K., and Zhu, L.P., 2015, Improving the antifouling property of poly(vinyl chloride) membranes by poly(vinyl chloride)-g-poly(methacrylic acid) as the additive, J. Appl. Polym. Sci., 132 (44), 42745.

[6] Zhu, H., and Zhu, S., 2015, A versatile and facile surface modification route based on polydopamine for the growth of MOF films on different substrates, Can. J. Chem. Eng., 93 (1), 63–67.

[7] Bai, L., Liang, H., Crittenden, J., Qu, F., Ding, A., Ma, J., Du, X., Guo, S., and Li, G., 2015, Surface modification of UF membranes with functionalized MWCNTs to control membrane fouling by NOM fractions, J. Membr. Sci., 492, 400–411.

[8] Kwon, Y.N., Hong, S., Choi, H., and Tak, T., 2012, Surface modification of a polyamide reverse osmosis membrane for chlorine resistance improvement, J. Membr. Sci., 415-416, 192–198.

[9] Farahani, M.H.D.A., and Vatanpour, V., 2018, A comprehensive study on the performance and antifouling enhancement of the PVDF mixed matrix membranes by embedding different nanoparticulates: Clay, functionalized carbon nanotube, SiO2 and TiO2, Sep. Purif. Technol., 197, 372–381.

[10] Otitoju, T.A., Ahmad, A.L., and Ooi, B.S., 2016, Polyvinylidene fluoride (PVDF) membrane for oil rejection from oily wastewater: A performance review, J. Water Process Eng., 14, 41–59.

[11] Yu, S., Zhang, X., Li, F., and Zhao, X., 2018, Poly(vinyl pyrrolidone) modified poly(vinylidene fluoride) ultrafiltration membrane via a two-step surface grafting for radioactive wastewater treatment, Sep. Purif. Technol., 194, 404–409.

[12] Ding, Y.H., Floren, M., and Tan, W., 2016, Mussel-inspired polydopamine for bio-surface functionalization, Biosurf. Biotribol., 2 (4), 121–136.

[13] Sileika, T.S., Barrett, D.G., Zhang, R., Lau, K.H.A., and Messersmith, P.B., 2013, Colorless multifunctional coatings inspired by polyphenols found in tea, chocolate, and wine, Angew. Chem. Int. Ed., 52 (41), 10766–10770.

[14] Kang, S.M., Hwang, N.S., Yeom, J., Park, S.Y., Messersmith, P.B., Choi, I.S., Langer, R., Anderson, D.G., and Lee, H., 2012, One-step multipurpose surface functionalization by adhesive catecholamine, Adv. Funct. Mater., 22 (14), 2949–2955.

[15] Wei, Q., Zhang, F., Li, J., Li, B., and Zhao, C., 2010, Oxidant-induced dopamine polymerization for multifunctional coatings, Polym. Chem., 1 (9), 1430–1433.

[16] Wang, J., Hou, L., Yan, K., Zhang, L., and Yu, Q.J., 2018, Polydopamine nanocluster decorated electrospun nanofibrous membrane for separation of oil/water emulsions, J. Membr. Sci., 547, 156–162.

[17] Kirschner, A.Y., Chang, C.C., Kasemset, S., Emrick, T., and Freeman, B.D., 2017, Fouling-resistant ultrafiltration membranes prepared via co-deposition of dopamine/zwitterion composite coatings, J. Membr. Sci., 541, 300–311.

[18] Lee, H., Dellatore, S.M., Miller, W.M., and Messersmith, P.B., 2007, Mussel-inspired surface chemistry for multifunctional coatings, Science, 318 (5849), 426–430.

[19] Sousa, M.R.S., Lora-Garcia, J., and López-Pérez, M.F., 2018, Modelling approach to an ultrafiltration process for the removal of dissolved and colloidal substances from treated wastewater for reuse in recycled paper manufacturing, J. Water Process Eng., 21, 96–106.

[20] Vela, M.C.V., Blanco, S.Á., García, J.L., and Rodríguez, E.B., 2009, Analysis of membrane pore blocking models adapted to crossflow ultrafiltration in the ultrafiltration of PEG, Chem. Eng. J., 149 (1-3), 232–241.

[21] Chen, G.E., Sun, L., Xu, Z.L., Yang, H., Huang, H.H., and Liu, Y.J., 2015, Surface modification of poly(vinylidene fluoride) membrane with hydrophilic and anti-fouling performance via a two-step polymerization, Korean J. Chem. Eng., 32 (12), 2492–2500.

[22] Zhao, X., and Liu, C., 2019, Efficient preparation of a novel PVDF antifouling membrane based on the solvent-responsive cleaning properties, Sep. Purif. Technol., 210, 100–106.

[23] Bittner, S., 2006, When quinones meet amino acids: Chemical, physical and biological consequences, Amino Acids, 30 (3), 205–224.

[24] Ding, L., Gao, J., and Chung, T.S., 2019, Schiff base reaction assisted one-step self-assembly method for efficient gravity-driven oil-water emulsion separation, Sep. Purif. Technol., 213, 437–446.

[25] Li, F., Ye, J., Yang, L., Deng, C., Tian, Q., and Yang, B., 2015, Surface modification of ultrafiltration membranes by grafting glycine-functionalized PVA based on polydopamine coatings, Appl. Surf. Sci., 345, 301–309.

[26] Qin, A., Li, X., Zhao, X., Liu, D., and He, C., 2015, Engineering a highly hydrophilic PVDF membrane via binding TiO2 nanoparticles and a PVA layer onto a membrane surface, ACS Appl. Mater. Interfaces, 7 (16), 8427–8436.

[27] Liu, C., Wu, L., Zhang, C., Chen, W., and Luo, S., 2018, Surface hydrophilic modification of PVDF membranes by trace amounts of tannin and polyethyleneimine, Appl. Surf. Sci., 457, 695–704.

[28] Sun, C., and Feng, X., 2017, Enhancing the performance of PVDF membranes by hydrophilic surface modification via amine treatment, Sep. Purif. Technol., 185, 94–102.

[29] Shi, H., Xue, L., Gao, A., Fu, Y., Zhou, Q., and Zhu, L., 2016, Fouling-resistant and adhesion-resistant surface modification of dual layer PVDF hollow fiber membrane by dopamine and quaternary polyethyleneimine, J. Membr. Sci., 498, 39–47.

[30] Chen, P.C., and Xu, Z.K., 2013, Mineral-coated polymer membranes with superhydrophilicity and underwater superoleophobicity for effective oil/water separation, Sci. Rep., 3, 2776.

[31] Xue, S., Li, C., Li, J., Zhu, H., and Guo, Y., 2017, A catechol-based biomimetic strategy combined with surface mineralization to enhance hydrophilicity and anti-fouling property of PTFE flat membrane, J. Membr. Sci., 524, 409–418.

[32] Vela, M.C.V, Blanco, S.Á., García, J.L., Gozálvez-Zafrilla, J.M., and Rodríguez, E.B., 2007, Modelling of flux decline in crossflow ultrafiltration of macromolecules: Comparison between predicted and experimental results, Desalination, 204 (1–3), 328–334.

[33] Chakrabarty, B., Ghoshal, A.K., and Purkait, M.K., 2008, Ultrafiltration of stable oil-in-water emulsion by polysulfone membrane, J. Membr. Sci., 325 (1), 427–437.

[34] Song, L., 1998, Flux decline in crossflow microfiltration and ultrafiltration: mechanisms and modeling of membrane fouling, J. Membr. Sci., 139 (2), 183–200.

[35] Muhammad Sanusi, N.F.A., Mohd Yusoff, M.H., Seng, O.B., Marzuki, M.S., and Abdullah, A.Z., 2018, Ultrafiltration based on various polymeric membranes for recovery of spent tungsten slurry for reuse in chemical mechanical polishing process, J. Membr. Sci., 548, 232–238.

DOI: https://doi.org/10.22146/ijc.43314

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