超临界CO_2诱导相分离法制备石墨烯改性PVDF膜的研究
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摘要
以聚偏氟乙烯(PVDF)为基体,N,N-二甲基甲酰胺(DMF)为溶剂,通过超临界CO_2诱导相转化法制备PVDF/石墨烯微孔膜,并对其微观形貌、热稳定性能、热力学性能、晶型转化和亲水性能等进行表征。结果表明,在8 MPa,45℃的制备条件下,低含量石墨烯掺杂比可以制备得到良好网络结构的PVDF微孔膜,孔径和粗糙度均有所降低,亲水性能提高,整体热稳定性提高;石墨烯添加对微孔膜热力学性能的影响较小,但增强了PVDF晶型转换,趋向于形成更多的β或γ晶型。
A type of graphene-modified polyvinylidene fluoride(PVDF) membranes were fabricated by supercritical CO_2-induced phase separation using DMF as a solvent, and their morphology, thermal stability, thermodynamic properties, crystal transformation and hydrophilicity were studied. The results indicated that the microporous membranes obtained a good network structure at a low content of graphene under the process conditions of 8 MPa and 45 ℃. The pore size and roughness of the membranes were found to decrease, and however their hydrophilicity and thermal stability were improved. In addition, the introduction of graphene had little effect on thermodynamic properties but enhanced the transition of crystal form to form more β or γ crystals.
A type of graphene-modified polyvinylidene fluoride(PVDF) membranes were fabricated by supercritical CO_2-induced phase separation using DMF as a solvent, and their morphology, thermal stability, thermodynamic properties, crystal transformation and hydrophilicity were studied. The results indicated that the microporous membranes obtained a good network structure at a low content of graphene under the process conditions of 8 MPa and 45 ℃. The pore size and roughness of the membranes were found to decrease, and however their hydrophilicity and thermal stability were improved. In addition, the introduction of graphene had little effect on thermodynamic properties but enhanced the transition of crystal form to form more β or γ crystals.
引文
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[23] XING Y,ZHANG H,LIN J.Preparation and Properties of Carbon Coated Cobalt Nanoparticles/Polydimethylsiloxane Composite Thermal Interface Materials[J].Acta Materiae Compositae Sin,2015(6):1 590-1 595.
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[2] CAO J H,ZHU B K,JI G L.Preparation and Characteri-zation of PVDF-HFP Microporous Flat Membranes by Supercritical CO2 Induced Phase Separation[J].Journal of Membrance Science,2005(266):102-109.
[3] STEPHAN M A,RENGANATHAN N G,GOPUKUMAR S,et al.Cycling Behavior of Poly(vinylidene fluo-ride-hexafluoro propylene) (PVDF-HFP) Membranes Prepared by Phase Inversion Method[J].Materials Chemistry & Physics,2004,85(1):6-11.
[4] HUANG S,WU G,CHEN S.Preparation of Microporous Poly(vinylidene fluoride) Membranes via Phase Inversion in Supercritical CO2[J].Journal of Membrane Science,2007,293(1):100-110.
[5] HUANG Y J,QIN Y W,WANG N,et al.Reduction of Graphite Oxide with a Grignard Reagent for Facile In Situ Preparation of Electrically Conductive Polyolefin/Graphene Nanocomposites[J].Macromolecular Chemistry & Phy-sics,2012,213(7):720-728.
[6] WU T,ZHOU B,ZHU T,et al.Facile and Low-cost Approach Towards a PVDF Ultrafiltration Membrane with Enhanced Hydrophilicity and Antifouling Performance via Graphene Oxide/Water-bath Coagulation[J].Rsc Advances,2015,5(11):7 880-7 889.
[7] RAMANATHAN T,STANKOVICH S,DIKIN D A.Graphitic Nanofillers in PMMA Nanocomposites—An Investigation of Particle Size and Dispersion and Their Influence on Nanocomposite Properties[J].Journal of Polymer Science Part B:Polymer Physics,2012(50):589-589.
[8] KALAITZIDOU K,FUKUSHIMA H,DRZAL L T.A New Compounding Method for Exfoliated Graphite-polypropylene Nanocomposites with Enhanced Flexural Properties and Lower Percolation Threshold[J].Composites Science and Technology,2007(67):2 045-2 051.
[9] ZHENG W,LU X,WONG S C.Electrical and Mechanical Properties of Expanded Graphite-reinforced High-density Polyethylene[J].Journal of Applied Polymer Science,2010(91):2 781-2 788.
[10] ZOU J F,YU Z Z,PAN Y X.Conductive Mechanism of Polymer/graphite Conducting Composites with Low Percolation Threshold[J].Journal of Polymer Science Part B Polymer Physics,2010(40):954-963.
[11] MA B,YANG J,SUN Q.Influence of Cellulose/[Bmim]Cl Solution on the Properties of Fabricated NIPS PVDF Membranes[J].Journal of Materials Science,2017(52):1-12.
[12] ZHAO C,XU X,CHEN J.Effect of Graphene Oxide Concentration on the Morphologies and Antifouling Pro-perties of PVDF Ultrafiltration Membranes[J].Journal of Environmental Chemical Engineering,2013(1):349-354.
[13] KIM J H,MIN B R,WON J,et al.Phase Behavior and Mechanism of Membrane Formation for Polyimide/DMSO/Water System[J].Journal of Membrane Science,2001,187(1):47-55.
[14] WANG L J,LI Z S,REN J Z,et al.Preliminary Studies on the Gelation Time of Poly(ether sulfones) Membrane-forming System with an Elongation Method[J].Journal of Membrane Science,2006,275(1):46-51.
[15] WITTE P V D,DIJKSTRA P J,BERG J W A V D,et al.Phase Separation Processes in Polymer Solutions in Relation to Membrane Formation[J].Journal of Membrane Science,1996,117(1/2):1-31.
[16] XIANG Y,LIU F,XUE L.Under Seawater Superoleophobic PVDF Membrane Inspired by Polydopamine for Efficient Oil/Seawater Separation[J].Journal of Membrane Science,2015(476):321-329.
[17] CHINNAKKANNU K C,MUTHUKARUPPAN A,PERIYANNAN G.Synthesis and Characterization of 1,1-bis(3-methyl-4-hydroxyphenyl)Cyclohexane Polybenzoxazine-organoclay Hybrid Nanocomposites[J].Acta Materialia,2009(57):782-794.
[18] XU B,ZHENG Q,SONG Y.Calculating Barrier Properties of Polymer/Clay Nanocomposites:Effects of Clay Layers[J].Polymer,2006(47):2 904-2 910.
[19] LAROCHE G,MAROIS Y,GUIDOIN R.Polyvinylidene fluoride (PVDF) as a Biomaterial:From Polymeric Raw Material to Monofilament Vascular Suture[J].Journal of Biomedical Materials Research,1995(29):1 525-1 536.
[20] RAMASUNDARAM S,YOON S,KIM K J,et al.Preferential Formation of Electroactive Crystalline Phases in Poly(vinylidene fluoride)/Organically Modified Silicate Nanocomposites[J].Journal of Polymer Science Part B:Polymer Physics,2010,46(20):2 173-2 187.
[21] LEI Y,CEBE P.Effect of Nanoclay on Relaxation of Poly(vinylidene fluoride) Nanocomposites[J].Journal of Polymer Science Part B:Polymer Physics,2010,47(24):2 520-2 532.
[22] 虞锦洪.高导热聚合物基复合材料的制备与性能研究[D].上海:上海交通大学,2012.
[23] XING Y,ZHANG H,LIN J.Preparation and Properties of Carbon Coated Cobalt Nanoparticles/Polydimethylsiloxane Composite Thermal Interface Materials[J].Acta Materiae Compositae Sin,2015(6):1 590-1 595.
[24] SAFARPOUR M,KHATAEE A,VATANPOUR V.Effect of Reduced Graphene Oxide/TiO2,Nanocomposite with Different Molar Ratios on the Performance of PVDF Ultrafiltration Membranes[J].Separation and Purification Technology,2015(140):32-42.