锌型一维链状晶体/PVDF共混膜的制备及性能
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摘要
为了改善聚偏氯乙烯(PVDF)膜的亲水性,以具有金属活性位点Zn~(2+)和亲水基团—COOH的亲水性锌型一维链状晶体(ZnL)为填料,采用非溶剂致相分离法(NIPS)制备ZnL/PVDF共混膜;通过原子力显微镜、X射线衍射、扫描电子显微镜及水接触角、水通量、截留率等一系列测试手段探究添加不同含量ZnL对ZnL/PVDF共混膜结构、性能的影响。结果表明:ZnL晶体均匀的分布在PVDF膜中,并且没有出现明显颗粒聚集现象,证明ZnL晶体与PVDF聚合物有较好的相容性;亲水性ZnL晶体的加入明显提高了PVDF膜的亲水性,当ZnL晶体质量分数为0.50%时,其水通量达到99.6 L/(m~2·h),比纯膜水通量增加150%,并且其截留率下降幅度较低;随着ZnL晶体含量的增加,拉伸强度呈现先升高再降低状态,当ZnL晶体质量分数为0.50%时,共混膜的拉伸强度为3.39 MPa,比原膜的拉伸强度增加了10%。
In order to improve the hydrophilicity and antifouling performance of polyvinylidene fluoride(PVDF) membranes,ZnL/PVDF blending membranes were prepared by non-solvent phase method(NIPS) with hydrophilic zinc-type chain crystal(ZnL) with metal active site Zn~(2+) and hydrophilic group —COOH as fillers. The effect of adding different content of ZnL on the structure and properties of ZnL/PVDF blending membrane was investigated by means of atomic force microscope(AFM), X-ray diffraction(XRD), scanning electron microscope(SEM) and so on. The results show that the ZnL crystal is uniformly distributed in the PVDF membrane and it is proved that ZnL crystal has good compatibility with PVDF polymer. In addition, the addition of hydrophilic ZnL crystal can obviously improve the hydrophilicity of PVDF membrane and when the content of ZnL crystal is 0.50%, the water flux reached 99.6 L/(m~2·h), which was increased by 150% than that of the pure PVDF membrane, and the decrease of the rejection rate was lower than that of the pure membrane. With the increase of the content of ZnL crystal, the tensile strength increases first and then decreases. When the content of ZnL crystal is 0.50%, the tensile strength is 3.39 MPa, which is 10% higher than that of the pure PVDF membrane.
In order to improve the hydrophilicity and antifouling performance of polyvinylidene fluoride(PVDF) membranes,ZnL/PVDF blending membranes were prepared by non-solvent phase method(NIPS) with hydrophilic zinc-type chain crystal(ZnL) with metal active site Zn~(2+) and hydrophilic group —COOH as fillers. The effect of adding different content of ZnL on the structure and properties of ZnL/PVDF blending membrane was investigated by means of atomic force microscope(AFM), X-ray diffraction(XRD), scanning electron microscope(SEM) and so on. The results show that the ZnL crystal is uniformly distributed in the PVDF membrane and it is proved that ZnL crystal has good compatibility with PVDF polymer. In addition, the addition of hydrophilic ZnL crystal can obviously improve the hydrophilicity of PVDF membrane and when the content of ZnL crystal is 0.50%, the water flux reached 99.6 L/(m~2·h), which was increased by 150% than that of the pure PVDF membrane, and the decrease of the rejection rate was lower than that of the pure membrane. With the increase of the content of ZnL crystal, the tensile strength increases first and then decreases. When the content of ZnL crystal is 0.50%, the tensile strength is 3.39 MPa, which is 10% higher than that of the pure PVDF membrane.
引文
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[20]YU J,WANG C Q,XIANG L,et al.Enhanced C3H6/C3H8separation performance in poly(vinyl acetate)membrane blended with ZIF-8 nanocrystals[J].Chemical Engineering Science,2018,179:1-12.
[21]张华,李祥鹏,张雯,等.功能化锌金属有机骨架对刚果红染料的吸附[J].天津工业大学学报,2018,37(1):26-31.ZHNAG H,LI X P,ZHANG W,et al.Adsorption of congo red dye by organic skeleton of functional zinc metal[J].Journal of Tianjin Polytechnic University,2018,37(1):26-31(in Chinese).
[22]ARJMANDI M,PAKIZEH M,SAGHI M,et al.Study of separation behavior of activated and non-activated MOF-5 as filler on MOF-based mixed-matrix membranes in H2/CO2separation[J].Petroleum Chemistry,2018,58(4):317-329.
[23]GUILERA G,STEED J W.Topological control in coordination polymers by non-covalent forces[J].Chemical Communications,1999(16):1563-1564.
[24]SUN H Z,TANG B B,WU P Y.Hydrophilic hollow zeolitic imidazolate framework-8 modified ultrafiltration membranes with significantly enhanced water separation properties[J].Journal of Membrane Science,2018,551:283-293.
[2]NEJATI S,BOO C,OSUJI C O,et al.Engineering flat sheet microporous PVDF films for membrane distillation[J].Journal of Membrane Science,2015,492:355-363.
[3]GUILLEN-BURRIEZA E,THOMAS R,MANSOOR B,et al.Effect of dry-out on the fouling of PVDF and PTFE membranes under conditions simulating intermittent seawater membrane distillation(SWMD)[J].Journal of Membrane Science,2013,438:126-139.
[4]HOU F F,LI B A,XING M H,et al.Surface modification of PVDF hollow fiber membrane and its application in membrane aerated biofilm reactor(MABR)[J].Biorasearch Technology,2013,140:1-9.
[5]严丽.溶液共混法对PVDF膜改性的研究[D].上海:东华大学,2012.YAN L.Research of solution blending in modification of PVDFmembrane[D].Shanghai:Donghua University,2012(in Chinese).
[6]赵永红,张梅,朱宝库,等.两亲性超支化聚合物对PVDF膜的共混改性[J].膜科学与技术,2008,28(4):71-76.ZHAO Y H,ZHANG M,ZHU B K,et al.Modification of PVDF porous membrane by blending with amphiphilic hyperbranched polymer[J].Membrane Science and Technology,2008,28(4):71-76(in Chinese).
[7]DZINUN H,OTHMAN M H D,ISMAIL A F,et al.Morphological study of co-extruded dual-layer hollow fiber membranes incorporated with different TiO2loadings[J].Journal of Membrane Science,2015,479:123-131.
[8]YI X S,ZHU Y G,WANG D X,et al.Adsorption mechanism of oil-in-water on a TiO2/Al2O3-polyvinyline fluoride(PVDF)ultrafiltration membrane[J].Langmuir,2018,34(34):9907-9916.
[9]XU H P,LANG W Z,YAN X,et al.Preparation and characterizations of poly(vinylidene fluoride)/oxidized multi-wall carbon nanotube membranes with bi-continuous structure by thermally induced phase separation method[J].Journal of Membrane Science,2014,467:142-152.
[10]SONG S S,CAO M,SHAN H T,et al.Polyhedral oligomeric silsesquioxane functionalized carbon nanotubes for high thermal conductive poly(vinglidene fluoride)composite membrane[J].Materials and Design,2018,156:242-251.
[11]耿宏章,许春霞,王文一,等.碳纳米材料/聚偏氟乙烯杂化膜的制备及性能[J].天津工业大学学报,2018,37(4):1-6.GENG H Z,XU C X,WANG W Y,et al.Preparation and performance of carbon nanomaterials/polyvinylidene fluoride hybrid membrane[J].Journal of Tianjin Polytechnic University,2018,37(4):1-6(in Chinese).
[12]SHEN X,XIE T,WANG J G.An anti-fouling poly(vinylidene fluoride)hybrid membrane blended with functionalized ZrO2nanopartocles for efficient oil/water separation[J].RSC Advances,2017,7(9):5262-5271.
[13]ZHANG Y Q,LYU X.Effect of porous YxFeyZr1-x-yO2coated TiO2solid superacid nanoparticles on polyvinylidene fluoride membranes properties[J].Journal of Membrane Science,2016,520:54-65.
[14]LIANG S,KANG Y,TIRAFERRI A,et al.Highly hydrophilic polyvinylidene fluoride(PVDF)ultrafiltration membranes via postfabrication grafting of surface-tailored silica nanoparticles[J].ACS Applied Materials and Interfaces,2013,5(14):6694-6703.
[15]WEI C J,DAI F Y,LIN L G.Simplified and robust adhesivefree superhydrophobic SiO2-decorated PVDF membranes for efficient oil/water separation[J].Journal of Membrane Science,2018,555:220-228.
[16]CHENG X,JIANG Z,CHENG X,et al.Bimetallic metal-organic frameworks nanocages as multi-functional fillers for waterselective membranes[J].Journal of Membrane Science,2018,545:19-28.
[17]LUO H B,WANG M,LIU S X,et al.Proton conductance of a superior water-stable metal-organic framework and its composite membrane with poly(vinylidene fluoride)[J].Inorganic Chemistry,2017,56(7):4169-4175.
[18]MA D C,PEH S B,HAN G,et al.Thin-film nanocomposite(TFN)membranes incorporated with super-hydrophilic metalorganic framework(MOF)UiO-66:Toward enhancement of water flux and salt rejection[J].ACS Applied Materials and Interfaces,2017,9(8):7523-7534.
[19]GUO Y,WANG X B,HU P,et al.ZIF-8 coated polyvinylidenefluoride(PVDF)hollow fiber for highly efficient separation of small dye molecules[J].Applied Materials Today,2016,5:103-110.
[20]YU J,WANG C Q,XIANG L,et al.Enhanced C3H6/C3H8separation performance in poly(vinyl acetate)membrane blended with ZIF-8 nanocrystals[J].Chemical Engineering Science,2018,179:1-12.
[21]张华,李祥鹏,张雯,等.功能化锌金属有机骨架对刚果红染料的吸附[J].天津工业大学学报,2018,37(1):26-31.ZHNAG H,LI X P,ZHANG W,et al.Adsorption of congo red dye by organic skeleton of functional zinc metal[J].Journal of Tianjin Polytechnic University,2018,37(1):26-31(in Chinese).
[22]ARJMANDI M,PAKIZEH M,SAGHI M,et al.Study of separation behavior of activated and non-activated MOF-5 as filler on MOF-based mixed-matrix membranes in H2/CO2separation[J].Petroleum Chemistry,2018,58(4):317-329.
[23]GUILERA G,STEED J W.Topological control in coordination polymers by non-covalent forces[J].Chemical Communications,1999(16):1563-1564.
[24]SUN H Z,TANG B B,WU P Y.Hydrophilic hollow zeolitic imidazolate framework-8 modified ultrafiltration membranes with significantly enhanced water separation properties[J].Journal of Membrane Science,2018,551:283-293.