原位生成法制备Fe_3O_4/PSF磁性复合超滤膜的研究
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摘要
以截留分子量为30000的聚砜商品膜为基膜,采用原位生成法制备出Fe_3O_4/PSF磁性复合超滤膜,随后对所制膜的表面形貌、内部结构和分离性能进行了表征,并考察了FeCl_2浓度、NaOH浓度、反应温度和反应时间对所制膜平均孔径的影响。
稳定性实验结果表明,在实验室条件下原位生成法具有较好的稳定性。扫描电镜结果表明,粒子主要沉积在聚砜基膜孔道中;XRD和XPS分析表明,聚砜基膜中沉积的主要成分是Fe_3O_4纳米粒子,根据XRD图谱结果计算出粒子的平均粒径为6.99nm;XPS结果显示,所制磁性复合超滤膜中很有可能形成了Fe-O-S键;液液界面法测得,磁性复合超滤膜的平均孔径从无磁场下的9.36nm减小到0.8T磁场下的8.54nm。在外加磁场下,磁性复合超滤膜对不带电的溶菌酶截留率增大,对带电的溶菌酶截留率减小。经过分析认为,磁性复合超滤膜在磁场下的超滤机理,主要是磁场诱导效应和磁致伸缩效应。
单因素试验得到的最佳制备条件为:FeCl_2乙醇溶液浓度为0.2mol/L、NaOH水溶液浓度为2mol/L、反应温度为60℃和反应时间为45min;正交试验结果表明,影响磁性复合超滤膜孔径的因素按影响程度从大到小依次为:FeCl_2浓度＞反应温度＞NaOH浓度＞反应时间。
With polysulfone commercial membrane as substrate material,Fe_3O_4/PSF magnetic composite ultrafiltration membrane was prepared.Then the properties of the membrane prepared,such as surface morphology,internal structure and separation performance,were characterized.Effects of iron dichloride concentration,sodium hydroxide concentration,reactive temperature and reactive time on average pore diameter of the membrane prepared were investigated.
The result of stability experiment showed that the stability of in situ synthesis method was good in experimental conditions;The result of SEM showed that most particles deposited in the pore of the polysulfone membrane; XRD and XPS analysis indicated that particles deposited in the pore were mainly Fe_3O_4,and the average particle size of the particles calculated from XRD result was about 6.99nm;The result of XPS indicated that Fe-O-S bond was very likely formed in the magnetic composite ultrafiltration membrane prepared;Liquid-liquid displacement method measured that the average pore size declined from 9.36nm without magnetic field to 8.54nm in magnetic field with the intensity of 0.8T.The rejection to uncharged lysozyme of magnetic composite ultrafiltration membrane rose in magnetic field,while the rejection to charged lysozyme declined in magnetic field.After analysis,we realized that the rejection mechanisms of magnetic composite ultrafiltration membrane in magnetic field consisted of the magnetoinductive effect and magnetostrictive effect.
Based on the result of single factor test,the optimum preparing conditions were as follows:iron dichloride concentration 0.2mol/L,sodium hydroxide concentration 2mol/L,reactive temperature 60℃,reactive time 45min.The result of orthogonal test indicated that the effectiveness of factors on the average pore diameter of the magnetic composite ultrafiltration membrane were in this order:iron dichloride concentration＞reactive temperature＞sodium hydroxide concentration＞reactive time.
稳定性实验结果表明,在实验室条件下原位生成法具有较好的稳定性。扫描电镜结果表明,粒子主要沉积在聚砜基膜孔道中;XRD和XPS分析表明,聚砜基膜中沉积的主要成分是Fe_3O_4纳米粒子,根据XRD图谱结果计算出粒子的平均粒径为6.99nm;XPS结果显示,所制磁性复合超滤膜中很有可能形成了Fe-O-S键;液液界面法测得,磁性复合超滤膜的平均孔径从无磁场下的9.36nm减小到0.8T磁场下的8.54nm。在外加磁场下,磁性复合超滤膜对不带电的溶菌酶截留率增大,对带电的溶菌酶截留率减小。经过分析认为,磁性复合超滤膜在磁场下的超滤机理,主要是磁场诱导效应和磁致伸缩效应。
单因素试验得到的最佳制备条件为:FeCl_2乙醇溶液浓度为0.2mol/L、NaOH水溶液浓度为2mol/L、反应温度为60℃和反应时间为45min;正交试验结果表明,影响磁性复合超滤膜孔径的因素按影响程度从大到小依次为:FeCl_2浓度＞反应温度＞NaOH浓度＞反应时间。
With polysulfone commercial membrane as substrate material,Fe_3O_4/PSF magnetic composite ultrafiltration membrane was prepared.Then the properties of the membrane prepared,such as surface morphology,internal structure and separation performance,were characterized.Effects of iron dichloride concentration,sodium hydroxide concentration,reactive temperature and reactive time on average pore diameter of the membrane prepared were investigated.
The result of stability experiment showed that the stability of in situ synthesis method was good in experimental conditions;The result of SEM showed that most particles deposited in the pore of the polysulfone membrane; XRD and XPS analysis indicated that particles deposited in the pore were mainly Fe_3O_4,and the average particle size of the particles calculated from XRD result was about 6.99nm;The result of XPS indicated that Fe-O-S bond was very likely formed in the magnetic composite ultrafiltration membrane prepared;Liquid-liquid displacement method measured that the average pore size declined from 9.36nm without magnetic field to 8.54nm in magnetic field with the intensity of 0.8T.The rejection to uncharged lysozyme of magnetic composite ultrafiltration membrane rose in magnetic field,while the rejection to charged lysozyme declined in magnetic field.After analysis,we realized that the rejection mechanisms of magnetic composite ultrafiltration membrane in magnetic field consisted of the magnetoinductive effect and magnetostrictive effect.
Based on the result of single factor test,the optimum preparing conditions were as follows:iron dichloride concentration 0.2mol/L,sodium hydroxide concentration 2mol/L,reactive temperature 60℃,reactive time 45min.The result of orthogonal test indicated that the effectiveness of factors on the average pore diameter of the magnetic composite ultrafiltration membrane were in this order:iron dichloride concentration＞reactive temperature＞sodium hydroxide concentration＞reactive time.
引文
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[42]窦永华,张玲,古宏晨.单分散Fe_3O_4纳米粒子的合成、表征及其自组装[J].功能材料,2007,38(1):119-122.
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[50]姜云鹏,王榕树.纳米SiO_2/PVA复合超滤膜的制备及性能研究[J].高分子材料科学与工程,2002,18:177-180.
[51]陈超,张裕卿.Al_2O_3-聚砜复合超滤膜用于中水处理的研究[J].天津大学学报,2006,2:219-222.
[52]Rameev B Z,Yildiz F,Aktas B,et al.Ion synthesis and FMR studies of iron and cobalt nanoparticles in polyimides[J].Microelectronic Engineering,2003,69(24):330-335.
[53]Ferre R,Ounadjela K,Dubios S,et al.Magnetization process in nickel and cobalt electrodeposited nanowires[J].Physical Review B,1997,56(21):14066-14075.
[54]曹渊,陶长元,杜军,杨修明,张丙怀.纳米Ni粒子/PTFE复合磁性膜的制备及表征[J].材料导报,2005,19(7):119-121.
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[2]Tansel B,Regula J,Shalewitz R.Treatment of fuel oil and crude oil contaminate waters by ultrafiltration membranes[J].Desalination,1995,102:301-311.
[3]R Ghosh,Z F Cui.Protein purification by ultrafiltration with pre-treated membrane[J].Membrane Sci.,2000,167:47-53.
[4]A Bottino,G Capannelli,V D'Asti,et al.Preparation and properties of novel organic-inorganic porous membranes[J].Sep.Purif.Technol,2001,22:269-275.
[5]L Yan,Y Shui Li,Effect of nano-sized Al2O3-particle addition on PVDF ultrafiltration membranes performance[J].Membr.Sci.,2006,276:162-167.
[6]潘见等.一种截留率可调控的电磁约束分离膜.中国发明专利,№200610040159.1
[7]Pjian,H Yahui.Preparation of polysulfone-Fe_3O_4 composite ultrafiltration membrane and its behavior in magnetic field[J].Membrane Sci.,2006,284:9-16.
[8]P Jian,H Yahui,J Minghui,Z Jinglong,C Yan.The purification of Ginkgo biloba extraction by polysulfone- Fe_3O_4 composite ultrafiltration membrane[J].Desalination(已录用).
[9]潘见,何亚荟,赵金龙,晋明会.聚砜-Fe_3O_4磁性复合超滤膜的机理分析[J].膜科学与技术(已录用).
[10]潘见,何亚荟,赵金龙,晋明会,聚砜-Fe_3O_4磁性复合超滤膜的制备与表征[J].高分子材料科学与工程,2008,24(7):151-154.
[11]潘见,何亚荟,晋明会,赵金龙.聚砜-Fe_3O_4磁性复合超滤膜的制备及应用[J].食品科学,2008,29(05):159-161
[12]S P努内斯,K V派内曼.化学工业中的膜技术[M].化学工业出版社,2005:6-7.
[13]王湛等.膜分离技术基础[M].化学工业出版社,2006:213.
[14]S P Nunes.Recent advances in the controlled formation of pores in membranes[J].Trends in Polymer Science,1997,5:187.
[15]G E Gaides,A J Mchugh.Gelation in an amorphous polymer:a discussion of its relation to membrane formation[J].Ploymer,1989,30:2118.
[16]S P Nunes,T Inoue.Evidence for spinodal decomposition and nucleation and growth mechanisms during membrane formation[J].Membrane Sci.,1996,111:93.
[17]L Zeman,T Fraser.Formation of air-cast cellulose acetate membranes.Part Ⅰ:Study of macrovoid formation[J].Membrane Sci.,1993,84:93.
[18]M Mulder.Basic Principles of Membrane Technology[J].Kluwer Academic,1991.
[19]A Castro(Akzona) Methods for Making Microporous Products.U.S.Pat.,4247498,January 1981.
[20]D R Lloyd,S SKim,K E Kinzer.Microporous membrane formation via thermally-induced phase separation[J].Membrane Sci.,1991,64:1.
[21]S Loeb,S Sourirajan.Sea water demineralization by means of an osmotic membrane[J].Advanced Chem.Ser.,1962,38:117.
[22]高道江,王建华,超微磁性Fe_3O_4粒子的制备[J].四川师范大学学报:自然科学版,1997,20(6):94-97.
[23]邹涛,郭灿雄,段雪等.强磁性Fe_3O_4纳米粒子的制备及其性能表征[J].精细化工,2002,19(12):707-710.
[24]秦润华,姜炜,刘宏英等.材料导报,2003,17(9):66-68.
[25]宋丽贤,卢忠远,刘德春等.分解沉淀法制备磁性纳米Fe_3O_4的研究及表征[J].化工进展,2006,25(1):54-57.
[26]海岩冰,袁红雁,肖丹.微波法制备纳米Fe_3O_4[J].化学研究与应用,2006,18(6):744-746.
[27]唐波,葛介超,王春先等.金属氧化物纳米材料的制备新进展[J].化工进展,2002,21(10):707-712.
[28]孟哲,张冬亭,王春平.光谱实验室,2003,20(4):489-491.
[29]杨喜云,龚竹青,郑雅杰等.功能材料,2005,36(5):667-670.
[30]Thapa D,Palkar V R,Kurup M B,et al.Mater.Lett.,2004,58:2692-2694
[31]李发伸,王涛,王颖.物理学报,2005,54(7):3100-3104
[32]Kumar R V,Koltypin Y,Xu X N,et al.Appl.phys.,2001,89(11):6324-6328.
[33]Yu W G,Zhang T L,Zhang J G,et al.Mater.Lett.,2006,60:2998-3001.
[34]Qu S C,Yang H B,Ren D W,et al.Colloid Interf.Sci.,1999,215:190-192.
[35]涂国荣,刘翔峰,杜光旭等.精细化工,2004,21(9):641-644.
[36]耿全荣,蒋荣立,刘光芬等.Fe_3O_4磁流体的水热法制备与表征[J].苏州科技学院学报工程技术版,2006,19(1):51-53.
[37]柴波,张文军,李德忠.微乳法制备W/O型Fe_3O_4磁流体及其清除水面浮油模拟研究[J].环境化学,2005,24(4):419-422.
[38]Arturom,Quintela L,Rivas J.Chemical reactions in microemulsions:a powerful method to obtain ultrafine particles[J].Journal of Colloid and Interface Science,1993,158(2):446-451.
[39]周洁,马明,张宇等.不同尺寸Fe_3O_4磁性粒子的制备和表征[J].东南大学学报自然科学版,2005,35(4):615-618.
[40]Hyeon T,Lee S S,Park J,et al.Synthesis of highly crystalline and monodisperse maghemite nano-crystallites without a size- selection process[J].J Am Chem Soc,2001,123(12):798-801.
[41]陈辉.高温分解法合成Fe_3O_4磁性纳米微粒[J].河南化工,2004(2):11-12.
[42]窦永华,张玲,古宏晨.单分散Fe_3O_4纳米粒子的合成、表征及其自组装[J].功能材料,2007,38(1):119-122.
[43]Morais P C,Azevedo R B,Rabelo D,et al.Chem.Mater.,2003,15(13):2485-2487.
[44]Rabelo D,Limae C D,Reis A C,et al.Nano.Lett.,2001,1(2):105-108.
[45]Chen L,Yang W J,Yang C Z.Mater.Sci.,1997,32:3571-3575.
[46]Shchukin D G,Radtchenko I L,Sukhorukov G B.Mater.Lett.,2003,57:1743-1747.
[47]Si S,Kotal A,Mandal T K,et al.Chem.Mater.,2004,16:3489-3496.
[48]L MingLiang,Z JianQing.Hydrophilic modification of poly(ether sulfone)ultrafiltration membrane surface by self-assembly of TiO_2nanoparticles[J].Applied Surface Science,2005,249:76-84.
[49]Nunes P S,Peinemann K V,Ohlrogge K,et al.Membr.Sci.,1999,157:212-219.
[50]姜云鹏,王榕树.纳米SiO_2/PVA复合超滤膜的制备及性能研究[J].高分子材料科学与工程,2002,18:177-180.
[51]陈超,张裕卿.Al_2O_3-聚砜复合超滤膜用于中水处理的研究[J].天津大学学报,2006,2:219-222.
[52]Rameev B Z,Yildiz F,Aktas B,et al.Ion synthesis and FMR studies of iron and cobalt nanoparticles in polyimides[J].Microelectronic Engineering,2003,69(24):330-335.
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