用原子力显微镜研究聚乙烯醇分离膜的结构

分别用饱和硫酸钠/氢氧化钠溶液和丙酮作为凝固浴制备聚乙烯醇（PVA）分离膜,在原子力显微镜（AFM）下观测发现：前者膜的表面结构与致密膜相似,后者则呈现出平均孔径为53nm的多孔膜结构,但二者都具有球粒状结构.实验证实,选用适当的凝固浴才能制备出聚乙烯醇多孔膜.     

高吸附量纤维素膜的制备及其对Pb2+的吸附性能

以纤维素为原料,氢氧化钠、尿素、硫脲为溶剂体系制备纤维素膜,研究凝固浴的种类、H2SO4体积分数、凝固温度和凝固时间对纤维素膜吸附Pb~(2+)的影响。采用准二级动力学模型研究吸附速率的快慢;采用SEM、比表面积和平均孔径、FTIR和XRD分析纤维素膜的结构和吸附机理;采用TG对纤维素膜的热性能进行分析。结果表明,以体积分数为7%的H2SO4为凝固浴、凝固温度为40℃、凝固时间为120min时,纤维素膜对Pb~(2+)的吸附量达到最大,为343.0mg/g。纤维素膜吸附Pb~(2+)符合准二级动力学模型。纤维素膜由表面致密变为含有孔洞的结构,吸附Pb~(2+)后孔洞被填满,纤维素膜中的C=O键和N—H键与Pb~(2+)产生螯合作用。纤维素膜中部分纤维素结晶型由Ⅰ型转变为Ⅱ型,结晶度降低;纤维素膜的热稳定性高于纤维素。     

高溶剂含量第1凝固浴停留时间对PVDF膜结构和性能的影响

以聚偏氟乙烯(PVDF)、聚乙烯吡咯烷酮(PVP)、二甲基乙酰胺(DMAc)为铸膜液体系,采用高含量溶剂DMAc水溶液作为第1凝固浴,水为第2凝固浴组成的双凝固浴制备PVDF中空纤维膜.通过扫描电镜(SEM)形貌观察,纯水水通量和BSA截留率测试,探讨了第1凝固浴停留时间对PVDF-PVP中空纤维膜性能与结构的影响.结果表明,随着膜丝在高溶剂含量第1凝固浴中停留时间从0变化至10s,膜丝纯水通量在2s时下降,之后持续增加,而BSA截留率不断降低.SEM显示随停留时间延长,膜表面孔隙率增加,亚层指状孔增多,大孔孔径增大,亚层海绵结构变得疏松.在停留时间为10s时,膜水通量达315 L·m-2.h-1,BSA截留率86％,可做为制备高通量PVDF超滤膜的最佳成形条件.     

凝固浴对聚芳硫醚砜分离膜结构与性能的影响

采用沉浸凝胶法制备了聚芳硫醚砜(PASS)分离膜,并探究了复合凝固浴以及双凝固浴对分离膜结构与性能的影响。利用扫描电子显微镜观察了PASS分离膜的形态结构,统计了孔径大小并计算了孔隙率,用超滤杯测试了分离膜的水通量及其渗透和分离性能,用万能材料测试机测试了分离膜的力学性能。结果表明:在复合凝固浴中,随着复合凝固浴溶剂浓度的增加,PASS分离膜表面的孔径逐渐增大,支撑层也由非对称的指状结构逐渐过渡为对称的海绵状结构;采用双凝固浴,可结合瞬时分相与延时分相制备表面孔径大、支撑层非对称并且贯穿性较好的PASS分离膜。     

废旧涤棉再生纤维素膜的制备及其结构与性能研究

以废旧涤棉牛仔布为原料,采用离子液体实现了涤棉中棉纤维的分离溶解一体化,成功制备了透明再生纤维素膜,并进一步探究了不同凝固浴(水和乙醇)对其结构与性能的影响.试验结果表明:离子液体溶剂法实现了涤棉的清洁高效分离,溶解再生后的纤维素发生了晶型转变,凝固浴种类显著影响再生纤维素膜的结构和性能,再生纤维素膜的拉伸强度远高于常...     

双凝固浴对膜蒸馏聚偏氟乙烯膜结构性能的影响

以聚偏氟乙烯(PVDF)、磷酸-N,N-二甲基乙酰胺为铸膜液体系,采用非溶剂相转化法,通过双凝固浴制备高性能的PVDF疏水微孔膜。采用正交实验的方法,考察凝固浴条件对PVDF膜结构和性能的影响。结果表明,双凝固浴法对膜的结构和性能有很大的影响,随着第1凝固浴中乙醇含量的增加,固液分相逐渐占据主导,促进了膜表面微纳米粗糙结构的形成,提高了膜表面的疏水性。以温度为60℃的质量分数40%乙醇作为第1凝固浴,浸泡时间20 s,温度60℃的水作为第2凝固浴所制备的PVDF膜,其直接接触膜蒸馏通量为28.3 kg/(m2·h),孔隙率为84.5%,平均孔径为1.05μm,接触角为116.8°。     

CA／PAN-Al2O3有机-无机复合超滤膜的制备

以醋酸纤维素(CA)及聚丙烯腈(PAN)为膜材料,以纳米三氧化二铝(Al2O3)为添加剂,通过浸入-沉淀相转化法制备了有机-无机超滤膜,从凝固浴温度及组成两个方面考察成膜规律.试验结果表明,凝固浴温度及组成对膜性能有较大影响,综合膜水通量及截留率多方面进行考虑,凝固浴温度50℃较为适宜;凝固浴中加入表面活性剂,膜的水通量及截留率均得到改善.     

凝固浴体系对PVDF超滤膜性能与结构的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)、聚乙烯基吡咯烷酮(PVP)为铸膜液,水、二甲基乙酰胺(DMAC)、PVP体系为凝固浴,制备外压中空纤维超滤膜。研究了凝固浴中DMAC和PVP含量以及凝固浴温度对膜性能和结构的影响。结果表明,凝固浴中DMAC含量的增加可以提高超滤膜的通量、断裂伸长率和表面的孔径,降低膜丝拉力;PVP含量对膜通量、拉力与断裂伸长率有非线性影响,当着PVP的质量分数大于12%时,支撑层孔径明显增加;凝固浴温度升高可以增加膜的通量,而对孔隙率、拉力和断裂伸长率则影响不大。当凝固浴中DMAC和PVP的质量分数分别为35%和12%、凝固浴温度为70℃时,可以得到性能较好得超滤膜。     

次氯酸钠处理多孔PAN纤维的结构与吸附性能研究

以聚丙烯腈/聚乙烯吡咯烷酮/二甲基亚砜(PAN/PVP/DMSO)三元体系为纺丝液,以DMSO/H_2O为凝固浴,在凝固浴温度为60℃下,通过湿法纺丝制备了具有介孔结构的多孔PAN/PVP纤维;用次氯酸钠(NaClO)对多孔PAN/PVP纤维进行处理,制得了NaClO@PAN/PVP纤维,采用场发射扫描电镜、元素分析仪和氮气气体吸附仪对处理前后纤维的表面形貌、元素组成、比表面积和孔径进行了表征,研究了凝固浴浓度和温度对PAN/PVP纤维和NaClO@PAN/PVP纤维的PVP含量及比表面积和孔径的影响。结果表明:经NaClO处理后,NaClO@PAN/PVP纤维中氧含量减少,氮含量增多,PVP含量减少,纤维表面变得光滑,平均孔径减小,孔数增多,比表面积增大;随着凝固浴DMSO浓度增大或温度升高,PAN/PVP纤维,NaClO@PAN/PVP纤维中的PVP含量降低,但其比表面积随凝固浴浓度的增大而减小,随凝固浴温度的升高而先升高后减小;在凝固浴DMSO质量分数为0,温度为60℃的条件下制得的PAN纤维、PAN/PVP纤维、NaClO@PAN/PVP纤维的比表面积分别为38,96,108 m~2/g,平均孔径分别为22.7,20.4,19.0 nm;PAN/PVP纤维、NaClO@PAN/PVP纤维的最可几孔径分布在40 nm左右,属于介孔结构。     

PVDF-PAN-纳米粘土杂化中空纤维超滤膜纺丝工艺研究

以聚偏氟乙烯和聚丙烯腈为主要膜材料、N,N-二甲基乙酰胺为溶剂、无水LiCl和有机纳米粘土为添加剂,采用干-湿相转化法纺丝工艺制备杂化中空纤维超滤膜,研究了干程、外凝胶浴温度、芯液温度和组成等纺丝工艺参数对杂化膜微观结构和分离性能的影响.SEM观察发现,中空纤维膜有较致密的外表面和多孔的内表面,干程对膜的横截面结构和表面形态都有影响:增加芯液含量有利于抑制大孔结构的产生,使孔径变小,结构致密,芯液为质量分数40%无水乙醇时,制得的膜对BSA截留率达到99%.试验结果表明,在较高的凝胶浴温度和较大的干程下制得的膜有较高的水通量和较低的截留率;凝胶浴温度升高,膜的力学性能加强,铸膜液中聚合物的质量分数为16%时,最大拉伸强度为3.16 MPa.     

Influence of coagulation bath on morphology of cellulose membranes prepared by NMMO method

To control the morphology of cellulose membranes used for separation, they were prepared by the NMMO method using water, methanol, ethanol and their binary solution as coagulation baths. Morphologies of the surface and cross section of dry membranes were observed. The pore structure parameters of wet membranes were determined. By comparison, the process and mechanism of pore formation in dry membranes were suggested, and the relativity of cellulose crystal size to average pore diameter in wet membranes and their influences were discussed. The results show that the morphology of dry membranes is clearly varied with coagulation baths, while the porosity of wet membranes is almost constant. Porous structures can appear in the compact region of dry membranes due to swelling from water. These pores have a virtual effect on the average pore diameter of wet membranes. By changing the composition of coagulation baths, the microstructure of cellulose membranes in a dry or wet environment can be adjusted separately.     

Influence of coagulation bath on morphology of cellulose membranes prepared by NMMO method

To control the morphology of cellulose membranes used for separation, they were prepared by the NMMO method using water, methanol, ethanol and their binary solution as coagulation baths. Morphologies of the surface and cross section of dry membranes were observed. The pore structure parameters of wet membranes were determined. By comparison, the process and mechanism of pore formation in dry membranes were suggested, and the relativity of cellulose crystal size to average pore diameter in wet membranes and their influences were discussed. The results show that the morphology of dry membranes is clearly varied with coagulation baths, while the porosity of wet membranes is almost constant. Porous structures can appear in the compact region of dry membranes due to swelling from water. These pores have a virtual effect on the average pore diameter of wet membranes. By changing the composition of coagulation baths, the microstructure of cellulose membranes in a dry or wet environment can be adjusted separately. __________ Translated from Journal of Chemical Engineering of Chinese Universities, 2007, 21(3): 398–403 [译自: 高校化学工程学报]     

Preparation and characterization of dense cellulose film for membrane application

Regenerated cellulose films were prepared with environmentally friendly process by utilized N‐methylmorpholine‐N‐oxide (NMMO)‐Cellulose system. To prepare a dense cellulose film for membrane application, some parameter process which influence porous forming such as cellulose DP, cellulose concentration, addition NMMO in coagulation bath, coagulation bath temperature, and drying condition were investigated. We resumed that the porosity and pore size of cellulose membrane decrease with lower cellulose DP, higher cellulose concentration, addition of NMMO in coagulation bath, applying room temperature in coagulation bath and drying, and applying vacuum on drying process resulted in membranes with porosity in range of 24–41% and pore size 13.4–20.2 nm. The main factor for controlling porosity and pore size of dense cellulose membrane was coagulation process condition especially addition of NMMO into coagulation bath. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dry-jet wet electrospinning of native cellulose microfibers with macroporous structures from ionic liquids

In this study, we have provided a review of electrospun cellulose micro/nanofibers from ionic liquids (ILs) and cosolvents from which we identify a lack of previous studies focusing on the structural morphology of the dry-jet wet electrospun native cellulose fibers from ILs. We have therefore aimed to investigate factors influencing the structural morphology of cellulose/IL electrospun fibers and investigate the coagulation parameters on this morphology. The electrospinning of 10% w/v cellulose/([C2MIM][OAc]/MIM) (1/1, v/v) solution was shown to produce macroporous fibers with average diameters of 2.8 ± 1.4 μm with pore sizes from 100 to 200 nm. We have found that coagulation bath type and immersion time affect the morphological structure of the electrospun fibers. The fiber spinnability, formation, and morphological structure are mainly dependent on the method used to collect and coagulate/solidify the fibers. The physical properties of the dissolved cellulose were measured and these are discussed in terms of the solution spinnability. The structural morphology of the electrospun cellulose fibers was characterized by scanning electron microscopy, and finally the extraction of IL from the fiber body was confirmed by nuclear magnetic resonance. The electrospun cellulose fibers morphology shows the formation of both micron and nanometer sized fibers with different morphological “macroporous” structures. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47153.     

Effects of coagulation-bath conditions on polyphenylsulfone ultrafiltration membranes

Polyphenylsulfone(PPSU)ultrafiltration membrane with different structures was prepared by non-solvent-induced phase separation.The effects of coagulation bath conditions(concentration and temper-ature)on membrane morphology,pure water flux,pore size,porosity,and contact angle were studied and discussed based on ternary-phase diagrams.Results indicated that water had stronger coagulant power than ethanol,and that the morphology of the membrane prepared from the polyphenylsulfone/1-methyl-2-pyrrolidinone/H2O(PPSU/NMP/H2O)system had finger-like structures.Conversely,sponge-like struc-tures were observed for the PPSU/NMP/(NMP-H2O)and PPSU/NMP/(70NMP-EtOH-H2O)systems.Ethanol also greatly influenced on membrane structures.According to the Scanning electronic micro-scopy(SEM)image,the composition(mass fraction)of casting solution is 16％PPSU-84％NMP and the coagulation bath consisting of 70％NMP-26％H2O-4％C2H5OH.Meanwhile,the PPSU ultrafiltration mem-brane with spong-like was prepared under 8℃coagulation bath.The formation of sponge-like structure reduces the pure water flux of ppsu membrane from 488.39 L·m-2·h-1 to 36.04 L m-2·h-1.It also reduces the gas permeability,porosity,and pore size of the membrane.The addition of ethanol and NMP into the coagulation bath increases the roughness of the PPSU ultrafiltration membrane and reduces the hydrophilicity of the membrane.     

Study on the control of pore sizes of membranes using chemical methods: Part III. The performance of carbonates and bicarbonates in the membrane-making process by the chemical reaction

In this paper, polyvinylidene fluoride (PVDF)/polymethyl acrilate (PMMA)/cellulose acetate (CA) blend UF membranes were prepared by chemical reaction introduced phase-inversion method. The results of the experiment show that: (1) The membrane pore size distribution is more uniform due to the presence of carbonates or bicarbonates in the coagulation bath; (2) No more than the stoichiometric ratio amount of carbonates or bicarbonates in the coagulation bath can effectively improve the membrane pore size distribution and make the pore size of membrane more uniform; (3) The membrane prepared by carbonates solution as a working solution in coagulation bath possess superior performance than that by bicarbonates.     

纤维素/NMMO溶液及其薄膜的制备与性能研究

以水质量分数为13.3%的N-甲基吗啉-N-氧化物(NMMO)为溶剂溶解棉浆粕,制备质量分数为5%～11%的纤维素/NMMO溶液。将所得溶液制备纤维素薄膜,考察了纤维素/NMMO溶液的稳定性,研究了凝固浴温度和组成对纤维素薄膜的成膜性、断面形态及力学性能的影响。结果表明:纤维素/NMMO溶液随着浓度增大,其粘度先增大后减小,再急剧上升;纤维素/NMMO溶液在玻璃介质中稳定性较好,微量Cu~(2+),Fe~(3+)等杂质存在时,其稳定性显著下降;纤维素薄膜随凝固浴温度升高,其透明性、拉伸强度和断裂伸长率均下降;相对于水,含有乙醇和NMMO的凝固浴能减缓双扩散的速度,使纤维素薄膜的拉伸强度略有提高,断裂伸长率出现不同程度下降。     

聚醚砜中空纤维膜的成形条件与形态结构研究

采用扫描电镜探讨经双向拉伸聚醚砜(PES)中空纤维膜的纺制工艺条件与结构之间的关系。在膜的中部通入填充液,随着填充液压力的增大,中空纤维膜的壁厚明显减小,同时纤维膜表面的孔明显增多。随着凝固浴质量分数的增加,中空纤维膜表面的孔径先减小后增大,而中空纤维膜接近外表面的皮层逐渐变厚。随着凝固浴拉伸率的提高,中空纤维膜在外径不变的情况下壁厚减小,内表面积增加;纤维变薄而且更为致密。     

Effects of coagulation bath temperature and polyvinylpyrrolidone content on flat sheet asymmetric polyethersulfone membranes

In this study, effects of coagulation bath temperature (CBT) and polyvinylpyrrolidone (PVP K15) concentration as a pore former hydrophilic additive on morphology and performance of asymmetric polyethersulfone (PES) membranes were investigated. The membranes were prepared from a PES/ethanol/NMP system via phase inversion induced by immersion precipitation in a water coagulation bath. The morphology of prepared membranes was studied by scanning electron microscopy (SEM), contact angle measurements, and mechanical property measurements. Permeation performance of the prepared membranes was studied by separation experiments using pure water and bovine serum albumin (BSA) solution as feed. The obtained results indicate that addition of PVP in the casting solution enhances pure water permeation flux and BSA solution permeation flux while reducing protein rejection. Increasing CBT results in macrovoid formation in the membrane structure and increases the membrane permeability and decreases the protein rejection. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers