Effects of coagulation bath temperature on structure and performance of poly(vinyl butyral) hollow fiber membranes via thermally induced phase separation

Poly （vinyl butyral） （PVB） hollow fiber membranes were fabricated via thermally induced phase separation （TIPS）. The effects of coagulation bath temperature （CBT） on the structure and performance of membranes were investigated in detail. The morphologies of the membranes were studied by scanning electron microscopy （SEM）, the performances of water permeability, rejection, breaking strength and elongation were measured, respectively. The results indicate that all the membranes have the asymmetric morphology and the thickness of the skin layer decreases and the pore size of the outer layer increases with the increase of CBT. The permeability of membranes prepared at air gap 1.0 cm and take-up speed 0.253 m/s increases from 1.047×10-7 to 5.909×10-7 m3/（m2·s-kPa） with the CBT increasing from 20 ℃ to 40℃, and sharply increases to 35.226×10 7 m3/（m2.s.kPa）once the CBT arrives at 50 ℃. While the carbonic ink rejections have no significant decrease, totally exceed 98%, but that of acid-maleic acid copolymer greatly decreases with the increase of CBT. Both the breaking strength and elongation decrease with the increase of CBT.

Electrokinetic phenomena of poly(vinyl butyral) hollow fiber membranes in different electrolyte solutions

The streaming potential of poly（vinyl butyral） （PVB） hollow fiber membrane was studied in different electrolyte solutions （including NaCl, KCl, CaCl2 and MgCl2）, the effects of ionic strength, ion valence and pH value on the streaming potential （SP） of the membrane were investigated. The zeta potentials and surface charge densities of the membrane were estimated on the basis of Helmholtz-Smoluchowski equation and Gouy-Chapmann theory. The results show that the PVB membrane has a weak negative charge due to the specific adsorption of ions. Moreover, the streaming potential, the zeta potential and the surface charge density of the membrane depend strongly on the salt concentration and the type and valence of ions. The iso-electric point （IEP） of the PVB membrane is arotmd 3.0 in the monovalent media （NaC1 and KC1） and 3.5 in divalent electrolytes （CaCl2 and MgCl2）. A few retentions were obtained for PVB membrane in low concentration solutions. This result verifies that the negative charged membrane surface can reject inorganic solutes by means of electrostatic repulsion effect even though the size of membrane pores is much larger than the size of salts.

A Hybrid Membrane of Poly(vinyl alcohol) and Phosphotungstic Acid for Fuel Cells

Proton conducting membranes composed of phosphotungstic acid (PWA) and poly(vinyl alcohol) (PVA)were prepared. Conductivity and Fourier transform infrared spectrometer(FTIR) measurements show that most ofthe acid embedded are stable in the PVA matrix when the membrane is immerged in water or methanol solution atroom temperature. Conductivity of the composite membranes scatters around 10-3 S.cm-1 at room temperature.The methanol crossover through the membranes is about an order of magnitude lower than that through Nafion117 membrane.

Functionalised Poly(Vinyl Alcohol)/Graphene Oxide as Polymer Composite Electrolyte Membranes

Crosslinked poly(vinyl alcohol)(PVA)based composite films were prepared as polyelectrolyte membranes for low temperature direct ethanol fuel cells(DEFC).The membranes were functionalised by means of the addition of graphene oxide(GO)and sulfonated graphene oxide(SGO)and crosslinked with sulfosuccinic acid(SSA).The chemical structure was corroborated and suitable thermal properties were found.Although the addition of GO and SGO slightly decreased the proton conductivity of the membranes,a significant reduction of the ethanol solution swelling and crossover was encountered,more relevant for those functionalised with SGO.In general,the composite membranes were stable under simulated service conditions.The addition of GO and SGO particles permitted to buffer the loss and almost retain similar proton conductivity than prior to immersion.These membranes are alternative polyelectrolytes,which overcome current concerns of actual commercial membranes such as the high cost or the crossover phenomenon.

Effect of silver-nanoparticles generated in poly(vinyl alcohol)membranes on ethanol dehydration via pervaporation

Pervaporation is an important membrane separation method of chemical engineering.In this work,silver-nanoparticles-poly(vinyl alcohol)nanocomposite membranes(AgNPs-PVA)are produced for the sake of improving its potentials for pervaporation of ethanol–water mixture so that the usual opposite trend between membrane selectivity and permeation can be reduced.The nanocomposite membranes are fabricated from an aqueous solution of poly(vinyl alcohol)with silver nanoparticles via the in-situ generation technique in the absence of any reducing agent.Successful generation of the nano size silver is measured by the UV–vis spectrum showing a single peak at 419 nm due to the plasmonic effect of silver nanoparticles.Our nanocomposite AgNPs-PVA membranes are characterized using scanning electron microscope(SEM),Fourier-transform infrared(FT-IR)spectroscopy,X-ray diffraction and thermogravimetric analysis(TGA).The pervaporation tests of our new AgNPs-PVA membranes show good results since at a higher temperature and higher ethanol concentration in the feed,the prepared membranes are highly permeable for the water having stable selectivity values and therefore our membranes show better performance compared to that of the other PVA-based nanocomposite membranes.

Graphene quantum dots doped poly(vinyl alcohol)hybrid membranes for desalination via pervaporation

Pervaporation desalination by highly hydrophilic materials such as poly(vinyl alcohol)(PVA)based separation membrane is a burgeoning technology of late years.However,the improvement of membrane flux in pervaporation desalination has been a difficult task.Here,a novel hybrid membrane with doped graphene oxide quantum dots(GOQDs)which is rich in hydrophilic groups and small size into the matrix of PVA was prepared to improve the membrane flux.The membranes structures were described by field emission scanning electron microscopy(FESEM),atomic force microscopy(AFM),Fourier transform infrared(FT-IR),differential scanning calorimetry(DSC),thermogravimetric analysis(TGA)and X-ray diffraction(XRD).And more,Water contact angle,swelling degree,and pervaporation properties were carried out to explore the effect of GOQDs in PVA matrix.In addition,GOQDs content in the hybrid membrane,NaCl concentration,and feed temperature were investigated accordingly.Moreover,the hydrogen bonds between PVA chains were weakened by the interaction between GOQDs and PVA chains.Significantly,the hybrid membrane with optimized doped GOQDs content,200 mg·L^(-1),displays a high membrane flux of 17.09 kg·m^(-2)·h^(-1)and the salt rejection is consistently greater than 99.6%.

Study of Pneumococcal Surface Protein, PspA, Incorporated in Poly(Vinyl Alcohol) Hydrogel Membranes

This study investigates poly(vinyl alcohol) (PVA) membranes as controlled release micro-matrices, which can be useful in therapeutic applications for optimizing the administration of drugs. Currently, the use of hydrogels is limited by protein size. This study investigates the delivery of PspA, a large protein of approximately 38 kD. Pneumococcal surface protein A (PspA) has been shown to provide protective immunity against pneumococcal infection and is considered as a pneumococcal vaccine. The protein release experiments demonstrated that from an initial pH 7.4, approximately 60% of PspA diffuse into a neutral environment with an initial burst and a declining rate reaching equilibrium. The results indicate that the protein was successfully incorporated and released from the membrane over time. The hydrogel and protein interaction is temporary, and the membrane system is ideal for protein drug delivery. The data confirm that the protein did not aggregate and was active after release. The protein release is promising and a step forward to develop microneedles to facilitate high molecular weight protein delivery as well as vaccine delivery.

Preparation and characterization of the antifouling porous membranes from poly(vinylidene fluoride)-graft-poly(N-vinyl pyrrolidone) powders

Porous membranes were prepared using the phase inversion method from poly(vinylidene fluoride)-graftpoly(N-vinyl pyrrolidone)(PVDF-g-PVP) powders, which were synthesized via γ-ray induced graft polymerization(pre-irradiation). Chemical compositions, thermal behavior, morphology and hydrophilicity of the membranes were characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, element analysis, thermalgravimetric analysis, differential scanning calorimetry, scanning electron microscopy and contact angle measurements, respectively. Permeation experiments were conducted to evaluate the water flux,and the dynamic BSA fouling resistance performances were investigated, too. All the experimental results indicate that the PVDF-g-PVP membranes demonstrate better separation performances over the pristine PVDF membrane.

Separation Performance of Sodium Alginate/Poly(Vinyl Pyrrolidone)Membranes for Aqueous/Dimethylformamide Mixtures by Vapor Permeation and Vapor Permeation with Temperature Difference Methods

In this study sodium alginate (NaAlg)/poly (vinyl pyrrolidone) (PVP) blend membranes were prepared and crosslinked with CaCl2 (0.1 Molarity (M)) for the separation of aqueous/dimethylformamide (DMF) mixtures. Membranes were characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and their performance was examined by varying experimental parameters such as feed composition (0 - 100 wt%), operating temperature (30℃ - 50℃) and membrane thickness (30 - 90 micrometer (μm)). Blending NaAlg with PVP, decreased separation factor whereas increased the permeation rate as the permeation temperature was increased in Vapor Permeation (VP) and Vapor Permeation with Temperature Difference (TDVP) methods. In the TDVP method, the separation factors increased and the permeation rates decreased as the temperature of the membrane surrounding is decreased. The highest separation factor of 60 was obtained in TDVP method for 90 wt% DMF concentration in the feed.

Removal of manganese from waste water by complexation-ultrafiltration using copolymer of maleic acid and acrylic acid

Copolymer of maleic acid and acrylic acid （PMA-100）, combining with polyvinyl butyral （PVB） ultrafiltration membrane was used for the removal of Mn（II） from waste water by complexation-ultrafiltration. The carboxylic group content of PMA-100 and the rate of complexation reaction were measured. Effects of the mass ratio of PMA-100 to Mn（II） （n）, pH, background electrolyte, etc on the rejection rate （R） and permeate flux （J） were investigated. The results show that carboxylic group content of PMA-100 is 9.5 mmol/g. The complexation of Mn（II） with PMA-100 is rapid and completed within 5 min at pH 6.0. Both R and J increase with pH increasing in the range of 2.5-7.0, and R increases with the increase of n at pH 6.0 while J is little affected. The background electrolyte leads to the decrease of R, and CaCl2 has much greater effect on R than NaCl at the same ionic strength.

Chain Dynamics Heterogeneity in Plasticized Poly(vinyl butyral)(PVB) as Elucidated by Solid-State NMR

The chain dynamics heterogeneity of the poly(vinyl butyral)(PVB) plasticized by triethylene glycol bis(2-ethylhexa noate)(TEG-EH) was investigated by various solid-state NMR techniques.The plasticized PVB shows two domains in distinct molecular dynamics differences,namely,rigid and soft domains,where the latter is the plasticizer-rich domain.The time domain low field NMR was first used to investigate the dynamics heterogeneity of the plasticized PVB,and the results show the decreasing activated energy of components in the soft domain of plasticized PVB(E_a=20.2 kJ/mol) as compared with that of the pristine one(E_a=24.3 kJ/mol).Detailed dynamics heterogeneity was obtained by high-field NMR with site-specific features.The quadrupole-echo ~2H-NMR was adopted to elucidate the dynamics heterogeneity of the vinyl alcohol(VA) units,where only the hydroxyl group of VA is deuterated.The ~1H-^(13)C WISE NMR spectra show that there is not much difference in the mobility of the VB unit in PVB with and without plasticizer,whereas the glass transition temperature differed by approximately 53℃.This is further supported by Torchia's T_1 relaxation measurements.The origin of such an unusual phenomenon is attributed to the critical role of the remaining VA(~22%) in the soft domain,where the VA units locally aggregate through hydrogen bonding.Also,the existence of a mobility gradient in the VB unit has been demonstrated.Moreover,the mobility difference for VB with different stereo-geometry(meso or racemic conformation) is observed for the first time.This indicates the importance of modulating the ratio of meso over racemic VB for controlling the macroscopic perfo rmance of PVB.

Effects of F127 on Properties of PVB/F127 Blend Hollow Fiber Membrane via Thermally Induced Phase Separation

Hydrophilic poly(vinyl butyral)(PVB) /Pluronic F127(F127) blend hollow fiber membranes were prepared via thermally induced phase separation(TIPS) ,and the effects of blend composition on the performance of hydrophilic PVB/F127 blend hollow fiber membrane were investigated.The addition of F127 to PVB/polyethylene glycol(PEG) system decreases the cloud point temperature,while the cloud point temperature increases slightly with the addition of F127 to 20%(by mass) PVB/F127/PEG200 system when the concentration of F127 is not higher than 5%(by mass) .Light scattering results show that the initial inter-phase periodic distance formed from the phase separation of 20%(by mass) PVB/F127/PEG200 system decreases with the addition of F127,so does the growth rate during cooling process.The blend hollow fiber membrane prepared at air-gap 5mm,of which the water permeability increases and the rejection changes little with the increase of F127 concentration.For the membrane prepared at zero air-gap,both water permeability and rejection of the PVB/F127 blend membrane are greater than those of PVB membrane,while the tensile strength changes little.Elementary analysis shows that most F127 in the polymer solution can firmly exist in the polymer matrix,increasing the hydrophilicity of the blend membrane prepared at air-gap of 5mm.

Responsive Hybrid Poly(vinyl alcohol)Hydrogel Membranes with Embedded Microgels as Valves

The research and application of responsive materials have long been hampered by their complicated designs and tedious construction processes.Besides,many current responsive materials show retard or weak responsiveness.In this study,responsive hybrid poly(vinyl alcohol)hydrogel membranes with embedded poly(N-isopropylacrylamide-acrylic acid)microgels as valves were constructed by simple mixing and subsequent freezing-thawing process.In the structure of the membranes,the matrix poly(vinyl alcohol)chains thread through and entangle with the microgels,and the microgels are firmly constrained within the hybrid hydrogel network.The fast and sharp temperature responsiveness of the embedded microgels was largely retained and endowed the hydrogel membrane with excellent temperature and pH responsiveness.Moreover,the hydrogel membrane showed excellent fatigue resistance in both temperature and pH-responsive flux examination.This study presented the great potential of these hybrid hydrogel membranes in biomedical applications and provided a new strategy for the future design and construction of responsive biomaterials.

磺化聚乙烯醇/侧链磺化聚芳醚酮交联复合膜的制备与性能

通过溶液共混热处理方法,制备了磺化聚乙烯醇(SPVA)含量不同的SPVA/侧链磺化聚芳醚酮交联复合膜(Cr-SSPxx)。交联网络结构有效增强了交联复合膜的力学性能、热稳定性、氧化稳定性及尺寸稳定性,扫描电镜显示,交联复合膜呈现了更好的相容性和均一性。随交联度增加,交联复合膜的溶胀率呈现明显下降趋势,在25℃和80℃时,Cr-SSP30膜的溶胀率分别仅有3.7%和7.6%。由于SPVA对醇有阻碍作用,以及交联网络结构增加了膜的致密性,故该系列Cr-SSPxx膜展现出非常优秀的阻醇性能,交联复合膜的甲醇渗透率明显低于纯S-SPAEK膜和磺化聚乙烯醇/侧链型磺化聚芳醚酮复合膜,Cr-SSP30膜的甲醇渗透率仅为9.4×10^(-8) cm^(2)/s。虽然与磺化聚乙烯醇/侧链型磺化聚芳醚酮复合膜相比,交联复合膜的质子传导率有所降低,但由于独特的侧链磺化结构能够促进质子传导,质子传导率最低的Cr-SSP30膜的传导率在25℃和80℃时也都分别达到了0.034 S/cm和0.065 S/cm,同时表现出了更高的质子选择性,能够满足直接甲醇燃料电池(DMFC)的使用要求,有望在DMFC中得到应用。

Rheology of Poly(vinyl butyral)Solution Containing Fumed Silica in Correlation with Electrospinning

The rheological properties in question are influenced by many factors, ranging from the characteristics of the given polymer or solvent to the flowing conditions. The primary focus of this study is to analyse the rheological behaviour of poly（vinyl butyral）—Mowital B 60 H—（PVB） solutions dissolved in methanol and a blend of these with fumed silica nanoparticles. The preparation of the nanofibrous web and the quality of nanofibres were correlated with the rheology of the polymer solution. It was discerned that drastically intensifying shear viscosity and the elasticity of the solution exerted a negligible effect on the formation of fibres, a finding which has rarely been discussed in the literature. The morphologies and structures of the PVB/silica nanofibrous membranes were investigated by scanning electron microscopy, thermogravimetric analysis and Fourier transform infrared spectroscopy.

聚乙烯醇缩丁醛/氧化铝杂化高分子材料的研究

由异丙醇铝与乙酰丙酮反应制备铝 乙酰丙酮螯合物 ,由此通过控制水解制备Al2 O3 溶胶 .该溶胶与聚乙烯醇缩丁醛分子上残存的羟基发生交联生成有机 无机溶胶 (OIS) .OIS经成型和干燥后即可方便地形成耐溶剂性的有机 无机杂化高分子材料 ,如透明薄膜和高弹纤维 .将OIS涂覆在碳纤维束丝上 ,热处理无机化后 ,可得到非常均匀致密的无定形氧化铝 -碳涂层 .

聚乙烯醇/纳米纤维素复合膜的渗透汽化性能及结构表征

将聚乙烯醇/纳米纤维素(PVA/NCC)复合膜应用于乙醇-水混合溶液的渗透汽化脱水过程,探讨了纳米纤维素对膜的溶胀性能、机械性能和渗透汽化性能的影响;利用原子力显微镜(AFM)探测了纳米纤维素的形貌特征;采用傅里叶变换红外光谱仪(FTIR)、扫描电镜(SEM)、差示扫描量热仪(DSC)和热重分析仪(TGA)对膜结构和热性能进行了表征.研究结果表明,棒状的纳米纤维素与PVA基体间形成了强烈的氢键作用且均匀分散在PVA基质中;纳米纤维素的加入提高了膜的熔融温度,增加了膜的热稳定性,有效地抑制了膜的溶胀,并提高了膜的机械性能;在PVA中添加纳米纤维素可以提高膜的渗透汽化分离性能,用纳米纤维素含量为2%的复合膜在80℃时分离体积分数为90%的乙醇水溶液,膜的分离因子达到347,比未加入纳米纤维素时提高24%;而渗透通量为288 g/(m2.h),比未加入纳米纤维素时下降11%.

聚乙烯醇/聚乙烯吡咯烷酮碱性复合膜的制备及其性能

通过在不同浓度KOH溶液中进行掺杂,制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.详尽考察了膜的组成、微观结构、热稳定性、离子电导率和甲醇吸收率.结果表明,PVA与PVP两者具有较好的相容性,当m(PVA)∶m(PVP)=1∶0.5时,膜断面致密、均匀,未发生大尺度相分离.PVP的混入可以极大提高复合膜的电导率和热稳定性.当m(PVA)∶m(PVP)=1∶1时,复合膜的电导率可达2.01×10-3 S.cm-1.PVA/PVP/KOH膜的甲醇吸收率随温度的升高没有明显变化,100℃时其甲醇吸收率仅为同条件下Nafion 115膜的1/4.这表明该复合膜有望作为一种新型的碱性直接甲醇燃料电池用固体电解质膜且可提高膜的使用温度.

聚丙烯酰胺/蒙脱土纳米复合物-聚乙烯醇共混膜的制备及其渗透汽化性能

用原位聚合法制备聚丙烯酰胺/蒙脱土(PAM/MMT)纳米复合材料,通过透射电镜研究了蒙脱土在聚丙烯酰胺基体中的形貌和分布.结果表明,蒙脱土以片层结构分布在聚合物基体中.用超声波分散聚乙烯醇和聚丙烯酰胺-蒙脱土共混铸膜液制得共混膜,用红外吸收光谱和扫描电镜研究了两者的相互作用和形貌.考察了共混膜在异丙醇-水混合溶液中的溶胀吸附性能及共混比和蒙脱土含量对膜分离性能的影响,结果显示,聚乙烯醇膜中添加适量的蒙脱土纳米粒子可以大大改善膜的分离选择性.

双极膜技术在电氧化制备3-甲基-2-吡啶甲酰胺中的应用

分别以戊二醛和Fe3+改性壳聚糖和海藻酸钠并分别与柔性链聚乙烯醇(PVA)共混,制备了Fe-SA-CS-GA/PVA聚合物双极膜.测定膜的红外光谱,I-V工作曲线,Na+与Cl-透过双极膜的迁移数,离子交换容量及阴阳两极室中OH-及H+的变化,并以扫描电镜观察膜表面和界面层形态.IR与接触角分析结果表明,CS经GA/PVA改性后其亲水性能得到显著提高.将SA-CS/PVA双极膜及Nafion膜应用于电氧化制备3-甲基-2-吡啶甲酰胺.实验结果表明,以SA-CS/PVA双极膜为隔膜合成3-甲基-2-吡啶甲酰胺的产率达到49.8%,高于以Nafion膜为隔膜的产率.与传统的的方法相比,该方法的反应条件温和且能有效利用能源.