纤维编织管增强型中空纤维膜研究

采用二维编织技术将聚丙烯腈(PAN)长丝编织成中空纤维编织管作为增强体,分别以聚丙烯腈(PAN)和聚偏氟乙烯(PVDF)为成膜聚合物,N,N-二甲基乙酰胺(DMAc)为溶剂,聚乙烯吡咯烷酮(PVP)为添加剂,调制铸膜液,采用同心圆挤出-涂覆法制备了PAN纤维编织管同质增强型PAN中空纤维膜和异质增强型PVDF中空纤维膜.研究表明,所得PAN纤维编织管增强型中空纤维膜断裂强度最大可超过75 MPa,在伸长率10%范围内,表面分离层与增强体之间界面结合良好;表面分离层具有类似于非对称膜的结构,铸膜液可浸入纤维编织管纤维空隙中,铸膜液浸入部分固化后未影响膜的通透性能;随成膜聚合物浓度增加,膜纯水通量减小,牛血清白蛋白(BSA)截留率增大;随添加剂PVP浓度增加,膜的纯水通量先增大后减小,在8 wt%左右达最大值,BSA截留率随PVP浓度增加而单调增加;同质增强型中空纤维膜界面结合程度优于异质增强型.     

PVDF膜改性方法研究进展

本文介绍了目前国内外聚偏氟乙烯(PVDF)超滤膜改性中常用的膜表面改性方法和膜材料改性方法。PVDF膜表面改性主要通过膜表面的物理改性、磺化改性、表面接枝改性、光化学改性、低温等离子体改性等方法来实现;而PVDF膜材料的改性主要是通过PVDF与亲水性高分子材料或小分子无机粒子的共混以及膜材料本体的化学改性来实现。改性PVDF膜的亲水性增强,使水通量增加,提高了机械性能,改善了抗污染性,增加了膜的使用寿命。     

PVDF膜改性的方法研究

本文介绍了目前国内外聚偏氟乙烯(PVDF)超滤膜改性中常用的膜表面改性方法和膜材料改性方法。PVDF膜表面改性主要通过膜表面的物理改性、磺化改性、表面接枝改性、光化学改性、低温等离子体改性等方法来实现;而PVDF膜材料的改性主要是通过PVDF与亲水性高分子材料或小分子无机粒子的共混以及膜材料本体的化学改性来实现。改性PVDF膜的亲水性增强,使水通量增加,提高了机械性能,改善了抗污染性,增加了膜的使用寿命。     

PSF-SPES共混中空纤维超滤膜制备的研究

以聚砜(PSF)、磺化聚醚砜(SPES)和醋酸纤维素(CA)为膜材料,水为内凝胶剂,采用干湿法制备了PSF-SPES共混中空纤维超滤膜,探讨了PSF-SPES铸膜液中SPES离子交换容量(IEC)、SPES浓度、添加剂、外凝胶剂的选择和热处理对膜性能的影响。所得共混超滤膜性能如下:w=0.0 0 1的Na2SO4截留率19.9%,通量62 L/(h.m2.MPa);w=0.001的PEG4000截留率78.2%,通量85 L/(h.m2.MPa)。此外,以PSF-SPES中空纤维为支撑膜,采用醋酸纤维素作为涂层液,研究了CA/PSF-SPES复合超滤膜性能,讨论了CA/PSF-SPES共混中空纤维超滤膜结构。     

凝固浴温度对PVDF铸膜液相分离过程和膜结构的影响

采用皮-亚两步凝胶成膜机理探讨了凝固浴温度对PVDF铸膜液的相分离行为及其膜结构的影响.采用浊度法测定不同温度时铸膜液体系的热力学性质,光透射仪测定不同凝固浴温度时沉淀速率对膜的形态和性能的影响.结果显示:皮层的生成主要受热力学性质控制,随着凝固浴温度的提高,皮层由液固分相转变为液液分相,延时时间缩短,皮层由相互融合的球粒致密结构转变为多孔结构.亚层的生成主要受皮层结构和溶剂/非溶剂相互扩散的影响,膜亚层主要发生液液分相;随凝固浴温度升高,分相速率加快,大孔发展更充分,膜的孔隙率和气通量提高,但结晶度降低.     

添加剂对PVDF相转化过程及膜孔结构的影响

研究了PVP、PEG及LiCl 3种成孔添加剂下PVDF DMAc H2 O 添加剂体系的成膜机理 .无论那种添加剂的铸膜液相转换成膜过程中都存在凝胶分相和液液分相两种相变方式 ,在 30～ 6 0℃时凝胶分相在较低的非溶剂浓度下先于液液分相发生 ,LiCl作为添加剂较PEG、PVP对铸膜液有较强的致凝胶作用 ,成膜过程中凝胶分相段时间依PVP、PEG、LiCl的顺序延长 ,导致液液分相初始分相点处聚合物浓度增大 ,阻止了大孔结构的充分发展 .制得的膜依PVP、PEG、LiCl的顺序有效孔隙率和通量降低 ,结晶度升高 .以LiCl为添加剂制得的膜几乎不改变PVDF膜的疏水性 ,而以PVP或PEG为添加剂的膜隔水压差降低约 2 0kPa .     

低截留分子量PPES超滤膜的制备

以杂萘联苯聚醚砜(PPES)为膜材料、N-甲基吡咯烷酮(NMP)为溶剂、有机小分子丙醇(PrOH)和无机小分子氯化锂(LiCl)作为混合添加剂,采用相转化法制备超滤膜.研究了聚合物浓度、混合添加剂配比、凝胶浴温度等对膜结构和性能的影响.结果表明:随聚合物浓度的增大,膜的纯水通量下降,截留率升高;混合添加剂,在PrOH含量为12%、LiCl含量为1.5%时,可制得纯水通量为252 L/(m2·h),对聚乙二醇1000(PEGl000)截留率为96%的超滤膜;随凝胶浴温度的升高,膜的纯水通量增加.     

TEP-DMAc混合溶剂对PVDF膜性能的影响

利用非溶剂相转化法(NIPS)制备聚偏氟乙烯(PVDF)膜,考察了聚乙二醇(PEG200)与N,N-二甲基乙酰胺(DMAc)的质量比对膜分相速率和膜性能的影响,讨论了以磷酸三乙酯(TEP)和DMAc的混合液作溶剂对PVDF膜凝胶速率、膜结构和膜通量的影响。结果表明:PEG200的加入减弱了溶剂对聚合物的溶解能力,但铸膜液的分相行为由延迟分相转变为瞬时分相,膜通量提高。随着混合溶剂中TEP含量的增大,铸膜液的黏度增大,分相速率减慢;在高质量比m(TEP)/m(DMAc)时,膜表面的孔增多,指状孔膜结构逐渐消失,整个膜截面呈海绵状,膜通量变大,力学性能提高。     

表面喷雾N,N-二甲基乙酰胺/水-浸没沉淀相转化法制备PVDF多孔膜的结构和性能

在刮制的聚偏氟乙烯(PVDF)铸膜液上喷雾N,N-二甲基乙酰胺/水(DMAc/H₂O)混合溶液进行表面凝胶,随后将表面凝胶的液膜浸入凝固浴中使沉淀相转变成PVDF多孔膜。考察了喷雾溶液中DMAc的体积分数(φ(DMAc))对平板PVDF多孔膜结构和性能的影响。结果显示,随着φ(DMAc)增加,膜上表面的β晶含量逐渐减少,α晶含量逐渐增多,但是膜总体的结晶度逐渐增加,孔隙率和平均孔径先增加后减小。通过扫描电镜观察,喷雾了DMAc/H₂O混合溶液的PVDF膜上表面为多孔皮层,且随着φ(DMAc)的增加,上表面球形晶粒逐渐增加,断面由指状大孔结构转变为海绵状孔结构。当喷雾中φ(DMAc)=30%时,膜的水通量和牛血清白蛋白(BSA)截留率达到最大。     

PVDF/ZrO_2杂化膜的制备及吸附牛血红蛋白的性能

将3-氨丙基三乙氧基硅烷(APTES)表面修饰的ZrO2纳米颗粒添加到聚偏氟乙烯(PVDF)铸膜液中制备了PVDF/ZrO2杂化膜,应用SEM,TG-DTA和XRD对其结构进行了表征.结果表明,ZrO2纳米颗粒沉积在PVDF膜孔内和膜表面;ZrO2的掺杂改变了PVDF膜孔径的大小,杂化膜的孔径随着ZrO2粒子负载量的增加而增大.对牛血红蛋白(BHb)的吸附实验结果表明,PVDF/ZrO2杂化膜对BHb的吸附量显著高于PVDF原膜,当BHb初始浓度为150μg/mL,pH=7,吸附时间为45 min时,PVDF/ZrO2杂化膜的平衡吸附量为0.181 mg/cm2.其吸附动力学符合一级动力学模型;吸附等温线符合Langmuir等温方程式.     

Molecular elucidation of morphology and mechanical properties of PVDF hollow fiber membranes from aspects of phase inversion, crystallization and rheology

This study explores the fundamental science of fabricating poly(vinylidene fluoride) (PVDF) hollow fiber membranes as well as elucidates the correlation among membrane morphology, crystallinity and mechanical properties as functions of non-solvent additives and dope rheology in the phase inversion process. A series of non-solvents (i.e. water, methanol, ethanol, isopropanol) are used either as non-solvent additives in the dope or as a component in the external coagulant. Depending on the strength of the non-solvent, the phase inversion of semi-crystalline PVDF membranes is dominated by liquid–liquid demixing or solid–liquid demixing accompanying crystallization. As a result, the membrane morphology transforms from an interconnected-cellular type to an interconnected-globule transition type with lower mechanical strengths when adding water, methanol, ethanol, or isopropanol into the spinning dopes or into the coagulation bath. The crystallinity and size of spherulitic globules in the morphology are controlled by the amounts of non-solvents presented in the systems. The rheological behavior of dope solutions is explored and the relationship between elongation viscosity and mechanical properties has been elaborated. Analytical methods and molecular dynamics simulations are employed to provide insights mechanisms from the views of thermodynamic and kinetic aspects as well as the state of polymer chains involved in the phase inversion process.     

Preparation and characterization of polyvinylidene fluoride (PVDF) hollow fiber membranes

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared by dry/wet and wet phase inversion methods. In spinning these PVDF hollow fibers, dimethylacetamide (DMAc) and polyvinyl pyrrolidone (PVP) were used as a solvent and an additive, respectively. Water was used as the external coagulant. Water or ethanol was used as the internal coagulants. The membranes were characterized in terms of water flux, molecular weight cut-off for the wet membranes. Gas permeation fluxes and effective surface porosity were determined by a gas permeation method for the dried membranes. The cross-sectional structures were examined by scanning electron microscopy. The effects of polymer concentration, air-gap, PVP molecular weight, PVP content in the polymer dope, and the internal coagulant on the permeation properties and membrane structures were examined. Highly permeable PVDF hollow fiber membranes could be prepared from a polymer dope containing low molecular weight PVP and using ethanol as the internal coagulant.     

From protein denaturant to protectant: comparative molecular dynamics study of alcohol/protein interactions

It is well known that alcohols can have strong effects on protein structures. For example, monohydric methanol and ethanol normally denature, whereas polyhydric glycol and glycerol protect, protein structures. In a recent combined theoretical and NMR experimental study, we showed that molecular dynamics simulations can be effectively used to understand the molecular mechanism of methanol denaturing protein. In this study, we used molecular dynamics simulations to investigate how alcohols with varied hydrophobicity and different numbers of hydrophilic groups (hydroxyl groups) exert effects on the structure of the model polypeptide, BBA5. First, we showed that methanol and trifluoroethanol (TFE) but not glycol or glycerol disrupt hydrophobic interactions. The latter two alcohols instead protect the assembly of the α- and β-domains of the polypeptide. Second, all four alcohols were shown to generally increase the stability of secondary structures, as revealed by the increased number of backbone hydrogen bonds formed in alcohol/water solutions compared to that in pure water, although individual hydrogen bonds can be weakened by certain alcohols, such as TFE. The two monohydric alcohols, methanol and TFE, display apparently different sequence-dependence in affecting the backbone hydrogen bond stability: methanol tends to enhance the stability of backbone hydrogen bonds of which the carbonyl groups are from polar residues, whereas TFE tends to stabilize those involving non-polar residues. These results demonstrated that subtle differences in the solution environment could have distinct consequences on protein structures.     

Evaluation of selected‐ion flow‐tube mass spectrometry for the measurement of ethanol,methanol and isopropanol in physiological fluids: effect of osmolality and sample volume

Selected‐ion flow‐tube mass spectrometry (SIFT‐MS) is particularly suited for the analysis of volatile low molecular weight compounds. We have evaluated this technique for the assay of different alcohols in aqueous solutions, including blood plasma, and in particular whether the osmolality or sample volume affected vapourisation. Solutions of three different alcohols (methanol, ethanol and isopropanol) ranging from 0.005 to 50 mmol/L were prepared in deionised water (0 milliosmol), phosphate‐buffered saline (690 mOsm), isotonic saline (294 mOsm) and plasma (296 mOsm). The vapour above the sample (50 to 1000 µL) contained in air‐tight tubes at 37°C was aspirated into the instrument. The outputs for ethanol, methanol and isopropanol were linear over the concentration range and independent of the sample volume and relatively independent of the osmolar concentration. SIFT‐MS can reliably and accurately measure common alcohols in the headspace above aqueous solutions, including serum/plasma. This novel application of SIFT‐MS is easy to follow, requires no sample preparation and the wide dynamic range will facilitate measurement of alcohols present from normal metabolism as well as when taken in excess or in accidental poisoning. Copyright © 2009 John Wiley & Sons, Ltd.     

Modification of polysulfone hollow fiber ultrafiltration membranes using hyperbranched polyesters with different molecular weights

A series of hyperbranched polyesters (HBPEs) using trimethylolpropane (TMP) as a core were synthesized via an esterification reaction, and the molecular weights of these HBPEs were 1600, 2260, 3370, and 5170 g/mol, respectively. Then, these HBPEs were added into dope solutions to prepare PSf hollow fiber membranes via a wet‐spinning method. When the HBPE molecule weight increased from 1600 to 5170 g/mol, the initial viscosities of the PSf–HBPE–PEG400–DMAc dope solutions increased, and the shear‐thinning phenomenon of these dope solutions became increasingly obvious. When these dope solutions were immersed into the deionized water, the demixing rate increased with an increase in the HBPE molecule weight at first and then decreased; this results in the increase of membrane porosity and the coexistence of finger‐like and sponge‐like structures. With the addition of HBPE, the start pure water contact angle and the mean effective pore size of the membranes decreased, and the J_w increased. For the mechanical properties of the membranes, the breaking strength and the elongation of the membranes also increased. Copyright © 2015 John Wiley & Sons, Ltd.     

Light scattering and membrane formation studies on polysulfone solutions in NMP and in mixed solvents of NMP and ethyl acetate

The relationship between the characteristics of the polymer dope solution and the skin formation mechanism as well as the performance of the asymmetric membrane has been investigated. The solution characteristics have been studied on the polysulfone (PSf) dope solution as a function of the concentrations of both polymer and the cosolvent, ethyl acetate (EA), by dynamic light scattering. An anomalous light scattering was observed at small angles in both PSf/NMP and PSf/NMP:EA (6:4 by weight) solutions, indicating the inhomogeneity of the dope solutions. In the case of the PSf/NMP:EA (6:4) solution, an integrally skinned asymmetric membrane without defects having high gas selectivity was obtained while the membrane from the PSf/NMP solution had a defective skin. The scattered light intensity of the dope solution of PSf/NMP:EA (6:4) increased with the aging time while no notable change was observed in the PSf/NMP solution. The characteristics of the solution affect the final morphology of the membrane, particularly when phase separation occurred significantly before the immersion into the gelation medium.     

Study on the toxic interaction of methanol, ethanol and propanol against the bovine hemoglobin (BHb) on molecular level

The toxic interaction of methanol, ethanol and propanol with bovine hemoglobin (BHb) at protein molecular level was studied by resonance light scattering (RLS), fluorescence, ultraviolet-visible absorption (UV-vis) and circular dichroism (CD) techniques. The experimental results showed that the three alcohols all had toxic effects on BHb and the effects increased along with the increasing alcohol dose. The results of RLS and fluorescence spectroscopy showed that alcohols can denature BHb. They changed the microenvironment of amino acid residues and led to molecular aggregation. The decreasing order of the influence is propanol, ethanol and methanol. The results of UV-vis and CD spectra revealed that alcohols led to conformational changes of BHb, including the loosening of the skeleton structure and the decreasing of α-helix in the second structure. The changes generated by propanol were much larger than those by methanol and ethanol.     

Influence of ethanol on lipid membranes: from lateral pressure profiles to dynamics and partitioning

We have combined experiments with atomic-scale molecular dynamics simulations to consider the influence of ethanol on a variety of lipid membrane properties. We first employed isothermal titration calorimetry together with the solvent-null method to study the partitioning of ethanol molecules into saturated and unsaturated membrane systems. The results show that ethanol partitioning is considerably more favorable in unsaturated bilayers, which are characterized by their more disordered nature compared to their saturated counterparts. Simulation studies at varying ethanol concentrations propose that the partitioning of ethanol depends on its concentration, implying that the partitioning is a nonideal process. To gain further insight into the permeation of alcohols and their influence on lipid dynamics, we also employed molecular dynamics simulations to quantify kinetic events associated with the permeation of alcohols across a membrane, and to characterize the rotational and lateral diffusion of lipids and alcohols in these systems. The simulation results are in agreement with available experimental data and further show that alcohols have a small but non-vanishing effect on the dynamics of lipids in a membrane. The influence of ethanol on the lateral pressure profile of a lipid bilayer is found to be prominent: ethanol reduces the tension at the membrane-water interface and reduces the peaks in the lateral pressure profile close to the membrane-water interface. The changes in the lateral pressure profile are several hundred atmospheres. This supports the hypothesis that anesthetics may act by changing the lateral pressure profile exerted on proteins embedded in membranes.     

Direct measurement of rheologically induced molecular orientation in gas separation hollow fibre membranes and effects on selectivity

Asymmetric polysulfone hollow fibre membranes for gas separation were spun using a dry/wet spinning process. An optimised four component dope solution was used: 22% (w/w) polysulfone, 31.8% (w/w) N,N-dimethylacetamide, 31.8% (w/ w) tetrahydrofuran and 14.4% (w/w) ethanol. Fibres were spun at low- and high-dope extrusion rates and hence at different levels of shear. Molecular orientation in the active layer of the membranes was measured by plane-polarised infrared spectroscopy. Gas permeation properties (permeability and selectivity) were evaluated using pure carbon dioxide and methane. The spectroscopy indicated that increased molecular orientation occurs in the high-shear membranes. The selectivities of these membranes were heightened and even surpassed the recognised intrinsic selectivity of the membrane polymer. The results suggest that increased shear during spinning increases molecular orientation and, in turn, enhances selectivity.     

Catalytic Ethanolysis of Kraft Lignin into High‐Value Small‐Molecular Chemicals over a Nanostructured α‐Molybdenum Carbide Catalyst

We report the complete ethanolysis of Kraft lignin over an α‐MoC_1?x/AC catalyst in pure ethanol at 280 °C to give high‐value chemicals of low molecular weight with a maximum overall yield of the 25 most abundant liquid products (LP25) of 1.64 g per gram of lignin. The LP25 products consisted of C₆–C₁₀ esters, alcohols, arenes, phenols, and benzyl alcohols with an overall heating value of 36.5 MJ kg^?1. C₆ alcohols and C₈ esters predominated and accounted for 82 wt % of the LP25 products. No oligomers or char were formed in the process. With our catalyst, ethanol is the only effective solvent for the reaction. Supercritical ethanol on its own degrades Kraft lignin into a mixture of small molecules and molecular fragments of intermediate size with molecular weights in the range 700–1400, differing in steps of 58 units, which is the weight of the branched‐chain linkage C₃H₆O in lignin. Hydrogen was found to have a negative effect on the formation of the low‐molecular‐weight products.