不同分子量聚丙烯腈共混膜的制备与表征

将普通分子量聚丙烯腈(C-PAN,Mw=18 000)与超高分子量聚丙烯腈(UHMW-PAN,Mw=1 780 000)共混,采用干-湿相转化法制备不对称共混膜.考察了聚合物浓度、共混比、凝胶浴温度、刮膜厚度、添加剂浓度等对膜结构及性能的影响.采用扫描电镜、纯水通量和BSA截留率等测试手段对所制备膜的结构及性能进行表征.结果表明:共混比及成膜过程对共混膜的结构及性能有重要影响.当铸膜液浓度为12%,C-PAN/UHMW-PAN共混比为2∶3,凝胶浴温度为40℃,刮膜厚度为100μm时,共混膜的纯水通量为580L/(m~2·h),BSA截留率为99.99%.随添加剂浓度增加,交联膜大孔结构减少,海绵状孔结构增加,导致其纯水通量降低,BSA截留率增加,膜的结构可以通过上述因素进行结构调控.     

制膜工艺条件对PVC/SPES共混膜性能的影响

采用溶剂-非溶剂扩散致相分离的方法,在不同制膜条件下(铸膜液聚合物含量、铸膜液温度、凝胶浴温度和凝胶浴组成)制备了PVC/SPES共混膜,并对膜的纯水通量、截留率、断裂强度、耐污染性能和膜的断面结构等性能进行了测试,从而探讨制膜工艺条件对PVC/SPES共混膜微观结构及性能的影响.通过对不同聚合物含量的共混膜的纯水通量、截留率、机械性能和耐污染性能测试比较,得到PVC/SPES共混膜的最佳制膜条件:聚合物质量分数为16％,铸膜液温度为70℃,凝胶浴温度为20℃,凝胶浴为纯水.     

己二酸调控聚醚砜/磺化聚砜致密超滤膜结构及染料/盐选择分离性能

以聚醚砜(PES)和亲水性磺化聚砜(SPSf)为原料进行共混,以己二酸为致孔剂,采用非溶剂致相分离法(NIPS)制备PES/SPSf致密超滤膜(UF),重点考察铸膜液中己二酸含量对PES/SPSf共混膜结构和性能的影响规律.结果表明,随着铸膜液中己二酸含量增加,铸膜液黏度逐渐增加,膜断面结构逐渐由指状孔转变为海绵体结构.当己二酸添加质量分数为11%以及聚合物质量分数为31%(PES/SPSf=84/16)时,所制备共混膜断面为完全的海绵体结构.该膜切割分子量(MWCO)约为7 250,平均孔径约为1.81 nm,纯水通量为144 L/(m~2·h)(操作压力0.2 MPa).共混膜处理刚果红(CR)与Na_2SO_4混合液时,对刚果红截留率保持在100%,Na_2SO_4截留率25%,显示出优异的染料和盐选择分离性和稳定性.处理靛蓝磺酸钠(IC)/CR/Na_2SO_4三元体系时,其染料截留率分别为93.1%和100%,同样表现出优异的染料和盐选择分离性和稳定性.     

纳米纤维素及凝胶浴对复合膜结构和性能调控的研究

采用浸没沉淀相转化法制备纳米纤维素(NCC)/聚砜(PSF)复合膜材料。考察了不同浓度(10%、30%、50%)乙醇凝胶浴及NCC添加量对膜结构和性能的影响机制。通过扫描电子显微镜(SEM)观察了复合膜材料断面和皮层的孔结构,发现凝胶浴中乙醇浓度的增加使得聚砜膜逐渐由非对称膜向对称膜转变。NCC的添加使膜表面自由能下降,不同浓度的乙醇凝胶浴和NCC添加量对复合膜的机械性能、截留率、孔隙率和纯水通量等性能有很大的调控作用。     

聚醚砜血浆蛋白分离中空纤维膜的研制

采用干-湿相转化法纺丝工艺纺制聚醚砜中空纤维膜,研究了聚乙二醇(PEG)含量、入水距离对聚醚砜中空纤维膜性能的影响.结果表明,随PEG含量的增加,PES中空纤维膜的纯水通量、溶茵酶的清除率增大,牛血清的截留率、爆破压力略有下降;随着入水距离的增大,PES中空纤维膜水通量、溶菌酶的清除率逐渐下降,牛血清的截留率变化并不明显.     

血液分离用聚偏氟乙烯中空纤维膜的制备

采用干-湿相转化法制备聚偏氟乙烯(PVDF)中空纤维膜.实验结果表明,随着纺丝原液中添加剂PEG含量的升高,膜的结构趋于疏松,膜的水通量增大,膜对牛血清的截留率都在98%以上,并保持了良好的机械性能;随着纺丝原液中添加剂PVP含量的升高,膜的结构过于疏松,压密化现象明显,致使膜的水通量减小,膜对牛血清白蛋白的截留卒上升,机械性能明显下降;共同加入PEG和PVP并保持总量不变,改变二者的比例关系,随着PVP在添加剂中所占比例增多,纯水通量先上升后由于压密作用而下降,泡点、破裂压力、断裂强力、拉伸伸长率均下降.随着添加剂中PVP含量从0增加到28.8%,膜对牛血清白蛋白的截留率从98.0%骤降到64.1%,之后,随着添加剂中PVP含量再增加,截留率基本维持在60%左右.     

聚乙烯醇缩丁醛超滤膜的制备

用聚乙烯醇缩丁醛(PVB)作为本体高分子材料,用浸没沉淀相转化法制备PVB不对称超滤膜;扫描电镜照片显示所制膜的超滤结构.研究了PVB本体浓度、制膜间隙、凝胶浴温度以及乙酸添加剂等因素对PVB不对称超滤膜性能的影响;比较了乙酸及聚乙烯基吡咯烷酮(PVP)作为添加剂对大孔径PVB超滤膜皮层结构的影响.当PVB本体浓度为12%时,膜的纯水通量及牛血清白蛋白(BSA)溶液通量分别为876.4 L/(m2.h)和89.8 L/(m2.h),此时膜对BSA的截留率为96.8%;PVB膜纯水通量随着制膜间隙的增加及凝胶浴温度的上升而降低;乙酸及PVP的添加均提高了PVB超滤膜的纯水通量,通量增加幅度分别为136%和171%.     

凝固浴组成对PVDF-g-PACMO共聚物膜结构与抗污染性能的影响

采用亲水、无毒、生物相容性好、对蛋白质吸附有排斥作用的丙烯酰吗啉(ACMO)对聚偏氟乙烯(PVDF)本体进行亲水改性,研究了凝固浴中不同乙醇含量(乙醇:去离子水的质量比分别为0∶100,15∶85,30∶70,45∶55)对PVDFg-PACMO共聚物膜抗污染性能的影响。结果表明,随着凝固浴中乙醇含量的增加,膜断面孔结构向海绵状转变,膜平均孔径和孔隙率增大,纯水通量增加,牛血清蛋白(BSA)截留率降低,膜表面亲水性增加,抗污染性能提高。当凝固浴中乙醇质量分数为45%时,膜表面BSA的吸附量由115.4μg/cm2降至20.6μg/cm2,通量恢复率高达97.6%,总污染指数低至0.148。因此,通过改变凝固浴中乙醇的含量,能使PVDF-g-PACMO膜表面亲水性明显提高,制得了具有良好抗蛋白质污染能力的改性PVDF膜。     

活性炭填充对聚砜超滤膜性能的影响

采用相转化法制备聚砜(PSF)超滤膜,通过正交实验确定了较优的制膜条件,并用活性炭填充制备了共混的聚砜超滤膜,考察了活性炭加入量对膜的水通量、牛血清白蛋白(BSA)截留率及孔隙率的影响,以及操作条件对填充膜性能的影响。结果表明,最优化制膜条件为:添加剂聚乙二醇(PEG-400)含量为8%,蒸发时间为60s,纯水作为凝固浴,在此条件下制得的膜水通量达到212.6L/(m2.h),BSA截留率为84.1%。活性炭填充对膜水通量和截留率有明显影响,在活性炭含量为0.5%～1.5%时,膜通量随操作压力增大而增大,而截留率变化不大。     

CA/PSf共混超滤膜的制备及性能研究

以聚砜(PSf)为基膜材料,醋酸纤维素(CA)为共混膜材料,N,N-二甲基乙酰胺(DMAc)为溶剂,去离子水为凝固浴,采用非溶剂致相分离法(NIPS法)制备CA/PSf共混平板超滤膜.综合考察了共混膜有机物溶出量,铸膜液聚合物浓度和共混比以及不同凝固浴组成对膜结构、水通量、水接触角、孔隙率、蛋白质截留率的影响.结果表明:相对于传统的以聚乙烯吡咯烷酮(PVP)作为添加剂的共混膜,使用CA作为添加剂,共混膜有机物溶出量大幅降低.随着CA含量的增加,共混膜孔隙率逐渐增大,亲水性增加.另外,随着凝胶浴中溶剂含量的增大,共混膜纯水通量不断降低,BSA截留率逐渐升高,膜形态结构变得更加致密.     

具有催化与渗透汽化双功能的纳米TiO2和Al2O3填充复合膜性能

采用聚丙烯腈(PAN)中空纤维超滤膜作为支撑底膜,经戊二醛(GA)表面交联的聚乙烯醇(PVA)作为渗透汽化层,以及纳米TiO2或Al2O3填充的全氟磺酸树脂(PFSA)作为催化层,制备了催化与渗透汽化双功能复合膜,考察了其亲水性能、对乙酸乙酯塔顶粗酯的渗透汽化分离性能、催化酯化反应性能以及机械性能.实验结果表明:催化与渗透汽化双功能复合膜具有良好的亲水性和机械性能,渗透通量可达到179g/(m2.h),相对应的分离系数为95,渗透物中不含乙酸乙酯,同时可显著缩短酯化反应达到相同转化率的时间.     

Plasma-treated polyethersulfone coated with crosslinked poly(vinyl alcohol): composite membranes for pervaporation dehydration of ethanol

Composite membranes with crosslinked poly(vinyl alcohol) matrix as selective layer coated on a polyethersulfone supporting porous layer were prepared aiming at separating ethanol/water mixtures by pervaporation. A polyethersulfone asymmetric microporous membrane was synthesized by the wet phase inversion process. The support membrane was then exposed to air plasma to activate the surface. The selective dense layer was obtained by coating of PVA and a crosslinking agent over the polyethersulfone substrate, followed by thermal treatment. The morphology was examined by scanning electron microscopy (SEM) for both, support membrane and the coated polymeric layers. Surface physicochemical properties were evaluated through measuring the contact angle (θ) and the estimation of surface free energy (γ_S) and adhesion work. The surface chemical composition of support membrane and coated hydrophilic layers were characterized by infrared spectra with horizontal attenuated total reflectance (FT-IR/HATR). The swelling degree of PVA dense membranes, and the pervaporation performance of the crosslinked PVA/PES composite membranes, manufactured with several coating steps, were evaluated with water/ethanol (20/80 wt%) mixtures at temperatures in the range of 30–60 C. Results of the effective pervaporation dehydration of ethanol are discussed in terms of membrane morphology and the solution-diffusion transport mechanism.     

支撑层对PDMS复合膜渗透汽化性能的影响

以相转化法制备的聚偏氟乙烯(PVDF)、聚丙烯腈(PAN)、聚砜(PSF)三种多孔膜作为支撑层,制备聚二甲基硅氧烷(PDMS)复合膜用于渗透汽化乙醇/水混合物的分离。采用能量色散X射线光谱仪(EDX)定量表征了PDMS在支撑层表面的厚度(L0)和支撑层内的渗入深度(Li),研究发现,PDMS在各支撑层表面的厚度、支撑层内渗入的厚度有显著差异,PDMS复合膜的渗透通量与(L0+Li)间存在近似的线性关系,表明PDMS在支撑层中渗入深度不同是造成不同底膜支撑的PDMS复合膜渗透汽化性能差异的根本原因。文中提出选择层总厚度(Lt=L0+Li)概念,通过线性拟合得到PDMS复合膜渗透通量与Lt之间的定量关系,可以用来估算PDMS复合膜的渗透通量,并预测复合膜渗透通量极大值。     

基于树枝型聚合物的膜与膜过程研究进展

树枝型聚合物是具有内部疏松、外部致密、端基官能团众多等结构的高度支化聚合物,这些特点使得树枝型聚合物具有多种不同于线性聚合物的特性,与膜和膜技术相结合有特殊意义.介绍了树枝型聚合物气体分离膜、支撑液膜、离子交换膜、膜表面改性以及树枝型聚合物参与的膜过程等方面的研究进展,简要展望了基于树枝型聚合物的分离膜与膜技术的发展趋势.     

Flexural vibration of a pyrocomposite hollow cylinder

Flexural vibration of an infinite pyrocomposite circular hollow cylinder composed of an inner and outer pyroelectric layer of class 6 bonded together by a linear elastic material with voids (LEMV) is studied. The exact frequency equation is obtained for traction-free surfaces with continuity conditions at the interfaces. Numerical results in the form of data and dispersion curves for the first and second modes of the flexural vibration of the cylinder ceramic-1/Adhesive/ceramic-2 by taking the adherents as BaTio₃ and the adhesive as an existing carbon fibre-reinforced polymer (CFRP) or as a hypothetical LEMV layer with and without voids are compared with that of a single-layered pyroelectric hollow cylinder. The damping is analyzed through the imaginary parts of the complex frequencies.     

添加剂对制备对称状PVDF膜的结构与蛋白吸附性能的影响

以聚偏氟乙烯(PvDF)为膜材料,通过浸没沉淀法制备得到开放性网络状对称结构的PVDF膜.考察不同添加剂对膜结构的影响.结果表明,与溶剂磷酸三乙酯(TEP)相容性良好的添加剂(乙醇,聚乙二醇,乙酸乙酯)所成膜表面结构均匀,孔隙率较大,蛋白吸附量较高;与溶剂相容性较差的添加剂(水,甘油)使得铸膜液组成接近于分相区,成膜过...     

基于两尺度代表体元的含孔隙复合材料单层板弹性常数预测

为预测含孔隙复合材料单层板的弹性常数,以单向纤维增强复合材料单层板为研究对象,首先,基于细观力学方法,提出了一种基于两尺度代表体元的含孔隙复合材料单层板弹性常数预测方法;然后,基于纤维排列和孔隙特征,建立了纤维-基体尺度的代表体元模型和含孔隙复合材料单层板的代表体元模型,并采用有限元方法求解弹性常数;接着,采用周期对称边界条件,在纤维-基体尺度先进行第1步等效,得到不含孔隙复合材料单层板的弹性常数;最后,在含孔隙复合材料单层板的代表体元模型上进行第2步等效,完成了含孔隙复合材料单层板弹性常数的预测。结果显示:应用该方法得到的计算结果与试验数据吻合较好;结合纤维、基体弹性常数及孔隙形态的模型,该方法可以反映各因素对复合材料单层板弹性常数的影响。      

Axisymmetric vibration of piezocomposite hollow circular cylinder

Summary The axisymmetric vibration of a piezoelectric laminated hollow circular cylinder has been studied for an imperfect interface model. The frequency equation is derived for traction free inner and outer surfaces of the hollow cylinder with continuity conditions at the bonding interfaces. The composite cylinder is composed of two different piezoelectric materials belonging to 6 mm class and a hypothetical Linear Elastic Material with Voids (LEMV) as bonding layer. Numerical solutions of the frequency equation are obtained for the composite cylinder ceramic(1)/LEMV/ceramic(2). Computational results are presented as dispersion curves as well as in tables to characterize the attenuation of axial waves for three layered cylinders with and without voids in the thin LEMV layer.     

Potassium-selective electrodes with stable and geometrically well-defined internal solid contact based on nanoparticles of polyaniline and plasticized poly(vinyl chloride)

Solid contact potassium-selective electrodes with the internal ion-to-electron transduction layer composed of plasticized poly(vinyl chloride) (PVC) and 2-20% (m/m) of polyaniline (PANI) nanoparticles, with the mean particle size of 8 nm, have been studied in this paper. UV-vis measurements in pH buffer solutions between pH 0 and 12 show that the electrically conducting emeraldine salt (ES) form of PANI has exceptionally good pH stability. Membranes of PANI nanoparticles were mainly in the ES form even at pH 12, in contrast to electrochemically prepared PANI(Cl) films, which are converted completely to the nonconducting form already at pH 6. Long-term UV-vis measurements with the PANI membranes in contact with aqueous buffer solution at pH 7.5 showed no degradation of the ES form. The PANI nanoparticles are homogenously mixed in the PVC-based solid contact (SC) layer. Only the uppermost part of the SC layer is to a minor extent dissolved in the outer potassium-selective PVC membrane. This enabled the preparation of geometrically well-defined inner SC layers, thus improving the reproducibility of the solid contact electrodes and resulting in good mechanical strength between the inner and outer membranes.     

Computations of permeability tensor coefficients and anisotropy of asphalt concrete based on microstructure simulation of fluid flow

Asphalt concrete is the most widely used material for building the surface layer of pavements. It is a porous material that consists of a non-uniform arrangement of asphalt binder, aggregate particles and air voids. One of the primary factors controlling pavement performance is the fluid flow characteristics within the surface asphalt concrete layer.

This paper focuses on the numerical simulation of fluid flow in the three-dimensional (3-D) microstructure of asphalt concrete, and the calculation of permeability from the flow field. The asphalt concrete microstructure was captured using the non-destructive X-ray computed tomography (CT) technique. X-ray CT images were processed in order to identify and retain interconnected air voids and eliminate isolated voids. This image processing enhanced the efficiency of the model as it does not have to solve for flow in isolated voids that do not contribute to fluid flow. The X-ray CT images were analyzed and the results were used to determine the relationship between air void distribution and permeability directional distribution or anisotropy.

The computed permeability values were found to have good correlation with the experimental measurements. The major and minor principal directions of the permeability tensor were found to correspond to the horizontal and vertical directions, respectively. The results indicated that the non-uniform spatial distribution of air voids created more open flow paths in the horizontal directional than the vertical direction, and hence was the much higher permeability in the horizontal directions.