合成高分子膜透气速率的温度依赖性

近年来以气体选择性分离为目的的合成高分子膜的研究取得了巨大的进步。气体分离膜的两个基本性能参数是透气速率J及选择系数α。同一个膜,在较高温度使用时,往往是J值增大,α值下降,因此选择适当地操作温度,以便得到最佳的J-α搭配是很重要的。本文讨论了甲基硅橡胶(MSR)、天然橡胶(NR)、乙丙橡胶(EPR)、聚乙烯(PE)、聚(4-甲基戊烯-1)(TPX)等材料的均质膜或复合膜,在不同温度下的氧、氮透过速率,计算了各种膜材料的氧、氮表观透过活化能,并对其本质进行了探讨。     

磷钨酸/磺化杂萘联苯聚醚酮复合质子交换膜的制备及其性能

制备了基于磷钨酸(PWA)与磺化杂萘联苯聚醚酮(SPPEK)的无机-有机复合质子交换膜, 红外光谱测试结果表明, 复合膜中PWA通过端氧和桥氧共同与SPPEK发生作用; 由SEM照片看出, 对磺化度为58%的SPPEK, PWA掺杂量为20%和40%时杂多酸的分散良好, 掺杂量为60%时膜内出现颗粒聚集; PWA在水中的溶出性测试发现, 用水处理4天, 各复合膜中PWA的溶出率均低于10%; PWA/SPPEK膜具有良好的质子导电性, PWA掺杂量高于40%、磺化度为58%的SPPEK为基质的复合膜在100 ℃以上的电导率接近甚至超过Nafion115膜的电导率, 复合膜的电导率和水含量均随PWA掺杂量的增加而增加; 随着PWA掺杂量的增加复合膜的阻醇性能下降, 但除PWA掺杂量60%、SPPEK磺化度58%的复合膜外, 所制备的多种复合膜的甲醇透过系数均低于Nafion115膜.     

磺化聚醚醚酮/三羧基丁烷膦酸锆复合质子交换膜的研究

通过在磺化聚醚醚酮(SPEEK)中掺杂1,2,4-三羧基丁烷-2-膦酸锆(Zr(PBTC))制备出SPEEK/Zr(PBTC)复合质子交换膜.结果表明,与纯SPEEK膜相比,Zr(PBTC)的掺杂能降低复合膜的吸液量及甲醇透过系数,且随着Zr(PBTC)含量的增加,这种作用越趋明显.在室温至80℃范围内,复合膜的甲醇透过系数在10-7cm2.s-1数量级上,远小于Nafion115膜.在饱和湿度下,当温度大于90℃时,含40wt%Zr(PBTC)的复合膜电导率超过Nafion115膜,并在160℃时达到0.36S.cm-1.使用温度的提高及在高温下的高电导率表明该复合膜适合在高温DMFC中使用.     

紫外光固化的聚氨酯－丙烯酸酯－纤维素复合膜

再生纤维素膜(甘蔗渣浆制)表面直接用紫外光固化聚氨酯-丙烯酸酯制备出防水性复合膜。由红外光谱和扫描电镜研究了复合膜的结构。同时,测定了膜的防水性、力学性能、水汽透过性和尺寸稳定性。实验结果表明,当聚氨酯：丙烯酸酯为40:55(质量比),在400W紫外光下固化5min制得的复合膜具有致密的表面结构和较好的性能,该膜经水浸泡后其断裂强度可达干膜的90%,浸水收缩率和膨胀率均小于2.5%,水汽渗透量仅为再生纤维素膜的1/4.由此表明复合膜的防水性和尺寸稳定性明显提高。此外,该复合膜在可见光区的透光率在80%～90%之间,而且对紫外光有屏蔽作用。     

氧化石墨烯/聚电解质层层自组装制备单价离子选择性膜

采用层层自组装法在改性聚丙烯腈(PAN)膜表面交替沉积聚乙烯亚胺(PEI)和聚丙烯酸-氧化石墨烯(PAA-GO)混合液,制得了单价离子选择性复合膜。X射线衍射(XRD)测试结果表明成功合成了氧化石墨烯(GO)并在复合膜中均匀分散。扫描电镜(SEM)观察结果证实了多层聚电解质PEI/PAA-GO成功地组装在基膜上,并用紫外-可见(UV-Vis)光谱进一步证实了组装过程的均匀性和连续性。接触角和性能测试表明加入GO后,复合膜的亲水性和单价阳离子的选择性明显增大。这种高通量、高选择性的防污复合膜在分离和水的软化方面有很好的应用前景。     

PVDF亲水复合膜的制备及表征

聚偏氟乙烯(PVDF)膜材料存在强疏水性的缺陷,亲水化改性是解决该问题的主要途径。以PVDF为基膜材料、聚乙烯醇(PVA)为共混材料、N,N-二甲基乙酰胺(DMAc)为溶剂,采用相转化法制备PVDF/PVA复合膜。考察了复合膜的PVDF/PVA共混比、固含量、低分子化合物添加剂、聚合物添加剂等非溶剂添加剂对复合膜接触角的影响。结果表明,当PVDF/PVA共混比为7/3,固含量为13%时,制备的复合膜接触角为22.92°;当添加剂为无水氯化锂、纳米二氧化硅、聚乙烯吡咯烷酮(PVP)时,复合膜接触角分别从53.12°、30.51°和41.89°都降低到了0°,亲水性提高,其中纳米二氧化硅作为添加剂时复合膜亲水性最好;当添加剂为丙三醇、PMMA、PEG时,复合膜接触角都增大,亲水性变差。     

等离子体聚合制备气体分离膜研究概况

本文叙述了近年来等离子体聚合技术制备气体分离膜,主要是富氧膜的研究进展。着重介绍等离子体聚合制备复合膜的类型及结构、气体透过特性、等离子体反应参数对复合膜气体透过性的影响。     

基于Nafion-聚溴甲酚绿-石墨烯纳米复合膜修饰玻碳电极的NO电化学传感器北大核心CSCD

本文构建了Nafion-聚溴甲酚绿-石墨烯纳米复合膜修饰玻碳电极(Nafion/PBG/GO/GCE)。研究表明,该复合膜修饰电极对NO的电化学氧化具有明显的催化作用。同时,该复合膜具有较大的比表面和较快的电子转移速率,从而建立了一种NO的高灵敏、快响应电化学传感方法。结果显示,NO在Nafion/PBG/GO/GCE上的氧化峰电流与其浓度在1.0×10^(-7)~2.25×10^(-4)mol/L范围内呈良好线性关系,其检出限为2.0×10^(-8)mol/L。此外,该传感器还具有良好的重现性、选择性和稳定性,可用于生物样品中NO含量的实时动态监测。     

磺化聚醚砜/磷酸硼复合质子交换膜的制备与性能

采用sol-gel法成功制备了一系列有望用于高温质子交换膜燃料电池的新型磺化聚醚砜(SPES)/磷酸硼(BPO4)复合膜, 并经热重分析(TGA)-傅立叶变换红外光谱(FTIR)联用技术、差示扫描量热仪(DSC)、扫描电子显微镜(SEM)等对膜的结构和性能进行了表征. 结果表明, 复合膜较纯SPES膜具有更高的热稳定性和玻璃化转变温度, 较低的溶胀性及较高的氧化稳定性; SEM图片显示BPO4在聚合物基体中的分布十分均匀, 这将有利于连续质子传输通道的形成; 复合膜的质子传导率随BPO4含量的增加而增加, 当温度超过120 ℃后, 复合膜仍保持着较高的质子传导率, 这表明该复合膜在高温质子交换膜燃料电池中具有良好的应用前景.     

含氟共聚物与钴卟啉复合膜的制备及促进氧输送性能

研究了甲基丙烯酸八氟戊酯-乙烯基咪唑共聚物与钴卟啉复合膜的制备及钴卟啉与氧络合、促进输送性能.共聚物中的咪唑基与钴卟啉的第五配位点在溶液中络合,制得的复合膜具有快速和可逆的氧结合特性.温度降低,钴卟啉与氧络合的平衡常数增加;膜中的钴卟啉与氧络合平衡常数大于N,N-二甲基甲酰胺(DMF)溶液中的平衡常数.钴卟啉与氧络合和选择性地促进氧的输送使共聚物/钴卟啉复合膜的氧渗透系数和氧/氮选择系数提高.     

Characterization and gas permeation of polycarbonateliquid crystal composite membrane

Polymer/liquid crystal composite membranes were cast from a 1,2-dichloroethane solution of polycarbonate (PC) and N-(4-ethoxybenzylidene-4'-n- butylaniline) (EBBA). The mixing state of the polymer/liquid crystal composite membrane was investigated on the basis of differential scanning calorimetry, x-ray, density, sorption isotherm and sorption—desorption studies and also by electron microscopic observations. EBBA molecules in the composite membrane exist in an almost molecularly dispersed state up to an EBBA fraction of 30 wt%, and in the case of EBBA fractions above 30 wt% form a crystal domain as the mutual continuous phase among the network of polycarbonate fibrils. The composite membrane containing EBBA of 60 wt% can be handled as a homogeneous medium when considering gas permeation.The diffusive permeability coefficient to water reveals a distinct jump in the vicinity of the crystal—liquid crystal phase transition temperature of EBBA. The permeability coefficients, P, to hydrocarbon gases increases 100-200 times over several degrees in the phase transition temperature range. P for hydrocarbon gases decreases with increasing number of carbon atoms below the phase transition temperature, but increases with increasing number of carbon atoms above it. These results suggest that the permeation process is predominantly controlled by diffusion mechanism below the transition temperature of EBBA, while the solubility factor significantly affects gas permeation above it.     

渗透汽化法分离二氧六环－水混合物

研究了二氧六环一水混合物在ＰＶＡ（聚乙烯酸）－ＰＡＮ（聚丙烯腈）复合膜中的渗透汽化分离性能。结果表明透过速率Ｑ和分离系数α均随料液温度的提高而增大。α随料液中二氧六环浓度的提高而增大，Ｑ的变化趋势相反．有代表性的数据是在９０℃对９５％的二氧六环水溶液，α可达１９８１，Ｑ＝７３．８ｇ／ｍ２·ｈ．在低浓度二氧六环溶液时扩散过程对选择性起主要作用。而高浓度时溶解选择性是主要的，随着分离温度的提高，扩散或溶解均提高了选择性。     

STUDIES ON THE PERMEABILITY OF P VC/EBBA OVERLAPPED ULTRATHIN COMPOSITE MEMBRANES MODIFIED BY PLASMA-POLYMERIZATION WITH FLUOROCARBON MONOMERS

The PVC/EBBA ultrathin composite membranes with thickness of about 100 nm were prepared by spreading the solution on water surface. The overlapped composite membrane showed a characteristic aggregation structure in which the polymer matrix exists as a three-dimensional spongy network and the liquid crystal domains werc observed. Tne surface modification for the overlapped membranes was carried out by means of plasma-polymerization with the monomers of fluorocarbon compounds. Both Arrhenius plots of permeability coefficients for oxygen ((?)_O_2) in the membrane samples before and after modification showed significant increase in the vicinity of the T_(KN) of EBBA.     

Changes of electrochemical responses of the bulk solution species by thermotropic permeability of liquid crystalline membranes coated on electrodes

Liquid crystalline/polymer composite membrane-coated electrodes were prepared by casting a 1,2-dichloroethane solution of N-(4-ethoxybenzylidene)-4′-n-butylaniline (EBBA) and polycarbonate (PC) on an electrode surface. The temperature-dependence of the permeability of the EBBA/PC composite membrane on electrodes to Fe(CN)^3?₆ ion as a solution-phase redox ion was investigated by means of hydrodynamic voltammetry at a rotating disk electrode. The permeability changed with temperature over the range of the crystalline-nematic-phase transition temperature of EBBA. It is demonstrated that the observed temperature-dependence of the permeability reflects the thermotropic properties of EBBA in the EBBA/PC composite membrane. Furthermore, the dependence of the limiting current of the steady-state current-potential curves for the reduction of Fe(CN)^—₆ at the EBBA/PC composite membrane-coated electrode upon the membrane thickness, the blend ratio of EBBA and PC and the concentration of Fe(CN)^3?₆ in a bulk solution was examined in order to understand the transport process of Fe(CN)^?3₆ through the EBBA/PC composite membrane from the membrane/solution interface to the electrode/membrane interface. The transport process of Fe(CN)^3?₆ within the membrane was found to obey Fick's Law.     

Enhanced antifouling performance of ZnS/GO/PVDF hybrid membrane by improving hydrophilicity and photocatalysis

In order to improve the antifouling performance of PVDF membrane, a novel zinc sulfide/graphene oxide/polyvinylidene fluoride (ZnS/GO/PVDF) composite membrane was prepared by immersed phase inversion method. The surface morphology, crystal structure, photocatalytic activity, and antifouling property of the as‐prepared membranes were systematically studied. Results showed that the ZnS/GO/PVDF hybrid membranes were successfully fabricated with uniform surface. The hybrid membrane surface possessed higher hydrophilicity with water contact angle decreasing from 77.1° to 62.2°. The permeability of the hybrid membrane was therefore enhanced from 222.9 to 326.1 L/(m² hour). Moreover, bovine serum albumin (BSA) retention experiment showed that the hybrid membrane separation was also promoted by 7.2%. The blending of ZnS and GO enhanced the hydrophilic and photocatalytic performances of PVDF membrane, which mitigated the membrane fouling effectively. This novel hybrid membrane could accelerate the practical application of photocatalytic technology in membrane separation process.     

顺丁橡胶／酯－醚液晶复合膜的富氧性能研究

首次制成顺丁橡胶（ＰＢ）与具有二重液晶相转变（近晶相，向列相）的液晶化合物双４－（４’－乙氧基苯甲酰氧基）苯甲酸一缩乙二醇酯（ＤＥＢＥＢ）的复合膜并研究了其富氧性能。ＰＢ／ＤＥＢＥＢ复合膜在液晶含量１０％时，室温下具有比基质聚合物ＰＢ膜大几倍的氧透过系数（ｐｏ２）。透过系数与温度的关系曲线呈现“Ｎ”型特征。这些现象与液晶的二重相变行为和膜的形态结构有关。     

Comparison of short range interactions in nematic liquid crystals A 2H-NMR study of 5CB-d19 as a solute

Previous studies using dideuterium as a solute have demonstrated the importance for orientation of the interaction between the solute molecular quadrupole moment and the average electric field gradient present in liquid crystals. With the aim of learning about additional orientational mechanisms, we have studied the temperature dependence of the ²H-NMR spectra of the liquid crystal 5CB-d₁₉ as the solute in three liquid crystal mixtures: 55 wt % 1132/EBBA, 56·5 wt % 1132/EBBA and 70 wt % 5CB/EBBA. In these mixtures, the contribution from the environment to the average electric field gradient at the ²H nucleus of dideuterium is zero. The spectra of 5CB-d₁₉ in the mixtures 55 wt % 1132/EBBA and 56·5 wt % 1132/EBBA are equivalent, but are different from those in 70 wt % 5CB/EBBA. The spectra of 5CB in 55 wt % 1132/EBBA and 70 wt % 5CB/EBBA are analysed using two different models for the short range potential, and param eters of the models are used to compare the potentials in the different mixtures. For a given spectral splitting of the chain C₁ deuteron, the reduced short range potential is the same in all three mixtures studied. The spectral differences observed are a consequence of different nematic-isotropic phase transition temperatures combined with the effect of trans/gauche-isomerization in the hydrocarbon chain.     

填充型具有微孔结构的磺化聚芳醚砜/聚醚砜复合质子交换膜的制备及性能

制备了基于磺化聚芳醚砜(SPAES)及聚醚砜(PES)的填充型复合质子交换膜, 研究了其吸水率、 尺寸变化、 热-机械特性、 质子电导率、 甲醇透过性及稳定性等性能. 通过浸入沉淀相转化法, 采用磺化度分别为30%(S30), 40%(S40)及50%(S50)的SPAES与PES制备了系列微孔型复合质子交换膜 Sx-y(x为SPAES的磺化度, y为SPAES的质量分数); 然后利用真空抽滤法在微孔中填充S50制备了相应的填充型复合质子交换膜Sx-y+F50. 结果表明, 由于微孔的引入及皮层结构的存在, Sx-y膜在低离子交换容量(IEC)条件下仍具有较高的电导率、 优良的机械强度、 优异的化学稳定性及较低的甲醇透过性. 经S50填充后, Sx-y+F50膜的IEC及电导率明显提升, 甲醇透过率大幅下降, 但机械强度及化学稳定性未见劣化. 其中S30-40+F50膜(IEC=0.69 mmol/g)的综合性能最佳, 其质子电导率在90 ℃水中达到50.4 mS/cm; 经140 ℃水处理24 h后失重率仅为8.2%, 质子电导率降低仅9%; 经过芬顿试剂(3% H₂O₂, 20 mg/L FeSO₄, 80 ℃, 1 h)处理后失重率仅为0.66%; 甲醇透过率仅为6.8×10^-8 cm²/s.     

新型聚合物／液晶复合膜的研究：Ⅰ.膜材料对气体分离性能的影响

用顺丁橡胶，丁苯橡胶及聚氯乙烯与带有ＣＨ２＝ＣＨ－端基的液晶化合物共混，溶液浇铸法成膜，橡胶／液晶复合膜利用Ｓ２Ｃｌ２蒸气交联。用体积法测定膜的透气性，着重研究了不同基质材料及不同液晶类型对气体分离性能的影响。结果表明顺丁橡胶／液晶复合膜的透气系数最高，且分离性能也最好。     

SEPARATION OF PROPANE FROM PROPANE/NITROGEN MIXTURES USING PDMS COMPOSITE MEMBRANES BY VAPOUR PERMEATION

 This study deals with polydimethylsiloxane (PDMS)/polyvinylidene fluoride (PVDF) composite membranes for propane separation from propane/nitrogen mixtures, which is relevant to the recovery of propane in petroleum and chemical industry. The surface and cross-section morphology of PDMS/PVDF composite membranes was observed by scanning electron microscope (SEM). The surface morphology of PDMS/PVDF composite membranes is very dense. There are three layers, the thin dense top layer, finger-like porous middle layer and sponge-like under layer in the cross-section SEM image of PDMS/PVDF composite membranes. The effects of the types of cross-linking agents and pressure on the membrane permselectivity were investigated. The permeability of nitrogen was independent of feed pressure. However, the permeability of propane increased with the pressure increasing for all membranes. The membrane cured by a tri-functional crosslinker with attached vinyl groups had better performance than the tetra-functional one, in both selectivity and permeation flux. The total permeation flux is 1.769× 10^-2 cm³(STP)/(cm²·s) and the separation factor is 19.17 when the mole percent of propane in the gas mixture is 10 at the 0.2 MPa pressure difference and 25°C.