磺化CS/PVA交联阳离子交换膜的制备与表征

壳聚糖是来源广泛、廉价、低毒的高分子化合物,具有作为离子交换膜材料的潜在优势。通过将壳聚糖(CS)与1,3-丙烷酸内酯(PS)的开环磺化反应获得离子交换能力。为提高其力学性能和克服磺化以后成膜性下降的缺点,采取与聚乙烯醇(PVA)共混、加入正硅酸四乙酯(TEOS)通过溶胶-凝胶反应实现交联。采用流延法制备出一系列磺化CS含量不同的新型磺化壳聚糖/聚乙烯醇/二氧化硅杂化阳离子交换膜。运用ATR-FTIR、SEM、TGA、DMA进行表征,并测试了杂化膜的离子交换容量、水含量及线性膨胀率等。结果表明:离子交换容量的范围是0.10~0.65 mmol/g,水含量和线性膨胀率的范围分别为10%~25%,15%~20%。     

PVA基杂化膜道南渗析去除Cu~(2+)影响因素探讨

离子交换膜是发展道南渗析去除Cu~(2+)的关键部分。首先由单体聚合制备含有离子交换基团的共聚物,然后以PVA为基体,通过溶胶凝胶法制备了一系列不同共聚物质量分数的PVA基有机-无机杂化阳离子交换膜。在此基础上,评价道南渗析去除Cu~(2+)性能。通过分析渗透通量,系统讨论了共聚物质量分数、接受侧H+浓度对道南渗析去除Cu~(2+)的效果的影响。结果表明,随着共聚物和PVA的质量比从0.25∶4增加到1∶4,Cu~(2+)的渗透通量从4.825×10~(-10)mol/cm~2·s增加到10.01×10~(-10)mol/cm2·s;而接受侧H+浓度的增加对渗透通量的影响呈现先增加后保持基本不变的变化趋势。膜结构和接受侧H+浓度两者协同影响杂化阳离子交换膜道南渗析去除Cu~(2+)性能。     

新型聚乙烯醇/硅系杂化膜的制备及渗透性能

采用溶胶-凝胶法制备了聚乙烯醇（PVA）/γ-氨丙基三乙氧基硅氧烷（APTEOS）有机/无机杂化膜。用FTIR和XRD对杂化膜进行了表征。测定了膜在乙醇/水溶液中的溶胀行为。考察了杂化膜对85%（质量）的乙醇/水溶液的渗透蒸发分离性能。加入APTEOS降低了PVA的结晶度,有效控制了膜的溶胀,呈现出优良的分离性能。随着APTEOS含量的增加,杂化膜的选择性急剧增加,在5.0%（质量）时达到最大值;同时膜的渗透通量迅速增加。解决了PVA膜trade-off效应。     

聚乙烯醇/二氧化硅杂化膜的制备及渗透蒸发分离环己醇（酮）/环己烷

以聚乙烯醇（PVA）和正硅酸乙酯（TEOS）为原料,经溶胶-凝胶（sol-gel）法制备了不同二氧化硅（SiO2）含量的 PVA/SiO2杂化膜。傅里叶变换红外光谱（FT-IR）表明,随着SiO2含量增大,1060cm?1和970cm?1处Si—O—Si特征吸收峰的相对强度逐渐加强,说明TEOS与PVA发生了交联反应;同时膜的分解温度从248℃升高到342℃。杂化膜的SiO2含量从10 %增大到40 %,其玻璃态温度从115℃升高到124℃。以水为溶剂,测定了杂化膜的耐溶剂性能,与PVA膜相比,杂化膜的耐溶剂性能显著提高。以质量比为0.950/0.025/0.025的环己烷/环己醇/环己酮为原料,测定杂化膜的分离性能,结果表明SiO2含量从10 %增大到40 %,通量从15.94 g/(m2?h)升高到75.69 g/(m2?h),环己醇的分离因子从1.8升高到2.65。     

一类含柔性侧链结构质子交换膜的制备与性能

通过利用含侧甲基结构聚芳醚砜的溴化和接枝磺化反应，制备得到一系列结构单元中含有4个柔性侧链结构的磺化聚芳醚砜质子交换膜（4SPAES-x）。通过1HNMR表征其化学结构，并利用原子力显微镜对膜材料的相分离形态结构进行分析，证实所制膜材料具有良好的亲水/疏水相分离形态结构。4SPAES-x膜的离子交换容量在1.12~1.74 mmol/g，30 ℃时的吸水率、溶胀率和质子传导率分别在11%~32%、7%~22%和21~86 mS/cm，均随磺化比例的增大而增大。4SPAES-25膜组装的钒流单电池在40 mA/cm2电流密度下最高能量效率为83.3%，高于Nafion 115的81.5%。此外，该单电池的效率还具有良好的循环稳定性。     

壳聚糖/聚乙烯醇/壳寡糖抑菌纳米纤维膜的制备和性能研究

以壳聚糖（CS）为基材,使用静电纺丝的方法制备了搭载壳寡糖（CHOS）的CS/聚乙烯醇（PVA）/CHOS纳米纤维膜,并对纳米纤维膜的微观形貌、结构、抑菌性、亲水性以及溶解性能进行了研究。研究发现：CS/PVA/CHOS纳米纤维膜具备均匀密致的微观形貌;FT-IR测试表明,CHOS以物理混合的形式分散在CS/PVA/CHOS纳米纤维膜中;XRD测试表明,CHOS的加入改变了纳米纤维膜的结晶性,促进了各组分之间的相容性;水接触角测试表明纳米纤维膜具备良好的亲水性,在m（CS）：m（PVA）：m（CHOS）=20：80：10时,CS/PVA/CHOS纳米纤维膜的接触角相比于m（CS）：m（PVA）=20：80的CS/PVA纳米纤维膜由59.8°下降到37.5°;抑菌性能和溶解性能测试表明,m（CS）：m（PVA）：m（CHOS）=20：80：10时的CS/PVA/CHOS纳米纤维膜相比于未搭载CHOS的CS/PVA纳米纤维膜,抑菌性提升了38.9%,溶解率提升了38.6%。     

纳米ZnO含量对PVDF阳离子交换膜性能的影响

通过碱化、接枝和磺化反应制备了不同含量的纳米ZnO粒子的聚偏氟乙烯(PVDF)有机-无机杂化阳离子交换膜,研究ZnO纳米粒子含量对膜性能的影响。采用扫描电子显微镜(SEM)和傅里叶变换红外光谱(FT IR)表征膜结构,采用电化学工作站交流阻抗法等表征膜综合性能。结果表明,接枝和磺化反应在PVDF链上引入了苯乙烯和磺酸基团。当纳米ZnO粒子的质量分数为1.5%时膜的综合性能达到最佳,膜的离子交换容量为2.36 mmol/g、水的质量分数为158.7%、膜迁移数为91.44%,氧化后质量损失率为2.84%,可用于电驱动分离或其他电化学过程。     

季铵化壳聚糖-聚乙烯醇阴离子交换膜的制备

利用壳聚糖(CS)制备季铵化壳聚糖(QCS),将其与聚乙烯醇(PVA)共混后制得一系列不同配比的QCS/PVA阴离子交换膜,对膜的吸水率、溶胀度、离子交换率等进行了测试和分析。结果表明:季铵化壳聚糖与聚乙烯醇有较好的相容性;膜的吸水率、溶胀度、离子交换率随季铵化壳聚糖含量增大而增大;共混膜结构均匀,热稳定性良好。     

交联壳聚糖/聚乙烯醇/蜗牛黏液复合膜的制备及性能研究

采用延流法制备了香兰素（V）交联的壳聚糖/聚乙烯醇/蜗牛黏液（CS/PVA/SM）复合膜,并通过热重分析仪（TG）、扫描电子显微镜（SEM）和万能材料试验机等研究了不同CS/SM配比对复合膜光学性能、水蒸气和氧气阻隔能力、力学性能、热力学性能及生物降解性能等的影响。结果表明,CS/PVA/SM复合膜为可降解的亲水性薄膜,当CS溶液/SM溶液体积比为5/3时,复合膜性能优良,其抗氧化活性为87.51 %,其水蒸气透过率比纯CS膜降低了75.16 %,不透明度降低了87.74 %,拉伸强度提高了16.04 %,断裂伸长率提高了28.26倍;随着SM含量的增加,复合膜的热稳定性有所降低;CS溶液/SM溶液体积比为5/1、5/2和5/3时,复合膜表现出良好的相容性;SM的添加使复合膜具有很好的延展性和柔韧性,V的添加提高了复合膜的拉伸强度和抗氧化能力;所制备的CS/PVA/SM复合膜在食品包装领域中有潜在的应用前景。     

凹凸棒土杂化粒子改性聚乙烯醇/壳聚糖复合膜的结构与性能研究

采用表面引发接枝聚合法制备凹凸棒土接枝聚丙烯酰胺杂化粒子(ATP-g-PAAm),以此改性聚乙烯醇/壳聚糖复合膜(PVA/CS).采用傅里叶红外光谱(FTIR)、差示扫描量热(DSC)、热失重分析(TG)等对三元复合膜(PVA/CS/ATP-g-PAAm)进行了表征,考察了杂化粒子含量对复合膜力学性能、热性能、吸湿率和...     

介孔碳掺杂磺化聚酰亚胺质子膜的制备与性能

以有序介孔碳(CMK)为掺杂剂,在乙醇中超声分散后与磺化聚酰亚胺的间甲酚溶液直接混合,然后采用流延法制备掺杂质子交换膜。环镜扫描电子显微镜表征发现CMK在膜中分散均匀。通过吸水率、溶剂吸收率、尺寸变化、电导率、甲醇透过率、力学性能及稳定性等测试发现掺杂膜虽然电导率有所下降,但其吸水率下降了15%~26%;抗溶胀性提高了15%~30%;热稳定性提高了约20~30℃;抗氧化性增大了1.3~1.5倍;水稳定性和力学性能也显著提高。     

Chitosan/titanate Nanotube Hybrid Membrane with Low Methanol Crossover for Direct Methanol Fuel Cells

Titanate nanotubes (TNTs) about 10 nm in diameter and 200–600 nm in length were hydrothermally synthesized, and then incorporated into a chitosan (CS) matrix to fabricate chitosan/titanate nanotube (CS/TNT) hybrid membranes for a direct methanol fuel cell (DMFC). These hybrid membranes were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray powder diffraction (XRD), thermogravimetry (TG), and positron annihilation lifetime spectroscopy (PALS). Moreover, their performances, including mechanical strength, water and methanol uptake, methanol permeability, and proton conductivity were determined. SEM results demonstrated that TNTs dispersed homogeneously in the hybrid membranes. Mechanical strength and TG measurements demonstrated that the mechanical and thermal stability of CS/TNT hybrid membranes were much higher than those of pure chitosan membranes. PALS analysis revealed that the fractional free volume (FFV) of CS/TNT hybrid membranes increased with the incorporation of TNTs and, thus, resulting in the reduction of methanol crossover. In all as‐prepared membranes, the hybrid membrane containing 15 wt % TNTs exhibited the highest mechanical strength of 85.0 MPa, low methanol permeability of 0.497 · 10^–6 cm²·s^–1, and proton conductivity of 0.0151 S·cm^–1, which had the potential for DMFC applications.     

Fabrication and characterization of sulfonated polybenzimidazole/sulfonated imidized graphene oxide hybrid membranes for high temperature proton exchange membrane fuel cells

The sulfonated polybenzimidazole (sPBI)/sulfonated imidized graphene oxide (SIGO) was evaluated to be a potential candidate for high temperature proton exchange membranes fuel cells (HT-PEMFCs). Multifunctionalized covalently bonded SIGO is incorporated in sPBI matrix to resolve the drawbacks such as low proton conductivity, poor water uptake, and ion-exchange capacity (IEC) of sPBI polymer, synthesized by direct polycondensation in phosphoric acid for the application of proton exchange membranes. Strong hydrogen bonding among multifunctional groups established a neighborhood of interconnected hydrophobic graphene sheets and organic polymer chains. It provides hydrophobic–hydrophilic phase separation and facile proton hopping architecture. The optimized sPBI/SIGO (15 wt %) revealed 2.45 meq g⁻¹ IEC; 5.81 mS cm⁻¹ proton conductivity [120 °C and 10% relative humidity (RH)] and 2.45% bound water content. The maximum power density of the sPBI/SIGO-15 membrane was 0.40 W cm⁻² at 160 °C (5% RH) and ambient pressure with stoichiometric feed of H₂/air. This recommends that sPBI/SIGO composite membranes are compatible candidate for HT-PEMFCs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47892.     

Sulfonated polyimide copolymers based on 4,4′-diaminostilbene-2,2′-disulfonic acid and 3,5,3′,5′-tetramethylbenzidine with enhanced solubility

A new series of six-membered ring sulfonated polyimides with different combinations of two comonomers in the nonsulfonated diamine was prepared by one-step high-temperature polycondensation in m-cresol to improve the solubility of the resulting sulfonated polyimides. They are based on 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4′-diaminostilbene-2,2-disulfonic acid sulfonated diamine, and equimolar mixture of 3,5,3′,5′-tetramethylbenzidine (TMB) and 4,4′-oxydianiline, bis(4-aminophenyl)methane, or bis(4-(aminophenoxy)-4-phenyl)isopropylidene nonsulfonated diamines. The introduction of TMB comonomer in the nonsulfonated diamine resulted in a remarkable improvement in the solubility of the resulting polyimides in comparison with the corresponding single-monomer nonsulfonated diamine polyimides. Flexible, transparent, and tough membranes were prepared by solution casting method from the different polyimides. The membranes were characterized with FTIR and ¹H-NMR spectroscopy, differential scanning calorimetry, thermogravimetric analysis, water uptake, and ion-exchange capacity measurements. They exhibit high thermal stability and good correlation between the ion-exchange capacity and water uptake values.     

Novel Hollow Titania Spheres‐Chitosan Hybrid Membranes with High Isopropanol Dehydration Performance

A new kind of hollow titania spheres‐chitosan (hTiO₂‐CS) hybrid membranes was prepared by a physical blending method. hTiO₂ spheres were found to disperse well in the as‐prepared hTiO₂‐CS hybrid membranes. Their incorporation can reduce the chitosan crystallinity and enhance slightly its hydrophilicity and thermal stability. Subsequently, hTiO₂‐CS/PAN composite membranes comprising of the hTiO₂‐CS hybrid membrane as separation layer and a polyacrylonitrile (PAN) membrane as support layer were fabricated. Compared to the CS/PAN membrane, all of them exhibit a much better flux and separation factor for a 90 wt % aqueous solution of isopropanol at 80 °C. This promising kind of composite membranes may find potential application in the dehydration of alcohols.     

Heterogeneous ion-selective membranes: the influence of the inert matrix polymer on the membrane properties

Heterogeneous ion-exchange membranes were prepared by mixing small particles of sulfonated poly(1,4-phenylene sulfide) or sulfonated styrene–divinylbenzene copolymer with a matrix polymer. Four kinds of polymers were tested as a matrix: highly flexible linear polyethylene, medium-flexible fluoroelastomer, rigid polystyrene (all highly hydrophobic) and hydrophilic cellulose prepared by hydrolysis of cellulose acetate butyrate. Membrane morphologies were studied by scanning electron microscopy, IR spectroscopy and density measurements. Subsequently, the membranes were characterised with respect to their swelling in water, electrochemical characteristics and transport properties. Ion-exchange capacity and proton conductivity together with the permeability to hydrogen and methanol were investigated. The important impact of the ion-exchange particles as well as of the polymer matrix used was observed. The increasing rigidity of the polymer matrix resulted in a decrease in membrane permeability, but at the same time in deterioration of its ion-exchange capacity and subsequently of the proton conductivity, too. This was explained in terms of the limited elasticity of the polymer matrix, in each sample under study, which does not allow the ion-exchange particles to swell to an identical degree.     

Effect of dispersion state of Cloisite15A® on the performance of SPEEK/Cloisite15A nanocomposite membrane for DMFC application

The introduction of 2,4,6‐triaminopyrimidine (TAP) into sulfonated poly(ether ether ketone) (SPEEK)/Cloisite15A® nanocomposite membranes were investigated for the purpose of maintaining low methanol permeability and suppressing swelling in direct methanol fuel cell (DMFC). SPEEK with 63% of degree of sulfonation (DS) was prepared by sulfonation of PEEK. Cloisite15A (7.5 wt %) along with various weight loading of TAP was incorporated into SPEEK matrix via solution intercalation method. The effect of TAP loading on the SPEEK/Cloisite15A/TAP morphology was studied. The beneficial impact of the SPEEK/Cloisite15A/TAP morphology on the physicochemical properties of the membrane was further discussed. Swelling behavior, ion exchange capacity (IEC), proton conductivity, and methanol permeability of the resultant membranes were determined as a function of Cloisite15A and TAP loadings. Uniform distribution of Cloisite15A particles in the SPEEK polymer matrix in the homogenous SPEEK/Cloisite15A/TAP nanocomposite membranes was confirmed by scanning electron microscopy and X‐ray diffraction. The water uptake of the SPEEK nanocomposite membranes decreased dramatically in the presence of TAP. The significant selectivity of SP/7.5/7.5 nanocomposite membranes could indicate a potential feasibility as a promising electrolyte for DMFC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Sulfonated poly(ether sulfone)/silica composite membranes for direct methanol fuel cells

A series of sulfonated poly(ether sulfone) (SPES)/silica composite membranes were prepared by sol–gel method using tetraethylorthosilicate (TEOS) hydrolysis. Physico–chemical properties of the composite membranes were characterized by thermogravimetric analysis (TGA), X‐ray diffraction (XRD), scanning electron microscope–energy dispersive X‐ray (SEM–EDX), and water uptake. Compared to a pure SPES membrane, SiO₂ doping in the membranes led to a higher thermal stability and water uptake. SEM–EDX indicated that SiO₂ particles were uniformly embedded throughout the SPES matrix. Proper silica loadings (below 5 wt %) in the composite membranes helped to inhibit methanol permeation. The permeability coefficient of the composite membrane with 5 wt % SiO₂ was 1.06 × 10^?7 cm²/s, which was lower than that of the SPES and just one tenth of that of Nafion® 112. Although proton conductivity of the composite membranes decreased with increasing silica content, the selectivity (the ratio of proton conductivity and methanol permeability) of the composite membrane with 5 wt % silica loading was higher than that of the SPES and Nafion® 112 membrane. This excellent selectivity of SPES/SiO₂ composite membranes could indicate a potential feasibility as a promising electrolyte for direct methanol fuel cell. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A study on the preparation and properties of the heterogeneous cation-exchange membranes of sulfonated polystyrene/divinyl benzene on an acetal base

The heterogeneous acetal-based membranes containing 50, 60, 70, 80, and 90% (w/w) of the sulfonated polystyrene crosslinked with 7% divinyl benzene were fabricated and studied. In addition, the heterogeneous acetal-based membranes of 85% (w/w) sulfonated polystyrene crosslinked with 1, 4, and 7% divinyl benzene were also prepared and studied. The gel water content, dimensional stability, ion-exchange capacity, area and specific ohmic resistance, permselectivity, and rate of ion exchange of the acetal-based membranes were determined. The sulfonated polystyrene crosslinked with 7% divinyl benzene resin was found to be the better material for preparing the acetal-based membrane with comparable good characteristics. A commercially available heterogeneous membrane (Shanghai Chemicals, 3361) of dry-molding sulfonated polystyrene–divinyl benzene resin was used as the reference membrane for the present investigation. © 1995 John Wiley & Sons, Inc.     

New organic–inorganic hybrid membranes based on sulfonated polyimide/aminopropyltriethoxysilane doping with sulfonated mesoporous silica for direct methanol fuel cells

A series of novel composite methanol‐blocking polymer electrolyte membranes based on sulfonated polyimide (SPI) and aminopropyltriethoxysilane (APTES) doping with sulfonated mesoporous silica (S‐mSiO₂) were prepared by the casting procedure. The microstructure and properties of the resulting hybrid membranes were extensively characterized. The crosslinking networks of amino silica phase together with sulfonated mesoporous silica improved the thermal stability of the hybrid membranes to a certain extent in the second decomposition temperature (250–400°C). The composite membranes doping with sulfonated mesoporous silica (SPI/APTES/S‐mSiO₂) displayed superior comprehensive performance to the SPI and SPI/APTES membranes, in which the homogeneously embedded S‐mSiO₂ provided new pathways for proton conduction, rendered more tortuous pathways as well as greater resistance for methanol crossover. The hybrid membrane with 3 wt % S‐mSiO₂ into SPI/APTES‐4 (SPI/A‐4) exhibited the methanol permeability of 4.68 × 10^?6 cm² s^?1at 25°C and proton conductivity of 0.184 S cm^?1 at 80°C and 100%RH, while SPI/A‐4 membrane had the methanol permeability of 5.16 × 10^?6 cm² s^?1 at 25°C and proton conductivity of 0.172 S cm^?1 at 80°C and 100%RH and Nafion 117 exhibited the values of 8.80 × 10^?6 cm² s^?1 and 0.176 S cm^?1 in the same test conditions, respectively. The hybrid membranes were stable up to about 80°C and demonstrated a higher ratio of proton conductivity to methanol permeability than that of Nafion117. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012