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1.
Organic–inorganic hybrids based on poly(vinyl alcohol) (PVA)/SiO2 hybrid membranes containing sulfonic acid groups were prepared using the sol–gel process under acidic conditions. The PVA/sulfosuccinic acid (SSA)/silica hybrid membranes were fabricated from different SSA contents. The proton conductivity and methanol permeability of the hybrid membranes were studied with changing SSA content from 5 to 25 wt.%. It was found that the proton conductivity and the methanol permeability were dependent on the SSA content both as a crosslinking agent, and as a donor of the hydrophilic SO3H group. Up to an SSA content of about 20 wt.%, both of these properties decrease, and above this SSA content, they begin to increase with increasing SSA content. The proton conductivities of the PVA/SSA/silica membranes were in the range of 10−3 to 10−2 S/cm, and the methanol permeabilities ranged between 10−8 and 10−7 cm2/s. The presence of silica particles in the organic polymer matrix, which reduce the free water ratio of the membranes, results in hybrids with markedly reduced methanol permeabilities. These characteristics of the PVA/SSA/silica hybrid membranes are desirable for future applications related to direct methanol fuel cells.  相似文献   

2.
This work deals with water-swollen hydrogel membranes for potential CO2 separation applications, with an emphasis on elucidating the role of water in the membrane for gas permeation. A series of hydrogel membranes with a wide range of water contents (0.9–10 g water/g polymer) were prepared from poly(vinyl alcohol), chitosan, carboxyl methyl cellulose, alginic acid and poly(vinylamine), and the permeation of CO2, H2, He and N2 through the membranes at different pressures (200–800 kPa) was studied. The gas permeabilities through the dry dense membranes were measured as well to evaluate the resistance of the polymer matrix in the hydrogel membranes. It was shown that the gas permeability in water-swollen membrane is lower than the gas permeability in water, and the selectivity of the water-swollen membranes to a pair of gases is close to the ratios of their permeabilities in water. The permeability of the water-swollen membranes increases with an increase in the swelling degree of the membrane, and the membrane permeability tends to level off when the water content is sufficiently high. A resistance model was proposed to describe gas permeation through the hydrogel membranes, where the immobilized water retained in the polymer matrix was considered to form transport passageways for gas permeation through the membrane. It was shown that the permeability of hydrogel membranes was primarily determined by the water content in the membrane. The model predictions were consistent with the experimental data for various hydrogel membranes with a wide range of water contents (0.4–10 g water/g polymer).  相似文献   

3.
以2,6-二甲基聚苯醚(PPO)为原料, 经溴代及N-甲基咪唑季铵化反应, 制备了N-甲基咪唑季铵化PPO, 并进行了红外光谱(FTIR)和氢核磁共振波谱(1H NMR)表征.所得季铵化产物与聚乙烯醇(PVA)按不同比例共混后用戊二醛交联成膜, 在碱性液中浸泡转化为OH-型, 得到一系列阴离子交换膜.通过扫描电子显微镜(SEM) 、交流阻抗(AC)、拉伸实验和热重分析(TGA)等手段考察了膜的微观形貌及电导率、力学性能、热稳定性及耐碱性等性能.结果表明, 膜的外观形貌平整均一; 含水率为50.4%~151.2%; 溶胀度为79.2%~164.2%; 离子交换容量为0.47~1.52 mmol/g; 90℃时, M4膜的电导率高达49.1 mS/cm; 断裂伸长率达到128%, 极大改善了PPO膜应力易裂的状况.同时, N-甲基咪唑鎓基团分解温度达到170℃, 高于常用的阴离子交换膜中的季铵基团(120℃).在2 mol/L的NaOH溶液中浸泡192 h后, 电导率仅下降19%, 具备良好的耐碱性能力.  相似文献   

4.
A new alcohol dehydration membrane, poly(vinyl alcohol)—chitosan blended composite membrane (PVA-CS) has been prepared. This membrane has high selectivity and promising permeability, especially in separating ethanol—water near the azeotropic region (Jt > 200 g/m2 h, w/e > 500, 70°C). The separating characteristics, which vary with feed composition, operating temperature and the surface structure of the membrane, are determined and the results agree well with the theoretical predictions.

The characteristics of mechanical strength, stability and resistance to water were also determined. The results show that they are considerably enhanced by blending and crosslinking, in comparison with PVA composite membranes.  相似文献   


5.
Polyurethane (PU) and polyurethane–poly(methylmethacrylate) (PMMA) blend membranes were used in gas separation studies. The effects of blend composition, temperature, and pressure on the permeability, diffusivity, and solubility of CO2, H2, O2, CH4, and N2 were investigated. The separation factors of some gas pairs were also evaluated. Positron annihilation lifetime spectroscopy was applied to assess free volume changes as a function of blend composition and temperature. Free volume size increases by approximately 30% with increasing temperature from 10 to 40 °C for all blends studied. The permeability of all gases decreases by approximately 55% with the addition of 30 wt% of PMMA. The permeation process is governed by diffusion, except that of CO2. In relation to the behavior of gas transport as a function of temperature, some important observations are (i) CO2 presents the lowest permeation activation energy value (28 kJ/mol), and (ii) gas pair selectivity increases at low temperatures and is high for gas pairs that present differences in permeation activation energies as high as 15 kJ/mol for the CO2/CH4 gas pair. Furthermore, the study with pressure variations shows that: (i) at elevated pressure, the PU and the blend membrane permeability to CO2 and H2 increases by approximately 35%, and (ii) oxygen-to-nitrogen selectivity increases with pressure as a consequence of the decrease in the permeability to nitrogen in the case of the 30%-PMMA blend.  相似文献   

6.
乔宗文  陈涛 《应用化学》2019,36(8):917-923
在制备氯甲基化聚砜(CPS)的基础上,以1,2-二羟基苯-3,5-二磺酸钠为试剂,通过亲核取代反应制备一种侧链末端为磺酸基团的侧链型磺化聚砜(PS-BDS),并采用溶液浇注法制备相应的质子交换膜(PEM),研究温度对PEM性能的影响规律。 结果表明,由于亲水基团远离疏水聚合物主链,该PEM能够形成亲水微区远离疏水微区的相分离结构,亲水区域对主链的影响较小,该PEM在高磺化度下仍能保持较好的尺寸稳定性,随着温度的升高,PEM的吸水率(WU)、吸水溶胀率(SW)和质子传导率(PC)升高,其中PS-BDS-4(离子交换容量为1.57 mmol/g)在25和85 ℃时的SW仅为22.1%和55.0%,甲醇的渗透率(DK)仅为10.17×10-7 cm2/s,低于商业化的Nafion115(16.8×10-7 cm2/s)和Nafion117(23.8×10-7 cm2/s),表现出很好的综合性能。  相似文献   

7.
Incorporation of water-soluble drugs in PLGA microspheres   总被引:1,自引:0,他引:1  
Poly(lactide-co-glycolide) (PLGA) microspheres containing blue dextran, as a model of water-soluble drugs, were prepared from w1/o/w2 emulsions by using a microhomogenizer and a solvent evaporation method. Effects of preparation conditions, such as, concentration of poly(vinyl alcohol) (PVA) in w2 phase, viscosity of inner soluble water phase, volume ratio of oil phase to w1 phase in primary emulsion, PLGA concentration in oil phase, and molecular weight or composition of PLGA, upon the properties of PLGA microspheres containing water-soluble drugs were examined. Concentration of poly(vinyl alcohol) (PVA), the dispersant dissolved in w2 phase of secondary emulsion did not show any effects on the final particle size. On the other hand, volume ratio of oil phase to water one in primary emulsion affected the final particle size, which seemed to be related to the local PLGA concentration in w1/o emulsions. That is, the particle size increased as the volume ratio of w1 phase against oil phase, w1/o (v/v), increased. The loading efficiency, however, was not affected by the volume ratio of w1/o (v/v), but affected by blue dextran concentration in w1 phase. Higher loading efficiency was observed in PLGA microspheres prepared from w1 phase containing lower concentration of blue dextran. Blue dextran solution (inner water phase) with the lower viscosity may result in the lower leakage ratio of blue dextran during the preparation procedure. Increases in concentration and molecular weight of PLGA made particle size larger.  相似文献   

8.
Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (1H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO2, N2, CH4 gases and CO2/N2 gas mixture (20 vol% CO2 and 80 vol% N2) and CO2/CH4 gas mixture (10 vol% CO2 and 90 vol% CH4). The plots of gas permeance or flux versus feed gas pressure imply that CO2 permeation through the membranes follows facilitated transport mechanism whereas N2 and CH4 permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO2/N2 gas mixture, the membranes with 10 wt% PAAm content show the highest CO2 permeance of about 1.80 × 10−5 cm3 (STP) cm−2 s−1 KPa−1 and CO2/N2 selectivity of 80 at 0.1 MPa feed gas pressure. For CO2/CH4 gas mixture, the membranes with 20 wt% PAAm content display the highest CO2 permeance of about 1.95 × 10−5 cm3 (STP) cm−2 s−1 KPa−1 and CO2/CH4 selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO2 permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO2 permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.  相似文献   

9.
由于MOF(金属有机骨架)膜与基底之间的作用力较薄弱,所以制备具有高的H_2渗透性和H_2/CO_2选择性的致密连续的大面积金属有机骨架膜仍具有巨大挑战。本文选取多孔Al_2O_3作为基底,在表面涂覆一层PIM-1(一种固有微孔聚合物),并对其进行羧基化处理,使得表面具有大量的羧基基团,随后利用羧基与金属之间的相互作用,原位生长得到了两种致密连续的聚合物支撑的MOF膜(PIM-1-COOH/ZIF-8和PIM-1-COOH/HKUST-1)。通过XRD的表征可以看出MOF膜是纯相的并且具有较高的结晶性;SEM的测试结果表明MOF膜是致密连续的并且MOF膜与基底之间紧密结合。气体分离测试结果表明,这两种MOF膜对H_2具有较高的渗透性以及H_2/CO_2选择性。在常温常压下,对于PIM-1-COOH/ZIF-8和PIM-1-COOH/HKUST-1膜,H_2/CO_2双组分气体的分离系数分别为7.32、9.69,并且它们H_2的渗透通量分别高于3.16×10~(-6)、1.14×10~(-6) mol·m~(-2)·s~(-1)·Pa~(-1)。在单组份测试中,这两种MOF膜的H_2/CO_2的理想分离系数分别为7.70、12.04;H_2的渗透通量分别高达3.73×10~(-6)、3.86×10~(-6) mol·m~(-2)·s~(-1)·Pa~(-1),这就表明这两种MOF膜有望在H_2的纯化和分离方面广泛应用。  相似文献   

10.
Polyethylenimine (PEI) was cross-linked by polyepichlorohydrin (PECH) and the swelling behavior of cross-linked PEI-Co complex membranes in water was studied. The equilibrium swelling ratio of PEI-Co complex membranes is lower and the swelling rate is slower than that of cross-linked PEI membranes without cobalt ion complexation. Both the equilibrium swelling ratio and swelling rate of PEI-Co complex membranes increase with increasing the molar ratio of PEI to PECH. The equilibrium swelling ratio of PEI-Co complex membranes remains almost constant with the change of the membrane thickness or temperature. The diffusion mechanism of water through PEI-Co complex membranes was also discussed, and it is found that the diffusion of water primarily obeys Fickian’s law, and the activation energy of diffusion is calculated to be 40.4 kJ/mol.  相似文献   

11.
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.  相似文献   

12.
氯化铅纳米线的胶束模板诱导合成及其机理研究   总被引:12,自引:1,他引:11  
一维纳米材料由于在光学、磁学、微电子学等领域中具有广阔的应用前景而引起了科技工作者的广泛兴趣 .目前 ,研究得最多的一维纳米材料为碳纳米管 [1,2 ] ,它的某些性质已得到实际应用 .而纳米线 (纳米丝、纳米纤维 )的研究尚处于初始阶段 ,至今已合成或制备出的纳米线只有硫化钼、硫化镉、氮化镓、砷化铟、硫酸钙、碳酸钡、碳化硼、锡 -铅、金、银、铋等十余种 [3~ 16 ] ,尚未见有氯化铅纳米线的报道 .氯化铅晶体通常呈九配位三帽三方柱层状结构 ,具有方向上的电性差异 .当进入纳米尺寸时 ,可能产生奇异的理化现象 .本文用反相胶团或 W/ …  相似文献   

13.
制备了高性能的AlPO4-14分子筛膜. 首先通过控制反应溶胶中水和模板剂的含量制备了形貌均一的AlPO4-14分子筛, 分子筛的尺寸为15~18 mm; 然后采用晶种法即在反应凝胶中加入分子筛作为晶种进一步调控分子筛的大小, 使得AlPO4-14分子筛的尺寸从15~18 mm减小到2~3 mm, 得到形貌均一的纯相片状晶体, 同时有效缩短了制备时间; 最后以多孔管状莫来石为支撑体, 采用二次生长法制备AlPO4-14分子筛膜. 考察了2种不同大小的晶种对膜形貌和性能的影响, 发现以大尺寸的分子筛(15~18 mm)作为晶种制备的分子筛膜的分离层存在较多缺陷, 而采用小尺寸的晶种(2~3 mm)制备的膜层较均一致密. AlPO4-14分子筛膜经高温脱除模板剂后仍然保持着纯相的AlPO4-14晶型, 表明二次生长法促进了AlPO4-14晶体在膜层中的生长且使其具有更高的结晶度和热稳定性. 在25 ℃, 100 kPa下, AlPO4-14分子筛膜对H2/CH4, CO2/CH4和H2/CF4的理想分离因子分别为28, 40和1047, 且H2和CO2的渗透速率分别为6.3×10 -7和9×10 -7 mol·(m 2·s·Pa) -1; 对等摩尔CO2/CH4混合气体的分离因子为81.5, 且CO2的渗透速率为8.8×10 -7 mol·(m 2·s·Pa) -1.  相似文献   

14.
New types of supported Pd membranes were developed for high temperature H2 separation. Sequential combinations of boehmite sol slip casting and film coating, and electroless plating (ELP) steps were designed to synthesize “Pd encapsulated” and “Pd nanopore” membranes supported on -Al2O3 hollow fibers. The permeation characteristics (flux, permselectivity) of a series of unaged and aged encapsulated and nanopore membranes with different Pd loadings were compared to those of a conventional 1 μm Pd/4 μm γ-Al2O3/-Al2O3 hollow fiber membrane. The unaged encapsulated membrane exhibited good performance with ideal H2/N2 separation factors of 3000–8000 and H2 flux 0.4 mol/m2 s at 370 °C and a transmembrane pressure gradient of 4 × 105 Pa. The unaged Pd nanopore membranes had a lower initial flux and permselectivity, but exhibited superior performance with extended use (200 h). At the same conditions the unaged 2.6 μm Pd nanopore membrane had a H2 flux of 0.16 mol/m2 s and separation factor of 500 and the unaged 0.6 μm Pd nanopore membrane had a H2 flux of 0.25 mol/m2 s and separation factor of 50. Both nanopore membranes stabilized after 40 h of operation, in contrast to a continued deterioration of the permselectivity for the other membranes. An analysis of the permeation data reveals a combination of Knudsen and convective transport through membrane defects. A phenomenological, qualitative model of the synthesis and resulting structure of the encapsulated and nanopore membranes is presented to explain the permeation results.  相似文献   

15.
The polyethersulfone (PES)-zeolite 3A, 4A and 5A mixed matrix membranes (MMMs) were fabricated with a modified solution-casting procedure at high temperatures close to the glass transition temperatures (Tg) of polymer materials. The effects of membrane preparation methodology, zeolite loading and pore size of zeolite on the gas separation performance of these mixed matrix membranes were studied. SEM results show the interface between polymer and zeolite in MMMs experiencing natural cooling is better (i.e., less defective) than that in MMMs experiencing immediate quenching. The increment of glass transition temperature (Tg) of MMMs with zeolite loading confirms the polymer chain rigidification induced by zeolite. The experimental results indicate that a higher zeolite loading results in a decrease in gas permeability and an increase in gas pair selectivity. The unmodified Maxwell model fails to correctly predict the permeability decrease induced by polymer chain rigidification near the zeolite surface and the partial pore blockage of zeolites by the polymer chains. A new modified Maxwell model is therefore proposed. It takes the combined effects of chain rigidification and partial pore blockage of zeolites into calculation. The new model shows much consistent permeability and selectivity predication with experimental data. Surprisingly, an increase in zeolite pore size from 3 to 5 Å generally not only increase gas permeability, but also gas pair selectivity. The O2/N2 selectivity of PES-zeolite 3A and PES-zeolite 4A membranes is very similar, while the O2/N2 selectivity of PES-zeolite 5A membranes is much higher. This implies the blockage may narrow a part of zeolite 5A pores to approximately 4 Å, which can discriminate the gas pair of O2 and N2, and narrow a part of zeolites 3A and 4A pores to smaller sizes. It is concluded that the partial pore blockage of zeolites by the polymer chains has equivalent or more influence on the separation properties of mixed matrix membranes compared with that of the polymer chain rigidification.  相似文献   

16.
傅婧  乔锦丽  马建新 《物理化学学报》2010,26(11):2975-2981
碱性固体电解质膜的稳定性是影响其在电化学领域应用的一个重要因素.本文在前期研究工作的基础上,通过直接共混和化学交联修饰制备出了聚乙烯醇/聚乙烯吡咯烷酮(PVA/PVP)碱性聚合物电解质膜.采用傅里叶变换红外(FTIR)光谱、热重分析(TGA)、扫描电镜(SEM)和交流阻抗等方法详细考察了复合膜的分子结构、热稳定性、化学稳定性、氧化稳定性和尺寸稳定性.红外光谱结果表明,PVP成功地混入聚合物基体中,在1672cm-1处表现出来自于PVP第I带C襒O的强吸收峰.TGA结果表明,提高掺杂的KOH溶液浓度对PVA/PVP碱性膜的热稳定性没有明显影响.SEM分析结果表明,复合膜经高温、高浓度碱(80℃,10mol·L-1)处理后,其断面结构仍致密均匀,未出现类似小孔等膜降解情况,此时膜电导率(1.58×10-3S·cm-1)相比室温相同碱液时提高91.5%,表明PVA/PVP膜具有很好的耐碱化学稳定性.同时,PVA/PVP碱性膜表现出良好的抗氧化性,在60℃的3%和10%H2O2溶液中处理均没有观察到明显的质量损失,150h后仍能保持原膜质量的89%和85%.此外,由于膜内形成致密的内互交联网络结构,复合膜在水中800h之后也表现出很好的同向性和电导率稳定性.  相似文献   

17.
Ternary mixtures of PVA/Citric acid (CA)/water and PVA/Succinic acid (SA)/water were gamma irradiated to various doses in air at ambient temperature. Gelation % vs dose curves were constructed and swelling behavior of gels with maximum conversions was studied. In maximum gelled systems 80% of CA used in the feed composition was retained in the gel structure whereas this was only 20% for SA. The volume of swelling of ionic PVA gels increased from 230% to 530% for PVA/CA systems when pH was increased from 2.6 to 7.5. Less significant increase in swelling was observed for PVA/SA gels, from 250% to 330% in the same pH interval. The incorporation of SA and CA groups onto PVA networks improved remarkably the affinity of these structures for Co2+ and Ni2+ ion uptake.  相似文献   

18.
Microporous silica membranes deposited on porous supports by filtration   总被引:3,自引:0,他引:3  
Water based particulate silica sols have been coated onto Anodisc® filters by filtration. The membranes prepared by this technique are more uniform than those formed by slip-casting. The average diameter of the silica particles used in these studies is 6 nm. Unsupported silica membranes formed from these sols have a microporous structure. The adhesion between silica and the alumina support is influenced by the sol pH. Coating thickness can be controlled by the concentration and volume of the sol filtered. Polyvinyl alcohol (PVA) was used to improve adhesion and to prevent cracking during drying. When the PVA/SiO2 ratio by weight is less than 20%, the membranes retain their microporosity after firing. The membranes prepared by this filtration method have their pore size in Knudsen diffusion range.  相似文献   

19.
Sodium poly(gamma-glutamic acid) (PGA), a water-soluble and biodegradable polypeptide, was reacted with polyvinyl alcohol (PVA) to form hydrogel without any chemical treatment. The gelation occurred probably due to physical cross-linking of polymer chains by interpenetrating hydrogen bonding. From the results of thermal analysis, PGA/PVA exhibited better thermal stability than native PVA. Although the swelling ratio decreased with the increase of PGA content, however, the water resistance and retention were improved. The tensile strength of the PGA/PVA hydrogel membranes was about 15-30% lower than that of the native PVA, whereas the elongation was increased 2.0-2.6 times. The amount of protein adsorbed and platelets adhered on the PGA/PVA membranes were significantly curtailed with increasing PGA content, thereby showing improved blood compatibility. The as-fabricated hydrogels were proven to be non-cytotoxic evaluated in vitro by L-929 fibroblast incubation. Overall results demonstrate that the non-cytotoxic PGA/PVA hydrogels, due to better water resistance, mechanical properties and blood compatibility could be very promising candidates for blood-contacting medical devices.  相似文献   

20.
弋瑛  俞贤达 《应用化学》1993,10(1):77-79
前曾报道聚乙烯醇(PVA)与脂肪醛缩合后亲水性的羟基减少,影响到其薄膜的透湿性和透气性,本文考察PVA及其三种脂肪族缩醛物膜在加湿条件下的透气性。 PVA膜为10%PVA水溶液用流涎法制成。缩醛膜为PVA缩醛衍生  相似文献   

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