Silica was succesfully incorporated into cation exchange polymer membranes, CL-25T and Nafion 417, utilizing sol-gel process.
As dipping time increased, increase in silica uptake in membrane was observed. In Nafion 417 membrane, no relationship was
found between the silica uptake and the change in ion exchange capacity. But CL-25T which has larger pores than Nafion 417
shows proportional decrease in ion exchange capacity with increasing silica uptake. It suggests that the pore structure of
membrane and the size control of silica sol are important to modify the structure of composite membranes. In CL-25T membranes
modified by silica, the transport rate of IPA (isopropyl alcohol) increased with increasing OH- concentration on the pore surface. 相似文献
The effect of Phosphotungstic acid (PWA) on the proton conductivity and morphology of zirconium phosphate (ZrP), porous polytetrafluoethylene (PTFE), glycerol (GLY) composite membrane was investigated in this work. The composite membranes were synthesized using two approaches: (1) Phosphotungstic acid (PWA) added to phosphoric acid and, (2) PWA + silicic acid were added to phosphoric acid. ZrP was formed inside the pores of PTFE via the in situ precipitation. The membranes were evaluated for their morphology and proton conductivity. The proton conductivity of PWA–ZrP/PTFE/GLY membrane was 0.003 S cm?1. When PWA was combined with silicic acid, the proton conductivity increased from 0.003 to 0.059 S cm?1 (became about 60% of Nafion’s). This conductivity is higher than the proton conductivity of Nafion–silica–PWA membranes reported in the literature. The SEM results showed a porous structure for the modified membranes. The porous structure combined with this reasonable proton conductivity would make these membranes suitable as the electrolyte component in the catalyst layer for direct hydrocarbon fuel cell applications. 相似文献
In this work, a porous polypropylene (PP)/nano carbon black (CB) composite was facilely fabricated via immiscible co-continuous polymer blend and subsequent dissolution process. The porous structure was generated from co-continuous polymer blend, which was exploited as the substrate for depositing nano CB. The interconnected micro pores of the co-continuous polymer blend and nano pores derived from agglomerated CB resulted in a significant enhancement of conductivity. Comparing with the conventional carbon composite obtained through dual-percolation method, the electrical conductivity of PP/CB composite increased 10 orders of magnitude with CB loading ranged from 1 wt% to 5 wt%. Moreover, it was found that the percolation threshold of PP/CB composite decreased nearly 80% compared with that of as-mixed sample. The enhanced conductivity and much lower percolation make this novel method a potential way for fabricating porous conductive materials for advanced application. 相似文献
Microporous polypropylene (PP) nanocomposite membranes are in great demand in various fields such as energy harvesting, water purification, and other industrial applications. Thin films of PP/natural rubber (NR) blend nanocomposite have been prepared by melt mixing and the membranes are made porous by extracting the NR phase from the blend. The present study gives a better insight into the nanoparticle shape and localization-tailored porous morphology of PP membrane. Thermodynamic prediction of nanofiller localization and its impact on morphology were studied. 2D clay platelets in PP matrix tune the morphology of the porous membrane into lamellar, whereas spherical nanofillers give elongated spherical pores. The localization of nanoparticles was observed using transmission electron microscope, which is also confirmed from theoretical prediction of localization of nanofillers with the help of interfacial energy and surface tension. Thermal studies reveal that nanofillers enhance the thermal stability of polymers. Mechanical studies reveal that nanoparticles improve the mechanical properties of the system. 2D platelet shaped-nanofillers enhance the mechanical strength of the polymer up to 39%, which is higher than that obtained for 3D spherical nanofillers. Nanofiller shape and localization have a great influence in deciding the properties and porosity of the membrane. 相似文献
Creating secondary pores in the intermediate layer of hierarchical ceramic membranes successfully increases the permeability of bi-layered membranes by reducing the density of the separating layer. With the optimum secondary pore volume, the permeability of the silica/γ-alumina membrane with low secondary volume is enhanced with a satisfactory retention of organic ions and inorganic ions. However, the silica layer is not well formed when excessive secondary pores were generated in the intermediate layer. This is likely because the bimodal porous structure of γ-alumina with high secondary pore volume is inadequate to prevent the penetration of silica sol into the α-alumina support during dip coating. Thus, the bi-layered membrane with high secondary pore volume shows insufficient retention of Reactive Orange 16 dye and NaCl at low pH. 相似文献
Biomedical polyurethane (BPU) porous membranes with controlled morphology and excellent permeability and mechanical properties were prepared via a method involving a phase inversion induced by water micro-droplets, which were generated by an ultrasonic atomizer. The cross-section morphology, air permeability and mechanical properties of the porous membranes were investigated. The SEM images demonstrated that the adjacent pores were connected by a micro-hole, serving as a “backdoor” for the pore. An interconnected porous structure was obtained, improving the air permeability of the BPU membrane relative to the membrane produced by immersion precipitation. Our studies indicated that the diameter of the pores in the membrane depended on the solution viscosity, allowing porous membranes with a desired morphology to be obtained by adjusting the polymer concentration and solution viscosity. The application of micro-droplets of water during membrane preparation reduced the exchange rate between the solvent and nonsolvent, resulting in the microphase separation of polymer molecules and the formation of a uniform porous structure in the membrane, which improved the air permeability and mechanical properties of the BPU porous membranes. This is a simple and effective preparation method for high-performance porous membranes with potential applications in tissue engineering scaffolds, controlled-release drug delivery and vascular grafts. 相似文献
The effect of pre‐modification on the interaction of macroporous substrates (membranes) with mainly micro‐ and mesoporous polymer monoliths has been studied. Bulk, porous polymer monoliths were synthesized to optimize the synthesis conditions and their pore morphology, and the data were used as benchmark for this study. Pre‐modification of the entire pore surface of PP microfiltration membranes and PET track‐etched membranes by UV‐initiated grafting with PEGMA was performed using well‐established methods, including coating with the photo‐initiator, benzophenone. Subsequently, these membranes were functionalized by filling the pores with porous polymer monoliths from MAA and EDMA and compared with membranes that had been functionalized without the pre‐modification step. The materials were characterized mainly by the degree of grafting, SEM and by the gas‐adsorption‐isotherm method. The DG values, after composite‐membrane preparation under identical conditions, were not influenced by the pre‐modification. However, it could be clearly seen from the SEM images that the pre‐modification step prevents the formation of voids at the monolith‐membrane pore interface. Larger specific surface area and pore volume values for composite membranes, prepared after pre‐modification, fully support the SEM results. Especially large differences in pore structure between the two different composite membranes were found in the mesopore range. The results of this study indicate that it is possible to prepare porous, composite membranes where the trans‐membrane transport is exclusively controlled by the pore and surface structure of a functional polymeric monolith, for example, made from a molecularly‐imprinted polymer.
Intermediate temperature operation of polymer electrolyte fuel cells has been pointed out to be a promising option to overcome most of the technological problems of the current PEM system and new classes of electrolyte membrane have been investigated elsewhere. Proton conducting organic/inorganic nano-hybrid polymer electrolyte membranes have been synthesized in the present work. The membranes were synthesized by bridging temperature tolerant polyether polymers such as PEO or PTMO to inorganic silicate moieties to form organic/inorganic hybrid macromolecules. The hybrid membranes become proton conducting polymer electrolytes by doping with heteropolyacids such as 12-phosphotungstic acid (PWA). The conducting properties of the membrane were studied by modifying the polyether structure, molecular weight, PWA concentration, water content, and also various processing conditions. The membranes are flexible and thermally stable due to the temperature tolerant inorganic frameworks of the macromolecules. The proton conductivity of the membranes is in a range from 10–3–10–2 S/cm up to 140 °C under controlled humidity. 相似文献
Nano SiO2-P(VDF-HFP) composite porous membranes were prepared as the matrix of porous polymer electrolytes through in situ composite method based on hydrolysis of tetraethoxysilane and phase inversion. SEM, TEM, DSC and AC impedance analysis were carried out. It is found that the in situ prepared nano silica was homogeneously dispersed in the polymeric matrix, enhanced conductivity and electrochemical stability of porous polymer electrolytes, and improved the stability of the electrolytes against lithium metal electrodes. The in situ composite method was found to be much better than the direct composite method in lowering the interfacial resistance between electrolyte and lithium metal electrode. Moreover, cycle test of lithium batteries using lithium metal as anode and sulfur composite material as cathode showed that the electrolyte based on in situ composite of silica presented stable charge-discharge behavior and little capacity loss of battery. 相似文献
Silica aerogels with a surface area as high as 773?m2?g?1 and a density of 0.077?g?cm?3 were produced from rice husk via sol–gel process and ambient pressure drying. A particulate composite material was prepared by adding silica aerogel particles of three different particle sizes (powder, granules and bead) to unsaturated polyester resin with a fixed volume fraction of 30%. Thermogravimetric and thermal conductivity studies revealed that silica aerogel composites were having higher thermal stability and thermal insulation than the neat resin. It was suggested that the preservation of aerogel pores from resin intrusion is important for better thermal properties. Larger silica aerogel particles have more porous area (unwetted region) which results in a lower degradation rate and lower thermal conductivity of the base polymer. However, the addition of silica aerogel into resin has reduced the tensile modulus of the polymer matrix where smaller particle size displayed higher toughness than those with bigger particle size. 相似文献
Proton-exchange membrane fuel cells have emerged as a promising emission free technology to fulfill the existing power requirements of the 21st century. Nafion® is the most widely accepted and commercialized membrane to date and possesses excellent electrochemical properties below 80 °C, under highly humidified conditions. However, a decrease in the proton conductivity of Nafion® above 80 °C and lower humidity along with high membrane cost has prompted the development of new membranes and techniques. Addition of inorganic fillers, especially silicate-based nanomaterials, to the polymer membrane was utilized to partially overcome the aforementioned limitations. This is because of the lower cost, easy availability, high hydrophilicity and higher thermal stability of the inorganic silicates. Addition of silicates to the polymer membrane has also improved the mechanical, thermal and barrier properties, along with water uptake of the composite membranes, resulting in superior performance at higher temperature compared to that of the virgin membrane. However, the degrees of dispersion and interaction between the organic polymer and inorganic silicates play vital roles in improving the key properties of the membranes. Hence, different techniques and solvent media were used to improve the degrees of nanofiller dispersion and the physico-chemical properties of the membranes. This review focuses mainly on the techniques of silicate-based nanocomposite fabrication and the resulting impact on the membrane properties. 相似文献
Hybrid membranes incorporating an inorganic and organic component are receiving much attention as promising solid electrolytes for fuel cells. Recent developments in the approaches to the preparation of hybrid membranes are described. The preparation and characterisation, including their performance in a hydrogen – oxygen fuel cell, of two examples of hybrid systems based on sulfonated polyaryletherketone are described. The examples are chosen to illustrate the formation in situ of inorganic particles, either in a pre-formed membrane, or in a polymer solution. sPEEK-modified silica and sPEEK-zirconium phosphate membranes provide power densities of 0.62 W/cm2 at 100 °C. 相似文献
Protein adsorption was performed by a polymer brush prepared by atom-transfer radical polymerization (ATRP) to a porous inorganic
membrane. The porous inorganic membrane, Shirasu Porous Glass made from silica, was modified with a halogen-containing compound
to bind the active species for the polymerization. Glycidyl methacrylate was polymerized from the halogen compound by ATRP
for a prescribed time, and subsequently chemically modified. The progression of the chemical modification allowed the membrane
to lower the phosphate-buffer flux of the porous membrane due to the attachment of the polymer brush. Bovine serum albumin
(BSA), as a model protein, was adsorbed at 12 mg per gram of the membrane in permeating BSA solution through the polymer-brush-attached
porous membrane. 相似文献
The separation performance of two different commercially available tubular inorganic membranes was studied for solvent dehydration. The separation layers consisted of A-type zeolite and microporous silica. The membrane characteristics were determined as function of operating conditions such as feed composition, temperature, and permeate pressure in pervaporation and vapor permeation. Among different membranes of the same batch, flux and selectivity were reproducible within 10%. The partial flux of water as the preferentially permeating component increases linearly with the water vapor pressure difference between feed and permeate and depends only marginally (viscosity influence) upon the properties of the organic component. The flux of the organic (retained) component is low and can best be described by assuming a substance and membrane specific permeance (flux over partial pressure difference) that is independent of composition. At very low water concentration in the feed one would expect a strong increase in permeability of the retained component through non-zeolite pores and larger silica pores as predicted by pure component measurements. However, this effect was not observed in mixtures within the concentration range studied here. A temperature rise improves flux rates exponentially while selectivity remains high. Thus, higher module cost in comparison to polymeric membranes can be compensated by reduced membrane area if a higher operating temperature can be chosen. Flux and selectivity decline as a function of permeate pressure with decreasing driving force. In vapor permeation with inorganic membranes superheating of the vaporous feed improves their performance while for polymeric materials a steep flux decline is observed. High flux and selectivity are obtained in the separation of water from alcohols. The normalized flux values of the A-type zeolite membrane are roughly 10 kg/m2 h bar with a mixture selectivity of 2000 for methanol, 4000 for ethanol and 8000 for n-butanol. The average permeance of the amorphous silica membrane lies above 12 kg/m2 h bar with mixture selectivity of 50 for methanol, 500 for ethanol and 2000 for n-butanol. The separation mechanism is mainly based on adsorption and diffusion enhanced by shape selectivity and size exclusion in some cases. The transport characteristics could be described with a simple transport model based on normalized permeate fluxes. With regard to the operation stability of the membranes, no deterioration of the performance was observed for the A-type zeolite in solvent dehydration or in separation of water from reaction mixtures. The silica membrane showed an initial conditioning effect involving a rearrangement of Si-OH groups with an increase in selectivity and decrease in flux of about 30%. After a few hours the performance stabilized and remained constant during further operation. 相似文献
Organic/inorganic composite membranes with different inorganic heteropolyacid (HPA) additives maintain sufficient proton conductivities for atmospheric pressure elevated temperature (>100 °C) polymer electrolyte fuel cell (PEFC) operation. However, membrane and membrane electrode assembly (MEA) processing is severely curtailed because of the solubility of the HPA additives in aqueous media. Composite membranes with the HPA (phosphotungstic acid; PTA) additive rendered insoluble by ion exchanging protons with larger cations such as Cs+, NH4+, Rb+ and Tl+ were fabricated. The additive loss in aqueous media was lowered from nearly 100% (unmodified HPA) to about 5% (modified HPA). The membranes were robust, and demonstrated low H2 crossover currents of around 2 mA/cm2 for a 28 μm thick membrane. All membranes were evaluated at high temperatures and low relative humidities in an operating fuel cell. The conductivities of the composite membranes at 120 °C and 35% relative humidity were on the order of 1.6 × 10−2 S/cm. 相似文献