Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers...Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers to achieve production scalability and low-cost manufacturing.However,the current literature predominantly focuses on the design of polymer architectures to obtain high permeability and selectivity,while the art of fabricating gutter layers is usually safeguarded by industrial manufacturers and appears lackluster to academic researchers.This is the first report aiming to provide a comprehensive and critical review of state-of-the-art gutter layer materials and their design and modification to enable TFC membranes with superior separation performance.We first elucidate the importance of the gutter layer on membrane performance through modeling and experimental results.Then various gutter layer materials used to obtain high-performance composite membranes are critically reviewed,and the strategies to improve their compatibility with the selective layer are highlighted,such as oxygen plasma treatment,polydopamine deposition,and surface grafting.Finally,we present the opportunities of the gutter layer design for practical applications.展开更多
High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which ...High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.展开更多
Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water (O/W) mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., ...Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water (O/W) mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., a porous ceramic membrane substrate, a polyvinylidene fluoride (PVDF) ultrafiltration sub-layer, and a polyamide/polyvinyl alcohol (PVA) composite thin top-layer. The PVDF polymer was east onto the tubular porous ceramic membranes with an immersion precipitation method, and the polyamide/PVA composite thin top-layer was fabricated with an inteffaeial polymerization method. The effects of the sub-layer composition and the recipe in the inteffaeial polymerization for fabricating the top-layer on the structure and performance of composite membranes were systematically investigated. The prepared composite membranes showed a good performance for treating the O/W microemulsions with a mean diameter of about 2.41μm. At the operating pressure of 0.4MPa, the hydraulic permeability remained steadily about 190L·m^-2·h^-1, the oil concentration in the permeate was less than 1.6mg·L^-1, and the oil rejection coefficient was always higher than 98.5% throughout the operation from the beginning.展开更多
Worldwide environment has resulted in a limit on the sulfur content of gasoline.It is urgent to investigate the desulfurization of gasoline.The polydimethylsiloxane(PDMS)/polyetherimide(PEI)composite membranes were pr...Worldwide environment has resulted in a limit on the sulfur content of gasoline.It is urgent to investigate the desulfurization of gasoline.The polydimethylsiloxane(PDMS)/polyetherimide(PEI)composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope(SEM).The membranes were used for sulfur removal from gasoline by pervaporation.The effects of feed temperature,sulfur content in the feed and PDMS layer thickness on membrane performance were investigated,and an activation energy of permeation was obtained.Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor.The total flux varied little with the increase of sulfur content in the feed,but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline,and then the variation was little.The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor.The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.展开更多
Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with hi...Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with high transport resistance from the conventional interfacial polymerization hampers their applications.The controllable fabrication of a thin PA active layer is essential for high separation efficiency but still challenging.Herein,a covalent organic framework TpPa-1 interlayer was firstly deposited on a polyethersulfone(PES)substrate to reduce the thickness of PA active layer in interfacial polymerization.The abundant pores of TpPa-1 increase the local concentration of amine monomers by adsorbing piperazine molecules,while hydrogen bonds between hydrophilic groups of TpPa-1 and piperazine molecules slow down their diffusion rate.Arising from those synergetic effects,the PA active layer is effectively reduced from 200 nm to 120 nm.By optimizing TpPa-1 interlayer and PA active layer,the water flux of resultant membranes can reach 171.35 L·m^-2·h^-1·MPa^-1,which increased by 125.4%compared with PA/PES membranes,while the rejection rates of sodium sulfate and dyes solution remained more than 90%and 99%,respectively.Our strategy may stimulate rational design of ultrathin PA-based nanofiltration membranes with high performances.展开更多
Nanocrystalline cellulose(NCC)/poly(lactic acid)(PLLA) composite membranes were prepared by the solution casting method.Physical and chemical modifications were performed to improve the compatibility of NCC and PLLA.T...Nanocrystalline cellulose(NCC)/poly(lactic acid)(PLLA) composite membranes were prepared by the solution casting method.Physical and chemical modifications were performed to improve the compatibility of NCC and PLLA.The results indicated that the NCC dispersibility of the composite membranes with chemical modification were superior to that of the composite membranes with physical modification.Moreover,the chemical modification NCC not only had a large effect on the nucleation and growth of the crystals,but also affected the crystal forms of PLLA.This was because chemical reactions took place between the silicone of silane coupling agent(KH-570) and the hydroxyl groups of NCC during blending.The chemical modification NCC could be dispersed stably in the PLLA matrix,and it played the role of a nucleating agent.展开更多
Composite membranes with polyvinyl alcohol (PVA),sulphonated poly ether ether ketone (SPEEK) and phosphotungstic acid (PWA) were prepared using solvent casting method.The proton conductivities of such membranes were f...Composite membranes with polyvinyl alcohol (PVA),sulphonated poly ether ether ketone (SPEEK) and phosphotungstic acid (PWA) were prepared using solvent casting method.The proton conductivities of such membranes were found to be in the order of 10^(-3) S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy.The crystalline properties were studied by X-ray diffraction analysis.The thermal properties were determined by TGA and DSC techniques.The tensile strength and perce...展开更多
To separate salts of metals and non-electrolytes, the approach of dialysis through the composite membranes (CMs) is proposed. CM is a combination of cation and anion exchange areas. In the composite membrane, cations ...To separate salts of metals and non-electrolytes, the approach of dialysis through the composite membranes (CMs) is proposed. CM is a combination of cation and anion exchange areas. In the composite membrane, cations and anions are transferred through the respective exchange areas simultaneously without violation of macroscopic electro-neutrality. This provides a better transfer of salts than conventional ion exchange membranes (IEMs). The dialysis of the ethylene glycol aqueous salt solutions through the CMs was investigated. We have shown that the transport of salts through the composite membranes is more intensive (unlike IEM providing no transfer of salts from weakly mineralized aqueous solutions due to the Donnan exclusion) and the ethylene glycol transfer is not very significant, that is the basis of effective separation. The possibility to use of composite membranes for metal salt and other electrolyte separation is discussed.展开更多
Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane (PDMS) and poly (ethylene glycol) diacrylate ...Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane (PDMS) and poly (ethylene glycol) diacrylate (PEGDA) composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.展开更多
Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic...Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.展开更多
A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalize...A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups (SiOx-S) was added into the SPEEK matrix (DS = 55.1%) to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S (15%, by mass) membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S (20%, by mass) membrane could withstand temperature up to 145℃, at which in 100% relative humidity (RH) its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.展开更多
A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a g...A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surtace by PVA reacned up to 86.8% when me PVA content m me membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of coagulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The membrane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.展开更多
The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly (ether sulfone) (PES) support layer was first hydrophilically ...The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly (ether sulfone) (PES) support layer was first hydrophilically modified with poly(vinyl alcohol) (PVA) via surface segregation during the phase inversion process. Gelatin (GE) was then cast on the PVA-modified PES support layer as the active layer followed by crosslinking to fabricate composite membranes for ethanol dehydration. The enrichment of PVA on the surface of support layer improved interfacial compatibility of the as-prepared GE/PVA-PES composite membrane. The water contact angle measurement and X-ray photoelectron spectroscopy (XPS) data confirmed the surface segregation of PVA with a surface coverage density of -80%. T-peel test showed that the maxima/force to separate the support layer and the active layer was enhanced by 3 times compared with the GE/PES membrane. The effects of PVA content in the support layer, crosslinking of GE active layer and operating parameters on the pervaporative dehydration performance were investigated. The operational stability of the composite membrane was tested by immersing the membrane in ethanol aqueous solution for a period of time. Stable pervaporation performance for dehydration of 90% ethanol solution was obtained for GE/PVA-PES membrane with a separation factor of -60 and a permeation flux of -1910 g.m^-2.h1 without peeling over 28 days immersion.展开更多
Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes o...Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.展开更多
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 ch...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 s...展开更多
In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation b...In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.展开更多
In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology....In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO_2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite(TFC) membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl)-1-propyne](PTMSP). This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the CO_2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine(PEI) and poly(ethyleneglycol) diglycidyl ether(PEGDGE) as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1-2.5 μm. The claimed membranes showed the following characteristics: CO_2 permeance is equal to 50—54 m^3(STP)/(m^2 h bar)(18,500—20,000 GPU), ideal CO_2/N_2 selectivity is 3.6-3.7, and their selective layers are insoluble in chloroform. Thus, the developed highpermeance TFC membranes are considered as a promising supports for further modification by enhanced CO_2 selective layer formation.展开更多
Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) ...Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by COand CHadsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the COpermeance and CO/CHideal selectivity. Based on the regression coefficients of the obtained models, the COpermeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO/CHideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the COpermeance and43% enhancement in the CO/CHideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of COin the membranes resulted in the enhancement of COpermeability with increase in gas pressure.展开更多
Poly (N,N-dimethylaminoethyl methacrylate)-poly (ethylene glycol methyl ether methacrylate) (PDMAEMA-PEGMEMA) and cesium fluoride (CsF) were blended and used as the separation material of composite membranes.H...Poly (N,N-dimethylaminoethyl methacrylate)-poly (ethylene glycol methyl ether methacrylate) (PDMAEMA-PEGMEMA) and cesium fluoride (CsF) were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone (PSf) hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU (1 GPU=10-6 cm3 (STP)/(cm 2 s cmHg)),and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride (KF),due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.展开更多
Gold nanoparticles-dimethylsiloxane(AuNPs-PDMS) membrane is a novel composite material in biochemical technology an d micro-electro-mechanical system(MEMS) research.It is widely used in biomed ici ne,biochemical detec...Gold nanoparticles-dimethylsiloxane(AuNPs-PDMS) membrane is a novel composite material in biochemical technology an d micro-electro-mechanical system(MEMS) research.It is widely used in biomed ici ne,biochemical detection and en vironmental protection due to its biocompatibility,elasticity and electric char acteristics.In this paper,the characteristics of the composite membrane were d escribed,and four methods for fabricating AuNPs-PDMS composite membranes were reviewed in detail.Besides,the advantages and disadvantages of the four method s were summarized,and the present problems and future researches were proposed.展开更多
基金support from the U.S.Department of Energy National Energy Technology Laboratory(DE-FE0031736)the New York State Foundation for Science,Technology and Innovation(NYSTAR).
文摘Industrial thin-film composite(TFC)membranes achieve superior gas separation properties from high-performance selective layer materials,while the success of membrane technology relies on high-performance gutter layers to achieve production scalability and low-cost manufacturing.However,the current literature predominantly focuses on the design of polymer architectures to obtain high permeability and selectivity,while the art of fabricating gutter layers is usually safeguarded by industrial manufacturers and appears lackluster to academic researchers.This is the first report aiming to provide a comprehensive and critical review of state-of-the-art gutter layer materials and their design and modification to enable TFC membranes with superior separation performance.We first elucidate the importance of the gutter layer on membrane performance through modeling and experimental results.Then various gutter layer materials used to obtain high-performance composite membranes are critically reviewed,and the strategies to improve their compatibility with the selective layer are highlighted,such as oxygen plasma treatment,polydopamine deposition,and surface grafting.Finally,we present the opportunities of the gutter layer design for practical applications.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.12075172,12375288,12205089,and 12105048)National Key R&D Program of China(Grant No.2019YFA0210003)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110817).
文摘High-performance proton exchange membranes are of great importance for fuel cells.Here,we have synthesized polycarboxylate plasticizer modified MIL-101-Cr-NH_(2)(PCP-MCN),a kind of hybrid metal-organic framework,which exhibits a superior proton conductivity.PCP-MCN nanoparticles are used as additives to fabricate PCP-MCN/Nafion composite membranes.Microstructures and characteristics of PCP-MCN and these membranes have been extensively investigated.Significant enhancement in proton conduction for PCP-MCN around 55℃ is interestingly found due to the thermal motion of the PCP molecular chains.Robust mechanical properties and higher thermal decomposition temperature of the composite membranes are directly ascribed to strong intermolecular interactions between PCP-MCN and Nafion side chains,i.e.,the formation of substantial acid–base pairs(-SO_(3)^(-)…^(+)H–NH-),which further improves compatibility between additive and Nafion matrix.At the same humidity and temperature condition,the water uptake of composite membranes significantly increases due to the incorporation of porous additives with abundant functional groups and thus less crystallinity degree in comparison to pristine Nafion.Proton conductivity(σ)over wide ranges of humidities(30-100%RH at 25℃)and temperatures(30-98℃ at 100%RH)for prepared membranes is measured.The s in PCPMCN/Nafion composite membranes is remarkably enhanced,i.e.0.245 S/cm for PCP-MCN-3wt.%/Nafion is twice that of Nafion membrane at 98℃ and 100%RH,because of the establishment of well-interconnected proton transport ionic water channels and perhaps faster protonation–deprotonation processes.The composite membranes possess weak humidity-dependence of proton transport and higher water uptake due to excellent water retention ability of PCP-MCN.In particular,when 3 wt.%PCP-MCN was added to Nafion,the power density of a single-cell fabricated with this composite membrane reaches impressively 0.480,1.098 W/cm^(2) under 40%RH,100%RH at 60℃,respectively,guaranteeing it to be a promising proton exchange membrane.
基金Supported by the Trans-century Training Programme Foundation for the Talents by the Ministry of Education of China (No.2002-48).
文摘Fouling-resistant ceramic-supported polymer composite membranes were developed for removal of oil-in-water (O/W) mieroemulsions. The composite membranes were featured with an asymmetric three-layer structure, i.e., a porous ceramic membrane substrate, a polyvinylidene fluoride (PVDF) ultrafiltration sub-layer, and a polyamide/polyvinyl alcohol (PVA) composite thin top-layer. The PVDF polymer was east onto the tubular porous ceramic membranes with an immersion precipitation method, and the polyamide/PVA composite thin top-layer was fabricated with an inteffaeial polymerization method. The effects of the sub-layer composition and the recipe in the inteffaeial polymerization for fabricating the top-layer on the structure and performance of composite membranes were systematically investigated. The prepared composite membranes showed a good performance for treating the O/W microemulsions with a mean diameter of about 2.41μm. At the operating pressure of 0.4MPa, the hydraulic permeability remained steadily about 190L·m^-2·h^-1, the oil concentration in the permeate was less than 1.6mg·L^-1, and the oil rejection coefficient was always higher than 98.5% throughout the operation from the beginning.
基金Supported by the National Basic Research Program of China(2009CB623404)the National Natural Science Foundation of China(50708109,20736003)the National High Technology Research and Development Program of China(2007AA06Z317)
文摘Worldwide environment has resulted in a limit on the sulfur content of gasoline.It is urgent to investigate the desulfurization of gasoline.The polydimethylsiloxane(PDMS)/polyetherimide(PEI)composite membranes were prepared by casting a PDMS solution onto porous PEI substrates and characterized by scanning electron microscope(SEM).The membranes were used for sulfur removal from gasoline by pervaporation.The effects of feed temperature,sulfur content in the feed and PDMS layer thickness on membrane performance were investigated,and an activation energy of permeation was obtained.Experimental results indicated that higher feed temperature yielded higher total flux and lower sulfur enrichment factor.The total flux varied little with the increase of sulfur content in the feed,but the sulfur enrichment factor first increased with the amount of thiophene added into the gasoline,and then the variation was little.The increase of PDMS layer thickness resulted in a smaller flux but a larger sulfur enrichment factor.The result indicates that the PDMS/PEI composite membranes are promising for desulfurization by pervaporation.
基金supported by the Open Project Program of State Key Laboratory of Petroleum Pollution Control(Grant No.PPC2017014)CNPC Research Institute of Safety and Environmental Technology。
文摘Polyamide(PA)-based thin-film composite membranes exhibit enormous potential in water purification,owing to their facile fabrication,decent performance and desirable stability.However,the thick PA active layer with high transport resistance from the conventional interfacial polymerization hampers their applications.The controllable fabrication of a thin PA active layer is essential for high separation efficiency but still challenging.Herein,a covalent organic framework TpPa-1 interlayer was firstly deposited on a polyethersulfone(PES)substrate to reduce the thickness of PA active layer in interfacial polymerization.The abundant pores of TpPa-1 increase the local concentration of amine monomers by adsorbing piperazine molecules,while hydrogen bonds between hydrophilic groups of TpPa-1 and piperazine molecules slow down their diffusion rate.Arising from those synergetic effects,the PA active layer is effectively reduced from 200 nm to 120 nm.By optimizing TpPa-1 interlayer and PA active layer,the water flux of resultant membranes can reach 171.35 L·m^-2·h^-1·MPa^-1,which increased by 125.4%compared with PA/PES membranes,while the rejection rates of sodium sulfate and dyes solution remained more than 90%and 99%,respectively.Our strategy may stimulate rational design of ultrathin PA-based nanofiltration membranes with high performances.
文摘Nanocrystalline cellulose(NCC)/poly(lactic acid)(PLLA) composite membranes were prepared by the solution casting method.Physical and chemical modifications were performed to improve the compatibility of NCC and PLLA.The results indicated that the NCC dispersibility of the composite membranes with chemical modification were superior to that of the composite membranes with physical modification.Moreover,the chemical modification NCC not only had a large effect on the nucleation and growth of the crystals,but also affected the crystal forms of PLLA.This was because chemical reactions took place between the silicone of silane coupling agent(KH-570) and the hydroxyl groups of NCC during blending.The chemical modification NCC could be dispersed stably in the PLLA matrix,and it played the role of a nucleating agent.
基金supported by the Department of Science and Technology,India (SR/FTP/CS-33/2005 dated 11-08-2005).
文摘Composite membranes with polyvinyl alcohol (PVA),sulphonated poly ether ether ketone (SPEEK) and phosphotungstic acid (PWA) were prepared using solvent casting method.The proton conductivities of such membranes were found to be in the order of 10^(-3) S/cm in the fully hydrated condition at room temperature as measured by impedance spectroscopy.The crystalline properties were studied by X-ray diffraction analysis.The thermal properties were determined by TGA and DSC techniques.The tensile strength and perce...
文摘To separate salts of metals and non-electrolytes, the approach of dialysis through the composite membranes (CMs) is proposed. CM is a combination of cation and anion exchange areas. In the composite membrane, cations and anions are transferred through the respective exchange areas simultaneously without violation of macroscopic electro-neutrality. This provides a better transfer of salts than conventional ion exchange membranes (IEMs). The dialysis of the ethylene glycol aqueous salt solutions through the CMs was investigated. We have shown that the transport of salts through the composite membranes is more intensive (unlike IEM providing no transfer of salts from weakly mineralized aqueous solutions due to the Donnan exclusion) and the ethylene glycol transfer is not very significant, that is the basis of effective separation. The possibility to use of composite membranes for metal salt and other electrolyte separation is discussed.
基金Supported by the National Basic Research Program of China (2009CB623406), the National Natural Science Foundation of China (20990222) and the Natural Science Foundation of Jiangsu Province (BK2009021, SBK200930313).
文摘Composite membranes have attracted increasing attentions owing to their potential applications for CO2 separation. In this work, ceramic supported polydimethylsiloxane (PDMS) and poly (ethylene glycol) diacrylate (PEGDA) composite membranes were prepared. The microstructure and physicochemical properties of the compos- ite membranes were characterized. Preparation conditions were systematically optimized. The gas separation performance of the as-prepared membranes was studied by pure gas and binary gas permeation measurement of CO〉 N2 and H〉 Experiments showed that PDMS, as silicone rubber, exhibited larger permeance and lower separation factors. Conversely, PEGDA composite membrane presented smaller gas permeance but higher ideal selectivity for CO2/N2. Compared to the performance of those membranes using polymeric supports or freestanding membranes, the two kinds of ceramic supported composite membranes exhibited higher gas permeance and acceptable selectivity. Therefore, the ceramic supported composite membrane can be expected as a candidate for CO2 separation from light gases.
文摘Pervaporation(PV),as an environmental friendly and energy-saving separation technology,has been received increasing attention in recent years.This article reviews the preparation and application of macroporous ceramic-supported polymer composite pervaporation membranes.The separation materials of polymer/ceramic composite membranes presented here include hydrophobic polydimethylsiloxane(PDMS) and hydrophilic poly(vinyl alcohol)(PVA),chitosan(CS) and polyelectrolytes.The effects of ceramic support treatment,polymer solution properties,interfacial adhesion and incorporating or blending modification on the membrane structure and PV performance are discussed.Two in-situ characterization methods developed for polymer/ceramic composite membranes are also covered in the discussion.The applications of these composite membranes in pervaporation process are summarized as well,which contain the bio-fuels recovery,gasoline desulfuration and PV coupled proc-ess using PDMS/ceramic composite membrane,and dehydration of alcohols and esters using ceramic-supported PVA or PVA-CS composite membrane.Finally,a brief conclusion remark on polymer/ceramic composite mem-branes is given and possible future research is outlined.
基金Supported by the State Key Development Program for Basic Research of China (2008CB617502), the National Natural Science Foundation of China (20606025), and Program for Changjiang Scholars and Innovative Research Team in University of China (IRT0641).
文摘A sulfonated poly(ether ether ketone) (SPEEK) membrane with a fairly high degree of sulfonation (DS) can swell excessively and even dissolve at high temperature. To solve these problems, insolvable functionalized silica powder with sulfonic acid groups (SiOx-S) was added into the SPEEK matrix (DS = 55.1%) to prepare SPEEK/ SiOx-S composite membranes. The decrease in both the swelling degree and the methanol permeability of the membranes was a dose-dependent result of addition of the SiOx-S powder. Pure SPEEK membrane swelled 52.6% at 80℃, whereas the SPEEK/SiOx-S (15%, by mass) membrane swelled only 27.3% at the same temperature. From room temperature to 80℃, all SPEEK/SPEEK/SiOx-S composite membranes had methanol permeability of about one order of magnitude lower than that ofNafion115. Compared with pure SPEEK membranes, the addition of the SiOx-S powder not only leads to higher proton conductivity, but also increases the dimensional stability at higher temperatures, and greater proton conductivity can be achieved at higher temperature. The SPEEK/SiO4-S (20%, by mass) membrane could withstand temperature up to 145℃, at which in 100% relative humidity (RH) its proton conductivity exceeded slightly that of Nafion 1 15 membrane and reached 0.17 S·cm^-1, while pure SPEEK membrane dissolved at 90℃. The SPEEK/SiOx-S composite membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.
基金Supported by the State Key Development Program for Basic Research of China (2009CB623404)Program for New Century Excellent Talents in University,the Programme of Introducing Talents of Discipline to Universities (B06006)State KeyLaboratory for Modification of Chemical Fibers and Polymer Materials (Dong Hua University)
文摘A facile surface segregation method was utilized to fabricate poly(vinyl alcohol)-polyethersulfone (PVA-PES) composite membranes. PVA and PES were first dissolved in dimethyl sulfoxide (DMSO), then casted on a glass plate and immersed in a coagulation bath. During the phase inversion process in coagulation bath, PVA spontaneously segregated to the polymer solution/coagulation bath interface. The enriched PVA on the surface was further crosslinked by glutaraldehyde. Scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy dispersive spectrometer (EDS) confirmed the integral and asymmetric membrane structure with a dense PVA-enriched surface and a porous PES-enriched support, as well as the surface enrichment of PVA. The coverage fraction of the membrane surtace by PVA reacned up to 86.8% when me PVA content m me membrane recipe was 16.7% (by mass). The water contact angle decreased with the increase of PVA content. The effect of coagulation bath type on membrane structure was analyzed. The membrane pervaporation performance was evaluated by varying the PVA content, the annealing temperature, feed concentration and operation temperature. The membrane exhibited a fairly good ethanol dehydration capacity and long-term operational stability.
基金Supported by the New Century Excellent Talents in University(NCET-10-0623)National Natural Science Foundation for Distinguished Young Scholars(21125627)+1 种基金National Basic Research Program of China(2009CB623404)State Key Laboratory for Modification of Chemical Fibers and Polymer Materials(Dong Hua University)
文摘The interfacial compatibility of composite membrane is an important factor to its structural stability, andseparation performance. In this study, poly (ether sulfone) (PES) support layer was first hydrophilically modified with poly(vinyl alcohol) (PVA) via surface segregation during the phase inversion process. Gelatin (GE) was then cast on the PVA-modified PES support layer as the active layer followed by crosslinking to fabricate composite membranes for ethanol dehydration. The enrichment of PVA on the surface of support layer improved interfacial compatibility of the as-prepared GE/PVA-PES composite membrane. The water contact angle measurement and X-ray photoelectron spectroscopy (XPS) data confirmed the surface segregation of PVA with a surface coverage density of -80%. T-peel test showed that the maxima/force to separate the support layer and the active layer was enhanced by 3 times compared with the GE/PES membrane. The effects of PVA content in the support layer, crosslinking of GE active layer and operating parameters on the pervaporative dehydration performance were investigated. The operational stability of the composite membrane was tested by immersing the membrane in ethanol aqueous solution for a period of time. Stable pervaporation performance for dehydration of 90% ethanol solution was obtained for GE/PVA-PES membrane with a separation factor of -60 and a permeation flux of -1910 g.m^-2.h1 without peeling over 28 days immersion.
基金Projects(212006065,21666018)supported by the National Natural Science Foundation of China
文摘Al2O3 ceramic powder was applied to modify the large pores defects on the surface of the porous metal Ti support,in situ oxidation method was a convenient method to prepare defect free ceramic/Ti composite membranes on this basis.In situ oxidation conditions experimental results show that the best condition for preparing the TiO2-Al2O3/Ti composite membrane is under 800°C for 2 h,and the microstructure and pore sizes of the TiO2-Al2O3/Ti composite membranes are affected obviously.The thickness and composition of the TiO2/Ti composite membranes are determined by SEM and XRD completely.The pore size distribution of the composite membrane is measured by bubble pressure method,the most probable aperture is about 3.12μm,while the average pore size of defect free TiO2-Al2O3/Ti is about 3.23μm.After ultrasonic treatment,the slight weight change of membranes reveals no observable change,which indicates that TiO2-Al2O3/Ti composite membranes maintain a good stability.
基金supported by the China Postdoctoral Science Foundation(No20060400436)the Major State Basic Research Program of China(No2009CB623404)+3 种基金National Natural Science Foundation of China(Nos20736003,20676067)National High Technology Research and Development Program of China(No2007AA06Z317)Foundation of Ministry of Education of China(No20070003130) Foundation of the State Key Laboratory of Chemical Engineering(SKL-ChE-08A01)
文摘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 s...
基金Supported by Key Projects in the National Science & Technology Pillar Program (2011BAC08B00)
文摘In this paper, poly(amide-6-β-ethylene oxide) (PEBA1657) copolymer was used to prepare multilayer polyetherimide (PEI)/polydimethylsiloxane (PDMS)/PEBA1657/PDMS composite membranes by dip-coating method. Permeation behaviors of ethylene, ethane, propylene, propane, n-butane, methane and nitrogen through the multilayer composite membranes were investigated over a range of operating temperature and pressure. The permeances of light hydrocarbons through PEI/PDMS/PEBA1657/PDMS composite membranes increase with their increasing condensability, and the olefins are more permeable than their corresponding paraffins. For light hydrocarbons, the gas permeances increase significantly as temperature increasing. When the transmembrane pressure difference increases, the gas permeance increases moderately due to plasticization effect, while their apparent activation energies for permeation decrease.
基金supported by the European Community's Seventh Framework Program FP7 under the grant agreement no.608555(HiPerCap)
文摘In the development of the composite gas separation membranes for post-combustion CO_2 capture, little attention is focused on the optimization of the membrane supports, which satisfy the conditions of this technology. The primary requirements to the membrane supports are concerned with their high CO_2 permeance. In this work, the membrane supports with desired characteristics were developed as high-permeance gas separation thin film composite(TFC) membranes with the thin defect-free layer from the crosslinked highly permeable polymer, poly[1-(trimethylsilyl)-1-propyne](PTMSP). This layer is insoluble in chloroform and can be used as a gutter layer for the further deposition of the CO_2-selective materials from the organic solvents. Crosslinking of PTMSP was performed using polyethyleneimine(PEI) and poly(ethyleneglycol) diglycidyl ether(PEGDGE) as crosslinking agents. Optimal concentrations of PEI in PTMSP and PEGDGE in methanol were selected in order to diminish the undesirable effect on the final membrane gas transport characteristics. The conditions of the kiss-coating technique for the deposition of the thin defect-free PTMSP-based layer, namely, composition of the casting solution and the speed of movement of the porous commercial microfiltration-grade support, were optimized. The procedure of post-treatment with alcohols and alcohol solutions was shown to be crucial for the improvement of gas permeance of the membranes with the crosslinked PTMSP layer having thickness ranging within 1-2.5 μm. The claimed membranes showed the following characteristics: CO_2 permeance is equal to 50—54 m^3(STP)/(m^2 h bar)(18,500—20,000 GPU), ideal CO_2/N_2 selectivity is 3.6-3.7, and their selective layers are insoluble in chloroform. Thus, the developed highpermeance TFC membranes are considered as a promising supports for further modification by enhanced CO_2 selective layer formation.
文摘Three phase PebaxMH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by COand CHadsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the COpermeance and CO/CHideal selectivity. Based on the regression coefficients of the obtained models, the COpermeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO/CHideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the COpermeance and43% enhancement in the CO/CHideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of COin the membranes resulted in the enhancement of COpermeability with increase in gas pressure.
基金supported by the Chinese Ministry of Science and Technology(973 Program,No. 2009CB623405)the National Natural Science Foundation of China(NSFC program,20706051 and 20836006)
文摘Poly (N,N-dimethylaminoethyl methacrylate)-poly (ethylene glycol methyl ether methacrylate) (PDMAEMA-PEGMEMA) and cesium fluoride (CsF) were blended and used as the separation material of composite membranes.Hollow fiber composite membranes were fabricated by coating the blend on polysulfone (PSf) hollow fiber substrate.Introduction of fluorine ion improved the separation performance of the membrane.The concentration of coating solution was adjusted to obtain a membrane with high permeance.The composite membrane showed good performance with the CO2 permeance of 30.4 GPU (1 GPU=10-6 cm3 (STP)/(cm 2 s cmHg)),and selectivities to CO2/N2,CO2/CH4,CO2/H2 and O2/N2 of 47.2,37.6,1.75 and 4.70,respectively.Potassium fluoride (KF),due to its low cost,was also used as a substitute of CsF to prepare composite membrane and the permeation data showed that CsF can be replaced by KF.The effect of operating temperature on the permeation properties of the composite membrane was also investigated.
基金National Natural Science Foundation of China (No.51105267, No.91123036)China Postdoctoral Science Foundation(No.2011M500542, No.2012T50248)+1 种基金National Research Foundation for the Doctoral Program of Higher Education of China (No.20111402120007)Shanxi Provincial Foundation for Returned Scholars (No.2011x10)
文摘Gold nanoparticles-dimethylsiloxane(AuNPs-PDMS) membrane is a novel composite material in biochemical technology an d micro-electro-mechanical system(MEMS) research.It is widely used in biomed ici ne,biochemical detection and en vironmental protection due to its biocompatibility,elasticity and electric char acteristics.In this paper,the characteristics of the composite membrane were d escribed,and four methods for fabricating AuNPs-PDMS composite membranes were reviewed in detail.Besides,the advantages and disadvantages of the four method s were summarized,and the present problems and future researches were proposed.