Nano filter from sintered rice husk silica membrane

A nano filter showing the Knudsen flow was demonstrated by a modification of a membrane constructed from rice husk silica. The membrane was prepared by pressing and sintering micron sized rice husk silica with 4 nm pores. The membrane showed a permeability of 5.2 x 10(-8) mol m(-1) sec(-1) Pa(-1) for H2 and ratios of gas permeability 2.1 and 3.2 for k(H2)/k(CH4) and k(H2)/k(CO2), respectively. When the membrane was treated by filtration of approximately 100 nm sized rice husk silica particles, the permeability decreased to 4.9 x 10(-8) mol m(-1) sec(-1) Pa(-1) and the ratios increased to 2.2 and 3.4. In the case of the membrane after treatments with the dispersion and chemical deposition of tetraethylorthosilicate (TEOS), the corresponding permeability and ratios of the membrane were 1.8 x 10(-8) mol m(-1) sec(-1) Pa(-1), and 2.9 and 4.5, respectively. From the change of the ratio of gas permeability for the membrane with modifications, it is suggested that approximately 100 nm sized rice husk silica particles pack the large pores among the micron sized rice husk silica particles while the chemical deposition of tetraethylorthosilicate (TEOS) reveals the gas flow through 4 nm pores in the rice husk silica by blocking large pores.     

A study on electric conductivity of phosphoric acid supported on nano-pore rice husk silica in H2/Pt/H3PO4 / RHS/Pt/O2 fuel cells

PEMFC (Polymer Electrolyte Membrane Fuel Cell) is widely considered as an energy conversion system from the chemical energy of hydrogen to electric energy. But, hydrogen fuel obtained from hydrocarbons has trace amount of carbon monoxide which is a potential poison for platinum electrode at the cell operating temperature approximately 100 degrees C and it becomes a huddle for the general usage of PEMFC. On the other hand PAFC (Phosphoric Acid Fuel Cell) operates at a higher temperature and the platinum electrode oxidizes carbon monoxide poison while there is a leakage problem of the liquid phase. To combine the advantages of two fuel cells, the electrolyte systems of phosphoric acid supported silica on ceramics are recently being tested. In this study, we investigated the nm pore rice husk silica as a support for phosphoric acid and tested the electric conductivity of the silica plate and the characteristics of a prototype fuel cell H2/Pt/H3PO4 / RHS/Pt/O2 at 100-200 degrees C. The conductivity of H3PO4/RHS was 8 mS cm(-1) above 175 degrees C under 200 torr H2O. In the fuel cell, the apparent conductance of the electrolyte from I-V characteristics was 2.45 mS/cm at 160 degrees C under 1 atm H2 and air at present.     

Gas sensing property of perovskite SrTi(1-x)Fe(x)O3_delta fabricated by thick film planar technology

Planar sensor of SrTi(1-x)Fe(x)O3-delta, x = 0.4 and 0.6, with perovskite structure was fabricated on alumina substrate using thick film technology. Electrical resistance was measured as a function of thermal treatment conditions, atmosphere, time and temperature. Sensing property was also measured as a function of temperature and the gases of O2, CH4, CO, CO2, NO and NO2. The resistance of SrTi(1-x)Fe(x)O3-delta is lower than those of SrTiO3 or SrFeO3. TCR (temperature coefficient of resistance) of zero over 550 degrees C was measured for the composition of SrTi(1-x)Fe(x)O3-delta after thermal treatment at 1100 degrees C in air atmosphere only. The perovskite SrTi(1-x)Fe(x)O3-delta didn't show any response to CH4, CO, CO2, NO and NO2, but an excellent response and recovery characteristics with oxygen concentration.     

Organic-templating approach to synthesis of nanoporous silica composite membranes (l): TPA-templating and CO2 separation

Nanoporous silica composite membranes for gas separation have been synthesized by dip-coating the tetrapropylammonium (TPA)-templating silica sols on tubular alumina supports (pore size 2.8–100 nm), followed by eliminating the template via heat-treating at 550–600°C. The NMR spectroscopy of TPABr-silica hybrid composites obtained from the templated silica sols confirmed that TPA molecules (i.e., final pores) were uniformly distributed in the silica matrix. The average pore size and the specific surface area of an unsupported membrane prepared by firing the TPABr (6 wt%)-silica hybrid composite at 600°C were below 18 Å and 830 m²/g, respectively. Any defects such as cracks or pin-holes on the surface of amorphous silica composite membranes were not observed. The CO₂/N₂ separation factor of their composite membranes varied from 3.2 to 10.3 and their gas permeability from 10^–8 to 10^–9 mol/m² · s · Pa depending on the microstructure of aluminar supports.     

Protein-repellent silicon nitride surfaces: UV-induced formation of oligoethylene oxide monolayers

The grafting of polymers and oligomers of ethylene oxide onto surfaces is widely used to prevent nonspecific adsorption of biological material on sensors and membrane surfaces. In this report, we show for the first time the robust covalent attachment of short oligoethylene oxide-terminated alkenes (CH(3)O(CH(2)CH(2)O)(3)(CH(2))(11)-(CH═CH(2)) [EO(3)] and CH(3)O(CH(2)CH(2)O)(6)(CH(2))(11)-(CH═CH(2)) [EO(6)]) from the reaction of alkenes onto silicon-rich silicon nitride surfaces at room temperature using UV light. Reflectometry is used to monitor in situ the nonspecific adsorption of bovine serum albumin (BSA) and fibrinogen (FIB) onto oligoethylene oxide coated silicon-rich silicon nitride surfaces (EO(n)-Si(x)N(4), x > 3) in comparison with plasma-oxidized silicon-rich silicon nitride surfaces (SiO(y)-Si(x)N(4)) and hexadecane-coated Si(x)N(4) surfaces (C(16)-Si(x)N(4)). A significant reduction in protein adsorption on EO(n)-Si(x)N(4) surfaces was achieved, adsorption onto EO(3)-Si(x)N(4) and EO(6)-Si(x)N(4) were 0.22 mg m(-2) and 0.08 mg m(-2), respectively. The performance of the obtained EO(3) and EO(6) layers is comparable to those of similar, highly protein-repellent monolayers formed on gold and silver surfaces. EO(6)-Si(x)N(4) surfaces prevented significantly the adsorption of BSA (0.08 mg m(-2)). Atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), X-ray reflectivity and static water contact angle measurements were employed to characterize the modified surfaces. In addition, the stability of EO(6)-Si(x)N(4) surfaces in phosphate-buffered saline solution (PBS) and alkaline condition (pH 10) was studied. Prolonged exposure of the surfaces to PBS solution for 1 week or alkaline condition for 2 h resulted in only minor degradation of the ethylene oxide moieties and no oxidation of the Si(x)N(4) substrates was observed. Highly stable antifouling coatings on Si(x)N(4) surfaces significantly broaden the application potential of silicon nitride-coated microdevices, and in particular of microfabricated filtration membranes.     

以无机盐为原料制备钇稳定的氧化锆超滤膜

用无机盐ＺｒＯＣｌ_２·８Ｈ_２Ｏ和Ｙ（ＮＯ_３）_３·６Ｈ_２Ｏ为原料,以溶胶－凝胶技术路线,在多孔氧化铝支撑体上成功地制备了记稳定的氧化锆（ＹＳＺ）陶瓷膜．扫描电子显微镜（ＳＥＭ）分析表明,用沉淀、胶溶、成膜的溶胶－凝胶技术,不能制备表面无龟裂的ＹＳＺ膜．沉淀用共沸蒸馏法干燥,得到高分散性的ＹＳＺ粉体,再用超声法制备ＹＳＺ氧化物胶体,通过浸渍成膜,ＳＥＭ分析证明,ＹＳＺ膜表面无明显缺陷．室温氮气渗透实验进一步证明,膜结构完整．用等温氮吸附实验测定了无支撑体膜的孔径大小和分布,平均孔径约为６ｎｍ．用激光散射技术测定ＹＳＺ胶体粒子平均半径为１１６ｎｍ,透射电子显微镜观察表明,胶体粒子由大小约为２０ｎｍ的晶粒组成．     

Atomic layer deposition of SiO2 thin films using tetrakis(ethylamino)silane and ozone

We examined the atomic layer deposition (ALD) of silicon dioxide thin films on a silicon wafer by alternating exposures to tetrakis(ethylamino)silane [Si(NHC2H5)4] and O3. The growth kinetics of silicon oxide films was examined at substrate temperatures ranging from 325 to 514 degrees C. The deposition was governed by a self-limiting surface reaction, and the growth rate at 478 degrees C was saturated at 0.17 nm/cycle for Si(NHC2H5)4 exposures of 2 x 10(6) L (1 L = 10(-6) Torr x s). The films deposited at 365-404 degrees C exhibited a higher deposition rate of 0.20-0.21 nm/cycle. However, they contained impurities, such as carbon and nitrogen, and showed poor film qualities. The concentration of impurities decreased with increasing substrate temperature. It was found that the films deposited in the high-temperature regime (478-514 degrees C) showed excellent physical and electrical properties equivalent to those of LPCVD films.     

Eu-doped titania nanofibers: processing, thermal behaviour and luminescent properties

Undoped and Europium-doped titania nanofibers have been fabricated by electrospinning technique, using a single multielement Titanium/Europium source. In this communication we present the synthesis, structural and spectroscopic characterisation of Eu-doped TiO2 nanofibers starting from polyvinylpyrrolidone, titanium tetraisopropoxide (Ti(OiPr)4) and Eu(hfa)3 x diglyme (Hhfa = 1,1,1,5,5,5-hexafluoroacetyacetone, diglyme = CH3O(CH2CH2O)2CH3). The chosen system allowed to investigate a wide compositional range, i.e., from 3 to 10% mol of Eu3+. Microstructure was studied by means of scanning electron microscopy (SEM), thermal behaviour followed by thermogravimetric and differential thermal analysis (TG-DTA). Phase analysis was performed by means of X-ray diffraction (XRD) and high temperature X-ray diffraction analysis (HT-XRD) up to 1100 degrees C. Luminescence properties were investigated by means of luminescence spectroscopy, using a laser excitation source at 395 nm. All electrospun materials consisted of randomly oriented nanofibers of fairly uniform diameter. The average fiber size was 80-100 nm and 40 nm for, respectively, Eu-doped and undoped TiO2 calcinated at 500 degrees C. The presence of Europium shifted toward higher values either the crystallization temperature of anatase and the anatase to rutile phase transition, the latter being accompanied by the formation of the Eu2Ti2O7 phase. The doped samples showed a strong luminescence of Eu3+ ions. The emission spectra were dominated by the 5D0 --> 7F2 emission, suggesting a notable distortion around the Eu3+ ions. The broadening of the bands pointed to the presence of a relevant inhomogeneous disorder around the Eu3+ sites. The Eu3+ doped TiO2 nanofibers showed a higher emission intensity with respect to the PVP/TiO2 ones.     

Preparation, characterization, and application of an enzyme-immobilized magnetic microreactor for flow injection analysis

Enzyme-immobilized magnetic microparticles (EMMP) have been prepared for use as a microreactor in flow injection analysis (FI). The microparticles were directly injected into the FI system. Their retention occurred within the flow line by small permanent magnets located near the detector. The analytical utility of this concept was illustrated by the assay of glucose using glucose oxidase (GOx), immobilized microparticles, and amperometric detection of liberated hydrogen peroxide. The microparticles were derived from silica gel (nominal pore diameter, 15-80 nm) by impregnation with a citric acid/ethanol solution and a ferric nitrate/ethanol solution and then by calcination in a nitrogen atmosphere to produce ferrimagnetic fine particles of spinel-type iron oxide (gamma-Fe(2)O(3)) inside the pore. They were characterized by X-ray diffraction. The calibration curve of the glucose sample (2 microL injected) was linear between 2.5 x 10(-6) and 5 x 10(-4) mol/L (R = 0.9995), and the detection limit was 1.0 x 10(-6) mol/L or 0.36 ng of injected glucose (S/N = 3). The repeatability for a 5 x 10(-4) mol/L glucose solution was RSD = 1.5% (n = 6). Application to the assay of glucose in a fermentation broth is illustrated. The GOx MMP were stable and active for more than eight months when kept at 10 degrees C.     

亲水性高分子-陶瓷复合膜的制备与表征

采用均质的氧化铝支撑体和不同表面层孔径的非对称氧化铝支撑体直接接枝聚丙烯酸(PAA)制备亲水性PAA-Al2O3复合膜。对所制备出复合膜的红外光谱(IR)分析、光电子能谱(XPS)分析、扫描电子显微镜(SEM)分析和表面的水接触角分析表明,成功地制备出了PAA-Al2O3复合膜。在相同实验条件下对所制备的复合膜进行纯水和纯乙醇的通量实验以及质量分数95%乙醇的脱水分离试验表明,最适合用于制备PAA-Al2O3复合膜的陶瓷膜支撑体是孔径为2～3μm的均质氧化铝支撑体,用其制备的复合膜的分离因子为139.33,通量为0.61kg/(m2.h),可以达到分离效率高、通量较大的效果.     

Synthesis and characterization of silicalite powders and membranes with micro–meso bimodal pores

Silicalite sols containing silicalite agglomerates of 150–380 nm in size were synthesized by hydrothermal synthesis for 0.5–3 days. Silicalite powders and supported silicalite membranes containing micro-meso bimodal pores were prepared by the sol–gel method using these silicalite sols. The silicalite powders contain intracrystalline zeolitic pores (0.54 nm) and intercrystalline mesopores of about 3–4 nm in diameter. For the silicalite powders the mesopore size decreases and mesopore surface area increases with increasing silicalite agglomerate size as a result of a change of the shape of silicalite agglomerates from round to more faceted one. Continuous silicalite thin films of thicknesses ranging from 3 μm to 12 μm were made on α-alumina by the sol–gel dip-coating method. The supported silicalite membranes also contain both zeolitic pores and mesoporous intercrystalline pores. The single gas He permeance of the 3 μm thick α-alumina supported silicalite membrane was found to be from 2.7 × 10⁻⁶ to 3.3 × 10⁻⁶ mol/m² s Pa. These bimodal pore zeolite powders offer the potential as catalysts and sorbents with improved efficiency. The bimodal pore zeolite membrane can be used as support for zeolite and other membranes and as compact packed-bed reactor for chemical reaction.     

聚乙烯基三苯乙炔基硅烷的制备及热性能分析

为研究聚乙烯基三苯乙炔基硅烷树脂的热性能,以苯乙炔和乙烯基三氯硅烷为原料,运用格利雅反应合成了乙烯基三苯乙炔基硅烷单体,并通过红外(FT-IR)、核磁(1H-NMR,13C-NMR,29Si-NMR)证实了合成产物.以此单体为原料,通过热聚合法制备了聚乙烯基三苯乙炔基硅烷树脂,并采用TGA-DTG研究该聚合物的热分解动力学,计算了相应动力学参数.结果表明:该树脂的热分解温度(Td5%)在550℃左右,800℃时聚合物的残炭率约80%;用Kissinger法和Ozawa法求得的聚合物热分解活化能分别为266.55和236.89 k J/mol;用Crane法求得聚合物的热分解反应级数为0.93,近似为一级反应.     

KOH活化法制备气体分离用炭分子筛膜

选用KOH为活化剂,利用化学活化法制备炭分子筛膜,考察在热塑性酚醛树脂(PFNR)涂膜液中添加不同质量分数的KOH对炭分子筛膜的影响.结果表明,在炭化过程中,KOH的加入可促进炭分子筛膜孔径的均匀分布,使炭分子筛膜具有发达的孔隙结构.当KOH在PFNR中的添加量从0％增加到4％时,H2的渗透速率由23.68×10-10 mol·m-2·s-1·pa-1提高到28.6×10-10 mol·m-2·s-1·Pa-1;但H2/N2和H2/CH4的分离系数明显下降,分别从471.3下降到147.5、540下降到270.CO2/CH4和O2/N2的分离系数只有轻微下降.     

Resizing metal-coated nanopores using a scanning electron microscope

Electron beam-induced shrinkage provides a convenient way of resizing solid-state nanopores in Si(3) N(4) membranes. Here, a scanning electron microscope (SEM) has been used to resize a range of different focussed ion beam-milled nanopores in Al-coated Si(3) N(4) membranes. Energy-dispersive X-ray spectra and SEM images acquired during resizing highlight that a time-variant carbon deposition process is the dominant mechanism of pore shrinkage, although granular structures on the membrane surface in the vicinity of the pores suggest that competing processes may occur. Shrinkage is observed on the Al side of the pore as well as on the Si(3) N(4) side, while the shrinkage rate is observed to be dependent on a variety of factors.     

PMDA-ODA型聚酰亚胺炭/碳纳米管杂化膜的制备及气体分离性能研究

针对现有气体分离炭膜存在的渗透速率低等问题, 提出并设计在PMDA-ODA型聚酰亚胺前驱体中掺杂碳纳米管, 经高温热解后制备炭/碳纳米管杂化膜. 分别采用透射电镜(TEM)、X射线衍射分析(XRD)和气体渗透实验对炭/碳纳米管杂化膜的微观结构和分离性能进行表征. 实验结果表明, 在PMDA-ODA型聚酰亚胺前驱体中掺杂碳纳米管后, 碳纳米管与炭基体之间形成明显的“界面间隙”, 打破了原有炭膜中由乱层炭构成的无序微孔结构, 重新构建了杂化炭膜的孔隙结构. 与纯炭膜相比, 杂化炭膜的气体渗透速率大幅增加, 其中O₂的渗透速率增大接近4倍(达到1576 Barrer), 而O₂/N₂的分离选择性仅降低17%.     

Electrochemical synthesis of antimony nanowires and analysis of diffusion layers

Synthesis of an array of antimony nanowires was performed by electrodeposition within a porous polycarbonate membrane. The sizes of pores range from 30 to 400 nm in diameter and their densities vary from 2 x 10(+6) to 2 x 10(+9) pores/cm2. To obtain optimal conditions for nanowire preparation, plating behavior was investigated by a potentiostatic method with two types (continued or pulsed) of polarization. The chronoamperometry revealed that responses depend on the type of polarization and on the pore density of the membrane. With high-density membranes, the diffusion layers of each individual pore immediately overlap when they reach the external part of the membrane. This leads to an abrupt decrease of current intensity. This phenomenon is not observed with low-density membranes because of the greater distance between pores. This mechanism, which was investigated in antimony nanowire plating, is applicable to electrodeposition of other types of materials.     

几种HQDEA型聚醚酰亚胺的透气性能

合成了四种双醚二酐(HQDEA)型聚醚酰亚胺,研究了它们对H_2、CO_2、O_2、N_2和CH_4五种气体的透过性能。结果表明,这类聚醚酰亚胺的分子结构,特别是取代基的位置对透气性和透气选择性有很大的影响。酰亚胺键邻位甲基取代聚醚酰亚胺(HQDEA-DMMDAI)兼具有高的透气性和透气选择性。     

Enhancing the oxygen permeability of BaCo(0.7)Fe(0.2)Nb(0.1)O(3-δ) membranes by coating GdBaCo(2-x)Fe(x)O(5+δ) for partial oxidation of coke oven gas to syngas

The dense ceramic membranes BaCo(0.7)Fe(0.2)Nb(0.1)O(3-δ) (BCFN) combined with GdBaCo(2-x)Fe(x)O(5+δ) (0 ≤ x ≤ 2.0) surface modification layers was investigated for hydrogen production by partial oxidation reforming of coke oven gas (COG). As oxygen permeation of BCFN membrane is controlled by the rate surface exchange kinetics, the GdBaCo(2-x)Fe(x)O(5+δ) materials improve the oxygen permeation flux of the BCFN membrane by 20-44% under helium atmosphere at 750 °C. The maximum oxygen permeation flux reached 14.4 mL min(-1) cm(-2) in the GdBaCoFeO(5+δ) coated BCFN membrane reactor at 850 °C, and a CH(4) conversion of 94.9%, a H(2) selectivity of 88.9%, and a CO selectivity of 99.6% have been achieved. The GdBaCo(2-x)Fe(x)O(5+δ) coating materials possess uniform porous structure, fast oxygen desorption rate and good compatibility with the membrane, which showed a potential application for the surface modification of the membrane reactor.     

Ion channel mimetic micropore and nanotube membrane sensors

This paper describes synthetic micropore and nanotube membranes that mimic the function of a ligand-gated ion channel; that is, these membranes can be switched from an "off" state (no or low ion current through the membrane) to an "on" state (higher ion current) in response to the presence of a chemical stimulus. Ion channel mimics based on both microporous alumina and Au nanotube membranes were investigated. The off state was obtained by making the membranes hydrophobic by chemisorbing either a C18 silane (alumina membrane) or a C18 thiol (Au nanotube membrane). Water and electrolyte are forbidden from entering these very hydrophobic pores/nanotubes. The transition to the on state was induced by the partitioning of a hydrophobic ionic species (e.g., a drug or a surfactant) into the membrane. The membrane switches to the on state because at a sufficiently high concentration of this ionic analyte species, the pores/nanotubes flood with water and electrolyte. A pH-responsive membrane was also prepared by attaching a hydrophobic alkyl carboxylic acid silane to the alumina membrane.     

Characterization of low-k dielectric SiCOH films deposited with decamethylcyclopentasiloxane and cyclohexane

Ultra low-k dielectric SiCOH films were deposited with decamethylcyclopentasiloxane (DMCPSO, C10H30O5Si5) and cyclohexane (C6H12) precursors by plasma-enhanced chemical vapor deposition at the deposition temperature between 25 and 200 degrees C and their chemical composition and deposition kinetics were investigated in this work. Low dielectric constants of 1.9-2.4 were obtained due to intrinsic nanoscale pores originating from the relatively large ring structure of DMCPSO and to the relatively large fraction of carbon contents in cyclohexane. Three different deposition regions were identified in the temperature range. Deposition rates increased with temperature below 40 degrees C and decreased as temperature increased to 75 degrees C with apparent activation energies of 56 kJ/mol x K at < 40 degrees C, -26 kJ/mol x K at 40-100 degrees C, respectively. In the temperature region of 40-100 degrees C hydrocarbon deposition and decomposition process compete each other and decomposition becomes dominant, which results in apparent negative activation energy. Deposition rates remain relatively unaffected with further increases of temperature above 100 degrees C. FTIR analysis and deposition kinetic analysis showed that hydrocarbon deposition is the major factor determining chemical composition and deposition rate. The hydrocarbon deposition dominates especially at lower temperatures below 40 degrees C and Si-O fraction increases above 40 degrees C. We believe that dielectric constants of low-k films can be controlled by manipulating the fraction of deposited hydrocarbon through temperature control.