Hydrogen isotope permeability of membranes with inhomogeneous properties along the thickness of material

The problem of hydrogen permeation through membranes with inhomogeneous properties along the thickness has been considered as the limiting case of permeation through a multilayered membrane when the layer thicknesses tend to zero. The steady-state permeability equation for multilayer membranes and membranes with inhomogeneous properties along the thickness has been derived. The diffusion equation for the case of inhomogeneous solubility in a membrane has been obtained.     

SHI induced nano track polymer filters and characterization

Swift heavy ion irradiation produces damage in polymers in the form of latent tracks. Latent tracks can be enlarged by etching it in a suitable etchant and thus nuclear track etch membrane can be formed for gas permeation / purification in particular for hydrogen where the molecular size is very small. By applying suitable and controlled etching conditions well defined tracks can be formed for specific applications of the membranes. After etching gas permeation method is used for characterizing the tracks. In the present work polycarbonate (PC) of various thickness were irradiated with energetic ion beam at Inter University Accelerator Centre (IUAC), New Delhi. Nuclear tracks were modified by etching the PC in 6N NaOH at 60 (±1) °C from both sides for different times to produce track etch membranes. At critical etch time the etched pits from both the sides meet a rapid increase in gas permeation was observed. Permeability of hydrogen and carbon dioxide has been measured in samples etched for different times. The latent tracks produced by SHI irradiation in the track etch membranes show enhancement of free volume of the polymer. Nano filters are separation devices for the mixture of gases, different ions in the solution and isotopes and isobars separations. The polymer thin films with controlled porosity finding it self as best choice. However, the permeability and selectivity of these polymer based membrane filters are very important at the nano scale separation. The Swift Heavy Ion (SHI) induced nuclear track etched polymeric films with controlled etching have been attempted and characterized as nano scale filters.      

Hydrogen permeation of Pd-coated V90Al10 alloy membranes at different pressures in the presence and absence of carbon dioxide

The hydrogen permeation characteristics of alloy membranes based on Pd-coated V₉₀Al₁₀ alloy membrane have been investigated in the pressure range 1-3 atm under pure hydrogen and hydrogen-carbon dioxide gas mixture at 450 °C. Hydrogen permeation experiments have been confirmed that hydrogen flux was 21.1 ml/min/cm² for a Pd-coated V₉₀Al₁₀ alloy membrane (thickness: 0.5 mm) using pure hydrogen as the feed gas. It has been found that Pd-coated V₉₀Al₁₀ alloy membranes exhibit good resistance to hydrogen embrittlement in pure hydrogen atmosphere. After different hydrogen permeation flux tests under different pressure condition in presence of hydrogen-carbon dioxide gas mixture, the characteristics of the Pd-coated V₉₀Al₁₀ alloy membranes were examined by ex-situ analysis techniques. The loss of cell performance observed in the presence of hydrogen-carbon dioxide gas mixture is mainly attributed to both physical and chemical degradations of membrane, which led to structural changes in the Pd-coated V₉₀Al₁₀ alloy membrane.     

Characterization of nuclear tracks by positron annihilation and gas permeation

The application of polymeric membrane in combination with metallic films can be used for gas purification in particular for hydrogen where the molecular size is very small. The affinity of hydrogen to certain metals assists the flow of hydrogen, although it restricts the permeation of other gases. However, the flow rate is very small in dense membranes. Attempts have been made to generate nuclear tracks in polymeric membranes to control the gas flow. These tracks can be characterized by positron lifetime spectroscopy and gas permeation measurements. The long lifetime of ortho-positronium gives the estimate of size of the track-free volume of the order of 0.25 nm. The nuclear tracks can be modified by a chemical etching process. The chemical etching normally takes place from both sides of the membrane. When the etched pits from both sides meet, a rapid increase in gas permeation is observed. The size of the nano opening of the track has been observed for two different gases hydrogen and carbon dioxide, which have a molecular size of 0.2 and 0.4 nm, respectively.     

玻璃微球壁厚和预充气工艺对气体渗透性能的影响

 以空心玻璃微球为研究对象，利用高压充气系统充气，测量了不同条件下玻璃微球对氘气在室温条件下的气体渗透系数。研究结果表明：微球的壁厚对气体渗透系数影响较大，2 mm以上厚壁球的气体渗透系数约5.0×10^-22 mol·m^-1·s^-1·Pa^-1，而壁厚小于1 mm时，渗透系数约1.56×10^-20 mol·m^-1·s^-1·Pa^-1，两者相差30倍。预充气挑选工艺对微球的气体渗透系数也产生一定影响，对于薄壁空心玻璃微球一次充放气气体渗透系数增加约50％，两次充放气则增大一倍左右。对上述影响因素进行了初步的探讨，气体渗透系数改变的主要原因是玻璃微球表面的结构裂纹、空位和缺陷。     

Transport properties of SrCe0.95Y0.05O3−δ and its application for hydrogen separation

Transport properties of SrCe_0.95Y_0.05O_3−δ were studied by impedance spectroscopy and by measuring open-cell voltage (OCV) and gas permeation. Ionic transference numbers were determined by measuring the OCV of concentration cells and water vapor evolution of an O₂/H₂ fuel cell. We observed interfacial polarization on the basis of the I–V curves obtained by discharging a hydrogen concentration cell or an O₂/H₂ fuel cell. The observed high protonic conductivity (high proton and low oxide ion transference numbers) makes SrCe_0.95Y_0.05O_3−δ a potential material for hydrogen separation. From proton conductivity measurements, under a given hydrogen partial pressure difference of 4%/0.488%, the hydrogen permeation rate (of a dense membrane with 0.11 cm in thickness) was calculated to be ≈0.072 cm³ (STP) cm⁻² min⁻¹ at 800°C, whereas the permeation rate calculated from short-circuit current measurements was ≈0.023 cm³ (STP) cm⁻² min⁻¹ at 800°C. The difference between calculated and observed permeation rates is probably due to interfacial polarization.     

Permeability,Solubility, and Diffusivity of Methane and Butane in Diphenylsiloxane-Dimethylsiloxane Copolymer Membranes

Permeation and sorption of methane and n-butane gases in polydimethylsiloxane (PDMS) and diphenylsiloxane-dimethylsiloxane (DPh-DM) block copolymer membranes were studied at room temperature and different upstream pressures. The membranes were prepared via room temperature vulcanization of vinyl terminated siloxanes through platinum catalyzed hydrosilylation reactions by mixing stoichiometric amounts of polymer, crosslinker, and catalyst, and casting of the mixture solutions with hexane. Composite membranes of polysiloxanes on a polyacrylonitrile microporous support were synthesized for permeation experiments and single layer dense films were used in sorption experiments. The effect of upstream pressure on permeability, solubility, and diffusivity of these membranes was evaluated. It was found that selectivity of the DPh-DM copolymer membrane for n-C₄H₁₀ relative to CH₄ was up to 19% higher than that in PDMS membrane. Both solubility and diffusivity selectivities had positive contributions in permselectivity improvement. The improvement in selectivity was attained with less than a 6% decrease in permeability of n-C₄H_10. Up to 11% improvement in selectivity was also obtained in mixed gas experiment.     

Surface characterization of Pd/Ag23 wt% membranes after different thermal treatments

Hydrogen permeation measurements of 1.5-10 μm thick Pd/Ag23 wt% membranes before and after thermal treatments at 300 °C in air (both sides) or in the temperature range 300-450 °C in N₂ (feed side) and Ar (permeate side) were performed. Accompanying changes in surface topography and chemical composition were subsequently investigated by atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) depth profiling. For a 2 μm thick membrane, the surface roughness increased for all annealing temperatures applied, while a temperature of 450 °C was required for an increase in roughness of both membrane surfaces to occur for the 5 μm membrane. The thickest membrane, of 10 μm, showed changed surface roughness on one side of the membrane only and a slight decrease in hydrogen permeance after all heat treatments in N₂/Ar. X-ray photoelectron spectroscopy investigations performed after treatment and subsequent permeation measurements revealed segregation of silver to the membrane surfaces for all annealing temperatures applied. In comparison, heat treatment at 300 °C in air resulted in significantly increased hydrogen permeance accompanied by increasing surface roughness. Upon exposure to oxygen, Pd segregates to the surface to form a 2-3 nm thick oxide layer (PdO), with more complex segregation behavior after subsequent reduction and permeance measurements in pure hydrogen. The available permeance data for the Pd/Ag23 wt% membranes after heat treatment in air at 300 °C is found to depend linearly on the inverse membrane thickness, implying bulk limited hydrogen permeation for thicknesses down to 1.5-2.0 μm.     

Mg–Al LDH reinforced PMMA nanocomposites: a potential material for packaging industry

Poly-methylmethacrylate/Mg–Al layered double hydroxide (PMMA/LDH) based nanocomposites have successfully been synthesised with varying LDH content by in situ polymerisation technique and systematically studied by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT IR), UV-Visible spectroscopy and microscopic (FE SEM and HR TEM) analysis. In particular, thermogravimetric analysis (TGA) and gas barrier properties measurement were carried out to assess the suitable application of these materials. The thermal property of PMMA/LDH composites was compared with neat PMMA and an enhancement in thermal stability was noticed with gradual increase in LDH content in the composite. Gas permeability measurement data showed significant decrease in oxygen permeability value of the PMMA/LDH nanocomposites in comparison to the pristine PMMA. Enhancement in thermal stability along with significant reduction in oxygen permeability of PMMA upon composite formation indicate the possible application of these materials in packaging industries.     

Bifunctional Au-nanorod@Fe3O4 nanocomposites: synthesis, characterization, and their use as bioprobes

Membrane gas separation technology has been rapidly growing for industrial applications such as air separation, carbon dioxide (CO₂) separation from natural gas production, hydrogen separation, etc. Needs for CO₂ separation are increasing as carbon capture technology has been recognized as an essential part when combating the global warming issue. Membrane gas separation technology deals with mass transport phenomena through the membrane engineered on a sub-nanoscale controlling transport properties of small gas molecules such as CO₂, N₂, O₂, H₂, etc. In this review, we will report on the recent developments in capture technologies utilizing various membranes including nano-engineered thermally rearranged (TR) polymers. TR polymer membranes show high gas permeability as well as good separation properties, especially in CO₂ separation processes such as from post-combustion flue gas and natural gas sweetening.     

Hydrogen permeability through sandwich membranes

The problem of hydrogen permeability through sandwich membranes and membranes with nonhomogeneous (by depth) properties as the limiting case of permeability through a sandwich membrane when the thickness of the layers tends to zero is considered. The equation of permeability through sandwich membranes and nonhomogeneous membranes in the steady-state regime is obtained. Analytical dependencies of the permeability reduction factor in four limiting cases are found.     

Windowless argon excimer source for surface modification

The article describes applications of a novel windowless argon excimer source for surface modification. Experimental results on etching of polymeric surfaces, degradation of organic surface residues, surface activation and modification of gas permeability and selectivity of polymeric membranes are presented. Moreover, radical formation from the excimer source and surface curing of liquid acrylates are examined. Typical treatment times are in the range of minutes for photolytic decomposition effects and seconds for UV curing effects. The surface modification effects induced by the argon excimer source were analysed by XPS, ESR, IR-spectroscopy, white light reflection spectroscopy, scanning electron microscopy, micro-hardness and permeation measurements.     

Significant modifications in the electrical properties of poly(methyl methacrylate) thin films upon dispersion of silver nanoparticles

Electrical conductivity of thin solid films of PMMA with dispersed silver nanoparticles, synthesized by a novel method, was studied in dark conditions by changing the applied voltage and temperature and also under photoexcitation (by a mercury lamp, 125 W) at room temperature. Anomalous hysteresis in current-temperature characteristics during heating and cooling cycles was observed. The hysteresis-like behaviour was explained on the basis of the movements of molecules associated with different parts of a PMMA matrix and diffusion of silver nanoparticles in the PMMA matrix. Dark current in the PMMA films with dispersed silver nanoparticles has been observed to be higher than the corresponding current in the PMMA films without silver nanoparticles due to the creation of conduction paths by the silver nanoparticles/nanoclusters. The photoresponse in the thin solid films of PMMA with dispersed silver nanoparticles was the reverse of that observed in thin solid films of PMMA without silver nanoparticles. A decrease in photocurrent under illumination of light was observed due to the destruction of conduction paths by the illumination of light.     

热处理条件对PVA薄膜阻氢性能的影响

 采用XRD测定了PVA薄膜在不同热处理条件下的结晶度，并用自行设计的渗氢系数测量系统研究了在不同热处理条件下的PVA薄膜阻氢性能的变化规律。结果表明，PVA薄膜的热处理温度越高，其结晶度越高，越有利于提高PVA薄膜的阻氢性能，但热处理温度宜选择在180℃以下，以防止PVA薄膜热降解，另一方面，在PVA的玻璃化转变温度以下进行热处理同样能够提高PVA薄膜的阻氢性能，而醇解度较低的PVA薄膜在玻璃化转变温度以下经热处理后的阻氢性能提高的幅度较大。     

Effect of nitrogen addition on hydrogen incorporation in diamond nanorod thin films

The effect of nitrogen addition in the feed gas on the finally incorporated amount of hydrogen in the diamond nanorods (DNRs) thin films has been investigated. The Raman spectroscopy measurements helped to understand the structural and quality changes with increasing nitrogen gas flow rate during CVD deposition. The hydrogen concentration was measured with 3.0 MeV He²⁺ beam using elastic recoil detection analysis technique and it was found that with the addition of nitrogen, the hydrogen concentration was increased. The results of non-Rutherford backscattering spectroscopy (NRBS) used to measure the amount of nitrogen in the DNRs thin films have shown that the incorporated nitrogen is below the detection limit of NRBS technique. Our results suggested that the addition of nitrogen has affected the overall quality of diamond films in two ways; increasing the thickness of diamond films by increasing the non-diamond carbon content and increasing the hydrogen impurity incorporation. The role of nitrogen additive on diamond growth and hydrogen incorporation is discussed.     

Molecular simulations of phenol and ibuprofen removal from water using multilayered graphene oxide membranes

We present here non-equilibrium molecular dynamic simulations concerning the separation of phenol and ibuprofen as impurities compounds (ICs) in water by novel graphene oxide (GO) membranes. The coupling between water permeability and impurity rejection is studied as a function of membrane thickness and concentration, focusing on the underlying molecular phenomena. Results show that water permeability decreases as the number of layers increases. Moreover, molecular sieving can be achieved by tuning the number of GO layers and the surface chemistry of the sheet: water flow through layers is up to 20% faster than that in graphene layers, because of strong hydrogen bonded interactions with the oxygenated groups. Analysis of the simulation results suggests that upon adsorbing on the GO surface, the translational motion of ICs in water would be supressed. Nevertheless, hydrophilicity affects the permeability for membranes with high O/C ratio, owing to these strong hydrogen bonds. Furthermore, 100% rejection for the ICs can be obtained for most of the GO membranes with four layers. This study elucidates the important role of hydrophilic interactions in GO membranes to become ideal candidates for removal of organic pollutants from water, showing the applicability of molecular simulations to obtain molecular insights into this problem.     

Synthesis and characterization of polyester bionanocomposite membrane with ultrasonic irradiation process for gas permeation and antibacterial activity

Optically active bionanocomposite membranes composed of polyester (PE) and cellulose/silica bionanocomposite (BNCs) prepared with simple, green and inexpensive ultrasonic irradiation process. It is a novel method to enhance the gas separation performance. The novel optically active diol containing functional trifluoromethyl groups was prepared in four steps reaction and it was fully characterized by different techniques. Commercially available silica nanoparticles were modified with biodegradable nanocellulose through ultrasonic irradiation technique. Transmission electron microscopy (TEM) analyses showed that the cellulose/silica composites were well dispersed in the polymer matrix on a nanometer scale. The mechanical properties nanocomposite films were improved by the addition of cellulose/silica. Thermo gravimetric analysis (TGA) data indicated an increase thermal stability of the PE/BNCs in compared to the pure polymer. The results obtained from gas permeation experiments showed that adding cellulose/silica to the PE membrane structure increased the permeability of the membranes. The increase in the permeability of the gases was as follows: P_CH4 (38%) <P_N2 (58%) <P_CO2 (88%) <P_O2 (98%) Adding silica nanoparticles into the PE matrix, improved the separation performance of carbon dioxide/methane and carbon dioxide/nitrogen gases. Increasing the cellulose/silica mass fraction in the membrane increased the diffusion coefficients of gases considered in the current study. Further, antimicrobial test against pathogenic bacteria was carried out.     

Modifying the surface of a hydrogen permselective palladium–silver membrane

Thin films of Pd–23% Ag composition are obtained by means of magnetron sputter deposition. The surfaces of the films are modified via the electrolythic deposition of finely divided palladium. The hydrogen permeabilities of samples of membranes (both smooth and modified with palladium black) are compared. A marked increase in the hydrogen permeability of the modified membrane is observed, compared to the smooth membrane. The dependence of the rate of hydrogen fluence on the excess pressure is approximated by a curve of the first order, demonstrating the limitations of the process of hydrogen permeation by hydrogen superficial dissociation.     

氢在HR－1不锈钢中迁移特性的热动力方法研究

本文研究了氢在ＨＲ－１不锈钢中热动力驱动的宏观迁移特性。用不同的方法（电化学方法和１０５ｐａ氢压强下高温气相法）使试样充氢，然后研究加热升温放气规律，得到了在有意义的温度范围内出气峰的位置以及氢在ＨＲ－１材料中扩散、溶解、渗透系数与温度的关系，并与渗透法测得的结果和国外类似实验结果符合得较好。这些数据对估计未来聚变堆中氚的投料量和氚的渗透漏失有实际意义。     

Sorption and permeation of gaseous molecules in amorphous and crystalline PPX C membranes: molecular dynamics and grand canonical Monte Carlo simulation studies

Amorphous and crystalline poly (chloro-p-xylylene) (PPX C) membranes are constructed by using a novel computational technique, that is, a combined method of NVT+NPT-molecular dynamics (MD) and gradually reducing the size (GRS) methods. The related free volumes are defined as homology clusters. Then the sorption and the permeation of gases in PPX C polymers are studied using grand canonical Monte Carlo (GCMC) and NVT-MD methods. The results show that the crystalline PPX C membranes provide smaller free volumes for absorbing or transferring gases relative to the amorphous PPX C area. The gas sorption in PPX C membranes mainly belongs to the physical one, and H bonds can appear obviously in the amorphous area. By cluster analyzing on the mean square displacement of gases, we find that gases walk along the x axis in the crystalline area and walk randomly in the amorphous area. The calculated permeability coefficients are close to the experimental data.