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The hydrogen infrastructure involves hydrogen production, storage and delivery for utilization with clean energy applications. Hydrogen ingress into structural materials can be detrimental due to corrosion and embrittlement. To enable safe operation in applications that need protection from hydrogen isotopes, this review article summarizes most recent advances in materials design and performance characterization of barrier coatings to prevent hydrogen isotopes’ absorption ingress and permeation. Barriers are crucial to prevent hydride formation and unwanted hydrogen effects to increase safety, materials’ lifetime and reduce cost for applications within nuclear and renewable energy. The coating may be applied on a material that requires protection from hydrogen pick-up, transport and hydride formation in hydrogen storage containers, in pipelines, spent nuclear fuel storage or in nuclear reactors. While existing, commercial coatings that have been much in use may be satisfactory for various applications, it is desirable to evaluate whether alternative coating concepts can provide a greater resistance to hydrogen isotope permeation along with other improved properties, such as mechanical strength and thermal resistance. The information presented here is focusing on recent findings within the past 5–7 years of promising hydrogen barriers including oxides, nitrides, carbon, carbide, MAX-phases and metals and their mechanical strength, hydrogen pick-up, radiation resistance and coating manufacturing techniques. A brief introduction to hydrogen permeation is provided. Knowledge gaps were identified to provide guidance for material’s research prospects.

Type IV hydrogen storage cylinders comprise a polymer liner and offer advantages such as lightweight construction, high hydrogen storage density, and good fatigue performance. However, they are also characterized by higher hydrogen permeability. Consequently, it is crucial for the polymer liner material to exhibit excellent resistance to hydrogen permeation. International organizations have established relevant standards mandating hydrogen permeation tests for the liner material of type IV on-board hydrogen storage cylinders. This paper provides a comprehensive review of existing research on hydrogen permeability and the hydrogen permeation test methods for the polymer liner material of type IV on-board hydrogen storage cylinders. By delving into the hydrogen permeation mechanism, a better understanding can be gained, offering valuable references for subsequent researchers in this field. This paper starts by thoroughly discussing the hydrogen permeation mechanism of the liner material. It then proceeds to compare and analyze the hydrogen permeation test methods specified by various standards. These comparisons encompass sample preparation, sample pretreatment, test device, test temperature and pressure, and qualification indicators. Then, this study offers recommendations aimed at enhancing the hydrogen permeation test method for the liner material. Additionally, the influence of test temperature, test pressure, and polymer material properties on the hydrogen permeability of the liner material is discussed. Finally, the influences of the test temperature, test pressure, and polymer material properties on the hydrogen permeability of the liner material are discussed. Future research direction on the hydrogen permeability and hydrogen permeation test method of the liner material of the type IV hydrogen storage cylinder has been prospected.

Despite being only one-atom thick, defect-free graphene is considered to be completely impermeable to all gases and liquids 1 – 10 . This conclusion is based on theory 3 – 8 and supported by experiments 1 , 9 , 10 that could not detect gas permeation through micrometre-size membranes within a detection limit of 10 5 to 10 6 atoms per second. Here, using small monocrystalline containers tightly sealed with graphene, we show that defect-free graphene is impermeable with an accuracy of eight to nine orders of magnitude higher than in the previous experiments. We are capable of discerning (but did not observe) permeation of just a few helium atoms per hour, and this detection limit is also valid for all other gases tested (neon, nitrogen, oxygen, argon, krypton and xenon), except for hydrogen. Hydrogen shows noticeable permeation, even though its molecule is larger than helium and should experience a higher energy barrier. This puzzling observation is attributed to a two-stage process that involves dissociation of molecular hydrogen at catalytically active graphene ripples, followed by adsorbed atoms flipping to the other side of the graphene sheet with a relatively low activation energy of about 1.0 electronvolt, a value close to that previously reported for proton transport 11 , 12 . Our work provides a key reference for the impermeability of two-dimensional materials and is important from a fundamental perspective and for their potential applications. Graphene is shown to be impermeable to helium and several other gases, except for hydrogen, which is attributed to the strong catalytic activity of ripples in the graphene sheet.

Gas transport through metal-organic framework membranes (MOFs) was switched in situ by applying an external electric field (E-field). The switching of gas permeation upon E-field polarization could be explained by the structural transformation of the zeolitic imidazolate framework ZIF-8 into polymorphs with more rigid lattices. Permeation measurements under a direct-current E-field poling of 500 volts per millimeter showed reversibly controlled switching of the ZIF-8 into polar polymorphs, which was confirmed by x-ray diffraction and ab initio calculations. The stiffening of the lattice causes a reduction in gas transport through the membrane and sharpens the molecular sieving capability. Dielectric spectroscopy, polarization, and deuterium nuclear magnetic resonance studies revealed low-frequency resonances of ZIF-8 that we attribute to lattice flexibility and linker movement. Upon E-field polarization, we observed a defibrillation of the different lattice motions.

Gas separation membranes is largely beholden to the notable breakthroughs in material science as the permselectivity of most of the membranes is still far below the Robeson upper bond. Therefore, in this work, zeolitic imidazolate framework −90 (ZIF-90) particles are introduced into cellulose triacetate polymer matrix (CTA) as filler to fabricate mixed matrix membranes (MMMs). The filler/polymer loading was varied from 0.5 and 1.5 wt.% and based on the SEM images obtained, the fabricated MMMs showed minimum sign of particles agglomeration in the polymer matrix. The overall CO 2 permeability of MMM was enhanced up to 1400.0% at 1.5 wt.% ZIF-90 loading compared to pure CTA membrane. Thus, ZIF-90 particles can be considered as a potential filler for the formation of MMM with improved enhanced gas permeation performance, which is potential for its application in gas separations.

The electrochemical permeation test is one of the most used methods for characterising hydrogen diffusion in metals. The flux of hydrogen atoms registered in the oxidation cell might be fitted to obtain apparent diffusivities. The magnitude of this coefficient has a decisive influence on the kinetics of fracture or fatigue phenomena assisted by hydrogen and depends largely on hydrogen retention in microstructural traps. In order to improve the numerical fitting of diffusion coefficients, a permeation test has been reproduced using FEM simulations considering two approaches: a continuum 1D model in which the trap density, binding energy and the input lattice concentrations are critical variables and a polycrystalline model where trapping at grain boundaries is simulated explicitly including a segregation factor and a diffusion coefficient different from that of the interior of the grain. Results show that the continuum model captures trapping delay, but it should be modified to model the trapping influence on the steady state flux. Permeation behaviour might be classified according to different regimes depending on deviation from Fickian diffusion. Polycrystalline synthetic permeation shows a strong influence of segregation on output flux magnitude. This approach is able to simulate also the short-circuit diffusion phenomenon. The comparison between different grain sizes and grain boundary thicknesses by means of the fitted apparent diffusivity shows the relationships between the registered flux and the characteristic parameters of traps.

Hydrogen barrier coatings are protective layers consisting of materials with a low intrinsic hydrogen diffusivity and solubility, showing the potential to delay, reduce or hinder hydrogen permeation. Hydrogen barrier coatings are expected to enable steels, which are susceptible to hydrogen embrittlement, specifically cost-effective low alloy-steels or light-weight high-strength steels, for applications in a hydrogen economy. Predominantly, ceramic coating materials have been investigated for this purpose, including oxides, nitrides and carbides. In this review, the state of the art with respect to hydrogen permeation is discussed for a variety of coatings. Al2O3, TiAlN and TiC appear to be the most promising candidates from a large pool of ceramic materials. Coating methods are compared with respect to their ability to produce layers with suitable quality and their potential for scaling up for industrial use. Different setups for the characterisation of hydrogen permeability are discussed, using both gaseous hydrogen and hydrogen originating from an electrochemical reaction. Finally, possible pathways for improvement and optimisation of hydrogen barrier coatings are outlined.

Gas permeation through nanoscale pores is ubiquitous in nature and has an important role in many technologies 1 , 2 . Because the pore size is typically smaller than the mean free path of gas molecules, the flow of the gas molecules is conventionally described by Knudsen theory, which assumes diffuse reflection (random-angle scattering) at confining walls 3 – 7 . This assumption holds surprisingly well in experiments, with only a few cases of partially specular (mirror-like) reflection known 5 , 8 – 11 . Here we report gas transport through ångström-scale channels with atomically flat walls 12 , 13 and show that surface scattering can be either diffuse or specular, depending on the fine details of the atomic landscape of the surface, and that quantum effects contribute to the specularity at room temperature. The channels, made from graphene or boron nitride, allow helium gas flow that is orders of magnitude faster than expected from theory. This is explained by specular surface scattering, which leads to ballistic transport and frictionless gas flow. Similar channels, but with molybdenum disulfide walls, exhibit much slower permeation that remains well described by Knudsen diffusion. We attribute the difference to the larger atomic corrugations at molybdenum disulfide surfaces, which are similar in height to the size of the atoms being transported and their de Broglie wavelength. The importance of this matter-wave contribution is corroborated by the observation of a reversed isotope effect, whereby the mass flow of hydrogen is notably higher than that of deuterium, in contrast to the relation expected for classical flows. Our results provide insights into the atomistic details of molecular permeation, which previously could be accessed only in simulations 10 , 14 , and demonstrate the possibility of studying gas transport under controlled confinement comparable in size to the quantum-mechanical size of atoms. Specular scattering of atoms of helium gas flowing through atomically flat, two-dimensional channels results in frictionless gas flow, which is much faster than expected assuming purely diffusive scattering.

Topical drug delivery is an attractive alternative to conventional methods because of advantages such as non-invasive delivery, by-pass of first pass metabolism, and improved patient compliance. However, several factors such as skin, physicochemical properties of the drug, and vehicle characteristics influence the permeation. Within a formulation, critical factors such as concentration of drug, physical state of drug in the formulation, and organoleptic properties affect the flux across the skin. The aim of the study was to develop and investigate topical semisolid preparations (creams and gels) with ibuprofen as the model drug and investigate the effect of various formulation parameters on the in-vitro performance across the Strat-M® membrane using flow-through cells. In addition, the physical stability of the developed formulations was investigated by studying viscosity, pH, and appearance. All the formulations developed in the study had appealing appearance with smooth texture and no signs of separation. Viscosity and pH of the formulations were acceptable. Cumulative amount of drug permeated at the end of 24 h was highest for clear gel (3% w/w ibuprofen; F6: 739.6 ± 36.1 µg/cm2) followed by cream with high concentration of ibuprofen in suspended form (5% w/w; F3: 320.8 ± 17.53 µg/cm2), emulgel (3% w/w ibuprofen; F5: 178.5 ± 34.5 µg/cm2), and cream with solubilized ibuprofen (3% w/w; F2A: 163.2 ± 9.36 µg/cm2). Results from this study showed that permeation of ibuprofen was significantly influenced by formulation parameters such as concentration of ibuprofen (3% vs. 5% w/w), physical state of ibuprofen (solubilized vs. suspended), formulation type (cream vs. gel), mucoadhesive agents, and viscosity (high vs. low). Thus, findings from this study indicate that pharmaceutical formulation scientists should explore these critical factors during the early development of any new topical drug product in order to meet pre-determined quality target product profile.

This study investigates water separation from NaCl-containing isopropanol (IPA) solutions using mordenite (MOR) zeolite membranes via pervaporation (PV). MOR membranes were synthesized through secondary growth and evaluated under various NaCl concentrations and solvent compositions. The PV tests demonstrated a significant trade-off between separation factor and permeation flux: as NaCl concentration increased from 10 wt% to 25 wt%, the water/IPA separation factor rose nearly 10-fold, while permeance dropped by four orders of magnitude. SEM images confirmed NaCl crystallization on the membrane surface at higher concentrations. Gas permeation tests revealed up to a 10-fold increase in N2 permeability and improved selectivity after PV testing, likely due to the removal of residual solvents and pore activation. Furthermore, solubility measurements using Mohr titration indicated that NaCl solubility decreased linearly in H2O/EtOH mixtures but showed non-linear, unstable behavior in H2O/IPA systems due to solvent heterogeneity and hydrogen-bond clustering. These findings suggest that IPA systems are more prone to salt concentration polarization, which complicates accurate concentration measurement. Overall, this work highlights the dual role of MOR membranes in enabling water-selective separation while inducing crystallization, with potential for integrated membrane-crystallization processes in saline wastewater treatment.