Filler effects on H₂ diffusion in nitrile butadiene rubbers (NBRs) blended with carbon black and silica fillers of different concentrations are first investigated by employing a volumetric analysis. Total uptake, solubility, and diffusivity of hydrogen for ten filled-NBR, including neat NBR, are determined in an exposed pressure range of 1.3 MPa~92.6 MPa. Filler dependence on hydrogen uptake and diffusion is distinctly observed in the NBRs blended with high abrasion furnace (HAF) carbon black (CB) fillers compared to NBRs blended with medium thermal furnace (MT) CB and silica filler, which is related to the specific surface area of carbon black and interface structure. The HAF CB filled-NBR follows dual sorption behavior combined with Henry’s law and the Langmuir model, responsible for two contributions of solubility from polymer and filler. However, a single gas sorption behavior coming from the polymer is observed satisfying Henry’s law up to 92.6 MPa for NBR blended with MT CB filled-NBR and silica filled-NBR. Diffusion demonstrates Knudsen and bulk diffusion behavior below and above, respectively, at certain pressures. With increasing pressure, the filler effect on diffusion is reduced, and diffusivity converges to a value. The correlation observed between diffusivity and filler content (or crosslink density) is discussed.

Filler effects on H₂ permeation properties in sulfur-crosslinked ethylene propylene diene monomer (EPDM) polymers blended with two kinds of carbon black (CB) and silica fillers at different contents of 20 phr–60 phr are investigated by employing volumetric analysis in the pressure exposure range of 1.2 MPa~9.0 MPa. A linear relationship is observed between the sorbed amount and pressure for H₂ gas, which is indicative of Henry’s law behavior. The hydrogen solubility of EPDM composites increases linearly with increasing filler content. The magnitude of hydrogen solubility for the filled EPDM composites is dependent on the filler type. The hydrogen solubility is divided into two contributions: hydrogen absorption in the EPDM polymer and hydrogen adsorption at the filler surface. Neat EPDM reveals pressure-dependent bulk diffusion behavior. However, with increasing filler content, the diffusivity for the filled EPDM composites is found to be independent of pressure. The magnitude of filler effects on the hydrogen permeation parameter is measured in the order of high abrasion furnace CB~semireinforcing furnace CB ˃ silica, whose effect is related to the specific surface area of CB particles and interfacial structure. The correlation between the permeation parameters and filler content (or crosslink density) is discussed.

Rubber materials play a key role in preventing hydrogen gas leakage in high-pressure hydrogen facilities. Therefore, it is necessary to investigate rubber materials exposed to high-pressure hydrogen to ensure operational safety. In this study, permeation, volume swelling, hydrogen content, and mechanical characteristics of acrylonitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluorocarbon (FKM) samples exposed to pressures of 35 and 70 MPa were investigated. The results showed that the volume recovery and hydrogen desorption behavior of EPDM with the highest permeation were fast whereas those of FKM with the lowest permeation were slow. The volume of NBR with the highest hydrogen content expanded after decompression. In contrast, FKM swelled the most despite having the lowest hydrogen content. After exposure to high-pressure hydrogen, the compression set (CS) slightly increased due to internal cracks, but the tensile strength decreased significantly with increasing pressure despite the absence of cracks in the fracture area of all tensile specimens. It was concluded that the decrease in tensile strength is closely related to the volume increase because of the relationship between the relative true strength and the volume ratio.

H₂ permeation in peroxide-crosslinked EPDM blended with carbon black (CB) and silica fillers was studied at pressures ranging from 1.2 MPa to 90 MPa via the volumetric analysis technique. H₂ uptake in the CB-filled EPDM revealed dual-sorption behaviors via Henry’s law and the Langmuir model, which were attributed to H₂ absorption by the polymer chains and H₂ adsorption at the filler interfaces, respectively. Additionally, single-sorption mechanisms were observed for neat EPDM and silica-blended EPDM according to Henry’s law, indicating H₂ absorption by the polymer chain. The linear decreases in the diffusivity with filler content for the silica-blended EPDMs were attributed to increases in the diffusion paths caused by the filler. Exponential decreases in the diffusivity with increasing filler content and in the permeation with the physical/mechanical properties for CB-filled EPDMs were caused by decreases in the fractional free volume due to increased densities for the EPDM composites. Moreover, good filler-dependent correlations between permeability and density, hardness, and tensile strength were demonstrated for EPDMs used as sealing materials for O-rings. From the resulting equation, we predicted the permeation value without further measurements. Thus, we can select EPDM candidates satisfying the permeation guidelines used in hydrogen infrastructure for the future hydrogen economy.

With the increasing interest in hydrogen energy, the stability of hydrogen storage facilities and components is emphasized. In this study, we analyzed the effect of high-pressure hydrogen gas treatment in silica-filled EPDM composites with different silica contents. In detail, cure characteristics, crosslink density, mechanical properties, and hydrogen permeation properties were investigated. Results showed that material volume, remaining hydrogen content, and mechanical properties were changed after 96.3 MPa hydrogen gas exposure. With an increase in the silica content, the crosslink density and mechanical properties increased, but hydrogen permeability was decreased. After treatment, high-silica-content composites showed lower volume change than low-silica-content composites. The crack damage due to the decompression caused a decrease in mechanical properties, but high silica content can inhibit the reduction in mechanical properties. In particular, EPDM/silica composites with a silica content of above 60 phr exhibited excellent resistance to hydrogen gas, as no change in their physical and mechanical properties was observed.

Polyethylene (PE) is widely used as a gas-sealing material in packing films and gas transport pipes. A technique for evaluating the permeability of water-insoluble gases has recently been developed. This technique is a volumetric analysis that is used to calculate the gas permeability by measuring the gas uptake and diffusivity. With this technique, we investigated the permeability of pure gases, such as H₂, He, N₂, O₂ and Ar, enriched under high pressure up to 9 MPa in low-density polyethylene (LDPE), ultrahigh molecular weight polyethylene (UHMWPE) and high-density polyethylene (HDPE). The gas uptake showed a linear pressure-dependent behavior that followed Henry’s law, and the diffusivity was independent of the pressure. Furthermore, the logarithmic diffusivity values of the five gases linearly decreased as their molecular kinetic diameters increased. The logarithmic solubility values linearly increased as the critical temperatures of the gases increased. The calculated permeability results were correlated with the volume fraction of the amorphous phase and the fractional free volume. This result newly showed that the amorphous phase was directly correlated to the fractional free volume.