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.

This study investigated the synergistic effect of carbon black/multi-wall carbon nanotube (CB/MWCNT) hybrid fillers on the physical and mechanical properties of Ethylene propylene diene rubber (EPDM) composites after exposure to high-pressure hydrogen gas. The EPDM/CB/CNT hybrid composites were prepared by using the EPDM/MWCNT master batch (MB) with 10 phr CNTs to enhance the dispersion of CNTs in hybrid composites. The investigation included a detailed analysis of cure characteristics, crosslink density, Payne effect, mechanical properties, and hydrogen permeation properties. After exposure to 96.3 MPa hydrogen gas, the hydrogen uptake and the change in volume and mechanical properties of the composites were assessed. We found that as the MWCNT volume fraction in fillers increased, the crosslink density, filler–filler interaction, and modulus of hybrid composites increased. The hydrogen uptake and the solubility of the composites decreased with an increasing MWCNT volume fraction in fillers. Moreover, after exposure to hydrogen gas, the change in volume and mechanical properties exhibited a diminishing trend with a higher MWCNT volume fraction. We conclude that the hybridization of CB and CNTs formed strong filler–filler networks in hybrid composites, consequently reinforcing the EPDM composites and enhancing the barrier properties of hydrogen gas.

We investigated the influence of two fillers—CB (carbon black) and silica—on the H₂ permeation of EPDM polymers crosslinked with sulfur in the pressure ranges 1.2–90 MPa. H₂ uptake in the CB-blended EPDM revealed dual sorption (Henry’s law and Langmuir model) when exposed to pressure. This phenomenon indicates that H₂ uptake is determined by the polymer chain and filler-surface absorption characteristics. Moreover, single sorption characteristics for neat and silica-blended EPDM specimens obey Henry’s law, indicating that H₂ uptake is dominated by polymer chain absorption. The pressure-dependent diffusivity for the CB-filled EPDM is explained by Knudsen and bulk diffusion, divided at the critical pressure region. The neat and silica-blended EPDM specimens revealed that bulk diffusion behaviors decrease with decreasing pressure. The H₂ diffusivities in CB-filled EPDM composites decrease because the impermeable filler increases the tortuosity in the polymer and causes filler–polymer interactions; the linear decrease in diffusivity in silica-blended EPDM was attributed to an increase in the tortuosity. Good correlations of permeability with density and tensile strength were observed. From the investigated relationships, it is possible to select EPDM candidates with the lowest H₂-permeation properties as seal materials to prevent gas leakage under high pressure in H₂-refueling stations.

Time-dependent emitted H₂ content modeling via a reliable diffusion analysis program was performed for H₂-enriched polymers under high pressure. Here, the emitted hydrogen concentration versus elapsed time was obtained at different diffusivities and volume dimensions for cylinder-, sphere- and sheet-shaped specimens. The desorption equilibrium time, defined as the time when the H₂ emission content is nearly saturated, was an essential factor for determining the periodic cyclic testing and high-pressure H₂ exposure effect. The equilibrium time in the desorption process was modeled. The equilibrium time revealed an exponential growth behavior with respect to the squared thickness and the squared diameter of the cylinder--shaped specimen, while it was proportional to the squared diameter for the sphere-shaped specimen and to the squared thickness for the sheet-shaped specimen. Linear relationships between the reciprocal equilibrium time and diffusivity were found for all shaped polymers. The modeling results were confirmed by analysis of the solutions using Fick’s second diffusion law and were consistent with the experimental investigations. Numerical modeling provides a useful tool for predicting the time-dependent emitted H₂ behavior and desorption equilibrium time. With a known diffusivity, a complicated time-dependent emitted H₂ behavior with a multi-exponential form of an infinite series could also be predicted for the three shaped samples using a diffusion analysis program.