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.
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.
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.
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.
In a high-pressure hydrogen environment, the sealing rubber material is swelled by hydrogen, and the mechanical and tribological properties are reduced, causing various problems in the sealing performance. The focus of this study was the effect of the filler type and content on the tribological characteristics of rubber after exposure to high-pressure hydrogen. Acrylonitrile butadiene rubber specimens were exposed to high-pressure hydrogen at 96.6 MPa, and the change in the amount of wear with time after exposure was observed. The wear test was performed using a pin-on-disc ball tip to measure the amount of wear before and after hydrogen exposure of the materials under fixed revolutions per minute and normal load. Scanning electron microscopy was used to observe the wear track and cross section of the specimen to examine the changes in the wear mechanism after hydrogen exposure and to analyze the wear mechanism for each filler. The results of this study are expected to contribute to the evaluation of the tribological properties of the sealing materials used in hydrogen environments.