Investigation of Physical and Mechanical Characteristics of Rubber Materials Exposed to High-Pressure Hydrogen.

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.

Characterizing the Diffusion Property of Hydrogen Sorption and Desorption Processes in Several Spherical-Shaped Polymers.

We developed a method for characterizing permeation parameters in hydrogen sorption and desorption processes in polymers using the volumetric measurement technique. The technique was utilized for three polymers: nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM), and fluoroelastomer (FKM). The total uptake (C∞), total desorbed content (C0), diffusivity in sorption (Ds), and diffusivity in desorption (Dd) of hydrogen in the polymers were determined versus the sample diameter used in both processes. For all the polymers, the diameter dependence was not detected for C∞ and C0. The average C∞ and C0 at 5.75 MPa were 316 wt∙ppm and 291 wt∙ppm for NBR, 270 wt∙ppm and 279 wt∙ppm for EPDM, and 102 wt∙ppm and 93 wt∙ppm for FKM. The coincidence of C∞ and C0 in the sorption and desorption process indicated physisorption upon introducing hydrogen molecules into the polymers. The larger Dd in the desorption process than Ds could be attributed to an increased amorphous phase and volume swelling after decompression. The equilibrium time to reach the saturation of the hydrogen content in both processes was experimentally confirmed as proportional to the squared radius and consistent with the COMSOL simulation. This method could be used to predict the equilibrium time of the sorption time, depending on the radius of the polymers without any measurement.

Characterization technique of gases permeation properties in polymers: H2, He, N2 and Ar gas.

We demonstrate a simple experimental technology for characterizing the gas permeation properties of H2, He, N2 and Ar absorbed in polymers. This is based on the volumetric measurement of released gas and an upgraded diffusion analysis program after high-pressure exposure. Three channel measurements of sorption content of gases emitted from polymers after decompression are simultaneously conducted, and then, the gas uptake/diffusivity as a function of exposed pressure are determined in nitrile butadiene rubber (NBR), ethylene propylene diene monomer (EPDM) rubbers, low-density polyethylene (LDPE) and high-density polyethylene (HDPE), which are used for gas sealing materials under high pressure. The pressure-dependent gas transport behaviors of the four gases are presented and compared. Gas sorption follows Henry's law up to 9 MPa, while pressure-dependent diffusion behavior is not observed below 6 MPa. The magnitude of the diffusivity of the four gases decreases in the order DHe > DH2 > DAr > DN2 in all polymers, closely related to the kinetic diameter of the gas molecules. The dependence of gas species on solubility is in contrast to that on diffusivity. The linear correlation between logarithmic solubility and critical temperature of the gas molecule was newly observed.

Effect of Functional Fillers on Tribological Characteristics of Acrylonitrile Butadiene Rubber after High-Pressure Hydrogen Exposures.

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.

Filler Effects on H2 Diffusion Behavior in Nitrile Butadiene Rubber Blended with Carbon Black and Silica Fillers of Different Concentrations.

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.

Volume Dependence of Hydrogen Diffusion for Sorption and Desorption Processes in Cylindrical-Shaped Polymers.

In the actual application of gas transport properties under high pressure, the important factors are sample size dependence and permeation efficiency, related to gas sorption. With a modified volumetric analysis technique, we firstly measured the overall diffusion properties and equilibrium times for reaching the saturation of hydrogen content in both hydrogen sorption and desorption processes. The measured parameters of total uptake (C∞), total desorbed content (C0), diffusion coefficient in sorption (Ds), diffusion coefficient in desorption (Dd), sorption equilibrium time (ts) and desorption equilibrium time (td) of hydrogen in two polymers were determined relative to the diameter and thickness of the cylindrical-shaped polymers in the two processes. C∞ and C0 did not demonstrate an appreciable volume dependence for all polymers. The identical values of C∞ and C0 indicate the reversibility between sorption and desorption, which is interpreted by the occurrence of physisorption by sorbed hydrogen molecules. However, the measured diffusivity of the polymers was found to be increased with increasing thickness above 5 mm. Moreover, the larger Dd values measured in the desorption process compared to Ds may be attributed to an increased amorphous phase and volume swelling caused by increased hydrogen voids and polymer chain scission after decompression. The ts and td were found to be linearly proportional to the square of the thickness above an aspect ratio of 3.7, which was consistent with the numerical simulations based on the solution of Fick's law. This finding could be used to predict the ts in a polymer without any measurement, depending on the sample size.

Filler Influence on H2 Permeation Properties in Sulfur-CrossLinked Ethylene Propylene Diene Monomer Polymers Blended with Different Concentrations of Carbon Black and Silica Fillers.

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 Uptake and Diffusion Characteristics in Sulfur-Crosslinked Ethylene Propylene Diene Monomer Polymer Composites with Carbon Black and Silica Fillers after High-Pressure Hydrogen Exposure Reaching 90 MPa.

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.

Gas chromatography techniques to evaluate the hydrogen permeation characteristics in rubber: ethylene propylene diene monomer.

We established an ex-situ technique for evaluating hydrogen gas permeability by thermal desorption analysis (TDA) gas chromatography (GC) and by self-developed diffusion analysis software. Absorbed hydrogen mass in rubber, related to the GC-peak area, is recorded as a function of elapsed time after decompressing the hydrogen under high-pressure. From the charging amount (CH0) and diffusivity (D) obtained by the developed diffusion analysis program, the solubility(S) and permeability(P) is evaluated via Henry's law and P = SD, respectively. The techniques were applied to ethylene propylene diene monomer (EPDM) rubber, sealing material candidates in hydrogen infrastructures. EPDM sample mixed with carbon black fillers showed dual hydrogen diffusion behaviors, whereas EPDM sample without carbon black showed a single hydrogen diffusion behavior. There was no appreciable pressure or size dependence on D, S and P. P are consistent with that measured by different researcher within the expanded uncertainty.

Impedance spectroscopy for in situ and real-time observations of the effects of hydrogen on nitrile butadiene rubber polymer under high pressure.

Nondestructive impedance spectroscopy (IS) was developed and demonstrated to detect the effects of hydrogen on nitrile butadiene rubber exposed to hydrogen gas (H2) at high pressures up to 10 MPa. IS was applied to obtain an in situ and real-time quantification of H2 penetration into and its desorption out of rubber under high pressure. The diffusion coefficients of H2 were also obtained from the time evolution of the capacitance, which were compared with those obtained by thermal desorption gas analysis. The in situ measurements of the capacitance and the dissipation factor under various pressures during cyclic stepwise pressurization and decompression demonstrated the diffusion behaviour of H2, the phase of the rubber under high pressure, the transport properties of H2 gas, and the physicochemical interaction between H2 and the rubber. These phenomena were supported by a COMSOL simulation based on the electric current conservation equation and scanning electron microscopy (SEM) observations.

Hydrogen Sensing Using Paper Sensors with Pencil Marks Decorated with Palladium.

Paper-based sensors fabricated using the pencil-on-paper method are expected to find wide usage in many fields owing to their low cost and high reproducibility. Here, hydrogen (H2) detection was realized by applying palladium (Pd) nanoparticles (NPs) to electronic circuits printed on paper using a metal mask and a pencil. We confirmed that multilayered graphene was produced by the pencil, and then characterized Pd NPs were added to the pencil marks. To evaluate the gas-sensing ability of the sensor, its sensitivities and reaction rates in the presence and absence of H2 were measured. In addition, sensing tests performed over a wide range of H2 concentrations confirmed that the sensor had a detection limit as low as 1 ppm. Furthermore, the sensor reacted within approximately 50 s at all H2 concentrations tested. The recovery time of the sensor was 32 s at 1 ppm and 78 s at 1000 ppm. Sensing tests were also performed using Pd NPs of different sizes to elucidate the relationship between the sensing rate and catalyst size. The experimental results confirmed the possibility of fabricating paper-based gas sensors with a superior sensing capability and response rate.