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The dielectric permittivity in polymers, fluoroelastomers and ethylene propylene diene monomers was measured as a function of both frequency and temperature. Several relaxation processes were revealed and analyzed through a developed algorithm to analyze the relaxation. The β and the α relaxations were observed and occurred in that order as the temperature was increased. Maxwell-Wagner-Sillars contributions, including conduction, were present at high temperatures and low frequencies. The molecular chains responsible for the relaxation processes were assigned by using molecular modeling with the dipole moment included. The activation energy, Vogel-Fulcher temperature and glass transition temperature were also obtained.

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.

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.

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.

The dielectric permittivity of synthetic rubber polymers, nitrile butadiene rubber (NBR) and ethylene propylene diene monomer (EPDM), with both frequency and temperature variations, was thoroughly investigated by dielectric relaxation spectroscopy (DRS). The spectrum versus frequency of DRS was analyzed with the semiempirical Havriliak–Negami formula and conductivity contribution by employing the newly developed “dispersion analyzer” analysis program. The main dielectric relaxations called the α- and β-processes, associated with the cooperative motion of chains in polymers, were discovered in the low-temperature region. In the high-temperature region, we found Maxwell–Wagner–Sillars (MWS) relaxation associated with polymer interfacing and normal-mode (α’) relaxation responsible for end-to-end dipole vector motion. The activation energies of schematic molecular chains responsible for the relaxation processes were obtained with the information about its motional mode. The glass transition temperature and dipole moment for the side group were also determined and compared with those from previous studies. In the EPDM specimen, the peaks of α- and β-relaxation merged at high temperature and were separated with decreasing temperature. The first observations of both merging and splitting were consistent with the results on the temperature dependency of the relaxation strength. Both contour mapping and three-dimensional plots for the two rubbers provide visual information for the distribution and mapping of relaxation.

The complex dielectric permittivity of fluoroelastomers in response to both frequency and temperature variations was thoroughly investigated by dielectric relaxation spectroscopy. To characterize the various types of relaxation processes, the dispersion spectra of permittivity in the frequency domain were successively deconvoluted using a newly developed simulation program that uses the empirical Havriliak-Negami model based on the Debye dielectric model and conductivity contribution. At 233 K ≤ T ≤ 290 K, the α and β relaxation processes were independently observed; they merged at T ≥ 290 K. At T > 303 K, and both Maxwell-Wagner-Sillars (MWS) relaxation, known as interfacial polarization, and conductivity relaxation processes were observed. From the α relaxation process, which is related to the glass transition phenomenon, the glass transition temperature Tg was determined using the Vogel-Fulther-Tamman-Hesse (VFTH) temperature dependence law; the result was similar to the estimate of Tg obtained using differential scanning calorimetry. The temperature dependence of conductivity complies well with VFTH behaviors, whereas the β and MWS processes can be described using the Arrhenius temperature dependence law. The corresponding activation energies of the rotational side groups and DC conductivity were obtained.

Three techniques for determining the hydrogen permeation properties of rubber samples were developed based on the volumetric and gravimetric measurements of released H2 gas after sample decompression. These methods include gas chromatography (GC) by thermal desorption analysis (TDA), volumetric collection (VC) measurement of hydrogen by graduated cylinder and gravimetric (GM) measurement by electronic balance. By measuring the released hydrogen against elapsed time after the decompression of pressure, the charging amount (C0) and diffusivity (D) were obtained with the developed diffusion analysis program. From these values, the solubility (S) and permeability (P) of polymers were evaluated through the relations of Henry's law and P = S D , respectively. The developed techniques were applied to three kinds of spherically shaped sealing rubber materials. D, S and P were analyzed as a function of pressure. The transport behaviors obtained in the three methods are discussed and compared with the characteristics of each measuring technique. The correlations between transport parameters and carbon black filler or density are discussed.