Publications

Wilson, Mark A.; Frischknecht, Amalie F.; Brownell, Matthew P.

Elastomeric rubbers serve a vital role as sealing materials in the hydrogen storage and transport infrastruc- ture. With applications including O-rings and hose-liners, these components are exposed to pressurized hydrogen at a range of temperatures, cycling rates, and pressure extremes. Cyclic (de)pressurization is known to degrade these materials through the process of cavitation. This readily visible failure mode occurs as a fracture or rupture of the material and is due to the oversaturated gas localizing to form gas bubbles. Computational modeling in the Hydrogen Materials Compatibility Program (H-Mat), co-led by Sandia National Laboratories and Pacific Northwest National Laboratory, employs multi-scale sim- ulation efforts to build a predictive understanding of hydrogen-induced damage in materials. Modeling efforts within the project aim to provide insight into how to formulate materials that are less sensitive to high-pressure hydrogen-induced failure. In this document, we summarize results from atomistic molec- ular dynamics simulations, which make predictive assessments of the effects of compositional variations in the commonly used elastomer, ethylene propylene diene monomer (EPDM).

Brownell, Matthew P.; Wilson, Mark A.; Frischknecht, Amalie F.

Two classes of hydrogen gas are observed in pressurized EPDM. The H₂ gas with slower diffusional dynamics localizes away from crosslinks.

Macromolecules

Brownell, Matthew P.; Frischknecht, Amalie F.; Wilson, Mark A.

Elastomeric rubber materials serve a vital role as sealing materials in the hydrogen storage and transport infrastructure. With applications including O-rings and hose liners, these components are exposed to pressurized hydrogen at a range of temperatures, cycling rates, and pressure extremes. High-pressure exposure and subsequent rapid decompression often lead to cavitation and stress-induced damage of the elastomer due to localization of the hydrogen gas. Here, we use all-atom classical molecular dynamics simulations to assess the impact of compositional variations on gas diffusion within the commonly used elastomer ethylene-propylene-diene monomer (EPDM). With the aim to build a predictive understanding of precursors to cavitation and to motivate material formulations that are less sensitive to hydrogen-induced failure, we perform systematic simulations of gas dynamics in EPDM as a function of temperature, gas concentration, and cross-link density. Our simulations reveal anomalous, subdiffusive hydrogen motion at pressure and intermediate times. We identify two groups of gas with different mobilities: one group exhibiting high mobility and one group exhibiting low mobility due to their motion being impeded by the polymer. With decreasing temperatures, the low-mobility group shows increased gas localization, the necessary precursor for cavitation damage in these materials. At lower temperatures, increasing cross-link density led to greater hydrogen gas mobility and a lower fraction of caged hydrogen, indicating that increasing cross-link density may reduce precursors to cavitation. Finally, we use a two-state kinetic model to determine the energetics associated with transitions between these two mobility states.

Wilson, Mark A.; Frischknecht, Amalie F.; Brownell, Matthew P.

Abstract not provided.