Subdiffusive High-Pressure Hydrogen Gas Dynamics in Elastomers

Brownell, Matthew; Frischknecht, Amalie L.; Wilson, Mark A.

doi:10.1021/acs.macromol.2c00204

Subdiffusive High-Pressure Hydrogen Gas Dynamics in Elastomers

Journal Article · Tue May 10 00:00:00 EDT 2022 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.2c00204· OSTI ID:1877123

Brownell, Matthew ^[1]; ^[1]; ^[1]

Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

We report 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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC05-76RL01830; NA0003525

OSTI ID:: 1877123

Report Number(s):: SAND2022-8320J; 707446

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 10 Vol. 55; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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