This study integrates experimental investigation with molecular dynamics simulations to elucidate the hydrogen transport mechanisms in polyetheretherketone(PEEK)and polytetrafluoroethylene(PTFE),offering fundamental i...This study integrates experimental investigation with molecular dynamics simulations to elucidate the hydrogen transport mechanisms in polyetheretherketone(PEEK)and polytetrafluoroethylene(PTFE),offering fundamental insights into the barrier properties of high-performance polymeric materials.Experimental results demonstrate that PEEK exhibits superior hydrogen barrier performance compared to PTFE at both ambient and elevated temperatures.However,detailed molecular dynamics simulations uncover a distinctive,enthalpy-driven"high solubility-low diffusivity"transport mechanism:although PEEK displays higher hydrogen solubility due to its stronger thermodynamic affinity,its diffusion coefficient is markedly lower than that of PTFE.This mechanism remains operative across a broad operational temperature range(233 K to358 K),yet its influence on overall permeability is strongly temperature-dependent.At room and high temperatures,the exceptionally low diffusivity of PEEK governs the entire permeation process,establishing its effectiveness as a high-performance hydrogen barrier material.In contrast,under low-temperature conditions(e.g.,233 K),the general suppression of diffusion allows the high solubility of PEEK to dominate,resulting in greater overall permeability than PTFE and giving rise to a performance“reversal”phenomenon.This distinct transport behavior originates from the strong non-covalent interactions between hydrogen molecules and the aromatic rings as well as polar functional groups present in the amorphous regions of PEEK,which simultaneously enhance solubility and impose significant kinetic energy barriers.The"structure-mechanism"correlation framework established in this work provides a robust theoretical foundation for the rational design of next-generation hydrogen barrier materials tailored to specific operational temperature requirements.展开更多
基金financially supported by the National Natural Science Foundation of China(No.5247401)the Research and Technology Development Project of the China National Petroleum Corporation(No.2021DJ5002(JT))。
文摘This study integrates experimental investigation with molecular dynamics simulations to elucidate the hydrogen transport mechanisms in polyetheretherketone(PEEK)and polytetrafluoroethylene(PTFE),offering fundamental insights into the barrier properties of high-performance polymeric materials.Experimental results demonstrate that PEEK exhibits superior hydrogen barrier performance compared to PTFE at both ambient and elevated temperatures.However,detailed molecular dynamics simulations uncover a distinctive,enthalpy-driven"high solubility-low diffusivity"transport mechanism:although PEEK displays higher hydrogen solubility due to its stronger thermodynamic affinity,its diffusion coefficient is markedly lower than that of PTFE.This mechanism remains operative across a broad operational temperature range(233 K to358 K),yet its influence on overall permeability is strongly temperature-dependent.At room and high temperatures,the exceptionally low diffusivity of PEEK governs the entire permeation process,establishing its effectiveness as a high-performance hydrogen barrier material.In contrast,under low-temperature conditions(e.g.,233 K),the general suppression of diffusion allows the high solubility of PEEK to dominate,resulting in greater overall permeability than PTFE and giving rise to a performance“reversal”phenomenon.This distinct transport behavior originates from the strong non-covalent interactions between hydrogen molecules and the aromatic rings as well as polar functional groups present in the amorphous regions of PEEK,which simultaneously enhance solubility and impose significant kinetic energy barriers.The"structure-mechanism"correlation framework established in this work provides a robust theoretical foundation for the rational design of next-generation hydrogen barrier materials tailored to specific operational temperature requirements.
