Revealing the Hydrogen Permeation Mechanism in Polyetheretherketone and Polytetrafluoroethylene: From Experimental Validation to Molecular-level Interpretation

Hong-Lin Zhang; Wen-Tao Hu; Jie Xiao; Tian-Lei Li; Yuan-Hua Lin

doi:10.1007/s10118-025-3483-7

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Revealing the Hydrogen Permeation Mechanism in Polyetheretherketone and Polytetrafluoroethylene: From Experimental Validation to Molecular-level Interpretation

RESEARCH ARTICLE | Updated：2026-01-13

- Revealing the Hydrogen Permeation Mechanism in Polyetheretherketone and Polytetrafluoroethylene: From Experimental Validation to Molecular-level Interpretation
- Chinese Journal of Polymer Science Vol. 44, Issue 1, Pages: 278-298(2026)
- Affiliations：
  
  a.State Key Laboratory of Oil & Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu 610500, China
  b.School of New Energy and Materials, Southwest Petroleum University, Chengdu 610500, China
  c.China Petroleum Engineering Construction Corporation Southwest Branch, Chengdu 610000, China
- Author bio：
  
  yhlin28@163.com
- Funds：
- DOI：10.1007/s10118-025-3483-7
  CLC：
- Received：31 July 2025，
  
  Accepted：31 October 2025，
  
  Published Online：17 December 2025，
  
  Published：15 January 2026
- Accepted：
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Zhang, H. L.; Hu, W. T.; Xiao, J.; Li, T. L.; Lin, Y. H. Revealing the hydrogen permeation mechanism in polyetheretherketone and polytetrafluoroethylene: from experimental validation to molecular-level interpretation. Chinese J. Polym. Sci. 2026, 44, 278–298

Hong-Lin Zhang, Wen-Tao Hu, Jie Xiao, et al. Revealing the Hydrogen Permeation Mechanism in Polyetheretherketone and Polytetrafluoroethylene: From Experimental Validation to Molecular-level Interpretation[J]. Chinese Journal of Polymer Science, 2026, 44(1): 278-298.
Zhang, H. L.; Hu, W. T.; Xiao, J.; Li, T. L.; Lin, Y. H. Revealing the hydrogen permeation mechanism in polyetheretherketone and polytetrafluoroethylene: from experimental validation to molecular-level interpretation. Chinese J. Polym. Sci. 2026, 44, 278–298 DOI： 10.1007/s10118-025-3483-7.

Hong-Lin Zhang, Wen-Tao Hu, Jie Xiao, et al. Revealing the Hydrogen Permeation Mechanism in Polyetheretherketone and Polytetrafluoroethylene: From Experimental Validation to Molecular-level Interpretation[J]. Chinese Journal of Polymer Science, 2026, 44(1): 278-298. DOI： 10.1007/s10118-025-3483-7.

摘要

Polyetheretherketone (PEEK) exhibits a superior hydrogen barrier performance over polytetrafluoroethylene (PTFE). Our integrated study reveals an enthalpy-driven mechanism: strong non-covalent interactions enhance solubility but create kinetic traps that severely suppress diffusion. This provides a new

enthalpy-based strategy for designing advanced barrier materials.

Abstract

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

nthalpy-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 to 358 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.

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