Molecular simulation of hydrogen permeation behavior of polyamide 6 liner material for type IV hydrogen storage cylinder

doi:10.19491/j.issn.1001-9278.2024.08.010

Abstract

Abstract:

In this work， the permeability of hydrogen in the polymer polyamide 6 （PA6） was studied by molecular simulation methods at different temperatures （30， 40， 60 and 80^{℃） and pressures （82， 87.5， 98 and 103 MPa）. Meanwhile， the permeability mechanism of hydrogen was analyzed. The results indicated that as the temperature increases， the adsorption heat and free volume fraction gradually increases， the thermal motion intensifies and the molecular motion space increases. And the solubility， diffusion and permeability coefficient of hydrogen in PA6 all increase. At a pressure of 103 MPa， increasing the temperature has the greatest impact on the permeability coefficient， which increases by 88.3 %. With the increase of pressure， the interaction between hydrogen and PA6 molecular chains decreases and the free volume fraction decreases， so the solubility， diffusion and permeability coefficient of hydrogen in PA6 all show a downward trend. When the temperature was 60^{℃， the pressure had the most significant influence on the permeability coefficient， which decreased by 38.6 %. The permeation mechanism of hydrogen in PA6 includes the aggregation adsorption process in the low potential energy region and the diffusion process of intra⁃cavity vibration⁃inter⁃cavity transition formed in the free volume. With the increase of temperature， the movement of hydrogen molecules becomes active and there are more inter⁃cavity jumps. When the pressure increases， the change is opposite.}}

Key words: polyamide 6, hydrogen, diffusion, adsorption, permeation, molecular simulation

CLC Number:

TQ320.2

ZHANG Xuemin, ZHAI Lizhen, LI Houbu, QI Guoquan, HUANG Shangbin, ZHANG Dongna, YANG Zhifeng, ZHANG Xiaoyu. Molecular simulation of hydrogen permeation behavior of polyamide 6 liner material for type IV hydrogen storage cylinder[J]. China Plastics, 2024, 38(8): 62-68.

Figures/Tables 15

Fig.1. Molecular model

Fig.2. Models of the cell structure

Fig.3. Changes of the density of PA6 cell model during relaxation

Fig.4. Tg of the PA6 cell

Fig.5. Adsorption isotherm of H2 in PA6 under different pressure at 30 ℃

Fig.6. Solubility coefficients of H2 in PA6 under different conditions

Fig.7. Adsorption heat of H2 in PA6 under different conditions

压力/MPa	吸附前总能量	吸附后总能量	能量差
82.0	-11 871.986	-12 094.935	-222.949
87.5	-12 198.001	-12 350.550	-152.549
98.0	-11 946.988	-11 985.665	-38.678
103.0	-12 266.005	-12 297.004	-30.999

Tab.1. Total system energy of adsorption process under different pressure at 30 ℃

Fig.8. （a） adsorption density distribution and （b） isodensity display of H2 molecules in PA6

Fig.9. Mean square displacement curves of H2 in PA6 under different pressure at 30 ℃

Fig.10. Diffusion coefficients of H2 in PA6 under different conditions

Fig.11. Free volume distribution of H2/PA6 cells

Fig.12. Free volume fraction of H2 in PA6 under different conditions

Fig.13. Three⁃dimensional diffusion trajectory and displacement⁃time curves of H2 molecules in PA6

Fig.14. Permeability coefficients of H2 in PA6 under different conditions

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