The influence of gas sorption on damage nucleation of a semicrystalline polymer during coupled diffuso‐mechanical monotonic loading in tension was investigated for the first time. Alpha‐poly(vinylidene fluoride) was mechanically strained under the presence of two chemically different gases, hydrogen and carbon dioxide, at a temperature of 30°C and a pressure up to 120 bar. The cavitation damage at the microstructure scale after gas decompression was assessed from a careful SEM and TEM micrographs analysis. Compared with SEM, TEM allowed quantifying the smallest cavities (ten‐nanometer size). If decompression in hydrogen appeared to have only a slight effect on cavitation however, carbon dioxide showed a detrimental effect on damage nucleation with the exhibition of a significant population of small cavities. On the other hand, tension under gas pressure is more sensitive to hydrogen than to carbon dioxide. Once interaction with gaseous carbon dioxide takes place the plasticizing effect is in competition with damage by cavitation. POLYM. ENG. SCI., 54:2139–2146, 2014. © 2013 Society of Plastics Engineers

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