https://sam.ensam.eu:443 The DSpace digital repository system captures, stores, indexes, preserves, and distributes digital research material. Sat, 07 Mar 2026 00:30:04 GMT 2026-03-07T00:30:04Z http://hdl.handle.net/10985/8623 Time to failure prediction in rubber components subjected to thermal ageing: A combined approach based upon the intrinsic defect concept and the fracture mechanics BEN HASSINE, Mouna; NAÏT-ABDELAZIZ, M; ZAÏRI, F; TOURCHER, C; MARQUE, Gregory; COLIN, Xavier In this contribution, we attempt to derive a tool allowing the prediction of the stretch ratioat failure in rubber components subjected to thermal ageing. To achieve this goal, the mainidea is to combine the fracture mechanics approach and the intrinsic defect concept. Using an accelerated ageing procedure for an Ethylene–Propylene–Diene Monomer (EPDM), it is first shown that the average molar mass of the elastically active chains (i.e. between crosslinks) can be used as the main indicator of the macromolecular network degradation. Byintroducing the time–temperature equivalence principle, a shift factor obeying to an Arrhenius law is derived, and master curves are built as well for the average molar mass as for the ultimate mechanical properties. Fracture mechanics tests are also achieved and the square root dependence of the fracture energy with the average molar mass is pointed out. Moreover, it is shown that the mechanical response could be approximated by the phantom network theory, which allows to relate the strain energy density function to the average molar mass. Assuming that the fracture of a smooth specimen is the consequence of a virtual intrinsic defect whose the size can be easily estimated, the stretch ratio at break can be therefore computed for any thermal ageing condition. The estimated values are found in a very nice agreement with EPDM experimental data, making this approach a useful tool when designing rubber components for moderate to high temperature environments. Wed, 01 Jan 2014 00:00:00 GMT http://hdl.handle.net/10985/8623 2014-01-01T00:00:00Z BEN HASSINE, Mouna NAÏT-ABDELAZIZ, M ZAÏRI, F TOURCHER, C MARQUE, Gregory COLIN, Xavier In this contribution, we attempt to derive a tool allowing the prediction of the stretch ratioat failure in rubber components subjected to thermal ageing. To achieve this goal, the mainidea is to combine the fracture mechanics approach and the intrinsic defect concept. Using an accelerated ageing procedure for an Ethylene–Propylene–Diene Monomer (EPDM), it is first shown that the average molar mass of the elastically active chains (i.e. between crosslinks) can be used as the main indicator of the macromolecular network degradation. Byintroducing the time–temperature equivalence principle, a shift factor obeying to an Arrhenius law is derived, and master curves are built as well for the average molar mass as for the ultimate mechanical properties. Fracture mechanics tests are also achieved and the square root dependence of the fracture energy with the average molar mass is pointed out. Moreover, it is shown that the mechanical response could be approximated by the phantom network theory, which allows to relate the strain energy density function to the average molar mass. Assuming that the fracture of a smooth specimen is the consequence of a virtual intrinsic defect whose the size can be easily estimated, the stretch ratio at break can be therefore computed for any thermal ageing condition. The estimated values are found in a very nice agreement with EPDM experimental data, making this approach a useful tool when designing rubber components for moderate to high temperature environments. http://hdl.handle.net/10985/9269 Peroxide cross-linking of EPDMs having high fractions of ethylenic units SHABAN, Amin; MARQUE, Gregory; MONCHY-LEROY, Carole; COLIN, Xavier The considerable amount of research in the literature has practically allowed the elucidation of the mechanism of peroxide cross-linking of ethylene–propylene–diene–monomer rubber (EPDM), which occurs through a radical chain reaction initiated by the thermal decomposition of the peroxide molecule. According to this radical chain reaction, all types of labile hydrocarbon bonds (i.e., allylic, methynic, and methylenic CH bonds) would be exposed to alkoxy radicals and involved in the formation of the elastomeric network. However, for high fractions of ethylenic units (typically ≥60 mol.%), simple chemical kinetics and thermochemical analyses have shown that the radical attack would essentially occur on the methylenic CH bonds. Starting from this assertion, a simplified mechanistic scheme has been proposed for the three commercial EPDMs under study. The corresponding kinetic model, derived from this new scheme by using the basic concepts of the chemical kinetics, provides access to the changes in concentration of the main reactive chemical functions (against exposure time), among which are double bonds and changes in cross-linking density. The validity of these predictions has been eventually successfully verified by five distinct analytical techniques frequently used for studying the cross-linking of rubbers. Wed, 01 Jan 2014 00:00:00 GMT http://hdl.handle.net/10985/9269 2014-01-01T00:00:00Z SHABAN, Amin MARQUE, Gregory MONCHY-LEROY, Carole COLIN, Xavier The considerable amount of research in the literature has practically allowed the elucidation of the mechanism of peroxide cross-linking of ethylene–propylene–diene–monomer rubber (EPDM), which occurs through a radical chain reaction initiated by the thermal decomposition of the peroxide molecule. According to this radical chain reaction, all types of labile hydrocarbon bonds (i.e., allylic, methynic, and methylenic CH bonds) would be exposed to alkoxy radicals and involved in the formation of the elastomeric network. However, for high fractions of ethylenic units (typically ≥60 mol.%), simple chemical kinetics and thermochemical analyses have shown that the radical attack would essentially occur on the methylenic CH bonds. Starting from this assertion, a simplified mechanistic scheme has been proposed for the three commercial EPDMs under study. The corresponding kinetic model, derived from this new scheme by using the basic concepts of the chemical kinetics, provides access to the changes in concentration of the main reactive chemical functions (against exposure time), among which are double bonds and changes in cross-linking density. The validity of these predictions has been eventually successfully verified by five distinct analytical techniques frequently used for studying the cross-linking of rubbers.