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| Richaud, Emmanuel; Le Gac, Pierre-yves; Verdu, Jacques. |
| Thermal ageing of thin films of unstabilized polydicyclopentadiene (pDCPD) at several temperatures ranging from 120 to 30°C was investigated by means of carbonyl build up by FTIR with ammonia derivatization, double bond titration, mass uptake measurement, hydroperoxides titration by iodometry and DSC coupled with sulfur dioxide treatment. In the temperature range under investigation, pDCPD is in glassy state and it oxidizes faster than common polymers oxidized at rubbery state (e.g. polydienic elastomers). Using the kinetic analysis, these results were ascribed to increased initiation rate due to catalyst residues, some possible intramolecular processes favoring propagation, or a very low termination rate of oxidation radical chains because of the control... |
| Tipo: Text |
Palavras-chave: Polydicyclopentadiene; Thermal oxidation; Kinetics; Molecular mobility. |
| Ano: 2014 |
URL: http://archimer.ifremer.fr/doc/00175/28646/27073.pdf |
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| Defauchy, Virginie; Le Gac, Pierre-yves; Guinault, Alain; Verdu, Jacques; Recher, Gilles; Drozdzak, Renata; Richaud, Emmanuel. |
| The in situ thermal oxidation of thin unstabilized polydicyclopentadiene was studied by TGA to monitor mass gain, and DSC to characterize hydroperoxides concentration. Results were discussed using kinetic analysis, which allowed the estimation of activation energies for key reactions of the oxidation process. Activation energy for termination was shown to be higher than in hydrocarbon liquids, which was discussed from the theory of diffusion controlled reactions, and a possible link with local motions associated with sub-glassy transition. Activation energy of thermal decomposition of hydroperoxides was found lower than for model hydroperoxides, suggesting an accelerating effect of organometallic catalysts. Despite those two results that indicate a poor... |
| Tipo: Text |
Palavras-chave: Polydicyclopentadiene; Thermal oxidation; Segmental mobility; Catalysis; Diffusion limited oxidation. |
| Ano: 2017 |
URL: http://archimer.ifremer.fr/doc/00388/49904/50476.pdf |
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| Le Gac, Pierre-yves; Roux, Gerard; Davies, Peter; Fayolle, Bruno; Verdu, Jacques. |
| Water sorption has been studied gravimetrically for polychloroprene rubber samples, first at a fixed hygrometric ratio (98% HR) and several temperatures (25, 40, 60 and 80°C) for samples of 1.9 and 3.8 mm thickness (Constant Temperature and Hygrometry, CTH experiments), then at fixed temperature (40°C) and several hygrometric ratios ranging from 0 to 95% HR on samples of 0.1 mm thickness (DVS experiments). CTH experiments reveal an abnormal sorption behavior: after an apparently fickian transient period, the water absorption continues at almost constant rate, no equilibrium is observed after more than 2500 hours, whatever the temperature. DVS experiments reveal a very low Henry’s solubility but the formation of clusters at water activities higher than 40%.... |
| Tipo: Text |
Palavras-chave: Polychloroprene; Water sorption; Clustering. |
| Ano: 2014 |
URL: http://archimer.ifremer.fr/doc/00188/29903/28350.pdf |
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| Le Gac, Pierre-yves; Broudin, Morgane; Roux, Gérard; Verdu, Jacques; Davies, Peter; Fayolle, Bruno. |
| Tensile properties and crack propagation properties, especially critical strain energy release rate in mode I, GIC, have been used to investigate fracture properties of elastomers and their relationships with microstructure. These investigations were mainly based on a series of comparisons: first, the behaviour of polychloroprene rubber (CR), undergoing stress hardening due to strain induced crystallization (SIC) and oxidative crosslinking (OCL) was compared with that of chlorinated polyethylene (CPE), which undergoes SIC but not OCL, and with a polyurethane based on hydroxyl terminated polybutadiene (PU) which undergoes OCL but not SIC. Comparisons were also made on CR between fracture behaviour at ambient temperature, where SIC occurs and at 100°C where... |
| Tipo: Text |
Palavras-chave: Fracture; Rubber; Oxidation. |
| Ano: 2014 |
URL: http://archimer.ifremer.fr/doc/00184/29546/27872.pdf |
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| Le Gac, Pierre Yves; Roux, Gerard; Verdu, Jacques; Davies, Peter; Fayolle, Bruno. |
| Thermal oxidation in air at atmospheric pressure, in the 80-140°C temperature range and in oxygen at 100°C in the 0.02-3 MPa pressure range, of unvulcanized, unstabilized, unfilled polychloroprene (CR) has been characterized using FTIR and chlorine concentration measurement. The kinetic analysis was focused on double bond consumption. A mechanistic scheme involving unimolecular and bimolecular hydroperoxide decomposition, oxygen addition to alkyl radicals, hydrogen abstraction on allylic methylenes, alkyl and peroxyl additions to double bonds and terminations involving alkyl and peroxy radicals was elaborated. The corresponding rate constants were partly extracted from the literature and partly determined from experimental data using the kinetic model... |
| Tipo: Text |
Palavras-chave: Polychloroprene; Oxidation; Radical chain; Kinetics. |
| Ano: 2014 |
URL: http://archimer.ifremer.fr/doc/00199/31010/29413.pdf |
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