Radiochemical ageing of an amine cured epoxy network. Part II: kinetic modelling

Devanne, T.; Bry, A.; Raguin, N.; Sebban, Muriel; Palmas, P.; Audouin, L.; Verdú, J.

doi:10.1016/j.polymer.2004.07.041

Cited by 28 publications

(25 citation statements)

References 13 publications

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“…In DGEBA group, as assumed by Devanne et al [24,25], the crosslinking between two radicals hold by 2-hydroxypropyl ether groups seems unlikely for two reasons:…”

Section: On the Origins Of Glass Transition Changes During Ageingmentioning

confidence: 99%

Thermal-oxidation of epoxy/amine followed by glass transition temperature changes

Ernault

Richaud

Fayolle

2017

Polymer Degradation and Stability

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Thermal oxidation of three epoxy resins differing by the nature of prepolymer (bisphenol A diglycidyl ether and 1,4-butanediol diglycidyl ether) and hardener (isophorone diamine and 4,7,10-Trioxa-1,13tridecanediamine) was studied by monitoring changes in glass transition temperature using DSC. Results were discussed using the DiMarzio's approach in which parameters are estimated from an additive group contribution. This theory allowed a fair assessment of T g values for unaged networks. During oxidation, epoxy networks were shown to undergo chain scissions occurring in great part in hydroxypropyl ether and isophorone groups. However, the exploitation of T g changes showed the coexistence and even the predominance of crosslinking in materials having linear aliphatic segments. The DiMarzio's approach was used to discuss the possibility of intramolecular cyclization or intermolecular crosslinks which were shown to predominate. Crosslinks were tentatively justified from a mechanistic point of view and quantified depending on experimental conditions.

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“…In DGEBA group, as assumed by Devanne et al [24,25], the crosslinking between two radicals hold by 2-hydroxypropyl ether groups seems unlikely for two reasons:…”

Section: On the Origins Of Glass Transition Changes During Ageingmentioning

confidence: 99%

Thermal-oxidation of epoxy/amine followed by glass transition temperature changes

Ernault

Richaud

Fayolle

2017

Polymer Degradation and Stability

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“…the distance below which the reaction constant is expected to depend only on thermochemistry or steric hindrance. [42,43]. It led to many theoretical developments but a scarce estimation of the involved kinetic parameters.…”

Section: On the Activation Energy Of Oxidation Processmentioning

confidence: 99%

Kinetic analysis of polydicyclopentadiene oxidation

Defauchy

Gac

Guinault

et al. 2017

Polymer Degradation and Stability

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is an open access repository that collects the work of Arts et Métiers ParisTech researchers and makes it freely available over the web where possible. b s t r a c tThe 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 thermal stability of thin pDCPD films, measurements of oxygen diffusivity at several temperatures show that oxidation remains confined in a relatively thin surface layer which would allow the pDCPD properties to be preserved.

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“…12). In the latter period, it can be tried to estimate the number s of chain scissions per mass unit from T g values, using Di Marzio's relationship [21,22]:…”

Section: Physical Modificationsmentioning

confidence: 99%

Thermal and radio-oxidation of epoxy coatings

Galant

Fayolle

Kuntz³

et al. 2010

Progress in Organic Coatings

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Degradation induced by thermal (50-110 • C) and radio-oxidation of low T g epoxy-amine networks has been studied. It has been found that oxidation leads mainly to amide groups formation at the vicinity of tertiary amines whatever ageing conditions (thermal or radio-oxidation at 200 Gy h −1). In addition, some species as acids, peracids or formates have been revealed indicating a chain scission process. Physical modifications as T g decrease and soluble fraction increase due to chain scission process, have been correlated with chemical modifications.

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Radiochemical ageing of an amine cured epoxy network. Part II: kinetic modelling

Cited by 28 publications

References 13 publications

Thermal-oxidation of epoxy/amine followed by glass transition temperature changes

Thermal-oxidation of epoxy/amine followed by glass transition temperature changes

Kinetic analysis of polydicyclopentadiene oxidation

Thermal and radio-oxidation of epoxy coatings

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