Emmanuel Richaud

Rate constants of oxidation of unsaturated fatty esters studied by chemiluminescence

This study deals with oxidation kinetics of three unsaturated fatty esters: methyl oleate, methyl linoleate and methyl linolenate at temperatures ranging from 90 to 150 °C. The reaction was monitored by chemiluminescence. A kinetic model was derived from a simple mechanistic scheme, in which initiation is due to hydroperoxides decomposition, whereas propagation results from the abstraction of the most labile hydrogen and termination results only from the bimolecular combination of peroxyl radicals. Analysis of induction period duration indicated that hydroperoxides mainly decompose by a bimolecular process. The model well predicts the main features of the experimental chemiluminescence curves. Kinetic parameters of the three unsaturated fatty esters were assessed from inverse method and discussed.

Diffusion of mineral oils in ethylene-vinyl acetate copolymer

This paper reports a study of mineral oil diffusion through a filled ethylene-vinyl acetate crosslinked polymer, together with some comparisons with aliphatic linear hydrocarbons. Permeation was monitored by classical gravimetric measurements leading to values of diffusion coefficient at several temperatures ranging from 23 to 120°C. A change in activation energy of diffusivity was observed at ca 70°C for mineral oils but not for simple hydrocarbons. The obtained diffusivity values and this curvature were discussed diffusion models derived from free volume theory. A relationship between D and boiling temperature was observed and tentatively justified.

Investigation of Model Fuel Effects on Thermal Oxidation of Polyethylene

This work deals with a study of stabilizers extraction by ethanol‐cyclohexane mixtures simulating ethanol based biofuels. It appears that the extractive power of cyclohexane is considerably stronger then ethanol one. In other words, from this point of view, ethanol based biofuels are less aggressive than a pure hydrocarbon.

Radiochemical Ageing of Aromatic Polymers PEEK, PSU and Kapton®

This article deals with degradation mechanism of three aromatic polymers submitted to γ‐rays in air at 60° C. Tg measurements and GPC results indicated that thin samples (thickness lower than 200 μm) undergo mostly chain scission whereas sol gel analysis and rheometric measurements showed that thicker ones undergo mainly crosslinking. Both results are explained by oxygen diffusion control of oxidation resulting in the formation of a superficial oxidized layer experimentally observed by μATR InfraRed in which oxidative processes orientate rather to chain scission than crosslinking. Experimental results also allowed discussing relative oxidative stability, sensitivity of Tg to chain scission concentration, and crosslinking mechanism (Y or H).A new approach to the problem of gravitational waves detection based on simultaneous timing of several pulsars and subsequent expansion of the post-fit timing data into components of different spectral kind (with different spectral indices) is proposed. Presence of a signal caused by stochastic gravitational waves in spectral components is tested with the two-point angular correlation function as proposed in the pulsar timing array. This new approach was applied to timing data of a few millisecond pulsars and allowed to detect a signature similar to one predicted for gravitational wave background at relatively high confidence level: correlation coefficient between experimental and theoretical two-point correlations

Influence of thermo-oxidation on dielectric and mechanical properties of epoxy/amine resins

\rho=0.82\pm 0.07

On the degelation of networks – Case of the radiochemical degradation of methyl methacrylate – ethylene glycol dimethacrylate copolymers

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Hydrolytic ageing of polyester networks - Role of a plasticizer

This objective of this work is to compare the changes of electrical and mechanical properties during thermo-oxidation of epoxy, in order to improve the choice of end life criterion. The thermal oxidation of DGEBA totally cured with linear aliphatic hardener is investigated under several temperature and oxygen pressure. Chemical changes are followed thanks to infra-red spectroscopy, macromolecular changes thanks to differential scanning calorimetry (changes of Tg). During thermo-oxidation at 110°C in air, volume resistivity and tensile properties in terms of modulus and deformation at break changes are assessed. The results show a formation of polar groups corresponding to oxidation products and a decrease of molecular mobility associated to a crosslinking process. Furthermore, it appears that the oxidation process leads to an embrittlement process whereas electrical properties are not significantly modified.

New Developments in the Field of Radiochemical Ageing of Aromatic Polymers

Methyl methacrylate networks were synthetized and submitted to radiochemical degradation. Ageing was monitored by means of sol-gel analysis and glass transition temperature measurements. Networks were shown to undergo exclusively chain scission process leading to the degelation of network. The critical conversion degree corresponding to degelation (loss of all elastically active chains) is discussed regarding a statistical theory.

Review: degradation-induced embrittlement in semi-crystalline polymers having their amorphous phase in rubbery state

This paper reports the hydrolytic ageing of polyester urethane based elastomer networks containing various amount of a plasticizer. Degradation was monitored by mechanical properties and swelling ratio changes. An analysis of the early stages of degradation showed this plasticizer decreased the polymer sensitivity towards hydrolysis. Some possible reasons were discussed. The most likely is that adding plasticizer during polymerization changes the network initial architecture with more dangling chains of which hydrolysis does not change the elastic properties.

Effect of oxygen pressure on the oxidation kinetics of unstabilised polypropylene

Polymers having an aromatic backbone polymers have a high mechanical strength and a high modulus. Their aromaticity increases their resistance for use in relatively severe conditions especially in aerospace and nuclear industry for which lifetime prediction is a key issue. For example, a challenge for nuclear plants is to extend lifetime from the initially planned 40 years duration to 50 or 60 years, which makes necessary to determine lifetime by a non-empirical method. Since polymers mechanical failure originates from chain scission or crosslinking of the backbone, the ideal method of lifetime prediction would first involve the elaboration of a kinetic model for chain scission and crosslinking. Then, the changes of molecular mass would be related to the changes of mechanical properties using the available laws of polymers physics. Lifetime would be then determined using a pertinent lifetime criterion. A noticeable difficulty comes here from the fact that oxidation, which plays a key major role in chain scission, is diffusion controlled and thus heterogeneously distributed in sample thickness. It is crucial, indeed, to determine experimentally and to predict this depth distribution of chain scission and crosslinking because it will play a key role on fracture properties. This chapter will be henceforward devoted to the effect of aromaticity on radiostability, the effect on temperature on the chain scission/crosslinking competition, the diffusion limited oxidation (which will be illustrated by the effect of dose rate, atmosphere and sample thickness), then some concluding remarks on oxidative stability of aromatic polymers and the possible link with the absence of macromolecular mobility below Tg. We will start by some basics of radiochemistry which are necessary for the good understanding of this paper, and especially the quantitative treatment for crosslinking and chain scission.