Co-oxidation kinetic model for the thermal oxidation of polyethylene-unsaturated substrate systems

The thermal oxidation of polyethylene (PE) impregnated by the methyl esters of unsaturated fatty acids (UFEs) was studied using chemiluminescence, and infra-red spectrophotometry. It was shown that the presence of UFEs accelerates the PE aging process. This can be interpreted as a co-oxidation phenomenon. In this study, the previously established models for PE and UFEs self-oxidation have been coupled in order to develop a co-oxidation model. Using the existing rate constants for the PE and UFEs selfoxidations, this model can simulate the complex shape of the kinetic curves of PE-UFE co-oxidatio

Ageing and Durability of Organic Polymers

“Ageing” is any slow and irreversible phenomenon (under usage conditions) of a material’s structure, morphology or composition, under the effects of its own instability and/or interaction with the environment. Any condition is considered to be slow when the kinetics are not apprehensible in a time scale which is compatible with economic restraints. The classic approach of predicting long-term behavior consists of carrying out accelerated tests simulating, as accurately as possible, natural ageing and to presume that the hierarchy of stability for several materials is the same in accelerated and natural ageing. The modern approach consists of developing a kinetic model derived from analyzing degradation materials. Accelerated ageing is, then, used to identify the model parameters

Organic polymers

Natural organic materials (wood, horn, skin, etc.) have been used since the dawn of humanity. Textile fabrication from vegetal fibers (linen, cotton, etc.) or from animals (silk, wool, etc.) reached an “industrial” stage from the Middle Ages onwards. The idea of changing raw matter by specific physical or chemical treatment (dyeing fibers, leather tanning, etc.) is practically as ancient as the applications themselves. In the 19th century, however, a new idea emerged: chemically modifying natural substances (fibers, skins, etc.) so as to make them into completely different from the natural forms

Degradation of epoxy coatings under gamma irradiation

Epoxy networks based on Diglycidyl ether of bisphenol A (DGEBA) and cured with Jeffamines (POPA) or polyamidoamine (PAA) were gamma irradiated at 25 1C in air. Dose rates of 50, 200 or 2000 Gy h- 1 for doses up 100 kGy were used. Structural changes were monitored by IR spectrophotometry, DSC and sol–gel analysis. Both networks display some common features: for I Z 200 Gy h- 1, reaction products grow proportionally to time and the rate is a decreasing function of dose rate. The simplest explanation is that peroxy radicals are the main precursors of these products (in the dose rate domain under study), through a unimolecular rearrangement of which an hypothetical mechanism is proposed. DGEBA–POPA are more reactive then DGEBA–PAA networks (according to IR criteria), that can be attributed to the high reactivity of tertiary CH bands in polyoxypropylene segments. The oxidation of these sites leads to methyl ketones. A simple kinetic model in which methyl ketones result from rearrangements of tertiary peroxyls and from tertiary alkoxyls was proposed. It leads to an expression of the radiochemical yield of methyl ketones (G(MK)) of the form GðMKÞ¼ a þ bI-1=2 where a and b are parameters depending of elementary rate constants. Experimental G(MK) values are reasonably well fitted by this equation. In DGEBA–PAA networks, a wide variety of oxidation products, among which amides predominate, can be observed. In these networks, chain scissions predominate over crosslinking, whereas a slight predominance of crosslinking was observed, at least for the lowest dose rate, in DGEBA–POPA

Thermo-oxidative aging of epoxy coating systems

tThe thermo-oxidative behavior of unformulated (unfilled) samples of epoxy coatings has been studiedat five temperatures ranging from 70◦C to 150◦C. Two epoxy networks based on diglycidyl ether ofbisphenol A (DGEBA), respectively, cured by jeffamine (POPA) or polyamidoamine (PAA) were compared.Infrared spectrophotometry (IR), differential scanning (DSC) and sol–gel analysis (SGA) were used tomonitor structural changes.Thermal oxidation leads to carbonyl and amide formation in both systems. POPA systems appear moresensitive to oxidation than PAA ones. Thermal oxidation leads to predominant chain scission as evidencedby the decrease of glass transition temperatures (Tg) and increase of sol fraction

Tensile properties of polyproylene fibres

As soon as it appeared on the market, one half century ago, polypropylene (PP) appeared as a promising fibre-forming polymer but with some difficulties in processing due to a lack of control of its viscoelastic properties and in durability due to its low stability to oxidation. These difficulties were progressively resolved in the last decades by a sharper control of synthesis conditions e.g. of stereoregularity and molar mass distribution, and by a better knowledge of oxidation and stabilization mechanisms. These research efforts allowed PP to invade a very wide range of fibre applications, from disposable diapers to geotextiles

Coping with collaborative and competitive episodes within collaborative remote laboratories

International audienceIn this paper, we provide an original approach to the support of group awareness within collaborative remote laboratories. Computer Supported Collaborative Learning sessions present successively collaborative and emulation episodes. The idea developed here is the elaboration of an architecture for dealing with those two aspects of collaborative sessions for practical remote hands-on approaches. Our purpose is to manage and enhance the learning experience brought to the students who are using collaborative remote laboratories by managing several synchronous accesses made on the remote laboratories platform itself. This contribution relies on an original domain ontology and the associated knowledge management system

Oxidation of unvulcanized, unstabilized polychloroprene: A kinetic study

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 derived from the mechanistic scheme in an inverse approach. Among the specificities of polychloroprene, the following were revealed: The rate of double bond consumption is a hyperbolic function of oxygen pressure that allows a law previously established for the oxidation of saturated substrates to be generalized. CR oxidation is characterized by the absence of an induction period that reveals the instability of hydroperoxides. The kinetic analysis also reveals that peroxyl addition is faster than hydrogen abstraction but slower in CR than in common hydrocarbon polydienes

Budget européen : triomphe de la logique comptable.

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Water clustering in polychloroprene

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 1.8 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 h, whatever the temperature. DVS experiments reveal a very low Henry's solubility but the formation of clusters at water activities higher than 40%. The water diffusivity is almost independent of activity below 50% HR and decreases rapidly when activity increases above 50%. Contrary to CTH experiments, equilibrium is reached in DVS and the difference is not simply linked to the well-known effect of sample thickness on diffusion rate. The results allow hypotheses such as hydrolysis or osmotic cracking to explain the abnormal sorption phenomenon to be rejected. It is suggested that clusters could be polymer-water complexes having a linear/branched structure able to grow without phase separation that could explain the reversibility of sorption-desorption cycles. The difference of behavior between thin 0.1 mm and thicker 1.8 or 3.8 mm samples could be due to an effect of swelling stresses