Thermal oxidation kinetics of additive free polyamide 6-6

Thermal aging of an additive free PA 6-6 has been elucidated at 90, 100, 120, 140, 150 and 160 C in airventiled ovens by Fourier transform infrared spectrophotometry, viscosimetry in molten state and uniaxial tensile testing. Oxidation of methylene groups starts after a considerably shorter induction period but reaches a lower maximal rate than in additive free PE. Cleavage of CeN bonds constitutes the main source of chain scissions. It leads to the formation of aldehyde chain-ends and a catastrophic decrease in molar mass. Embrittlement occurs at a very low conversion ratio of the oxidation process, in particular when the concentration of aldehyde chain-ends reaches a critical value of [PH¼O]F z 5.6 10 3 mol l 1, corresponding to a critical value of the number average molar mass ofMnFz17 kg mol 1. At this stage, the entanglement network in the amorphous phase is deeply damaged. A non-empirical kinetic model has been derived from the oxidation mechanistic scheme previously established for PE, but improved by adding elementary reactions specific to polyamides such as the rapid decomposition of unstable hydroxylated amide groups. This model describes satisfyingly the main features of the thermal oxidation kinetics of PA 6-6, but also of other types of aliphatic polyamides studied previously in the literature such as: PA 6, PA 12 and PA 4-6, as long as it is not controlled by oxygen diffusion. At the same time, it confirms the existence of an universal character for the thermal oxidation kinetics of aliphatic polyamides whatever their origin, i.e. their initial molar mass, crystallinity ratio, concentration of impurities, structural irregularities, etc

CHEMO-MECHANICAL MODEL FOR PREDICTING THE LIFETIME OF EPDM RUBBERS

A chemo-mechanical model has been developed for predicting the long-term mechanical behavior of EPDM rubbers in a harsh thermal oxidative environment. Schematically, this model is composed of two complementary levels: The “chemical level” calculates the degradation kinetics of the macromolecular network that is introduced into the “mechanical level” to deduce the corresponding mechanical behavior in tension. The “chemical level” is derived from a realistic mechanistic scheme composed of 19 elementary reactions describing the thermal oxidation of EPDM chains, their stabilization against oxidation by commercial antioxidants but also by sulfide bridges, and the maturation and reversion of the macromolecular network. The different rate constants and chemical yields have been determined from a heavy thermal aging campaign in air between 70 and 170 °C on four distinct EPDM formulations: additive free gum, unstabilized and stabilized sulfur vulcanized gum, and industrial material. This “chemical level” has been used as an inverse resolution method for simulating accurately the consequences of thermal aging at the molecular (concentration changes in antioxidants, carbonyl products, double bonds, and sulfide bridges), macromolecular (concentration changes in chain scissions and cross-link nodes), and macroscopic scales (weight changes). Finally, it gives access to the concentration changes in elastically active chains from which are deduced the corresponding changes in average molar mass MC between two consecutive cross-link nodes. The “mechanical level” is derived from a modified version of the statistical theory of rubber elasticity, called the phantom network theory. It relates the elastic and fracture properties to MC if considering the macromolecular network perfect, and gives access to the lifetime of the EPDM rubber based on a relevant structural or mechanical end-of-life criterion. A few examples of simulations are given to demonstrate the reliability of the chemo-mechanical model

Time to failure prediction in rubber components subjected to thermal ageing: A combined approach based upon the intrinsic defect concept and the fracture mechanics

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

Modélisation du vieillissement thermique et mécanique d'une protection externe en EPDM de jonctions rétractables à froid

L'objectif de cette thèse est l'étude des conséquences de la thermo-oxydation sur la structure chimique et le comportement mécanique d'un Ethylène Propylène Diène Monomère (EPDM). Afin de déterminer les modifications à différentes échelles structurales, quatre formulations modèles sont étudiées : la gomme pure, les matrices vulcanisées stabilisée et non stabilisée et l'élastomère industriel. L'ensemble des échantillons est vieilli entre 70 et 170C dans l'air ou sous vide puis caractérisé par divers outils analytiques. La thermogravimétrie donne accès aux variations de masse résultant de l'incorporation d'oxygène et l'émission de composés volatils. L'analyse infrarouge permet de suivre les évolutions des espèces chimiques. Les essais de gonflement, de chromatographie et de spectrométrie mécanique permettent de calculer les nombres de coupures de chaînes et d'actes de réticulation à chaque instant. Sur la base de ces résultats, un modèle cinétique général de thermo-oxydation de la matrice EPDM est proposé et en partie validé. Les conséquences du vieillissement thermique sur le comportement mécanique de l'élastomère industriel sont mises en évidence par des essais de traction uniaxiale et de multi-relaxation à température ambiante et vitesse de déformation initiale de 10-3 s-1. L'impact du vieillissement thermique sur les propriétés ultimes et les réponses à l'équilibre et hors équilibre est examiné. Un critère prédictif de rupture basé sur la mécanique de la rupture est proposé. Enfin, le couplage vieillissement thermique - contrainte mécanique est étudié par des essais relaxation de contraintes continues entre 130 et 170C dans l'air. Les modifications de la microstructure pendant le vieillissement thermique sont intégrées dans les équations constitutives du modèle mécanique macroscopique afin de proposer un outil de prédiction du comportement à long terme de l'élastomère industriel. La simulation numérique montre une bonne adéquation avec les résultats expérimentaux.The aim of this work is to study the consequences of the thermal oxidation on the chemical structure and mechanical behavior of an Ethylene-Propylene-Diene Monomer (EPDM). In order to determine the structural changes at different scales, four model formulations have been considered: free additive gum, stabilized and unstabilized vulcanized matrix and industrial rubber. All samples were aged between 70 and 170C in air or vacuum and characterized by several analytical tools. Thermogravimetry gives access to weight variations due to oxygen grafting and volatile compounds release. Infrared analysis is used to follow chemical species evolutions. Swelling tests, chromatographic and mechanical spectrometry tests allow calculating the number of chain scission and cross-linking events at any time. Based on these results, a general kinetic model is proposed and partially validated for EPDM matrix thermal oxidation. The consequences of thermal ageing on the mechanical behavior of the industrial rubber are pointed out by monotonic tensile and stress relaxation tests at room temperature and a 10-3 s-1- initial strain rate. The impact of thermal ageing on ultimate properties and equilibrium and non-equilibrium response are examined. Finally, the coupling between thermal ageing and mechanical stress is studied by continuous stress relaxation tests between 130 et 170C in air. The microstructural modifications during thermal ageing are introduced into the constitutive equations of the macroscopic mechanical model in order to propose a predictif tool of the long time behavior of the industrial rubber. The numerical simulation is in good agreement with experimental results.PARIS-Arts et Métiers (751132303) / SudocSudocFranceF

Investigation and modelling of the water transport properties in unfilled EPDM elastomers

The water sorption properties (i.e. diffusivity and solubility) of three unfilled vulcanized EPDMs were investigated in wet atmosphere (typically between 0 and 95% RH) and in pure distilled water (denoted as 100% RH) at 70 °C with an IGAsorp dynamic sorption analyzer. In the 0–0.5 activity range, all EPDMs obey to the usual Fick and Henry's laws. In contrast, at activities higher than 0.5, the water sorption behavior of all EPDMs deviates from these two laws because of the formation of water clusters. Park's equation was used for simulating accurately the sorption isotherms and thus, accessing Henry's constant and the average size of water clusters. In wet atmospheres, clusters would be composed of about 8 ± 4 molecules corresponding approximately to the size of free volume holes. In contrast, in pure distilled water, clusters consist in a much larger number of water molecules (between 55 and 71) presumably because of an exacerbated swelling of EPDM samples. Thus, immersion in water solution is more drastic than exposure to fully saturated wet atmosphere. The impact of the EPDM formulation (nature and content of crosslinking agent) on these experimental results is clearly of the second order of magnitude

Bacteriological and physico-chemical assessment of wastewater in different region of Tunisia: impact on human health

<p>Abstract</p> <p>Background</p> <p>In many parts of the world, health problems and diseases have often been caused by discharging untreated or inadequately treated wastewater. In this study, we aimed to control physico-chemical parameters in wastewater samples. Also, microbiological analyses were done to reveal <it>Salmonella </it>strains and each <it>Escherichia coli </it>(<it>E.coli</it>) pathotype.</p> <p>Findings</p> <p>Sixty wastewater samples were collected from fifteen different regions of Tunisia. All physico-chemical parameters (pH, residual free chlorine, total suspended solids, biological oxygen demand, and chemical oxygen demand) were evaluated.</p> <p>For microbiological analyses, samples were filtered to concentrate bacteria. DNA was extracted by boiling and subjected to polymerase chain reaction (PCR) using different pairs of primers.</p> <p>The mean pH values recorded for the sampling point were above the WHO pH tolerance limit. The total suspended solids (TSS) concentrations varied between 240 mg/L and 733 mg/L in entrance points and between 13 mg/L and 76 mg/L in exit points. In entrance points, the studied wastewater has an average COD concentration that varied between 795 mg/mL to 1420 mg/mL. Whereas, BOD concentration of the wastewater ranged between 270 mg/L to 610 mg/L. In exit points, COD concentration varied between 59 mg/L and 141 mg/L, whereas BOD concentration ranged from 15 mg/L to 87 mg/L.</p> <p>The bacteriological control of wastewaters showed that, in entrance points, <it>Escherichia coli </it>(<it>E.coli</it>) was detected at the rate of 76.6%. Three <it>E.coli </it>pathotypes were found: ETEC (53.3%), EAEC (16.6%) and EIEC (6.6%).</p> <p>Concerning the ETEC isolated strains, 8 of 16 (50%) have only the heat-labile toxin gene, 5 of 16 (31.2%) present only the heat-stable toxin gene and 3 of 16 (18.7%) of strains possess both heat-labile toxin gene and heat-stable toxin gene. In exist point, the same pathotypes were found but all detected ETEC strains present only the "est" gene.</p> <p>Concerning <it>Salmonella </it>isolated strains; percentages of 66.6% and 20% were found in entrance and exit points respectively.</p> <p>Conclusions</p> <p>Wastewaters contain a large amount of pathogenic bacteria that present a real impact on human health. Assessment wastewater treatment stations have to consider in account enterobacterial pathogens as potential pathogens that should be correctly controlled.</p

Modelling of thermal and mechanical ageings of an external protection of a cold shrinkable junction made of EPDM rubber

L'objectif de cette thèse est l'étude des conséquences de la thermo-oxydation sur la structure chimique et le comportement mécanique d'un Ethylène Propylène Diène Monomère (EPDM). Afin de déterminer les modifications à différentes échelles structurales, quatre formulations modèles sont étudiées : la gomme pure, les matrices vulcanisées stabilisée et non stabilisée et l'élastomère industriel. L'ensemble des échantillons est vieilli entre 70 et 170°C dans l'air ou sous vide puis caractérisé par divers outils analytiques. La thermogravimétrie donne accès aux variations de masse résultant de l'incorporation d'oxygène et l'émission de composés volatils. L'analyse infrarouge permet de suivre les évolutions des espèces chimiques. Les essais de gonflement, de chromatographie et de spectrométrie mécanique permettent de calculer les nombres de coupures de chaînes et d'actes de réticulation à chaque instant. Sur la base de ces résultats, un modèle cinétique général de thermo-oxydation de la matrice EPDM est proposé et en partie validé. Les conséquences du vieillissement thermique sur le comportement mécanique de l'élastomère industriel sont mises en évidence par des essais de traction uniaxiale et de multi-relaxation à température ambiante et vitesse de déformation initiale de 10-3 s-1. L'impact du vieillissement thermique sur les propriétés ultimes et les réponses à l'équilibre et hors équilibre est examiné. Un critère prédictif de rupture basé sur la mécanique de la rupture est proposé. Enfin, le couplage vieillissement thermique - contrainte mécanique est étudié par des essais relaxation de contraintes continues entre 130 et 170°C dans l'air. Les modifications de la microstructure pendant le vieillissement thermique sont intégrées dans les équations constitutives du modèle mécanique macroscopique afin de proposer un outil de prédiction du comportement à long terme de l'élastomère industriel. La simulation numérique montre une bonne adéquation avec les résultats expérimentaux.The aim of this work is to study the consequences of the thermal oxidation on the chemical structure and mechanical behavior of an Ethylene-Propylene-Diene Monomer (EPDM). In order to determine the structural changes at different scales, four model formulations have been considered: free additive gum, stabilized and unstabilized vulcanized matrix and industrial rubber. All samples were aged between 70 and 170°C in air or vacuum and characterized by several analytical tools. Thermogravimetry gives access to weight variations due to oxygen grafting and volatile compounds release. Infrared analysis is used to follow chemical species evolutions. Swelling tests, chromatographic and mechanical spectrometry tests allow calculating the number of chain scission and cross-linking events at any time. Based on these results, a general kinetic model is proposed and partially validated for EPDM matrix thermal oxidation. The consequences of thermal ageing on the mechanical behavior of the industrial rubber are pointed out by monotonic tensile and stress relaxation tests at room temperature and a 10-3 s-1- initial strain rate. The impact of thermal ageing on ultimate properties and equilibrium and non-equilibrium response are examined. Finally, the coupling between thermal ageing and mechanical stress is studied by continuous stress relaxation tests between 130 et 170°C in air. The microstructural modifications during thermal ageing are introduced into the constitutive equations of the macroscopic mechanical model in order to propose a predictif tool of the long time behavior of the industrial rubber. The numerical simulation is in good agreement with experimental results

Modélisation du vieillissement thermique et mécanique d’une protection externe en EPDM de jonctions rétractables à froid

The aim of this work is to study the consequences of the thermal oxidation on the chemical structure and mechanical behavior of an Ethylene-Propylene-Diene Monomer (EPDM). In order to determine the structural changes at different scales, four model formulations have been considered: free additive gum, stabilized and unstabilized vulcanized matrix and industrial rubber. All samples were aged between 70 and 170°C in air or vacuum and characterized by several analytical tools. Thermogravimetry gives access to weight variations due to oxygen grafting and volatile compounds release. Infrared analysis is used to follow chemical species evolutions. Swelling tests, chromatographic and mechanical spectrometry tests allow calculating the number of chain scission and cross-linking events at any time. Based on these results, a general kinetic model is proposed and partially validated for EPDM matrix thermal oxidation. The consequences of thermal ageing on the mechanical behavior of the industrial rubber are pointed out by monotonic tensile and stress relaxation tests at room temperature and a 10-3 s-1- initial strain rate. The impact of thermal ageing on ultimate properties and equilibrium and non-equilibrium response are examined. Finally, the coupling between thermal ageing and mechanical stress is studied by continuous stress relaxation tests between 130 et 170°C in air. The microstructural modifications during thermal ageing are introduced into the constitutive equations of the macroscopic mechanical model in order to propose a predictif tool of the long time behavior of the industrial rubber. The numerical simulation is in good agreement with experimental results.L'objectif de cette thèse est l'étude des conséquences de la thermo-oxydation sur la structure chimique et le comportement mécanique d'un Ethylène Propylène Diène Monomère (EPDM). Afin de déterminer les modifications à différentes échelles structurales, quatre formulations modèles sont étudiées : la gomme pure, les matrices vulcanisées stabilisée et non stabilisée et l'élastomère industriel. L'ensemble des échantillons est vieilli entre 70 et 170°C dans l'air ou sous vide puis caractérisé par divers outils analytiques. La thermogravimétrie donne accès aux variations de masse résultant de l'incorporation d'oxygène et l'émission de composés volatils. L'analyse infrarouge permet de suivre les évolutions des espèces chimiques. Les essais de gonflement, de chromatographie et de spectrométrie mécanique permettent de calculer les nombres de coupures de chaînes et d'actes de réticulation à chaque instant. Sur la base de ces résultats, un modèle cinétique général de thermo-oxydation de la matrice EPDM est proposé et en partie validé. Les conséquences du vieillissement thermique sur le comportement mécanique de l'élastomère industriel sont mises en évidence par des essais de traction uniaxiale et de multi-relaxation à température ambiante et vitesse de déformation initiale de 10-3 s-1. L'impact du vieillissement thermique sur les propriétés ultimes et les réponses à l'équilibre et hors équilibre est examiné. Un critère prédictif de rupture basé sur la mécanique de la rupture est proposé. Enfin, le couplage vieillissement thermique - contrainte mécanique est étudié par des essais relaxation de contraintes continues entre 130 et 170°C dans l'air. Les modifications de la microstructure pendant le vieillissement thermique sont intégrées dans les équations constitutives du modèle mécanique macroscopique afin de proposer un outil de prédiction du comportement à long terme de l'élastomère industriel. La simulation numérique montre une bonne adéquation avec les résultats expérimentaux

Vieillissement thermoélectrique d’un câble HTA : évolution des propriétés chimiques et diélectriques de l’isolant PRC

National audienc

Dielectric spectroscopy response and mechanical properties of XLPE mini-cable aged under thermal stresses

International audienc