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The DSpace digital repository system captures, stores, indexes, preserves, and distributes digital research material.Fri, 23 Feb 2024 06:32:11 GMT2024-02-23T06:32:11ZA new analytical model for predicting the thermal oxidation kinetics of composite organic m atrices. Application to diamine cross-linked epoxy
http://hdl.handle.net/10985/19940
A new analytical model for predicting the thermal oxidation kinetics of composite organic m atrices. Application to diamine cross-linked epoxy
ESSATBI, Fatima; DELOZANNE, Justine; MOREAU, Gurvan; COLIN, Xavier
The system of differential equations derived from the so-called “closed-loop” mechanistic scheme was solved analytically by applying realistic proportionality assumptions between the different concentrations of reactive species during the entire course of the thermal oxidation. This new method of analytical resolution allowed obtaining a sounder kinetic model accurately describing the three first stages of the thermal oxidation kinetics: the induction period, the auto-acceleration of the oxidation kinetics at the end of the induction period, and the steady-state regime. This kinetic model was used to identify the thermal oxidation behavior at 120 and 150°C in a large range of oxygen partial pressures (typically between 0.21 and 10 bars) of two epoxy-diamine (EPO-DA) matrices. In addition, the kinetic model was used to determine the accelerated aging conditions representative of the cruising flight of a commercial airliner. It was found that the oxygen partial pressure must be increased much more than the temperature to avoid any deformation of the structural degradation state in the two EPO-DA matrices, thus leading to the definition of extreme environmental conditions very difficult to access in practice.
Fri, 01 Jan 2021 00:00:00 GMThttp://hdl.handle.net/10985/199402021-01-01T00:00:00ZESSATBI, FatimaDELOZANNE, JustineMOREAU, GurvanCOLIN, XavierThe system of differential equations derived from the so-called “closed-loop” mechanistic scheme was solved analytically by applying realistic proportionality assumptions between the different concentrations of reactive species during the entire course of the thermal oxidation. This new method of analytical resolution allowed obtaining a sounder kinetic model accurately describing the three first stages of the thermal oxidation kinetics: the induction period, the auto-acceleration of the oxidation kinetics at the end of the induction period, and the steady-state regime. This kinetic model was used to identify the thermal oxidation behavior at 120 and 150°C in a large range of oxygen partial pressures (typically between 0.21 and 10 bars) of two epoxy-diamine (EPO-DA) matrices. In addition, the kinetic model was used to determine the accelerated aging conditions representative of the cruising flight of a commercial airliner. It was found that the oxygen partial pressure must be increased much more than the temperature to avoid any deformation of the structural degradation state in the two EPO-DA matrices, thus leading to the definition of extreme environmental conditions very difficult to access in practice.Towards a general kinetic model for the thermal oxidation of epoxy-diamine networks. Effect of the molecular mobility around the glass transition temperature
http://hdl.handle.net/10985/19198
Towards a general kinetic model for the thermal oxidation of epoxy-diamine networks. Effect of the molecular mobility around the glass transition temperature
ESSATBI, Fatima; DELOZANNE, Justine; MOREAU, Gurvan; COLIN, Xavier
The kinetic model previously established for describing the thermal oxidation of polymethylenic substrates has been successfully generalized to a series of six epoxy-diamine networks (EPO-DA) characterized by very different glass transition temperatures. This model is derived from the so-called “closed-loop” mechanistic scheme which consists in a radical chain reaction initiated by the decomposition of hydroperoxides and propagating via the C-H bonds located in α of heteroatoms (N and O). The numerous model parameters were determined by applying a “step by step” procedure combining experiment and simulation. On the one hand, oxygen transport properties (i.e. coefficients of oxygen diffusion and solubility) were estimated from a compilation of literature data. On the other hand, rate constants and formation yields were determined by inverse solving method from the measurements of oxygen consumption and carbonyl build-up performed on six different EPO-DA networks between 25 and 200 °C and between 0.16 and 20 bars of oxygen partial pressure in our laboratory or in the literature. It was found that the molecular mobility mainly affects the rate constants of the elementary reactions involving the reactive species in the lowest concentration, i.e. peroxy radicals. In fact, the rate constant k6 of the apparent termination of peroxy radicals is reduced by about five orders of magnitude when passing from rubbery to glassy state due to the freezing of large amplitude cooperative molecular movements. In contrast, the rate constant k3 of the propagation of oxidation, involving peroxy radicals but also the polymer substrate, is only changed by one order of magnitude around the glass transition temperature. The introduction of the effect of molecular mobility into the Arrhenius laws of k6 and k3 allows building master curves and finally, proposing a single kinetic model for the whole family of EPO-DA networks.
Wed, 01 Jan 2020 00:00:00 GMThttp://hdl.handle.net/10985/191982020-01-01T00:00:00ZESSATBI, FatimaDELOZANNE, JustineMOREAU, GurvanCOLIN, XavierThe kinetic model previously established for describing the thermal oxidation of polymethylenic substrates has been successfully generalized to a series of six epoxy-diamine networks (EPO-DA) characterized by very different glass transition temperatures. This model is derived from the so-called “closed-loop” mechanistic scheme which consists in a radical chain reaction initiated by the decomposition of hydroperoxides and propagating via the C-H bonds located in α of heteroatoms (N and O). The numerous model parameters were determined by applying a “step by step” procedure combining experiment and simulation. On the one hand, oxygen transport properties (i.e. coefficients of oxygen diffusion and solubility) were estimated from a compilation of literature data. On the other hand, rate constants and formation yields were determined by inverse solving method from the measurements of oxygen consumption and carbonyl build-up performed on six different EPO-DA networks between 25 and 200 °C and between 0.16 and 20 bars of oxygen partial pressure in our laboratory or in the literature. It was found that the molecular mobility mainly affects the rate constants of the elementary reactions involving the reactive species in the lowest concentration, i.e. peroxy radicals. In fact, the rate constant k6 of the apparent termination of peroxy radicals is reduced by about five orders of magnitude when passing from rubbery to glassy state due to the freezing of large amplitude cooperative molecular movements. In contrast, the rate constant k3 of the propagation of oxidation, involving peroxy radicals but also the polymer substrate, is only changed by one order of magnitude around the glass transition temperature. The introduction of the effect of molecular mobility into the Arrhenius laws of k6 and k3 allows building master curves and finally, proposing a single kinetic model for the whole family of EPO-DA networks.