Embrittlement processes occurring during thermal oxidation are investigated for stabilized and unstabilized polyamide 11 samples differing by their thicknesses and initial molar masses. Tensile tests were carried out in the temperature range between room temperature and 110 C in order to investigate the influence of mechanical testing temperature on the embrittlement coordinates. In the same time, molar mass and crystalline morphology are monitored by size exclusion chromatography (SEC) and DSC/SAXS measurements respectively. The experimental results point out the existence of a critical molar mass for ductile-brittle transition M 0 c about 10 kg mol À1 , independent of sample initial molar mass or stabilization, but depending on tensile testing temperature. However, even if oxidation chain scissions are shown to be clearly responsible for the loss of mechanical properties at failure, the structure-property relationships governing ductile-brittle transition require a mixed criterion involving molar mass and crystalline morphology, especially the interlamellar distance. For this purpose, specific molar mass e crystalline morphology relationships are investigated.

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. products. The ratio of carbonyl groups over chain scissions is about 7.5 at low conversions and about 2.5 at high conversions, showing that α amino alkoxy radicals are mainly transformed into imides without chain scission.

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. To cite this version :Emmanuel RICHAUD, Octavie OKAMBA-DIOGO, Bruno FAYOLLE, Jacques VERDU, Jean GUILMENT, François FERNAGUT -Review : Auto-oxidation of aliphatic polyamides -Polymer Degradation and Stability -Vol. 98, p.1929 -1939-2013 Any correspondence concerning this service should be sent to the repository The literature on oxidation kinetics of polyamides and model compounds has been reviewed in order to try to extract suitable information for non-empirical kinetic modeling. Polyamide characteristics are systematically compared to polyolefin ones, these latter being more extensively studied. From kinetic analysis point of view, it is shown that oxidation attacks predominantly a amino methylenes of which C eH bond is considerably weaker than the other methylenes. As a result, propagation by H abstraction is considerably faster in polyamides than in polyethylene for instance. Termination by radical combination is also very fast. Another cause of PA oxidizability is the instability of a amino hydroperoxides linked to the inductive effect of nitrogen. This instability is responsible for many key features of oxidation kinetics especially the absence of induction period.The main stable oxidation products are imides resulting from disproportionation processes meanwhile chain scissions resulting from rearrangements of a amino alkyls by b-scission are also significant process although their yield appears lower than in polyolefins.

The oxidation kinetics of unstabilized polyamide 11 thin film under oxygen pressures up to 2.0 MPa was studied by means of ferrous ion method for hydroperoxides titration, size exclusion chromatography (SEC) for molar weight measurements and in situ FTIR monitoring for carbonyl build up. Oxidation was shown not to be limited by oxygen diffusion which militates in favor of the use of a simple kinetic model for simulating experimental data. The kinetic parameters of this model were estimated from literature for initiation and propagation, and from selective experiments such as ageing under several oxygen pressures for the estimation of the termination rate constants, or exposures under inert atmosphere to investigate the solid state polymerization effects and tentatively check the boundary conditions of the model. The kinetic model simulates satisfyingly the overall experimental results using the minimal number of adjustable parameters (except for some reactions difficult to be experimentally isolated and studied).

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