This work deals with the elucidation of the mode of action of polyols used to stabilise PA66 against thermal oxidation above 200°C, using dipentaerythritol as an example polyol. Light microscopic investigations showed the acceleration of the formation of the degraded surface layer by DPE and an increased abrasion stability of the degraded layer. This results in slower degraded layer growth due to the resulting higher oxygen diffusion limitation. In glass fibre reinforced PA66, this is further enhanced by the synergistic effect of the polyol stabilisation with the glass fibre reinforcement by increasing fibre-matrix adhesion and hence reduced debonding and surface cracking. The higher fibre-matrix adhesion also results in an enhancement of the nucleating effect of the fibre and thus higher crystallinity and smaller crystallites, further increasing the oxygen diffusion limitation. The torsional force curves during compounding, the lower molecular weight of DPE-stabilised compared to unstabilised PA66, the mechanical properties as well as the complete extractability of DPE from unreinforced PA66 after processing proved that DPE does not react with the polyamide during compounding under vacuum. Instead, increased degradation by hydrolysis occurs due to the higher moisture content. In contrast, chain extension or cross-linking reactions of the polyol with the oligomeric degradation products of PA66 during ageing were demonstrated by molar mass analysis as well as the extractable fraction of DPE. By comparing erythritol, dipentaerythritol and a novolak, it was shown that these reactions depend significantly on the reactivity of the hydroxyl groups and thus on the structure of the polyol. Secondary hydroxyl groups have a significantly lower reactivity than primary hydroxyl groups and therefore lead to a slower and steadier increase in molecular weight. Aromatic hydroxyl groups, however, do not lead to chain extension reactions with the degradation products, instead aromatic polyols act as a primary antioxidants. Due to the higher oxygen diffusion limitation in glass fibre reinforced PA66, the chain extension reactions are shifted to longer ageing times due to the lower concentration of degradation products. In addition, the essential influence of the hygroscopy of the polyol and the associated entrained moisture was demonstrated. Light microscopic examinations of unconditioned samples, samples conditioned in a standard climate and water-stored samples showed a clear increase in the degraded layer thickness at the beginning of ageing with increasing moisture content due to the additional hydrolysis. By means of differential calorimetry, an increase in crystallinity due to water-induced crystallisation at the beginning of ageing and increased post-crystallisation in the first hours of ageing were also documented. Overall, the oxygen diffusion limitation is thus significantly increased by the introduced moisture. With additional conditioning, these effects are significantly stronger due to the higher moisture contents and thus lead to a delay of the chain extension reactions of DPE with the thermo-oxidative degradation products of PA66 to later ageing times. However, due to the rapid evaporation at 200°C, the humidity only plays a role up to about 8 h of ageing, after which only the effects due to the higher crystallinity and edge layer thickness remain. Lastly, it was proven that co-stabilisation with a copper stabiliser does not change the mode of action of the polyol at 200°C, but only leads to a delay of the chain extension reactions of DPE with the degradation products due to the reduced thermo-oxidation. The influence of DPE on the formation and growth of the degraded layer does not change either, although higher degraded layer thicknesses are obtained due to the low decomposition rate in the presence of the copper stabiliser. At 200°C, the molecular weight and the retention of mechanical properties showed that the copper stabiliser alone only slightly reduced chain scission, while the combination of DPE and copper stabiliser significantly reduced chain scission. At 150°C the addition of DPE only led to a reduction in thermo-oxidative chain scission from 1500 h of ageing compared to the purely copper-stabilised compound. | English |