Ageing of PVC for outdoor applications: role of water and inorganic fillers

Abstract

In most of polymer ageing studies conducted at laboratory, there is a trend to underestimate some of the parameters involved in natural exposure, leading to poor simulation results and low reliability of the real world phenomena. Moreover, the nature of polymer and its formulation should be taken into account due to possible synergies and antagonisms between environment and polymer additives. Among the underestimated parameters, we can stress the role of ambient humidity and inorganic fillers. These additives are usually considered to be inert regarding the degradation induced by radiation. In this work, four different PVC formulations, designed for outdoor applications, in the form of calendered films were submitted to artificial accelerated ageing under different radiation sources, without and with spray of water, and to natural exposure. The influence of the different photo-oxidation conditions was evaluated by means of Xray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIRS). The photo-oxidation of PVC can be studied by FTIR measurements following the formation of oxidation products of carbonyl type, due to radical attack to the double bonds in the molecular structure of PVC, enhanced by radiation and temperature. Results have shown that relative rates of PVC degradation reactions are different under different photo-oxidative conditions. XPS results show that, in technical PVC formulations, the fraction of chloride ion trapped in the inorganic filler is a better parameter to measure the PVC degradation (measured by the yellowing index variation) than the amount of total remaining (or lost) chlorine in the surface. When the ageing method includes water jets, the top superficial layer made from the inorganic filler and the organic products from the PVC degradation is removed and leaves behind a much more homogeneous layer which is more resistant towards ageing than the “as processed” one that contains defects introduced by the calendering process. XPS also makes clear that zinc-calcium additive is a better thermal stabilizer than the dibutyltinmaleate and the presence of the tinuvin P retards the PVC degradation. The best simulation of the natural weathering of such PVC materials in laboratory conditions needs to consider, besides the light, the intervention of water jets and/or humidity as well as the existence of light and dark periods.