The behaviour of antioxidants in polyolefins under conditions of U.V. exposure

The effects of antioxidants and stabilizers on the oxidative degradation of polyolefins (low density polyethylene [LDPE] and polypropylene [PPJ have been studied after subjecting to prior high temperature processing treatments. The changes in the both chemical and physical properties of unstabilized polymers occurring during processing were found to be strongly dependent on the amount of oxygen present in the mixer. Subsequent thermal and photo-oxidation showed very similar characteristics and the chromophore primarily responsible for:both thermo and photooxidative degradation of unstabilized polymers was found to be hydroperoxide formed during processing. Removal of hydroperoxide by heat treatment in an inert atmosphere although increasing ketonic carbonyl concentration, markedly decreased the rate of photo-oxidation, introducing an induction period similar to that of an unprocessed sample. It was concluded that hydroperoxides are the most important initiators in normally processed polymers during the early stages of photo-oxidation. Antioxidants such as metal dithiocarbamates which act by destroying peroxides into non-radica1 products were found to be efficient melt stabilizers for polyolefins and effective UV stabilizers during the initial photo-oxidation stage, whilst a phenolic antioxidant, n-octadecyl-3-(3',5'-di-terbutyl 4'hydroxypheny1) propionate (Irganox 1076) retarded photo-oxidation rate in the later stages. A typical 'UV absorber' 2-hydroxy-4-octyloxy-benzophenone (HOBP) has a minor thermal antioxidant action but retarded photo-oxidation at all stages. A substituated piperidine derivative, Bis [2.2.6.6-tetramethylpiperidlnyl-4] sebacate (Tinuvin 770) behaved as an pro-oxidant during thermal oxidation of polyolefins but was an effective stabilizer against UV light. The UV absorber, HOBP synergised effectively with both peroxide decomposing antioxidants (metal dithiocarbamates) and a chain-breaking antioxidant (Irganox 1076) during photo-oxidation of the poymers studed whereas the combined effect was additive during thermal oxidation. By contrast, the peroxide decornposers and chain-breaking antioxidant (Irganox 1076) which were effective synergists during thermal oxidation of LDPE· were antagonistic during photo-oxidation. The mechanisms of these processes are discussed.

Coupled heat and mass transfer in concrete exposed to fire

The first investigation of this study is concerned with the reasonableness of the assumptions related to diffusion of water vapour in concrete and with the development of a diffusivity equation for heated concrete. It has been demonstrated that diffusion of water vapour does occur in concrete at all temperatures and that the type of diffusion is concrete is Knudsen diffusion. Neglecting diffusion leads to underestimating the pressure. It results in a maximum pore pressure of less than 1 MPa. It has also been shown that the assumption that diffusion in concrete is molecular is unreasonable even when the tortuosity is considered. Molecular diffusivity leads to overestimating the pressure. It results in a maximum pore pressure of 2.7 MPa of which the vapour pressure is 1.5 MPa while the air pressure is 1.2 MPa. Also, the first diffusivity equation, appropriately named 'concrete diffusivity', has been developed specifically for concrete that determines the effective diffusivity of any gas in concrete at any temperature. In thick walls and columns exposed to fire, concrete diffusivity leads to a maximum pore pressures of 1.5 and 2.2 MPa (along diagonals), respectively, that are almost entirely due to water vapour pressure. Also, spalling is exacerbated, and thus higher pressures may occur, in thin heated sections, since there is less of a cool reservoir towards which vapour can migrate. Furthermore, the reduction of the cool reservoir is affected not only by the thickness, but also by the time of exposure to fire and by the type of exposure, i.e. whether the concrete member is exposed to fire from one or more sides. The second investigation is concerned with examining the effects of thickness and exposure time and type. It has been demonstrated that the build up of pore pressure is low in thick members, since there is a substantial cool zone towards which water vapour can migrate. Thus, if surface and/or explosive spalling occur on a thick member, then such spalling must be due to high thermal stresses, but corner spalling is likely to be pore pressure spalling. However, depending on the exposure time and type, the pore pressures can be more than twice those occurring in thick members and thought to be the maximum that can occur so far, and thus the enhanced propensity of pore pressure spalling occurring on thin sections heated on opposite sides has been conclusively demonstrated to be due to the lack of a cool zone towards which moisture can migrate. Expressions were developed for the determination of the maximum pore pressures that can occur in different concrete walls and columns exposed to fire and of the corresponding times of exposure.