Investigation of the oxidative degradation mechanisms and melt stabilisation of a new generation metallocene polytehylene

The two main objectives of the research work conducted were firstly, to investigate the processing and rheological characteristics of a new generation metallocene catalysed linear low density polyethylene (m-LLDPE), in order to establish the thermal oxidative degradation mechanism, and secondly, to examine the role of selected commercial stabilisers on the melt stability of the polymers. The unstabilised m-LLDPE polymer was extruded (pass I) using a twin screw extruder, at different temperatures (210-285°C) and screw speeds (50-20rpm) and was subjected to multiple extrusions (passes, 2-5) carried out under the same processing conditions used in the first pass. A traditional Ziegler/Natta catalysed linear low density polyethylene (z-LLDPE) produced by the same manufacturer was also subjected to a similar processing regime in order to compare the processability and the oxidative degradation mechanism (s) of the new m-LLDPE with that of the more traditional z-LLDPE. The effect of some of the main extrusion characteristics of the polymers (m-LLDPE and z-LLDPE) on their melt rheological behaviour was investigated by examining their melt flow performance monitored at two fixed low shear rate values, and their rheological behaviour investigated over the entire shear rates experienced during extrusion using a twin-bore capillary rheometer. Capillary rheometric measurements, which determine the viscous and elastic properties of polymers, have shown that both polymers are shear thinning but the m-LLDPE has a higher viscosity than z-LLDPE and the extent of reduction in viscosity of the former when the extrusion temperature was increased from 210°C to 285°C was much higher than in the case of the z-LLDPE polymer. This was supplied by the findings that the m-LLDPE polymer required higher power consumption under all extrusion conditions examined. It was fUliher revealed that the m-LLDPE undergoes a higher extent of melt fracture, the onset of which occurs under much lower shear rates than the Ziegler-based polymer and this was attributed to its higher shear viscosity and narrower molecular weight distribution (MWD). Melt flow measurements and GPC have shown that after the first extrusion pass, the initial narrower MWD of m-LLDPE is retained (compared to z-LLDPE), but upon further multiple extrusion passes it undergoes much faster broadening of its MWD which shifts to higher Mw polymer fractions, paliicularly at the high screw speeds. The MWD of z-LLDPE polymer on the other hand shifts towards the lower Mw end. All the evidence suggest therefore the m-LLDPE undergoes predominantly cross-linking reactions under all processing conditions whereas z-LLDPE undergoes both cross-linking and chain scission reactions with the latter occurring predominantly under more severe processing conditions (higher temperatures and screw speeds, 285°CI200rpm). The stabilisation of both polymers with synergistic combinations of a hindered phenol (Irganox 1076) and a phosphite (Weston 399) at low concentrations has shown a high extent of melt stabilisation in both polymers (extrusion temperatures 210-285°C and screw speeds 50-200rpm). The best Irganox 1076/Weston 399 system was found to be at an optimum 1:4 w/w ratio, respectively and was found to be most effective in the z-LLDPE polymer. The melt stabilising effectiveness of a Vitamin E/Ultranox 626 system used at a fraction of the total concentration of Irganox 1076/Weston 399 system was found to be higher in both polymers (under all extrusion conditions). It was found that AOs which operate primarily as alkyl (Re) radical scavengers are the most effective in inhibiting the thermal oxidative degradation of m-LLDPE in the melt; this polymer was shown to degrade in the melt primarily via alky radicals resulting in crosslinking. Metallocene polymers stabilised with single antioxidants of Irganox HP 136 (a lactone) and Irganox E201 (vitamin E) produced the highest extent of melt stability and the least discolouration during processing (260°C/1 OOrpm). Furthermore, synergistic combinations of Irganox HP I 36/Ultranox 626 (XP-60) system produced very high levels of melt and colour stability (comparable to the Vitamin E based systems) in the mLLDPE polymer. The addition of Irganox 1076 to an Irganox HP 136/Ultranox 626 system was found not to result in increasing melt stability but gave rise to increasing discolouration of the m-LLDPE polymer. The blending of a hydroxylamine (lrgastab FS042) with a lactone and Vitamin E (in combination with a phosphite) did not increase melt stability but induced severe discolouration of resultant polymer samples.

Viscosity of aged bio-oils from fast pyrolysis of beech wood and miscanthus:shear rate and temperature dependence

The viscosity of four aged bio-oil samples was measured experimentally at various shear rates and temperatures using a rotational viscometer. The experimental bio-oils were derived from fast pyrolysis of beech wood at 450, 500, and 550 °C and Miscanthus at 500 °C (in this work, they were named as BW1, BW2, BW3, and MXG) in a bubbling fluidized bed reactor. The viscosity of all bio-oils was kept constant at various shear rates at the same temperature, which indicated that they were Newtonian fluids. The viscosity of bio-oils was strongly dependent upon the temperature, and with the increase of the temperature from 30 to 80 °C, the viscosity of BW1, BW2, BW3, and MXG decreased by 90.7, 93.3, 92.6, and 90.2%, respectively. The Arrhenius viscosity model, which has been commonly used to represent the temperature dependence of the viscosity of many fluids, did not fit the viscosity-temperature experimental data of all bio-oils very well, especially in the low- and high-temperature regions. For comparison, the Williams-Landel-Ferry (WLF) model was also used. The results showed that the WLF model gave a very good description of the viscosity-temperature relationship of each bio-oil with very small residuals and the BW3 bio-oil had the strongest viscosity-temperature dependence.