Computer simulation modelling of polymer ageing.

Detailed information of the underlying mechanisms of macromolecular disintegration processes is not always fully available from lab-based experiments and GPC. A powerful computer simulation technique was thus indispensable in this respect whilst saving time, labour and expense. This project aims to develop an interactive computer program to capture the behaviour of a complex reactor and offer the following functionality: mathematical calculations, graph/chart generation, processing simulation-experiment pertaining to user-given scission and environmental characteristics, data saving and re-loading etc, Windows-style menu-driven interfaces provide templates for easy implementation of complex mathematical algorithms -a new simulation technique (Slider interfaces) presented in the thesis, based on cellulose-ageing study in electrical transformers (Heywood, 2000). A novel statistical concept was introduced to significantly improve real-tune performance of mathematical calculations to simulate polymer chain fragmentation phenomena, enabling transformation of the simple iterative to a semi-iterative and instant calculation algorithm. Three new mathematical functions were constructed - (a) Monte Carlo Dynamic (Slider), (b) Algebraic Exact, (c) Markov Statistical models, initially using an arbitrary time scale for degradation. Real-time simulation was developed using three time model variants that included the interpretation of deviations in the order reaction rate from linearity to an exponential type function. The above transformation enhanced reproducibility and accuracy of degraded MWD curve sampling whilst then- graphical display & clarity via 'Cubic B-Spline' smoothing-algorithm. Complex models were created from a ranking ensemble of single scission mechanisms, structured with levels of probability constructs to effectively simulate GPC-like curve-deformities and side-shifts. The simulation results provided new information in the following key areas: the temporal shift patterns of MWD/PCLD under different ageing conditions graphical comparisons between simulated and observed Idnetic and scission parameters. the dominant types of scission strategy at different reactor conditions, the dependence of reaction behaviour on the polymer structural order. An alternative way of predicting life expectancy of an ageing polymer via relating time- temperature to the magnitude of intermediate MWD curve shifts that is independent on DP. The latter is an average value and subjected to errors. An equation was derived for this. Introduction of a binary tree "death time" algorithm for calculation of the life expectancy of different categories of polymer chain species. Non-iterative techniques developed here opens up new avenues of further research. The developed algorithms and computer program may provide ample scope for investigating the ageing of other industrially important polymers and can be utilised in other areas of polymer research with little modification where probability distribution is sought