Computational modeling of polymerization and degradation of complex polymer systems

Oil paintings are complex works of art, even on the molecular level. This chemistry can be captured in a computational model and used to study polymer films through non-invasive means. However, there are numerous challenges in simulating how the complex polymers like those in painted works cure and degrade, mainly regarding the balance of tractability and accuracy of different computational models.
In this dissertation, a key thread is the application of modeling techniques and the limits and advantages of different methods. Especially when dealing with complex chemical systems, it is imperative to consider the bounds and the objectives of a problem, as different methods can focus on certain measures of interest. Art inspires the pursuit of technical solutions found in the complex problems related to cultural heritage science.
Following an introduction, Chapter 2 summarizes the chemistry and state of the field for studying oil paint and its model systems. Chapter 3 is oriented in the broader polymer reaction engineering field studying the pyrolysis-induced depolymerization of polyethylene and polypropylene with global and mechanistic models. Drying oil chemistry is considered in Chapter 4 with an existing model for the autoxidation of ethyl linoleate (EL) that is extended and used to estimate kinetic parameters based on data from experiments of artificially accelerated drying of EL. Finally, Chapter 5 describes a new multifunctional, mechanistic model that combines automated reaction network generation with graph theory and stochastic simulation for a generic system and then applied to EL autoxidation.