Radical polymerisation (RP) has for many years been an industrially important process, and the kinetics of the process remains an active area of research. As polymerisation proceeds, converting monomer (small molecules) into polymer (long chain molecules), chemical species of a variety of chain lengths are produced. Recent work has pointed toward the fact that rate coefficients for polymerisation reactions (specifically, termination and propagation) are often dependent on the chain-length of the reacting species. The focus of this thesis is to study the effects of chain-length-dependent reactions on the kinetics of RP, by using computer-based modeling and comparing the results of such modeling with experimental data. This enables the understanding of otherwise inexplicable trends and the building of more mechanistically detailed and accurate models for RP kinetics. In Chapter 2, a new model for termination is developed, connecting observations and analyses of termination kinetics at short chain lengths (particularly small molecule studies) with other observations and analyses at long chain lengths (conventional RP kinetics studies) in order to construct a model for termination that is shown to be capable of coherently describing termination kinetics at any chain length. In Chapter 3, this new model for termination is tested at short chain lengths on polymerisations with large quantities of added chain transfer agent. With the inclusion of chain-length-dependent propagation in the model, the model for termination is validated. Chapter 4 is aimed at extending an existing reduced-variable, compact, 'universal' description of steady-state RP kinetics by incorporating all known chain-length dependent reactivities. This both increases computational efficiency over other approaches and provides easily evaluated, approximate analytical expressions for RP kinetics. This foundational theory is applied in Chapter 5 to reach a deeper understanding of the behaviour of the model, and show how experimental data may readily be analysed to extract information about chain-length-dependent termination kinetics. In Chapter 6, the effect of chain-length dependent reactivities on the important technique of single-pulse pulsed-laser polymerisation is investigated, and this technique is validated as the best experimental method for investigation of termination kinetics. In general, a central result of this thesis is that chain-length-dependent reactivities, when acknowledged and properly incorporated into models, can explain many phenomena in RP kinetics which otherwise seem difficult to account for. No exceptions to this principle have been found.

Radical polymerisation (RP) has for many years been an industrially important process, and the kinetics of the process remains an active area of research. As polymerisation proceeds, converting monomer (small molecules) into polymer (long chain molecules), chemical species of a variety of chain lengths are produced. Recent work has pointed toward the fact that rate coefficients for polymerisation reactions (specifically, termination and propagation) are often dependent on the chain-length of the reacting species. The focus of this thesis is to study the effects of chain-length-dependent reactions on the kinetics of RP, by using computer-based modeling and comparing the results of such modeling with experimental data. This enables the understanding of otherwise inexplicable trends and the building of more mechanistically detailed and accurate models for RP kinetics. In Chapter 2, a new model for termination is developed, connecting observations and analyses of termination kinetics at short chain lengths (particularly small molecule studies) with other observations and analyses at long chain lengths (conventional RP kinetics studies) in order to construct a model for termination that is shown to be capable of coherently describing termination kinetics at any chain length. In Chapter 3, this new model for termination is tested at short chain lengths on polymerisations with large quantities of added chain transfer agent. With the inclusion of chain-length-dependent propagation in the model, the model for termination is validated. Chapter 4 is aimed at extending an existing reduced-variable, compact, 'universal' description of steady-state RP kinetics by incorporating all known chain-length dependent reactivities. This both increases computational efficiency over other approaches and provides easily evaluated, approximate analytical expressions for RP kinetics. This foundational theory is applied in Chapter 5 to reach a deeper understanding of the behaviour of the model, and show how experimental data may readily be analysed to extract information about chain-length-dependent termination kinetics. In Chapter 6, the effect of chain-length dependent reactivities on the important technique of single-pulse pulsed-laser polymerisation is investigated, and this technique is validated as the best experimental method for investigation of termination kinetics. In general, a central result of this thesis is that chain-length-dependent reactivities, when acknowledged and properly incorporated into models, can explain many phenomena in RP kinetics which otherwise seem difficult to account for. No exceptions to this principle have been found.

This thesis sought to lay the foundation for an application for tracking K-12 teacher activities. Its primary contribution is a descriptive model of K-12 activities. The work's starting point, the Faculty Activities System project, is an ETSU initiative that seeks to produce a tool for university-level academic accountabilities management. It was possible to adapt the FAS project's data model for K-12 activities. The resulting model was validated by experts in the field of education and teachers and administrators across Tennessee. A second strategy for model validation, using national and state legislation and expert recommendations, determined that the model did well at capturing teachers' professional growth and contributions to the school and community, but fell short at capturing student improvement, the learning environment, teaching strategies, portfolios, and self-assessment. The data model was realized as a multi-file XML schema, which was tested for well-formedness and validity using a sample data document.