The research involved determining the processes that occur during dye diffusion thermal transfer printing. Dye diffusion printing is a novel method of printing photo quality graphics from a personal computer. The process involves two polymer films coming into contact, one containing a dye, and the diffusion of the dye from this donor sheet onto the receiving sheet using heating elements to drive the diffusion process. In this high temperature, high pressure, and short time scale regime undesirable adhesion between the two polymer sheets is observed. It is this adhesion and its mechanisms that were investigated. Several types of homopolymers were used in.an attempt to obtain information on the processes involved in the adhesion of the two films during the printing stage. Initially dyes were absent from the polymer films to examine the polymer adhesion alone. It was hoped that the principal factors involved in the unusual joint forming conditions could be explained. The unusual conditions are high heat (250°C) and short time span (10-15 milliseconds). Polystyrene, poly (methyl methacrylate) and poly (vinyl acetate) were chosen to determine the effect of Glass Transition Temperature (T g), surface energies and molecular weight on the polymer adhesion. Initial results showed that the adhesion was a complex system. but it became clear that the t g of the polymers and the presence of small molecules and contaminants· were very important. Work with commercial polymers was undertaken to transfer the knowledge gained from the homopolymers to the more complicated commercial systems using poly (vinyl. chloride) and poly (vinyl butyral). To expand the understanding of the results small molecules and dyes were added to these commercial polymers to examine their effects. The surface of the samples were analysed using X-ray Photoelectron Spectroscopy (XPS) and Fourier Transform Infrared Spectroscopy (FTIR). This was used to determine if there was any migration of the small molecules to the surface of the polymer films. It was also useful in indicating the location of the dyes and how much penetration into the polymers is achieved by them. Atomic Force Microscopy (AFM) was implemented to analyse the surface morphology and gave an insight into the mechanism of the small molecule migration. The conclusions drawn were that the presence of small molecules had significant affect on the adhesion of the polymers. Compatible small molecules would act as plasticisers and lower the T g of the polymers giving rise to higher adhesion. Small molecules that were incompatible were found to migrate to the surface in large quantities and would act as weak boundary layers, significantly reducing the adhesion. Work in this area has shown that an autolayering mechanism is occurring that may be useful in producing a release mechanism for the commercial products.