Almost all laser materials processing operations require the simultaneous use of an process or assist gas. This paper examines the use of O2, Ar, N2 and He as process gasses during the firing of a vitreous enamel to form a single-stage ceramic tile grout seal with a high power diode laser (HPDL) and the effects thereof on the surface condition of the glaze. The findings revealed marked differences in the surface condition of the HPDL generated enamel glaze depending upon the process gas used. The use of O2 as the process gas was seen to result in glazes with far fewer microcracks and porosities than those generated with any of the other three gasses, particularly He. Such differences were found to be due to the ability of the smaller O2 gas molecules to dissolve molecularly into the open structure of the HPDL generated enamel glaze and also, the inherent reactiveness of O2 which consequently effects exothermic reactions when it is used as a process gas. Both occurrences were seen, in turn, to affect the cooling rate and therefore the tendency of the molten glaze to generate microcracks when cooled
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