When you raise the pressure the boiling point of water increases which makes steam which is hotter than 100C. This is not 'superheated' because it is still at the boiling point (which is raised by pressure). This will condense on things inside the autoclave and dump the its heat into the thing killing anything on it. If you superheat the steam it is just as effective as air, which is to say not very. If you want to know more than that, you need to ask someone else, because that's about the extent of my knowledge.