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In this work, we used mass spectrometry to investigate ammonia (NH 3) formed during the nitrocarburizing and nitriding processes of α-Fe sintered and low alloy steel by using d.c. glow discharges in different N 2 /H 2 /CH 4 gas concentration mixtures. Experiments were conducted using two different configurations: one to collect and analyze species probed primarily in the bulk of the plasma, at a position distant from the heated sample; and the other to collect and analyze species very close to the reactive surface of the heated sample in such a way as to allow the analysis of lower concentration or residence time species, formed at the plasma/sample surface interface. Use of these configurations contributed to the investigation of the physical chemistry involved in the above plasma processes. An exchange the expected stoichiometry in ammonia formation in N 2 /H 2 /CH 4 mixtures, with a shift towards higher nitrogen consumption, is observed and is interpreted an indication of nitrogen removal from the surface associated with ammonia and carbonitrides/nitrides formation. The present results point to the existence of a correlation between the nitrocarburizing and nitriding processes with respect to the formation of non-stoichiometric ammonia as a product.

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