What did we learn on the reactive element effect in chromia scale since Pfeil's patent?



Materials able to form protective chromia, Cr2O3, are most of time good candidates to be used at high temperatures in oxidizing atmospheres. Minor element additions are necessary to increase their mechanical or chemical properties. Among them, the reactive elements (RE) are highly efficient to improve the high temperature oxidation behavior of alloys. Their addition in small quantity is enough to greatly decrease the oxidation rates, but above all to drastically increase the oxide scale adherence to the base materials. That was the key point of what observed Pfeil 75 years ago. Since that date, many results have been published, many theories have been proposed, and many discussions have been engaged. Until now, the reasons why RE are so efficient are not fully understood, several hypotheses have been proposed in order to explain their beneficial effect on the oxide scale formation. According to the large amounts of published papers on this topic, there is probably no single theory envisageable to explain their role, whatever their nature, the tested materials and then the native oxide scale, as well as the nature of the oxidizing atmosphere. The decrease of the oxidation rate and the improvement of the oxide layer adherence are the final results due to RE additions. Generally, RE additions favor the nucleation and the growth of scales. They decrease the oxide grain size, and consequently could change scale plasticity and creep, which can modify the growth and/or thermal stresses generated within the scale during its growth or its cooling to room temperature. They prevent the detrimental sulfur effect and suppress dislocation climb in the metal and, then, limit cation transport (poisoned interface model). 75th Pfeil's patent anniversary seems good to make a pause in order to analyze what we really understood on the reactive element effect in chromia-forming materials.