The addition of reactive elements can have a significant effect on the oxidation behavior of alumina- and chromia-forming alloys. A model has been developed to explain the effects associated with the addition of reactive elements that is based on the segregation of reactive-element ions to scale grain boundaries and the metal-oxide interface. Reactive-element ions use these interaces as pathways for diffusion from the metal substrate to the gas interface of the scale. The driving force for this outward diffusion is the oxygen potential gradient across the scale. Doping of the scale grain boundaries results in scale growth primarily by inward oxygen diffusion, while doping at the metal-oxide interface slows the growth of interfacial voids and thus improves scale adhesion.

Experimental observations in support of the dynamic-segregation theory to explain the reactive-element effect

Currentunderstanding of the complex interrelationships among growth kinetics, microstructure, and adhesion of protective Cr2O3 and Al2O3 scales is critically reviewed. Similarities and differences in the behavior of these two systems are highlighted. The morphology of the alloy-scale interface appears to be a critical factor. Recent ideas are advanced to interpret the effect of oxygen-active elements on the development of a tortuous interface conducive to improved scale tenacity.

/pdf/microstructure-adhesion-and-growth-kinetics-of-protective-2v2aeq1h8a.pdf

Microstructure, adhesion and growth kinetics of protective scales on metals and alloys

The oxidation behavior of an Fe-27%Cr-4%Al alloy and similar alloys containing 0.023% and 0.82% Y in 1 atm oxygen at 1200°C has been examined. The oxide formed on the yttrium-free alloy develops a highly convoluted configuration, apparently resulting from lateral growth of the oxide. The latter leads to oxide detachment from the alloy at temperature and extensive spalling during cooling. It is postulated that lateral growth results from the formation of oxide within the existing oxide layer by reaction between oxygen diffusing inward down the oxide grain boundaries and aluminum diffusing outward through the bulk oxide. Additions of yttrium to the alloy apparently prevent the formation of oxide within the oxide layer, the oxide-forming reaction occurring as the alloy-oxide interface. Thus lateral growth is prevented and spalling during cooling does not occur. Secondary advantages conferred by the addition of 0.82% Y to the alloy are the prevention of void formation at the alloy-oxide interface, the avoidance of alloy grain growth during oxidation, and the creation of an oxide “keying” or “pegging” effect.

The influence of yttrium additions on the oxide-scale adhesion to an iron-chromium-aluminum alloy

Some recent developments in the understanding of the oxidation of alloys at elevated temperatures are reviewed, with special reference to binary and ternary alloys upon which many commercial materials are based. Following an initial classification of alloy systems, certain basic principles and their limitations are considered, including factors determining whether an alloy displays surface scaling only, internal oxidation only, or both phenomena; the mode of distribution of cations in an oxide solid solution growing on an alloy; and doping and the Wagner-Hauffe rules. Previous alloy oxidation theory has concerned itself principally with steady-state oxidation but, in practice, behavior of the oxidizing sample in approaching the steady state, both upon initial exposure to the environment and after scale spalling induced isothermally or during thermal cycling, is often as important. Such behavior is illustrated in terms of scale establishment and with respect to compositional changes in the subjacent alloy, the importance of certain alloy and oxide properties being emphasized. After further brief consideration of steady-state scaling, the causes and consequences of breakaway oxidation are presented. The role of major and minor concentrations of third elements on scaling behavior is discussed. The paper concludes with brief reference to situations not considered in detail and with aspects requiring further study.

High-temperature oxidation of alloys

Reactive element additions may promote the formation of protective oxide scales on high temperature alloys, and improve long term oxidation resistance by limiting the rate of scale growth and inhibiting scale failure processes. Various modifications to transport properties and mechanical behaviour have been proposed to explain the observed benefits. These mechanisms are reviewed with reference to available experimental evidence. Key steps in enhancing oxidation resistance are probably the provision of reactive element oxide particles for incorporation into a scale and consequent segregation of reactive element ions to high diffusivity pathways and interfaces. Such behaviour is consistent with known variations in protection resulting from changes in reactive element type, concentration, and initial distribution.MST/1055

J. Boustead

Papers

The identification of thin healing layers at the base of oxide scales on FeCr base alloys

The influence of group IIIA metals on the oxidation of Fe-Cr alloys