D. P. Whittle

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

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.

ENHANCED DIFFUSION OF OXYGEN DURING INTERNAL OXIDATION OF NICKEL-BASE ALLOYS

Abstract The depths of internal oxidation of Ni-Al (0.5–4 wt.%) alloys oxidized in the temperature range 800–1100°C in either Ni/NiO packs or in 1 atm oxygen are virtually independent of the alloy composition; with Ni-Cr (1–5 wt.%) alloys the depths decrease with increasing Cr content, in accord with classical theory. A model incorporating enhanced diffusion of oxygen along the incoherent interface between the internal oxide particles and the alloy matrix is proposed, since in the Ni-Al system the internal oxide particles show considerable elongation in the growth direction. In contrast, in the Ni-Cr system, the oxide particles are approximately spherical, and are not interconnected. Agreement between experiment and theory is satisfactory if the ratio of diffusion coefficients of oxygen along the interface and in the bulk lattice is of the order of 102−103. There are also differences between alloys oxidized in Ni/NiO packs, when no surface scale forms and samples oxidized in 1 atm oxygen when a surface Ni...

Improvements in oxidation resistance by dispersed oxide addition: Al2O3-forming alloys

The improvement in oxidation resistance produced by small additions of active elements to Al2O3-forming CoCrAl alloys is primarily dependent on the formation of oxide pegs which grow into the alloy around the internal oxide particles of the active element; void formation at the alloy-scale interface is also suppressed. The distribution of these pegs is critical and this paper demonstrates that an internal oxidation pretreatment can be used to convert the active element to its oxide in a controlled manner, thereby optimizing the peg distribution. Al2O3-forming CoCrAl containing 1% Hf or Ce is internally oxidized in a sealed quartz capsule containing a 50/50 powder mixture of CoAl-Al2O3; it was not possible to oxidize internally Y-containing alloys. The isothermal and cyclic oxidation resistance of these alloys is superior to that of alloys not given a prior treatment. Detailed metallographic examination indicates that the prior internal oxidation treatment produces a finer, more uniform distribution of oxide pegs penetrating into the alloy which is more efficient in combatting scale spallation. Furthermore, the lower residual hafnium content in the alloy minimizes large HfO2 precipitates and the formation of gross Al2O3 intrusions, which can initiate scale failure. Thus, by internally oxidizing the alloy first, the advantages of a high alloy Hf content (1%) in producing sufficient oxide pegs, but of the right size, coupled with minimal thickening of the surface scale, can be achieved.

The morphological and structural development of internal oxides in nickel-aluminum alloys at high temperatures

The formation and development of internal oxides in Ni-Al alloys containing 1–4 wt.% Al in Ni-NiO packs and in 1 atm oxygen at 800 to 1100°C have been studied. The internal oxide particles were relatively fine, closely spaced, and mainly acicular, although more granular near the surface. They were identified as Al2O3 at the advancing front, but NiAl2O4 at the surface and at a significant distance from that surface. Growth of internal oxide particles resulted in the development of significant compressive stresses in the internal oxide zone when formed in Ni-NiO packs. These stresses led to grainboundary sliding at the higher temperatures and extrusion of weak, internal oxide-denuded zones adjacent to alloy grain boundaries. At the lower temperatures, these stresses also resulted in significant preferential penetration of oxides down grain boundaries and sub-grain boundaries. Stress development and resulting phenomena were much less significant during oxidation in 1 atm oxygen because vacancies injected from the external NiO scale accommodated the volume increase during growth of internal oxide particles.

The high-temperature internal oxidation and intergranular oxidation of nickel-chromium alloys

Abstract The development of internal oxides and intergranular oxides in dilute NiCr alloys, containing 1–5% Cr, in NiNiO packs and in 1 atm oxygen at 800–1100°C has been investigated. The internal oxide particles were relatively coarse and widely spaced and were Cr2O3, except for a narrow band adjacent to the surface where NiCr2O4 particles were also present. Several types of intergranular oxide were developed in the Ni/NiO packs, with preferential penetration being more extensive in the higher chromium-containing alloys at the lower temperatures. Discrete intergranular oxide particles were formed deep in the alloy beneath bands of Cr2O3 which developed over intersections of the alloy grain boundaries with the surface, or beneath continuous or discontinuous grain-boundary oxides near the surface, possibly due to the development of a relatively flat oxygen profile and a steep chromium gradient in the subjacent alloy. In the presence of a thickening NiO external scale, preferential intergranular oxidation was much less extensive than in the Ni/NiO packs as the rapid growth of the scale prevented development of Cr2O3-rich surface bands.

Development of preferential intergranular oxides in nickel-aluminum alloys at high temperatures

The development of intergranular oxides in dilute Ni-Al alloys containing 0.55–4.10% Al in Ni-NiO packs and in 1 atm oxygen at 800–1100°C has been examined. In the Ni-NiO packs, preferential intergranular oxide penetration as well as internal oxidation occurs in every case, except in the higher aluminum-containing alloys at 1100°C. Several different types of intergranular oxide morphology were observed, depending on alloy aluminum concentration and on temperature. The oxides in the more dilute alloys are thin and relatively continuous and are accompanied by preferential penetration of internal oxide particles in the adjacent grains. Thicker intergranular oxides are precipitated in the more concentrated alloys while, in some situations, numerous fine oxide particles are formed well ahead of the main intergranular oxide. The intergranular oxidation is facilitated by high stress development in the specimens due to increases in volume as internal and intergranular oxides are formed. These stresses create microvoids in the grain boundaries immediately ahead of the advancing internal and intergranular oxides, resulting in preferential nucleation and growth of further intergranular oxides. This is the case particularly at the lower temperatures where other stress-relief processes cannot operate. The resulting relatively continuous, incoherent intergranular oxide-metal interface allows a high flux of oxygen to the advancing intergranular oxide front. Preferential intergranular oxidation is much less extensive in the presence of a thickening external NiO scale, due to accommodation of the volume increases on internal oxide formation by vacancies injected into the alloy from the growing cationdeficient scale.

Influence of small Pt additions on Al2O3 scale adherence

The effects of small Pt additions (1 or 3 wt.%) on the oxidation behavior of Co-10Cr-11Al and a similar alloy containing Hf have been studied. An intermetallic phase was present in the alloy containing Hf and Pt but not in that containing Pt alone. The size and distribution of the intermetallic was comparable to that of similar alloys containing oxide dispersions produced by a controlled internal oxidation treatment. As a consequence it promoted the formation of inwardly growing Al2O3 pegs that helped key the surface scale to the substrate and improve the scale-metal adhesion in both isothermal and cyclic oxidation tests. The improvement in overall oxidation resistance relative to an addition-free alloy was considerable, and similar to that of the best oxide dispersion-containing alloys.

The development of internal and intergranular oxides in nickel-chromium-aluminium alloys at high temperature

The development of internal oxides, intergranular oxides and internal voids in Ni-15.1Cr-1.1Al and Ni-28.8Cr-1.0Al during oxidation in 1 atm oxygen at 1000° to 1200°C has been studied. In both cases, the formation of an external Cr2O3-rich scale causes vacancies to be generated in the alloy due to the different diffusion rates of chromium towards the alloy-scale interface and of nickel back into the bulk alloy. At 1000°C, condensation of these vacancies at the alloy grain boundaries facilitates formation of intergranular oxides while, at 1200°C, the vacancies condense to give voids in the grains and grain boundaries. Internal oxides are formed at both temperatures. The internal and intergranular oxides are mainly α-Al2O3, although some Cr2O3-rich oxides are produced near the alloy-scale interface. Possible mechanisms for the development of the internal and intergranular oxides in these alloys are discussed and related to the observed oxide morphologies and compositions.

Oxidation of Fe-C alloys in the temperature range 600–850°C

The oxidation behavior of Fe-C alloys in the temperature range 600–850°C has been studied. CO2evolved during oxidation was measured using an infrared gas analyzer. The presence of C lowers the oxidation rate relative to that of pure Fe and this has been related to the rejection of carbon at the alloy-scale interface causing poor contact between scale and alloy. As a result, the scale contains a higher proportion of magnetite, which reduces its overall growth rate. Very little carbon is lost to the atmosphere. The ease with which the rejected carbon is incorporated into the alloy depends on the alloy structure.

THE FORMATION OF SOLID SOLUTION OXIDES DURING INTERNAL OXIDATION

The diffusion processes occurring when binary alloys react with oxygen to form an oxide that contains both alloy components in solid solution, either exclusively as internal oxide or in combination with a surface scale, have been analyzed and compared with experimental results for Fe-Mn and Ni-Co alloys. The experimental results available for the Fe-Mn system were obtained under conditions of exclusive internal oxidation, and good agreement was obtained between calculated and experimental results. In the Ni-Co system, a surface scale and a zone of internal oxidation develop. Agreement between calculated and experimental depths of internal penetration is acceptable if the diffusivity of oxygen in the alloy is 3.8×10−6 cm2/sec at 1100°C. Agreement between calculated and experimental concentration profiles is not very good.