The influence of grain-boundary segregation of Y in Cr2O3 on the oxidation of Cr metal. II. Effects of temperature and dopant concentration

The oxidation behavior of pure Cr and Cr implanted with Y was studied as a function of temperature (900 and 1025°C) and ion-implantation dose (1×10¹⁵ and 2×10¹⁶ Y ions/cm²). The microstructures of the Cr₂O₃ scales were affected by both of the variables studied. Yttrium ions segregated at the grain boundaries in the Cr₂O₃ scales formed on the implanted alloys and the concentration of Y at the grain boundaries decreased with a decrease in the dose of implanted Y. The mechanism of growth of the Cr₂O₃ scales was altered by the presence of the Y ions at the Cr₂O₃ grain boundaries only when a critical concentration of Y at the grain boundaries was exceeded.     

Diffusion of18O in massive Cr2O3 and in Cr2O3 scales at 900°C and its relation to the oxidation kinetics of chromia forming alloys

The lattice and grain-boundary diffusion coefficients of¹⁸O atP _{O 2}=0.1 atm and at 900°C were determined in massive Cr₂O₃ and in Cr₂O₃ scales which were grown on a Ni–30Cr alloy. The diffusion profiles were established by SIMS and analyzed considering two domains in the case of polycrystalline Cr₂O₃ (massive or scales), the first one relative to apparent diffusion and the second to grain-boundary diffusion. A ridge model is proposed for Cr₂O₃ scales to modify thef value, fraction of sites associated with the grain boundary. With such a model,f is equal to 0.0006 and 0.0005 for the scales formed during 15 hr and 165 hr, respectively. The oxygen-lattice diffusion coefficients determined in Cr₂O₃ scales are in very good agreement with those in massive Cr₂O₃. With some assumptions, our diffusion data lead to a calculated parabolic oxidation constant equal to the experimental one. Scale growth occurs by countercurrent diffusion of oxygen and chromium, mainly by grain-boundary diffusion.     

Effect of Y2O3 additions on the plasticity of sintered Cr2O3

We have carried our constant strain-rate compression tests on polycrystalline Cr₂O₃ and Cr₂O₃ doped with 0.09 wt. % Y₂O₃ to establish whether there exists an effect of Y₂O₃ on the plasticity of Cr₂O₃. This study is motivated by previous work on the oxidation of alloys containing reactive-element additions. In that work, it has been observed that the addition of oxygen-active elements, such as Y to alloys that form Cr₂O₃ or Al₂O₃ oxide layers upon exposure at high temperature, strongly enhances the adhesion of the oxide layer to the base alloy as compared with alloys without reactive-element additions. We have found that at 1200°C (1) chromia exhibits limited plasticity at high temperatures, and (2) the presence of Y in the oxides does not enhance plasticity compared with addition-free oxides.     

Reactive-element effect of electrodeposited Y2O3 oxide films on the oxidation of Fe−25Cr and Fe−25Cr−10Al alloys

Thin Y₂O₃ films were deposited by the electrochemical deposition-pyrolysis process on Fe–25Cr and Fe–25Cr–10Al alloys. The influence of the films on the oxidation behavior of the alloys was studied at 850°C and 1000°C. The results showed that Y₂O₃ films remarkably decreased the oxidation rate of Cr₂O₃-forming alloys and spallation of the scales, but they did not decrease the oxidation rate of the Al₂O₃-forming alloys, although they do reduce the spallation of Al₂O₃ scales. Y₂O₃ films remarkably change the morphology of the scales on both alloys, depending on the oxidation temperatures. These results show that the reactive-element effects of Y₂O₃ films on the Cr₂O₃ formers and Al₂O₃ formers are different.     

The influence of reactive-element coatings on the high-temperature oxidation of pure-Cr and high-Cr-content alloys

The influence of various reactive-element (RE) oxide coatings (Y₂O₃, CeO₂, La₂O₃, CaO, HfO₂, and Sc₂O₃) on the oxidation behavior of pure Cr, Fe–26Cr, Fe–16Cr and Ni–25Cr at 900°C in O₂ at 5×10^–3 torr has been investigated using the¹⁸O/SIMS technique. Polished samples were reactively sputtercoated with 4 nm of the RE oxide and oxidized sequentially first in¹⁶O₂ and then in¹⁸O₂. The effectiveness of each RE on the extent of oxidation-rate reduction varied with the element used. Y₂O₃ and CeO₂ coatings were found to be the most beneficial, whereas Sc₂O₃ proved to be ineffective, for example, for the oxidation of Cr. SIMS sputter profiles showed that the maximum in the RE profile moved away from the substrate-oxide interface during the early stages of oxidation. After a certain time the RE maximum remained fixed in position with respect to this interface, its final relative position being dependent on the particular RE. The position of the RE maximum within the oxide layer also varied with the substrate composition. For all coatings¹⁸O was found to have diffused through the oxide to the substrate-oxide interface during oxidation, the amount of oxide at this interface increasing with increasing time. The SIMS data confirm that for coated substrates there has been a change in oxidegrowth mechanism to predominantly anion diffusion. The RE most probably concentrates at the oxide grain boundaries, generally as the binary oxide (RE) CrO₃. Cr³⁺ diffusion is impeded, while oxygen diffusion remains unaffected.     

Evaporation of Cr2O3 in Atmospheres Containing H2O

Stainless steels in atmospheres containing H₂O form a Cr₂O₃ scale in the early stage of oxidation. However, the Cr₂O₃ scale gradually degrades with time. In order to determine the effect of H₂O on the deterioration of a Cr₂O₃ scale, the evaporation behavior of Cr₂O₃ in N₂–O₂–H₂O atmospheres was investigated. The rate of mass loss in an N₂–O₂–H₂O atmosphere was found to be one order of magnitude higher than the rates in N₂–O₂ and N₂–H₂O atmospheres, indicating that deterioration of the Cr₂O₃ scale is likely to occur in mixed atmospheres of oxygen and water vapor. Volatilization of Cr₂O₃ is probably based on the following reactions: 1/2Cr₂O₃(s)+3/4O₂(g)+H₂O(g)=CrO₂(OH)₂(g). However, it is also speculated that the reaction, Cr₂O₃(s)+2/3O₂(g)=2CrO₃(g), affects the evaporation of Cr₂O₃ at temperatures higher than 1323 K. The evaporation rate of Cr₂O₃ is roughly comparable to the growth rate of the Cr₂O₃ scale. Therefore, a Cr₂O₃ scale can be degraded by the evaporation of Cr₂O₃.     

Influence of a mixed Al2O3+Cr2O3 superficial coating on the non-isothermal oxidation behavior of Fe and Fe-Cr alloys

The non-isothermal oxidation behavior of electrolytic-grade iron and Fe-Cr alloys in dry air has been studied using linear heating rates of 6 K/min, 10 K/ min, and 15 K/min up to a final temperature of 1273–1473 K. Some of the iron and iron-chromium alloy samples were given a surface treatment by dipping them in an aqueous solution containing both Cr and Al ions before their oxidation studies. This pretreatment has resulted in improved oxidation resistance and scale adherence as depicted by no scale rupture even after a second thermal cycle. Mass changes were recorded gravimetrically, and scales have been characterized by SEM, EPMA, and x-ray diffraction analyses.     

Effect of internal oxidation pretreatments and Si contamination on oxide-scale growth and spalling

Internal oxidation pretreatments carried out in quartz capsule with a Rhines pack were found to have a profound effect on the subsequent oxidation behavior of alloys. Specimens of Co-15 wt.% Cr, Co-25 wt.% Cr, Ni-25 wt.% Cr, and Ni-25 wt.% Cr-1 wt.% Al were tested at 1100°C after pre-oxidation treatments. Even without the development of internal oxide particles, pretreated binary CoCr and NiCr alloys oxidized with significantly lower rates. Selective oxidation of chromium was observed on the non-Cr₂O₃-forming Co-base alloys, whereas on the Cr₂O₃-forming Ni-base alloys, elimination of base-metal oxide, reduction in the Cr₂O₃ growth rate, and better scale adhesion were found. These effects were more apparent with pre-oxidation temperatures greater than 1000°C and with longer pretreatment times. Contaimination of Si from the quartz is believed to be the cause.     

An investigation of the growth-mechanism of Cr2O3 on pure chromium in 1 atm oxygen at 950° C

The growth mechanism of Cr₂O₃ scale formed when pure chromium was oxidized at 950°C in oxygen at 1 atm pressure has been investigated. Isotope tracer techniques were used to determine the growth sites of the oxide. The scale was buckled extensively, with the convex side always toward the gas, never the reverse. The following growth-mechanism is proposed. Initially growth occurs entirely by cation diffusion, with new oxide being formed at the oxide-gas interface. Then, at a time that is not the same for all parts of the scale, the growth mechanism changes to one in which new oxide is formed within the outer part of the scale.     

Effect of Y2O3 dispersoids in 80Ni-20Cr alloy on the early stages of oxidation at low-oxygen potential

Specimens of a 80Ni-20Cr type alloy, with and without Y₂O₃ dispersoid particles, were oxidized at 1000°C in H₂/H₂O mixtures where the partial pressure of oxygen (P _{O 2}) was varied between 10₃ and 10₂₄ atm. Oxide particles nucleated homogeneously on both alloys, and preferential nucleation on dispersoid particles at the surface was not observed. Continuous Cr₂O₃ films formed slightly faster at aP _{O 2} of 10^–21 atm on the alloy containing the dispersoid, but the difference was negligible at higher pressures. Oxidation atP _{O 2}=10^-19 and 10^–21 atm involved both the formation of Cr₂O₃ and the evaporation of chromium. Thin films of -Al₂O₃ were observed on both alloys after oxidation atP _{O 2}.     

Interfacial segregation during oxidation in O2 at 1173 K of CeO2-coated Fe-20Cr alloys

The interfacial segregation of sulphur and carbon during the oxidation in 1 torr O₂ at 1173 K of Fe-20Cr alloy, which was either free of Ce, alloyed with 0.078 wt.% Ce, or sputter-coated with a 4 nm-thick CeO₂ layer, was studied using polyatomic SIMS. Oxidation periods were up to 19 hr. During oxidation, sulphur and carbon accumulated at the alloy-oxide interface region of both uncoated and coated alloys. The amount of segregated sulphur did not vary appreciably with time, whereas carbon increased with time. The total amount of segregants was similar for both uncoated and coated alloys, although the scales formed on the sputter-coated alloy maintained adhesion and were about 10 times thinner than those on the uncoated alloys.     

Reoxidation of chromium with densified Cr2O3 Scales

Preoxidized chromium specimens have been high vacuum annealed at 1200° and 1300°C to produce densified Cr ₂O₃ scales. These specimens have been reoxidized at the same temperatures at 10^–6 atm O₂. The initial reoxidation is linear with time and is concluded to reflect a volume diffusion controlled transport through the densified scale. The corresponding parabolic rate constant (w² = k_pt)is given by k_p=1.4 · 10^–2 exp(–235,000/RT)(gram of O) ²/cm⁴ sec. It is tentatively concluded that outward chromium diffusion predominates in an inner layer of the Cr₂O₃ scales and inward oxygen diffusion in an outer layer. Under the experimental conditions it has not been possible to maintain growth of the Cr₂O₃ scales controlled by volume diffusion. The new oxide layer consists of fine crystallites; the oxide grows at grain boundaries within the scales. This causes sideways growth of the scale, breakdown of the originally densified layer, and an increased rate of reaction.     

Mechanical and tribological properties of plasma-sprayed Cr3C2-NiCr, WC-Co, and Cr2O3 coatings

Mechanical properties such as Young’s moduli and fracture toughness of plasma-sprayed Cr₃C₂-NiCr, WC-Co and Cr₂O₃ coatings were measured. The tribological properties of the three kinds of coatings were investigated with a block-on-ring self-mated arrangement under water-lubricated sliding. Furthermore, the influences of the mechanical properties on the tribological properties of the coatings were also examined. It was found that the Young’s moduli, bend strengths and fracture toughness of the coatings were lower than the corresponding bulk materials, which may be attributed to the existence of pores and microcracks in the coatings. Among the three kinds of coatings, the magnitude of wear coefficients, in decreasing order, is Cr₃C₂-NiCr, WC-Co and Cr₂O₃, and the wear coefficient of Cr₂O₃ coating was less than 1 × 10⁻⁶mm³N⁻¹m⁻¹. The wear mechanisms of the coatings were explained in terms of microcracking and fracturing, and water deteriorated wear performance of the coatings. The higher the fracture toughness and the lower the porosity and length of microcracking of the coating, the more the wear-resistance of the coating.     

18O Tracer studies of Al2O3 scale formation on NiCrAl alloys

Diffusion processes in Al ₂ O ₃ scales formed on NiCrAl + Zr alloys were studied by the proton activation technique employing the ¹⁸ O isotope as a tracer. The ¹⁸ O profiles identified a zone of oxide penetration beneath the external scale. Both this subscale formation and the outer Al ₂ O ₃ scale thickness were shown by this technique to increase with Zr content in the alloy. Estimated k _p 's from scale thicknesses were in agreement with gravimetric measurements for various Zr levels. Alternate exposures in O and ¹⁸ O revealed that oxygen inward transport was the primary growth mechanism. A qualitative analysis of these ¹⁸ O profiles indicated that the oxygen transport was primarily via short-circuit paths, such as grain boundaries.     

The effect of aluminum as an alloying addition or as an implant on the high-temperature oxidation of Ni-25Cr

The oxidation behavior of aluminum-implanted Ni-25Cr and Ni-25Cr containing 1 wt.% Al has been studied at 1000°C and 1100°C in oxygen. As did Y alloying addition or Y-implantation, 1 wt.% Al added to Ni-25Cr prevented nodular formation of Ni-containing oxides, improved spalling resistance of the scale upon cooling to a similar degree, and eliminated the formation of large voids between the alloy and the scale at the oxidation temperature. However, the Al addition did not alter the rate of growth of the Cr₂O₃ scale, nor did it change the growth direction. Al-implantation produced no effect even when the maximum concentration and depth of penetration were adjusted to be identical with those of the yttrium in the Y-implanted alloy. The implications of these results concerning the reactive element effect are discussed.     

The influence of alloying elements on the development and maintenance of protective scales

Some of the important principles that determine the establishment, growth and long-term maintenance of protective Cr₂O₃, Al₂O₃ and SiO₂ scales on hightemperature iron-, nickel- and cobalt-base alloys are reviewed and discussed. Emphasis is placed on the effects of alloying elements and other additions, such as third elements and reactive elements or oxide dispersions, on each of these processes. Particular attention is paid to transport processes in the scales and the importance of short-circuit paths. Some of the important parameters that influence the long-term mechanical stability of such scales are considered and evaluated.     

Plasma spray coating of spray-dried Cr2O3/wt.% TiO2 powder

An agglomerated Cr₂O₃/wt.%TiO₂ powder has been fabricated by the spray drying process under different parameters. The spray-dried powder has well-agglomerated particles of spherical shape. In the conditions of the high slurry feed rate and low binder concentration in the slurry, the powder has large cavities inside some particles and ruggedness over their surface. The optimum plasma spray feed rate has been found by examining the spraying behavior of the powder and melted state of particles. The plasma spray coating has been performed under different process variables such as spraying distance and plasma power. These parameters strongly affect the characteristics of the coated layer: microstructure, hardness, and bond strength.     

Oxide scale adhesion and impurity segregation at the scale/metal interface

The chemistry at scale/metal interfaces was studied using scanning Auger microscopy after removal of the scale in ultra-high vacuum using an in situ scratching technique. Al₂O₃ and Cr₂O₃ scales formed between 900°C and 1100°C on Fe-18 wt.% Cr-5 wt.% Al and on Ni-25 wt.% Cr alloys, respectively, were investigated. The adhesion of these scales was determined qualitatively by way of micro-indentation and scratching on the surface oxide. All of the alumina scales fractured to the same degree to expose the metal surface, regardless of the oxidation temperature. The chromia-forming alloy on the other hand, developed more adherent scales at lower oxidation temperatures. About 20 at.% sulfur was found at the metal surface in all cases, and its presence was not only detected on interfacial voids, but also on areas where the scale was in contact with the alloy at temperature. Results from this study clearly demonstrated that sulfur as an alloying impurity does segregate to the scale/alloy interface. However, for alumina scales and chromia scales, the effect of this segregation on oxide adhesion is noticeably different.     

Nano/Micro-Laminated (ZrO2–Y2O3)/(Al2O3–Y2O3) Composite Coatings and Their Oxidation Resistance

Nano/micro-laminated (ZrO₂–Y₂O₃)/(A1₂O₃–Y₂O₃) composite coatings were deposited onto an Fe–25Cr–7Ni–N alloy substrate by using alternate electrochemical and sintering processes. The thickness of each layer was in the range of 80–500 nm. Experimental results indicated that the multi-laminated coatings were more effective in providing oxidation resistance than monolithic ZrO₂–Y₂O₃ or A1₂O₃–Y₂O₃ coatings, with the oxidation resistance of the former increasing with increasing number of laminated layers. The microstructural studies suggest that the laminated coatings possess the advantages of these two types of coatings and avoid the weakness of single ZrO₂–Y₂O₃ or A1₂O₃–Y₂O₃ coatings. Reactive elements Y and Zr also played a role in this nano-layered setting in improving the oxidation resistance of the coatings.     

The effect of an Al2O3 dispersion on the adhesion of Al2O3 scales on aluminized Co-10% Cr alloys

The beneficial effect of dispersions of reactive-metal oxide particles on the adhesion of Cr₂O₃ and Al₂O₃ scales formed on heat-resisting alloys is wellknown. It has been shown that an Al₂O₃ dispersion in an alloy can improve the adhesion of a Cr₂O₃ scale, and it is of particular interest in assessing the various theoretical proposals for the effect to determine whether such a dispersion can affect the adhesion of an Al₂O₃ scale. In this investigation, a Co–10% Cr–1 % Al alloy was first internally oxidized to form an Al₂O₃ dispersion. This alloy was then aluminized so that on subsequent oxidation an Al₂O₃ scale developed. It was shown that the dispersion did indeed improve the scale adhesion. The implications of this result are discussed.