Materials Science Forum Vols. 522-523

Abstract: To suppress interdiffusion between the coating and alloy substrate in addition to ensuring slow oxide growth at very high temperatures advanced coatings were developed, and they were classified into four groups, (1) the diffusion barrier coating with a duplex layer structure, an inner σ−(Re-Cr-Ni) phase as a diffusion barrier and outer Ni aluminides as an aluminum reservoir formed on a Ni based superalloy, Hastelloy X, and Nb-based alloy. (2) the up-hill diffusion coating with a duplex layer structure, an inner TiAl2 + L12 and an outer β-NiAl formed on TiAl intermetallic and Ti-based heat resistant alloys by the Ni-plating followed by high Al-activity pack cementation. (3) the chemical barrier coating with a duplex layer structure, an inner* γ + β + Laves three phases mixture as a chemical diffusion barrier and an outer Al-rich γ-TiAl as an Al reservoir formed by the two step Cr / Al pack process. (4) the self-formed coating with the duplex structure, an inner α-Cr layer as a diffusion barrier and an outer β-NiAl as an Al-reservoir on Ni-(20
50)at% Cr alloy changed from the δ-Ni2Al3 coating during oxidation at high temperature. The oxidation properties of the coated alloys were investigated at temperatures between 1173 and 1573K in air for up to 1,000 hrs (10,000 hrs for the up-hill diffusion coating). In the diffusion barrier coating the Re-Cr-Ni alloy layer was stable, existing between the Ni-based superalloy (or Hastelloy X) and Ni aluminides containing 12
50at%Al when oxidized at 1423K for up to 1800ks. It was found that the Re-Cr-Ni alloy layer acts as a diffusion barrier for both the inward diffusion of Al and outward diffusion of alloying elements in the alloy substrate. In the chemical barrier coating both the TiAl2 outermost and Al-rich γ-TiAl outer layers maintained high Al contents, forming a protective Al2O3 scale, and it seems that the inner, γ, β, Laves three phase mixture layer suppresses mutual diffusion between the alloy substrate and the outer/outermost layers.

Abstract: Iron and nickel, model alloys of Ni-Cu and Fe-Cr, and commercial heat resisting alloys were exposed at 650-680oC to flowing CO-H2-H2O gases which were supersaturated with respect to carbon. All ferritic materials, including chromia and alumina formers, developed a coke deposit of carbon nanotubes, the growth of which was catalysed by nanoparticles of Fe3C. Austenitic materials formed graphite filaments and clusters in association with nanoparticles of austenite. Graphite cluster formation was suppressed by alloying copper with nickel. The sensitivity of coking kinetics to alloy copper content was consistent with a mechanism involving graphite nucleation within the subsurface metal. Chromia forming alloys resisted dusting until damage to the scale could no longer be repaired by Cr2O3 regrowth, and carbon gained access to chromium – depleted metal.

Abstract: The passive oxidation mechanism of CVD SiC was discussed from experimental results with high-temperature thermogravimetry and thermodynamic analyses. The bubble formation temperature around 1900 K could be too low for an oxygen inward diffusion limited process but conform to a CO outward diffusion limited process. The parabolic rate constant (kp) had weak oxygen partial pressure (PO2) dependence, kp ∝ PO2 n where n = 0.09 to 0.12. These n values may be consistent with the CO outward diffusion limited process. The activation energy of kp obtained in the present study, 210 kJ/mol, could suggest a different mechanism from the well-approved oxygen molecule permeation limited process at lower temperatures below 1600 K. Amorphous phase was significantly contained in SiO2 scales formed in an N2-O2 atmosphere. No effect of the amorphous formation on kp was identified.

Abstract: Estimation of void formation in oxide scale is important for predicting exfoliation of the oxide scale. Void formation in magnetite scale formed on iron at 823 K has been elucidated by chemical potential distribution, flux of oxide ion and its divergence. This calculation also estimates a effective diffusion coefficient, which includes both lattice diffusion and grain boundary diffusion in magnetite scale. The resulting effective diffusion coefficients give the quantitative elucidation of the morphology of the magnetite scale. The divergence of oxide ion explains well a position and an amount of void in magnetite scale.

Abstract: It is shown from the oxidation results that, for Fe-Cr, Ni-Cr, Co-Cr binary alloys with and without internal Cr2O3 precipitations after exposure, continuous external Cr2O3 scales formed on their surfaces, especially at the initial stage. It is therefore suggested that the transitions of oxidation for these alloys take place from externally to internally. There are two types of transitions for alloys: (1) the transition from temporary external oxidation to internal oxidation; and (2) the transition from permanent external oxidation to internal oxidation. The thermodynamic conditions for these transitions have been analyzed, and the criterion for prediction of the minimum solute concentration of a binary solid solution alloy required for the second transition has been derived. It is also suggested that the external oxide scale is an important factor to determine the formation of pure solvent metal nodules on the surfaces.

Abstract: Copper and nickel are accumulated in steels when steel scrap is used as steel sources. It is well known that copper causes hot shortness problem and nickel suppresses the effect of copper. In this paper, the behaviour of copper and nickel during oxidation is investigated. Steels containing copper and nickel were oxidized and the distribution of copper and nickel in the scale was examined. It was found that copper is not only enriched at the scale/metal interface but also exists in upper magnetite layer as a state of solid solution and along grain boundaries of the wustite layer as metal phase. From these results an assumption has been proposed that the liquid copper migrates from the scale/metal interface to the magnetite layer along the grain boundaries. On the other hand, nickel enriched in steel side near the scale/metal interface with copper. The metal particles containing nickel and copper remain inside the scale. Nickel also has an effect of the uneven scale/metal interface formation.

Abstract: Modern analytical techniques are useful to characterize oxide films and to study oxide growth processes. This paper will summarize some of our work on the high temperature oxidation of both metals and semiconductors. Systems considered include binary III-V semiconductors, e.g. GaAs, which unlike silicon does not normally form high-quality native oxide. For GaAs, the influence of deuterium in the substrate and surface platinum have been evaluated with respect to oxide growth. Both aluminum-containing alloys (FeCrAl and NiAl) and semiconductors (AlGaAs, InAlAs and InAlP) are included. The objective is to produce good quality protective and insulating aluminum-containing oxides. In these studies, the application of several modern surface- analytical techniques, particularly Auger electron spectroscopy, X-ray photoelectron spectroscopy and secondary ion mass spectrometry, complemented by other techniques, e.g. transmission electron microscopy and X-ray analysis provides useful information on the chemical composition of the oxides and leads to a better understanding of oxidation and corrosion phenomena. In the case of AlGaAs and InAlP, thermal oxidation produces aluminum-containing oxides that have good insulating characteristics which makes the oxide films potentially useful for some device applications.

Abstract: In order to contribute to a better understanding of the processes, which occur in the structure of FeCrAl alloys during oxidation, in situ – studies by two-dimensional high temperature X-ray diffraction (2D-XRD) using a global area detector and grazing incidence with a monocapillary have been performed. The 2D-XRD yields simultaneously with the identification of the oxides and their formation kinetics information about the grain size, grain shape, stresses, texture as well as grain movements during the oxidation process of both oxide and metal. Two commercial FeCrAl alloys with different reactive element additions were investigated in the temperature range of 850°C to 1100°C. In the range of 1100°C already in the first 5 min the alloy grains become coarse and appear as single spots along the lateral profile in the 2D-XRD pattern. Dynamic displacement of these spots along the 2θ – axis during the exposure indicates the formation of stresses, which differ from grain to grain. Initially, re-crystallisation and grain growth dominate and grains disappear and new grains appear. On further exposure the grains twist continuously with 1° to 3° per hour, depending on the alloy. The “dancing grain” effect of the alloy is probably related with growth stresses in the oxide scale and influenced by the bulging of the foil. Simultaneously, α-Al2O3 is detected from the first pattern after 5 min and shows an enhanced formation rate in the first 15 min of the oxidation. The α-Al2O3 grains are with 0.3 to 0.4 4m extremely fine and, a dense well adherent scale is observed even after 1 h.

Abstract: The oxidation behaviour of a commercial low carbon, low silicon steel in flowing air at 600-920°C was investigated. Parabolic oxidation kinetics was observed at all temperatures. Three oxidation kinetics zones with different oxidation activation energies were identified. The mechanisms responsible for the different oxidation kinetics are discussed.

Abstract: An analytical study of high-temperature corrosive failure in a waste incineration plant was conducted using a new type EPMA equipped with a Schottky type field emission gun. For sample preparation, a cross-section polisher that uses an argon ion beam was applied. Both the element distribution through the alloy substrate to the scale and the chemical states of sub-micron sized corrosion products were revealed, leading to inferences about the corrosion mechanism.