Papers by Author: Shigenari Hayashi

Abstract: This chapter is dedicated to the description of high temperature oxidation of both chromia and alumina forming alloys. The defect structures of iron and chromium are firstly reviewed. The effects of elements on stainless steel oxidation behaviour are further addressed. For the chromia-forming stainless steel, the oxidation rate is reduced with the increased silicon content but not in a monotonic manner. Titanium and niobium can reduce breakaway oxidation of Fe–18Cr–10Ni austenitic stainless steel. Titanium can enhance the adhesion of scale to the Fe–18Cr by mechanical keying effect of TiO₂ formed at the steel/scale interface. For the alumina-forming stainless steel, the formation of alumina and its transformation during oxidation are reviewed. Chromium can be added to reduce the critical aluminium content in the steels in order to form alumina at high temperatures. The addition of reactive elements with appropriate level can improve scale adhesion and reduce the steel oxidation rate. Refractory element like molybdenum can increase strength of material but also accelerate the oxidation rate of the steels containing reactive elements. The development of new alumina-forming austenitic alloy grades is finally described.

Abstract: The corrosion of carbon steel is major infrastructure degradation problem in practically all industries, including chemical materials, mineral, and petrochemical industries. Coating on carbon steel is one of the techniques which required improving corrosion resistance in extreme environments. In present work, NiCoCrAl was diffusion-coated onto low carbon steel by electrodeposition for NiCo and pack cementation for Cr and Al. The cross section of coated specimen was observed and analyzed using SEM and TEM. Two types of coating processes have been challenging the formation of bond-coat layer on carbon steel substrate with different temperature coating process. SEM and EDS results show that the coating comprises three layers: intermetallics zone of Ni (Al) and Al (Cr), interdiffusion zone of Ni (Co), and there is the substrate. By XTEM observation, it was found that γ (Ni,Fe) and ζ hexagonal structure were identified in all specimens. Orthorhombic structure with the Al₃Ni was identified in specimen developed at temperature of 800^OC. Further, the top surface of a 1000^OC specimen has two phases of β-NiAl and ζ hexagonal structure. In order to understand the performance of two types coating system with different temperature process, oxidation test at temperature of 800^OC for 100 hours has been carried out and the result shows that coating system which was developed at 800^OC has better oxidation resistance compare to 1000^OC coating system.

Abstract: The hot rolling at temperature range of 1100 °C to 862 °C and subsequent air-cooling induce a formation of the coarse ferrite grains in the 9CrODS steels. This coarse ferrite is produced by transformation from the severely hot rolled γ-grains to ferrite. Formation process and mechanism of the transformed coarse ferrite are interpreted in terms of a nucleation, growth and coalescence of the same variant ferrite grains under a variant restriction rule.

Abstract: Very thin Fe-coatings, ~50nm, were found to suppress metastable Al₂O₃ formation on Fe-50Al and Ni-50Al alloys in our previous study. The authors proposed a mechanism whereby α-Al₂O₃ precipitates from the Al-saturated Fe₂O₃, which was formed during initial oxidation, since α-Al₂O₃ and α-Fe₂O₃ have isomorphous structures. In order to confirm the proposed mechanism, in-situ measurements were made of structural changes in the oxide scales formed on FeAl with and without Fe coating during heating and subsequent isothermal high temperature oxidation by synchrotron radiation with a two-dimensional X-ray detector. Diffraction peaks from Fe₂O₃ were initially observed at around 350°C on Fe-coated samples. The lattice parameter of the Fe₂O₃ initially increased linearly due to thermal expansion, but then rapidly decreased due to the formation of a solid solution of Fe₂O₃-Al₂O₃. α-Al₂O₃ started to appear at around 800°C, but no peaks from metastable Al₂O₃ were observed. The diffraction peaks from the α-Al₂O₃ on Fe-coated samples consisted of two distinct peaks, indicating that the α-Al₂O₃ had two different lattice parameters. These results suggest that the α-Al₂O₃ was formed not only by precipitation from the Al-saturated Fe₂O₃, but also by oxidation of Al in the substrate.

Abstract: High temperature cyclic oxidation behavior of γ'-base Ni-25Al-10Pt (in at.%) alloy was investigated at 1000°C in air with and without 30vol.%H₂O. The oxidation mass gain during the initial stage of oxidation was similar in both atmospheres, but the oxidation rate in air+H₂O was lower in the longer steady-state oxidation stage. Metastable Al₂O₃, which formed during the initial stage of oxidation, transformed completely after about 100hr of oxidation in dry air. The transformation to α-Al₂O₃ also occurred in air+H₂O, but complete transformation to α-Al₂O₃ was not observed during the oxidation time in the present study. θ-Al₂O₃ grains remained for longer on the α-Al₂O₃ layer in air+H₂O and became significantly coarser with oxidation time. The present results indicate that water vapor delays the metastable to α-Al₂O₃ phase transformation, and decreases the growth rate of α-Al₂O₃.

Abstract: As high-temperature metallic materials, Co-base ODS alloys were produced by means of mechanical alloying, spark plasma sintering and hot rolling. Co-3wt%Al-1.2wt%Hf-ODS alloy was found to be an attractive composite like material, which is formed by spinodal like decomposition. The metastable phases were traced by hard phase containing dense oxide particles and soft one containing less oxide particles. Their tensile stress at 1,000 °C was improved by Hf addition that forms Y₂Hf₂O₇ type oxide particles and shortens their space distance.

Abstract: Nb, Al and Y2O3 powders were mechanically alloyed together with 5 wt% stearic acid. The heavy plastic deformation of the powders by mechanical alloying led significant hardening to 970 Hv and the reduced grain size to 10 nm. Nb-Al base ODS alloys consolidated by HIP at 1500 °C and 150 MPa for 0.5 h gave the dual phase of Nb solid solution and Nb3Al compound. The oxide particles are of the hexagonal type YAlO3 (YAH), with the size of 50 nm to 200 nm. The high-temperature ductility at 1200 °C and capability of the grain growth at 2000 °C were confirmed.

Abstract: The oxidation behavior of Fe-20at.%Cr-10at.%Al alloys with a small amount of an additional element such as W, Cu, Mn, Nb, Mo, Re, Co or Ti was investigated at 900 °C for up to 625hr. The fourth element addition to the FeCrAl alloy could be classified into two groups; elements (Mn, Nb, Ti) that are contained in the Al2O3 scale, and elements (W, Mo, Re, Co) which are not present in the scale. In the latter case, the elements (W, Cu) caused scale spallation. The rumpling of alloys with Mn, Nb or Ti was smaller than that of the other alloys. The surface of the alloy with Ti was the smooth. Pt marker experiments suggested that the Al2O3 scale formed on the alloy with Ti grew by inward diffusion of O, whilst the Al2O3 scale formed on the FeCrAl alloy grew by both outward diffusion of Al and inward diffusion of O. This different growth behavior due to the elements incorporated in the Al2O3 scale could have an effect on the surface rumpling behavior.

Abstract: A duplex layer, outer Pt-modified γ’-Ni3Al + γ-Ni and inner multi-barrier σ- Re(Cr,Ni,W), coating system was formed on a Ni-based single crystal 4th generation superalloy. Oxidation behavior of the coated alloy was investigated under thermo-cycling conditions, and analyzed by EPMA and XRD. During cyclic oxidation 1hr at 1100°C and 20 min at room temperature, a slow growing α-Al2O3 formed for up to 400 cycles and its spallation was rare. The parabolic rate constant of mass change was 6.3x10-16 kg2m-4s-1. The Pt-modified γ’-Ni3Al + γ-Ni contained 19Al, 12Pt, 4Cr, and 3Co in at%, and their concentration profiles were almost flat across the outer layer. The multi-barrier, σ-Re(Cr,Ni,W) contained 40Re, 23Cr, 17Ni, 7Al, 4W, 3.5Mo, and 3Co in at%. Furthermore, the γ’-Ni3Al containing Pt was newly formed between the multibarrier and bulk alloy substrate. It was concluded that the σ-Re(Cr,Ni,W) is compatible with the Ptmodified γ’-Ni3Al in the multi-diffusion barrier coating on Ni-based single crystal, 4th generation superalloy at high temperatures.

Abstract: High temperature oxidation / creep deformation behavior of a diffusion barrier coated Hastelloy-X alloy, with large grain size ~500μm, was investigated at 970°C in air with external tensile stress of 22.5, 27.5, 32, and 40MPa. The diffusion barrier coating formed on Hastelloy-X consisted of a duplex structure with an inner diffusion barrier layer of Re-Cr-Ni alloy, and an outer oxidation resistant layer of β-NiAl. Un coated bare Hastelloy-X alloy with same grain size was also examined under the same conditions for comparison. The composition of the as-coated diffusion barrier coating was (15~21)Ni, (33~37)Cr, (30~33)Re, (11~15)Mo, and (9~14)Fe. This composition corresponds to σ-phase in the Ni-Cr-Re ternary system, which is known as a topologically close packed, TCP phase. The composition of this diffusion barrier layer did not change during the experiment. The oxide scales formed after creep testing on the coated and un-coated alloy surfaces were needle-like θ-Al2O3, and Cr2O3 with small amount of FeCr2O4, respectively. Grain boundary oxidation was also found in the subsurface region of the un-coated alloy. The Al2O3 scale exhibited severe spallation, and many cracks were formed perpendicular to the stress direction. However, no spallation or cracks were observed in the Cr2O3. The creep rupture times for the diffusion barrier coated alloy were about 1.5 times longer than those for bare alloy at all creep stress conditions. The fracture surface after rupture indicates that fracture occurred along alloy grain boundaries in both the coated and un-coated alloy substrate. Many cavities and cracks were observed within the diffusion barrier coated alloy substrate. These cavities and cracks tended to propagate from the substrate toward the diffusion barrier layer, and then stopped at the Re-Cr-Ni / β-NiAl interface. Cracks formed in the un-coated alloy initiated at the tip of grain boundary oxides, and propagated into alloy substrate. However no major cavities were observed inside the alloy substrate. The stress index, n, for both specimens was about 6, and this indicates that the deformation mechanism of both samples was dislocation creep. These results suggest that the Re-Cr-Ni diffusion barrier layer acts as a barrier against the movement of dislocations at the interface with the alloy surface.