Microprocesses of metal dusting on nickel and Ni-base alloys

Microstructural and microchemical investigations were carried out on nickel and Inconel 600 after exposure to strongly carburizing atmospheres at temperatures of about 600 to 650°C to study their metal dusting behaviour. Contrary to iron and low-alloy steels, where metal dusting proceeds via the formation and disintegration of a metastable carbide M₃C, both nickel and Inconel 600 directly disintegrate. Inside the metal this disintegration proceeds by formation of thin graphite filaments of nearly 10 nm in diameter, the atomic basal planes of which are oriented perpendicular to the surface thus effecting a high reactivity at the growth front. Subsequently, fine particles or larger parts of the metal surface layer are released, which are buried in the deposited graphite layer on the surface. In case of Inconel 600, containing Cr with mass contents of about 15%, the disintegration can be delayed by the formation of a chromium oxide layer, but no safe protection against metal dusting is obtained.     

Behavior of direct reduced iron and hot briquetted iron in the upper blast furnace shaft: Part I. Fundamentals of kinetics and mechanism of oxidation

It is considered that the use of prereduced ferrous materials and sources of metallic iron such as direct reduced iron (DRI) or hot briquetted iron (HBI) improves the productivity of the blast furnace (BF). However, oxidation of DRI/HBI can occur in the upper zone of the BF, which may increase the content of the reducing gases but may not decrease the coke rate substantially. The behavior of DRI and HBI was investigated by measuring the rate of oxidation of the materials in CO₂ gas in a temperature range of 400 °C to 900 °C. In addition, the microstructure of “as-received” and oxidized materials was examined. The iron oxide phases formed due to oxidation were determined using X-ray diffraction (XRD) and a vibrating sample magnetometer. The results of isothermal experiments indicated that the kinetics of oxidation of metallic iron is slow at 400 °C. In DRI samples, the initial rate is controlled by the limited mixed control of chemical kinetics at the iron/iron oxide interface and pore mass transfer, whereas gas diffusion in pores is the rate governing step during the final stages of oxidation. The oxidation of wustite from iron is found to be faster than the oxidation of the former to magnetite. The structure of DRI after oxidation resembled a “reverse topochemical-oxide on the surface metal in the center” structure at 600 °C to 700 °C. The final iron oxide phase formed in DRI after oxidation was magnetite and not hematite. The oxidation of HBI was limited to the surface of the samples at lower temperatures; at 900 °C, moderate oxidation was observed and a topochemical iron oxide layer was formed.     

Effect of H2S on formation and decomposition of Fe3C and Fe5C2 under metal dusting conditions

The high temperature corrosion process metal dusting leads to the formation and decomposition of metastable iron carbides at the surface of iron samples. A small amount of H₂S in the carburising atmosphere causes the adsorption of sulphur onto the sample surface, which decreases the carbon transfer rate and retards or suppresses the start of metal dusting. The extent of retardation of metal dusting depends on temperature, carbon activity and H₂S content. The higher the carbon activity the higher the H₂S content required for suppression of metal dusting. At very high carbon activities a second iron carbide, Fe₅C₂ (Hägg carbide), forms on the cementite surface. The carburisation experiments were conducted at 500°C using CO‐H₂‐H₂O‐H₂S gas mixtures. The microstructural investigations show that both metastable carbides decompose during metal dusting.     

Oxidation of Alloy 600 and Alloy 690: Experimentally Accelerated Study in Hydrogenated Supercritical Water

The objective of this study is to determine whether the oxidation of Alloys 600 and 690 in supercritical water occurs by the same mechanism in subcritical water. Coupons of Alloys 690 and 600 were exposed to hydrogenated subcritical and supercritical water from 633 K to 673 K (360 °C to 400 °C) and the oxidation behavior was observed. By all measures of oxide character and behavior, the oxidation process is the same above and below the supercritical line. Similar oxide morphologies, structures, and chemistries were observed for each alloy across the critical point, indicating that the oxidation mechanism is the same in both subcritical and supercritical water. Oxidation results in a multi-layer oxide structure composed of particles of NiO and NiFe₂O₄ formed by precipitation on the outer surface and a chromium-rich inner oxide layer formed by diffusion of oxygen to the metal-oxide interface. The inner oxide on Alloy 600 is less chromium rich than that observed on Alloy 690 and is accompanied by preferential oxidation of grain boundaries. The inner oxide on Alloy 690 initially forms by internal oxidation before a protective layer of chromium-rich MO is formed with Cr₂O₃ at the metal-oxide interface. Grain boundaries in Alloy 690 act as fast diffusion paths for chromium that forms a protective Cr₂O₃ layer at the surface, preventing grain boundary oxidation from occurring.     

Corrosion Behavior of Alloy 625 in PbSO4-Pb3O4-PbCl2-ZnO-10?Wt?Pct CdO Molten Salt Medium

Corrosion behavior and degradation mechanisms of alloy 625 under a 47.288 PbSO₄-12.776 Pb₃O₄-6.844PbCl₂-23.108ZnO-10CdO (wt pct) molten salt mixture under air atmosphere were studied at 873?K, 973?K, and 1073?K (600?°C, 700?°C, and 800?°C). Electrochemical impedance spectroscopy (EIS), open circuit potential (OCP) measurements, and potentiodynamic polarization techniques were used to evaluate the degradation mechanisms and characterize the corrosion behavior of the alloy. Morphology, chemical composition, and phase structure of the corrosion products and surface layers of the corroded specimens were studied by scanning electron microscopy/energy-dispersive X-ray (SEM/EDX) and X-ray map analyses. Results confirmed that during the exposure of alloy 625 to the molten salt, chromium was mainly dissolved through an active oxidation process as CrO₃, Cr₂O₃, and CrNbO₄, while nickel dissolved only as NiO in the system. Formation of a porous and nonprotective oxide layer with low resistance is responsible for the weak protective properties of the barrier layer at high temperatures of 973?K and 1073?K (700?°C and 800?°C). There were two kinds of attack for INCONEL 625, including general surface corrosion and pitting. Pitting corrosion occurred due to the breakdown of the initial oxide layer by molten salt dissolution of the oxide or oxide cracking.     

Structure and chemistry of Nb/sapphire interfaces,with and without interlayers of Sb and Cr

The microstructure and chemistry of interfaces between sputter-deposited Nb coatings and (0001) sapphire surfaces, with and without interlayers of Cr and Sb, have been determined by using high resolution transmission electron microscopy (HRTEM). The changes in the microstructure and chemistry in the interfacial region resulting from annealing the samples are determined. All samples were annealed at 600°C for 24 h and 1200°C for 10 min, except the Nb/Sb sapphire samples which were heat-treated at 400 and 600°C with a 24 h hold time. All interface systems in the as-deposited state feature a 2.5 nm thick uniform Al₂O₃ layer, caused by sputter-cleaning of the sapphire surface prior to any interlayer or coating deposition. After annealing at 1200°C for 10 min, the amorphous layer completely recrystallizes, and hemispherical voids, 10–20 nm diameter, are formed at the Nb/Al₂O₃ interface. In the Nb/Cr/Al₂O₃ system, in addition to voids and the recrystallization of the amorphous layer, the continuous Cr layer is reduced to a Cr₂Nb intermetallic reaction compound. Finally, for the Nb/Sb/Al₂O₃ samples, annealing at 400°C for 24 h results in a hitherto unreported, Nb-Sb amorphization reaction.     

Evaluation of Metal Dusting Behavior in Reformer Tube Made of HP–Nb Alloy on the Outer Surfaces

The metal dusting behavior of Iron–Chromium–Nickel heat resistant HP–Nb steel specimen was investigated at the outer surfaces while the methane gas was passed inside the hole of the specimen. After an exposure of 130 h in a flowing methane (CH₄) gas at 680 °C, different dispersed corrosion products were formed on the outer surface of the specimen near the hole. Conventional metallography and scanning electron microscopy were used to identify the microstructure of the reaction products. Energy dispersive X-ray spectroscopy was used for microchemical analysis. The phases produced on the surface were identified by X-ray diffraction. Some of reaction products found as surface deposits on the outer surfaces of specimen near the hole contained Fe and Cr carbides, Fe, Cr and Ni oxides, scale of Ni, Fe particles and free C. Results revealed that carbon nano-filaments materials could be formed during disintegration of heat resistant HP–Nb steel under metal dusting environment.     

Tensile properties of tempered chromium steels in the temperature range 0°to 700°C

Steels containing 0.2 pet C and 0 to 12 pct Cr have been tempered for different times or recrystallized at 700°C and subsequently tensile tested at 100°C temperature intervals in the range 0° to 700°C. At all temperatures, the strength of the as-tempered steels depends primarily on the dislocation structure inherited from the martensite transformation and work softening observed during deformation at 600° and 700° is attributable to recovery of this structure. Strain enhanced precipitation of M₃C is observed after deformation at 200° to 600°C in all the steels, independent of the nature of the carbide present after tempering. Serrated yielding occurs at temperatures increasing from 200° to 400°C with increasing chromium content and is associated with an increase in strength and strain-hardening rate in all cases. It is concluded that dynamic strain-aging results from dislocation locking by chromium-interstitial complexes in the alloy steels. T. Mukherjee, formerly Research Student, Department of Metallurgy, University of Sheffield, Sheffield England. This paper is based upon a thesis submitted by T. Mukherjee in partial fulfillment of the requirements of the degree of Doctor of Philosophy at the University of Sheffield.     

Influence of annealing treatment on the formation of nano/submicron grain size AISI 301 Austenitic stainless steels

Nano/submicron austenitic stainless steels have attracted increasing attention over the past few years due to fine structural control for tailoring engineering properties. At the nano/submicron grain scales, grain boundary strengthening can be significant, while ductility remains attractive. To achieve a nano/submicron grain size, metastable austenitic stainless steels are heavily cold-worked, and annealed to convert the deformation-induced martensite formed during cold rolling into austenite. The amount of reverted austenite is a function of annealing temperature. In this work, an AISI 301 metastable austenitic stainless steel is 90 pct cold-rolled and subsequently annealed at temperatures varying from 600 °C to 900 °C for a dwelling time of 30 minutes. The effects of annealing on the microstructure, average austenite grain size, martensite-to-austenite ratio, and carbide formation are determined. Analysis of the as-cold-rolled microstructure reveals that a 90 pct cold reduction produces a combination of lath type and dislocation cell-type martensitic structure. For the annealed samples, the average austenite grain size increases from 0.28 μm at 600 °C to 5.85 μm at 900 °C. On the other hand, the amount of reverted austenite exhibits a maximum at 750 °C, where austenite grains with an average grain size of 1.7 μm compose approximately 95 pct of the microstructure. Annealing temperatures above 750 °C show an increase in the amount of martensite. Upon annealing, (Fe, Cr, Mo)₂₃C₆ carbides form within the grains and at the grain boundaries.     

Creep Rupture Strength and Microstructure of Low C-10Cr-2Mo Heat-Resisting Steels with V and Nb

The new ferritic heat-resisting steels of 0.05C-10Cr-2Mo-0.10V-0.05Nb (Cb) composition with high creep rupture strength and good ductility have already been reported. The optimum amounts of V and Nb that can be added to the 0.05C-10Cr-2Mo steels and their effects on the creep rupture strength and microstructure of the steels have been studied in this experiment. The optimum amounts of V and Nb are about 0.10 pct V and 0.05 pct Nb at 600 °C for 10,000 h, but shift to 0.18 pct V and 0.05 pct Nb at 650 °C. Nb-bearing steels are preferred to other grades on the short-time side, because NbC precipitation during initial tempering stages delays recovery of martensite. On the long-time side, however, V-bearing steels have higher creep rupture strength. By adding V to the steels, electron microscopic examination reveals a stable microstructure, retardation during creep of the softening of tempered martensite, fine and uniform distribution of precipitates, and promotion of the precipitation of Fe₂Mo.     

Carbide precipitation and high-temperature strength of hot-rolled high-strength,low-alloy steels containing Nb and Mo

The effects of a Mo addition on both the precipitation kinetics and high-temperature strength of a Nb carbide have been investigated in the hot-rolled high-strength, low-alloy (HSLA) steels containing both Nb and Mo. These steels were fabricated by four-pass hot rolling and coiling at 650°C, 600°C, and 550°C. Microstructural analysis of the carbides has been performed using field-emission gun transmission electron microscopy (TEM) employing energy-dispersive X-ray spectroscopy (EDS). The steels containing both Nb and Mo exhibited a higher strength at high temperatures (∼600 °C) in comparison to the steel containing only Nb. The addition of Mo increased the hardenability and led to the refinement of the bainitic microstructure. The proportion of the bainitic phase increased with the increase of Mo content. The TEM observations revealed that the steels containing both Nb and Mo exhibited fine (<10 nm) and uniformly distributed metal carbide (MC)-type carbides, while the carbides were coarse and sparsely distributed in the steels containing Nb only. The EDS analysis also indicated that the fine MC carbides contain both Nb and Mo, and the ratio of Mo/Nb was higher in the finer carbides. In addition, electron diffraction analysis revealed that most of the MC carbides had one variant of the B-N relationship ((100)_MC//(100)_ferrite, [011]_MC//[010]_ferrite) with the matrix, suggesting that they were formed in the ferrite region. That is, the addition of Mo increased the nucleation sites of MC carbides in addition to the bainitic transformation, which resulted in finer and denser MC carbides. It is, thus, believed that the enhanced high-temperature strength of the steels containing both Nb and Mo was attributed to both bainitic transformation hardening and the precipitation hardening caused by uniform distribution of fine MC particles.     

Surface Selective Oxide Reduction During the Intercritical Annealing of Medium Mn Steel

Third generation advanced high-strength steels achieve an excellent strength–ductility balance using a cost-effective alloy composition. During the continuous annealing of medium Mn steel, the formation of an external selective oxide layer of MnO has a negative impact on the coating quality after galvanizing. A procedure to reduce the selective oxide was therefore developed. It involves annealing in the temperature range of 1073 K to 1323 K (800 °C to 1050 °C) in a HN_x gas atmosphere. Annealing at higher temperatures and the use of larger H₂ volume fractions are shown to make the gas atmosphere reducing with respect to MnO. The reduction of the surface MnO layer was observed by SEM, GDOES, and cross-sectional TEM analysis.     

Calcination temperature effect on La0.67Ca0.33MnO3 nanoparticle using simple citrate pyrolysis process

A new simple route was used to synthesize nanosized crystalline La_0.67Ca_0.33MnO₃ perovskite type complex oxide by simple citrate pyrolysis process using a metal salts, La, Ca, Mn as starting materials. To obtain the LCMO nanoparticles the precursor was carried out at various calcination temperatures viz. 500° C, 600° C, 700° C, 800° C for very short time only ～ 60 minutes. The synthesized LCMO nanoparticles were characterized by powder XRD, FTIR, TGA/DTA, SEM. The precursor could be completely decomposed into complex oxide at temperature below 500° C according to the TGA/DTA results. XRD demonstrates that the decomposed species is composed of perovskite-type structure at calcination temperature of 600° C for 60 minutes. The crystalline size that depends on the calcination temperature of the precursor is in the range of 11–22 nm as determined by Scherrer Formula. All the prepared samples have high purity perovskite structure which is orthorhombic. The chemical bonds were identified by the measurements of Infrared IR transmission spectra carried out with powder samples in which KBr was used as a carrier. The IR spectra revealed that stretching and bending modes influenced by calcination temperature. Morphology and grain size were studied through scanning electron microscopy.     

Effect of Temperature on Scale Morphology of Fe-1.5Si Alloy

Because of the effect of silicon on the formation of oxide scale, red scale is the main surface defect of hot-rolled Fe-Si plate, making the scale difficult for descaling compared with carbon steel. Thermogravimetric analyzer (TGA) is used to simulate isothermal oxidation process of Fe-1.5Si alloy for 60 min under air condition, and the temperature range is from 700 to 1200 °C. Electron probe microanalysis (EPMA) is used to observe cross-sectional scale morphology and analyze elemental distribution of the scale. Relational graph of temperature, scale thickness and scale structure is obtained. It is found that scale structure (outer Fe oxide layer+inner FeO/Fe₂SiO₄ layer+internal Si oxide precipitates) is almost unchanged with temperature except at 1000 and 1200 °C. At 1000 °C internal Si oxide precipitates cannot be found at the subsurface of the alloy, and at 1200 °C FeO/Fe₂ SiO₄ not only forms a layer as usual but also penetrates into the outer Fe oxide layer deeply.     

Corrosion properties of austenitic Cr-Mn-Ni-N steels with various manganese concentrations

The structure and corrosion properties of two high-nitrogen 05Kh20AN8MF steels additionally alloyed with 9 and 17% Mn have been studied. Metallographic, X-ray diffraction, and fractographic studies show that both steels have an austenitic structure and high plasticity properties after quenching from 1100 and 1100°C and subsequent aging at 500°C for 2 h. The steel alloyed with 9% Mn and 0.58% V exhibit a higher strength. Both steels have a higher corrosion resistance in a 3.5% NaCl aqueous solution than 12Kh18N9T steel. After aging at 400–600°C, the corrosion rate and the sensitivity to stress corrosion cracking increase.     

Adhesion energy in the metal/oxide system for the case of high-temperature oxidation of nickel-based superalloys

The microstructure of the oxide layer is studied and the adhesion energy of the metal/oxide interface is determined after high-temperature isothermal oxidation (T = 1150°C) of a single-crystal commercial René N5 nickel alloy. Experiments upon heating and rapid cooling are performed to initiate failure of the oxide layer. The elastic energy of the metal/oxide interface is determined using the model of circular buckling followed by edge delamination. Calculations are conducted for a homogeneous alumina layer and with allowance for the multilayer structure that forms at the initial stages of alloy oxidation. The adhesion energy is 72 and 27 J/m2 for these cases, respectively.     

Effects of Rolling and Cooling Conditions on Microstructure and Tensile and Charpy Impact Properties of Ultra-Low-Carbon High-Strength Bainitic Steels

Six ultra-low-carbon high-strength bainitic steel plates were fabricated by controlling rolling and cooling conditions, and effects of bainitic microstructure on tensile and Charpy impact properties were investigated. The microstructural evolution was more critically affected by start cooling temperature and cooling rate than by finish rolling temperature. Bainitic microstructures such as granular bainites (GBs) and bainitic ferrites (BFs) were well developed as the start cooling temperature decreased or the cooling rate increased. When the steels cooled from 973 K or 873 K (700 °C or 600 °C) were compared under the same cooling rate of 10 K/s (10 °C/s), the steels cooled from 973 K (700 °C) consisted mainly of coarse GBs, while the steels cooled from 873 K (600 °C) contained a considerable amount of BFs having high strength, thereby resulting in the higher strength but the lower ductility and upper shelf energy (USE). When the steels cooled from 673 K (400 °C) at a cooling rate of 10 K/s (10 °C/s) or 0.1 K/s (0.1 °C/s) were compared under the same start cooling temperature of 873 K (600 °C), the fast cooled specimens were composed mainly of coarse GBs or BFs, while the slowly cooled specimens were composed mainly of acicular ferrites (AFs). Since AFs had small effective grain size and contained secondary phases finely distributed at grain boundaries, the slowly cooled specimens had a good combination of strength, ductility, and USE, together with very low energy transition temperature (ETT).     

Elevated temperature oxidation of laser surface engineered composite boride coating on steel

The effects of long duration exposure of laser surface engineered composite boride coating on plain carbon steel in air at high temperatures were investigated in this study. Exposures at 600 °C, 800 °C, and 1000 °C for 10, 30, and 50 hours of composite-TiB₂ coated samples were conducted to study oxide scale growth and morphology. Kinetics of oxidation of the coating during elevated temperature exposures were separately studied using the thermogravimetric analysis (TGA) technique. The oxidation rate for all samples was parabolic in nature and the oxidation kinetic rate constant, K, increased with increasing temperature of exposure. Activation energy, Q for composite TiB₂ coating was found to be 205 kJ/mol. A thick (>35 μm) oxide layer formed for all duration of exposure at temperatures ≥800 °C. In case of 1000 °C exposure, a very thick (>150 μm) oxide layer was formed, which was separated from the substrate. X-ray diffractometry analysis revealed the complex nonstoichiometric nature of the oxides of type Ti _a O _b , Fe _m O _n , and Fe _x Ti _y O _z . Profilometric measurements indicated an increase in the surface roughness of the oxide layer with an increase in temperature of exposure. These physical observations indicated that the nature and morphology of the oxides formed at various temperatures and duration of exposure are complex.     

Structural features and properties of the laser-deposited nickel alloy layer on a KhV4F tool steel after heat treatment

The study and application of the materials that are stable in the temperature range up to 1000°C are necessary to repair forming dies operating in this range. Nickel-based alloys can be used for this purpose. The structural state of a nickel alloy layer deposited onto a KhV4F tool steel and then heat treated is investigated. KhV4F tool steel (RF GOST) samples are subjected to laser deposition using a pulsed Nd:YAG laser. A nickel-based material (0.02C–73.8Ni–2.5Nb–19.5Cr–1.9Fe–2.8Mn) is employed for laser deposition. After laser deposition, the samples are subjected to heat treatment at 400°C for 5 h, 600°C for 1 h, 800°C for 1 h, and 1000°C for 1 h. The microstructure, the phase composition, and the microhardness of the deposited layer are studied. The structure of the initial deposited layer has relatively large grains (20–40 μm in size). The morphology is characterized by a cellular–dendritic structure in the transition zone. The following two structural constituents with a characteristic dendritic structure are revealed: a supersaturated nickel-based γ solid solution and a chromium-based bcc α solid solution. In the initial state and after heat treatment, the hardness of the deposited material (210–240 HV_0.1) is lower than the hardness of the base material (400–440 HV_0.1). Only after heat treatment at 600°C for 1 h, the hardness increases to 240–250 HV0.1. Structure heredity in the form of a dendritic morphology is observed at temperatures of 400, 600, and 800°C. The following sharp change in the structural state is detected upon heat treatment at 1000°C for 1 h: the dendritic morphology changes into a typical α + γ crystalline structure. The hardness of the base material decreases significantly to 160–180 HV_0.1. The low hardness of the deposited layer implies the use of the layer material in limited volume to repair the forming surfaces of dies and molds for die casting. However, the high ductility of the deposited layer of the nickel-based material is a prerequisite for a high stability under thermocycling loading conditions.