High Temperature Corrosion of a Ternary Ni–29Mo–4Fe Alloy in a Mixed Hydrogen Chloride–Water Vapour Atmosphere

Abstract

The corrosion of a Ni–29Mo–4Fe (wt-%) ternary alloy in an atmosphere containing HCl, water vapour and some free oxygen has been studied at 600° and 700°c. The alloy shows a linear weight loss as a function of time, due to the formation of different volatile compounds predicted on thermodynamic grounds for the system, but at the same time it is covered by a complex scale composed mainly of oxides but containing also some chlorine. Comparison with the corrosion behaviour of the corresponding binary Ni–29Mo alloy shows that the addition of iron has a deleterious effect on the corrosion resistance of the alloy in this environment at 700°c, although it is slightly beneficial at 600°c. Possible reasons for this effect are discussed on the basis of the observed scale structure and of the formation of iron compounds.     

A New Technique for Preparation of High-Grade Titanium Slag from Titanomagnetite Concentrate by Reduction–Melting–Magnetic Separation Processing

This paper proposes a new technique for preparation of high-grade titanium slag from Panzhihua vanadium titanomagnetite concentrate by reduction–melting–magnetic separation processing. Chemical analysis, x-ray diffraction, and scanning electron microscopy in conjunction with energy-dispersive spectroscopy were used to characterize the samples. The effective separation of iron and titanium slag could be realized by melting metallized pellets at 1550°C for 60 min with the addition of 1% CaO (basicity of 1.1) and 2% graphite powder. The small iron particles embedded in the slag could be removed by fine grinding and magnetic separation process. The grade of TiO₂ in the obtained high-grade titanium slag reached 60.68% and the total recovery of TiO₂ was 91.25%, which could be directly applied for producing titanium white by the sulfuric acid process. This technique provides an alternative method to use vanadium titanomagnetite concentrate of the Panzhihua area in China.     

Shape Memory Effect Induced by Stress-induced α' Martensite in a Metastable Fe–Cr–Ni Austenitic Stainless Steel

It is not clear whether a shape memory effect(SME) can be realized by stress-induced α' martensite in metastable austenitic stainless steels although the stress-induced ε martensite in these materials can result in the SME. To clarify this problem, the relationship between the shape recovery and the reverse transformation of the stress-induced ε and α' martensite in a 304 stainless steel was investigated. The results show that the stress-induced α' martensite can result in the SME when heating above 773 K. After deformation at 77 K and step heating or directly holding at 1073 K, two-stage shape recoveries below 440 K and above 773 K can be obtained due to the reverse transformation of the stress-induced e martensite and α' martensite, respectively. After deformation at room temperature, the α' martensite produced can result in the SME only when directly holding at 1073 K. The intrusion of more dislocations before the formation of the α' martensite at room temperature than at 77 K is the reason that the α' martensite induced at room temperature cannot result in the SME in the case of slow heating. The recovered strains resulting from the stress-induced ε and α' martensite are proportional to the amounts of their reverse transformation, respectively.     

In situ observation of solidification behavior in undercooled Pd–Cu–Ni–P alloy by using a confocal scanning laser microscope

In the undercooled melt of Pd₄₀Cu₃₀Ni₁₀P₂₀ alloy, the solidification behavior including the nucleation and growth of crystals at the micrometer level has been observed in situ by use of a confocal scanning laser microscope combined with an infrared image furnace. The Pd₄₀Cu₃₀Ni₁₀P₂₀ alloy specimens were cooled from the liquid state to various undercooled states under a helium gas flow. Images of solidification progress were obtained by the charge-coupled device image sensor of the confocal scanning laser microscope. Depending on the degree of undercooling, the morphology of the solidification front changed among various types: faceted front, columnar dendritic front, cellular grain and equiaxed grain, etc. The velocities of the solid–liquid interface were measured to be 10⁻⁵–10−7 m/s, which are at least two orders of magnitude higher than the theoretical crystal growth rates. Combining the morphologies observed in the three undercooling regimes and their solidification behaviors, we conclude that phase separation takes place in the undercooled molten Pd₄₀Cu₃₀Ni₁₀P₂₀ alloy. The continuous-cooling–transformation (CCT) diagram was derived from the experimental time–temperature-transformation diagram constructed from solidification onset times under various isothermal annealing conditions. The CCT diagram suggests that the critical cooling rate for glassy solidification is about 1.8 K/s, which is in agreement with previous calorimetric findings.     

Analysis of phases in a Cu–Cr–Zr alloy

Phases of a Cu–0.31%Cr–0.21%Zr alloy were analyzed by scanning electronic microscope and energy dispersive X-ray spectroscopy (EDXS) and transmission electronic microscope (TEM). The EDXS results showed that there are three types of phases in the alloy, Cu-matrix, chromium-rich and zirconium-rich phases; coarse phases mainly consist of zirconium-rich phase. TEM result showed that fine chromium distributed in matrix and Cu₅₁Zr₁₄ phase was found in matrix.     

Sulfuric acid leaching of low-grade refractory tantalum–niobium and associated rare earths minerals in Panxi area of China

By mineral liberation analyzer(MLA) automated quantitative system, the niobium–tantalum ore in this study was classified as refractory mineral of low-grade which was mainly composed of fergusonite, polycrase, ilmenorutile, and bastnasite. Most of niobium and rare earth metals were disseminated in these minerals(particle sizes of 95% rare earth elements40μm), which cannot be concentrated through traditional floatation process and treated by the current hydrofluoric acid leaching in industry application. It is necessary to develop a new approach to recovery these valuable metals. In this study, an improved method is proposed to extract these metals, which includes acid roasting and sulfuric acid leaching. The influence of mineralogy, acid concentration, leaching temperature, leaching time, and liquid to solid ratio was experimentally studied. It is observed that after the ground ore(-74μm) was roasted at 350 °C for 2 h with sulfuric acid(18.4 mol·L-1) in the ore to acid mass ratio of 1:1,and then the roasting residue reacted with 25% sulfuric acid at 90 °C for 2h, the recovery rate of rare earth elements reaches[90%, and the leaching extent of niobium can reach 84%.     

High-temperature deformation in a Ta–W alloy

High-temperature deformation was investigated in a Ta–2.5 wt% W commercially available tantalum alloy, at temperatures in the range of 1523–1723 K and at a stress range extending from 35 MPa to 210 MPa. The experimental data, which cover several orders of magnitude of strain rate, show that the stress dependence of creep rate is high and that the temperature dependence of creep rate is higher than that for self-diffusion in tantalum. An analysis of the experimental data indicates that a threshold stress for creep exists, and that the temperature dependence of the threshold stress is much stronger than that attributable to the shear modulus. By considering the effect of the threshold stress and its temperature dependence on creep plots, it is demonstrated that the true creep characteristics of Ta–2.5 wt% W are consistent with those reported for solid-solution alloys at high stresses. In particular, the creep behavior of the alloy exhibits a transition from a region controlled by viscous glide to a high-stress region related to the breakaway of dislocations from solute-atom atmospheres. An examination of creep substructure in Ta–2.5 wt% W reveals the presence of interaction between moving dislocations and dispersion particles. It is suggested that such an interaction provides the most likely source of the threshold stress for creep in the alloy.     

Anodic Behaviour of 17–7 Precipitation Hardening Stainless Steel in Acid Media

Abstract

The anodic behaviour of 17–7 precipitation hardening stainless steel in 0.5 M H₂SO₄ and 0.5 M H₂SO₄ + Cl^? solutions was investigated in detail. The coulometric areas of the two anodic peaks in the potentiodynamic curve in the chloride-free solution are dependent upon the duration of the free corrosion between the preliminary cathodic activation and the starting of the potentiodynamic scan. When the free corrosion time exceeds 6 minutes the peak at the more active potential disappears completely.

The influence of the free corrosion time was much less evident in the presence of chloride ions; in these conditions anodic currents were greater.

It was also established that the two anodic peaks correspond to the active-passive transitions relative to the two phases composing the steel: austenite and δ-ferrite. This was seen by potentiostatically etching the steel in the active dissolution ranges of both anodic peaks.

Finally it was shown, both micrographically and by comparing the anodic curves of pickled and polished specimens, that ordinary nitric–hydrofluoric pickling solutions selectively attack the austenite.     

Improvement of Oxidation Behavior of a Ti–48Al–2Cr Alloy by a Nitridation Treatment

The effect of a nitridation treatment for 10 hr at 800°C on the oxidation resistance of a Ti–48Al–2Cr (at.%) alloy in air at 800°C was evaluated. Results prove that nitridation decreases by about 40% the total mass gain of nonnitrided material, although the oxidation mechanism is the same for both materials. The oxidation can be divided into two stages. The formation of a nonprotective mixed alumina–rutile scale during the transient stage results in a high oxidation rate. A further decrease in the oxidation rate arises from the establishment of an external alumina-rich layer during the steady stage. The main difference between the scale developed on both materials is the continuous nature of the nitride layer present in the nitrided material during the entire exposure. The thin continuous nitride layer formed during the nitridation treatment acts beneficially as a diffusion barrier, preventing oxygen dissolution in the ₂-Ti₃Al phase during the transient stage. Furthermore, the oxygen gradient through the oxide scale is kept low, because no oxygen is removed at the scale–alloy interface.     

Hardening precipitation in a Mg–4Y–3RE alloy

Early stages of precipitation in a Mg–Y–Nd based alloy aged at 150 °C have been studied using TEM and small angle X-ray scattering (SAXS). The former brings information concerning nature, morphology and size of precipitates, and the latter adds qualitative and quantitative information concerning populations of precipitates in terms of size and volume fraction. Precipitation at 150 °C involves formation of DO₁₉ monoplanar precipitates, which further develop into the β″ and β′ phases having platelet and globular morphologies, respectively. TEM observations on samples aged at 150 °C reveal the formation mechanism of the bco-β′ structure by the ordering of monoplanar DO₁₉-β″ precipitates. Additional examinations at 250 °C revealed the DO₁₉-β″→bco-β′ transformation, as well as β₁ precipitates. Estimation of the volume fraction deduced from SAXS is discussed on the basis of the TEM results.     

Studying recovery processes in a strain-hardened Al–Mg–Mn–Fe–Si alloy

The material of a shell structure subjected to 20-year use under ambient conditions has been studied. The structure and mechanical characteristics of a strain-hardened AMg6 alloy, as well as the effect of subsequent holdings of this alloy for 10–3000 h at temperatures of 50, 70, 80, 100, 130, 150, 180, and 220°C, on changes in its dislocation structure and mechanical characteristics have been investigated. It has been shown that, in the structures under study, the AMg6 alloy has a cellular structure with a high density of dislocations and the ultimate strength σ_u = 445.5 ± 2.5 MPa, the proof stress σ_0.2 = 326.5 ± 3.5 MPa, and the relative elongation δ = 11.7 ± 0.5%. Polygonization in the alloy occurs at a temperature of 220°C and the initial stage of the recovery process corresponds to a temperature range of 50–100°С in which the softening process can be divided into two stages, i.e., stage (1) of active softening due to the interaction of point defects with each other and stage (2) of the stabilization of the characteristics of the alloy.     

Defect-induced Au precipitation in Fe–Au and Fe–Au–B–N alloys studied by in situ small-angle neutron scattering

Nanoscale Au precipitation in high-purity Fe–Au and Fe–Au–B–N alloys has been studied by in situ small-angle neutron scattering during isothermal aging at 550 °C and complementary ex situ transmission electron microscopy. The high temperature precipitation behavior in samples having received different degrees of cold deformation has been studied to explore the potential self-healing of deformation-induced defects by Au precipitation. It is found that dislocations induced by prior plastic deformation strongly facilitate the formation of Au precipitates, as no significant precipitation is observed for undeformed samples. Defect-induced Au precipitates are formed both at dislocations and along grain boundaries where the defect density is high. The fact that the Au atoms only precipitate on deformation-induced defects demonstrates that solute gold atoms act as efficient self-healing agents in the ferrous matrix. The addition of B and N is found to retard the Au precipitation.     

Direct observation of dislocation dissociation and Suzuki segregation in a Mg–Zn–Y alloy by aberration-corrected scanning transmission electron microscopy

Crystal defects in a plastically deformed Mg–Zn–Y alloy have been studied on the atomic scale using aberration-corrected scanning transmission electron microscopy, providing important structural data for understanding the material’s deformation behavior and strengthening mechanisms. Atomic scale structures of deformation stacking faults resulting from dissociation of different types of dislocations have been characterized experimentally, and modeled. Suzuki segregation of Zn and Y along stacking faults formed through dislocation dissociation during plastic deformation at 300 °C is confirmed experimentally on the atomic level. The stacking fault energy of the Mg–Zn–Y alloy is evaluated to be in the range of 4.0–10.3 mJ m^?2. The newly formed nanometer-wide stacking faults with their Zn/Y segregation in Mg grains play an important role in the superior strength of this alloy at elevated temperatures.     

Non-equilibrium Phases Formed in Cu–In–Se–Te System Synthesized by Melt-Quench Method

Non-equilibrium phases formed in melt-quenched Cu In(SexTe1-x)2system, where x = 0.1, 0.2, 0.4, 0.5, 0.6,0.8 and 0.9, have been studied using Rietveld refinement of the crystal structure and Raman spectroscopy. Results of structure refinement have showed that all the samples, except the Cu In(Se0.1Te0.9)2, are heterogeneous. All the observed non-equilibrium phases are quaternary system and are found to have chalcopyrite structure(I"42d), in accordance with the Cu In Te2–Cu In Se2 phase diagram. The lattice constants deduced from the refinement have showed linear variation with Se content. A detailed analysis of the characteristic A1 modes present in the Raman spectrum of individual sample has corroborated the results obtained from the structure analysis. The position of A1 mode of individual phase is found to vary linearly with Se content, which suggests that Cu In(SexTe1-x)2system exhibits single-mode behaviour.     

Microstructure of phases in a Cu–Zr alloy

The morphology and crystallography of phases in the Cu-0.12% Zr alloy were investigated by scanning electron microscope(SEM), transmission electron microscope(TEM), and high-resolution transmission electron microscope(HRTEM). The results show that the as-cast microstructure of Cu–Zr alloy is mainly Cu matrix and eutectic structure which consist of Cu and Cu5Zr phases with a fine lamellar structure. The disk-shaped and plateliked Cu5Zr phases with fcc structure are found in the matrix, in which habit plane is parallel to {111}a plane of the matrix.Between the copper matrix and Cu5Zr phase,there exists an orientation relationship of [112]a|| [011]Cu5Zr;(111)a||(111)Cu5Zr. The space structure model of Cu5Zr phase can be established.     

Stress–strain relationship between ferrite and martensite in a dual-phase steel studied by in situ neutron diffraction and crystal plasticity theories

The stress–strain relationship between ferrite and martensite phases in the commercial dual-phase DP980 steel was studied using in situ neutron diffraction and the crystal plasticity finite element method (CPFEM). The phase identification method based on the image quality of electron backscatter diffraction and a filtering process was used to obtain information concerning individual crystallographic orientations for ferrite and martensite phases in DP980 steel. The (2 0 0) and (2 1 1) lattice strains of ferrite and martensite phases were measured along the loading and transverse directions as a function of macroscopic stress using in situ neutron diffraction. A CPFEM based on representative volume elements (RVE) was applied to determine the microscopic hardening parameters for each phase by fitting the measured macroscopic stress and measured (2 0 0) and (2 1 1) lattice strains. The microscopic hardening parameters for each phase successfully captured the influence of the crystallographic orientation of the ferrite phase on the localization of shear strain and the behavior of ductile failure in RVE of the unit cell during uniaxial tension.     

Defects caused by precipitation of in liquid copper–nickel–aluminium–bronze alloys dissolved carbon and removal by treatment of melt

Castings made of copper–nickel–aluminium bronze (CuAl₁₀Fe₅Ni₅) alloys regularly show defects in the thick, slowly solidifying parts of the castings, which give rise to rejections. Metallographic examination has been made on material of scrap castings showing porosity accompanied with film-like inclusions located beside the iron rich κ_II phases. Investigations of large failed cast structures of copper–nickel–aluminium bronze show the same characteristic defects on which fatigue cracks initiate and grow. Investigation has been made to the nature and the cause of appearance of the film-like inclusions. Microanalysis indicates a high intensity of carbon at the place of the film-like inclusions. Hereafter, an investigation has been made into the solubility of carbon in liquid copper–nickel–aluminium bronze, and it is found that besides hydrogen, also carbon is soluble in copper–nickel–aluminium bronze alloys. The appearance of the carbon as flakes in the fracture surface of materials with defects does suspect there is a nucleating effect on the formation of microporosity causing the defects. To prevent the formation of the casting defects by the interaction between solved hydrogen and carbon, it is necessary to remove the carbon as far as possible by treatment of the melt.