Activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag and their application to the recycling of Ni–Co–Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni–Co–Fe-based end-of-life(EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO–Al_2O_3–SiO_2 slag. The activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B =(%CaO)/(%SiO_2) = 1, where B is the basicity. We observed that controlling the slag composition at approximately B = 1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

Mineral-phase evolution and sintering behavior of MO–SiO_2–Al_2O_3–B_2O_3 (M = Ca,Ba) glass-ceramics by low-temperature liquid-phase sintering

In this work, network former SiO_2 and network intermediate Al_2O_3 were introduced into typical low-melting binary compositions CaO·B_2O_3, CaO·2B_2O_3, and BaO·B_2O_3 via an aqueous solid-state suspension milling route. Accordingly, multiple-phase aluminosilicate glass-ceramics were directly obtained via liquid-phase sintering at temperatures below 950°C. On the basis of liquid-phase sintering theory, mineral-phase evolutions and glass-phase formations were systematically investigated in a wide MO–SiO_2–Al_2O_3–B_2O_3(M = Ca, Ba) composition range. The results indicate that major mineral phases of the aluminosilicate glass-ceramics are Al_(20)B_4O_(36), CaAl_2Si_2O_8, and BaAl_2Si_2O_8 and that the glass-ceramic materials are characterized by dense microstructures and excellent dielectric properties.     

Synthesis of a NiTi_2–AlNi–Al_2O_3 nanocomposite by mechanical alloying and heat treatment of Al–TiO_2–NiO

The aim of the present study was to investigate the phases formed during ball milling of Al–TiO_2–NiO. For this purpose, a mixture of Al–TiO_2–NiO with a molar ratio of 6:1:1 was used. Characterization of the milled powders by X-ray diffraction, differential thermal analysis, field-emission scanning electron microscopy, and transmission electron microscopy showed the formation of nanocrystalline NiTi_2 along with AlNi. A thermodynamical investigation confirmed that NiO was reduced by Al during ball milling, which consequently promoted TiO_2 reduction and the formation of NiTi_2. Al is capable of reducing NiO either during ball milling or at temperatures above the melting point of Al; by contrast, TiO_2 can be reduced by Al only by milling.     

Reusing oxide-based pulverised fly ash and medical waste particles to develop electroless nickel composite coatings(Ni–P/fly ash and Ni–P/SiO_2–Al_2O_3)

Recycling and reusing materials from waste have become a nexus in the development of sustainable materials, leading to more balanced technologies. In this study, we developed a composite coating by co-depositing recycled ceramic particles, pulverised fly ash(PFA) and medical ceramics(MC), into a nickel–phosphorus matrix using a typical electroless plating process. Scanning electron microscopy(SEM) images indicated well-dispersed particles in the Ni–P matrix. However, compared with the MC particles, the PFA particles were distributed scantily with a lower content in the matrix, which could be due to the less impingement effect during the co-deposition. A modified microstructure with refined grains was obtained for the PFA-incorporated composite coating, as seen in the SEM micrograph. The X-ray diffraction result of the MC-incorporated composite coating showed the formation of Nix Siy phases in addition to the typical Ni3 P phases for the heattreated electroless Ni–P coatings. Upon heat treatment, the PFA-reinforced composite coating, due to a modified microstructure, exhibited a higher microhardness up to HK0.05 818, which is comparable to that of the traditional SiC particle-embedded composite coating(HK0.05 825).The findings can potentially open up a new strategy to further advance the green approach for industrial surface engineering.     

Microstructural evolution and mechanical properties of an Fe–18Ni–16Cr–4Al base alloy during aging at 950℃

The development of Gen-IV nuclear systems and ultra-supercritical power plants proposes greater demands on structural materials used for key components. An Fe–18Ni–16Cr–4Al (316-base) alumina-forming austenitic steel was developed in our laboratory. Its microstructural evolution and mechanical properties during aging at 950℃ were investigated subsequently. Micro-structural changes were characterized by scanning electron microscopy, electron backscatter diffraction, and transmission electron microscopy. Needle-shaped NiAl particles begin to precipitate in austenite after ageing for 10 h, whereas round NiAl particles in ferrite are coarsened during aging. Precipitates of NiAl with different shapes in different matrices result from differences in lattice misfits. The tensile plasticity increases by 32.4% after aging because of the improvement in the percentage of coincidence site lattice grain boundaries, whereas the tensile strength remains relatively high at approximately 790 MPa.     

Shear-thinning behavior of the CaO–SiO_2–CaF_2–Si_3N_4 system mold flux and its practical application

Satisfying the mold-flux performance requirements for high-speed continuous casting necessitates the development of a new non-Newtonian-fluid mold flux with shear-thinning behavior, i.e., a mold flux whose viscosity is relatively high under lower shear rates and relatively low under higher shear rates. In this work, a mold flux that exhibits shear-thinning behavior was developed by adding different amounts of Si_3N_4 to the CaO–SiO_2–CaF_2 mold flux. The shear-thinning behavior was investigated using a rotational viscometer. In addition, the microstructure of the newly prepared slags was studied by high-temperature Raman spectroscopy and X-ray photoelectron spectroscopy. The results showed that the mechanism of shear-thinning was attributable to a temporary viscosity loss caused by the one-way shear stress, whereas the corresponding magnitude of shear-thinning was closely related to the degree of polymerization(DP). Finally, the non-Newtonian fluid mold flux was used for laboratory casting tests, which revealed that the mold flux could reduce slag entrapment and positively affect the continuous casting optimization.     

For progress in natural science: Materials international investigations of structural phase transformation and THz properties across metal–insulator transition in VO_2/Al_2O_3 epitaxial films

Vanadium dioxide (VO2) epitaxial thin films on (0001)-oriented Al2O3 substrates were prepared using radio frequency (RF) magnetron sputtering techniques. To study the metal-insulator-transition (MIT) mechanism and extend the applications of VO2 epitaxial films at terahertz (THz) band, temperature-dependent X-ray diffraction (XRD) and THz time domain spectroscopy of the VO2 epitaxial films were performed. Both the lattice constants and THz transmission exhibited a similar and sharp transition that was similar to that observed for the electrical resistance. Consequently, the MIT of the VO2/Al2O3 epitaxial films should be co-triggered by the structural phase transition and electronic transition. Moreover, the very large resistance change (on the order of ~103) and THz response (with a transmission modulation ratio of ~87%) in the VO2/Al2O3 epitaxial heterostructures are promising for electrical switch and electro-optical device applications.     

Low-temperature densification sintering and properties of CaAl_2Si_2O_8 ceramics with MeO·2B_2O_3(Me=Ca,Sr,Ba)

Dense CaAl2Si2O8 ceramics were prepared via a two-step sintering process at temperatures below 1000°C. First, pre-sintered Ca Al2Si2O8 powders containing small amounts of other crystal phases were obtained by sintering a mixture of calcium hydroxide and kaolin powders at 950°C for 6 h. Subsequently, the combination of the pre-sintered ceramic powders with Me O·2B2O3(Me = Ca, Sr, Ba) flux agents enabled the low-temperature densification sintering of the CaAl2Si2O8 ceramics at 950°C. The sintering behavior and phase formation of the CaAl2Si2O8 ceramics were investigated in terms of the addition of the three MeO·2B2O3 flux agents. Furthermore, alumina and quartz were introduced into the three flux agents to investigate the sintering behaviors, phase evolvements, microstructures, and physical properties of the resulting CaAl2Si2O8 ceramics. The results showed that, because of their low-melting characteristics, the MeO·2B2O3(Me = Ca, Sr, Ba) flux agents facilitated the formation of the CaAl2Si2O8 ceramics with a dense microstructure via liquid-phase sintering. The addition of alumina and quartz to the flux agents also strongly affected the microstructures, phase formation, and physical properties of the CaAl2Si2O8 ceramics.     

Hot-corrosion behavior of Cr_2O_3–CNT-coated ASTM-SA213-T22 steel in a molten salt environment at 700°C

The present work investigates the hot-corrosion behavior of carbon nanotube(CNT)-reinforced chromium oxide coatings on boiler steel in a molten salt(Na_2SO_4–60 wt%V_2O_5) environment at 700°C under cyclic conditions. The coatings were deposited via the high-velocity oxygen fuel process. The uncoated and coated steel samples were subjected to hot corrosion in a silicon tube furnace at 700°C for 50 cycles. The kinetics of the corrosion behavior was analyzed through mass-gain measurements after each cycle. The corrosion products were analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray analysis techniques. The results revealed that uncoated steel suffered spallation of scale because of the formation of nonprotective Fe_2O_3 scale. The coated steel samples exhibited lower mass gains with better adhesiveness of oxide scale with the steel alloy until the end of exposure. The CNT-reinforced coatings were concluded to provide better corrosion resistance in the hot-corrosion environment because of the uniform dispersion of CNTs in the coating matrix and the formation of protective chromium oxides in the scale.     

Evolution of ferronickel particles during the reduction of low-grade saprolitic laterite nickel ore by coal in the temperature range of 900–1250℃ with the addition of CaO–CaF_2–H_3BO_3

The method of producing ferronickel at low temperature(1250–1400℃) has been applied since the 1950s at Nippon Yakin Kogyo,Oheyama Works, Japan.Limestone was used as an additive to adjust the slag composition for lowering the slag melting point.The ferronickel product was recovered by means of a magnetic separator from semi-molten slag and metal after water quenching.To increase the efficiency of magnetic separation, a large particle size of ferronickel is desired.Therefore, in this study, the influences of CaO, CaF_2, and H_3BO_3 additives on the evolution of ferronickel particle at ≤1250℃ were investigated.The experiments were conducted at 900–1250℃ with the addition of CaO,CaF_2, and H_3BO_3.The reduction processes were carried out in a horizontal tube furnace for 2 h under argon atmosphere.At 1250℃, with the CaO addition of 10 wt% of the ore weight, ferronickel particles with size of 20 μm were obtained.The ferronickel particle size increased to 165μm by adding 10 wt% CaO and 10 wt% CaF_2.The addition of boric acid further increased the ferronickel particle size to 376 μm, as shown by the experiments with the addition of 10 wt% CaO, 10 wt% CaF_2, and 10 wt% H_3BO_3.     

Activity coefficient of NiO in SiO2-saturated MnO–SiO2slag and Al2O3-saturated MnO–SiO2–Al2O3slag at 1623 K

As a part of the fundamental study related to the reduction smelting of spent lithium-ion batteries and ocean polymetallic nodules based on MnO–SiO₂slags,this work investigated the activity coefficient of NiO in SiO₂-saturated Mn O–Si O₂slag and Al₂O₃-saturated Mn O–SiO₂–Al₂O₃slag at 1623 K with controlled oxygen partial pressure levels of 10^-7,10^-6,and 10^-5Pa.Results showed that the solubility of nickel oxide in the slags increased with increasing oxygen partial pressure.The nickel in the Mn O–Si O₂slag and Mn O–Si O₂–Al₂O₃slag existed as Ni O under experimental conditions.The addition of Al₂O₃in the Mn O–Si O₂slag decreased the dissolution of nickel in the slag and increased the activity coefficient of Ni O.Furthermore,the activity coefficient of Ni O(γN_(i O)),which is solid Ni O,in the Si O₂saturated Mn O–Si O₂slag and Al₂O₃saturated Mn O–Si O₂–Al₂O₃slag at 1623 K can be respectively calculated asγN_(i O)=8.58w(Ni O)+3.18 andγN_(i O)=11.06w(Ni O)+4.07,respectively,where w(Ni O)is the Ni O mass fraction in the slag.     

Comparative study on the corrosion behavior of X52, 3Cr,and 13Cr steel in an O_2–H_2O–CO_2 system: products,reaction kinetics,and pitting sensitivity

The corrosion behaviors of X52, 3Cr low-alloy steel, and 13Cr stainless steel were investigated in an O_2–H2O–CO_2 environment at various temperatures and O_2–CO_2 partial-pressure ratios. The results showed that the corrosion rates of X52, 3Cr, and 13Cr steels increased with increasing temperature. The corrosion rates slowly increased at temperatures less than 100°C and increased sharply when the temperature exceeded 100°C. In the absence of O_2, X52, 3Cr, and 13Cr exhibited uniform corrosion morphology and Fe CO3 was the main corrosion product. When O_2 was introduced into the system, various forms of Fe_2O_3 appeared on the surface of the samples. The Cr content strongly influenced the corrosion resistance. The 3Cr steel with a low Cr content was more sensitive to pitting than the X52 or 13Cr steel. Thus, pitting occurred on the surface of 3Cr when 1.25 MPa of O_2 was added; this phenomenon is related to the non-uniform distribution of Crin 3Cr.     

A new synthetic route to MgO–MgAl_2O_4–ZrO_2 highly dispersed composite material through formation of Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase:synthesis and physical properties

Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase was successfully synthesized from analytical-grade Mg O,α-Al_2O_3,MgAl_2O_4,and ZrO_2 under an N_2 atmosphere.The sintering temperature was varied from 1650 to 1780°C,and the highest amount of Mg_5Al_(2.4)Zr_(1.7)O_(12) appeared in the composite material when the sintering temperature was 1760°C.According to our research of the formation mechanism of Mg_5Al_(2.4)Zr_(1.7)O_(12),the formation and growth of MgAl_2O_4 dominated when the temperature was not higher than 1650°C.When the temperature was higher than 1650°C,MgO and ZrO_2 tended to diffuse into MgAl_2O_4 and the Mg_5Al_(2.4)Zr_(1.7)O_(12) solid solution was formed.When the temperature reached 1760°C,the formation of Mg_5Al_(2.4)Zr_(1.7)O_(12) was completed.The effect of Mg Al_2O_4 spinel crystals was also studied,and their introduction into the composite material promoted the formation and growth of Mg_5Al_(2.4)Zr_(1.7)O_(12).A highly dispersed MgO–Mg Al_2O_4–ZrO_2 composite material was prepared through the decomposition of the Mg_5Al_(2.4)Zr_(1.7)O_(12) metastable phase.The as-prepared composite material showed improved overall physical properties because of the good dispersion of MgO,MgAl_2O_4,and ZrO_2 phases.