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.     

Fluoride evaporation and crystallization behavior of CaF2–CaO–Al2O3–(TiO2) slag for electroslag remelting of Ti-containing steels

To elucidate the behavior of slag films in an electroslag remelting process, the fluoride evaporation and crystallization of CaF₂–CaO–Al₂O₃–(TiO₂) slags were studied using the single hot thermocouple technique. The crystallization mechanism of TiO₂-bearing slag was identified based on kinetic analysis. The fluoride evaporation and incubation time of crystallization in TiO₂-free slag are found to considerably decrease with decreasing isothermal temperature down to 1503 K. Fish-bone and flower-like CaO crystals precipitate in TiO₂-free slag melt, which is accompanied by CaF₂ evaporation from slag melt above 1503 K. Below 1503 K, only near-spherical CaF₂ crystals form with an incubation time of less than 1 s, and the crystallization is completed within 1 s. The addition of 8.1wt% TiO₂ largely prevents the fluoride evaporation from slag melt and promotes the slag crystallization. TiO₂ addition leads to the precipitation of needle-like perovskite (CaTiO₃) crystals instead of CaO crystals in the slag. The crystallization of perovskite (CaTiO₃) occurs by bulk nucleation and diffusion-controlled one-dimensional growth.     

Effect of the CaO/SiO2 mass ratio and FeO content on the viscosity of CaO-SiO2-“FeO”-12wt%ZnO-3wt%Al2O3 slags

An effective process for recycling lead from hazardous waste cathode ray tubes (CRTs) funnel glass through traditional lead smelting has been presented previously. The viscous behavior of the molten high lead slag, which is affected by the addition of funnel glass, plays a critical role in determining the production efficiency. Therefore, the viscosities of the CaO-SiO₂-"FeO"-12wt%ZnO-3wt%Al₂O₃ slags were measured in the current study using the rotating spindle method. The slag viscosity decreases as the CaO/SiO₂ mass ratio is increased from 0.8 to 1.2 and also as the FeO content is increased from 8wt% to 20wt%. The breaking temperature of the slag is lowered substantially by the addition of FeO, whereas the influence of the CaO/SiO₂ mass ratio on the breaking temperature is complex. The structural analysis of quenched slags using Fourier transform infrared (FTIR) spectroscopy and Raman spectroscopy reveals that the silicate network structure is depolymerized with increasing CaO/SiO₂ mass ratio or increasing FeO content. The[FeO₆]-octahedra in the slag melt increase as the CaO/SiO₂ mass ratio or the FeO content increases. This increase can further decrease the degree of polymerization (DOP) of the slag. Furthermore, the activation energy for viscous flow decreases both with increasing CaO/SiO₂ mass ratio and increasing FeO content.     

Sintering Behavior and Microstructure of diphasic β-Sialon/Al2O3 Composites

Six compositions with different ratio of β-Sialon/Al₂O₃ were synthesized from Al₂O₃, Si₃N₄ and SiO₂ by sintering with 3%Y₂O₃(mass fraction) as addition under the cover with powders of SiC+C and at nitrogen atmosphere. Theeffects of atmosphere, sintering temperature and composition on the sintering behavior were studied. The results showedthat the composites reached the best sintering behavior with the highest density about 92% at 1 650℃ under the weakreduction atmosphere. Finally the relative density of diphasic β-Sialon and β-Sialon/Al₂O₃ composites were studied andpredicted using ANN (Artificial Neural Networks) method and the results were experimental examined by fore randomsamples.     

Thermodynamic analysis and preparation of β-SiC/ZrO2 composites

A predominance area diagram for the Zr-Si-C-O system at 1773 K was plotted according to correlative thermodynamic data. β-SiC/ZrO₂ composites were prepared based on the phase diagram by carbothermal reduction of zircon (ZrSiO₄) in argon atmosphere. Zircon and carbon black were mixed according to the C/ZrSiO₄ mass ratio of 0.2, and with 0, 1wt% and 2wt% extra addition of La₂O₃. Phase evolution of the mixture was investigated at 1723-1803 K by X-ray powder diffraction, and the microstructure of the product prepared at 1803 K for 4 h was examined by scanning electronic microscope. The results show that the decomposition of ZrSiO₄ and the formation of β-SIC can be promoted by increasing the heating temperature and adding La₂O₃. The β-SiC/ZrO₂ composites can be prepared at 1803 K for 4 h in a mixture of zircon, carbon black and La₂O₃, and the contents of β-SIC and m-ZrO₂ in the product sample with 2wt% La₂O₃ reach the highest values of 10.8wt% and 89.2wt%, respectively. The crystal size of the products is about 200 nm.     

Activity coefficients of NiO and CoO in CaO-Al2O3-SiO2 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-Al₂O₃-SiO₂ 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-Al₂O₃-SiO₂ slag. The activity coefficients of NiO and CoO in CaO-Al₂O₃-SiO₂ 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)/(%SiO₂)=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.     

Roasting and leaching behaviors of vanadium and chromium in calcification roasting–acid leaching of high-chromium vanadium slag

Calcification roasting–acid leaching of high-chromium vanadium slag (HCVS) was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium. The effects of the purity of CaO, molar ratio between CaO and V₂O₅ (n(CaO)/n(V₂O₅)), roasting temperature, holding time, and the heating rate used in the oxidation–calcification processes were investigated. The roasting process and mechanism were analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and thermogravimetry–differential scanning calorimetry (TG–DSC). The results show that most of vanadium reacted with CaO to generate calcium vanadates and transferred into the leaching liquid, whereas almost all of the chromium remained in the leaching residue in the form of (Fe_0.6Cr_0.4)₂O₃. Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with CaO. Moreover, CaO was more likely to combine with vanadium, as further confirmed by thermodynamic analysis. When the HCVS with CaO added in an n(CaO)/n(V₂O₅) ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10℃/min from room temperature to 950℃ and maintained at this temperature for 60 min, the leaching ratios of vanadium and chromium reached 91.14% and 0.49%, respectively; thus, efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium. Furthermore, the oxidation and calcification reactions of the spinel phases occurred at 592 and 630℃ for n(CaO)/n(V₂O₅) ratios of 0.5 and 5, respectively.     

Preparation of ferronickel from nickel laterite via coal-based reduction followed by magnetic separation

The sticking phenomenon between molten slag and refractory is one of the crucial problems when preparing ferronickel from laterite ore using rotary hearth furnace or rotary kiln processes. This study aims to ameliorate sticking problems by using silicon dioxide (SiO₂) to adjust the melting degree of the briquette during reduction roasting. Thermodynamic analysis indicates that the melting temperature of the slag gradually increases with an increase in the SiO₂ proportion (SiO₂/(SiO₂ + Al₂O₃ + MgO) mass ratio). Experimental validations also prove that the briquette retains its original shape when the SiO₂ proportion is greater than 75wt%, and sticking problems are avoided during reduction. A ferronickel product with 8.33wt% Ni and 84.71wt% Fe was prepared via reductive roasting at 1500℃ for 90 min with a SiO₂ proportion of 75wt% and a C/O molar ratio of 1.0 followed by dry magnetic separation; the corresponding recoveries of Ni and Fe reached 75.70% and 77.97%, respectively. The microstructure and phase transformation of reduced briquette reveals that the aggregation and growth of ferronickel particles were not significantly affected after adding SiO₂ to the reduction process.     

Phosphate enrichment mechanism in CaO–SiO2–FeO–Fe2O3–P2O5 steelmaking slags with lower binary basicity

The addition of silica to steelmaking slags to decrease the binary basicity can promote phosphate enrichment in quenched slag samples. In this study, we experimentally investigated phosphate enrichment behavior in CaO–SiO₂–FeO–Fe₂O₃–P₂O₅ slags with a P₂O₅ content of 5.00% and the binary basicity B ranging from 1.0 to 2.0, where the (%Fe_tO)/(%CaO) mass percentage ratio was maintained at 0.955. The experimental results are explained by the defined enrichment degree R_C2S-C3P of solid solution 2CaO·SiO₂–3CaO·P₂O₅ (C₂S–C₃P), where R_C2S-C3P is a component of the developed ion and molecule coexistence theory (IMCT)–N_i model for calculating the mass action concentrations N_i of structural units in the slags on the basis of the IMCT. The asymmetrically inverse V-shaped relation between phosphate enrichment and binary basicity B was observed to be correlated in the slags under applied two-stage cooling conditions. The maximum content of P₂O₅ in the C₂S–C₃P solid solution reached approximately 30.0% when the binary basicity B was controlled at 1.3.     

Effect of NaCl on synthesis of ZrB2 by a borothermal reduction reaction of ZrO2

ZrB₂ powders were synthesized via a borothermal reduction reaction of ZrO₂ with the assistance of NaCl under a flowing Ar atmosphere. The optimal temperature and reaction time were 1223 K and 3 h, respectively. Compared with the reactions conducted without the addition of NaCl, those performed with the addition of an appropriate amount of NaCl finished at substantially lower temperatures. However, the addition of too much NaCl suppressed this effect. With the assistance of NaCl, a special morphology of polyhedral ZrB₂ particles covered with ZrB₂ nanosheets was obtained. Moreover, the experimental results revealed that the special morphology was the result of the combined effects of B₂O₃ and NaCl. The formation of the special microstructure is explained on the basis of the "dissolution-recrystallization" mechanism.     

TiO2对含铬高钛熔分渣熔化性能和黏度的影响

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag (CaO–SiO₂–MgO–Al₂O₃–TiO₂–Cr₂O₃) with TiO₂ contents ranging from 38.63wt% to 42.63wt% was conducted. The melting properties were investigated with a melting-point apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO₂ content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO₂ content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO₂ content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO₂.     

In situ reaction mechanism of MgAlON in Al-Al2O3-MgO composites at 1700℃ under flowing N2

The Al-Al₂O₃-MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M₁, M₂, and M₃, respectively, were prepared at 1700℃ for 5 h under a flowing N₂ atmosphere using the reaction sintering method. After sintering, the Al-Al₂O₃-MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M₁ was composed of MgO and MgAl₂O₄. Compared with specimen M₁, specimens M₂ and M₃ possessed MgAlON, and its production increased with increasing aluminum addition. Under an N₂ atmosphere, MgO, Al₂O₃, and Al in the matrix of specimens M₂ and M₃ reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al-Al₂O₃-MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N₂ atmosphere, the partial pressure of oxygen is quite low; thus, when the Al-Al₂O₃-MgO composites were soaked at 580℃ for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al₂O₃ diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al₂O₃ to form MgAl₂O₄. When the temperature was greater than (1640 ±10)℃, AlN diffused into Al₂O₃ and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and MgAl₂O₄ at high temperatures because of their similar spinel structures.     

18wt%Cr–8wt%Ni不锈钢中增塑性MnO–Al2O3–SiO2基非金属夹杂物的演变及其浸泡性能

The properties of MnO–Al₂O₃–SiO₂-based plasticized inclusion are likely to change during soaking  process due to its low melting point. In this study, the evolution of the MnO–Al₂O₃–SiO₂-based inclusion of 18wt%Cr?8wt%Ni stainless steel under isothermal soaking process at 1250°C for different times was investigated by laboratory-scale experiments and thermodynamic analysis. The results showed that the inclusion population density increased at the first stage and then decreased while their average size first decreased and then increased. In addition, almost no Cr₂O₃-concentrated regions existed within the inclusion before soaking, but more and more Cr₂O₃ precipitates were formed during soaking. Furthermore, the plasticity of the inclusion deteriorated due to a decrease in the amount of liquid phase and an increase in the high-melting-point-phase MnO–Cr₂O₃ spinel after the soaking process. In-situ observations by high-temperature confocal laser scanning microscopy (CLSM) confirmed that liquid phases were produced in the inclusions and the inclusions grew rather quickly during the soaking process. Both the experimental results and thermodynamic analysis conclude that there are three routes for inclusion evolution during the soaking process. In particular, Ostwald ripening plays an important role in the inclusion evolution, i.e., MnO–Al₂O₃–SiO₂-based inclusions grow by absorbing the newly precipitated smaller-size MnO–Cr₂O₃ inclusions.     

Microstructure and properties of Ag–Ti3SiC2 contact materials prepared by pressureless sintering

Ti₃SiC₂-reinforced Ag-matrix composites are expected to serve as electrical contacts. In this study, the wettability of Ag on a Ti₃SiC₂ substrate was measured by the sessile drop method. The Ag–Ti₃SiC₂ composites were prepared from Ag and Ti₃SiC₂ powder mixtures by pressureless sintering. The effects of compacting pressure (100–800 MPa), sintering temperature (850–950℃), and soaking time (0.5–2 h) on the microstructure and properties of the Ag–Ti₃SiC₂ composites were investigated. The experimental results indicated that Ti₃SiC₂ particulates were uniformly distributed in the Ag matrix, without reactions at the interfaces between the two phases. The prepared Ag–10wt%Ti₃SiC₂ had a relative density of 95% and an electrical resistivity of 2.76×10-3 mΩ·cm when compacted at 800 MPa and sintered at 950℃ for 1 h. The incorporation of Ti₃SiC₂ into Ag was found to improve its hardness without substantially compromising its electrical conductivity; this behavior was attributed to the combination of ceramic and metallic properties of the Ti₃SiC₂ reinforcement, suggesting its potential application in electrical contacts.     

Fabrication of Fe–TiC–Al2O3 composites on the surface of steel using a TiO2–Al–C–Fe combustion reaction induced by gas tungsten arc cladding

The aim of the present study was to fabricate Fe–TiC–Al₂O₃ composites on the surface of medium carbon steel. For this purpose, TiO₂–3C and 3TiO₂–4Al–3C–xFe (0 ≤ x ≤ 4.6 by mole) mixtures were pre-placed on the surface of a medium carbon steel plate. The mixtures and substrate were then melted using a gas tungsten arc cladding process. The results show that the martensite forms in the layer produced by the TiO₂–3C mixture. However, ferrite–Fe₃C–TiC phases are the main phases in the microstructure of the clad layer produced by the 3TiO₂–4Al–3C mixture. The addition of Fe to the TiO₂–4Al–3C reactants with the content from 0 to 20wt% increases the volume fraction of particles, and a composite containing approximately 9vol% TiC and Al₂O₃ particles forms. This composite substantially improves the substrate hardness. The mechanism by which Fe particles enhance the TiC + Al₂O₃ volume fraction in the composite is determined.     

La2O3–Al2O3 –SiO2 glass-infiltrated 3Y-TZP all-ceramic composite for the dental restora tive application

The 3 mol% yttria stabilized tetragonal zirconia polycrystals (3Y-TZP) powder had three particle size distributions, while the fine one was lower than 100 nm. The 3Y-TZP compact was prepared by dry-pressing under pressures ranged from 10 to 30 MPa and then presintered at 1250°C for 2 h. The matrix dry-pressed under the pressure of 20 MPa had a porosity of 16.7% and could be easily processed by computer aided design and computer aided manufacturing (CAD/CAM), and which had been infiltrated by the La2O3–Al2O3–SiO2 glass at 1200°C for 4 h. The flexural strength and fracture toughness of the composite were 710.7 MPa and 6.51 MPa m^1/2, respectively. The low shrinkage (0.3%) of the composite can satisfy the net-shape fabrication standard. XRD results illustrated that zirconia in the La2O3–Al2O3–SiO2 glass-infiltrated 3Y-TZP all-ceramic composite was mainly in the tetragonal phase. SEM and EDS results indicated that the pores of the matrix were almost filled by the La2O3–Al2O3 –SiO2 glass     

Preparation of nano-TiO2/diatomite-based porous ceramics and their photocatalytic kinetics for formaldehyde degradation

Diatomite-based porous ceramics were adopted as carriers to immobilize nano-TiO₂ via a hydrolysis-deposition technique. The thermal degradation of as-prepared composites was investigated using thermogravimetric-differential thermal analysis, and the phase and microstructure were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and transmission electron microscopy. The results indicated that the carriers were encapsulated by nano-TiO₂ with a thickness of 300-450 nm. The main crystalline phase of TiO₂ calcined at 650℃ was anatase, and the average grain size was 8.3 nm. The FT-IR absorption bands at 955.38 cm-1 suggested that new chemical bonds among Ti, O, and Si had formed in the composites. The photocatalytic (PC) activity of the composites was investigated under UV irradiation. Furthermore, the photodegradation kinetics of formaldehyde was investigated using the composites as the cores of an air cleaner. A kinetics study showed that the reaction rate constants of the gas-phase PC reaction of formaldehyde were κ=0.576 mg·m-3·min-1 and K=0.048 m3.     

Effect of diboron trioxide on the crushing strength and smelting mechanism of high-chromium vanadium-titanium magnetite pellets

The effect of diboron trioxide (B₂O₃) on the crushing strength and smelting mechanism of high-chromium vanadium-titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma-atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy-energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B₂O₃ content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B₂O₃ content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B₂O₃ content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B₂O₃. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B₂O₃ content.     

Carbothermic reduction of vanadium titanomagnetite with the assistance of sodium carbonate

The carbothermic reduction of vanadium titanomagnetite concentrate(VTC)with the assistance of Na₂CO₃was conducted in an argon atmosphere between 1073 and 1473 K.X-ray diffraction and scanning electron microscopy were used to investigate the phase transformations during the reaction.By investigating the reaction between VTC and Na₂CO₃,it was concluded that molten Na₂CO₃broke the structure of titanomagnetite by combining with the acidic oxides(Fe₂O₃,TiO₂,Al₂O₃,and SiO₂)to form a Na-rich melt and release FeO and MgO.Therefore,Na₂CO₃accelerated the reduction rate.In addition,adding Na₂CO₃also benefited the agglomeration of iron particles and the slag–metal separation by decreasing the viscosity of the slag.Thus,Na₂CO₃assisted carbothermic reduction is a promising method for treating VTC at low temperatures.     

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.