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.     

Comprehensive model for a slag bath in electroslag remelting process with a current-conductive mould

A mathematical model was developed to describe the interaction of multiple physical fields in a slag bath during electroslag remelting (ESR) process with a current-conductive mould. The distributions of current density, magnetic induction intensity, electromagnetic force, Joule heating, fluid flow and temperature were simulated. The model was verified by temperature measurements during remelting 12CrMoVG steel with a slag of 50wt%-70wt% CaF₂, 20wt%-30wt% CaO, 10wt%-20wt% Al₂O₃, and ≤ 10wt% SiO₂ in a 600 mm diameter current-conductive mould. There is a good agreement between the calculated temperature results and the measured data in the slag bath. The calculated results show that the maximum values of current density, electromagnetic force and Joule heating are in the region between the corner electrodes and the conductivity element. The characteristics of current density distribution, magnetic induction intensity, electromagnetic force, Joule heating, velocity patterns and temperature profiles in the slag bath during ESR process with current-conductive mould were analyzed.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction by coupling combustion with recycling flue gas in iron ore sintering process

A new process called ‘NO _x reduction by coupling combustion with recycling flue gas (RCCRF)’ was proposed to decrease NO _x emission during the iron ore sintering process. The simulation test of NO _x reduction was performed over sintered ore and in the process of coke combustion. Experimentally, NO _x reduction was also carried out by sintering pot test. For sintered ore, the amount of NO _x emission is reduced by 15wt%–25wt% at 400–550°C using 2.0vol% H₂ or 2.0vol% CO, or reduced by 10wt%–30wt% at 560–720°C using 0.15vol% NH₃. NO _x reduction is around 10wt% by coupling combustion of pyrolysis gas and coke, or around 16wt% by recycling flue gas into coke combustion. By RCCRF, the maximum NO _x reduction ratio is about 23wt% in coke combustion experiment and over 40wt% in sintering pot test.     

Effect of TiO<Subscript>2</Subscript> on the viscosity and structure of low-fluoride slag used for electroslag remelting of Ti-containing steels

The viscosity of CaF₂-CaO-Al₂O₃-MgO-(TiO₂) slag was measured using a rotating crucible viscometer. Raman spectroscopy analysis was performed to correlate the viscosity to slag structure. The viscosity of the slag was found to decrease with increasing TiO₂ content in the slag from 0 to 9.73wt%. The activation energy decreased from 95.16 kJ/mol to 79.40 kJ/mol with increasing TiO₂ content in the slag. The introduction of TiO₂ into the slag played a destructive role in Al-O-Al structural units and Q4 units by forming simpler structural units of Q2 and Ti₂O₆4- chain. The amount of Al-O-Al significantly decreased with increasing TiO₂ content. The relative fraction of Q4 units in the[AlO₄]5--tetrahedral units shows a decreasing trend, whereas the relative fraction of Q2 units and Ti₂O₆4- chain increases with increasing TiO₂ content accordingly. Consequently, the polymerization degree of the slag decreases with increasing TiO₂ content. The variation in slag structure is consistent with the change in measured viscosity.     

Dripping and evolution behavior of primary slag bearing TiO<Subscript>2</Subscript> through the coke packed bed in a blast-furnace hearth

To investigate the flow of primary slag bearing TiO₂ in the cohesive zone of blast furnaces,experiments were carried out based on the laboratory-scale packed bed systems.It is concluded that the initial temperature of slag dripping increases with decreasing FeO content and increasing TiO₂ content.The slag holdup decreases when the FeO content is in the range of 5wt%-10wt%,whereas it increases when the FeO content exceeds 10wt%.Meanwhile,the slag holdup decreases when the TiO₂ content increases from 5wt% to 10wt% but increases when the TiO₂ content exceeds 10wt%.Moreover,slag/coke interface analysis shows that the reaction between FeO and TiO₂ occurs between the slag and the coke.The slag/coke interface is divided into three layers:slag layer,iron-rich layer,and coke layer.TiO₂ in the slag is reduced by carbon,and the generated Ti diffuses into iron.     

Effect of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO-Al₂O₃-SiO₂ (CAS) glass-ceramics were prepared via a melting method using naturally cooled yellow phosphorus furnace slag as the main raw material. The effects of the addition of Fe₂O₃ on the crystallization behavior and properties of the prepared glass-ceramics were studied by differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The crystallization activation energy was calculated using the modified Johnson-Mehl-Avrami equation. The results show that the intrinsic nucleating agent in the yellow phosphorus furnace slag could effectively promote the crystallization of CAS. The crystallization activation energy first increased and then decreased with increasing amount of added Fe₂O₃. At 4wt% of added Fe₂O₃, the crystallization activation energy reached a maximum of 676.374 kJ·mol-1. The type of the main crystalline phase did not change with the amount of added Fe₂O₃. The primary and secondary crystalline phases were identified as wollastonite (CaSiO₃) and hedenbergite (CaFe(Si₂O₆)), respectively.     

Effect of slag composition on the cleanliness of 28MnCr5 gear steel in the refining processes

The equilibrium reaction between CaO—Al₂O₃—SiO₂—MgO slag and 28MnCr5 molten steel was calculated to obtain the suitable slag composition which is effective for decreasing the oxygen content in molten steel. The dissolved oxygen content [O] in molten steel under different top slag conditions was calculated using a thermodynamic model and was measured using an electromotive force method in slag–steel equilibrium experiments at 1873 K. The relations among [O], the total oxygen content (T.O), and the composition of the slag were investigated. The experimental results show that both [O] and T.O decrease with decreasing SiO₂ content of the slag and exhibit different trends with the changes in the CaO/Al₂O₃ mass ratio of the slag. Increasing the CaO/Al₂O₃ mass ratio results in a decrease in [O] and an increase in T.O. To ensure that T.O ≤ 20 ppm and [O] ≤ 10 ppm, the SiO₂ content should be controlled to <5wt%, and the CaO/Al₂O₃ mass ratio should be in the range from 1.2 to 1.6.     

Characteristics of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>, MnS,and TiN inclusions in the remelting process of bearing steel

The Al₂O₃, MnS, and TiN inclusions in bearing steel will deteriorate the steel's mechanical properties. Therefore, elucidating detailed characteristics of these inclusions in consumable electrode during the electroslag remelting process is important for achieving a subsequently clean ingot. In this study, a confocal scanning violet laser microscope was used to simulate the remelting process and observe, in real time, the behaviors of inclusions. The obtained images show that, after the temperature exceeded the steel solidus temperature, MnS and TiN inclusions in the specimen began to dissolve. Higher temperatures led to faster dissolution, and the inclusions disappeared before the steel was fully liquid. In the case of an observed Al₂O₃ inclusion, its shape changed from angular to a smooth ellipsoid in the region where the solid and liquid coexisted and it began to dissolve as the temperature continued to increase. This dissolution was driven by the difference in oxygen potential between the inclusion and the liquid steel.     

Microwave sintering of Ca<Subscript>0.6</Subscript>La<Subscript>0.2667</Subscript>TiO<Subscript>3</Subscript> microwave dielectric ceramics

Ca_0.6La_0.2667TiO₃ ceramics were prepared by conventional and microwave sintering techniques and their sinterability, microstructure, and microwave dielectric properties were investigated in detail for comparison. Densified Ca_0.6La_0.2667TiO₃ ceramics were obtained by microwave sintering at 1350°C for 30 min and by conventional sintering at 1450°C for 4 h. An unusual phenomenon was found that some larger grains (grain size range: 8–10 μm) inclined to assemble in one area but some smaller ones (grain size range: 2–4 μm) inclined to gather in another area in the microwave sintered ceramics. The microwave dielectric properties of Ca_0.6La_0.2667TiO₃ ceramics prepared by microwave sintering at 1350°C were as follows: dielectric constant (ɛ _r) = 119.6, quality factor (Qf) = 17858.5 GHz, and temperature coefficient of resonant frequency (τ _f) = 155.5 ppm/°C. In contrast, the microwave dielectric properties of the ceramics prepared by conventional sintering at 1450°C were ɛ _r = 117.4, Qf = 13375 GHz, and τ _f = 217.2 ppm/°C.     

The giant magnetocaloric effect in Gd<Subscript>5</Subscript>Si<Subscript>2</Subscript>Ge<Subscript>2</Subscript> with low purity gadolinium

The giant magnetocaloric effect Gd5Si2Ge2 alloy was prepared with 99wt% low purity commercial Gd. Powder XRD and magnetic measurements showed that the Gd5Si2Ge2 alloy annealed at 1200℃ for 1h had a significant magnetic- crystallographic first order phase transition at about 270 K. The maximal magnetic entropy change is 17.55 J· kg^-1· K^-1 under a magnetic field change of 0-5 T. The distinct increase of magnetic entropy change belongs to the first-order phase transition from the orthorhombic Gd5Si4-type to the monoclinic Gd5Si2Ge2-type after high temperature heat-treatment.     

Electrical conductivity optimization of the Na3AlF6-Al2O3-Sm2O3 molten salts system for Al-Sm intermediate binary alloy production

Metal Sm has been widely used in making Al-Sm magnet alloy materials. Conventional distillation technology to produce Sm has the disadvantages of low productivity, high costs, and pollution generation. The objective of this study was to develop a molten salt electrolyte system to produce Al-Sm alloy directly, with focus on the electrical conductivity and optimal operating conditions to minimize the energy consumption. The continuously varying cell constant (CVCC) technique was used to measure the conductivity for the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ electrolysis medium in the temperature range from 905 to 1055℃. The temperature (t) and the addition of Al₂O₃ (W(Al₂O₃)), Sm₂O₃ (W(Sm₂O₃)), and a combination of Al₂O₃ and Sm₂O₃ into the basic fluoride system were examined with respect to their effects on the conductivity (κ) and activation energy. The experimental results showed that the molten electrolyte conductivity increases with increasing temperature (t) and decreases with the addition of Al₂O₃ or Sm₂O₃ or both. We concluded that the optimal operation conditions for Al-Sm intermediate alloy production in the Na₃AlF₆-AlF₃-LiF-MgF₂-Al₂O₃-Sm₂O₃ system are W(Al₂O₃) + W(Sm₂O₃)=3wt%, W(Al₂O₃):W(Sm₂O₃)=7:3, and a temperature of 965 to 995℃, which results in satisfactory conductivity, low fluoride evaporation losses, and low energy consumption.     

Near-infrared to visible up-conversion emissions of Er^3＋ doped Al2O3 powders derived from the sol-gel method

The Er3 doped Al2O3 powders were prepared by the sol-gel method using the aluminium isopropoxide [Al(OC3H7)3]-derived Al2O3 sols with addition of the erbium nitrate [Er(NO3)3.5H2O]. The different phase structure, including three crystalline types of (Al,Er)2O3 phases, γ, θ, α, and two Er-Al-O phases, ErAlO3 and Al10Er6O24, was obtained with the 1 mol% Er3 doped Al2O3 powders at the different sintering temperatures of 600―1200℃. The green and red up-conversion emissions centered at about 523, 545 and 660 nm, corresponding respectively to the 2H11/2, 4S3/2→4I15/2 and 4F9/2→4I15/2 transitions of Er3 , were detected by a 978 nm semiconductor laser diodes excitation. The phase structure and OH content had evident influence on the up-conversion emissions intensity. The maximum intensities of both the green and red emissions were obtained respectively for the Er3 doped Al2O3 powders sintered at 1200 ℃, which was composed mainly of α-(Al,Er)2O3, less of ErAlO3 and Al10Er6O24 phases, and with the least OH content. The two-photon absorption up-conversion process was involved in the green and red up-conversion emissions of the Er3 doped Al2O3 powders.     

Preparation and radar-absorbing properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/Yb<Subscript>2</Subscript>O<Subscript>3</Subscript> composite powder

Al₂O₃/TiO₂/Fe₂O₃/Yb₂O₃ composite powder was synthesized via the sol-gel method. The structure, morphology, and radar-absorption properties of the composite powder were characterized by transmission electron microscopy, X-ray diffraction analysis and RF impedance analysis. The results show that two types of particles exist in the composite powder. One is irregular flakes (100-200 nm) and the other is spherical Al₂O₃ particles (smaller than 80 nm). Electromagnetic wave attenuation is mostly achieved by dielectric loss. The maximum value of the dissipation factor reaches 0.76 (at 15.68 GHz) in the frequency range of 2-18 GHz. The electromagnetic absorption of waves covers 2-18 GHz with the matching thicknesses of 1.5-4.5 mm. The absorption peak shifts to the lower-frequency area with increasing matching thickness. The effective absorption band covers the frequency range of 2.16-9.76 GHz, and the maximum absorption peak reaches -20.18 dB with a matching thickness of 3.5 mm at a frequency of 3.52 GHz.     

Shear-thinning behavior of the CaO-SiO2-CaF2-Si3N4 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 Si₃N₄ to the CaO-SiO₂-CaF₂ 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.     

Effect of SiO<Subscript>2</Subscript> addition on the microstructure and electrical properties of ZnO-based varistors

The microstructure and electrical properties of ZnO-based varistors with the SiO₂ content in the range of 0–1.00mol% were prepared by a solid reaction route. The varistors were characterized by scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectrometry, inductively coupled plasma-atomic emission spectrometry, and X-ray photoelectron spectroscopy. The results indicate that the average grain size of ZnO decreases with the SiO₂ content increasing. A new second phase (Zn₂SiO₄) and a glass phase (Bi₂SiO₅) are found. Element Si mainly exists in the grain boundary and plays an important role in controlling the Bi₂O₃ vaporization. The electric measurement shows that the incorporation of SiO₂ can significantly improve the nonlinear properties of ZnO-based varistors, and the nonlinear coefficients of the varistors with SiO₂ are in the range of 36.8–69.5. The varistor voltage reaches the maximum value of 463 V/mm and the leakage current reaches the minimum value of 0.11 μA at the SiO₂ content of 0.75mol%.     

Synthesis, Characterization and Calorimetry of Ni（C4H8N2O3）2Cl2

A coordination complex was synthesized from NiCl2 and dipeptide glycylglycine（GG）. It was characterized by element analysis, NMR and TG methods, and then was determined to be Ni（C4HsN2O3）2Cl2. Using an isoperibolic reaction calorimeter, the standard molar enthalpy of formation of Ni（GG）2Cl2（solid） has been determined to be -（1 674.66±2.02） kJ · mol^-1 at 298.15 K.     

Preparation and characterization of γ-La<Subscript>2</Subscript>S<Subscript>3</Subscript> nanoparticles from thermal decomposition

To synthesize pure γ-La₂S₃ at lower temperature, lanthanide complex La(Et₂S₂CN)₃·phen, containing La-S bond, was chosen as the precursors to decompose. The obtained samples were characterized by X-ray power diffraction (XRD), field-emission scanning electron microscopy (FE-SEM) with an energy dispersive spectrometer and UV-Vis diffuse reflectance spectra. The decomposition mechanism of the lanthanide complex was studied by thermogravimetric analyses (TGA). The results show that the obtained samples are cubic phase particles with sizes among 20–50 nm and the band gap is 2.97 eV, which is bigger than that of its bulk crystal. TG/DTG results indicate that La(Et₂S₂CN)₃·phen decomposed to γ-La₂S₃ via La₄(Et₂S₂CN)₃ as an intermediate product.     

Electrorheological effect of Ti-bearing blast furnace slag with different TiC contents at 1500℃

The electrorheological properties of CaO-SiO₂-Al₂O₃-MgO-TiO₂-TiC slags were investigated to enhance understanding of the effect of TiC addition on the viscosity, yield stress, and fluid pattern of Ti-bearing slags in a direct-current electric field. The viscosities and shear stresses of 4wt% and 8wt% TiC slags were found to increase substantially with increasing electric field intensity, whereas virtually no rheological changes were observed in the 0wt% TiC slag. The Herschel-Bulkley model was applied to demonstrate that the fluid pattern of the 4wt% TiC slag was converted from that of a Newtonian fluid to that of a Bingham fluid in response to the applied electric field; and the static yield stress increased linearly with the square of the electric field intensity.     

Synthesis and characterization of monoclinic TiO<Subscript>2</Subscript> nanosheets

A novel two-step method for the synthesis of monoclinic titanium oxide （i.e. TiO2（B）） nanosheets is presented in this report. The method is featured by two steps： 1） synthesis of hydrogen titanate nanosheets, followed by 2） calcination of the titanate nanosheets at elevated temperatures. The hydrogen titanate nanosheets were prepared first by autoclaving anatase TiO2 powders, obtained by air cal- cining an ethanol-gel of Ti（OH）4 at 500℃, in aqueous NaOH （10 mol/L） at 150-200℃, and then by washing with hydro- chloric acid under supersonic irradiation. While sizes of the nanosheets were found to increase with increasing the temperature of the hydrothermal treatment, the calcination at 400-500℃ of the hydrogen titanate nanosheets that were synthesized at higher autoclaving temperatures （180-200℃） produced monoclinic TiO2 nanosheets with a uniform morphology. By contrast, the same calcination of the titanate nanosheets synthesized at the autoclaving temperature 180℃ led to anatase TiO2 nanoparticles.     

Composition dependence of viscosity for Al（1-x）Mgx（0≤x≤0. 10） alloys

Viscosities of molten Al（1-x）Mgx（0≤x≤0. 10 alloys have been measured in the temperature range of 973 K--1173 K by a torsional oscillation cup method. The viscosity dependence on temperature for Al（1-x）Mgx（0≤x≤0. 10 melts obeys Arrhenius equation. The viscosity increases with increasing magnesium concentration in the investigated system. There is an important relationship between viscosity and its glass-forming ability for metallic melt.