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.     

Effect of Al_2O_3 on the viscosity of CaO–SiO_2–Al_2O_3–MgO–Cr_2O_3 slags

We investigated the effect of Al_2O_3 content on the viscosity of CaO–SiO_2–Al_2O_3–8wt%MgO–1wt%Cr_2O_3 (mass ratio of CaO/SiO_2is 1.0,and Al_2O_3 content is 17wt%–29wt%) slags.The results show that the viscosity of the slag increases gradually with increases in the Al_2O_3content in the range of 17wt%to 29wt%due to the role of Al_2O_3 as a network former in the polymerization of the aluminosilicate structure of the slag.With increases in the Al_2O_3 content from 17wt%to 29wt%,the apparent activation energy of the slags also increases from 180.85 to 210.23 k J/mol,which is consistent with the variation in the critical temperature.The Fourier-transform infrared spectra indicate that the degree of polymerization of this slag is increased by the addition of Al_2O_3.The application of Iida’s model for predicting the slag viscosity in the presence of Cr_2O_3 indicates that the calculated viscosity values fit well with the measured values when both the temperature and Al_2O_3 content are at relatively low levels,i.e.,the temperature range of 1673 to 1803 K and the Al_2O_3 content range of 17wt%–29wt%in CaO–SiO_2–Al_2O_3–8wt%MgO–1wt%Cr_2O_3 slag.     

Effect of the CaO/SiO_2 mass ratio and FeO content on the viscosity of CaO–SiO_2–“FeO”–12wt%ZnO–3wt%Al_2O_3 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–SiO_2–"FeO"–12wt%ZnO–3wt%Al_2O_3 slags were measured in the current study using the rotating spindle method. The slag viscosity decreases as the CaO/SiO_2 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/SiO_2 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/SiO_2 mass ratio or increasing FeO content. The [FeO_6]-octahedra in the slag melt increase as the CaO/SiO_2 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/SiO_2 mass ratio and increasing FeO content.     

Reaction mechanisms between molten CaF_2-based slags and molten 9CrMoCoB steel

Investigating the reaction mechanism between slag and 9CrMoCoB steel is important to develop the proper slag and produce qualified ingots in the electroslag remelting(ESR) process. Equilibrium reaction experiments between molten 9CrMoCoB steel and the slags of 55 wt%CaF_2–20 wt%CaO–3 wt%MgO–22 wt%Al_2O_3–xwt%B_2O_3(x = 0.0, 0.5, 1.0, 1.5, 2.0, 3.0) were conducted. The reaction mechanisms between molten 9 CrMoCoB steel and the slags with different B_2O_3 contents were deduced based on the composition of the steel and slag samples at different reaction times. Results show that B content in the steel can be controlled within the target range when the B_2O_3 content is 0.5 wt% and the FeO content ranges from 0.18 wt% to 0.22 wt% in the slag. When the B_2O_3 content is ≥1 wt%, the reaction between Si and B_2O_3 leads to the increase of the B content of steel. The additions of SiO_2 and B_2O_3 to the slag should accord to the mass ratio of [B]/[Si] in the electrode, and SiO_2 addition inhibits the reaction between Si and Al_2O_3.     

Evolution of plasticized MnO–Al_2O_3–SiO_2-based nonmetallic inclusion in 18wt%Cr-8wt% Ni stainless steel and its properties during soaking process

The properties of MnO–Al_2O_3–SiO_2-based plasticized inclusion are likely to change during soaking process due to its low melting point. In this study, the evolution of the MnO–Al_2O_3–SiO_2-based inclusion of 18 wt%Cr-8 wt%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 Cr_2O_3-concentrated regions existed within the inclusion before soaking, but more and more Cr_2O_3 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-pointphase MnO–Cr_2O_3 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–Al_2O_3–SiO_2-based inclusions grow by absorbing the newly precipitated smaller-size MnO–Cr_2O_3 inclusions.     

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.     

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF_2–CaO–SiO_2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO–SiO_2–MgO–FeO–MnO–Al_2O_3–TiO_2–CaF_2 was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step(RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide(Mn O), the apparent activation energy of the demanganization reaction was estimated to be 189.46 k J·mol~(–1) in the current study, which indicated that the mass transfer of Mn O in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface"(SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.     

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 slag on oxide inclusions in carburized bearing steel during industrial electroslag remelting

Industrial experiments with three types of slags were performed to investigate the effect of slag on oxide inclusions during electroslag remelting(ESR) process. G20CrNi2Mo bearing steel was used as the consumable electrode and remelted using a 2400-kg industrial furnace. The results showed that most inclusions in the electrode were low-melting-point CaO-MgO-Al_2O_3. After ESR, all the inclusions in ingots were located outside the liquid region. When the slag consisted of 65.70 wt% CaF_2, 28.58 wt% Al_2O_3, and 4.42 wt% CaO was used, pure Al_2O_3 were the dominant inclusions in ingot, some of which presented a clear trend of agglomeration. When the ingot was remelted by a multi-component slag with 16.83 wt% CaO, a certain amount of sphere CaAl_4O_7 inclusions larger than 5 μm were generated in ingot. The slag with 8.18 wt% CaO exhibited greater capacity to control the inclusion characteristics. Thermodynamic calculations indicated that the total Ca and Mg in ingots were attributed from the relics in electrode and strongly influenced by the slag composition. The formation of ingot inclusions was calculated by FactSage~(TM) 7.0, and the results were basically in accordance with the observed inclusions, indicating that a quasi-thermodynamic equilibrium could be obtained in the metal pool.     

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.     

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.     

Behavior of phosphorus enrichment in dephosphorization slag at low temperature and low basicity

At low basicity and low temperature, the dephosphorization behavior and phosphorus distribution ratio(L_P) between slag and molten steel in the double slag and remaining slag process were studied with a 180 t basic oxygen furnace industrial experiment.The dephosphorization slags with different basicities were quantitatively analyzed.At the lower basicity range of 0.9–2.59, both L_P and dephosphorization ratio were increased as the basicity of dephosphorization slag increased.Dephosphorization slag consisted of dark gray P-rich, light gray liquid slag,and white Fe-rich phases.With increasing basicity, not only did the morphologies of different phases in the dephosphorization slag change greatly, but the area fractions and P_2O_5 content of the P-rich phase also increased.The transfer route of P during dephosphorization can be deduced as hot metal → liquid slag phase + Fe-rich phase → P-rich phase.     

Desulfurization ability of refining slag with medium basicity

The desulfurization ability of refining slag with relative lower basicity (B) and Al₂O₃ content (B = 3.5–5.0; 20wt%–25wt% Al₂O₃) was studied. Firstly, the component activities and sulfide capacity (C_S) of the slag were calculated. Then slag-metal equilibrium experiments were carried out to measure the equilibrium sulfur distribution (L_S). Based on the laboratorial experiments, slag composition was optimized for a better desulfurization ability, which was verified by industrial trials in a steel plant. The obtained results indicated that an MgO-saturated CaO-Al₂O₃-SiO₂-MgO system with the basicity of about 3.5–5.0 and the Al₂O₃ content in the range of 20wt%–25wt% has high activity of CaO (a_CaO), with no deterioration of C_S compared with conventional desulfurization slag. The measured L_S between high-strength low-alloyed (HSLA) steel and slag with a basicity of about 3.5 and an Al₂O₃ content of about 20wt% and between HSLA steel and slag with a basicity of about 5.0 and an Al₂O₃ content of about 25wt% is 350 and 275, respectively. The new slag with a basicity of about 3.5–5.0 and an Al₂O₃ content of about 20wt% has strong desulfurization ability. In particular, the key for high-efficiency desulfurization is to keep oxygen potential in the reaction system as low as possible, which was also verified by industrial trials.     

Variation and optimization of acid-dissolved aluminum content in stainless steel

As a key step in secondary refining, the deoxidation process in clean stainless steel production is widely researched by many scholars. In this study, vacuum oxygen decarburization (VOD) deoxidation refining in a 40-t electric arc furnace + VOD + ingot casting process was analyzed and optimized on the basis of Al deoxidation of stainless steel and thermodynamic equilibrium reactions between the slag and steel. Under good stirring conditions in VOD, the deoxidation reaction reaches equilibrium rapidly, and the oxygen activity in the bulk steel is controlled by the slag composition and Al content. A basicity of 3–5 and an Al content greater than 0.015wt% in the melt resulted in an oxygen content less than 0.0006wt%. In addition, the dissolved oxygen content decreased slightly when the Al content in the steel was greater than 0.02wt%. Because of the equilibrium of the Si–O reaction between the slag and steel, the activity of SiO₂ will increase while the Si content increases; thus, the Si content should be lowered to enable the formation of a high-basicity slag. A high-basicity, low-Al₂O₃ slag and an increased Si content will reduce the Al consumption caused by SiO₂ reduction.     

Reaction mechanisms between molten CaF2-based slags and molten 9CrMoCoB steel

Investigating the reaction mechanism between slag and 9CrMoCoB steel is important to develop the proper slag and produce qualified ingots in the electroslag remelting(ESR) process. Equilibrium reaction experiments between molten 9CrMoCoB steel and the slags of 55 wt%CaF2–20 wt%CaO–3 wt%MgO–22 wt%Al2O3–xwt%B2O3(x = 0.0, 0.5, 1.0, 1.5, 2.0, 3.0) were conducted. The reaction mechanisms between molten 9 CrMoCoB steel and the slags with different B2O3 contents were deduced based on the composition of the steel and slag samples at different reaction times. Results show that B content in the steel can be controlled within the target range when the B2O3 content is 0.5 wt% and the FeO content ranges from 0.18 wt% to 0.22 wt% in the slag. When the B2O3 content is ≥1 wt%, the reaction between Si and B2O3 leads to the increase of the B content of steel. The additions of SiO2 and B2O3 to the slag should accord to the mass ratio of [B]/[Si] in the electrode, and SiO2 addition inhibits the reaction between Si and Al2O3.     

Equilibrium between Slag and Molten Iron in the Direct Alloying of Steel with Nb2O5-Bearing Slag

Equilibrium between slag and molten iron at 1600℃ was investigated for the direct alloying of steel with Nb2O6-bearing slag. The activity of niobium oxide in the slag was measured. The αNb2O5 is in the range of 10-2-10-4. TheδNb2O5 is ranged in 10°-10-2.Niobium partition decreases with the increase of[Si]% and CaO/SiO2. When α[0] and FeO decrease, niobium partition decreases too. TheδNb2o5 and the ratio of siO2 toγNb2O5 decrease with the incre-ase of slag basicity. The suitable thermodynamic conditions in direct alloying of steel with Nb2O5-bearing slag have been found.     

Dynamic mass variation and multiphase interaction among steel,slag, lining refractory and nonmetallic inclusions: Laboratory experiments and mathematical prediction

The mass transfer among the multiphase interactions among the steel, slag, lining refractory, and nonmetallic inclusions during the refining process of a bearing steel was studied using laboratory experiments and numerical kinetic prediction. Experiments on the system with and without the slag phase were carried out to evaluate the influence of the refractory and the slag on the mass transfer. A mathematical model coupled the ion and molecule coexistence theory, coupled-reaction model, and the surface renewal theory was established to predict the dynamic mass transfer and composition transformation of the steel, the slag, and nonmetallic inclusions in the steel. During the refining process,Al_2 O_3 inclusions transformed into Mg O inclusions owing to the mass transfer of [Mg] at the steel/refractory interface and(Mg O) at the slag/refractory interface. Most of the aluminum involved in the transport entered the slag and a small part of the aluminum transferred to lining refractory, forming the Al_2 O_3 or Mg O·Al_2 O_3. The slag had a significant acceleration effect on the mass transfer. The mass transfer rate(or the reaction rate) of the system with the slag was approximately 5 times larger than that of the system without the slag. In the first 20 min of the refining, rates of magnesium mass transfer at the steel/inclusion interface, steel/refractory interface, and steel/slag interface were x, 1.1 x, and 2.2 x,respectively. The composition transformation of inclusions and the mass transfer of magnesium and aluminum in the steel were predicted with an acceptable accuracy using the established kinetic model.     

Effect of Fe_2O_3 on the crystallization behavior of glass-ceramics produced from naturally cooled yellow phosphorus furnace slag

CaO–Al_2O_3–SiO_2(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 Fe_2O_3 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 Fe_2O_3.At 4wt% of added Fe_2O_3,the crystallization activation energy reached a maximum of 676.374 k J×mol-1.The type of the main crystalline phase did not change with the amount of added Fe_2O_3.The primary and secondary crystalline phases were identified as wollastonite(CaSiO_3) and hedenbergite(Ca Fe(Si_2O_6)),respectively.     

Effect of Y_2O_3 content in the pack mixtures on microstructure and oxidation resistance of B–Y modified silicide coating

B–Y modified silicide coatings were prepared on Nb–Si based alloy by pack cementation at 1300 ℃ for 10 h. The effect of Y_2O_3 content in the pack mixtures on microstructure and oxidation resistance of the coatings was investigated. The results show that the four coatings have similar structures, which possess a(Nb,X)Si_2 outer layer and a(Nb,X)_5Si_3 transitional layer. Y_2O_3 content in the pack mixtures has an obvious effect on the Si content in the coating. The mass gains of the coatings prepared with 0.5, 1, 2 and 3 wt% Y_2O_3 in pack mixtures are 2.33, 1.96, 2.05 and 2.86 mg/cm~2 after oxidation at 1250 ℃ for 100 h, respectively. The coating prepared with 1 wt% Y_2O_3 exhibits the best oxidation resistance due to the formation of a dense glass-like borosilicate scale.     

Influence of TiO_2 on the melting property and viscosity of Cr-containing high-Ti melting slag

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag(CaO–SiO_2–MgO–Al_2O_3–TiO_2–Cr_2O_3) with TiO_2 contents ranging from 38.63 wt% to 42.63 wt% was conducted. The melting properties were investigated with a meltingpoint 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 TiO_2 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 TiO_2 content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO_2 content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO_2.