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.     

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.     

Mineral-phase evolution and sintering behavior of MO-SiO2-Al2O3-B2O3 (M=Ca,Ba) glass-ceramics by low-temperature liquid-phase sintering

In this work, network former SiO₂ and network intermediate Al₂O₃ were introduced into typical low-melting binary compositions CaO·B₂O₃, CaO·2B₂O₃, and BaO·B₂O₃ 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℃. On the basis of liquid-phase sintering theory, mineral-phase evolutions and glass-phase formations were systematically investigated in a wide MO-SiO₂-Al₂O₃-B₂O₃ (M=Ca, Ba) composition range. The results indicate that major mineral phases of the aluminosilicate glass-ceramics are Al₂₀B₄O₃₆, CaAl₂Si₂O₈, and BaAl₂Si₂O₈ and that the glass-ceramic materials are characterized by dense microstructures and excellent dielectric properties.     

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.     

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.     

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.     

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.     

Corrosion resistance evaluation of highly dispersed MgO-MgAl2O4-ZrO2 composite and analysis of its corrosion mechanism: A chromium-free refractory for RH refining kilns

The corrosion resistance behavior of a highly dispersed MgO-MgAl₂O₄-ZrO₂ composite refractory material is examined by testing with high-basicity and low-basicity RH (Ruhrstahl-Hereaeus) slags. The composite material exhibits greater resistance to the RH slags than the traditional MgO-Cr₂O₃ composite, MgO-ZrO₂ composite, and MgO-MgAl₂O₄-ZrO₂ composite. On the basis of the microstructural analysis and mechanisms calculations, the corrosion resistance behavior of the MgO-MgAl₂O₄-ZrO₂ composite is attributable to its highly dispersed structure, which helps protect the high activity of ZrO₂. When in contact with the slag, ZrO₂ reacts with CaO to form the stable phase CaZrO₃, which protects MgAl₂O₄ against corrosion, thereby enhancing the corrosion resistance of the composite.     

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.     

Effects of SiO2 on the preparation and metallurgical properties of acid oxidized pellets

The effects of SiO₂ content on the preparation process and metallurgical properties of acid oxidized pellets, including compressive strength, reduction, and softening–melting behaviors, were systematically investigated.Mineralogical structures, elemental distribution, and pore size distribution were varied to analyze the mechanism of the effects.The results show that with an increase in SiO₂ content from 3.51 wt%to 7.18 wt%, compressive strength decreases from 3150 N/pellet to 2100 N/pellet and reducibility decreases from 76.5% to 71.4%.The microstructure showed that pellets with high SiO₂ content contained more magnetite in the mineralogical structures.Additionally, some liquid phases appeared, which hindered the continuous crystallization of hematite.Also, the softening–melting properties of the pellets clearly deteriorated as the SiO₂ content increased.With increasing SiO₂ content, the temperature range of the softening–melting zone decreased, and the maximum differential pressure and the comprehensive permeability index increased significantly.When acid oxidized pellets are used as the raw materials for blast furnace smelting, it should be combined with high basicity sinters to improve the softening–melting behaviors of the comprehensive charge.     

1623 K时SiO2饱和的MnO–SiO2渣和Al2O3饱和的MnO–SiO2–Al2O3渣中NiO的活度系数

MnO–SiO₂二元系作为废旧锂离子电池、海洋锰结核还原熔炼过程中的基础渣型,测定有价金属（如镍）在渣中的溶解度、活度及活度系数热力学数据十分必要。为此,本文测定了温度1623 K、氧分压10?7,10?6,和10?5 Pa时SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的溶解度和活度系数。结果表明:在试验条件下,镍在MnO–SiO₂渣和MnO–SiO₂–Al₂O₃渣中主要以NiO形式存在,且渣中NiO的溶解度随着氧分压增加而增加;向MnO–SiO₂渣中加入Al₂O₃可以降低渣中镍的溶解度,增加NiO的活度系数。此外,SiO₂饱和的MnO–SiO₂渣和Al₂O₃饱和的MnO–SiO₂–Al₂O₃渣中NiO的活度系数（γ_NiO,以纯固体NiO为参考态）可分别按如下公式计算:γ_NiO = 8.58w(NiO) + 3.18; γ_NiO=11.06w(NiO) + 4.07, 其中,w(NiO)为渣中NiO的质量分数。     

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.     

Microwave absorption properties of SiC@SiO2@Fe3O4 hybrids in the 2-18 GHz range

To enhance the microwave absorption performance of silicon carbide nanowires (SiCNWs), SiO₂ nanoshells with a thickness of approximately 2 nm and Fe₃O₄ nanoparticles were grown on the surface of SiCNWs to form SiC@SiO₂@Fe₃O₄ hybrids. The microwave absorption performance of the SiC@SiO₂@Fe₃O₄ hybrids with different thicknesses was investigated in the frequency range from 2 to 18 GHz using a free-space antenna-based system. The results indicate that SiC@SiO₂@Fe₃O₄ hybrids exhibit improved microwave absorption. In particular, in the case of an SiC@SiO₂ to iron(Ⅲ) acetylacetonate mass ratio of 1:3, the microwave absorption with an absorber of 2-mm thickness exhibited a minimum reflection loss of -39.58 dB at 12.24 GHz. With respect to the enhanced microwave absorption mechanism, the Fe₃O₄ nanoparticles coated on SiC@SiO₂ nanowires are proposed to balance the permeability and permittivity of the materials, contributing to the microwave attenuation.     

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.     

低温低碱度脱磷渣中磷的富集行为

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 P₂O₅ 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.     

硫酸溶液中IrO2–ZrO2二元氧化物涂层的电化学行为及耐蚀性

In this study, we prepared Ti/IrO₂–ZrO₂ electrodes with different ZrO₂ contents using zirconium-n-butoxide (C₁₆H₃₆O₄Zr) and chloroiridic acid (H₂IrCl₆) via a sol–gel route. To explore the effect of ZrO₂ content on the surface properties and electrochemical behavior of electrodes, we performed physical characterizations and electrochemical measurements. The obtained results revealed that the binary oxide coating was composed of rutile IrO₂, amorphous ZrO₂, and an IrO₂–ZrO₂ solid solution. The IrO₂–ZrO₂ binary oxide coatings exhibited cracked structures with flat regions. A slight incorporation of ZrO₂ promoted the crystallization of the active component IrO₂. However, the crystallization of IrO₂ was hindered when the added ZrO₂ content was greater than 30at%. The appropriate incorporation of ZrO₂ enhanced the electrocatalytic performance of the pure IrO₂ coating. The Ti/70at%IrO₂–30at%ZrO₂ electrode, with its large active surface area, improved electrocatalytic activity, long service lifetime, and especially, lower cost, is the most effective for promoting oxygen evolution in sulfuric acid solution.     

Thermodynamic Behavior of Manganese and Phosphorus between Liquid Iron and CaO-MgO-SiO2-Al2O3-FetO-MnO-P2O5 Slags

The thermodynamic behavior of manganese and phosphorus between liquid iron and CaO-MgO-SiO₂-Al₂O₃-Fe_tO-MnO-P₂O₅ ladle slag system was addressed by investigating the thermodynamic equilibria between liquid iron containing Mn and P and the ladle slag at 1873 K. The Mn distribution ratio L_Mn increases with increasing Fe_tO content and decreasing the basicity ((%CaO + %MgO)/(%SiO₂ + %Al₂O₃ + %P₂O₅)) in slag, while the P distribution ratio L_p seems to be increased as Fe_tO content and the basicity increases. The values of L_Mn and L_p decrease by the addition of Al₂O₃ into slag. The expression of the dependence of L_Mn and L_p on the basicity and Fe_tO content in slag was obtained.     

Structural and electrical properties of HCl-polyaniline-Ag composites synthesized by polymerization using Ag-coated (NH4)2S2O8 powder

Ag nanoparticles were sputter-deposited on ammonium persulfate ((NH₄)₂S₂O₈) powder to obtain (NH₄)₂S₂O₈-Ag powder, which was used to synthesize the HCl-doped polyaniline-Ag (HCl-PANI-Ag) composite via a polymerization procedure. The Ag nanoparticles were dispersed in the HCl-PANI matrix, and their sizes mainly ranged from 3 to 6 nm. The Ag nanoparticles did not affect the structure of emeraldine salt in the composite, and they increased the ordered crystalline regions in the HCl-PANI matrix. The HCl-PANI-Ag composite had a conductivity of (6.8 ±0.1) S/cm, which is about four times larger than that of the HCl-PANI. The charge transport mechanism in the composite is explained by the three-dimensional Mott variable-range hopping (3D-Mott-VRH).     

利用氧化基粉煤灰粉和医疗废弃物颗粒开发无电镀镍基复合涂层 (Ni–P/粉煤灰和Ni-P/Ni–P/SiO2–Al2O3)

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 Ni_xSi_y phases in addition to the typical Ni₃P phases for the heat-treated electroless Ni–P coatings. Upon heat treatment, the PFA-reinforced composite coating, due to a modified microstructure, exhibited a higher microhardness up to HK_0.05 818, which is comparable to that of the traditional SiC particle-embedded composite coating (HK_0.05 825). The findings can potentially open up a new strategy to further advance the green approach for industrial surface engineering.     

H2O2溶液对钛种植体表面的处理

The surface treatment is important for titanium and its alloys as promising candidates for dental implantation due to their bioinert surface. Titanium surface samples were modified using H₂O₂ solution at different times up to 72 h to boost their bioactivity. According to the results of the field emission scanning electron microscopy test, some nanostructures are formed on the surface of treated titanium samples and increased in size by increasing the time of treatment up to 24 h. After 24 h of application, the sharpness of nanostructures decreased and the micro-cracks and discontinuity in the coating surface increased. The results of the X-ray diffraction study and Raman spectroscopy revealed that anatase (TiO₂) was formed on the surface of treated titanium samples. The peak intensity of Raman spectroscopy increased with an improvement in treatment time of up to 24 h and then decreased due to the discontinuity of the coating. Full wettability and ability to form apatite were reached at 6 h of treatment. It is clear that the treatment time has a significant effect on the surface treatment of titanium using the H₂O₂ solution.