Preparation method of Ti powder with oxygen concentration of <1000 ppm using Ca

Abstract

To reduce the high oxygen concentration of commercial Ti powder and to obtain Ti powder with the oxygen concentration of <1000 ppm, we utilised two types of deoxidation pots to conduct deoxidation experiments: below the melting point of Ca using a contact deoxidation pot (experiment A), and above its melting point using a non-contact deoxidation pot (experiment B). To obtain Ti in powder form even after deoxidation above the melting point of Ca, we developed a new non-contact deoxidation pot in the experiments. In experiment A, the oxygen concentration in the Ti powder decreased down to 50% compared with the initial stage (2200 ppm). In experiment B, the oxygen concentration reduced to ～63% at the deoxidation temperature of 1000°C. As a result, Ti powder with 820 ppm of oxygen concentration could be prepared using the non-contact deoxidation pot with Ca.     

A Study on the Electrochemical Deoxidation Using ZrO2 Based Solid Electrolyte and a Periodic DC Voltage

An electrochemical deoxidation using a ZrO₂ based solid electrolyte was investigated to control the interfacial oxygen concentration between the molten steel and ZrO₂. The electrochemical deoxidation cell consisted of an MgO stabilized ZrO₂ and an external power supply. In a previous study with constant external DC voltage, the oxygen concentration at the interface between the solid electrolyte and the molten steel was decreased to 2.2 ppm, which was the limit caused by the cathodic over‐potential when a constant external DC voltage was applied. In the present study, a novel process of using a periodic or cyclic voltage for the electrochemical deoxidation cell was developed, to surpass this limitation caused by the over‐optential of the electrochemical cell and thus decreasing the oxygen concentration to sub‐ppm levels at the interface between the molten Fe and the solid electrolyte.     

Titanium powder prepared by magnesiothermic reduction of Ti2+ in molten salt

A process to produce titanium powder from Ti²⁺ in the molten salt was confirmed experimentally. It consists of two steps. In the first step, titanium (IV) chloride gas dissolves in the molten salt as the titanium (II) chloride by reacting chemically with the metallic titanium or magnesium. In the second step, this molten salt is exposed to the metallic reductant Mg for the final reduction to the metallic Ti powder. Experimentally, the feed of TiCl₄ gas and the subsequent reaction with Ti prepared the molten salt containing 5 to 10 mass pct Ti²⁺. By Mg reduction of this salt, the well-isolated fine Ti particles were recovered. The powder morphology and particle size depended on the Ti²⁺ concentration, reduction temperature, time, and concentration of the by-product MgCl₂. The stirring by argon gas bubbling effectively grew the fine and round particles to a few tens of microns in size.     

Thermodynamics of calcium and oxygen in molten titanium and titanium-aluminum alloy

The deoxidation equilibrium of molten titanium and titanium-aluminum alloys saturated with solid CaO has been measured in the temperature range from 1823 to 2023 K. The equilibrium constant of reaction CaO (s)=Ca (mass pct in Ti,Ti-Al)+O (mass pct in Ti,Ti-Al) and the interaction parameter between calcium and oxygen were determined for Ti, TiAl, and TiAl₃. The standard Gibbs energy of reaction for TiAl was obtained as follows: $$\Delta G^\circ = 279,000 - 103TJ/mol$$ The possibilities for the deoxidation of titanium and titanium-aluminum alloys by using calcium-based fluxes are discussed.     

我国熔盐电解法制备稀土金属及其合金工艺技术进展

介绍了我国熔盐电解法制备稀土金属及其合金工艺技术的发展历程、现状与发展趋势.经过近60年的发展,氟化物体系氧化物电解工艺已经成为当今生产稀土金属及其合金的最重要的和最主要的生产工艺,我国已经基本形成了完整的、具有完全知识产权的熔盐电解工业技术体系和创新体系;分析总结了当前稀土熔盐电解工艺技术的特点及存在的问题,指出造成目前稀土电解高能耗、高排放的最根本的原因是电解槽型即平行上插阴阳极结构决定的,提出开发节能、环保、大型、高效的稀土电解新技术及设备是稀土电解发展的方向;认为液态下阴极电解制备稀土金属及合金新技术由于阴阳极距可减小至6～7cm,阴、阳极电流密度较小,电解槽压可降低至5～6V,可降低能耗、减少含氟气体排放,具有突出的节能减排潜力,是下一代工业化生产稀土金属及合金的新型电解槽,也是今后稀土电解新技术研究领域的重点发展方向;此外,熔盐电解法制备重稀土中间合金由于具备突出的节能减排效果和成本优势,也是当前的重要开发领域.     

Cathodic deoxygenation of the alpha case on titanium and alloys in molten calcium chloride

The oxygen-enriched alpha case on titanium and alloys was successfully deoxygenated to satisfactory levels by electrolysis in molten CaCl₂, in which the cathode was made from the metal to be refined. The oxygen distribution in the metal before and after electrolysis was characterized by microhardness tests, scanning electron microscopy (SEM), and energy-dispersive X-ray (EDX). The electrolysis has been carried out at voltages sufficiently below that for the decomposition of CaCl₂, and the results obtained suggest that the alpha case deoxygenation follows a simple oxygen ionization mechanism in which the oxygen in the metal is simply ionized at the cathode/electrolyte interface, dissolves in the molten salt, and then discharges at the anode. It is shown that by applying the electrochemical method, the alpha cases on both commercially pure titanium (CP Ti) and the Ti-6Al-4V alloy can be effectively deoxygenated. In particular, due to the removal of oxygen, the original alpha case (single phase) on the Ti-6Al-4V alloy has been converted back to the two-phase microstructure.     

Direct electrolytic preparation of chromium powder

Chromium oxide powder (Cr₂O₃) was slip cast or pressed into small cylindrical pellets which were then sintered in air. The sintered pellets were attached to a current collector to form an assembled cathode. Constant-voltage (2.7 to 2.8 V) electrolysis, with a graphite anode, was performed in molten CaCl₂ (950 °C). After electrolysis, the pellets were removed from the molten salt and washed in water. Scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) analysis, and fusion elemental analysis all confirmed that, when electrolyzed for a period longer than 4 hours, the Cr₂O₃ pellets were fully reduced to Cr metal. The oxygen content in the product depended on electrolysis time. Typically, for a 6-hour electrolysis, less than 0.2 wt pct oxygen was found in the product, with the current efficiency and energy consumption being 75 pct and 5 kWh/kg, respectively. The fully reduced pellet had a friable strength and could be manually crushed into a powder composed of cubic crystallites, very uniform in size, that grew with the electrolysis time, up to 50 μm (15 hours). The unique product morphology (cubic crystallites) differs drastically from the nodular morphology observed in other metals prepared by similar methods and is rarely seen among various commercial metal powders. A reduction mechanism is proposed, emphasizing the surface metallization at the early stage of electrolysis through the propagation of the metal-oxide-electrolyte three-phase interline (3PI).     

Electrochemical deoxidation of titanium

Removal of oxygen in titanium using an electrochemical technique was examined at temperatures around 1223 K with the purpose of obtaining nearly oxygen-free titanium. Titanium and carbon electrodes, immersed in molten CaCl₂, served as cathode and anode, respectively, with an external DC source. CaCl₂ was employed to produce the deoxidant calcium and to facilitate the reaction by decreasing the activity of the by-product CaO. By applying about 3 V between the electrodes, the calcium potential in CaCl₂ was increased at the titanium cathode surface and titanium samples of the cathode could be deoxidized by the electrolytically produced deoxidant calcium or by calcium of high activity in the CaCl₂ flux. Resulting O²⁻ species, mainly present as the deoxidation product CaO in the flux, reacted at the carbon anode to form CO (or CO₂) gas which was removed from the system. Titanium wires containing 1400 mass ppm oxygen were deoxidized to less than 100 mass ppm, whereas the carbon concentration increased by about 50 mass ppm. In some cases, the oxygen concentration in titanium samples was lowered to a level less than 10 mass ppm that could be determined by conventional inert gas fusion analysis. The behavior of contaminants, such as carbon and nitrogen, is also discussed.     

Deoxidation of Liquid Copper with Reducing O<Subscript>2</Subscript>/CH<Subscript>4</Subscript> Flames

The rate of deoxidation of molten copper during top blowing with various reducing gases has been investigated using thermogravimetry. It was observed that the rate of deoxidation increases with an increasing flow rate of H₂ or CO and that H₂ is a more effective reducing reagent than CO. The rate of deoxidation using methane was measured for O₂/CH₄ ratios from 1.5 to 2.0. As expected, the deoxidation rate decreased with an increasing O₂/CH₄ feed ratio because the flame became less reducing. For all tests, initially there is a linear decrease in mass as oxygen is removed. However, for some experiments, after some time, a sudden acceleration in the rate of mass loss occurs. Using video and X-ray imaging, it was found that this pattern corresponded to gas evolution from within the molten copper. This finding can be explained by the sudden water vapor evolution because the hydrogen dissolved in the copper reacts with the remaining oxygen, and “boiling” takes place, leading to an enhanced stirring of the copper.     

A thermodynamic model for deoxidation equilibria in steel

For relattively dilute solutions of oxygen and a deoxidizer M (M=Al, Cr, Ca, Mg, ...) in molten Fe, a thermodynamic model is proposed wherein the dissolved species are M*O associates as well as unassociated M and O atoms. At higher metal concentrations, a small amount of M ₂*O associates also form. Experimental deoxidation equilibria for 15 deoxidizers M are quantitatively reproduced at all temperatures, with only a constant, temperature-independent and composition-independent empirical parameter for the Gibbs energy of formation of each associate. The deoxidation behavior of Mg, Ca, and Ba is elucidated for the first time. The parameters are stored in a database, which can be used to predict complex deoxidation equilibria in multicomponent steels.     

Deoxidation of titanium aluminide by Ca-Al alloy under controlled aluminum activity

Removal of oxygen in titanium aluminide (TiAl) by chemically active calcium-aluminum (Ca-AI) alloy was carried out around 1373 K with the purpose of obtaining extra-low-oxygen TiAl. The deoxidation experiments were preceded by an investigation of the phase equilibria of the system Ti-Al-Ca at 1273 and 1373 K. The compositions of the Ca-AI alloy deoxidant, which equilibrates with TiAl, and the experimental conditions suitable for the deoxidation were of particular interest. In experiments in which Ti-Al samples were submerged in liquid Ca-AI alloys at 1373 K, the surfaces of the samples severely deteriorated and became nodular. When TiAl powders were mixed with CaO and the deoxidant was supplied in vapor form, powders which initially contained 510, 1100, and 4200 ppm O were deoxidized to about 160, 490, and 670 ppm O after deoxidation at 1373 K in 86.4 ks (1 day). Among many conditions tested, the use of TiAl powders mixed with CaCl₂ was most effective for deoxidation at 1373 K. CaCl₂ was used as a flux to facilitate the deoxidation by decreasing the activity of the deoxidation product CaO. In the case that TiAl powders mixed with CaCl₂ and reacted with Ca-AI vapor at 1373 K for 86.4 ks, the powders initially containing 510, 1100, and 4200 mass ppm O were deoxidized to a level of 62, 140, and 190 mass ppm O, respectively. No significant change in morphology of the particle after deoxidation was observed. The titanium and nitrogen concentrations in the powders remained constant, whereas calcium, which was present only in trace amounts initially, increased up to 160 mass ppm after the deoxidation treatment.     

Calciothermic reduction of titanium oxide in molten CaCl<Subscript>2</Subscript>

Titanium oxides were reduced to metallic titanium using the liquid calcium floating on the molten CaCl₂. A part of Ca dissolved into CaCl₂ and reacted with TiO₂ settled below CaCl₂. The by-product CaO also dissolved by about 20 mol pct into CaCl₂, which was effective in reducing the oxygen concentration in the obtained Ti particles. The compositional region in the Ca-CaCl₂-CaO system was examined for the less oxygen contamination in Ti and the better handling in leaching. A large amount of the residual calcium oxidized the titanium powder in leaching. The metallic Ti powder less than 1000 mass ppm oxygen could be obtained only for 3.6 ks using 5 to 7 mol pct Ca-CaCl₂ at 1173 K. The powder was slightly sintered like sponge, and contained approximately 1500 ppm Ca. The anatase phae, the intermediate product in the refining process of TiO₂, could be also supplied as raw material as well as rutile.     

Modification and Minimization of Spinel(Al<Subscript>2</Subscript>O<Subscript>3</Subscript>·<Emphasis Type="Italic">x</Emphasis>MgO) Inclusions Formed in Ti-Added Steel Melts

High-melting-point inclusions such as spinel(Al₂O₃·xMgO) are known to promote clogging of the submerged entry nozzle (SEN) in a continuous caster mold. In particular, Ti-alloyed steels can have severe nozzle clogging problems, which are detrimental to the slab surface quality. In this work, the thermodynamic role of Ti in steels and the effect of Ca and Ti addition to the molten austenitic stainless steel deoxidized with Al on the formation of Al₂O₃·xMgO spinel inclusions were investigated. The sequence of Ca and Ti additions after Al deoxidation was also investigated. The inclusion chemistry and morphology according to the order of Ca and Ti are discussed from the standpoint of spinel formation. The thermodynamic interaction parameter of Mg with respect to the Ti alloying element was determined. The element of Ti in steels could contribute to enhancing the spinel formation, because Ti accelerates Mg dissolution from the MgO containing refractory walls or slags because of its high thermodynamic affinity for Mg ( e_\textMg^\textTi = - 0. 9 3 3). ( {e_{\text{Mg}}^{\text{Ti}} = - 0. 9 3 3}). Even though Ti also induces Ca dissolution from the CaO-containing refractory walls or slags because of its thermodynamic affinity for Ca ( e_\textCa^\textTi = - 0.119 ), \left( {e_{\text{Ca}}^{\text{Ti}} = - 0.119} \right), dissolved Ca plays a role in favoring the formation of calcium aluminate inclusions, which are more stable thermodynamically in an Al-deoxidized steel. The inclusion content of steel samples was analyzed to improve the understanding of fundamentals of Al₂O₃·xMgO spinel inclusion formation. The optimum processing conditions for Ca treatment and Ti addition in austenitic stainless steel melts to achieve the minimized spinel formation and the maximized Ti-alloying yield is discussed.     

Dispersion of fine primary inclusions of MgO and ZrO2 in Fe-10 mass pct Ni alloy and the solidification structure

The homogeneous dispersion of primary inclusions of MgO and ZrO₂ was studied in an Fe-10 mass pct Ni alloy as a function of the holding time at 1873 K and the cooling rate. The spatial size distribution was estimated from the planar size distribution obtained in a cross section by applying the Schwartz-Saltykov transformation. It was found that the content of insoluble Mg or Zr estimated from the size distribution agreed with that obtained from chemical analysis. The influence on the solidification macrostructure such as columnar dendrite, equiaxed dendrite, and globular crystal of dissolved Mg or Zr and inclusion particles having the mean diameter of roughly 1 μm was investigated. The area fraction of globular crystals in the Mg deoxidation decreased with increasing dissolved Mg content (>30 mass ppm) in the presence of MgO particles. In the Zr deoxidation, however, globular crystals were only observed in the presence of ZrO₂ particles without respect to the presence of dissolved Zr.     

Thermodynamic laws of the oxygen solubility in liquid metals (Ni,Co, Fe,Mn, Cr) and the formation of oxygen-containing solutions in the alloys based on them

The solubility of oxygen in liquid Ni, Co, Fe, Mn, and Cr metals (Group IV in the periodic table) has been found for the first time. Linear dependences of the oxygen solubility on the standard Gibbs energy for the oxidation reaction of a liquid metal with gaseous oxygen are found. The revealed function of oxygen solubility is of scientific importance and allows one to develop a theory of oxygen solutions in liquid metals and liquid multicomponent metallic compositions and to calculate the energies of mixing of liquid metals with oxygen from ΔG _MO ^° for metal oxidation reactions with allowance for pseudoregular-solution model equations. Using the energies of mixing and metal compositions, we calculated the equilibrium oxygen concentrations in a metal molten pool at the end of oxidation stage of melting 08Kh18N10T steel in an arc furnace. This fact indicates practical importance of the found function of the oxygen solubility in metals.     

Calciothermic reduction of titanium oxide and <Emphasis Type="Italic">in-situ</Emphasis> electrolysis in molten CaCl<Subscript>2</Subscript>

A concept for calciothermic direct reduction of titanium dioxide in molten CaCl₂ is proposed and experimentally tested. This production process consists of a single cell, where both the thermochemical reaction of the calciothermic reduction and the electrochemical reaction for recovery of the reducing agent, Ca, coexist in the same molten CaCl₂ bath. A few molar percentages of Ca dissolve in the melt, which gives the media a strong reducing power. Using a carbon anode and a Ti basket-type cathode in which anatase-type TiO₂ powder was filled, a metallic titanium sponge containing 2000 ppm oxygen was produced after 10.8 ks at 1173 K in the CaCl₂ bath. The optimum concentration of CaO in the molten CaCl₂ was 0.5 to 1 mol pct, to shorten the operating time and to achieve a lower oxygen content in Ti.     

Thermodynamics on the formation of spinel (MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) inclusion in liquid iron containing chromium

The stability diagram of MgO, spinel solid solution (MgO·(Al _X Cr_1−X )₂O₃), and sesquioxide solid solution ((Al _Y Cr_1−Y )₂O₃) as a function of Mg, Al, and O contents at a constant chromium content (18 mass pct) in liquid iron is drawn at 1873 K. The interaction parameters between Mg and other solutes (Al, Cr, Ni, Ti, Si, and C) are determined by the experimental method, which assures equilibrium between Mg vapor and liquid iron, were applied to calculate the diagram. Titanium deoxidation is not recommended for the prevention of spinel formation, because Ti accelerates Mg dissolution from refractory or slag due to its high affinity for Mg (e _Mg ^Ti = − 0.64). The standard Gibbs free energies of formation for the three inclusions (periclase, spinel, and sesquioxide solid solutions) and the tielines between two solid solutions were calculated with the aid of the regular solution model and the thermochemical F*A*C*T database computing system, respectively. The phase stability regions and oxygen content in steel for the current Fe-Mg-Al-Cr (18 mass pct)-O system are compared with those of the previous non-Cr system. Detailed information on the spinel composition according to Mg and Al contents is also available from the present stability diagram.     

镁提高钢水纯净度的研究

 在真空感应炉内分别向42CrMo钢液单独加入铝进行脱氧、铝脱氧后加入钙进行钙处理、铝脱氧后加入镁进行镁处理三种不同的工艺条件,得出镁处理的铝脱氧钢总氧含量略低于钙处理的铝脱氧钢,并且明显低于单独用铝脱氧的钢。用镁处理铝脱氧钢中单位面积上夹杂的个数比钙处理铝脱氧钢降低了将近2/3,比单独用铝脱氧钢中单位面积上夹杂的个数降低了将近4/5。并且用镁处理的铝脱氧钢中绝大多数都是细小、尺寸小于2 μm的镁铝尖晶石类夹杂,它们对钢的性能几乎不会产生影响。     

Formation of Inclusions in Ti-Stabilized 17Cr Austenitic Stainless Steel

The behavior and formation mechanisms of inclusions in Ti-stabilized, 17Cr Austenitic Stainless Steel produced by the ingot casting route were investigated through systematic sampling of liquid steel and rolled products. Analysis methods included total oxygen and nitrogen contents, optical microscopy, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results indicate that the composition of inclusions was strongly dependent on the types of added alloying agents. During the AOD refining process, after the addition of ferrosilicon alloy and electrolytic manganese, followed by aluminum, the composition of inclusions changed from manganese silicate-rich inclusions to alumina-rich inclusions. After tapping and titanium wire feeding, pure TiN particles and complex inclusions with Al₂O₃-MgO-TiO _x cores containing TiN were found to be the dominant inclusions when [pct Ti] was 0.307 mass pct in the molten steel. These findings were confirmed by thermodynamic calculations which indicated that there was a driving force for TiN inclusions to be formed in the liquid phase due to the high contents of [Ti] and [N] in the molten steel. From the start of casting through to the rolled bar, there was no further change in the composition of inclusions compared to the titanium addition stage. Stringer-shaped TiN inclusions were observed in the rolled bar. These inclusions were elongated along the rolling direction with lengths varying from 17 to 84 µm and could have a detrimental impact on the corrosion resistance as well as the mechanical properties of the stainless steel products.