Influence of titanium and molybdenum oxides on the surface and bulk properties of oxide-fluoride slags

The influence of titanium and molybdenum oxides on the surface tension and density of the Al₂O₃-CaO-CaF₂ melt is investigated. It is found that the addition of 4–25 mol % TiO₂ and 3 mol % MoO₃ to the melt at 1773–1923 K promotes a decrease in surface tension and an increase in density. The manifestation of complexing properties by titanium and molybdenum is found for the studied oxide-fluoride slags, and the sizes and structure of structural units are revealed.     

The Thermodynamics of Some Transition Metals in Molten Slags

In the present paper, the thermodynamic behaviour of transition metals, such as Cr, Ti, Nb and V in molten slags is systematically analysed based on a literature survey. These metals exist in molten slags with multi valences. Oxygen partial pressure, slag basicity, total content of each transition metal, content of each component in slag, and temperature are the influential factors on their thermodynamic properties in molten slags. Higher basicity and strong oxidative atmosphere are generally favourable for the stable existence of transition‐metal ions with higher oxidation states. Temperature is a factor that is less influential than the above‐mentioned ones. For a transition metal in molten slag, the concentration ratio of ions of different valences depends on the activity coefficient ratio of their oxides. The present paper summarizes the activity studies regarding the transition metal oxides in various molten slags. For chromium and titanium oxides, information on CaO? SiO₂ based systems is involved. For titanium oxides, its thermodynamic behaviour in MnO? SiO₂ based slags is introduced. For niobium and vanadium, the information in Na₂O? SiO₂, CaO? CaF₂? SiO₂ systems is provided. Thermodynamic studies are described for Nb₂O₅? MnO? SiO₂ molten slag equilibrated with liquid iron at 1828 K.     

A novel crucible-less inert gas atomisation method of producing titanium powder for additive manufacturing

A novel low-cost gas atomisation technology producing spherical titanium powder (wire induction heating gas atomisation, WIGA) has been developed for additive manufacturing. Combined with the gas atomisation principle, the characteristics of WIGA were analysed. The effects of the gas pressure, metal temperature and the wire-feeding speed on the particle size of the titanium powder were studied. The results indicated that the decreases in mass median particle diameter (D₅₀) and the increases in efficiency of fine size powders occurred with the increase in gas atomisation pressure and melting temperature and with the decrease of wire-feed speed. The optimum parameters are that the main gas pressure (P₀) is 4.0?MPa, the degree of superheat of the metal melt is 350°C and the wire-feed speed is 50?mm?s^?1. On the condition, the D₅₀ of titanium powder was 40.2?μm and powder morphology was spherical. Satellites rarely existed on the surface of particles.     

Boriding of titanium OT4 from powder saturating media

The possibility of application of boriding media based on boron carbide—which additionally contain chromium, titanium, and silicon—for the diffusion hardening of titanium alloys is considered. Boriding in amorphous boron is performed for comparison. The microstructure, elemental composition, and phase composition of diffusion coatings on the OT4 titanium alloy formed by saturation in powder media are investigated. Hardening boride layers are formed on the titanium alloy form saturating media based on amorphous boron and multicomponent mixtures based on boron carbide. In all cases, the phase composition of the coating corresponds to phases TiB, Ti₂B₅, and Fe₂Ti. It is revealed that coatings from 30 to 150 μm thick are formed in conditions of the solid-phase saturation of titanium from powder mixtures due to the diffusion. Temperature-temporal conditions of formation of boride layers on OT4 titanium from powder saturating media are investigated and optimal modes for the formation of operable boride coatings are established. The optimal temperature range for processes of chemical-thermal boriding of titanium (900–1150°C) and saturation time (from 2.5 to 5 h) are determined. The maximal thickness of the operable boride coating on the OT4 titanium alloy is established, being from 180 μm in the case of saturation from B_amorph and up to 240 μm for the 50% B₄C + 20% SiC + 25% CrB₂ + 5% NaCl mixture at 950°C and saturation time of 4 h. Herewith, it should be noted that it was considered that the largest coating thickness is that retaining on the hardened sample surface.     

钒钛钢渣配制AC-13型沥青混合料的研究

钒钛钢渣具有较好的力学和表面特性,研究了其作为AC-13型沥青混合料集料的可行性。结果认为,钒钛钢渣可以作为AC-13型沥青混合料的集料,该沥青混合料的配合比设计为:钒钛钢渣(4.75~13.2 mm)、钒钛钢渣粉(0.075~4.75 mm)、矿粉三者之比为58∶40∶2,外配油石比最佳比例为4.9%。     

Structure and Properties of Dysprosium Titanate Powder Produced by the Mechanochemical Method

The structure and main physicochemical properties of dysprosium titanate powders prepared by mechanochemical synthesis from the low-temperature modification of titanium oxide and modification of dysprosium oxide are investigated applying X-ray phase analysis (XPA), scanning electron microscopy, Raman spectroscopy (Raman spectra), transmission electron microscopy, and chemical analysis. It is established based on XPA that the initial oxides completely transform into X-ray amorphous dysprosium titanate (Dy₂TiO₅) during the mechanochemical treatment of a mixture for 30–60 min. A microelectron diffraction pattern of Dy₂TiO₅ powders prepared by mechanosynthesis has a ring structure characteristic of the X-ray amorphous phase with a certain amount of inclusions of a crystalline phase. The dysprosium titanate powder fabricated by induction melting possesses the regular cubic crystalline lattice with a parameter of 3.4 Å.     

不同制备工艺对金属钛粉微观性质及应用的影响研究

金属钛粉末在增材制造等新型成形方法中得到越来越广泛的应用,目前主要通过熔盐电解法和气体雾化法来制取。借助X射线衍射技术(XRD)、扫描电镜(SEM)、比表面积测试(BET)、热重-差热分析法(TGA-DSC)等检测方法,从物相结构、晶胞参数、微观形貌、表面状态、热稳定性等方面,对采用熔盐电解和气体雾化2种不同工艺制取的金属钛粉的性质和应用进行全面对比分析。结果表明,电解钛粉微观形貌不规则,同一性差,适合作为粉末冶金原料和热还原剂;气雾化钛粉微观形貌为均匀球状,表面不易吸附气体杂质,比表面积为3.69 m~2/g,更适宜作为增材制造的原材料。     

Electrochemical Corrosion and Impedance Studies of Porous Ti–xNb–Ag Alloy in Physiological Solution

Porous titanium (Ti) and its alloys are promising materials for orthopedic applications due to their low elastic modulus, high strength, excellent corrosion resistance, and biocompatibility. In this study, the porous Ti–xNb–5Ag (x = 25, 30 and 35 wt%) alloys were synthesized using the powder metallurgy approach. The effects of Nb content on the porosity, mechanical properties, and electrochemical corrosion behavior of the alloys were investigated. XRD analysis revealed that the porous alloys mainly consist of α-Ti, β-Ti, intermetallic compound (Ti₄Nb), and oxides of TiO₂ and NbO phases. Porous alloys possess the porosity ranging from 57 to 65%, due to the addition of NH₄HCO₃ (45 wt%). Increase in Nb content lead to a reduction in the elastic modulus and compression strengths of the sintered porous Ti–xNb–5Ag alloys. All three developed porous Ti–xNb–5Ag alloys show the optimum combination of elastic modulus and compression strength, which is suitable for orthopedic applications. These porous alloys exhibit excellent electrochemical corrosion resistance in the simulated body fluids, and the samples having low porosity exhibit higher corrosion resistance than high-porosity samples.

     

Titanium–hydroxyapatite composite biomaterial for dental implants

Abstract

The objective of the present study was to investigate high velocity compaction of titanium powder and to prepare a dense composite biomaterial of titanium and hydroxyapatite with the purpose of forming dental components with improved early healing properties. A high purity titanium powder was compacted using high velocity compaction to study the density distribution. Then, a titanium–hydroxyapatite composite was prepared by mixing titanium powders and hydroxyapatite grains. Dental implant components were formed from the high velocity compacted specimens, exposing the hydroxyapatite grains at the component surface. The green density reached more than 98·5% after more than one impact. The composite was heated to 500°C, enough to bind the titanium grains, but to avoid observable reactions. Compacted pure titanium could be sintered to full density. The heated composite material reached 99% density, no reaction was observed between titanium and hydroxyapatite, and the composite material could be formed into dental implants.     

粉末压片-能量色散X射线荧光光谱法测定钛精矿中6种组分

采用化学湿法分析时,钛精矿中钛极易水解并形成难溶的偏钛酸析出,给分析带来极大的阻碍,同时分析周期长,方法繁杂。实验采用粉末压片法制样,能量色散X射线荧光光谱法(EDXRF)同时测定钛精矿中硫、磷、氧化锰、五氧化二钒、氧化钙、氧化镁。选取钛精矿粒度为40μm,以硼酸为粘连剂,压片压力为25MPa,保压时间为60s压制光滑、无裂痕的样片。选用4~5个钛精矿标准样品制作校准曲线,同时采用基本参数法进行基体效应的校正,各待测组分校准曲线的线性相关系数均不小于0.997,各组分检出限为0.00049%~0.076%。按照实验方法测定钛精矿样品中硫、磷、氧化锰、五氧化二钒、氧化钙、氧化镁,测定结果的相对标准偏差(RSD,n=8)为0.71%~7.9%;方法用于测定两个钛精矿标准样品中硫、磷、氧化锰、五氧化二钒、氧化钙、氧化镁,测定值与认定值结果一致。     

Effect of Electron-Beam Treatment on Wear-Resistant Coatings Applied by Electroexplosive Sputtering

TiC–Mo, TiC–Ni, TiB₂–Mo, and TiB₂–Ni coatings applied to the surface of Hardox 450 steel by electroexplosive sputtering are subjected to electron-beam treatment, After electroexplosive application, the surface relief of the coatings includes features such as deformed solidifying microglobules, buildup, microcraters, microcracks, and peeling. After electron-beam treatment, the microglobules, buildup, microcraters, and microcracks disappear from the coating surface. A polycrystalline structure containing cellular elements is formed. After electron-beam treatment, the surface roughness is 1.1–1.2 μm. The thickness of the layers modified by the electron beam in the electroexplosive coatings depends linearly on the surface energy density. The greatest coating thickness is observed when using the TiB₂–Mo system; the coating thickness is least for the TiC–Ni system. That may be attributed to the thermophysical properties of the coatings. The following substructures are observed in the coatings: cellular, striated, fragmented, and subgranular. Grains with chaotically distributed dislocations and reticular dislocations are also observed. Electron-beam treatment leads to the formation of composite filled structure over the whole cross section of the remelted layer. The structure formed in this layer is more disperse and uniform than in coatings formed without electron-beam treatment. The inclusions of titanium carbide or titanium diboride in the molybdenum or nickel matrix are 2–4 times smaller than immediately after electroexplosive sputtering. Within the molybdenum or nickel grains and at their boundaries, rounded particles of secondary phase (titanium carbide or titanium diboride) are observed. They may be divided into two classes by size: particles of the initial powder (80–150 nm) that have not dissolved on irradiation; and particles formed on solidification of the melt (10–15 nm). In the electroexplosive powder coatings, the structure is mainly formed by dynamic rotation of the sprayed particles, which form a vertical structure both in the coating and in the upper layers of the substrate. The coatings have excellent operational properties: nano- and microhardness, elastic modulus of the first kind, and wear resistance in dry slipping friction.     

Oxidation of porous nanocrystalline titanium nitride. II. Scale structure and composition

We have used x-ray phase analysis to study the composition of the products of reaction between oxygen and nanocrystalline powders with particle sizes 15, 40, 55, and 80 nm, and also specimens pressed (and sintered) from them. The powders were oxidized in air at 100°C (400 h) to 500°C (5 min), while the sintered specimens were oxidized at 600–900°C for 15, 120, and 240 min. In all cases, in the initial oxidation step the oxynitride Ti(O_xN_y) is formed, which over time is oxidized to TiO, Ti₂O₃, Ti₃O₅, TiO₂ (anatase) and TiO₂ (rutile). In the range 600–800°C, formation of a continuous oxide layer and conversion of anatase to rutile slows down diffusion of oxygen in the scale. We have established that at 900°C, the growth rate of the scale thickness increases and so the reflections from the oxynitride are barely noticeable on the diffraction patterns taken from the surface of the oxidized specimen. In these diffraction patterns, along with strong reflections from the rutile, we also observed weak reflections from lower oxides and anatase, which may be due to reaction between oxygen and the titanium ions diffused to the scale surface. We have concluded that at T > 850°C, the mechanism for oxidation of TiN changes. This is due to superposition of counterdiffusion of titanium ions on the diffusion of oxygen. __________ Translated from Poroshkovaya Metallurgiya, Nos. 3–4(448), pp. 72–78, March–April, 2006.     

Integrated product and process development of powder metallurgy hub for automotive clutch

ABSTRACT

With the development of new near-net shape forming process, powder metallurgy has been widely used in the manufacturing of automobiles and their parts. This paper proposes a novel integrated product and process development (IPPD) methodology for clutch hub via powder metallurgy, and the manufacturing-oriented design is carried out. The three-dimensional model of the hub is established and simulated by ANSYS. A Fe–C-Cu–Ni–Mo material system for the powder metallurgy clutch hub is created, and a corresponding process scheme is developed. Through material metallographic analysis and experimental verification, the results show that the powder metallurgy clutch hub developed by the IPPD technology can meet the requirements of automotive applications in terms of strength and durability. The IPPD methodology and new near-net shape forming technology can be widely applied to automotive parts such as gear flanges.     

Thermodynamic and experimental study of role of sintering atmospheres and graphite additions on oxide reduction in Astaloy CrM powder compacts

Abstract

Several atmospheres based on N₂–H₂ gaseous mixtures, with occasional additions of CH₄ were used to study the sintering behaviour of Astaloy CrM at temperatures of 1100 and 1240°C. Theoretical thermodynamic calculations and sintering experiments, with and without admixed graphite additions, were carried out devoting particular attention to the oxide reduction reactions. The role of carbon in the reduction of oxides is discussed with reference to Boudouard's reaction, proposing the indirect carbothermal reduction as the controlling mechanism. The microstructural characterisation of the material included inspection of the powder particles as well as sintered specimens. It was established that the Astaloy CrM particles contain two distinct types of oxides. One associated with the particle surface and another, mainly constituted by Cr, forming a dispersion of internal oxides. These internal oxides were microstructurally characterised, both directly and by carbon extraction replicas. A selection of powder mixtures containing 0 and 0.4%C additions were used for obtaining tensile specimens in order to assess neck development, by the strength and elongation obtained under various atmospheres and temperature combinations.     

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.     

The use of titanium aluminides to form electric-spark coatings

Titanium aluminides (TiAl₃, TiAl, Ti₃Al) fabricated by powder metallurgy were used as alloying electrodes for the formation of electric-spark coatings. Intermetallic coatings were deposited on steel substrates in argon or nitrogen. The microstructure and composition of fabricated coatings were investigated by scanning electron microscopy, X-ray structural analysis, and electron probe microanalysis. It is established that initial Ti–Al intermetallic phases are present in fabricated coatings; however, the ratio between Ti and Al concentrations is shifted to aluminum compared with the stoichiometric one. When depositing titanium aluminide in the nitrogen medium, titanium nitride is additionally formed in surface layers. Thermal and tribotechnical tests showed that the Ti₃Al coating deposited in nitrogen possesses high wear resistance and heat resistance.     

Friction Stir Surfacing Route: Effective Strategy for the Enhancement of Wear Resistance of Titanium Alloy

Titanium alloys are widely used in aerospace applications due to their properties like high strength to weight ratio, good corrosion and creep resistance. Poor wear resistance of these alloys limits their use in tribological applications. Friction surfacing technique is now recognized as an effective solution to surface engineer the light weight high strength alloys to make them suitable for general engineering applications involving wear and corrosion. The present work pertains to a study on wear resistance of surface coating of boron carbide on Ti–6Al–4V alloy using friction surfacing technique. Coating was formed by placing the boron carbide powder into the holes of predetermined depth on the surface and was characterized by metallography, electron probe micro analysis and dry sliding wear testing. The present study revealed that titanium alloy could be friction surfaced with boron carbide powder. The coating exhibited excellent wear resistance, which is attributed to the formation of strong metallurgical bond with the substrate. In the present work an attempt has also been made to compare the wear behaviour of surface composite layer on titanium alloy with that of conventionally used engineering materials such as mild steel and austenitic stainless steel. Wear data clearly revealed that wear resistance of friction stir surfaced composite layer is better than that of mild steel and stainless steel. This study demonstrated that friction stir surfacing is an effective strategy for the enhancement of wear resistance of titanium alloys.     

TiB whisker coating on titanium surfaces by solid-state diffusion: Synthesis,microstructure, and mechanical properties

The study demonstrates the feasibility of synthesizing TiB whiskers on titanium (Ti) surfaces by solid-state diffusion to form a hard and wear-resistant coating. The microstructural and mechanical properties of the TiB coating layer have also been investigated. The TiB coating was formed by the solid-state diffusion of boron (B) from a powder mixture containing amorphous boron, Na₂CO₃ powder, and charcoal (activated) powder. The diffusion process was carried out at various temperatures ranging from 800 °C to 1000 °C for various periods of time ranging from 1 to 24 hours. The amount of Na₂CO₃ in the mixture was also varied. It has been found that pristine and extremely fine TiB whiskers form on the surfaces of titanium, with the whiskers growing more or less normal to the surface. A maximum coating thickness of about 218 μm was observed for the pack diffusion conditions at 850 °C for 24 hours with 15 pct Na₂CO₃. The kinetics of TiB formation was found to follow the growth rates in bulk composites. The X-ray diffraction (XRD) patterns of the coatings revealed the dominant TiB peaks with a very few TiB₂ peaks, with small intensity at higher temperature and time. The surface hardness of the coated layer increased to a Vickers hardness of about 550 kgf/mm² due to the presence of TiB whiskers in the coating. It is shown that pack diffusion of boron in the solid state is a simple and very effective means of generating hard and wear-resistant coatings on titanium.     

金属增材制造用钛粉制备研究

金属增材制造技术正朝着产业化的方向发展,钛粉是金属增材制造领域的主流原料之一。本文概述了钛及钛合金的熔炼技术,重点介绍了感应熔炼,并对目前主流的钛粉制备技术进行了对比和分析,包括基本原理、优缺点和影响粉末特性的因素等。此外,还介绍了数值模拟在钛粉制备上的应用,并对钛粉制备工艺在金属增材制造领域的发展做出了展望。     

Investigation into the Structure Formation and Properties of Materials in the Copper–Titanium Disilicide System

The structure formation and properties during infiltration, free sintering, and spark-plasma sintering in Cu–(12.5–37.5 vol %) powder materials Ti₃SiC₂ are investigated by electron microscopy, X-ray phase analysis, and energy-dispersion analysis. The independence of the phase composition of composite materials (CMs) on the sintering method and temperature in a range of 900–1200°C is established. The peculiarities of formation of the CM structure during sintering are the intercalation of silicon from titanium carbosilicide and the formation of a carbon solid solution based on Ti₅Si₃(C) titanium disilicide, small amounts of titanium carbide, silicon carbide, and TiSi₂ silicide. An increase in Ti₃SiC₂ in the CM certainly lowers electrical conductivity, but considerably increases the hardness, strength, and electroerosion wear resistance of CM electrodes for electroerosion broaching.