Electrochemical Deoxidation of Titanium and Its Alloy Using Molten Magnesium Chloride

Metallurgical and Materials Transactions B - Oxygen was directly removed from pure titanium and a Ti-6Al-4V alloy by electrolysis in molten MgCl2 at 1173 K (900 °C), where the metal...     

Mechanochemical processing of nanocrystalline Ti-6Al-4V alloy

Synthesis of nanocrystalline Ti-6Al-4V was explored using mechanochemical processing. The reaction mixture was comprised of CaH₂, Mg powder, anhydrous AlCl₃, anhydrous VCl₃, and TiCl₄. The milled powder (reaction product) primarily consisted of nanocrystalline alloy hydride having a composition (Ti-6Al-4V)H_1.942, along with MgCl₂ and CaCl₂ as by-products. Aqueous solutions of nitric acid, sulfuric acid, and 1 pct sodium sulfite were found to be very effective in leaching of the chlorides from the milled powder. The (Ti-6Al-4V)H_1.942 on dehydrogenation at 375°C resulted in nanocrystalline Ti-6Al-4V alloy powder.     

Formation of Calcium Titanate During Electroreduction of TiO2 in Molten CaCl2 Bath

The direct electrochemical reduction of a TiO₂ cathode in a molten CaCl₂ bath to produce titanium metal invariably results in the formation of CaTiO₃ as an intermediate product. To obtain even more insight into the formation of CaTiO₃, experiments are performed in open-circuit conditions as well as at a cell voltage of 2?V for different time periods. In this study, we examine the conversion of TiO₂ to CaTiO₃ in the molten CaCl₂ bath. Prolonged electrolysis experiments are conducted and the newly transformed phases are analyzed using X-ray diffraction (XRD). The formation of CaTiO₃ and its subsequent transformation to different species during reduction is discussed. An approach for preparing CaTiO₃ chemically by treating the TiO₂ electrode in CaCl₂ bath and subsequently reducing it by electrochemical means to produce titanium metal has been proposed.     

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.     

Brazing of Ti-6Al-4V and niobium using three silver-base braze alloys

Evaluations of the (infrared)-brazed Ti-6Al-4V and niobium joints using three silver-base braze alloys have been extensively studied. According to the dynamic wetting angle measurement results, the niobium substrate cannot be effectively wetted by all three braze alloys. Because the dissolution of Ti-6Al-4V substrate causes transport of Ti into the molten braze, the molten braze dissolved with Ti can effectively wet the niobium substrate during brazing. For infrared-brazed Ti-6Al-4V/Ag/Nb joint, it is mainly comprised of the Ag-rich matrix. The TiAg reaction layer is observed at the interface between the braze and Ti-6Al-4V substrate. In contrast, Ti-rich, Ag-rich, and interfacial TiAg phases are found in the furnace-brazed specimen. The dominated Ti-rich phase in the joint is caused by enhanced dissolution between the molten braze and Ti-6Al-4V substrate. The infrared-brazed Ti-6Al-4V/72Ag-28Cu/Nb joint is mainly comprised of the Ag-rich matrix and Ag-Cu eutectic. With increasing the brazing temperature or time, the amount of Ag-Cu eutectic is decreased, and the interfacial Cu-Ti reaction layer(s) is increased. The infrared brazed joint has the highest average shear strength of 224.1 MPa. The averaged shear strength of the brazed joint is decreased with increasing brazing temperature or time, and its fracture location changes from the braze alloy into the interfacial reaction layer(s) due to excessive growth of the Cu-Ti intermetallics. The infrared-brazed Ti-6Al-4V/95Ag-5Al/Nb joint is composed of Ag-rich matrix and TiAl interfacial reaction layer. With increasing the brazing time, the amount of Ag-rich phase is greatly decreased, and the interfacial reaction layer becomes Ti₃Al due to enhanced dissolution of Ti-6Al-4V substrate into the molten braze. The average shear strength of the infrared-brazed joint is 172.8 MPa. Additionally, the existence of an interfacial Ti₃Al reaction layer significantly deteriorates the shear strength of the furnace-brazed specimen.     

Advances in titanium metal injection molding

The approaches to production of titanium powder injection molded parts are reviewed. Historically, oxygen levels have been too high for structural use (particularly with the Ti-6Al-4V alloy). However, recent advances in starting powders, binders and sintering facilities now allow oxygen levels in the Ti-6Al-4V alloy to be controlled to about 0.2 wt.% oxygen. This should result in significant expansion of the titanium PIM market place into aerospace, automobiles, surgical instruments, dentistry, communication devices (such as computers and cell phones), knives and guns. __________ Translated from Poroshkovaya Metallurgiya, Vol. 46, No. 5–6 (455), pp. 118–125, 2007.     

Effects of oxygen and heat treatment on the mechanical properties of alpha and beta titanium alloys

Two alloys, Ti-6Al-2V and Ti-2Al-16V, simulating the alpha and beta phases of Ti-6A1-4V, respectively, were prepared with oxygen concentrations from 0.07 to 0.65 wt pct (0.20 to 1.83 at. pct). Their microstructure, deformation behavior, and strength were investigated with X-ray diffraction, microscopy, and mechanical tests to determine the effects of oxygen concentration and heat treatment. In both alloys the hardness increases in identical fashion with the square root of oxygen concentration. The alloys' strengths also depend on heat treatment, but in different ways. Whereas the alpha alloy is non-age-hardenable, the beta alloy's strength can be doubled by aging. The hardening effect of oxygen is generally unaffected by heat treatment, except for the alloys with the highest oxygen concentrations. During aging of the alpha a small amount of Ti₃Al can form, and slight age-hardening occurs. The ductility of the alpha alloy is little affected by aging. On the other hand, oxygen causes a change from good ductility at low oxygen concentration (0.07 wt pct) to total brittleness at 0.65 wt pct oxygen, independent of heat treatment. In the beta alloy there are complex phase transformations depending on heat treatment. Its deformation behavior varies from very ductile in solutiontreated and quenched (STQ) condition to totally brittle in aged conditions. The aging embrittlement appears to be caused by alpha and some omega precipitation. Decoration of the beta grain boundaries with precipitates accounts for the intergranular brittle fracture. Oxygen, on the other hand, is not an embrittler, although it reduces the ductility of the beta alloy.     

Effect of activity differences on hydrogen migration in dissimilar titanium alloy welds

The effect of alloy composition on hydrogen activity was measured for seven titanium alloys as a means to determine the tendency for hydrogen migration within dissimilar metal welds. The alloys were: Ti-CP, Ti-3A1-2.5V, Ti-3Al-2.5V-3Zr, Ti-3Al-2Nb-lTa, Ti-6A1, Ti-6A1-4V, and Ti-6Al-2Nb-lTa-0.8Mo. Hydrogen pressure-hydrogen concentration relationships were determined for temperatures from 600 ‡C to 800 ‡C and hydrogen concentrations up to approximately 3.5 at. pct (750 wppm). Fusion welds were made between Ti-CP and Ti-CP and between Ti-CP and Ti-6A1-4V to observe directly the hydrogen redistribution in similar and dissimilar metal couples. Hydrogen activity was found to be significantly affected by alloying elements, particularly Al in solid solution. At a constant Al content and temperature, an increase in the volume fraction ofΒ reduced the activity of hydrogen in α-@#@ Β alloys. Activity was also found to be strongly affected by temperature. The effect of temperature differences on hydrogen activity was much greater than the effects resulting from alloy composition differences at a given temperature. Thus, hydrogen redistribution should be expected within similar metal couples subjected to extreme temperature gradients, such as those peculiar to fusion welding. Significant hydrogen redistribution in dissimilar alloy weldments also can be expected for many of the compositions in this study. Hydride formation stemming from these driving forces was observed in the dissimilar couple fusion welds. In addition, a basis for estimating hydrogen migration in titanium welds, based on hydrogen activity data, is described.     

Effect of activity differences on hydrogen migration in dissimilar titanium alloy welds

The effect of alloy composition on hydrogen activity was measured for seven titanium alloys as a means to determine the tendency for hydrogen migration within dissimilar metal welds. The alloys were: Ti-CP, Ti-3A1-2.5V, Ti-3Al-2.5V-3Zr, Ti-3Al-2Nb-lTa, Ti-6A1, Ti-6A1-4V, and Ti-6Al-2Nb-lTa-0.8Mo. Hydrogen pressure—hydrogen concentration relationships were determined for temperatures from 600 °C to 800 °C and hydrogen concentrations up to approximately 3.5 at. pct (750 wppm). Fusion welds were made between Ti-CP and Ti-CP and between Ti-CP and Ti-6A1-4V to observe directly the hydrogen redistribution in similar and dissimilar metal couples. Hydrogen activity was found to be significantly affected by alloying elements, particularly Al in solid solution. At a constant Al content and temperature, an increase in the volume fraction of β reduced the activity of hydrogen in α-β alloys. Activity was also found to be strongly affected by temperature. The effect of temperature differences on hydrogen activity was much greater than the effects resulting from alloy composition differences at a given temperature. Thus, hydrogen redistribution should be expected within similar metal couples subjected to extreme temperature gradients, such as those peculiar to fusion welding. Significant hydrogen redistribution in dissimilar alloy weldments also can be expected for many of the compositions in this study. Hydride formation stemming from these driving forces was observed in the dissimilar couple fusion welds. In addition, a basis for estimating hydrogen migration in titanium welds, based on hydrogen activity data, is described.     

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).     

Transient-evoked otoacoustic emissions and contralateral suppression in patients with unilateral tinnitus

OBJECTIVE: Finding an optimal soldering system for a titanium prosthesis has become increasingly important with the successful introduction of titanium and titanium alloys to dentistry. This study examined the effect of corrosion on the strength of the soldered joints of pure titanium and Ti-6Al-4V alloys joined using various solders. METHODS: Commercially pure titanium and Ti-6Al-4V alloy rods (2 mm in diameter; 25 mm long) were soldered in an argon atmosphere using four solders: two kinds of titanium-based solder, a gold-based solder, and a silver-based solder. Tensile strengths were examined before or after immersion treatments. Specimens were immersed in either a 0.9% NaCl or 1.0% lactic acid solution held at 35 degrees C for 3 and 8 wk. The amounts of various metal elements released were determined by atomic absorption photospectroscopy. The natural potentials and potentiodynamic polarization behavior of the soldered specimens in 0.9% NaCl or 1.0% lactic acid were determined by a computer-assisted corrosion measurement system. The results were analyzed by ANOVA and Student's t-test. RESULTS: The cp-titanium and Ti-6Al-4V samples soldered with titanium-based solders exhibited tensile strengths of 300-400 MPa and were not significantly affected by immersion in either solution (no significant difference at p < 0.05). The strengths of both the cp-titanium and titanium alloy specimens soldered with gold-based solder were significantly lower than for any of the other specimens and were affected by immersion in the 0.9% NaCl solution (p < 0.01). The cp-titanium and Ti-6Al-4V specimens that were soldered with titanium-based solders did not show any transpassive regions or breakdown in the natural electrode potential range. On the contrary, the specimens soldered with gold-based and silver-based solders showed transpassive regions or breakdown potentials at less than 0 mV in 0.9% NaCl solution. SIGNIFICANCE: It is recommended that titanium-based solder be employed for titanium and titanium alloys.     

Alpha case thickness modeling in investment castings

The alpha case thickness at the surface of a Ti-6Al-4V (wt pct) step wedge investment casting has been measured and successfully predicted. The prediction uses temperature-time results obtained from a heat flow simulation of the casting. The temperature-time results were coupled to a simple model for diffusion of oxygen into the beta phase during continuous cooling. Oxygen concentration and microhardness profiles were measured from the surface in contact with the ZrO₂ face coat of the shell mold into the interior of the casting. The oxygen content in the metal at the shell mold interface was between 5 and 9.5 wt pct in general agreement with a thermodynamic calculation for bcc Ti in contact with ZrO₂. At the limit of the alpha case region, as determined by standard metallographic technique, the oxygen concentration was found to be no more than 0.02 wt pct above the level of oxygen in the bulk alloy. Using this information and one particular literature value for the activation energy for diffusion of oxygen, a nearly linear relationship was obtained between the measured and predicted alpha case thicknesses at various positions on the casting surface. Reduction of the prefactor of this diffusion coefficient by a factor of 7.5 produces excellent agreement between predicted and measured alpha case thicknesses. Such a reduction is not inconsistent with the scatter of literature values for the diffusion coefficient.     

Kinetics of biaxial dome formation by transformation superplasticity of titanium alloys and composites

By thermally cycling through their transformation temperature range, coarse-grained polymorphic materials can be deformed superplastically, owing to the emergence of transformation mismatch plasticity (or transformation superplasticity) as a deformation mechanism. This mechanism is presently investigated under biaxial stress conditions during thermal cycling of unalloyed titanium, Ti-6Al-4V, and their composites (Ti/10 vol. pct TiC _p , Ti-6Al-4V/10 vol. pct TiC _p , and Ti-6Al-4V/5 vol. pct TiB _w ). During gas-pressure dome bulging experiments, the dome height was measured as a function of forming time. Adapting existing models of biaxial doming to the case of transformation superplasticity where the strain-rate sensitivity is unity, we verify the operation of this deformation mechanism in all experimental materials and compare the biaxial results directly to new uniaxial thermal cycling results on the same materials. Finally, existing thickness distribution models are compared with experimentally measured profiles.     

Ti-6A14V合金表面改性技术

Ti-6Al4V合金作为一种重要的钛合金,其使用量占到了钛合金总使用量的75％～85％,但其耐磨性差、阻燃性差、疏水疏冰性能差、生物相容性不理想等性能缺陷在一定程度上限制了其在某些领域中的应用。首先对Ti-6Al4V合金在各个领域应用时,其性能缺陷的表现形式及危害进行了概述,然后介绍了目前改善Ti-6Al4V合金性能缺陷所普遍采用的以及具有创新性的表面改性技术,评述了部分表面改性技术的优缺点,最后提出了需对Ti-6Al4V合金表面改性技术进一步研究的方向。     

Co-deformation processing and modeling of <Emphasis Type="Italic">In-Situ</Emphasis> multiphase composites

A series of in-situ, deformation-processed metal matrix composites were produced by direct powder extrusion of blended constituents. The resulting composites are comprised of a metallic Ti-6Al-4V matrix containing dispersed and co-deformed discontinuously reinforced-intermetallic matrix composite (DR-IMC) reinforcements. The DR-IMCs are comprised of discontinuous TiB₂ particulate within a titanium trialuminide or near-γ Ti-47Al matrix. Thus, an example of a resulting composite would be Ti-6Al-4V+40 vol pct (Al₃Ti+30 vol pct TiB₂) or Ti-6Al-4V+40 vol pct (Ti-47Al+40 vol pct TiB₂), with the DR-IMCs having an aligned, high aspect ratio morphology as a consequence of deformation processing. The degree to which both constituents deform during extrusion has been examined using systematic variations in the percentage of TiB₂ within the DR-IMC, and by varying the percentage of DR-IMC within the metal matrix. In the former instance, variation of the TiB₂ percentage effects variations in relative flow behavior; while in the latter, varying the percentage of DR-IMC within the metallic matrix effects changes in strain distribution among components. The results indicate that successful co-deformation processing can occur within certain ranges of relative flow stress; however, the extent of commensurate flow will be limited by the constituents’ inherent capacity to plastically deform.     

Involvement of tachykinins in endotoxin-induced airway hyperresponsiveness

Three new titanium alloys with Zr, Nb, Ta, Pd and In as alloying elements were developed and compared with currently used implant metals, namely, pure Ti and Ti-6Al-4V alloy, in terms of mechanical and corrosion properties, and cytotoxicity. New alloys showed comparable mechanical properties with that of the Ti-6Al-4V alloy, but increased corrosion potential, somewhat decreased breakdown potential and increased corrosion rate. There were no significant differences in cell growth on the surface of the various metal specimens, indicating that the cells cannot differentiate between the passivated surfaces of the various Ti metals.     

On a Testing Methodology for the Mechanical Property Assessment of a New Low-Cost Titanium Alloy Derived from Synthetic Rutile

Mechanical property data of a low-cost titanium alloy derived directly from synthetic rutile is reported. A small-scale testing approach comprising consolidation via field-assisted sintering technology, followed by axisymmetric compression testing, has been designed to yield mechanical property data from small quantities of titanium alloy powder. To validate this approach and provide a benchmark, Ti-6Al-4V powder has been processed using the same methodology and compared with material property data generated from thermo-physical simulation software. Compressive yield strength and strain to failure of the synthetic rutile-derived titanium alloy were revealed to be similar to that of Ti-6Al-4V.     

超声对熔盐电解法制备Al-7Si-Sc合金组织的影响

Al-Si系合金在现代工业、交通等领域广泛应用,合金元素钪可进一步改善其加工和使用性能.采用超声协同熔盐电解法制备Al-7S-Sc三元合金,研究探索超声作用对合金组织及强化相分布的影响.发现超声协同熔盐电解制得合金中Sc含量提高,团簇共晶硅组织和AlSi₂Sc₂相显著细化,共晶硅团簇尺寸由约500降低至200 μm,减小约60%,细化后AlSi₂Sc₂相分布均匀.超声协同电解法可显著优化Al-7Si-Sc合金组织,有助于控制改善现行工艺中合金元素偏聚、组织不均匀现象.      

Optimization of Blended-Elemental Powder-Based Titanium Alloy Extrusions for Aerospace Applications

The process of canless extrusion in ambient environment, using cold isostatic pressed, and vacuum-sintered, direct-consolidated blended-elemental hydrided ADMA titanium powder, mixed with master alloy powder for the Ti-6Al-4V composition, has been successfully demonstrated. However, these initially processed unoptimized powder-based extrusions also exhibited oxygen content of about 3000 ppm, within the ASTM B817 Standard, but exceeding the AMS Specification 4935 maximum limit of 2000 ppm, and with pre-extrusion residual hydrogen within 300–500 ppm resulting in post-extrusion void nucleation aligned with the extrusion direction. Additional optimization of extrusion billets during the CIP-and-sintering steps has been successfully demonstrated reducing both oxygen and hydrogen contents to levels at or below the AMS Specification limits for Ti-6Al-4V composition (oxygen content of 2000 ppm maximum, and hydrogen content of 125 ppm maximum). Processing-microstructure-property correlations of the optimized, AMS-4935-Specification-conformant, Ti-6Al-4V blended-elemental powder-based product form exhibited an overall mechanical property balance matching that of double-arc-remelted ingot-based extrusions. Property matching was not only in terms of static mechanical properties (room-temperature tensile properties, and monotonic fracture toughness K _IC (K _Q) values), but also in terms of dynamic fatigue properties (combined S/N plus da/dN properties), as well as stress-corrosion resistance, as measured in terms of K _ISCC threshold values.     

Direct Laser Fabrication of Ti-25V-15Cr-2Al-0.2C (wt?pct) Burn-Resistant Titanium Alloy

Direct laser fabrication has been used to deposit multilayers of burn-resistant titanium alloy onto the surface of Ti697 (Ti-11Sn-5Zr-2.25Al-0.25Si) alloy by feeding Ti-25V-15Cr-2Al-0.2C (wt pct) powder into the laser molten pool. The microstructure and mechanical properties of the deposited layers have been studied to identify the importance of laser conditions on properties/microstructure. The observations are discussed in terms of the optimum laser conditions and thus the potential of using BuRTi (Ti-25V-15Cr-2Al-0.2C) to tip blades of high-temperature titanium alloys to provide burn resistance.