Thermodynamic assessment of the Ti–B system

A consistent thermodynamic data set for the Ti–B system is obtained by means of CALPHAD technology. The sublattice model is used to describe the solid solution phases: (Ti%)₁(B, Va%)_0.5 and (Ti%)₁(B, Va%)₃ for the terminal solution (Ti) and (βTi), and Ti₁(B%, Ti)₁ and (B, Ti%)₁(B%, Ti)₂ for the compound solution TiB and TiB₂, respectively. The intermetallic compound Ti₃B₄ is treated as a stoichiometric compound. The liquid solution phase is assumed to be a substitutional solution with Redlich–Kister formula for the expression of its excess Gibbs energy. The complete T–x phase diagram for the Ti–B binary system is given. The calculation results agree well with experiments.     

Constitution, structural chemistry and magnetism in the ternary system Ce–Ag–Si

Phase relations were established for the Ce–Ag–Si system at 850°C by means of X-ray diffraction, light optical microscopy and quantitative electron probe microanalysis. Phase equilibria are characterised by the existence of extended solid solutions starting from the binaries: Ce(Ag_xSi_1−x)_2−y (ThSi₂-type), Ce(Ag_1−xSi_x)_1−y (unknown structure type) and Ce(Ag_1−xSi_x)_2−y (unknown structure type). Three ternary phases were found to exist, CeAg₂Si₂ (ThCr₂Si₂-type), Ce(Ag_xSi_1−x)_2−y (AlB₂-type) and the new ternary compound CeAgSi₂ with unknown structure type. Magnetic behaviour was studied from magnetic susceptibility and magnetisation measurements down to 1.7 K and employing magnetic fields up to 5 T. Soft ferromagnetism is observed for CeAg_xSi_2−x (AlB₂-type) below 5 K. Alloys Ce(Ag_xSi_1−x)_2−y with 0.08<x_Ag<0.30 (ThSi₂-type) encounter ferromagnetic order below 7 K. For x_Ag=0.31 the ferromagnetic interaction changes to antiferromagnetism with T_N=5.7 K. For CeAgSi₂ ferrimagnetic or canted antiferromagnetic order is indicated below 7 K.     

The phase relationship in the Fe–Pb–Sb ternary system at 500 K

The phase relationship of the Fe–Pb–Sb ternary system at 500 K has been studied mainly by means of X-ray powder diffraction with the aid of differential thermal analysis and optical microscope. There are three three-phase regions, five two-phase regions and five single-phase regions in this ternary system at 500 K. No ternary compounds were found.     

Investigation of the interaction of the components in the Y–Si–Sb system at 670 K

Phase equilibria were established in the Y–Si–Sb ternary system at 670 K. The investigation of the phase relations was based on X-ray diffraction experiments made on arc-melted alloys, which were annealed up to 720 h. The 670 K isothermal section consists of 8 three-phase, 12 two-phase and 11 single-phase regions. The formation of a solid solution of Si in the binary YSb compound (8 at.% Si) has been observed. In the Y–Si–Sb system solid solutions between the isostructural binary compounds Y₅Si₃–Y₅Sb₃ form a continuous series. One ternary compound was observed: Y₅Si₂Sb₂ (Tm₅Si₂Sb₂ str. type, Cmca space group, a=1.4971(2), b=0.7855(2) and c=0.7820(2) nm).     

Ti–V–Mn based alloys for hydrogen compression system

Ti–V–Mn based hydrides are one family of alloys with improved hydrogenation properties and they have a great potential to replace the AB₅ alloys as the sorption materials in hydrogen compression systems, although there still are many problems associated with their use, including unstable reversible hydrogen capacity and unfavorable thermodynamic properties. To gain a better understanding on the effect of the substitution elements and to optimize the alloy composition for high storage capacity, the influence of the alloy stoichiometry was investigated. Ti–Zr–V–Mn alloys were prepared by arc melting technique and were annealed in vacuum at temperature above 900 °C to obtain great sorption properties. Hydrogen absorption and desorption kinetics and PCT characteristics of these alloys at ambient temperature were measured and compared. These hydrogen storage features were also discussed in relation to the effect of alloy element compositions. Ti–Zr–V–Mn alloy cycling behavior was also examined.     

Laser treatment and PVD TiN coating of Ti–6Al–4V alloy

Laser gas assisted processing can be used to modify the surface properties of Ti–6Al–4V alloy through the use of gaseous interaction with the laser melted surface. Laser surface melting of titanium and its alloys in nitrogen to form a layer of TiN embedded in a metallic matrix which is enriched in alloying elements has attracted considerable interest. The surface roughness of the laser-treated surface is poor, therefore, a secondary processing becomes essential. In the present study, duplex treatment of Ti–6Al–4V alloy was carried out. The alloy surface was melted initially under a controlled nitrogen atmosphere, which in turn resulted in a laser-induced nitrided surface. The resulting workpiece surface, then, was PVD TiN coated. In order to assess the wear properties of the resulting surface, friction tests were carried out. SEM, XRD and microhardness were carried out for microstructural analysis and material characterization. It was found that the adhesion of the TiN coating to the base alloy improved considerably in the case of laser-treated workpieces and smooth transition in plastic shearing resistance between the TiN coating and the base alloy enhanced the wear properties of the laser-treated surface.     

Analytical electron microscopy of C-free and C-containing Ti–15–3

Optical microscopy, analytical scanning and transmission electron microscopy have been used to interpret the influence of C on the ageing response of Ti–15–3 (Ti–15V–3Al–3Sn–3Cr (wt.%)). It has been found that the addition of carbon reduces the extent of oxygen segregation to grain boundaries and thus reduces the tendency for grain boundary alpha to form during ageing. The ageing response and the scale of precipitation at 600 °C have been found to depend on the heating rate used. The as-quenched microstructure is characterised by striations typical of pre-martensite-type contrast with a spacing of about 20–25 nm. Diffraction patterns in as-quenched samples show diffuse scattering in addition to the maxima associated with this large spacing. The striations and diffuse scattering anneal out at ageing temperatures above 400 °C. Contrary to earlier work no evidence has been obtained for omega in as-quenched or aged samples. The alpha precipitation is on a finer scale than can be accounted for by the carbides or by the dislocations punched out by the carbides. This conclusion, taken together with the absence of any evidence for omega, leads to the view that the presence of carbon in solution, rather than the carbides, limits diffusion of oxygen and provides additional nucleation sites for alpha – perhaps through vacancy–carbon–oxygen complexes.     

The phase equilibria of the Al–Ce–Ni system at 500 °C

The phase equilibria at 500 °C in the Al–Ce–Ni system in the composition region of 0–33.3 at.% Ce are investigated using XRD and SEM/EDX techniques applied to equilibrated alloys. The previously reported ternary phases and the variation of the lattice parameters versus the composition for different solid solution phases are investigated. It is confirmed that τ₂(Al₂CeNi) exists at 500 °C, while τ₃(Al₅Ce₂Ni₅) does not exist at 500 °C. A new compound τ₉ with composition of about Al₃₅Ce_16.5Ni_48.5 is found. The solubility of Ni in Al₁₁Ce₃ and αAl₃Ce is generally about 1 at.%, while the solubility of Ni in Al₂Ce is measured to be 2.7 at.%. The solubility of Ce in Al₃Ni, Al₃Ni₂, AlNi and AlNi₃ is all less than 1 at.%. The solubility of Al in CeNi₅, Ce₂Ni₇ and CeNi₃ is measured to be 30.4, 4.8 and 9.2 at.%, respectively, while there is no detectable solubility for Al in CeNi₂. A revised isothermal section at 500 °C in the Al–Ce–Ni system has been presented.     

The Er–Ni–B system

The phase diagram of the ternary Er–Ni–B system at 1070 K has been built using the results of X-ray diffraction. As a result of our research the existence of twelve ternary borides has been confirmed, the composition of the boride ErNi₇B₃ (space group I4₁/amd, own structure type) has been refined and three new compounds have been found, namely: ErNi_6.5B₃ (cubic structure), Er_0.917Ni_4.09B (space group P6/mmm, own structure type), ErNi₈B₂ (unknown structure). The two latter borides exist only in as-cast samples.     

Experimental study of Ti–Sn–Y system phase equilibria at 473 K

The phase equilibria of the Ti–Sn–Y ternary system at 473 K have been investigated mainly by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and differential thermal analysis (DTA). The existences of 10 binary compounds, Ti₃Sn, Ti₂Sn, Ti₅Sn₃, Ti₆Sn₅, Ti₂Sn₃, Sn₃Y, Sn₂Y, Sn₁₀Y₁₁, Sn₄Y₅ and Sn₃Y₅ were confirmed. The 473 K isothermal section was found to consist of 13 single-phase regions, 23 two-phase regions and 11 three-phase regions. There is no new ternary compound found in the work. None of the phases in this system reveals a remarkable homogeneity range at 473 K.     

Production of Al–Ti–B master alloys from Ti sponge and KBF4

It is of great interest to replace the K₂TiF₆ salt so as to reduce the volume of fluoride-bearing particulate material to be added to the aluminium melt in the popular “halide salt” process. Ti sponge was used in the present work as the source of Ti in the production of an Al–5Ti–1B grain refiner. Addition of Ti granules into molten aluminium, either premixed with or before KBF₄ salt, has produced Al–5Ti–1B alloys where the boride particles were relatively few and predominantly of the AlB₂ type. The grain refining efficiency of these alloys were far from satisfactory. TiB₂ was the dominant boride phase with sufficient number of blocky aluminide particles when Ti, in excess of the TiB₂ stoichiometry was supplied before hand and the balance was reserved for co-addition with KBF₄. Al₃Ti particles were generated soon after the Ti solubility limit was exceeded in the first step while the boride particles were subsequently produced by the reaction between molten aluminium, KBF₄ and K₂TiF₆. The Al–5Ti–1B master alloy thus produced provided an adequate grain refining performance while the amount of particulate material to be added to the aluminium melt was reduced by nearly 30%.     

The isothermal section of the Ti–Co–Zr ternary system at 773 K

The phase equilibria of the Ti–Co–Zr ternary system at 773 K have been investigated mainly by powder X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive analysis (EDX). The isothermal section consists of 16 single-phase regions, 31 two-phase regions and 16 three-phase regions. There are 11 binary compounds, i.e. CoZr₃, CoZr₂, CoZr, Co₂Zr, Co₂₃Zr₆, Co₁₁Zr₂, TiCo₃, h-TiCo₂, c-TiCo₂, TiCo, Ti₂Co in the system. The existence of two ternary compounds Co₁₀Ti₇Zr₃ and Co₆₆Ti₁₇Zr₁₇ has been confirmed at 773 K. Co₂Zr, CoZr₃ and TiCo have a range of homogeneity. The solubilities of Ti in CoZr was determined to be up to 8.1 at.% Ti.     

Effect of the salt addition practice on the grain refining efficiency of Al–Ti–B master alloys

The impact of the salt addition practice on the microstructure and grain refining efficiency of Al–Ti–B alloys produced by the “halide salt” route was investigated. The grain refining performance of an experimental Al–5Ti–1B master alloy was optimized when the halide salts were pre-mixed before addition to aluminium melt at 800 °C during the production of the grain refiner. The stirring action provided during salt addition was found to degrade, while a high rate of addition was found to improve, the grain refining efficiency. In view of the above, an improved salt addition practice to ensure an exceptional grain refining performance is claimed to comprise the following steps: melting commercial purity aluminium ingot; addition of pre-mixed salts to molten aluminium at 800 °C, at once to facilitate a rapid salt reaction, gently mixing the salts with the aluminium melt without introducing any stirring. The grain refiner master alloy thus produced gives an average grain size of 102 μm 2 min after inoculation.     

An improved practice to manufacture Al–Ti–B master alloys by reacting halide salts with molten aluminium

The well-established “halide salt” route was employed in the present work to produce Al–Ti–B grain refiner alloys with consistent, good properties. The holding step in the production cycle was revised, however, to avoid oxidation of the molten alloy which is believed to be responsible for the relatively low Ti recoveries and thus for the inadequate and inconsistent grain refining efficiency. Stirring during holding was found to degrade the grain refining properties when molten potassium aluminium fluride salt was left on the molten alloy to avoid excessive oxidation. Likewise, holding temperatures higher than 800 °C and holding times longer than 30 min both had an undesirable effect on the grain refining performance. The experimental Al–5Ti–1B grain refiner alloy produced according to the present method provided consistent and better overall grain refining performance.     

High-strength superelastic Ti–Ni microtubes fabricated by sputter deposition

Ti–Ni microtubes are attractive materials for biomedical devices, such as micro-catheters and micro-stents, but it is difficult to fabricate them with dimensions of less than 100 μm by conventional tube-drawing. In this study, Ti–Ni microtubes with 50 μm inner diameter and a tube wall thickness of 6 μm was successfully fabricated using a novel method in which Ti–Ni was sputter-deposited on a Cu wire with a diameter of 50 μm. All the microtubes exhibited shape memory behavior after crystallization at 873 K for 3.6 ks. Microtubes fabricated without rotating the Cu wire during deposition have low fracture strength due to the columnar grains and non-uniform tube wall thickness. Microtubes fabricated by depositing Ti–Ni on a rotating wire have a uniform wall thickness and the fracture strength increased with increasing rotation speed. Microtubes made by the rotating-wire method exhibited superelasticity of 3% strain at room temperature with high fracture stress of 950 MPa, suggesting that they are suitable for practical applications.     

Solid-state phase equilibria in the Gd–Co–Al ternary system at 1173 K

A portion of the isothermal section (1173 K) of the phase diagram of the Gd–Co–Al ternary system (up to 33.3 at.% Gd) were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersion spectroscopy (EDS) techniques. Fourteen single-phase regions (including solid solution regions of the binary compounds), twenty-five two-phase regions and twelve three-phase regions were found to exist at this isothermal section. In the GdCo₂–GdAl₂ system, the existence of the GdCo_0.74Al_1.26 phase is identified and it has a composition range of 30–45 at.% Al, the maximum solid solubility of Al in GdCo₂ is about 15 at.%, and Co in GdAl₂ is about 16 at.%. Besides, the maximum solid solubility of Al in Co, Gd₂Co₁₇ and GdCo₅ is about 6, 17 and 25 at.%, respectively, the maximum solid solubility of Gd in Co, CoAl is below 2 at.% and the solid solubility range is from 47 to 61 at.% Al in CoAl phase. In this work, no new ternary compounds were observed.     

Evaluation of hydrogen absorption properties of Ti–0.2 mass% Pd alloy in fluoride solutions

The hydrogen absorption properties of Ti–0.2 mass% Pd (Ti–0.2Pd) alloy in 2.0% and 0.2% acidulated phosphate fluoride (APF) and neutral 2.0% NaF solutions (25 °C) has been evaluated by hydrogen thermal desorption analysis. During the early stage of immersion (120 h) in the 2.0% APF solution, the amount of absorbed hydrogen was lower than 500 mass ppm. A thermal desorption of hydrogen primary appearing with a peak at 500–600 °C and a broad desorption ranging from 100 to 400 °C were observed. In the 0.2% APF solution, the amount of absorbed hydrogen saturated at 100–200 mass ppm; the thermal desorption of hydrogen appeared with a single peak at 550 °C. In the 2.0% NaF solution, hydrogen absorption was negligible even after 1000 h of immersion, although corrosion pits were observed. The results of the present study suggest that the hydrogen absorption of Ti–0.2Pd alloy, as compared with commercial pure titanium, is suppressed in fluoride solutions.