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.     

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.     

Origin of 2-stage R-phase transformation in low-temperature aged Ni-rich Ti–Ni alloys

After aging at intermediate temperatures (400–500 °C), Ni-rich Ti–Ni alloys undergo an abnormal 3-stage martensitic transformation behavior (1-stage R and 2-stage B19′), which stems from a preferential Ti₃Ni₄ precipitation around grain boundary. On the other hand, if aged at low-temperatures (250–300 °C), they undergo 2-stage R-phase transformation, but the origin of this strange phenomenon is unclear. In the present study, we made a systematic study of this phenomenon by considering the grain boundary effect and composition effect. We found that all single crystals undergo 1-stage R-phase transformation; in contrast, the transformation behavior of polycrystals is dependent on Ni content: low-Ni (50.6Ni, 51Ni) polycrystals undergo 2-stage R-phase transformation while high-Ni (52Ni) polycrystals undergo 1-stage R-phase transformation. The abnormal 2-stage R-phase transformation is attributed to a large-scale compositional heterogeneity in B2 matrix between grain boundary region and grain interior, due to the heterogeneity in precipitate density between the grain boundary and grain interior. But for high-Ni polycrystals, precipitates are essentially homogeneously distributed across the whole grain and this leads to normal 1-stage R-phase transformation. The different transformation behavior of low-Ni and high-Ni polycrystals stems from a competition between two opposing tendencies: (1) for preferential precipitation in the grain boundary; (2) for homogeneous precipitation across the whole grain with high-Ni content. The difference between the effect of intermediate-temperature and low-temperature aging lies in the difference in the ability for long-range diffusion of Ni (from the grain interior to the grain boundary), which results in whether or not Ti₃Ni₄ precipitates can form in the grain interior. Our results lead to a unified explanation for different transformation behaviors of both low-temperature and intermediate-temperature aged alloys in terms of the kinetics of precipitation in supersaturated polycrystals.     

Formation of a tetragonal phase hydride in Ti–Mo–H system

The structural relationship between the hydride phases in Ti–Mo–H solid solution system (Mo content up to 15 at% in the alloy) during dehydrogenation process under annealing has been studied by conventional and in situ X-ray powder diffraction and transmission electron microscopy (TEM) analysis. During dehydrogenation, the saturated hydrides of the Ti–Mo alloys with fcc δ-phase structure transfer into bcc β-phase at higher temperatures. An associated hydrogen concentration reduction for the δ-phase hydride is observed in the process. However, as the hydrogen concentrations decrease to certain values (H/M  1.1–1.7), the unsaturated δ-phase formed at high temperature would become unstable at lower temperature, and transfer into a tetragonal phase (denoted the -phase here). Unlike that of the -phase in Ti–H system, the phase transition does not occur for the saturated δ-phase with hydrogen concentration close to the stoichiometric limit. The hydrogen concentration of this -phase hydride is in between that of the tetragonal γ and -phase in Ti–H system, but more close to the γ-phase. The occurrence region of this -phase expands along with the increase of the Mo content in the alloys. The phase has a lattice similar to that of the -phase in Ti–H system with corresponding fct unit-cell c/a < 1.     

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.     

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.     

An investigation of the Pd–Ag–Ru–Gd quaternary system phase diagram

On the basis of the Ag–Pd–Gd, Ag–Ru–Gd and Pd–Ru–Gd ternary systems, the partial phase diagram of Pd–Ag–Ru–Gd (Gd < 25 at.%) quaternary system has been studied by means of X-ray diffraction analysis, differential thermal analysis, electron probe microanalysis and optical microscopy. The 700 °C isothermal sections of the Ag–Pd–5Ru–Gd, Ag–Pd–20Ru–Gd and Ag–Pd–50Ru–Gd (Gd ≤ 25 at.%) phase diagrams were determined, respectively. And the 700 °C isothermal section of the Pd–Ag–Ru–Gd (Gd ≤ 25 at.%) quaternary system phase diagram was finally inferred. The section consists of four single-phase regions: solid solution Pd(Ag), (Ru), Pd₃Gd and Ag₅₁Gd₁₄; five two-phase regions: Pd(Ag) + (Ru), Pd(Ag) + Ag₅₁Gd₁₄, (Ru) + Ag₅₁Gd₁₄, Pd(Ag) + Pd₃Gd and (Ru) + Pd₃Gd; three three-phase regions: Pd(Ag) + Pd₃Gd + (Ru), Pd(Ag) + Ag₅₁Gd₁₄ + (Ru) and (Ru) + Ag₅₁Gd₁₄ + Pd₃Gd; one four-phase region Pd(Ag) + (Ru) + Ag₅₁Gd₁₄ + Pd₃Gd. No new quaternary intermetallic phase has been found.     

Grain refinement of a Fe3Al-based alloy using κ-Fe3AlC precipitate particles stimulating nucleation of recrystallization

Effects of particle distribution level on recrystallization were investigated in a Fe₃Al-based alloy containing coarse κ-Fe₃AlC precipitate particles. Volume fraction of 10–12% of rod-like κ particles with different size and interparticle spacing was introduced within the Fe₃Al matrix by changing the cooling rate from 1200 °C, which is above the precipitation temperature of the κ phase. These samples were warm rolled at 700 °C to a total reduction of 75%. Annealing of the warm rolled samples produced complete recrystallized structures. The average recrystallized grain size against interparticle spacing showed a valley-shaped curve with a minimum size of 20 μm. Orientation analyses of the warm rolled samples with high resolution EBSD method revealed that the valley shape of the curve may be explained by the particle stimulated nucleation density of recrystallization around κ particles, dependent on the particle distribution.     

Mechanical properties of WC–10Co cemented carbides sintered from nanocrystalline spray conversion processed powders

Mechanical properties and microstructures of nanocrystalline WC–10Co cemented carbides were investigated. The nanocrystalline WC–10Co cemented carbide powders were manufactured by reduction and carbonization of the nanocrystalline precursor powders which were prepared by spray drying process of solution containing ammonia meta-tungstate (AMT) and cobalt nitrate. The WC powders were about 100 nm in diameter mixed homogeneously with Co binder phase and were sintered at 1375 °C under a pressure of 1 mTorr. In order to compare the microstructures and mechanical properties with those of nanocrystalline WC–10Co, commercial WC powders in a diameter range of 0.57–4 μm were mixed with Co powders, and were sintered at the same conditions as those of nanocrystalline powders. TaC, Cr₃C₂ and VC of varying amount were added into nanocrystalline WC–10Co cemented carbides as grain growth inhibitors. To investigate the microstructure of Co binder phase in the WC–10Co cemented carbides, Co–W–C alloy was fabricated at the temperature of sintering process for the WC–10Co cemented carbides. The hardness of WC–10Co cemented carbides increased with decreasing WC grain size following a Hall–Petch-type relationship. The fracture toughness of WC–10Co cemented carbides increases with increasing HCP/FCC ratio of Co binder phase by HCP/FCC phase transformation.     

The ternary system: silicon–titanium–uranium

Phase equilibria in the system Si–Ti–U were established at 1000 °C by optical microscopy, EMPA and X-ray diffraction. Two ternary compounds were observed and were characterised by X-ray powder data refinement: (1) stoichiometric U₂Ti₃Si₄ (U₂Mo₃Si₄-type) with a small homogeneity region of about 3 at.% exchange U/Ti and (2) U_2−xTi_3+xSi₄ (Zr₅Si₄-type) extending at 1000 °C for 0.7<x<1.3. Mutual solubility of U-silicides and Ti-silicides was found to be below about 1 at.%. The Ti,U-rich part of the diagram was also investigated at 850 °C establishing the tie-lines to the low temperature compounds U₂Ti and U₃Si. U₂Ti₃Si₄ is weakly paramagnetic following a Curie–Weiss law above 50 K with μ_eff.=2.67 μ_B/U, Θ_P=−150 K and χ₀=1.45×10⁻³ emu/mol (18.2×10⁻⁹ m³/mol).     

Influence of tin on the structure and properties of as-cast Ti-rich Ti–Si alloys

By the methods of DTA, X-ray diffraction, metallography and microprobe analysis, phase equilibria in the Ti-corner (more than 50 at.% Ti) of the Ti–Si–Sn system were studied. The solidus projection and the melting diagram (solidus+liquidus) were constructed. A new ternary compound T of composition Ti₅Si_1.2–1.6Sn_1.8–1.4 was found to form with the crystal structure of W₅Si₃-type. The ternary eutectic equilibrium L↔β-Ti+Ti₅Si₃+Ti₃Sn was established to occur at 1460 °C with the composition of the invariant point E at 77Ti–9Si–14Sn. Microhardness measurements were carried out for the primary grains of the alloys with 5 at.% Si.     

The performance of Al–Ti–C grain refiners in twin-roll casting of aluminium foilstock

The master alloys based on the Al–Ti–B system have been used extensively for refining the grain structure of aluminum alloys. The quality-related problems linked with the TiB₂ particles, however, have generated an interest in the Al–Ti–C grain refiners as an acceptable replacement for Al–Ti–B master alloys. TiC particles are smaller than the TiB₂ particles and are less prone to agglomeration. Al–3Ti–0.15C grain refiners have been in use for some time in several alloy systems. Much of the work reported on this alloy, however, has been from DC casting while performance data in strip casting is not available. In the present work, a commercial Al–3Ti–0.15C grain refiner was employed in the twin-roll casting of AA8111 foilstock. Its grain refining efficiency was compared with that of the Al–5Ti–0.2B master alloy, the standard grain refiner in aluminium industry for the manufacture of aluminium foil products.     

Phase transformation and morphology of the intermetallic compounds formed at the Sn–9Zn–3.5Ag/Cu interface in aging

The morphology and phase transformation of the intermetallic compounds (IMCs) formed at the Sn–9Zn–3.5Ag/Cu interface in a solid-state reaction have been investigated by X-ray diffraction (XRD), transmission electron microscopy (TEM), electron diffraction (ED), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS). The monoclinic η′-Cu₆Sn₅ transforms to the hexagonal η-Cu₆Sn₅ and the orthorhombic Cu₅Zn₈ transforms to the body-centered cubic (bcc) γ-Cu₅Zn₈ as aged at 180 °C. The scallop-shaped Cu₆Sn₅ layer is retained after aging at 180 °C for 1000 h. In the solid-state reaction, Ag is repelled from η′-Cu₆Sn₅ and reacts with Sn to form Ag₃Sn, and the Cu₅Zn₈ layer decomposes. Kirkendall voids are not observed at the Sn–9Zn–3.5Ag/Cu interface even after aging at 180 °C for 1000 h.     

VC, Cr3C2 and NbC doped WC–Co cemented carbides prepared by pulsed electric current sintering

WC–12 wt.% Co grade cemented carbides doped with 0.9 wt.% VC, NbC or Cr₃C₂ grain growth inhibitor were consolidated by pulsed electric current sintering (PECS), also known as spark plasma sintering (SPS), in the solid state at 1240 °C for 2 min. The microstructure and properties of the PECS material grades are compared with those of pressureless sintered grades, liquid phase sintered at 1420 °C for 1 h. Microstructural and hardness characterization revealed that both the chemical composition and sintering technique play an important role on the WC grain growth and final mechanical properties. To obtain a nanometer sized WC–Co microstructure, it is essential to carefully select the grain growth inhibitor in addition to the application of a fast thermal densification cycle by means of spark plasma sintering.     

Tailored sintering of VC-doped WC–Co cemented carbides by pulsed electric current sintering

WC–12 wt.% Co powder mixtures with 0, 0.45 or 0.9 wt.% VC additions were consolidated by solid state pulsed electric current sintering (PECS) for 2 min at 1080–1240 °C. The influence of the sintering condition and VC concentration on the densification, WC grain growth and mechanical properties of the cemented carbides were investigated. Finite element simulation revealed that the radial temperature gradient inside the sintering powder compacts could be homogenised using a carbon felt insulation surrounding the graphite die set-up.     

A comparative study of precipitation behavior of Heusler phase (Ni2TiAl) from B2-TiNi in Ni–Ti–Al and Ni–Ti–Al–X (X=Hf, Pd, Pt, Zr) alloys

In support of the design of high strength TiNi-based shape-memory alloys, the precipitation of L2₁–Ni₂TiAl phase from a supersaturated B2–TiNi matrix at 600 and 800 °C is studied using transmission and analytical electron microscopy (TEM/AEM), and 3D atom-probe microscopy (3DAP) in Ni–Ti–Al and Ni–Ti–Al–X (X=Hf, Pd, Pt, Zr) alloys. A B2/L2₁ fully coherent two-phase microstructure is confirmed to be analogous to the classical γ/γ′ system in terms of precipitate shape, spatial distribution and a minimum distance of separation between L2₁ precipitates as dictated by the interplay between strain and interfacial energies. The effects are also confirmed to disappear with loss of coherency. These results lend further support, at least qualitatively, to the theoretical predictions of microstructural dynamics of coherent aggregates. Selected cohesive properties of stable and virtual B2 compounds are calculated by an ab initio method, showing good agreement with measured site occupancy and lattice parameters. A simple analysis of the L2₁ precipitate size evolution suggests that in the case of alloys with Al, Zr or Hf substitution for Ti, the precipitates follow coarsening kinetics at 600 °C and growth kinetics at 800 °C, while for alloys with Pd or Pt substitution for Ni, precipitates follow one kinetic behavior at both temperatures. The temperature-dependent partitioning behaviors of Hf, Pd, Pt and Zr are established by quantitative microanalysis using AEM and nanoscale analysis using 3DAP. Both Hf and Zr prefer to partition to the B2 phase at 800 °C while they exhibit reverse behavior at 600°C. Pt also partitions to B2 at 800 °C, while Pd partitions to the L2₁ phase at both 600 and 800 °C. To describe the composition dependence of the lattice parameter of multicomponent B2 and L2₁ phases, the atomic volumes of Al, Hf, Ni, Ti and Zr in B2 and L2₁ phases are determined, providing a model for the control of interphase misfit in alloy design.     

Production of submicrocrystalline structure in large-scale Ti–6Al–4V billet by warm severe deformation processing

The “abc” deformation method for production of large-scale billets with submicrocrystalline structure was developed. A large billet of Ti–6Al–4V alloy (150-mm diameter × 200-mm length) with a homogeneous submicrocrystalline structure was produced. The refined structure with a grain/subgrain size of about 0.4 μm leads to a substantial mechanical properties improvement.     

Austenite stability in Fe–Mn–Si-based shape memory alloys

The stability of austenite in a number of Fe–Mn–Si-based shape memory alloys has been investigated. It was found that a grain boundary precipitate of BCC structure is formed over a wide range of alloy compositions and heat treatment temperatures. This grain boundary phase has been identified as the chi (χ) phase. Although up to 3 vol.% of the grain boundary precipitate was generated by isothermal aging in the range 500–800 °C, it was found not to markedly affect the mechanical properties or the shape memory effect. Nano-indentation indicated that the hardness and strength of the parent and precipitate phase are very similar, as are their compositions.     

The 260 °C phase equilibria of the Sn–Sb–Ag ternary system and interfacial reactions at the Sn–Sb/Ag joints

The isothermal section of the Sn–Sb–Ag ternary system at 260 °C has been determined in this study by experimental examination. Experimental results show no existence of ternary compounds in the Sn–Sb–Ag system. Two extensive regions of mutual solubility have been determined. The one located between the two binary isomorphous phases, Ag₃Sn and Ag₃Sb, is labeled as and the other one located between the two binary isomorphous phases, Ag₄Sn and Ag₄Sb, is labeled as ξ. The phase is a very stable phase and is in equilibrium with ξ, Sb, SbSn, Sb₂Sn₃, and liquid Sn phases. Each of the Sb and SbSn phases has a limited solubility of Ag. Only one stoichiometric compound, Sb₂Sn₃, exists. Besides phase equilibria determination, the interfacial reactions between the Sn–Sb alloys and the Ag substrate were investigated at 260 °C. It was found that the phase formations in the Sn–Sb/Ag couples are very similar to those in the Sn/Ag couples.