Corrosion and hydrogen absorption of commercially pure zirconium in acid fluoride solutions

The corrosion and hydrogen absorption of commercially pure zirconium have been investigated in acidulated phosphate fluoride (APF) solutions. Upon immersion in 2.0% APF solution of pH 5.0 at 25 °C, a granular corrosion product (Na₃ZrF₇) deposits over the entire side surface of the specimen, thereby inhibiting further corrosion. In 0.2% APF solution, marked corrosion is observed from the early stage of immersion; no deposition of the corrosion product is observed by scanning electron microscopy. A substantial amount of hydrogen absorption is confirmed in both APF solutions by hydrogen thermal desorption analysis. The amount of absorbed hydrogen of the specimen immersed in the 2.0% APF solution is smaller than that in the 0.2% APF solution in the early stage of immersion. The hydrogen absorption behavior is not always consistent with the corrosion behavior. Hydrogen thermal desorption occurs in the temperature range of 300–700 °C for the specimen without the corrosion product. Under the same immersion conditions, the amount of absorbed hydrogen in commercially pure zirconium is smaller than that in commercially pure titanium as reported previously. The present results suggest that commercially pure zirconium, compared with commercially pure titanium, is highly resistant to hydrogen absorption, although corrosion occurs in fluoride solutions.     

Susceptibility to delayed fracture of alpha-beta titanium alloy in fluoride solutions

The susceptibility to delayed fracture of the alpha-beta titanium alloy Ti-6Al-4V has been investigated in acidic and neutral fluoride solutions at room temperature. The time to fracture decreased with increasing applied stress in 2.0% and 0.2% acidulated phosphate fluoride (APF) solutions at pH 5.0. The time to fracture in the 2.0% APF solution was shorter than that in the 0.2% APF solution, although at an applied stress higher than 1000 MPa, the times to fracture were almost the same in both the solutions. For immersion in the 0.2% APF solution, when the applied stress was lower than 700 MPa, delayed fracture did not occur within 1000 h. The fracture surface of specimens immersed in the 2.0% APF solution exhibited brittleness associated with hydrogen absorption, while that in the 0.2% APF solution was ductile and characterized macroscopically as having a cup-cone morphology. The amounts of hydrogen absorbed in 2.0% and 0.2% APF solutions for 24 h were approximately 200 and 30 mass ppm, respectively. As the immersion time increased, the amount of hydrogen absorbed in the 2.0% APF solution increased, whereas that in the 0.2% APF solution hardly increased. In neutral 2.0% and 0.2% NaF solutions, the delayed fracture did not occur within 1000 h, although general corrosion was observed. These results indicate that the susceptibility to delayed fracture of alpha-beta titanium alloy, compared with those of the alpha titanium and beta titanium alloy reported previously, is low in acidic and neutral fluoride solutions.     

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.     

Remarkable improvement of hydrogen sorption kinetics in magnesium catalyzed with Nb2O5

Kinetics of hydrogen absorption and desorption reactions was investigated on the MgH₂ composite doped with 1 mol% Nb₂O₅ as a catalyst by ballmilling. The composite after dehydrogenation at 200 °C absorbed gaseous hydrogen of 4.5 mass% even at room temperature under lower pressure than 1 MPa within 15 s and finally its capacity reached more than 5 mass%. On the other hand, the catalyzed MgH₂ after rehydrogenation desorbed 6 mass% hydrogen at 160 °C under purified He flow, which followed the first order reaction. From the Kissinger plot, the activation energy for hydrogen desorption was estimated to be 71 kJ/mol H₂, indicating the product was significantly activated due to the catalytic effect of Nb₂O₅.     

Features of the HDDR process in R–Fe–B ferromagnetic alloys (R is a mixture of Nd, Pr, Ce, La, Dy and others)

Features of the conventional hydrogenation, disproportionation, desorption, recombination (HDDR) and solid-HDDR processes in some R–Fe–B (R is a mixture of Nd, Pr, Ce, La, Dy) ferromagnetic alloys were studied in the temperature range 20–990 °C and pressure range from 1×10⁻³ Pa to 0.1 MPa. This was carried out by means of differential thermal analysis (DTA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) methods. The hydride of the initial phase is formed by heating to 115 °C. The disproportionation of the alloys occurs in the temperature range from 320 to 800 °C. Φ-phase constitutes the base of the initial alloys. Among the disproportionation products, R-hydride, -Fe and two borides (Fe₂B and R_1.1Fe₄B₄) were revealed. The initial phase in all the alloys is recovered after heating in vacuum to a temperature of 990 °C. Full hydrogen desorption occurs in two temperature ranges with the peaks at 200–320 and 630–715 °C.     

A method to enhance cyclic reversibility of NiTiHf high temperature shape memory alloys

The effect of severe plastic deformation via equal channel angular extrusion (ECAE) at 650 °C on the thermal cyclic response of the 49.8Ni–42.2Ti–8Hf (in at.%) high temperature shape memory alloy was investigated. The improved thermal cyclic stability under constant tensile stresses in the ECAEd samples was attributed to the increase in critical shear stress levels for dislocation slip, which would accompany the martensitic phase transformation, due to the microstructural refinement and increase in favorable dislocation density.     

Effect of Cu on the magnetic properties and reducibility of Fe2TiO5

Ferrites have been studied for several years due to their wide use as magnetic materials for telecommunications, audio and video, power transformers and many other applications.

Equimolar mixtures of Fe₂O₃ and TiO₂ were fired in a muffle furnace at 1200 °C for 4 h. Mixed samples were prepared by replacing TiO₂ with calculated amounts of CuO (x = 0.2, 0.4, 0.6, 0.8 and 1 mol). The synthesized samples were characterized with X-ray diffraction and their magnetic properties were measured using vibrating-sample magnetometer. The microstructure of the sample was examined using reflected light microscope and scanning electron microscope. The formation of Fe₂TiO₅, Fe₅CuO₈, Cu₂TiO₃ and CuFeO₂ phases were detected whereas their magnetic properties increased with increasing the added mole ratio of Cu²⁺ ions. The isothermal reduction kinetics of synthesized nanocrystallites Ti–Cu mixed ferrite compacts were studied at 500 °C using hydrogen gas. It was found that the reduction rate and the reduction extent increased with increasing the extent of Cu²⁺ (0.2–1) whereas the maximum reduction extent (100%) was detected for pure Cu ferrite (Cu²⁺) while the minimum reduction extent (12%) was detected for pure iron titanate (Cu²⁺ = 0). The magnetic properties showed a drastic improvement upon reduction with hydrogen gas.     

Evaluation of hydrogen absorption behaviour during acid etching for surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys

The hydrogen absorption behaviour during acid etching for the surface modification of commercial pure Ti, Ti-6Al-4V and Ni-Ti superelastic alloys has been investigated on the basis of the surface morphology, electrochemical behaviour and hydrogen thermal desorption analysis. To simulate the conventional acid etching for the improvement of the biocompatibility of Ti alloys, the specimens are immersed in 1 M HCl, 1 M H₂SO₄ or 0.5 M HCl + 0.5 M H₂SO₄ aqueous solution at 60 °C. Upon immersion, commercial pure Ti absorbs substantial amounts of hydrogen irrespective of the type of solution. In H₂SO₄ or HCl + H₂SO₄ solutions, the hydrogen absorption occurs for a short time (10 min). For Ti-6Al-4V alloy, no hydrogen absorption is observed in HCl solution, whereas hydrogen absorption occurs in other solutions. For Ni-Ti superelastic alloy, the amount of absorbed hydrogen is large, resulting in the pronounced degradation of the mechanical properties of the alloy even for an immersion time of 10 min, irrespective of the type of solution. The hydrogen absorption behaviour is not necessarily consistent with the morphologies of the surface subjected to corrosion and the shift of the corrosion potential. The hydrogen thermal desorption behaviour of commercial pure Ti and Ni-Ti superelastic alloy are sensitively changed by acid etching conditions. The present results suggest that the evaluation of hydrogen absorption is needed for each condition of acid etching, and that the conventional acid etching often leads to hydrogen embrittlement.     

Effects of potential, temperature and pH on hydrogen absorption and thermal desorption behaviors of Ni-Ti superelastic alloy in 0.9% NaCl solution

The effects of electrochemical potential, solution temperature and pH on the hydrogen absorption and desorption behaviors of Ni-Ti superelastic alloy immersed in 0.9% NaCl solution for 2 h have been investigated systematically by hydrogen thermal desorption analysis. For hydrogen cathodic charging under constant applied potential, upon increasing solution temperature, the critical potential for the hydrogen absorption very slightly shifts to a noble direction. As solution pH decreases, the critical potential for the hydrogen absorption shifts markedly to a noble direction and approaches to the corrosion potential; the critical current density for the hydrogen absorption slightly decreases. At a less noble potential than the critical potential for the hydrogen absorption, the amount of absorbed hydrogen increases markedly with decreasing applied potential. For hydrogen cathodic charging under constant current density, the amount of absorbed hydrogen increases with increasing solution temperature and decreasing solution pH. The basic hydrogen desorption behavior only slightly depends on solution temperature or pH. Nevertheless, hydrogen desorption at low temperatures for specimens subjected to cathodic charging under constant current density is observed distinctly as compared with that under constant applied potential.     

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.     

Structural chemistry and phase relations in intermetallic systems Ti–{Pd,Pt}–Al

Phase relations in the ternary systems Ti–{Pd,Pt}–Al have been experimentally established for the partial isothermal sections at 950°C in the Pd/Pt-poor region (<25 at.% Pd/Pt). The investigation is based on X-ray powder diffraction, metallography, SEM and EMPA techniques on about 45 alloys, which were prepared by various methods employing arc melting, levitation melting under argon or by powder reaction sintering in closed crucibles. Three ternary compounds were observed at 950°C in the Ti–Pd–Al system: τ₃-(Ti,Pd)(Ti,Pd,Al)₂ with Laves-MgZn₂-type, τ₂-(Ti,Al)₆(Ti,Pd,Al)₂₃₊₁ with a filled Th₆Mn₂₃₊₁-type and τ₁-(Ti,Pd,Al)(Ti,Pd,Al)₃ with AuCu₃-type. Due to the wide extension of the Laves phase field, there is no compatibility among γTiAl and τ₂-(Ti,Al)₆(Ti,Pd,Al)₂₃₊₁. The Ti–Pt–Al system at 950°C contains three ternary compounds: τ₃-(Ti,Al)(Ti,Pt,Al)₂ with Laves-MgZn₂-type, τ₂-(Ti,Al)₆(Ti,Pt,Al)₂₃₊₁ with the filled Th₆Mn₂₃₊₁-type and τ₁-(Ti,Pt,Al) with Cu-type. Compatibility exists for Al-rich γTiAl and τ₂-(Ti,Al)₆(Ti,Pt,Al)₂₃₊₁. The typical feature for both alloy systems studied is the three-phase equilibrium: ₂Ti₃Al+γTiAl+τ₃-(Ti,Pd/Al)(Ti,Pd/Pt,Al)₂. The solid solubility of palladium and platinum in the binary titanium aluminides, as observed from EMPA and X-ray data, is rather small and at 950°C accounts to about 2.5 at.% Pd and 2.0 at.% Pt. Two new oxide compounds Ti₃PdAl₂O_x and Ti₃PtAl₂O_x with a filled Ti₂Ni-type are observed in both quaternary systems.     

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.     

Synthesis and thermal stability of nano-crystalline vanadium disilicide

Nano-crystalline vanadium disilicide was successfully synthesized using vanadium tetrachloride and silicon as starting materials via reduction–silication route at 650 °C in the molten salt solution of magnesium chloride and sodium chloride in an autoclave. X-ray powder diffraction patterns indicated that the product was hexagonal VSi₂ (a=4.572 Å, c=6.372 Å). Transmission electron microscopy images showed that the particle size of the product was in the range of 40–60 nm in diameter. There was a strong absorption peak at 271 nm in the UV-Vis absorption spectra. The oxidation of nano-crystalline VSi₂ began to proceed at the temperature of 400 °C in air. But the product had high thermal oxidation stability below 1000 °C. It can be used as an antioxidation coating material.     

Hydrogen evolution from cathodically charged titanium aluminide alloy Ti–24Al–11Nb

A Ti₃Al-based titanium aluminide alloy, Ti–24Al–11Nb, was cathodically charged with hydrogen in a 5% H₂SO₄ aqueous solution for various charging times, and the formation and dissociation of the hydride, the hydrogen evolution behavior and the total hydrogen uptake were investigated mainly by means of X-ray diffractometry and thermal desorption spectroscopy (TDS). The same kind of hydride phase as observed previously in Ti–25Al alloy (hexagonal hydride) was presumably formed in the Ti–24Al–11Nb alloy after cathodic charging. No damage, such as cracks, was induced by hydrogen charging. Two kinds of TDS peaks, one probably corresponding to hydride dissociation and the other to hydrogen dissolution in the normal lattice site, were found after longer hydrogen charging. It is suggested that niobium addition to Ti₃Al-based titanium aluminide alloy may reduce hydrogen susceptibility during cathodic charging.     

The effect of sequential and continuous high-energy impact mode on the mechano-chemical synthesis of nanostructured complex hydride Mg2FeH6

The effect of sequential and continuous high-energy impact mode in the magneto-mill Uni-Ball-Mill 5 on the mechano-chemical synthesis of nanostructured ternary complex hydride Mg₂FeH₆ was studied by controlled reactive mechanical alloying (CRMA). In the sequential mode the milling vial was periodically opened under a protective gas and samples of the milled powder were extracted for microstructural examination whereas during continuous CRMA the vial was never opened up to 270 h duration. MgO was detected by XRD in sequentially milled powders while no MgO was detected in the continuously milled powder. The abundance of the nanostructured ternary complex hydride Mg₂FeH₆, produced during sequential milling, and estimated from DSC reached 44 wt.% after 188 h, and afterwards it slightly decreased to 42 wt.% after 210 and 270 h. In contrast, the DSC yield of Mg₂FeH₆ after continuous CRMA for 270 h was 57 wt.%. Much higher yield after continuous milling is attributed to the absence of MgO. This behavior provides strong evidence that MgO is a primary factor suppressing formation of Mg₂FeH₆. The DSC hydrogen desorption onset temperatures are close to 200 °C while the desorption peak temperatures for all powders are below 300 °C and the desorption process is completed within the range 10–20 min. Within the investigated nanograin size range of 5–13 nm, the DSC desorption onset and peak temperatures of β-MgH₂ and Mg₂FeH₆ do not exhibit any trend with nanograin (crystallite) size of hydrides. TPD hydrogen desorption peaks from the powders containing a single ternary complex hydride Mg₂FeH₆, are very narrow, which indicates the presence of small but well-crystallized hydride particles. Their narrowness provides good evidence that the phase composition, bulk hydrogen distribution and hydride particle size distribution are very homogeneous. The overall amount of hydrogen desorbed in TPD from single-hydride Mg₂FeH₆ powders is somewhat higher than that observed in DSC and TGA desorption.

The powder milled sequentially for 270 h and desorbed in a Sieverts-type apparatus at 250 and 290 °C, yielded about a half of the hydrogen content obtained during DSC and TGA tests. No desorption of hydrogen was detected in a Sieverts-type apparatus at 250 and 290 °C after 128 and 70 min, respectively, from the powder continuously milled for 270 h. The latter easily desorbed 3.13 and 2.83 wt.% hydrogen in DSC and TGA tests, respectively.     

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.     

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.     

Hydriding characteristics of FeTi/Pd films

The hydrogen storage properties of thin films of FeTi evaporated on Si substrates and covered with 20 nm Pd were studied. The films serve as a model system for powdered FeTi, with grains that are (partly) covered with Pd. This material could serve as a practical hydrogen storage material. The 20 nm Pd layer prevents the oxidation of the FeTi layer during air exposure up to temperatures of 200 °C and during H charging and discharging in impure hydrogen. The FeTi is a mixture of amorphous and nano-crystalline material. Two FeTi compositions (43 at.% Fe, i.e. Ti-rich, and 56 at.% Fe, i.e. Fe-rich) were studied. The H charging and discharging characteristics as a function of temperature and pressure are determined from a differential pressure measurement for Fe and Ti-rich material before and after annealing. After discharging in vacuum at a temperature of 150 °C a H residue of H/M  0.12 is observed. The recoverable charging capacity of FeTi (also after many cycles) is 0.9 ΔH/M (H atoms per metal atom) for RT charging at 2700 mbar and vacuum discharging at 150 °C.     

Synthesis of NaAlH4-based hydrogen storage material using milling under low pressure hydrogen atmosphere

The present study highlights the advantages of milling NaH/Al under moderate hydrogen pressure as a favourable production step for NaAlH₄-based hydrogen storage materials. Firstly, it is demonstrated that NaAlH₄ can be obtained by applying a moderate hydrogen pressure (6–12 bar) during milling of NaH and Al with and without the presence of an inexpensive catalyst (TiCl₄). The yield of NaAlH₄ depends critically on process parameters, such as hydrogen pressure and milling time. A fully converted product is capable of reversible hydrogen storage without any activation procedure. Under optimized conditions, a capacity of 4.2 wt.% was achieved and kinetics in the first desorption are comparable to NaAlH₄ doped with TiCl₃. Secondly, the synthesis has been optimized towards shorter milling times. By applying a few absorption/desorption cycles to material that was partially converted during milling, almost full reversible storage capacity can be reached. In addition, kinetics is extremely enhanced. For example, such material exhibits an optimum capacity already after two sorption cycles at 100 bar and 125 °C and allows to absorb 80% of the reversible hydrogen content within a few minutes.