Reactive ball milling to produce nanocrystalline ZnO

Ball milling of zinc powders in oxygen atmosphere leads to nanocrystalline ZnO. The average grain size has a value of 9 nm. The zinc oxidation proceeds gradually. It is compared with the combustion oxidation reactions of metals (Zr, Ti, Fe and Sn) reported previously. We propose a new parameter ΔH/C_p(metal) instead of simplified adiabatic temperature to judge if the mechanochemical oxidation of a particular metal happens via gradual or combustion reaction.

Structure effect on the oxygen permeation properties of barium bismuth iron oxide membranes

In this work, we investigated the oxygen permeation properties of barium bismuth iron oxide within the family of [Ba_2−3xBi_3x−1][Fe_2xBi_1−2x]O_2+3x/2 for x = 0.17–0.60. The structure changed progressively from cubic to tetragonal and then to hexagonal as function of x in accordance with the different relative amounts of bismuth on A-site and B-site of ABO_3−δ perovskite lattices. We found that the oxygen flux and electrical conductivity correlated strongly, and it was prevalent for the cubic structure (x = 0.33–0.40) which conferred the highest oxygen flux of 0.59 ml min⁻¹ cm⁻² at 950 °C for a disk membrane x = 0.33 with a thickness of 1.2 mm. By reducing the thickness of the disk membrane to 0.8 mm, the oxygen flux increased to 0.77 ml min⁻¹ cm⁻², suggesting both surface kinetics and ion diffusion controlled oxygen flux, though the former was more prominent at higher temperatures. For disk membranes x = 0.45–0.60, the perovskite structure changed to tetragonal and hexagonal, and the oxygen flux was insignificant below 900 °C, clearly indicating electron conduction properties only. However, for two compositions with relatively high bismuth content, e.g. x = 0.55 and 0.60, there was a sudden and significant rise of oxygen permeability above 900 °C, by more than one order of magnitude. These materials changed conduction behavior from metallic to semiconductor at around 900 °C. These results suggest the advent of mixed ionic electronic conducting properties caused by the structure transition as bismuth ions changed their valence states to compensate for the oxygen vacancies formed within the perovskite lattices.

Effect of surface roughness of Ti, Zr, and TiZr on apatite precipitation from simulated body fluid

Some of the critical properties for a successful orthopedic or dental implant material are its biocompatibility and bioactivity. Pure titanium (Ti) and zirconium (Zr) are widely accepted as biocompatible metals, due to their non-toxicity. While the bioactivity of Ti and some Ti alloys has been extensively investigated, there is still insufficient data for Zr and titanium-zirconium (TiZr) alloys. In the present study, the bioactivity, that is, the apatite forming ability on the alkali and heat treated surfaces of Ti, Zr, and TiZr alloy in simulated body fluid (SBF), was studied. In particular, the effect of the surface roughness characteristics on the bioactivity was evaluated for the first time. The results indicate that the pretreated Ti, Zr and TiZr alloy could form apatite coating on their surfaces. It should be noted that the surface roughness also critically affected the bioactivity of these pretreated metallic samples. A surface morphology with an average roughness of approximately 0.6 microm led to the fastest apatite formation on the metal surfaces. This apatite layer on the metal surface is expected to bond to the surrounding bones directly after implantation.

Extrusion properties of a Zr-based bulk metallic glass

The extrusion behavior of Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 metallic glasses in the supercooled liquid region was investigated. Good extrusion formability was observed under low strain rates at temperatures higher than 395 °C. The metallic glasses were fully extruded without crystallization and failure within the range of T=395–415 °C under strain rates from 5×10⁻³ s⁻¹ to 5×10⁻² s⁻¹, and the deformation behavior of the metallic glasses during the extrusion was found to be in a Newtonian viscous flow mode by a strain rate sensitivity of 1.0.

Porous Ti-Nb-Zr alloy through powder metallurgy for biomedical applications

This work investigated the structure and properties relationship, surface modification, biocompatibility and bioactivity of a porous Ti-Nb-Zr alloy. The porous alloy exhibited inter-connected porous structure, good biocompatibility and high mechanical strength with an elastic modulus close to that of bone. Porous Ti-Nb-Zr alloys are thus promising biomaterials for hard tissue replacement.

Processing of biocompatible porous Ti and Mg

A new powder manufacturing process for Ti and Mg metallic foams designs porosity, pore size and morphology. These open-cellular foams (pores: 200–500 μm) have exceptional characteristics (e.g., Ti foam porosity 78%, compressive strength 35 MPa, Young's modulus 5.3 GPa). Anticipated applications include biocompatible implant materials.

Effect of relaxation on pressure sensitivity index in a Zr-based metallic glass

Shear-banding features of as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass were investigated through Rockwell indentation tests. Isothermal annealing of the as-cast samples was conducted at temperatures below its glass transition temperature, Tg. The exothermal enthalpy during continuous heating below Tg decreases with increasing annealing temperature, indicating the gradual reduction of free-volume upon annealing. The observation on the morphology of shear-banding pattern around the indents implies a reduced shear bands activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of Rockwell indent decrease from 88° for the as-cast sample to 79° for the sample annealed at 633 K for 1 h, indicating a pressure sensitive plasticity. By Mohr–Coulomb criterion, the pressure sensitive index can be obtained on the basis of the measured 2θ, which increases with increasing annealing temperature, indicating an increase of “atomistic friction” due to the reduction of the free volume upon annealing.

Indentation study on the pressure sensitivity of a ZR-based bulk metallic glass

Spherical indentation test was conducted on as-cast and annealed Zr_41.2Ti_13.8Cu_12.5Ni₁₀Be_22.5 bulk metallic glass, and the evolution of the morphology of the deformation zone of indents upon annealing was investigated. The DSC traces of the as-cast and annealed samples show that the enthalpy change at the glass transition, ΔH, decreases with the increasing of annealing temperature, indicating the reduction of the free volume upon annealing. The morphology of the indents implies a reduced shear band activity in the annealed samples. The included angles (2θ) between two families of shear bands emanating from the edge of spherical indent in the as-cast and the annealed samples were measured to be in the range of 88-79°, which decrease with the increasing of annealing temperature, indicating pressure sensitive plasticity in the as-cast and annealed samples. By Mohr–Coulomb criterion, the pressure sensitive index, α, can be obtained on the basis of the measured 2θ. The sensitivity index increases with increasing temperature, implying an increase of 'atomistic friction' due to the reduction of the free volume upon annealing.

Effect of heat-treatment atmosphere on the bond strength of apatite layer on Ti substrate

Objectives
The purpose of this study was to investigate the bond strength of apatite layer on titanium (Ti) substrate coated by biomimetic method and to improve the bonding of apatite layer to Ti substrate by optimizing the alkali heat-treatment process.

Methods
Ti plates pre-treated with an alkali solution of 10 M sodium hydroxide (NaOH) were heat-treated at 600 °C for 1 h at different atmospheres: in air and in vacuum. A dense apatite layer formed on top of the sodium titanate layer after soaking the alkali and heat-treated Ti samples in simulated body fluid (SBF) for up to 3 weeks. The bond strengths of the sodium titanate layer on Ti substrate, and apatite layer on the sodium titanate layer, were measured, respectively, by applying a tensile load. The fracture sites were observed with a scanning electron microscope (SEM).

Results
The apatite layer on the substrate after alkali heat-treatment in air achieved higher bond strength than that on the substrate after alkali heat-treatment in vacuum. It was found that the interfacial structure between the sodium titanate and Ti substrate has a significant influence on the bond strength of the apatite layer.

Significance
It is advised that titanium implants can achieve better osseointegration under load-bearing conditions by depositing an apatite layer in vivo on a Ti surface subjected to alkali and heat-treated in air.

Deformation twinning and the hall-petch relation in commercial purity ti

The effect of grain size and deformation temperature on the behavior of wire-drawn a-Ti during compression has been examined. At strains of 0.3, the flow stress exhibited a negative Hall–Petch slope. This is proposed to result from the prevalence of twinning during the compressive deformation. Electron backscattered diffraction revealed that {1012} was the most prolific twin type across all the deformation temperatures and grain sizes examined. Of the twinning modes observed, {1122} twinning was the most sensitive to the grain size and deformation temperature. The range of morphologies exhibited by deformation twins is also described.

Nucleation and growth during reactions in accumulative roll bonding of Ti/Al multilayers

A two-stage process in the formation of TiAl₃ was found in the accumulative roll bonding (ARB) Ti/Al multilayers. The distribution of layer spacing did not become broad enough to lose the main features of the double exothermal behaviour. A modified model based on thin films was set up to describe the kinetic characteristics of the formation of TiAl₃ in ARB samples.

The kinetics of two-stage formation of TiAl3 in multilayered Ti/Al foils prepared by accumulative roll bonding

The solid-state reactions of Ti/Al multilayered samples produced by Accumulative Roll Bonding (ARB) have been investigated using differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. The kinetics of the formation of the intermetallic compound TiAl3 was highlighted. Experimental evidence and analysis of the data shows that, there was a two-stage process in the formation of TiAl₃ in the ARB Ti/Al reactive multilayered samples. Calorimetric and microstructural analyses also suggest that the interdiffusion of Al and Ti which led to solid solutions preceded the formation of intermetallic compounds. Despite the apparent chaos in the thickness of the ARB multilayered samples, the distribution of layer spacing did not become broad enough to lose the main features of the double exothermal behaviour. Isothermal DSC shows a larger Avarami constant in ARB Ti/Al multilayered structures than was found in Ti/Al thin films. A modified model based on thin films was set up to describe the kinetic characteristics of the formation of the intermetallic compound TiAl₃ in ARB samples.

Effect of structure relaxation on the plastic deformation behaviour in a Zr-based BMG under indenter

Vickers and nano indentations were performed on a structurally relaxed Zr₄₁Ti₁₄Cu_12.5Ni₁₀Be_22.5 bulk metallic glass (BMG), and the evolution of the shear bands in the relaxed BMG was investigated and compared to that in the as-cast alloy. Results indicate that the plastic deformation in the BMG with structure relaxation is accommodated by the semicircular (primary) and radial (secondary) as well as tertiary shear bands. Quantitatively, the shear band density in the relaxed alloy was much lower than that in the as-cast alloy. The annihilation of free volume caused by the annealing was responsible for the embrittlement of the sample with structure relaxation.

Plastic deformation in a partially crystallized Zr-based BMG under Vickers indenter

Vickers indentations were carried out on an anneal-introduced partially crystallized Zr₄₁Ti₁₄Cu_12.5 Ni₁₀Be_22.5 bulk metallic glass (BMG), and the evolution of the shear bands in this samplewas investigated and compared to the as-cast, aswell as the structurally relaxed counterparts. The results indicate that the plastic deformation in the partially crystallized BMG was accommodated by the semi-circular (primary) and radial (secondary) shear bands. A full crack or flake that was produced due to the spring back during the load removal was observed. The shear band density in the annealed alloy which was dispersed with crystalliteswas significantly lower than that of the as-cast alloy. The difference of the shear band features among the three kinds of alloy status, i.e., partially crystallized, structurally relaxed and as-cast alloys was discussed in terms of the free volume in the BMGs and the characteristics of nano-composites. It has been demonstrated that the plasticity for the three statuses of alloys queues in the descending order as the as-cast, annealed with partial crystallization, and annealed without crystallization.

Stoichiometric changes in lithium conducting materials based on Li1+xAlxTi2−x(PO4)3: impedance, X-ray and NMR studies

The lithium fast-ion conductor, Li_1+xAl_xTi_2−x(PO₄)₃ (LATP) has been modified via changes in stoichiometry during the processing steps. The resultant changes have been followed using ²⁷Al MAS NMR, X-ray powder diffraction and impedance spectroscopy. The most important changes were those of the form Li_1.3+4yAl_0.3Ti_1.7−y(PO₄)₃. It was possible to remove the AlPO₄ phase (both tridymite and berlinite polymorphs), as monitored by X-ray diffractograms and ²⁷Al NMR spectra. Consequently, these changes appear to result in increased grain boundary conductivity of the LATP material.