Thermodynamic characterization of Al–Cr,Al–Zr,and Al–Cr–Zr alloy systems

Abstract

The equilibrium phase diagrams of Al–Cr, Al–Zr, and Al–Cr-Zr, with particular reference to aluminium-rich alloys, have been critically reviewed. On the basis of these, and consistent with measured thermodynamic values, the binary systems have been thermodynamically characterized. Using these characterizations, phase equilibria have been extrapolated in the ternary, with the intention of augmenting the sparse experimental information concerning the equilibrium liquidus (0–10 at.%Cr, Zr) and solid solution range of aluminium in Al–Cr–Zr. Using the same parameters that define the equilibrium phase relationships, metastable phase relationships can also be extrapolated into the ternary.

MST/418     

Structure,mechanical properties,and grindability of dental Ti–Zr alloys

Structure, mechanical properties and grindability of a series of binary Ti-Zr alloys with zirconium contents ranging from 10 to 40 wt% have been investigated. Commercially pure titanium (c.p. Ti) was used as a control. Experimental results indicated that the diffraction peaks of all the Ti-Zr alloys matched those for alpha Ti. No beta-phase peaks were found. The hardness of the Ti-Zr alloys increased as the Zr contents increased, and ranged from 266 HV (Ti-10Zr) to 350 HV (Ti-40Zr). As the concentration of zirconium in the alloys increased, the strength, elastic recovery angles and hardness increased. Moreover, the elastically recoverable angle of Ti-40Zr was higher than of c.p. Ti by as much as 550%. The grindability of each metal was found to be largely dependent on the grinding conditions. The Ti-40Zr alloy had a higher grinding rate and grinding ratio than c.p. Ti at low speed. The grinding rate of the Ti-40Zr alloy at 500 m/min was about 1.8 times larger than that of c.p. Ti, and the grinding ratio was about 1.6 times larger than that of c.p. Ti. Our research suggested that the Ti-40Zr alloy has better mechanical properties, excellent elastic recovery capability and improved grindability at low grinding speed. The Ti-40Zr alloy has a great potential for use as a dental machining alloy.     

Microstructure and precipitation in Al–Li–Cu–Mg–(Mn,Zr) alloys

Abstract

Hot rolled Al–6Li–1Cu–1Mg–0·2Mn (at.-%) (Al–1·6Li–2·2Cu–0·9Mg–0·4Mn, wt-%) and Al–6Li–1Cu–1Mg–0·03Zr (at.-%) (Al–1·6Li–2·3Cu–1Mg–0·1Zr, wt-%) alloys developed for age forming were studied by tensile testing, electron backscatter diffraction (EBSD), three-dimensional atom probe (3DAP), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC). For both alloys, DSC analysis shows that ageing at 150°C leads initially to formation of zones/clusters, which are later gradually replaced by S phase. On ageing at 190°C, S phase formation is completed within 12 h. The precipitates identified by 3DAP and TEM can be classified into (a) Li rich clusters containing Cu and Mg, (b) a plate shaped metastable precipitate (similar to GPB2 zones/S″), (c) S phase and (d) δ′ spherical particles rich in Li. The Zr containing alloy also contains β′ (Al₃Zr) precipitates and composite β′/δ′ particles. The β′ precipitates reduce recrystallisation and grain growth leading to fine grains and subgrains.     

Structure,mechanical properties and grindability of dental Ti–10Zr–X alloys

This study aimed to investigate the structure, mechanical properties and grindability of a binary Ti–Zr alloy added to a series of alloying elements (Nb, Mo, Cr and Fe). The phase and structure of Ti–10Zr–X alloys were evaluated using an X-ray diffraction (XRD) for phase analysis and optical microscope for microstructure of the etched alloys. Three-point bending tests were performed using a desk-top mechanical tester. Grindability was evaluated by measuring the amount of metal volume removed after grinding for 1 min at each of the four rotational speeds of the wheel (500, 750, 1000 or 1200 m/min). Results were compared with c.p. Ti, which was chosen as a control. Results indicated that the phase/crystal structure, microstructure, mechanical properties and grindability of the Ti–10Zr alloy can be significantly changed by adding small amounts of alloying elements. The alloying elements Nb, Mo, Cr and Fe contributed significantly to increasing the grinding ratio under all grinding conditions, although the grinding rate of all the metals was found to be largely dependent on grinding speed. The Ti–10Zr–1Mo alloy showed increases in microhardness (63%), bending strength (40%), bending modulus (30%) and elastic recovery angle (180%) over those of c.p. Ti, and was also found to have better grindability. The Ti–10Zr–1Mo alloy could therefore be used for prosthetic dental applications if other conditions necessary for dental casting are met.     

Microstructure,mechanical and corrosion properties of Mg–Nd–Zn–Sr–Zr alloy as a biodegradable material

Abstract

The Mg–2·5Nd–0·3Zn–0·1Sr–0·4Zr (wt-%) alloy was prepared by gravity casting. Solution treatment and extrusion were conducted. The microstructure, mechanical properties, and corrosion behaviour of the alloy under as cast, T4-treated, and as extruded conditions were evaluated using scanning electron microscope, tensile test, microhardometre, immersion test, and electrochemical test. The results show that the as extruded alloy exhibits the highest ultimate tensile strength (231 MPa), elongation (36·6%), and microhardness (57·8 HV). The as cast alloy shows the best corrosion resistance because the relative continuously distributed eutectic phase with noble corrosion potential acts as a corrosion barrier. The as extruded Mg–Nd–Zn–Sr–Zr alloy with high ductility and good corrosion resistance is desirable for preparing biodegradable implants.     

Atomic bonding and mechanical properties of Al–Li–Zr alloy

The atomic bonding of Al–Li alloy with minor Zr is calculated according to the “Empirical Electronic Theory in Solids”. The result shows that the stronger interaction between Al and Zr atoms, which leads to form the Al–Zr segregation regions, promotes the precipitation of Al₃Zr particles and produces a remarkable refinement of Al₃Li grains in the alloy. Because there are the strongest covalent Al–Zr bonds in Al₃Zr and Al₃(Zr, Li) particles, these covalent bonds can cause a great resistance for dislocation movement, and is favorable to strengthen the alloy. On the other hand, with precipitating the Al₃(Zr, Li) particles, it causes the coherent interphase boundary energy of Al/Al₃Li to decrease, and atomic bonding is well matched in between the interface of two phases.     

Thermal diffusivity of submicro- and nanocrystalline Zr–2.5% Nb and Zr–50% Nb alloys at high temperatures

Measurement data are given for the thermal diffusivity of Zr–2.5% Nb and Zr–50% Nb alloys both with the usual polycrystalline structure and with submicro- and nanocrystalline structures at high temperatures, which were determined in the automated mode using the dynamic technique of plane temperature waves.     

Microstructures, mechanical properties and in vitro corrosion behaviour of biodegradable Mg–Zr–Ca alloys

The microstructures, mechanical properties, corrosion behaviour and biocompatibility of the Mg–Zr–Ca alloys have been investigated for potential use in orthopaedic applications. The microstructures of the alloys were examined using X-ray diffraction analysis, optical microscopy and scanning electron microscopy. The mechanical properties of Mg–Zr–Ca alloys were determined from compressive tests. The corrosion behaviour has been investigated using an immersion test and electrochemical measurement. The biocompatibility was evaluated by cell growth factor using osteoblast-like SaOS2 cell. The experimental results indicate that the hot-rolled Mg–Zr–Ca alloys exhibit much finer microstructures than the as-cast Mg–Zr–Ca alloys which show coarse microstructures. The compressive strength of the hot-rolled alloys is much higher than that of the as-cast alloys and the human bone, which would offer appropriate mechanical properties for orthopaedic applications. The corrosion resistance of the alloys can be enhanced significantly by hot-rolling process. Hot-rolled Mg–0.5Zr–1Ca alloy (wt %) exhibits the lowest corrosion rate among all alloys studied in this paper. The hot-rolled Mg–0.5Zr–1Ca and Mg–1Zr–1Ca alloys exhibit better biocompatibility than other studied alloys and possess advanced mechanical properties, corrosion resistance and biocompatibility, suggesting that they have a great potential to be good candidates for orthopaedic applications.     

Synthesis, structural, electrical and dielectric properties of Zn–Zr doped strontium hexaferrite nanoparticles

Zinc-Zirconium doped Strontium hexaferrite SrZn_xZr_xFe_12?2xO₁₉ (where x = 0.0, 0.2, 0.4, 0.6, 0.8, 1.0) have been successfully synthesized via sol–gel auto combustion technique. The as-synthesized samples were characterized by thermo gravimetric analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The X-ray powder diffraction results showed that the sample was single phase with the space group of P6₃/mmc. The lattice constant ‘a’ almost remains constant while ‘c’ increases as Zn–Zr concentration ‘x’ increases. The crystallite size obtained from XRD data is in the range of 36–47 nm. The average grain size as determined by SEM was found in the range of 40–90 nm. EDS analysis showed that the composition obtained is near stoichiometric. D.C. electrical resistivity measurements were carried out within the temperature range of 300–923 K. It is observed that the resistivity decreases whereas the drift mobility increases as Zn–Zr content ‘x’ increases. The activation energy is found to decrease with the concentration ‘x’. Dielectric measurements were carried out within the frequency range of 50 Hz–5 MHz. It is found that dielectric constant (ε′) and dielectric loss tangent (tan δ) both increases as the Zn–Zr concentration ‘x’ increases. Moreover, the structural, morphological, electrical and dielectric properties of Sr–M ferrite powders were strongly depend upon the synthesis condition.     

Design and mechanical characterization of a Zr–Nb–O–P alloy

In this study, Sn-free Zr–1.5Nb–O–P alloys were manufactured and their mechanical properties were characterized. The ultimate tensile strength (UTS) of cold rolled Zr–1.5Nb–O–P alloy with 160 ppm phosphorous (680 MPa) were close to that of a commercially available Zr–1Nb–1Sn–0.1Fe alloy (720 MPa), achieving a good mechanical strength without the addition of Sn, an effective solution strengthening element. The UTS of recrystallized Zr–1.5Nb–O–P alloy with 160 ppm phosphorous (533 MPa) was far greater than that of a commercially available Zr–1Nb–O (323 MPa) because of the strengthening due to higher Nb and oxygen content combined with phosphorous strengthening. The activation volumes for the cold rolled Zr–1.5Nb–P alloys were not much different from those of annealed Zr–1.5Nb–P alloys despite the higher dislocation density in the cold rolled alloys. Insensitivity of the activation volume to the dislocation density and the decrease of the activation volume with the addition of phosphorous support the suggestion linking the activation volume with the activated bulge of dislocations limited by segregation of oxygen and phosphorous atoms.     

Microstructure,corrosion behavior and cytotoxicity of Zr–Nb alloys for biomedical application

In this work, the effects of Nb content on microstructure and corrosion behaviors of biomedical Zr–Nb alloys were systematically studied. The results of XRD analysis and optical microscopy indicated that the experimental Zr–Nb alloys had a duplex structure of α and β phases, and the content of β phase increased with the increase of Nb content. The electrochemical impedance spectroscopy (EIS) studies showed an improvement on the resistance of the spontaneous oxide film with increasing Nb content. The EIS data, fitted by R_s(Q_pR_p) model, suggested a single passive film formed on the experimental material surfaces. Polarization tests in Hank's solution revealed a nobler electrochemical behavior of the Zr–Nb alloys after alloying Nb to pure Zr. The corrosion resistance increased with increasing Nb content, as indicated by lower corrosion current densities and passive current densities and higher pitting potentials. The major components on the surfaces of the corroded Zr–Nb alloy samples detected by XPS were ZrO₂ and Nb₂O₅. The biocompatibility of Zr–Nb alloys was primarily evaluated by culturing L-929 cells in the extraction media of Zr–Nb alloy samples and excellent results were obtained. All of these above results suggested that the Zr–22Nb alloy, among the experimental alloys, showed a promising potential for biomedical applications.     

Composition and lattice parameters of silicide and matrix in cast Ti–Si–Al–Zr alloys

Abstract

The silicide chemistry, i.e. the type, composition, and lattice parameters of the silicide in as cast titanium based Ti–Si–Al–Zr alloys, has been studied. It has been shown that the stoichiometry of the silicide in the alloys can be expressed as (Ti_1?x , Zr_x)₅(Si_l?y, Al_y) _2·76?3·04(0≤X< 0·2, 0≤y<0·1). The presence of Al and Zr in the silicide increases its lattice parameters. Addition of Al coarsens the eutectic silicide and slows the formation of secondary silicide precipitates by solid state reaction. Addition of zirconium refines the eutectic silicide and promotes secondary silicide precipitation. The silirides are low in Al and rich in Zr, whereas the Ti matrix is rich in Al and low in Zr. The lattice parameters of the Ti matrix are decreased by Al and increased by Zr.

MST/1427     

Influence of fluoride treatment on surface properties,biodegradation and cytocompatibility of Mg–Nd–Zn–Zr alloy

Fluoride treatment is a commonly used technique or pre-treatment to optimize the degradation kinetic and improve the biocompatibility of magnesium-based implant. The influence of changed surface properties and degradation kinetics on subsequent protein adsorption and cytocompatibility is critical to understand the biocompatibility of the implant. In this study, a patent magnesium alloy Mg–Nd–Zn–Zr alloy (JDBM) designed for cardiovascular stent application was treated by immersion in hydrofluoric acid. A 1.5 μm thick MgF₂ layer was prepared. The surface roughness was increased slightly while the surface zeta potential was changed to a much more negative value after the treatment. Static contact angle test was performed, showing an increase in hydrophilicity and surface energy after the treatment. The MgF₂ layer slowed down in vitro degradation rate, but lost the protection effect after 10 days. The treatment enhanced human albumin adsorption while no difference of human fibrinogen adsorption amount was observed. Direct cell adhesion test showed many more live HUVECs retained than bare magnesium alloy. Both treated and untreated JDBM showed no adverse effect on HUVEC viability and spreading morphology. The relationship between changed surface characteristics, degradation rate and protein adsorption, cytocompatibility was also discussed.     

Microstructures and mechanical properties of Mg–Zn–Zr–Dy wrought magnesium alloys

Microstructures and phase compositions of as-cast and extruded ZK60–xDy (x?= 0–5) alloys were analysed by optical microscope, scanning electron microscope, X-ray diffraction and differential scanning calorimetry. Meanwhile, the tensile mechanical property was tested. With increasing Dy content, Mg–Zn–Dy new phase increases gradually, while MgZn₂ phase decreases gradually to disappear. As-cast microstructure is refined gradually; meanwhile extruded one is refined further with decreasing average grain size to 1 μm for ZK60–4·32Dy alloy. Second phase, tending to distribute along grain boundary by continuous network in as-cast state, breaks and distributes dispersedly in extrusion state. As-cast tensile mechanical property remains almost unchanged at ambient temperature; however, extruded ones are enhanced significantly at ambient and elevated temperatures, respectively. Tensile strength at 298 and 473 K increases gradually from 355 and 120 MPa for ZK60 alloy to 395 and 171 MPa for ZK60–4·32Dy alloy, respectively. Extruded tensile fractures exhibit a typical character of ductile fracture.     

Sc and Sc–Zr effects on microstructure and mechanical properties of Be–Al alloy

Herein, we investigated the effects of Sc and Sc–Zr on the microstructure and mechanical properties of Be–Al alloy, showing that Sc alloying resulted in Be grain refinement and reduced the secondary dendritic arm spacing (SDAS) of these grains by 1/3, whereas Sc–Zr alloying further decreased the SDAS to 7.5?µm and afforded equiaxed/cellular-like morphology with further refined Be grains. The above alloying resulted in the formation of intermetallic compounds (Be₁₃Sc, Be₁₃Zr, and Al₃(Sc_1–xZr_x)), increasing the macrohardness of the Be–Al alloy, with the microhardness and elastic modulus of the Be phase increasing to a larger extent than those of Al. Importantly, Sc–Zr alloying resulted in better microstructure modification and mechanical reinforcement than Sc alloying.     

Experimental investigation and thermodynamic description of the Mg–Y–Zr system

The Mg–Y–Zr system was studied via experimental investigation and thermodynamic modeling. Four diffusion couples and four key alloys of the Mg–Y–Zr system at 500 °C were prepared. The phase relations of the Mg–Y–Zr system were investigated by means of X-ray diffraction, scanning electron microscopy, and electron probe microanalysis. No ternary compound was found at 500 °C. The solubility of (αZr) in the Mg–Y intermetallics, i.e., Mg₂₄Y₅, Mg₂Y and MgY, was determined to be negligible. The differential scanning calorimetry measurement was performed on the Mg–Y–Zr alloys to obtain the phase transition temperature. The present thermodynamic calculations of the Mg–Y–Zr system matched well with the experimental data. The presently established Mg–Y–Zr phase diagram can offer a better understanding of the recent processing technique of creep-resistant magnesium alloys.     

In vitro degradation behavior and cytocompatibility of Mg–Zn–Zr alloys

Zinc and zirconium were selected as the alloying elements in biodegradable magnesium alloys, considering their strengthening effect and good biocompatibility. The degradation rate, hydrogen evolution, ion release, surface layer and in vitro cytotoxicity of two Mg–Zn–Zr alloys, i.e. ZK30 and ZK60, and a WE-type alloy (Mg–Y–RE–Zr) were investigated by means of long-term static immersion testing in Hank’s solution, non-static immersion testing in Hank’s solution and cell-material interaction analysis. It was found that, among these three magnesium alloys, ZK30 had the lowest degradation rate and the least hydrogen evolution. A magnesium calcium phosphate layer was formed on the surface of ZK30 sample during non-static immersion and its degradation caused minute changes in the ion concentrations and pH value of Hank’s solution. In addition, the ZK30 alloy showed insignificant cytotoxicity against bone marrow stromal cells as compared with biocompatible hydroxyapatite (HA) and the WE-type alloy. After prolonged incubation for 7 days, a stimulatory effect on cell proliferation was observed. The results of the present study suggested that ZK30 could be a promising material for biodegradable orthopedic implants and worth further investigation to evaluate its in vitro and in vivo degradation behavior.     

Surface modification of Ti–Nb–Zr–Sn alloy by thermal and hydrothermal treatments

Surface modifications by thermal and hydrothermal treatments in solution with calcium ions were investigated with the aim of improving bioactivity and wear resistance of a Ti–Nb–Zr–Sn alloy. The results showed that the first step of thermal treatment at 600 °C significantly increases the surface hardness and energy by forming oxides of Ti and Nb. The second step of hydrothermal treatment in a boiled supersaturated Ca(OH)₂ solution induces a bioactive layer containing CaTiO₃, CaCO₃, Ca(OH)₂ and TiO₂. Using this treatment, a complete Ca–P layer can be formed within 3 days of soaking in simulated body fluid (SBF). The origin of such fast apatite formation was analyzed by comparison with single step thermal or hydrothermal treatment and with thermal plus hydrothermal treatment without calcium ions. The results suggest that the increase of surface energy by thermal treatment and the incorporation of calcium ions by the hydrothermal treatment in calcium ion solution play important roles in the formation of bioactive apatite.