Formation and thermal stability of Ca–Mg–Zn and Ca–Mg–Zn–Cu bulk metallic glasses

Several Ca–Mg–Zn and Ca–Mg–Zn–Cu bulk metallic glasses were produced by copper mold casting method. The alloy compositions were selected using specific criteria recently identified by the authors. The glass transition temperature, crystallization temperature, temperature interval of the supercooled region, melting temperature as well as heats of crystallization, and melting are reported for these alloys.     

Mechanical and bio-corrosion properties of quaternary Mg–Ca–Mn–Zn alloys compared with binary Mg–Ca alloys

Binary Mg–xCa alloys and the quaternary Mg–Ca–Mn–xZn were studied to investigate their bio-corrosion and mechanical properties. The surface morphology of specimens was characterized by X-ray diffraction (XRD), Fourier-transformed infrared spectroscopy (FTIR), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results of mechanical properties show that the yield strength (YS), ultimate tensile strength (UTS) and elongation of quaternary alloy increased significantly with the addition of zinc (Zn) up to 4 wt.%. However, further addition of Zn content beyond 4 wt.% did not improve yield strength and ultimate tensile strength. In contrast, increasing calcium (Ca) content has a deleterious effect on binary Mg–Ca alloys. Compression tests of the magnesium (Mg) alloys revealed that the compression strength of quaternary alloy was higher than that of binary alloy. However, binary Mg–Ca alloy showed higher reduction in compression strength after immersion in simulated body fluid. The bio-corrosion behaviour of the binary and quaternary Mg alloys were investigated using immersion tests and electrochemical tests. Electrochemical tests shows that the corrosion potential (E_corr) of binary Mg–2Ca significantly shifted toward nobeler direction from −1996.8 to −1616.6 mV_SCE with the addition of 0.5 wt.% manganese (Mn) and 2 wt.% Zn content. However, further addition of Zn to 7 wt.% into quaternary alloy has the reverse effect. Immersion tests show that the quaternary alloy accompanied by two secondary phases presented higher corrosion resistance compared to binary alloys with single secondary phase. The degradation behaviour demonstrates that Mg–2Ca–0.5Mn–2Zn alloy had the lowest degradation rate among quaternary alloys. In contrast, the binary Mg–2Ca alloy demonstrated higher corrosion rates, with Mg–4Ca alloy having the highest rating. Our analysis showed the Mg–2Ca–0.5Mn–2Zn alloy with suitable mechanical properties and excellent corrosion resistance can be used as biodegradable implants.     

Microstructure and mechanical properties of Mg–8Li–xAl–0.5Ca alloys

The effect of the Al content on the microstructure and mechanical behaviour of Mg–8Li–xAl–0.5Ca alloys is investigated. The experimental results show that an as-cast Mg–8Li–0.5Ca alloy is mainly composed of α-Mg, β-Li and granular Mg₂Ca phases. With the addition of Al, the amount of α-Mg phase first increases and then decreases. In addition, the intermetallic compounds also obviously change. The microstructure of the test alloys is refined due to dynamic recrystallisation that occurs during extrusion. The mechanical properties of extruded alloys are much more desirable than the properties of as-cast alloys. The as-extruded Mg–8Li–6Al–0.5Ca alloy exhibits good comprehensive mechanical properties with an ultimate tensile strength of 251.2?MPa, a yield strength of 220.6?MPa and an elongation of 23.5%.     

Dissolution and adhesion behaviour of radio-frequency magnetron-sputtered Ca–P coatings

Radio-frequency magnetron sputtering deposition was used to produce calcium phosphate sputter coatings with three different thicknesses (0.1, 1 and 4 m) on titanium discs. Half of the as-sputtered coatings were subjected to an additional heat treatment for 2 h at 500°C. X-ray diffraction demonstrated that annealing at 500°C changed the amorphous 1 and 4 m sputtered coatings into an amorphous–crystalline structure, while the amorphous 0.1 m changed in a crystalline apatite structure. Further, scanning electron microscopy (SEM) inspection demonstrated that annealing of the 1 and 4 m coatings resulted in the appearance of some cracks. The dissolution behaviour of these Ca–P coatings was determined in a simulated body fluid. It was found that after incubation for 4 weeks the dissolution was determined by the crystallinity of the deposited coating. SEM and Fourier transform infrared evaluation showed that all the heat-treated sputter coating appeared to be stable under the test conditions and a Ca–P precipitate was always deposited on the coating surface. On the other hand, the amorphous 0.1 and 1 m coatings dissolved completely within 4 weeks, while the amorphous 4 m coating showed only signs of surface dissolution. Scratch testing demonstrated that there is a linear correlation between the critical load, L _c, and the coating thickness. A heat treatment for the CaP-4 coating resulted in an additional decrease in the critical load. On the basis of these findings, we conclude that already a 0.1 m heat-treated Ca-P sputter coating is of sufficient thickness to show in-vitro adequate bioactive and adhesive properties.     

The Effect of Sn Substitution of Pb on Microstructure and Superconducting Properties of Bi–Pb–Sr–Ca–Cu–O Superconductor

The effect of substitution of Pb by Sn in Bi_1.6Pb_0.4?x Sn _x Sr₂Ca₂Cu₃ O _δ samples at x = 0.0, 0.1, 0.2, and 0.3 on the critical transition temperature and structural properties was investigated in this work. All the samples were prepared by the solid-state reaction method. The prepared samples were characterized by X-ray diffraction (XRD), resistance–temperature curve (R–T), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The Sn ⁴⁺ substitution of Pb ²⁺ caused significant changes in the properties of the samples. The formation of the (Bi, Pb)-2212 phase was stabilized and the T _c (onset) was improved at the x = 0.2 level of Sn ⁴⁺ substitution. The SEM micrographs have shown that the structure of the sample with x = 0.2 became more dense. However, samples with x = 0.1 and 0.3 have not shown zero resistance by EDS analysis because of oxygen deficiency.     

In-vitro cytotoxicity and in-vivo biocompatibility of as-extruded Mg–4.0Zn–0.2Ca alloy

In this paper, the in-vitro cytotoxicity and the in-vivo compatibility of Mg–4.0Zn–0.2Ca alloy are studied. The cytotoxicity of Mg–4.0Zn–0.2Ca alloy is examined by MTT method on osteoblast cells. The in-vivo behavior of Mg–4.0Zn–0.2Ca alloy is investigated on rabbits. It has been found that Mg–4.0Zn–0.2Ca alloy extract has no cytotoxicity on osteoblast cells. Three months after in-vivo experiment, about 35–38% magnesium alloy implant has been degraded and a degradation layer which is composed of Ca, P, O and Mg has been formed on the magnesium alloy implants. Histological analysis showed that new bone is observed around magnesium implant without inflammation reaction. In-vitro and in-vivo test indicated that the Mg–4.0Zn–0.2Ca alloy has good biocompatibility.     

Influence of La–B–Zn glass on the sintering and microwave dielectric properties of Ca–Nd–Ti ceramics

The effects of La₂O₃–B₂O₃–ZnO (LBZ) glass on the sintering behaviors, phase structures, microstructures and the microwave dielectric properties of perovskite type Ca_0.6Nd_0.26TiO₃ (CNT) ceramics were studied. It indicates that the LBZ glass has an obvious effect on lowering the sintering temperature without damaging the microwave dielectric properties of the CNT ceramics. Small amounts of LBZ glass significantly lowered the sintering temperatures of CNT ceramics and obtained excellent microwave dielectric properties. However, too much LBZ glass is leading to inferior dielectric properties. The CNT ceramics doped with 3 wt% LBZ can be well sintered at 975 °C for 4 h and shows good properties: ε_r = 87.87, Q × f = 8132 GHz (f = 3.3 GHz), τ_f = +244.63 ppm/°C.     

Characterisation and thermodynamic calculations of biodegradable Mg–2.2Zn–3.7Ce and Mg–Ca–2.2Zn–3.7Ce alloys

In the present study, the effect of Ca (0.5–6?wt-%) content on the microstructure, phase formation, and mechanical properties and in vitro degradation behaviour of Mg–2.2Zn–3.7Ce alloys were investigated. Microstructural analysis and thermodynamic calculations also showed that Mg–2.2Zn–3.7Ce alloy contain α-Mg, Mg₁₂Ce and CeMgZn₂, while after adding 0.5?wt-% Ca to Mg–2.2Zn–3.7Ce alloy, IM1 (Ca₃Mg_xZn_15?x) (4.6?≤?x?≤?12) phase was detected. Further addition of Ca to 6?wt-% resulted in forming Mg₂Ca besides α-Mg, Mg₁₂Ce and IM1 with the absence of CeMgZn₂. The tensile strength and elongation of the Mg–Ca–2.2Zn–3.7Ce alloys increase with increasing Ca content up to 1.5?wt-%, while further addition of Ca to 6?wt-% has a reversed effect. Similarly, the degradation rate of the alloys increased first with increasing Ca content and then decreased.     

Enhancing mechanical properties of Mg–Sn alloys by combining addition of Ca and Zn

We developed new wrought Mg–2Sn–1Ca wt.% (TX21) and Mg–2Sn–1Ca–2Zn wt.% (TXZ212) alloys with high strength and ductility simultaneously, produced by conventional casting, homogenization and indirect extrusion. A partial dynamically recrystallized microstructure, with the micron-/nano-MgSnCa particles and G.P. zones dispersing, was obtained in TX21 alloy extruded at 260 °C (TX21-260). The TX21-260 alloy exhibited yield strength (YS) of 269 MPa, ultimate tensile strength (UTS) of 305 MPa, while those of the TX21 alloy extruded at 300 °C decreased to be 207 MPa and 230 MPa respectively. For TXZ212-260 alloy, on the other hand, MgSnCa, MgZnCa and MgZn₂ phases were observed, and the average grain size increased to be ∼5 μm. The YS and UTS of TXZ212-260 alloy evolved to be 218 MPa and 285 MPa, and the elongation (EL) reached as high as 23%. The high strengths of TX21-260 alloy were expected due to the high number density of nano-MgSnCa phases, G.P. zones and ultra-fine grain size (∼0.8 μm). The high EL of 23% in TXZ212-260 alloy was consistent with the high work-hardening rate, which was attributed to the larger grain size, more high angular grain boundaries, presence of more nano-particles and the weaker texture.     

Synthesis,Temperature Behavior,and Hydrolytic Stability of Na–Zr and Ca–Zr Phosphate Molybdates and Phosphate Tungstates

Inorganic Materials - We have synthesized Na1 – xZr2(PO4)3 – x(ХO4)x and Сa0.5 – xZr2(PO4)3 – x(ХO4)x (X = Mo, W; 0 ≤ x ≤...     

Precipitation hardening of Zr-modified Mg–Ca–Zn alloy

The microstructure and mechanical properties of Mg–Ca–Zn alloys with 1 wt.% Zr were investigated in as-cast and heat-treated conditions. A substantial decrease in grain size (from 65 μm for the Mg–Ca–Zn base alloy to 22 μm) was observed. The alloy was solution treated at 410 °C for up to 96 h followed by aging at 175 °C for up to 24 h. Conventional techniques, X-ray diffraction, EM + EDS, and TEM were used to characterize the microstructure of the alloy. The microstructure obtained after heat treatment had equiaxed grains with evenly distributed binary phase Zn₂Zr. The binary Mg₂Ca and ternary Mg₂Ca₆Zn₃ phases were identified in the matrix and at grain boundaries surrounded by precipitate-depleted zones (PDZs). The thermal stability of the Zr-modified alloys was examined by microhardness measurements conducted after prolonged exposures of the alloys to elevated temperatures. It was found that Zr is a structure-stabilizing factor. Its influence was associated with the formation of Zn₂Zr phase that does not undergo coarsening at the elevated temperatures used (due to the low diffusivity of Zr). The nanoscale mechanical properties of grain boundary PDZs were analyzed using combined nanoindentation and atomic force microscopy. These mechanical properties were then correlated to the composition and precipitate distribution in PDZs. An increase in the solution treatment duration from 10 to 96 h at 410 °C resulted in expansion of PDZs from ~0.75 to ~3 μm, while the following aging at 175 °C for up to 24 h did not lead to a detectable change in PDZs. The analysis indicates that the lowest hardness was found in the region where Zn₂Zr precipitates density was low, regardless of the solute concentration.     

Effects of minor additions of Ce and Y on as cast microstructure of Mg–3Sn–2Ca magnesium alloy

Abstract

The effects of minor additions of Ce and Y on the as cast microstructure of Mg–3Sn–2Ca (wt-%) magnesium alloy are investigated and compared. Results indicate that adding minor Ce or Y to Mg–3Sn–2Ca alloy does not cause formation of any new phases in the alloy. The as cast Mg–3Sn–2Ca alloy with addition of 0·5 wt-%Ce or Y is still composed of α-Mg, CaMgSn and Mg₂Ca phases. However, after adding 0·5 wt-%Ce or Y to Mg–3Sn–2Ca alloy, not only the formation of CaMgSn phase in the alloy is suppressed but also the CaMgSn phases in the alloy are effectively refined. In addition, adding 0·5 wt-%Ce to Mg–3Sn–2Ca alloy exhibits higher refinement efficiency to the CaMgSn phase in the alloy than adding 0·5 wt-%Y. Further investigations need to be considered in order to understand the difference of minor Ce and Y with regard to the refinement of CaMgSn phase in the Mg–3Sn–2Ca alloy.     

Structure and dielectric properties of a new series of pyrochlores in the Ca–Sm–Ti–M–O (M = Nb and Ta) system

The present work investigates the dielectric properties of pyrochlore type oxides, Ca–Sm–Ti–M–O (M = Nb and Ta) in the low frequency region (100 Hz–1 MHz) over the temperature range 30–100 °C. The 1 MHz dielectric constants (K) of these oxides are in the range 23–108 and show low variation with frequency (1 kHz–1 MHz). The temperature coefficient of dielectric constant (TCK) over the temperature range varies from positive to negative values in the range 48 to −107 ppm/°C. Rietveld analysis of the X-ray diffraction data establishes a cubic pyrochlore-type phase in the space group Fd3 m (no. 227).The grain morphology observation by scanning electron microscope shows well sintered grains.     

Microstructure,mechanical and bio-corrosion properties of Mn-doped Mg–Zn–Ca bulk metallic glass composites

The effects of Mn substitution for Mg on the microstructure, mechanical properties, and corrosion behavior of Mg_69 ? xZn₂₇Ca₄Mn_x (x = 0, 0.5 and 1 at.%) alloys were investigated using X-ray diffraction, compressive tests, electrochemical treatments, and immersion tests, respectively. Microstructural observations showed that the Mg₆₉Zn₂₇Ca₄ alloy was mainly amorphous. The addition of Mn decreases the glass-forming ability, which results in a decreased strength from 545 MPa to 364 MPa. However, this strength is still suitable for implant application. Polarization and immersion tests in the simulated body fluid at 37 °C revealed that the Mn-doped Mg–Zn–Ca alloys have significantly higher corrosion resistance than traditional ZK60 and pure Mg alloys. Cytotoxicity test showed that cell viabilities of osteoblasts cultured with Mn-doped Mg–Zn–Ca alloys extracts were higher than that of pure Mg. Mg_68.5Zn₂₇Ca₄Mn_0.5 exhibits the highest bio-corrosion resistance, biocompatibility and has desirable mechanical properties, which could suggest to be used as biomedical materials in the future.     

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.