Mg-6Al-(Sr,Ca)合金的显微组织和蠕变性能

系统研究了Mg-6Al-2Sr和Mg-6Al-(1-2)Sr-1Ca合金在水冷模铸造和压铸态下的显微组织、力学及蠕变性能．Mg-6Al-2Sr合金的铸态组织由α-Mg和沿枝晶界分布呈片状的α-Mg+Al4Sr共晶相组成．在Mg-6Al-2Sr基础上加入少量的Ca,合金中的Al4Sr被Mg2Ca取代,且出现了Mg—Al—Sr三元中间相,合金的抗蠕变性能显著提高．对蠕变后试样进行的扫描电镜观察表明, Mg-6Al合金中添加Sr和Ca后形成的中间相均具有很高的热稳定性．Mg-6Al-2Sr合金蠕变后的试样中出现了β-Mg17Al12相的非连续析出;而采用Sr和Ca复合合金化的试样显微组织在蠕变后无明显变化,也未析出β相,因而显著地提高了合金的抗蜗变性能．与水冷模铸造试样相比,压铸试样具有更细的显微组织和更高的室温与高温力学性能,但抗蠕变性能略低．

Effects of cooling rate on microstructure,mechanical and corrosion properties of Mg-Zn-Ca alloy

Mg69Zn27Ca4 alloys with diameters of 1.5, 2 and 3 mm were fabricated using copper mold injection casting method. Microstructural analysis reveals that the alloy with a diameter of 1.5 mm is almost completely composed of amorphous phase. However, with the cooling rate decline, a little α-Mg and MgZn dendrites can be found in the amorphous matrix. Based on the microstructural and tensile results, the ductile dendrites are conceived to be highly responsible for the enhanced compressive strain from 1.3% to 3.1% by increasing the sample diameter from 1.5 mm to 3 mm. In addition, the Mg69Zn27Ca4 alloy with 1.5 mm diameter has the best corrosion properties. The current Mg-based alloys show much better corrosion resistance than the traditionally commercial wrought magnesium alloy ZK60 in simulated sea-water.

Effect of Sr addition on microstructure of as-cast Mg-Al-Ca alloy

The microstructure evolution of Mg-Al-Ca alloys modified by the addition of strontium was investigated. It was found that Sr addition leads to the coarsening of α-Mg matrix. However, with the Sr content increasing from 0.1% to 0.5%, the grain size decreases from 83.9 to 65.8 μm. The addition of Sr ranging from 0.1% to 0.3% refines the Al2Ca phase. It changes the morphology of the Al2Ca phase from bone-shaped to granular or banding, and increases its volume fraction. The decrease of grain size of the α-Mg matrix is due to the increase of the effective undercooling degree of the melt and the constitutional undercooling in a diffusion layer ahead of the advancing solid/liquid interface in the alloy modified by the Sr additions. The modification mechanism of Al2Ca is attributed to the adsorption of Sr additions to the Al2Ca crystal. When the Sr content increases to 0.5%, the alloy is over-modified.

Microstructure, mechanical and bio-corrosion properties of as-extruded Mg-Sn-Ca alloys

The as-extruded Mg？Sn？Ca alloys were prepared and investigated for orthopedic applications via using optical microscopy, scanning electron microscopy, X-ray diffraction, as well as tensile, immersion and electrochemical tests. The results showed that, with the addition of 1% Sn and the Ca content of 0.2%？0.5%, the microstructure of the as-extruded Mg？Sn？Ca alloys became homogenous, which led to increased mechanical properties and improved corrosion resistance. Further increase of Ca content up to 1.5% improved the strength, but deteriorated the ductility and corrosion resistance. For the alloy containing 0.5% Ca, when the Sn content increased from 1% to 3%, the ultimate tensile strength increased with a decreased corrosion resistance, and the lowest yield strength and ductility appeared with the Sn content of 2%. These behaviors were determined by Sn/Ca mass ratio. The analyses showed that as-extruded Mg？1Sn？0.5Ca alloy was promising as a biodegradable orthopedic implant.

Effects of minor Ca on as-cast microstructures and mechanical properties of Mg-3Ce-1.2Mn-0.9Sc and Mg-4Y-1.2Mn-0.9Sc alloys

The effects of the addition of 0.6%Ca（mass fraction） on the as-cast microstructure and mechanical properties of the Mg-3Ce-1.2Mn-0.9Sc and Mg-4Y-1.2Mn-0.9Sc magnesium alloys were investigated and compared by optical microscopy and scanning electron microscopy,differential scanning calorimetry analysis,and tensile and creep tests.The results indicate that the addition of 0.6%Ca to the Mg-3Ce-1.2Mn-0.9Sc and Mg-4Y-1.2Mn-0.9Sc alloys can refine the grains of the two alloys.At the same time,the addition of 0.6%Ca to the Mg-3Ce-1.2Mn-0.9Sc and Mg-4Y-1.2Mn-0.9Sc alloys can effectively improve the tensile properties of the two alloys.In addition,the addition of 0.6%Ca can also improve the creep properties of the Mg-3Ce-1.2Mn-0.9Sc alloy but is not beneficial to the creep properties of the Mg-4Y-1.2Mn-0.9Sc alloy.The different effects of minor Ca on the creep properties of the Mg-3Ce-1.2Mn-0.9Sc and Mg-4Y-1.2Mn-0.9Sc alloys are possibly related to the difference in the solid solubilities of Ce and Y in Mg.

Poisoning-free effect of calcium on grain refinement of Mg-3%Al alloy containing trace Fe by carbon inoculation

Mg-3%Al alloy was modified by combining Ca addition with carbon inoculation. The effects of Fe addition and addition sequence on the grain refinement were investigated. A higher grain refining efficiency could be obtained for the Mg-Al alloy modified by combining Ca addition with carbon inoculation. Fe addition and addition sequence had no obvious effect on the grain refinement. Ca addition could effectively avoid grain-coarsening resulting from Fe in the carbon-inoculated Mg-Al alloy. The Al-C-O particles, actually being Al4C3, should act as potent substrates for a-Mg grains in the sample treated by combining Ca addition with carbon inoculation. However, the duplex-phase particles of AI4C3 coated on Al-Fe or Al-C-Fe should be the potent substrates for a-Mg grains if Fe existed in the Mg-Al melt. Ca addition can contribute to the formation of the particles of Al4C3 coated on Al-Fe or Al-C-Fe, regardless of the Fe addition sequence. The poisoning effect of Fe was effectively inhibited in the carbon-inoculated of Mg-Al alloy due to Ca addition, namely, Ca has a poisoning-free effect.

As-cast microstructures and mechanical properties of Mg-4Zn-x Y-1Ca(x=1.0, 1.5, 2.0, 3.0) magnesium alloys

The as-cast microstructures and mechanical properties of Mg?4Zn?xY?1Ca (x=1.0, 1.5, 2.0 and 3.0, mass fraction, %) alloys were investigated and compared. The results indicate that all the as-cast alloys are mainly composed ofα-Mg, Mg2Ca, Ca2Mg6Zn3,I (Mg3YZn6) andW (Mg3Y2Zn3) phases. However, with Y content increasing from 0.86% to 2.68%, the amount of the Ca2Mg6Zn3 phase gradually decreases but that of theI (Mg3YZn6) andW (Mg3Y2Zn3) phases gradually increases. Furthermore, an increase in Y content from 0.86% to 2.68% also causes the grain size of the as-cast alloys to gradually decrease. In addition, the tensile and creep properties of the as-cast alloys vary with Y content. Namely, with Y content increasing from 0.86% to 2.68%, the creep properties gradually increase, whereas the tensile properties firstly increase and attain the maximum at 1.77% Y, beyond that they decrease. Amongst the as-cast alloys with 0.86% Y, 1.19% Y, 1.77% Y and 2.68% Y, the alloy with 1.77% Y exhibits the relatively optimal tensile and creep properties.

Corrosion degradation behavior of Mg-Ca alloy with high Ca content in SBF

The corrosion degradation behavior of a Mg-Ca alloy with high Ca content aiming for a potential bone repair material in the simulated body fluid（SBF） was investigated.The microstructure and phase constitution of the pristine Mg-30%Ca（mass fraction） alloy were characterized with scanning electron microscopy（SEM） and X-ray diffraction（XRD）.The Mg-30%Ca alloy samples were immersed in the SBF for 90 d,and the morphology,composition and cytotoxicity of the final corrosion product were examined.It is found that Mg-30%Ca alloy is composed of α-Mg and Mg2 Ca phases.During the corrosion process in the SBF,the Mg2 Ca phase acts as an anode and the α-Mg phase acts as a cathode.The final corrosion product of the Mg-30%Ca alloy in SBF includes a small amount of black precipitates and white suspended particles.The white suspended particles are Mg（OH）2 and the black particles are believed to have a core-shell structure.The cytotoxicity experiments indicate that these black precipitates do not induce toxicity to cells.

Formation characteristic of Ca-P coatings on magnesium alloy surface

A chemical method was used to deposit dicalcium phosphate dehydrate coatings on AZ91 magnesium alloy. The aim was to improve the biodegradation behavior of magnesium alloy in a simulated body fluid. The microstructures of the coating before and after immersion in the simulated body fluid were characterized by scanning electron microscopy （SEM） and X-ray diffraction （XRD） The results indicated that the dicalcium phosphate dehydrate coatings exhibited two morphologies during the pre-calcification process. The titration speed of the pre-calcification process had great influence on the morphologies of the pre-calcification coatings. As the soaking time increased, the diffraction peaks of dicalcium phosphate dehydrate disappeared and hydroxyapatite precipitated on the coated substrate surfaces. This indicates the dissolution of dicalcium phosphate dehydrate during the immersion process. The structures of the dicalcium phosphate dehydrate coatings and the formation mechanisms of the hydroxyapatite coatings were investigated in detail.

Microstructure and mechanical properties of as-cast Mg-Sn-Ca alloys and effect of alloying elements

The effect of Sn, Ca, Al, Si and Zn addition on the compressive strength of cast Mg-Sn-Ca （TX） alloys was studied in the temperature range of 25-250 °C and correlated with the microstructure. The Sn to Ca mass ratio up to 2.5 contributes to the formation of Mg2Ca phase at the grain boundaries and CaMgSn in the matrix, while a ratio of 3 gives only CaMgSn phase mostly in the matrix. While the compressive strength decreases with the increase in temperature, for Sn/Ca up to 2.5, a plateau occurs in 100-175 °C, which is attributed to the strengthening by Mg2Ca. However, for ratio of 3, the strength is lower and decreases more gradually. Mg-3Sn-2Ca （TX32） has the highest strength and the addition of 0.4%Al increases its strength but simultaneous addition of Si lowers the strength. Likewise, the addition of Zn improves its strength but simultaneous addition of Al slightly decreases the strength. The results are correlated with the types of intermetallic phases that form in various alloys.

Effect of fluoride treatment on corrosion behavior of Mg-Ca binary alloy for implant application

The influence of hydrofluoric acid（HF） treatment on the corrosion behavior of the Mg-0.5Ca alloys was investigated by immersion specimen in sodium hydroxide and HF solutions with various concentrations and durations at room temperature.Microstructural evolutions of the specimens were characterized by atomic force microscopy,X-ray diffraction,field-emission scanning electron microscopy.The corrosion resistance was examined through potentiodynamic polarization and immersion test in Kokubo solution.The results revealed that the fluoride treated Mg-0.5Ca alloys produced by immersion in 40% HF provided more uniform,dense and thicker coating layer（12.6 μm） compared with the 35% HF treated specimen.The electrochemical test showed that the corrosion resistance of fluoride treated specimen was 35 times higher compared with the untreated Mg-0.5Ca alloy specimen in Kokubo solution.In vitro degradation rate of the fluoride treated specimens was much lower than untreated Mg-0.5Ca alloy in Kokubo solution.After immersion test the surface of 40% HF treated sample showed a few corrosion dots,while untreated specimens were fully covered by corrosion products and delamination.Fluoride treated Mg-0.5Ca alloy with 40% HF is a promising candidate as biodegradable implants due to its low degradation kinetics and good biocompatibility.

Fabrication of fine-grained,high strength and toughness Mg alloy by extrusion−shearing process

A novel extrusion-shearing(ES) composite process was designed to fabricate fine-grained, high strength and tough magnesium alloy. The structural parameters of an ES die were optimized by conducting an orthogonal simulation experiment using finite element software Deform-3D, and Mg-3 Zn-0.6 Ca-0.6 Zr(ZXK310) alloy was processed using the ES die. The results show that the optimized structural parameters of ES die are extrusion angle(α) of 90°, extrusion section height(h) of 15 mm and inner fillet radius(r) of 10 mm. After ES at an extrusion temperature and a die temperature of 350 °C, ZXK310 alloy exhibited good ES forming ability, and obvious dynamic recrystallization occurred in the forming area. The grain size decreased from 1.42 μm of extrusion area to 0.85 μm of the forming area. Owing to the pinning of second phase and formation of ultrafine grains, the tensile strength, yield strength and elongation of alloy reached 362 MPa, 289 MPa and 21.7%, respectively.

Microstructure,mechanical properties and corrosion behavior of quaternary Mg−1Zn−0.2Ca−xAg alloy wires applied as degradable anastomotic nails

The microstructure,mechanical properties and corrosion behavior of quaternary degradable Mg−1Zn−0.2Ca−xAg(x=1,2,4 wt.%)alloy wires,intended as anastomotic nails,were investigated.It was found that these Ag-containing alloy wires mainly consist of Mg matrix and Ag17Mg54 phase,characterized by SEM,EDS,XRD and TEM.Tensile and knotting tests results demonstrate the superior mechanical properties of these alloy wires.Especially,Mg−1Zn−0.2Ca−4Ag alloy exhibits the highest mechanical properties,i.e.an ultimate tensile strength of 334 MPa and an elongation of 8.6%.Moreover,with increasing Ag content,the corrosion rates of these alloy wires remarkably increase due to the formation of more micro-galvanic coupling between Mg matrix and Ag17Mg54 phase,shown by mass loss and scanning Kelvin probe force microscopy(SKPFM)results.The present alloy can be completely degraded within 28 d,satisfying the property requirements of anastomotic nails.

Deformation and recrystallization texture,microstructure and kinetics of Pb-Ca-Sn alloy

A Pb-0.08Ca-2Sn alloy was subjected to rolling at room temperature to different final thicknesses.Annealing treatments at temperature ranging from 80 to 120 °C led to recrystallization of the samples as shown by resistivity and micro-hardness measurements.The deformation texture determined through X-ray diffraction is qualitatively the Brass type.The measured Lankford anisotropy parameter R and its evolution are close to the determined one using a self consistent approach.The R value evolution with angle to rolling direction shows the presence of planar anisotropy and poor drawability.The recrystallization in annealing at 80-120 °C is achieved within time period up to 3×104 s.The recrystallization texture is a retained deformation texture with an emerging Cube component.

Refinement and strengthening mechanism of Mg−Zn−Cu−Zr−Ca alloy solidified under extremely high pressure

Mg−Zn−Cu−Zr−Ca samples were solidified under high pressures of 2-6 GPa.Scanning electron microscopy and electron backscatter diffraction were used to study the distribution of Ca in the microstructure and its effect on the solidification structure.The mechanical properties of the samples were investigated through compression tests.The results show that Ca is mostly dissolved in the matrix and the Mg_(2)Ca phase is formed under high pressure,but it is mainly segregated among dendrites under atmospheric pressure.The Mg_(2)Ca particles are effective heterogeneous nuclei ofα-Mg crystals,which significantly increases the number of crystal nuclei and refines the solidification structure of the alloy,with the grain size reduced to 22μm at 6 GPa.As no Ca segregating among the dendrites exists,more Zn is dissolved in the matrix.Consequently,the intergranular second phase changes from MgZn with a higher Zn/Mg ratio to Mg7Zn3 with a lower Zn/Mg ratio.The volume fraction of the intergranular second phase also increases to 22%.Owing to the combined strengthening of grain refinement,solid solution,and dispersion,the compression strength of the Mg-Zn-Cu-Zr-Ca alloy solidified under 6 GPa is up to 520 MPa.

Microstructural evolution and creep properties of Mg-4Sn alloys by addition of calcium up to 4 wt.%

The effects of addition of calcium up to 4 wt.% on the microstructure and creep properties of Mg-4 Sn alloys were investigated by the impression creep test. Impression creep tests were performed in temperature range between 445 and 475 K under normalized stresses σ/G(where σ is the stress;G is the shear modulus) between 0.0225 and 0.035. Optical microscopy and scanning electron microscopy were used to study the microstructure of samples. It is observed that the addition of Ca more than 2 wt.% suppresses less stable Mg Sn2 phase, and instead forms more thermally stable phases of Ca-Mg-Sn and Mg2 Ca at the grain boundaries which improve the creep resistance of Mg-4 Sn alloys. According to the stress exponents(6.04<n<6.89) and activation energies(101.37 k J/mol<Q<113.8 k J/mol) which were obtained from the impression creep tests, it is concluded that the pipe diffusion climb controlled dislocation creep is the dominant creep mechanism.

In-situ layered double hydroxides on Mg−Ca alloy:Role of calcium in magnesium alloy

Mg−Al layered double hydroxides(LDHs),produced on cast Mg−xCa(x=0.5,0.8,2.0,wt.%)alloys by an in-situ growth method,showed good corrosion resistance compared to the bare magnesium substrate.The influence mechanism of the second phase(Mg_(2)Ca)on LDHs production was investigated.Increasing Ca content increased the amount of Mg_(2)Ca,decreasing the grain size and the corrosion rate of the alloys.The increased amount of the second phase particles and the grain refinement promoted the growth of LDHs,and thus led to the decreasing of corrosion rate of the Mg−xCa alloys with LDHs.A higher Mg_(2)Ca amount resulted in forming fluffy LDHs.Due to the dual effects of the second phase(Mg_(2)Ca)for LDHs growth and microgalvanic corrosion,LDHs/Mg−0.8Ca showed the lowest corrosion rate.

Fine-grained Mg−1Mn−0.5Al−0.5Ca−0.5Zn alloy with high strength and good ductility fabricated by conventional extrusion

Mg−1Mn−0.5Al−0.5Ca−0.5Zn(wt.%)alloy was fabricated by conventional extrusion at 673 K with an extrusion ratio of 25:1,followed by aging at 473 K.The microstructure was characterized by scanning electron microscopy,electron back-scattered diffraction,and transmission electron microscopy.The mechanical properties were determined by the tensile test.The peak-aged sample shows fine recrystallized grains with an average grain size of 1.7μm.Area fraction of Al−Ca particles in the alloy increases significantly after peak aging.Meanwhile,botháañandác+añdislocations were observed to remain in the alloy after hot extrusion.Thus,the peak-aged sample exhibits simultaneously high strength and good ductility with the ultimate tensile stress,tensile yield stress,and tension fracture elongation of 320 MPa,314 MPa,and 19.0%,respectively.

Al-matrix composite based on Al-Ca-Ni-La system additionally reinforced by L12 type nanoparticles

The structure of the quaternary Al?(2?4)wt.%Ca?Ni?La system near the aluminum corner has been studied using computational analysis in the Thermo-Calc program and experimental studies(electron microscopy,microprobe analysis and X-ray diffraction).Based on the phase equilibria data obtained,the experimental projection of the liquidus surface and solid state phase-field distribution of the Al?Ca?Ni?La system have been proposed.Microstructure studies reveal that the alloys with the 2?4 wt.%Ca,2?4 wt.%Ni and 1?3 wt.%La ranges have an ultra-fine hypoeutectic structure with 30%volume fraction of eutectic intermetallics,which allows one to classify these alloys as natural Al-matrix composites.The ultra-fine eutectic structure produces significant strengthening,the magnitude of which can be well described using the modified Orowan looping mechanism model.Small additives of Zr and Sc(0.2 and 0.1 wt.%,respectively)lead to significant strengthening(by^25%)due to the formation of L12 type phase(Al3(Zr,Sc))nanoparticles during annealing of the alloy at 350?400℃.Due to the high volume fraction of eutectic intermetallics,the new alloys have low coefficients of thermal expansion and high thermal stability of the structure and mechanical properties.

Corrosion properties of ECAP-processed Mg-Al-Ca-Mn alloys with separate Al2Ca and Mg2Ca phases

To investigate the effect of separate Al_(2)Ca and Mg_(2)Ca phases on the corrosion properties of Mg−Al−Ca−Mn alloys,OM,SEM,immersion and electrochemical tests were conducted on the as-cast and ECAP Al_(2)Ca-containing(2Ca)and Mg_(2)Ca-containing(4Ca)alloys.At the beginning of corrosion,the two as-cast alloys are corroded slowly compared with ECAP alloys.With prolonging the corrosion time,the corrosion of ECAP alloys becomes slighter than that of as-cast alloys,which is mainly ascribed to the dispersion and refinement of the second phase in ECAP alloys.Moreover,the corrosion degree of 2Ca alloys is always slighter than that of 4Ca alloys,suggesting that Al_(2)Ca phase is more beneficial to the enhancement of corrosion resistance of Mg−Al−Ca−Mn based alloys than Mg_(2)Ca phase.Finally,based on the examinations of corrosion surface and electrochemical testing results,different corrosion mechanisms caused by the distributions and morphology of Al_(2)Ca and Mg_(2)Ca phases are discussed.