The effect of native point defect thermodynamics on off-stoichiometry in β-Mg17Al12

The mechanical strength of Mg–Al–Zn alloys can be affected by a fine spatial dispersion of β-Mg₁₇Al₁₂ precipitates in the Mg matrix. In an effort to understand the phase stability and the unusual asymmetric off-stoichiometry observed in β-Mg₁₇Al₁₂, we have performed a series of first-principles density functional theory (DFT) calculations of bulk and defect properties of Mg₁₇Al₁₂. Specifically, we consider native point defects (i.e. vacancies and anti-sites) in all four sublattices of Mg₁₇Al₁₂, i.e. 2a, 8c, 24g (Mg) and 24g (Al). The T = 0 K static energies of defect Mg₁₇Al₁₂ supercells indicate that anti-site defects are energetically favored over vacancies, and the lowest anti-site defect formation energies are in 24g sites for both Al_Mg and Mg_Al. These Al-rich and Mg-rich anti-site defect formation energies are similar in magnitude, and thus do not explain the asymmetric off-stoichiometry of Mg₁₇Al₁₂. We also investigate the effect of atomic vibrations via DFT phonon calculations on native point defect free energies of Mg₁₇Al₁₂ and combine these entropic contributions with the point defect formation energies to evaluate the thermodynamics of off-stoichiometry in this phase. We find that the formation of the Al_Mg anti-site is not strongly stabilized by vibrational entropy. Thus, we conclude that the observed asymmetry in the off-stoichiometry of the β-Mg₁₇Al₁₂ phase in the Mg–Al phase diagram is not explained by simple native point defect thermodynamics, and must involve a more complicated defect formation mechanism, such as multi-defect clustering.     

B2-RuAl点缺陷结构的第一原理计算

采用第一原理赝势平面波方法,计算了B2-RuAl金属间化合物的基本物性及其点缺陷结构的几何、能态与电子结构,通过对不同点缺陷结构形成热与形成能的计算与比较,分析和预测了RuAl金属间化合物中点缺陷结构的种类与存在形式.结果表明：RuAl金属间化合物的点缺陷主要是Ru空位和Al反位,在富Ru合金中主要为Ru反位,在富Al合金中则主要是Al反位.这些点缺陷主要以Ru-Ru双空位和Al-Al双反位的组态结构形式出现,并且双空位以Ru-Ru为第一近邻时其点缺陷结构最稳定,而双反位则是以Al-Al为第三近邻时稳定性最高.进一步通过对NiAl和RuAl不同点缺陷结构Cauchy压力的比较,发现点缺陷对RuAl塑性的降低程度比NiAl低,因而含有点缺陷的实际合金的室温塑性RuAl比NiAl好.     

Point defect structures of YAl2 and ZrCo2 Laves phase compounds by first-principles calculations

In Laves phase alloys with prominent size mismatch between constituent atoms and/or large negative enthalpy of formation, the existence of vacancies as the dominant point defect type is often suggested. However, there are not enough experimental data to prove or disprove these arguments. Employing first-principles calculations, we study the point defect structures of YAl₂ and ZrCo₂ C15 Laves phases, as both compounds exhibit large size mismatch between constituent atoms, and large negative enthalpy of formation. We find that one must go beyond the simple geometrical or enthalpy arguments in determining the point defect structures of these alloys. In both compounds, the point defect structure is found to be dominated by the anti-site defects on the larger atom-rich side of the stoichiometry.     

Thermoelectric performance of Mg2−xCaxSi compounds

Thermoelectric materials Mg_2−xCa_xSi (x = 0, 0.01, 0.03, 0.05, 0.07, 0.1) compounds have been prepared by vacuum melting followed by hot-pressing. Effects of the substitution of Ca for Mg on phase structures and the thermoelectric properties of the hot-pressed compounds were investigated. It was found that the alloying of Ca in Mg₂Si based compounds increases the electrical conductivity and decreases the Seebeck coefficient of the compounds, due to the electronegativity difference between Ca and Mg. The dimensionless figures of merit of Mg₂Si and Mg_1.99Ca_0.01Si reach, respectively, 0.41 and 0.34 at 660 K.     

Comparative studies of grain refinement of commercial purity Mg by CaO and Ca addition

ABSTRACT

The comparative studies of grain refinement of commercial purity Mg by CaO/Ca addition have been investigated by using TP-1 tests, optical microscope, XRD characterisation and TEM (STEM) observation along with EDX analysis. Experimental results showed that Ca/CaO addition significantly refines the grain structure of commercial purity Mg. Compared with Ca addition, CaO exhibits finer grain size and the average grain size remains invariable with further CaO addition. CaO addition is readily reduced to Ca by Mg melt and forms Mg₂Ca on the surface of MgO particles. First-principle calculations were used to understand the nucleation of Mg₂Ca layer by a coherent interface model calculating the work of adhesion and the interface energy between Mg₂Ca and α-Mg. The combination of experiments and calculations showed that the formation of Mg₂Ca layer on MgO facilitates the nucleation of α-Mg and then refines the grain structure by Ca or CaO addition.     

Defect structures in ZrCo2 Laves phase

Point defect structures in the C15 ZrCo₂ alloys were studied by bulk density and X-ray lattice parameter measurements. It was found that, for the ZrCo₂ alloys quenched from 1000°C, the lattice parameter increases linearly as the Zr content increases up to 33.3 at.% Zr. The lattice parameter of the Laves phase remains constant for the alloys with Zr content higher than 33.3 at.%, indicating that the solubility range of Zr in ZrCo₂ on the Zr-rich side is essentially zero. The constitutional defects were found to be of the anti-site type. Thermal vacancies exhibiting a maximum at the stoichiometric composition were observed in the ZrCo₂ Laves phase alloys after quenching from 1250 and 1000°C, with higher thermal vacancies obtained from 1250°C. The defect structures in the ZrCo₂ phase may be correlated to the relative magnitude of formation enthalpies for anti-site and quadruple defects in this compound. Thermal vacancy concentration at a level of 1% in ZrCo₂ does not affect fracture toughness at room temperature.     

High-Strength Low-Alloy (HSLA) Mg–Zn–Ca Alloys with Excellent Biodegradation Performance

This article deals with the development of fine-grained high-strength low-alloy (HSLA) magnesium alloys intended for use as biodegradable implant material. The alloys contain solely low amounts of Zn and Ca as alloying elements. We illustrate the development path starting from the high-Zn-containing ZX50 (MgZn5Ca0.25) alloy with conventional purity, to an ultrahigh-purity ZX50 modification, and further to the ultrahigh-purity Zn-lean alloy ZX10 (MgZn1Ca0.3). It is shown that alloys with high Zn-content are prone to biocorrosion in various environments, most probably because of the presence of the intermetallic phase Mg₆Zn₃Ca₂. A reduction of the Zn content results in (Mg,Zn)₂Ca phase formation. This phase is less noble than the Mg-matrix and therefore, in contrast to Mg₆Zn₃Ca₂, does not act as cathodic site. A fine-grained microstructure is achieved by the controlled formation of fine and homogeneously distributed (Mg,Zn)₂Ca precipitates, which influence dynamic recrystallization and grain growth during hot forming. Such design scheme is comparable to that of HSLA steels, where low amounts of alloying elements are intended to produce a very fine dispersion of particles to increase the material’s strength by refining the grain size. Consequently our new, ultrapure ZX10 alloy exhibits high strength (yield strength R _p = 240 MPa, ultimate tensile strength R _m = 255 MPa) and simultaneously high ductility (elongation to fracture A = 27%), as well as low mechanical anisotropy. Because of the anodic nature of the (Mg,Zn)₂Ca particles used in the HSLA concept, the in vivo degradation in a rat femur implantation study is very slow and homogeneous without clinically observable hydrogen evolution, making the ZX10 alloy a promising material for biodegradable implants.     

Phase equilibria in Mg-rich corner of Mg–Ca–RE (RE=Gd,Nd) systems at 400 °C

The phase equilibria in Mg-rich corner of Mg–Ca–Gd and Mg–Ca–Nd ternary systems at 400 °C were determined through the equilibrated alloy method by using XRD, SEM, EPMA and DSC. Partial isothermal sections in Mg-rich corner of Mg–Ca–Gd and Mg–Ca–Nd ternary systems at 400 °C were constructed from 13 alloys. A three-phase region of α–Mg, Mg₄₁RE₅ and Mg₂Ca was determined in both ternary systems. It is formed by a similar ternary eutectic reaction L→α-Mg+Mg₂Ca+Mg₄₁RE₅ at 499.6 °C and 505.6 °C, respectively. It is found that the maximum solubility of Ca in Mg₅Gd is 3.68% (molar fraction) and 3% of Gd can be dissolved in Mg₂Ca in the Mg–Ca–Gd system at 400 °C. While in the Mg–Ca–Nd system the maximum solubility of Ca in Mg₄₁Nd₅ is 3.57% and 1.24% of Nd can be dissolved in Mg₂Ca at 400 °C. Other three-phase equilibria existing in Mg-rich corner of Mg–Ca–Gd system are α-Mg+Mg₅Gd+T and Mg₅Gd+Mg₂Ca+T and the three-phase equilibrium in Mg-rich corner of Mg–Ca–Nd system is Mg₃Nd+Mg₂Ca+ Mg₄₁Nd₅.     

Effect of Ca addition on microstructure and impression creep behavior of cast AZ61 magnesium alloy

Microstructure and creep properties of AZ61 alloy containing 1 and 3 wt.% Ca were investigated. The creep properties were examined using impression method under different stresses between 200 and 500 MPa at the temperature ranging from 423 to 491 K. The microstructure of AZ61 alloy contains α(Mg) matrix and Mg₁₇Al₁₂ intermetallic phases. It is shown that adding Ca to AZ61 alloy reduces the amount of Mg₁₇Al₁₂ phase via forming (Mg, Al)₂Ca phase; furthermore, increasing the Ca content to 3 wt.% leads to the formation of (Mg, Al)₂Ca phase, as well as the elimination of the Mg₁₇Al₁₂ phase. Creep properties of AZ61 alloy are improved with the Ca addition. The improvement in creep properties is attributed to the reduction in the amount of Mg₁₇Al₁₂ phase and the formation of (Mg, Al)₂Ca phase with high thermal stability. According to the obtained creep data, it is concluded that the pipe diffusion−climb controlled dislocation creep is the dominant creep mechanism and Ca addition has no influence on this mechanism. The effect of pre-deformation on the creep properties of AZ61+3%Ca alloy reveals that the creep resistance of the alloy depends on the continuity of (Mg, Al)₂Ca phase. It is decreased by reducing the phase continuity.     

Microstructure,anticorrosion, biocompatibility and antibacterial activities of extruded Mg−Zn−Mn strengthened with Ca

To find suitable biodegradable materials for implant applications, Mg?6Zn?0.3Mn?xCa (x=0, 0.2 and 0.5, wt.%) alloys were prepared by semi-continuous casting followed by hot-extrusion technique. The microstructure and mechanical properties of Mg?6Zn?0.3Mn?xCa alloys were investigated using the optical microscope, scanning electron microscope and tensile testing. Results indicated that minor Ca addition can slightly refine grains of the extruded Mg?6Zn?0.3Mn alloy and improve its strength. When 0.2 wt.% and 0.5 wt.% Ca were added, the grain sizes of the as-extruded alloys were refined from 4.8 to 4.6 and 4.2 μm, respectively. Of the three alloys studied, the alloy with 0.5 wt.% Ca exhibits better combined mechanical properties with the ultimate tensile strength and elongation of 334 MPa and 20.3%. The corrosion behaviour, cell viability and antibacterial activities of alloys studied were also evaluated. Increasing Ca content deteriorates the corrosion resistance of alloys due to the increase of amount of effective cathodic sites caused by the formation of more Ca₂Mg₆Zn₃ phases. Cytotoxicity evaluation with L929 cells shows higher cell viability of the Mg?6Zn?0.3Mn?0.5Ca alloy compared to Mg?6Zn?0.3Mn and Mg?6Zn?0.3Mn? 0.2Ca alloys. The antibacterial activity against Staphylococcus aureus is enhanced with increasing the Ca content due to its physicochemical and biological performance in bone repairing process.     

Ca Addition Effects on the Microstructure,Tensile and Corrosion Properties of Mg Matrix Alloy Containing 8 wt.% Mg<Subscript>2</Subscript>Si

The microstructure, tensile properties and corrosion behavior of the Mg-8 wt.% Mg₂Si-x%Ca alloy have been studied by the use of optical microscopy, scanning electron microscopy equipped with energy-dispersive spectroscopy, x-ray diffraction, standard tensile testing, polarization test and electrochemical impedance spectroscopy (EIS) measurements. Microstructural studies indicated that Ca modifies both primary and eutectic Mg₂Si phase. It was found that the average size of primary Mg₂Si particles is about 60 μm, which is dropped by about 82% in the alloy containing 0.05 wt.% Ca. By the addition of different Ca contents, Ca-rich intermetallics (i.e., CaSi₂ and CaMgSi) were formed. The modification mechanism of adding Ca during solidification was found to be due to the strong effect of CaMgSi phase as a heterogonous nucleation site, apart from CaSi₂ which was reported before, for Mg₂Si intermetallics. Tensile testing results ascertained that Ca addition enhances both ultimate tensile strength (UTS) and elongation values. The optimum amount of Ca was found to be 0.1 wt.%, which improved UTS and elongation values from about 130 MPa and 2% to 165 MPa and 5.5%, whereas more Ca addition (i.e., 3 wt.%) reduced the tensile properties of the alloy to about 105 MPa and 1.8%, which can be due to the formation of CaMgSi intermetallics with deteriorating needle-like morphology. Polarization and EIS tests also showed that the Mg-3%Si-0.5%Ca alloy pronounces as the best anti-corrosion alloy. Nevertheless, further added Ca (up to 3 wt.%) deteriorated the corrosion resistance due to predominance of worse galvanic coupling effect stemmed from the presence of stronger CaMgSi cathode in comparison with Mg₂Si. With higher Ca additions, an adverse effect was seen on corrosion resistance of the Mg-3%Si alloy, as a result of forming a weak film on the alloy specimen surface.     

Microstructural control and hardening response of Mg–6Zn–0.5Er–0.5Ca alloy

The effects of heat treatment on microstructures and hardening response of Mg–6Zn–0.5Er–0.5Ca(wt%) alloy were investigated by optical microscope(OM), scanning electron microscope(SEM), and transmission electron microscope(TEM) in this paper. The results show that the Mg–6Zn–0.5Er–0.5Ca alloy contains Mg_3Zn_6Er_1 quasicrystalline phase(Iphase) and Ca_2Mg_6Zn_3 phase under as-cast condition. Most of the Ca_2Mg_6Zn_3 phases and I-phases dissolve into matrix during heat treatment at 475 ℃ for 5 h. After the as-solution alloy was aged at 175 ℃ for 36 h, a large amount of MgZn_2 precipitate with several nanometers precipitate. It is suggested that the trace addition of Ca results in refining the size of the precipitate, and the presence of the nanoscale MgZn_2 phase is the main factor to improve the peak-aged hardness greatly to 87 HV, which increases about 40 % compared with that of as-cast alloy.     

V掺杂Ni3Al点缺陷结构及合金化效应的第一性原理研究

基于密度泛函理论的第一性原理平面波赝势方法研究了V掺杂Ni3Al合金的电子结构和点缺陷结构.通过计算与实验结果对比选择了适合Ni3Al合金计算的近似方法,计算了含有各个缺陷的晶胞的晶格常数,形成热和结合能,点缺陷的形成能和平衡浓度,态密度和电荷密度.计算结果表明:Ni3Al合金中反位缺陷较空位缺陷易形成,NiAl是Ni3Al合金中最主要的反位缺陷,Al位最易形成缺陷,在1400 K时,空位缺陷的浓度远远低于反位缺陷的浓度.V加入Ni3Al合金体系中能提高合金的稳定性.     

Point defect concentrations of L1_2-Al_3X(Sc,Zr,Er)

The point defect concentrations of Ll_2-Al_3 X(Sc,Zr,Er) were systematically investigated using the firstprinciple calculations with thermodynamics approach.The results show that the constitutional point defects of offstoichiometric Ll_2-Al_3 X(Sc,Zr,Er) prefer to occur in X sublattice,that is X anti-site in X-rich alloy and X vacancy in Al-rich alloy,respectively.And A1 anti-site also has a high density in Al-rich Ll_2-Al_3 X(Sc,Er).It is found that the point defect concentrations of stoichiometric Ll_2-Al_3 X(Sc,Zr) follow in the sequence as: A1 vacancies(V_(A1)) X vacancies(V_X) X anti-sites(X_(Al)) A1 antisites(Al_X).The point defect concentration of stoichiometric Al_3 Er is similar to that of L12-A13 X(Sc,Zr).The result suggests that the A1 vacancy(V_(A1)) is a dominant point defect in L12-A13 X(Sc,Zr,Er).A simple parameter Hv_x-Hv_(Al) can be used for a rough estimation of the point defect concentrations in Ll_2-Al_3 X structure.Some rules of point defect concentrations for L1_2-Al_3 X(Sc,Zr,Er) are also revealed.     

Mechanism of debismuthizing with calcium and magnesium

In order to further understand the debismuthizing mechanism with calcium and magnesium, the influence of adding amount of calcium on the bismuth removal from lead was examined. A part of the debismuthizing dross samples were studied by electron probe microanalysis (EPMA). The results show that the calculated bismuthide governing debismuthizing process is Ca₃Mg₇Bi₈, which may be a mixture of Ca₃Bi₂, CaBi, CaBi₃ and Mg₃Bi₂. And the bismuthide formed during the debismuthizing process exists in two states: one is free bismuthide in the matrix of dross, and the other is symbiotic with Pb–Ca phase.     

Effects of Cu on the corrosion behavior and microstructure of Mg–Zn–Ca bulk metallic glass

For the purpose of developing biodegradable magnesium alloys with suitable properties for biomedical applications, Mg–Zn–Ca–Cu metallic glasses were prepared by copper mold injection methods. In the present work, the effect of Cu doping on mechanical properties, corrosion behavior, and glass-forming ability of Mg₆₆Zn₃₀Ca₄ alloy was studied. The experimental findings demonstrated that the incorporation of Cu decreases the corrosion resistance of alloys, but increases the microhardness and degradation rate slightly. However, the addition of a trace amount of Cu can make the samples have antibacterial properties. Therefore, Mg–Zn–Ca–Cu has great advantages in clinical implantation and is the potential implant material.     

微量Ca添加对铸造Mg-Sm-Gd基合金显微组织与力学性能的影响（英文）

主要通过透射电子显微镜、高角度环形暗场扫描透射电子显微镜和拉伸测试研究微量Ca元素对Mg-Sm-Gd-Zn-Zr合金显微组织和力学性能的影响。结果表明,Mg-Sm-Gd-Zn-Zr合金中主要第二相为Zn元素富集的Mg₃RE相,Ca元素添加不仅可以细化晶粒,还可以促进Mg₅RE相和溶质原子富集的层错形成。此外,共格界面表明Mg₃RE相可以作为Mg₅RE相的形核位点,这些均有利于合金力学性能的提高。     

Ab Initio Calculated Thermodynamic Properties of Mo5SiB2 Phase and Nb5SiB2 Phase

Due to their attractive high-temperature properties, multiphase Mo-Si-B alloys in the Mo-rich Mo-Si-B ternary system have been identified for high-temperature applications. The ternary intermetallic T₂ (Mo₅SiB₂) phase is a central feature of the phase equilibria within this ternary system. Experimental stability analyses of the T₂ phase shows its broad homogeneous composition ranges that can yield a constitutional defect structure such as vacancies for Mo-rich compositions and antisite defects for Mo-lean compositions. Previous thermodynamic model did not conform to the defect structures as reported in experiments, and thus subsequently a new sublattice thermodynamic model for the T₂ phase is initiated in this study. To support the new sublattice thermodynamic model, ab initio calculations were implemented to compute formation energy data. The calculated formation energy data explain a source for broad compositional homogeneity range of T₂ structure.     

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 (Mg₂Ca) on LDHs production was investigated. Increasing Ca content increased the amount of Mg₂Ca, 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 Mg₂Ca amount resulted in forming fluffy LDHs. Due to the dual effects of the second phase (Mg₂Ca) for LDHs growth and microgalvanic corrosion, LDHs/Mg?0.8Ca showed the lowest corrosion rate.     

Ca–Mg–Zn–(Ag) bulk metallic glasses prepared by unidirectional quenching

We fabricated ternary Ca–Mg–Zn and quaternary Ca–Mg–Zn–Ag bulk metallic glasses with diameter of 7 mm by unidirectional quenching into water-cooled Ga–In–Sn liquid alloys. It was suggested that the electromagnetic stirring caused by induction eddy current facilitated the glass formation. Glass forming ability of Ca_62.5Mg_17.5Zn_20?xAg_x (x = 0, 1, 3, 5, 7, 9) system was dependent on Ag content. It was found that in the system the in-situ formed crystalline phases enhanced the second-stage crystallization, whereas there seemed no contribution to the third-stage crystallization.