In Mg-Ca alloys the grain refining mechanism,in particular regarding the role of nucleant substrates,remains the object of debates.Although native MgO is being recognised as a nucleating substrate accounting for grain...In Mg-Ca alloys the grain refining mechanism,in particular regarding the role of nucleant substrates,remains the object of debates.Although native MgO is being recognised as a nucleating substrate accounting for grain refinement of Mg alloys,the possible interactions of MgO with alloying elements that may alter the nucleation potency have not been elucidated yet.Herein,we design casting experiments of Mg-xCa alloys varied qualitatively in number density of native MgO,which are then comprehensively studied by advanced electron microscopy.The results show that grain refinement is enhanced as the particle number density of MgO increases.The native MgO particles are modified by interfacial layers due to the co-segregation of Ca and N solute atoms at the MgO/Mg interface.Using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy,we reveal the nature of these Ca/N interfacial layers at the atomic scale.Irrespective of the crystallographic termination of MgO,Ca and N co-segregate at the MgO/Mg interface and occupy Mg and O sites,respectively,forming an interfacial structure of a few atomic layers.The interfacial structure is slightly expanded,less ordered and defective compared to the MgO matrix due to compositional deviations,whereby the MgO substrate is altered as a poorer template to nucleate Mg solid.Upon solidification in a TP-1 mould,the impotent MgO particles account for the grain refining mechanism,where they are suggested to participate into nucleation and grain initiation processes in an explosive manner.This work not only reveals the atomic engineering of a substrate through interfacial segregation but also demonstrates the effectiveness of a strategy whereby native MgO particles can be harnessed for grain refinement in Mg-Ca alloys.展开更多
The phase equilibria in Mg-rich corner of Mg-Ca-Gd and Mg-Ca-Nd ternary systems at 400℃ were determined through the equilibrated alloy method by using XRD, SEM, EPMA and DSC. Partial isothermal sections in Mg-rich co...The phase equilibria in Mg-rich corner of Mg-Ca-Gd and Mg-Ca-Nd ternary systems at 400℃ 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 ℃ were constructed from 13 alloys. A three-phase region of a-Mg, Mg41RE5 and Mg2Ca was determined in both ternary systems. It is formed by a similar ternary eutectic reaction L→a-Mg＋Mg2Ca＋Mg41RE5 at 499.6 ℃ and 505.6 ℃, 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 ℃. 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 ℃. Other three-phase equilibria existing in Mg-rich corner of Mg-Ca-Gd system are a-Mg＋MgsGd＋T and MgsGd＋Mg2Ca＋T and the three-phase equilibrium in Mg-rich corner of Mg-Ca-Nd system is Mg3Nd＋Mg2Ca＋ Mg41Nd5.展开更多
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...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.展开更多
This work reported the effect of extrusion speeds on the microstructures and mechanical properties of Mg-Ca binary alloy.The results showed that yield strength of the as-extruded Mg-1.2wt.%Ca alloys decrease from∼360...This work reported the effect of extrusion speeds on the microstructures and mechanical properties of Mg-Ca binary alloy.The results showed that yield strength of the as-extruded Mg-1.2wt.%Ca alloys decrease from∼360MPa to∼258MPa as the ram speed increases from 0.4mm/s to 2.4 mm/s,and the elongation increases from∼3.9%to∼12.2%.The microstructure changes from bimodal grain feature to the complete dynamical recrystallization(DRX)with increase of the extrusion speed.The ultrafine DRXed grains in size of∼0.85μm,the numerous nano-Mg_(2)Ca particles dispersing along the grain boundaries and interiors,as well as the high density of residual dislocations,should account for the high strength.It is believed that the high degree of dynamic recrystallization and the resulting texture randomization play the critical roles in the ductility enhancement of the high-speed extruded Mg alloys.展开更多
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...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.展开更多
Highly porous Mg-Ca-Zn-Co alloy scaffolds for tissue engineering applications were produced by powder metallurgy based space holder-water leaching method.Mg-Ca-Zn-Co alloy foam can be used as a scaffold material in ti...Highly porous Mg-Ca-Zn-Co alloy scaffolds for tissue engineering applications were produced by powder metallurgy based space holder-water leaching method.Mg-Ca-Zn-Co alloy foam can be used as a scaffold material in tissue engineering.Carbamide was used as a space holder material.Fluoride conversion coating was synthesized on the alloy by immersion treatment in hydrofluoric acid(HF).Increasing Zn content of the alloy increased the elastic modulus.Ca addition prevented the oxidation of the specimens during sintering.Electrochemical corrosion behaviour of the specimens was examined in simulated body fluid.Corrosion rate decreased with Zn addition from1.0%up to3.0%(mass fraction)and then increased.Mass loss of the specimens initially decreased with Zn addition up to about3%and then increased.Fluoride conversion coating increased the corrosion resistance of the specimens.展开更多
The production cost will be greatly reduced if nitrogen can be used instead of inert gas in the spray forming process of magnesium alloys, but the heat from the reaction between magnesium alloys and nitrogen makes mag...The production cost will be greatly reduced if nitrogen can be used instead of inert gas in the spray forming process of magnesium alloys, but the heat from the reaction between magnesium alloys and nitrogen makes magnesium alloy burn easily. To solve the problem above, the ignition point of Mg-Ca alloy under nitrogen atmosphere was studied using a home-made experimental device and DSC-DTA. Results show that under nitrogen atmosphere, Ca addition has a great effect on the ignition point of Mg alloy. The ignition point of the Mg-5Ca bulk even exceeds 1,030℃, and the alloy can be held for 30 min at 900℃ without burning;while the average ignition point of Mg-5Ca powders is lower than 700℃, and it increases with the increasing particle size. Moreover, the purity of nitrogen must be in a certain scope;Mg-Ca alloy shows a higher ignition point under nitrogen with a purity of 99.5%. Based on the experimental results, the best adding content of Ca and the purity of nitrogen were determined, and the security and economic performance of preparing magnesium alloys by spray deposition were improved with nitrogen as atomizing gas.展开更多
基金financial support under grant number EP/N007638/1supported by EPSRC under grant number EP/W021080/1
文摘In Mg-Ca alloys the grain refining mechanism,in particular regarding the role of nucleant substrates,remains the object of debates.Although native MgO is being recognised as a nucleating substrate accounting for grain refinement of Mg alloys,the possible interactions of MgO with alloying elements that may alter the nucleation potency have not been elucidated yet.Herein,we design casting experiments of Mg-xCa alloys varied qualitatively in number density of native MgO,which are then comprehensively studied by advanced electron microscopy.The results show that grain refinement is enhanced as the particle number density of MgO increases.The native MgO particles are modified by interfacial layers due to the co-segregation of Ca and N solute atoms at the MgO/Mg interface.Using aberration-corrected scanning transmission electron microscopy and electron energy loss spectroscopy,we reveal the nature of these Ca/N interfacial layers at the atomic scale.Irrespective of the crystallographic termination of MgO,Ca and N co-segregate at the MgO/Mg interface and occupy Mg and O sites,respectively,forming an interfacial structure of a few atomic layers.The interfacial structure is slightly expanded,less ordered and defective compared to the MgO matrix due to compositional deviations,whereby the MgO substrate is altered as a poorer template to nucleate Mg solid.Upon solidification in a TP-1 mould,the impotent MgO particles account for the grain refining mechanism,where they are suggested to participate into nucleation and grain initiation processes in an explosive manner.This work not only reveals the atomic engineering of a substrate through interfacial segregation but also demonstrates the effectiveness of a strategy whereby native MgO particles can be harnessed for grain refinement in Mg-Ca alloys.
基金Projects(50731002,50971136) supported by the National Natural Science Foundation of China
文摘The phase equilibria in Mg-rich corner of Mg-Ca-Gd and Mg-Ca-Nd ternary systems at 400℃ 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 ℃ were constructed from 13 alloys. A three-phase region of a-Mg, Mg41RE5 and Mg2Ca was determined in both ternary systems. It is formed by a similar ternary eutectic reaction L→a-Mg＋Mg2Ca＋Mg41RE5 at 499.6 ℃ and 505.6 ℃, 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 ℃. 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 ℃. Other three-phase equilibria existing in Mg-rich corner of Mg-Ca-Gd system are a-Mg＋MgsGd＋T and MgsGd＋Mg2Ca＋T and the three-phase equilibrium in Mg-rich corner of Mg-Ca-Nd system is Mg3Nd＋Mg2Ca＋ Mg41Nd5.
基金Project(51271131)supported by the National Natural Science Foundation of China
文摘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.
基金This work is supported by National Natural Science Foundation of China(Nos.51525101,U1610253,51701211,and 51971053)funded by the Project of Promoting Talents in Liaoning province(No.XLYC1808038)+2 种基金H.C.Pan acknowledges the financial assistance from the State Key Laboratory of Solidification Processing in NPU(No.SKLSP201920)the Fundamental Research Funds for the Central Universities(No.N2002011)joint R&D fund of Liaoning-Shenyang National Research Center for Materials Science(No.2019JH3/30100040).
文摘This work reported the effect of extrusion speeds on the microstructures and mechanical properties of Mg-Ca binary alloy.The results showed that yield strength of the as-extruded Mg-1.2wt.%Ca alloys decrease from∼360MPa to∼258MPa as the ram speed increases from 0.4mm/s to 2.4 mm/s,and the elongation increases from∼3.9%to∼12.2%.The microstructure changes from bimodal grain feature to the complete dynamical recrystallization(DRX)with increase of the extrusion speed.The ultrafine DRXed grains in size of∼0.85μm,the numerous nano-Mg_(2)Ca particles dispersing along the grain boundaries and interiors,as well as the high density of residual dislocations,should account for the high strength.It is believed that the high degree of dynamic recrystallization and the resulting texture randomization play the critical roles in the ductility enhancement of the high-speed extruded Mg alloys.
基金supported financially by Ministry of Higher Education of Malaysia under the Vote Number 78610
文摘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.
基金Project(214M438)supported by the Scientific and Technological Research Council of Turkey(TUBITAK)Projects(20795,42796)supported partially by Scientific Research Projects Coordination Unit of Istanbul University,Turkey
文摘Highly porous Mg-Ca-Zn-Co alloy scaffolds for tissue engineering applications were produced by powder metallurgy based space holder-water leaching method.Mg-Ca-Zn-Co alloy foam can be used as a scaffold material in tissue engineering.Carbamide was used as a space holder material.Fluoride conversion coating was synthesized on the alloy by immersion treatment in hydrofluoric acid(HF).Increasing Zn content of the alloy increased the elastic modulus.Ca addition prevented the oxidation of the specimens during sintering.Electrochemical corrosion behaviour of the specimens was examined in simulated body fluid.Corrosion rate decreased with Zn addition from1.0%up to3.0%(mass fraction)and then increased.Mass loss of the specimens initially decreased with Zn addition up to about3%and then increased.Fluoride conversion coating increased the corrosion resistance of the specimens.
基金financially supported by the National Natural Science Foundation of China under grant No.50904035the University-Industry Cooperation Projects(grant No.2009B090300148,2010B090400244),Guangdong Province of China
文摘The production cost will be greatly reduced if nitrogen can be used instead of inert gas in the spray forming process of magnesium alloys, but the heat from the reaction between magnesium alloys and nitrogen makes magnesium alloy burn easily. To solve the problem above, the ignition point of Mg-Ca alloy under nitrogen atmosphere was studied using a home-made experimental device and DSC-DTA. Results show that under nitrogen atmosphere, Ca addition has a great effect on the ignition point of Mg alloy. The ignition point of the Mg-5Ca bulk even exceeds 1,030℃, and the alloy can be held for 30 min at 900℃ without burning;while the average ignition point of Mg-5Ca powders is lower than 700℃, and it increases with the increasing particle size. Moreover, the purity of nitrogen must be in a certain scope;Mg-Ca alloy shows a higher ignition point under nitrogen with a purity of 99.5%. Based on the experimental results, the best adding content of Ca and the purity of nitrogen were determined, and the security and economic performance of preparing magnesium alloys by spray deposition were improved with nitrogen as atomizing gas.
