Preparation, microstructure and degradation performance of biomedical magnesium alloy fine wires

With the development of new biodegradable Mg alloy implant devices, the potential applications of biomedical Mg alloy fine wires are realized and explored gradually. In this study, we prepared three kinds of Mg alloy fine wires containing 4 wt% RE(Gd/Y/Nd) and 0.4 wt% Zn with the diameter less than 0.4 μm through casting, hot extruding and multi-pass cold drawing combined with intermediated annealing process. Their microstructures, mechanical and degradation properties were investigated. In comparison with the corresponding as-extruded alloy, the final fine wire has significantly refined grain with an average size of 3–4 μm, and meanwhile shows higher yield strength but lower ductility at room temperature. The degradation tests results and surface morphologies observations indicate that Mg–4Gd–0.4Zn and Mg–4Nd–0.4Zn fine wires have similar good corrosion resistance and the uniform corrosion behavior in SBF solution. By contrast, Mg–4Y–0.4Zn fine wire shows a poor corrosion resistance and the pitting corrosion behavior.     

α′ Type Ti– Nb– Zr alloys with ultra-low Young''s modulus and high strength

a’ phase based Ti-Nb-Zr alloys with low Young’s modulus and high strength were prepared,and their microstructure and mechanical properties were characterized.It was revealed that the lattice expansion by Nb and Zr addition as well as the presence of a few of a" martensite might be responsible for the low modulus achieved.Ti-15Nb-9Zr alloy,with ultralow modulus of 39 GPa and high strength of850 MPa,could be a potential candidate for biomedical applications.     

Ti – Cu– Zr–Fe– Nb ultrafine structur e-dendrite composites with good mechanical properties and biocompat ibility

Ti-Cu-Zr-Fe-Nb ultrafine structure-dendrite composites were designed by inducing Nb and more Ti to a Ti-Cu-Zr-Fe glass-forming alloy composition and prepared by copper mold casting.The composite alloys consist of β-Ti dendrites and ultrafine-structured CuTi₂ and CuTi phases as well as a trace amount of glassy phase.The volume fraction of β-Ti dendrites increases with the increase in content of Nb which acted as the β-Ti phase stabilizer in the alloys.The composites exhibit high compressive yield strength exceeding1200 MPa,maximum strength around 1800 MPa and low Young’s modulus around 48 GPa.The plasticity of the alloys is strongly influenced by the volume fraction and morphology of the dendritic β-Ti phase,and the compressive plastic strain was enlarged from 5.9%for the 4 at%Nb alloy to 9.2%for the 8 at%Nb alloy.The preliminary cell culture experiment indicated good biocompatibility of the composite alloys free from highly toxic elements Ni and Be.These Ti-based composite alloys are promising to have potential structural and biomedical applications due to the combination of good mechanical properties and biocompatibility.     

A β-type TiNbZr alloy with low modulus and high strength for biomedical applications

The effect of thermo-mechanical treatment on the mechanical properties of a novel β-type Ti–36Nb–5Zr(wt%) alloy has been investigated.The solution treated alloy consists of β and α″ phases and exhibits a two-stage yielding with a low yield stress(around 100 MPa). After cold rolling at a reduction of 87.5% and subsequent annealing treatment at 698 K for 25 min, a fine microstructure with nanosized α precipitates distributed in small β grains as well as high density of dislocations was obtained to achieve a yield strength of 720 MPa and a ultimate tensile strength of 860 MPa. In spite of the formation of α precipitates, the β-stabilizers are not enriched in the parent β matrix due to the short duration and low temperature of the thermal treatment, resulting in a low chemical stability of β phase. The low stability of β phase and the small volume fraction of α precipitates produce a low Young’s modulus of 48 GPa. Such an excellent combination of low elastic modulus and high strength in mechanical properties indicates great potential for biomedical applications.     

Influence of stacking fault energy on formation of long period stacking ordered structures in Mg–Zn–Y–Zr alloys

The influence of alloying elements on the stacking fault energy (SFE) of Mg–Y–Zn–Zr alloys was calculated by using first-principles, and the microstructure of as-cast Mg-1.05Y-0.79Zn-0.07Zr (mole fraction, %) alloy prepared by conventional casting was investigated by SEM, TEM and HRTEM. The block-like long period stacking ordered (LPSO) phase, the lamellar LPSO phase and stacking faults were observed simultaneously and the lamellar LPSO structure and stacking faults were both formed on (0001)_α-Mg habit plane and grown or extended along [01i0]_α-Mg direction. The calculation results by the first-principles showed that the addition of Y can sharply decrease the stacking fault energy of the Mg–Zn–Y–Zr alloy, while Zn slightly increases the stacking fault energy of the alloy. The influence of stacking fault energy on the formation of LPSO was discussed. It shows that LPSO may nucleate directly through stacking faults and the lower stacking fault energy was in favor of formation of LPSO.     

长周期堆垛有序结构强化Mg-Zn-Y合金的组织与性能

为研究长周期堆垛有序( LPSO)结构对Mg-Zn-Y变形镁合金组织与性能的影响,通过铸造和热挤压工艺制备了Mg97Zn1Y2和Mg94Zn2Y4合金.采用扫描电子显微镜、透射电子显微镜以及电子万能试验机等研究了2种合金在铸态、退火态以及挤压态下的显微组织和力学性能.研究结果表明,Mg97Zn1Y2和Mg94Zn2Y4合金的铸态组织均由α-Mg和18R型LPSO相构成,LP-SO相连接成网状分布在晶界.经500℃退火36 h后,Mg97 Zn1 Y2合金中部分块状LPSO相分解为细层片状,结构由18R转变为14H,但在Mg94Zn2Y4合金中未观察到LPSO相结构类型的转变.通过挤压变形,LPSO相沿挤压方向排列,合金强度得到大幅度提高,Mg97Zn1Y2和Mg94Zn2Y4合金的抗拉强度分别达到319和390 MPa.     

Effect of pickling processes on the microstructure and properties of electroless Ni–P coating on Mg–7.5Li–2Zn–1Y alloy

The electroless plating Ni–P is prepared on the surface of Mg–7.5Li–2Zn–1Y alloys with different pickling processes.The microstructure and properties of Ni–P coating are investigated.The results show that the Ni–P coatings deposited using the different pickling processes have a different high phosphorus content amorphous Ni–P solid solution structure,and the Ni–P coatings exhibit higher hardness.There is higher phosphorus content of Ni–P amorphous coating using 125 g/L Cr O3and 110 ml/L HNO3(w68%)than using 180 g/L Cr O3and 1 g/L KF during pre-treatment,and the coating structure is more compact,and the Ni–P coatings exhibit more excellent adhesion with substrate(Fcup to22 N).The corrosion potential of Ni–P coating is improved and exhibits good corrosion resistance.As a result,Mg-7.5Li-2Zn-1Y alloy is remarkably protected by the Ni–P coating.     

Effect of Sr on microstructure and aging behavior of Mg–14Li alloys

The as-cast and as-extruded Mg–14 wt%Li–x Sr ( x=0.14, 0.19, 0.39 wt%) alloys were,respectively, prepared through a simple alloying process and hot extrusion. The effects of Sr addition on microstructure and aging behavior of the Mg–14 wt%Li–xSr alloys were studied. The results indicated that β(Li) and Mg2Sr were the two primary phases in the microstructures of both as-cast and as-extruded Mg–14 wt%Li–xSr alloys. Interestingly, with the increase of Sr content from 0.14 wt% to 0.39 wt%, the grain sizes of the as-cast and as-extruded Mg–14 wt%Li–xSr alloys markedly decreased from 5000mm and 38mm to 330 mm and 22mm respectively, while no obvious changes of the micro-hardness and microstructure of the as-extruded alloys were observed during the aging treatment.     

Effects of Sn addition on microstructure and mechanical properties of Mg- Zn-Al alloys

The effects of Sn addition(0, 0.5, 1.0, 2.0 and 3 wt%) on microstructure of Mg-4Zn-1.5Al alloy in cast and extruded states were investigated, and the mechanical properties of as-extruded Mg-4Zn-1.5Al-xSn studied. The experimental results showed that the as-cast Mg-4Zn-1.5Al alloy was composed of two phases α-Mg and Mg_(32)(Al, Zn)_(49), while Sn-containing alloys consisted of α-Mg, Mg_(32)(Al, Zn)_(49) and Mg_2Sn phases, and Mg_(32)(Al, Zn)_(49) was not detected after extruding due to that the most of them dissolved into the matrix during the homogenized treatment. The addition of Sn refined the grains of as-cast and as-extruded Mg-Zn-Al alloys obviously. It was noted that the basal texture intensity reduced with increasing Sn content significantly in as-extruded Mg-Zn-Al alloys. The tensile tests results indicated that Sn addition improve the tensile strength of the extruded alloys,while it had a harmful effect on the ductility. When the addition of Sn was 2 wt%, the ultimate tensile strength(UTS), yield strength(YS) and elongation(ε_f) of the alloy were 280 MPa, 147 MPa and 17.4%, respectively.     

Minor-alloyed Cu-Ni-Si alloys with high hardness and electric conductivity designed by a cluster formula approach

Cu-Ni-Si alloys are widely used due to their good electrical conductivities in combination with high strength and hardness. In the present work, minor-alloying with M =(Cr, Fe, Mo, Zr) was conducted for the objective of further improving their hardness while maintaining their conductivity level. A cluster-plus-glue-atom model was introduced to design the compositions of M-alloyed Cu-Ni-Si alloys, in which an ideal composition formula[(Ni,Si,M)-Cu_(12)]Cu_3(molar proportion) was proposed. To guarantee the complete precipitation of solute elements in fine δ-Ni_2 Si precipitates, the atomic ratio of(Ni,M)/Si was set as 2/1. Thus the designed alloy series of Cu_(93.75)(Ni/Zr)_(3.75)Si_(2.08)(Cr/Fe/Mo)_(0.42)(at%) were arc-melted into ingots under argon atmosphere, and solidsolutioned at 950 ℃ for 1 h plus water quenching and then aged at 450 ℃ for different hours. The experimental results showed that these designed alloys exhibit high hardness(HV 1.7 GPa) and good electrical conductivities(≥ 35% IACS). Specifically, the quinary Cu_(93.75)Ni_(3.54)Si_(2.08)(Cr/Fe)_(0.42)Zr_(0.21) alloys(Cu-3.32 Ni-0.93 Si-0.37(Cr/Fe)-0.30 Zr wt%) possess both a high hardness with HV = 2.5-2.7 GPa, comparable to the highstrength KLFA85 alloy(Cu-3.2 Ni-0.7 Si-1.1 Zn wt%,HV= 2.548 GPa),and a good electrical conductivity(35-36% IACS).     

Peculiar aging response of near b Ti–25 Nb–2Mo–4Sn alloy for biomedical applications

In this paper,aging response of a recently developed near β Ti-25Nb-2Mo-4Sn(wt%) alloy with high strength and low modulus was investigated intensively.The experimental results from X-ray diffraction and transmission electron microscopy showed that the aging production of the Ti-2524 alloy was(β+ω) or(β+α) even under the same aging treatment condition,depending on the pre-treatments prior to the aging.Solid evidence confirmed the competition between stable α phase and metastable ω phase during the decomposition of β phase on aging.Different aging response of Ti-2524 alloy can be attributed to high-density dislocations and grain boundaries which suppress the formation of ω,and alternatively promote a phase formation.This provides a thermo-mechanical approach to inhibit deleterious ω phase formation and assist fine α phase precipitation.Upon an appropriate aging treatment,superior mechanical properties of high ultimate tensile strength(1233 MPa) and low elastic modulus(77 GPa) were achieved in Ti-2524 alloy.     

Effect of long-period stacking ordered phase on microstructure, mechanical property and corrosion resistance of Mg alloys: A review

Magnesium alloys containing long period stacking ordered (LPSO) phase have been received a great deal of attention in the last decade owing to their excellent comprehensive properties of mechanical strength and corrosion resistance. In this paper, some fundamental aspects of LPSO containing Mg alloys have been reviewed, including: (1) microstructural characterization, formation conditions and the associated phase transformation of LPSO phases in Mg alloys; (2) deformation mechanism of LPSO phases and their influence on the deformation mechanism of the Mg matrix; (3) effect of LPSO structure on the mechanical performance such as tensile strength, creep resistance, fracture toughness and fatigue strength; (4) corrosion behavior of LPSO containing Mg alloys and their possible applications as the biomaterials. Moreover, some remaining unsolved issues of the LPSO containing Mg alloys and the future target about how to further improve their service properties have been also described.     

Effect of Mn content on the microstructure and mechanical properties of Mg–6Li–4Zn-xMn alloys

The as-cast Mg–6Li–4Zn-xMn alloys were prepared and extruded at 280 ​°C with an extrusion ratio of 25:1. The effects of Mn content on the microstructure and mechanical properties of Mg–6Li–4Zn-xMn alloys were investigated in this study. The XRD results show that Mg–6Li–4Zn–xMn alloys consisted of α-Mg (hcp) ​+ ​β-Li (bcc) duplex structured matrix, MgLi₂Zn and Mn phases. The grains of the extruded Mg–6Li–4Zn–xMn alloys were refined by dynamic recrystallization during the extrusion process. The EBSD results show that the extruded alloys had basal textures. The grain size of the extruded alloys decreased while the basal texture was strengthened with the increasing Mn addition. The TEM results show that a large amount of nanoscale Mn precipitates existed in the extruded Mg–6Li–4Zn–1.2Mn alloy, which can effectively inhibit the dynamic recrystallized (DRXed) grains growth during the hot extrusion and is beneficial to the improvement of mechanical properties. Mg–6Li–4Zn–1.2Mn alloy in this research possesses the best mechanical properties with the ultimate tensile strength and yield strength of 321 ​MPa, 250 ​MPa, respectively.     

A first-principles study of displacive β to ω transition in Ti-V alloys

The ground state properties of β and ω phases in Ti-(0–30 at%)V alloys were calculated, and subsequently thermodynamics and energy barriers of the displacive β to ω transition were investigated by first-principles. The results show that the lattice parameters of β and ω phases decreases with increasing V content in Ti-V alloys. The principal lattice strains for the β to ω transition are highly compositional dependent, and the volume variation decreases with increasing V content. The mechanical stability of the ω phase increases initially at the V content around 10 at% and then decreases with increasing V content. Based on the quasiharmonic Debye model, a metastable diffusionless phase diagram has been established, showing that the ω phase is thermodynamically more stable than the β phase at room temperature, anticipating a spontaneous transition from β to ω phases in Ti-V alloys. The calculations of energy pathways indicate that there is an energy barrier during the displacive βto ω transition in Ti-V alloys at temperatures from 100 to 500 K, but not at 0 K.     

Optimization of dual effects of Mg– 1Ca alloys on the behavior of chondrocytes and osteoblasts in vitro

Mg ions can enhance the proliferation and redifferentiation of chondrocytes and the osteogenic differentiation of osteoblasts at specific concentrations, respectively. However, degradation of Mg alloys at varying degradation rates could lead to complex changes in the surrounding tissue environment, such as changes in the dynamic concentration of Mg ions and subsequent p H value. Considering the above mentioned factors, the comprehensive effects of Mg alloys on chondrocytes and osteoblasts behaviors have not yet been optimized. In this study, we evaluated the effects of Mg–1Ca microspheres on cell behavior with an aim to optimize conditions favorable for both cell types. Cells were cultured with Mg–1Ca microspheres prepared using the following concentrations: 250 μg/ml, 500 μg/ml and 1000 μg/ml. At specific time points,cytotoxicity, expression of specific genes and extracellular matrix deposition by cells(Alizarin Red Staining of osteoblasts and Alcian blue staining for chondrocytes) were evaluated. The experimental results revealed that Mg–1Ca microspheres prepared at a concentration of 250 μg/ml were optimum for both cell types, where chondrocytes were found to be in hypertrophy state while osteoblasts in close proximity to the microspheres showed osteogenetic differentiation. Interestingly, a slight change in osteoblasts behavior was observed nearer to and at a relative distance away from Mg–1Ca microspheres, an important observation for administering the application of microspheres as potential scaffolds.     

Corrosion behavior of Mg–Y alloy in NaCl aqueous solution

The corrosion behavior of Mg–(0.25, 2.5, 5, 8 and 15)Y alloys in 3.5wt.% NaCl aqueous solution was investigated. It was found that the degree of corrosion deterioration increased with increasing immersion time up to 2 h. Corrosion modes for the alloys with low and high content of Y element were general corrosion and pitting corrosion, respective ly, and the threshold content for the corrosion mode change was 2.5% for the tested alloys. The experimental results showed that the addition of Y refined the grain of the alloy, and the distribution, i.e., continuous or not, of the Mg24Y5 phases had great effect on the corrosion rate and corrosion mode.     

Microstructure s and mechanical properties of Ti3Al/Ni-based superalloy joints arc welded with Ti –Nb and Ti– Ni – Nb filler alloys

Dissimilar joining of Ti3Al-based alloy to Ni-based superalloy has been carried out using gas tungsten arc(GTA) welding technology with Ti–Nb and Ti–Ni–Nb filler alloys.The joint welded with the Ti–Nb filler alloy contained much less interfacial brittle phases than the one using the Ti–Ni–Nb filler alloy.The average room-temperature tensile strength of the joint welded with Ti–Nb was 202 MPa and the strength value of the one welded with Ti–Ni–Nb was 128 MPa.For both fillers,the weak links of the dissimilar joints were the weld/In718 interfaces.The presence of TiNi,TiNi3 and Ni3Nb intermetallic compounds in the joint welded with Ti–Ni–Nb induced microcracks at the weld/In718 interface and deteriorated the mechanical properties of the joint.And the adoption of the Ti–Nb filler alloy decreased the formation tendency of interfacial brittle phases to some extent and thus enhanced the tensile strength of the joint.     

A Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous filler metal for improving the strength of Ti–6Al–4V alloy brazing joint

Ti_(50)Zr_(27)Cu_8Ni_4Co_3Fe_2Al_3Sn_3(at%) amorphous filler metal with low Cu and Ni contents in a melt-spun ribbon form was developed for improving mechanical properties of Ti–6Al–4V alloy brazing joint through decreasing brittle intermetallics in the braze zone. Investigation on the crystallization behavior of the multicomponent Ti–Zr–Cu–Ni–Co–Fe–Al–Sn amorphous alloy indicates the high stability of the supercooled liquid against crystallization that favors the formation of amorphous structure. The Ti–6Al–4V joint brazed with this Ti-based amorphous filler metal with low total content of Cu and Ni at 1203K for 900s mainly consists of α-Ti, β-Ti,minor Ti–Zr-rich phase and only a small amount of Ti_3Cu intermetallics, leading to the high shear strength of the joint of about 460 MPa. Multicomponent composition design of amorphous alloys is an effective way of tailoring filler metals for improving the joint strength.     

Microstruct ural evolution and mechanical behavior of metastable β -type Ti – 25Nb–2Mo – 4Sn alloy with high strength and low modulus

This paper presents a systematic study of newly developed metastable β-type Ti-25Nb-2Mo-4Sn (wt%) alloy with high strength and low elastic modulus, with focus on the microstructural evolution and mechanical behavior associated with aging. The pre-treatment (solution treatment or cold rolling) prior to aging exerts substantial influence on the subsequent aging response including microstructural evolution and mechanical behavior. Even under the same aging treatment, the aging products could be (β+ω), or alternatively (β+α), depending on the pre-treatments. This interesting aging response was discussed on the basis of the mechanism for ω formation. High-density dislocation tangles and grain boundaries induced by severe cold rolling play a key role in hindering the transition from β to isothermal ω, favoring the precipitation of α phase on aging. By aging cold-rolled specimen for short time, superior mechanical properties, i.e. high ultimate strength of ～1113 MPa and low elastic modulus of ～65 GPa, achieved in Ti-25Nb-2Mo-4Sn alloy. The characterization of microstructural evolution and compositional change indicated that the precipitation of fine α does not cause the enrichment of β-stabilizers in β matrix upon a short-time aging, guaranteeing low elastic modulus of the short-time aged specimen. Meanwhile, fine α precipitates as well as dislocations play a crucial part in strengthening, giving rise to its high yield strength and high ultimate tensile strength.     

Effects of Zn content on the microstructure and the mechanical and corrosion properties of as-cast low-alloyed Mg–Zn–Ca alloys

The effects of Zn content on the microstructure and the mechanical and corrosion properties of as-cast low-alloyed Mg–xZn–0.2Ca alloys (x=0.6wt%, 2.0wt%, 2.5wt%, hereafter denoted as 0.6Zn, 2.0Zn, and 2.5Zn alloys, respectively) are investigated. The results show that the Zn content not only influences grain refinement but also induces different phase precipitation behaviors. The as-cast microstructure of the 0.6Zn alloy is composed of α-Mg, Mg₂Ca, and Ca₂Mg₆Zn₃ phases, whereas 2.0Zn and 2.5Zn alloys only contain α-Mg and Ca₂Mg₆Zn₃ phases, as revealed by X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Moreover, with increasing Zn content, both the ultimate tensile strength (UTS) and the elongation to fracture first increase and then decrease. Among the three investigated alloys, the largest UTS (178 MPa) and the highest elongation to fracture (6.5%) are obtained for the 2.0Zn alloy. In addition, the corrosion rate increases with increasing Zn content. This paper provides an updated investigation of the alloy composition–microstructure–property relationships of different Zn-containing Mg–Zn–Ca alloys.