The impact of different volume fractions of crystalline structures on the electrochemical behaviour of Mg67Zn29Ca4 alloys for biomedical applications

ABSTRACT

In this work, the influence of various volume fractions of the crystalline phase in an amorphous matrix of Mg₆₇Zn₂₉Ca₄ alloys was investigated for its corrosion resistance for biodegradable applications. An amorphous Mg₆₇Zn₂₉Ca₄ alloy was successfully fabricated using melt casting into a copper mould. Then, to obtain different ratios of the crystalline phase in an amorphous matrix, the obtained amorphous rods with 3?mm diameters were annealed at 190, 230, 250, and 400°C. The volume fraction of the crystalline phase was measured by X-ray diffraction, and the microstructures of the obtained alloys were determined based on scanning electron microscopy images. Electrochemical testing was conducted in simulated body fluid at 37°C. This report shows that the ratio of the volume fractions of amorphous and crystalline phases in alloy microstructures strongly influences their corrosion behaviours. The alloy with a fully amorphous structure was the most resistive in the analysed media.     

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.     

Phase selection and performance of Mg–Cu–Y amorphous composite with different Mg/Cu ratios

In this article, Mg–Cu–Y alloys with two different Mg/Cu ratios(in at%) were prepared using a watercooled copper mold. Scanning electron microscopy and X-ray diffraction were applied to analyze the microstructure and phase composition. Moreover, corrosion resistance and wear resistance were studied systematically. The results show that both Mg65 Cu25 Y10 and Mg60 Cu30 Y10 alloys could form a composition of crystalline and amorphous phases. Although the microstructure of Mg65 Cu25 Y10 consists of an amorphous phase and a-Mg, Mg2 Cu, and Cu2 Y crystalline phases, the microstructure of Mg60 Cu30 Y10 alloy mainly consists of the amorphous phase and a-Mg, Mg2 Cu. With reducing Mg/Cu ratio, the alloys have better corrosion resistance and wear resistance. The mechanism has also been discussed in detail.     

Corrosion behavior of as-cast Mg68Zn28Y4 alloy with/-phase

Mg₆₈Zn₂₈Y₄ alloys with stable icosahedral quasicrystals (Zn₆₀Mg₃₀Y₁₀) were prepared by cast method. By simulating the environment of ocean, the alloy was eroded in 3.5% (mass fraction) NaCl for 2, 4 and 30 h. The microstructures of the samples and eroded alloys were analyzed by OM and SEM. The compositions and the quasiperiodic structures were identified respectively by EDS and TEM. And the corrosion potential and corrosion current density before and after immersion were measured by potentiodynamic polarization measurements in 3.5% NaCl. The results show that I-phases grow in the mode of conglomeration, piling and transfixion. The Mg₇Zn₃ matrix and α(Mg) solid solution are eroded badly, while W-phase is eroded partially. At the same time, the I-phases exhibit excellent corrosion resistance property. The resistance to corrosion of Mg₆₈Zn₂₈Y₄ alloy is improved by increasing exposed I-phases. With adding element Y to Mg₆₈Zn₃₂ alloy, the corrosion current is decreased by one order of magnitude. And after the immersion of as-cast Mg₆₈Zn₂₈Y₄ alloy for 30 h, the corrosion current density is reduced by two orders of magnitude compared with that of uneroded Mg₆₈Zn₃₂ alloy.     

The effect of Ca on corrosion behavior of heat‐treated Mg–Al–Zn alloy

The effect of 0.5, 1.0, and 1.5 wt% Ca additions on the microstructure and corrosion resistance of the heat‐treated Mg–Al–Zn alloy was investigated. Addition of 0.5 wt% Ca did not form any new phase but suppressed the discontinuous precipitation of the β ‐Mg₁₇Al₁₂ phase by being dissolved in both the second phase and magnesium matrix. In the materials containing higher amounts of Ca, however, metallographic investigation shows that Ca added to Mg–Al–Zn can obviously decrease the size of β ‐Mg₁₇Al₁₂ and forms Al₄Ca intermetallic compounds in the shape of bone‐like morphology. The corrosion tests used include constant immersion technique, and potentiodynamic polarization experiments and salt spray test. Surface examination and analytical studies were carried out using optical and scanning electron microscopy, EDX, and XRD. The results of corrosion tests show that magnesium alloy Mg–Al–Zn with 1.0 wt% Ca addition has the best corrosion resistance behavior.     

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.     

Characterization of plasma electrolytic oxidation coatings formed on Mg–Li alloy in an alkaline silicate electrolyte containing silica sol

We investigate the influence of silica sol addition on the ceramic coatings of Mg–Li alloy by plasma electrolytic oxidation (PEO) in an alkaline silicate electrolyte. Scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy, and energy dispersive spectroscopy are employed to characterize the microstructure and composition of the ceramic coatings. The anti‐corrosion behavior of the ceramic coatings is evaluated by potentiodynamic polarization measurements in conjunction with electrochemical impedance analysis. The ceramic coating formed in the electrolyte containing silica sol contains SiO₂ and Mg₂SiO₄ phase and has more uniform morphology and higher corrosion resistance than that formed in the electrolyte without addition of silica sol.     

Microstructure characterization and effect of extrusion temperature on biodegradation behavior of Mg-5Zn-1Y-xCa alloy

Microstructure and biodegradation behavior of as-cast and hot extruded Mg-5Zn-1Y alloy containing different amounts of calcium (0.0%, 0.1%, 0.5%, and 1.0%, mass fraction) were explored. The extrusion process was conducted at three different temperatures of 300, 330, and 370 °C. Chemical composition, phase constitution, microstructure, and biodegradation behavior of the alloys were investigated. The macro- and micro-scopic examination revealed that the addition of Ca refines the grain structure and forms an intermetallic phase, Ca₂Mg₆Zn₃. The hot extrusion process resulted in breaking the intermetallic phases into fine particles routed to the extrusion direction. Moreover, dynamic recrystallization happened in almost all alloys, and more bimodal microstructure was formed in the alloys when the alloys were extruded at 370 °C. Polarization curves showed no passive region, which indicated that active polarization dominated in the alloys; therefore, grain refining through Ca addition and dynamic recrystallization over hot extrusion operation increased biodegradation rate. The results show that the as-cast Mg-5Zn-1Y-0.1Ca alloy provides the highest corrosion resistance, and the extruded Mg-5Zn-1Y-0.5Ca alloy at 300 °C shows the lowest biodegradation rate among the extruded alloys. Therefore, hot extrusion does not always improve the biodegradation behavior of magnesium alloys.     

Cr元素对Fe基块体非晶合金形成能及腐蚀性能影响的研究

利用微合金化技术,制备了Fe_68.4-xCo_7.6Si₇B₁₀P₅C₂Cr_x (x=0, 1, 2, 3)非晶合金,并分别使用单辊急冷甩带法和铜模铸造法制备了带状和棒状样品。借助XRD、DSC、DTA表征该非晶合金系的热力学性能与非晶形成能;并进一步采用电化学动电位极化曲线法研究了该非晶合金系在硫酸溶液中的的耐腐蚀性能。实验结果表明,通过微量添加Cr元素的方法,使该合金系的非晶形成能普遍提高,当Cr元素添加量为2%时,获得了该系列非晶合金中的最大过冷液体区间(ΔTx=57K),并且成功制备了直径为5mm的圆棒状样品;同时,由于Cr元素的添加,在1N浓度的硫酸溶液中,材料表面上形成富含Cr元素的保护层,可以有效阻止材料内部的进一步腐蚀,耐腐蚀性能明显得到改善。     

Mg67Zn28Ca5 bulk metallic glass formation understood via close-packed icosahedron Zn2Mg11 eutectic cluster

Cluster characteristics of Mg₅₁Zn₂₀ binary phase are analyzed using atomic density radial distribution method. Then icosahedron Zn₂Mg₁₁ cluster, having the highest relative atomic density 2.45, is highlighted because of the most close-packed structure. Using cluster-plus-glue-atom model and Zn₂Mg₁₁ cluster, eutectic composition Zn_28.1Mg_71.9 of Mg–Zn binary system can be simply expressed as: [Zn₂Mg₁₁] + (Zn_2.5Mg_0.5). Therefore the most efficient packing icosahedron Zn₂Mg₁₁ is also eutectic-related cluster. Finally, using general cluster formula [cluster](glue atoms)_x(x = 1, 3), Mg-based Mg₆₇Zn₂₈Ca₅ bulk metallic glass may be deciphered via the most close-packed eutectic cluster Zn₂Mg₁₁ as: [Zn₂Mg₁₁] + (Zn₂Ca₁).     

Effect of cerium addition on microstructure and corrosion resistance of die cast AZ91 magnesium alloy

A novel AZ91 Ce containing magnesium alloy characterized by excellent corrosion resistance is fabricated by adding rare earth Ce (cerium) in the form of a Mg‐Ce master alloy. The metallographic investigation shows that Ce added to AZ91 can obviously decrease the size of β‐Mg₁₇Al₁₂ and forms Al₁₁Ce₃ intermetallic compounds in the shape of fine needles. The corrosion tests and electrochemical measurements indicate that the corrosion resistance of AZ91 Ce containing magnesium alloy is obviously higher than that of AZ91. Furthermore, increasing the content of Ce in the magnesium alloy can further enhance the corrosion resistance. X‐ray photoelectron spectroscopy (XPS) reveals that Ce can be incorporated into corrosion products in the form of CeO₂ in the course of corrosion. Based on the preliminary analysis, the addition of Ce can improve the corrosion resistance of AZ91 by decreasing the size of β‐Mg₁₇Al₁₂ and enhancing the protective effectiveness of corrosion products.     

Effect of ageing treatment on microstructures,mechanical properties and corrosion behavior of Mg-Zn-RE-Zr alloy micro-alloyed with Ca and Sr

Effects of ageing treatment on the microstructures, mechanical properties and corrosion behavior of the Mg-4.2Zn-1.7RE-0.8Zr-xCa-ySr [x=0, 0.2 (wt.%), y=0, 0.1, 0.2, 0.4 (wt.%)] alloys were investigated. Results showed that Ca or/and Sr additions promoted the precipitation hardening behavior of Mg-4.2Zn-1.7RE-0.8Zr alloy and shortened the time to reaching peak hardness from 13 h to 12 h. The maximum hardness of 77.1±0.6 HV for the peak-aged Mg-4.2Zn-1.7RE-0.8Zr-0.2Ca-0.2Sr alloy was obtained. The microstructures of peak-aged alloys mainly consist of α-Mg phase, Mg₅₁Zn₂₀ phase and ternary T-phase. The Zn-Zr phase is formed within the α-Mg matrix, and the Mg₂Ca phase is formed near T-phase due to the enrichment of Ca in front of the solid-liquid interface. Furthermore, fine short rod-shaped β′₁ phase is precipitated within the α-Mg matrix in the peak-aged condition. The peak-aged Mg-4.2Zn-1.7RE-0.8Zr-0.2Ca-0.2Sr alloy exhibits optimal mechanical properties with an ultimate tensile strength of 208 MPa, yield strength of 150 MPa and elongation of 3.5%, which is mainly attributed to precipitation strengthening. In addition, corrosion properties of experimental alloys in the 3.5wt.% NaCl solution were studied by the electrochemical tests, weight loss, hydrogen evolution measurement and corrosion morphology observation. The results suggest that peak-aged alloys show reduced corrosion rates compared with the as-cast alloys, and minor additions of Ca and/or Sr improve the corrosion resistance of the Mg-4.2Zn-1.7RE-0.8Zr alloy. The peak-aged Mg-4.2Zn-1.7RE-0.8Zr-0.2Ca-0.2Sr alloy possesses the best corrosion resistance, which is mainly due to the continuous and compact barrier wall constructed by the homogeneous and continuous second phases.

     

Corrosion and chemical behavior of Mg97Zn1Y2-1wt.%SiC under different corrosion solutions

To explore the corrosion properties of magnesium alloys, the chemical behavior of a high strength Mg₉₇Zn₁Y₂-1 wt.%Si C alloy in different corrosion environments was studied. Three solutions of 0.2 mol·L^-1 NaCl, Na₂SO₄ and NaNO₃ were selected as corrosion solutions. The microstructures, corrosion rate, corrosion potential, and mechanism were investigated qualitatively and quantitatively by optical microscopy(OM), scanning electron microscopy(SEM), immersion testing experiment, and electrochemical test. Microstructure observation shows that the Mg₉₇ Zn₁Y₂-1 wt.%Si C alloy is composed of α-Mg matrix, LPSO(Mg₁₂ ZnY) phase and Si C phase. The hydrogen evolution and electrochemical test results reflect that the Mg₉₇Zn₁Y₂-1 wt.%SiC in 0.2 mol·L^-1 Na Cl solution has the fastest corrosion rate, followed by Na₂SO₄ and NaNO₃ solutions, and that the charge-transfer resistance presents the contrary trend and decreases in turn.     

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.     

Composite cerium oxide/titanium oxide thin films for corrosion protection of AZ91D magnesium alloy via sol–gel process

Anti‐corrosive composite cerium oxide/titanium oxide (CeO₂/TiO₂) thin films were successfully prepared on an AZ91D magnesium alloy substrate by applying cerium oxide (CeO₂) thin films as the inner layer with a sol–gel process. Composition and surface morphology of the thin films were analyzed using X‐ray diffraction (XRD) and scanning electron microscope (SEM). XRD showed that the composite films consisted of cerianite and anatase phases. The wettability of the thin films was evaluated by water contact angles measurements. Potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) tests were used to evaluate the corrosion behavior of the bare substrate and coated samples in 3.5 wt% sodium chloride solution (3.5 wt% NaCl). The results demonstrated that titanium oxide (TiO₂) thin film mainly dominated the corrosion resistance of samples and the composite films with excellent hydrophilicity could significantly improve the corrosion resistance of AZ91D magnesium alloy.     

Effect of different aging processes on the corrosion behavior of new Al–Cu–Li–Zr–Sc alloys

The intergranular corrosion and exfoliation corrosion behaviors of Al–Cu–Li–Zr–Sc alloys under different aging effects, such as single‐stage aging, strain aging, and double‐stage aging, were studied. Among the three aging treatments, single‐stage aging resulted in the best resistance to corrosion, followed by double‐stage aging; strain aging resulted in the worst corrosion resistance. A 3.5% precooling strain could increase the dislocation density, which promoted the precipitation of corrosion‐prone T₁ phase and increased the corrosion driving force of the alloy. Double‐stage aging made the precipitated T₁ phases finer and more uniform and reduced the number of equilibrium phases at grain boundaries, thus improving the corrosion properties of the alloy. The corrosion susceptibility of the alloy was attributed to the T₁ phase and precipitate‐free zone (PFZ), and the underlying corrosion mechanism was revealed as preferential dissolution of the equilibrium phase at grain boundaries and its surrounding distortion zone, followed by expansion of the PFZ along the grain boundaries, resulting in the development of corrosion from the grain boundaries to the intragranular regions.     

Conversion coating treatment for AZ91 magnesium alloys by a permanganate‐REMS bath

A permanganate‐rare earth metal salt (REMS) chemical conversion bath was applied to a sample of AZ91 magnesium alloy in this study, a red‐brown conversion coating formed subsequently on the sample surface. The test results of this coating with a scanning electron microscope (SEM) showed that there existed net‐like cracks on the surface of the treated magnesium alloy. With the analyses of X‐ray Diffraction (XRD) and X‐ray Photoelectron Spectroscopy (XPS), a further study of this coating indicated that the coating was structurally amorphous and mainly composed of CeO₂, MnO, MnO₂, MgO, Mg(OH)₂ and MgAl₂O₄. Furthermore, the electrochemical polarization tests showed that compared with the samples treated by the chrome‐based method, the open‐circuit potential of the magnesium alloy coated in permanganate‐REMS bath moved from ? 1.34 V_SCE to ? 1.28 V_SCE and the anodic current density of the alloy, at the same potential, decreased evidently in simulated sweat fluid. The cracks in the chemical conversion coating should be caused by the phase structure of the magnesium alloy. During the chemical conversion process, the localized corrosion micro‐cell led to the formation of the net‐like cracks on the surface. Simultaneously, the dehydration of the surface coating after treatment also accelerated the formation of the cracks at the coating surface.     

双脉冲镀对低温熔融盐镀中Al-Mn合金层的影响

   以铁片为基体,分别采用直流和双脉冲电源,在AlCl₃-NaCl-KCl-MnCl₂低温熔融盐中获得了Al-Mn合金镀层.用SEM、金相、EDS和XRD研究了Al-Mn合金镀层表面形貌、沉积速度、组成结构及耐腐蚀性能.结果表明,双脉冲镀层更致密,表面更平整,但沉积比直流镀慢;在MnCl₂含量相同的条件下,双脉冲镀层中Mn含量更高;合金镀层结构随镀层中Mn含量的增加,经铝固熔体与非晶相混合、单一非晶态、非晶相与晶态Al₈Mn₅混合三个阶段;单一非晶态镀层耐蚀性比双相镀层好,Mn含量相当的双脉冲镀层耐蚀性比直流镀层好.     

Corrosion behaviour of the amorphous Mg65Y10Cu15Ag10 alloy

The corrosion behaviour of the amorphous Mg₆₅Y₁₀Cu₁₅Ag₁₀ alloy as well as of its crystalline multiphase counterpart was studied in alkaline electrolytes and compared with that of the amorphous Mg₆₅Y₁₀Cu₂₅ alloy. Electrochemical investigations were carried out in 0.3 M H₃BO₃/Na₂B₄O₇ buffer solution with pH=8.4 and in 0.1 M NaOH solution with pH=13. Tafel plots were recorded and cyclic potentiodynamic polarisation tests were conducted, transients were measured at anodic potentials. Potentiostatically formed surface layers were characterised by Auger electron spectroscopy and atomic force microscopy. Changes in the corrosion behaviour were noticed which are attributed to the presence of silver. The passive layers formed in the two electrolytes were quite different in the composition as well as in morphology. The layer growth mechanisms also showed some variation presumably mainly due to the presence of silver, though copper still seems to play a dominant role in the passivation of this alloy in the weakly alkaline solution. The amorphous alloys displayed superior corrosion behaviour compared to the crystalline alloy, because of the absence of the heterogeneties existing in crystalline alloys.     

添加RE和Ti元素对Zn-2.5Al-3Mg合金微观结构和耐腐蚀性能的影响

采用XRD、SEM、TEM和XPS等研究了RE和Ti元素对Zn-2.5Al-3Mg合金微观结构和耐蚀性的影响。结果表明,Zn-2.5Al-3Mg合金的微观结构由富Zn相、二元共晶（Zn-MgZn₂/Mg₂Zn₁₁）和三元共晶（Zn/Al/Mg₂Zn₁₁）组成,而含有RE和Ti元素的合金中出现了新相(Ce_1-xLa_x)Zn₁₁和Al₂Ti。电化学阻抗谱表明,相对于Zn-2.5Al-3Mg合金,Zn-2.5Al-3Mg-0.1RE-0.2Ti合金的耐蚀性得到了显著的提高。XPS分析结果表明,RE元素的添加促进腐蚀产物Zn₅(CO₃)₂(OH)₆和MgAl₂O₄的形成,而RE和Ti元素的同时添加促进腐蚀产物 Zn₅(CO₃)₂(OH)₆、ZnAl₂O₄和MgAl₂O₄的形成,且都抑制了疏松多孔ZnO的生成。Zn₅(CO₃)₂(OH)₆、ZnAl₂O₄和MgAl₂O₄能够很好地粘附在试样表面,提供一层致密的保护层,从而提高Zn-2.5Al-3Mg合金的耐腐蚀性。