Fabrication and corrosion behavior of HA/Mg-Zn biocomposites

The thermal-treated hydroxyapatite (HA) particles, Mg and Zn powders were used to prepare the HA/Mg-Zn composites with different HA contents by means of powder metallurgy technology. The microstructures, formation phases, and corrosion behaviors in simulated body fluid (SBF) were studied in comparison with pure magnesium and HA/Mg composites fabricated by the same preparation technology. As a result, no evident reaction happened between HA particles and Mg matrix during sintering process, and Zn atoms diffused into Mg matrix to form a single phase Mg-Zn alloy matrix. The addition of HA particles changed the corrosion mechanism of Mg matrix. During the corrosion process, HA particles would adsorb PO₄³⁻ and Ca²⁺ ions efficiently and induce the deposition of Ca-P compounds on the surface of composites. HA could improve the corrosion resistance of magnesium matrix composites in SBF and restrain the increase of pH of SBF. Furthermore, the addition of Zn was favorable to improve the corrosion resistance of HA/Mg composites due to the densification of composites and the formation of Mg-Zn alloy matrix.     

In vitro degradation,hemolysis and MC3T3-E1 cell adhesion of biodegradable Mg–Zn alloy

In this study a kind of patent binary Mg–6 wt.%Zn magnesium alloy was investigated as degradable biomedical material. The results of in vitro degradation including electrochemical measurements and immersion tests in simulated body fluid (SBF) revealed that zinc could elevate both the corrosion potential and Faraday charge transfer resistance of magnesium and thus improve the corrosion resistance. XRD and EDS analysis proved that the corrosion products on the surface of Mg–Zn contained hydroxyapatite (HA), Mg(OH)₂ and other Mg/Ca phosphates, which could reduce the degradation rate. The degradation process of magnesium alloy and the mechanism of corrosion layer formation were also discussed in this work, i.e. the byproducts of degradation of magnesium, Mg²⁺ and OH^?, reacted with the phosphate and Ca²⁺ in the SBF, thus the corrosion layer containing HA, Mg(OH)₂ and other magnesium-substituted apatite precipitated in corrosion pits and covered the surface of magnesium alloy.The hemolysis test found that the hemolysis rate of Mg–Zn was 3.4%, which is lower than the safe value of 5% according to ISO 10993-4. For the cell culture experiments, after 2 h incubation the pre-osteoblastic cell MC3T3-E1 was able to adhere and spread on the corrosion layer of Mg–Zn alloy, indicating that despite the fluctuation of pH value of DMEM culture solution, Mg–Zn alloy could still support the earlier adhesion of pre-osteoblastic cells on the surface. Hemolysis and adhesion of cells display good biocompatibility of Mg–Zn alloy in vitro.     

微波辅助法制备镁合金的植酸镁/羟基磷灰石复合涂层及其耐蚀性能

采用微波辅助法在AZ31镁合金表面制备了植酸镁/羟基磷灰石(PA/HA)复合涂层。利用FESEM、EDS、XRD和电化学性能测试等方法表征涂层的表面形貌、物相组成以及耐蚀性能,探究了植酸溶液的pH值对PA/HA复合涂层形貌及耐蚀性能的影响,并通过浸泡实验研究了镁合金及PA/HA复合涂层在模拟体液(SBF)中的降解矿化行为。结果表明:在植酸预处理中,植酸溶液的pH=5.0时制备得到的PA/HA复合涂层表面均匀、无裂纹,与镁合金基底的界面结合良好;并且在此pH值下PA/HA复合涂层包覆镁合金样品的交流阻抗最大,自腐蚀电流密度最小,说明其耐蚀性最好。在SBF中,PA/HA复合涂层能够快速诱导磷灰石的生成,并显著提高镁合金基底的耐蚀性能。     

医用Mg-Zn-Ca-Mn合金在PBS模拟体液中的腐蚀行为

利用真空感应熔炼,采用金属模浇铸制备了Mg(100-x-y-z)-Znx-Cay-Mnz四元合金。使用光学显微镜、X射线衍射仪、扫描电镜及能谱仪对合金进行分析和表征。探讨了合金在PBS模拟体液中的腐蚀行为。结果表明,Ca、Zn及Mn原子的复合加入可显著细化合金的铸态显微组织;镁合金的腐蚀发生于晶粒内部,至晶界处终止;当加入2.0%的Zn和0.5%的Ca时,铸态合金的抗腐蚀性能最佳(平均腐蚀速率为0.77mm/a);当Zn、Ca含量均大于1%时,固溶时效态合金的腐蚀速率下降为铸态的1/2～1/4,表现出优异的耐蚀性;固溶时效处理可有效减少Mg2Ca相的体积分数,改善其分布,提高合金的耐蚀性能。     

Phosphating treatment and corrosion properties of Mg–Mn–Zn alloy for biomedical application

A phosphating treatment was applied to Mg–Mn–Zn alloy in order to improve the corrosion resistance. Surface morphology and phase constitute were observed and identified by SEM, EDS, SAXS, XRD and XPS. SEM observation showed that a rough and crystalline reaction layer was formed on the surface of Mg alloy. With the increasing of phosphating time, the layer became thicker and denser. It has been showed that the reaction layer was mainly composed of brushite (CaHPO₄ · 2H₂O). Small amount of Zn²⁺ was also detected by XPS and EDS. The corrosion resistance of the phosphated samples was measured by the electrochemical polarization and the immersion test in comparison with the bare alloy. The results manifested that the corrosion resistance of Mg alloy was improved by the phosphating treatment, and the corrosion resistance increased with the increase of the phosphating time within 50 min. Immersion tests showed that the phosphate layer could protect magnesium alloy from fast corrosion. The brushite layer has been transformed into hydroxyapatite (HA) during the immersion in the simulated body fluid (SBF) solution, which suggested the brushite layer could provide good biocompatibility.     

Properties of ultrafine-grained Mg-based composites modified by addition of silver and hydroxyapatite

In this study, hydroxyapatite and silver were added to Mg–1Zn–1Mn–0.3Zr alloy to fabricate ultrafine-grained metal matrix composites. Grain sizes of approximately 85?nm were recorded by atomic force microscopy for the Mg–1Zn–1Mn–0.3Zr–5 wt-% HA–1 wt-% Ag composite. The contact angles in water and simulated body fluid on the ultrafine-grained Mg–1Zn–1Mn–0.3Zr-based composites were determined. Following a hydrofluoric acid treatment, the surface wettability changed from hydrophilicity to hydrophobicity. The electrochemical test showed that the corrosion resistance of the fluoride-treated specimens was higher, when compared with the untreated samples. The Mg–1Zn–1Mn–0.3Zr–5 wt-% HA and Mg–1Zn–1Mn–0.3Zr–5?wt-% of HA–1 wt-% Ag composites modified with MgF₂ have a higher degree of biocompatibility, which makes them potential candidates for medical applications     

Development and evaluation of a magnesium–zinc–strontium alloy for biomedical applications — Alloy processing,microstructure, mechanical properties,and biodegradation

A new biodegradable magnesium–zinc–strontium (Mg–Zn–Sr) alloy was developed and studied for medical implant applications. This first study investigated the alloy processing (casting, rolling, and heat treatment), microstructures, mechanical properties, and degradation properties in simulated body fluid (SBF). Aging treatment of the ZSr41 alloy at 175 °C for 8 h improved the mechanical properties when compared to those of the as-cast alloy. Specifically, the aged ZSr41 alloy had an ultimate tensile strength of 270 MPa, Vickers hardness of 71.5 HV, and elongation at failure of 12.8%. The mechanical properties of the ZSr41 alloy were superior as compared with those of pure magnesium and met the requirements for load-bearing medical implants. Furthermore, the immersion of the ZSr41 alloy in SBF showed a degradation mode that progressed cyclically, alternating between pitting and localized corrosion. The steady-state average degradation rate of the aged ZSr41 alloy in SBF was 0.96 g/(m²·hr), while the pH of SBF immersion solution increased. The corrosion current density of the ZSr41 alloy in SBF solution was 0.41 mA/mm², which was much lower than 1.67 mA/mm² for pure Mg under the same conditions. In summary, compared to pure Mg, the mechanical properties of the new ZSr41 alloy improved while the degradation rate decreased due to the addition of Zn and Sr alloying elements and specific processing conditions. The superior mechanical properties and corrosion resistance of the new ZSr41 alloy make it a promising alloy for next-generation implant applications.     

镁-羟基磷灰石/聚乳酸复合材料的制备及表征

为改善羟基磷灰石(HA)/聚乳酸(PLA)复合材料降解后产生的局部酸性环境,提出Mg-HA/PLA复合材料的新体系,采用溶液共混法结合注塑工艺获得Mg-HA/PLA复合材料。采用扫描电镜、X射线衍射仪分析复合材料的显微相貌及物相组成,电子拉伸试验机测试复合材料的力学性能,模拟体液浸泡分析其降解特性。结果表明,采用溶液共混结合注塑工艺可以制备该复合材料;HA与Mg在PLA基体中未出现明显的团聚;HA、Mg与PLA三者保持各自物相;与5%(质量分数)HA/PLA复合材料相比,1.5%(质量分数)Mg添加对5%(质量分数)HA/PLA复合材料的力学性能影响不明显;Mg-HA/PLA复合材料浸泡4周后的pH值为7.41,而HA/PLA复合材料则为6.95。     

Microstructure,mechanical property,bio-corrosion and cytotoxicity evaluations of Mg/HA composites

Mg/HA (10 wt.%, 20 wt.% and 30 wt.%) composites were prepared by pure magnesium and hydroxyapatite (HA) powders using powder metallurgy (PM) method. The microstructure, mechanical property, corrosion and cytotoxicity of these Mg/HA composites were studied, with the bulk pure magnesium as control. The results showed that the main constitutional phases of Mg/HA composites were simply α-Mg and HA. The HA particulates distributed uniformly in Mg matrix for Mg/10HA composite, and few HA clustering occasionally spread over the Mg/20HA composite, whereas severe agglomeration of HA particulates could be seen for Mg/30HA composite. The yield tensile strength of Mg/10HA composite increased compared with that of the as-extruded bulk pure magnesium, yet the yield tensile strength, ultimate tensile strength and ductility of Mg/HA composites decreased with the further increase of HA content. The corrosion rate of Mg/HA composites increased with the increment of HA content. The cytotoxicity tests indicated that Mg/10HA extract showed no toxicity to L-929 cells, whereas Mg/20HA and Mg/30HA composite extracts induced significantly reduced cell viability.     

Influence of Heat Treatments on In Vitro Degradation Behavior of Mg‐6Zn Alloy Studied by Electrochemical Measurements

The influence of heat treatment on the in vitro degradation of Mg‐6Zn alloy is studied by electrochemical measurements. After solid‐solution treatment, the microstructure of the Mg‐6Zn becomes more homogeneous, along with an elevated charge‐transfer resistance in SBF and a reduced corrosion current density. After ageing treatment, the discrete intermetallic γ‐MgZn phase enhances the cathodic hydrogen evolution and impairs the corrosion resistance of the alloy. Galvanic cells are expected on ageing, but the ageing process makes the microstructure of the alloy homogeneous. Heat treatment alters the in vitro degradation behavior of Mg‐6Zn alloy and is applicable in adjusting the biodegradation rate.     

Microstructure,mechanical properties and corrosion behaviour of Al–Si–Mg alloy matrix/zircon and alumina hybrid composite

In the present study, the effect of reinforcement on microstructure, mechanical properties and corrosion behaviour of aluminium–silicon–magnesium (Al–Si–Mg) alloy matrix hybrid composites reinforced with varying amounts of zircon and alumina has been investigated. Hardness and room temperature compressive tests were performed on Al–Si–Mg alloy as well as composites. Hardness and compressive strength was found to be higher for composites containing 3.75?% ZrSiO₄?+?11.25?% Al₂O₃. Similarly, Al–Si–Mg alloy and its composites were studied for corrosion behaviour in 1 N HCl corrosive media. The weight loss of all the composites was found to decrease with time due to the formation of passive oxide layer on the sample surface. The results obtained indicate that composites exhibit superior mechanical properties and corrosion resistance compared to unreinforced alloy.     

Influence of Mg Addition on Graphite Particle Distribution in the Al Alloy Matrix Composites

Al alloy matrix composites reinforced with copper-coated graphite particle have been prepared by melt stirring process in this work. The effect of the addition of Mg on distribution of the graphite particles has been investigated. Scanning electron microscopy (SEM) was used to observe the micro-morphology of Al alloy matrix composites reinforced with graphite particles. Meanwhile, the content of graphite was analyzed in the different position of casting by dissolution method and the mechanical properties of the composites were detected. The results show that the content of graphite increase with increasing Mg content; the graphite particles distribute uniformly in the particle reinforced metal matrix composites (PMMC) with 0.6 wt pct Mg; however, the agglomeration of the graphite particles is observed obviously in the matrix when Mg content is more than 1.0 wt pct. In addition, the proper Mg addition amount is beneficial to enhance the mechanical properties of the graphite particles reinforced Al alloy matrix composites and the abrasion resistance of the materials due to a reduce friction coefficient.     

Initial stages of corrosion within Mg-Zn-Y-Zr alloy in 1 g/l NaCl solution

Corrosion behavior of as-cast and heat treated Mg-Zn-Zr-Y alloy was studied in 1 g/l NaCl solution. The as-cast alloy was the least resistant to pitting corrosion. Its Mg-Zn solid solution matrix was the structural constituent responsible for corrosion susceptibility due to the presence of Zn-lean regions. Homogenization of the Zn distribution within the matrix significantly increased the corrosion resistance of the alloy. Grain boundaries, which contain intermetallic phases, were resistant to corrosion attack, thus impeding corrosion propagation.     

Corrosion behavior of Al–60 vol.% SiCp composites in NaCl solution

In this study, corrosion behavior of pure Al and Al–4 wt.% Mg alloy matrix composites, comprising 60 vol.% SiC particles, has been investigated. Composites were produced by pressure infiltration technique at 750 °C. The corrosion tests were carried out in 3.5 wt.% NaCl environment up to 28 days. The weight loss of the composites increased with increasing duration time up to 3–5 days then remained constant. Scanning electron microscopy (SEM) analysis showed that Al–4 wt.% Mg alloyed matrix composite exhibited higher corrosion resistance than pure Al matrix composite although potentiodynamic polarisation measurements showed higher i_corr values of Al–4 wt.% Mg alloyed matrix composites than pure Al matrix composites. Experimental results revealed that precipitation of Mg₂Si as a result of reaction between Al–Mg alloy and SiC particle has a beneficial effect on corrosion resistance of Al–4Mg alloy matrix composites due to interruption of the continuity of the matrix channels within the pressure infiltrated composites.     

超声辅助制备β-磷酸三钙/Mg-Zn-Ca生物复合材料及性能

在生物Mg合金基体中添加β-磷酸三钙（β-TCP）颗粒可以调控其力学性能及腐蚀降解性能,满足人体不同植入部位的服役需求。本研究在机械搅拌铸造的基础上,采用超声方法对Mg基复合材料的熔体进行辅助处理,制备了β-TCP添加量为1%（质量比）、Zn含量为3%（质量比）、Ca含量为0.2%（质量比）的β-TCP/Mg-Zn-Ca可降解生物复合材料,对超声处理制备的β-TCP/Mg-Zn-Ca复合材料的显微组织、力学性能和腐蚀行为与未超声处理制备的β-TCP/Mg-Zn-Ca复合材料进行了对比研究。结果表明：超声处理可以细化β-TCP/Mg-Zn-Ca复合材料的显微组织,有利于β-TCP复合颗粒的均匀分散;β-TCP/Mg-Zn-Ca复合材料在模拟体液环境下的耐蚀性得到提高;其屈服强度、抗拉强度和伸长率分别为211.54 MPa、334.32 MPa和7.28%,与未超声处理的β-TCP/Mg-Zn-Ca复合材料相比,分别提高了8.44%、4.67%和17.99%。     

Quasicrystal-reinforced Mg alloys

The formation of the icosahedral phase (I-phase) as a secondary solidification phase in Mg–Zn–Y and Mg–Zn–Al base systems provides useful advantages in designing high performance wrought magnesium alloys. The strengthening in two-phase composites (I-phase + α-Mg) can be explained by dispersion hardening due to the presence of I-phase particles and by the strong bonding property at the I-phase/matrix interface. The presence of an additional secondary solidification phase can further enhance formability and mechanical properties. In Mg–Zn–Y alloys, the co-presence of I and Ca₂Mg₆Zn₃ phases by addition of Ca can significantly enhance formability, while in Mg–Zn–Al alloys, the co-presence of the I-phase and Mg₂Sn phase leads to the enhancement of mechanical properties. Dynamic and static recrystallization are significantly accelerated by addition of Ca in Mg–Zn–Y alloy, resulting in much smaller grain size and more random texture. The high strength of Mg–Zn–Al–Sn alloys is attributed to the presence of finely distributed Mg₂Sn and I-phase particles embedded in the α-Mg matrix.     

镁合金表面纳米二氧化铈/磷酸盐复合转化膜的制备及其防护性能

添加纳米颗粒可改善金属表面膜层的性能,但目前添加纳米颗粒改善镁合金表面磷化膜性能的报道较少。通过向磷化处理液中添加纳米二氧化铈(nano-CeO_2)颗粒在镁合金表面制备了一层纳米二氧化铈/磷酸盐复合转化膜,采用X射线衍射仪(XRD)、X射线光电子能谱(XPS)、电化学阻抗谱(EIS)和极化曲线等手段研究了添加nano-CeO_2颗粒对膜层成分和防护性能的影响,讨论了nano-CeO_2颗粒的作用机制。结果表明:复合转化膜的相成分为Zn_3(PO_4)_2·4H_2O、Zn_2Mg(PO_4)_2和CeO_2,在单组分磷化膜成分的基础上多出了CeO_2相。在硼酸缓冲溶液中,单组分磷化膜的膜层电阻(R_c)和低频阻抗值(R_(0.01 Hz))分别为561.74 kΩ·cm~2和938.11 kΩ·cm~2,而复合转化膜的R_c和R_(0.01 Hz)分别为2 428.98 kΩ·cm~2和3 985.61 kΩ·cm~2;与此同时,覆盖复合转化膜镁合金的腐蚀电流密度为4.05×10~(-7)A/cm~2,而覆盖单组分磷化膜镁合金的为8.38×10~(-6)A/cm~2,R_c和R_(0.01 Hz)的增大以及J_(corr)的减小说明复合转化膜的防护作用明显优于单组分磷化膜的防护作用。nano-CeO_2颗粒的作用机制主要归因于两个方面:第一,nano-CeO_2颗粒在处理液中的添加有利于磷酸盐晶核的形成;第二,nano-CeO_2颗粒作为一种不溶性固体粒子在膜层中的存在可以强化膜层的物理屏蔽效应。     

Fabrication and characterization of magnesium–fluorapatite nanocomposite for biomedical applications

Recent studies indicate that there is a high demand for magnesium alloys with adjustable corrosion rates, suitable mechanical properties, and the ability for precipitation of a bone-like apatite layer on the surface of magnesium alloys in the body. An approach to this challenge might be the application of metal matrix composites based on magnesium alloys. The aim of this work was to fabricate and characterize a nanocomposite made of AZ91 magnesium alloy as the matrix and fluorapatite nano particles as reinforcement. A magnesium–fluorapatite nanocomposite was made via a blending–pressing–sintering method. Mechanical, metallurgical and in vitro corrosion measurements were performed for characterization of both the initial materials and the composite structure. The results showed that the addition of fluorapatite nano particle reinforcements to magnesium alloys can improve the mechanical properties, reduce the corrosion rate, and accelerate the formation of an apatite layer on the surface, which provides improved protection for the AZ91 matrix. It is suggested that the formation of an apatite layer on the surface of magnesium alloys can contribute to the improved osteoconductivity of magnesium alloys for biomedical applications.     

Microstructure and corrosion properties of as sub-rapid solidification Mg–Zn–Y–Nd alloy in dynamic simulated body fluid for vascular stent application

Magnesium alloy stent has been employed in animal and clinical experiment in recent years. It has been verified to be biocompatible and degradable due to corrosion after being implanted into blood vessel. Mg–Y–Gd–Nd alloy is usually used to construct an absorbable magnesium alloy stent. However, the corrosion resistant of as cast Mg–Y–Gd–Nd alloy is poor relatively and the control of corrosion rate is difficult. Aiming at the requirement of endovascular stent in clinic, a new biomedical Mg–Zn–Y–Nd alloy with low Zn and Y content (Zn/Y atom ratio 6) was designed, which exists quasicrystals to improve its corrosion resistance. Additionally, sub-rapid solidification processing was applied for preparation of corrosion-resisting Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys. Compared with the as cast sample, the corrosion behavior of alloys in dynamic simulated body fluid (SBF) (the speed of body fluid: 16 ml/800 ml min⁻¹) was investigated. The results show that as sub-rapid solidification Mg–Zn–Y–Nd alloy has the better corrosion resistance in dynamic SBF due to grain refinement and fine dispersion distribution of the quasicrystals and intermetallic compounds in α-Mg matrix. In the as cast sample, both Mg–Zn–Y–Nd and Mg–Y–Gd–Nd alloys exhibit poor corrosion resistance. Mg–Zn–Y–Nd alloy by sub-rapid solidification processing provides excellent corrosion resistance in dynamic SBF, which open a new window for biomedical materials design, especially for vascular stent application.     

Effect of creep-aging processing on corrosion resistance of an Al–Zn–Mg–Cu alloy

Creep-aging forming, combining both the aging treatment and forming process, has recently drawn much attention of researchers. In this study, the effects of creep-aging processing on the corrosion resistance of an Al–Zn–Mg–Cu alloy are studied. Results show that the corrosion resistance of the studied Al–Zn–Mg–Cu alloy is sensitive to creep-aging processing parameters (creep-aging temperature and applied stress). With the increase of creep-aging temperature, the corrosion resistance first increases and then decreases. Increasing the applied stress can deteriorate the electrochemical corrosion resistance and improve the exfoliation corrosion resistance. The creep-aging processing can change the size and distribution of precipitates in the aluminum matrix, which significantly affects the corrosion resistance. The discontinuous grain boundary precipitates and narrow precipitate-free zones can enhance the corrosion resistance.