Surface characterization and cytocompatibility evaluation of silanized magnesium alloy AZ91 for biomedical applications

Abstract

Mg alloys with high Al contents have superior corrosion resistance in aqueous environments, but poor cytocompatibility compared to that of pure Mg. We have silanized the cast AZ91 alloy to improve its cytocompatibility using five different silanes: ethyltriethoxysilane (S1), 3-aminopropyltriethoxysilane (S2), 3-isocyanatopyltriethoxysilane (S3), phenyltriethoxysilane (S4) and octadecyltriethoxysilane (S5). The surface hydrophilicity/hydrophobicity was evaluated by water contact angle measurements. X-ray photoelectron analysis was performed to investigate the changes in surface states and chemical composition. All silane reagents increased adsorption of the albumin to the modified surface. In vitro cytocompatibility evaluation revealed that silanization improved cell growth on AZ91 modified by silane S1. Measurement of the concentration of Mg²⁺ ions released during the cell culture indicated that silanization does not affect substrate degradation.     

AZ91D镁合金超疏水膜层的制备及其表征

采用简单易行的化学刻蚀方法,通过硝酸刻蚀、化学镀银和硬脂酸自组装改性处理,在AZ91D镁合金表面上成功制备出了超疏水膜层,进一步解释了该制备工艺的化学反应机理。利用扫描电子显微镜和视频光学接触角测量仪对AZ91D镁合金表面超疏水膜层的微观形貌和润湿性能进行了表征,利用能谱仪和光谱仪测定了膜层的表面化学组成。结果显示,釆用上述方法处理后的AZ91D镁合金表面呈现出良好的疏水性,水滴在试样表面的表观接触角为153°,滚动角为4°。     

消失模铸造AZ91镁合金的研究

研究了ZA91镁合金消失模铸造时铸件的厚度,位置和真空度对铸件质量,组织及力学性能的影响,真空度是决定铸件质量的一个关键的工艺因素,无真空时浇注铸件易产生浇不足缺陷,但真空度过大又会导致形成粘砂和气孔等缺陷,真空浇注射明显细化组织,但真空度进一步增大时细化效果野 不明显,铸件显微组织具有很大的壁厚效应,然 位置对组织的影响与是否采用抽真空措施有关,铸件壁厚较小时,铸件的力学性能总体较差,断裂源自Mg/Mg17Al12界面、且主要是以解决理形式的脆性断裂。     

Damping behaviour of AZ91 magnesium alloy with cracks

The amplitude-dependent damping of a commercial magnesium cast alloy AZ91 was determined at room temperature by measurement of the logarithmic decrement of free decaying vibrations of bending beams clamped at one side. In order to generate cracks in the specimens they were subjected to (1) isochronal heat treatments for 1 h at temperatures above 400 °C with succeeding quenching in cold water and (2) controlled fatigue bending loading in the same equipment also used for the damping measurements. After both treatments, the amplitude-dependent damping curves show a maximum for strains 10⁻⁵ to 10⁻³, which can be correlated with the presence of cracks and can be explained by a simple rheological model based on crack damping. This maximum is enhanced when the number of loading cycles or the quenching temperature is increased which can be explained by crack nucleation. Crack growth with increasing number of loading cycles shifts the maximum to lower strains.     

Corrosion behavior of AZ91 magnesium alloy in dilute NaCl solutions

The corrosion behavior of AZ91 magnesium alloy in dilute NaCl solutions was studied using electrochemical measurements, whereby a corrosion map in terms of electrode potential and chloride concentration [Cl⁻] was obtained. AZ91 alloy exhibited the corrosion and passivation zones in dilute NaCl solutions. The passivation zone became narrow with increasing [Cl⁻]. The values of open-circuit potential were in the passivation zone when the [Cl⁻] was less than 0.5 mol/L. XRD patterns showed the presence of the Mg(OH)₂, Mg₅(CO₃)₄(OH)₂·8H₂O and MgO phases in the corrosion product, whereas the latter two phases found in the passive film.     

AZ91D镁合金阳极氧化与热扩散渗铝复合膜层的研究

将阳极氧化与热扩散相结合对AZ91D镁合金表面进行低温渗铝处理,利用扫描电镜、光学显微镜和X射线衍射仪对所得膜层的形貌、相结构及耐腐蚀性能进行了研究,并对复合膜层改善镁合金基体耐腐蚀性能的过程进行了分析.研究表明,该复合膜层是由MgO和金属间化合物Mg17Al12以及被γ相(Mg17Al12)包裹住的α-Mg晶粒共同组成;AZ91D镁合金表面的阳极氧化和热扩散渗铝复合膜层能显著提高镁合金基体材料的耐腐蚀性能.     

Simulation and experimental investigation of FSP of AZ91 magnesium alloy

A thermo-mechanical simulation of the friction stir processing (FSP), using the DEFORM 3D software based on Lagrangian implicit, was developed and verified by the experimental results. Simulation can successfully predict the temperature and effective strain distributions. Material flow around the tool pin was examined using the point tracking. It was found that the major part of material flow occurs at the advancing side, and consequently, stirred zone (SZ) stretches toward the advancing side. However, material at the retreating side moves slightly in backward direction. The material deformation and the peak temperature influence on the microstructural characters and can determine the width of SZ. Based on the simulation, effective strain and temperature histories of material around the tool pin were also calculated. The amount of effective strain and peak temperature required for recrystallization at the advancing and retreating sides as well as at the bottom of SZ was determined. Therefore, the width of SZ can be predicted by the simulation.     

The effect of PVD coatings on the corrosion behaviour of AZ91 magnesium alloy

In this study, multilayered AlN (AlN + AlN + AlN) and AlN + TiN were coated on AZ91 magnesium alloy using physical vapour deposition (PVD) technique of DC magnetron sputtering, and the influence of the coatings on the corrosion behaviour of the AZ91 alloy was examined. A PVD system for coating processes, a potentiostat for electrochemical corrosion tests, X-ray difractometer for compositional analysis of the coatings, and scanning electron microscopy for surface examinations were used. It was determined that PVD coatings deposited on AZ91 magnesium alloy increased the corrosion resistance of the alloy, and AlN + AlN + AlN coating increased the corrosion resistance much more than AlN + TiN coating. However, it was observed that, in the coating layers, small structural defects e.g., pores, pinholes, cracks that could arise from the coating process or substrate and get the ability of protection from corrosion worsened were present.     

AZ91D镁合金托弹板半固态触变模锻研究

为了掌握半固态触变模锻中工艺参数对成形零件的微观组织和力学性能的影响规律,借助拉伸试验机和金相显微镜对AZ91D镁合金托弹板的半固态触变模锻过程进行了研究.AZ91D镁合金半固态坯料分别采用传统SIMA法和新SIMA法制备.结果表明:压力对托弹板零件的充型过程有很大影响,当压力为500 kN,托弹板零件充型不满;当压力为2000 kN,托弹板零件充型良好.坯料加热温度和保温时间对托弹板零件的力学性能有一定影响.当压力为2000 kN,模具预热温度为450 ℃,坯料在545 ℃保温20 min时,新SIMA法制备的半固态坯半固态触变模锻成形的托弹板零件获得最佳的力学性能.与传统SIMA法相比,新SIMA法制备的半固态坯成形的托弹板零件的室温力学性能和100℃的高温力学性有很大提高.     

Damping properties of porous AZ91 magnesium alloy reinforced with copper particles

Abstract

The well distributed open porous AZ91 magnesium alloy reinforced with copper particles was successfully prepared through powder metallurgy route based on space holder method. Its damping properties were characterised by internal friction and the internal friction measurement in a temperature range from room temperature to 100°C was performed by a multifunction internal friction apparatus. Experimental results revealed that the damping capacity of the porous AZ91 magnesium alloy was increased as a result of the addition of copper particle and the increase was further enhanced with increasing volume fraction of copper particle. Attempt is performed to correlate the increase in damping with the microstructural change arising due to the addition of copper particles. It was suggested that the increase should be related to the appearance of plastic zone and thus an increase in dislocation density at the matrix particles interfaces.     

AZ91D镁合金化学镀Ni-P/Ni-W-P双层镀层研究

为了提高镁合金的耐磨耐蚀性,研究了一种镁合金直接化学镀Ni-P/Ni-W-P双层镀层的方法.采用扫描电镜(SEM)和X-射线衍分析射仪(XRD)分析了镀层的微观结构.对镀层进行了极化曲线分析,并进行了盐酸腐蚀试验和结合力试验.结果表明,该复合镀层组织致密无孔,具有较高的显微硬度和高耐蚀性.镀层硬度可达622HKV,试样在10%的HCl溶液中可保持近3h不腐蚀基体,对镁合金起到很好的保护作用.     

AZ91及AZ91-Y合金复合干摩擦性能的对比

为了探究AZ91镁合金的复合干摩擦行为,以未淬火45钢为摩擦副,在不同载荷下(100,200,300 N),开展AZ91及Y含量为1.0%(质量分数)合金的复合干摩擦实验。采用OM,XRD,SEM等观察合金的磨损形貌并分析磨损机理。结果表明:增加法向载荷,两试样复合磨损率线性增加但摩擦因数却逐渐减小;Al 2Y硬质颗粒可细化晶粒、弱化相界面开裂倾向以提高AZ91-Y合金耐磨性。100,300 N法向载荷下,AZ91-Y合金主要磨损机制分别为磨粒磨损和剥离磨损,与基体(AZ91)一致,其磨损率分别降低了21.7%和5.9%。     

Superplasticity and grain boundary sliding in rolled AZ91 magnesium alloy at high strain rates

The superplastic deformation characteristics and microstructure evolution of the rolled AZ91 magnesium alloys at temperatures ranging from 623 to 698 K (0.67–0.76 T_m) and at the high strain rates ranging from 10⁻³ to 1 s⁻¹ were investigated with the methods of OM, SEM and TEM. An excellent superplasticity with the maximum elongation to failure of 455% was obtained at 623 K and the strain rate of 10⁻³ s⁻¹ in the rolled AZ91 magnesium alloys and its strain rate sensitivity m is high, up to 0.64. The dominant deformation mechanism in high strain rate superplasticity is still grain boundary sliding (GBS), which was studied systematically in this study. The dislocation creep controlled by grain boundary diffusion was considered the main accommodation mechanism, which was observed in this study.     

Hot cracking in tungsten inert gas welding of magnesium alloy AZ91D

Abstract

Plates of 3–5 mm in thickness were extracted from an AZ91D ingot and then butt joints of the plates were produced using tungsten inert gas (TIG) welding method. The TIG arc was also used to deposit welding beads on some of the thin plates. No cracking was found in the butt joints. However, hot cracking was always observed to propagate from the heat affected zone (HAZ) under the welding bead into the weld metal right after a welding bead was deposited on the thin plate. Metallographic and fractographic evidence was obtained to show that the hot cracking is 'liquation cracking' in the partially melted HAZ under the high thermal stresses. In the butt joints, the weld metal has the finest grains, highest strength and best ductility, and the HAZ was found to be the 'weakest link'.     

变形的AZ91D镁合金半固态等温压缩的力学行为

为了了解等径道角挤压(ECAE)的AZ91D镁合金在半固态压缩变形中的力学特征,利用半固态温压缩实验、Gleeble1500实验机和金相显微镜对其在半固态压缩变形中的力学行为进行了研究.结果表明:ECAE的AZ91D镁合金在半固态等温压缩中变形由固相晶粒本身的塑性变形、液相包围着固相晶粒的滑动和转动构成;该材料的真应力-真应变曲线由应力激增阶段、应力下降阶段、稳态阶段和应力增加阶段组成;随保温时间的增加或变形温度的升高,获得相同应变量的真应力明显下降,稳态应力和峰值应力也明显下降;随应变速率的增加,稳态应力增加.     

Study on microstructure of squeeze casting AZ91D alloy

Abstract

The present paper reports the investigation of the microstructure distribution of squeeze cast AZ91D alloy. The microstructure of squeeze cast AZ91D alloy is not uniform and is composed of four zones, which are chilled layer, segregation zone, pressured crystallisation area and hot spot area respectively. Moreover, in the pressured crystallisation area, the microstructure sequence in the transverse section from the outside to the inside could be divided into four sublayers, such as fine equiaxial dendrite area, dendrite area with a high directivity, confusion dendrite area and disorder dendrite area. The volume fraction of the intermetallic compound Mg₁₇Al₁₂ also varied with the location. The volume fraction of Mg₁₇Al₁₂ in the pressured crystallisation area is the largest except in the segregated zone.     

AZ91D镁合金锌系磷化膜成膜机理和生长过程的研究

以磷酸盐化学转化膜为研究体系,采用SEM、XRD、OCP等分析方法及检测手段,研究AZ91D镁合金系磷酸盐化学转化膜的成膜机理、膜层结构及生长过程。研究发现AZ91D镁合金在磷化液中成膜过程分5个阶段:初始成核(1～5s)、基体快速溶解(5～60s)、晶体快速生长(1～2min)、膜层稳态生长(2～10min)和膜层沉积溶解平衡阶段(10min以后)。AZ91D镁合金表面的磷酸盐晶核的形成并非在金属进入溶液的最初时刻一次形成,是分批形成。最先形成的晶核逐渐长大,新的晶核不断生成,磷酸盐晶粒对其表面的覆盖度逐渐增大,直至各个晶粒逐渐长大相互接界,将其表面完全覆盖,结晶过程结束。晶核的形成未优先发生在基体金属的晶界上,随着晶核的生长和外延而形成磷化膜。     

Surface coatings for improving the corrosion resistance and cell adhesion of AZ91D magnesium alloy through environmentally clean methods

Two different coatings, Mg-Al hydrotalcite and aragonite (CaCO₃), were produced on die-cast AZ91D Mg alloy (Mg-9wt.%Al-1wt.%Zn) through environmentally clean methods. The corrosion resistance and human mesenchymal stem cell adhesion properties of the coatings on AZ91D were investigated. Results showed that through environmentally clean methods, both Mg-Al hydrotalcite and aragonite CaCO₃ surface coatings could be produced on AZ91D surfaces. These coatings increased the corrosion potential and polarization resistance and decreased the corrosion rate of AZ91D in simulated body fluid. Both surface coatings also improved stem cell spreading and interaction in culture. Further long-term animal testing is suggested before these surface coatings can be recommended for use in clinical applications.     

乙醇胺添加剂对AZ91D镁合金表面磷化膜耐蚀性能的影响研究

以磷酸盐化学转化膜为研究体系,采用动电位极化和交流阻抗分析方法及检测手段,研究乙醇胺添加剂及其浓度对AZ91D镁合金磷化膜耐蚀性能的影响.研究发现,(1)乙醇胺(MEA)作为添加剂可有效改善AZ91D镁合金表面磷化膜的耐蚀性能.在MEA添加量为1.2g/L时,磷化膜的耐蚀性最好.添加乙醇胺1.2g/L时制备的磷化膜,在3.5%(质量分数)NaCl溶液中的耐蚀性能比AZ91D镁合金基体提高了10倍;(2)MEA浓度在0.4～1.2g/L时,磷化膜的R_(ct)随MEA浓度增加成线性增长关系.MEA浓度1.2g/L时达到最大值.磷化膜的R_p在MEA浓度为1.2g/L时达到最高值.当MEA浓度继续增加时,R_p明显下降.MEA浓度控制在0.8＜C_(MEA)＜1.6g/L时获得的磷化膜的耐蚀性能最好.     

AZ91镁合金抗高温蠕变性能的研究和发展

综述了国内外AZ91镁合金抗高温蠕变性能的研究进展,重点讨论了其蠕变机理及提高其抗高温蠕变性能的方法,对AZgl镁合金抗高温蠕变性能的研究方向提出了一些看法和展望.