AZ31镁合金表面含纳米羟基磷灰石微弧氧化涂层的制备及性能研究

目的改善AZ31镁合金的耐腐蚀性能及生物活性。方法使用微弧氧化技术,分别在以六偏磷酸钠为主盐的电解液和以六偏磷酸钠为主盐、以纳米羟基磷灰石(HA)为添加剂的电解液中,在AZ31镁合金表面制备了微弧氧化涂层。通过扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)表征了涂层的微观形貌、元素特征和相组成。通过电化学方法和浸泡实验考察了涂层的耐蚀性。通过细胞实验评价了两种涂层的细胞相容性。结果电解液中的HA可以进入到微弧氧化涂层中,含HA的微弧氧化涂层较不含HA的更致密,且有封孔现象。电化学方法及浸泡实验结果表明,含HA的微弧氧化涂层的耐腐蚀性能更好。细胞表面粘附实验和细胞增殖实验也表明,经表面纳米HA微弧氧化处理后的AZ31镁合金生物相容性更好,且对MC3T3-E1细胞的增殖有促进作用。结论六偏磷酸钠电解液中添加纳米HA,可以在AZ31镁合金表面制备出含HA的微弧氧化涂层,且其耐腐蚀性能和生物活性均优于不含HA的微弧氧化膜。     

等离子体电解氧化膜的工艺优化及耐腐蚀性能评价

对镁合金等离子体电解氧化膜的表面制备工艺进行了研究.采用正交设计法优化实验方案,对最佳工艺条件下制备的氧化膜的微观形貌、相组成进行了研究;采用点滴腐蚀、动电位极化曲线、循环阳极极化曲线、电化学阻抗谱及浸泡腐蚀试验对AZ31镁合金及等离子体电解氧化膜的耐腐蚀性能进行了综合评价.结果表明,制备的等离子体电解氧化膜的最佳工艺为KOH 4g/L、硅酸盐20 g/L、氧化电压300 V、氧化时间30 min;氧化膜主要成分为MgSiO3和Mg2SiO4,经过等离子体电解氧化之后其显微硬度、耐点滴腐蚀、耐均匀腐蚀和耐点腐蚀性能较AZ31镁合金均有较大提高.     

SiCw/AZ91镁基复合材料的微弧氧化行为及涂层的耐腐蚀性能

采用微弧氧化表面处理技术在SiCw/AZ91镁基复合材料表面制备保护性涂层.通过与AZ91镁合金对比,研究镁基复合材料的微弧氧化行为及其形貌特征,并采用电化学方法评价了微弧氧化涂层的耐腐蚀性能.结果表明,SiC晶须的存在影响了基底材料表面阻挡层的形成,使复合材料的微弧氧化行为不同于基体合金.与合金相比,在恒电流模式下进行微弧氧化的过程中复合材料的电压随时间的演变趋势不够理想,而且在相同工艺条件下复合材料的起弧时间比合金要长.复合材料在微弧氧化过程中偶尔会出现烧蚀现象.虽然SiC晶须会影响复合材料表面涂层的形成,微弧氧化处理仍然能够增强镁基复合材料的耐腐蚀性能,使其自腐蚀电位提高,腐蚀电流降低.当采用恒压模式制备涂层时,涂层耐腐蚀性能随电压的提高而增强.     

低温超音速火焰喷涂铝-微弧氧化复合膜的制备与性能研究

先采用低温超音速火焰喷涂技术在AZ91D镁合金表面沉积一层致密的Al涂层,再采用微弧氧化技术进行微弧氧化处理,进而获得复合涂层。对热喷涂铝涂层微弧氧化的成膜过程、氧化膜微观结构和成分、复合涂层的耐腐蚀性能等进行了研究,并与在2024铝合金及AZ91D镁合金表面的微弧氧化过程和氧化膜层进行了对比。结果表明:在Al涂层上微弧氧化形成的微弧氧化膜呈多孔珊瑚状,相结构主要为γ-Al2O3,没有微裂纹产生,其微弧氧化过程与2024铝合金的微弧氧化大致相同;复合涂层具有良好的抗盐雾腐蚀性能,可显著提高镁合金的耐蚀性。     

脉冲频率对镁合金微弧氧化膜层在仿生液中耐蚀性的影响

研究了微弧氧化过程中不同电源脉冲频率下制备的膜层在仿生液中的电化学腐蚀行为。对膜层及腐蚀产物的微观组织,孔隙率,腐蚀形貌及相组成进行了分析。采用动电位极化曲线(Tafel)和电化学阻抗谱(EIS)法对膜层的耐腐蚀性能进行评价。结果表明,脉冲频率对AZ31镁合金微弧氧化膜层的耐蚀性有重要影响,随着频率的增加,腐蚀电流密度减小,而电化学阻抗增大。因此在本研究范围内,频率3000 Hz下制备的微弧氧化膜层具有最强的耐腐蚀性能。     

正向电压对镁合金微弧氧化膜层相结构的影响

采用微弧氧化技术,以30g/L的磷酸钠为电解液,利用系统的XRD手段研究了正向电压对AZ31镁合金表面微弧氧化膜层不同厚度的相组成,计算出晶粒尺寸、晶面间距和残余应力的分布规律.结果表明:电压不同膜层中各深度相的衍射峰强度、相组成和结晶度都不同,其中Mg3(PO4)2 (200)峰的晶粒尺寸随电压增加而变粗,且同一电压制备的膜层在同一晶向不同厚度的晶粒尺寸不一样,其值呈至膜层表面距离减小而减小,晶面间距也呈减小趋势;MgO相组成的涂层残余应力处于拉应力,其值随电压增加而显著减小.     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

镁合金表面磷酸盐转化膜研究

研究了以Zn(H2PO4)2为主盐的溶液在AZ31和AZ61镁合金表面进行磷酸盐转化膜处理的工艺.通过正交试验确定了溶液成分和工艺参数,采用光学显微镜、扫描电镜、能谱仪、X射线衍射仪等分析了镁合金磷酸盐转化膜的结构和组成,利用中性盐雾试验等研究了膜的耐蚀性.讨论了镁合金表面磷酸盐转化反应过程以及转化膜可能的耐蚀原理.结果表明,镁合金磷酸盐转化膜结晶细致,微观表面粗糙,膜的主要成分是[Zn3(PO4)2·4H2O]·[Zn2Mg(PO4)2·4H2O],转化膜与涂层的结合力可以达到1级,涂层经3%盐水腐蚀360 h无明显变化,经中性盐雾腐蚀144 h无明显变化.     

AZ91D镁合金微等离子体氧化陶瓷层的耐腐蚀性研究

采用微等离子体氧化方法在AZ91D镁合金表面制备陶瓷层.利用扫描电镜、X射线分析陶瓷层微观组织结构,通过盐雾试验方法测试处理过的AZ91D镁合金耐腐蚀性能.结果表明,AZ91D镁合金经过微等离子体表面氧化处理后,陶瓷层由表面的疏松层和内部致密层所组成,疏松层里有较多的孔隙;致密层孔隙较少且与基体结合牢固;微等离子体氧化陶瓷膜的相结构主要由MgAl2Si3O12,β-Mg2SiO4,(Mg4Al14)(Al4Si2)O20等含硅的尖晶石型氧化物和δ-MgAl28O4等Mg,Al复合氧化物构成.AZ91D镁合金经微等离子体氧化处理后,基体被氧化膜覆盖,使其抗腐蚀性能显著提高,试样表面有陶瓷膜的AZ91D镁合金在盐雾试验中的腐蚀速率是AZ91D镁合金腐蚀速率的1/8.61.     

La(NO3)3与Ce(NO3)3比例对AZ31镁合金微弧氧化涂层显微硬度与耐磨性能的影响

针对镁合金耐磨性偏低的问题,利用微弧氧化技术在AZ31镁合金表面制备陶瓷涂层,探究微弧氧化电解液中添加La(NO_3)_3与Ce(NO_3)_3比例对AZ31镁合金微弧氧化(MAO)涂层显微硬度以及摩擦因数的影响。结果表明:AZ31镁合金微弧氧化涂层主要由MgO、MgSiO_3和MgSiO_4等相组成,未检测到原始添加的La和Ce等氧化物相。La(NO_3)_3与Ce(NO_3)_3添加能够降低镁合金涂层表面的微孔尺寸。随着电解液中La(NO_3)_3与Ce(NO_3)_3的添加比例增加,显微硬度呈现出先增加后降低的趋势。与未添加稀土复合盐相比,电解液添加稀土盐后微弧氧化涂层的显微硬度有所提高。添加La(NO_3)_3与Ce(NO_3)_3不同比例,涂层表面粗糙度在6.1～7.6μm范围内变化,相比未添加稀土盐获得涂层的粗糙度降低约2～3μm。电解液中添加La(NO_3)_3与Ce(NO_3)_3复合盐后,所获得的微弧氧化涂层的摩擦因数降低。     

Characterization and corrosion behavior of ceramic coating on magnesium by micro-arc oxidation

In this study, the commercial pure magnesium was coated in different aqueous solutions of Na₂SiO₃ and Na₃PO₄ by the micro-arc oxidation method (MAO). Coating thickness, phase composition, surface and cross sectional morphology and corrosion resistance of coatings were analyzed by eddy current method, X-ray diffraction (XRD), scanning electron microscope (SEM) and tafel extrapolation method, respectively. The average thickness of the coatings ranged from 52 to 74 μm for sodium silicate solution and from 64 to 88 μm for sodium phosphate solution. The dominant phases on the coatings were detected as spinal Mg₂SiO₄ (Forsterite) and MgO (Periclase) for sodium silicate solution and Mg₃(PO₄)₂ (Farringtonite) and MgO (Periclase) for sodium phosphate solution. SEM images reveal that the coating is composed of two layers as of a porous outer layer and a dense inner layer. The corrosion results show the coating consisting Mg₂SiO₄ is more resistant to corrosion than that containing Mg₃(PO₄)₂.     

Effects of applied voltage on the microstructure and properties of hydroxyapatite bioceramic coatings formed on Ti7Cu5Sn titanium alloy by micro-arc oxidation

The effects of the applied voltage on the morphology, composition and corrosion behaviour of Ti7Cu5Sn coated were investigated. At applied voltages lower than 250?V, the composite coatings consist of anatase-TiO₂, rutile-TiO₂, DCPD(CaHPO₄·2H₂O) and a small amount of amorphous calcium phosphate phase. When the applied voltage is increased, the ceramic coatings transform from DCPD (CaHPO₄·2H₂O) to HA (Ca₁₀(PO₄)₆(OH)₂, 300?V), and new phases of Ca₂P₂O₇, CaTiO₃ and TCP(Ca₃(PO₄)₂) form at 350?V. The passive current densities at body potential are one order of magnitude lower than that of the uncoated sample, indicating better corrosion resistance. The MAO film is a tri-layer system: a compact inner layer, a mesosphere porous oxide layer, and an outer layer.     

Anti-corrosion microarc oxidation coatings on SiCP/AZ31 magnesium matrix composite

The corrosion-resistant ceramic coatings up to 80 μm thick were fabricated on SiC_P/AZ31 magnesium matrix composite by microarc oxidation (MAO) technique in Na₃PO₄ + KOH + NaF solution. The microstructure, composition and phase constituent of ceramic coatings were analyzed by SEM and XRD, and the electrochemical corrosion behaviour of coatings was evaluated by the electrochemical polarization method. The thicker coating is compact and displays a good adhesion to the composite substrate. The ceramic coatings consist of MgO, Mg₂SiO₄, MgF₂, Mg₃(PO₄)₂, furthermore, a few residual SiC phases were also found in the coatings by means of SEM observation and EDX analysis. Most of SiC reinforced particles in the oxidized composite substrate have transformed into the oxides under microarc discharge sintering, but a few residual SiC reinforcements in the MAO coatings have not disrupted the continuity of coatings. So the corrosion resistance of the SiC_P/AZ31 composite is greatly improved by MAO surface treatment, however, the corrosion resistance of coated composite also depends on the coating thickness.     

Investigation of wear and corrosion resistance of nanocomposite coating formed on AZ31B Mg alloy by plasma electrolytic oxidation

Ceramic-WC coatings were prepared on AZ31 B Mg alloy by plasma electrolytic oxidation (PEO) from a phosphate based bath containing suspended tungsten carbide nanoparticles at various process times. Scanning electron microscope results indicated that increase of coating time and incorporation of tungsten carbide into the ceramic coating during the PEO process led to a decrease in the number and diameter of coating pores. Phase analysis showed that the nanocomposite coating was composed of MgO, Mg₃(PO₄)₂ and WC. Tribological properties and corrosion behaviour of uncoated AZ31 B Mg alloy and ceramic coatings were evaluated using a pin-on-disc tribometer and potentiodynamic polarisation technique in 3.5% NaCl solution, respectively. The wear and electrochemical tests showed that wear and corrosion resistance of ceramic-WC nanocomposite coatings were better than ceramic only ones. In addition, wear and corrosion behaviour of coatings improved with increasing the coating time.     

Corrosion characterization of microarc oxidation coatings formed on Mg–7Li alloy

Ceramic coatings with thickness of 27 µm were fabricated on Mg–7Li alloy in Na₂SiO₃–C₆H₁₈O₂₄P₆ solution by microarc oxidation (MAO). The morphology and phase composition of MAO coatings were characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD). The corrosion behavior of the bare and MAO coated Mg–7Li alloy was investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Results showed that the MAO coatings were composed of MgO, Li₂O, and Mg₂SiO₄, and there existed some micropores on the coating surface with a diameter of 3–20 µm. The corrosion potential (E_corr) and corrosion current density (I_corr) of the MAO coated alloy were about ?1.4761 V and 7.204 × 10^?7 A/cm², respectively. The E_corr of the MAO coated alloy increased by 109.6 mV and its I_corr decreased by three orders compared with that of the bare Mg–7Li alloy. The EIS plots indicated that the impedance of the MAO coated alloy was 15 times higher than that of the bare alloy. The fitting parameters showed that the resistance of the MAO coatings was far greater than that of the bare alloy. The dense intermediate layer and the transition layer of the MAO coatings acted as a barrier to hinder the proceeding of solution permeation, remarkably improving the corrosion resistance of the Mg–7Li alloy.     

纯Ti表面微弧氧化-碱热处理仿生陶瓷膜的制备及耐蚀性

采用微弧氧化-碱热处理在纯Ti表面制备了含有羟基磷灰石(HA)的仿生陶瓷膜。利用SEM,XRD和电化学工作站等手段研究了膜层的形貌、物相及其耐蚀性。结果表明:在乙酸钙-磷酸二氢钙电解液体系中微弧氧化(MAO),纯Ti表面形成一层含Ca和P的TiO2多孔陶瓷膜。经水热处理后,膜层表面的孔洞变小、致密性增加,膜层中还出现了鳞状、层片状以及针棒状的HA。在Hank's模拟体液中,MAO膜和微弧氧化-碱热处理(MAOAH)膜均表现出较好的耐蚀性。MAO膜经模拟体液腐蚀后,形成了缺钙型HA(Ca8.86(PO4)6(H2O2)2)和CaTiO3;而模拟体液中的阴离子与MAOAH膜层的氧化物作用使膜层孔洞直径和深度增加。     

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。     

Duplex-layered manganese phosphate conversion coating on AZ31 Mg alloy and its initial formation mechanism

A duplex-layered phosphate conversion coating was obtained on AZ31 Mg alloy by substituting NaF bath with a citric bath. The morphology, composition and corrosion resistance of the coating were investigated using SEM, EDS, SPM and electrochemical methods. A three-stage mechanism for initial formation of the coating was proposed: Dissolution of the loose oxide film and deposition of Mg₃(PO₄)₂ and AlPO₄, formation of a composite intermediate layer of Mg₃(PO₄)₂, AlPO₄ and Mg(OH)₂, and deposition of manganese phosphate nuclei followed by growth and lamination of the nuclei. The nuclei preferentially deposit at the Al–Mn phase surface and near the grain boundary.     

Formation of dicalcium phosphate dihydrate on magnesium alloy by micro-arc oxidation coupled with hydrothermal treatment

A layer containing dicalcium phosphate dihydrate (DCPD) and β-Ca₃(PO₄)₂ was prepared on magnesium alloy by hydrothermal treatment of micro-arc oxide (MAO) layer. The biocorrosion resistance of the oxide layers before and after hydrothermal treatment was analyzed by anodic polarization and electrochemical impedance spectroscopy (EIS) in Hank’s solution. The prepared MAO layers consisted mainly of MgO and MgAl₂O₄, and Ca and P inside the oxide layers existed with amorphous phase. Hydrothermal treatments not only made the amorphous Ca and P change into DCPD and β-Ca₃(PO₄)₂ crystals, but also improved the biocorrosion resistance of magnesium alloys, especially the pitting corrosion resistance.     

Formation of bioactive anticorrosion coatings on resorbable implants by plasma electrolytic oxidation

Calcium phosphate coatings (Ca/P = 1.61) containing magnesium oxide MgO and hydroxyapatite Ca₁₀(PO₄)₆(OH)₂ accelerating the growth of bone tissue have been prepared by the method of plasma electrolytic oxidation (PEO) on MA8 magnesium alloy. The phase and element compositions, morphology, and anticorrosion properties of coatings were investigated. Such PEO layers were found to essentially reduce the corrosion rate of magnesium alloy (polarization resistance being increased by two orders). This makes it possible to consider the formed PEO coatings as likely anticorrosion layers for medical bioresorbable implants.