AZ91D压铸镁合金微弧氧化膜层的显微硬度分析

为了研究压铸镁合金AZ91D微弧氧化膜层显微硬度,在三种溶液及不同电参数条件下制备了微弧氧化膜层,分析了脉冲频率、占空比、电压、溶液成分及其电导率等参数对膜层显微硬度的影响.试验结果表明,镁合金微弧氧化处理可使其表面硬度大幅提高.锆盐溶液处理膜层的显微硬度高,与膜层相组成中含有ZrO2陶瓷有关.电源脉冲频率、占空比、电压、处理时间参数的增加,都使镁合金微弧氧化膜层的显微硬度增加.在一定范围内增加溶液的电导率,可使膜层的显微硬度提高.     

复合电解液中ZK60镁合金的微弧氧化机理

在优化的铝酸钠-磷酸钠复合电解液体系中,以ZK60镁合金为研究对象进行微弧氧化实验,并结合电压-时间曲线和微弧氧化各个阶段膜层的微观形貌以及物相分析等方面对复合电解液体系中微弧氧化过程及成膜机理进行了探讨。结果表明,该体系下微弧氧化过程分为了氧化膜生成阶段、微弧氧化膜层快速生长阶段和电压微小下降过程以及微弧氧化膜层的修整阶段。膜层的物相分析表明微弧氧化初期膜层主要成分为MgO,Mg和MgZn2,中后期膜层中的主体相为尖晶石结构的MgAl2O4和方镁石结构的MgO,微弧氧化的最后阶段对膜层的物相组成没有影响。     

电流密度对镁合金微弧氧化膜层性能的影响

在电流密度分别为3、6、9、12A/dm2时,用微弧氧化的方法在碱性电解液体系中制备了镁合金微弧氧化膜,考察了不同电流密度对生成的氧化膜层厚度、硬度的影响规律;用XRD分析了氧化膜层的相结构;并采用NaCl溶液浸泡试验和中性盐雾试验,考察了氧化膜的耐蚀性能.结果显示：随着电流密度的增大,膜层的厚度、硬度均呈增加的趋势;陶瓷层主要由MgO、Mg2SiO4和非晶相组成;得到的氧化膜层具有优良的耐蚀性能.     

纯镁和AZ91HP镁合金微弧氧化膜性能比较

在环保型电解液中,采用电压-时间曲线、等离子体发射光谱仪(ICP)、扫描电镜(SEM)等方法研究了纯镁和AZ91HP两种基体材料对氧化过程、氧化膜表面形貌及成分的影响.根据电压-时间曲线,在氧化时间分别为1 min和5 min时,AZ91HP镁合金的电流效率比纯镁低,可能是由AZ91HP中的合金元素铝氧化并进入氧化膜中导致裂缝增加,成为析氧中心所导致的.在AZ91HP镁合金上生成的氧化膜孔的均匀性没有纯镁好,并且最大孔的直径比在纯镁上的氧化膜大.EDS分析表明,随着氧化时间延长,氧化膜中Si和P含量增加;而在氧化时间相同的情况下,两种基体上形成的氧化膜成分没有明显区别.ICP方法没有检测到氧化溶液中含有Mg~(2+)和Al~(3+),表明这两种离子在溶液中的浓度很低.     

AZ91D镁合金表面微弧氧化陶瓷膜微观结构与组成的研究

采用自制的恒流非对称方波电源用微弧氧化法在AZ91D镁合金表面制备了耐腐蚀陶瓷膜,通过微观分析手段对微弧氧化膜的截面特征、元素成分分布及表面膜的相组成进行了分析,研究了微弧氧化工艺参数对膜层表面形貌、微观结构与组成等的影响.结果表明,提高电流密度会造成组织疏松微孔孔径增大;硅酸盐溶液中微弧氧化制得的陶瓷膜优于铝酸盐溶液.而且电解液中的离子可参与成膜反应,硅酸盐溶液体系镁合金微弧氧化陶瓷层主要由MgO和Mg_2SiO_4相组成,铝酸盐溶液体系微弧氧化膜层主要由MgAl_2O_4相组成.     

硼酸钠浓度对镁合金阳极化的影响

采用电压-时间曲线、全浸腐蚀实验、极化曲线法、X射线衍射法（XRD）、扫描电镜（SEM）、能量色散谱仪（EDS）和X射线光电子能谱法（XPS）等方法研究了AZ91D镁合金在含不同浓度四硼酸钠的阳极化溶液中的阳极氧化行为和膜层的成分、结构.结果表明：在文中给定工艺中,AZ91D镁合金的阳极化过程可分为3个阶段：电火花出现之前的致密层生成阶段;少量小电火花出现的多孔层生成阶段;出现较大电火花的多孔膜层稳定生长阶段.阳极氧化过程中,随着阳极氧化溶液Na2B4O7浓度的升高,出现电火花的时间延长,出现电火花时的电压值升高;膜层厚度增加,膜层上的孔径增大.阳极化膜层中主要含有Mg^2＋、O^2-、Si^4＋和B^3＋,主要相结构为MgO、MgSiO3和Mg3B2O6.四硼酸钠浓度对阳极化膜的耐蚀性影响较大,当四硼酸钠浓度为160 g/L时,膜层耐蚀性能最好.     

电流密度对镁合金微弧氧化膜层性能的影响

在电流密度分别为3、6、9、12 A/dm2时,用微弧氧化的方法在碱性电解液体系中制备了镁合金微弧氧化膜,考察了不同电流密度对生成的氧化膜层厚度、硬度的影响规律;用XRD分析了氧化膜层的相结构;并采用NaCl溶液浸泡试验和中性盐雾试验,考察了氧化膜的耐蚀性能。结果显示:随着电流密度的增大,膜层的厚度、硬度均呈增加的趋势;陶瓷层主要由MgO、Mg2SiO4和非晶相组成;得到的氧化膜层具有优良的耐蚀性能。     

AZ91镁合金不同厚度微弧氧化膜层耐蚀性能研究

在铝酸盐体系溶液中对AZ91镁合金进行微弧氧化处理,用扫描电镜对所得不同厚度的微弧氧化膜层形貌进行观察;通过盐雾试验进行耐腐蚀性能测试;用X射线衍射仪进行膜层成分分析.结果表明:镁合金微弧氧化膜层在初期膜层表面平整,微孔尺寸小、密度大、分布均匀,随着膜厚增加膜层致密性提高,微孔数量减少,但表面粗糙度增加,耐蚀性能随膜厚的增加呈现先增加后降低的变化规律,膜厚在20～30 μm时膜层具有较好的耐蚀性,膜层主要由MgAl2O4和MgO两相组成.     

AZ91D合金的阳极氧化新工艺

研制了一种新型镁合金的无Cr阳极氧化配方 ,对镁合金进行阳极化处理 .溶液的主要成分为NaOH、NaSiF6和有机添加剂 .XRD、SEM、XPS测试结果表明 ,氧化膜主要由MgO、MgAl2 O4 和 2Al2 O3 ·2SiO2 ·H2 O组成 .3 5 %NaCl水溶液动电位极化结果说明 ,氧化膜有良好耐点蚀性能 .合金中Si、Al元素的氧化弥补了Mg氧化时的体积收缩 ,氧化膜无裂纹 ,为其耐点蚀提供了条件 .阳极化后Al、Si元素在表面均匀分布 ,是氧化膜具有良好保护作用的原因之一 .     

负向电压对镁合金微弧氧化膜层的影响

研究了负向电压对镁合金微弧氧化陶瓷膜层的表面形貌,厚度及相组成的影响,试验结果表明负向电压对膜层的质量影响很大,它能使膜层表面空隙率降低且光滑平整,并显著提高镁合金微弧氧化的膜层厚度,但同时负向电压的变化应控制在一定范围之内.经对微弧氧化试样的膜层进行SEM、XRD以及厚度的检测,分析了不同负向电压对镁合金微弧氧化膜层的影响,得到一组较为稳定的正负向电压参数,使得镁合金微弧氧化膜层的效果得到较好的提高.     

Anodization of Mg-alloy AZ91 in NaOH solutions

Anodic oxide films were grown on the Mg-Al-Zn alloy AZ91 in NaOH-solution and examined by electron microscopy, X-ray diffraction and micro-Raman spectroscopy. The anodic film consists of an inner barrier layer and an outer porous layer. The thin barrier layer is hydrated or contains Mg(OH)₂. The porous layer was identified as crystalline MgO (periclase) and contains tunnels formed by breakdown/repair events, which involve plasma-electrolytic reactions. The micro-Raman-spectrum indicates the formation of a highly disordered zone around the tunnels. Applied current density, potential limit, electrolyte concentration and alloy phase were identified as parameters which have an influence on density and diameter of the tunnels.     

钛合金阳极氧化膜在Hank''''s溶液中的腐蚀行为

利用扫描电镜(SEM)和恒电位阶跃法，研究了不同工艺条件下得到的钛合金(TC4)阳极氧化膜在Hank’s模拟体液中的耐蚀性。分析了不同电解液组成、电解液温度及阳极氧化时间对其耐蚀性的影响。结果表明在磷酸溶液中生成的氧化膜耐蚀性较好，此外电解液的温度、极化时间对膜层耐蚀性也有显著影响。     

The influences of duty cycle on the bonding strength of AZ31B magnesium alloy by microarc oxidation treatment

The process of microarc oxidation was studied as a pre-treatment for adhesive bonding of magnesium alloys. Porous microarc oxidation films on AZ31B magnesium alloy were prepared in a sodium silicate electrolyte by a high-frequency bipolar pulsing mode. The influences of duty cycle on film porosity and lap-shear strength of the bonding joints were studied. The higher duty cycle increased the film porosity and slightly decreased the thickness of the oxide film. The microarc oxidation film consisted mainly of MgO and MgSiO₃. The increase of duty cycle resulted in the increase of MgO in the oxide film. As the duty cycle increased, the lap-shear strength increased. The highest lap-shear strength 24.5 MPa was obtained under the duty cycle of 40%. The reason was attributed to the larger porosity and enhanced mechanical interlocking effect.     

氧化次数对制备多孔阳极氧化铝膜的影响

在8℃、0.3 mol/L浓度的草酸电解液中,施加40 V直流电压,采用两步阳极氧化法在高纯度铝箔上制备了多孔阳极氧化铝（AAO）膜。用场发射扫描电镜（FESEM）对一次、二次氧化制备的多孔氧化铝膜的表面形貌进行了表征。用XRD对原始铝箔及用二次氧化法制备的氧化铝膜的相结构进行了表征。用TEM观察了扩孔后多孔膜的通透性。结果表明,用二次阳极氧化制备的多孔膜明显比用一次法制得的更规则、有序和更厚,为非晶态的Al2O3。     

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.     

Mixed Oxide Films Formed on Titanium Alloy by Plasma Electrolytic Oxidation

The structure and the properties of oxide films formed on titanium in the diphosphate based electrolytes by plasma electrolytic oxidation in the spark-discharge regime at application of inter-electrode voltage 100 to 130 V have been studied. A possibility to obtain oxide layers containing alloying elements by the modification of the composition of electrolytes has been stated. It was found that the chemical and phase composition as well as the topography, the microstructure and the grain size of the formed layers depend on the electrolyte composition, applied current density and inter-electrode voltage. The effect of the chemical composition of the formed mixed oxide films on the corrosion resistance and catalytic activity has been discussed.     

The effect of phosphate on MAO of AZ91D magnesium using AC power source

A rapid and convenient anodization technology with AC power source to obtain the MAO films formed on magnesium alloy AZ91D in phosphate bath (base electrolyte + Na₃PO₄) with or without aluminate and silicate was studied. The corrosion resistance of the anodic films was studied by electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization techniques and the microstructure and composition of films were examined by SEM and XRD. The results show that Na₃PO₄can promote the occurrence of sparking during the MAO process, while abundant heat generated by sparking might enhance the formation of the glassy phase of the compound when the electrolyte contains the additives of NaAlO₂and Na₂SiO₃simultaneously. The optimized MAO film is ivory‐white smooth by naked eye, while presents porous and microcracks in microscopic scale. The anodic film formed in the alkaline solution with optimized parameters possesses superior corrosion resistance by electrochemical test. The XRD pattern shows that the components of the anodized film consist of MgO, MgAlO₂, and MgSiO₃. No oxide crystal with P element can be found.     

Effects of electrolyte pH and temperature on dielectric properties of anodic oxide films formed on niobium

The effects of electrolyte pH and temperature on the structure and properties of anodic oxide films formed on niobium in phosphoric acid solution with the addition of NH₄OH for pH adjustment have been investigated. The film thickness formed at the same voltage slightly increased with increasing pH and significantly increased with increasing electrolyte temperature. The capacitance of the film was independent of electrolyte pH in an acid region, while it notably increased with increasing pH in an alkaline region. The relative permittivity of the film changed 43.7-80.5 when the electrolyte pH was increased from 1.6 to 10. The incorporation depth and content of phosphorus in the film were markedly suppressed at pH 10, and nitrogen was found to penetrate into a depth of 70%. Furthermore, the apparent transport number of Nb⁵⁺ ion decreased from 0.26 to 0.02 by a pH increase from 1.6 to 10. The notable changes in structure and dielectric properties of the anodic niobia film formed in the alkaline region would primarily be caused by the different incorporation behavior of electrolyte species such as phosphorous and nitrogen.     

Crystallization of anodic titania on titanium and its alloys

Crystallization of amorphous anodic films grown at constant current density on sputtering-deposited titanium, and Ti-Si and Ti-Al alloys, in ammonium pentaborate electrolyte, has been examined directly by transmission electron microscopy. In the case of titanium, anatase develops at relatively low voltage in the inner film region, formed by inward migration of oxygen species. In contrast, the outer film region, formed at the film/electrolyte interface, is composed of amorphous oxide only. Oxide crystals are particularly found near the plane, separating the two regions, which is located at a depth of 35-38% of the film thickness. Oxide zones, of size ∼ 1 nm, with a relatively ordered structure, developed at the metal/film interface, are considered to lead to transformation of the inner region structure. The incorporation into the film of either aluminium or silicon species suppresses the formation of crystalline oxide to much increased voltages. However, eventually nanocrystals form at ∼40% of the film thickness, probably originating from pre-cursor nuclei in the air-formed on the as-deposited alloy.     

Characterization of plasma electrolytic oxide formed on AZ91 Mg alloy in KMnO4 electrolyte

The aim of this work is to investigate microstructure, corrosion resistance characteristics and nanohardness of the oxide layer on AZ91 Mg alloy by applying different voltage with KMnO₄ contained solution. There are lots of closed pores that are filled with another oxide compound compared with the typical surface morphology with pore coated until 350 V of coating voltage. The thickness of oxide layer increases with increasing coating voltage. The oxide layer formed on AZ91 Mg alloy in electrolyte with potassium permanganate consists of MgO and Mn₂O₃. Corrosion potential of the oxide layer on AZ91 Mg alloy obtained at different plasma electrolytic oxidation(PEO) reaction stages increases with increasing coating voltage. The corrosion resistance of AZ91 Mg alloy depends on the existence of the manganese oxide in the oxide layer. The inner barrier layer composed of the MgO and Mn₂O₃ may serve as diffusion barrier to enhance the corrosion resistance and may partially explain the excellent anti-corrosion performance in corrosion test. Nanohardness values increase with increasing coating voltage. The increase in the nanohardness may be due to the effect of manganese oxide in the oxide layer on AZ91 Mg alloy coated from electrolyte containing KMnO₄.