Influence of potassium pyrophosphate in electrolyte on coated layer of AZ91 Mg alloy formed by plasma electrolytic oxidation

The effect of potassium pyrophosphate in the electrolyte on plasma electrolytic oxidation (PEO) process for AZ91 Mg alloy was investigated. The morphologies and chemical compositions of the coating layer on the AZ91 Mg alloy were evaluated and corrosion resistance was also estimated by potentiodynamic polarization analysis. The coating layer on AZ91 Mg alloy coated from the Bath 2 containing 0.03 mol/L of potassium pyrophosphate for 360 s exhibited considerably dense structure and contained 11%–18% (mass fraction) of phosphorous. The higher content of phosphorous of coating layer coated from Bath 2 could be detected at the bottom of oxide layer, which strongly implied that the phosphorous ion might be concentrated at the barrier layer. Corrosion potential of coating layer of AZ91 Mg alloy increased and corrosion current density decreased with increasing the concentration of potassium pyrophosphate. The polarization resistance (R_p) of coating layer of AZ91 Mg alloy coated from Bath 2 was 4.65×10⁷ Ω/cm², which was higher than that (R_p=3.56×10⁴ Ω/cm²) of the sample coated from electrolyte without potassium pyrophosphate. The coating layer coated from Bath 2 containing 0.03 mol/L potassium pyrophosphate exhibited the best corrosion resistance.     

磁控溅射和等离子体电解氧化双重工艺处理AZ31镁合金的耐蚀和耐磨性能

为了提高AZ31镁合金的耐磨和耐腐蚀性能,通过磁控溅射法在合金表面涂覆约11μm的纯铝层,然后分别在铝酸盐和硅酸盐电解液中通过等离子电解氧化(PEO)进行表面处理.涂层的性能通过干滑动摩擦试验和电化学腐蚀试验进行研究.铝酸盐涂层在10和20 N的负载下均表现出良好的耐磨性能;硅酸盐涂层只在较低的载荷下(10 N)表现出...     

Effect of electrolyte on mechanical properties of AZ31B Mg alloy in electrolytic plasma processing

Coatings on Mg alloys were prepared using NaOH + Na₂SiO₃ as basic electrolyte containing electrolyte of Na₂SiF₆ or NaF. EPP treatment was carried out on AZ31 Mg alloys matrix under a hybrid voltage of AC of 200 V combined with DC of 260 V for 30 min. Structural and morphological analyses of ceramic coatings were analyzed by XRD and SEM. Wear and hardness of coatings were measured by pin-on disk test and Vickers hardness test. The coatings formed in Na₂SiF₆ and NaF electrolytes were mainly composed of MgO and Mg₂SiO₄. The measured micro-hardness of coating formed in Na₂SiF₆ electrolyte was found to be over HV 1100, while, coating formed in NaF electrolyte possessed micro-hardness of HV ～900. These results show that the mechanical properties of AZ31B Mg alloys can be enhanced by the proper selection of electrolyte agent.     

电解质对AZ91D镁合金微弧氧化的影响

在Na2SiO3和NaAlO2为主成膜剂的硅铝复合电解液中,利用交流脉冲电源对AZ91D镁合金进行微弧氧化处理,研究主成膜剂含量的变化对微弧氧化过程及膜层特性的影响规律。利用扫描电镜(SEM)和膜层测厚仪分别研究了膜层的微观形貌和膜层厚度,通过电化学阻抗谱(EIS)测试膜层在3.5%NaCl中性溶液中的耐蚀性能。结果表明,随着主成膜剂含量的增加,微弧氧化过程中起弧电压和终止电压均呈下降的变化趋势,而膜层耐蚀性则基本呈先增大后降低的变化趋势,膜厚的变化趋势与其耐蚀性一致;Na2SiO3含量的变化对膜层内部致密层和外部疏松层的耐蚀性均有影响,而NaAlO2含量的变化则主要影响膜层内部致密层的耐蚀性;适量的主成膜剂含量是获得致密耐蚀膜层的关键。     

Corrosion behaviour of Sn-containing oxide layer on AZ91D alloy formed by plasma electrolytic oxidation

Corrosion phenomenon of magnesium alloys is one of the limits for using magnesium alloys in automotive and aerospace industries. The aim of this study is the development of Sn-containing protective oxide coating by a simple plasma electrolytic oxidation in KOH/KF/Na₃PO₄ electrolyte on AZ91D magnesium alloy in galvanostatic mode. The film morphology and composition were analysed by SEM coupled with EDS, XRD and Raman spectroscopy. In the oxide, tin is mainly incorporated as crystallised MgSn(OH)₆ compound in the layer. The main properties of Sn-containing oxide coating on AZ91D are both keeping the corrosion rate at open-circuit conditions at an acceptable value, and providing a sufficient passivation plateau to reduce the pitting sensibility. The lather characteristic, revealed by pitting tests, addresses the major drawback of magnesium alloys which often undergo important galvanic coupling in service. Consequently, the addition of low stannate concentration in the electrolyte to form Sn-rich anodic oxide on magnesium alloys represents an interesting way to synthesize protective coatings by PEO in a short time of anodization.     

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.     

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.     

微弧氧化处理对铝合金耐霉菌腐蚀特性的影响

在2A12铝合金表面制备了微弧氧化膜层,按照国家军用标准霉菌测试方法对微弧氧化膜层的耐腐蚀性能进行了测试,通过扫描电镜(SEM)、X射线衍射分析(XRD)对铝合金基体及微弧氧化膜层霉菌腐蚀前后的微观结构、相组成进行了表征。结果表明,未经过微弧氧化处理的铝合金表面有少量的霉菌生长,表面产生了一定数量的点蚀坑,长霉等级为1级。经过微弧氧化处理试样表面未发现霉菌生长,长霉等级为0级。微弧氧化处理可以有效提高铝合金表面耐霉菌腐蚀性能,扩大其应用范围。     

Tribological and corrosion behavior of PEO coatings with graphite nanoparticles on AZ91 and AZ80 magnesium alloys

The effect of the addition of graphite nanoparticles into the electrolyte used to produce plasma electrolytic oxidation (PEO) coatings on AZ91 and AZ80 magnesium alloys was studied. The corrosion and wear resistances of the obtained coatings were investigated. A solution that contained both phosphates and silicates was used as electrolyte. Moreover, two different PEO treatment times were studied. The corrosion resistance was analyzed with potentiodynamic polarization and EIS tests; the wear resistance was investigated with a flat on ring tribometer. The results were related to the morphology, microstructure, elemental composition and thickness evaluated with SEM analysis. The presence of the graphite nanoparticles increased the thickness, produced a densification of the coating and sealed the pores on the surface, thus improving both the corrosion and wear resistance. The increase in the corrosion and wear resistances was more evident for AZ91 than for AZ80 due to the higher aluminum content.     

Incorporation mechanism of colloidal TiO2 nanoparticles and their effect on properties of coatings grown on 7075 Al alloy from silicate-based solution using plasma electrolytic oxidation

Plasma electrolytic oxidation (PEO) was applied using a pulsed unipolar waveformto produce Al₂O₃−TiO₂ composite coatings from sol electrolytic solutions containing colloidal TiO₂ nanoparticles. The sol solutions were produced by dissolving 1, 3, and 5 g/L of potassium titanyl oxalate (PTO) in a silicate solution. Scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction, and Raman spectroscopy were applied to characterizing the coatings. Corrosion behavior of the coatings was investigated using polarization and impedance techniques. The results indicated that TiO₂ enters the coating through all types of micro-discharging and is doped into the alumina phase. The higher level of TiO₂ incorporation results in the decrease of surface micro-pores, while the lower incorporation shows a reverse effect. It was revealed that the higher TiO₂ content makes a more compact outer layer and increases the inner layer thickness of the coating. Electrochemical measurements revealed that the coating obtained from the solution containing 3 g/L PTO exhibits higher corrosion performance than that obtained in the absence of PTO. The coating produced in the absence of PTO consists of γ-Al₂O₃, δ-Al₂O₃ and amorphous phases, while α-Al₂O₃ is promoted by the presence of PTO.     

电解液成分对等离子体电解氧化TC4合金腐蚀行为和摩擦学性能的影响（英文）

在TC4合金表面制备4种典型等离子体电解氧化(PEO)涂层,研究电解质组成对PEO涂层腐蚀行为和摩擦学性能的影响。结果表明,PEO涂层的腐蚀行为和摩擦学性能与电解质成分密切相关。在含NaH₂PO₂的电解液中制备的PEO涂层由于内氧化膜较致密而具有最好的耐蚀性能,而在含NaAlO₂的电解液中制备的PEO涂层由于含有Al₂O₃而具有最好的摩擦学性能。为制备具有良好耐蚀性和耐磨性的PEO涂层,以NaH₂PO₂和NaAlO₂为电解液主要成分制备了复合PEO涂层。     

Environmentally assisted cracking behaviour of plasma electrolytic oxidation coated AZ31 magnesium alloy

Abstract

A wrought AZ31 magnesium alloy was plasma electrolytic oxidation (PEO) coated in phosphate and silicate based alkaline electrolytes. The effect of these PEO coatings on the stress corrosion cracking (SCC) behaviour of the alloy was investigated by slow strain rate tensile (SSRT) tests in ASTM D1384 solution. The untreated and PEO coated AZ31 magnesium alloy specimens were found to be susceptible to SCC, despite the fact that the PEO coatings offered an excellent general corrosion resistance. The results of the polarisation tests on the untreated AZ31 alloy specimen after prolonged immersion in ASTM D1384 electrolyte suggested the formation of a film on the surface constituted by the corrosion products. The cracking of this film and the evolution/ingress of hydrogen at these defective sites during the SSRT tests in the corrosive environment was believed to be responsible for the SCC of the untreated alloy. Similarly, the cracking of the PEO coatings during the SSRT test, the consequent exposure of the underneath magnesium alloy substrate and the associated electrochemical reactions were attributed as reasons for the SCC of the PEO coated specimens. The transgranular mode of fracture in all the cases avowed that the hydrogen induced cracking was the mechanism of SCC.     

邻苯二甲酸氢钾-硼酸盐电解液中AZ91D镁合金的阳极氧化(英文)

研究 AZ91D 镁合金在邻苯二甲酸氢钾-硼酸盐碱性环保型电解液中的阳极氧化行为。考察邻苯二甲酸氢钾对阳极氧化膜层性能的影响,并利用扫描电镜(SEM)、X 射线衍射(XRD)、动电位极化和电化学阻抗(EIS)进行分析表征。结果表明,邻苯二甲酸氢钾的浓度对阳极氧化成膜过程,氧化膜的表面形貌、厚度、相结构和耐腐蚀性能都有重要影响。在硼酸盐电解液中加入适量的邻苯二甲酸氢钾以后,制得的阳极氧化膜表面光滑、致密,与镁合金基体的结合力强,具有优异的耐腐蚀性能。     

电解质对镁合金微弧氧化表面膜组织与腐蚀性能的影响

采用SEM、TEM、EDX、XRD、AUTOLAB电化学工作站分析比较两种电解质（硅酸盐体系和有机胺体系）直流微弧氧化处理AZ91D合金表面涂层的成分、组织结构和涂层的动电位极化曲线。虽然两种电解质体系涂层元素成分和组成相相同,均为金属相、MgO相和Mg2SiO3相,但有机胺电解质体系的涂层中非金属相（MgO、Mg2SiO4）相对含量高于硅酸盐处理体系,有机胺体系获得的涂层表面均匀致密性也优于硅酸盐体系。有机胺体系获得的涂层在3.5%NaCl中性介质中的腐蚀电流密度、腐蚀电压分别为0.29μA/cm^2和522 mV,与硅酸盐体系处理涂层相比,前者的抗腐蚀能力有很大幅度的提高。     

Amorphous coatings deposited on aluminum alloy by plasma electrolytic oxidation

Amorphous [Al-Si-O] coatings were deposited on aluminum alloy by plasma electrolytic oxidation (PEO). The process parameters, composition, micrograph, and mechanical property of PEO amorphous coatings were investigated. It is found that the growth rate of PEO coatings reaches 4.44μm/min if the current density is 0.9 mA/mm^2. XRD results show that the PEO coatings are amorphous in the current density range of 0.3 - 0.9 mA/mm^2. EDS results show that the coatings are composed of O, Si and A1 elements. SEM results show that the coatings are porous. Nano indentation results show that the hardness of the coatings is about 3 - 4 times of that of the substrate, while the elastic modulus is about the same with the substrate. Furthermore, a formation mechanism of amorphous PEO coatings was proposed.     

锆-4合金的直流等离子电解氧化及膜层的性能(英文)

在硅酸盐、磷酸盐、焦磷酸盐或其混合电解液中对锆-4 合金进行等离子电解氧化。通过实验确定合适的工艺参数,并运用电化学技术、显微硬度、SEM、XRD 等技术对膜层性能进行表征。结果表明:在纯的硅酸盐电解液中得到的膜层很不均匀,且在添加磷酸盐后,膜层均匀性仍然很差。在焦磷酸盐体系中得到的膜层比较均匀,但硬度低。在焦磷酸盐体系中添加硅酸盐后,膜层的均匀性和硬度都得到改善。XRD 结果表明,膜层的主要成分为单斜氧化锆和四方氧化锆。添加硅酸盐后,有利于四方氧化锆的形成。极化曲线结果表明,在焦磷酸盐以及焦磷酸盐与硅酸盐混合体系中得到的膜层具有较强的耐蚀性。     

镁合金表面PEF膜与PEO膜腐蚀防护行为的对比研究

目的 对比研究镁合金表面新型等离子体电解氟化(PEF)膜与传统等离子体电解氧化(PEO)膜的腐蚀防护行为.方法 分别在中性和酸性腐蚀介质中,通过开路电位监测和动态电位极化曲线测试表征了膜层的电化学腐蚀行为,通过浸泡实验和盐雾实验表征了膜层的长效腐蚀行为.通过SEM、EDS和XRD等方法表征了膜层的原始微观结构和组成,分析了腐蚀形貌和腐蚀产物.结果 PEF膜与PEO膜均可以为镁合金基材提供有效的腐蚀防护作用.相较于PEO膜,PEF膜在浸泡实验和盐雾实验中,都具有更为优异的腐蚀防护性能,但在动态电位极化测试中,具有更正的自腐蚀电位和更大的自腐蚀电流密度,表明其腐蚀倾向更低,但腐蚀速率更高.结论 总体而言,PEF膜在中性和酸性环境中都具有更好的腐蚀防护性能.PEO膜在中性环境中的腐蚀防护失效机制主要是腐蚀介质的扩散,在酸性环境中的腐蚀防护失效机制主要是膜层化合物的溶解和消耗;PEF膜在中性和酸性环境中的腐蚀防护失效机制都是腐蚀介质的扩散.