负向电压对AZ31B镁合金表面微弧氧化膜结构和耐蚀性的影响

以Na2Si O3-Na OH-Na F溶液为电解液,采用双极性非对称脉冲电源的恒压加载方式,制备AZ31B镁合金表面微弧氧化膜。以扫描电镜和极化曲线为表征手段,研究在固定正向电压(260 V)条件下,负向电压对膜层形貌及腐蚀性能的影响。结果表明:负向电压40 V,氧化处理10~15 min,可获得致密层较厚的耐蚀微弧氧化膜;负向电压高于60 V,膜层容易烧蚀,表面产生大尺寸微裂纹,导致膜层耐蚀性能降低。适当的负向电压能够显著提高膜层的致密性,但必需控制电压的范围和氧化处理的时间。     

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.     

负向电流密度对镁合金微弧氧化电压及陶瓷膜的影响

以恒流模式在含有硅酸钠、氟化钾、甘油、氢氧化钾的电解液中对AM50镁合金进行微弧氧化。研究了正向电流密度恒定时,负向电流密度对正向电压及陶瓷膜表面形貌、显微硬度和厚度的影响。结果表明,不同负向电流密度对应的正向电压随时间的变化都呈先快速增长后趋于稳定的变化趋势,而随负向电流密度的增大,不同负向电流密度对应的正向电压(同一时刻)呈先增加后逐渐降低的变化趋势;随负向电流密度的增大,氧化膜表面微孔数量先减少后增加,而陶瓷膜表面微孔孔径变化不大,都在1～5μm范围内;提高负向电流密度有利于增加微弧氧化陶瓷膜的硬度与厚度。     

正向电压对ZK60镁合金微弧氧化过程及膜层的影响

在自主研制的铝酸钠一磷酸钠复合电解液体系中,采用不同的正向电压(220~340 V)对ZK60变形镁合金进行微弧氧化,在镁合金表面制备陶瓷膜层。利用扫描电镜、超景深光学显微镜及能谱仪观察分析膜层组织,通过电流变化及放电现象分析微弧氧化过程,并用全浸实验和电化学阻抗法测试膜层在3.5%NaCl(质量分数)介质中的耐腐蚀性能。结果表明:电流平稳阶段是膜层的主要生长阶段,正向电压是微弧氧化过程的重要驱动力,电压过高或过低都不利于获得优质膜层。280V正向电压下制备的膜层组织较为均匀致密,其腐蚀速率较低,为0.2054g/(m~2·h),此时膜层电化学阻抗模值为正向电压340 V下膜层的3倍。     

电压对6061铝合金表面微弧氧化膜形成的影响

采用微弧氧化法在6061铝合金表面制备微弧氧化膜,研究氧化电压对微弧氧化正负向电流、膜层厚度和生长率的影响。结果表明,正向和负向电压分别为460 V和130 V时,正负向电流波动明显,膜层均匀,厚度为118μm,膜的生长率为3.93μm/min,膜层由疏松层和致密层组成,致密层所占比例约为95%。     

Na2SiO3电解液体系下正负向电压对Ti6Al4V合金微弧氧化膜层特性的影响

采用Na2SiO3电解液体系,在不同的正、负向电压条件下对Ti6Al4V合金进行微弧氧化.利用测厚仪、SEM、XRD等手段分析微弧氧化膜厚度、表面形貌、相组成,研究正、负向电压对氧化膜层特性的影响规律.试验结果表明,负向电压恒定在80V时,随着正向电压由350V增加到400V,氧化膜厚度由48μm增加至94μm;固定正向电压为380V,负向电压由50V增加至90V,氧化膜厚度先增加,后减小;正、负向在380V/80V时获得的氧化膜致密且与基体结合良好;正向电压增加,有利于得到更多的锐钛矿相TiO2;增加负向电压,有利于得到更多的金红石相TiO2.     

负向电压与氧化时间对AZ91D微弧氧化膜层形成特性的影响

在硅酸盐体系下对AZ91D镁合金进行了微弧氧化处理,研究了负向电压和氧化时间对微弧氧化膜层特性的影响,并通过XRD、金相显微镜及SEM对氧化膜进行了相结构和表面形貌的分析.结果表明,随着负向电压的提高,膜厚逐渐增加,表面孔洞增大,但孔洞及微裂纹的数量减少,当负向电压为120 V时,膜厚达到157μm,孔洞及裂纹数量最少.延长氧化时间,使得微弧氧化膜层厚度增加,膜层生长速率先增大后减小.氧化膜层主要由立方结构MgO和镁橄榄石相Mg2SiO4构成,衍射谱中未发现Mg的衍射峰,氧化膜层致密性较好.陶瓷膜层由致密层和疏松层组成且与基体结合紧密.     

添加剂对镁合金微弧氧化的影响

为了解添加剂对镁合金微弧氧化陶瓷膜的成膜速度及微观组织结构的影响,用自制的微弧氧化实验装置对AZ91D压铸镁合金进行了微弧氧化,并用SEM、XRD分析其微观组织结构.结果表明,在槽液中添加Al复合化合物使起弧电压和稳态电压降低,氧化陶瓷膜的生成速度增加、硬度增大,膜层致密性提高,陶瓷膜中的晶胞以垂直于基底面的方式生长,陶瓷氧化膜中主要存在的相有Al2O3、MgAl2O4和MgO.但当含Al复合化合物的质量分数在30%以上时,其致密性和硬度反而下降.     

负向电压对纯钛微弧氧化膜层结构特征的影响

采用微弧氧化技术,以β-甘油磷酸钠和乙酸钙混合溶液为电解液,在固定正向电压(450 V)和氧化时间(5 min)等参数情况下,研究了负向电压对纯钛表面微弧氧化膜层的相组成和形貌的影响规律.结果表明:负向电压为100～200V时,微弧氧化膜层较均匀,膜层由二氧化钛和磷酸三钙组成;负向电压升至300V,膜层表面被严重烧蚀,其主要物相为钛酸钙.     

镁合金等离子体微弧氧化过程控制的研究

研究AZ31镁合金微弧氧化过程中不同控制参数对膜性能的影响。镁合金微弧氧化中存在一个二次放电过程,它会对已长成的膜起破坏作用。通过改变溶液成分或浓度可对镁合金微弧氧化临界点的出现时间进行控制。在此基础上进一步研究一次放电不同控制过程对膜层性能的影响,发现采用渐进式升压方式能提高膜的致密层和疏松层的比例,但对膜的总厚度影响不大。合适的阴极匹配电压,可减小功耗,降低气孔率,改善膜的性能。     

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.     

NH4F浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响

目的 考察乙二醇-氟化铵电解液中氟化铵浓度对镁合金表面微弧氧化制备氟化物膜层结构和性能的影响,提高镁合金氟化物膜层的耐腐蚀性能。方法 在含不同浓度NH4F的EG-NH4F电解液中,采用微弧氧化的方法制备氟化物膜层,NH4F质量浓度分别为40、60、80、100、120 g/L。通过扫描电子显微镜(SEM)、X射线能量色散谱仪(EDS)和X射线衍射仪(XRD),对膜层表面微观形貌和成分组成进行分析,并通过电化学测试表征了膜层的腐蚀防护性能,通过盐雾试验评估了膜层长效防腐蚀行为,通过SEM和EDS表征了腐蚀形貌和腐蚀产物。结果 在EG-NH4F中制备膜层的物相组成主要是MgF2。随着NH4F浓度的提高,微弧氧化的起弧电压与工作电压均逐渐减小,膜层中氟含量逐渐增加,膜层的孔径减小,孔数量分布更加均匀,膜层表面粗糙度降低。质量浓度为100 g/L NH4F的膜层自腐蚀电流密度(Jcorr)为2.226×10^‒7 A/cm²,较镁合金基材降低了1个数量级,极化电阻Rp增大到90.156 kΩ.cm²,其阻抗模量|Z|f=0.01 Hz=8.55×10⁵ Ω.cm²,与镁合金基材的阻抗模量|Z|f=0.01 Hz=8.86×10² Ω.cm²相比,提高了3个数量级。结论 微弧氧化处理能够显著改善AZ31镁合金的腐蚀防护性能。NH4F浓度的增加有利于提高膜层的耐腐蚀性能,质量浓度为100 g/L NH4F的膜层耐腐蚀性能最优。     

镁合金微弧氧化-电泳复合膜层的腐蚀性能

镁合金微弧氧化-电泳复合处理作为新型的表面处理工艺,极大地提高了镁合金的耐蚀性,满足了工业化要求。通过考察在不同工艺条件下制备镁合金微弧氧化-电泳复合膜层的耐蚀性,研究其腐蚀机理,结果表明:微弧氧化-电泳复合膜层的耐蚀性取决于有机层的致密性以及复合膜层间的结合状态。致密性越好、结合力越大,复合膜层的耐蚀性越好。     

Comparison of electrochemical corrosion behaviour of MgO and ZrO2 coatings on AM50 magnesium alloy formed by plasma electrolytic oxidation

Two types of PEO coatings were produced on AM50 magnesium alloy using pulsed DC plasma electrolytic oxidation process in an alkaline phosphate and acidic fluozirconate electrolytes, respectively. The phase composition and microstructure of these PEO coatings were analyzed by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The corrosion behaviour of the coated samples was evaluated by open circuit potential (OCP) measurements, potentiodynamic polarization tests, and electrochemical impedance spectroscopy (EIS) in neutral 0.1 M NaCl solution. The results showed that PEO coating prepared from alkaline phosphate electrolyte consisted of only MgO and on the other hand the one formed in acidic fluozirconate solution was mainly composed of ZrO₂, MgF₂. Electrochemical corrosion tests indicated that the phase composition of PEO coating has a significant effect on the deterioration process of coated magnesium alloy in this corrosive environment. The PEO coating that was composed of only MgO suffered from localized corrosion in the 50 h exposure studies, whereas the PEO coating with ZrO₂ compounds showed a much superior stability during the corrosion tests and provided an efficient corrosion protection. The results showed that the preparation of PEO coating with higher chemical stability compounds offers an opportunity to produce layers that could provide better corrosion protection to magnesium alloys.     

Wear and corrosion behavior of clay containing coating on AM 50 magnesium alloy produced by aluminate-based plasma electrolytic oxidation

This study aims to examine the effect of clay micro particles addition on the microstructure, wear and corrosion behavior of PEO coatings on AM 50 magnesium alloy. PEO coatings were prepared using an aluminate-based electrolyte with and without the presence of 5 g/L clay particles. The structure and composition of the coatings were evaluated using SEM, EDS and XRD. The wear investigations were conducted using a ball-on-disk tribometer at 2, 5 and 10 N loads. The corrosion behavior of the coatings was examined using polarization and EIS tests in 0.5 wt.%NaCl. The results revealed that the addition of clay particles deteriorated the wear resistance of the coatings under the loads of 5 and 10 N. The SEM examinations of the worn surfaces indicated that a combination of adhesive and abrasive wear mechanisms was activated for the coating with clay particles. The poor wear performance of the clay-incorporated coating was related to its lower adhesion strength and higher roughness. The potentiodynamic polarization examinations revealed that the addition of clay particles slightly decreased the corrosion rate of the coatings. Corrosion resistance of the clay-containing coating was attributed to its compactness, as indicated by the results of EIS tests.     

Influence of process parameters on electrolytic plasma discharging behaviour and aluminum oxide coating microstructure

In this study, a plasma electrolytic oxidation process (PEO) was used to produce oxide coatings on commercially pure aluminum (Al 1100) at two different current modes, pulsed unipolar and bipolar modes. Optical emission spectroscopy (OES) in the visible and near ultraviolet (NUV) band (285 nm-800 nm) was employed to investigate the PEO plasma. The emission spectra were recorded and plasma temperature profile versus processing time was constructed using line intensity ratios method. Scanning Electron Microscopy (SEM) with energy dispersive x-ray analysis (EDS) was used to study the coating microstructure and coating cross section. It was found that the plasma discharge behavior significantly influenced the microstructure and the morphology of the oxide coatings. The main effect came from the strongest discharges which were initiated at the interface between the substrate and the coating. Through manipulation of process parameters to control or reduce the strongest discharge, the density and quality of the coating layers could be modified. This work demonstrated that by adjusting the ratio of the positive to negative pulse currents as well as their timing in order to eliminate the strongest discharges, the quality of the coatings was considerably improved.     

Growth mechanism and corrosion behavior of ceramic coatings on aluminum produced by autocontrol AC pulse PEO

Ceramic coatings are produced on aluminum alloy by autocontrol AC pulse Plasma Electrolytic Oxidation (PEO) with stabilized average current. Transient signal gathering system is used to study the current, voltage, and the transient wave during the PEO process. SEM, OM, XRD and EDS are used to study the coatings evolution of morphologies, composition and structure. TEM is used to study the micro profile of the outer looser layer and inner compact layer. Polarization test is used to study the corrosion property of PEO coatings in NaCl solution. According to the test results, AC pulse PEO process can be divided into four stages with different aspects of discharge phenomena, voltage and current. The growth mechanism of AC PEO coating is characterized as anodic reaction and discharge sintering effect. PEO coating can increase the corrosion resistance of aluminum alloy by one order or two; however, too long process time is not necessarily needed to increase the corrosion resistance. In condition of this paper, PEO coating at 60 min is the most protective coating for aluminum alloy substrate.     

Microstructure and corrosion behavior of plasma electrolytic oxidation coated magnesium alloy pre-treated by laser surface melting

An AZ91D magnesium alloy was treated using duplex techniques of laser surface melting (LSM) and plasma electrolytic oxidation (PEO). The microstructure, composition and corrosion behavior of the laser melted surface, PEO coatings, LSM–PEO duplex coatings as well as the as-received specimen were characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), X-ray diffraction (XRD) and electrochemical corrosion tests, respectively. Especially, the effect of LSM pre-treatment on the microstructure, composition and corrosion resistance of the PEO coatings was investigated. Results showed that the corrosion resistance of AZ91D alloy was marginally improved by LSM due to the refinement of grains, redistribution of β-phase (Mg₁₇Al₁₂) and increase of Al on the surface. Both the PEO and duplex (LSM–PEO) coatings improved significantly the corrosion resistance of the AZ91D alloys, while the duplex (LSM–PEO) coating exhibited better corrosion resistance compared with the PEO coating.     

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.     

Substitution of hexavalent chromate conversion treatment with a plasma electrolytic oxidation process to improve the corrosion properties of ion vapour deposited AlMg coatings

In this paper plasma electrolytic oxidation (PEO) is examined as a potentially beneficial post-deposition treatment for Al-5 wt.%Mg coatings deposited onto Ti alloy substrates using Ion Vapour Deposition (IVD), with a view to replacing toxic hexavalent chromate conversion treatments and at the same time enhancing the barrier protection properties of such IVD coatings. The aqueous corrosion behaviour of PEO layers formed on IVD coatings was evaluated by means of potentiodynamic polarisation scans, open circuit potential measurements and electrochemical impedance spectroscopy. Normally, IVD aluminium-based coatings require a post-coat shot peening treatment to densify the coating structure; however it was found that PEO layers could be formed successfully on as-deposited IVD coatings deposited onto Ti alloy substrates, providing a cost effective process to improve corrosion behaviour. PEO treatment provides unique improvements in the corrosion resistance of IVD coatings; the PEO layer possesses effective anticorrosion properties in aqueous environments containing Cl⁻ ions. A more positive corrosion potential, lower corrosion current and increased polarisation resistance were recorded for PEO layers, compared to traditional chromate conversion treatments.