电压对AZ31镁合金微弧氧化涂层微观结构及腐蚀性能的影响

为研究过程参数对镁合金微弧氧化涂层的微观结构及耐腐蚀性能的影响,在AZ31镁合金基体上,采用不同电压,在电解液磷酸三钠(Na3PO4)中制备微弧氧化涂层.采用扫描电子显微镜(SEM)及光学显微镜,分析膜层腐蚀前后的微观组织结构;通过X射线衍射仪(XRD)分析涂层样品腐蚀前后的相组成.采用动电位极化曲线和电化学阻抗谱(EIS)测试对涂层的耐腐蚀性能进行评价.结果表明:AZ31镁合金微弧氧化涂层主要由Mg3(PO4)2,MgO,Mg和少量MgAl2O4组成,腐蚀产物由Mg(OH)2,quintinite和Ca10(PO4)6 (OH)2组成.在电压为325 V,频率3 000 Hz,氧化时间为5 min下制备的微弧氧化涂层具有最致密均匀的微观形貌和最小的腐蚀电流密度,因此表现出最强的耐腐蚀性能.     

镁合金微弧氧化膜耐蚀性表征方法的对比研究

制备结构、性能相近的AZ91D镁合金微弧氧化膜,通过浸泡、点滴及电化学实验表征膜层的耐蚀性,并结合SEM分析膜层腐蚀前后的表面形貌。本研究中6种耐蚀性检测方法的结果均表明：AZ91D镁合金经微弧氧化处理后耐蚀性显著提高; 失重与增重现象的共存使浸泡实验不能准确评定微弧氧化膜层耐蚀性的优劣; 点滴实验可以较快较准确地反映膜层的耐蚀性,但采纳点滴液开始变色的时间点为评价依据更合适,且测试耐蚀性较好的膜层时,点滴液中硝酸的含量提高到标准中的至少两倍时,才能达到快速检测的目的; 循环伏安、Tafel 极化、开路电位和电化学阻抗谱4种电化学实验能反映诸如腐蚀电位、腐蚀电流密度、阻抗值等更多的信息,可以进一步研究膜层的耐蚀原因。膜层的耐蚀性除了与膜厚、化学成分有关外,还与微观结构膜层内部和表面的密切相关。     

Characterization of the corrosion performances of as-cast Mg–Al and Mg–Zn magnesium alloys with microarc oxidation coatings

In the present study, corrosion-protective microarc oxidation (MAO) coatings were prepared on AZ31B, AZ80, and ZK60 cast magnesium alloy substrates in an alkaline silicate electrolyte. The corrosion performances of the uncoated and MAO-coated alloys were investigated using electrochemical and salt spray chamber corrosion tests. The microstructure characterization and experimental results show that among the three alloys studied, the ZK60 Mg alloy exhibited the best and AZ31B the least corrosion resistance under the salt spray conditions. The MAO coating provided robust corrosion protection of the Mg substrates and resulted in a significant decrease in the corrosion rate of the alloys by 3–4 orders of magnitude. The MAO coating on ZK60 alloy showed better corrosion protectiveness than that on the AZ series alloys due to the incorporation of different alloying elements in the coating, especially the Zn and Al elements, which are from the Mg substrate. The corrosion performances and mechanisms of the uncoated and MAO-coated Mg alloys are interpreted in terms of the microstructure and phase/chemical compositions of both the substrates and coatings.     

Mg合金的腐蚀与防护

介绍了Mg合金的腐蚀原理、腐蚀类型以及合金元素在镁合金中的作用。综述了Mg合金的化学转化膜、阳极氧化、微弧氧化、化学镀等经典的表面处理方法 ,以及快速凝固工艺和表面改性技术对Mg合金表面耐蚀性能的影响。Mg合金易发生全面腐蚀、电偶腐蚀、点蚀、应力腐蚀和高温氧化。解决Mg合金腐蚀的方法有 :一是研究新合金 ,提高Mg合金自身的热力学稳定性 ,稀土Mg合金是最有前途的耐蚀合金 ;二是通过表面处理使Mg合金表面富SiO2 和Al2 O3 、含SiC和F-等物质或获得的非晶态的涂层结构能有效地提高Mg合金的耐蚀耐磨性能 ;三是改进加工工艺 ,快速凝固和激光退火不仅能获得力学性能优秀的Mg合金产品 ,还能获得纳米结构的表面涂层防护膜 ,提高Mg合金的耐蚀耐磨性能。使镁合金表面涂层结构纳米化、玻璃化是表面处理工艺的发展趋势。     

氟钛酸钾添加对铝镁复合板微弧氧化涂层结构及耐蚀性的影响

为研究氟钛酸钾(K₂TiF₆)添加对Al-Mg复合板微弧氧化涂层结构和耐腐蚀性能的影响,在硅酸盐-氢氧化钠电解液体系中加入不同浓度的氟钛酸钾(0、1、2和3 g·L^-1),利用微弧氧化技术(MAO)在Al-Mg复合板表面制备陶瓷氧化物涂层。通过SEM、XRD、EDS和电化学工作站等对制备陶瓷氧化物涂层显微组织、相组成、形貌及耐蚀性能进行表征。添加K₂TiF₆后,Al-Mg复合板Al侧的涂层厚度、表面孔隙率和表面粗糙度随K₂TiF₆浓度的增加呈下降的趋势(24.2～18.4μm、6.8%～5.3%、3.55～2.23),Mg侧涂层呈上升趋势(21.0～26.6μm、3.6%～5.3%,3.35～4.33),此外涂层中的Ti和F元素含量增加,各样品的耐蚀性均有所提高。添加K₂TiF₆为2 g·L^-1时,两侧涂层的耐蚀性最好,其中R_t均比未添加的样品增加...     

非阀金属的等离子体电解氧化研究进展

等离子体电解氧化技术通常用于Al、Mg、Ti等阀金属表面形成高性能陶瓷层,较少涉及非阀金属。主要介绍了碳钢、铜、锌及其合金等“非阀金属”的等离子体电解氧化技术的最新进展。列举了碳钢在不同的电解液成分、电参数、氧化时间等工艺参数条件下制备所得涂层的相关性能,阐述了碳钢在等离子体电解氧化过程中绝缘膜击穿优于气膜击穿的成膜理论。分析了铜及其合金在硅酸盐、铝酸盐、磷酸盐及其混合电解液中的等离子体电解氧化行为,并探究了涂层的耐腐蚀和耐摩擦性能及形成机理。阐述了在不同的工艺参数下锌及其合金在耐腐蚀、耐摩擦、气敏传感和生物降解性的研究,并且论述了阀金属与非阀金属成膜的差异所在。最后,对非阀金属等离子体电解氧化技术后续的发展进行了展望。     

Characterization and wear resistance of macro-arc oxidation coating on magnesium alloy AZ91 in simulated bedy fluids

The mechanical characteristics ofthe macro-arc oxidation(MAO) coating on Mg alloy AZ91 were examined by means of nano scratch tester.The corrosion and erosion corrosion behavior of AZ91 with and without MAO coating were investigated by using potentiodynamic electrochemical technique and micro-abrasion tribometer in simulated body fluids,respectively.The influence of HCO3-ions on the erosion corrosion was discussed.The results show that the coating and its substrate are in a pronounced bond.The MAO coating inereases1-2 orders of magnitude of the corrosion resistance of AZ91 alloy.HCO3-ions enhance the corrosion rates of the AZ91 alloys more significantly than the alloys with MAO coating.However,there exists an obvious passivation process of AZ91 without coating in the HCO3-solutions.Moreover,an MgCO3 film formed in HCO3-containing solutions leads to an enhancement in micro-wear resistance.MAO coating deteriorates the erosion corrosion resistance of AZ91 alloy due to the formation of oxidation debris resulted from the broken MAO coating.     

Effects of electric parameters on microstructure and properties of MAO coating fabricated on ZK60 Mg alloy in dual electrolyte

Micro-arc oxidation (MAO) process was carried out in a dual electrolyte system of NaAlO2 and Na3PO4 on ZK60 Mg alloys to explore the effect of electric parameters including current density, frequency, duty cycle and oxidation time on the evolution of coatings and other characteristics. The microstructural characteristics of coatings were observed by scanning electron microscopy (SEM) combined with the analysis of voltage-time responses during MAO process. Test of weight loss was conducted at a 3. 5％ NaCl solution to assess the resistance to corrosion. The results indicate that the current density and duty cycle play key roles on the coating quality. The peak voltage during MAO process increased with the increase in current density but the coating would be more easily detached when the current density was beyond a critical value. Voltage during MAO and microstructure of the coating were affected remarkably by duty cycle, and corrosion resistance was improved greatly when duty cycle was 40％. By means of single variable experiments, MAO process with optimized electric parameters was developed, which corresponds to the current density of 20 A·dm-2, frequency of 500 Hz, duty cycle of 40％ and oxidation time of 15 min.     

Laser Surface Engineering of Magnesium Alloys: A Review

Magnesium (Mg) and its alloys are well known for their high specific strength and low density. However, widespread applications of Mg alloys in structural components are impeded by their insufficient wear and corrosion resistance. Various surface engineering approaches, including electrochemical processes (plating, conversion coatings, hydriding, and anodizing), gas-phase deposition (thermal spray, chemical vapor deposition, physical vapor deposition, diamond-like coatings, diffusion coatings, and ion implantation), and organic polymer coatings (painting and powder coating), have been used to improve the surface properties of Mg and its alloys. Recently, laser surface engineering approaches are attracting significant attention because of the wide range of possibilities in achieving the desired microstructural and compositional modifications through a range of laser?Cmaterial interactions (surface melting, shock peening, and ablation). This article presents a review of various laser surface engineering approaches such as laser surface melting, laser surface alloying, laser surface cladding, laser composite surfacing, and laser shock peening used for surface modification of Mg alloys. The laser?Cmaterial interactions, microstructural/compositional changes, and properties development (mostly corrosion and wear resistance) accompanied with each of these approaches are reviewed.     

超高频脉冲电流作用下纳米Al2O3颗粒对Mg-Gd-Y-Zr合金微弧氧化涂层的影响

目的 进一步提高Mg-Gd-Y-Zr合金微弧氧化涂层的耐腐蚀性能。方法 采用超高频微弧氧化技术在含有Al2O3纳米颗粒的溶液中制备了微弧氧化涂层。利用扫描电子显微镜(FESEM)、能谱仪(EDS)和X射线衍射仪(XRD)对微弧氧化涂层的表面形貌、截面形貌、成分和晶体结构进行分析。利用极化曲线和电化学阻抗谱(EIS)测试了涂层的耐腐蚀性能。结果 频率由0.5 kHz提升至20 kHz后,涂层表面放电孔洞面积由0.07~24.4 μm²降低至0.08~6.3 μm²,涂层的孔隙率由6.47%减小至3.35%。Al2O3纳米颗粒的添加使超高频涂层表面形成大量自封闭孔洞结构,进而进一步降低了涂层表面的孔径面积(0.1~ 4.63 μm²)和孔隙率(0.97%)。极化试验表明,提高频率至20 kHz,涂层的自腐蚀电流密度由4.7×10^‒6 A/cm²降低至4.7×10^‒7 A/cm² ,添加 Al2O3纳米颗粒,涂层的自腐蚀电流密度进一步降低至1.7×10^‒7 A/cm²,表明其耐蚀性能显著提高。阻抗谱显示,20 kHz-Al涂层具有最大的阻抗,说明该工艺可有效提高微弧氧化涂层的耐蚀性能。 结论 超高频可有效降低放电孔洞尺寸,提高微弧氧化涂层的致密性,改善涂层的耐腐蚀性能。超高频与Al2O3纳米粒子的协同作用使涂层表面形成自封闭孔洞结构,进一步提高微弧氧化涂层的致密性和耐腐蚀性能。     

镁合金微弧氧化复合膜研究进展

微弧氧化（MAO）表面处理技术常用于改善镁合金的特定性能,但MAO膜容易产生微孔和微裂纹从而降低镁合金的耐蚀性。为了提高镁合金微弧氧化膜的使用寿命,主要综述了国内外MAO工艺过程调节措施和MAO膜后处理技术的最新研究进展,重点介绍了近年来国内外镁合金MAO复合膜的研究热点。着重介绍了通过工艺过程调节提高镁合金MAO膜长期保护性能的几项措施：通过电参数和电源类型调节协同电解液成分调整提高MAO膜耐蚀性;通过加入电解液添加剂提高MAO电解液稳定性和电导率;利用具有自封孔作用的添加剂可以参与成膜的特点提高MAO膜致密性;通过复合工艺在MAO膜传统封孔后进一步封闭孔隙。此外,详细介绍了包括疏水涂层、化学镀、类金刚石涂层、生物膜涂层等复合膜工艺的研究进展,强调了复合膜不仅耐蚀性高而且具有功能化应用前景：超疏水复合膜对镁基底具有主动的腐蚀保护作用,超疏水膜协同MAO膜可以提高表面的疏水性;镀镍层致密无微孔且与MAO膜交错咬合能够改善镁MAO膜的导电性和耐蚀性;MAO涂层代替金属缓冲层能够提高类金刚石涂层和基体界面结合强度;生物复合涂层不仅耐蚀性高还具有促进细胞增殖和分化生物活性的作用。最后,基于镁...     

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。     

6061铝合金表面新型黄色微弧氧化陶瓷层的制备与表征

目的 研究6061铝合金表面新型微弧氧化黄色陶瓷层的制备工艺,并对其微观结构、成分、硬度、耐蚀性能等进行表征。方法 在以Na2SiO3为基础的电解液中加入Na2SnO3进行微弧氧化处理,制备出黄色微弧氧化陶瓷层,并与传统白色、黄色、黑色微弧氧化陶瓷层作对比。采用SEM和EDS分析膜层表面形貌和元素分布,借用XPS对膜层进行成分表征,使用硬度计测试其表面硬度,采用电化学工作站和人造海水腐蚀实验评价陶瓷层的抗腐蚀性能。结果 随着电解液中Na2SnO3浓度的增加,陶瓷层中Sn元素含量增加,Si元素含量减少,陶瓷层黄色饱和度不断增强。黄色含Sn陶瓷层制备过程中,电解液中的SnO32-在高温高压下转化为SnO2,导致陶瓷层硬度达到365HV,高于白色与黑色陶瓷层。在3.5% NaCl溶液中进行电化学测试,黄色含Sn陶瓷层的腐蚀电流密度与腐蚀电位分别为9.34×10-9 A/cm2和-0.34 V,耐蚀性优于白色和黄色含Mn陶瓷层。结论 在电解液中添加Na2SnO3可在铝合金表面生成具有较高硬度和耐蚀性能良好的类似沙漠黄色的陶瓷层,为铝及其合金在多领域的应用奠定了一定的实验基础。     

镁合金微弧氧化技术的研究进展

结合国内外微弧氧化技术的研究成果,综述了成膜过程火花放电机理及陶瓷层的生长过程,总结了电解液组成、电源类型、工作模式、电参数以及基体材料等对微弧氧化膜性能的影响。根据近年来微弧氧化技术用于镁合金表面处理的发展状况,介绍并分析了几种封孔处理的优化方法,重点介绍了工艺更为简单的原位封孔技术。同时也对镁合金微弧氧化技术的发展趋势和应用前景进行了展望。     

The effect of substrate composition on the electrochemical and mechanical properties of PEO coatings on Mg alloys

Plasma electrolytic oxidation (PEO) is a unique surface treatment technology which is based on anodic oxidation forming ceramic oxide coatings on the surface of light alloys such as Mg, Al and Ti. In the present study, PEO coatings prepared on AZ91D, AZ31B, AM60B and AM50B Mg alloys have been investigated. Surface morphology and elemental composition of coatings were determined using scanning electron microscope (SEM) equipped with energy dispersive spectrometer (EDS). SEM results showed that the coating exhibited a porous top surface layer and a subsequent dense layer with micro-pores and shrinkage cracks. Phase analysis of coatings was carried out by X-ray diffraction (XRD). XRD analyses indicated that PEO coatings on AZ alloys had higher amount of Periclase (MgO) followed by the presence of Spinel (MgAl₂O₄) e.g. on the AZ91D alloy compared to that on AM series alloys. In order to examine the effect of substrate composition on adhesion strength of PEO coating scratch tests were carried out. Electrochemical corrosion tests were undertaken by means of potentiodynamic polarization technique in 3.5% NaCl solution at room temperature (20 ± 2 °C). Corrosion test results indicated that the corrosion rates of coated Mg alloys decreased by nearly two orders of magnitude as compared to bare Mg alloys. PEO coatings on AZ series alloys showed better corrosion resistance and higher adhesion properties than AM series alloys. In addition to the PEO processing parameters, such are mainly attributes of the compositional variations of the substrate alloys which are responsible for the formation, phase contents and structural properties of the PEO coatings.     

高低电压下不同厚度微弧氧化膜抗蚀电化学响应对比研究

目的 对比研究具有不同厚度的微弧氧化膜的抗蚀电化学响应.方法 通过调整电压,在硅酸盐电解液体系中,于AZ91D镁合金表面制备具有不同厚度的微弧氧化膜层.利用SEM、EPMA和XRD研究膜层的微观形貌、元素及物相组成,进而采用循环伏安(CV)法、动电位极化曲线和电化学阻抗谱(EIS),对比研究该膜层的抗蚀电化学响应.结果 AZ91D镁合金经微弧氧化处理后,其抗蚀性得以显著提高,但不同厚度的膜层的抗蚀电化学响应不同.相比低电压下制备的薄膜,高电压下制备的厚膜的抗蚀物相含量高,CV曲线环面积和腐蚀电流密度均降低了约1个数量级,线性极化电阻增大了约3.7倍,且其阻抗模值更高,膜层抗蚀性更优.两膜层的腐蚀失效过程不同.厚膜的腐蚀过程主要经历了2个阶段:腐蚀介质逐渐渗入膜层和腐蚀介质渗透至膜基界面侵蚀基体.薄膜的腐蚀过程经历了3个阶段:腐蚀介质逐渐渗入膜层、腐蚀介质渗透至膜基界面侵蚀基体和膜层完全失效.结论 厚膜呈现出较弱的腐蚀倾向和优异的抗蚀性能,三种电化学测试的结果都能较好地相互印证,但在揭示膜层的腐蚀过程和腐蚀机制时各自的深入程度不同.     

镁合金表面腐蚀防护技术研究进展

镁合金较差的耐腐蚀性能限制了其大规模应用。利用表面腐蚀防护技术可以有效改善镁合金的耐蚀性能,延长镁合金的服役寿命。因此,可靠的表面腐蚀防护技术是突破镁合金应用瓶颈的关键。从镁合金表面腐蚀防护技术的分类入手,阐述了各种防护技术的基本原理。在此基础上,综述了近年来镁合金腐蚀防护技术的研究进展,包括电化学方法、化学方法及其他表面腐蚀防护方法等,阐明了各种技术的优缺点及适用范围,并对镁合金表面防护技术的发展趋势进行了展望。经过多年的发展,镁合金表面防护技术的理论研究和应用日臻完善,现有的表面防护方法一定程度上都能为镁合金基体提供腐蚀防护作用。然而,随着镁合金应用范围的扩展,相关结构件常会面临恶劣的服役环境。因此,单一的表面腐蚀防护技术已经很难满足工业领域对镁合金材料的迫切需求,多种表面处理技术联合制备的复合涂层具有广阔的应用前景。镁合金表面防护技术当前正朝着功能化和智能化的复合涂层方向发展,同时对制备工艺的安全环保性也提出了更高要求。未来除了保证高耐蚀性外,开发多功能智能涂层对提升防护层的长效防护能力、拓宽镁合金的应用范围具有重大的现实和长远意义。     

Fabrication and characterization of micro‐arc oxidation (MAO) coatings on Mg‐Li alloy in alkaline polyphosphate electrolytes without and with the addition of K2TiF6

Micro‐arc oxidation (MAO) has been accomplished on Mg‐Li alloy in alkaline polyphosphate electrolytes without and with the addition of 10 g/L K₂TiF₆. The surface/cross‐section microstructures of the fabricated coatings were analyzed by scanning electron microscope (SEM); the compositions of the fabricated MAO coatings were analyzed by X‐ray diffraction (XRD) and energy dispersive X‐ray analysis (EDAX); the corrosion behaviors of bare and MAO coated Mg‐Li alloys were evaluated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) in 3.5 wt% NaCl solution. Novel hybrid MAO coatings which showed hybrid composition of MgF₂/Ti₂O₅/Ti₆O₁₁/MgO, as well as hybrid structure of a dense inner layer, a dense outer layer and an intermediate layer with some sealed/semi‐sealed pores, had been fabricated on Mg‐Li alloy in alkaline polyphosphate electrolytes with the addition of K₂TiF₆. Meanwhile, the corrosion resistance of the fabricated MAO coatings was improved obviously as the result of the addition of K₂TiF₆ in the electrolytes. Moreover, the multiple roles of ${\rm TiF}_{{\rm 6}}^{{\rm 2}{-} } $ on the MAO process accounted for the fabrication of the corrosion‐resistant hybrid MAO coatings.     

纯镁表面等离子体电解渗硼与微弧氧化复合膜的制备及耐蚀性

目的 在纯镁表面制备新型复合膜,以提高其耐蚀性.方法 先在硼砂系电解液中对纯镁进行等离子体电解渗硼(PEB)处理,预制表面改性层,然后在硅酸盐系电解液中对其进行微弧氧化(MAO)处理,从而获得PEB+MAO新型复合膜.分别使用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线衍射仪(XRD)分析膜层的微观结构、元素分布及物相组成,膜层的耐蚀性则通过动电位极化曲线和电化学阻抗谱(EIS)来表征.结果 纯镁的等离子体电解渗硼过程经历了电离、置换、吸附和扩散四个阶段,获得的PEB表面改性层由氧化层和扩散层组成.在PEB+MAO复合膜的生长过程中,膜层在其厚度方向存在重叠的现象,而不是逐层的简单堆积.等离子体电解渗透时,硼元素渗入后所形成的渗层区域降低了纯镁基体表面的化学活性,改善了其微观组织结构,进而使PEB+MAO复合膜的腐蚀电流密度较基体、单一PEB改性层和单一微弧氧化膜层分别降低了3、2、1个数量级.同时,EIS研究也表明,PEB+MAO复合膜可以提供相对较长时间的抗蚀保护.另外,分析了PEB表面改性层的生成机理以及PEB+MAO复合膜的形成过程,并建立了物理模型.结论 PEB预处理会显著影响PEB+MAO复合膜的厚度、致密性及成分,继而明显提高纯镁的耐蚀性.该新型的复合膜制备方法有望进一步推广到镁合金上,以提高其耐蚀性和承载能力.     

Corrosion resistance of calcium-modified zinc phosphate conversion coatings on magnesium–aluminium alloys

The influence of the microstructure of the calcium-modified zinc phosphate (Zn–Ca–P) conversion coatings of Mg–Al alloys on corrosion resistance was investigated using OM and SEM and hydrogen evolution tests. The results demonstrated that the Zn–Ca–P coatings markedly enhanced the corrosion resistance of the alloys. The microstructure and chemical compositions of the alloys exerted a significant influence on the corrosion resistance of their coatings. A model was proposed to elucidate the formation mechanism of the porous Zn–Ca–P coating on the AM30 alloy.