镁合金化学转化膜

综述了镁合金化学转化膜技术的现状，主要涉及化学转化处理工艺及在多种不同处理液中所得到的转化膜的特性，最后还展望了今后镁合金化学转化膜的发展趋势。     

镁合金表面稀土转化膜研究进展

镁合金作为结构材料具有十分突出的性能,但镁的低电位导致其耐蚀性很差,大大限制了镁合金的广泛应用.化学转化膜作为一种简单、有效的防腐蚀表面处理方法得到了迅速发展.相较目前成熟但污染严重的铬酸盐转化膜处理工艺,稀土盐转化处理因其良好的环境友好性和耐蚀性能而备受关注.总结了稀土盐转化膜的成膜工艺及膜的性能、膜的组成及微观形貌、膜的形成机理以及膜的耐腐蚀机理等方面的研究现状,提出了转化膜的一些技术问题,并展望了该技术的发展趋势.     

镁合金表面稀土铈盐转化膜的制备与耐蚀性能

目的在镁合金表面制备稀土铈盐转化膜,以改善镁合金的耐蚀性能。方法利用化学转化技术在镁合金表面制备出稀土铈盐转化膜,进而采用SEM、EDAX及电化学测试技术等系统研究铈盐浓度、添加剂含量、转化时间和转化温度对转化膜形貌、成分和耐蚀性能的影响。结果稀土铈盐转化膜呈金黄色,由Mg、Ce和O组成,表面存在网状裂纹。转化膜的耐蚀性随铈盐浓度、添加剂含量、转化温度、转化时间的增加呈现先增加后降低的变化规律。结论稀土铈盐转化膜由Mg和Ce的氢氧化物和氧化物组成。铈盐转化膜的最佳工艺条件为:Ce(NO3)3质量浓度10~15 g/L,H2O2添加含量25~50 m L/L,转化温度40℃,转化时间30 min。经稀土铈盐转化处理后,镁合金的耐蚀性能得到了明显的改善。     

镁合金表面稀土转化膜工艺研究进展

镁合金稀土转化膜技术是一种环保型镁合金表面处理新技术。从单一稀土转化和复合稀土转化两个方面,综述了近年来国内外镁合金表面稀土转化膜工艺的研究现状及进展,简要讨论了稀土转化膜的成膜机理和耐腐蚀机理,指出了稀土转化膜技术目前存在的问题,并展望了这一技术的发展前景。     

AZ91镁合金表面铈基稀土转化膜的制备及腐蚀电化学行为

考察了铈盐溶液中的AZ91镁合金电化学行为,包括开路电位,阴、阳极极化行为等,并据此开展了Ce(NO3)3为主盐的稀土盐转化膜研究,在AZ91镁合金表面形成无毒、无污染的铈盐化学转化膜,并研究成膜规律及其耐蚀行为.采用电化学阻抗谱技术优化了处理时间、温度、Ce(NO3)3液浓度和促进剂等因素对膜层结构和膜层耐蚀性能的影响,并获得了最好的成膜条件:处理温度为35℃,时间为30 min,主盐Ce(NO3)3的浓度为0.02 mol/L和促进剂H2O2浓度为4 mL/L.结果表明:采用优化后的工艺能够在AZ91镁合金表面获得宏观黄色致密、微观具有微小裂纹并分层的膜层,表层Ce含量较高.工艺优化制备的稀土化学转化膜能有效提高镁合金的耐蚀性能,有效抑制阴、阳极反应,自腐蚀电位提高250 mV,自腐蚀电流密度降低2个数量级.长期全浸实验结果表明,转化膜能有效提高镁合金的耐腐蚀性能,浸泡60 h后,保护性大大降低.     

Mg-Gd-Y-Zr合金表面铈转化膜制备及耐蚀性能

采用容量法研究了Mg-Gd-Y-Zr合金表面铈转化膜的耐蚀性能,通过正交试验获得在其表面制备铈转化膜的最佳条件:pH值为10.0,成膜时间为30 min,成膜促进剂的浓度为0.05 mol/L,成膜温度为25 ℃.其影响程度为pH值>成膜时间>成膜促进剂的浓度>成膜温度.比较了铈转化膜、铬酸盐转化膜及光板镁合金在3.5%NaCl溶液中的耐蚀行为.实验结果表明铈转化膜显著地提高了镁合金的耐腐蚀性能.     

添加剂及pH对压铸镁合金AZ91D植酸转化膜的影响

采用不同的植酸水溶液对压铸镁合金AZ91D进行化学转化处理,通过SEM、EDS、浸泡法研究了添加剂及pH值对转化膜膜厚、形貌及耐蚀性能的影响.结果表明:pH值由3增大到5时,转化膜的膜厚和耐蚀性呈先增大后减小的趋势,当pH=4时膜厚达到最大值,且耐蚀性能最好.加入添加剂后所得到的化学转化膜的膜厚和耐蚀性能都相对未加添加剂的化学转化膜有所增大,同时加入添加剂后的转化膜表面裂纹明显变小.在选用Ca(NO3)2、偏钒酸铵、酒石酸钠作添加剂的植酸溶液中所形成的转化膜的性能最佳.     

不锈钢稀土铈转化膜的研究

研究了不锈钢在稀土铈盐中的化学转化成膜工艺,通过L9(34)正交试验研究了最佳成膜工艺参数,采用化学点滴试验、阳极极化曲线测试分析和表征了转化膜的耐蚀性能,并用光学显微镜观测了转化膜的表面形貌.结果表明:高浓度的稀土铈在不锈钢表面可形成棕色转化膜,低浓度稀土铈形成黄色的转化膜;转化膜形成使不锈钢的腐蚀电位从未经稀土处理的20 mV提高到稀土处理后的200～1000mV.通过对转化膜表面形貌的观测,得出了膜的耐蚀性随表面光滑程度的提高、颜色的加深而增强.     

AZ31镁合金双稀土转化膜的TiO2溶胶处理

采用TiO2溶胶对双稀土转化膜进行处理,膜的表面形成了新的膜层.SEM表明经TiO2溶胶处理后双稀土转化膜表面有新物质覆盖在裂纹中,使裂纹减小,未露出内层膜,膜层变得均匀完整.极化曲线和交流阻抗对TiO2处理后的双稀土转化膜进行电化学测试,表明采用TiO2处理后试样的腐蚀电位由-1.143 V升高到-0.747V,腐蚀电流密度降低了两个数量级,并且交流阻抗谱的容抗弧半径增大,极化电阻由1.61 kΩ增大到1.81 kΩ,试样的耐腐蚀性得到了明显的提高.     

镁合金表面稀土转化膜的磷酸盐致密化及性能

首先在AZ91镁合金表面上制备出镧铈双稀土转化膜,然后利用(NH_4)_3PO_4溶液进行致密化处理。采用扫描电镜(SEM)、X射线衍射仪(XRD)、高温氧化和电化学方法对致密化之后的转化膜形貌与性能进行研究。结果表明,对应用正交试验法确定的镧铈双稀土转化膜进行致密化处理的最佳工艺参数为:处理温度50℃、(NH_4)_3PO_4质量浓度5%、处理时间4 min。致密化后的膜层裂纹明显减少,表面致密性提高,很好地改善了对基体的覆盖度。经致密后的双稀土转化膜主要由稀土氧化物、氢氧化物、磷酸盐和氧化镁组成。致密化后的膜层耐蚀性显著提高。致密化后的双稀土转化膜的抗高温氧化性能优于未经致密化处理的双稀土转化膜。     

Corrosion resistance,composition and structure of RE chemical conversion coating on magnesium alloy

Golden yellow rare earths chemical conversion coating was obtained on the surface of magnesium alloy by immersing in cerium sulfate solution.The corrosion resistance of RE conversion coating was evaluated using inmersion test and potentiodynamic polarization measurements in 3.5%NaCl solution.The morphologies of samples before corrosion and after corrosion were observed by SEM.The structures and compositions of the RE conversion coating were studied by means of XPS,XRD and IR.The results show that,the con...     

AZ91D镁合金无铬铈盐转化膜的正交试验研究

为了代替剧毒Cr^6＋化学转化膜处理工艺,采用硝酸铈以及高锰酸钾为无铬化学转化处理液的主要成膜成分,通过正交试验优化了以Ce（NO3）3,为主盐的镁合金铈盐化学转化膜工艺,并对成膜规律进行了研究。试验表明,本工艺所获得的铈盐化学转化膜具有优良的外观和良好的耐腐蚀性。此外,借助扫描电镜分析手段对转化膜的微观形貌进行了分析,还对氧化膜成膜机制进行了探讨。     

Enhanced corrosion performance of magnesium phosphate conversion coating on AZ31 magnesium alloy

Magnesium phosphate conversion coating (MPCC) was fabricated on AZ31 magnesium alloy for corrosion protection by immersion treatment in a simple MPCC solution containing Mg²⁺ and PO^3?₄ ions. The MPCC on AZ31 Mg alloy showed micro-cracks structure and a uniform thickness with the thickness of about 2.5 µm after 20 min of phosphating treatment. The composition analyzed by energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy revealed that the coating consisted of magnesium phosphate and magnesium hydroxide/oxide compounds. The MPCC showed a significant protective effect on AZ31 Mg alloy. The corrosion current of MPCC was reduced to about 3% of that of the uncoated surface and the time for the deterioration process during immersion in 0.5 mol/L NaCl solution improved from about 10 min to about 24 h.     

镁合金环保型化学转化膜工艺研究

采用环保型化学转化工艺,利用扫描电镜、X射线衍射和全浸蚀等分析试验手段,研究了AZ91D镁合金锡酸盐化学转化膜的形貌、相结构及耐腐蚀性.结果表明,转化膜主要由镁的α相、β相和MgSnO2·3H2O组成;该环保型化学转化工艺可获得由近球状微粒构成的银白色膜层,表面均匀平整.该膜层的耐蚀性能优于传统含铬DOW7工艺形成的防护膜,且所用成膜液无铬,符合环保要求.     

Microstructure and properties of oxalate conversion coating on AZ91D magnesium alloy

The oxalate coating formed on AZ91D magnesium alloy by chemical conversion treatment methods in oxalate salt solutions was investigated. The surface morphologies and chemical composition of coating were examined using scanning electron microscopy (SEM) equipped with energy dispersive analysis of X-ray (EDX). Electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves and salt spray tests were employed to evaluate corrosion protection of the coating to substrate in 5% NaCl solution. The mechanism of coating formations was also considered in details. The results indicate that a compact and dense surface morphology with fine particle clusters of the oxalate coating on magnesium alloy is presented, which mainly consists of oxide or/and organic of Mg, Al and Zn. And the anti-corrosion of the magnesium after oxalate conversion treatment is better than that of the magnesium substrate. The results of salt spray test for oxalate coating is evaluated as Grade 9 according to ASTM B117. The electric resistance of oxalate chemical conversion coating to substrate is below 0.1 Ω.     

Influence of pH value on chromate-free conversion coating for magnesium alloys

Many factors were found to have effects on the conversion coatings for AZ31 alloy, alloy the most important one in producing high quality conversion coatings is found to be the control of the pH value. The influence of pH value on the conversion coating including color, thickness, adhesion and surface morphology was studied. The performance of conversion coating was examined by cross cut test, SEM method and salt immersion. The results show that the variation ofpH value causes surface treatment process unstably. The conversion coating can obtain as pH value ranging from 3.0 to 5.0, while it presents dark, thick and bad adhesion under lower pH value. The conversion coatings have good combination of thickness and adhesion when pH value ranging from 4.0 to 4.5, and it exhibits a good corrosion resistance.     

Organic-magnesium complex conversion coating on AZ91D magnesium alloy

An organic-magnesium complex conversion (OMCC) coating on AZ91D magnesium alloy was obtained by treating in a solution containing organic compounds. SEM, FESEM and XPS were used to examine the surface morphology, thickness and structure of the conversion coatings. The results show that the continuous and uniform conversion coating is deposited on AZ91D alloy and the main component of the coatings is organic compound containing benzene ring, which forms a chemical bond with magnesium. The polarization measurement and salt spray test show that the corrosion resistance of the conversion coating is much higher than that of traditional chromate conversion coating.     

Barium phosphate conversion coating on die-cast AZ91D magnesium alloy

Poor corrosion resistance limits the application of magnesium alloys.Conversion coating is widely used to protect magnesium alloys because of easy operation and low cost.A novel conversion coating on die-cast AZ91D magnesium alloy containing barium salts was studied.The optimum concentrations of Ba(NO_3)_2,Mn(NO_3)_2 and NH_4H_2PO_4 are 25 g/L,15 mL/L and 20 g/L,respectively,based on orthogonal test results.The treating time,solution temperature and pH value are settled to be 5-30 min, 50-70℃and 2.35-3.0...     

AZ31镁合金表面磷酸盐-高锰酸盐化学转化膜性能的试验研究

用磷酸盐-高锰酸盐在AZ31镁合金表面制备出无铬化学转化膜,并采用金相显微分析、扫描电镜分析、能谱分析、X-射线衍射分析、电化学方法、中性盐雾试验分别对化学转化膜封孔处理前后的表面形貌、成分、相结构和耐蚀性进行检测和评价.研究结果表明,无铬化学转化处理可以显著提高镁合金的耐蚀性,封孔后处理可以有效地封闭化学转化膜中存在的孔隙,并进一步提高镁合金的耐蚀性.