In situ observation of formation and spreading of micro-droplets on magnesium and its alloy under cyclic wet-dry conditions

The formation and spreading of micro-droplets on pure magnesium and its alloy in an atmosphere of water vapor under cyclic wet-dry conditions was studied using an environmental scanning electron microscope (ESEM). The in situ observations indicated that the corrosion product stimulated the formation and spreading of micro-droplets, and the grain boundaries for pure magnesium and β phase for AZ91 magnesium alloy had no influences on this process. The oxygen concentration on the surface generally increased with the wetting time. The corrosion products decreased the corrosion rate.     

Al扩散涂层对AZ91D Mg合金耐腐蚀性能的影响

通过磁控溅射Al和真空退火的方法,在AZ91DMg合金表面得到Al扩散涂层.利用XRD衍射和SEM观察表征了表面层的相组成和形貌;利用动电位极化测试研究了原始的和经表面处理的AZ91D在3.5%NaCl溶液中的腐蚀行为.结果表明:经上述表面处理的合金表面层结构为Mg-Al金属间化合物,自腐蚀电位提高,腐蚀电流密度减小,耐腐蚀性能提高.     

压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为

采用电化学方法研究了压铸镁合金AZ91D在酸性NaCl溶液中的腐蚀行为,并用扫描电镜观察了腐蚀形貌,对腐蚀产物进行了能谱分析.研究结果表明:在酸性溶液环境下,随着Cl-浓度的升高,镁合金的平衡腐蚀电位降低,线性阻抗减小,腐蚀电流增大;随着pH值的减小,晶界出现腐蚀开裂现象;富Al相的耐蚀性高于基体相,在酸性环境中,腐蚀产物主要为MgO和Mg(OH)2     

Effects of Mn on Corrosion Resistant Property of AZ91 Alloys

采用电化学、静态失重、盐雾腐蚀法研究了Mn对热处理态AZ91合金耐蚀性能的影响,利用扫描电镜观察试样的微观形貌,用X射线衍射仪分析合金的物相组成和腐蚀产物。结果表明,Mn与AZ91合金中的Al形成了独立相Al6Mn,该相溶解到Mg固溶体中提高了Mg的电极电位,进而提高了合金的耐腐蚀性;Mn加入后使合金的自腐蚀电位升高,自腐蚀电流密度降低,降低了合金的腐蚀速率,进而提高了合金的耐腐蚀性能,且三种实验方法都表明AZ91-0.8Mn合金的耐腐蚀性能最好。     

AZ91D镁合金电偶腐蚀的扫描Kelvin探针研究

利用扫描Kelvin探针技术(SKP)研究AZ91D镁合金与316L不锈钢偶接件在盐雾试验中电偶腐蚀规律。通过在中性盐雾试验不同周期的表面腐蚀形貌的观察和伏打电位分布图的测量结果分析表明,AZ91D镁合金电偶腐蚀效应与偶接阴阳极的伏打电位差密切相关,AZ91D镁合金与316L不锈钢偶接件存在较大的电位差(约为–1.28V),其电偶腐蚀效应非常显著。在盐雾试验初始阶段,腐蚀主要发生在偶接界面AZ91D镁合金一侧,该腐蚀区域的伏打电位增加幅度较大,而316L不锈钢受到保护没有发生明显腐蚀。随着盐雾试验时间的延长,AZ91D镁合金腐蚀加快,腐蚀产物覆盖区域不断扩大,24h盐雾试验后,偶接件的平均伏打单位差由原始的–1.29V增加到–1.53V,AZ91D镁合金的电偶腐蚀效应加大。由于AZ91D镁合金在盐雾中生成的腐蚀产物对基体具有一定的保护作用,当腐蚀产物不断增加并覆盖表面,偶接件的电位差减小导致AZ91D镁合金的电偶腐蚀效应降低。     

AZ91D镁合金微弧氧化膜的腐蚀行为研究

利用双向全波脉冲电源对AZ91D镁合金在硅酸盐体系中进行了微弧氧化处理,通过电化学阻抗谱(EIS)测试、极化曲线分析并结合XRD和SEM等分析方法对微弧氧化处理的镁合金腐蚀行为进行了研究.结果表明,微弧氧化膜表面分布着几微米的微孔,微弧氧化膜中主要含有MgF2,Mg2SiO4和Al2O3.AZ91D镁合金经过微弧氧化处理之后,耐蚀性能明显提高,自腐蚀电流密度降低3个数量级,自腐蚀电位高出约300 mV,阻抗值高出3个数量级,研制的微弧氧化膜对镁合金具有很好的防腐保护性能.     

Influences of Ca and Y Addition on the Microstructure and Corrosion Resistance of Vacuum Die-Cast AZ91 Alloy

The influences of Ca and Y additions on the microstructure and corrosion resistance of vacuum die-cast AZ91 alloys were investigated by optical microscope,electron scanning microscope,weight-loss test,and electrochemical corrosion experiment.The results indicate that the Ca or Ca and Y additions refined the microstructure and decreased the amount of Mg17Al12 phase on grain boundaries in the alloys.Meanwhile,the addition of Ca and Y led to the formation of network Al2 Ca phase and rod-like Al2 Y phase,improved the corrosion resistance of AZ91 magnesium alloy.Compared with AZ91 alloy,the corrosion rate of AZ91–1.5Ca–1.0Y alloy was decreased to 16.2%,and its corrosion current density was dropped by one order of magnitude after immersion in 3.5 wt% NaCl solution for 24 h.     

AZ91D镁合金表面激光熔覆Al-TiC涂层组织和性能的研究

目的研究Al-TiC涂层组织和性能的特性,以提高镁合金涂层的硬度和耐蚀性能。方法采用Nd:YAG固体激光器,在AZ91D镁合金表面通过激光熔覆制备Al-TiC涂层,采用光学显微镜、X射线衍射仪、显微硬度计、电化学工作站,对熔覆层的组织形貌、物相结构、显微硬度和耐蚀性能进行测定和分析。结果 Al-TiC涂层的主要组成相有AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,Al和TiC等。激光熔覆层的厚度约为0.35 mm,表面成型良好,结合层晶粒细小,熔覆层与镁合金基体之间结合良好,呈大波浪形。熔覆层试样的平均显微硬度为224HV,约为基体显微硬度(62HV)的4倍,由此表明熔覆层对镁合金硬度有明显的增强作用。镁合金基体的自腐蚀电位为-1.475 V,自腐蚀电流密度为7.556×10~(–5) A/cm~2,熔覆层试样的自腐蚀电位为-1.138V,自腐蚀电流密度为4.828×10~(–5) A/cm~2,与镁合金基体相比,熔覆层的腐蚀电位值增加,腐蚀电流密度值变小,熔覆层的耐蚀性能得到提高。结论采用激光熔覆技术,能够在AZ91D镁合金基体表面制备Al-TiC涂层,由于硬质相AlTi_3(C,N)_(0.6),Al_3Mg_2,Mg_2Al_3,TiC等的存在,熔覆层的显微硬度和耐蚀性能显著提高。     

AZ91D镁合金电偶腐蚀的研究

在自来水和3.5%NaCl溶液中测试了铸造AZ91D镁合金与铝合金、锌合金、Q235碳钢和Cu偶合后的电偶腐蚀行为,研究了腐蚀环境、偶接材料和阴阳极面积比(CAAR)对铸造AZ91D镁合金电偶腐蚀行为的影响。在电偶腐蚀过程中测量溶液的pH值以及电偶腐蚀电流;用失重法计算了铸造AZ91D镁合金的电偶腐蚀速率,利用SEM观察了AZ91D镁合金的腐蚀形貌,并对腐蚀产物进行XRD分析。结果表明,AZ91D镁合金在电偶腐蚀过程中会使溶液的pH值升高,并伴有以Mg(OH)₂为主的腐蚀产物的生成;溶液中Cl^-的存在会加速AZ91D镁合金的电偶腐蚀速率;低氢过电位金属Q235碳钢和Cu对AZ91D镁合金的电偶腐蚀加速效果明显高于中氢过电位金属铝合金和锌合金,偶接材料的极化性能对AZ91D镁合金的电偶腐蚀速率有较大影响。同时,大的阴阳极面积比会加速AZ91D镁合金的电偶腐蚀速率,且AZ91D镁合金的电偶腐蚀电流随阴阳极面积比的增大而呈线性增长趋势。     

Comparison of corrosion behaviors of AZ31, AZ91, AM60 and ZK60 magnesium alloys

The corrosion behaviours of four kinds of rolled magnesium alloys of AZ31, AZ91, AM60 and ZK60 were studied in 1 mol/L sodium chloride solution. The results of EIS and potentiodynamic polarization show that the corrosion resistance of the four materials is ranked as ZK60＞AM60＞AZ31＞AZ91. The corrosion processes of the four magnesium alloys were also analyzed by SEM and energy dispersive spectroscopy(EDS). The results show that the corrosion patterns of the four alloys are localized corrosion and the galvanic couples formed by the second phase particles and the matrix are the main source of the localized corrosion of magnesium alloys. The corrosion resistance of the different magnesium alloys has direct relationship with the concentration of alloying elements and microstructure of magnesium alloys. The ratio of the β phase in AZ91 is higher than that in AZ31 and the β phase can form micro-galvanic cell with the alloy matrix, as a result, the corrosion resistance of AZ31 will be higher than AZ91. The manganese element in AM60 magnesium alloy can form the second phase particle of AlMnFe, which can reduce the Fe content in magnesium alloy matrix, purifying the microstructure of alloy, as a result, the corrosion resistance of AM60 is improved. However, due to the more noble galvanic couples of AlMnFe and matrix, the microscopic corrosion morphology of AM60 is more localized. The zirconium element in ZK60 magnesium alloy can refine grain, form stable compounds with Fe and Si, and purify the composition of alloy, which results in the good corrosion resistance of ZK60 magnesium alloy.     

Application of cyclic upsetting-extrusion to semi-solid processing of AZ91D magnesium alloy

The microstructural evolution of AZ91D magnesium alloy prepared by means of the cyclic upsetting-extrusion and partial remelting was investigated. The effects of remelting temperature and holding time on microstructure of semi-solid AZ91D magnesium alloy were studied. Furthermore, tensile properties of thixoextruded AZ91D magnesium alloy components were determined. The results show that the cyclic upsetting-extrusion followed by partial remelting is effective in producing semi-solid AZ91D magnesium alloy for thixoforming. During the partial remelting, with the increase of remelting temperature and holding time, the solid grain size increases and the degree of spheroidization tends to be improved. The tensile mechanical properties of thixoextruded AZ91D magnesium alloy components produced by cyclic upsetting-extrusion and partial remelting are better than those of the same alloy produced by casting.     

无铬转化膜预处理提高AZ91D镁合金化学镀Ni-P的腐蚀性能(英文)

在化学镀Ni-P层和AZ91D镁合金之间生成磷酸锰、单宁酸或钒转化膜预处理层,以取代传统的铬酸盐加氢氟酸预处理工艺。电化学测试结果表明:与传统的铬酸盐处理加化学镀相比,镁合金上的无铬转化膜加化学镀镍磷具有低的腐蚀电流密度和更正的腐蚀电位,能够减少基体上化学镀层的腐蚀。因此,镀层具有致密的细晶结构,适当的磷含量、低孔隙度和良好的耐蚀性并且和基体结合良好的涂层可以取代传统的铬酐钝化加化学镀的工艺。     

Effect of TiO2 nanoparticles on the microstructure and corrosion behavior of MAO coatings on magnesium alloy

The microstructure and corrosion behavior of the micro‐arc oxidation (MAO) coatings modified by TiO₂ on AZ91 magnesium alloys were investigated by SEM, EDS, XRD, electrochemical analysis and drop test, respectively. The modified MAO coatings were consisted of not only MgAl₂O₄ and MgO, which usually could be found in MAO coatings on the AZ91 alloys, but also a small quantity of Ti. With increasing the contents of TiO₂ nanoparticles from 0 to 4.8 g/L in the electrolyte, the coatings thickness increased from 19 to 24 µm, and the color of the MAO coating changed from light gray to dark. The addition of TiO₂ could effectively decrease the number of the pores and improve the density of the coatings. The corrosion potential of the modified coatings positively shifted about 180 mV and the corrosion current density declined and the drop time increased. The mechanism of the corrosion resistances of the modified coatings lay in the fact that TiO₂ nanoparticles could increase the thickness and the density of the coatings on the AZ91 magnesium alloys.     

Kontaktkorrosion einer Magnesiumlegierung mit beschichteten Bauteilen

Galvanic corrosion behaviour of magnesium alloy in contact with coated components Electrochemical investigations were carried out to examine galvanic corrosion in preparation for the use of steering gear made from a magnesium, pressure die‐casting. The aim was to characterize various joining elements of the steering gear (e.g. hold‐down devices, threaded bushings, plugs, screws) with different types and qualities of protective coating with regard to the risk of galvanic corrosion in magnesium alloy AZ91. In addition the change in the polarization resistance was determined for one coating system after contact with AZ91 and compared with data without contact. The quality of the coatings is very important to prevent galvanic corrosion. This was demonstrated using as an example, KTL coated systems of various quality. The evaluation of current density potential curves of the coatings only allows a gradation of the top coat qualities in relatively short time, but the problems which can actually appear at contact to AZ91 aren't recognized.     

激光表面强化对镁合金在模拟体液中腐蚀行为的影响

目的通过对镁合金表面进行激光强化处理,改善医用AZ91D镁合金在模拟体液中的耐腐蚀性能。方法采用不同脉宽的Nd:YAG脉冲激光对医用AZ91D镁合金表面进行处理,激光能量密度分别为28、23、18 J/mm~2,对激光处理后镁合金强化层的组成、显微结构、厚度、元素分布以及耐腐蚀性能等进行测试和分析。结果 AZ91D经过激光强化处理后形成致密的强化层,强化层中相的组成与基材相的组成相同,均由α-Mg和β-Mg_(17)Al_(12)组成,强化层的厚度达到300μm。Mg和Mg_(17)Al_(12)的X射线衍射峰均向低角度偏移(约0.2°),且镁合金表面晶粒均得到细化,β相的大小从平均55.705μm减小到平均6.447μm。EDS分析表明,经过激光处理后,Mg的质量分数由82.88%减少为70.13%,Al的质量分数由16.28%增加为28.08%,且Al的分布更均匀。激光处理后,镁合金在模拟体液中的电化学测试结果表明,镁合金的腐蚀电位从原来的-1274mV增加到-1215 mV,腐蚀电流密度从8.920×10~(-5) A/cm~2减小为8.826×10~(-6) A/cm~2,同时,阻抗也从原来的1000Ω增加到60 000Ω,可知激光强化镁合金的耐腐蚀性能较原始镁合金的耐腐蚀性能均有一定程度的改善。结论医用AZ91D镁合金在不同脉宽的Nd:YAG脉冲激光处理后,表面晶粒得到了细化,强化层中富集Al,在模拟体液中的耐腐蚀性能得到改善。     

Enhanced corrosion behavior and mechanical properties of AZ91 magnesium alloy developed by ultrasonic-assisted friction stir processing

In this study, ultrasonic-assisted friction stir processing (UaFSP) and friction stir processing (FSP) were conducted on AZ91 magnesium alloy sheets, and their microstructure, corrosion behavior, and mechanical properties were comparatively investigated. Scanning electron microscopy, open-circuit potential, and potentiodynamic polarization were used to study the corrosion behavior of the material. Electrochemical measurements reveal that employing UaFSP, the corrosion rate of the AZ91 magnesium alloy was significantly reduced where lower corrosion current density for UaFSP specimens was obtained (2.09 µA/cm²) compared with 3.42 µA/cm² for the FSP and 6.82 µA/cm² for the base metal. This is mainly attributed to the alteration of morphology and better distribution of the β-Mg₁₇Al₁₂ phase during UaFSP. By using ultrasonic vibration in FSP, a finer grain structure was obtained, which improved the tensile strength and hardness of the AZ91 Mg alloy.     

铝基非晶纳米晶复合涂层研究

采用自动化高速电弧喷涂系统,用自行研制的粉芯丝材,在AZ91镁合金基体表面上制备出Al-Ni-Y-Co非晶纳米晶复合涂层.采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、透射电子显微镜(TEM)分析了Al-Ni-Y-Co非晶纳米晶复合涂层的微观形貌和组织结构,结果表明Al-Ni-Y-Co非晶纳米晶复合涂层是由非晶相和纳米晶化相共同组成的,涂层结构致密,孔隙率约为1.8%.Al-Ni-Y-Co非晶纳米晶复合涂层的平均显微Vickers硬度值为311.7 HV0 1,结合强度为26.8 MPa.涂层的抗磨损耐腐蚀性能优于Al涂层和AZ91镁合金基体;其相对耐磨性约为Al涂层的10倍,为AZ91镁合金的6倍;其自腐蚀电位值正于Al涂层及AZ91镁合金,自腐蚀电流密度值约为Al涂层的1/2,AZ91镁合金的1/5;其腐蚀后的表面形貌比Al涂层和AZ91镁合金平整,点蚀较少.Al-Ni-Y-Co非晶纳米晶复合涂层的耐磨防腐综合性能优异.     

前处理工艺对镁合金钛/锆转化膜耐蚀性能的影响

研究了酸洗以及酸洗+碱洗前处理工艺对AZ91D镁合金无铬、无裂纹、低能耗钛/锆转化膜耐蚀性能的影响。结果表明,单独的酸洗前处理使得AZ91D镁合金表面的α相优先溶解,合金表面粗糙度增加,不利于钛/锆转化膜耐蚀性能的增加。合理地利用酸洗+碱洗调整AZ91D镁合金表面化学状态能够有效提高钛/锆化学转化膜的耐蚀性能。     

AZ91D熔体中原位合成TiC颗粒及冲刷腐蚀性能

利用原位合成反应法,在不同温度(740、760和780℃)下对AZ91D镁合金熔体保温40min,制备了TiC/AZ91D镁基复合材料。借助光学显微镜和X射线衍射仪,对TiC/AZ91D镁基复合材料的组织形貌和物相进行观察和分析,并对制备的复合材料在质量分数为3.5%的NaCl溶液+石英砂条件下进行冲刷腐蚀磨损试验。结果表明,在740℃保温40min制备的复合材料主要由α-Mg、β-Mg17Al12和Al3Ti组成。保温温度分别为760℃和780℃时,AZ91D镁合金中均出现了原位合成的TiC颗粒,并且随温度升高,TiC的数量增加。此外,TiC/AZ91D镁基复合材料在3.5%的NaCl溶液+石英砂中的冲刷腐蚀磨损性能随保温温度的升高而增加。经780℃保温40min后的复合材料呈出最好的耐冲刷腐蚀磨损性能,相比于AZ91D镁合金提高了60.5%。     

Influence of substrate composition on the formation of phytic acid conversion coatings

In this paper, the formation and corrosion resistance of the phytic acid conversion coatings on Mg, Al, and AZ91D magnesium alloy were contrastively investigated using scanning electronic microscopy (SEM), Auger electron spectroscopy (AES), Fourier transform infrared spectroscopy (FTIR), electronic probe microscopic analyzer (EPMA), electronic balance, and electrochemical methods. The influence of phytic acid conversion coating as a middle layer on the properties of the paint on magnesium alloys was also investigated. The results show that the formation process of the conversion coatings is evidently influenced by the compositions of the substrate. The coating on pure aluminum is thinner and compacter than that on pure magnesium and the coating formed on α phase in AZ91D magnesium alloy is thinner but denser than that on β phase. The phytic acid conversion coatings formed on Mg, Al, and AZ91D magnesium alloy can all increase their corrosion resistance. The active functional groups of hydroxyl and phosphate radical are rich in the conversion coatings, which can improve the bonding between the organic paint and magnesium alloy and then improve their corrosion resistance.