AZ91D合金表面铈转化膜成膜工艺及其耐腐蚀性的研究

  通过正交试验确定了AZ91D 镁合金在CeCl₃H₂O₂体系中的最佳成膜条件.利用扫描电镜对转化膜进行形貌观察和成分分析,利用浸泡集气和电化学方法了膜层的耐腐蚀性能.结果表明,在最佳成膜条件下,形成的膜层均匀、致密.在3.5% NaCl溶液和0.15 mol/L H₃BO₃/0.05 mol/L Na₂B₄O₇缓冲溶液中的动电位极化测试表明,最佳条件下铈盐转化处理可使合金的腐蚀电位正移,腐蚀电流密度明显降低,起到一定的防护作用.     

PREPARATION OF MICROARC OXIDATION COATING ON (Al2O3-SiO2)sf/AZ91D MAGNESIUM MATRIX COMPOSITE AND ITS ELECTROCHEMICAL IMPEDANCE SPECTROSCOPIC ANALYSIS\par

在硅酸盐电解液体系中, 采用交流微弧氧化方法在增强体体积分数为33%的 (Al₂O₃-SiO₂)_sf/AZ91D镁基复合材料表面制备出完整的保护性氧化膜. 利用SEM, EDS和XRD分析了氧化膜的形貌、成分和相组成, 测量了膜层的显微硬度分布. 采用电化学阻抗谱(EIS)评价了微弧氧化表面处理前后复合材料的电化学腐蚀性能, 确立了不同浸泡时间对应的等效电路. 结果表明, 微弧氧化膜主要由MgO和Mg₂SiO₄相组成, 最大硬度达到1017 HV. 氧化膜电化学阻抗模值|Z|与镁合金基体相比大幅度提高, 耐腐蚀性能明显高于基体. 在3.5%NaCl溶液里浸泡96 h后, EIS出现感抗弧, 显示膜内部开始出现点蚀破坏. 氧化膜耐蚀性由膜内致密层特性所决定.     

温度和硫离子对N80钢CO2腐蚀电化学行为影响

应用电化学阻抗谱、EIS扫描电镜(SEM)及能谱（EDS）研究了温度和硫离子交互作用下,N80钢的CO₂腐蚀电化学行为及腐蚀膜的形貌与组成.结果表明：温度和硫离子对N80钢CO₂腐蚀电化学行为影响显著;硫离子加入后试样表面吸附着一层腐蚀膜;随着油田地层水中S^2-浓度的增加,传递电阻R₁、膜电阻R₂及扩散阻抗W增加,膜电容Q₂减小;腐蚀膜主要由FeS及少量FeCO₃组成;其致密性随硫离子含量增加和温度升高而增强.               

锂含量对镁锂合金表面碳酸锂膜层耐蚀性的影响

利用低温等离子体在LAZ141镁锂合金表面制备绿色环保且高耐蚀的碳酸锂膜层是一种全新的镁锂合金表面处理技术,为进一步探索合金中Li含量对所形成的碳酸锂膜层结构及耐蚀性能的影响,本文采用SEM、EDS、EIS和析氢测试等方法对不同Li含量镁锂合金的碳酸锂膜层进行了表征和分析。研究结果表明：合金基体中Li含量决定了膜层中Li₂CO₃成分的含量,当合金中Li含量达到10 wt. %以上时,膜层外层能够形成主要由Li₂CO₃成分构成的保护层;电化学测试及析氢结果表明,该保护层能够在0.6 M氯化钠溶液中将膜层阻值提高2个数量级以上并将析氢速率降低3倍以上。     

不锈钢电化学着黑色工艺与成膜机理研究

采用电化学着色法对不锈钢着黑色进行了研究,讨论了钝化处理、着色液组成等因素对着色的影响,测定了着色膜的耐磨性和耐蚀性,并根据着色膜的组成、微观结构分析了成膜机理.结果表明:钝化和封闭处理能明显提高着色膜的耐磨性和抗色变性;电化学分析表明在1 mol/L H2SO4溶液、3.5%NaC l溶液和10%NaOH溶液中,着色膜腐蚀电位比不锈钢基体分别正移1130、565和790 mV,且腐蚀电流密度都比相应介质中的小;扫描电镜和能谱结果显示膜层为封闭块状结构,着色膜主要成分是Fe、Cr、Mn等元素,封闭处理能明显减少其裂纹数目.该成膜反应机理为:1)不锈钢基体的溶解形成大量的M e2+;2)金属/溶液界面上的M e2+与Cr3+水解形成合金氧化膜沉积在基体表面上;3)电化学致密过程中4H2MoO4+2SO42-+4H+2(MoO)2SO4+6H2O+6[O]和M e+[O]=M eO反应是着色膜致密的主要原因.     

铁素体不锈钢的晶间腐蚀性能研究

    分别采用Cu-CuSO₄-16% H₂SO₄沸腾试验和电化学再活化方法研究了八种400系列铁素体不锈钢的晶间腐蚀性能.结果表明：C含量及稳定化元素是影响铁素体不锈钢晶间腐蚀性能的关键因素;电化学测量方法评价铁素体不锈钢的晶间腐蚀性能时易受晶粒再活化的影响,可结合电镜观察表面提高测量的准确性.     

不锈钢电化学着色工艺及着色膜的XPS研究

介绍了不锈钢电化学着色工艺,采用正交试验的方法对不锈钢电化学着色的试验方案进行了优化,得出最佳试验方案;用X射线光电子能谱(XPS)对不锈钢着色膜的元素组成和元素价态进行了分析,这对着色膜层的进一步开发和应用有十分重要的作用.     

热浸镀锌层上钼酸盐转化膜的腐蚀电化学性能

    将热镀锌钢在含10 g/L Na₂MoO₄·2H₂O、pH为5的溶液中60℃下处理10~300秒,获得了钼酸盐转化膜试样.应用极化曲线和电化学交流阻抗谱(EIS)研究了转化膜层在5% NaCl水溶液的耐蚀性能.结果表明,经钼酸盐转化处理后的镀锌钢板,其腐蚀电流密度下降,极化电阻升高,阴极极化作用明显增强,腐蚀保护效率显著提高,电化学阻抗值提高了一个数量级;低频扩散阻抗值随处理时间的增加先增大后减小,表明腐蚀电解质在转化膜层孔隙中扩散的难易程度先增加后下降.     

镁锂合金表面含聚苯胺复合涂层的防腐性能研究

    以过硫酸铵为氧化剂,磺基水杨酸为掺杂剂,用化学氧化法合成了聚苯胺 - 二氧化硅(PANI- SiO₂)复合材料;通过FTIR,XRD和SEM对PANI-SiO₂复合材料进行表征;以PANI-SiO₂粉末为功能成分,环氧树脂为成膜物质,在镁锂合金表面制备了PANI-SiO₂/环氧树脂复合涂层,用开路电位和交流阻抗谱研究了涂层的防腐蚀性能.结果表明,在3.0 mass%的NaC1溶液中,PANI-SiO2/环氧树脂复合涂层具有很好的防腐性能,且认为PANI的存在使得镁锂合金表面生成一层钝化膜.     

固溶处理对Al-Zn-In-Mg-Ti-Mn合金电化学性能的影响

    研究了510℃×10 h固溶处理对Mn含量不同的Al-Zn-In-Mg-Ti-Mn合金在人造海水中的腐蚀电化学性能的影响.结果表明：固溶处理使该合金的电流效率下降,但对其自腐蚀电位影响不大;当合金中Mn含量较高时,固溶处理可改善其腐蚀过程中的表面腐蚀状况,降低工作电位,而电流效率下降不大;等效电路R_S(C₁(C₂R_t)(QR)(L₁R_ad1)(L₂R_ad2)(L₃R_ad3))能较好地拟合该合金在3%NaCl溶液中腐蚀的EIS谱,基本反映了其电化学腐蚀过程.     

彩色化学镀镍磷合金镀层研究

探讨了在钢表面获得彩色化学镀镍层的方法,分析了各种工艺因素对色彩的影响,同时对彩色镀层的耐磨、耐蚀性能也进行了比较.结果表明:用钼酸铵作着色剂,并采用先镀镍,后着色的工艺,通过控制着色处理的工艺参数,可获得不同的色彩,并可保持镀层原有的耐磨、耐蚀性能.最后对形成彩色镀层的机理也进行了初步分析.     

Influence of molybdate species on the tartaric acid/sulphuric acid anodic films grown on AA2024 T3 aerospace alloy

AA2024 T3 alloy specimens have been anodised in tartaric acid/sulphuric media and tartaric acid/sulphuric media containing sodium molybdate; molybdate species were added to the anodising bath to enhance further the protection provided by the porous anodic film developed over the macroscopic alloy surface. Morphological characterisation of the anodic films formed in both electrolytes was undertaken using scanning electron and transmission electron microscopies; the chemical compositions of the films were determined by Rutherford backscattering spectroscopy that was complemented by elemental depth profiling using rf-glow discharge optical emission spectrometry. The electrochemical behaviour was evaluated using potentiodynamic polarisations and electrochemical impedance spectroscopy; the corrosion performance was examined after salt spray testing. The porous anodic film morphology was little influenced by the addition of molybdate salt, although thinner films were generated in its presence. Chemical composition of the anodic film was roughly similar; however, addition of sodium molybdate in the anodizing bath resulted in residues of molybdate species in the porous skeleton and improved corrosion resistance measured by electrochemical techniques that was confirmed by salt spray testing.     

铝材化学法不同着色效果条件的研究

采用硫酸阳极氧化膜无机染料化学着色方法,通过实验研究了着色液浓度、温度、着色时间等因素对着色效果的影响,确定了同一体系着不同颜色的最佳工艺条件,再经过一系列的性能测试,讨论了着不同颜色后铝材的性质.一般情况下,随浓度和时间增加,着色膜颜色会逐渐加深,但不会改变色系.相对浓度和时间而言,温度对着色效果影响很大,如果温度太高,氧化膜会被封孔,而着不上颜色,所以控制好温度对着不同颜色效果很重要.该工艺操作简便,溶液可循环利用;着色膜耐蚀性、耐晒性和致密性良好.     

适合着色的镁合金多孔氧化膜的工艺研究

采用L9(34)正交试验,研究了一种无铬、无氟、无磷的适合着色的镁合金环保型阳极氧化工艺,测定了阳极氧化过程中槽电压随时间的变化曲线,并采用SEM和XRD分析了氧化膜的表面形貌、结构和成分.结果表明:阳极氧化膜主要由MgO、Mg2AlO4、MgSiO3和Al2O3组成,膜层为白色,光滑均匀,为不规则多孔结构,其孔径约1～3μm.这种多孔膜具有良好的着色效果,并且能对涂层起很好的锚着作用,提高了涂层与基底的结合力.     

热镀Zn层钼酸盐钝化工艺

研究了用低毒性钼酸盐取代剧毒的重铬酸盐对热镀 Zn层进行钝化的工艺,探讨了钝化液组成、pH值、钝化处理温度及时间对钝化成膜及膜层耐 蚀性的影响.中性盐雾腐蚀(NSS)试验表明,采用该工艺可获得耐蚀性与低Cr钝化相当的具有 较为均匀的淡黄或浅蓝色钝化膜.     

Properties of fluoride film and its effect on electroless nickel deposition on magnesium alloys

The physical characteristics and microstructure of the fluoride film formed during activation were investigated using SEM,XPS and SAM,and its stability in electroless nickel(EN) bath was analyzed.The effects of the fluoride film on EN deposition were studied additionally.The results show that the fluoride film on magnesium alloys is a kind of porous film composed of MgF2 with thickness of 1.6-3.2 μm.The composition of the activation bath and pretreatment of EN processing have influence on the composition of the fluoride film.The fluoride is stable and dissolves little in EN bath;as a result,the fluoride film can protect magnesium substrate from the corrosion of EN bath.The composition of fluoride determines the initial deposition of EN and part of the fluoride film finally exists as inclusion in EN coating.     

Development of an alkali-metal-free bath for electroless deposition of Co-W-P capping layers for copper interconnections

A bath containing alkali-metal-free chemicals was developed for electroless deposition of Co-W-P thin films on a copper substrate and an optimisation of bath compositions was made. Ammonium cobalt sulphate, ammonium tungstate and ammonium hypophosphite were used as the precursors of cobalt, tungsten and phosphorus, respectively. Dimethylamine borane and ammonium citrate were used as reducing and complexing agents, respectively. It was found that the cobalt content, film thickness and grain size increased with increase in cobalt ion concentration in the bath. Tungsten in the films increased from 1 to 6 at.% when its concentration in the bath was increased from 0.001 to 0.009 M. A variation of phosphorus content from 2 to 12 at.% was made by increasing its concentration from 0.01 to 0.05 M. It was found that the deposition rate decreased with increasing citrate ion concentration. Amorphous films were obtained when the combined amount of phosphorus and tungsten exceeded 12 at.% in the films. The crystalline film had small spherical crystallites with diameter less than 40 nm.     

无铬复合钝化膜的微观组织结构及耐腐蚀性能

目的解决热镀锌钢板表面六价铬钝化工艺所产生的环境污染问题。方法以钼酸铵、纳米硅溶胶、单宁酸、硅烷偶联剂KH151和KH792为主要原料配制新型环保的无铬复合钝化液,在镀锌板表面制备钝化膜。采用扫描电子显微镜(SEM)、能谱仪(EDS)和X射线光电子能谱仪(XPS)分析无铬复合钝化膜表面的微观形貌、元素组成和化学成分,用电化学工作站测试Mo元素对镀锌板耐蚀性的影响,使用中性盐雾实验研究不同皮模量时膜层的耐蚀性。结果无铬复合钝化膜中的Mo元素可以抑制微裂纹的产生和发展,阻挡腐蚀性介质向金属基体扩散,提高复合硅烷膜的电阻。复合钝化膜的电化学交流阻抗比硅烷钝化膜提高了1.6倍,与六价铬钝化膜接近,可以有效抑制腐蚀电化学反应的发生,降低反应速度,提高膜层的耐蚀性。皮膜量为892 mg/m2时,膜层的腐蚀面积为0,耐蚀性达到六价铬钝化膜水平;皮膜量为1252 mg/m2时,耐蚀性能优异。结论制备的无铬复合钝化膜结合了硅烷钝化膜和钼酸盐钝化膜两方面的优点,提高了膜层的致密性和结合性,膜层耐腐蚀性接近/达到了六价铬钝化的效果。     

A comparative study of molybdate/silane composite films on galvanized steel with different treatment processes

Two types of molybdate/silane composite films were obtained on the surface of hot-dip galvanized steel sheets by either directly immersing in a solution containing silane and molybdate as additive (single-step process), or firstly immersing in a molybdate solution, then in a silane solution (two-step process). The chemical compositions and microstructures of the films were examined by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and reflection absorption infrared spectroscopy (RAIR). The corrosion resistances were investigated by electrochemical measurements and neutral salt spray (NSS) test. The results showed that the molybdate/silane composite film formed in the single-step process had a similar double-layer structure as that obtained in the two-step process. The inner layer was composed mainly of the elements O, Mo, Zn, and P, similar to the single molybdate film; whereas the outer layer was composed mainly of the elements C, O and Si, similar to the single silane film. Compared with the single molybdate or silane film, the corrosion current of the composite films was reduced and the impedance of the films was increased. Accordingly, the corrosion resistance of the composite films was remarkably enhanced to a level which was comparable to or even surpassing that of the conventional chromate passivation film.     

A comparative study of the electrochemical deposition of molybdenum oxides thin films on copper and platinum

Molybdenum oxides thin films electrochemical deposition was performed using solutions of peroxo-polymolybdate at pH 2.3 and ammonium molybdate at pH 5.5 as precursors and smooth copper and platinum as supports. The deposition has been carried out at constant potentials in the range of −600 to −800 mV vs. Ag/AgCl (sat. KCl). The thin films deposited on copper were then heated at 350 and 450 °C in argon. In the case of thin films deposited from ammonium molybdate and heated at 450 °C, the XRD spectra reveal, along with MoO₂, the presence of Cu₆Mo₅O₁₈ phase. For the thin films prepared from peroxo-polymolybdate and subjected to the same heat treatment, the only XRD phase present was MoO₂. Thermogravimetric (TG) analysis was performed on samples prepared by scraping away the thin films (molybdate precursors) from the copper support. Before heat treatment, the AFM images of the as-deposited thin film reveal a granular morphology, with diameters in the 20–80 nm range.