AZ91D镁合金表面转化膜腐蚀及防护涂层性能研究

采用高锰酸盐、钼酸盐、锡酸盐转化液分别对AZ91D镁合金进行表面化学转化,得到三种不同的化学转化膜。分别通过SEM、EDS和全浸试验研究不同转化膜的表面微观形貌、成分和腐蚀率,通过划格法和中性盐雾试验法研究转化膜外部有机涂层的附着性能和耐蚀性能。结果表明,高锰酸盐和钼酸盐转化膜表面具有大量微细裂纹,锡酸盐转化膜表面呈鱼鳞状,均为后续涂装提供了具有一定粗糙度的表面。锡酸盐转化膜的耐蚀性最好,高锰酸盐转化后并涂层的附着力和耐蚀性能最好。     

锡酸盐转化前处理对镁合金化学镀镍镀层的影响

目的利用锡酸盐转化膜中间层避免化学镀镍镀层与金属基体的直接接触,降低其产生原电池腐蚀的趋势,提高镁合金化学镀镍层的耐蚀性及稳定性。方法采用锡酸盐化学转化膜技术在AZ31镁合金表面制备锡酸盐转化膜层,然后通过直接化学镀镍技术在该膜层上沉积Ni-P镀层。利用SEM、EDS、浸泡析氢、电化学测试等手段,研究了复合镀层的显微结构、相组成、耐蚀性。结果锡酸盐转化膜由细小均匀的球形颗粒堆积而成,颗粒之间存在空隙,为直接化学镀镍时镍磷的初始沉积提供了可能。化学转化膜表面沉积的化学镀镍层均匀致密,形成典型的胞状结构。基体-化学转化膜-化学镀Ni-P合金层三者之间的结合良好,保证了复合镀层优良的耐蚀性能。结论化学镀Ni-P层能够在不经过钯活化处理的条件下直接在锡酸盐转化膜上沉积,锡酸盐转化膜中间层避免了Ni-P阴极性镀层与阳极性镁基体的直接接触,降低了Ni-P镀层局部缺陷对整体防护效果的影响,提高了镀层的耐蚀性及耐久性。     

载波钝化对AZ91D镁合金锡酸盐化学转化膜耐蚀性能的影响

用载波钝化方法控制AZ91D镁合金锡酸盐转化膜成膜过程,用扫描电镜（SEM）观察该转化膜的表面形貌,用极化曲线和电化学阻抗谱研究载波钝化对该转化膜耐蚀性能的影响。结果表明, 载波钝化使AZ91D镁合金表面生成一层颗粒直径略大于传统浸泡处理的锡酸盐转化膜,其耐蚀性能显著提高。     

Electrodeposition of zinc on AZ91D magnesium alloy pre‐treated by stannate conversion coatings

A stannate chemical conversion process followed by an activation procedure was employed as the pre‐treatment process for AZ91D magnesium alloy substrate. Zn was electroplated onto the pre‐treated AZ91D magnesium alloy surface from pyrophosphate bath to improve the corrosion resistance and the solderability. The surface morphologies of conversion coating and zinc coating were examined with scanning electron microscope (SEM). The phase composition of conversion coating was investigated by X‐ray diffraction (XRD). The electrochemical corrosion behavior of the coatings in the corrosive solution was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). The experimental results showed that the activated stannate chemical conversion coating provided a suitable interface between zinc coating and the AZ91D magnesium alloy substrate. The corrosion resistance of the AZ91D substrate was improved by the zinc coating.     

Electroless Ni-Sn-P coating on AZ91D magnesium alloy and its corrosion resistance

An electroless Ni-Sn-P coating was deposited on AZ91D magnesium alloy in an alkaline-citrate-based bath where nickel sulphate and sodium stannate were used as metal ion sources and sodium hypophosphite was used as a reducing agent. The phase structure of the coating was amorphous. SEM and attached EDS observation revealed the presence of dense and uniform nodules in the ternary coating and the content of tin was 2.48wt.%. Both the electrochemical analysis and the immersion test in 10% HCl solution proved that the ternary Ni-Sn-P coating exhibited better corrosion resistance than the Ni-P coating in protecting the magnesium alloy substrate.     

Corrosion of AZ91D magnesium alloy with a chemical conversion coating and electroless nickel layer

A chemical conversion treatment and an electroless nickel plating were applied to AZ91D alloy to improve its corrosion resistance. By conversion treatment in alkaline stannate solution, the corrosion resistance of the alloy was improved to some extent as verified by immersion test and potentiodynamic polarization test in 3.5 wt.% NaCl solution at pH 7.0. X-ray diffraction patterns of the stannate treated AZ91D alloy showed the presence of MgSnO₃ · H₂O, and SEM images indicated a porous structure, which provided advantage for the adsorption during sensitisation treatment prior to electroless nickel plating. A nickel coating with high phosphorus content was successfully deposited on the chemical conversion coating pre-applied to AZ91D alloy. The presence of the conversion coating between the nickel coating and the substrate reduced the potential difference between them and enhanced the corrosion resistance of the alloy. An obvious passivation occurred for the nickel coating during anodic polarization in 3.5 wt.% NaCl solution.     

Effect of permanganate concentration on the formation and properties of phosphate/permanganate conversion coating on AZ31 magnesium alloy

This study investigated the role of permanganate in phosphate solutions in the formation and corrosion resistance of phosphate/permanganate coatings on AZ31 magnesium alloys. Experimental results showed that permanganate was reduced to manganese (IV) oxide together with the dissolution of magnesium during the conversion coating treatment. Adding more permanganate to the phosphate solution resulted in a thinner coating with a compact magnesium oxide layer contacting the AZ31 plate. Moreover, the thinner coating had fewer cracks and displayed higher polarization resistance and corrosion resistance than the thicker counterpart formed in the solution with less permanganate.     

镁合金化学镀中预处理氟化镁膜的特征与作用

对镁合金的表面前处理工艺进行研究,探讨氟化镁在化学镀层中的存在形式及作用。结果表明：酸浸使镁合金表面形成一层氧化物膜;活化过程生成的氟化镁不具备反应活性,对镁合金基体有保护作用,使之免于受镀液的过度腐蚀;对化学镀层断口进行SEM元素分布分析显示氟化镁层集中存在于镁合金基体与Ni-P镀层之间;但过度活化会导致化学镀层孔隙率升高,以3.5%NaCl溶液为介质的动电位极化测试表明,过度活化会导致化学镀层耐蚀性下降。     

A291D镁合金锡酸盐转化膜形成机理和腐蚀行为研究

通过正交试验确定了以焦磷酸盐和锡酸盐为主要成分的镁合金化学转化处理的最佳工艺.用集气法和电化学方法评价了转化膜在中性NaCl溶液(NaCl的质量分数为3.5%)中的腐蚀行为;用扫描电镜和X射线衍射分析了转化膜的结构和形貌,探讨了转化膜的形成机理.结果表明:锡酸盐转化处理后在镁合金表面形成了以MgSnO3·H2O为主要成分的转化膜,转化膜由细小的球形颗粒密积而成;腐蚀性能评价证明它可对基体合金起到一定的防护作用.     

Mg-10Li-1Zn合金锡酸盐转化膜的制备及其耐蚀性能研究

采用含有锡酸钠和磷酸二氢钾两种成分的转化液,在Mg-10Li-1Zn合金表面上得到锡酸盐化学转化膜,研究了该转化膜的微观结构、成膜机制及抗腐蚀性能。结果表明,此膜层均匀、连续,主要由MgSnO3、Mg3（PO4）2和SnO组成。腐蚀试验结果显示,该转化膜改善了基体合金的抗腐蚀能力。     

Effect of HCl pre-treatment on corrosion resistance of cerium-based conversion coatings on magnesium and magnesium alloys

The corrosion protection afforded by a cerium conversion coating, formed by immersion in a solution containing rare earth salt and hydrogen peroxide, on pure magnesium and two magnesium alloys, AZ91 and AM50, has been studied. The effect of HCl pre-treatments on the morphology and on the corrosion resistance of the cerium conversion layer was investigated. A thicker and more homogeneous distribution of the conversion coating was obtained when the sample surface was pre-treated with acid. Higher amounts of cerium on the surface of the pre-treated samples were detected. The cerium conversion coating increased the corrosion resistance of the alloys because it ennobled the corrosion potential and decreased both the anodic and cathodic current. The acid pre-treatment further increased the corrosion resistance of the coated alloys. After five days of immersion in chloride environment the untreated samples showed localized corrosion while the chemical conversion coated samples appeared unaffected.     

pH值对AZ91D镁合金表面植酸转化膜的影响

在pH值不同的几种植酸转化液中对AZ91D镁合金进行表面转化处理,利用扫描电镜及自带能谱仪、Tafel曲线和阻抗谱等分析手段,结合NaCl水溶液点滴实验,研究了pH值对植酸转化膜表面成分及耐蚀性的影响.结果表明:在酸性条件下形成的植酸转化膜的耐蚀性较好;转化液的pH值会影响植酸螯合物的形成和转化膜的物质组成,进而影响转化膜的耐蚀性能;在酸性条件下,镁合金表面形成的植酸转化膜应属于电子导体膜,它阻碍了腐蚀介质与基体的接触,同时抑制腐蚀产物的扩散,对镁合金起到防护作用.     

Ceria/stannate multilayer coatings on AZ91D Mg alloy

In this work, CeO₂/stannate multilayer coatings on AZ91D magnesium alloy were successfully obtained by chemical conversion and sol–gel dip coating. The stannate conversion coatings were prepared from a stannate aqueous bath containing Na₂SnO₃, CH₃COONa, Na₃PO₄ and NaOH at different temperatures and immersion times. Ceria films were produced on stannate/AZ91D starting from Ce(III) nitrate solutions in H₂O. In some cases, the PVA was added as chelating agent. Ceria top coatings were fired at 200 °C for 1 h. Coating microstructure was examined by FE-SEM. Finally, the corrosion resistance features of the coatings were tested by the electrochemical impedance spectroscopy (EIS) in 3 wt.% NaCl solution. The effect of PVA addition was evaluated in terms of microstructure and corrosion resistance features. CeO₂/stannate multilayer films, 3 μm thick, uniform, well adherent and nearly crack free were obtained. The formation of CeO₂ phase was confirmed by XRD and XPS analyses. The XPS depth profiles showed a limited diffusion of Mg towards the ceramic film. The EIS tests showed a significant improvement of corrosion resistance of the multilayer coatings (~ 16.6 kΩ after 48 h in NaCl solution) with respect to the blank alloy (~ 2.4 kΩ after 48 h in NaCl solution).     

有机添加剂对AZ91D镁合金锡酸盐转化膜性能的影响

采用化学转化法在镁合金表面制备锡酸盐转化膜。采用硫酸铜点滴实验、电化学交流阻抗(EIS)测试和Tafel曲线、扫描电子显微镜(SEM)测试和X射线衍射分析(XRD)等方法检测膜层的性能。研究了几种有机添加剂(Tartaric acid、Citric acid、Phytic acid、EDTA、Sodium dodecyl sulfate)对膜层耐蚀性的影响,结果表明溶液中添加SDS后,转化膜的硫酸铜点滴时间由35 s提高到了86 s,明显提高转化膜的耐腐蚀性能,膜层的形貌为呈"颗粒"状紧凑的连接到一起,该膜层的主要成分为Mg Sn(OH)6、Mg(OH)2。     

Stannate and permanganate conversion coatings on AZ31 magnesium alloy

The formation of stannate and permanganate–phosphate conversion coatings on AZ31 magnesium alloy was investigated in situ by EIS measurements and their protective performances were studied by different electrochemical techniques in diluted (0.05 M) sodium sulphate solution.The influence that short or long treatment times exert on the performances of such conversion coatings is discussed. While permanganate–phosphate baths always built layers characterized by penetrating cracks, long stannate baths produced layers without interconnected porosity, but were defective. This accounted for the initial greater protectiveness achieved with the stannate treatment; nevertheless, the easy penetration of the electrolytic solution through such a layer quickly decreased its corrosion resistance.     

A two-step roll coating phosphate/molybdate passivation treatment for hot-dip galvanized steel sheet

A two-step roll coating passivation treatment employing phosphate followed by molybdate solutions has been performed on hot-dip galvanized (GI) steel sheet. The phosphate coating was primarily porous, amorphous Zn phosphate. A second step coating treatment resulted in more hemispherical Zn phosphate particles and the incorporation of molybdate ions and molybdenum oxide into the existing phosphate coating, giving rise to an improved corrosion resistance. The coating reaction during the second step roll coating treatment and the corrosion protection afforded by the second step molybdate treatment are discussed, with emphases on the comparison with the coating formed via immersion.     

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.     

镁合金磷酸盐 /氮化硅双层复合膜结构及耐蚀性能研究

目的针对传统镁合金化学转化膜裂纹尺寸大、耐腐蚀性差等问题,制备一种镁合金磷酸盐/氮化硅双层结构的抗腐蚀复合膜。方法先对镁合金进行传统磷酸盐转化处理,再运用等离子体增强化学气相沉积技术沉积氮化硅膜层,分析复合膜的形貌、元素分布、表面电位及极化曲线,并与磷酸盐转化膜进行对比。结果氮化硅膜层能在磷酸盐转化膜裂纹处选择性优先沉积,从而在相当程度上填补转化膜层的裂纹,形成致密的复合膜结构。具有复合膜结构的镁合金表面电位和腐蚀电位明显高于传统磷酸盐转化处理的镁合金。结论镁合金表面制备磷酸盐/氮化硅双层复合膜后,抗腐蚀能力明显高于传统磷酸盐转化处理的镁合金。     

AZ31镁合金表面锡酸盐化学转化膜的研究

对AZ31镁合金表面采取锡酸盐化学转化处理,采用对比试验测定了转化膜在质量分数3.5%NaCl溶液中的腐蚀率,利用扫描电镜(SEM)及能谱(EDS)观察分析了转化膜的形貌和元素含量.结果表明:经锡酸盐转化后的AZ31镁合金的腐蚀率为2.65mm/a,未经转化的AZ31镁合金的腐蚀率为30.36mm/a,耐蚀性有明显提高;锡酸盐转化液pH值在3.5～12范围时对AZ31镁合金均形成了转化膜保护层.     

α-Al2 O3微粒对铸造Al-Si合金微弧氧化膜耐蚀性的影响

目的通过共生沉积技术将α-Al2O3微粒引入到铸造Al-Si合金微弧氧化膜中,并研究其对膜层耐蚀性的影响。方法利用SEM和XRD分析α-Al2O3微粒对微弧氧化膜微观结构及成分的影响。通过极化曲线、交流阻抗谱及中性盐雾试验评价膜层的耐蚀性。结果α-Al2O3微粒复合改变了微弧氧化膜的组成及结构。微弧氧化膜呈双层结构,表面存在大量微孔,主要组成为γ-Al2O3;加入α-Al2O3微粒后,微弧氧化复合膜的表面微孔大幅减少,致密度提高,且膜层中α-Al2O3相增多。此外,α-Al2O3微粒复合改善了微弧氧化膜的耐蚀性。微弧氧化膜在质量分数为3.5%的Na Cl溶液中的自腐蚀电流密度约为1.476×10-5A/cm2,多孔层电阻Rp及阻挡层电阻Rb分别为0.259 kΩ·cm2及69.18 kΩ·cm2,耐盐雾试验时间为1200 h。加入α-Al2O3微粒后,微弧氧化复合膜的自腐蚀电流密度仅为微弧氧化膜层的28%,Rp大幅增加至274.5 kΩ·cm2,且Rb也上升了一个数量级,耐盐雾试验时间可达1440 h。结论α-Al2O3微粒的引入可以大幅提高铸造Al-Si合金微弧氧化膜的耐蚀性。