Influence of Zn-Ni alloy electrodeposition techniques on the coating corrosion behaviour in chloride solution

The aim of this research work is to optimize the plating conditions during electrodeposition of Zn-Ni alloys. Electrodeposits of Zn-Ni alloys have been synthesized from sulphate bath using cyclic voltammetry and chronopotentiometry techniques under different conditions. X-ray diffraction measurements reveal that the alloys consisted of <gamma>-Ni₅Zn₂₁ and pure zinc phases. The composition and morphology of the deposits have been also studied and discussed. The surface analyses indicate that the deposition took place with the formation of Zn-Ni alloy coatings, containing at least 10 wt.% Ni. In order to obtain better barrier properties and corrosion resistance, coated steel samples have been immersed in 3% NaCl solution and studied using potentiodynamic stripping and electrochemical impedance spectroscopy. The process of dezincification is reduced when the coated steel is electroplated by chronopotentiometry (5 mA and 10 mA). In addition, these samples exhibit an improved morphology and fine grain size as compared with deposits electroplated by cyclic voltammetry.     

电沉积电位对锌镍合金镀层耐蚀性的影响

采用电化学沉积方法在DH36船板钢表面制备了锌镍合金镀层。采用扫描电镜(SEM),能谱仪(EDS)和X射线衍射仪(XRD)等研究了电化学沉积电位对锌镍合金镀层形貌、化学成分和晶体结构的影响。结果表明:随着沉积电位的升高,锌镍合金镀层由无法覆盖整个基底表面到均匀致密覆盖,再到较大微纳米颗粒层覆盖,证明沉积速率越来越大。由EDS和XRD分析可知,在较低电位下沉积,锌镍电沉积过程属于正常共沉积,而在较高电位沉积时,锌镍电沉积过程属于异常共沉积。电化学极化曲线测试表明,在电沉积电位为-1.2 V时所获得的锌镍合金镀层的耐腐蚀性最好。     

Electroplating and characterization of Zn-Ni, Zn-Co and Zn-Ni-Co alloys

Zn-Ni, Zn-Co and Zn-Ni-Co coatings were electrodeposited on mild steel from an acidic chloride bath containing p-aminobenzenesulphonic acid (SA) and gelatin. These additives changed the phase content in the coatings, most likely as a result of their adsorption at the surface of the cathode. The effect of gelatin was more pronounced than that of SA. The Faradaic efficiency was higher than 90%. As the current density was increased or the bath temperature was decreased, the concentration of the nobler metal in the coating increased. Both concentrations of Ni and Co in the ternary alloy increased as the applied current density was increased. Nickel and cobalt were found to have a synergistic catalytic effect. The thickness of all coatings increased as the applied current density was increased. The hardness increased with current density to a peak value, and then decreased. The rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, while the rates of Ni and Co deposition were not. The anomalous codeposition was explained by the great difference between the exchange current densities of Zn and the iron-group metal. Potentiodynamic polarization scans and electrochemical impedance spectroscopy showed that the corrosion resistance of the ternary Zn-Ni-Co alloy coatings was approximately 10 times higher than that of Zn-Ni and 7 times higher than that of Zn-Co. The improved corrosion resistance of the ternary alloy was attributed to its surface chemistry, phase content, texture, and surface morphology. The ternary Zn-Ni-Co coating may thus replace the conventional Zn-Ni and Zn-Co coatings in a variety of applications.     

Role of cadmium on corrosion resistance of Zn-Ni alloy coatings

Cadmium (Cd) catalyzed Zn-Ni alloy plating has been accomplished galvanostatically on mild steel (MS) using gelatin and glycerol as additives. The effect of addition of Cd into Zn-Ni bath has been examined in terms of nickel (Ni) content and corrosion resistance of Zn-Ni-Cd ternary alloy coatings. The process and product of electrolysis under different concentrations of additives and Cd have been investigated by cyclic voltammetry (CV). The effects of current density (c.d.) on Ni content of the alloy have been studied by spectrophotometric method, supported by EDX analysis. The deposition has been carried out under different concentrations of Cd ranging from 0.004 to 0.1 M. The corrosion rates (CR) of Zn-Ni alloy coatings have been found to decrease drastically with addition of Cd. It has been also revealed that the CR of binary Zn-Ni alloy coatings decreased with the increase of Cd concentration only up to a certain optimal concentration, i.e., up to 0.02 M, and then remained unchanged. An effort to change the anomalous type of codeposition into normal one by changing the molar ratios of the metal ions, i.e. [Cd²⁺]/[Ni²⁺] as 0.01, 0.05 and 0.25 has remained futile. CV study demonstrated an important role of Cd in mutual depositions of Zn²⁺ and Ni²⁺ ions by its preferential adsorption, thus leading to the increased Ni content of the alloy. The bath composition and operating parameters have been optimized for deposition of bright and uniform Zn-Ni-Cd alloy coatings. Changes in the surface morphology and phase structure of Zn-Ni alloy coatings due to addition of Cd has been confirmed by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) study respectively. Experimental investigations so as to identify the role of Cd in codeposition Zn-Ni alloy coatings have been carried out and the results are discussed.     

Effect of current density on composition and structure of electrodeposited Au–Ni alloy coatings

Abstract

The effect of current density on composition and structure of galvanic Au–Ni alloy coatings electrodeposited from weakly acidic additive free electrolyte was investigated. At low current density (up to ～10 mA cm^?2), light yellow coloured alloys enriched with Au are deposited. At higher current density the Ni content is abruptly increased and the coatings become coarse and dark. Deposits with an average content of Ni up to ～50 at-% were obtained. Only a small amount of Ni (up to 20 at-%) takes part in the formation of non-equilibrium super saturated Au–Ni solid solution. The remainder of the Ni is deposited in the interglobular space as an amorphous Ni oxide–hydroxide or as Ni bearing hydroxide salts. Besides Ni, the alloy coatings contain C, N, O, K and H.     

Effect of voltage on microstructure and corrosion resistance of microarc oxidation coatings on CP-Ti

The surface modification of commercially pure titanium (CP-Ti) by microarc oxidation (MAO) under different voltages was investigated using 1%H₃PO₄ solution as an electrolyte. The microstructure, phase composition and elemental distribution of ceramic coatings were investigated using scanning electron microscopy (SEM) and X-ray diffraction. The corrosion behaviour of the coating was also examined by potentiodynamic polarisation testing in a 3·5 wt-%NaCl solution. Micropore oxide films were formed on all the sample groups by MAO. The thickness and micropore size of the MAO coating increased with the increasing voltage. Energy dispersive X-ray spectroscopy results indicate that Ti, O and P became incorporated into the MAO coatings. At a low voltage of 250 V, the MAO coatings were composed of amorphous, P₂O₅, TiP₂O₇ and titania phases (rutile and anatase). Variation of treatment voltages increased the ceramic coatings from an amorphous structure to a phase structure, and the P₂O₅ phase disappeared. The corrosion potential Φ_corr of the MAO sample shifted towards nobler directions, and the corrosion density I_corr fell significantly compared with that of the bare CP-Ti. Corrosion testing showed that the sizes of the micropore of the MAO samples obviously decrease, and the MAO surface becomes smooth.     

The advantage of ultrasound during electrodeposition on morphology and corrosion stability of Zn-Co alloy coatings

ABSTRACT

The influence of ultrasound agitation on the properties of electrodeposited Zn-Co coatings was analysed and compared with coatings deposited by using magnetic stirring. The morphology and chemical composition of the deposits were analysed by scanning electron microscopy coupled with energy dispersive X-ray spectroscopy. X-ray diffraction was used in examining the crystallographic orientation and phase composition of the coatings. It was found that utilising ultrasound during deposition enhanced the compactness, homogeneity and corrosion resistance of the coatings compared to deposition with magnetic stirring of the plating solution. Magnetically stirred coatings were dendritic and porous, whereas coatings produced under ultrasound agitation were more homogeneous and dense. The higher the ultrasound intensity applied the higher the cobalt content in the coating. The corrosion resistance of Zn-Co coatings was improved by ultrasound agitation, with the best results obtained at 20?W?cm^?2 of ultrasound intensity.     

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.     

显微组织对Zr-Sn-Nb-Fe锆合金耐腐蚀性能的影响

将Zr-Sn-Nb-Fe锆合金样品分别进行不同热处理,在350℃、16.8MPa、0.01mol.L-1LiOH高压水溶液中腐蚀,并用高分辨透射电镜(HR-TEM)研究它们的显微组织和析出相粒子。结果表明,冷轧前在800℃保温的两种样品的耐腐蚀性能好于680℃保温的两种样品,冷轧后500℃保温样品的耐腐蚀性能好于560℃保温样品。HR-TEM分析表明800℃/500℃处理样品耐腐蚀性能最好的原因是析出相粒子中Nb含量较高,从而降低了Nb元素在基体αZr中的固溶含量。     

Electrodeposition of Zn-Ni, Zn-Fe and Zn-Ni-Fe alloys

Zn-Fe, Zn-Ni and Zn-Ni-Fe coatings were electrodeposited galvanostatically on mild steel from acidic baths (pH 3.5) consisted of ZnCl₂, NiCl₂, FeCl₂, gelatin, sulfanilic (p-aminobenzenesulfonic) acid and ascorbic acid. Cyclic voltammetry showed that the effect of gelatin was more pronounced than that of sulfanilic acid, and that the deposition of the ternary alloy behaved differently from the deposition of the binary alloys. In all three systems, the Faradaic efficiency was higher than 88%, the rate of Zn deposition was heavily influenced by mass-transport limitation at high applied current densities, and the deposition was of anomalous type. For each applied current density, the concentrations of Ni and Fe in the ternary alloy were higher than the corresponding concentrations in the binary alloys. The hardness of Zn-Ni coatings was the highest, while that of Zn-Fe coatings was the lowest. The Zn-Ni-Fe coatings were the smoothest, had distinguished surface morphology, and contained ZnO in the bulk, not just on the surface. The lowest corrosion rate in each alloy system (214, 325 and 26 μm year⁻¹ for Zn-Ni, Zn-Fe and Zn-Ni-Fe, respectively) was characteristic of coatings deposited at 30, 30 and 40 mA cm^− 2, respectively. The higher corrosion resistance of the ternary alloy was also reflected by a higher corrosion potential, a higher impedance and a higher slope of the Mott-Schottky line. The enhanced corrosion behavior of the ternary alloy was thus attributed to its chemical composition, phase content, roughness and the synergistic effect of Ni and Fe on the n-type semiconductor surface film.     

激光功率对FeCoNiCrMo高熵合金/氧化石墨烯复合涂层组织及耐腐蚀性能的影响

以17-4PH不锈钢为基体材料,采用激光熔覆技术在不同激光功率(1600, 1800, 2000, 2200 W)下制备了FeCoNiCrMo高熵合金/氧化石墨烯复合涂层,研究了复合涂层的显微组织、物相组成、显微硬度分布和耐腐蚀性能。结果表明,制备的FeCoNiCrMo高熵合金/氧化石墨烯复合涂层的微观组织由体心立方(BCC)固溶体和M₂₃C₆、M₇C₃、Co₂C等金属间化合物组成;随着激光功率的增加,金属间化合物形成的析出相增加,涂层耐腐蚀性能先增加后降低。当激光功率为2000 W时,涂层的硬度最高,且具有最佳的耐腐蚀性能,其自腐蚀电位为0.631 V,约为基体的2.66倍,自腐蚀电流密度为0.319 μA/cm²。激光功率是影响FeCoNiCrMo高熵合金/氧化石墨烯复合涂层组织及耐腐蚀性的显著因素,激光功率的增大促进了涂层中碳化物析出相的生长,有利于提高涂层硬度与耐腐蚀性能,但过高的激光功率下生成的大量硬质金属间化合物增大了涂层的裂纹敏感性,涂层产生明显裂纹,导致涂层耐腐蚀性能降低。     

Corrosion resistance of cerium‐based chemical conversion coatings on AA5083 aluminium alloy

In this paper the effect of several parameters, such as temperature, time of immersion, cerium ions and hydrogen peroxide concentration, pH of the conversion solution, on the composition and morphology of the conversion layer are investigated as well as on its corrosion resistance in chloride environments. The cerium‐based chemical conversion coatings ennobles the corrosion potential and inhibits both the cathodic and anodic reactions rate. Using a cerium (III) chloride solution a not homogeneous coating is obtained and agglomerates with a “dry‐mud” morphology of mixed cerium‐aluminium oxide are deposited above the cathodic intermetallic particles, while using a cerium (III) nitrate solution the coating is more uniform but thinner than that obtained with cerium (III) chloride. Solution temperature below 50°C and time of immersion of 10 minutes produces a coating with better corrosion resistance.     

Increasing the wear and corrosion resistance of magnesium alloy (AZ91D) with electrodeposition from eco-friendly copper- and trivalent chromium-plating baths

Mg alloy, AZ91D, which has a two-phase structure, was successfully electroplated in an alkaline Cu-plating bath. The Cu-coated Mg alloy specimen was further electroplated in eco-friendly acidic Cu and then trivalent Cr baths to obtain an anti-wear and anti-corrosion Cr/Cu coating. Experimental results show that the wear and corrosion resistance of the Mg alloy specimen was considerably improved by trivalent Cr electrodeposition. The hardness of the as-plated Cr deposit was drastically increased by using reduction-flame heating for 0.5 s. The above-mentioned results were measured via bonding strength, hardness, wear and corrosion tests. A superior wear and corrosion resistance was obtained when a Cu-coated Mg alloy specimen was electroplated with a trivalent Cr deposit, followed by heating with reduction-flame heating for 0.5 s.     

The effects of heat treatments on hardness and wear resistance in Ni-W alloy coatings

The relationship of processing parameters, microstructure, and mechanical responses of the electrodeposited nickel-tungsten alloys exposed to elevated temperatures in the range 700-1100 °C are investigated. Reverse pulse electrodeposition technique is employed to control the tungsten content and nanocrystalline grain size of the deposits. The application of heat treatment at 700 °C on the alloy with high tungsten content (22 at.%) and small grain size (3 nm) gives hardness enhancement and a small decrease in wear resistance. Prolonging annealing duration and increasing annealing temperature promote more grain growth and reductions of both hardness and wear resistance, despite the formations of secondary phases. For alloys with lower tungsten contents (6% and 13%) and larger grain sizes (13 and 56 nm), higher degrees of grain growth coupled with monotonic decline of hardness are observed. The study indicates that the electrodeposited nickel-tungsten alloys with a high tungsten content potentially serve as strong candidates for high temperature applications.     

Sol-gel silica coatings on ZE41 magnesium alloy for corrosion protection

Silica coatings have been applied on the surface of ZE41 magnesium alloy following the organic sol-gel route and the dip-coating technique. Three different concentrations of sol solution and two densification temperatures of the coating (400 °C and 500 °C) were used to optimize the compaction of the coatings and as a result reach the corrosion protection of the metallic substrate tests in 3.5 wt.% NaCl aqueous solution. Crack-free coatings with thickness in the 2-3 μm were obtained on the ZE41 magnesium alloy. The combination of high alkoxide concentration in the sol-gel formulation, and the high sintering temperature (500 °C) leads to coating (D500) with the optimal physical barrier against the corrosion process. This coating was capable of resisting more than 7 days in contact with the aggressive electrolyte suffering minor corrosion degradation. A corrosion mechanism for each of the tested specimens has been proposed.     

国内钢的显微组织耐蚀性研究概述

通过查阅大量的文献,分别从各种钢种的分析方法、加工工艺、合金化元素和不同组织对钢屈强强度、抗拉强度、屈强比、塑性、韧性和耐腐蚀性等方面的影响,特别是钢的耐腐蚀性能做出归纳。结果表明,钢的两大研究路线就是热处理和合金化,比如通过轧制、增大冷却风速、添加微量的稀土元素或是添加多元合金元素等,减小晶粒尺寸,改变珠光体片层结构,细化了片层间距,进而改变金相组织,改善了钢的屈强强度、塑性、韧性和耐腐蚀等性能。鉴于此,希望能帮助到更多的学者研究出更具成熟的工业化钢种,对世界工业化的发展、科技的发展、人类社会的进步有着重要意义。     

退火温度对AlCrMnFeNiCu0.8高熵合金组织与耐蚀性能的影响

采用真空电弧熔炼法制备了AlCrMnFeNiCu_0.8高熵合金,并在200、400、600、800 ℃下进行真空退火处理4 h,利用光学显微镜(OM)、X射线衍射仪(XRD)表征了合金的组织和晶体结构,使用标准三电极系统CHI660D电化学工作站分析了合金的耐蚀性能。结果表明,合金的微观组织表现为富Cu区和贫Cu区,主要由Fe-Cr固溶体、Al-Ni固溶体和富Cu固溶体组成,随着退火温度的升高,BCC结构较强,FCC结构较弱。在400 ℃退火下合金具有最正的自腐蚀电位(-0.584 V)和最低的自腐蚀电流密度(0.6618 μA·cm^-2),在600 ℃和800 ℃退火条件下,阻抗图谱中出现了明显的扩散效应,导致了合金耐蚀性降低。     

Electrochemical studies on the electrodeposited Zn-Ni-Co ternary alloy in different media

The electroplating of ternary Zn-Ni-Co alloy, surface morphology and corrosion resistance were investigated and contrasted with the characteristics of Zn-Ni electrodeposits. The investigation of electrodeposition was carried out using cyclic voltammetry and galvanostatic techniques, while potentiodynamic polarization resistance and anodic linear sweeping voltammetry techniques were used for corrosion study. Under the examined conditions, the electrodeposition of the alloy was of anomalous type. It was found that the obtained Zn-Ni-Co alloy exhibited more preferred surface appearance and better corrosion resistance compared to Zn-Ni alloy that electrodeposited at similar conditions. During the cathodic scan of cyclic voltammetry, a cathodic peak at − 574 mV is appeared and correlated with the deposition of sulfur liberated from the reduction of sulphate group in the presence of H⁺. Up to four anodic peaks were obtained by cyclic voltammetry technique, two correlated with zinc oxidation from pure deposited Zn and γ-Ni₅Zn₂₁ phases and two correlated with oxidation of cobalt and nickel, were observed. The phase structure, surface morphology and chemical composition of the deposits were characterized by means of X-ray diffraction analysis, scanning electron microscopy and atomic absorption spectroscopy, respectively.     

Effect of current density on corrosion resistance of micro-arc oxide coatings on magnesium alloy

Oxide coatings were prepared on magnesium alloys in electrolyte solution of Na2SiO3 at different current densities (3, 4 and 5 A/cm2) with micro-arc oxidation process. X-ray diffractometry (XRD) results show that the oxide coatings formed on magnesium alloys are mainly composed of MgO and MgAl2O4 phases; in addition, the content of MgO increases with increasing the current density. The morphology and surface roughness of the coatings were characterized by confocal laser scanning microscopy (CLSM). The results show that the surface roughness (Ra) decreases with increasing the current density. Moreover, the electrochemical corrosion results prove that the MgO coating produced in the electrolyte Na2SiO3 at current density of 5 A/cm2 shows the best corrosion resistance.