Nanofabricated multilayer coatings of Zn-Ni alloy for better corrosion protection

As an effort to increase the corrosion resistance of conventional monolayer Zn-Ni alloy coating, the multilayer Zn-Ni alloy coating have been done electrolytically on mild steel (MS), using gelatin and glycerol as additives. Multilayered, or more correctly composition modulated multilayer alloy (CMMA) coatings have been developed using square current pulse. Successive layers of alloys, in nanometric scale having alternately changing composition were fabricated by making the cathode current to cycle between two values, called cyclic cathode current densities (CCCD’s). The coatings having different configuration, in terms of composition and thicknesses of individual layers were developed and their corrosion performances were evaluated by electrochemical methods. The corrosion rate (CR)’s were found to decrease drastically with progressive increase in number of layers (up to 300 layers), and then increased. The coating configurations have been optimized for best protection against corrosion. The CMMA Zn-Ni coating having 300 layers was found to be about 37 times more corrosion resistant than corresponding monolayer alloy, developed from same bath for same time. High protection efficacy of the coatings were attributed to alternate layers of alloys having different surface structure and composition, supported by Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) study, respectively. Optimization procedure has been explained, and results are discussed.     

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.     

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。     

The influence of pulse parameters on Zn-Ni alloy coatings plated on AZ91 magnesium alloy

The influence of pulse parameters on zinc-nickel coatings plated on AZ91 magnesium alloy is investigated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The particles of zinc-nickel alloy plated on AZ91 magnesium alloy become smaller and the surface roughness decreases with the increase of current density and frequency. However, long plating times and a high ratio of t_on/t_off have decremental effects on the particles and surface roughness. The contents of crystal phases of zinc-nickel alloy coatings are higher under pulse current deposition than under direct current. The frequency, current density, plating time and ratio of t_on/t_off have different impacts on the thickness and Ni content of zinc-nickel coatings.     

Development of compositionally modulated multilayer Zn-Ni deposits as replacement for cadmium

Compositionally modulated multilayer (CMM) Zn-Ni deposits were electrodeposited from single acidic bath (pH = 4.7) by using a potentiostatic sequence. The Zn and Ni composition in the alloy was tailored as a function of distance from the steel substrate. X-ray diffraction studies of the deposit showed the presence of γ-phase with a composition of Ni₅Zn₂₁. The corrosion properties of modulated multilayer coatings were studied in 5% NaCl solution using electrochemical corrosion techniques. The polarization resistance of the deposits varied as a function of Ni content between 1700 and 3440 Ω. CMM Zn-Ni with 20 wt% Ni exposed in ASTM B117 salt spray test did not show any red rust formation after 400 h.     

Electrochemical studies of Zn-Ni alloy coatings from non-cyanide alkaline bath containing tartrate as complexing agent

The Zn-Ni alloys have been electro-deposited from a non-cyanide alkaline bath containing tartrate as a complexing agent for Ni²⁺ ions. A water soluble polymer is used as a brightener. It was prepared by the reaction of epiclorohydrin with hexamethylenetetramine and mercaptobenzimidazol. Its effect on co-deposition process was examined. It was found that adding brightener in plating bath has a great effect on the cyclic voltammogram and galvanostatic measurements during the electrodeposition. Under the examined conditions, the electrodeposition of the alloys was of anomalous type. X-ray diffraction measurements revealed that the alloys consisted δ-phase (Ni₃Zn₂₂). The composition and morphology of the deposits were also studied by using scanning electron microscopy (SEM) and energy dispersive analysis X-ray (EDAX), respectively. The effect of optimum plating bath conditions on the corrosion resistance is studied by Tafel polarization.     

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).     

Effect of electrodeposition conditions on the composition, microstructure, and corrosion resistance of Zn-Ni alloy coatings

The formation, composition, and structure of electrodeposited zinc-nickel alloys were investigated. It has been shown that both anomalous and normal codeposition of zinc and nickel can be realized by changing the bath composition and deposition conditions, with the nickel content in the resultant deposit being varied in a wide range (from 2 to 90 at.%). It has been also shown that the ammonical diphosphate electrolyte allows deposition of Zn-Ni coatings with a homogeneous phase structure (Ni₅Zn₂₁ and Ni₃Zn₂₂ intermetallides, a solid solution of Zn in Ni, or a solid solution of Ni in Ni₅Zn₂₁), whereas the weak acid chloride electrolyte produces two-phase coatings consisting of Ni₅Zn₂₁ with the admixture of polycrystalline Zn or Ni. The Zn-Ni coating with a nickel content of 19 at.% consisting of Ni₅Zn₂₁ intermetallic phase exhibits the highest corrosion resistance.     

Development and tribological characterisation of nanostructured Zn-Ni and Zn-Co coatings: a comparative study

Zn-Ni and Zn-Co alloy coatings were electrodeposited on mild steel from sulphate-based baths. The morphology, microstructure, microhardness and tribological behaviours of the coatings have been studied and discussed. While the Zn-5wt-% Co layers presented a nanocrystalline simple nodular structure (45?±?5?nm), the Zn-14wt-% Ni showed a particular structure called cauliflower morphology (30?±?7?nm). The X-ray diffraction analysis showed that each of the electrodeposits was formed from zinc solid solution with a uniform zinc-cobalt intermetallic phase γ₂ (CoZn₁₃) for Zn-5wt-% Co alloy. However, a single γ-phase (intermetallic compound Ni₅Zn₂₁) was presented for the Zn-14wt-% Ni alloys. The Zn-14wt-% Ni films were found to be harder and rougher than the Zn-5wt-% Co layers. Plastic deformation and oxide layers production were the main wear mechanisms for the investigated coatings. The Zn-14wt-% Ni coatings were found to have the best wear resistance due to their microhardness and particular structure.     

Zinc–nickel alloy coatings electrodeposited from a chloride bath using direct and pulse current

Zinc–nickel alloys were electrodeposited on steel from chloride bath by direct and pulse current. Some electric variables (average current density, pulse frequency, duty cycle) and some important bath conditions (ratio of Ni²⁺/Zn²⁺ in bath, temperature) on chemical compositions, current efficiency, microhardness and surface appearance of coatings were studied. At low current densities, transition from anomalous to normal co-deposition was observed for both direct and pulse current. Pulse current seems to increase brightness of the coating and to decrease the precipitation of zinc hydroxide at the cathode surface. In addition, applied pulse current increases the percentage of nickel in deposits. Pulse frequency and duty cycle had little effect on the chemical composition of deposits. The polarization curve of zinc–nickel deposition with pulse current is shifted to positive potentials in comparison with direct current curves. The temperature of the plating bath had a very strong effect on the composition of the deposits. This is primarily the result of intrinsically slow nickel kinetics. The hardness of Zn–Ni alloy coatings (approx. 220 VHN) was greater than the hardness of zinc coating (approx. 161 VHN). The hydroxide suppression mechanism for Zn–Ni co-deposition has been confirmed.     

Formulation and evaluation of nano-structured polymeric coatings for corrosion protection

The effect of the addition of multi-walled carbon nano-tubes (MWCNT) to epoxy and vinyl chloride/vinyl acetate copolymer coatings on their ability to protect the substrates was studied. Coatings were formulated from these resins with and without MWCNT reinforcement. Steel substrates were prepared and coated with each formulated coating and submerged in 5% NaCl solution to study their corrosion resistance by means of Electrochemical Impedance Spectroscopy (EIS). In addition, thin films from these polymers, with and without nano-reinforcement, were cast. Dogbone specimens were cut in order to study their mechanical properties. Some of these specimens were immersed in the NaCl solution for two weeks in order to compare their mechanical properties with samples not exposed to salt water. Optical microscopy was used to capture the progress of sample corrosion. EIS measurements showed that the addition of MWCNTs to epoxy and vinyl chloride/vinyl acetate copolymer (VYHH) coatings increased their charge transfer resistance in comparison with the neat coatings. This is an indication of the enhanced corrosion protection of the nano-coatings. In addition, mechanical strength tests, both before and after immersion in 5% NaCl solution, showed that thin films from both epoxy and VYHH resins containing MWCNTs had improved strength, an indication of an improvement in the coatings' cohesive properties.     

Fabrication and microstructural characterization of nano-structured WC/Co coatings

In the present investigation, the microstructure of nano tungsten carbide/cobalt (WC/Co) coating layers fabricated by detonation-gun spraying has been studied. Phase identification and three-dimensional distribution of constituent elements have been accomplished by using an ultra high-resolution transmission electron microscope (TEM) and a three-dimensional atom probe tomography (3D-APT), respectively. The microstructures of WC/Co coating layer containing superfine carbides were observed in various forms, i.e., unmelted, partially melted and fully melted regions. TEM and APT results revealed that the WC phase has been decomposed into crystalline W₂C, W and complex amorphous phases during high temperature detonation spraying and rapid quenching process.     

Effect of current pulses on fracture morphology in superplastic deformation of 2091 Al Li alloy

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Comparative corrosion tests of multilayer Ni-Cr coatings

Comparative corrosion studies have been carried out on different versions of multilayer Ni-Cr coatings by applying the Corrodkote test and controlling the polarity, the potential differences and the thickness of the nickel layers, as well as the microsporosity of the final chromium plate. The best corrosion resistance was displayed by the systems which included a convenient combination of double-nickel and microporous chromium layers. A correlation has been established between the results of the corrosion tests and the electrochemical polarization measurements. The studies confirmed the possibility of evaluating and forecasting the protective properties of multilayer Ni-Cr coatings by simultaneous checking of the polarity, the potential difference, the thickness of the nickel layers and the microporosity of the chromium layer.     

电沉积Co-Cr3C2纳米复合涂层的热稳定性

研究了电沉积Co-Cr3C2纳米复合涂层的热稳定性.析出相Cr3C2颗粒均匀弥散地分布在涂层中,质量分数大约为30％.600℃以上退火导致涂层当中形成孔隙.400℃以下和600℃以上退火分别有利于Co纳米晶粒沿[002]和[220]方向生长.低于400℃退火可以同时获得优异的耐磨性和高硬度.经低于400℃退火,涂层的摩擦系数达到0.12,而经200℃退火后的涂层的摩擦系数低至0.04.     

脉冲电流对铸轧Al-Mg合金组织的影响

通过轧辊引人电脉冲,研究了不同的脉冲电流对铸轧Al-Mg合金组织的影响.对比实验结果表明:施加不同脉冲电流后铸轧出的薄带显微组织变化显著,合适的电脉冲强度处理使晶粒明显细化.与没有施加电脉冲的组织比较,成分偏析现象得到改善,内部组织差异明显减轻.采用电流密度5.5×106A·m-2处理时其显微组织表现为呈近球形颗粒且分...     

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.     

Corrosion study of Ni/Zn compositionally modulated multilayer coatings using electrochemical impedance spectroscopy

Ni/Zn compositionally modulated multilayer (CMM) coatings were deposited using dual bath technique. Coatings corrosion performance was evaluated using electrochemical impedance spectroscopy (EIS) during extended immersion times up to 48 h. The results of electrochemical impedance spectroscopy showed that Ni/Zn CMM coatings had better corrosion resistance compared to that of the zinc single layer coating. The modified corrosion product which is formed on the Ni/Zn CMM coatings during extended exposure times and also a good barrier effect of the nickel layer against aggressive species in these coatings can be two important reasons for high corrosion performance and so protection performance of the Ni/Zn CMM coatings.     

直流与脉冲电沉积Ni-Cr合金镀层的结构及耐蚀性

用直流电沉积(DC)、脉冲电沉积(PC)技术在低碳钢表面制备Ni-Cr合金镀层,采用X射线衍射(XRD)、扫描电镜(SEM)、原子力显微镜(AFM)等方法,研究了电沉积方式对合金镀层晶粒结构和表面形貌的影响;用浸泡法和电化学极化法测试了合金镀层在3.5%(质量分数)Na Cl溶液中的耐蚀性。结果表明,电沉积方式对镀层结构和性能有较大影响:PC方式得到的合金镀层,其纳米晶尺寸更小(由45 nm减小为26 nm),镀层表面致密性更高;表现在性能上,与DC相比,PC合金镀层的显微硬度更大(由7000 MPa增加到8250 MPa),耐蚀性更好(自腐蚀电位由–0.624V正移到–0.477 V,腐蚀电流密度由1.911×10~(-4)A/cm~2减小到2.587×10~(-5) A/cm~2)。     

真空蒸馏Zn-Ni二元合金气−液相平衡研究

在系统压力5～10 Pa、蒸馏温度1173～1423 K条件下,开展Zn-Ni二元合金真空蒸馏实验研究.结果表明:液相中Ni含量(质量分数)由18.21％增至96.05％时,气相中的Zn含量由0增至99.9966％,并且通过实验获得真空蒸馏中Zn-Ni二元合金的气?液平衡(Vapor-liquid equilibriu...