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.     

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.     

Electrochemical behavior of nickel in HNO<Subscript>3</Subscript> and the effect of chloride ions

The electrochemical behavior of nickel in HNO₃ solutions of varying concentrations was examined using the cyclic voltammetry and potentiodynamic anodic polarization techniques. The anodic branch of the cyclic voltammogram is characterized by one anodic dissolution peak and a passivation region before oxygen evolution. The cathodic branch shows only one cathodic reduction peak corresponding to the reduction of HNO₃. Analysis of the anodic polarization data shows features of both reversible and irreversible reactions pointing to the complexity of the system. CT⁻ ions enhance the active dissolution of nickel in HNO₃ due to the adsorption on the bare metal surface and cause destruction of the passive film and initiation of pitting corrosion.     

A SERS investigation of the electrodeposition of Au in a phosphate solution

The spectroelectrochemical behaviour of cyanide and phosphate ions adsorbed on a Au electrode during electrodeposition and corrosion in a KAu(CN)₂ phosphate bath was studied by in situ SERS (Surface Enhanced Raman Spectroscopy) and cyclic voltammetry. SERS spectra exhibiting features corresponding to CN⁻ and PO₄⁻ vibrations were recorded under potentiostatic control in an interval from − 1600 to + 1500 mV vs. Ag/AgCl. Surface CN⁻ species are the dominating ones under both cathodic and anodic polarisations. As far as the phosphate vibrations are concerned, bands related to PO₄⁻ are visible in both cathodic and anodic conditions. A fluorescence background was evident in the potential range − 1300 ÷ + 1300 mV. At cathodic potentials phosphate ion adsorption on electrode surface prevails over cyanide for potentials more cathodic than − 1000 mV. At − 700 mV a discontinuity is noticed in the Stark tuning of CN⁻, probably due to a change of Au(CN)₂⁻ adsorption mechanism. At anodic potentials bands due to cyanide oxidation could be observed.     

Development of nano-structured cyclic multilayer Zn-Ni alloy coatings using triangular current pulses

Cyclic multilayer alloy (CMA) deposits of Zn-Ni were developed on mild steel from sulphate bath having thiamine hydrochloride (THC) and citric acid (CA) as additives. CMA coatings were developed galvanostatically using triangular current pulses, under different conditions of cyclic cathode current density (CCCD’s) and number of layers. The corrosion behaviors of the coatings were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy methods, and were compared with that of monolayer Zn-Ni alloy of same thickness. At optimal configuration, CMA coating represented as, (Zn-Ni)_2.0/5.0/300 was found to exhibit ∼40 times better corrosion resistance compared to monolayer alloy, (Zn-Ni)_3.0. Cyclic voltammetry study demonstrated that THC and CA have improved the appearance of the deposit by complexation with metal ions. The corrosion protection efficacy of CMA coatings was attributed to the difference in phase structure of the alloy in successive layers, evidenced by XRD analysis. The formation of multilayer and corrosion mechanism was analyzed by Scanning Electron Microscopy (SEM) study.     

DCOIT复合Zn-Ni合金抗菌镀层的制备及其耐SRB腐蚀性能研究

目的 提高Zn-Ni合金镀层的耐微生物腐蚀性能。方法 在硫酸盐电镀液中添加梯度浓度的4,5-二氯-N-辛基-4-异噻唑啉-3-酮（DCOIT）,利用恒电流沉积方法,在碳钢表面阴极电沉积获得DCOIT复合Zn-Ni合金镀层。通过电沉积电位监测与电流效率计算评价DCOIT对电沉积过程的影响,利用扫描电子显微镜、电子能谱、X射线晶体衍射等研究DCOIT对Zn-Ni复合镀层形貌、结构与Ni含量的影响,使用傅里叶红外吸收光谱和荧光显微观察法验证DCOIT的成功复合及复合镀层的抗菌性能,最后将DCOIT复合Zn-Ni合金镀层暴露于硫酸盐还原菌（SRB）中,监测菌液的pH与菌体浓度,同时计算镀层的腐蚀速率,并观察镀层的腐蚀形貌,评价复合镀层的耐SRB腐蚀性能。结果 DCOIT在电沉积过程中会吸附在沉积表面,造成沉积电位负移,并略微降低了电流效率。DCOIT的添加显著改变了复合镀层的形貌、结构与Ni含量,其Ni含量与DCOIT的添加量呈线性增长关系,导致其晶体结构转变。DCOIT以有效形式存在于复合Zn-Ni合金镀层中,并显示出抗菌性能,DCOIT添加量为2 mmol/L时,镀层中的复合量最高,抗菌性能最好。最后,DCOIT复合Zn-Ni合金镀层能有效抑制环境中SRB的生长与代谢,自身腐蚀速率减慢,耐蚀性能明显增强。结论 DCOIT能够以有效形式复合于Zn-Ni合金镀层内部,并有效提高了镀层的抗菌性能,使其获得增强的耐SRB腐蚀性能。     

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.     

SECM Study of Effect of Chromium Content on the Localized Corrosion Behavior of Low-Alloy Steels in Chloride Environment

This paper investigates the effect of chromium (Cr) content (0, 1, 3 and 5% Cr) in epoxy-coated alloy steel against corrosion using in situ electrochemical techniques such as EIS and SECM in a 3% NaCl solution. The EIS results revealed that the epoxy-coated Cr steel exhibited higher impedance values than carbon steel, which is attributed to the greater resistance of Cr steel toward corrosion. Based on the cyclic voltammogram results, the tip potentials were set at ?0.7, 0.04 and 0.60 V for determining the concentration of dissolved oxygen at cathodic region, and oxidation of Cr²⁺ and Fe²⁺ at anodic region, respectively. The SECM measurements showed that, the tip current in the anodic region has decreased with increase in Cr content of the sample, which indicates that the oxidation of Fe²⁺ and Cr²⁺ decreases (corrosion is reduced) with the increase in Cr content of the steel. Besides, 5% Cr steel can maintain the highest corrosion resistance, and 1 and 3% Cr steels have higher corrosion resistance than the 0% Cr steel. This higher corrosion resistance of Cr steel samples could be due to the formation of Cr-rich hydro-oxide layers [Cr(OH)₃ as a corrosion product] on the surface of the samples. Thus, the epoxy-coated Cr alloy steel has greater corrosion resistance in a chloride-containing environment than the carbon steel. Hence, epoxy-coated Cr alloy steel can be successfully used as a construction material in structures.     

The effects of spark anodizing treatment of pure titanium metals and titanium alloys on corrosion characteristics

This study evaluated the surface characteristics of oxide films on commercially pure titanium metals (CP-Ti; Grade 2 and Grade 3) and titanium alloy (Ti6Al4V and Ti6Al7Nb) samples formed by an anodic oxidation treatment, and investigated the effects of anodization on the corrosion characteristics. FE-SEM, XRD, and Raman spectroscopy were used to evaluate the micromorphology and crystalline structure of the oxide films. The corrosion resistance of the sample groups was evaluated using open-circuit potential and cyclic polarization tests. After anodic oxidation up to dielectric breakdown with the same electric current, 150-200 nm-sized pores were distributed homogeneously on pure titanium metal samples, partially occluded pores were observed on the Ti6Al4V alloy, and there was an inhomogeneous size and distribution of pores on the Ti6Al7Nb alloy. The titanium dioxide films formed through anodic oxidation contained a phase mixture of anatase and rutile. The cyclic polarization tests showed that all the tested sample groups were not susceptible to localized corrosion. The as-received and anodically oxidized CP-Ti grade 3 groups showed a higher corrosion resistance than the other groups. The mean E_corr values of the anodically oxidized sample groups, except for the anodized Ti6Al7Nb alloy, showed higher values than those of the respective as-received sample groups. In particular, the Ti6AL7Nb alloy showed a statistically higher E_corr value in the anodized group than in the as-received group (p < 0.05).     

Corrosion behaviour of the extruded and unidirectionally solidified Al-Al4Ca eutectic alloy in a neutral sodium chloride solution

The corrosion behaviour of extruded and unidirectionally solidified Al-Al₄Ca eutectic alloy in a neutral sodium chloride solution has been compared with the behaviour of commercially pure Al and Al-Cu alloy. From both anodic and cathodic cyclic linear potentiodynamic measurements and from S.E.M. observations it was possible to point out that the corrosion behaviour of unidirectionally solidified alloy is substantially equal to that of the extruded alloy, slightly different from that of commercially pure Al and better than Al-Cu alloy. Therefore, the use of this new lamellae-reinforced Al-Al₄Ca composite is promising, even though from the corrosion point of view further studies involving different techniques and conditions (solutions, temperature, surface state, stress, etc.) should be undertaken.     

Selective Dissolution of Electrodeposited Zn-Ni Alloy Coatings

The corrosion of Zn-Ni alloy coatings in pure and NaHCO, containing Nad solutions was investigated under open circuit potential conditions. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) techniques were applied for the alloy surface characterisation, while direct current plasma emission spectrometry was used for test solution and corrosion product film analysis. It has been established that Zn dissolves preferentially leaving a top layer slightly enriched with Ni. However, this layer does not act as a barrier layer for the further corrosion attack. The presence of NaHCO₃, in NaC! solution causes a reduction in the corrosion rales of Zn-Ni alloy and the thickness of corrosion product (oxide) film, as well as affecting the ratio of the soluble and insoluble fractions of ionised Zn and Ni and the development of the surface morphology. In a pure NaCl solution Zn-Ni corrosion occurred with surface roughening, while in the presence of NaHCO₃ the process was accompanied by surface smoothing.     

Corrosion resistance of carbon steel in simulated concrete pore solution in presence of 1-dihydroxyethylamino-3-dipropylamino-2-propanol as corrosion inhibitor

The inhibition behaviour of 1-dihydroxyethylamino-3-dipropylamino-2-propanol (HPP) as an environment friendly corrosion inhibitor for reinforcing steel was investigated in simulated concrete pore solution contaminated by 0·1 mol L^?1 Cl^? by means of linear polarisation resistance, electrochemical impedance spectroscopy and cyclic voltammetry (CV). The surface morphology and corrosion products were also examined by scanning electron microscopy and X-ray diffraction (XRD). The results show that HPP can effectively inhibit the corrosion of reinforcing steel. The CV interpreted the corrosion inhibitor by restraining the reaction of cathodic reduction and anodic oxide. The XRD shows that the corrosion inhibitor reduces Cl^? adsorption on oxide film and reduces the production of corrosion products. In the conditions of this investigation, HPP behaves as an anodic corrosion inhibitor, protecting steel against corrosion in chloride contaminated environments.     

The Influence of KCl and HCl on the High-Temperature Oxidation of a Fe-2.25Cr-1Mo Steel at 400 °C

The influence of alkali- and chlorine-containing compounds on the corrosion of superheater alloys has been studied extensively. The current paper instead investigates the corrosive effects of KCl and HCl under conditions relevant to waterwall conditions. A low-alloy (Fe-2.25Cr-1Mo) steel was exposed to KCl(s), 500 vppm HCl(g) and (KCl?+?HCl) in the presence of 5%O₂ and 20% H₂O at 400 °C. The results indicate that alloy chlorination by KCl occurs by an electrochemical process, involving cathodic formation of chemisorbed KOH on the scale surface and anodic formation of solid FeCl₂ at the bottom of the scale. The process is accompanied by extensive cracking and delamination of the iron oxide scale, resulting in a complex, convoluted scale morphology. Adding 500 vppm HCl to the experimental environment (KCl?+?HCl) initially greatly accelerated the formation of FeCl₂ at the scale/alloy interface. The accelerated alloy chlorination is attributed to HCl reacting with KOH at the scale surface, causing the cathodic process to be depolarized. A rapid slowing down of the rate of chlorination and corrosion in KCl?+?HCl environment was observed which was attributed to the electronically insulating nature of the FeCl₂ layer which forms at the bottom of the scale, disconnecting the anodic and cathodic regions.

     

Electrochemical oxidation of WC in acidic sulphate solution

The electrochemical oxidation of WC in aqueous solutions is critical for the functional stability of hardmetals in aggressive environments. The oxidation of WC and the nature of the oxides formed in 0.1 M sulphuric acid under electrochemical polarisation have been studied by electrochemical methods (cyclic voltammetry, chronoamperometry). The structure and composition of the electrochemically treated surfaces has been analysed by X-ray diffraction, surface Raman spectroscopy and energy dispersive analysis of characteristic X-rays. The morphology of the attacked surfaces was investigated by scanning electron microscopy. Anodic attack gives rise to hydrous WO₃ forming a continuous film which tends to develop pits. Alternated anodic and cathodic polarisation yields a very similar composition, but with a lower degree of hydration. The morphology is characterised by micrometric loose grains forming by disruption of the larger grains of the pristine sintered WC surface. The electrochemical conditions giving rise to the inception of WO₃ formation by WC oxidation could be accurately identified by monitoring the inception of the development of the cathodic loop corresponding to the electrochemical behaviour of the electrochromic material.     

8-羟基喹啉修饰Fe-W非晶镀层及其耐蚀性

采用电化学方法，研究了8—羟基喹啉修饰Fe—W非晶镀层工艺及其耐蚀性．通过恒压阳极氧化，在Fe—W非晶合金表面形成8—羟基喹啉修饰膜，但膜层耐蚀性较差．在修饰液中加入乙二胺和溶纤剂等助剂，可在电极表面形成一层稳定的彩色修饰膜，铬酸盐封闭处理能增强修饰电极的抗蚀效果．极化曲线测试结果表明，抗蚀层阻滞了氧的阴极还原反应及阳极反应，提高了Fe—W合金镀层在中性NaCl介质中的耐蚀性．     

Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at ∼0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO₃ during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO₃ inside of the TiO₂ surface layer seems to be constant.     

Preparation of MgO coatings on magnesium alloys for corrosion protection

MgO coating is formed on magnesium alloy by anodic electrodeposition in 6 M KOH solution, whereas Mg(OH)₂ coating is produced by anodization in 10 M KOH solution, which could be successively converted to MgO by calcination in air at 450 °C. The evolution of morphology, structure and composition of anodic film obtained on Mg alloy is investigated using scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray diffraction (XRD). Potentiodynamic polarization measurements show that the as-grown MgO protective coatings are very effective in improving the corrosion resistance of magnesium alloy compared to bare metallic magnesium.     

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.     

Ni含量对Zn-Ni合金镀层的耐蚀性影响

    采用中性盐雾试验对Zn-Ni合金镀层的耐蚀行为进行了研究,并用扫描电镜、辉光放电光谱仪和X射线衍射仪等手段分析了不同Ni含量的Zn Ni合金镀层的微观形貌与结构、成分变化规律以及腐蚀产物.结果表明:（1）随着镀层的不断沉积,Ni的含量先增加后减小,在镀层中出现Ni的富积层;（2）Ni含量在5%~15%范围内时,Zn-Ni合金镀层的相结构体现出很复杂的结构特征:（3）经过钝化处理的Zn-Ni合金镀层的耐蚀性远高于镀Zn钝化层、镀Cd钝化层和Cd-Ti合金镀层的耐蚀性;（4）Zn-Ni合金镀层腐蚀产物主要是ZnO和ZnCl₂·4Zn(OH)₂,并且含有少量的2ZnCO₃·3Zn(OH)₂.     

Corrosion characterization of Mg-8Li alloy in NaCl solution

The corrosion mechanism of Mg-8Li alloy in NaCl solution was investigated by electrochemical testing and SEM observation. The electrochemical results indicated that the corrosion resistance of Mg-8Li alloy in 0.1 M NaCl solution gradually deteriorated with increasing of immersion time expect for 2 h immersion, which was consistent with the SEM observation of corrosion morphology. Mg-8Li alloy exhibited filiform type of attack under significant anodic control of magnesium solution reaction. The cathodic reaction was driven by hydrogen evolution reaction. The presence of filiform corrosion also proved a resistant oxide film naturally formed on the surface of Mg-8Li alloy.