On texture, corrosion resistance and morphology of hot-dip galvanized zinc coatings

Texture is an important factor which affects the coating properties. Chemical composition of the zinc bath can strongly influence the texture of hot-dip galvanized coatings. In this study, lead content of the zinc bath was changed from 0.01 wt.% to 0.11 wt.%. Specimens were prepared from zinc baths of different lead content and its texture was evaluated using X-ray diffraction. Corrosion behaviour was analyzed by Tafel extrapolation and linear polarization tests. To study the corrosion products of the specimens, salt spray test was employed. Also, the spangle size of the specimens was determined using line intercept method. From the experimental results it was found that (00.2) basal plane texture component would be weakened by increasing the lead content of the zinc and conversely, (20.1) high angle pyramidal texture components strengthened. Besides, coatings with strong (00.2) texture component and weaker (20.1) component have better corrosion resistance than the coatings with weak (00.2) and strong (20.1) texture components. In addition, surface morphology would be changed and presence of basal planes decreases at the coating surface due to the increase of lead in the zinc bath. Furthermore, spangle size would be increased by increasing the lead content of the zinc bath. Investigation on the effects of skin pass rolling showed that in this case, (00.2) basal texture component and corrosion resistance of the skin passed specimens, in comparison with non-skin passed specimens, have been decreased.     

Effect of deformation on the electrochemical behavior of hot-dip galvanized steel sheets

The main purpose of employing pre-coated steel sheets is to minimize corrosion of steel. However, coatings can be severely affected by forming processes. In the forming processes, due to the different modes of deformation, the strain levels are different and so can affect the properties of the coatings to a varying degree. Special attention has to be paid to the influence of deformation conditions on the performance of the coating, as regards protection against corrosion. The adhesion of the coating must remain good, and the surface should not be damaged during forming. Therefore, it is necessary to study the behavior of its corrosion resistance against the deformation.In this work, effect of strain path on the corrosion behavior of hot-dip galvanized steel sheets has been studied. Corrosion behavior of hot-dip galvanized steel sheets at various strain levels has been evaluated under four different strain paths namely, biaxial, plane strain, uniaxial (drawing) and tensile modes. The sheets were deformed by a limiting dome height test (LDH) set-up. A correlation between the degree of deformation and the loss in extent of corrosion protection offered by the coating has been established by carrying out electrochemical studies such as potentiodynamic polarization and impedance spectroscopy (EIS) in 3.5% NaCl solution. The present study shows that increase in deformation increases the extent of delamination of the coating for all the modes of deformation. The severity of deformation on delamination, however, has been found to vary in the order of, tensile < uniaxial < plane < biaxial.     

Process and performance of hot dip zinc coatings containing ZnO and Ni-P under layers as barrier protection

A new coating system of under layer for hot dip zinc coating was explored as an effective coating for steel especially for application in relatively high aggressive environments. The influence of different barrier layers formed prior to hot dip galvanization was investigated to optimize high performance protective galvanic coatings. The deposition of ZnO and Ni-P inner layers and characteristics of hotdip zinc coatings were explored in this study. The coating morphology was characterized by scanning electron microscope (SEM) analysis. The hot dip zinc coatings containing under layer showed substantial improvement in their properties such as good adhesion, and high hardness. In addition, a decrease in the thickness of the coating layer and an enhancement of the corrosion resistance were found. Open circuit potential (OCP) of different galvanized layers in different corrosive media viz. 5% NaCl and 0.5 M H₂SO₄ solutions at 25 ± 1 °C was measured as a function of time. A nobler OCP was exhibited for samples treated with ZnO and Ni than sample of pure Zn; this indicates a dissolution process followed by passivation due to the surface oxide formation. The high negative OCP can be attributed to the better alloying reaction between Zn and Fe and to the sacrificial nature of the top pure zinc layer.     

Electrical conductivity of chromate conversion coating on electrodeposited zinc

For certain applications of galvanized steel protected with conversion coatings it is important that the surface is electrically conductive. This is especially important with mating surfaces for electromagnetic compatibility. This paper addresses electrical conductivity of chromate conversion coatings. A cross-matrix study using different zinc plating techniques by different labs showed that the main deciding factor is the type of zinc-plating bath used rather than the subsequent chromating process. Thus, chromated zinc plate electrodeposited from cyanide baths is non-conductive while that from alkaline (non-cyanide) and acid baths is conductive, even though the plate from all the bath types is conductive before conversion coating. The results correlate well with the microscopic structure of the surfaces as observed with scanning electron microscopy (SEM) and could be further corroborated and rationalized using EDX and Auger spectroscopies.     

Microstructure-electrochemical property correlation in electrodeposited CuFeNiCoCr high-entropy alloy-graphene oxide composite coatings

This study investigates the microstructure-electrochemical property correlation in high-entropy alloy-graphene oxide (HEA-GO) composite coatings. HEA coating containing Cu, Fe, Cr, Co, and Ni was electrodeposited over mild steel. Graphene oxide (GO) content in the coating was varied by changing the amount of GO in the electrolyte bath during the electrodeposition. Corrosion behaviour of the coatings was examined through potentiodynamic polarisation and electrochemical impedance spectroscopy methods. It was observed that with an increase in the GO amount, the corrosion resistance of HEA-GO composite coatings progressively increased. Microstructural charaterisation, using the transmission electron microscopy technique, revealed that the addition of GO enhanced the amount of Cr in the coatings and also produced a layered microstructure with Cu and Cr-rich layer covering the coating surface. Both these factors along with the impermeability of GO facilitated enhancement in the corrosion resistance. Major application areas that require protective coatings over mild steel are oil and gas pipe lines, structural components exposed to marine environments, automobiles, industrial cleaning, etc.     

Preparation of the Ni-P composite coating co-deposited by nano TiC particles and evaluation of it's corrosion property

In current research, low carbon steel plates were coated by Ni-P electroless method. The effect of adding different concentrations (ranging from 0.01 g/l to 0.5 g/l) of TiC nano-sized particles to the plating bath on deposition rate, surface morphology and corrosion behavior of Ni-P-TiC composite coatings were investigated. The surface morphology and the relevant structure were evaluated by scanning electron microscopy (SEM) and X-ray diffraction (XRD). Corrosion behavior of the coated steel was evaluated by electrochemical impedance spectroscopy (EIS) and polarization techniques. The results showed that addition of TiC nano-particles to Ni-P electroless bath not only changes the surface morphology of Ni-P coating, but also improves corrosion resistance of the steel in comparison with TiC free Ni-P electroless coating. In addition, the deposition rate of coating was also affected by incorporation of TiC particles. It was also found that improvement in corrosion resistance largely depends on the phosphorous and TiC concentrations on the coatings.     

Nanocrystalline soft ferromagnetic Ni-Co-P thin film on Al alloy by low temperature electroless deposition

Soft ferromagnetic ternary Ni-Co-P films were deposited onto Al 6061 alloy from low temperature Ni-Co-P electroless plating bath. The effect of deposition parameters, such as time and pH, on the plating rate of the deposit were examined. The results showed that the plating rate is a function of pH bath and the highest coating thickness can be obtained at pH value from 8 to10. The surface morphology, phase structure and the magnetic properties of the prepared films have been investigated using scanning electron microscopy (SEM), X-ray diffraction analysis (XRD) and vibrating magnetometer device (VMD), respectively. The deposit obtained at optimum conditions showed compact and smooth with nodular grains structure and exhibited high magnetic moments and low coercivety. Potentiodynamic polarization corrosion tests were used to study the general corrosion behavior of Al alloys, Ni-P and Ni-Co-P coatings in 3.5% NaCl solution. It was found that Ni-Co-P coated alloy demonstrated higher corrosion resistance than Ni-P coating containing same percent of P due to the Co addition. The Ni-Co-P coating with a combination of high corrosion resistance, high hardness and excellent magnetic properties would be expected to enlarge the applications of the aluminum alloys.     

Electrochemical impedance spectroscopy and X-ray photoelectron spectroscopy study of the corrosion behaviour of galvanized steel and electroplating steel

The efficiency of a formula containing 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (tolyltriazole) and decanoic acid as corrosion inhibitor for galvanized steel and electroplating steel in aqueous solution have been determined by electrochemical impedance spectroscopy (EIS) techniques. The experimental data obtained from this method show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour in the presence of different concentration of decanoic acid (DA) in the formula was also investigated by EIS. Results obtained reveal that, the formula is a good inhibitor for galvanized steel and electroplating steel in aqueous solution, the better performance was obtained in the case of galvanized steel. The ability of the inhibitor to be adsorbed on the surface was dependent on the nature of metal. X-ray photoelectron spectroscopy surface analysis with inhibitor shows that it's chemisorbed at the galvanized and electroplating steel/aqueous solution interface.     

Electrodeposition and properties of Zn-nanosized TiO2 composite coatings

Nanosized TiO₂ particles were prepared by sol-gel method. The TiO₂ particles were co-deposited with zinc from a sulphate bath at pH 4.5 using electrodeposition technique. The corrosion behavior of the coatings was assessed by electrochemical polarization, impedance, weight-loss and salt spray tests. Wear resistance and microhardness of the composite coating was measured. The smaller grain size of the composite coatings was observed in the presence of TiO₂ and it was confirmed by the images of scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques.     

Electrofabrication of multilayer Fe–Ni alloy coatings for better corrosion protection

Electrofabrication of multilayer Fe–Ni alloy coatings were accomplished successfully on mild steel and their corrosion behaviors were studied. Multilayer comprised of alternatively formed ‘nano-size’ layers of Fe–Ni alloy of different composition have been produced from a single bath having Fe²⁺and Ni²⁺ ions using modulated (i.e. periodic pulse control) current density (cd). The deposition conditions were optimized for both composition and thickness of individual layers for best performance of the coatings against corrosion. The deposits were analyzed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), Hardness Tester, electrochemical AC and DC methods respectively. The multi layered deposits showed better corrosion resistances compared to the monolayer Fe–Ni (CR = 3.77 mm year^?1) coating deposited using DC from the same bath; the maximum corrosion resistance being shown by the coating having 300 layers, deposited at cyclic cathodic current densities of 2.0 and 4.0 A dm^?2 (CR = 0.03 mm year^?1). Drastic improvement in the corrosion performance of multilayer coatings were explained in the light of changed kinetics of mass transfer at cathode and increased surface area due to modulation and layering.     

Real-time monitoring of laser welding of galvanized high strength steel in lap joint configuration

Two different cases regarding the zinc coating at the lap joint faying surface are selected for studying the influence of zinc vapor on the keyhole dynamics of the weld pool and the final welding quality. One case has the zinc coating fully removed at the faying surface; while the other case retains the zinc coating on the faying surface. It is found that removal of the zinc coating at the faying surface produces a significantly better weld quality as exemplified by a lack of spatters whereas intense spatters are present when the zinc coating is present at the faying surface. Spectroscopy is used to detect the optical spectra emitted from a laser generated plasma plume during the laser welding of galvanized high strength DP980 steel in a lap-joint configuration. A correlation between the electron temperature and defects within the weld bead is identified by using the Boltzmann plot method. The laser weld pool keyhole dynamic behavior affected by a high-pressure zinc vapor generated at the faying surface of galvanized steel lap-joint is monitored in real-time by a high speed charge-coupled device (CCD) camera assisted with a green laser as an illumination source.     

Corrosion behaviour of galvanized steel and electroplating steel in aqueous solution: AC impedance study and XPS

The efficiency of a new triazole derivative, namely, 2-{(2-hydroxyethyl)[(4-methyl-1H-1,2,3-benzotriazol-1-yl)methyl]amino}ethanol (TTA) has been studied for corrosion inhibition of galvanized steel and electroplating steel in aqueous solution. Corrosion inhibition was studied using electrochemical impedance spectroscopy (EIS). These studies have shown that TTA was a very good inhibitor. Data obtained from EIS show a frequency distribution and therefore a modelling element with frequency dispersion behaviour, a constant phase element (CPE) has been used. The corrosion behaviour of galvanized steel and electroplating steel in aqueous solution was also investigated in the presence of 4-methyl-1H-benzotriazole (TTA unsubstituted) by EIS. These studies have shown that the ability of the molecule to adsorb on the steel surface was dependent on the group in triazole ring substituent. X-ray photoelectron spectroscopy surface analysis with TTA shows that it chemisorbed on surface of galvanized steel and electroplating steel.     

Physical and electrochemical characterizations of Ni-SiO2 nanocomposite coatings

Advances in materials performance often require the development of composite system. In the present investigation, SiO₂-reinforced nickel composite coatings were deposited on a mild steel substrate using direct current electrodeposition process employing a nickel acetate bath. Surface morphology, composition, microstructure and crystal orientation of the Ni and Ni-SiO₂ nanocomposite coatings were investigated by scanning electron microscope, energy dispersive X-ray spectroscopy and X-ray diffraction analysis, respectively. The effect of incorporation of SiO₂ particles in the Ni nanocomposite coating on the microhardness and corrosion behaviour has been evaluated. Smooth composite deposits containing well-distributed silicon oxide particles were obtained. The preferred growth process of the nickel matrix in crystallographic directions <111>, <200> and <220> is strongly influenced by SiO₂ nanoparticles. The average crystallite size was calculated by using X-ray diffraction analysis and it was ~23 nm for electrodeposited nickel and ~21 nm for Ni-SiO₂ nanocomposite coatings. The crystallite structure was fcc for electrodeposited nickel and Ni-SiO₂ nanocomposite coatings. The incorporation of SiO₂ particles into the Ni matrices was found to improve corrosion resistance of pure Ni coatings. The corrosion potential (E _corr) in the case of Ni-SiO₂ nanocomposite coatings had shown a negative shift, confirming the cathodic protective nature of the coating. The Ni-SiO₂ composite coatings have exhibited significantly improved microhardness (615 HV) compared to pure nickel coatings (265 HV)     

水性丙烯酸聚氨酯涂料中反应性缓蚀剂掺入及其耐蚀性能

利用磷酸和双酚A环氧树脂反应得到功能性缓蚀剂羟基环氧磷酸酯(HEP). 将其添加到水性羟基丙烯酸树脂中,再与水性异氰酸酯固化剂交联,制备了水性羟基环氧磷酸酯/丙烯酸聚氨酯复合涂层(HEP-APU). 由于磷酸酯基团可以与金属基体发生反应,在金属表面形成一层磷化膜,极大的提升了金属的抗闪蚀能力. 利用电化学阻抗谱和极化曲线研究HEP-APU复合涂层对Q235碳钢在3.5wt% NaCl溶液中耐蚀性能. 结果表明,HEP-APU涂料对Q235碳钢具有优越的钝化和耐腐性能,且当HEP在水性丙烯酸聚氨酯涂料中质量分数为0.5%时,所得到的复合涂层的防腐性能最佳.     

Studies on influence of zinc immersion and fluoride on nickel electroplating on magnesium alloy AZ91D

The effect of zinc immersion and the role of fluoride in nickel plating bath were mainly investigated in nickel electroplating on magnesium alloy AZ91D. The state of zinc immersion, the composition of zinc film and the role of fluoride in nickel plating bath were explored from the curves of open circuit potential (OCP) and potentiodynamic polarization, the images of scanning electron microscopy (SEM) and the patterns of energy dispersive X-ray (EDX). Results show that the optimum zinc film mixing small amount of Mg(OH)₂ and MgF₂ is obtained by zinc immersion for 30-90 s. The corrosion potential of magnesium alloy substrate attached zinc film will be increased in nickel plating bath and the quantity of MgF₂ sandwiched between magnesium alloy substrate and nickel coating will be reduced, which contributed to produce nickel coating with good performance. Fluoride in nickel plating bath serves as an activator of nickel anodic dissolution and corrosion inhibitor of magnesium alloy substrate. 1.0-1.5 mol dm⁻³ of F⁻ is the optimum concentration range for dissolving nickel anode and protecting magnesium alloy substrate from over-corrosion in nickel plating bath. The nickel coating with good adhesion and high corrosion resistance on magnesium alloy AZ91D is obtained by the developed process of nickel electroplating. This nickel layer can be used as the rendering coating for further plating on magnesium alloys.     

金属表面碳涂层对激光等离子体辐射的影响

 阐述了激光诱导击穿光谱技术的基本原理,分析了金属材料表面光学性质与激光诱导等离子体辐射强度的关系,建立了空气中进行等离子辐射研究的试验装置,测量了不同厚度碳层下激光等离子体的发射光谱强度。实验结果表明：当一束近红外高能量脉冲激光（能量为5 J）作用于覆盖有约18 μm厚度碳层的标钢样品时,激光等离子体的发射光谱强度提高了16%～22%;证明了金属样品表面覆盖碳层能够提高激光等离子体辐射强度。     

Improvement of hot-dip zinc coating by enriching the inner layers with iron oxide

The performance of hot-dip galvanic coating formed on steel not only depends on the alloy composition of the superficial layer but also significantly, on the composition of the inner alloy layers at the coating/substrate interface. Further, the presence of barrier oxide layers, if any can also improve the performance of galvanic coating. In the present work, the effect of inner iron oxide barrier layer formed prior to hot-dip galvanization was investigated. A continuous and adherent iron oxide layer was formed on steel by anodic oxidation of the steel substrate. Although the wettability of oxide surface by liquid zinc was initially poor, the increase in dipping time and the transition of the oxide layer to unstable form due to the presence of Cl⁻ ion in the flux facilitated localized growth of Fe-Zn alloy phases. The inhibitive nature of the oxide layer was temporary, since the presence of Cl⁻ induces micro cracks on the oxide surface thereby facilitating better zinc diffusion. The modification of the substrate structure during galvanization was found to influence the galvanizing process significantly. The present study predicts scope for application of this process for protection of rusted steel specimens too.     

In-situ identification of iron--zinc intermetallics in galvannealed steel coatings and iron oxides on exposed steel

Identification of all the compounds present in various coatings on steels is particularly difficult. Non-destructive, in-situ analysis is necessary if the fraction of each compound as well as its probable layering within the coating, is to be determined. Mössbauer spectroscopy is one valuable probe capable of uniquely identifying all iron compounds which form as coatings on steel and other iron alloy surfaces. To investigate a complete coating several criteria need to be considered. Removing the coating inevitably leaves a small and perhaps important component intact on the substrate. Therefore investigating the coating as it remains intact on the steel is important if complete identification of the iron compounds is to be made. This also preserves crystalline texture or preferred growth orientation within the coating to which the Mössbauer effect is sensitive. Mössbauer spectroscopy is a non-destructive technique which allows the integrity of the coating to be maintained during analysis. The combined transmission and scattering Mössbauer geometries generally result in accurate analysis of the coating composition. For the scattering geometry added information on compound layering is obtained if separate Mössbauer spectra are recorded using the re-emitted gamma rays as well as the conversion electrons and subsequently emitted X-rays. In-situ scattering Mössbauer spectroscopy has been used to characterize the iron--zinc alloys which form in the coatings of commercially produced corrosion resistant galvannealed sheet steel, a product of great interest to automotive producers. The results show that different amounts of four iron--zinc phases are present depending on the production conditions of the coating. The different phases are also distinctly layered. Mössbauer analyses of corrosion coatings formed on the surface of steels which have been exposed to different environments has also been undertaken. Materials include structural steels exposed for up to 25 years in marine, rural and industrial environments, and the interior surfaces of boiler pipes subjected to adverse chemical and temperature environments.     

Corrosion Evaluation of Very Rapid High-Current Vacuum Arc Coatings

The corrosion resistance of Al alloy, Ni, and stainless steel coatings deposited on 1010 steel sample anodes using pulsed high-current vacuum arcs was investigated as a function of the arc parameters. Coating thicknesses of up to 30 ?m were obtained from a sequence of six 70-ms pulses, indicating effective coating rates of up to 72 ?m/s. The thicker coatings, and the best corrosion protection, were obtained at higher currents (600-900 A) and short gaps (3 mm). The coatings were generally well bonded to the substrate. The composition of the coatings was approximately that of the source electrode. With optimal arc parameters, all three coating materials gave full corrosion protection during a 5-h salt-spray test, and Al and Ni coatings showed no signs of corrosion after a 48-h test.     

Corrosion properties of aluminium coatings deposited on sintered NdFeB by ion-beam-assisted deposition

Pure Al coatings were deposited by direct current (DC) magnetron sputtering to protect sintered NdFeB magnets. The effects of Ar⁺ ion-beam-assisted deposition (IBAD) on the structure and the corrosion behaviour of Al coatings were investigated. The Al coating prepared by DC magnetron sputtering with IBAD (IBAD-Al-coating) had fewer voids than the coating without IBAD (Al-coating). The corrosion behaviour of the Al-coated NdFeB specimens was investigated by potentiodynamic polarisation, a neutral salt spray (NSS) test, and electrochemical impedance spectroscopy (EIS). The pitting corrosion of the Al coatings always began at the voids of the grain boundaries. Bombardment by the Ar⁺ ion-beams effectively improved the corrosion resistance of the IBAD-Al-coating.