X-ray photoelectron and scanning Auger electron spectroscopy study of electrodeposited ZnCr coatings on steel

Zn–Cr alloyed coatings electrochemically deposited are of high interest for leading steel manufacturing companies because of their novel properties and high corrosion resistance compared with conventional Zn coatings on steel. For tuning and optimizing the properties of the electrodeposited Zn–Cr coatings, a broad range of the deposition conditions must be studied. For this reason, two different types of material were investigated in this study, one with a low electrolyte temperature and one with an elevated electrolyte pH, compared with the standard values. Because different corrosion performance and delamination behaviour of the layers were observed for the two types, advanced surface analysis was conducted to understand the origin of this behaviour and to discover differences in the formation of the coatings. The topmost surface, the shallow subsurface region, and the whole bulk down to the coating–steel interface surface were analysed in detail by X-ray photoelectron spectroscopy (XPS) and high-resolution scanning Auger electron spectroscopy to determine the elemental and the chemical composition. For better understanding of the resulting layer structure, multiple reference samples and materials were measured and their Auger and XPS spectra were fitted to the experimental data. The results showed that one coating type is composed of metallic Zn and Cr, with oxide residing only on the surface and interface, whereas the other type contains significant amounts of Zn and Cr oxides throughout the whole coating thickness.     

Zinc–Nickel Electroplating from Alkaline Electrolytes Containing Amino Compounds

As found from polarization curves, in alkaline solutions, depending on the potential sweep rate, the action of brighteners based on a polymeric tetraalkylammonium salt (PTAS) can decrease or increase the hydrogen evolution overpotential. In the presence of Zn(II) complexes, the inhibiting action of PTAS on the cathodic hydrogen evolution increases. Some PTAS-based brighteners that ensure production of Zn–Ni alloy coatings uniform in thickness and composition from alkaline electrolytes are proposed. The degree of alloying of Zn–Ni coatings can be controlled by modifying the electrolyte with amino compounds.     

Studies on electrodeposition of Zn–MoS<Subscript>2</Subscript> nanocomposite coatings on mild steel and its properties

Pure zinc and Zn–MoS₂ composite coatings were prepared by electrodeposition from zinc sulfate–chloride bath containing uniformly dispersed MoS₂ nanoparticles. The effect of MoS₂ on the deposition properties morphology, crystallographic orientation, and corrosion behavior were studied. The electrokinetic properties (zeta potential) and size distribution statistics in plating bath for the particles were evaluated using dynamic light scattering experiments. The Zn and Zn–MoS₂ deposition process was studied by linear polarization and cyclic voltammetry. Scanning electron microscopy, energy dispersive X-ray analysis, X-ray diffraction analysis, and potentiodynamic polarization measurements were used to characterize the coatings. The addition of MoS₂ to the electrolyte significantly changed the microstructure and crystallographic orientation of the zinc deposits and enhanced the corrosion resistance of the coatings. The morphological and electrochemical properties of the zinc coatings were observed to be significantly affected by the incorporation of MoS₂ particles into the zinc matrix.     

Electrochemical studies on Zn deposition and dissolution in sulphate electrolyte

The electrochemical deposition and dissolution of Zn on Pt electrode in sulphate electrolyte was investigated by electrochemical methods in an attempt to contribute to the better understanding of the more complex Zn–Cr alloy electrodeposition process. A decrease of the Zn electrolyte pH (from 5.4 to 1.0) so as to minimise/avoid the formation of hydroxo-products of Cr in the electrolyte for deposition of alloy coatings decreases the current efficiency for the Zn reaction, but the rate of the cathode reaction increases significantly due to intense hydrogen evolution. The results of the investigations in Zn electrolytes with pH 1.0–1.6 indicate that Zn bulk deposition is preceded by hydrogen evolution, stepwise Zn underpotential deposition (UPD) and formation of a Zn–Pt alloy. Hydrogen evolution from H₂O starts in the potential range of Zn bulk deposition. Data obtained from the electrochemical quartz crystal microbalance (EQCM) measurements support the assumption that electrochemical deposition of Zn proceeds at potentials more positive than the reversible potential of Zn. Anodic potentiodynamic curves for galvanostatically and potentiostatically deposited Zn layers provide indirect evidence about the dissolution of Zn from an alloy with the Pt substrate. The presumed potential of co-deposition of Cr (−1.9 V vs. Hg/Hg₂SO₄) is reached at a current density of about 300 mA cm⁻².     

Properties of Zinc alloy electrodeposits produced from acid and alkaline electrolytes

Zinc–cobalt (Zn–Co) and zinc–nickel (Zn–Ni) alloy electrodeposits each prepared from acid and alkaline formulations were compared for their properties. Compared to alkaline baths, acid baths offer higher metal percent of the alloying element and higher current efficiency. In alkaline baths, the variation of metal percent in deposit with current density is less significant, but that of current efficiency with current density is more. Electrolyte pH does not change significantly in alkaline solutions compared to acid solutions. X-ray diffraction evaluation of Zn–Co deposits from both electrolytes indicated their presence in the η-phase, while Zn–Ni shows pure γ-phase for deposits obtained from alkaline solutions and the existence of γ-phase with traces of η-phase of zinc for deposits obtained from the acid electrolytes. Scanning electron microscope examination shows finer grain structure for deposits obtained from alkaline solutions, and atomic force microscope studies confirm their nanostructure with reduced surface roughness. Deposits obtained from the alkaline baths exhibited higher corrosion resistance probably due to their nanostructure.     

Thermally formed oxide films on Al–6Zn–XMg (<Emphasis Type="Italic">X</Emphasis> = 0 and 2 mass%) alloys heated in different gases

In this study, thermogravimetric analysis (TG) testing is used to measure the mass loss of polished Al–6Zn–XMg (X = 0 and 2 mass%) alloy samples heated at 773 K for 6 h in dry air or nitrogen gas. The progressive development of thermally formed oxides on an Al–6Zn–XMg (X = 0 and 2 mass%) alloy as shown by X-ray diffractometer analyses is discussed. Zn-spinel and Mg-spinel are detected on the Al–6Zn and Al–6Zn–2Mg alloy samples, respectively, and then heated in the dry air atmosphere; AlN and Mg₃N₂ are detected in alloy samples heated in nitrogen gas. The chain reactions that cause the serrated change in the mass loss curve are proposed and discussed.     

Electrodeposition of Zn–TiO<Subscript>2</Subscript> nanocomposite films—effect of bath composition

Zn–TiO₂ nanocomposite films were prepared by pulsed electrodeposition from acidic zinc sulphate solutions on a Ti support. The influence on the composite structural and morphological characteristics of Zn²⁺ and TiO₂ concentrations in the deposition bath has been investigated. The characterisation of the samples was made by X-ray diffraction and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM/EDS). For all the obtained coatings, the anatase and rutile phases’ most intense diffraction lines were observed between 24° and 28° 2θ, confirming the formation of the Zn–TiO₂ nanocomposite. X-ray diffraction data show that the presence of the TiO₂ nanoparticles plays a remarkable influence on the preferred orientation of the metal matrix. For the more diluted solution, a dependence between the metallic matrix grain size and the concentration of TiO₂ in bath is observed. The grain size decreases with the increasing on the nanoparticle amounts. The SEM results for Zn and Zn–TiO₂ deposits indicate that the nanoparticles have a strong influence on the deposit surface morphology, which is caused by the changes on the deposition mechanism.     

Pulsed Electrodeposition of Zinc–Manganese Alloys

High-quality Zn–Mn coatings with an Mn content reaching 50% are obtained from citrate–sulfate solutions in pulsed electrolysis at a pulse length of 0.1 ms to 1 s. Due to the formation of a blocking film of citrate–hydroxide zinc compounds, cathodic potential increases with time, which helps reach a codeposition potential of Mn ions. An electrolysis with a pulsed current superposed on a dc increases the Mn content and makes no impact on the coating quality.     

Surface Characterisation of Water-Atomised Al–Zn–Mg–Cu Alloy Powders by SIMS and AES

 The present paper focuses on the characterisation of surface composition and alloying element in-depth distribution of water-atomised Al–Zn–Mg–Cu alloy powders by secondary ion mass-spectrometry and Auger electron spectroscopy. A pronounced segregation of Mg and some impurities (Fe, Ca, S) concurrently with some Zn depletion are observed on the powder surface. The oxide film formed on the powder surface mainly consists of Al and Mg oxides. The film is non-uniform in thickness: rather coarse surface oxide islands coexist with surface areas covered by a thin (<1.8 nm) oxide layer. The extent of surface oxidation is strongly affected by solidification conditions: The average thickness of the surface oxides increases with increasing particle size or with decreasing cooling rate. All alloying elements are homogeneously distributed in the bulk of individual particles. No significant differences in chemical composition between different particles of a given powder are observed. Received November 26, 1999. Revision September 25, 2001.     

Pulse plating effect on microstructure and corrosion properties of Zn–Ni alloy coatings

The influence of pulse plating parameters on the surface morphology, grain size, lattice imperfection and corrosion properties of Zn–Ni alloy has been studied. The coatings were electrodeposited in an alkaline cyanide-free solution. AFM was applied for surface morphology examination, XRD measurements were carried out for phase composition and texture analysis, electron probe microanalysis was used for alloy chemical composition studies, while electrochemical techniques were applied for corrosion performance evaluation. The pulse plated Zn–Ni coatings appeared to consist of the γ-Zn₂₁Ni₅ phase and the composition of the alloy depended on the plating parameters. The grain size, lattice imperfection and homogeneity of grain distribution were established to be the main factors determining corrosion behaviour of the coating. Presented at the 4th Baltic Conference on Electrochemistry, Greifswald, March 13–16, 2005     

Electrochemical deposition and corrosion stability of Zn–Co alloys

Electrochemically deposited Zn–Co alloys under various deposition conditions were investigated using anodic linear sweep voltammetry for phase structure determination, scanning electron microscopy for surface morphology analysis, atomic absorption spectroscopy for determination of chemical composition, and polarization measurements and open circuit potential measurements for determination of corrosion properties. The influence of deposition current density, temperature, and composition of deposition solution on the phase structure and corrosion properties of Zn–Co alloys was studied. It was shown that the ratio of cobalt to zinc ions in the plating bath strongly affects the chemical content and phase structure, as well as corrosion stability, of Zn–Co alloys. Zn–Co alloys deposited from plating baths with the lowest and the highest ratios of cobalt and zinc ions exhibited the lowest corrosion rate.     

Changes of the Cu electrode real surface area during the process of electroless copper plating

The surface area (nanoscale roughness) of copper coatings deposited from electroless plating solutions containing Quadrol, L(+)- and DL(∓)-tartrate as Cu(II) ion ligands was measured using underpotential deposition thallium monolayer formation. Surface roughness of Cu coatings depends on the plating solution pH and the Cu(II) ligand, and varies over a wide range. In L(+)-tartrate and Quadrol solutions (pH 12.5–13.3) the roughness factor R _f is low and is equal to 2–3 and 4–6, respectively (substrate: electrodeposited Cu; R _f=2.2). Cu coatings of higher surface area are obtained in DL(∓)-tartrate (pH 12.3–12.7) and Quadrol (pH 12.0) solutions: R _f reaches 20–30. The correlation between R _f and Cu deposition rate was found in L(+)-tartrate solution. The Cu surface area changes are discussed in terms of partial electrochemical reactions of the autocatalytic Cu deposition process, and the decisive role of cathodic Cu(II) reduction from adsorbed Cu(II) complex species. Received: 2 November 1999 / Accepted: 22 February 2000     

Electrodeposition and characterization of zinc–nickel–iron alloy from sulfate bath: influence of plating bath temperature

The electrodeposition of ternary zinc–nickel–iron alloy was studied in acidic sulfate bath. The comparison between Zn, Ni, and Fe deposition and Zn–Ni and Zn–Ni–Fe co-deposition revealed that the remarkable inhibition of Ni and Fe deposition takes place due to the presence of Zn²⁺ in the plating bath. The increase in corrosion resistance of ternary deposits is not only attributed to the formation of γ-Ni₂Zn₁₁ phase but also to iron co-deposition and formation of iron phase. It was also found that the bath temperature has a great effect on the surface appearance and the deposit composition. The investigation was carried out using cyclic voltammetry and galvanostatic techniques for electrodeposition, while linear polarization resistance and anodic linear sweeping voltammetry techniques were used for corrosion study. Morphology and chemical composition of the deposits were characterized by means of scanning electron microscopy and atomic absorption spectroscopy.     

Use of a capacitively coupled microwave plasma (CMP) with Ar, N2 and air as working gases for atomic spectrometric elemental determinations in aqueous solutions and oils

A comparative study was performed of 600 W capacitively coupled microwave plasmas (CMP) with different plasma gases (Ar, N₂ and air) and aerosol generation with the aid of a Légère pneumatic nebulizer. Detection limits with the different working gases are in the order of 15–4000 ng/mL for Fe, Cr, Zn, Mg and Ca in aqueous solutions. The influence of organic solutions on the stability of the plasma is discussed. The determination of Co, Cr, Fe, Mg and Ni in different oil samples by OES is described, using an air-CMP and pneumatic nebulization after dilution of the oils by 20% with cyclohexane. The detection limits for these elements are in the 100–400 ng/g range. Results obtained for a waste motor oil for the elements mentioned in the concentration range of 4–50 μg/g were found to be in good agreement with those obtained by ICP-OES after digestion of the oils at high pressure in PTFE vessels. Received: 10 March 1997 / Revised: 23 May 1997 / Accepted: 30 May 1997     

Use of a capacitively coupled microwave plasma (CMP) with Ar, N2 and air as working gases for atomic spectrometric elemental determinations in aqueous solutions and oils

A comparative study was performed of 600 W capacitively coupled microwave plasmas (CMP) with different plasma gases (Ar, N₂ and air) and aerosol generation with the aid of a Légère pneumatic nebulizer. Detection limits with the different working gases are in the order of 15–4000 ng/mL for Fe, Cr, Zn, Mg and Ca in aqueous solutions. The influence of organic solutions on the stability of the plasma is discussed. The determination of Co, Cr, Fe, Mg and Ni in different oil samples by OES is described, using an air-CMP and pneumatic nebulization after dilution of the oils by 20% with cyclohexane. The detection limits for these elements are in the 100–400 ng/g range. Results obtained for a waste motor oil for the elements mentioned in the concentration range of 4–50 μg/g were found to be in good agreement with those obtained by ICP-OES after digestion of the oils at high pressure in PTFE vessels. Received: 10 March 1997 / Revised: 23 May 1997 / Accepted: 30 May 1997     

Electrochemical polarisation and galvanic couple behaviour of the primary phase of 55% Al–Zn coating investigated using band microelectrodes (BME) and band microelectrode arrays

Electrochemical polarisation experiments have shown that anodic dissolution processes on Al–40% Zn alloys are significantly enhanced in chloride compared to sulfate-based electrolytes. The aluminium content of the alloys allowed passive behaviour to be observed in sulfate electrolyte even in the presence of zinc-rich precipitates on the surface. Electrolyte pH affected cathodic processes, which was attributed to the rate of proton reduction and the passivity of the surface. Monitoring the OCP of the alloy band during polarisation of neighbouring zinc electrodes in band microelectrode (BME) arrays showed that generation of alkaline pH at the zinc electrodes affected the OCP of the alloy when the inter-electrode spacing was 10, 50, and 200 μm. Where elements of a BME array were close enough to interact via mass transport, the overall galvanic behaviour of the cell was found to be anodic or cathodic, whereas the alloy was consistently cathodic with respect to zinc in galvanic cells at larger separations. Dedicated to the 80th birthday of Keith B. Oldham.     

Aqueous Equilibrium and Solution Structural Studies of the Interaction of N,N′-bis(4-imidazolymethyl)etylenediamine with Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) Metal Ions

Divalent metal complexes of N,N′-bis(4-imidazolymethyl)etylenediamine (EMI) have been studied using potentiometric and spectroscopic techniques (UV-Vis and NMR methods) in aqueous 0.1 mol⋅L⁻¹ KCl supporting electrolyte at 25 °C. Final models and overall stability constants for the complexes of Ca(II), Cd(II), Co(II), Cu(II), Mg(II), Mn(II), Ni(II), Pb(II) and Zn(II) have been established by potentiometry for all M(II)–EMI systems, except for Co(II)–EMI. The data revealed that EMI forms ML complexes with all M(II)–EMI systems, which is the dominant species over a wide range of pH except for the Ca(II)–EMI and Mg(II)–EMI systems. Formation of the MnHL complex was also found for Mn(II)–EMI solutions. In addition, the UV-Vis and ¹H NMR results allowed us establish the coordination modes for the metal complexes between EMI with Cd(II), Cu(II), Ni(II) and Zn(II).     

Photocatalytic Reduction of Zn(II) with Participation of ZnS Nanoparticles

We have studied the photochemical processes occurring in colloidal ZnS solutions containing zinc chloride and sodium sulfite as additives. Irradiation of such systems leads to reduction of Zn(II), the rate of which increases as the size of the ZnS nanoparticles decreases. Based on analysis of the kinetic curves for the reaction, we hypothesize that photoreduction of Zn(II) is a two-electron process. __________ Translated from Teoreticheskaya i Eksperimental'naya Khimiya, Vol. 41, No. 4, pp. 231–235, July–August, 2005.     

Photoelectrochemical performance of bilayered Fe–TiO<Subscript>2</Subscript>/Zn–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> thin films for solar generation of hydrogen

A visible-light sensitive bilayered photoanode of Fe–TiO₂/Zn–Fe₂O₃ has been developed by spray pyrolytically depositing Zn–Fe₂O₃ layers onto predeposited Fe–TiO₂ thin film on ITO substrate. Fe–TiO₂/Zn–Fe₂O₃ photoelectrodes were characterized by XRD, Raman, AFM, UV-vis absorption spectroscopy. Photoelectrochemical properties of bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode were studied by Mott–Schottky curves and I–V characteristics. Bilayered Fe–TiO₂/Zn–Fe₂O₃ photoelectrode was observed to possess much higher separation efficiency of photogenerated charge carriers and could generate nine times better photocurrent density than pure Fe–TiO₂. Solar to hydrogen conversion efficiency exhibited by this electrode was 0.77%.     

Trace amounts determination of lead,zinc and copper by adsorptive stripping voltammetry in the presence of dopamine

A selective and sensitive method for simultaneous determination of lead, zinc and copper by adsorptive differential pulse cathodic stripping voltammetry is presented. The method is based on adsorptive accumulation of the complexes of Pb(II), Zn(II), and Cu(II) ions with dopamine onto hanging mercury drop electrode (HMDE), followed by reduction of adsorbed species by differential pulse cathodic stripping voltammetry. The effect of experimental parameters such as pH, dopamine concentration, accumulation time and potential and scan rate were examined. Under the optimized conditions, linear calibration curves were established for the concentration of Pb, Zn, and Cu in the ranges of 5–150, 5–250, and 1–150 ng/mL, respectively. Detection limits of 0.06, 0.25, and 0.04 ng/mL for Pb, Zn, and Cu were obtained. An application of the proposed method is reported for the determination of these elements in some real samples such as natural waters and alloys.