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     

Experimental investigation and thermodynamic modeling of the Au–Ge–Ni system

Abstract  

Phase equilibria in the Au–Ge–Ni ternary system were studied by means of scanning electron microscopy, electron probe microanalysis, X-ray diffraction, and differential scanning calorimetry. The phase relations in the solid state at 600 °C as well as a vertical section at Au₇₂Ge₂₈–Ni were established. No ternary compound was found at 600 °C. On the basis of the experimental phase equilibria data, a thermodynamic model of the Au–Ge–Ni ternary system was developed using the CALPHAD method. Thermodynamically calculated phase diagrams are shown at 600 °C, in two vertical sections and the liquidus projection. Reasonable agreement between the calculations and the experimental results was achieved.     

Specific Features of Energy Dispersive X-Ray Electron Probe Microanalysis in the Low Vacuum Mode

Experimental data on the generation and detection of characteristic X-radiation of elements in electron probe microanalysis of dielectric samples in the low vacuum mode without the deposition of conducting coatings are discussed. The main advantage of the considered method of analysis is the stability of the intensity ratio between diagnostic analyte lines in the wide range of currents of the electron probe and gas phase pressure in the chamber in the range 60–130 Pa, sufficient for obtaining undistorted images of the surface of dielectrics. The stability of the intensity ratio ensures obtaining correct data of the quantitative analysis of nonconducting samples without the deposition of conducting coatings. The main features of low-vacuum microanalysis for the range of gas phase pressures used are discussed, which can create additional difficulties in the study. Among such features is a possibility of the manifestation of reflexes of gas-phase elements, significant underestimation of the relative emission intensity from lighter elements in the composition of the studied samples, loss of scanning locality in the analysis of small sites on the sample surface. An example of the correct quantitative elemental analysis of a dielectric surface without the deposition of an electroconductive coating for a number of aluminosilicates is presented.     

Studies on the oxygen sensitivity and microstructure of sol–gel based organic–inorganic hybrid coatings doped with platinum porphyrin dye

Hybrid organic–inorganic nanocomposite coatings were prepared by copolymerizing tetraethylorthosilicate with ethyltriethoxysilane with an acid catalysis process. Oxygen sensor coatings were fabricated by doping the hybrid sol with platinum meso-tetra(pentfluorophenyl) porphyrin. Photophysical properties and oxygen sensitivity of the sensor coatings were studied. The microstructure of the coatings was examined using optical microscopy and scanning electron microscopy. The effect of sol–gel process conditions like precursor silane molar ratio, acid concentration and stirring time of the sol on the oxygen sensitivity and surface microstructure of the sensor coating was studied. Oxygen sensitivity and surface morphology of the coatings were dependent on the sol–gel process parameters.     

Electrodeposition behavior of Mg with Zn from acidic sulfate solutions

Electrodeposition of Mg with Zn in acidic sulfate solutions with polyethylene glycol and octadecyl dimethyl benzyl ammonium chloride as additives was investigated by scanning electron microscopy, X-ray diffraction, and potentiodynamic polarization techniques. The results show that these two compounds act in a synergetic way to suppress Zn deposition markedly and facilitate Mg reduction. Zn–0.46%Mg coatings are produced under high cathodic current densities, which have lower corrosion potentials than Zn coatings and hydrogen evolution in neutral chloride solutions. Magnesium hydroxide may cause current oscillations at high cathodic polarizations in plating solutions without zinc salts due to its formation and peel-off. An “induced co-deposition” mechanism is proposed for Zn–Mg alloy electrodeposition.     

Grazing-exit electron probe X-ray microanalysis (GE-EPMA): Fundamental and applications

Electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) has been studied under grazing-exit conditions. That is, characteristic X-rays are detected at a very small take-off (exit) angle; the technique is known as grazing-exit electron probe microanalysis (GE-EPMA). Fundamental aspects, instrumentation, and characteristics of grazing-exit electron probe X-ray microanalysis method are described here. Since the observation depth decreases as the exit angle decreases, theoretically to a few nanometers, surface analysis is possible in grazing-exit electron probe X-ray microanalysis. Of course, the size of the electron beam is also small—less than 1 μm, enabling localized surface analysis. In the case of total reflection X-ray spectrometry that allows surface analysis, the whole sample surface must be flat. However, the requirement for flatness is not as strict in grazing-exit electron probe X-ray microanalysis. Grazing-exit electron probe X-ray microanalysis measurements can easily be applied using a commercially available electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) instrument. To change and control the exit angle in grazing-exit electron probe X-ray microanalysis, the inclination of the sample stage or movement of the X-ray detector is all that is required. Theoretically, this study shows that grazing-exit electron probe X-ray microanalysis would be useful in improving the lateral resolution of the sample surface. In addition, the study demonstrates that grazing-exit electron probe X-ray microanalysis can be applied successfully for surface, thin-film, and particle analyses. As an optional method of electron probe microanalysis, grazing-exit electron probe X-ray microanalysis will be useful in expanding the research fields of normal electron probe microanalysis.     

Preparation and characterization of copper/silver bimetallic nanowires with core‐shell structure

Core‐shell copper/silver bimetallic nanowires were prepared by replacement reaction with citric acid and polyvinylpyrollidone at room temperature. A uniform silver coating was obtained by strictly controlling the molar ratio of Ag/Cu. The copper/silver composite was characterized by X‐ray diffraction, scanning electron microscopy, electron probe microanalysis and X‐ray photoelectron spectroscopy. Microscopic analysis shows that a well‐copper/silver core‐shell structure was formed. Thermo‐gravimetry and differential thermal analysis to the composite nanowires show that the silver coatings efficiently inhibit the oxidation of Cu. Copyright © 2015 John Wiley & Sons, Ltd.     

Influence of pulse parameters on nanocrystalline zinc coatings electrodeposited from acidic sulfate electrolyte

The influence of pulse electrodeposition parameters (i.e., current-on time, current-off time and peak current density) on the grain size and orientation of zinc deposits was investigated in acidic sulfate electrolyte. The scanning electron microscopy (SEM) and X-ray diffraction (XRD) analyses indicate that the pulse parameters play an important role in the grain refinement of nanocrystalline zinc coatings. As varying peak current density (1–2 A/cm²), current-on time (1–6 ms) and current-off time (4–18 ms), nanocrystalline zinc coatings are produced in the grain range 60 to 35 nm. The pulse parameters have a slight influence on the orientation of nanocrystalline zinc coatings. Published in Russian in Elektrokhimiya, 2009, vol. 45, No. 3, pp. 310–315. The article is published in the original.     

Study of Thin Oxide Films by Electron, Ion and Synchrotron Radiation Beams

 Titanium oxide and zirconium oxide thin films deposited on silicon substrates were characterised using electron probe microanalysis (EPMA), Rutherford backscattering spectroscopy (RBS), time-of-flight elastic recoil detection analysis (TOF-ERDA) and scanning photoelectron microscopy (SPEM). The composition and mass thickness of the films were determined and the results of different methods compared. It was revealed that the synchrotron radiation used for SPEM studies caused considerable modification of zirconia films grown at low temperatures.     

A comparison of redox processes for polypyrrole/dodecylsulfate films in aqueous and non-aqueous media

Polypyrrole/dodecylsulfate (PPy/DDS) films were synthesized in aqueous and ethanolic solutions and investigated in aqueous, ethanolic, methanolic and acetonitrile solutions by cyclic voltammetry (CV). The amounts of anions and cations in the films before and after electrochemical treatment were determined by electron probe microanalysis (EPMA); the film morphology was studied by scanning electron microscopy (SEM). The results prove that the mobility of bulky DDS^– ions in PPy increases in the order: water<acetonitrile<ethanol<methanol. It was found that dopant DDS^– ions can be easily removed from PPy matrix swollen in alcohols or acetonitrile by electrochemical reduction or by soaking in electrolyte solutions of these solvents. The influence of electrochemical treatment on the change of doping level in aqueous solution is essentially less and depends on the cations in the test solution. Although the electroneutrality of PPy/DDS films during redox cycling is realized mainly by movement of the cations in aqueous solution and by movement of the anions in organic solvents, nevertheless the participation of anions in aqueous and cations in organic solvents is also established. The redox properties of PPy/DDS are more dependent on the solvent of the test solutions than of the synthesis solutions. Electronic Publication     

Application of Sputter-Assisted EPMA to Depth Profile Analysis

 A common problem in depth profile measurement is the calibration of the depth scale. The new technique of sputter assisted electron probe microanalysis offers the possibility of calculating the composition as well as the depth scale solely from the acquired X-ray intensity data without further information, e.g. sputter rates. To achieve a depth resolution that is smaller than the depth of information of the electron probe, i.e. 0.1–1 μm, special deconvolution algorithms must be applied to the acquired data. To assess the capabilities of this new technique it was applied to a Ti/Al/Ti multilayer on Si under different measurement conditions. Quantitative depth profiles were obtained by application of a deconvolution algorithm based on maximum entropy analysis. By comparison of these profiles with AES depth profiles and AFM roughness measurements, it was shown that the limiting factor to the achievable depth resolution is the occurrence of surface roughening induced by the sputtering process rather than the relatively large depth of information of the electron probe. We conclude that for certain applications sputter-assisted EPMA can be regarded as a valid depth profiling technique with a depth resolution in the nm range.     

Detection Limits of Grazing-Exit EPMA for Particle Analysis

 In conventional electron probe microanalysis (EPMA), the electron-induced X-rays are measured at large take-off angles of about 45°. In the grazing exit EPMA (GE-EPMA) method, they are measured at small angles (< 1°). X-rays emitted from deep positions can not be detected at grazing exit angles due to refraction effects at sample-vacuum interface; therefore, it is possible to measure X-rays emitted only from near the surface with a low background. GE-EPMA is especially suitable for the analysis of particles deposited on a flat sample carrier. The detection limits of GE-EPMA were investigated for artificial particles (Al₂O₃, Fe₂O₃ and PbO₂ , particle sizes: 1 ∼ 18 μm) deposited on flat sample carriers of Au thin films–Si wafers. The detection limits improved with decreasing exit angle. The detection limits for characteristic X-rays at an exit angle of approximately 1.1° were 2–4 times lower than at 45°. A minimum detection limit of ca. 0.1% was obtained for Al in small particles.     

Phase equilibria in the Al-Cu-Fe system at a temperature of 853 K in the aluminum enriched region

The phase equilibria in the Al-Cu-Fe system at 853 K in the aluminum enriched region are studied using the methods of scanning and transmission electron microscopy, X-ray phase analysis, and electron probe microanalysis. An isothermal cross section of the system is constructed. Crystal lattice parameters of the phases based on binary and ternary compounds are determined. Approximant phases are not found to form in the quasicrystalline i-phase region.     

Analysis of Early Medieval Glass Beads – The Raw Materials to Produce Green, Orange and Brown Colours

 Monochrome coloured glass beads of the Merovingians (5^th–7^th cent. AD) have been examined by different analytical methods. The elemental composition of a large number of mostly unprepared beads have been measured non-destructively by X-ray fluorescence analysis. After subtracting the content of the colouring oxides of the glass beads and normalising the residual values to 100% an identical soda-lime-glass matrix was obtained. X-ray diffraction was used for the identification of the crystalline colouring and opacifying pigments (SnO₂, Cu, Cu₂O, PbSnO₃), and scanning electron microscopy as well as electron probe microanalysis were applied to study the microstructure and the composition of white, brown, green, orange and yellow coloured glass beads. Oxidised metals, alloys (lead, copper, bronze, brass and mixtures of them) and iron smelting slag have been identified as raw materials to colour the soda-lime-glass.     

Analytical Techniques Applied in Optimization of Electrophoretic Deposition of Thin Film YBCO Superconductors

 YBa₂Cu₃O _7−x (x = 0.1–0.2) compounds (YBCO) were produced by the oxalate coprecipitation and the solid state reaction methods. The powders obtained were used for the production of YBCO superconducting coatings on Pt/Si wafers, by the electrophoretic deposition technique. The optimum process conditions for the production of both powders and coatings were found by using a combination of modern analytical techniques. The thermal treatment of the samples was followed by thermogravimetry (TG) and differential scanning calorimetry (DSC). The optimization and characterization of the superconducting properties of the powders and coatings were achieved by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), optical microscopy, magnetic susceptibility and electrical resistivity measurements.     

Account of the background in wavelength dispersive X-ray electron probe microanalysis based on the simulation of bremsstrahlung X-radiation

The potentials of six approximation functions described in the literature and used to simulate bremsstrahlung X-radiation in electron probe microanalysis are analyzed within a uniform approach. An algorithm based on the use of wave spectra is proposed for determining the parameters of the functions. It is found that the calculated values of some parameters of approximation functions considerably differ from those presented by the authors of the functions. It is found that the quality of approximating bremsstrahlung X-radiation is strongly affected by the method of calculating the average atomic number of the sample and the corrections for matrix effects. In the wavelength range 0.1 ≤ λ ≤ 1.2 nm for atomic numbers 10 ≤ Z ≤ 83 and accelerating voltages 15 ≤ E ₀ ≤ 25 kV, the best function ensures background estimation with a relative standard deviation of 3–6%, which is comparable with the relative standard deviation of the direct background measurement in routine electron probe microanalysis. The use of the calculation method of the background account at λ > 1.2 nm is complicated because of the significant uncertainty of the absorption factor in the long-wavelength region for the majority of elements.     

Nickel- and copper-containing oxide films on titanium

We have studied the composition and structure of films 20–30 μm thick prepared by plasmaassisted electrochemical oxidation (PEO) and additionally modified by impregnation in aqueous solutions of nickel and copper nitrates and then annealed. The investigative tools used were powder X-ray diffraction, electron probe microanalysis (EPMA), X-ray photoelectron spectroscopy (XPS), and atomic force microscopy. Unmodified film/titanium composites have a certain catalytic activity in CO oxidation to CO₂ at temperatures above 300°C; for modified layers, these temperatures are noticeably higher. Modification influences the surface structure, relief, and elemental composition. Relations between the composition and catalytic properties of the oxide layers are discussed.     

TiO2 nanotube array film prepared by anodization as anode material for lithium ion batteries

TiO₂ array film fabricated by potentiostatic anodization of titanium is characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and charge–discharge measurements. The XRD results indicated that the TiO₂ array is amorphous, and after calcination at 500 °C, it has the anatase form. The pore size and wall thickness of TiO₂ nanotube arrays synthesized at different anodization voltages are highly dependent on the applied voltage. The electrochemical performance of the prepared TiO₂ nanotube array as an electrode material for lithium batteries was evaluated by galvanostatic charge–discharge measurement. The sample prepared at 20 V shows good cyclability but low discharge capacity of 180 mA h cm⁻³, while the sample prepared at 80 V has the highest discharge capacity of 340 mA h cm⁻³.     

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.     

Porous metallic substrates for superconducting coatings

By an example of porous metal tubes and thin plates prepared from the stainless steel powder a simple method is described of preparation of porous metallic substrates for superconducting coatings. The tubes outer diameter is 12 mm, length up to 300 mm, wall thickness about ∼1.5 mm. The plate size is 85×85 mm, thickness 1 mm. We used the classic method of powder metallurgy, without any fillers. After sintering, the tube had a density 2.5–3.4 g cm⁻³ and open porosity 55–65%. The microstructure of the tubes and plates surfaces and breaks was studied using scanning electron microscopy. The porous tubes were prepared also from powdered copper, nickel, titanium, and chromium, as well as from mixtures of stainless steel and copper, nickel and pseudoalloy Cu(30%)-Cr. The first coatings with superconducting compound MgB₂ were prepared.