Electrochemical and structural characterization of sputter-deposited Mg–Nb and Mg–Nb–Al–Zn alloy films

Nanocrystalline Mg–Nb and Mg–Nb–Al–Zn alloy films were deposited by dc magnetron sputtering on glass and quartz substrates in a wide range of niobium concentrations from 6 to 80 at.%. Structural, electrochemical and corrosion properties of the films were studied by X-ray diffraction, dc voltammetry, electrochemical impedance spectroscopy and electrochemical quartz crystal microbalance. Development of body-centred cubic Nb structure in the Mg–Nb alloy matrix yielded the effects of lattice contraction, grain refining and electrochemical passivity. The measurements showed high corrosion resistance of the films in alkaline solutions when niobium content was one third or more. An increased corrosion resistance was achieved by introducing minor amounts of Al (ca. 2 at.%). In particular, such Al effect was pronounced at lower Nb concentrations (20 to 30 at.%). Semiconductor properties of spontaneously formed oxide on Mg–Nb alloy were studied by Mott–Schottky plots, which indicated highly doped n-type oxide structures on Mg–Nb surface. The paper fills some gap in understanding of niobium–magnesium systems, which show potential for applications in hydrogen storage, switchable mirrors and corrosion protection.     

Formation of gold-capped silicon nanocolumns on silicon substrate

Gold-capped silicon nanocolumns regularly distributed over silicon substrate were obtained. The columns length was roughly 100 nm; their deviation from perpendicular axis was less than 2°. The diameter of the columns was of the order of 10 nm or below of that. The proposed procedure of nanostructuring included the following main steps: deposition of aluminum thin layer (100–500 nm) by magnetron sputtering on (100) oriented Si wafers; formation of porous self-ordered alumina structures by electrochemical anodizing of the Al film in oxalic acid; electroless inversion of Au in alumina pores; and reactive ion etching. The obtained Si–Au structures are of importance as the platforms for biosensing applications, while the gold-free structures are of interest in photovoltaics.

     

Advances in detection of magnetic fields induced by electrochemical reactions—a review

The paper summarizes achievements in applications of superconducting quantum interference device (SQUID) magnetometry in electrochemical activity sensing, especially in that related to remote corrosion detection. The studies deal with application of the SQUIDs operating in liquid helium or nitrogen with a spatial resolution of magnetic field detection of the order of a millimeter or greater. This made it possible to observe macroscopic magnetic fields, which originated from the large-scale surface currents (ionic and electronic), which resulted from electrochemical potential gradients on electrochemical interfaces. The gradients owed to variations in temperature, alloy composition, sample geometry, electrolyte flow characteristics (velocity, direction, and turbulence), etc. The measurements demonstrated the capability of SQUIDs to remotely sense corrosion across the integrated media consisting of gaseous and solid dielectrics, metal, and electrolyte. The results have shown the potential of magnetometry for practical corrosion detection in the restricted locations such as in ground or concrete. Despite significant efforts, the field is considered to be at an early stage from both fundamental and practical points of view. Contribution to special issue “Magnetic field effects in Electrochemistry”.     

Silicon surface texturing by electro-deoxidation of a thin silica layer in molten salt

A new method of silicon surface texturing is reported, which is based on thin silica layer electrochemical reduction in molten salts. A thermal silica layer grown on p-type silicon was potentiostatically reduced in molten calcium chloride at 850 °C. Typical nano–micro-formations obtained at different stages of electrolysis were demonstrated by SEM. X-ray diffraction measurements confirmed conversion of the amorphous thermal silica layer into crystalline silicon. The proposed approach shows promise in photovoltaic applications, for instance, for production of antireflection coatings in silicon solar cells.     

Sulfide-enhanced electrochemical capacitance of cobalt hydroxide on nanofibered parent substrate

Two approaches—substrate nanostructuring and incorporation of sulfide—were studied with the aim to increase electrochemical capacitance of cobalt (hydro)oxide. A fiber structure of cobalt was deposited electrochemically with the fibers in the order of tens of nanometers in thickness and hundreds of nanometers in length. Cobalt hydroxide film was formed on the nanostructured substrate by anodic polarization in an alkaline solution. The hydroxide formation and its electrochemical capacitance have been studied by cyclic voltammetry in conjunction with the electrochemical quartz crystal microbalance (EQCM). An irreversible behavior was typical of the first anodic polarization cycle; it turned gradually to a reversible one during subsequent cycling. EQCM measurements indicated exponential electrode mass growth during the first cycle, with subsequent transition to a quasipassive state. The redox transitions Co(II) → Co(III) → Co(IV), which determine pseudocapacitance, did not cause remarkable electrode mass change. The electrochemical capacitance of the nanofiber sample was found up to five times higher when compared to that formed on conventional cobalt (abraded surface). Specifics of “per 1 g” evaluation of capacitance performance is discussed. Measurements showed that about 10% of the entire hydroxide structure took part in the capacitive process. The capacitance value determined per 1 g of active Co(OH)₂ was in agreement with the limiting value predicted by the Faraday’s law (2,421 F g⁻¹) sulfide-enhanced system with 18% CoS exhibited up to three times higher capacitance when compared to that of the sulfide-free counterpart. The system shows promise for practical applications due to its low cost and technical simplicity.     

Remote sensing of aluminum alloy corrosion by SQUID magnetometry

Macroscopic magnetic fields were detected on corroding aluminum alloy (AA 2024) samples by SQUID magnetometry. The fields originated from corrosion reactions due to asymmetric sample geometry, electrolyte flow and differences in surface activity. Magnetic images were obtained by a SQUID magnetometer operating in liquid helium with a spatial resolution of approximately 1 mm. The measurements demonstrated SQUID capability for corrosion sensing across integrated media consisting of gaseous and solid dielectrics (air, plastics), an electronic conductor (aluminum alloy) and an ionic conductor (solution). The results show the potential of SQUID magnetometry for practical corrosion detection in restricted locations (hidden corrosion) and in subjects where solution flow is applied.Contribution to the 3rd Baltic Conference on Electrochemistry, GDASK-SOBIESZEWO, 23–26 APRIL 2003.Dedicated to the memory of Harry B. Mark, Jr. (February 28, 1934 – March 3rd, 2003)     

Formation of gold-capped silicon nanocolumns on silicon substrate

Gold-capped silicon nanocolumns regularly distributed over silicon substrate were obtained. The columns length was roughly 100?nm; their deviation from perpendicular axis was less than 2°. The diameter of the columns was of the order of 10?nm or below of that. The proposed procedure of nanostructuring included the following main steps: deposition of aluminum thin layer (100?C500?nm) by magnetron sputtering on (100) oriented Si wafers; formation of porous self-ordered alumina structures by electrochemical anodizing of the Al film in oxalic acid; electroless inversion of Au in alumina pores; and reactive ion etching. The obtained Si?CAu structures are of importance as the platforms for biosensing applications, while the gold-free structures are of interest in photovoltaics.     

Magnetometric corrosion sensing under hydrodynamic conditions

SQUID (Superconducting QUantum Interference Device) magnetometer operating in liquid helium with a special resolution of ca. 1 mm was used to study the magnetic fields produced by corrosion reactions under electrolyte flow conditions. Macroscopic magnetic field images were obtained on AA 2024 samples corroding in naturally aerated and oxygen-saturated NaCl solutions and 0.1 M NaOH. The fields originated from the macroscopic surface currents (ionic and electronic), which appear due to corrosion potential differences that resulted from differences in electrolyte flow characteristics (velocity, direction, and turbulence). The measurements demonstrated SQUID capability of remote corrosion sensing across the integrated media consisting of gaseous and solid dielectrics, metal, and electrolyte. The results have shown the potential of magnetometry for practical corrosion detection in the restricted locations (“hidden” corrosion) where solution flow is applied.     

Microgravimetric corrosion study of magnetron-sputtered Co-Cr-Mo and Ni-Cr-Mo alloys in an oxygen-containing atmosphere

A quartz crystal microbalance (QCM) has been used for in situ corrosion studies of magnetron-sputtered Co-Cr-Mo and Ni-Cr-Mo alloys, which are of great importance in various technical and medical applications. The corrosion monitoring has been performed in an oxygen-containing atmosphere and in NaCl solution. The alloys were deposited on quartz substrates by means of DC magnetron sputtering. X-ray photoelectron spectroscopy analysis showed that the composition of the deposits was similar to that of the magnetron-sputtering targets. X-ray diffraction revealed an amorphous structure of the sputtered deposits, while the casting alloys had a crystalline structure. The polarization resistance of sputtered alloys in NaCl solution was higher than the activity of conventional alloys, which implied a superior corrosion resistance of the sputtered deposits. Corrosion was initiated by supplying oxygen gas into a wet argon atmosphere and the QCM detected corrosion with nanogram resolution as the increase in mass. Corrosion currents were calculated from the mass versus time curves. The QCM appeared to be an effective tool for corrosive characterization of sputtered alloys in gaseous environments. A corrosion current calculation in solution was complicated by metal transfer to the liquid phase. Electronic Publication