Mediated and non-mediated electrochemical oxidation of isopropanol

Kinetic studies of the electrochemical generation of Ag(II) and Co(III) ions and the catalytic oxidation of isopropanol in acidic media are presented. Its mediated and non-mediated electrooxidation up to carbon dioxide is considered.     

Fabrication of silver-coated silicon nanowire arrays for surface-enhanced Raman scattering by galvanic displacement processes

Silver-coated silicon nanowire (SiNW) arrays were prepared utilizing galvanic displacement processes consisting of three steps: galvanic displacement deposition of silver particles using a HF-AgNO₃ or NH₄F-AgNO₃ aqueous solution; formation of SiNW arrays by a silver-assisted chemical etching process conducted in the HF-H₂O₂ aqueous solution; deposition of silver particles on the SiNW arrays from the NH₄F-AgNO₃ aqueous solution. The effects of the morphology of pre-deposited silver particles and deposition solution on the formation of silver-coated SiNW arrays were discussed. Surface-enhanced Raman scattering (SERS) performances have been studied using Rhodamine 6G (R6G) probe molecules on the silver-coated SiNW substrates.     

ZnSe‐based conductive nanotemplates for nanofabrication

We show that anodic etching of n‐type ZnSe crystalline substrates leads to the formation of pores which, after nucleation at surface defects, prove to follow the current lines, exhibiting multiplication until the front of the porous network covers the whole available space. No growth of crystallographically oriented pores has been observed in ZnSe. The formation of multilayer porous structures is realized, including layers subjected to successive porosification at two different length scales. The electrochemical pulsed deposition of arrays of Pt nanotubes in the porous ZnSe matrix is demonstrated. The obtained results show that porous ZnSe structures are promising for use as conductive and optically transparent nanotemplates for nanofabrication, in particular for the important application of metal nanotubes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electron beam treatments of electrophoretic ceramic coatings

In this work a method to densify ceramic coating obtained by electrophoresis and to improve its adhesion to the substrate is proposed. It consists in irradiating the coating surface by electron beam (EB). Alumina and alumina-zirconia coatings were deposited on stainless steel substrates and treated by low power EB. SEM, XRD and TEM characterizations demonstrated that the sintering occurred. Moreover, it is shown that on alumina-zirconia coating the EB irradiation produced a composite material consisting principally of tetragonal zirconia particles immersed in an amorphous alumina matrix. The adhesion stress of EB treated coating was estimated by stud pull test and it was found to be comparable to that of plasma-sprayed coatings.     

Microstructure and corrosion resistance behavior of ceramic coatings on biomedical NiTi alloy prepared by micro-arc oxidation

In this paper, ceramic coatings were prepared on biomedical NiTi alloys by micro-arc oxidation (MAO) in constant voltage mode. The current density-time response was recorded during the MAO process. The microstructure, element distribution and phase composition of the coatings prepared at different MAO treatment times were investigated by scanning electron microscopy (SEM), energy dispersive X-ray spectrometer (EDS), thin-film X-ray diffraction (TF-XRD) and X-ray photoelectron spectroscopy (XPS). The corrosion behavior of the coatings in 0.9% NaCl solution was evaluated by the potentiodynamic polarization test. It is found that the coatings become more compact with increasing the MAO treatment time, and the growth rate of coating decreases. The results of TF-XRD, EDS and XPS indicate that the coatings are composed of a large amount of γ-Al₂O₃ and a little α-Al₂O₃, TiO₂ and Ni₂O₃. The Ni content of the coatings is about 3 at.%, which is greatly lower than that of NiTi substrate. The bonding strength of coating-substrate is higher than 40 MPa for all the samples in this study. The corrosion resistance of the coatings is about two orders of magnitude higher than that of the uncoated NiTi alloy.     

Fabrication of microrods and microtips of InP by electrochemical etching

Here we presented a simple approach to fabricate the microstructures of InP by electrochemical etching. Microrods were formed while InP etched in 7 M HCl solutions for 30 s, and microtips were obtained while InP etched for 120 s. In addition, with increasing applied potential the surface of the microrods became smoother. The formation mechanism was also discussed in this article.     

Metal nanorod production in silicon matrix by electroless process

Metal filled Si nanopores, that is, metal nanorods in an Si matrix, are produced by an electroless process that consists of three steps: (1) electroless displacement deposition of metal nanoparticles from a metal salt solution containing HF; (2) Si nanopore formation by metal-particle-enhanced HF etching; and (3) metal filling in nanopores by autocatalytic electroless deposition. Ag nanoparticles produce Si nanopores whose sizes are a few tens of nm in diameter and ca. 50 nm deep. Au nanoparticles produce finer and straighter nanopores on Si than the Ag case. These nanopores are filled with a Co or a Co-Ni alloy by autocatalytic deposition using dimethylamine-borane as a reducing agent. Phosphinate can be used as a reducing agent for the Au-deposited-and-pore-formed Si. The important feature of this process is that the metal nanoparticles, that is, the initiation points of the autocatalytic metal deposition, are present on the bottoms of the Si nanopores.     

Effect of NaAlO2 concentrations on microstructure and corrosion resistance of Al2O3/ZrO2 coatings formed on zirconium by micro-arc oxidation

In this study, Al₂O₃/ZrO₂ composite coatings were prepared on Zr substrates by micro-arc oxidation (MAO) in the NaAlO₂-containing electrolytes, and the effect of NaAlO₂ concentration on the microstructure, bond strength, microhardness and corrosion resistance of coatings was systematically investigated. The study reveals that the adequate NaAlO₂ in the electrolyte (>0.2 M) is essential to the formation of needle-like α-Al₂O₃ in the coatings, and the amount of α-Al₂O₃ rises with the increase of the NaAlO₂ concentration. m-ZrO₂ and t-ZrO₂ are present in all of the coatings, but their relative amount largely depends on the amount of Al₂O₃. It is also found that as the NaAlO₂ concentration increases from 0.2 to 0.3 M, the coating becomes denser and thicker, and its bond strength, maximum microhardness and corrosion resistance increases as well. The coating formed at 0.3 M NaAlO₂ demonstrates the highest bond strength of 52 MPa, the maximum microhardness of 1600 Hv_0.2N and the superior corrosion resistance. However, the overhigh concentration of NaAlO₂ (0.35 M) is found harmful to the coating's microstructure and properties.     

Tip-induced local anodic oxidation on p-GaAs surface with non-contact atomic force microscopy

Nano-sized oxide structures resulted from localized electrochemical oxidation induced by a negatively biased atomic force microscopy (AFM) tip operated with the non-contact mode were fabricated on p-GaAs(1 0 0) surface. The geometrical characteristics of the oxide patterns and their dependences on various fabrication parameters, e.g., the anodization time, the biased voltages, the tip scanning rates, as well as the formation mechanism and relevant growth kinetics are investigated. Results indicate that the height of the protruded oxide dots grow exponentially as a function of time in the initial stage of oxidation and soon reaches a maximum height depending linearly with the anodized voltages, in according with the behaviors predicted by space charge limited local oxidation mechanism. In addition, selective micro-Auger analysis of the anodized region reveals the formation of Ga(As)O_x, indicating the prominent role played by the field-induced nanometer-size water meniscus in producing the nanometer-scale oxide dots and bumps on p-GaAs(1 0 0) surface.     

How the masters in Umbria,Italy, generated and used nanoparticles in art fabrication during the Renaissance period

Lustre was one of the most sophisticated techniques for the decoration of majolicas during the Renaissance period. Lustre consists of a thin metallic film containing silver, copper and other substances like iron oxide and cinnabar applied in a reducing atmosphere on a previously glazed ceramic. In this way, beautiful iridescent reflections of different colours (in particular gold and ruby-red) are obtained. The characterisation and the study of lustre-decorated majolicas is of great interest for archaeologists, but also offers possibilities for producing pottery with outstanding decoration today, following ancient examples, since nowadays Italian artisans are interested in the reproduction of the ancient recipes and procedures. Moreover, it can even suggest new procedures for obtaining uniform thin metallic films for technological applications. A study has been carried out on ancient lustre layers using numerous different analytical techniques such as XRD, SEM–EDX, TEM–EDX–SAED, ETAAS, ICP–OES, UV–vis reflectance spectroscopy and SAXS. Lustre films were shown to be formed by copper and silver clusters of nanometric dimension. The colour and the properties of the lustre films depend on the elemental composition of the impasto applied to the ceramic surface as well as on other factors like the metallic nanocluster dimension, the firing conditions, the underlying glaze composition and the procedure used. Received: 12 August 2002 / Accepted: 14 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +39-6/9067-2445, E-mail: pad@mlib.cnr.it     

On the growth of conversion chromate coatings on 2024-Al alloy

The initial growth of chromate conversion coatings on aluminium 2024-T3 alloy has been investigated by scanning Auger microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy. The coating initiation is shown to be influenced by the alloy microstructure. In agreement with previously proposed growth models, Cr(VI) to Cr(III) reduction begins on the Al-Cu-Fe-Mn intermetallic second-phase particles, which act as cathodic sites, and then over the entire Al matrix surface. The less noble Al-Cu-Mg second-phase particles demonstrate dual behaviour during the initial stage of coating; some dealloy, with formation of a Cu-rich sponge-like structure, while others show no evidence for etching during the first few seconds and coating deposits on them similar to the situation for the Al-Cu-Fe-Mn particles. XPS measurements show more Cr(III) at the very initial stage of nucleation and growth, whereas the amount of Cr(VI) in the coating increases with the length of the chromating treatment. This is discussed in relation to Raman spectroscopy measurements made in a separate study.     

Catalysis of dispersed silver particles on directional etching of silicon

Silver particles are dispersed on silicon by magnetron sputtering and post-annealing to investigate the catalytic effects of individual silver particles on wet etching of silicon surface. According to scanning electron microscopy, dispersed deep holes are present and the major etching direction is vertical to the surface of a Si(1 0 0) wafer or inclined to that on a Si(1 1 1) wafer. Our experiments indicate that the effect of the anisotropy of Si on directional etching is fundamental and the wafer resistivity and experimental process have important influence on the etching results. In addition, aggregation of silver particles and random horizontal etching on the surface of the wafer are caused by the local imbalance between the oxidant and HF. Our results enable better understanding of the catalytic effects of metal particles on silicon and are helpful to the preparation new silicon nanostructures.     

Characteristic of ceramic coatings on aluminum by plasma electrolytic oxidation in silicate and phosphate electrolyte

In the present work, four processes were carried out to produce ceramic coatings on aluminum substrate in two kinds of electrolytes (silicate and phosphate solution systems) using plasma electrolytic oxidation (PEO) technology. The voltage-time responses were recorded during different PEO processes. SEM/EDX and XRD were adopted to investigate the microstructure, elements distribution and phase composition of the coatings prepared in the two electrolyte systems. It is found that coatings produced in the silicate electrolyte have a more homogeneous morphology than those produced in the phosphate system. EDX analysis shows that silicon element tends to present primarily in the outer region of the coatings while phosphorus distributes uniformly throughout the coating thickness. According to the conventional anodic oxidation mechanism, a model is set up to explain the different characteristics of ceramic coatings fabricated in different electrolytes which is helpful to understand the growth mechanism of PEO coatings.     

Violet luminescence in Ge nanocrystals/Ge oxide structures formed by dry oxidation of polycrystalline SiGe

Nanocrystals of Ge surrounded by a germanium oxide matrix have been formed by dry thermal oxidation of polycrystalline SiGe layers. Violet (3.16 eV) luminescence emission is observed when Ge nanocrystals, formed by the oxidation of the Ge segregated during the oxidation of the SiGe layer, are present, and vanishes when all the Ge has been oxidized forming GeO₂. Based on the evolution of the luminescence intensity and the structure of the oxidized layer with the oxidation time, the recombination of excitons inside the nanocrystals and the presence of defects in the bulk oxide matrix are ruled out as sources of the luminescence. The luminescence is attributed to recombination in defects at the Ge sub-oxide interface between the Ge nanocrystals and the surrounding oxide matrix, which is GeO₂.     

Preparation of periodic mesoporous silica-included divacant Keggin units for the catalytic oxidation of styrene to synthesize styrene oxide

Periodic mesoporous composite catalysts, [(n-C₄H₉)₄N]₄[γ-SiW₁₀O₃₄(H₂O)₂]/SBA-15 (TBA-1*/SBA-15, where TBA-1* = [(n-C₄H₉)₄N]₄[γ-SiW₁₀O₃₄(H₂O)₂]), with TBA-1* loadings of 4.3-14.8% were prepared by simultaneous hydrolysis and co-condensation of the tetraethoxysilane (TEOS) in the presence of divacant Keggin-type polyoxometalate and triblock copolymer surfactant (P123) followed by hydrothermal treatment process. Structure integrity of the Keggin unit in as-prepared composites was studied by Fourier transform infrared spectroscopy (FT-IR), Raman scattering spectra, and ²⁹Si magic-angle spinning (MAS) NMR. Periodic mesoporous structure of the composites was evaluated by low-angle X-ray powder diffraction (LXRD) patterns, nitrogen porosimetry, and transmission electron microscope (TEM) measurements. As-prepared TBA-1*/SBA-15 was used as an heterogeneous oxidation catalyst for the styrene epoxidation reaction to synthesize styrene oxide in the presence of dilute H₂O₂ (30%), and influences of solvent, molar ratio of styrene to H₂O_2, TBA-1* loading on the styrene conversion, styrene oxide yield and selectivity were considered.     

Characterization of ultra-fast deposited polycrystalline graphite by a CO2 laser-assisted combustion-flame method

High deposition rate, 750 μm/min, crystalline graphite was deposited on WC substrates by a CO₂ laser-assisted combustion-flame method at laser powers between 300 and 800 W. The structures, which were identified as pillars, were characterized by various methods. The pillars were cylindrical in shape and grew to a size of approximately 3 mm in length and in a few minutes. The laser power did not affect the overall length of the pillar, but caused changes in the physical shape. X-ray and electron diffraction results revealed the pillars to be crystalline graphite regardless of the laser power. Investigation of the pillars by scanning electron microscopy showed two distinct microstructural areas: an inner core of dense material surrounded by an outer shell of lamellar-like material. The core/shell microstructure was unaffected by the level of CO₂ laser power.     

Formation of aligned silicon nanowire on silicon by electroless etching in HF solution

It was demonstrated that the etching in HF-based aqueous solution containing AgNO₃ and Na₂S₂O₈ as oxidizing agents or by Au-assisted electroless etching in HF/H₂O₂ solution at 50 °C yields films composed of aligned Si nanowire (SiNW). SiNW of diameters ∼10 nm were formed. The morphology and the photoluminescence (PL) of the etched layer as a function of etching solution composition were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence. It was demonstrated that the morphology and the photoluminescence of the etched layers strongly depends on the type of etching solution. Finally, a discussion on the formation process of the silicon nanowires is presented.     

The effect of powder preparation method on the corrosion and mechanical properties of TiN-based coatings by reactive plasma spraying

TiN-based composite coatings with and without the addition of Cr were deposited by reactive plasma spraying (RPS) in air. Both sintered and mixed powder of Ti and B₄C were used for the RPS process. A thermodynamic model was firstly used to estimate the complicated phase composition of composite coatings prepared by RPS. The phase composition, structures and properties of TiN-based coatings were investigated using XRD, SEM and a Vickers microhardness tester. The results show that the phases in TiN-based coatings do not generate according to priority of Gibbs free energy value due to non-equilibrium reactive course during thermal spraying. The coating deposited using sintered Ti and B₄C powder is composed of two main phases (TiN and TiN_0.3), two minor phases (Ti₂O₃ and TiB₂), and a small fraction of TiC phase. The composition of the coating deposited using the mixed powder with Cr added is predominantly in the TiN and TiB₂ phases, a smaller phase fraction of Ti₂O₃ and TiO₂, and some unreacted Cr. The Vickers microhardness of the coating deposited using sintered powder is higher than that of using mixed powder. The composite coating deposited using mixed powder with the addition of Cr shows superior corrosion resistant to that using sintered powder when tested in 3.5 wt.% NaCl electrolytic solution.     

The effect of chemical treatment on apatite-forming ability of the macroporous zirconia films formed by micro-arc oxidation

Macroporous and nano-crystalline zirconia film was prepared by micro-arc oxidation (MAO) of zirconium, and the effect of chemical treatment in H₂SO₄ or NaOH aqueous solutions on the microstructure and apatite-forming ability of the film was investigated. Compared with the MAO film, the chemically treated films do not exhibit apparent changes in phase component, morphology and grain size, however, have more abundant basic Zr-OH groups. The films treated with H₂SO₄ and NaOH solutions can induce apatite formation on their surfaces in simulated body fluids (SBF) within 1 day, whereas no apatite was detected on the untreated ZrO₂ surface by 30 days. It is believed that the enhanced apatite-forming ability of the chemically treated ZrO₂ films is related to the abundant basic Zr-OH groups on their surface.     

Effect of atmospheric pressure dielectric barrier discharge air plasma on electrode surface

In order to study the influence of plasma on electrode, atmospheric pressure dielectric barrier discharge (DBD) air plasma is employed here to treat copper electrode surface. Plasma is generated between the parallel plate electrodes by means of high voltage produced by a high-frequency power supply with transformer. Electrode surface alterations induced by air plasma are investigated by using field emission scanning electron microscope (FE-SEM), X-ray energy dispersion spectroscopy (EDS) and contact angle measurement. The results show that DBD air plasma removes the organic contaminant on surface and causes electrode surface roughness, oxidization and nitridation. In addition, surface wettability is also improved, as concluded from contact angle measurements.