Synthesis and properties of Co–Pt alloy silica core-shell particles

This paper describes a method for fabrication of silica-coated Co–Pt alloy nanoparticles in a liquid phase process. The Co–Pt nanoparticles were prepared from CoCl₂ (4.2 × 10⁻⁵ M), H₂PtCl₆ (1.8 × 10⁻⁵ M), citric acid (4 × 10⁻⁴ M) and NaBH₄ (1.2 × 10⁻² M) with a Co:Pt mole ratio of 7:3. The silica coating was performed in water/ethanol solution with a silane coupling agent, 3-aminopropyltrimethoxysilane (8 × 10⁻⁵ M), and a silica source, tetraethoxyorthosilicate (7.2 × 10⁻⁴ M) in the presence of the Co–Pt nanoparticles. Observations with a transmittance electron microscope and a scanning transmission electron microscope revealed that the Co-rich and Pt-rich nanoparticles were coated with silica. According to X-ray diffraction measurements, core particles were crystallized to metallic Co crystallites and fcc Co–Pt alloy crystallites with annealing in air at 300–500 °C. Magnetic properties of the silica-coated particles were strongly dependent on annealing temperature. Maximum values of 11.4 emu/g-sample for saturation magnetization and 365 Oe for coercive field were obtained for the particles annealed at 300 and 500 °C, respectively. Annealing at a temperature as high as 700 °C destroyed the coating structures because of crystallization of silica shell, resulting in reduction in saturation magnetization and coercive field.     

Electrochemical modification of Bi2S3 coatings in a nickel plating electrolyte

The electrochemical behavior of Bi₂S₃ coatings in Watts nickel plating electrolyte was investigated using the cyclic voltammetry, electrochemical quartz crystal microbalance, X-ray diffraction, and energy dispersive X-ray analysis methods. During the bismuth sulfide coating reduction in Watts background electrolyte in the potential region from −0.4 to −0.6 V, the Bi₂S₃ and Bi(III) oxygen compounds are reduced to metallic Bi, and the decrease in coating mass is related to the transfer of S²⁻ ions from the electrode surface. When the bismuth sulfide coating is reduced in Watts nickel plating electrolyte, the observed increase in coating mass in the potential region −0.1 to −0.4 V is conditioned by Ni²⁺ ions reduction before the bulk deposition of Ni, initiated by Bi₂S₃. In this potential region, the reduction of Bi(III) oxygen compounds can occur. After the treatment of as-deposited bismuth sulfide coating in nickel plating electrolyte at E = −0.3 V, the sheet resistance of the layer decreases from 10¹³ to 500–700 Ω cm. A metal-rich mixed sulfide Ni₃Bi₂S₂–parkerite is obtained when as-deposited bismuth sulfide coating is treated in Watts nickel plating electrolyte at a potential close to the equilibrium potential of the Ni/Ni²⁺ system and then annealed at temperatures higher than 120 °C.     

Inclusion of W in electroless Ni–B coating developed from a stabilizer free bath and investigation of its tribological behaviour

In the present study, tribological and corrosion behaviour of electroless Ni–B–W (ENB-W) coatings prepared from stabilizer-free baths and deposited on AISI 1040 steel substrates were examined. Three distinct coating bath temperatures (85 °C, 90 °C, and 95 °C) were varied for coating deposition. The coatings showed nodular morphology. Thermogravimetric study of ENB-W coatings revealed improved thermal stability attained at 95 °C bath temperature. The microhardness of ENB-W coating was 645, 690, and 720 HV₁₀₀ at bath temperatures of 85 °C, 90 °C, and 95 °C respectively. The inclusion of W to Ni–B coating enhanced the hardness by ∼150 HV₁₀₀. On a pin-on-disc tribometer, wear test was conducted. The precipitation of Ni (111) and its borides occurred post sliding wear at high temperatures (300 °C). Ni (111) crystallite size decreased because of high temperature sliding wear at 300 °C with an increase in coating bath temperature. With a reduction in crystallite size at high temperatures, both wear rate and COF decreases. The scratch hardness and first critical load of failure of the coatings was determined using a scratch tester. Using potentiodynamic polarization, corrosion resistance of ENB-W coatings in 3.5% NaCl was investigated. ENB-W coatings could provide shielding to AISI 1040 steel from corrosion. Though the corrosion resistance is poor with respect to lead stabilized coatings.     

Synthesis of Y<Subscript>3−x</Subscript>Lu<Subscript>x</Subscript>Al<Subscript>3</Subscript>MgSiO<Subscript>12</Subscript> garnet powders by sol–gel method

Y_3−xLu_xAl₃MgSiO₁₂ (x = 0–3) garnet powders were synthesized by an aqueous sol–gel method based on metal chelates with 1,2-ethanediol in aqueous media. Target samples were characterized by powder X-ray diffraction (XRD), scanning electron microscopy and reflection spectra. XRD analysis revealed that sintering of polycrystalline Y_3−xLu_xAl₃MgSiO₁₂ powders at 1,600 °C results in single-phase garnet materials.     

Effect of Zr/Ce molar ratio on the structure of powders and Zr1−x Ce x O2 coatings on quartz fiber reinforced polyimide matrix composites via sol–gel process

In this investigation, Zr_1−x Ce _x O₂ coatings were fabricated on quartz fiber reinforced polyimide matrix composites via sol–gel process at 400 °C. The phase evolution, structural and morphological characteristic of specimens were investigated by differential scanning calorimetric, Fourier transform infrared spectroscopy, powder X-ray diffraction and scanning electron microscopy. The significant phase evolution of final powders with the decreasing Zr/Ce molar ratio could be observed as follows: tetragonal (t′) → cubic + tetragonal (t′) → tetragonal (t″). BET specific surface areas of powders exhibited a decreased tendency with the increasing calcination temperature as well as the decreasing Zr/Ce molar ratio. The average crystallite size and the mean particle size increased with the elevated calcination temperature, while the particle size also increased with the increase in Ce content. The progressive addition of Ce could promote the sintering process and the densification of coating. Morphologies of coatings changed with the variation of the Zr/Ce molar ratio. The results indicate that Zr_0.75Ce_0.25O₂ coating with the Zr/Ce molar ratio of 3 is a stable uniform coating with excellent adhesion.     

Optimization on fabrication and performance of A-site-deficient La0.58Sr0.4Co0.2Fe0.8O3-δ cathode for SOFC

A-site-deficient perovskite cathode material La_0.58Sr_0.4Co_0.2Fe_0.8O_3 − δ (L58SCF) is coated on the yttria-stabilized zirconia electrolyte by screen-printing technique. Several key fabrication parameters including selection of additives (binder and pore former), effect of coating thickness, sintering temperature and time on the microstructure, and electrochemical performance of cathode are investigated by scanning electron microscopy and electrochemical impedance spectroscopy. We study the microstructure and the electrochemical property of the cathode with different kinds of additives. Results show that the cathode possesses fine microstructure, enough porosity, and ideal electrochemical property when polyvinyl butyral serves as both binder and pore former in the cathode. The cathode with three screen-printing coats (thickness 28 ± 7 μm, weight 6.07 ± 0.72 mg cm⁻²) sintering at 1,000 °C for 2 h shows lower polarization resistance of 0.183 Ω cm² at 800 °C. Based on the optimized parameters, the polarization resistances of the L58SCF–Ce_0.8Gd_0.2O_{1.9 – δ} composite cathode display the R _p values of 0.067 Ω cm² at 800 °C, 0.106 Ω cm² at 750 °C, 0.225 Ω cm² at 700 °C, and 0.550 Ω cm² at 650 °C.     

Physical and morphological characteristics and electrochemical behaviour in PEM fuel cells of PtRu /C catalysts

Platinum-ruthenium catalysts supported on carbon (PtRu/C) have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), specific surface area analysis (BET), X-ray photoelectron spectroscopy (XPS) and in proton exchange membrane (PEM) fuel cell tests. The results indicate the presence of strong metal-carbon interactions, which hinder the formation of a single-phase face-centered cubic (fcc) PtRu alloy. The particle size of the PtRu/C catalysts was smaller than both carbon-supported platinum (Pt/C) and ruthenium (Ru/C) catalysts. In the bimetallic electrocatalysts the intercrystallite distance decreased with respect to pure Pt and Ru metals. PEM fuel cell tests in H₂/air operation mode revealed a decrease of performance with increasing carbon content of the catalyst, at a fixed Pt loading. In H₂ + 100 ppm CO/air operation mode the maximum performance of the PEM fuel cell was attained at 0.63 atomic fraction Ru. Received: 2 December 1999 / Accepted: 27 January 2000     

ITO films on glass substrate by sol–gel technique: synthesis,characterization and optical properties

The present paper extensively demonstrates synthesis, characterization and optical properties of semiconductor indium tin oxide (ITO) thin films on glass substrate using sol–gel technique for gas sensor applications. Turbidity, pH values, wettability and rheological properties of the prepared solutions were measured to determine solution characteristics by turbidimeter, pH meter, contact angle goniometer and rheometer machines prior to coating process. Thermal, structural, microstructural, mechanical and optical properties of the coatings were characterized by differential thermal analysis–thermogravimetry (DTA/TG), fourier transform infrarared, X-ray diffraction (XRD), scanning electron microscopy, scratch tester, refractometer and spectrophotometer. Four different solutions were prepared by changing solvent concentration. Turbidity, pH, contact angle and viscosity values of the solutions were convenient for coating process. Glass substrates were coated using the solutions of InCl₃, SnCl₂, methanol and glacial acetic acid. The obtained gel films were dried at 300 °C for 10 min and subsequently heat-treated at 500 °C for 10 min in air. The oxide thin films were annealed at 600 °C for 60 min in air. DTA/TG results revealed that endothermic and exothermic reactions are observed at temperature between 70 and 560 °C due to solvent removal, combustion of carbon based materials and oxidation of Sn and In. The spectrum of ITO precursor film annealed at 500–600 °C shows an absence of absorption bands corresponding to organics and hydroxyls. In₂Sn₂O_7−x phase was dominantly found as well as SnO₂ with low intensity from XRD patterns. It was found that surface morphologies of the film change from coating island with homogeneous structures to regular surface and thinner film structures with increasing solvent concentration. The films prepared from the solutions with 8 mL methanol have better adhesion strength to the glass substrate among other coatings. Refractive index, thickness and band gap of ITO thin films were determined to be 1.3171, 0.625 μm and 3.67, respectively.     

Structural and optical properties of ZnO thin films by the spin coating Sol-Gel method

ZnO thin films were deposited onto glass subsrates by a Sol-gel spin coating method. The structural and optical properties of ZnO thin films were investigated. The molar ratios of the zinc acetate dihydrate to Monoethanolamine were maintained 1:1. The as-grown film was sintered 250 °C for 10 min, then annealed in air at 500 °C for 30 min. The XRD results indicate that ZnO films were strongly oriented to the c-axis of the hexagonal nature. Absorption measurements were carried out as a function of temperature with 10 K steps in the range 10–320 K. The band gap energy was measured 3.275 and 3.267 eV for 0.5 and 1.0 molarity (M) ZnO thin films at 300 K. The steepness parameters were observed between 10 and 320 K and their extrapolations converged at (E₀, α₀) = 3.65 eV, 172,819 cm⁻¹ and 3.70 eV, 653,436 cm⁻¹ for 0.5 and 1.0 M ZnO thin films, respectively.     

Sol–gel elaboration and structural investigations of Lu<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> planar waveguides

Europium actived Lu₂O₃ sol–gel transparent and crack free films were deposited by dipping on silica substrates. The film microstructure was studied by waveguide Raman spectroscopy (WRS) with annealing temperatures from 400 up to 1,000 °C and X-ray diffraction. The WRS results and TEM observations were correlated and showed that crystallization of the lutetium oxide phase into cubic phase occurs at 600 °C and is stable up to 1,000 °C, the crystallite size increasing between ±38 nm with annealing temperature ranging from 600 to 1,000 °C. Opto-geometrical parameters were determined by m-lines spectroscopy using four different wavelengths of laser sources in order to confirm the step-index profile of the as-prepared waveguides. The Eu³⁺ doped films heat-treated at 1,000 °C presented a constant thickness for the wavelengths 493, 543, 594 and 632.8 nm and a density of 8.4 g cm⁻³. High-resolution X-ray images were obtained.     

Optimization of process variables and corrosion properties of a multi layer silica sol gel coating on AZ91D using the Box–Behnken design

Anti-corrosion silica coating was prepared via the sol–gel method for AZ91D magnesium alloy using tetraethoxysilane and methyltriethoxysilane as precursors. Silica coating was deposited on fluorinated magnesium alloy substrates by dip coating. The surface morphology of the silica coating was characterized by scanning electron microscope (SEM). The corrosion properties were studied by electrochemical impedance measurements and polarisation technique in 3.5 wt% Sodium chloride solution. The results showed an improvement in the corrosion performance from these coatings. A three-factor, three-level design of experiment (DOE) with response surface methodology including a Box–Behnken design was run to evaluate the main and interaction effects of several independent formulation variables, which included precursor ratios MTES/TEOS (X₁), sintering temperature (X₃) and sol dilution (X₂) which measured the volume of the diluted sol divided by the initial volume of sol. The dependent variables included the corrosion current derived from the polarisation curve (i_cor = Y₁) and the coating resistance derived from the Nyquist curve (R_coat = Y₂). Optimizations were predicted to yield Y₁ and Y₂ values of 1.57018E–7A cm⁻² and 14279 Ω cm², when X₁, X₂, and X₃ were 3.36, 1.52 and 222, respectively.     

Bi1.5ZnNb1.5O7 cubic pyrochlore ceramics prepared by aqueous solution–gel method

Bi_1.5ZnNb_1.5O₇ cubic pyrochlore ceramic was successfully prepared by the aqueous solution method. The preparation, microstructure development and dielectric properties of ceramics were investigated. Homogeneous precalcined ceramics powders have a cubic pyrochlore phase after thermal treatment at the temperature as low as 450 °C. The aqueous solution–gel method, which Bi, Zn and Nb ions are chelated to form metal complexes, leading to the formation of cubic pyrochlore phase at low firing temperatures. No detectable intermediary phase such as BiNbO₄ or pseudo-orthorhombic pyrochlore is observed in the XRD patterns of ceramics at the sintering temperature range from 850 to 1,000 °C. The dielectric properties study revealed that the ceramics sintered at 900 °C show excellent performance with dielectric constant of 111 and dielectric loss of 2.3871 × 10⁻⁴ under 1 MHz at room temperature.     

Phase composition of electrodeposited silver-indium alloys

The phase composition of electrochemically obtained Ag-In alloy coatings electrodeposited at different conditions was determined. With the increase in the current density, both indium content and heterogeneity of the deposited layers increase. The amount of the indium-richer phase increase as well. Before the thermal treatment, the phases Ag, Ag₃In, and In₄Ag₉ are observed in coatings with spatio-temporal structures. As a result of heating the new phase Ag₄In appears at temperatures above 500 °C and indium is oxidized up to In₂O₃ from the oxygen in the heating chamber. Up to 500 °C, the spatio-temporal structures are still visible. Probably they consist of both Ag-rich α-phase and one of the phases of the alloy system with small indium content, such as Ag₄In or Ag₃In.     

Synthesis of electrospun BaSrTiO<Subscript>3</Subscript>/PVP nanofibers

Ba_1−x Sr _x TiO₃(x = 0–0.5, BST) nanofibers with diameters of 150–210 nm were prepared by using electrospun BST/polyvinylpyrrolidone (PVP) composite fibers by calcination for 2 h at temperatures in the range of 650–800 °C in air. The morphology and crystal structure of calcined BST/PVP nanofibers were characterized as functions of calcination temperature and Sr content with an aid of XRD, FT-IR, and TEM. Although several unknown XRD peaks were detected when the fibers were calcined at temperatures less than 750 °C, they disappeared with increasing the temperature (above 750 °C) due to its thermal decomposition and complete reaction in the formation of BST. In addition, the FT-IR studies of BST/PVP fibers revealed that the intensities of the O–H stretching vibration bands (at 3430 and 1425 cm⁻¹) became weaker with increasing the calcination temperature and a broad band at 540 cm⁻¹, Ti–O vibration, appeared sharper and narrower after calcination above 750 °C due to the formation of metal oxide bonds. However, no effect of Sr content on the crystal structure of the composites was detected.     

Preparation, characterization, and electrocatalytic properties of hybrid coatings of hexacyanometalate-doped-cationic films

Electrochemically active hybrid coatings based on cationic films, didodecyldimethylammonium bromide (DDAB), and poly(diallyldimethylammonium chloride) (PDDAC) are prepared on electrode surface by cycling the film-covered electrode repetitively in a pH 6.5 solution containing Fe(CN)₆ ³⁻ and Ru(CN)₆ ⁴⁻ anions. Modified electrodes exhibited stable and reversible voltammetric responses corresponding to characteristics of Fe(CN)₆ ^3−/4− and Ru(CN)₆ ^4−/3− redox couples. The cyclic voltammetric features of hybrid coatings resemble that of electron transfer process of surface-confined redox couple. Electrochemical quartz crystal microbalance results show that more amounts of electroactive anionic complexes partitioned into DDAB coating than those doped into PDDAC coating from the same doping solution. Peak potentials of hybrid film-bound redox couples showed a negative shift compared to those at bare electrode and this shift was more pronounced in the case of DDAB. Finally, the advantages of hybrid coatings in electrocatalysis are demonstrated with sulfur oxoanions.     

Surface characterization and dissolution study of biodegradable calcium metaphosphate coated by sol–gel method

Coatings of biomedical implant surfaces by a bioactive calcium phosphate film render bioactivity to the implant surface and shorten the healing time. In this present study, calcium metaphosphate (CMP) sol was synthesized by sol–gel method and coated onto the titanium alloys (Ti-6Al-4V). CMP sol was first synthesized by reacting Ca(NO₃)₂4H₂O (Sigma–Aldrich 99%, USA) with (OC₂H₅)₃P (Fluka 97%, Japan) in methyl alcohol. A stoichiometric Ca/P ratio of 0.5 was obtained by varying the amounts of the reactants. Sol was then coated on Ti-6Al-4V substrates by spin coating. The coated-specimens were then dried at 70 °C for 24 h, followed by a heat treatment at 650 °C for 1 h. Structural and chemical properties of the coatings were evaluated using XRD, SEM, and EPMA. The dissolution property of the coated-CMP layer was investigated by immersing the samples in the simulated body fluid (SBF) for 1, 3, 7 and 21 days. The concentration of Ca²⁺ released was measured using ICP. After heat treatment, SEM indicated a smooth and uniform CMP layer, with CMP grains of approximately 100 nm. The CMP phase was identified with δ-CMP (JCPDS #9-363). After immersion in SBF, coatings were observed to be roughened and porous. The concentration of Ca²⁺ in SBF was observed to increase over time, indicating continuous dissolution. The presence of titanium oxide phosphate compounds were also observed on CMP surfaces after immersion. It was thus concluded that the ability to control coating properties as well as the need for low heat treatment temperature offers advance for the use of CMP coating by sol–gel process on Ti-6Al-4V implant surfaces.     

Electrochemical performance of a novel CoTETA/C catalyst for the oxygen reduction reaction

In this communication, we report a novel CoTETA/C catalyst for the oxygen reduction reaction (ORR) which was prepared from a carbon-supported cobalt triethylenetetramine chelate, followed by heat treatment in an inert atmosphere. Electrochemical performances were measured using rotating disk electrode (RDE) technique and a PEM fuel cell test station. For a H₂–O₂ fuel cell system, the maximum output power density reached 162 mW cm^?2 at 25 °C with non-humidified reaction gases. We found a nanometallic face-centered cubic (fcc) α-Co phase embedded in the graphitic carbon after pyrolysis, based on X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements. These results indicated that CoTETA/C is a promising catalyst for the ORR.     

Thermogravimetric analysis and hot-stage Raman spectroscopy of cubic indium hydroxide

The transition of cubic indium hydroxide to cubic indium oxide has been studied by thermogravimetric analysis complimented with hot-stage Raman spectroscopy. Thermal analysis shows the transition of In(OH)₃ to In₂O₃ occurs at 219 °C. The structure and morphology of In(OH)₃ synthesised using a soft chemical route at low temperatures was confirmed by X-ray diffraction and scanning electron microscopy. A topotactical relationship exists between the micro/nano-cubes of In(OH)₃ and In₂O₃. The Raman spectrum of In(OH)₃ is characterised by an intense sharp band at 309 cm⁻¹ attributed to ν₁ In–O symmetric stretching mode, bands at 1137 and 1155 cm⁻¹ attributed to In-OH δ deformation modes, bands at 3083, 3215, 3123 and 3262 cm⁻¹ assigned to the OH stretching vibrations. Upon thermal treatment of In(OH)₃, new Raman bands are observed at 125, 295, 488 and 615 cm⁻¹ attributed to In₂O₃. Changes in the structure of In(OH)₃ with thermal treatment is readily followed by hot-stage Raman spectroscopy.     

On the sol–gel preparation of different tungstates and molybdates

The preparation and characterization of the M′–M′′–O nitrate–tartrate (M′ = Ca, Ba, Gd and M′ = W, Mo) precursor gels synthesized by simple, inexpensive, and environmentally benign aqueous sol–gel method is reported. The obtained gels were studied by thermal (TG/DSC) analysis. TG/DSC measurements revealed the possible decomposition pathway of synthesized M′–M′′–O nitrate–tartrate gels. For the synthesis of different metal tungstates and molybdates, the precursor gels were calcined at different temperatures (650, 800, and 900 °C). According to the X-ray diffraction (XRD) analysis data, the crystalline compounds CaMo_1-x W _x O₄ doped with Ce³⁺ ions, BaMo_1-x W _x O₄ doped with Eu³⁺ ions and Gd₂Mo₃O₁₂ were obtained from nitrate–tartrate gels annealed at 650–900 °C temperatures. The XRD data confirmed that the fully crystalline single-phase powellite, scheelite, or Gd₂(MoO₄)₃ structures were formed already at 650 °C. Therefore, the suggested sol–gel method based on the complexation of metal ions with tartaric acid is suitable for the preparation of mixed tungstates–molybdates at relatively low temperature in comparison with solid-state synthesis.     

Conductivity of semiconducting tin dioxide in dry air caused by oxygen chemical transformations and chemisorption

The conductivity of semiconducting tin dioxide (SnO₂) in pure nitrogen and dry air was studied over the temperature range ∼20−650°C. Conductivity was shown to be caused by chemical transformations of oxygen molecules on catalytically active oxide surfaces. It unambiguously corresponded to the formation of O⁻ and O²⁻ chemisorbed ions. The experimental data were used to construct the temperature dependences of the chemisorption of O⁻ and O²⁻. The formation of O⁻ ions was maximum at ≈200°C, and the formation of O²⁻ ions did not reach a maximum at 650°C and increased beyond this limit. The number of electrons entrapped by chemisorbed oxygen ions and the concentrations of oxygen ions at all formation stages were estimated.