Gold-Nickel Hydroxide Multi-Layers with Selective Absorption in the Visible Range

This work reports the growth of layered nickel hydroxide/gold films by sol-gel and dip-coating methods to obtain colored films for applications in switchable optical devices. The nickel and gold-based films were deposited on mica and glass plates from alcoholic sols. The distribution of electron density inhomogeneities (voids, nickel and gold particles) in the films was determined by means of small angle X-ray scattering (SAXS). The SAXS measurements were used to determine the nickel and gold particle sizes and to give guidelines to the appropriate chemical route to deposit homogeneous colored films. X-ray diffraction (XRD) was used to monitor the crystalline properties. Transmission electron microscopy (TEM) was used to observe the nanostructure of the gold particles and atomic force microscopy (AFM) to analyze the film surface. Spectral transmission was used to investigate the optical properties in these different layered systems, which present an absorption band in the visible region due to the gold aggregates. The composite material is deep blue. The analyses of SAXS data, TEM and AFM pictures are consistent, i.e., the formed Au particles are polydisperse in size and their clustering depends on the NiO _x H _y layer. The Au particles are polycrystalline, with [111]-preferred orientation, as determined by XRD. The nickel oxy-hydroxide matrix is amorphous.     

Preparation of TiO2 Sol Using TiCl4 as a Precursor

A titanium dioxide sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. The sol was prepared by a process where HCl was added to a gel of hydrated titanium oxide to dissolve it. The resulting aqueous titanic acid solution was heated to form titanium dioxide sol. The effects of preparation parameters were investigated. TiCl₄ was slowly added to distilled water at 5°C. Aqueous solution of sodium hydroxide was added to adjust the pH of the system to 8–12. After aging for a period of time, the peptized sol was filtered and sufficiently washed. The filtered cake was repulped in water. Hydrochloric acid was slowly added to the solution with stirring. After condensation reaction and crystallization, a transparent sol with suspended TiO₂ was formed. XRD results show that the crystalline phase was anatase. The suspended TiO₂ particles were rhombus primary particles with the major axis ca. 20 nm and the minor axis ca. 5 nm. The TiO₂ particles prepared at pH 8 had the largest surface area of 141 cm³/g and it was microporous. The compositions of the solution which yielded the smallest suspended TiO₂ particles were TiO₂:HCl (35% HCl) = 1:1 (molar ratio), concentration of TiO₂ = 10%. Hydroxypropyl cellulose with viscosity of 150–400 cps was added as a dispersant. The sol was excellent in dispersibility and long-term stability. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The dip-coating on glass can be less than three times to have one monolayer TiO₂. The transparent TiO₂ thin film had strong hydrophilicity after being illuminated by UV light.     

Study on the preparation and structure of positive sol composed of mixed metal hydroxide

Using precipitation method mixed metal hydroxide (MMH) positive sol was prepared. The preparation process and the properties of the sol were studied with powder XRD, TEM, particle size distribution determination system and microelectrophoresis instrument.The preparation of MMH was made as follows: Diluted ammonia water was added to the mixed solution of aluminum and magnesium chlorides which was prepared in the molar ratio of 1 1 or 1 2, or 1 3; then the pH values of the suspension at different amounts of ammonia water were measured. After that, the precipitate was aged for 5 h in the mother solution at room temperature, and washed after filtering. Finally, the filter cake was peptized at constant temperature of 333 K.The results showed that 1) preparation reaction was completed in three steps, 2) pH value was decisive factor, and 3) both the contents of magnesium and the -potential of MMH sol particles increased with pH values and finally remained constant. The mechanism of the reaction was that magnesium ions intercalated Al(OH)₃ crystal lattice, forming mixed metal hydroxide. The results also showed that positively charged MMH colloidal particle belonged to hexagonal system and three-layer superposition structure.     

γ-Al2O3负载的金溶胶的尺寸效应对CO催化氧化活性的影响

The relationship between particle size and catalytic activity of gold nanoparticle catalysts with γ-Al2O3 as support has been investigated. The catalysts were prepared via the gold sol with different particle sizes by micelle method, and their structures were characterized by HRTEM and XRD, respectively. Furthermore, the catalytic activities were tested by CO oxidation. Experimental results showed that the catalytic activity became much weaker when gold particles were increased from 3.2 to 6.6 nm. Additionally, the particle size was also a key factor to govern catalytic activity with regard to gold supported on TiO2 prepared by the methods of deposition-precipitation.     

Improving dispersion stability of zirconium hydroxide sol for preparing nano zirconia by the reverse precipitation

Zirconium hydroxide sol was prepared by the reverse precipitation method with ZrOCl₂ solution as raw material and the processing condition of the zirconium hydroxide sol was investigated. When the saturated absorption amount of the surfactant was 1.0?wt%, the pH value for the highest stability was shifted from 7.9 to 9.3 and the pH range for preparing stable zirconium hydroxide sol widened as 8.0-11.0. The suitable concentration of ZrOCl₂ solution for the efficient gelation keeping the high dispersion stability was investigated. The microwave drying was demonstrated to be suitable for preparation of nanoparticle. The characteristics of produced nano zirconia were discussed, which in results the shape of powder was spherical and the grain size was 35?nm at average with moderate dispersion.     

An experimental trial for the determination of the critical coagulation concentration using the sedimentation method

A method for determining the critical coagulation concentration (C _c) from the change in the transmittance of the sol with stand time after adding a coagulating agent is discussed. Potassium nitrate was used as the coagulating agent because the specific adsorption of electrolyte ions on the particle and the hydrolysis of electrolyte ions are negligible. Apparent critical coagulation concentrations,C _c ^a, of iron (III) hydroxide and silver iodide sols were obtained from the transmittance vs. potassium nitrate concentration curves for various stand times. The values ofC _c ^a decreased with increasing stand time. TheC _c ^a value obtained for the shortest stand time was closer toC _c obtained from the initial turbidity change of the sol by applying Rayleigh's law. The Hamaker constant for the particle in water was calculated from theC _c ^a value obtained at the shortest time and the experimentally determined outer Helmholtz plane potential. The calculated Hamaker constants were comparable to the theoretical values for iron (III) hydroxide and silver iodide.     

Synthesis and characterization of NiO nanoclusters via thermal decomposition

Thermal decomposition process has been developed to synthesize nickel oxide (NiO) nanoclusters via the reaction between a new precursor, nickel oxalate [Ni(O₄C₂)(H₂O)₄] and oleylamine (C₁₈H₃₇N). The combination of triphenylphosphine (C₁₈H₁₅P) and C₁₈H₃₇N were added as surfactants to control the particle size. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and ultraviolet–visible (UV–Vis) spectroscopy. The synthesized NiO nanoclusters have a cubic structure with average size 2–10 nm.     

Structure and Dielectric Properties of NiTiO3 Powders Synthesized by the Modified Sol–Gel Method

This study reports the synthesis of nickel titanate (NiTiO₃) powders by using the modified sol‐gel method, with nickel acetate tetrahydrate as the nickel source, titanium isopropoxide as the titanium source, and 2‐methoxyethanol as the solvent, followed by post‐heat treatment in air at temperatures ranging from 500 °C to 900 °C. The characteristics of powders were determined by X‐ray diffraction (XRD), FT‐infrared spectroscopy (FT‐IR), ultraviolet/visible spectroscopy (UV/Vis), and Raman spectroscopy. The particle size and surface area of the powders were also measured. The results indicated that single‐phase NiTiO₃ can be prepared using the modified sol‐gel method, followed by post‐heat treatment at the relatively low temperature of 550 °C. The crystallite sizes and particle sizes of NiTiO₃ powders increase in conjunction with the post‐heat treatment temperatures. However, the surface area of the powders shrinks as the post‐heat treatment temperatures increase. The dielectric constants of NiTiO₃ powders, based on the capacitance‐voltage analysis, are within a range of 13.2 to 17.8.     

Surfactant-assisted low-temperature thermal decomposition route to spherical NiO nanoparticles

Thermal decomposition has been employed to access spherical nickel oxide (NiO) nanoparticles from a new precursor, nickel-salicylate, [Ni(C₇H₅O₃)₂(H₂O)₄]. Surfactants, triphenylphosphine ((C₆H₅)₃P), and oleylamine (C₁₈H₃₅NH₂) were added to control the particle size. The products were characterized by X-ray diffraction, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy, and thermogravimetric analysis. TEM images showed particles nearly spherical having sizes 5–15?nm. The magnetism of NiO nanoparticles was studied with a vibrating sample magnetometer. Due to smaller particle size and increased surface uncompensated spins, a superparamagnetic behavior is observed. The synthetic process is simple and affords high-purity material at a relatively lower calcination temperature.     

Controllable synthesis of silica nanoparticle size and packing efficiency onto PVP-functionalized PMMA via a sol–gel method

This study aimed to investigate synthesis and adsorption behavior of silica nanoparticles onto polyvinylpyrrolidone (PVP)-functionalized poly(methyl methacrylate) under various conditions such as methanol/water ratio, ammonium hydroxide concentration, polymer contents, tetraethylorthosilicate contents, and total volume of solvent via sol–gel method. First, the copolymerization of methyl acrylate as a comonomer and 1-dodecanethiol as a chain transfer agent increased the thermal stability of the product; however, the uniformity of the PMMA particles decreased because of the chain transfer reaction. Second, the adsorption behavior and size of silica nanoparticles could be controlled by adjusting the silica synthesis conditions. The adsorbed silica particle size was greatly influenced by the ammonium hydroxide concentration and the addition of water further enhanced the size increase. However, increasing the water content reduced the packing efficiency of the adsorbed silica particles. Increasing the PVP-functionalized PMMA content at a fixed TEOS content linearly decreased the silica particle size. But TEOS concentration did not significantly affect the silica particle size. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 662–672     

Nanostructured NiO based all solid state electrochromic device

A nickel oxide film with a thickness of 445 nm was deposited from nickel acetate precursor using the sol–gel dip coating method. The NiO films exhibit optical transmission of 84% at 550 nm and direct energy gap (E _gd) value is 3.64 eV. The FTIR spectrum of the films confirms the formation of Ni–O bond. XRD spectrum reveals the formation of nano crystallites along (111) and (200) planes with a particle size of 17 nm. The electrochromic properties have been studied using cyclic voltammetric (CV) technique. The optical transmission of a glass/FTO/NiO/ZrO₂/FTO/glass EC device is reported.     

纳米二氧化硅复合悬浮液合成及聚合物吸附研究

从水玻璃合成了纳米硅溶胶,并以它为起始原核,通过水解钛酸正丁酯沉积二氧化钛,制得了稳定的二氧化钛复合二氧化硅纳米悬浮液,研究了添加的高分子两亲分散剂聚醚多胺在硅胶粒上的吸附和二氧化钛沉积过程中的贡献。研究结果表明,添加的聚醚多胺吸附在硅胶粒表面,有利于硅溶胶的稳定;钛酸正丁酯-丁醇-硫酸水解反应是可逆的,二氧化钛向硅胶粒定向沉积,这些沉积物呈无定形态,在沉积过程中,吸附的这些添加剂发生离子化,其阳离子端基形成的离子氛有利于二氧化钛沉积,并能减少胶粒粘接或团聚。     

Combination of Silica Sol and Potassium Silicate via Isothermal Heat Conduction Microcalorimetry

Isothermal heat conduction microcalorimetry was utilized as a novel characterization method to investigate the polymerization processes of silica with both thermodynamic and kinetic parameters when the combination of silica sol and potassium silicate was stirred at temperatures of 25.0, 35.0, and 45.0°C. The silica polymerization was characterized by the greater enthalpy change at each higher temperature and by the reaction orders of the silica sol and potassium silicate, which varied rapidly, instantaneously, and constantly from low to high all the time, up and down in an alternate manner. When the reaction order of the silica sol and potassium silicate was 3.0, the maximum rate constant occurred at 25.0°C (k=1.22×10^?4mol^?2·dm⁶·s^?1). The two temperature regions (25.0–35.0°C region with a faster rate and 35.0–45.0°C region with a lower rate) reflected a two‐stage oligomerization of silica monomers with different oligomers formed in a two‐step anionic mechanism. The measurements of particle size and pH value showed that the colloidal particles in the mixed silica sol and potassium silicate first dissolved, then "active" silica in the potassium silicate redeposited to make a distinct particle size distribution (Z‐average size, 33.0–14.9 nm at 25.0°C) influenced both by pH value (9.82–11.97 at 25.0°C) and the mass fraction (53, 65, 75, and 85 mass/%) of the silica sol in the mixture. The processes of combination of the silica sol and potassium silicate did not result from acid‐base neutralization reactions but from a complex polymerization of the "active" silica components which relate to silica monomers oligomerization with heat evolved (the total enthalpy changes, 1.6234–3.3882 J).     

Synthesis of High Dispersion and Uniform Nano-sized Flame Retardant-Used Hexagonal Mg(OH)<Subscript>2</Subscript>

Nanosized dispersive flake-like magnesium hydroxide (Mg(OH)₂) had been prepared by a hydrothermal method. In the process, when the surfactant polyvinyl pyrrolidone was added, high dispersion, small particle size and large specific surface area of hexagonal crystal magnesium hydroxide was obtained by ultrasonic dispersion and temperature program. The flame retardant of Mg(OH)₂ was systematically explored by scanning electron microscope (SEM), transmission electron microscopy, X-ray diffraction, BET analysis and thermo-gravimetric analysis tests. SEM showed the formation of uniform and small size magnesium hydroxide particle with hexagonal nanoscale. Under the optimized conditions, high nano-sized hexagonal Mg(OH)₂ was acquired with a mean particle size of 134 nm and a specific surface area of 26.66 m²/g. According to TGA results, the sample’s decomposition temperature was 626.9 K, which was consistent with the reported literature. It is vitally prospected that the prepared hexagonal Mg(OH)₂ is to be applied to the industry as a flame retardant.     

Preparation and Structure of Microporous Silica Membranes

Silica sols have been prepared in an alcoholic solution by hydrolysis and condensation of TEOS (tetra-ethyl-ortho-silicate) molecules as a function of water and nitric acid concentration. The polymers are intended as precursors for ceramic, gas separation membranes. These molecules show fractal behavior as determined by SAXS (Small Angle X-ray Scattering). Microporosity of dried and calcined silica polymers is determined by N₂-adsorption at 77 K. Fractal dimension and porosity increase with increasing acid concentration. Both the sol structure and the drying kinetics determine the porosity values. N₂-adsorption isotherms are not very suitable for the determination of pore size distributions of microporous silica.     

Synthesis of Nano‐Sized TiO2 Colloidal Sol and Its Optical Properties

Nano‐sized TiO₂ sol was prepared through a wet synthesis process. The synthesis procedure involved hydrolysis of TiCl₄, acid treatment, and a SiO₂ surface‐modifying process. Before surface modification, the TiO₂ suspension was treated with acid to remove Na ions, soluble TiO_2, and other impurities. The acid treatment of a TiO₂ suspension at a higher temperature was proved to be useful for effective SiO₂ modification. The colloidal sol provided high transparency in visible light as well as excellent UV‐shielding properties. Surface modification of TiO₂ particles with SiO₂ greatly improved both the dispersing stability in neutral pH and the photostability of TiO₂ colloidal sol.     

Synthesis of gold nanoparticles in sol–gel glass porogens containing [bmim][BF4] ionic liquid

The [bmim][BF₄] ionic liquid effect on gold nanoparticles formation in silica sol–gel materials is studied in order to produce gel-derived glasses with optical properties. The characteristic red color from gold nanoparticles is observed for transparent glass monoliths obtained sintering, between 365 and 425 °C, a silica sol–gel precursor containing HAuCl₄·3H₂O and [bmim][BF₄], under normal atmospheric conditions. The effect of sintering the ionogel at different temperatures (T_sint) or times (t_sint) on the optical properties, shape, size, and distribution of gold nanoparticles is discussed. Presence of the gold particles is observed using transmission electron microscopy images followed by energy dispersive X-ray spectroscopy analysis. The thermal decomposition of [bmim][BF₄] in the ionogel is investigate using calorimetric and spectroscopic techniques, and by analysis of volatile compounds released by the sol–gel material during sintering. With these results a mechanism for the formation of the gold nanoparticles is proposed, where a first ionic liquid degradation step provides the reductive environment that enables the gold nanoparticles production at the range of temperatures between 350 and 425 °C. Upon sintering the synthesized materials the ionic liquid acts as a sacrificial additive and the ionic liquid thermal decomposition products enables the formation of gold nanoparticles in the sol–gel matrix.     

Effect of sol-gel preparation method on particle morphology in pure and nanocomposite PZT thin films

Double-scale composite lead zirconate titanate Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin films of 360 nm thickness were prepared by a modified composite sol-gel method. PZT films were deposited from both the pure sol and the composite suspension on Pt/Al₂O₃ substrates by the spin-coating method and were sintered at 650°C. The composite suspension formed after ultrasonic mixing of the PZT nanopowder and PZT sol at the powder/sol mass concentration 0.5 g mL⁻¹. PZT nanopowder (≈ 40–70 nm) was prepared using the conventional sol-gel method and calcination at 500°C. Pure PZT sol was prepared by a modified sol-gel method using a propan-1-ol/propane-1,2-diol mixture as a stabilizing solution. X-ray diffraction (XRD) analysis indicated that the thin films possess a single perovskite phase after their sintering at 650°C. The results of scanning electron microscope (SEM), energy-dispersive X-ray (EDX), atomic force microscopy (AFM), and transmission electron microscopy (TEM) analyses confirmed that the roughness of double-scale composite PZT films (≈ 17 nm) was significantly lower than that of PZT films prepared from pure sol (≈ 40 nm). The composite film consisted of nanosized PZT powder uniformly dispersed in the PZT matrix. In the surface micrograph of the film derived from sol, large round perovskite particles (≈ 100 nm) composed of small spherical individual nanoparticles (≈ 60 nm) were observed. The composite PZT film had a higher crystallinity degree and smoother surface morphology with necklace clusters of nanopowder particles in the sol-gel matrix compared to the pure PZT film. Microstructure of the composite PZT film can be characterized by a bimodal particle size distribution containing spherical perovskite particles from added PZT nanopowder and round perovskite particles from the sol-matrix, (≈ 30–50 nm and ≈ 100–120 nm), respectively. Effect of the PZT film preparation method on the morphology of pure and composite PZT thin films deposited on Pt/Al₂O₃ substrates was evaluated.     

Influence of Electrolytes on the Thixotropy of Ferric Aluminum Magnesium Hydroxide‐Montmorillonite Suspensions

Abstract

The thixotropy of suspensions consisting of ferric aluminum magnesium hydroxide (Fe‐Al‐Mg‐MMH) and Na‐montmorillonite (MT) is examined with special emphasis on the influence of electrolytes. When NaCl or MgCl₂ is added into the Fe‐Al‐Mg‐MMH/MT suspension, the thixotropy of the suspension may change (if positive) from positive and complex into negative, but NaCl or MgCl₂ can't alter the thixotropic type of a negatively thixotropic suspension. When AlCl₃ was added to positive thixotropic system can be transformed to a complex one, whereas a complex and negative thixotropic suspension remains unchanged, for additions less than 0.01 mol/L; when the addition level of AlCl₃ increases, all types of thixotropic systems are changed to non‐thixotropic. In addition, NaCl and MgCl₂ make the initial viscosity measured after cessation of intensive shearing increase, but the value of the viscosity decreased rapidly with time. The equilibrium viscosity of the suspension decreased gradually with increasing concentrations of NaCl and MgCl₂ in the suspension. With increasing concentration of AlCl₃, the equilibrium viscosities of the positive thixotropic suspension and the complex thixotropic suspension increase at first, but decrease later, and the equilibrium viscosity of negative thixotropic suspensions decrease gradually.     

Nanoparticles of nickel oxide and nickel hydroxide using lyophilisomes of fibrinogen as template

Stable lyophilisomes of fibrinogen at pH 7.5 have been prepared by the method of a rapid freezing–heating and annealing sequence. Reduction of the lyophilisomes of the nickel–fibrinogen complex coated on solid substrates and subsequent heating showed formation of nickel hydroxide and finally nickel oxide. Ultraviolet–visible spectroscopy has been used to monitor the thin films of pure fibrinogen microcapsules, as well as the subsequent nucleation and growth of nanoparticles within the supramolecular structure. Transmission electron microscopy showed initially a thread-like structure which disappeared on continued heating, resulting in nanoparticles ranging from 10 to 50 nm. Particle-size distribution of product was analyzed by using X-ray diffraction (XRD), transmission electron microscopy (TEM) and the corresponding selected area electron diffraction (SAED), and Brunauer–Emmett–Teller (BET) N₂ adsorption. The results suggest that the NiO particles have a body-centered cubic structure and are well dispersed. The particle-size distribution ranges from 10 to 50 nm with an average particle size about 28 nm, and the specific surface area is 34 m²/g. Magnetic study carried out on the prepared nanoparticles showed a ferromagnetic behavior.