Optical and structural properties of aluminium oxide thin films prepared by a non-aqueous sol–gel technique

Clear aluminium oxide sols without precipitation were synthesized via a non-aqueous sol–gel technique using three different alcohols (ethanol, isopropanol and n-butyl alcohol) as solvent, aluminium sec-butoxide as a precursor and acetyl acetone as a chelating agent. Although all sols could be successfully used to prepare thin films, the most stable one was prepared with n-butyl alcohol. Highly transparent, homogenous and amorphous aluminium oxide thin films were obtained on Si substrates after a heat treatment at 500 °C. X-Ray photoelectron spectroscopy (XPS) and Fourier transform infrared absorption (FT-IR) spectroscopy revealed all films were hydroxide free. The optical and structural properties of the films were particularly investigated. Any significant difference except from thickness on the film properties was not observed by changing the alcohol. Refractive index was used as an indication of the porosity of the films and ranged from 1.54 to 1.60.     

Studying the interaction between silica nanoparticles and metals by spectrophotometry

The optical absorption spectra of water silica sols containing nanoparticles (NPs) of metals (Ag, Pd, Fe, and Pt) are investigated. Silica sols are obtained from natural hydrothermal solutions via membrane concentration (ultrafiltration). Water sols of silica with specific sizes, pH values, ζ potentials of SiO₂ NP surfaces, and low concentrations of SiO₂ NPs are used. Plasmon resonance in optical absorption spectra is used to study the interaction between silica and metal NPs. Parameters of plasmon resonance (position, height, and half-width of optical absorption bands), from which the degree of interaction is assessed, are determined. Relationships between the optical properties of the surfaces of nanoparticle-size silica particles, the method of their production, and the effect of adsorbed metal particles on these properties are established.     

Anomalous Concentration Dependences of Optical Density of Stable Nanodisperse Titanium Dioxide Hydrosols

Optical properties of two aggregative-stable nanodisperse TiO₂ hydrosols differed in sizes of crystalline particles were studied. These sols were found to have the anomalous concentration dependences of the optical density. It was suggested that these peculiarities are caused by an increase in structural order of the sols during their concentration.     

Effects of diethanolamine on the evolution of silver/titanium dioxide sol–gel process

In order to clarify the effects of diethanolamine (DEA) in the silver (Ag)/titanium dioxide (TiO₂) sol–gel process, sols with and without DEA, and films derived from these sols were prepared. The samples were investigated by X-ray diffraction, transmission electron microscopy, electron diffraction and optical absorption spectra. The results showed that metallic Ag clusters were formed in the sol with DEA and was absent in the sol without DEA. This indicated that DEA worked not only as the stabilizer but also as the reduce agent in Ag/TiO₂ sol–gel process. After annealed, Ag metallic nanoparticles were generated in the films derived from both the sols with and without DEA. The particles in the films derived from the sol with DEA were smaller than those from the sol without DEA. This can be ascribed to the limitation of the growth of Ag cluster formed in the sol with DEA during heat treatment. Mechanisms for the formation of metallic Ag in the Ag/TiO₂ sols and films were discussed. The effects of DEA in the sols and films were studied in detail.     

Organically Modified Silicates and Ceramics as Two-Phasic Systems: Synthesis and Processing

Based on the concept of controlling the particle size by the surface free energy, the growth of sol-gel derived nanoparticles (Al₂O₃, TiO₂, ZrO₂) has been investigated in presence of molecules with binding ability to the growing particles. The investigations show that the use of silanes, carboxylic acid or β-diketones allows to replace electrostatic sol stabilisation by steric sol stabilisation and through this, high solid content sols can be obtained. The introduction of these sols into orgaic or ormocer type of matrices leads to nano composites with degrees of filling up to 40 wt.-% without agglomeration and with high optical quality. Already developed TiO₂ containing bulk materials, ultrahard coatings on plastic and adhesives for fiber to chip coupling are examples for the usefulness of this alternative sol-gel route. The nanocomposite materials show interesting mechanical and thermomechanical properties such as high hardness or low thermal expansion compared to unfilled systems.     

Verfolgung der Verbrennungsreaktionen exothermer Massen auf Basis von Aluminium,Fluoriden und Kaliumnitrat mit Differentialthermoanalyse

DTA was applied to investigate the course of combustion of exothermic mixtures composed of aluminium, fluorides and potassium nitrate, and the results obtained were compared with the simultaneous results of X-ray investigations. The combustion of exothermic mixtures composed of aluminium, fluorides and potassium nitrate is similar to the combustion of mixtures where the potassium nitrate is substituted by sodium nitrate. Two exothermic reactions occur: between 400 and 520?, and between 800 and 1130?, in mixtures with sodium fluoride and between 450? and 650? and 850 and 1130? in mixtures with calcium fluoride. The reaction in the lower temperature range initiates the combustion of the mixture. In sodium fluoride mixtures this reaction takes place at lower temperature and seems to be more intense, since these mixtures inflame earlier than those with calcium fluoride. The reaction in the higher temperature range, which occurs at approximately the same temperature in the two cases, liberates the main part of the useful heat of the exothermic mixtures.     

Formation of grafted surface layers on silicon dioxide particles and their investigation by means of thermoprogrammed oxidation

Silica nanoparticles are obtained according to the Stober–Fink–Bohn method, and their surfaces are chemically modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. It is estimated that sols of porous silica nanoparticles (average sizes, 50–200 nm) form during primary chemical process; the average size of the particles can be increased to 400–500 nm by consecutive growth. Oxythermography (thermoprogrammed oxidation) measurements reveal a stepped dependence between the content of organic substance of nanoparticles and the duration of chemical modification reaction exists. It is concluded that this could be due to the formation of dense shell (or shells) as a result of sols aging between the cycles of growth; such shells impose diffusive restrictions when molecules penetrate into the pores of the internal volume of the particles.

     

Disposable, stable media for reproducible surface-enhanced Raman spectroscopy

Large numbers of identical and stable SE(R)RS [surface-enhanced (resonance) Raman]-active media, which are convenient to handle and manipulate but sufficiently inexpensive that they can be used once and then discarded, have been prepared by isolating nanoparticles from Ag and Au sols in hydrophilic polymer gels. The preparation simply involves mixing a suitable polymer with the sol to give a viscous suspension that can be coated onto a substrate and dried to form a hard translucent film. The films remain inactive until they are treated with aqueous analyte solution, which causes the film to swell and brings the analyte into contact with the active metal particles. The swollen films give strong SERS spectra which are effectively identical to those obtained from simple sols. The advantage of this method is that the dried polymers can be stored indefinitely before use and that they give a high degree of spectral reproducibility.     

The fluorolytic sol–gel reaction of aluminium alkoxides: a multinuclear MAS NMR study of structural influences of the synthesis parameters

The fluorolytic sol–gel reaction between aluminium alkoxides and non-aqueous HF leads, after drying in vacuum, to xerogels. These can be seen as intermediates for the preparation of aluminium fluorides with large surface areas having a great potential for application in diverse fields of heterogeneous catalysis. This work reports about a comprehensive systematic study of the involved local structures of the aluminium alkoxide fluorides and their changes provoked by (a) the variation of sol gel synthesis parameters, (b) a subsequent drying and (c) the exposure of the materials to different atmospheres. The main analytical tools are solid state MAS NMR investigations of the naturally abundant nuclei in these kinds of materials, namely ²⁷Al, ¹⁹F for probing the Al- and F-environments and ¹H and ¹³C for probing the organic moieties. The results of previous studies become more comprehensive and were underlined by the findings reported here.     

Synthesis of Ag and Ag/SiO2 sols by solvothermal method and their bactericidal activity

Ag and Ag/SiO₂ sols containing nanocrystalline silver particles can be advantageously prepared by solvothermal methods using an autoclave with conventional thermal or microwave heating. In this process, the reduction of silver salts can be realized with alcohols like ethanol in the presence of polyvinylpyrrolidone at temperatures of more than 120 °C. Furthermore a combination of silver salt reduction with hydrolysis of alkoxysilanes during the solvothermal process can yield Ag/SiO₂ composite sols. Particle size and crystallinity of as-prepared particles are analyzed by means of X-ray diffraction and high-resolution transmission electron microscopy. Nanosized silver particles gained by this process exhibit antimicrobial properties that are investigated in detail after application on textile fabrics.     

Synthesis and properties of alumina aerogels

The synthesis of alumina aerogels has been carried out by hydrolysis of aluminium isopropylate as an aerogel precursor dissolved in isopropanol or methanol, followed by gelation of the sols obtained and drying under supercritical conditions and calcination. The influence of two main preparation parameters, precursor concentration and reagents (water to aluminium isopropylate) mole ratio, on the physicochemical properties of aerogels was investigated.     

Preparation of Polyoxometalate-Stabilized Colloidal Solutions of Palladium Metal and Catalysts Supported on Them

Sols containing Pd(0) clusters with polyoxo anions are prepared by the reduction of colloidal solutions of polyhydroxo complexes of Pd(II) in the presence of Mo(VI), W(VI), V(V), and Nb(V) polyoxo anions. The cluster sizes varied within the limits of 1–10 nm depending on the nature of the polyoxo anion. The stability of sols toward coagulation depends on the ratio between the palladium and polyoxo anion amounts in solution and on the composition of the solvent. Supported Pd catalysts are obtained by the adsorption of particles from sols; Pd can exist in these catalysts as individual particles or associates or form filamentary structures.     

The effect of ozone on plasmon absorption of gold hydrosols. Quasi-metal and metal nanoparticles

The character of the interaction between ultrasmall gold nanoparticles and ozone is shown to be mainly governed by the particle structure. For borohydride sols of gold nanoparticles with sizes of ??3 nm, which are characterized by metallic properties, this interaction is reduced to reversible adsorption of ozone on their surface. At the same time, ozone adsorption on ??nonplasmon?? Au particles that have a diameter of 2 nm and a very defective structure results in their irreversible structural rearrangement and transition to a metallic state, which is accompanied by the appearance of a surface plasmon resonance. The set of the results obtained shows that nanoparticles of borohydride gold sols are more efficient as possible hemosensors of ozone than are larger particles synthesized by the citrate method.     

Magnetic birefringence of minerals

The earliest reports of magnetically induced optical birefringence included data for liquids, magnetic fluids and colloidal suspensions. Recent work has shown that with relatively straightforward apparatus, when carefully designed and aligned, measurable effects can be recorded even for suspensions of relatively weak diamagnetic materials, including mineral particles. By recording the magnitude of the birefringence induced in magnetic fields of up to two Tesla, a method for the analysis of the magnetic and optical characteristics of these diamagnetic colloids is evidenced. The principles, apparatus and methodology involved are described and novel data reported for the minerals attapulgite, bentonite, hectorite, kaolinite, montmorillonite and vermiculite. Preliminary experiments using pulsed fields on vermiculite sols show that, in favourable circumstances, estimates of particle size can be made by analysing signal response rates.     

Optical Properties of Sol-Gel Derived Vanadium Oxide Films

Vanadium oxide gels can be made from vanadate aqueous solutions or from vanadium alkoxides. The condensation of vanadic acid gives long ribbon-like oxide particles which macroscopically orient in the same direction in aqueous sols when their concentration is larger than 0.12 mol·l⁻¹. These anisotropic sols and gels should be considered as lyotropic nematic liquid crystals. Thick films in which ribbons align along the same direction can be deposited. These oriented coatings exhibit improved electrochemical properties as reversible cathodes for lithium batteries. Amorphous oxo-polymers are formed via the controlled hydrolysis of vanadium alkoxides. They allow the deposition of optically transparent thin films that exhibit interesting electrochromic properties and turn reversibly from yellow to green upon electrochemical reduction. Moreover these alkoxide derived films can be easily reduced into vanadium dioxide. These VO₂ thin films exhibit thermochromic properties and could be used as optical switches in the infrared. The transition temperature of these VO₂ films can be modified by doping the vanadium oxide with other cations.     

Synthesis of vinyl polymer-silica colloidal nanocomposites prepared using commercial alcoholic silica sols

The surfactant-free synthesis of vinyl polymer-silica nanocomposite particles has been achieved in aqueous alcoholic media at ambient temperature in the absence of auxiliary comonomers. Styrene, methyl methacrylate, methyl acrylate, n-butyl acrylate, and 2-hydroxypropyl methacrylate were homopolymerized in turn in the presence of three commercially available ultrafine alcoholic silica sols. Stable colloidal dispersions with reasonably narrow size distributions were obtained, with silica contents of up to 58% by mass indicated by thermogravimetric analysis. Particle size distributions were assessed using both dynamic light scattering and disk centrifuge photosedimentometry. The former technique indicated that the particle size increased for the first 1-2 h at 25 degrees C and thereafter remained constant. Particle morphologies were studied using electron microscopy. Most of the colloidal nanocomposites comprised approximately spherical particles with relatively narrow size distributions, but in some cases more polydisperse or nonspherical particles were obtained. Selected acrylate-based nanocomposites were examined in terms of their film formation behavior. Scanning electron microscopy studies indicated relatively smooth films were obtained on drying at 20 degrees C, with complete loss of the original particle morphology. The optical clarity of solution-cast 10 microm nanocomposite films was assessed using visible absorption spectrophotometry, with 93-98% transmission being obtained from 400 to 800 nm; the effect of long-term immersion of such films in aqueous solutions was also examined. X-ray photoelectron spectroscopy studies indicated that the surface compositions of these nanocomposite particles are invariably silica-rich, which is consistent with their long-term colloidal stability and also with aqueous electrophoresis measurements. FT-IR studies suggested that in the case of the poly(methyl methacrylate)-silica nanocomposite particles, the carbonyl ester groups in the polymer are hydrogen-bonded to the surface silanol groups. According to differential scanning calorimetry studies, the glass transition temperatures of several poly(methyl methacrylate)-silica and polystyrene-silica nanocomposites can be either higher or lower than those of the corresponding homopolymers, depending on the nature of the silica sol.     

Production of highly dispersed sodium chloride: Strategy and experiment

Various methods for obtaining highly dispersed sodium chloride in the form of powders and sols in organic solvents were studied and compared. These include the mechanical grinding in a ball mill, laser ablation, cryochemical method, solvent-substitution method, pyrolysis of an aerosol, and a number of chemical methods. The samples obtained were examined by X-ray diffraction, elemental analysis, transmission electron microscopy, and dynamic light scattering technique. The methods for obtaining highly dispersed NaCl were compared in three basic parameters: size of particles being obtained, their size distribution, and productivity. It was shown that, depending on a method used, sodium chloride particles with average sizes in the range from 15–30 nm to 10–20 μm can be obtained.     

Colloidal copper in aqueous solutions: radiation-chemical reduction,mechanism of formation,and properties

Colloidal copper has been obtained by -irradiation of aqueous solutions of copper (II) perchlorate in the presence of alcohol and polyethyleneimine (PEI). The sols are spherical particles about 4 nm in diameter, which are quickly oxidized by oxygen or other oxidants. When Cu^II is not entirely incorporated into the complex with PEI, disproportionation of Cu^I aqua complexes formed affords the metal, along with Cu₂O. Reduction of the PEI complex of Cu^I by hydrated electrons gives only colloidal copper. The copper ions can be reduced on the surface of silver sols. Optical parameters of the resulting bimetallic particles have been studied. The presence of copper ions leads to broadening of the absorption band associated with the silver sols and shifts it to the UV region, which is due to the transfer of electrons from copper to silver. Three copper monolayers are enough to cause plasmon absorption of colloidal copper.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 25–30, January, 1994.     

Synthesis and Some Properties of Cerium Dioxide Hydrosols

Cerium dioxide hydrosols are synthesized by peptizing with nitric acid a precipitate obtained by hydrolyzing cerium(III) nitrate. The synthesized sols are stable with respect to aggregation in both acidic (pH 1.5–3.0) and alkaline media (pH 9.0–11.0). The mean hydrodynamic radius of particles is about 25 nm. The isoelectric point corresponds to pH 6.2. The phase composition of sol particles is determined by X-ray diffraction at pH of the dispersion medium ranging from 1.5 to 3.0. The sol coagulation thresholds are determined in the presence of sodium nitrate and sulfate, as well as of mixed magnesium salt at various pH values of the dispersion medium. Assumptions are made concerning the nature of the aggregative stability of sols.     

Fabrication of surface-patterned ZnO thin films using sol–gel methods and nanoimprint lithography

Surface-patterned ZnO thin films were fabricated by direct imprinting on ZnO sol and subsequent annealing process. The polymer-based ZnO sols were deposited on various substrates for the nanoimprint lithography and converted to surface-patterned ZnO gel films during the thermal curing nanoimprint process. Finally, crystalline ZnO films were obtained by subsequent annealing of the patterned ZnO gel films. The optical characterization indicates that the surface patterning of ZnO thin films can lead to an enhanced transmittance. Large-scale ZnO thin films with different patterns can be fabricated by various easy-made ordered templates using this combination of sol–gel and nanoimprint lithography techniques.