Thermal analysis of organically modified siloxane melting gels

Hybrid melting gels were prepared by a sol–gel process, starting with a mono-substituted siloxane and a di-substituted siloxane, methyltrimethoxysilane (MTES) together with dimethyldimethoxysilane (DMDES). Five gel compositions were prepared with concentrations between 50% MTES–50% DMDES and 75% MTES–25% DMDES (in mol.%). The consolidation temperature, the treatment temperature after which the melting gel no longer softens, increased from 135 to 160 °C with a decrease in the amount of the mono-substituted siloxane. The glass transition temperature, recorded with differential scanning calorimetry, decreased from −0.3 to −56.7 °C with a decrease in the amount of the mono-substituted siloxane. When a sample was heat treated isothermally for 2 h at the consolidation temperature, the glass transition temperature increased by about 15°, indicating further crosslinking of the siloxane network.     

Synthesis and characterization of hybrid borosiloxane gels as precursors for Si–B–O–C fibers

The sol–gel method has been used for the synthesis of borosilicate gels from mixtures of methyltriethoxysilane (MTES) and dimethyldiethoxysilane (DMDES) and boric acid. The use of boric acid, B(OH)₃ allows the hydrolysis and condensation of hybrid silicon alkoxides without further addition of water or catalyst. The use of difunctional silicon units, –(CH₃)₂SiO– promote the formation, during the sol–gel process, of linear oligomers which facilitate fiber drawing before gelation. Gel characterization performed by FT-IR, XRD, TG-DTA and DCS analysis indicates the formation of a mixed network with incorporation of the boron units via =B-O-Si≡ bridges. The formation of borosiloxane bonds seems favored by the presence of DMDES. SiBOC glasses were obtained after pyrolysis of the borosilicate gels in argon atmosphere at 1000 °C. TG-DTA study indicates that the ceramic yield decreases by increasing the amount of DMDES. Gel fibers were successfully prepared from convenient partially-aged solutions by hand drawing. Pyrolysis of the obtained gel fibers under argon atmosphere at 1000 °C open the possibility to produce SiBOC homogeneous glass fibers with diameter as low as 10 μm.     

Formation of functional phosphosilicate gels from phytic acid and tetraethyl orthosilicate

Phosphosilicate gels with high phosphorus content (P mol% > Si mol%) have been prepared using phytic acid as the phosphorus precursor, with tetraethyl orthosilicate (TEOS). It is shown that the structure of phytic acid is maintained in both the sols and those gels dried at a low temperature (i.e. ≤120 °C). Solid state ²⁹Si and ³¹P NMR suggest that the gel network is primarily based on tetrahedral silicon and that phosphorus is not chemically incorporated into the silicate network at this point. X-ray diffraction shows the gel to be amorphous at low temperatures. After heat treatment at higher temperatures (i.e. up to 450 °C), P–O–Si linkages are formed and the silicon coordination changes from tetrahedral to octahedral. At the same time, the gel crystallizes. Even after this partial calcination, ³¹P NMR shows that a large fraction of phytic acid remains in the network. The function of phytic acid as chelating agent is also maintained in the gels dried at 120 °C such that its ability to absorb Ca²⁺ from aqueous solution is preserved.     

Synthesis of gadolinia-doped ceria gels and powders from acetylacetonate precursors

We report here the synthesis of gadolinia-doped ceria (GDC) gels and powders via the sol–gel method using cerium acetylacetonate and gadolinium acetylacetonate as precursors. The dependence of the morphology and nature of the sol–gel product on synthesis parameters has been investigated in detail. The sol is synthesized and gelled under various conditions to study the effects of (1) the hydrolysis ratio, (2) the reaction temperature, (3) the reaction time, (4) the addition of acetic acid, and (5) the as-synthesized condition versus the condition with subsequent calcination at 600 °C. It is found that all of these parameters exert strong influence on the morphology and nature of the sol–gel product. Crystalline GDC gels are produced when hydrolysis and gelation are carried out at 55–125 °C. Monolithic gels with low porosity and only micro cracks (shorter than 800 μm and less than 7 μm wide) can be formed with the proper drying procedure at ambient pressure. Although thermal exposure to 600 °C leads to grain growth, the size of GDC crystallites is still less than 9 nm after the thermal exposure.     

Fast responsive poly(<Emphasis Type="Italic">N,N</Emphasis>-diethylacrylamide) hydrogels with interconnected microspheres and bi-continuous structures

We prepared thermo-responsive polymer hydrogels by γ-ray irradiation of aqueous solutions of N, N-diethylacrylamide at different temperatures below and above its lower critical solution temperature (LCST). Poly(N, N-diethylacrylamide) gel had a transparent and homogeneous structure when the radiation-induced polymerization and crosslinking were carried out below the LCST (25 °C) of the polymer. On the other hand, cloudy and heterogeneous gels were formed at temperatures above the LCST of the polymer (>35 °C). From environmental scanning electron microscopy observations, the gels prepared at 35 and 40 °C were seen to show sponge-like bi-continuous porous structures, while those prepared at 50 °C showed a porous structure consisting of interconnected microspheres. For temperature changes between 10 and 40 °C, gels with porous structures showed rapid volume transitions on a time scale of about a minute, not only for shrinking but also for swelling processes, which is in remarkable contrast to the porous poly(N-isopropylacrylamide) hydrogels.     

Preparation and characterization of transparent TiO2 thin films coated on fused-silica substrates

The transparent TiO₂ thin films coated on fused-SiO₂ substrates were prepared by the sol–gel method and spin-coating technique. Effects of calcination temperature on crystal structure, grain size, surface texture, and light transmittance of the films were investigated. After calcining at 600–1,200 °C, the thicknesses of the TiO₂ films were all around 80 nm and the molecular structures of the films were anatase, even at 1,200 °C. The calcined TiO₂ films had the ultraviolet light (wavelength 200–400 nm) transmittances of ≤29% and the visible light (wavelength 400–800 nm) transmittance of ≥72%. By photocatalytically decomposing the methylene blue (MB) in water, the photocatalytic activities of the TiO₂ thin films were measured and represented using the characteristic time constant (τ) for the MB degradation. While the films prepared at 1,000 and 1,200 °C photodecomposed about 54 mol% of the MB in water (the corresponding τ ≈ 14.8 h) after exposing to 365-nm UV light for 12 h, the films prepared at 600 and 800 °C had smaller τ (≈9.0 h) and photodecomposed about 74 mol% of the MB in water at the same testing conditions.     

Colloidal crystallization of thermosensitive gel spheres of poly(<Emphasis Type="Italic">N</Emphasis>-isopropylacrylamide) with low degree of cross-linking

Morphology, phase diagram, and reflection spectroscopy of the colloidal crystals of thermosensitive gel spheres, poly(N-isopropylacrylamide) ((200–0.5), 318 and 116 nm in the hydrodynamic diameter at 25°C and 45°C, and 0.5% in the degree of cross-linking) were studied. Giant colloidal single crystals formed at very low gel concentrations. Densities of the gel spheres were 0.030 and 0.61 at 25°C and 45°C, respectively. Critical concentration of melting of gel spheres (0.8 wt.% without ion-exchange resins) decreased sharply to 0.015 wt.% at 25°C as the gel suspension was deionized exhaustively with coexistence of the mixtures of cation and anion exchange resins. These results demonstrate that the colloidal crystallization takes place by the extended electrical double layers formed around the gel spheres in addition of the excluded volume effect of the gels. Extent of the contribution of the electrical double layers on the crystallization increased sharply when the degree of cross-linking increased, the gel spheres shrank, and/or the density of the gel spheres increased.     

Preparation of calcium plumbate via different route

Calcium plumbate Ca₂PbO₄ was prepared by sol–gel methods (Pechini complex route with two varieties and water soluble polymer method) and by solid state reaction. The sol–gel prepared samples contained calcium plumbate as the only one phase as early as after 2 h annealing at 800 °C. Phase composition was detected by XRD measurement and by Raman spectroscopy. The next annealing at 800 °C for 24 h induced weak Pb losses displayed by present CaO (according to phase equilibrium) and confirmed by XRF measurement. The Pb losses were smaller for the sol–gel prepared samples probably due to earlier formation of Ca₂PbO₄. Microstructure and grain size were also established. Sol–gel prepared samples had regularly distributed grains with a small distribution interval with median value in order of 1 μm. Differences in microstructure of solid state and sol–gel samples are presented on SEM micrographs.     

Potentiometric titration behavior of poly(acrylic acid) within a cross-linked polymer network having amide groups

This study aimed to investigate the effect of COOH group distribution within a polymer network having amide groups, with which the COOH could form hydrogen bonds. We employed here two polyelectrolyte gels composed of N-isopropylacrylamide (NIPA) networks, either copolymerized with acrylic acid (AA) or within which poly(acrylic acid) (PAA) was entrapped. Both gels (AA–NIPA ∼ 1:4 mol/mol) were prepared by aqueous red-ox polymerization with N,N’-methylenebisacrylamide as the cross-linker. Finely divided gels in NaCl solutions (0.025 and 0.1 M) were titrated with NaOH and back-titrated with HCl at 25 °C. The results of the copolymer gel (CG) agreed well with those of a linear copolymer and a nanoscale gel which had a similar AA content to CG. However, marked differences were observed in the titration behaviors of the AA-copolymerized and PAA-entrapped gels, mainly due to the hydrogen bonding between the entrapped PAA chain and its surrounding NIPA network.     

Structural and optical characterization of Zn doped TiO<Subscript>2</Subscript> nanoparticles prepared by sol–gel method

Undoped and zinc-doped TiO₂ nanoparticles (Ti_1−xZn_xO₂ where x = 0.00–0.10) were synthesized by a sol–gel method. The synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM) and UV–VIS spectrometer. XRD pattern confirmed the tetragonal structure of synthesized samples. Average grain size was determined from X-ray line broadening using the Debye–Scherrer relation. The crystallite size was varied from 10 to 40 nm as the calcination temperature was increased from 350 to 800 °C. The incorporation of 3–5 mol% Zn²⁺ in place of the Ti⁴⁺ provoked a slight decrease in the size of nanocrystals as compared to undoped TiO₂. The SEM and TEM micrographs revealed the agglomerated spherical-like morphology with a diameter of about 10–30 nm and length of several nanometers, which is in agreement with XRD results. Optical absorption measurements indicated a blue shift in the absorption band edge upon 3–5 mol% zinc doping. Direct allowed band gap of undoped and Zn-doped TiO₂ nanoparticles measured by UV–VIS spectrometer were 2.95 and 3.00 eV at 550 °C, respectively.     

Organic–inorganic hybrid melting gels

Melting gels are a class of organically modified silica gels that are rigid at room temperature, flow at temperature T1 and consolidate at temperature T2 (T2 > T1), when crosslinking is complete. The process of (a) softening, (b) becoming rigid and (c) re-softening can be repeated many times. Mixtures of mono-substituted alkoxysilanes and di-substituted alkoxysilanes have been studied in a systematic way to identify suitable melting gel compositions. The mixtures and the resulting melting gels have been characterized for their softening temperatures and consolidation temperatures. With an interest in using these materials for sealing microelectronics, their physical properties have been measured.     

Thermal analysis of lipids isolated from various tissues of sheep fats

The physical–chemical properties and fatty acid composition of sheep subcutaneous, tallow, intestinal, and tail fats were determined. Sheep fat types contained C_16:0, C_18:0, and C_18:1 as the major components of fatty acid composition (19.56–23.40, 20.77–29.50, 32.07–38.30%, respectively). Differential scanning calorimetry (DSC) study revealed that two characteristic peaks were detected in both crystallization and melting curves. Major peaks (T _peak) of tallow and intestinal fats were similar and determined as 31.25–24.69 and 7.44–3.90 °C, respectively, for crystallization peaks and 15.36–13.44 and 45.98–44.60 °C, respectively, for melting peaks in DSC curves; but those of tail fat (18.29 and −2.13 °C for crystallization peaks and 6.56 and 33.46 °C for melting peaks) differed remarkably from those of other fat types.     

Facile preparation of transparent monolithic titania gels utilizing a chelating ligand and mineral salts

Highly homogeneous transparent titania gels have been successfully prepared from titanium alkoxide by a sol–gel method utilizing chelating agent, ethyl acetylacetate (EtAcAc), in the presence of strong acid anions. Only catalytic amount of a strong acid anion suppress the rapid hydrolysis of titanium alkoxide by blocking the nucleophilic attack of HO⁻ and H₂O, and the resultant moderate sol–gel reactions thus afford homogeneous gelation, leading to transparent monolithic titania gels. Gelation time can be widely controlled by changing amounts of water, chelating agent and salt. The ability of salts to suppress the too abrupt sol–gel reactions is strongly dependent on the electronegativity of anions and valence of cations. With employing NH₄NO₃ as a suppressing electrolyte, the obtained titania gels can be converted to pure TiO₂ by simple washing and heat-treatment, and transformations to anatase and rutile structures were found to start at 400 and 600 °C, respectively.     

Photocatalytic degradation of Orange II by titania addition to sol–gel glasses

Glasses on SiO₂–CaO–ZnO–B₂O₃–K₂O–Al₂O₃ oxide system modified by addition of titania (0, 3, 5, 12, and 20% w) have been prepared by sol–gel method. The obtained gels were aged, dried and fired at 600 °C/1 h in order to stabilise the glass. The resulting fired powders were characterised by UV–Vis–NIR spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM) and X-ray diffraction (XRD). Their photocatalytic capacity on the degradation of Orange II dye has been studied. The XRD and TEM studies indicate that system becomes amorphous with a nanostructured microstructure. From UV–Vis–NIR results the band gap calculated is around 3.5 eV for all modified glasses. Photoactivity of powders depends on amount of titania in glass composition and the specific surface area of prepared samples. The sample with highest surface area and lowest addition of titania (3% w sample) shows similar activity than commercial anatase used as reference.     

Properties of cellulose films prepared from NaOH/urea/zincate aqueous solution at low temperature

Cellulose films were successfully prepared from NaOH/urea/zincate aqueous solution pre-cooled to −13 °C by coagulating with 5% H₂SO₄. The cellulose solution and regenerated cellulose films were characterized with dynamic rheology, ultraviolet–visible spectroscope, scanning electron microscopy, wide angle X-ray diffraction, Fourier transform infrared (FT-IR) spectrometer, thermogravimetry and tensile testing. The results indicated that at higher temperature (above 65 °C) or lower temperature (below −10 °C) or for longer storage time, gels could form in the cellulose dope. However, the cellulose solution remained a liquid state for a long time at 0–10 °C. Moreover, there was an irreversible gelation in the cellulose solution system. The films with cellulose II exhibited better optical transmittance, high thermal stability and tensile strength than that prepared by NaOH/urea aqueous solution without zincate. Therefore, the addition of zincate in the NaOH/urea aqueous system could enhance the cellulose solubility and improve the structure and properties of the regenerated cellulose films.     

Synthesis and characterization of sol–gel derived Ag(Nb,Ta)O<Subscript>3</Subscript> nanopowder

Perovskite-type Ag(Nb_0.6Ta_0.4)O₃ nanopowder was prepared by the sol–gel process from the AgNO₃, Ta₂O₅ and Nb₂O₅, with help of K₂CO₃, avoiding use of strong corrosive acid or expensive niobium ethoxide and tantalum ethoxide. The results suggested that thermal decomposition of the xerogel took place when the xerogel was heated at 450 °C. Well-crystallized single-phased powder was obtained at low temperature about 680 °C. With the heat-treatment temperature increasing (680–1,100 °C), the intensity of the diffraction peaks increased. The crystallite size determined by Scherer formula and the result suggested that higher temperature lead to larger crystallite size. Moreover, the average grain size 30–50 nm was estimated by a field emission scanning electron microscope. The influence of holding time on microstructures indicated that the homogeneous and small grains were obtained at 800 °C for 2–4 h while larger ones for 8–16 h.     

Bright blue pigment CoAl<Subscript>2</Subscript>O<Subscript>4</Subscript> nanocrystals prepared by modified sol–gel method

Nanocrystalline films of magnetite have been prepared by a novel sol–gel route in which, a solution of iron (III) nitrate dissolved in ethylene glycol was applied on glass substrates by spin coating. Coating solution showed Newtonian behaviour and viscosity was found as 0.0215 Pa.s. Annealing temperature was selected between 291 and 350 °C by DTA analysis in order to obtain magnetite films. In-plane grazing angle XRD and TEM studies showed that magnetite phase was present upon annealing the films at 300 °C. The films had crack free surfaces and their thicknesses varied between ~10 and 200 nm. UV–Vis spectrum results showed that transmittance of the films increases with decreasing annealing temperature and increasing spinning rate. Up to 96% transmittance was observed between the wavelengths of 900–1,100 nm. Vibrating sample magnetometer measurements indicated that magnetite thin films showed ferromagnetic behavior and the saturation magnetization value was found as ~35 emu/cm³.     

Nano-sized polycrystalline bismuth silicon oxide powder by sol–gel technique

Bismuth silicon oxide (Bi₁₂SiO₂₀, BSO) nano crystalline powder was prepared by sol–gel technique using bismuth nitrate and tetraethyl orthosilicate as starting materials. The prepared samples were sintered at various temperatures (750 °C maximum) and characteristic sillenite single cubic phase with crystallite size ~38 nm (calculated from room temperature powder XRD measurements) was realized at 750 °C sintering temperature. SEM analysis showed that the powder contains the nano-sized particles with almost spherical morphology. The observed frequencies in room temperature FTIR spectrum could be assigned to Bi–O, Si–O and Bi–O–Si bonds. The FWHM (full width at half maximum) of the diffraction peaks decreased while the intensity of FTIR absorption lines increased with the increase in the sintering temperature indicating better bond formation and crystallization. The thermograph of the samples recorded in the temperature range 50–1,000 °C showed almost no weight loss after ~575 °C further confirmed the conclusion arrived at from XRD and FTIR analysis. The samples sintered at 750 °C showed about 50% absorbance in 400–600 nm region which was consistent with the pale yellow color of the sample. Broad blue emission centered ~478 nm was observed when excited by 350 nm radiation from a Xe-lamp. The intensity of this broad emission band increased while its FWHM decreased with the increase in sintering temperature. Self-trapped excitons could be responsible for this emission.     

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.     

Synthesis and characterization of nanocrystalline zinc aluminate spinel by sol–gel technique using modified alkoxide precursor

Nanosized zinc aluminate spinel (gahnite, ZnAl₂O₄) powders were prepared by sol−gel technique at low sintering temperatures. Aluminium-sec-butoxide [Al(O^sBu)₃] and zinc nitrate hexahydrate Zn(NO₃)₂ . 6H₂O were used as starting materials. Gels with and without chelating agent were prepared. Ethyl-acetoacetate (C₆H₁₀O₃) was used as a chelating agent in order to control the rate of hydrolysis of Al(O^sBu)₃. The dried gels and thermally treated samples were characterized by means of Differential Thermal Analysis and Thermo-Gravimetric Analysis (DTA, TGA), X-ray Diffraction (XRD), Fourier Transform Infrared spectroscopy (FTIR) and Transmission Electron Microscopy (TEM). The surface area was measured by Brunauer-Emmet-Teller (BET) adsorption–desorption isotherms. It has been established that chelation enables to obtain a transparent gel. The thermal evolution of gels was characterized by two crystallization processes in the range 200–400 °C and 600–700 °C. Both processes yielded pure ZnAl₂O₄ as evidenced by XRD, i.e. zinc aluminate spinel powders were produced by gel heat-treatment at temperatures as low as 300 °C. The average gahnite crystallite size for the samples sintered in the temperature range of 400–1000 °C has been calculated from the broadening of XRD lines revealing that nanocrystalline powders were prepared. The surface areas measured for the samples fired at 700 °C for 2 h were 43.1 and 62.6 m² g⁻¹, for sample without and with the chelating agent, respectively. TEM micrographs confirmed the nano-scale size of particles.