Preparation of Silicon Oxycarbide Glass Fibers by Sol-Gel Method—Effect of Starting Sol Composition on Tensile Strength of Fibers

Silicon oxycarbide (Si—O—C) glass fibers were prepared by heat-treating the gel fibers drawn from the solution containing tetra-ethyl-ortho-silicate (TEOS), tri-ethoxysilane (HTES) and methyl-tri-ethoxysilane (MTES) in the course of sol-gel reaction.The replacement of TEOS by HTES in the solution, with the molar ratio of MTES to total alkoxysilanes being kept constant at 1/3, resulted in remarkable improvement of tensile strength of the glass fibers prepared at 1300°C. The decrease in the content of free carbon was observed in such fibers, even by an amount as small as a few wt%, and was considered to be related to the suppression of devitrification of the fibers to form -SiC and to the enhancement of mechanical strength.     

Biodegradable and bioactive hybrid organic–inorganic PEG-siloxane fibers. Preparation and characterization

A mixture of triethoxysilanefunctionalized poly(ethylene glycol), f-PEG, and tetraethoxysilane, TEOS, was used as precursors in the preparation of continuous hybrid f-PEG-siloxane sol–gel derived fibers. The fibers were spun by extrusion through a spinneret. The thus prepared fibers had a diameter of 20–50 m. ²⁹Si-CPMAS NMR measurements confirmed that the functionalized PEG is incorporated into the siloxane network through covalent bonds. The hybrid fiber elasticity was much higher than that of fibers spun from sols with TEOS as the only source for silica. However, the f-PEG chain length plays a crucial role for the spinnability of the sol, since, as a result of bridging flocculation, macroscopic phase separation occurred readily with increasing chain length of the f-PEG. The fibers were shown to be effective substrates for the nucleation and growth of bone-like hydroxyapatite.     

Reduction of Cu2+ to Cu+ in Xerogels Prepared from (3-Aminopropyl)Trimethoxysilane

Silica gels doped with Cu²⁺ ions were prepared from the (3-aminopropyl) trimethoxysilane (APTMOS)/tetraethoxysilane (TEOS) systems. Sols showed a broad absorption peak at 640 nm, suggesting 3–5 coordination of the aminopropyl groups to Cu²⁺. For gels prepared from APTMOS and dried at room temperature, the 640 nm peak decreased and a red-shifted absorption appeared below 400 nm within a few months. The luminescence spectra of the xerogels showed emission bands at 430–470 and 510 nm. The former and latter bands are ascribed to Cu⁺ monomer and dimer emissions, respectively. These results indicate that Cu²⁺ ions are reduced to Cu⁺. When xerogels were prepared from APTMOS/TEOS = 1 (vol/vol), the color of xerogels was blue with an absorption peak at around 670 nm, indicating no reduction of Cu²⁺ ions.     

Preparation of coating films doped with gold metal particles from methyltriethoxysilane-tetraethoxysilane solutions

Silica coating films of 0.5–0.7 m in thickness doped with gold metal particles were prepared by heating gel coating films obtained from solutions of acid-catalyzed methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) mixture containing chlorauric acid tetrahydrate. Transparent coating films with deep blue, red, and purple colors were obtained. Changes in size and shape of the gold particles with the MTES content were observed. Lower MTES contents gave bigger and non-spherical particles, while higher MTES contents produced smaller and more spherical particles with a more uniform size distribution. The effect of heat-treatment temeprature on the shape, size, and size distribution of the metallic gold particles was also studied.On leave from Dipartimento di Ingegneria Meccanica, Sezione Materiali, Universita di Padova, Via Marzolo, 9-35131 Padova, Italy.     

Structure of hybrid organic–inorganic sols for the preparation of hydrothermally stable membranes

A procedure for the preparation of hybrid sols for the synthesis of organic–inorganic microporous materials and thin film membranes is reported. We describe silane reactivity and sol structure for acid-catalysed colloidal sols from mixtures of either tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES), or bis(triethoxysilyl)ethane (BTESE) and MTES. Early-stage hydrolysis and condensation rates of the individual silane precursors were followed with ²⁹Si liquid NMR and structural characteristics of more developed sols were studied with Dynamic Light Scattering. Condensation was found to proceed at more or less similar rates for the different precursors. Homogeneously mixed hybrid colloids can therefore be formed from precursor mixtures. The conditions of preparation under which clear sols with low viscosity could be formed from BTESE/MTES were determined. These sols were synthesised at moderate water/silane and acid/silane ratios and could be applied for the coating of defect-free microporous membranes for molecular separations under hydrothermal conditions.     

Fabrication and Properties of Doped Porous Polysiloxane Sol-Gel Layers on Optical Fibers

Polysiloxane porous layers doped with TiO- and phenyl-groups were fabricated by the sol-gel method. Starting sols were prepared from alkoxides using catalysis by HCl or HF. Stable SiO-TiO-sols were obtained by using HF. Porous gel layers with thicknesses of 0.3–1.1 m were coated on fiber surfaces or silicon wafers. Layers with the refractive index of 1.38–1.48 were prepared. The fractional porosity of the layers was estimated to be 0.1–0.35. The interactions of the layers with vapor or liquid chlorinated hydrocarbons, alcohols or aromatic hydrocarbons have been studied in immersing experiments by measuring the output light intensity from the fibers. The observed changes of the output intensity could be correlated to changes of the refractive index of the layer caused by the penetration of the tested chemicals into the layer pores.     

Sol-Gel Preparation of Silica Films with Controlled Surface Morphology and Their Application to a Low Reflective Glass

Silica coating films with various surface morphologies, such as flat, porous (with deep pores), concave-convex (with hills and valleys), and convex (with hills on flat plane) structure were prepared from a mixture of two kinds of sols derived from polymerized tetraethoxy-silane (TEOS) and methyltriethoxysilane (MTES). Different surface morphologies were obtained by varying the molar ratio r = MTES/TEOS of the coating solution. The surface was flat for r less than 2.5, porous for 2.5 r < 5, concave-convex for 5 r < 7.5, convex for 7.5 r < 13, and again flat for r larger than 13. For 2.5 r < 5, the apparent refractive index of the silica film with porous morphology was decreased to 1.23 by selecting the solvent and by controlling the relative humidity of the coating atmosphere and the heat treatment temperature. Coating of glass with silica films of low refractive index of 1.23 led to the low reflective glasses with visible light reflectance Rvis of less than 0.2%.     

Structure and properties of sol-gel coatings from methyltriethoxysilane and tetraethoxysilane

Acid catalyzed solutions of methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) were used to obtain bulk materials and silica coatings of about 2 m, after densification at 500°C. The structural evolution as a function of MTES content and heat treatment was studied.A higher content of MTES was found to enhance the maximum thickness of the coatings free of cracks. Critical thickness and shrinkage of the films were measured. MTES was also found to affect porosity and to play an important role in avoiding fractures in the films.     

Coating and water permeation properties of SiO2 thin films prepared by the sol-gel method on nylon-6 substrates

Nylon-6 substrates were coated with SiO₂ thin films by the sol-gel method and their water permeability coefficient was evaluated. Methyltriethoxysilane (MTES) and tetraethoxysilane (TEOS) were used as starting materials. The addition of MTES to TEOS has enabled the formation of crack-free thin films on the substrates. The thin films strongly adhered to the substrates. The water permeability coefficients of nylon-6 substrates coated with these thin films decreased with the increase in the ratio of TEOS to the total alkoxides. The pretreatment of the nylon-6 substrates with -aminopropyltriethoxysilane was found to be effective to suppress the water permeability. The water permeability was suppressed by about 40% under the optimal condition.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Mechanical and chemical properties of thick hybrid sol–gel silica coatings from acid and base catalyzed sols

Sol–gel silica hybrid coatings from acid and base catalyzed sols were examined. The sol precursors were tetraethyl orthosilicate (TEOS) and methyltriethoxysilane (MTES). It is generally accepted that the type of catalyst has a significant impact on the micro-structure of the resulting polysilicates. Weakly branched polymers are formed in acid catalyzed sols and highly branched, compact, particle like polymers are formed in base catalyzed sols. The mechanical and chemical properties of sol–gel derived silica coatings from acid and base catalyzed sols were studied as a function of the heat treatment temperature and time. Hardness and elastic modulus were measured by micro indentation measurements. The chemical composition of both types of coatings was characterized by X-ray photoelectron spectroscopy (XPS) and infrared spectroscopy (FTIR).     

Hybrid Sol-Gel Coatings Produced from TEOS and γ-MPS

Hybrids sols from tetraetoxysilane (TEOS) and 3-(methacryloxypropyl) trimethoxysilane (-MPS) were prepared in acid medium for different TEOS/-MPS ratios and were modified by the addition of a colloidal silica suspension. The stability of the different sols was evaluated by viscosity measurements; the sols showed a Newtonian behaviour and the ageing effect was negligible even after two months from their preparation. Coatings were obtained by dipping at different withdrawal rates and heat-treated between 150 and 250°C. Transparent coatings with thickness higher than 4 m were reached for most of the studied compositions. The surface microhardness of coatings for each composition and thermal treatment was evaluated by the pencil hardness test. The thermal stability was followed by simultaneous thermogravimetric and differential thermal analysis (TGA-DTA) determining the limit temperatures at which the coatings can be treated without losingits hybrid character. A structural analysis was made by deconvolution of Fourier transformed infrared spectra (FTIR) of self-supported films observing the influence of the organic groups on the silica network.     

Preparation of co‐polymethyl(alkoxy)siloxanes by acid‐catalyzed controlled hydrolytic copolycondensation of methyl(trialkoxy)silane and tetraalkoxysilane

Polymethyl(alkoxy)siloxane copolymers, poly(MTES‐co‐TEOS), and poly(MTMS‐co‐TMOS), are prepared by acid‐catalyzed controlled hydrolytic co‐polycondensation of methyl(trialkoxy)silane MeSi(OR)₃ (R = Et (MTES) and Me (MTMS)) and tetra‐alkoxysilane Si(OR)₄ (R = Et (TEOS) and Me (TMOS)), respectively. The products are purified by fractional precipitation to provide polymethyl(alkoxy)siloxane copolymers with molecular weight 1000–10,000 (poly(MTES‐co‐TEOS)) or 1700–100,000 (poly(MTMS‐co‐TMOS)) that are stable to self‐condensation. These polymers are soluble in common organic solvents except for hexane, and form flexible and transparent free‐standing films with a tensile strength of 4.0–10.0 MPa. The structure of the polymethyl(alkoxy)siloxane copolymers is thought to be a random or a block co‐polymer. They are found to provide coating films with an adhesive strength up to 10, a refractive index of 1.36–1.40, and a dielectric constant of 3.5–3.6. The products also show better weathering stability than polyethoxysiloxane due to the hydrolytic polycondensation of TEOS. Field emission‐scanning electron micrography analysis reveals that coating films are composed of a micro‐phase separated structure. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4732–4741     

Characterization of Electrochromic WO3-Layers Prepared by Sol-Gel Nanotechnology

Stable tungsten oxide coating sols suitable for electrochromic applications were prepared by a modified peroxotungstic acid route. Layers up to 250 nm thickness could be deposited on ITO-coated and/or FTO-coated glass substrates in a single dip-coating process. Optoelectrochemical measurements were employed to determine the variation of the electrochromic properties (change in optical density (OD) and switching times) of WO3-layers, investigated as a function of coating parameters, such as chamber humidity and the temperature of heat treatment. High resolution transmission electron microscopy (HR-TEM) has shown that the optimized layers possess a partially crystalline morphology with nanocrystalline regions 2–3 nm in size.     

Sol-Gel Fabrication and Properties of Silica Cores of Optical Fibers Doped with Yb3+, Er3+, Al2 O3 or TiO2

Optical cores of preforms for drawing optical fibers doped with Er3+ and Yb3+ were fabricated by the sol-gel method with the aim of increasing the thickness of glass layers coated in a single coating cycle and to determine the relation between the preparation conditions and optical properties of the fibers. Al2O3-P2O5-SiO2 and TiO2-P2O5-SiO2 glasses have been studied as matrices for entrapping the rare-earth elements. Input sols have been prepared from silicon and titanium alkoxides, AlCl3, ErCl3, YbCl3, POCl3, water and a modifier under acidic catalysis of HCl. The sols were coated on the inner wall of a silica substrate tube and the gel layers were sintered at high temperatures up to 2000°C after which the tube was collapsed into the preform. Continuous and homogenous glass films with the maximum thickness of about 8 m were fabricated. The influence of high-temperature heat treatment of the layers on their composition and optical attenuation was observed. The amplified stimulated emission of Er3+ around 1.55 m was measured under the excitation of the fibers by an Nd : YAG laser at 1.064 m.     

SiO<Subscript>2</Subscript> and TiO<Subscript>2</Subscript> nanoparticles in Aerosol OT reverse microemulsions: Synthesis and characterization

Stable SiO₂ and TiO₂ organosols were prepared by hydrolyzing tetraethyl orthosilicate (TEOS) in the presence of 6–12 M NH₃ and titanium(IV) isopropylate (TTIP) in reverse microemulsions of 0.12–0.25 M bis(2-ethylhexyl) sulfosuccinate (Aerosol OT, AOT) in n-decane with the aqueous pseudophase content of 2–3 vol %, 0.018–0.090 M TEOS, and 0.15–0.55 vol %, 0.003–0.025 M TTIP. The degree of hydrolysis was monitored by IR spectroscopy (for TEOS) and spectrophotometry (for TTIP). Oxide nanoparticles were characterized by photon-correlation spectroscopy (PCS) (D _h = 8–100 nm) and laser electrophoresis (ζ-potential = 7.4–11.6 mV). The occurrence of surface potential made it possible to separate the oxides from the excess of surfactant by nonaqueous electrophoresis and to determine particle sizes (7–40 nm) by means of transmission electron microscopy (TEM).     

Mullite Fibre Mats by a Sol-Gel Spinning Technique

Fine grained, microcrystalline mullite (Al_4+2x Si_2–2x O_10–x) fibre mats with a web-like structure were fabricated by a sol-gel spinning technique using a multi-orifice spinneret. Points of contact in gel fibre mats helped in the formation of a web-like fibrous body having reasonable strength and very little dust formation after calcination. Strong and resilient fibres with diameters in the range 3–12 m were obtained by a single-step sol-gel method from spinnable sols devoid of organics as the binder aid. Crystallization of -alumina and mullite at about 900°C and 1250°C, respectively was confirmed by differential thermal analysis (DTA) and X-ray diffraction (XRD). Thermogravimetry (TG) indicated the removal of most of the volatiles at about 500°C accompanied by a weight loss of about 48%. Scanning electron microscopy (SEM) shows the presence of small grains (80–150 nm in size) in the fibres calcined at 1250°C. Fourier transformed infrared spectroscopy (FTIR) indicated the sequence of transformations taking place during heat-treatment of gel fibres at different temperatures. The individual fibres in the mats calcined at 1250°C exhibited a tensile strength of 1300–1600 MPa.     

Sol-Gel Processing and Luminescent Properties of Rare-Earth Oxyfluoride Materials

Luminescent rare-earth oxyfluoride materials were prepared by a sol-gel method using trifluoroacetic acid as a fluorine source. Crystalline (La, Eu)OF powders and thin films were obtained by heating gels at typically 600–800°C. Transparent SiO₂-LaOF glass-ceramic thin films were also prepared by mixing the trifluoroacetate sols and silica sols, spin-coating on silica glass substrates and heating at temperatures 600–900°C. Eu³⁺ ions doped in the oxyfluoride materials exhibited a strong red ⁵D₀ ⁷F₂ emission (611 nm) by a charge-transfer (O^2–-Eu³⁺) excitation with ultra-violet radiation (265 nm). It was strongly suggested that the Eu³⁺ activators were preferentially incorporated into the crystalline LaOF phase in the SiO₂-LaOF glass-ceramics.     

A stability-indicating high-performance liquid chromatographic assay for the determination of some pharmaceutically important nitrocompounds

Summary A simple, rapid and precise stability-indicating high performance liquid chromatographic assay for the determination of furazolidone (I), nitrofurazone (II), nitrofurantoin (III), niridazole (IV) and nifuroxime (V) in pure form and in pharmaceutical preparations has been devloped.Reversed phase chromatography was conducted using a Lichrosorb R.P. 18 column (250×4 mm), with methanol-water-buffer pH3 (40555) eluent and detection at 365, 375, 367, 368 and 340 nm respectively. Calibration graphs were linear over the concentration ranges 3–18, 1–10, 1–10, 3–18 and 3–18 m·ml^–1. Reoveries from bulk drugs were 99.94–100.00 with a relative standard deviation of 1.02–1.61.Sunlight degradation of most of the studied drugs to 5-nitrofuraldehyde was observed. Accelerated stability studies have been carried out on each drug by exposure to sunlight for different time periods. Graphs of log of the remaining concentration (Log. C) against time indicated that photodecomposition of the nitrocompounds is a first order reaction. The proposed method was applied to some representative dosage forms and the results obtained were in good agreement with those obtained by the official methods.     

Simultaneous determination of fluocortolone, fluocortolone caproate and nicotinic acid benzylester in pharmaceutical preparations by TLC

Summary A direct quantitative thin-layer Chromatographic method for the determination of fluocortolone, fluocortolone caproate and nicotinic acid benzylester in the presence of each other in pharmaceutical preparations is described. The active ingredients were extracted from the preparations with an electronically controlled extraction apparatus within 15 min. Development of thin-layer chromatograms was carried out on silica gel 60 F254 precoated plates. All three active ingredients can be separated on one plate using one solvent system namely diethyl ether — hexane — benzene (75251) and determined directly by the remission method using a densitometer. Fluocortolone and fluocortolone caproate were measured at 243 nm and nicotinic acid benzylester at 263 nm. Evaluation of thinlayer chromatograms takes place on-line from the linear calibration curves using an IBM 1800 computer. The described method is suitable for analyses of these substances in pharmaceutical preparations, such as ointments and creams and can be well reproduced with a coefficient of variation between 1.3–3.5% for the three active ingredients.

---

Gleichzeitige Bestimmung von Fluocortolon, Fluocortoloncaproat und Nicotinsäurebenzylester in pharmazeutischen Zubereitungen durch DC