Mullite fibers prepared from an inorganic sol–gel precursor

Mullite fibers were prepared by sol–gel process using alumina sol and silica sol. Alumina sol was synthesised from dissolution of aluminum powder in aluminum chloride hexahydrate solution. The optimal spinning alumina sol could be obtain in the composition range of Al/AlCl₃·6H₂O molar ratio 3.4–3.8. The Al and Si components were mixed at the molecular level and linear molecules were formed in the mullite precursor sol. The dried mullite precursor gel fibers completely transformed to mullite fibers at 1,000 °C with a smooth surface and uniform diameter.     

Silver containing sol–gel derived silica thin films: effect of aluminum incorporation on optical,microstructural and bactericidal properties

Silver containing silica (Ag–SiO₂) thin films with and without aluminum (Al) were prepared on soda-lime-silica glass by spin coating of aqueous sols. The coating sol was formed through mixing tetraethyl orthosilicate [Si(OC₂H₅)₄]/ethanol solution with aqueous silver nitrate (AgNO₃) and aluminum nitrate nonahydrate [(AlNO₃)₃·9H₂O] solutions. The deposited films were calcined in air at 100, 300 and 500 °C for 2 h and characterized using x-ray diffraction, UV-visible and x-ray photoelectron spectroscopy. The effect of Al incorporation and calcination treatment on microstructure and durability of the films, and chemical/physical state of silver in the silica thin film have been reported. The bactericidal activity of the films was also determined against Staphylococcus aureus via disk diffusion assay studies before and after chemical durability tests. The investigations revealed that the optical, bactericidal properties and chemical durability of Ag–SiO₂ films can be improved by Al addition. The Al-modified Ag–SiO₂ thin films do not exhibit any coloring after calcination in the range of 100–500 °C, illustrating that silver is incorporated within the silica gel network in ionic form (Ag⁺). Al incorporation also improved the overall durability and antibacterial endurance of Ag–SiO₂ thin films.     

Mullite crystallization using fully hydrolyzed silica sol: the gelation temperature influence

Mullite is an aluminosilicate widely used as a structural material for high temperature applications. This paper studies the effect of the gelation temperature on the synthesis of two mullite precursors: polymeric and colloidal silica, using both in fully-hydrolyzed silica sol, derived from sodium silicate. The gels were synthesized using aqueous silicic acid and aluminum nitrate. Ethylene glycol was added into polymeric gels. Two gelation temperatures were used: 80 and 100 °C. In the polymeric precursor, the increasing of the gelation temperature caused an increase in the silica incorporation inside the mullite crystalline lattice at 1,000 °C, and it also generated an increase in the reaction extent at all calcination temperatures. In the colloidal precursors, these effects were more intense than in the polymeric precursors in terms of yield. Colloidal samples calcined at 1,250 °C crystallized cristobalite and alpha alumina in addition to mullite when they were previously gelled at 80 °C. On the other hand, the same sample gelled at 100 °C led to only crystallized mullite. The reaction extent increased by more than 20 % for colloidal samples gelled at 100 °C compared to colloidal samples gelled at 80 °C (calcined at 1,250 °C). This increase was due to the almost total incorporation of alumina and silica in the crystalline lattice of mullite.     

Kinetics of mullitization from sol-gel synthesized precursors

The aim of this study is to shed more light on the formation of mullite and the kinetics of mullitization from sol-gel synthesized precursors. Tetraethylorthosilicate (TEOS) and aluminum nitrate nonahydrate (ANN) were used, as a source of silica and alumina, respectively, for the synthesis of homogenous mullite precursor powder. The mullitization process was characterized by thermogravimetry (TG), differential thermal analysis (DTA), thermodilatometric analysis (TDA), and x-ray powder diffraction (XRD) techniques. It was found that mullite started to crystalize at temperatures of 1050, 1200, and 1241 °C as determined by XRD, DTA, and TDA, respectively?. Mullite crystallization kinetics was thoroughly investigated under isothermal and non-isothermal conditions using DTA. The activation energy for mullite formation was calculated, for different crystallization fractions, following the Freidman, Kissinger, Boswell, and Ozawa methods. The average values were found to be 1282.92, 1324.30, 1336.93, and 1283.09 kJ/mol, respectively. The kinetic parameters and the crystallization mechanism were determined and the results were compared with those available in the literature. The Sestak Berggren SB(m,n) model was found to be the most suitable for the determination of mullite crystallization mechanism. The calculated average values of the Gibbs free energy (ΔG^#), enthalpy (ΔH^#), and entropy (ΔS^#) for mullite formation, at different heating rates, were 433.98 kJ/mol, 1294.20 kJ/mol, and 566.23 J/mol.K, respectively.     

A comparative study of microstructural development in the sol–gel derived alumina–mullite nanocomposites using colloidal silica and tetraethyl orthosilicate

This paper compares the microstructure development of two alumina–15 vol% mullite composites during the sintering. The nanopowders of alumina–mullite composite were synthesized by the sol–gel method using aluminum chloride hexahydrate and two different silicon sources (colloidal silica in route 1 and tetraethyl orthosilicate in route 2). The alumina–mullite composites were prepared by pressing and sintering of the nanopowders. Although the intergranular mullites were observed in both routes, there were mullite particles in route 2 formed inside the alumina grains (intragranular mullite). Formation of the intragranular mullite is attributed to the drop in silica solubility, which occurs during the transition from metastable alumina to stable alumina. Compared to route 1, the relative density and the average grain size were increased and accelerated by route 2. The two-stage sintering is not useful for the mullite decomposition.     

The role of precursors in the structure of SiO2-Al2O3 sols and gels by the sol-gel process

Binary sols and gels of SiO₂-Al₂O₃ were prepared using tetraethyl orthosilicate and each of four aluminum compounds; aluminum di (sec-butoxide) ethylacetoacetic ester chelate (AC), aluminum nitrate nonahydrate (AN), aluminum formoacetate (AF), and boehmite sol (BS) made from aluminum i-propoxide. The structure and the evolution of the Si-O-Al bonds in SiO₂-Al₂O₃ sols and gels were investigated by ²⁷Al nuclear magnetic resonance (NMR), Infrared absorption spectra, DTA, and X-ray diffraction. The formation of Si-O-Al bonds differs depending on the aluminum compounds used as raw materials. The ratio of Al(IV) to {Al(IV) + Al(VI)} is related to the microstructural homogeneity of the gels. When AC is used as a raw material, the Si-O-Al bonds are formed in the sol state and resultant gel shows good microstructural homogeneity. In case of AN, the Si-O-Al bonds are not formed either in the sol or the wet gel state. The bonds are formed by drying the gel before heat-treatment temperature reaches 300 400°C, resulting in good microstructural homogeneous gel. When AF is used, the Si-O-Al bonds are formed in the sol state but the ratio of Al(IV) to {Al(IV) + Al(VI)} is lower than when using AC. Microstructural homogeneity of the gel is ranked between AC or AN and BS. Using BS, the Si-O-Al bonds are not formed in the sol solution, and the change in the coordination number of the gel is similar to that of boehmite gel. The Microstructural homogeneity of the gel is the worst among the BS gels, which were prepared by using the four aluminum raw materials.     

Synthesis,characterization and single crystal structure determination of aluminum alkoxydisilanolates: precursors for silica–alumina composite

Several novel aluminum alkoxydisilanolate complexes were prepared by reaction of triphenylsilanol with aluminum 2‐methoxyethoxide, aluminum 2‐ethoxyethoxide, aluminum sec‐butoxide and aluminum iso‐propoxide. All new complexes, [(Ph₃SiO)₂Al(OR)]₂ [where R = CH₂CH₂OCH₃ (1), CH₂CH₂OC₂H₅ (2), CH(CH₃)CH₂CH₃ (3) and CH(CH₃)₂ (4)] were characterized by elemental analysis, mass spectrometry and infrared spectroscopy (IR), as well as ¹H, ¹³C, ²⁹Si and ²⁷Al NMR spectroscopies. The solid‐state structures of the representative compound 2 and 4 were also verified by single‐crystal X‐ray analyses. Complexes 2 and 4 are dimers having distorted trigonal bipyramidal and tetrahedral coordination at the aluminum center, respectively. The ²⁷Al NMR spectrum of compound 2 showed that the solid‐state structure of the complex was not retained in solution, and tetracoordinated aluminum was found in solution in contrast to the pentacoordinated geometry in the solid state. The hydrothermal treatment of 1 and 4 at 200 °C and the subsequent calcination at 1000 °C resulted in the formation of alumina–silica composite (4SiO₂·Al₂O₃) with γ‐alumina in the silica matrix. Copyright © 2010 John Wiley & Sons, Ltd.     

Ferroelectric poly(vinylidene fluoride) PVDF films derived from the solutions with retainable water and controlled water loss

To obtain β‐phase dominant ferroelectric poly(vinylidene fluoride) (PVDF) homopolymer thin films on aluminum‐coated silicon substrates, the retaining and loss of water were manipulated by introducing several hydrated and hygroscopic chemicals in the precursor solutions, including aluminum nitrate nonahydrate, aluminum chloride hexahydrate, chromium nitrate nonahydrate, tetra‐n‐butylammonium chloride, and one hygroscopic but nonhydrated chemical, ammonium acetate. Their ability of retaining water during the thermal annealing of the films and the relationship between water retaining and the effects on promoting the β phase were investigated. The results showed an ideal scenario was that the added hydrated salts should be able to retain substantial amount of water during the PVDF crystallization to effectively promote the β phase but completely dehydrate or decompose at the further elevated annealing temperature in order to obtain β‐phase dominant PVDF film without substantially incorporating water and deteriorating the electrical properties. As one of the hydrated chemicals well satisfying the above requirements, Al(NO₃)₃·9H₂O, of different amounts was introduced to the PVDF precursor solutions and the optimal resulting β‐phase dominant ferroelectric PVDF thin films exhibited smooth morphology, low dielectric loss, high remnant polarization of 89 mC/m², and large effective piezoelectric coefficient d₃₃ of ?14.5 pm/V (under the clamping of the substrate). © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2410–2418, 2009     

Compatibility study of 1,3,3-trinitroazetidinewith some energetic components and inert materials

The compatibility of 1,3,3-trinitroazetidine (TNAZ) with some energetic components and inert materials of solid propellants was studied by using the pressure DSC method. Where, cyclotetramethylenetetranitroamine (HMX), cyclotrimethylenetrinitramine (RDX), nitrocellulose (NC), nitroglycerine (NG), 1.25/1-NC/NG mixture, lead 3-nitro-1,2,4-triazol-5-onate (NTO-Pb), aluminum powder (Al powder) and N-nitrodihydroxyethylaminedinitrate (DINA) were used as energetic components and hydroxyl terminated polybutadiene (HTPB), carboxyl terminated polybutadiene (CTPB), polyethylene glycol (PEG), polyoxytetramethylene- co-oxyethylene (PET), addition product of hexamethylene diisocyanate and water (N-100), 2-nitrodianiline (2-NDPA), 1,3-dimethyl-1,3-diphenyl urea (C₂), carbon black (C.B.), aluminum oxide (Al₂O₃), cupric 2,4-dihydroxybenzoate (β-Cu), cupric adipate (AD-Cu) and lead phthalate (φ-Pb) were used as inert materials. The results showed that the binary systems of TNAZ with HMX, NC, NG, NC+NG and DINA are compatible, with RDX and Al powder are slightly sensitive, with NTO-Pb, β-Cu, AD-Cu, C.B. and Al2O3 are sensitive, and with HTPB, CTPB, PEG, PET, N-100, 2-NDPA, C₂ and φ-Pb are incompatible.     

Preparation,characterization and compatibility studies of poly(DFAMO/AMMO)

Poly(3-difluoroaminomethyl-3-methyl oxetane (DFAMO)/3-azidomethyl-3-methyl oxetane (AMMO)) (PDA) can be used as an energetic pre-polymer in the binder systems of solid propellants and polymer-bonded explosives (PBXs). The cationic solution polymerization affords PDA using butane diol (BDO) and boron trifluride etherate (TFBE) as initiator and catalyst, separately. Its molecular structure is characterized and thermal decomposition behavior is investigated by thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). The copolymer has good thermal stability and exhibits a three-step mass-loss process with the first two steps mainly belonging to the thermal decomposition of difluoroamino and azido groups, respectively. DSC method is performed to evaluate the compatibility of PDA with some energetic components and inert materials. More than half of the selected materials are compatible with PDA, which including cyclotrimethylenetrinitramine (RDX), 2,4,6-trinitrotoluene (TNT), 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), pentaerythritol tetranitrate (PETN), ammonium perchlorate (AP), ammonium nitrate (AN), potassium nitrate (KNO₃), aluminum powder (Al), aluminum oxide (Al₂O₃), 2-nitrodiphenylamine (NDPA) and 1,3-diethyl-1,3-diphenyl urea (C₁).     

Selective Formation of Spinel Iron Oxide in Thin Films by Complexing Agent-Assisted Sol-Gel Processing

The structure of iron oxide was controlled by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands such as diols. Iron oxides were prepared by calcining the precursor polymers obtained from iron nitrate nonahydrate and diols. When the diols were 1,2-pentanediol, 1,2-hexanediol and 1,2-octanediol, α-Fe₂O₃ with corundum structure appeared exclusively or as the main crystalline phase, in spite of the amount of diol used and the calcination temperature. In the case of 1,2-decanediol and 1,2-dodecanediol, when five moles of the diols were used to one mole of iron nitrate and the calcination temperatures were below 400°C, ψ-Fe₂O₃ with spinel structure appeared as the main phase and, when less than five moles of the diols were used, α-Fe₂O₃ appeared exclusively or as the main phase, irrespective of the calcination temperature. This tendency was also observed in thin films. Thus, a transparent magnetic film composed of γ-Fe₂O₃ could be prepared by applying a benzene solution of the iron polymer, obtained with 5 equivalents of 1,2-decanediol, on quartz and calcining the gel film at 350°C.     

Alumina-titania oxides: Synthesis and characterization

Alumina-titania mixed oxides with nominal atomic ratios Al/Ti=25 and 2 have been synthesized by cohydrolysis of Al(OsecBu)₃ and Ti(OBu)₄. The oxides were amorphous at 500°C, showing only short range order. Ti was incorporated in alumina in a well dispersed way creating a true Al/Ti mixed oxide. The strength of surface acid sites and specific surface areas were increased at the higher Ti content. The TiO₂ anatase phase was avoided and rutile was formed directly at 900°C.     

Hydrothermal Synthesis of Silicoaluminophosphate with AEL Structure Using a Residue of Fluorescent Lamps as Starting Material

Silicoaluminophosphate molecular sieves of SAPO-11 type (AEL structure) were synthesized by the hydrothermal method, from the residue of a fluorescent lamp as a source or Si, Al, and P in the presence of water and di-propyamine (DPA) as an organic template. To adjust the P₂O₅/SiO₂ and Si/Al and ratios, specific amounts of silica, alumina, or alumina hydroxide and orthophosphoric acid were added to obtain a gel with molar chemical composition 1.0 Al₂O₃:1.0 P₂O₅:1.2 DPA:0.3 SiO₂:120 H₂O. The syntheses were carried out at a temperature of 473 K at crystallization times of 24, 48, and 72 h. The fluorescent lamp residue and the obtained samples were characterized by X-ray fluorescence, X-ray diffraction, scanning electron microscopy, and BET surface area analysis using nitrogen adsorption isotherms. The presence of fluorapatite was detected as the main crystalline phase in the residue, jointly with considered amounts of silica, alumina, and phosphorus in oxide forms. The SAPO-11 prepared using aluminum hydroxide as Al source, P₂O₅/SiO₂ molar ratio of 3.6 and Si/Al ratio of 0.14, at crystallization time of 72 h, achieves a yield of 75% with a surface area of 113 m²/g, showing that the residue from a fluorescent lamp is an alternative source for development of new materials based on Si, Al, and P.     

Control of structure and particle size of iron oxide on carrier oxide by the sol-gel method using organic polydentate ligands

It was tried to control the structure and particle size of iron oxide supported on a carrier by regulating the hydrolytic polymerization of aquo iron complexes with organic polydentate ligands. The iron oxide/carrier composites were prepared by calcining carrier oxides impregnated with organic ligands and Fe(NO₃)₃·9H₂O. When ligands were diacetone alcohol and ethanol, the structure of the iron oxide was exclusively corundum. But, with ligands such as ethylene glycol, citric acid and galacturonic acid, the structure of the iron oxide changed from corundum to spinel as the amount of ligands used increased. With both series of ring and straight chain saccharides, size of the iron oxide particles changed depending on saccharides used. It was thus concluded that the structure and particle size of iron oxide supported on a carrier can be regulated by using organic polydentate ligands.     

Adsorption of hydrocarbons from solutions and gas phase on silica and alumina modified with silver and gold ions

The paper reports the immobilization of Ag⁺ cations on alumina and silica and AuCl ₄ ^? anions on amino silica and alumina. The method of inverse gas chromatography have demonstrated that Ag(I)-silica is selective for the separation of alkanes, alkenes, alkines, and arenes. The dependence of the capacitance of Ag(I) and Au(III) composites with regard to phenylacetylene (PHA) on the nature of the carriers, surface concentration, and technique of immobilizing ion metals has been considered. The isotherms of the adsorption of PHA from solutions in octane have been measured. It has been revealed that the capacitance of composites with regard to toward PHA prepared by the immobilization of ammoniates of silver nitrate on silicon dioxide is several times higher than for composites based on alumina with the same silver concentration and composites prepared by the immobilization of silver nitrate on silicon dioxide. The capacitance of the Au(III) composite based on alumina for PHA is significantly higher than for that based on aluminum oxide. The highest capacitance for PHA (0.83 and 0.88 molecules per metal ion) is observed for Ag(I) silica and the Au(III) alumina composite. In the visible region, the diffuse reflection spectra of amino silica Au(III) composites have a significant shift of the maximum of adsorption band along with the decrease in the concentration of immobilized anions of AuCl ₄ ^? , which evinces the formation of coordination bonds between free amin?propyl groups of the silica carrier and gold atom. The formation of these bonds prevents the adsorption of PHA on amino silica Au(III) composites with low gold concentrations.     

Isobutane dehydrogenation over chromia alumina catalysts prepared from MIL-101: Insight into chromium species on activity and selectivity

Various mesoporous chromia alumina catalysts were prepared by five different methods based on a metal-organic framework MIL-101 and their catalytic performances over isobutane dehydrogenation were investigated. The highly dispersed chromium species were produced on catalyst KCr Al-I1 with largest specific surface area of 198 m2 g-1prepared with aluminium isopropoxide(Al(i-OC3H7)3) by ultrasonic impregnation method. However, the catalyst KCr Al-I2 synthesized by stirring impregnation possessed crystalline α-Cr2O3 phase, which was poorly dispersed. Two types of Cr-rich and Al-rich Crx Al2-xO3 solid solutions, designated as Cr Al-I and Cr Al-II phase, were formed over the catalysts KCr Al-I3(prepared by Al(i-OC3H7)3with nitric acid regulation), KCr Al-C4(prepared by aluminium chloride hexahydrate) and KCr Al-N5(prepared by aluminium nitrate nonahydrate). Catalytic evaluation results revealed that KCr Al-I1 exhibited the high isobutane conversion due to its highly dispersed chromium species. However, KCr Al-I3, KCr Al-C4 and KCr Al-N5 showed the higher isobutene selectivity(95.2%-96.4%) on account of the formation of chromia alumina solid solutions in the catalysts. Moreover, the solid solution over the chromia alumina catalysts could greatly suppress the coke formation.     

Sol–gel combustion synthesis and characterization of nanostructure copper chromite spinel

Nanocomposite copper chromite spinel was fabricated by sol–gel process using copper nitrate trihydrate, chromium nitrate nonahydrate, ethylene glycol, diethyl ether, and citric acid. The thermoanalytical measurements (TG–DTG), X-ray powder diffractometry (XRD), field emission scanning electron microscopy (FESEM), and energy dispersive X-ray analysis were used to characterize the structural and the chemical features of the nanocomposites. TG–DTG results showed that the major mass loss for copper(II) nitrate, chromium(III) nitrate as precursors occur at 258 and 140 °C, respectively. The major mass loss for dried gel of copper chromite occurs at 310 °C. XRD data revealed the formation of pure copper chromite after thermal decomposition at 1,000 °C for 2 h. The observation of XRD patterns reveals the presence of single-phase tetragonal spinel CuCr₂O₄. FESEM analysis of calcined composite was found to be in the range of 20–30 nm.     

Solid-liquid phase equilibria of binary salt hydrate mixtures involving ammonium alum

Summary The solid-liquid phase diagrams of binary mixtures of ammonium alum with ammonium iron(III) alum, with aluminum nitrate nonahydrate and with ammonium nitrate and of aluminum sulfate hexadecahydrate with aluminum nitrate nonahydrate are presented. The alum rich branches of the former three-phase diagrams were fitted by the Ott equation. The specific enthalpy of fusion/freezing of some compositions of the former three mixtures was determined by differential drop calorimetry.     

Thermal decomposition of some metal-organic precursors

In this paper we present a study on the synthesis of Fe(III) oxide, by thermal decomposition of some complex combinations of Fe(III) with carboxylate type ligands, obtained in the redox reaction between some polyols (ethylene glycol (EG), 1,2-propane diol (1,2PG), 1,3-propane diol (1,3PG) and glycerol (GL)) and NO₃ ^– ions (from ferric nitrate). Fe₂O₃ was obtained by thermal decomposition of the synthesized metal-organic precursors at low temperatures. γ-Fe₂O₃ was obtained as nanoparticles at 300°C, while at higher temperatures α-Fe₂O₃ starts to crystallize and becomes single phase at ~500°C. The formation of the metal-organic precursors and their thermal decomposition were studied by thermal analysis and FTIR spectroscopy.     

Aluminum Complexes with a Donor Polymer: New Route to Organic/Inorganic Polymer Hybrids

The formation of alumina particles from aluminum salts in the presence of poly(1-vinylimidazole) was investigated by quantitative ²⁷Al NMR, potentiometry and FTIR spectra. The interaction of poly(1-vinylimidazole) with aluminum chloride and nitrate in an aqueous medium stabilizes [AlO₄Al₁₂(OH)₂₄]⁷⁺ and less ordered polymeric particles. The addition of NaOH (NaOH: Al 2) results in water-insoluble organic/inorganic hydrogen-bonded composites. Stabilization of the complexes is realized by cooperative hydrogen N···H—O—Al bonds, without N Al donor-acceptor interactions.