In situ polymerization of silicic acid in polyethylene–octene elastomer: Properties and characterization of the hybrid nanocomposites

Silicic acid produced from sodium metasilicate hydrate and metallocene polyethylene–octene elastomer (POE) were chosen as the ceramic precursor and the continuous phase, respectively, for preparation of new hybrids by an in situ sol–gel process. To obtain a better hybrid, the acrylic acid‐grafted polyethylene–octene elastomer (POE‐g‐AA) prepared in our laboratory and used as the continuous phase was also investigated. Characterizations of POE/SiO₂ and POE‐g‐AA/SiO₂ composites were performed by Fourier transform infrared spectroscopy, ²⁹Si solid‐state nuclear magnetic resonance (NMR) spectrometry, X‐ray diffractometry, differential scanning calorimetry, thermogravimetry analysis, and an Instron mechanical tester. The POE‐g‐AA/SiO₂ hybrid could give the positive effect on the properties of POE/SiO₂ hybrid because the carboxylic acid groups of acrylic acid should act as coordination sites for the silica phase to form chemical bonds. The result of ²⁹Si solid‐state NMR spectra showed that Si atom coordination around SiO₄ units is predominantly Q₃ and Q₄. Also, the POE‐g‐AA/SiO₂ hybrid with 15 wt % SiO₂ gave the maximum values of tensile strength and glass‐transition temperature because excess particles might cause the separation between the organic and inorganic phases when the silica content was beyond this point. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 351–359, 2003     

Preparation and characterization of novel polyimide‐silica hybrids

Polyimide‐silica (PI‐SiO₂) hybrids were prepared from a novel polyimide (PI), derived from pyromellitic dianhydride (PMDA), 1,6‐bis(4‐aminophenoxy)hexane (synthesized) and 4,4′‐oxydianiline. SiO₂ networks (5–30 wt%) were generated through sol–gel process using either tetraethylorthosilicate (TEOS) or a mixture of 3‐aminopropyltriethoxysilane‐PMDA‐based coupling oligomers (APA) and TEOS. Thin, free standing hybrid films were obtained from the respective mixtures by casting and curing processes. The hybrid films were characterized using Fourier transform infrared, ²⁹Si nuclear magnetic resonance (NMR), field emission scanning electron microscopy (FE‐SEM), energy dispersive X‐ray spectrometry and atomic force microscopy (AFM) techniques. ²⁹Si NMR results provide information about formation of organically modified silicate structures that were further substantiated by FE‐SEM and AFM micrographs. Contact angle measurements and thermogravimetric thermograms reveal that the addition of APA profoundly influences surface energy, interfacial tension, thermal stability and the residual char yield of modified hybrids in comparison to those obtained by mixing only TEOS. It was found that reduced particle size, efficient dispersion and improved interphase interactions were responsible for the eventual property enhancement. Copyright © 2012 John Wiley & Sons, Ltd.     

Organic–inorganic hybrid materials. V. Dynamics and degradation of poly(methyl methacrylate) silica hybrids

Poly(methyl methacrylate)–silica hybrid materials (PMMA–SiO₂) were prepared by in situ polycondensation of alkoxysilane in the presence of trialkoxysilane‐functional PMMA. Infrared, differential scanning calorimetry, ²⁹Si and ¹³C nuclear magnetic resonance spectroscopy, and thermogravimetric analysis were used to study the PMMA–SiO₂ hybrids. The effects of the content and kind of the alkoxysilane on the dynamics and stability of the PMMA–SiO₂ hybrids were investigated in this study.The dynamics of SiO₂within hybrids were investigated with ²⁹Si–¹H cross‐polarization. The spin‐diffusion path length was on a nanometer scale estimated with the spin–lattice relaxation time in the rotating frame (T). The apparent activation energies for the degradation of the hybrids under air and nitrogen were evaluated by the van Krevelen method. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1972–1980, 2000     

Ce2Ti2SiO9 – das erste Titanat‐Silicat mit Cer – Präparation,Charakterisierung und Struktur

Ce₂Ti₂SiO₉ – the First Titanate‐Silicate with Cerium – Preparation, Characterization, and Structure Ce₂Ti₂SiO₉ was synthesized by chemical vapour transport in a temperature gradient (1050 °C → 900 °C) using Ce₂Ti₂O₇ as precursor and ammoniumchloride as transport agent. SiO₂ was provided from the wall of the used silica tubes. The chemical composition of the crystals was determined by EDX and EELS analysis. The structure of Ce₂Ti₂SiO₉ was determined and refined to R1 = 0.025, _wR2 = 0.067, respectively. The monoclinic phase crystallizes in the space group C2/m (No. 12) with a = 16.907(3) Å, b = 5.7078(8) Å, c = 7.574(2) Å, β = 111.38(2)° and Z = 4. Ti is octahedral, Si is tetrahedral surrounded by oxygen. Ce(1) is coordinated by eight, Ce(2) by ten oxygen atoms. There are edge connected chains of Ti(1)–O‐octahedra parallel [010] which are connected along [001] with each other by Ti(2)–O‐octahedra‐pairs and Si–O‐tetrahedra.     

SiO2–poly(amidoamine) dendrimer inorganic/organic hybrids

SiO₂–poly(amidoamine) (PAMAM) dendrimer hybrids were synthesized via (1) a Michael addition reaction between the dendrimer and 3‐(trimethoxysilyl) propyl acrylate, (2) the dissolution of the formed compound in methanol, and (3) the mixing of the latter solution with a methanol solution of partly hydrolyzed tetraethylorthosilicate (TEOS) and its casting on a glass substrate. ¹H NMR indicated that in the first step, 77% of the secondary amines were converted into tertiary amines when the fourth‐generation dendrimer was employed and 46% were converted when the second‐generation dendrimer was used. The final SiO₂–PAMAM dendrimer hybrids were obtained via the hydrolysis and condensation of the compound obtained via the Michael addition and the methanol solution of partly hydrolyzed TEOS. The compartmentalized structure of the hybrids due to the compartments of the dendrimers could be controlled by changing the dendrimer and the amount of TEOS. Scanning electron microscopy and transmission electron microscopy micrographs provided information about the structure of the hybrids. Like the PAMAM dendrimer, the SiO₂–PAMAM dendrimer hybrids exhibited a high metal ion complexing capacity because of the presence of the compartments of the dendrimer; they can be, however, much more easily handled, and, as demonstrated by thermogravimetric experiments, have much higher thermal resistance. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1443–1449, 2000     

Synthesis of polyethylene‐octene elastomer/SiO2‐TiO2 nanocomposites via in situ polymerization: Properties and characterization of the hybrid

In this study, a silicic acid and tetra isopropyl ortho titanate ceramic precursor and a metallocene polyethylene‐octene elastomer (POE) or acrylic acid grafted metallocene polyethylene‐octene elastomer (POE‐g‐AA) were used in the preparation of hybrids (POE/SiO₂? TiO₂ and POE‐g‐AA/SiO₂? TiO₂) using an in situ sol‐gel process, with a view to identifying a hybrid with improved thermal and mechanical properties. Hybrids were characterized using Fourier transform infrared spectroscopy, ²⁹Si solid‐state nuclear magnetic resonance (NMR), X‐ray diffraction, differential scanning calorimetry, thermogravimetry analysis, dynamic mechanical thermal analysis, and Instron mechanical testing. Properties of the POE‐g‐AA/SiO₂? TiO₂ hybrid were superior to those of the POE/SiO₂? TiO₂ hybrid. This was because the carboxylic acid groups of acrylic acid acted as coordination sites for the silica‐titania phase to allow the formation of stronger chemical bonds. ²⁹Si solid‐state NMR showed that Si atoms coordinated around SiO₄ units were predominantly Q₃ and Q₄. The 10 wt % SiO₂? TiO₂ hybrids gave the maximum values of tensile strength and glass transition temperature in both POE/SiO₂? TiO₂ and POE‐g‐AA/SiO₂? TiO₂. It is proposed that above this wt %, excess SiO₂? TiO₂ particles caused separation between the organic and inorganic phases. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1690–1701, 2005     

Synthesis of Mesoporous TiO2/SiO2 Hybrid Films as an Efficient Photocatalyst by Polymeric Micelle Assembly

Thermally stable mesoporous TiO₂/SiO₂ hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle‐assembly method. A triblock copolymer, poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO₂/SiO₂ hybrid films with different compositions can be synthesized. The presence of amorphous SiO₂ phase effectively retards the growth of anatase TiO₂ crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO₂/SiO₂ hybrid films are of very high quality, without any cracks or voids. The addition of SiO₂ phase to mesoporous TiO₂ films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO₂ film without SiO₂ phase.     

Formation and Thermal Stability of Gold–Silica Nanohybrids: Insight into the Mechanism and Morphology by Electron Tomography

Gold–silica hybrids are appealing in different fields of applications like catalysis, sensorics, drug delivery, and biotechnology. In most cases, the morphology and distribution of the heterounits play significant roles in their functional behavior. Methods of synthesizing these hybrids, with variable ordering of the heterounits, are replete; however, a complete characterization in three dimensions could not be achieved yet. A simple route to the synthesis of Au‐decorated SiO₂ spheres is demonstrated and a study on the 3D ordering of the heterounits by scanning transmission electron microscopy (STEM) tomography is presented—at the final stage, intermediate stages of formation, and after heating the hybrid. The final hybrid evolves from a soft self‐assembled structure of Au nanoparticles. The hybrid shows good thermal stability up to 400 °C, beyond which the Au particles start migrating inside the SiO₂ matrix. This study provides an insight in the formation mechanism and thermal stability of the structures which are crucial factors for designing and applying such hybrids in fields of catalysis and biotechnology. As the method is general, it can be applied to make similar hybrids based on SiO₂ by tuning the reaction chemistry as needed.     

Microstructure and protonic conductivity of H3PO4‐doped polyethylenimine–siloxane chemically covalently organic–inorganic hybrids

The chemically covalent polyethylenimine–siloxane hybrids doped with various amounts of ortho‐phosphoric acid (H₃PO₄) were prepared and characterized by FTIR, DSC, TGA, and solid‐state NMR spectra. The protonic conduction behavior of these materials was also investigated by means of impedance measurements. These observations indicate that the hydrogen bonding and protonic interactions exist between the dopant H₃PO₄ and the hybrid host, resulting in an increase in T _g of polyethylenimine segments. These hybrids are thermally stable up to 200 °C from TGA analysis. Conductivity studies show an Arrhenius behavior characteristic and the Grotthus‐like proton conduction, and a high conductivity of 10^?2–10^?3 S cm^?1 at 110 °C in dry atmosphere for the hybrid membrane with H₃PO₄/EI of 0.5. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2135–2144, 2006     

Photophysical Properties of a Novel Organic–Inorganic Hybrid Material: Eu(III)-β-Diketone Complex Covalently Bonded to SiO2/ZnO Composite Matrix

In this article, dibenzoylmethane (DBM) was first grafted with the coupling reagent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) to form precursor DBM–Si, and ZnO quantum dot was modified with 3-mercaptopropyltrimethoxysilane (MPS) to form SiO₂/ZnO nanocomposite particle. Then the precursor DBM–Si and the terminal ligand 1,10-phenthroline (phen) were coordinated to Eu³⁺ion to obtain ternary hybrid material phen–Eu–DBM–SiO₂/ZnO after hydrolysis and copolycondensation between the tetraethoxysilane (TEOS), water molecules and the SiO₂/ZnO network via the sol–gel process. In addition, for comparison, the binary hybrid material with SiO₂/ZnO network and ternary hybrid material with pure Si–O network were also synthesized, denoted as Eu–DBM–SiO₂/ZnO and phen–Eu–DBM–Si, respectively. The results reveal that hybrid material with SiO₂/ZnO network phen–Eu–DBM–SiO₂/ZnO exhibits the stronger red light, the longer lifetimes and higher quantum efficiency than hybrid material with pure Si–O network phen–Eu–DBM–Si, suggesting that SiO₂/ZnO is a favorable host matrix for the luminescence of rare earth complexes.     

Interfacial properties of thermally oxidized Ta2Si on Si

Many refractory metal silicides have received great attention due to their potential for innovative developments in the silicon‐based microelectronic industry. However, tantalum silicide, Ta₂Si, has remained practically unnoticed since its successful application in silicon carbide technology as a simple route for a high‐k dielectric formation. The thermal oxidation of Ta₂Si produces high‐k dielectric layers, (O? Ta₂Si)‐based on a combination of Ta₂O₅ and SiO₂. In this work, we investigate the interfacial properties of thermally oxidized (850–1050 °C) Ta₂Si on commercial silicon substrates. The implications of diffusion processes in the dielectric properties of an oxidized layer are analyzed. In particular, we observe migration of tantalum pentoxide nanocrystals into the substrate with increasing oxidation temperature. An estimation of the insulator charge and interfacial O? Ta₂Si/Si trap density is also presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Organic–inorganic hybrid membranes prepared from the sol–gel process of poly(butyleneadipate‐co‐terephthalate) and TiO2

Organic–inorganic hybrids based on poly(butyleneadipate‐co‐terephthalate)/titanium dioxide (PBAT/TiO₂) hybrid membranes were prepared via a sol–gel process. The PBAT/TiO₂ hybrid membranes were prepared for various PBAT/TiO₂ ratios. The resulting hybrids were characterized with a morphological structure, hydrophilicity, biodegradability, and thermal properties. The results showed that macrovoids underwent a transition into a sponge‐like membrane structure with the addition of TiO₂. After sol–gel transition, a strong interaction between the inorganic network and polymeric chains led to an increase in glass transition temperature (T_g), thermal degrading temperature, and hydrophilicity, and hence a higher biodegradability. According to X‐ray diffraction measurements of the crystal structure of the hybrid, the presence of TiO₂ did not change the crystal structure of PBAT. TiO₂ networks are uniformly dispersed into the PBAT matrix and no aggregation of TiO₂ networks in the hybrid membranes was observed through the small angle X‐ray scattering measurements. Thus, the sol–gel process of PBAT and TiO₂ can be used to prepare a hybrid with higher application temperature and faster biodegradation rate. Copyright © 2008 John Wiley & Sons, Ltd.     

Molecular dynamics in nanostructured polyimide–silica hybrid materials and their thermal stability

Molecular motion and thermal stability in two series of nanophase‐separated polyimide–silica (PI–SiO₂) hybrid materials with chemically bound components were studied. The hybrids were synthesized from p‐aminophenyltrimethoxysilane‐terminated poly(amic acid)s as PI precursors and tetramethoxysilane as a silica precursor via a sol–gel process. The hybrids differed in their PI chemical structure and chain length (number‐average molecular weight = 5.000, 7.500, or 10.000) and in their SiO₂ content, which ranged from 0 to 50 wt %. Differential scanning calorimetry, laser‐interferometric creep rate spectroscopy, and thermally stimulated depolarization current techniques were used for studying the dynamics from 100 to 650 K and from 10^?3 to 10^?2 Hz. Comparative thermogravimetric measurements were also carried out from 300 to 900 K. Silica nano‐ or submicrodomains that formed affected PI dynamics in two opposite directions. Because of the loosening of the molecular packing of PI chains confined to nanometer‐scale spaces between silica constraints, an enhancement of small‐scale motion, mostly at temperatures below the β‐relaxation region, occurred. However, a partial or total suppression of segmental motion could be observed above the β‐relaxation temperature, drastically so for the shortest PI chains at elevated silica contents and within or close to the glass‐transition range, because of the covalent anchoring of chain ends to silica domains. Large changes in thermal stability, including a 2.5‐fold increase in the apparent activation energy of degradation, were observed in the hybrids studied. A greater than 100 °C rise in long‐term thermal stability could be predicted for some hybrids with respect to pure PI. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1056–1069, 2002     

Preparation of poly(methyl acrylate‐co‐itaconic anhydride)/SiO2 hybrid materials via the sol–gel process—The effect of the coupling agent,inorganic content,and nature of the catalyst

Transparent poly(methyl acrylate‐co‐itaconic anhydride)/SiO₂ hybrid materials were prepared from methyl acrylate‐itaconic anhydride copolymer and tetraethoxysilane (TEOS) with the coupling agent (3‐aminopropyl)triethoxysilane (APTES) via a sol–gel process. The covalent bonds between the organic and inorganic phases were introduced by the in situ aminolysis of the itaconic anhydride units with APTES forming a copolymer bearing a triethoxysilyl group. These groups subsequently were hydrolyzed with TEOS and allowed to form a network. These reactions were monitored by Fourier transform infrared analysis. The amount of APTES had a dramatic influence on the gel time and sol fraction. The effect of APTES, the inorganic content, and the nature of the catalyst on the thermal properties and morphology of the hybrid materials were studied by differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy, and atomic force microscopy. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 321–328, 2000     

Silica–Polypyrrole Hybrids as High‐Performance Metal‐Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media

Constructing inorganic–organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO₂–polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO₂ /PPy NTs–CFs) as inexpensive and high‐performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO₂ and PPy, the SiO₂ uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal‐free SiO₂ /PPy NTs–CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long‐term durability.     

Organic–inorganic hybrid materials. I. Characterization and degradation of poly(imide–silica) hybrids

Poly(imide–silica) hybrid materials with covalent bonds were prepared by (3-aminopropyl)methyldiethoxysilane (APrMDEOS) terminated amic acid, water, and tetramethoxysilane (TMOS) via a sol–gel technique. Infrared (IR), ²⁹Si and ¹³C CP/MAS nuclear magnetic resonance (NMR) spectroscopy, and thermogravimetric analysis (TGA) were used to study hybrids containing various proportions of TMOS and hydrolysis ratios. The microstructure and chain mobility of hybrids were investigated by proton spin–spin relaxation T₂ measurements. The apparent activation energy E_a for degradation of hybrids in air was studied by the van Krevelen method. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 2275–2284, 1999     

TEOS–colloidal silica–PDMS‐OH hybrid formulation used for stone consolidation

The consolidation of materials concept, which consists of introducing a chemical substance (consolidant) into degraded stone, has been applied to architectural conservation. Silicon compounds such as tetraethoxysilane (TEOS) are frequently used as a base for commercial consolidant formulations due to their ability to form a siloxane polymer such as SiO₂. However, the silica xerogels deposited into the stone show poor performance and the gels obtained are non‐porous and tend to crack during the drying stage. In order to avoid the fractures and to improve gel properties, we propose the synthesis of a hybrid consolidant based on TEOS and fillers such as colloidal silica (200 nm in diameter) and hydroxy‐terminated polydimethylsiloxane (PDMS‐OH). Both additives enhance gel properties such as porosity and elasticity, leading to the formation of non‐fractured and permeable gels. Characterization of the hybrid xerogel was carried out by nitrogen adsorption and ²⁹Si MAS‐NMR. The properties of the hybrid xerogels were compared with those prepared from a formulation based on TEOS (T‐ME) with a composition similar to a commercial product. In order to evaluate the effectiveness of the hybrid consolidant, it was applied to tuff‐stone of historical monuments in the city of Guanajuato, Mexico. The tuff‐stone was also treated with the formulation T‐ME. Both treatments were studied by determining the percentage of consolidant deposited, evaluating changes in porosity and hardness of the treated stone. The applicability of the hybrid consolidant for the decayed tuff‐stone is under study. Copyright © 2010 John Wiley & Sons, Ltd.     

Acrylic polymer/silica hybrids prepared by emulsifier‐free emulsion polymerization and the sol–gel process

Acrylic polymer/silica hybrids were prepared by emulsifier‐free emulsion polymerization and the sol–gel process. Acrylic polymer emulsions containing triethoxysilyl groups were synthesized by emulsifier‐free batch emulsion polymerization. The acrylic polymer/silica hybrid films prepared from the acrylic polymer emulsions and tetraethoxysilane (TEOS) were transparent and solvent‐resistant. Atomic force microscopy studies of the hybrid film surface suggested that the hybrid films did not contain large (e.g., micrometer‐size) silica particles, which could be formed because of the organic–inorganic phase separation. The Si? O? Si bond formed by the cocondensation of TEOS and the triethoxysilyl groups on the acrylic polymer increased the miscibility between the acrylic polymer component and the silica component in the hybrid films, in which the nanometer‐size silica domains (particles) were dispersed homogeneously in the acrylic polymer component. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 273–280, 2006     

Unusual inorganic phase formation in ultraviolet‐curable organic–inorganic hybrid films

Inorganic–organic hybrid materials were prepared with a cycloaliphatic epoxide adduct of linseed oil with tetraethylorthosilicate (TEOS) oligomers via a cationic UV‐curing process. The TEOS oligomers were prepared in the presence of water and ethanol with hydrochloric acid as a catalyst. The TEOS oligomers were characterized with ¹H and ²⁹Si NMR and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. Hybrid films were cured, and the dynamic mechanical and thermal properties of the hybrid films were evaluated as a function of the TEOS oligomer content. The morphology of the hybrid films was examined with atomic force microscopy, transmission electron microscopy, and small‐angle light scattering. The microscopy and dynamic mechanical data indicated that the hybrid films were heterogeneous materials with various inorganic particle sizes dispersed within the organic matrix. In addition, ²⁹Si solid‐state NMR spectroscopy was used to investigate the coupling between the silicate region and organic regions. A schematic model is proposed to address structural features of hybrid materials. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1607–1623, 2005     

Synthesis and characterization of UV‐curable phosphorus containing hybrid materials prepared by sol–gel technique

In this study, a series of ultraviolet (UV)‐curable organic–inorganic hybrid coating materials containing phosphorus were prepared by sol–gel approach from acrylate end‐capped urethane resin, acrylated phenyl phosphine oxide oligomer (APPO), and inorganic precursors. TEOS and MAPTMS were used to obtain the silica network and Ti:acac complex was employed for the formation of the titania network in the hybrid coating systems. Coating performance of the hybrid coating materials applied on aluminum substrates was determined by the analysis techniques, such as hardness, gloss, impact strength, cross‐cut adhesion, taber abrasion resistance, which were accepted by international organization. Also, stress–strain test of the hybrids was carried out on the free films. These measurements showed that all the properties of the hybrids were enhanced effectively by gradual increase in sol–gel precursors and APPO oligomer content. The thermal behavior of the hybrid coatings was investigated by thermogravimetric analysis (TGA) analysis. The flame retardancy of the hybrid materials was examined by the limiting oxygen index (LOI); the LOI values of pure organic coating (BF) increased from 31 to 44 for the hybrid materials containing phosphorus (BF‐P:40/Si:10). The data from thermal analysis and LOI showed that the hybrid coating materials containing phosphorus have higher thermal stability and flame resistance properties than the organic polymer. Besides that, it was found that the double bond conversion values for the hybrid mixtures were adequate in order to form an organic matrix. The polycondensation reactions of TEOS and MAPTMS compounds were also investigated by ²⁹Si‐NMR spectroscopy. SEM studies of the hybrid coatings showed that silica/titania particles were homogenously dispersed through the organic matrix. In addition, it was determined that the hybrid material containing phosphorus and silica showed fibrillar structure. Copyright © 2009 John Wiley & Sons, Ltd.