Fluorinated Copolymer-Oxide Hybrids

A fluorinated copolymer/metal oxide hybrid is fabricated by refluxing a high hydroxyl content fluorinated copolymer with tetraethoxysilane. The resulting organic-inorganic hybrids are transparent throughout the entire compositional range if processed with HCl as a catalyst. They exhibit a continuous variation in hardness, hydrophobicity, and abrasion resistance, intermediary between the properties of the pure polymer and that of a silica gel. The catalyst has a strong influence over the microstructure of the hybrid. ²⁹Si MAS-NMR indicates the presence of highly condensed silica clusters within the structure of the hybrid. If a Nd(III) alkoxide is used instead of TEOS, a Nd ³⁺-doped fluoropolymer is obtained. These results indicate that when a fluorinated copolymer contains groups amenable to hydrolysis and condensation, cross-linking with a metal alkoxide is possible, leading to an interesting families of hybrids.     

Physical Properties of Sol-Gel Coatings

One of the most important applications of sol-gel technology is the fabrication of coatings. This is because of the possibility of applying oxide coatings with practically all types of chemical compositions at low ambient temperatures on many substrates of various shapes through the use of liquid solutions. Both oxides and different types of organic-inorganic hybrid coatings have been reported. Both oxides and hybrid coatings are usually amorphous at ambient temperatures but some oxides can be converted to the crystalline phase with heating. Regardless of the intended applications of the coatings their physical properties are always of importance. For instance, an anti-reflective coating for an automobile mirror is of little practical value unless it is fairly scratch-resistant. In this review which covers published information in the past fifteen years, some of the more important results of physical properties of sol-gel derived coatings are discussed firstly for oxides and then for organic-inorganic hybrids. It appears that properties such as the hardness of oxide coatings are inadequate unless the heat-treatment temperatures are in excess of about 400°C. The hybrid coatings, especially when they contain a dispersed phase of a hard solid like colloidal silica, can be processed at temperatures below about 150°C and can improve the performance of organic plastics such as the polycarbonates. There is insufficient scientific understanding of the relationship between physical properties and other interdependent variables such as processing conditions, chemistry and coating thickness. More research in this area will undoubtedly contribute to the availability of better and new coatings via the sol-gel approach.     

Some Factors Governing the Coating of Organic Polymers by Sol-Gel Derived Hybrid Materials

Organic-inorganic hybrid materials can exhibit some properties of organic polymers, such as toughness and elasticity, and/or that of ceramics, such as chemical stability and hardness. In this review, we discuss the main factors that should be considered when coating a polymeric substrate with a sol-gel derived organic-inorganic hybrid material. The effects of the solution characteristics, the polymer substrate chemistry and preparation, the application process and materials characteristics are considered. Examples of commercial and published systems are discussed. We find that due to the wide diversity of the systems investigated, it is difficult to be specific in recommending guidelines applicable to all systems. However, some general considerations can be made that should be useful in the design of functional hybrid coatings aimed at improving the characteristics of polymeric surfaces.     

Structures, Properties and Potential Applications of Ormosils

Ormosils are organic-inorganic hybrid solids in which the organic component may be chemically bonded to a silica matrix. Somewhat similar to inorganic silicate glasses, the structure of the silica network can be modified by the presence of organic groups. The resulting properties of the Ormosils are then governed by the type and concentration of organics used. Examples are presented in which the mechanical, electrical and optical properties of selected Ormosils can be influenced by organic groups. For instance, small amounts of polydimethylsiloxane (PDMS) added to a solution of TEOS will give an Ormosil about ten times harder than the hardest organic polymer. Larger amounts of PDMS (20%) will now yield an Ormosil which is as rubbery as organic rubber. Ormosils in which the organic and inorganic constituents are covalently bound to each other are the focus of this critical review. The potential applications of such Ormosils are discussed.     

Long-Term Protection of the Last Judgment Mosaic in Prague

A sol-gel coating was used in the long-term protection of the 14th Century mosaic situated above the gates of St. Vitus cathedral, in the center of Prague Castle. The choice of a sol-gel coating is the result of a research effort involving both on-site testing in Prague and accelerated ageing of various polymers and sol-gel materials in the laboratory. The coating selected for treatment of the entire 13 m × 10 m mosaic is a multi-layer system in which an organic-inorganic sol-gel layer is placed between the glass substrate and a fluoropolymer coating. This coating combination performed very well in an accelerated weathering chamber as well as during onsite testing. Since the top layer is scheduled to be removed and re-applied periodically, it is hoped that this concept will allow long term protection to the largest outdoors mosaic north of the Alps. On-site application of the coatings on the entire mosaic started in 1998 and will be completed in 2000.     

Synthesis of PDMS-Based Porous Materials for Biomedical Applications

Polydimethylsiloxane (PDMS) and tetraethoxysilane (TEOS)-based porous organically modified silicates (ORMOSILs) for biomedical applications were synthesized through a sol-gel process, using sucrose particles as templates. These materials were characterized by ²⁹Si CP-MAS NMR spectroscopy, thin film X-ray diffraction, and scanning electron microscopy. Their bioactivity was evaluated using a simulated body fluid (SBF) of Kokubo recipe. These materials had a bimodal porous structure with pores of 300–500 m and 10–50 m in diameter. NMR showed that the silanol groups of the PDMS chain cross-linked to silica derived from the hydrolysis and condensation of TEOS. The samples containing Ca(II) exhibited apatite deposition on the pore walls within 3 days in SBF.     

The Role of Fe in the Thermal Stabilization of Ormosils

The thermal stability of organically modified silicates (Ormosils) is limited by that of their organic constituent. In the case of the polydimethylsiloxane (PDMS)-silica hybrids, degradation of the PDMS begins around 250°C, which restricts their range of applications. Several strategies have been used to stabilize PDMS, such as substitution of the methyl groups by phenyl groups. Another strategy is the addition of very small amounts (typically about 1 wt%) of iron. This technique has been used successfully in the stabilization of liquid silicones. In the case of PDMS-SiO₂ hybrids, this small dopant concentration has a very significant effect on the thermal stability, increasing it by up to 200°C. However, very little is known of the mechanism of stabilization. In the present work we carry out an investigation of the materials in order to explain the mechanisms involved. The materials were investigated by liquid and solid state ²⁹Si NMR, BET, SEM, TGA and DMA. The data indicates that Fe plays a most significant role at the solution stage already. The structures of the hybrids with and without Fe are very different. In other words, the thermal stabilization mechanism appears to be due not so much a direct redox process taking place in the solid state (as in the case of liquid silicones) but rather, to differences in chemical structures induced by Fe in the liquid. Specifically, PDMS chain cleavage and increased cross-linking to SiO₂ appear to be the cause of the thermal stabilization.     

Sol-Gel Coatings for the Protection of Brass and Bronze

The effectiveness of sol-gel Ormosil coatings as barriers coatings has already been demonstrated, and it is natural to assume that such coatings can play a unique role in art conservation, where object corrosion and decay are often a major issue. The main feature of ormosil coatings that would make them preferable to polymers is their potentially higher stability to ultra-violet radiation, controlled porosity and good adhesion to many different substrates. The permeability to various gases can also be tailored with changes in the chemical structure. In previous work, we have applied the sol-gel process as part of a multiplayer coating in the conservation of the Last Judgment mosaic in Prague. In the present work, we explore the use of sol-gel organic-inorganic hybrid coatings on various copper alloy substrates frequently encountered in art conservation.     

New Lutetium Silicate Scintillators

Cerium-doped lutecium orthosilicate (LSO) is the most promising scintillator discovered in almost five decades. It exhibits a unique combination of important properties for x and gamma-ray spectroscopy: high density, fast decay, and large light yield. However, the practical use of LSO is hindered by difficulties related to its fabrication as a single crystal by the Czochralski method. We report on the usefulness of the sol-gel process in obtaining lutecium silicate scintillators. Upon appropriate drying and firing, lutetium silicate crystals can be grown in a silica matrix. The bulk, polycrystalline transparent scintillators are characterized by XRD, optical absorption, light decay measurement and gamma-ray spectral response. Their properties are comparable to that of traditional LSO single crystals.     

Detection of Gaseous Molecules by Capacitance Variation in Organically Modified Silicate (Ormosil) Films

The sorption properties of organically modified silicates (Ormosil) and Ormosil/TEOS films were investigated using a capacitor system. The accuracy of the capacitance measurement was less than 0.05 pF. The capacitance variation obtained was converted to a form of the partition coefficient which is related to the sorption property of the detector materials. The sorption properties can be explained by the reactivity of hydrogen-bonds of the chemical groups in Ormosils.The Karhunen-Loeve expansion, which is a pattern recognition technique, was used to obtain information on the hydrogen-bonding interaction between Ormosils, Ormosil/TEOS and four different gases. The character of the sorption properties of Ormosils varied widely from basic (amino and cyano groups) to acidic (silanol group). The patterns of 4 Ormosils and TEOS from the viewpoint of the acidity and basicity are similar to those shown by other organic detection-coatings.