Transparent Hybrid Materials Research Articles

Synthesis and characterisation of silica hybrids based on poly(ε-caprolactone-b-perfluoropolyether-b-ε-caprolactone)

Poly(ε-caprolactone-b-perfluoropolyether-b-ε-caprolactone) (PCL–PFPE–PCL) triblock copolymers having hydroxy end groups were readily functionalised with triethoxysilane end groups by reactions with 3-isocyanatopropyltriethoxysilane. Organic–inorganic hybrids were prepared by using the sol–gel process in the presence of tetraethoxysilane and hydroxy or triethoxysilane terminated PCL–PFPE–PCL. Fully transparent hybrid materials with high content of organic matter were obtained only in the case of alkoxysilane functionalised copolymers. For such systems the PCL–PFPE–PCL copolymer was so intimately mixed with the inorganic network to prevent crystallisation of the PCL segments. The progress of the sol–gel reaction was limited by the early vetrification of the reactive system, while the interpenetration of the organic phase was enhanced by curing the samples at 100 °C.

Properties of PVA-PSA hybrid materials prepared through the incorporation of polysilicic acid (PSA) into polyvinyl alcohol

A quick method of preparing transparent organic-inorganic hybrid material was studied. The hybrid, PVA/PSA, was prepared through incorporating the nanoscaled polysilicic acid (PSA) obtained through hydrolysis and condensation of metasilicate salt directly into a polyvinyl alcohol (PVA). The interfacial force, microstructure, and dynamic mechanical property of the hybrid were studied by means of spectroscopy (FTIR, X-ray diffraction and solid-state 29Si NMR) and dynamic mechanical analysis, and the results were compared with that of the hybrids, PVA/TEOS, prepared through the traditional sol-gel process. It was found that the microstructure of PVA/PSA was different from that of PVA/TEOS because of the different preparation methods. The structures of the crystals in both hybrids were similar to that of the pure PVA. Other physical properties, such as Tg, storage modulus, tensile strength and solvent resistance of the PVA/PSA hybrid, were improved significantly with the addition of the silica content. The extent of improvement was a little lower than that for the PVA/TEOS.

Properties of hybrid materials derived from hydroxy-containing linear polyester and silica through sol-gel process. I. Effect of thermal treatment

The transparent hybrid material, HLP/SiO2, was prepared by an in situ sol–gel process of tetraethoxysilane (TEOS) at 30°C in the presence of hydroxy-containing linear polyester (HLP) obtained by ring-opening reaction of diglycidyl ether of bisphenol A (DGEBA) with adipic acid under the catalyzation of triphenylphosphine (TPP). The hetero-associated hydrogen bonds between the HLP and the residual silanol of silica in the hybrids were investigated by FTIR spectroscopy. Upon heating the hybrid, the interfacial force between the HLP matrix and the silica network changed from hydrogen bonds into covalent Si—O—C bonds through dehydration of hydroxy groups in HLP with residual silanol groups in the silica network. The existence of covalent Si—O—C bonds was proved by solid-state 29Si-NMR spectra. Other properties such as tensile strength, glass transition temperature (Tg ), solubility, and thermal stability of the hybrids before and after heat treatment were studied in detail. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1179–1190, 2000

Photoreduction of Europium (III) in Sol-Gel Derived Inorganic-Organic Hybrid Materials

Eu2+-doped inorganic-organic hybrid materials, which are potentially suitable for a tunable laser in the near ultra violet and blue region, were prepared through the photoreduction of Eu3+ ions in the materials under the irradiation of the fourth harmonic wave light (266 nm) of the Nd:YAG laser. The hybrid materials doped with Eu3+ ions were prepared from Si(OCH3)4, CH3Si(OCH3)3, EuCl3 and chloropropyltrimethoxysilane (CPTM). After the prehydrolized silica sol was added to the Eu3+-containing solution, Eu3+-doped transparent inorganic-organic hybrid material was obtained by drying at 50°C. The emission peak around 450–475 nm due to the charge transfer transition (5d-4f) of Eu2+ ions increased with the laser irradiation time. Eu3+ ions were effectively photoreduced to Eu2+ ions in pore-free materials prepared at high CPTM to Eu3+ ratios. Eu2+ ions were generated by the photodecomposition of the bond between Eu3+ and Cl (Cl− or Cl(CH2)3 in CPTM).

Morphological investigation of hybrid materials composed of phenolic resin and silica prepared by in situ polymerization

Morphological investigations for hybrid materials composed of phenolic resin and silica, prepared by in situ polymerization of silicon alkoxide, were performed using TEM. Irregularly shaped silica particles a few tens of nanometres in size, composed of hyper-fine particles, are homogeneously dispersed in the transparent hybrid materials forming a partial or uniform silica network depending on the silica content. In the translucent hybrid materials, the dispersion of complex silica aggregates ( ca. 100 nm) were observed uniformly throughout the sample. In the opaque hybrid materials, silica particles of micrometre range were found to be incorporated uniformly, although the interface was uneven. Such large silica particles embedded in the hybrid material contain both silicon oxide and phenolic resin in an interpenetrating network of both components. It was considered that these different morphologies observed in transparent∼opaque hybrid materials are caused by freezing-in the silica aggregation at different stages in the course of phase-separation between phenolic resin and silica formed in situ. These morphological characteristics were also compared with those of conventional phenolic resin/silica glass composites.

Atomic Force Microscopy Study of Organic−Inorganic Hybrid Materials

A series of monolithic poly[methyl methacrylate-co-3-(trimethoxysilyl)propyl methacrylate]−silica hybrid materials have been prepared via the sol−gel reactions. The fracture surfaces of the materials were systematically examined with atomic force microscopy (AFM) as a function of the silica content from ∼23 to 100 vol %. For the transparent materials, the AFM image of the sample at a low silica content of 23 vol % is very smooth and essentially featureless while those at higher silica contents show relatively greater surface roughness and development of domains of various shapes and sizes. In sharp contrast, the optically translucent and phase-separated samples exhibit significantly higher surface roughness and larger domain size than all the transparent hybrid materials, suggesting that the transparent materials might have little or no organic−inorganic phase separation.

Biodegradable and biocompatible inorganic?organic hybrid materials. I. Synthesis and characterization

The hydroxyl or vinyl end-groups of linear or three-arm star-shaped poly(ε-caprolactone) (PCL) chains have been derivatized into triethoxysilane groups reactive in the sol-gel process. New transparent hybrid materials that combine tetraethylorthosilicate (TEOS) and PCL known for biodegradability and biocompatibility have accordingly been prepared. The sol-gel process is, however, limited by the early vitrification of the reactive system. However, thermal posttreatment can overcome these diffusional and/or kinetic limitations as assessed by a set of analytical methods. The thermal stability of PCL is improved by incorporation into the silica network. Conversely, the thermal stability of the ceramer depends on the effective PCL content. The extent of PCL incorporation into the silica network depends on PCL molecular weight, number, and reactivity of the PCL functional groups. IR spectroscopy has shown that hydrogen bonding occurs between the ester groups of PCL and residual OH groups of the silicate component. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 2295–2309, 1997

Poly(methyl methacrylate)–titania hybrid materials by sol–gel processing

Sol–gel derived poly(methyl methacrylate)–titania hybrid materials were synthesized by using acrylic acid or allyl acetylacetone (3-allyl-2,4-pentanedione) as coupling agent. Titanium butoxide modified with acrylic acid (or titanium isopropoxide modified with allyl acetylacetone) was hydrolysed to produce a titania network, and then poly(methyl methacrylate) (PMMA) chains, formed in situ through a radical polymerization, were chemically bonded to the forming titania network to synthesize a hybrid material. Transparent hybrid materials with different contents of titania were achieved. With increase of the titania content, the colours of the products changed from yellow to dark red. The synthesis process was investigated step by step by using Fourier transform–infrared spectroscopy, and the experimental results demonstrated that acrylate or acetylacetonato groups bound to titanium remain in the final hybrid materials. The thermal stability of the hybrid materials was considerably improved relative to pure PMMA. Field emission scanning electron microscopy analyses showed the hybrid materials are porous and pore diameters vary from 10–100 nm. The hybrid materials using allyl acetylacetone as coupling agent exhibited a thermochromic effect that neither pure PMMA nor titania exhibit.

Hybrid materials based on the reaction of polyorganophosphazenes and SiO2 precursors

New molecular composite materials can be prepared based on an inorganic oxide network and an organic polymer. The polymeric component generally requires low process temperatures, due to the presence of the organic backbone or side groups. A sol-gel process therefore is suitable for synthesizing the inorganic component by dissolving soluble polymers into sol-gel precursor solutions in order to obtain ceramic and polymeric solid phases. In this work polyorganophosphazenes were used because they have many technologically interesting properties (chemical, optical, electrical, mechanical). The methods to obtain covalent bonds between polymer and inorganic network and to obtain homogeneous, transparent hybrid materials without phase separation were studied. It was possible to avoid phase separation by preparing phosphazenes containing free hydroxyl functions and by adequately choosing the experimental conditions.

Poly(Methyl Methacrylate)-Titania Hybrid Materials by Sol-Gel Processing

Sol-gel derived Poly(methyl methacrylate)-titania hybrid materials were synthesized by using acrylic acid or allyl acetylacetone (3-allyl-2,4-pentanedione) as coupling agents. Titanium butoxide modified with acrylic acid (or titanium isopropoxide modified with allyl acetylacetone) was hydrolyzed to produce a titania network, and then poly (methyl methacrylate) (PMMA) chains formed in situ through a radical polymerization were chemically bonded to the forming titania network to synthesize a hybrid material. Transparent hybrid materials with different contents of titania were achieved. With the increase of the titania content, the colors of the products changed from yellow to dark red. The synthesis process was investigated step by step by using FTIR spectroscopy, and the experimental results demonstrated that acrylate or acetylacetonato groups bound to titanium remain in the final hybrid materials. The thermal stability of the hybrid materials was considerably improved relative to pure PMMA. Field emission scanning electron microscopy (FE-SEM) analyses showed the hybrid materials are porous and pore diameters vary from 1 Onm to I 00nm. The hybrid materials using allyl acetylacetone as the coupling agent exhibited thermochromic effects that both pure PMMA and titania do not have.

A fast convenient method to prepare hybrid sol-gel materials with low volume-shrinkages

We present a simple and fast method for the synthesis of polyacrylates-silica hybrid materials with significantly low volume shrinkages through the sol-gel reactions of tetraethyl orthosilicate and 2-hydroxyethyl methacrylate along with the free-radical polymerization of the acrylate monomer. The volume shrinkage from the processible sol to the final product was about 6–20% for the hybrid materials having the silica contents up to about 50 wt-%. As a result of the low shrinkage, crack-free, transparent and monolithic hybrid materials of relatively large sizes can be prepared within a short period of 6 to 12 hours. The formation of covalent bonding between the organic and the silica components in the hybrid materials was demonstrated. Thermal stability of the polyacrylate component in the hybrid materials were found to be higher than that of the bulk polymer. Other vinyl polymers such as poly(methyl methacrylate) and polyacrylonitrile have also been incorporated into the inorganic silica sol-gel matrix by using this method.

An internal doping method for the preparation of transparent hybrid xerogels containing nano-sized iron particles

Sol-gel copolymerization of iron tricarbonyl-2-(triisopropoxysilyl)-1,3-butadiene with 1,6-bistriethoxysilylhexane and 1,4-bistriethoxysilylbenzene followed by drying produced bridged polysilsesquioxane xerogels. These porous, transparent hybrid materials containing the iron metal precursor were irradiated (UV) and heated under vacuum resulting in the deposition of nano-sized iron particles doped in the xerogels. EDAX and electron diffraction techniques were used to characterize the iron phases. The TEM images of these doped xerogels provided additional information regarding the domain size of the iron phase.

Synthesis, characterization, and properties of new polystyrene-SiO2 hybrid sol-gel materials

A new family of organic-inorganic hybrid materials has been prepared by incorporating polystyrene structure units covalently into the SiO2 glass network via the sol-gel approach. The polymer precursors were synthesized by free-radical copolymerization of styrene with 3-(trimethoxysilyl)propyl methacrylate (MSMA) at various feeds. These copolymers were then hydrolyzed and co-condensed with tetraethyl orthosilicate in tetrahydrofuran at room temperature to afford monolithic polystyrene-SiO2 hybrid sol-gel materials having SiO2 contents of 15 to 84% by weight. The hybrid materials derived from the copolymers with MSMA contents greater than 22 mol% have excellent optical transparency. In these transparent hybrid materials, the polymer chains should be uniformly distributed in and covalently bonded to the amorphous SiO2 matrices. The bulk properties of these materials including density, refractive index, and hardness were found to be related to their molecular compositions and can be tailored by varying the polymer contents.

Synthesis and Characterization of New Alumina and Titania-Containing Hybrid Network Ceramer Materials from Sol-Gel Processing

Abstract Transparent hybrid materials have been prepared by incorporating either an alumina or titania alkoxide sol with triethoxysilane end-capped polytetramethylene oxide (PTMO) oligomer. In order to avoid undesirable precipitation after the addition of water, a β-dicarbonyl ligand, ethyl acetoacetate, was used. Triethoxysilane endcapped polytetramethylene oxide with a molecular weight of 2000 (g/mol) was chosen to react with either the alumina or titania sol to demonstrate the features of the reaction scheme. The extent of reaction leading to network formation has been qualitatively followed by infrared spectroscopy. A series of solid films were prepared by varying the molar ratio of either aluminum tri(sec-butoxide) or titanium tetraisopropoxide to ethyl acetoacetate, and the weight fraction of alumina or titania to that of PTMO. The refractive index as well as the general structure-property behavior of these hybrid materials were studied.

Structure-property behavior of new hybrid materials incorporating oligomeric poly(tetramethylene oxide) with inorganic silicates by a sol-gel process

Novel transparent hybrid materials incorporating triethoxysilane endcapped poly(tetramethylene oxide) with tetramethoxysilane have been successfully prepared by a sol-gel process. The molecular weight of PTMO has been varied to study its effect on the structure-property behavior of these hybrid materials. Mechanical properties and dynamic mechanical behavior have been measured; small angle X-ray scattering (SAXS) has been utilized to obtain structural information. Based on the experimental results, a simplified morphological model has been suggested to describe these new hybrid systems.