Sulfur-containing silsesquioxane hybrids with high refractive index and high Abbe number

Novel sulfur-containing silsesquioxane nanoparticles, (R_S–SiO_1.5) _n , having uniform size distribution, good solubility, and relatively high refractive index were synthesized by hydrolytic condensation of a triethoxysilane precursor derived from glycidol, followed by the esterification with sulfur-containing acid chlorides. Esterification of the water-soluble silsesquioxane nanoparticles with 3-(methylthio)propionyl chloride afforded silsesquioxane hybrid with a high density of chemically bonded peripheral methyl thioether groups, which was characterized by ¹H, ¹³C NMR, Fourier transform infrared spectroscopy, and thermogravimetric analysis measurements. The resulting product was soluble in various organic solvents, such as CHCl₃, acetone, tetrahydrofuran, dimethyl formamide, and dimethyl sulfoxide. The size of the sulfur-containing nanoparticles evaluated by X-ray diffraction was 2.1 nm. Transmission electron microscopy, gel permeation chromatography, and dynamic light scattering measurements indicated the formation of the nanoparticles having relatively narrow size distribution with an average particle diameter of less than 3 nm without aggregation. The sulfur content of the methyl thioether-containing silsesquioxane hybrid analyzed by elemental analysis was 16.1 %, which led to relatively high refractive index (n _D?=?1.588) and high Abbe number (34.4). Two sulfur-containing silsesquioxane hybrids with peripheral thiophene and phenyl thioether moieties were also obtained by the same procedure, and resulting hybrids showed high refractive indices of 1.605 and 1.627, and Abbe numbers of 31.8 and 24.3, respectively.     

Concentration dependent refractive index of a binary mixture at high pressure

In the present work binary mixtures of varying concentrations of two miscible hydrocarbons, 1,2,3,4-tetrahydronaphtalene (THN) and n-dodecane (C12), are subjected to increasing pressure up to 50 MPa in order to investigate the dependence of the so-called concentration contrast factor (CF), i.e., (?n/?c)(p, T), on pressure level. The refractive index is measured by means of a Mach-Zehnder interferometer. The setup and experimental procedure are validated with different pure fluids in the same pressure range. The refractive index of the THN-C12 mixture is found to vary both over pressure and concentration, and the concentration CF is found to exponentially decrease as the pressure is increased. The measured values of the refractive index and the concentration CFs are compared with values obtained by two different theoretical predictions, the well-known Lorentz-Lorenz formula and an alternative one proposed by Looyenga. While the measured refractive indices agree very well with predictions given by Looyenga, the measured concentration CFs show deviations from the latter of the order of 6% and more than the double from the Lorentz-Lorenz predictions.     

Mesoscale organization of nearly monodisperse flowerlike ceria microspheres

Nearly monodisperse flowerlike CeO2 microspheres were synthesized via a simultaneous polymerization-precipitate reaction, metamorphic reconstruction, and mineralization under hydrothermal condition as well as subsequent calcination. The obtained CeO2 microsphere consists of 20-30 nm thick nanosheets as petals. It has an open three-dimensional (3D) porous and hollow structure and possesses high surface area, large pore volume, and marked hydrothermal stability. It can be doped easily after synthesis, and the initial 3D texture is maintained. The controlling factors and a possible formation mechanism are discussed in detail. This novel material can be used as a support for catalysts with various purposes. With CuO loaded on flowerlike CeO2, the catalytic activities and hydrothermal stability of Cu/CeO2 for ethanol stream reforming were examined. At 300 degrees C, the H2 selectivity reached a maximum value of 74.9 mol %, while CO was not detected within the precision of the gas chromatogram. It produced a hydrogen-rich gas mixture in the wide temperature range (300-500 degrees C) and showed excellent hydrothermal stability at high temperature (550 degrees C), which is a good choice for ethanol processors for hydrogen fuel cell applications.     

Synthesis and self-assembly of nearly monodisperse nanoparticles of a naturally occurring polymer

Nearly monodisperse nanoparticles have been synthesized based on a naturally occurring polymer of hydropropylcellulose (HPC) using precipitation polymerization method. It is found that when the polydispersity index value of the HPC nanoparticles is less than 1.10, the HPC particles can self-assemble into an ordered structure, displaying bright colors. UV-visible spectroscopy reveals that the color shifts to a lower wavelength as the interparticle distance decreases following the Bragg diffraction equation. The HPC nanoparticle assembly in water has been further stabilized by covalently bonding neighboring particles to form a three-dimensional network. This network contains a large amount of water similar to a conventional bulk gel but displays colors as a result of its ordered structure.     

Preparation of thin silica films with controlled thickness and tunable refractive index

Silica films with controlled thickness and refractive index have been formed by the sequential adsorption of a cationic polyelectrolyte and silica sols. The conditions used to prepare the sol were varied, and allowed films with refractive indices as low as 1.16 to be obtained. The sequential adsorption technique allows the thickness of these films to be controlled in increments of 5-10 nm, depending on the desired refractive index. Scanning electron microscopy revealed that a low packing density of constituent silica particles was responsible for the low indices of these films. The as-adsorbed films are thermally robust; calcination at 500 degrees C resulted in only very small decreases in film thickness (by < or =1.8%) and refractive index (to as low as 1.14). After calcination, the silica films remained hydrophilic and sorbed water vapor from the atmosphere. As a result, the refractive indices of these films increased with increasing relative humidity (RH). The dependence of the refractive index on RH was eliminated by treating the calcined films with trimethylchlorosilane.     

Size-controlled synthesis of Au/Pd octopods with high refractive index sensitivity

Au/Pd octopods, nanostructures with eight branches and a primarily Au interior, have been synthesized as size-controlled samples through the manipulation of seed-mediated co-reduction. The position of their localized surface plasmon resonance can be controllably tuned throughout the visible and near-infrared regions, and this response is correlated with the structural features (branch length and tip width) of the octopods. These Au/Pd octopods were also found to be highly sensitive to changes in the local refractive index of the surrounding media and suitable substrates for surface enhanced Raman spectroscopy. These findings, coupled with their unique composition, highlight the multifunctional capabilities of the Au/Pd octopods and provide insight into the optical properties of architecturally controlled bimetallic nanostructures.     

Peculiarities of formation of optically transparent photocurable compound adhesive with high refractive index

The peculiarities of the formation of an optically transparent, photocurable composition with a high refractive index based on epoxy resin are studied. The optimal ratios of the components at which the fastest and most complete formation of three-dimensional structures occurs are established.     

Synthesis of silyl-functionalized oligothiophene-based polymers with bright blue light-emission and high refractive index

In this paper, we report the synthesis of partially conjugated polymers with a silyl-group-substituted oligothiophene and a short alkyl chain in the main chain by hydrosilylation polymerization and describe their optical properties such as luminescence and refractive index. The obtained polymers are found to have good solubility and processability. Moreover, the high steric hindrance of the silyl-group can inhibit the π-π interaction and intermolecular aggregation of the polymers. Hence, the emission of the obtained polymers was similar to that of the corresponding silyl-group-substituted oligothiophene. The polymers exhibit intense light blue fluorescence under UV irradiation and a high refractive index in the visible light region.     

Fabrication of transparent Pu/Zro2 nanocomposite coatings with high refractive index

<正>Transparent ZrO_2-polyurethane nanocomposites with high refractive index were prepared by dispersing ZrO_2 nanoparticles in a polyurethane matrix via ligand molecule engineering.TEM showed that the inorganic particles were well dispersed within the polymeric network with no significant macroscopic agglomeration.By controlling the phase separation it was possible to obtain transparent zirconia nanostructured coatings,characterized by improved mechanical and thermal properties.UV-Vis spectra indicated that the coatings still maintained transparency in the visible light.The refractive index of the UV-cured films depends linearly on the ZrO_2 content and varies from 1.475 to 1.625(20 wt%) at 633 nm.These coatings could find advanced applications in coatings of optical and electronic devices.     

Quantitative characterization of optical anisotropy in high refractive index films

Waveguide coupling measurements of polymers have largely concentrated on the application of mode analysis to the study of thin supported films (such as spin coatings). The use of prism coupling to study thick, freestanding polymer films, however, has not been reported. In this paper, the ability of prism coupling to characterize the three-dimensional optical properties of thick, freestanding polymer films and sheets is demonstrated. A modified prism coupling procedure is described that allows the determination of all three principal refractive indices in thick, three-dimensionally anisotropic freestanding films. A Metricon prism coupler is used in a manner similar to an Abbé refractometer for the measurement of isotactic polypropylene, poly(ethylene terephthalate), PMDA-ODA polyimide, and poly(phenylene sulfide). Three series of PMDA-ODA films are also investigated in this study. The first series has been drawn to different extensions from three-dimensionally random films. The second series has random orientation in the plane of the film but different degrees of planarity with respect to the through direction. The third series are commercial films of varying thickness. These three series of films are compared as to the optical an-isotropy that is developed from the three different fabrication processes. © 1993 John Wiley & Sons, Inc.     

Synthesis of nearly monodisperse polystyrene-polypeptide block copolymers via polymerisation of N-carboxyanhydrides

Primary amine hydrochlorides promote a well-controlled ring-opening polymerisation of Z-L-lysine-N-carboxyanhydride in DMF at 40-80 degrees C; the polystyrene-poly(Z-L-lysine) block copolymers synthesised exhibit a very narrow molecular weight distribution, close to a Poisson distribution.     

Transparent poly(bisphenol A carbonate)-based nanocomposites with high refractive index nanoparticles

Transparent organic-inorganic nanocomposites were successfully synthesized from sulfonic acid-modified poly(bisphenol A carbonate) (SPC) and TiO₂ or ZrO₂ nanoparticles. The dispersibility of nanoparticles was significantly improved by both the surface treatment of nanoparticles with phosphoric acid 2-ethylhexyl esters (PAEH) and the introduction of a sulfonic acid moiety into the PC chain. It was found that in some cases, crystallization of the matrix caused a reduction in transparency. Efficient dispersion of nanoparticles and the absence of crystallization resulted in highly transparent nanocomposites with up to 42 wt% TiO₂ and 50 wt% ZrO₂ nanoparticles. The refractive indices of the nanocomposites based on SPC increased with the increasing amount of nanoparticles. Theoretical equation based on Maxwell-Garnett effective medium theory provided reasonably close estimation of the refractive indices to the experimentally observed values. The prepared nanocomposites had lower thermal stability than the host matrix polymers.     

Preparation of monodisperse polystyrene latices

Summary A series of monodisperse polystyrene latices was prepared by using the direct and the seeding emulsion polymerization methods. The recipes for their preparation are given in full detail. Best results were obtained when using Aerosol MA (a surfactant of the sulfosuccinate series) as the emulsifier. The particle size distributions were evaluated from electron microscopic data. The average size of latex particles ranged from 200 to 950 m. The polydispersity ratios being very near unity and modal frequencies about 95% indicate a very high monodispersity of latex preparations. The reproducibility of the particle size distribution parameters was remarkably good. Significant deviation from theSmith-Ewart mechanism was found. A possible mechanism of the emulsifier action in the formation of monodisperse latices is postulated.

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Zusammenfassung Es wurde eine Serie von monodispersen Polystyrollatices dargestellt. Die experimentellen Bedingungen, unter welchen monodisperse Latices entstehen, wurden untersucht. Die Vorschriften sind genau angegeben. Mit Aerosol MA (einem oberflächenaktiven Mittel der Sulfosuccinatserie) als Emulgator wurden die besten Ergebnisse erhalten. Mittels Elektronenmikroskopie wurde die Verteilung der Teilchengrößen ermittelt. Die durchschnittliche Größe der Latexteilchen lag zwischen 200 und 950 m. Die Polydispersitätsquotienten lagen in unmittelbarer Nähe von 1, und die modalen Frequenzen um 95% indizierten eine sehr hohe Monodispersität der Latexproben. Die Reproduzibilität der Teilchengröße-Verteilung-Parameter war besonders ausgeprägt. Es wurde eine Abweichung vomSmith-Ewart-Mechanismus beobachtet. Der mögliche Mechanismus der Emulgatorwirkung bei Entstehung der monodispersen Latices wurde diskutiert.

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With 7 figures and 8 tables     

Preparation of polymer nanocomposites with “ultrahigh” refractive index

Nanocomposites of lead sulfide and several polymers, especially poly(ethyleneoxide), were prepared by coprecipitation of lead sulfide and polymer, followed by a drying and pressing procedure. Such nanocomposites consist of ca. 90% w/w (or ca. 50% v/v) lead sulfide, of particle dimensions of 2–40 nm. The refractive index of these materials is on the order of 3 and therefore, to the authors' best knowledge, is the highest reported for any polymer composite.     

Cellulose derivative/barium titanate composites with high refractive index,conductivity and energy density

Cellulose - This work deals with hydroxypropyl cellulose (HPC)/barium titanate (BT) composites, having small levels of perovskite-like BT loading, i.e. 0.5–2% and being designed for electric...     

Rayleigh scattering study and particle density determination of a high refractive index TiO2 nanohybrid polymer

We have experimentally carried out a Rayleigh scattering study of a high refractive index TiO(2) nanohybrid polymer. By employing the Rayleigh scattering technique with at least three different wavelengths, we can obtain the Rayleigh ratio of the TiO(2) nanohybrid polymer at each utilized wavelength. These measured Rayleigh ratios are then used to estimate the size of the nanoparticle and determine the number of nanoparticles per unit volume or particle density. Furthermore, this technique can be used to evaluate the dominant size of nanoparticles in the nanohybrid polymer mainly contributed to Rayleigh scattering.     

Preparation of monodisperse ellipsoidal polystyrene particles

A method is described for the preparation of monodisperse ellipsoidal particles of polystyrene in the colloidal size range. Monodisperse polystyrene particles were dispersed in a solution of polyvinyl alcohol. This dispersion was then allowed to form, by evaporation, a thin film of polyvinyl alcohol containing spherical polystyrene particles. Strips of this film were clamped into a metal frame, heated rapidly in an oil bath to 200°C and stretched to a predetermined extent in order to convert the spherical particles into ellipsoids; the film was then cooled. A wide range of axial ratios for a variety of initial particle sizes was obtained by this method.     

The stability of high refractive index polymer materials for high-density planar optical circuits

Owing to the structural flexibility, easy processing and fabrication capabilities, polymers are being increasingly attractive for a variety of optical applications. In order to increase the integration density of such optical circuits, higher index contrasts and, thus, polymers with considerably higher refractive index are essentially needed. An organometallic polymer and a conventional epoxy material are combined to form a compatible high index material. When cured at elevated temperatures, the organometallic polymer decomposes to form a highly dispersed metal oxide phase that imparts high index properties to the polymer films. These hybrid high refractive index polymer films must be stable in patterning of optical waveguide structure for photonic manufacturing. In this paper, we report the stability and optical characterization study of a modified organometallic high refractive index polymer film in manufacturing of optical waveguide devices.