Refractive index changes in amorphous SiO2 (silica) by swift ion irradiation

The refractive index changes induced by swift ion-beam irradiation in silica have been measured either by spectroscopic ellipsometry or through the effective indices of the optical modes propagating through the irradiated structure. The optical response has been analyzed by considering an effective homogeneous medium to simulate the nanostructured irradiated system consisting of cylindrical tracks, associated to the ion impacts, embedded into a virgin material. The role of both, irradiation fluence and stopping power, has been investigated. Above a certain electronic stopping power threshold (∼2.5 keV/nm), every ion impact creates an axial region around the trajectory with a fixed refractive index (around n = 1.475) corresponding to a certain structural phase that is independent of stopping power. The results have been compared with previous data measured by means of infrared spectroscopy and small-angle X-ray scattering; possible mechanisms and theoretical models are discussed.

Plasma-enabled growth of ultralong straight, helical, and branched silica photonic nanowires

This article reports on the lowerature inductively coupled plasma-enabled synthesis of ultralong (up to several millimeters in length) SiO2 nanowires, which were otherwise impossible to synthesize without the presence of a plasma. Depending on the process conditions, the nanowires feature straight, helical, or branched morphologies. The nanowires are amorphous, with a near-stoichiometric elemental composition ([O] / [Si] =2.09) and are very uniform throughout their length. The role of the ionized gas environment is discussed and the growth mechanism is proposed. These nanowires are particularly promising for nanophotonic applications where long-distance and channelled light transmission and polarization control are required.

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300 oC for 1 h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-Infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, C-O stretching of syringyl ring and aromatic C-H deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Diffusion and Creep in Silica-Doped Tetragonal Zirconia

Silica segregation at two grain junctions or in amorphous triple junction pockets can influence creep by altering the grain-boundary diffusion coefficient. Although the addition of silica to superplastic yttria-stabilized tetragonal zirconia enhances ductility, differences in reported creep parameters have limited critical identification of rate controlling mechanisms. The present study on a pure 3 mol% yttria-stabilized tetragonal zirconia (3YTZ) and 3YTZ with 0.39 or 3.9 wt% silica involved a detailed characterization of creep over a wide range of experimental conditions and also tracer diffusion measurements. The data broadly show transitions in creep stress exponents from n∼1 to ∼2 to ∼3 with a decrease in the stress. The data at high stresses are consistent with Coble diffusion creep, and creep at lower stresses is attributed to interface-controlled diffusion creep. Measurements indicated that silica does not have any significant influence on grain boundary or lattice diffusion, and this is consistent with the observation that 3YTZ and 3YTZ with 0.39% or 3.9% silica exhibit essentially identical creep behavior in the Coble creep regime. Silica influences the interface control process so that the transitions in stress exponents are pushed to lower stresses with an increase in silica content.

Loading of itraconazole into porous silica and silicon microparticles: characterization and dissolution tests

Most new drug molecules discovered today suffer from poor bioavailability. Poor oral bioavailability results mainly from poor dissolution properties of hydrophobic drug molecules, because the drug dissolution is often the rate-limiting event of the drug’s absorption through the intestinal wall into the systemic circulation. During the last few years, the use of mesoporous silica and silicon particles as oral drug delivery vehicles has been widely studied, and there have been promising results of their suitability to enhance the physicochemical properties of poorly soluble drug molecules. Mesoporous silica and silicon particles can be used to enhance the solubility and dissolution rate of a drug by incorporating the drug inside the pores, which are only a few times larger than the drug molecules, and thus, breaking the crystalline structure into a disordered, amorphous form with better dissolution properties. Also, the high surface area of the mesoporous particles improves the dissolution rate of the incorporated drug. In addition, the mesoporous materials can also enhance the permeability of large, hydrophilic drug substances across biological barriers. T he loading process of drugs into silica and silicon mesopores is mainly based on the adsorption of drug molecules from a loading solution into the silica or silicon pore walls. There are several factors that affect the loading process: the surface area, the pore size, the total pore volume, the pore geometry and surface chemistry of the mesoporous material, as well as the chemical nature of the drugs and the solvents. Furthermore, both the pore and the surface structure of the particles also affect the drug release kinetics. In this study, the loading of itraconazole into mesoporous silica (Syloid AL-1 and Syloid 244) and silicon (TOPSi and TCPSi) microparticles was studied, as well as the release of itraconazole from the microparticles and its stability after loading. Itraconazole was selected for this study because of its highly hydrophobic and poorly soluble nature. Different mesoporous materials with different surface structures, pore volumes and surface areas were selected in order to evaluate the structural effect of the particles on the loading degree and dissolution behaviour of the drug using different loading parameters. The loaded particles were characterized with various analytical methods, and the drug release from the particles was assessed by in vitro dissolution tests. The results showed that the loaded drug was apparently in amorphous form after loading, and that the loading process did not alter the chemical structure of the silica or silicon surface. Both the mesoporous silica and silicon microparticles enhanced the solubility and dissolution rate of itraconazole. Moreover, the physicochemical properties of the particles and the loading procedure were shown to have an effect on the drug loading efficiency and drug release kinetics. Finally, the mesoporous silicon particles loaded with itraconazole were found to be unstable under stressed conditions (at 38 qC and 70 % relative humidity).

Magnetic, electric, and dielectric properties of FeCo alloy nanoparticles dispersed in amorphous matrix

Nanocrystalline Fe53Co47 alloy was synthesized by a single-step transmetallation chemical method at room temperature. The Fe53Co47 alloy nanoparticles of 77 and 47 wt% were dispersed in silica matrix by the sol-gel process using tetraethyl orthosilcate. Structural studies reveal that the as-prepared alloy powders are in bcc phase and silica is in an amorphous state. The phase-transition temperature and Mossbauer spectra analysis of the Fe-Co alloy establishes the homogeneous alloy formation. A saturation magnetization of 218 emu/g was obtained for pure FeCo alloy at room temperature. Scanning electron microscopic analysis demonstrates the hollow-sphere morphology for FeCo alloy particles. Magnetic nanocomposite consisting of 47 wt% FeCo-silica shows enhanced thermal stability over the native FeCo alloy. Electrical and dielectric properties of 47 wt% FeCo-silica nanocomposites were investigated as a function of frequency and temperature. It was found that the dielectric constants and dielectric loss were stable throughout the measured temperature (310-373 K). Our results indicate that FeCo-silica nanocomposite is a promising candidate for high-frequency applications. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Preparation of β-SiAION from silica-alumina gel

Amorphous aluminosilicate gel powders have been subjected to carbothermal reduction and nitridation reaction at high temperature (1673 K). The influence of Al2O3 content in the gel powder on the nature and structure of the product phases has been examined. Between 5% and 9% Al2O3 in the gel powder, it is found that only β-SiAION is formed as the product of CTR/N reaction.

A molecular dynamics study of ambient and high pressure phases of silica: Structure and enthalpy variation with molar volume

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, alpha-PbO2-type, and pyrite-type for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase. (C) 2014 AIP Publishing LLC.

Non-resonant third-order non-linear optical properties of amorphous GeSe2 film

The real and imaginary parts of third-order susceptibility of amorphous GeSe2 film were measured by the method of the femtosecond optical heterodyne detection of optical Kerr effect at 805 nm with the 80 fs ultra fast pulses. The results indicated that the values of real and imaginary parts were 8.8 x 10(-12) esu and -3.0 x 10(-12) esu, respectively. An amorphous GeSe2 film also showed a very fast response within 200 fs. The ultra fast response and large third-order non-linearity are attributed to the ultra fast distortion of the electron orbits surrounding the average positions of the nucleus of Ge and Se atoms. (c) 2005 Elsevier B.V. All rights reserved.

The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

Light absorption in silicon quantum dots embedded in silica

The photon absorption in Si quantum dots (QDs) embedded in SiO2 has been systematically investigated by varying several parameters of the QD synthesis. Plasma-enhanced chemical vapor deposition (PECVD) or magnetron cosputtering (MS) have been used to deposit, upon quartz substrates, single layer, or multilayer structures of Si-rich- SiO2 (SRO) with different Si content (43-46 at. %). SRO samples have been annealed for 1 h in the 450-1250 °C range and characterized by optical absorption measurements, photoluminescence analysis, Rutherford backscattering spectrometry and x-ray Photoelectron Spectroscopy. After annealing up to 900 °C SRO films grown by MS show a higher absorption coefficient and a lower optical bandgap (∼2.0 eV) in comparison with that of PECVD samples, due to the lower density of Si-Si bonds and to the presence of nitrogen in PECVD materials. By increasing the Si content a reduction in the optical bandgap has been recorded, pointing out the role of Si-Si bonds density in the absorption process in small amorphous Si QDs. Both the photon absorption probability and energy threshold in amorphous Si QDs are higher than in bulk amorphous Si, evidencing a quantum confinement effect. For temperatures higher than 900 °C both the materials show an increase in the optical bandgap due to the amorphous-crystalline transition of the Si QDs. Fixed the SRO stoichiometry, no difference in the optical bandgap trend of multilayer or single layer structures is evidenced. These data can be profitably used to better implement Si QDs for future PV technologies. © 2009 American Institute of Physics.

Investigation of the Young's modulus and thermal expansion of amorphous titania-doped tantala films

The current generation of advanced gravitational wave detectors utilize titania-doped tantala/silica multilayer stacks for their mirror coatings. The properties of the low-refractive-index silica are well known; however, in the absence of detailed direct measurements, the material parameters of Young's modulus and coefficient of thermal expansion (CTE) of the high refractive index material, titania-doped tantala, have been assumed to be equal to values measured for pure tantala coatings. In order to ascertain the true values necessary for thermal noise calculations, we have undertaken measurements of Young's modulus and CTE through the use of nanoindentation and thermal-bending measurements. The measurements were designed to assess the effects of titania doping concentration and post-deposition heat-treatment on the measured values in order to evaluate the possibility of optimizing material parameters to further improve thermal noise in the detector. Young's modulus measurements on pure tantala and 25% and 55% titania-doped tantala show a wide range of values, from 132 to 177 GPa, dependent on both titania concentration and heat-treatment. Measurements of CTE give values of (3.9 +/- 0.1) x 10^-6 K^-1 and (4.9 +/- 0.3) x 10^-6 K^-1 for 25% and 55% titania-doped tantala, respectively, without dependence on post-deposition heat-treatment.

Electrocatalytic properties of Cu-Zr amorphous alloy towards the electrochemical hydrogenation of nitrobenzene

The Cu-Zr amorphous alloy was studied as an electrocatalyst towards the electrochemical hydrogenation of nitrobenzene. The electrocatalyst was activated by chemical etching in HF solution. Resulted changes in the morphology, chemical composition and crystalline structure of the electrocatalyst surface were characterised by scanning electron microscopy, X-ray diffraction and Auger electron spectroscopy. The electrocatalytic properties of the Cu-Zr amorphous alloy were assessed by voltammetric measurements. Due to the formation and aggregation of Zr residue modified Cu nanocrystals on the surface caused by the selective dissolution of Zr components in the chemical etching, the activated amorphous alloy is an effective electrocatalyst for the electrochemical reduction reaction of nitrobenzene with aniline as the main product. The positive shift of the peak potential and accompanying increase in the value of peak current in voltammograms with increasing Cu content and decreasing Zr content of the alloy surface in the chemical etching are indicative of improved electrocatalytic activity. (C) 2002 Elsevier Science B.V. All rights reserved.

Bluish-white emission from radical carbonyl impurities in amorphous Al2O3 prepared via the Pechini-type sol-gel process

Many efforts have been devoted to exploring novel luminescent materials that do not contain expensive or toxic elements, or do not need mercury vapor plasma as the excitation source. In this paper, amorphous Al2O3 powder samples were prepared via the Pechini-type sol-gel process. The resulting samples were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, field emission scanning electron microscopy (FESEM), photoluminescence (PL) excitation and emission spectra, kinetic decay, and electron paramagnetic resonance (EPR).

Sol-Gel Preparation of Zn2 Si04：Mn Phosphor Layers on Silica Spheres and Their Luminescent Properties

The synthesis and luminescence properties of Zn2SiO4:Mn phosphor layers on spherical silica spheres,i.e.,a kind of core-shell complex phosphor,Zn2SiO4:Mn@SiO2 were described.Firstly,monodisperse silica spheres were obtained via the Stober method by the hydrolysis of tetraethoxysilane(TEOS)Si(OC2H5)4 under base condition (using NH4OH as the catalyst).Secondly,the silica spheres were coated with a Zn2SiO4:Mn phosphor layer by a Pechini sol-gel process.X-ray diffraction(XRD),scanning electron microscope(SEM),energy-dispersive X-ray spectrum(EDS) and photoluminescence(PL) were employed to characterize the resulting complex phosphor.The results comfirm that 1000℃ annealed sample consists of crystalline Zn2SiO4:Mn shells and amorphous SiO2 cores.The phosphor show the green emission of Mn2+ at 521nm corresponding 4T1(4G)-6A1(6S) transition,and the possible luminescence mechanism is proposed.