Influence of pH on the incorporation and growth of Pb(2)CrO(5) crystallites in silica matrix

Pb(2)CrO(5) nanoparticles were embedded in an amorphous SiO(2) matrix by the sol-gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb(2)CrO(5)/SiO(2) compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka-Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb(2)CrO(5)/SiO(2) compounds were shown and discussed. In general, an acid pH initially dissolves Pb(2)CrO(5) nanoparticles and following heat treatment at 600 A degrees C crystallized into PbCrO(4) composition with grain size around 6 nm in SiO(2) matrix. No Pb(2)CrO(5) solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.

Influence of pH on the incorporation and growth of Pb2CrO5 crystallites in silica matrix

Pb2CrO5 nanoparticles were embedded in an amorphous SiO2 matrix by the sol-gel process. The pH and heat treatment effects were evaluated in terms of structural, microstructural and optical properties from Pb2CrO5/SiO2 compounds. X-ray diffraction (XRD), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectroscopy (EDS), and diffuse reflectance techniques were employed. Kubelka-Munk theory was used to calculate diffuse reflectance spectra that were compared to the experimental results. Finally, colorimetric coordinates of the Pb2CrO5/SiO2 compounds were shown and discussed. In general, an acid pH initially dissolves Pb2CrO5 nanoparticles and following heat treatment at 600 A degrees C crystallized into PbCrO4 composition with grain size around 6 nm in SiO2 matrix. No Pb2CrO5 solubilization was observed for basic pH. These nanoparticles were incorporated in silica matrix showing a variety of color ranging from yellow to orange.

Nonlinear optics in planar silica-on-silicon disk resonators

Optical frequency combs (OFCs) provide direct phase-coherent link between optical and RF frequencies, and enable precision measurement of optical frequencies. In recent years, a new class of frequency combs (microcombs) have emerged based on parametric frequency conversions in dielectric microresonators. Micocombs have large line spacing from 10's to 100's GHz, allowing easy access to individual comb lines for arbitrary waveform synthesis. They also provide broadband parametric gain bandwidth, not limited by specific atomic or molecular transitions in conventional OFCs. The emerging applications of microcombs include low noise microwave generation, astronomical spectrograph calibration, direct comb spectroscopy, and high capacity telecommunications.

In this thesis, research is presented starting with the introduction of a new type of chemically etched, planar silica-on-silicon disk resonator. A record Q factor of 875 million is achieved for on-chip devices. A simple and accurate approach to characterize the FSR and dispersion of microcavities is demonstrated. Microresonator-based frequency combs (microcombs) are demonstrated with microwave repetition rate less than 80 GHz on a chip for the first time. Overall low threshold power (as low as 1 mW) of microcombs across a wide range of resonator FSRs from 2.6 to 220 GHz in surface-loss-limited disk resonators is demonstrated. The rich and complex dynamics of microcomb RF noise are studied. High-coherence, RF phase-locking of microcombs is demonstrated where injection locking of the subcomb offset frequencies are observed by pump-detuning-alignment. Moreover, temporal mode locking, featuring subpicosecond pulses from a parametric 22 GHz microcomb, is observed. We further demonstrated a shot-noise-limited white phase noise of microcomb for the first time. Finally, stabilization of the microcomb repetition rate is realized by phase lock loop control.

For another major nonlinear optical application of disk resonators, highly coherent, simulated Brillouin lasers (SBL) on silicon are also demonstrated, with record low Schawlow-Townes noise less than 0.1 Hz^2/Hz for any chip-based lasers and low technical noise comparable to commercial narrow-linewidth fiber lasers. The SBL devices are efficient, featuring more than 90% quantum efficiency and threshold as low as 60 microwatts. Moreover, novel properties of the SBL are studied, including cascaded operation, threshold tuning, and mode-pulling phenomena. Furthermore, high performance microwave generation using on-chip cascaded Brillouin oscillation is demonstrated. It is also robust enough to enable incorporation as the optical voltage-controlled-oscillator in the first demonstration of a photonic-based, microwave frequency synthesizer. Finally, applications of microresonators as frequency reference cavities and low-phase-noise optomechanical oscillators are presented.

Surface-grafted silica linked with L-lactic acid oligomer: A novel nanofiller to improve the performance of biodegradable poly(L-lactide)

A new surface modification method by grafting L-lactic acid oligomer onto the surface silanol groups of silica nanoparticles has been developed. The surface-grafting reaction is confirmed by IR and Si-29 MAS NMR analyses. TEM and SEM results show that grafted SiO2 (g-SiO2) nanoparticles can be comparatively uniformly dispersed in chloroform or PLLA matrix, while the unmodified SiO2 nanoparticles tend to aggregate. The loading of g-SiO2 nanoparticles in poly(L-lactide) (PLLA) matrix greatly improves the toughness and tensile strength of this material. In contrast, the incorporation of un-grafted SiO2 nanoparticles into PLLA leads to the deterioration of its mechanical properties. DSC analysis shows that g-SiO2 nanoparticles can serve as a nucleating agent for the crystallization of PLLA in the composites. SEM characterization shows the tough characteristics and great interfacial combination strength for g-SiO2 (5wt%)/PLLA nanocomposites.

Enhancement of the stability of microporous silica films in non-aqueous solvents at elevated temperature

The effect of Al incorporation and pH adjustment during hydrolysis of the silica precursor on the thermal and structural stability of ordered microporous silica films with a 2D structure is presented. The structural stability of the films was determined from a combination of LA XRD/TEM data with porosity data obtained from ethanol adsorption isotherms. Thermogravimetric analysis and MR data were used to determine the template removal and the thermal stability. Stability of aluminium incorporated silica films has further been examined in several organic solvents with different polarity. A solvent with a higher polarity interacts more strongly with the films; the long-order structure disappeared after exposure to polar solvents. After exposure to non-polar solvents, the pore size uniformity was retained after 48 h. The samples with an Al/Si ratio of 0.007 showed the smallest d-spacing shift after exposure to hexane. The stability was further tested in the hydrogenation of phenylacetylene performed in a batch reactor over 1 wt.% Pd/Si(Al)O-2/Si (Al/Si = 0.007) films at 30 degrees C and 10 bar H-2 with hexane as solvent. No deactivation was observed in two subsequent hydrogenation runs. (C) 2009 Elsevier Inc. All rights reserved.

Biomass fly ash incorporation in cement based materials

In recent years, pressures on global environment and energy security have led to an increasing demand on renewable energy sources, and diversification of Europe’s energy supply. Among these resources the biomass could exert an important role, since it is considered a renewable and CO2 neutral energy resource once the consumption rate is lower than the growth rate, and can potentially provide energy for heat, power and transports from the same installation. Currently, most of the biomass ash produced in industrial plants is either disposed of in landfill or recycled on agricultural fields or forest, and most times this goes on without any form of control. However, considering that the disposal cost of biomass ashes are raising, and that biomass ash volumes are increasing worldwide, a sustainable ash management has to be established. The main objective of the present study is the effect of biomass fly ashes in cement mortars and concretes in order to be used as a supplementary cementitious material. The wastes analyzed in the study were collected from the fluidized bed boilers and grate boilers available in the thermal power plants and paper pulp plants situated in Portugal. The physical as well as chemical characterisations of the biomass fly ashes were investigated. The cement was replaced by the biomass fly ashes in 10, 20 and 30% (weight %) in order to investigate the fresh properties as well as the hardened properties of biomass fly ash incorporated cement mortar and concrete formulations. Expansion reactions such as alkali silica reaction (ASR), sulphate attack (external and internal) were conducted in order to check the durability of the biomass fly ash incorporated cement mortars and concretes. Alternative applications such as incorporation in lime mortars and alkali activation of the biomass fly ashes were also attempted. The biomass fly ash particles were irregular in shape and fine in nature. The chemical characterization revealed that the biomass fly ashes were similar to a class C fly ash. The mortar results showed a good scope for biomass fly ashes as supplementary cementitious materials in lower dosages (<20%). The poor workability, concerns about the organic content, alkalis, chlorides and sulphates stand as the reasons for preventing the use of biomass fly ash in high content in the cement mortars. The results obtained from the durability tests have shown a clear reduction in expansion for the biomass fly ash mortars/concretes and the binder blend made with biomass fly ash (20%) and metakaolin (10%) inhibited the ASR reaction effectively. The biomass fly ash incorporation in lime mortars did not improve the mortar properties significantly though the carbonation was enhanced in the 15-20% incorporation. The biomass fly ash metakaolin blend worked well in the alkali activated complex binder application also. Portland cement free binders (with 30-40 MPa compressive strength) were obtained on the alkali activation of biomass fly ashes (60-80%) blended with metakaolin (20-40%).

Surface reactivity enhancement of silica-based glass-ceramic scaffolds

A paradigm shift is taking place from using transplanting tissue and synthetic implants to a tissue engineering approach that aims to regenerate damaged tissues by combining cells from the body with highly porous scaffold biomaterials, which act as templates, guiding the growth of new tissue. The central focus of this thesis was to produce porous glass and glass-ceramic scaffolds that exhibits a bioactive and biocompatible behaviour with specific surface reactivity in synthetic physiological fluids and cell-scaffold interactions, enhanced by composition and thermal treatments applied. Understanding the sintering behaviour and the interaction between the densification and crystallization processes of glass powders was essential for assessing the ideal sintering conditions for obtaining a glass scaffolds for tissue engineering applications. Our main goal was to carry out a comprehensive study of the bioactive glass sintering, identifying the powder size and sintering variables effect, for future design of sintered glass scaffolds with competent microstructures. The developed scaffolds prepared by the salt sintering method using a 3CaO.P2O5 - SiO2 - MgO glass system, with additions of Na2O with a salt, NaCl, exhibit high porosity, interconnectivity, pore size distribution and mechanical strength suitable for bone repair applications. The replacement of 6 % MgO by Na2O in the glass network allowed to tailor the dissolution rate and bioactivity of the glass scaffolds. Regarding the biological assessment, the incorporation of sodium to the composition resulted in an inibition cell response for small periods. Nevertheless it was demonstrated that for 21 days the cells response recovered and are similar for both glass compositions. The in vitro behaviour of the glass scaffolds was tested by introducing scaffolds to simulated body fluid for 21 days. Energy-dispersive Xray spectroscopy and SEM analyses proved the existence of CaP crystals for both compositions. Crystallization forming whitlockite was observed to affect the dissolution behaviour in simulated body fluid. By performing different heat treatments, it was possible to control the bioactivity and biocompatability of the glass scaffolds by means of a controlled crystallization. To recover and tune the bioactivity of the glass-ceramic with 82 % crystalline phase, different methods have been applied including functionalization using 3- aminopropyl-triethoxysilane (APTES). The glass ceramic modified surface exhibited an accelerated crystalline hydroxyapatite layer formation upon immersion in SBF after 21 days while the as prepared glass-ceramic had no detected formation of calcium phosphate up to 5 months. A sufficient mechanical support for bone tissue regeneration that biodegrade later at a tailorable rate was achievable with the glass–ceramic scaffold. Considering the biological assessment, scaffolds demonstrated an inductive effect on the proliferation of cells. The cells showed a normal morphology and high growth rate when compared to standard culture plates. This study opens up new possibilities for using 3CaO.P2O5–SiO2–MgO glass to manufacture various structures, while tailoring their bioactivity by controlling the content of the crystalline phase. Additionally, the in vitro behaviour of these structures suggests the high potential of these materials to be used in the field of tissue regeneration.

Studies on in situ precipitated silica filled rubber composites with special reference to NR, NBR and SBR

Precipitated silica is the most promising alternative for carbon black in tyre tread compounds due to its improved performance in terms of rolling resistance and wet grip.But its poor processability is a serious limitation to its commercial application.This thesis suggests a novel route for the incorporation of silica in rubbers,i.e.,precipitation of silica in rubber latex followed by coagulation of the latex to get rubber-silica maseterbatch.Composites with in situ precipitated silica showed improved processability and mechanical properties,when compared to conventional silica composites.

Adsorption of Pb(2+), Cu(2+) and Cd(2+) in FDU-1 silica and FDU-1 silica modified with humic acid

Ordered mesoporous silica with cubic structure, type FDU-1, was synthesized under strong acid media using B-50-6600 poly(ethylene oxide)-poly(butilene oxide)-poly(ethylene oxide) triblock copolymer (EO(39)BO(47)EO(39)) and tetraethyl orthosilicate (TEOS). Humic acid (HA) was modified to the synthesis process at a concentration of 1.5 mmol per gram of SiO(2). Thermogravimetry, small angle X-ray diffraction, nitrogen adsorption and high resolution transmission electron microscopy were used to characterize the samples. The pristine FDU-1 and FDU-1 with incorporated 1.5 mmol of HA were tested for adsorption of Pb(2+), Cu(2+) and Cd(2+) in aqueous solution. Incorporation of humic acid into the FDU-1 silica afforded an adsorbent with strong affinity for Cd(2+), Cu(2+) and Pb(2+) from single ion solutions. Adsorption of Cu(2+) was significantly enhanced after incorporation of humic acid, a fact that can be explained by the formation of complexes with carboxylic and phenolic groups at low concentrations of the metal cation. The results demonstrated the potential applicability of FDU-1 with incorporated HA in the removal of low concentrations of heavy metal cations from aqueous solution, such as wastewaters, after usual precipitation of metal hydroxides in alkaline medium and proper pH conditioning in the range between 6 and 7. (C) 2007 Elsevier Inc. All rights reserved.

Montmorillonite (MMT) effect on the structure of poly(oxyethylene) (PEO)-MMT nanocomposites and silica-PEO-MMT hybrid materials

In this work we report the effects of incorporation of variable amounts (0.5-25%w/w) of montmorillonite in poly(oxyethylene) based materials in order to decrease the polymer crystallinity. Two different classes of materials were studied: silica-poly(oxyethylene)-montmorillonite hybrids prepared by the sol-gel route and poly(oxyethylene)-montmorillonite nanocomposites prepared by mixing the dry clay or the clay aqueous suspension into the melt poly(oxyethylene). The effects of monternorillonite loading on the poly(oxyethylene) crystallization control and on the nanostructural features were investigated by X-ray powder diffraction, small-angle X-ray scattering and differential scanning calorimetry. Experimental results show that free montmorillonite layers coexist with open aggregates and tactoids in the poly(oxyethylene)-montmorillonite nanocomposites, with different features depending on the filler proportion and preparation route. The intercalation of polymer chains in montmorillonite galleries markedly hinders the crystallization of the poly(oxyethylene) matrix. For hybrids materials the silica phase favors the exfoliation of montmorillonite tactoids, so that samples are predominantly constituted by dispersed platelets. (c) 2006 Elsevier B.V. All rights reserved.

Bifunctional silica nanoparticles for the exploration of biofilms of Pseudomonas aeruginosa

Luminescent silica nanoparticles are frequently employed for biotechnology applications mainly because of their easy functionalization, photo-stability, and biocompatibility. Bifunctional silica nanoparticles (BSNPs) are described here as new efficient tools for investigating complex biological systems such as biofilms. Photoluminescence is brought about by the incorporation of a silylated ruthenium(II) complex. The surface properties of the silica particles were designed by reaction with amino-organosilanes, quaternary ammonium-organosilanes, carboxylate-organosilanes and hexamethyldisilazane. BSNPs were characterized extensively by DRIFT, 13C and 29Si solid state NMR, XPS, and photoluminescence. Zeta potential and contact angle measurements exhibited various surface properties (hydrophilic/hydrophobic balance and electric charge) according to the functional groups. Confocal laser scanning microscopy (CLSM) measurements showed that the spatial distribution of these nanoparticles inside a biofilm of Pseudomonas aeruginosa PAO1 depends more on their hydrophilic/hydrophobic characteristics than on their size. CLSM observations using two nanosized particles (25 and 68 nm) suggest that narrow diffusion paths exist through the extracellular polymeric substances matrix. © 2013 Copyright Taylor and Francis Group, LLC.

Nanostructured materials based on mesoporous silica and mesoporous silica/apatite as osteogenic growth peptide carriers

The aim of this work was the preparation of inorganic mesoporous materials from silica, calcium phosphate and a nonionic surfactant and to evaluate the incorporation and release of different concentrations of osteogenic growth peptide (OGP) for application in bone regeneration. The adsorption and release of the labeled peptide with 5,6-carboxyfluorescein (OGP-CF) from the mesoporous matrix was monitored by fluorescence spectroscopy. The specific surface area was 880 and 484 m2 g- 1 for pure silica (SiO) and silica/apatite (SiCaP), respectively; the area influenced the percentage of incorporation of the peptide. The release of OGP-CF from the materials in simulated body fluid (SBF) was dependent on the composition of the particles, the amount of incorporated peptide and the degradation of the material. The release of 50% of the peptide content occurred at around 4 and 30 h for SiCaP and SiO, respectively. In conclusion, the materials based on SiO and SiCaP showed in vitro bioactivity and degradation; thus, these materials should be considered as alternative biomaterials for bone regeneration. © 2013 Elsevier B.V.

Enzymatic Solid-Phase Reactor Based on Silica Organofunctionalized with p-Phenylenediamine for Electrochemical Detection of Phenolic Compounds

A new biomaterial, based on silica organofunctionalized with p-phenylenediamine (p-PDA) and the enzyme peroxidase, was used in the development of an enzymatic solid-phase reactor. The analytical techniques used in the characterization showed that the organic ligand was incorporated into the silica matrix. Thus, the silica modified with p-PDA allowed the incorporation of peroxidase by the electrostatic interaction between the carboxylic groups present in the enzyme molecules and the amino groups attached to the silica. The enzymatic solid-phase reactor was used for chemical oxidation of phenols in 1, 4-benzoquinone that was then detected by chronoamperometry. The system allowed the analysis of hydroquinone with a detection limit of 83.6 nmol L-1. Thus, the new material has potential in the determination of phenolic compounds river water samples.

Development of Vapor Deposited Silica Sol-Gel Particles for a Bioactive Materials System to Direct Osteoblast Behavior

Tissue engineering and regenerative medicine have emerged in an effort to generate replacement tissues capable of restoring native tissue structure and function, but because of the complexity of biologic system, this has proven to be much harder than originally anticipated. Silica based bioactive glasses are popular as biomaterials because of their ability to enhance osteogenesis and angiogenesis. Sol-gel processing methods are popular in generating these materials because it offers: 1) mild processing conditions; 2) easily controlled structure and composition; 3) the ability to incorporate biological molecules; and 4) inherent biocompatibility. The goal of this work was to develop a bioactive vaporization system for the deposition of silica sol-gel particles as a means to modify the material properties of a substrate at the nano- and micro- level to better mimic the instructive conditions of native bone tissue, promoting appropriate osteoblast attachment, proliferation, and differentiation as a means for supporting bone tissue regeneration. The size distribution, morphology and degradation behavior of the vapor deposited sol-gel particles developed here were found to be dependent upon formulation (H2O:TMOS, pH, Ca/P incorporation) and manufacturing (substrate surface character, deposition time). Additionally, deposition of these particles onto substrates can be used to modify overall substrate properties including hydrophobicity, roughness, and topography. Deposition of Ca/P sol particles induced apatite-like mineral formation on both two- and three-dimensional materials when exposed to body fluids. Gene expression analysis suggests that Ca/P sol particles induce upregulation osteoblast gene expression (Runx2, OPN, OCN) in preosteoblasts during early culture time points. Upon further modification-specifically increasing particle stability-these Ca/P sol particles possess the potential to serve as a simple and unique means to modify biomaterial surface properties as a means to direct osteoblast differentiation.

Biogenic and lithogenic silica, silicic acid, production of biogenic silica, and irradiance measurements during the Ross Sea Bloom Project 1994-1996

The development of the seasonal phytoplankton bloom in the Ross Sea was studied during two cruises. The first, conducted in November-December 1994, investigated the initiation and rapid growth of the bloom, whereas the second (December 1995-January 1996) concentrated on the bloom's maximum biomass period and the subsequent decline in biomass. Central to the understanding of the controls of growth and the summer decline of the bloom is a quantitative assessment of the growth rate of phytoplankton. Growth rates were estimated over two time scales with different methods. The first estimated daily growth rates from isotropic incorporation under simulated in situ conditions, including 14C, 15N and 32Si uptake measurements combined with estimates of standing stocks of particulate organic carbon, nitrogen and biogenic silica. The second method used daily to weekly changes in biomass at selected locations, with net growth rates being estimated from changes in standing stocks of phytoplankton. In addition, growth rates were estimated in large-volume experiments under optimal irradiances. Growth rates showed distinct temporal patterns. Early in the growing season, short-term estimates suggested that growth rates of in situ assemblages were less than maximum (relative to the temperature-limited maximum) and were likely reduced due to low irradiance regimes encountered under the ice. Growth rates increased thereafter and appeared to reach their maximum as biomass approached the seasonal peak, but decreased markedly in late December. Differences between the major taxonomic groups present were also noted, especially from the isotopic tracer experiments. The haplophyte Phaeocystic antarctica was dominant in 1994 throughout the growing season, and it exhibited the greatest growth rates (mean 0.41/day) during spring. Diatom standing stocks were low early in the growing season, and growth rates averaged 0.100/day. In summer diatoms were more abundant, but their growth rates remained much lower (mean of 0.08/day) than the potential maximum. Understanding growth rate controls is essential to the development of predictive models of the carbon cycle and food webs in Antarctic waters.