Bioactive sol-gel glasses at the atomic scale:the complementary use of advanced probe and computer modeling methods

Sol-gel-synthesized bioactive glasses may be formed via a hydrolysis condensation reaction, silica being introduced in the form of tetraethyl orthosilicate (TEOS), and calcium is typically added in the form of calcium nitrate. The synthesis reaction proceeds in an aqueous environment; the resultant gel is dried, before stabilization by heat treatment. These materials, being amorphous, are complex at the level of their atomic-scale structure, but their bulk properties may only be properly understood on the basis of that structural insight. Thus, a full understanding of their structure-property relationship may only be achieved through the application of a coherent suite of leading-edge experimental probes, coupled with the cogent use of advanced computer simulation methods. Using as an exemplar a calcia-silica sol-gel glass of the kind developed by Larry Hench, in the memory of whom this paper is dedicated, we illustrate the successful use of high-energy X-ray and neutron scattering (diffraction) methods, magic-angle spinning solid-state NMR, and molecular dynamics simulation as components to a powerful methodology for the study of amorphous materials.

Viability Theory and Economic Modeling

A brief introduction into the theory of differential inclusions, viability theory and selections of set valued mappings is presented. As an application the implicit scheme of the Leontief dynamic input-output model is considered.

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.

Topologies on groups related to the theory of shape and generalized coverings

El presente trabajo consiste en dos partes diferenciadas: la principal de ellas (Cap tulos 1 y 2) est a dedicada a introducir estructura adicional en grupos que aparecen de manera natural en el contexto de la teor a de la forma. En la segunda parte (Cap tulo 3), se plantea c omo generalizar la teor a de espacios recubridores y, en particular, se propone una l nea de trabajo relacionada con la teor a de la forma. El punto de partida de esta tesis doctoral son los trabajos [25, 26, 68, 69, 70] en los que los autores introducen y utilizan algunas ultram etricas en el conjunto de los mor smos shape entre dos espacios topol ogicos punteados. En particular, si el dominio es (S1; 1); la construcci on realizada en [68] permite explicitar una ultram etrica en el grupo shape 1(X; x0) de un espacio m etrico compacto X; como ya fue observado en [69] y [80]. Si el espacio no es m etrico compacto, la construcci on nos lleva a utilizar el concepto de ultram etrica generalizada, en el sentido de Priess-Crampe y Ribenboim [78, 79]. En [7], D. K. Biss introduce la idea de topologizar el grupo fundamental de un espacio, de forma que la topolog a en 1(X; x0) sea una topolog a de grupo que permita detectar la (no) existencia de un recubridor universal para X: La forma de proceder sugerida es tomar en 1(X; x0)la toplog a cociente inducida por la topolog a compacto-abierta en el espacio de lazos (X; x0): Sin embargo, hay algunos errores en el art culo mencionado: en concreto, el error relacionado con el presente trabajo fue puesto de mani esto por P. Fabel en [33], mostrando que, en general, la operaci on de grupo en 1(X; x0)con la topolog a cociente no es continua. Utilizando un punto de vista similar, varios autores han tratado de dotar al grupo fundamental con una topolog a, de forma que 1(X; x0) sea un grupo topol ogico y la proyecci on q (X; x0){u100000} 1(X; x0)sea continua...

Assessment of a multiple-span bridge by dynamic testing, in-situ monitoring and numerical modeling

Peer reviewed

Machining Unidirectional Composites using Single-Point Tools : Analysis of Cutting Forces, Chip Formation and Surface Integrity

Peer reviewed

Surface quality and surface waves on subwavelength-structured silver films

We analyze the physical-chemical surface properties of single-slit, single-groove subwavelength-structured silver films with high-resolution transmission electron microscopy and calculate exact solutions to Maxwell’s equations corresponding to recent far-field interferometry experiments using these structures. Contrary to a recent suggestion the surface analysis shows that the silver films are free of detectable contaminants. The finite-difference time-domain calculations, in excellent agreement with experiment, show a rapid fringe amplitude decrease in the near zone (slit-groove distance out to 3–4 wavelengths). Extrapolation to slit-groove distances beyond the near zone shows that the surface wave evolves to the expected bound surface plasmon polariton (SPP). Fourier analysis of these results indicates the presence of a distribution of transient, evanescent modes around the SPP that dephase and dissipate as the surface wave evolves from the near to the far zone.

Heat fluxes and surface radiation measurements from Samoylov Island, Lena Delta, Siberia, October 2007 to March 2008

In this study, we present the winter time surface energy balance at a polygonal tundra site in northern Siberia based on independent measurements of the net radiation, the sensible heat flux and the ground heat flux from two winter seasons. The latent heat flux is inferred from measurements of the atmospheric turbulence characteristics and a model approach. The long-wave radiation is found to be the dominant factor in the surface energy balance. The radiative losses are balanced to about 60 % by the ground heat flux and almost 40 % by the sensible heat fluxes, whereas the contribution of the latent heat flux is small. The main controlling factors of the surface energy budget are the snow cover, the cloudiness and the soil temperature gradient. Large spatial differences in the surface energy balance are observed between tundra soils and a small pond. The ground heat flux released at a freezing pond is by a factor of two higher compared to the freezing soil, whereas large differences in net radiation between the pond and soil are only observed at the end of the winter period. Differences in the surface energy balance between the two winter seasons are found to be related to differences in snow depth and cloud cover which strongly affect the temperature evolution and the freeze-up at the investigated pond.

A suite of global, cross-scale topographic variables for environmental and biodiversity modeling, links to files in GeoTIFF format

Topographic variation, the spatial variation in elevation and terrain features, underpins a myriad of patterns and processes in geography and ecology and is key to understanding the variation of life on the planet. The characterization of this variation is scale-dependent, i.e. it varies with the distance over which features are assessed and with the spatial grain (grid cell resolution) of analysis. A fully standardized and global multivariate product of different terrain features has the potential to support many large-scale basic research and analytical applications, however to date, such technique is unavailable. Here we used the digital elevation model products of global 250 m GMTED and near-global 90 m SRTM to derive a suite of topographic variables: elevation, slope, aspect, eastness, northness, roughness, terrain roughness index, topographic position index, vector ruggedness measure, profile and tangential curvature, and 10 geomorphological landform classes. We aggregated each variable to 1, 5, 10, 50 and 100 km spatial grains using several aggregation approaches (median, average, minimum, maximum, standard deviation, percent cover, count, majority, Shannon Index, entropy, uniformity). While a global cross-correlation underlines the high similarity of many variables, a more detailed view in four mountain regions reveals local differences, as well as scale variations in the aggregated variables at different spatial grains. All newly-developed variables are available for download at http://www.earthenv.org and can serve as a basis for standardized hydrological, environmental and biodiversity modeling at a global extent.

Design of Transparent Conducting Electrodes and Surface Relief Gratings for Plasmonic Polymer Solar Cells

As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

Design of Transparent Conducting Electrodes and Surface Relief Gratings for Plasmonic Polymer Solar Cells

As the concept of renewable energy becomes increasingly important in the modern society, a considerable amount of research has been conducted in the field of organic photovoltaics in recent years. Although organic solar cells generally have had lower efficiencies compared to silicon solar cells, they have the potential to be mass produced via solution processing. A common polymer solar cell architecture relies on the usage of P3HT (electron donor) and PCBM (electron acceptor) bulk heterojunction. One of the main issues with this configuration is that in order to compensate for the high exciton recombination rate, the photoactive layer is often made very thin (on the order of 100 $%). This results in low solar cell photocurrents due to low absorption. This thesis investigates a novel method of light trapping by coupling surface plasmons at the electrode interface via surface relief gratings, leading to EM field enhancements and increased photo absorption. Experimental work was first conducted on developing and optimizing a transparent electrode of the form &'()/+,/&'() to replace the traditional ITO electrode since the azopolymer gratings cannot withstand the high temperature processing of ITO films. It was determined that given the right thickness profiles and deposition conditions, the MAM stack can achieve transmittance and conductivity similar to ITO films. Experimental work was also conducted on the fabrication and characterization of surface relief gratings, as well as verification of the surface plasmon generation. Surface relief gratings were fabricated easily and accurately via laser interference lithography on photosensitive azopolymer films. Laser diffraction studies confirmed the grating pitch, which is dependent on the incident angle and wavelength of the writing beam. AFM experiments were conducted to determine the surface morphology of the gratings, before and after metallic film deposition. It was concluded that metallic film deposition does not significantly alter the grating morphologies.

Tris(2-ethylhexyl) trimellitate (TOTM) as a potential industrial reference fluid for viscosity at high temperatures and high pressures: New viscosity, density and surface tension measurements

Tris(2-ethylhexyl) trimellitate (TOTM) was recently suggested as a reference fluid for industrial use associated with high viscosity at elevated temperature and pressure. Viscosity and density data have already been published on one sample covering the temperature range (303-373) K and at pressures up to about 65 MPa. The viscosity covered a range from about (9 to 460) mPa s. In the present article we study several other characteristics of TOTM that must be available if it were to be adopted as a standard. First, we present values for the viscosity and density obtained with a different sample of TOTM to examine the important feature of consistency among different samples. Vibrating-wire viscosity measurements were performed at pressures from (5 to 100) MPa, along 6 isotherms between (303 and 373) K. Density measurements were carried out from (293 to 373) K up to 68 MPa, along 4 isotherms, using an Anton Paar DMA HP vibrating U-tube densimeter. Secondly, we report a study of the effect of water contamination on the viscosity of TOTM, performed using an Ubbelhode viscometer under atmospheric pressure. Finally, in order to support the use of TOTM as a reference liquid for the calibration of capillary viscometers, values of its surface tension, obtained by the pendant drop method, are provided. (C) 2016 Elsevier B.V. All rights reserved.