906 resultados para Thermal and photochemical transformations


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We predict the existence of an anomalous crossover between thermal and shot noise in macroscopic diffusive conductors. We first show that, besides thermal noise, these systems may also exhibit shot noise due to fluctuations of the total number of carriers in the system. Then we show that at increasing currents the crossover between the two noise behaviors is anomalous, in the sense that the low-frequency current spectral density displays a region with a superlinear dependence on the current up to a cubic law. The anomaly is due to the nontrivial coupling in the presence of the long-range Coulomb interaction among the three time scales relevant to the phenomenon, namely, diffusion, transit, and dielectric relaxation time.

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Urolithiasis is identified to be a major urological disorder affecting people all over the world irrespective of their age, sex and race. Urinary stone samples resected from the urinary bladders of two patients belonging to tropical region, Kollam District of Kerala State, India are investigated by using XRD,SEM, EDAX, TGA, DSC and FTIR to understand its chemical structure. Uric acid shows exothermic peak around 432°C is due to the decomposition with the evolution of CO and cracking of the remaining products. Results of analytical studies reveal that samples under investigation consist mainly in uric acid and hydrated uric acid. Hydrogen bonding exists in hydrated uric acid samples

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Ein Drittel des weltweiten gesamten Energiebedarfs wird durch Gebäude verbraucht. Um diesen Energiebedarf teilweise zu decken, den erheblichen Energieverbrauch zu reduzieren und weiterhin andere Gebäudefunktionen beizubehalten, ist Gebäudeintegrierte Photovoltaik (BIPV) eine der am besten geeigneten Lösungen für die Gebäudenanwendung. Im Bezug auf eine Vielzahl von Gestalltungsmöglichkeiten, sind die Randbedingungen der BIPV-Anwendungen eindeutig anders im Vergleich zu Standard-PV-Anwendungen, insbesondere bezüglich der Betriebstemperatur. Bisher gab es nicht viele Informationen zu den relevanten thermischen Auswirkungen auf die entsprechenden elektrischen Eigenschaften zusammen mit thermischen und mechanischen relevanten Gebäudenfunktionen. Die meisten Hersteller übernehmen diese Eigenschaften von entsprechenden PV-Modulen und konventionellen Bauprodukten Normen, die zur ungenauen System- und Gebäudeplanungen führen. Deshalb ist die Untersuchung des thermischen Einflusses auf elektrische, thermische sowie mechanische Eigenschaften das Hauptziel der vorliegenden Arbeit. Zunächst wird das Temperatur-Model mit dem Power-Balance-Konzept erstellt. Unter Berücksichtigung der variablen Installationsmöglichkeiten und Konfigurationen des Moduls wird das Model auf Basis dynamischer und stationär Eigenschaften entwickelt. Im Hinblick auf die dynamische Simulation können der Energieertrag und Leistung zusammen mit der thermischen Gebäudesimulation in Echtzeit simuliert werden. Für stationäre Simulationen können die relevanten Gebäudefunktionen von BIPV-Modulen sowohl im Sommer als auch im Winter simuliert werden. Basierend auf unterschiedlichen thermischen und mechanischen Last-Szenarien wurde darüber hinaus das mechanische Model zusammen mit Variationen von Belastungsdauer, Montagesystem und Verkapselungsmaterialien entwickelt. Um die Temperatur- und Mechanik-Modelle zu validieren, wurden die verschiedenen Prüfeinrichtungen zusammen mit neuen Testmethoden entwickelt. Bei Verwendung der Prüfanlage „PV variable mounting system“ und „mechanical testing equipment“ werden zudem die verschiedenen Szenarien von Montagesystemen, Modul-Konfigurationen und mechanischen Belastungen emuliert. Mit der neuen Testmethode „back-bias current concept“ können zum einen die solare Einstrahlung und bestimmte Betriebstemperaturen eingestellt werden. Darüber hinaus wurden mit den eingangs erwähnten validierten Modellen das jeweilige elektrische, thermische und mechanische Verhalten auf andere Konfigurationen bewertet. Zum Abschluss wird die Anwendung von Software-Tools bei PV-Herstellern im Hinblick auf die entsprechenden Modellentwicklungen thematisiert.

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In a seminal paper, Aitchison and Lauder (1985) introduced classical kernel density estimation techniques in the context of compositional data analysis. Indeed, they gave two options for the choice of the kernel to be used in the kernel estimator. One of these kernels is based on the use the alr transformation on the simplex SD jointly with the normal distribution on RD-1. However, these authors themselves recognized that this method has some deficiencies. A method for overcoming these dificulties based on recent developments for compositional data analysis and multivariate kernel estimation theory, combining the ilr transformation with the use of the normal density with a full bandwidth matrix, was recently proposed in Martín-Fernández, Chacón and Mateu- Figueras (2006). Here we present an extensive simulation study that compares both methods in practice, thus exploring the finite-sample behaviour of both estimators

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Electrochemical reduction of the triangular clusters [Os-3(CO)(10)(alpha-dimine)] (alpha-dimine = 2,2'-bipyridine (bpy), 2,2'-bipyrimidine (bpym)) and [Os-3(CO)(10)(mu-bpym) ReBr(CO)(3)] produces primarily the corresponding radical anions. Their stability is strongly determined by the pi acceptor ability of the reducible alpha-dimine ligand, which decreases in the order mu-bpym > bpym >> bpy. Along this series, increasing delocalisation of the odd electron density in the radical anion over the Os(alpha-dimine) chelate ring causes weakening of the axial (CO)(4)Os-Os(CO)(2)(alpha-dimine) bond and its facile cleavage for alpha-diimine = bpy. In contrast, the cluster radical anion is inherently stable for the bridging bpym ligand, the strongest pi-acceptor in the studied series. In the absence of the partial delocalisation of the unpaired electron over the Re( bpym) chelate bond, the Os-3-core of the radical anion remains intact only at low temperatures. Subsequent one-electron reduction of [Os-3(CO)(10)(bpym)](center dot-) at T = 223 K gives the open-triosmium core (= Os-3*) dianion, [Os-3*(CO)(10)(bpym)](2-). Its oxidation leads to the recovery of parent [Os-3(CO)(10)( bpym)]. At room temperature, [Os-3*( CO)(10)(bpym)](2-) is formed along a two-electron (ECE) reduction path. The chemical step (C) results in the formation of an open- core radical anion that is directly reducible at the cathodic potential of the parent cluster in the second electrochemical (E) step. In weakly coordinating tetrahydrofuran, [Os-3*(CO)(10)( bpym)](2-) rapidly attacks yet non- reduced parent cluster molecules, producing the relatively stable open- core dimer [Os-3*(CO)(10)(bpym)](2)(2-) featuring two open- triangle cluster moieties connected with an ( bpym) Os - Os( bpym) bond. In butyronitrile, [Os-3*( CO)(10)(bpym)](2-) is stabilised by the solvent and the dimer [Os-3*(CO)(10)(bpym)](2)(2-) is then mainly formed by reoxidation of the dianion on reverse potential scan. The more reactive cluster [Os-3(CO)(10)(bpy)] follows the same reduction path, as supported by spectroelectrochemical results and additional valuable evidence obtained from cyclic voltammetric scans. The ultimate process in the reduction mechanism is fragmentation of the cluster core triggered by the reduction of the dimer [Os-3*(CO)(10)(alpha- diimine)](2)(2-). The products formed are [Os-2(CO)(8)](2-) and {Os(CO)(2)(alpha- diimine)}(2). The latter dinuclear fragments constitute a linear polymeric chain [Os( CO)(2)(alpha-dimine)] n that is further reducible at the alpha-dimine ligands. For alpha-dimine = bpy, the charged polymer is capable of reducing carbon dioxide. The electrochemical opening of the triosmium core in the [Os-3( CO)(10)(alpha-dimine)] clusters exhibits several common features with their photochemistry. The same Os-alpha-dimine bond dissociates in both cases but the intimate mechanisms are different.

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Myrosinase, a family of enzymes which coexist with glucosinolates in all Brassica vegetables, catalyses the hydrolysis of glucosinolates to yield compounds that can have beneficial effects on human health. In this study, the thermal and pressure inactivation of myrosinase from green cabbage was kinetically investigated. Thermal inactivation started at 35 C and inactivation kinetics was studied in the temperature range 35–55 C. Thermal inactivation of green cabbage myrosinase followed the well known consecutive step model. Pressure inactivation started at 300 MPa, even at 10 C, and the consecutive step model effectively described pressure inactivation in the range 300–450 MPa at 10 C. The combined effects of applying various pressures and temperatures on myrosinase inactivation kinetics were studied in the ranges 35–50 C and, 100–400 MPa. The inactivation followed first-order kinetics at all of the applied combinations. This study demonstrates that myrosinase from green cabbage is highly susceptible to both thermal and high pressure processing. Furthermore, it is also noted that myrosinase stability during processing appears to vary widely between different Brassica species.

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The persistence and decay of springtime total ozone anomalies over the entire extratropics (midlatitudes plus polar regions) is analysed using results from the Canadian Middle Atmosphere Model (CMAM), a comprehensive chemistry-climate model. As in the observations, interannual anomalies established through winter and spring persist with very high correlation coefficients (above 0.8) through summer until early autumn, while decaying in amplitude as a result of photochemical relaxation in the quiescent summertime stratosphere. The persistence and decay of the ozone anomalies in CMAM agrees extremely well with observations, even in the southern hemisphere when the model is run without heterogeneous chemistry (in which case there is no ozone hole and the seasonal cycle of ozone is quite different from observations). However in a version of CMAM with strong vertical diffusion, the northern hemisphere anomalies decay far too rapidly compared to observations. This shows that ozone anomaly persistence and decay does not depend on how the springtime anomalies are created or on their magnitude, but reflects the transport and photochemical decay in the model. The seasonality of the long-term trends over the entire extratropics is found to be explained by the persistence of the interannual anomalies, as in the observations, demonstrating that summertime ozone trends reflect winter/spring trends rather than any change in summertime ozone chemistry. However this mechanism fails in the northern hemisphere midlatitudes because of the relatively large impact, compared to observations, of the CMAM polar anomalies. As in the southern hemisphere, the influence of polar ozone loss in CMAM increases the midlatitude summertime loss, leading to a relatively weak seasonal dependence of ozone loss in the Northern Hemisphere compared to the observations.

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he classical problem of the response of a balanced, axisymmetric vortex to thermal and mechanical forcing is re-examined, paying special attention to the lower boundary condition. The correct condition is DΦ/Dt = 0, where Φ is the geopotential and D/Dt the material derivative, which explicitly accounts for a mass redistribution as part of the mean-flow response. This redistribution is neglected when using the boundary condition Dp/Dt = 0, which has conventionally been applied in this problem. It is shown that applying the incorrect boundary condition, and thereby ignoring the surface pressure change, leads to a zonal wind acceleration δū/δt that is too strong, especially near the surface. The effect is significant for planetary-scale forcing even when applied at tropopause level. A comparison is made between the mean-flow evolution in a baroclinic life-cycle, as simulated in a fully nonlinear, primitive-equation model, and that predicted by using the simulated eddy fluxes in the zonally-symmetric response problem. Use of the correct lower boundary condition is shown to lead to improved agreement.

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We investigate electron acceleration due to shear Alfven waves in a collissionless plasma for plasma parameters typical of 4–5RE radial distance from the Earth along auroral field lines. Recent observational work has motivated this study, which explores the plasma regime where the thermal velocity of the electrons is similar to the Alfven speed of the plasma, encouraging Landau resonance for electrons in the wave fields. We use a self-consistent kinetic simulation model to follow the evolution of the electrons as they interact with a short-duration wave pulse, which allows us to determine the parallel electric field of the shear Alfven wave due to both electron inertia and electron pressure effects. The simulation demonstrates that electrons can be accelerated to keV energies in a modest amplitude sub-second period wave. We compare the parallel electric field obtained from the simulation with those provided by fluid approximations.

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This study investigates the effects of temperature and pressure on inactivation of myrosinase extracted from black, brown and yellow mustard seeds. Brown mustard had higher myrosinase activity (2.75 un/mL) than black (1.50 un/mL) and yellow mustard (0.63 un/mL). The extent of enzyme inactivation increased with pressure (600-800 MPa) and temperature (30-70 °C) for all the mustard seeds. However, at combinations of lower pressures (200-400 MPa) and high temperatures (60-80 °C), there was less inactivation. For example, application of 300 MPa and 70 °C for 10 minutes retained 20%, 80% and 65% activity in yellow, black and brown mustard, respectively, whereas the corresponding activity retentions when applying only heat (70 °C, 10min) were 0%, 59% and 35%. Thus, application of moderate pressures (200-400 MPa) can potentially be used to retain myrosinase activity needed for subsequent glucosinolate hydrolysis.

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Thermochromic windows are able to modulate their transmittance in both the visible and the near-infrared field as a function of their temperature. As a consequence, they allow to control the solar gains in summer, thus reducing the energy needs for space cooling. However, they may also yield a reduction in the daylight availability, which results in the energy consumption for indoor artificial lighting being increased. This paper investigates, by means of dynamic simulations, the application of thermochromic windows to an existing office building in terms of energy savings on an annual basis, while also focusing on the effects in terms of daylighting and thermal comfort. In particular, due attention is paid to daylight availability, described through illuminance maps and by the calculation of the daylight factor, which in several countries is subject thresholds. The study considers both a commercially available thermochromic pane and a series of theoretical thermochromic glazing. The expected performance is compared to static clear and reflective insulating glass units. The simulations are repeated in different climatic conditions, showing that the overall energy savings compared to clear glazing can range from around 5% for cold climates to around 20% in warm climates, while not compromising daylight availability. Moreover the role played by the transition temperature of the pane is examined, pointing out an optimal transition temperatures that is irrespective of the climatic conditions.

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The objective of this work was to study the theological and thermal properties of film forming solutions (FFS) based on blends of gelatin and poly(vinyl alcohol) (PVA). The effect of the PVA concentration and plasticizer presence on the flow behavior, and viscoelastic and thermal properties of FFS was studied by steady-shear flow and oscillatory experiments, and also, by microcalorimetry. The FB presented Newtonian behavior at 30 degrees C, and the viscosity was not affected neither by the PVA concentration nor by the plasticizer. All FFS presented a phase transition during tests applying temperature scanning. It was verified that the PVA affected the viscoelastic properties of FFS by dilution of gelatin. This behavior was confirmed by microcalorimetric analysis. The behaviors of the storage (G`) and loss (G ``) moduli as a function of frequency of FFS obtained at 5 degrees C were typical of physical gels; with the G` higher than the G ``. The strength of the gels was affected by the PVA concentration. (C) 2009 Elsevier Ltd. All rights reserved.

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The objective of this work was to study the color, opacity, crystallinity, and the thermal and mechanical properties of films based on blends of gelatin and five different types of PVA [poly(vinyl alcohol)], with and without a plasticizer. The effect of the degree of hydrolysis of the PVA and the glycerol concentration on these properties was studied using colorimetry, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile mechanical tests. All films were essentially colorless (Delta E* < 5) and with low opacity ( Y <= 2.1). The DSC results were typical of partially crystalline materials, showing some phase separation characterized by a glass transition (T(g) = 40-55 degrees C), related to the amorphous part of the material, followed by two endothermic peaks related to the melting (T(m) = 100-160 and 170-210 degrees C) of the crystallites. The XRD results confirmed the crystallinity of the films. The film produced with PVA Celvol((R)) 418 (DH = 91.8%) showed the highest tensile resistance (tensile strength = 38 MPa), for films without plasticizer. However, with glycerol, the above-mentioned PVA and the PVA Celvol((R)) 504 produced the least resistant films of all the PVA types. But, although the mechanical properties of the blended films depended on the type of PVA used, there was no direct relationship between these properties and the degree of hydrolysis of the PVA. The properties studied were more closely dependent on the glycerol concentration. Finally, the mechanical resistance of the films presented a linear relationship with the glass transition temperature of the films. (c) 2007 Elsevier Ltd. All rights reserved.

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We have investigated the thermal and structural properties of different commercial dental resins: Filtek(TM) Z-350, Grandio(A (R)), Tetric Ceram(A (R)), and TPH Spectrum(A (R)). The purpose of the present study was to evaluate quantitatively the photo-polymerization behavior and the effect of filler contents on the kinetic cures of the dental resins by using Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FT-IR) techniques. We have successfully obtained the low and high glass transition T (g) values of the dental composite resins from DSC curves. It was also observed a good agreement between the both T (g) values, activation energies from thermal degradation, and the degree of conversion obtained for all samples. The results have shown that Tetric Ceram(A (R)) dental resin presented the higher T (g) values, activation energy of 215 +/- A 6 KJ mol(-1), and the higher degree of conversion (63%) when compared to the other resins studied herein.

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Pure Er:YAB (Er:YAl(3)(BO(3))(4)) nanometer-sized crystalline powder was produced from low cost chemical route, the polymeric precursor method. The initial homogeneous solutions were heat treated from 200 to 700A degrees C under oxygen atmosphere and the unique crystalline phase was synthesized at around 1150A degrees C. The thermal treatments and the initial stoichiometry play a very important role on the Er:YAB preparation. The thermal events of amorphous precursor resins and the crystallization process up to phase formation were investigated.