948 resultados para Time-resolved methods
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The Earth's upper mantle, mainly composed of olivine, is seismically anisotropic. Seismic anisotropy attenuation has been observed at 220km depth. Karato et al. (1992) attributed this attenuation to a transition between two deformation mechanisms, from dislocation creep above 220km to diffusion creep below 220km, induced by a change in water content. Couvy (2005) and Mainprice et al. (2005) predicted a change in Lattice Preferred Orientation induced by pressure, which comes from a change of slip system, from [100] slip to [001] slip, and is responsible for the seismic anisotropy attenuation. Raterron et al. (2007) ran single crystal deformation experiments under anhydrous conditions and observed that the slip system transition occurs around 8GPa, which corresponds to a depth of 260Km. Experiments were done to quantify the effects of water on olivine single crystals deformed using D-DIA press and synchrotron beam. Deformations were carried out in uniaxial compression along [110]c, [011]c, and [101]c, crystallographic directions, at pressure ranging from 4 to 8GPa and temperature between 1373 and 1473K. Talc sleeves about the annulus of the single crystals were used as source of water in the assembly. Stress and specimen strain rates were calculated by in-situ X-ray diffraction and time resolved imaging, respectively. By direct comparison of single crystals strain rates, we observed that [110]c deforms faster than [011]c below 5GPa. However above 6GPa [011]c deforms faster than [110]c. This revealed that [100](010) is the dominant slip system below 5GPa, and above 6GPa [001](010) becomes dominant. According to our results, the slip system transition, which is induced by pressure, occurs at 6GPa. Water influences the pressure where the switch over occurs, by lowering the transition pressure. The pressure effect on the slip systems activity has been quantified and the hydrolytic weakening has also been estimated for both orientations. Data also shows that temperature affects the slip system activity. The regional variation of the depth for the seismic anisotropy attenuation, which would depend on local hydroxyl content and temperature variations and explains the seismic anisotropy attenuation occurring at about 220Km depth in the mantle, where the pressure is about 6GPa. Deformation of MgO single crystal oriented [100], [110] and [111] were also performed. The results predict a change in the slip system activity at 23GPa, again induced by pressure. This explains the seismic anisotropy observed in the lower mantle.
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Combustion-generated carbon black nano particles, or soot, have both positive and negative effects depending on the application. From a positive point of view, it is used as a reinforcing agent in tires, black pigment in inks, and surface coatings. From a negative point of view, it affects performance and durability of many combustion systems, it is a major contributor of global warming, and it is linked to respiratory illness and cancer. Laser-Induced Incandescence (LII) was used in this study to measure soot volume fractions in four steady and twenty-eight pulsed ethylene diffusion flames burning at atmospheric pressure. A laminar coflow diffusion burner combined with a very-high-speed solenoid valve and control circuit provided unsteady flows by forcing the fuel flow with frequencies between 10 Hz and 200 Hz. Periodic flame oscillations were captured by two-dimensional phase-locked LII images and broadband luminosity images for eight phases (0°- 360°) covering each period. A comparison between the steady and pulsed flames and the effect of the pulsation frequency on soot volume fraction in the flame region and the post flame region are presented. The most significant effect of pulsing frequency was observed at 10 Hz. At this frequency, the flame with the lowest mean flow rate had 1.77 times enhancement in peak soot volume fraction and 1.2 times enhancement in total soot volume fraction; whereas the flame with the highest mean flow rate had no significant change in the peak soot volume fraction and 1.4 times reduction in the total soot volume fraction. A correlation (ƒv Reˉ1 = a+b· Str) for the total soot volume fraction in the flame region for the unsteady laminar ethylene flames was obtained for the pulsation frequency between 10 Hz and 200 Hz, and the Reynolds number between 37 and 55. The soot primary particle size in steady and unsteady flames was measured using the Time-Resolved Laser-Induced Incandescence (TIRE-LII) and the double-exponential fit method. At maximum frequency (200 Hz), the soot particles were smaller in size by 15% compared to the steady case in the flame with the highest mean flow rate.
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The optical-structural characteristics of the direct optical band-gap semiconducting series of surfactant template-mediated laminar (CdS)x(CdCl2)y(CnH2n+4N)z nanocomposites are reported. X-ray diffraction measurements of the nanocomposites exhibited interlaminar distances in the range 2.9-3.6 nm with observations of eighth order {0 0 l} diffraction planes indicative of a high degree of laminarity and crystallographic order. Diffuse reflectance measurements have determined that the profile of their emission spectrum is that of a direct band-gap with absorption edges in the range 2.11-2.40 eV, depending on the CdS mole fraction in the nanocomposite. Photoluminescence (PL) excitation and time-resolved PL spectroscopies give an estimate of the maximum relative absorbance of the nanocomposites at ∼420 nm while the minimum was observed at ∼560 nm. The main emission was observed at ∼700 nm with emission from doubly ionized sulphur vacancies observed at ∼615 nm at room temperature. The CdS-containing nanocomposite is thus a surfactant-mediated modular system with variable band-gap energy emission.
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Significant advances in understanding the fundamental photophysical behavior of single-walled carbon nanotubes (SWNTs) have been made possible by the development of ionic, conjugated aryleneethynylene polymers that helically wrap SWNTs with well-defined morphology. My contribution to this work was the design and synthesis of porphyrin-containing polymers and the photophysical investigation of the corresponding polymer-wrapped SWNTs. For these new constructs, the polymer acts as more than just a solubilization scaffold; such assemblies can provide benchmark data for evaluating spectroscopic signatures of energy and charge transfer events and lay the groundwork for further, rational development of polymers with precisely tuned redox properties and electronic coupling with the underlying SWNT. The first design to incorporate a zinc porphyrin into the polymer backbone, PNES-PZn, suffered from severe aggregation in solution and was redesigned to produce the porphyrin-containing polymer S-PBN-PZn. This polymer was utilized to helically wrap chirality-enriched (6,5) SWNTs, which resulted in significant quenching of the porphyrin-based fluorescence. Time-resolved spectroscopy revealed a simultaneous rise and decay of the porphyrin radical cation and SWNT electron polaron spectroscopic signatures indicative of photoinduced electron transfer. A new polymer, S-PBN(b)-Ph2PZn3, was then synthesized which incorporated a meso-ethyne linked zinc porphyrin trimer. By changing the absorption profile and electrochemical redox potentials of the polymer, the photophysical behavior of the corresponding polymer-wrapped (6,5)-SWNTs was dramatically changed, and the polymer-wrapped SWNTs no longer showed evidence for photoinduced electron transfer.
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Self-assembly of nanoparticles is a promising route to form complex, nanostructured materials with functional properties. Nanoparticle assemblies characterized by a crystallographic alignment of the nanoparticles on the atomic scale, i.e. mesocrystals, are commonly found in nature with outstanding functional and mechanical properties. This thesis aims to investigate and understand the formation mechanisms of mesocrystals formed by self-assembling iron oxide nanocubes. We have used the thermal decomposition method to synthesize monodisperse, oleate-capped iron oxide nanocubes with average edge lengths between 7 nm and 12 nm and studied the evaporation-induced self-assembly in dilute toluene-based nanocube dispersions. The influence of packing constraints on the alignment of the nanocubes in nanofluidic containers has been investigated with small and wide angle X-ray scattering (SAXS and WAXS, respectively). We found that the nanocubes preferentially orient one of their {100} faces with the confining channel wall and display mesocrystalline alignment irrespective of the channel widths. We manipulated the solvent evaporation rate of drop-cast dispersions on fluorosilane-functionalized silica substrates in a custom-designed cell. The growth stages of the assembly process were investigated using light microscopy and quartz crystal microbalance with dissipation monitoring (QCM-D). We found that particle transport phenomena, e.g. the coffee ring effect and Marangoni flow, result in complex-shaped arrays near the three-phase contact line of a drying colloidal drop when the nitrogen flow rate is high. Diffusion-driven nanoparticle assembly into large mesocrystals with a well-defined morphology dominates at much lower nitrogen flow rates. Analysis of the time-resolved video microscopy data was used to quantify the mesocrystal growth and establish a particle diffusion-based, three-dimensional growth model. The dissipation obtained from the QCM-D signal reached its maximum value when the microscopy-observed lateral growth of the mesocrystals ceased, which we address to the fluid-like behavior of the mesocrystals and their weak binding to the substrate. Analysis of electron microscopy images and diffraction patterns showed that the formed arrays display significant nanoparticle ordering, regardless of the distinctive formation process. We followed the two-stage formation mechanism of mesocrystals in levitating colloidal drops with real-time SAXS. Modelling of the SAXS data with the square-well potential together with calculations of van der Waals interactions suggests that the nanocubes initially form disordered clusters, which quickly transform into an ordered phase.
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Thesis (Ph.D.)--University of Washington, 2016-08
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As a way to gain greater insights into the operation of online communities, this dissertation applies automated text mining techniques to text-based communication to identify, describe and evaluate underlying social networks among online community members. The main thrust of the study is to automate the discovery of social ties that form between community members, using only the digital footprints left behind in their online forum postings. Currently, one of the most common but time consuming methods for discovering social ties between people is to ask questions about their perceived social ties. However, such a survey is difficult to collect due to the high investment in time associated with data collection and the sensitive nature of the types of questions that may be asked. To overcome these limitations, the dissertation presents a new, content-based method for automated discovery of social networks from threaded discussions, referred to as ‘name network’. As a case study, the proposed automated method is evaluated in the context of online learning communities. The results suggest that the proposed ‘name network’ method for collecting social network data is a viable alternative to costly and time-consuming collection of users’ data using surveys. The study also demonstrates how social networks produced by the ‘name network’ method can be used to study online classes and to look for evidence of collaborative learning in online learning communities. For example, educators can use name networks as a real time diagnostic tool to identify students who might need additional help or students who may provide such help to others. Future research will evaluate the usefulness of the ‘name network’ method in other types of online communities.
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To gain a better understanding of the fluid–structure interaction and especially when dealing with a flow around an arbitrarily moving body, it is essential to develop measurement tools enabling the instantaneous detection of moving deformable interface during the flow measurements. A particularly useful application is the determination of unsteady turbulent flow velocity field around a moving porous fishing net structure which is of great interest for selectivity and also for the numerical code validation which needs a realistic database. To do this, a representative piece of fishing net structure is used to investigate both the Turbulent Boundary Layer (TBL) developing over the horizontal porous moving fishing net structure and the turbulent flow passing through the moving porous structure. For such an investigation, Time Resolved PIV measurements are carried out and combined with a motion tracking technique allowing the measurement of the instantaneous motion of the deformable fishing net during PIV measurements. Once the two-dimensional motion of the porous structure is accessed, PIV velocity measurements are analyzed in connection with the detected motion. Finally, the TBL is characterized and the effect of the structure motion on the volumetric flow rate passing though the moving porous structure is clearly demonstrated.
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As fluoroquinolonas são antibióticos que têm um largo espectro de ação contra bactérias, especialmente Gram-negativas. O seu mecanismo de ação assenta na inibição de enzimas responsáveis pela replicação do DNA. Porém, devido ao seu uso indevido, o surgimento de resistência bacteriana a estes antibióticos tem-se tornado um grave problema de saúde pública. Uma vez que os seus alvos de ação se situam no meio intracelular, a redução da permeabilidade da membrana externa de bactérias Gram-negativas constitui um dos mecanismos de resistência mais conhecidos. Esta redução é associada à baixa expressão ou mutações em porinas necessárias para permitir o seu transporte, mais concretamente, da OmpF. Estudos prévios demonstraram que a coordenação de fluoroquinolonas com iões metálicos divalentes e 1,10-fenantrolina (genericamente designados metaloantibióticos) são potenciais candidatos como alternativa às fluoroquinolonas convencionais. Estes metaloantibióticos exibem um efeito antimicrobiano comparável ou superior à fluoroquinolona na forma livre, mas parecem ter uma via de translocação diferente, independente de porinas. Estas diferenças no mecanismo de captura podem ser fundamentais para contornar a resistência bacteriana. De forma a compreender o papel dos lípidos no mecanismo de entrada dos metaloantibióticos, estudou-se a interação e localização dos metaloantibióticos da Ciprofloxacina (2ª geração), da Levofloxacina (3ª geração) e Moxifloxacina (4ª geração) com um modelo de membranas de Escherichia coli desprovido de porinas. Estes estudos foram realizados através de técnicas de espectroscopia de fluorescência, por medições em modo estacionário e resolvida no tempo. Os coeficientes de partição determinados demonstraram uma interação mais elevada dos metaloantibióticos relativamente às respetivas fluoroquinolonas na forma livre, um facto que está diretamente relacionado com as espécies existentes em solução a pH fisiológico. Os estudos de localização mostraram que estes metaloantibióticos devem estar inseridos na membrana bacteriana, confirmando a sua entrada independente de porinas. Este mecanismo de entrada, pela via hidrofóbica, é potenciado por interações eletrostáticas entre as espécies catiónicas de metaloantibiótico que existem a pH 7,4 e os grupos carregados negativamente dos fosfolípidos da membrana. Desta forma, os resultados obtidos neste estudo sugerem que a via de entrada dos metaloantibióticos e das respetivas fluoroquinolonas deve ser diferente. Os metaloantibióticos são candidatos adequados para a realização de mais testes laboratoriais e uma alternativa promissora para substituir as fluoroquinolonas convencionais, uma vez que parecem ultrapassar um dos principais mecanismos de resistência bacteriana a esta classe de antibióticos.
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Nos dias de hoje as diferentes indústrias e sectores de atividade económica assentam os seus pilares de desenvolvimento na procura constante de fontes de melhoria, para que assim seja possível melhorar a relação qualidade / preço. Embora no setor industrial as melhorias e inovações tecnológicas surjam a cada dia, estas por si não chegam. Grande parte da otimização incorrida, quer na indústria de manufatura, quer na indústria de serviços, surge da “simples” eliminação de desperdícios, e da procura constante por fontes de melhoria. Com o objetivo traçado, a Grohe Portugal Componentes Sanitários, Lda. propôs a eliminação de desperdícios no âmbito do abastecimento de componentes às linhas de montagem existentes na sua fábrica em Albergaria-a-Velha. Este processo passa não só por uma otimização do tempo de abastecimento e das quantidades de abastecimento, mas também consiste na reestruturação das diferentes rotinas de abastecimento. Todo este processo de otimização estará assente no conceito de Mizusumashi. O Mizusumashi, ou comboio logístico como muitas vezes é referenciado, surge com o objetivo de separar a tarefa de abastecimento da função de montagem. A sua origem surge da adaptação do conceito de Milk Run (volta do leiteiro) à logística interna. Torna-se de relevo referir que, para que este “simples” conceito funcione com uma eficiência que proporcione a sua aplicação, são vastos os fatores que necessitam de ajustamentos ou mesmo, em alguns casos, de uma reestruturação completa. O trabalho desenvolvido nestas instalações fabris, e que culminou neste documento, teve como princípio a análise, avaliação e implementação de melhorias no sistema de abastecimento às linhas de montagem. Todo o processo de abastecimento foi analisado e desconstruído nas suas componentes, para que assim fosse possível desenhar o plano de reestruturação indicado. Foram implementadas melhorias de layout, tempos e tarefas. Os resultados foram positivos tendo em conta o objetivo inicial. Todo este plano foi pensado e documentado com o objetivo de tornar este sistema adaptável a possíveis mudanças. Foi possível então criar um sistema voltado para um plano de melhoria contínua. Com um abastecimento normalizado e rotinado a gestão de stocks é mais precisa diminuindo assim os desperdícios inerentes a estas funções.
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Tämän kandidaatintyön tarkoituksena on selvittää hitsien tarkastukseen käytettyjen NDT-menetelmien nykytilannetta. Työssä kerrotaan mitä reaaliaikainen NDT-tarkastus on ja mitä menetelmiä siihen voidaan käyttää. Työn tarkoituksena on antaa lukijalle kokonaiskuva NDT-tarkastuksen nykytilasta ja siinä käytettävistä menetelmistä. Tutkimus suoritettiin kirjallisuuskatsauksena. Kirjallisuuskatsaus on luonteeltaan toteava. Lähteiden etsintä suoritettiin suurimmalta osin Internet-hakuna. NDT-tarkastusmenetelmät voidaan jakaa kahteen pääkategoriaan; pinta- ja volumetrisiin menetelmiin. Kaikki tarkastusmenetelmät eivät sovellu reaaliaikaiseen tarkastukseen. Hitsien tarkastuksessa käytetyimmät reaaliaikaiset menetelmät ovat: ultraäänitarkastus, radiografinen tarkastus, optinen spektroskopia, termografia ja pyörrevirtatarkastus. Kaikilla reaaliaikaisilla menetelmillä on omat vahvuutensa ja heikkoutensa. Työssä esitetään myös CASE-esimerkkejä reaaliaikaisesta hitsien tarkastamisesta.Tärkeimpinä johtopäätöksinä voidaan nähdä se, että hitsien NDT-tarkastuksen onnistuminen on aina hyvin tapauskohtaista ja riippuu useista muuttujista. Tästä syystä tällä hetkellä NDT-tarkastusmenetelmistä ei voi valita parasta kaikkiin käyttökohteisiin sopivaa menetelmää. Monessa prosessissa NDT-tarkastustehokkuutta ei määritä mekaanisen laitteiston mittaustarkkuus, vaan tulosten analysointiin käytettyjen algoritmien tehottomuus. Tutkimuksessa esitetään myös idea hybridi-NDT-tarkastusjärjestelmästä, jolla saataisiin havaittua tehokkaasti sekä pinta-että volumetrisia virheitä.
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The length of wind turbine rotor blades has been increased during the last decades. Higher stresses arise especially at the blade root because of the longer lever arm. One way to reduce unsteady blade-root stresses caused by turbulence, gusts, or wind shear is to actively control the lift in the blade tip region. One promising method involves airfoils with morphing trailing edges to control the lift and consequently the loads acting on the blade. In the present study, the steady and unsteady behavior of an airfoil with a morphing trailing edge is investigated. Two-dimensional Reynolds-Averaged Navier-Stokes (RANS) simulations are performed for a typical thin wind turbine airfoil with a morphing trailing edge. Steady-state simulations are used to design optimal geometry, size, and deflection angles of the morphing trailing edge. The resulting steady aerodynamic coefficients are then analyzed at different angles of attack in order to determine the effectiveness of the morphing trailing edge. In order to investigate the unsteady aerodynamic behavior of the optimal morphing trailing edge, time-resolved RANS-simulations are performed using a deformable grid. In order to analyze the phase shift between the variable trailing edge deflection and the dynamic lift coefficient, the trailing edge is deflected at four different reduced frequencies for each different angle of attack. As expected, a phase shift between the deflection and the lift occurs. While deflecting the trailing edge at angles of attack near stall, additionally an overshoot above and beyond the steady lift coefficient is observed and evaluated.
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Understanding and measuring the interaction of light with sub-wavelength structures and atomically thin materials is of critical importance for the development of next generation photonic devices. One approach to achieve the desired optical properties in a material is to manipulate its mesoscopic structure or its composition in order to affect the properties of the light-matter interaction. There has been tremendous recent interest in so called two-dimensional materials, consisting of only a single to a few layers of atoms arranged in a planar sheet. These materials have demonstrated great promise as a platform for studying unique phenomena arising from the low-dimensionality of the material and for developing new types of devices based on these effects. A thorough investigation of the optical and electronic properties of these new materials is essential to realizing their potential. In this work we present studies that explore the nonlinear optical properties and carrier dynamics in nanoporous silicon waveguides, two-dimensional graphite (graphene), and atomically thin black phosphorus. We first present an investigation of the nonlinear response of nanoporous silicon optical waveguides using a novel pump-probe method. A two-frequency heterodyne technique is developed in order to measure the pump-induced transient change in phase and intensity in a single measurement. The experimental data reveal a characteristic material response time and temporally resolved intensity and phase behavior matching a physical model dominated by free-carrier effects that are significantly stronger and faster than those observed in traditional silicon-based waveguides. These results shed light on the large optical nonlinearity observed in nanoporous silicon and demonstrate a new measurement technique for heterodyne pump-probe spectroscopy. Next we explore the optical properties of low-doped graphene in the terahertz spectral regime, where both intraband and interband effects play a significant role. Probing the graphene at intermediate photon energies enables the investigation of the nonlinear optical properties in the graphene as its electron system is heated by the intense pump pulse. By simultaneously measuring the reflected and transmitted terahertz light, a precise determination of the pump-induced change in absorption can be made. We observe that as the intensity of the terahertz radiation is increased, the optical properties of the graphene change from interband, semiconductor-like absorption, to a more metallic behavior with increased intraband processes. This transition reveals itself in our measurements as an increase in the terahertz transmission through the graphene at low fluence, followed by a decrease in transmission and the onset of a large, photo-induced reflection as fluence is increased. A hybrid optical-thermodynamic model successfully describes our observations and predicts this transition will persist across mid- and far-infrared frequencies. This study further demonstrates the important role that reflection plays since the absorption saturation intensity (an important figure of merit for graphene-based saturable absorbers) can be underestimated if only the transmitted light is considered. These findings are expected to contribute to the development of new optoelectronic devices designed to operate in the mid- and far-infrared frequency range. Lastly we discuss recent work with black phosphorus, a two-dimensional material that has recently attracted interest due to its high mobility and direct, configurable band gap (300 meV to 2eV), depending on the number of atomic layers comprising the sample. In this work we examine the pump-induced change in optical transmission of mechanically exfoliated black phosphorus flakes using a two-color optical pump-probe measurement. The time-resolved data reveal a fast pump-induced transparency accompanied by a slower absorption that we attribute to Pauli blocking and free-carrier absorption, respectively. Polarization studies show that these effects are also highly anisotropic - underscoring the importance of crystal orientation in the design of optical devices based on this material. We conclude our discussion of black phosphorus with a study that employs this material as the active element in a photoconductive detector capable of gigahertz class detection at room temperature for mid-infrared frequencies.
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BACKGROUND: Regional differences in physician supply can be found in many health care systems, regardless of their organizational and financial structure. A theoretical model is developed for the physicians' decision on office allocation, covering demand-side factors and a consumption time function. METHODS: To test the propositions following the theoretical model, generalized linear models were estimated to explain differences in 412 German districts. Various factors found in the literature were included to control for physicians' regional preferences. RESULTS: Evidence in favor of the first three propositions of the theoretical model could be found. Specialists show a stronger association to higher populated districts than GPs. Although indicators for regional preferences are significantly correlated with physician density, their coefficients are not as high as population density. CONCLUSIONS: If regional disparities should be addressed by political actions, the focus should be to counteract those parameters representing physicians' preferences in over- and undersupplied regions.
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Tomato (Lycopersicon esculentum Mill.) is the second most important vegetable crop worldwide and a rich source of hydrophilic (H) and lipophilic (L) antioxidants. The H fraction is constituted mainly by ascorbic acid and soluble phenolic compounds, while the L fraction contains carotenoids (mostly lycopene), tocopherols, sterols and lipophilic phenolics [1,2]. To obtain these antioxidants it is necessary to follow appropriate extraction methods and processing conditions. In this regard, this study aimed at determining the optimal extraction conditions for H and L antioxidants from a tomato surplus. A 5-level full factorial design with 4 factors (extraction time (I, 0-20 min), temperature (T, 60-180 •c), ethanol percentage (Et, 0-100%) and solid/liquid ratio (S/L, 5-45 g!L)) was implemented and the response surface methodology used for analysis. Extractions were carried out in a Biotage Initiator Microwave apparatus. The concentration-time response methods of crocin and P-carotene bleaching were applied (using 96-well microplates), since they are suitable in vitro assays to evaluate the antioxidant activity of H and L matrices, respectively [3]. Measurements were carried out at intervals of 3, 5 and 10 min (initiation, propagation and asymptotic phases), during a time frame of 200 min. The parameters Pm (maximum protected substrate) and V m (amount of protected substrate per g of extract) and the so called IC50 were used to quantify the response. The optimum extraction conditions were as follows: r~2.25 min, 7'=149.2 •c, Et=99.1 %and SIL=l5.0 giL for H antioxidants; and t=l5.4 min, 7'=60.0 •c, Et=33.0% and S/L~l5.0 g/L for L antioxidants. The proposed model was validated based on the high values of the adjusted coefficient of determination (R2.wi>0.91) and on the non-siguificant differences between predicted and experimental values. It was also found that the antioxidant capacity of the H fraction was much higher than the L one.