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High-Efficiency and High-Frequency Resonant Converter Based Single-Stage Soft-Switching Isolated Inverter Design and Optimization with Gallium-Nitride (GaN)Wen, Hao 30 September 2021 (has links)
Isolated inverter can provide galvanic isolation which is necessary for some applications with safety regulations. Traditionally, a two-stage configuration is widely applied with isolated dc-dc stage and a sinusoidal pulse-width-modulated (SPWM) dc-ac stage. However, this two-stage configuration suffers from more components count, more complex control and tend to have lower efficiency and lower power density. Meanwhile, a large dc bus capacitor is needed to attenuate the double line frequency from SPWM for two-stage configuration. Therefore, the single-stage approach including an isolated dc-rectified sine stage and a line frequency unfolder is preferable. Since the unfolder circuit is at line frequency being almost lossless, the isolated dc-rectified sine stage becomes critical.
However, the relevant research for the single-stage isolated inverter is limited. People either utilize PWM based converter as dc-rectified sine stage with duty cycle adjustment or apply SRC or LLC resonant converter for better soft switching characteristics. For PWM based converter, hard switching restricts the overall inverter efficiency, while for SRC/LLC, enough wide voltage gain range and full range ZVS are the major issues.
This dissertation aims to provide solutions for a high-efficiency, high-frequency resonant converter based single-stage soft-switching isolated inverter design. The LLC and LCLCL resonant converters are applied as the isolated dc-rectified sine stage with variable frequency modulation (VFM). Therefore, the rectified sine wave generation consists of many dc-dc conversion with different switching frequencies and an efficient dc-rectified sine stage design needs each dc-dc conversion to be with high efficiency.
This dissertation will first propose the optimization methods for LLC converter dc-dc conversion. ZVS models are derived to ensure fully ZVS performance for primary side GaN devices. As a large part in loss breakdown, the optimization for transformer is essential. The LLC converter can achieve above 99% efficiency with proposed optimization approach. Moreover, the channel turn-off energy model is presented for a more accurate loss analysis.
With all the design and optimization considerations, a MHz LLC converter based isolated inverter is designed and a hybrid modulation method is proposed, which includes full bridge (FB) VFM for output high line region and half bridge (HB) VFM for output low line region. By changing from FB to HB, the output voltage gain is reduced to half to have a wider voltage gain range. However, the total harmonic distortion (THD) of output voltage at light load will be impacted since the voltage gain will be higher with lighter load at the maximum switching frequency.
A MHz LCLCL converter based isolated inverter is proposed for a better output voltage THD at light load conditions. The paralleled LC inside the LCLCL resonant tank can naturally create a zero voltage gain point at their resonant frequency, which shows superior performance for rectified sine wave generation. Besides the better THD performance, the LCLCL converter based isolated inverter also features for easier control, better ZVS performance and narrower switching frequency range.
Meanwhile, the LCLCL based inverter topology has bi-directional power flow capability as well. With variable frequency modulation for ac-dc, this topology is still a single-stage solution compared to the traditional two-stage solution including PFC + LLC configuration. / Doctor of Philosophy / Inverters can convert dc voltage to ac voltage and typically people use two-stage approach with isolated dc-dc stage and dc-ac stage. However, this two-stage configuration suffers from more components count, more complex control and tend to have lower efficiency and lower power density. Therefore, the single-stage solution with dc-rectified sine wave stage and a line frequency unfolder becomes appealing. The unfolder circuit is to unfold the rectifier sine wave to an ac sine wave at the output. Since the unfolder is at line frequency and can be considered lossless, the key design is for the dc-rectified sine stage.
The resonant converter featured for soft switching seems to be a good candidate. However, the inverter needs soft switching for the whole range and an enough wide voltage gain, which makes the design difficult, especially the target is high efficiency for the overall inverter. This dissertation aims to provide solutions for a high-efficiency, high-frequency resonant converter based single-stage soft-switching isolated inverter design. The LLC and LCLCL resonant converters are applied as the isolated dc-rectified sine stage with variable frequency modulation (VFM). Therefore, the rectified sine wave generation consists of many dc-dc conversion with different switching frequencies and an efficient dc-rectified sine stage design needs each dc-dc conversion to be with high efficiency.
The design considerations and optimization methods for the LLC dc-dc conversion are firstly investigated. Based on these approaches, a MHz LLC converter based isolated inverter is designed with proposed hybrid modulation method. To further improve the light load performance, a MHz LCLCL converter based isolated inverter topology is proposed. The paralleled LC inside the LCLCL resonant tank can naturally create a zero voltage gain point which shows superior characteristics for rectified sine wave generation. Moreover, the LCLCL resonant converter based topology has bi-directional capability as well so it can work well for ac voltage to dc voltage conversion.
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Uncertainty Quantification, State and Parameter Estimation in Power Systems Using Polynomial Chaos Based MethodsXu, Yijun 31 January 2019 (has links)
It is a well-known fact that a power system contains many sources of uncertainties. These uncertainties coming from the loads, the renewables, the model and the measurement, etc, are influencing the steady state and dynamic response of the power system.
Facing this problem, traditional methods, such as the Monte Carlo method and the Perturbation method, are either too time consuming or suffering from the strong nonlinearity in the system.
To solve these, this Dissertation will mainly focus on developing the polynomial chaos based method to replace the traditional ones. Using it, the uncertainties from the model and the measurement are propagated through the polynomial chaos bases at a set of collocation points. The approximated polynomial chaos coefficients contain the statistical information. The method can greatly accelerate the calculation efficiency while not losing the accuracy, even when the system is highly stressed.
In this dissertation, both the forward problem and the inverse problem of uncertainty quantification will be discussed. The forward problems will include the probabilistic power flow problem and statistical power system dynamic simulations. The generalized polynomial chaos method, the adaptive polynomial chaos-ANOVA method and the multi-element polynomial chaos method will be introduced and compared. The case studies show that the proposed methods have great performances in the statistical analysis of the large-scale power systems. The inverse problems will include the state and parameter estimation problem. A novel polynomial-chaos-based Kalman filter will be proposed. The comparison studies with other traditional Kalman filter demonstrate the good performances of the proposed Kalman filter. We further explored the area dynamic parameter estimation problem under the Bayesian inference framework. The polynomial-chaos-expansions are treated as the response surface of the full dynamic solver. Combing with hybrid Markov chain Monte Carlo method, the proposed method yields very high estimation accuracy while greatly reducing the computing time.
For both the forward problem and the inverse problems, the polynomial chaos based methods haven shown great advantages over the traditional methods. These computational techniques can improve the efficiency and accuracy in power system planning, guarantee the rationality and reliability in power system operations, and, finally, speed up the power system dynamic security assessment. / PHD / It is a well-known fact that a power system state is inherently stochastic. Sources of stochasticity include load random variations, renewable energy intermittencies, and random outages of generating units, lines, and transformers, to cite a few. These stochasticities translate into uncertainties in the models that are assumed to describe the steady-sate and dynamic behavior of a power system. Now, these models are themselves approximate since they are based on some assumptions that are typically violated in practice. Therefore, it does not come as a surprise if recent research activities in power systems are focusing on how to cope with uncertainties when dealing with power system planning, monitoring and control.
This Dissertation is developing polynomial-chaos-based method in quantifying, and managing these uncertainties. Three major topics, including uncertainty quantification, state estimation and parameter estimation are discussed. The developed method can improve the efficiency and accuracy in power system planning, guarantee the rationality and reliability in power system operations in dealing with the uncertainties, and, finally, enhancing the resilience of the power systems.
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Growth, fabrication, and investigation of light-emitting diodes based on GaN nanowiresMusolino, Mattia 04 January 2016 (has links)
Diese Arbeit gibt einen tiefgehenden Einblick in verschiedene Aspekte von auf (In,Ga)N/GaN Heterostrukturen basierenden Leuchtdioden (LEDs), mittels Molekularstrahlepitaxie entlang der Achse von Nanodrähten (NWs) auf Si Substraten gewachsen. Insbesondere wurden die Wachstumsparameter angepasst, um eine Koaleszierung der Nanodrähte zu vermindern. Auf diese Weise konnte die durch die NW-LEDs emittierte Intensität der Photolumineszenz (PL) um einen Faktor zehn erhöht werden. Die opto-elektronischen Eigenschaften von NW-LEDs konnten durch die Verwendung von Indiumzinoxid, anstatt von Ni/Au als Frontkontakt, verbessert werden. Zudem wurde demonstriert, dass auch selektives Wachstum (SAG) von GaN NWs auf AlN gepufferten Si Substraten mit einer guten Leistungsfähigkeit von Geräte vereinbar ist und somit als Wegbereiter für eine neue Generation von NW-LEDs auf Si dienen kann. Weiterhin war es möglich, strukturierte Felder von ultradünnen NWs durch SAG und thermische in situ Dekomposition herzustellen. In den durch die NW-LEDs emittierten Elektrolumineszenzspektren (EL) wurde eine Doppellinenstruktur beobachtet, die höchstwahrscheinlich von den kompressiven Verspannungen im benachbarten Quantentopf, durch die Elektronensperrschicht verursachten, herrührt. Die Analyse von temperaturabhängigen PL- und EL-Messungen zeigt, dass Ladungsträgerlokalisierungen nicht ausschlaggebend für die EL-Emission von NW-LEDs sind. Die Strom-Spannungs-Charakteristiken (I-V) von NW-LEDs unter Vorwärtsspannung wurden mittels eines Modells beschrieben, in das die vielkomponentige Natur der LEDs berücksichtigt wird. Die unter Rückwärtsspannung aktiven Transportmechanismen wurden anhand von Kapazitätstransientenmessungen und temperaturabhänigigen I-V-Messungen untersucht. Dann wurde ein physikalisches Modell zur quantitativen Beschreibung der besonderen I-V-T Charakteristik der untersuchten NW-LEDs entwickelt. / This PhD thesis provides an in-depth insight on various crucial aspects of light-emitting diodes (LEDs) based on (In,Ga)N/GaN heterostructures grown along the axis of nanowires (NWs) by molecular beam epitaxy on Si substrates. In particular, the growth parameters are adjusted so as to suppress the coalescence of NWs; in this way the photoluminescence (PL) intensity emitted from the NW-LEDs can be increased by about ten times. The opto-electronic properties of the NW-LEDs can be further improved by exclusively employing indium tin oxide instead of Ni/Au as top contact. Furthermore, the compatibility of selective-area growth (SAG) of GaN NWs on AlN-buffered Si substrates with device operation is demonstrated, thus paving the way for a new generation of LEDs based on homogeneous NW ensembles on Si. Ordered arrays of ultrathin NWs are also successfully obtained by combining SAG and in situ post-growth thermal decomposition. A double-line structure is observed in the electroluminescence (EL) spectra emitted by the NW-LEDs; it is likely caused by compressive strain introduced by the (Al,Ga)N electron blocking layer in the neighbouring (In,Ga)N quantum well. An in-depth analysis of temperature dependent PL and EL measurements indicates that carrier localization phenomena do not dominate the EL emission properties of the NW-LEDs. The forward bias current-voltage (I-V) characteristics of different NW-LEDs are analysed by means of an original model that takes into account the multi-element nature of LEDs based on NW ensembles by assuming a linear dependence of the ideality factor on applied bias. The transport mechanisms in reverse bias regime are carefully studied by means of deep level transient spectroscopy (DLTS) and temperature dependent I-V measurements. The physical origin of the detected deep states is discussed. Then, a physical model able to describe quantitatively the peculiar I-V-T characteristics of NW-LEDs is developed.
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Méthode de type Galerkin discontinu en maillages multi-éléments pour la résolution numérique des équations de Maxwell instationnaires / High order non-conforming multi-element Discontinuous Galerkin method for time-domain electromagneticsDurochat, Clément 30 January 2013 (has links)
Cette thèse porte sur l’étude d’une méthode de type Galerkin discontinu en domaine temporel (GDDT), afin de résoudre numériquement les équations de Maxwell instationnaires sur des maillages hybrides tétraédriques/hexaédriques en 3D (triangulaires/quadrangulaires en 2D) et non-conformes, que l’on note méthode GDDT-PpQk. Comme dans différents travaux déjà réalisés sur plusieurs méthodes hybrides (par exemple des combinaisons entre des méthodes Volumes Finis et Différences Finies, Éléments Finis et Différences Finies, etc.), notre objectif principal est de mailler des objets ayant une géométrie complexe à l’aide de tétraèdres, pour obtenir une précision optimale, et de mailler le reste du domaine (le vide environnant) à l’aide d’hexaèdres impliquant un gain en terme de mémoire et de temps de calcul. Dans la méthode GDDT considérée, nous utilisons des schémas de discrétisation spatiale basés sur une interpolation polynomiale nodale, d’ordre arbitraire, pour approximer le champ électromagnétique. Nous utilisons un flux centré pour approcher les intégrales de surface et un schéma d’intégration en temps de type saute-mouton d’ordre deux ou d’ordre quatre. Après avoir introduit le contexte historique et physique des équations de Maxwell, nous présentons les étapes détaillées de la méthode GDDT-PpQk. Nous réalisons ensuite une analyse de stabilité L2 théorique, en montrant que cette méthode conserve une énergie discrète et en exhibant une condition suffisante de stabilité de type CFL sur le pas de temps, ainsi que l’analyse de convergence en h (théorique également), conduisant à un estimateur d’erreur a-priori. Ensuite, nous menons une étude numérique complète en 2D (ondes TMz), pour différents cas tests, des maillages hybrides et non-conformes, et pour des milieux de propagation homogènes ou hétérogènes. Nous faisons enfin de même pour la mise en oeuvre en 3D, avec des simulations réalistes, comme par exemple la propagation d’une onde électromagnétique dans un modèle hétérogène de tête humaine. Nous montrons alors la cohérence entre les résultats mathématiques et numériques de cette méthode GDDT-PpQk, ainsi que ses apports en termes de précision et de temps de calcul. / This thesis is concerned with the study of a Discontinuous Galerkin Time-Domain method (DGTD), for the numerical resolution of the unsteady Maxwell equations on hybrid tetrahedral/hexahedral in 3D (triangular/quadrangular in 2D) and non-conforming meshes, denoted by DGTD-PpQk method. Like in several studies on various hybrid time domain methods (such as a combination of Finite Volume with Finite Difference methods, or Finite Element with Finite Difference, etc.), our general objective is to mesh objects with complex geometry by tetrahedra for high precision and mesh the surrounding space by square elements for simplicity and speed. In the discretization scheme of the DGTD method considered here, the electromagnetic field components are approximated by a high order nodal polynomial, using a centered approximation for the surface integrals. Time integration of the associated semi-discrete equations is achieved by a second or fourth order Leap-Frog scheme. After introducing the historical and physical context of Maxwell equations, we present the details of the DGTD-PpQk method. We prove the L2 stability of this method by establishing the conservation of a discrete analog of the electromagnetic energy and a sufficient CFL-like stability condition is exhibited. The theoritical convergence of the scheme is also studied, this leads to a-priori error estimate that takes into account the hybrid nature of the mesh. Afterward, we perform a complete numerical study in 2D (TMz waves), for several test problems, on hybrid and non-conforming meshes, and for homogeneous or heterogeneous media. We do the same for the 3D implementation, with more realistic simulations, for example the propagation in a heterogeneous human head model. We show the consistency between the mathematical and numerical results of this DGTD-PpQk method, and its contribution in terms of accuracy and CPU time.
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Transducteurs ultrasonores capacitifs multiéléments à couplage air pour un contrôle non destructif à focalisation dynamique de matériaux : modélisation, simulations numériques et expériences / Multi-element air-coupled capacitive ultrasonic transducer with dynamic focusing for non-destructive testing of materials : modelling, numerical simulations and experimentsZhang, Di 20 November 2013 (has links)
Cette thèse porte sur le développement d'un traducteur ultrasonore multi-élément capacitif à couplage air (MEACUT) et son utilisation dans le domaine du contrôle non destructif (CND) de matériaux. Un modèle est employé pour simuler numériquement ce traducteur, et pour optimiser sa conception. Un prototype est ensuite fabriqué, puis caractérisé expérimentalement pour quantifier ses performances. Son originalité réside dans le fait qu'il possède une large bande passante en fréquence, tout en offrant la possibilité d'une focalisation variable. Ce prototype est alors employé pour la détection d'un endommagement causé par impact, dans une plaque composite. Il est clairement constaté que la résolution spatiale du procédé d'inspection employé (C-scan) est fortement améliorée grâce aux performances techniques du MEACUT. Enfin, un modèle hybride 3D est développé pour simuler, rapidement et intégralement, ce procédé de CND. Le très bon accord obtenu entre prédictions numériques et mesures expérimentales laisse présager que cet outil de simulation pourra servir à mettre au point d'autres expérimentations de CND, qui pourront à leur tour exploiter les performances du MEACUT. / This thesis focuses on the development of a Multi-Element Air-coupled Capacitive Ultrasonic Transducer (MEACUT) and its use in the field of non-destructive testing (NDT) of materials. A numerical model is used to simulate the translator, and to optimize its design. A prototype is then built and experimentally characterized to quantify its performance. Its originality lies in the fact that it has a broad frequency bandwidth while offering the possibility of a dynamic focusing. This prototype is then used for the detection of damage caused by impact, in a composite plate. It is clearly found that the spatial resolution of the inspection process employed (C-scan) is greatly improved thanks to the technical performance MEACUT. Finally, a 3D hybrid model is developed to simulate quickly and fully, the process of NDT. The good agreement obtained between numerical predictions and experimental measurements suggests that this simulation tool can be used to develop other NDT experiments, which may in turn exploit the performance of MEACUT.
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Wideband and multi-element antennas for mobile applicationsSonkki, M. (Marko) 07 May 2013 (has links)
Abstract
This dissertation presents wideband and multi-element antennas for mobile applications. It is divided into the following main parts: modal theory, wideband antennas, multi-element antennas, and wideband multi-element antennas.
The radiating fields are first studied in terms of spherical scalar and vector modes, and it is shown how these modes correlate with the characteristic current modes on a planar mobile ground plane. The theory part shows how it is possible to excite the same modes on a conventional sphere and a rectangular planar mobile ground plane. The theory refers to the novel wideband antenna structures presented in this dissertation, in terms of current and radiating modes.
After studying the modes, the dissertation shows how to excite a radiating antenna mode within a wide frequency bandwidth. To gain this, two main approaches are taken. First, a quasi-complementary antenna (QCA) structure with an electric conductor and magnetic slot is presented, and its characteristics are studied. A QCA UWB antenna, and a QCA element excited with a monopole or a dipole, is presented. The QCA structure compensates for the imaginary part of the input impedance on wide frequency bandwidth, when, at the same time, the fundamental mode is excited to ensure good radiating properties.
The second approach uses a symmetrical feeding with two antenna elements to gain a wide frequency bandwidth, the relative -6 dB impedance bandwidth between 37.5–80%. When a field is symmetrically coupled to the conducting ground plane, the excitation avoids the awakening of higher order modes which might disturb the performance of the antenna.
It is also shown, by using multiple feeding elements, that the excitation of orthogonal higher order modes on a small radiating ground plane is possible. As the modes are orthogonal to each other, they present a very low correlation. By using this kind of approach, radiation pattern diversity can be obtained in mobile applications within a small volume.
On the other hand, when combining two QCA elements to a one multi-element antenna structure, a wideband diversity antenna with an 87.5% relative -6 dB impedance bandwidth, and a wideband MIMO antenna with a 95.0% relative -6 dB impedance bandwidth, are presented with excellent radiation and correlation properties. Also mutual coupling is need to be counted when multi-element antennas are designed.
When designing an efficient radiator, it is important to consider an antenna feeding in terms of wideband impedance matching and wideband baluns, not to spoil the antenna performance. The efficient antenna structures and feeding mechanisms are obtained by using commercial 3D electromagnetic simulators to find the desired wideband antenna characteristics. Prototype antennas are measured in most of the presented structures to show their functionality in real.
In general, the dissertation presents wideband antenna structures with radiating antenna modes excited on a planar conducting ground plane. The idea is to find structures and feeding mechanisms to excite the fundamental mode, or a certain radiating antenna mode, at a wide frequency bandwidth, by avoiding the excitation of higher order modes which might disturb the antenna performance. It is also shown that, by using multiple feeding elements, it is possible to excite higher order modes on a small antenna. / Tiivistelmä
Väitöskirjassa esitetään uusia laajakaistaisia ja monielementtiantenneja matkaviestimiin. Väitöskirja koostuu neljästä pääalueesta: pintavirtojen muototeoria, laajakaistaiset antennit, monielementtiantennit sekä laajakaistaiset monielementtiantennit.
Teoriaosassa säteilykenttiä on aluksi tutkittu pallon pinnalla sekä skalaaripotentiaaleina että pintavirtavektoreina, jonka jälkeen niitä on verrattu mobiilin laitteen maatason ominaispintavirtojen synnyttämiin säteilykenttiin. Teoriaosassa osoitetaan, että pallon pinnalla sekä tasomaisella suorakaiteen muotoisella pinnalla on mahdollista herättää samat säteilykentät. Myöhemmin väitöskirjassa esitettävien uudenlaisten antennirakenteiden ominaisuuksia verrataan teoriaosassa esitettyihin pintavirtoihin ja säteilykenttiin.
Teoriaosuuden jälkeen osoitetaan miten säteilevä sähkömagneettinen kenttä saadaan herätettyä laajalla taajuusalueella. Tähän on otettu kaksi eri lähestymistapaa, joista ensimmäisessä esitellään ja tutkitaan kvasikomplementaarista antennirakennetta (QCA). Kvasikomplementaarisessa antennirakenteessa sisääntuloimpedanssin imaginaariosa kompensoidaan yhdistämällä sähköinen johde ja magneettinen rako samaan antenniin. Samanaikaisesti perusmuoto herätetään laajalla taajuusalueella, jolla varmistetaan antennin hyvät säteilyominaisuudet koko toimintataajuusalueella.
Toisessa lähestymistavassa käytetään kahta symmetrisesti asetettua antennielementtiä, joita syötetään symmetrisesti samalla amplitudilla ja vaiheella. Kun sähkömagneettinen kenttä herätetään symmetrisesti, korkeamman kertaluvun muotojen herättäminen voidaan välttää laajalla taajuusalueella. Symmetrisesti syötetyillä antennirakenteilla saavutettu -6 dB suhteellinen impedanssikaistanleveys on 37.5–80 %.
Useita syöttöelementtejä käytettäessä voidaan mobiilin laitteen maatasossa herättää yhdellä pistetaajuudella monta toisistaan riippumatonta säteilykenttää. Koska herätetyt kentät ovat toisistaan riippumattomia, on niiden välinen korrelaatio myös pieni. Kyseisellä rakenteella on mahdollista toteuttaa säteilykuviodiversiteetti erittäin pienessä tilassa, kuten matkapuhelimessa.
Toisaalta, kun yhdistetään kaksi QCA-elementtiä yhdeksi monielementtiratkaisuksi, voidaan toteuttaa laajakaistainen diversiteettiantenni, jonka suhteellinen -6 dB impedanssikaistanleveys on 87.5 %. Vastaavasti kahdella laajakaistaisella QCA-elementillä toteutetulla MIMO-ratkaisulla päästään 95 % suhteelliseen -6 dB impedanssikaistanleveyteen. Molemmilla ratkaisuilla on erittäin hyvät säteilyominaisuudet sekä alhainen korrelaatio ja pieni keskinäiskytkentä antennielementtien välillä.
Suunniteltaessa toimivaa laajakaistaista antennirakennetta, on tärkeää ottaa huomioon antennisyötön impedanssisovitus, jotta antennin suorituskyky ei heikkenisi. Lisäksi balansoidussa rakenteissa tulee olla laajakaistainen baluni, jolla vältetään säteilykuvion vääristyminen. Väitöskirjan syöttöratkaisuissa on käytetty kaupallisia sähkömagneettisia simulaattoreita, joilla antennirakenne voidaan mallintaa kolmiulotteisesti, ja joilla laajakaistainen syöttö saadaan optimoitua haluttuun antenniin. Suurin osa esitellyistä antennirakenteista on simulointien lisäksi myös mitattu, jolloin niiden toimivuus käytännössä pystytään todentamaan rakentamalla prototyyppiantenni.
Yleisesti väitöskirjassa esitellään tasomaisia antenniratkaisuja johtavassa maatasossa, joissa säteilevät pintavirrat herätetään mahdollisimman laajalla taajuusalueella. Ideana on löytää laajakaistaisia antenni- ja syöttörakenteita, joilla saadaan herätettyä perusmuoto tai jokin muu haluttu muoto. Ajatuksena on välttää korkeamman kertaluvun muotojen herättäminen, jotka voivat pilata antennin suorituskyvyn. Väitöskirjassa osoitetaan myös, että pienikokoisella antennilla on mahdollista herättää korkeamman kertaluvun muotoja pistetaajuudella käyttämällä useita heräte-elementtejä.
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Inductively Coupled Plasma Atomic Emission Spectrometry : Exploring the Limits of Different Sample Preparation StrategiesKollander, Barbro January 2011 (has links)
This thesis describes two different sample preparation strategies for inductively coupled plasma atomic emission spectrometry (ICP-AES), and their ability regarding multi element quantification in complex samples. Sensitivity, repeatability, reproducibility and accuracy were investigated. The aim was to increase the over all efficiency, the speed of analysis, and/or the sensitivity of the analytical method. The intention was to measure analytes with concentrations ranging from ng/g to mg/g simultaneously. The aim was additionally to study chemical and physical processes occurring during the sample preparation, the sample transport to the plasma, and the atomization therein. In the first sample preparation strategy, a hydrophilic highly cross-linked iminodiacetate-agarose adsorbent, IDA-Novarose, was used for preconcentration of metal ions, and matrix elimination in natural water samples. The sorbent was synthesized with different binding capacities. The effect of the capacity on preconcentration, matrix elimination, and uptake capability at high flow rates was studied. For a high capacity IDA-Novarose (≥ 45 µmole/ml) quantitative uptake was seen even at high flow rates (100 ml/min) for Cu2+ with a high affinity to the adsorbent, and for Cd2+ with a moderate affinity. For lower capacities the uptake of Cd2+ was affected by the sample matrix and the flow rate. A method based on the determination of the conditional stability constant of the metal sorbent complex was suggested for the prediction of the sorbent capacity needed to obtain quantitative recovery and optimal matrix elimination. The sorbent was used in a flow system with online buffering for the analysis of a certified riverine water (SLRS-3), tap water and lake water. With few exceptions the results obtained by ICP-AES after preconcentration agreed well with the certified concentrations and results obtained by ICP-MS. The other sample preparation strategy discussed is a method for non digested biological samples from different animal organs for the multi element analysis by ICP-AES. This “mix and measure method” consists of a simple homogenization of the sample with a mixing rod in a small amount of neutral media, followed by dilution and direct measurement with ICP-AES. The total time of analysis is only a few minutes. The ability of this fast method to accurately quantify some elements of toxic, environmental, and/or physiological concern with the lowest possible sample dilution and the highest possible plasma load was evaluated. In 10 % liver slurry Cd, Co, and Sr, at concentration levels around 0.05 µg/g were quantified simultaneously with P and K around 2000 µg/g and with several other elements in between (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn). The relative standard deviation of repeated measurements of samples was around 5 - 6 % for regardless of the concentration of the element. The method was also used for fast screening of the elemental distribution in mice organs (brain, heart, kidney, liver, lung and spleen).
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