This licentiate thesis presents experimental studies concerning two parts of the electrochemical cell in the chlorate process: a cathode and an anode. Newly synthesized MnOx electrodes were investigated for the cathodic reaction, hydrogen evolution reaction (HER) in the chlorate process. In industry addition of toxic and carcinogenic chromium (VI) as sodium dichromate provides high efficiency. Here undesirable addition of sodium dichromate was avoided while high cathodic efficiency was achieved. Cathodic efficiency and selectivity towards HER, achieved by the MnOx electrodes annealed at different temperatures, were measured by means of mass spectrometry (MS).  The second study investigated oxygen evolution in the chlorate process, which is an anodic side reaction. The evolution of oxygen decreases anodic efficiency and also presents a safety risk due to occurrence of HER in the undivided cell. We followed the amount of produced oxygen by two types of the electrode TiRu, similar to that industrially used, and synthesized TiRuSnSb, by means of MS. The produced oxygen amount was compared to the amount produced by Pt. To our best knowledge, this was the first study that successfully disentangles three different sources of oxygen with good time resolution. Oxygen is produced by homogenous hypochlorite decomposition, heterogeneously by different catalysts present in the electrolyte solution and anodically during the electrolysis i.e. electrochemically. Different electrode materials catalyzed hypochlorite decomposition differently and led to a different volume of oxygen produced. / Denna licentiatavhandling redogör för experimentella studier av tvådelar av den elektrokemiska cell som används i kloratprocessen:katoden och anoden. Syntetiserade MnOx elektroder utvärderades för katodreaktionen,vätgasutveckling, i kloratprocessen. Industriellt tillsätts giftigt ochcancerogent krom(IV) som natriumdikromat för hög verkningsgrad. Denna studie uteslöt oönskad tillsats av natriumdikromat samtidigt som hög katodisk effektivitet erhölls. Katodisk effektivitet och selektivitet för vätgasutveckling, med MnOx elektroder,värmebehandlade vid olika temperaturer, uppmättes med masspektrometer. I den andra studien undersöktes syrgasutveckling i kloratprocessen,vilket är en anodisk sidoreaktion. Syrgasutvecklingen minskar den anodiska effektiviteten och utgör en säkerhetsrisk med anledning avden pågående vätgasutvecklingen i den odelade cellen. Vi uppmättemängden producerad syrgas med två olika elektroder TiRu, liknandeden som industriellt används, och syntetiserad TiRuSnSb, med masspektrometer. Den producerade syrgasmängden jämfördes med mängden producerat på Pt. Såvitt vi vet var detta den första studiesom särskiljer på tre olika syrgaskällor med god tidsupplösning. Syrgas produceras homogent av hypokloritsönderfall, heterogent av olika katalysatorer närvarande i elektrolyten och anodiskt vid elektrolys dvs. elektrokemiskt. Olika elektrodmaterial katalyserade hypokloritsönderfall olika och producerade olika volym syrgas. / <p>QC 2021-04-28</p>

>Magister Scientiae - MSc / A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of A comparative study of electrolysers using different anodic materials for the electrolysis of brine (sodium chloride) for the production of sodium hypochlorite as a source of available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. available chlorine for disinfection of rural water supplies has been undertaken. The electrolyser design used was tubular in form, having two chambers i.e. anode inside and cathode outside, separated by a tubular inorganic ceramic membrane. The anode was made of titanium rod coated with a thin layer of platinum and a further coat of metal oxide. The cathode was made of stainless steel wire. An assessment of these electrolysers was undertaken by studying the effects of some variable parameters i.e. current, voltage and sodium chloride concentration. The flow rate was kept unchanged at 50ml/h anolyte and 140ml/h catholyte since it was found to be optimum flow rate for chlorine generation. Figures of merit of the electrolysers were calculated on the basis of three sets of measurements. Analytical methods used for the determination of sodium hypochlorite concentration were iodometric and N, N-Diethyl-p- Phenylenediamine (DPD) titration methods. The DPD titration method was used to determine the chlorine concentration of less than 1mg/L, while the iodometric titration method was used to determine chlorine concentration of ImgIL and above. Sodium chlorate present in the hypochlorite solution was also determined using a spectrophotometric method. The cobalt oxide electrolyser has been shown to be superior as compared to the ruthenium dioxide and manganese dioxide electrolysers in terms of hypochlorite generation. Sodium chlorate was present but at concentration levels not hazardous for use in dosing water for drinking purposes. Analysis of hydroxyl radicals was undertaken since there were claims that these are produced during brine electrolysis. Hydroxyl radical analysis was not successful, since sodium hypochlorite and hypochlorous acid interfere using the analytical method described in this study.

No description available.

This paper reviews the responsibilities and liability of online marketplaces within the Digital Services Act (DSA) framework. The DSA, proposed by the European Union, represents a comprehensive legislative initiative to regulate digital platforms and intermediaries, with a particular emphasis on online marketplaces. Specifically, the focus of this paper is on the obligations imposed on online marketplaces, shedding light on the regulatory landscape governing their conduct and responsibilities. This paper aims to examine the implications of the extended responsibilities of online marketplaces under the DSA. The analysis explores potential changes in their levels of responsibility, obligations, and measures for handling user-generated content. Through this, the aim is to contribute to the debate on regulating digital platforms, shedding light on key aspects of online marketplace responsibilities. This is performed using a critical policy analysis methodology, examining the legal content of the DSA regulation, and analysing the practical consequences of its implementation, with a special focus on how the DSA ensures a responsible and sustainable retail environment and what the increased requirements mean for online marketplaces in practice.

Thesis is analyzing czech laws which are related to medical documentation. Describes the points  which are mandatory for information system, so the medical documentation can be stored electronically. Includes various algorithms for implementation of certain electronic signature and for  identification of person. This thesis deals with asymmetric cryptography, specifically RSA, DSA, and ECDSA. Describes the hash functions and their functions and their characteristics. Describes the principle of the certificate, ways of its obtaining, invalidation and their formats. Analyzes medical information system and suggests ways to create a program for signing medical records. Then based on that analysis, the program is implemented. At the conclusion of the work is discussed, if created program meets the criteria.

No description available.

Given the ever increasing reliance of today’s society on ubiquitous wireless access, the paradigm of dynamic spectrum access (DSA) as been proposed and implemented for utilizing the limited wireless spectrum more efficiently. Orthogonal frequency division multiplexing (OFDM) is growing in popularity for adoption into wireless services employing DSA frame- work, due to its high bandwidth efficiency and resiliency to multipath fading. While these advantages have been proven for many wireless applications, including LTE-Advanced and numerous IEEE wireless standards, one potential drawback of OFDM or its non-contiguous variant, NC-OFDM, is that it exhibits high peak-to-average power ratios (PAPR), which can induce in-band and out-of-band (OOB) distortions when the peaks of the waveform enter the compression region of the transmitter power amplifier (PA). Such OOB emissions can interfere with existing neighboring transmissions, and thereby severely deteriorate the reliability of the DSA network. A performance-enhancing digital pre-distortion (DPD) technique compensating for PA and in-phase/quadrature (I/Q) modulator distortions is proposed in this dissertation. Al- though substantial research efforts into designing DPD schemes have already been presented in the open literature, there still exists numerous opportunities to further improve upon the performance of OOB suppression for NC-OFDM transmission in the presence of RF front-end impairments. A set of orthogonal polynomial basis functions is proposed in this dissertation together with a simplified joint DPD structure. A performance analysis is presented to show that the OOB emissions is reduced to approximately 50 dBc with proposed algorithms employed during NC-OFDM transmission. Furthermore, a novel and intuitive DPD solution that can minimize the power regrowth at any pre-specified frequency in the spurious domain is proposed in this dissertation. Conventional DPD methods have been proven to be able to effectively reduce the OOB emissions that fall on top of adjacent channels. However more spectral emissions in more distant frequency ranges are generated by employing such DPD solutions, which are potentially in violation of the spurious emission limit. At the same time, the emissions in adjacent channel must be kept under the OOB limit. To the best of the author’s knowledge, there has not been extensive research conducted on this topic. Mathematical derivation procedures of the proposed algorithm are provided for both memoryless nonlinear model and memory-based nonlinear model. Simulation results show that the proposed method is able to provide a good balance of OOB emissions and emissions in the far out spurious domain, by reducing the spurious emissions by 4-5 dB while maintaining the adjacent channel leakage ratio (ACLR) improvement by at least 10 dB, comparing to the PA output spectrum without any DPD.

Les systèmes de communications sans fil ne cessent de se multiplier pour devenir incontournables de nos jours. Cette croissance cause une augmentation de la demande des ressources spectrales, qui sont devenues de plus en plus rares. Afin de résoudre ce problème de pénurie de fréquences, Joseph Mitola III, en 2000, a introduit l'idée de l'allocation dynamique du spectre. Il définit ainsi le terme " Cognitive Radio " (Radio Intelligente), qui est largement pressenti pour être le prochain Big Bang dans les futures communications sans fil [1]. Dans le cadre de ce travail on s'intéresse à la problématique du spectrum sensing qui est la détection de présence des Utilisateurs Primaires dans un spectre sous licence, dans le contexte de la radio intelligente. L'objectif de ce travail est de proposer des méthodes de détection efficaces à faible complexité et/ou à faible temps d'observation et ceci en utilisant le minimum d'information a priori sur le signal à détecter. Dans la première partie on traite le problème de détection d'un signal aléatoire dans le bruit. Deux grandes méthodes de détection sont utilisées : la détection d'énergie ou radiomètre et la détection cyclostationnaire. Dans notre contexte, ces méthodes sont plus complémentaires que concurrentes. Nous proposons une architecture hybride de détection des bandes libres, qui combine la simplicité du radiomètre et la robustesse des détecteurs cyclostationnaires. Deux méthodes de détection sont proposées qui se basent sur cette même architecture. Grâce au caractère adaptatif de l'architecture, la détection évolue au cours du temps pour tendre vers la complexité du détecteur d'énergie avec des performances proches du détecteur cyclostationnaire ou du radiomètre selon la méthode utilisée et l'environnement de travail. Dans un second temps on exploite la propriété parcimonieuse de la Fonction d'Autocorrelation Cyclique (FAC) pour proposer un nouvel estimateur aveugle qui se base sur le compressed sensing afin d'estimer le Vecteur d'Autocorrelation Cyclique (VAC), qui est un vecteur particulier de la Fonction d'Autocorrelation Cyclique pour un délai fixe. On montre par simulation que ce nouvel estimateur donne de meilleures performances que celles obtenues avec l'estimateur classique, qui est non aveugle et ceci dans les mêmes conditions et en utilisant le même nombre d'échantillons. On utilise l'estimateur proposé, pour proposer deux détecteurs aveugles utilisant moins d'échantillons que nécessite le détecteur temporel de second ordre de [2] qui se base sur l'estimateur classique de la FAC. Le premier détecteur exploite uniquement la propriété de parcimonie du VAC tandis que le second détecteur exploite en plus de la parcimonie la propriété de symétrie du VAC, lui permettant ainsi d'obtenir de meilleures performances. Ces deux détecteurs outre qu'ils sont aveugles sont plus performants que le détecteur non aveugle de [2] dans le cas d'un faible nombre d'échantillons.

Orientador: Rodnei Bertazzoli / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecanica / Made available in DSpace on 2018-08-05T06:46:31Z (GMT). No. of bitstreams: 1 Spitzer_Marcos_D.pdf: 1019872 bytes, checksum: 57974ac02038eb53169c99987a119811 (MD5) Previous issue date: 2005 / Resumo: O método de oxidação eletroquímica foi aplicado a soluções aquosas contendo cloranfenicol (CAP) e outros compostos orgânicos. Para isso, utilizou-se um anodo de óxido condutor, comercial, tipo DSA®, de composição 70TiO2-30RuO2 e um anodo de diamante dopado com boro (DDB) tipo comercial. Cada anodo foi instalado em um reator tipo filtro-presa, em escala de bancada, para processamento de 2 a 3 L de solução em modo de batelo-reciclo. Inicialmente, nos reatores construídos foram realizados estudos voltamétricos, em modo hidrodinâmico. Sobre um catodo de aço inoxidável, antes da evolução de H2, observou-se a redução do grupo NO2 do CAP a HO-NH- a pH=5, e em potenciais anódicos, sobre o DSA®, observou-se o início reação de evolução de O2 a partir de 1 V vs. ECS e que a presença de CAP reduz as correntes de evolução de O2. Sobre o DDB, o CAP é oxidado a partir de 0,6 V resultado na passivação do anodo. A partir de 2,2 V observa-se o início da evolução de O2 sobre o DDB, resultando na eliminação do filme passivador. Em seguida, eletrólises exaustivas foram realizadas, em modo galvanostático, com ambos os anodos, dentro da região de evolução de O2. Cinéticas de pseudo-primeira ordem foram observadas dos decaimentos ds CAP sobre o DSA®, na faixa de 50 a 180 mA cm-2, e sobre o DDB, na faixa de 10 a 30 mA cm-2. Os decaimentos da demanda química de O2 (DQO) e do carbono orgânico total (COT) também apresentaram essa cinética quando as reações de oxidação sobre o DDB tornavam-se controladas pelos processos de transporte de massa. A partir de eletrólises de soluções de K2SO4 com o DDB observou-se a geração de H2O2. Os números adimensionais Sherwood (Se), Reynolds (Re) e Schmidt (Sc) foram determinados a partir de dados de transporte de massa obtidos a partir de cinéticas da degradação do CAP em função da vazão. No reator composto de DSA® observou-se um regime de fluxo laminar a baixo de Re = 2000 e um regime de fluxo turbulento acima desse valor, como esperado para um reator de placas paralelas. No reator de DDB, devido o aumento da área da secção transversal do compartimento entre eletrodos, há uma elevação de turbulência da face do anodo, impedindo a formação de um regime de fluxo laminar bem definido. Utilizando um efluente real contendo fenóis e derivados, foram aplicadas valores apropriados de densidade de corrente (Jap) para aumento dos valores de eficiência de corrente e diminuição dos índices de consumo energético. Aplicando-se um perfil exponencial de Jap (t) obteve-se um rendimento de corrente médio de 95 % e um consumo de 23,5 kWh por kg de O2. Com isso foi possível propor um método de operação de reatores de DDB para elevação dos índices de eficiência. De modo geral, os anodos de Ti/70TiO2-30RuO2 e de DDB ótimos desempenhos para a eletroxidação de cloranfenicol (CAP) e outros compostos orgânicos e para redução da DQO e do COT / Abstract: Electrochemical oxidation was used as a method for organic pollutant degradation in aqueous media. In the technique was used in solutions containing chloramphenicol (CAP) and phenolic compounds. A commercial DSA® type anode, of composition 70TiO2-30RuO2, and a boron-doped diamond anode (BDD) were used. Each anode was mounted in a filter-press type reactor connected to a recirculating flow system with 3 L of capacity. Initially, voltammetric studies were carried out with electrochemical reactors operating in hydrodynamic mode. On the DSA® type anode O2 evolution reaction was observed after 1 V vs. SCE and the current densities for O2 evolution decreased when chloramphenicol was present in solution. On stainless steel cathode, before H2 evolution, reduction of NO2 group to HO-NH- group was observed for CAP molecule, at pH = 5. On DDB, the anode was passived with an organic film at potentials from 0.6 V. Current responses on DDB anode were restored after anodic treatments within O2 evolution range of potentials. On BDD, O2 evolution took place after 2.2 V vs SCE. Galvanostatic experiments were carried out within the range of potentials for O2 evolution. Pseudo-first order kinetics were observed for CAP concentration decay on the DSA® anode, when current densities (Jap) were ranged from 50 to 180 mA cm-2, and from 10 to 30 mA cm-2 on DDB anode. Chemical oxygen demand (COD) and total organic carbon (TOC) showed linear concentration decays when the oxidation reactions were controlled by charge transfer process and it showed exponential decays when these reactions were controlled by mass transfer process. H2O2 production on DDB anode was investigated as function of Jap. Dimensionless numbers and their mass transfer figures of merit were studied from mass transport data of CAP decays as function of several flow rates. In the reactor composed by DSA® anode, a laminar flow was observed below Reynolds (Re) equal 2000 and a turbulent flow was observed above this value. In the BDD reactor, the transition between laminar and turbulent flow was not observed. Using a real effluent composed by phenols and derivates, appropriate values of Jap was applied on DDB reactor to increase the anodic efficiency and to reduce the energy consumption per kg of O2. Applying an exponential profile of Jap in galvanostatic experiments, an anodic efficiency of 95% was reached, corresponding to an energy consumption of 23,5 kWh per kg of O2. From these results an operation method of BDD reactors arose in order to increase the performance of this electrochemical device. Good performances were observed when DSA® and BDD anodes were used in electrochemical oxidation of chloramphenicol and other organic pollutants, especially in BDD case / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

<p align="justify">Plusieurs métaux de notre vie courante sont obtenus industriellement au moyen de procédés électrolytiques. Un des procédés les plus communs est l’électro-obtention de cuivre, dans lequel le métal est déposé à la cathode tandis que l'oxygène se dégage à l'anode. Généralement, en usine, plusieurs anodes et cathodes, ayant une surface de 1 m2 et séparées par plus ou moins 10 cm sont alternées dans une cellule contenant une solution d'acide sulfurique riche en sulfate de cuivre. En fonction des conditions d'utilisation, les cathodes sont remplacées, après un certain temps, par des nouvelles de façon à récupérer le cuivre déposé. De ce fait, les anodes doivent être capables de résister sans se corroder, se déformer ou perdre leurs propriétés électrocatalytiques pendant de longues périodes. Au début, des alliages en Pb (pb-Ag, Pb-Ca-Sn,) ont été utilisés comme anodes. Malheureusement, malgré leur faible prix, ces anodes présentent des surtensions élevées et une faible résistance à la corrosion et au fluage. Par conséquent, une alternative aux anodes traditionnelles en 1 développée. Ce nouveau type d'anode, connu sous le nom d’anode dimensionnellement stable (DSA) est fabriquée à partir d'une tôle en Ti recouverte par un mélange d'oxydes de métaux nobles catalysant la réaction de dégagement d'oxygène. Différentes techniques peuvent être utilisées pour préparer la couche d'oxyde. La technique la plus souvent employée consiste à décomposer thermiquement une solution de chlorures contenant un ou plusieurs nobles. Malheureusement, ce type d'anode est cher et a tendance à perdre son activité électrocatalytique avec le temps.</p><p><p align="justify">Dans le but de produire une DSA à faible prix, pouvant résister de longues périodes sans se passiver, un nouveau type de DSA a été développé dans le présent travail. Cette anode est produite par électrodépôt d'un métal noble dans les pores d'un substrat microporeux en Ti/TiO2.</p><p><p align="justify">Ce travail a permis de démontrer qu'une DSA avec une concentration en métal noble peut être obtenue par la voie proposée. Il a été montré que les propriétés électriques et électrochimiques de ces DSAs sont directement liées aux caractéristiques morphologiques et structurales du en Ti/TiO2. Lorsque la couche barrière existant au fond des pores est suffisamment fine et que le film présente des défauts, la résistance me l'interface Ti/métal noble est faible. Ceci abouti à des DSAs possédant d'excellentes propriétés électrocatalytiques. Les DSAs optimales sont capables de résister à des conditions similaires à celles employées en industrie avec des surtensions de ~ 0.4 V, ce qui représente un gain de 50% par rapport aux surtensions normalement atteintes par les anodes traditionnelles en Pb.</p> / Doctorat en sciences appliquées / info:eu-repo/semantics/nonPublished