Optimum detergent dosage during a washing process depends on water quality, degree of pollution and quantity of laundry. Particularly, water quality is an important factor. Other parameters like carbonate- or non-carbonate hardness and calcium / magnesium (Ca / Mg) ratio in addition to total hardness of water have an impact on the amount of detergent. This work discusses the possibilities realizing a detergent sensor that measures important parameters for the washing process and assess the ideal necessary amount of detergent during the washing process. The approach is to combine impedance spectroscopy with cyclic voltammetry in order to determine both water quality and concentration of detergent in the suds which build up the basis for an optimum detergent dosage. The results of cyclic voltammetry show that it is possible to identify the Ca / Mg ratio and the carbonate hardness separately, which is necessary for the optimization of the washing process. Impedance measurements identify total hardness and detergent concentrations.

[pt] A busca pela diminuição da dependência de combustíveis fósseis faz com que a ciência avance, diariamente, na utilização de combustíveis ecológicos, como o H2. Uma das formas de sua obtenção é através da fotocatálise. Esse processo consiste em uma reação catalítica com o uso de energia, na forma de luz. A fotólise da água é amplamente utilizada, principalmente com luz solar como fonte luminosa, que é abundante e reduz os custos de sua produção. O desempenho desta reação depende da posição das bandas de condução (BC) e valência (BV) do fotocatalisador. O TiO2 é utilizado como fotocatalisador em diversas reações, inclusive para a produção de H2. Os fotocatalisadores utilizados na forma de pós nanométricos apresentam dificuldade de separação após a reação. A transformação do pó em um material compacto é uma alternativa para retirá-lo do meio reacional evitando perdas e custos com separação. Desse modo, a compactação do pó é uma alternativa para facilitar sua reciclagem. O principal método de sua produção é pelo processo de sinterização, que envolve temperaturas elevadas (geralmente, 75 por cento do ponto de fusão do material) e longo tempo, podendo durar até dias. Para diminuir os gastos energéticos, o processo de sinterização a frio é uma opção, que consiste na densificação do material com uso de pressão e um solvente (aquoso ou não) e, temperaturas de sinterização de até 500 Graus C. O objetivo do estudo consistiu na produção de pastilhas de TiO2, comercial, e P25, através de uma variação do método de sinterização a frio, onde aplicou-se a pressão no pó, junto com o solvente, antes de seu tratamento térmico. As pastilhas produzidas foram caracterizadas pelas técnicas de TGA/DSC, XRD, MEV, CV, e DRS. / [en] The quest to reduce dependence on fossil fuels makes science advance, daily, in the use of ecological fuels, such as H2. One of the ways to obtain it is through photocatalysis. This process consists on a catalytic reaction using energy, in the form of light. Water photolysis is widely used, mainly with sunlight as a light source, which is abundant and reduces production costs. The performance of this reaction depends on the position of the conduction (CB) and valence (VB) bands of the photocatalyst. TiO2 is used as a photocatalyst in several reactions, including the production of H2. Photocatalysts used in the form of nanometric powders have difficulty in separating after the reaction. The transformation of the powder into a compact material is an alternative to remove it from the reaction medium, avoiding losses and costs with separation. Thus, the compaction of the powder is an alternative to facilitate its recycling. The main method of its production is through the sintering process, which involves high temperatures (generally 75 percent of the material s melting point) and a long time, which can last up to days. To reduce energy costs, the cold sintering process is an option, which consists of densifying the material using pressure and a solvent (aqueous or not) and sintering temperatures of up to 500 C degrees. The aim of the study was the production of commercial TiO2 and P25 pellets, through a variant of the cold sintering method, where pressure was applied to the powder, with the proper solvent, before the heat treatment. The pellets produced were characterized by the techniques of TGA/DSC, XRD, SEM, CV, and DRS.

Rare earth and actinide metals, critical to security, medicine, and the economy, have been processed through methods such as solvent extraction and electrorefining. To minimize radiological waste and improve yield, a 'chloride volatility' process--also known as the chlorination and volatilization process (CVP)--has been proposed and demonstrated for processing rare earths. The process takes advantage of the low vapor pressure of rare earth chlorides (<700 >°C), CaCl2 was added to LaCl3 to lower the melting temperature. LaCl3 electrochemical behavior has not previously been studied in CaCl2. Cyclic voltammetry (CV) and square wave voltammetry (SWV) were applied to LaCl3 salts in CaCl2-LiCl and CaCl2 to study the metal ion behavior. Various electrode materials were compared at low CV scan rates (s-1) to determine compatibility with chlorine gas evolution. Experiments of eutectic LaCl3-CaCl2 were performed and analyzed to determine the efficacy of chlorine gas generation via electrolysis for the CVP. Through galvanostatic electrolysis, oxidation of chloride ions and subsequent chlorination of rare earth was demonstrated, with cerium chosen as the representative rare earth metal. Through a quadrupole mass spectrometer plumbed in line with the electrolytic cell, the quality of the generated gas was analyzed.

[ES] En la presente tesis doctoral se exponen los resultados obtenidos en el desarrollo inicial de un sistema multisensor, tipo lengua electrónica voltamétrica, para el control de la durabilidad de las estructuras de hormigón armado (EHA). Aunque los sistemas multisensores son ampliamente utilizados en diferentes ámbitos, como el del medio ambiente o de la industria alimentaria, su uso en las EHA es novedoso. Igualmente, resulta novedosa la utilización de sensores voltamétricos que, como se demuestra en esta tesis, son de gran eficacia en el análisis de parámetros relacionados con el deterioro del hormigón armado, mejorándose los modelos de durabilidad obtenidos a través de sensores potenciométricos. Todo ello, sin ser aumentada de manera inabordable la complejidad electrónica y computacional del sistema. El prototipo de lengua electrónica diseñado es un sistema de sensores híbridos que consta de cuatro electrodos de trabajo (Au, Ag, Ni e INOX). Se dice que es híbrido porque se usan técnicas tanto voltamétricas (voltametría cíclica) como impedimétricas (espectroscopia de impedancia). Se han utilizado metales nobles (Au y Ag), metales no nobles (Ni) y aleaciones de alta durabilidad (acero inoxidable) con el fin de obtener un comportamiento electroquímico más variado. En la fase previa al desarrollo del sistema se seleccionaron los metales a utilizar en los sensores que formarían parte del sistema multisensor. Para ello se realizó un número ingente de ensayos con distintos metales (Ir, Rh, Pt, Au, Ag, W, Ni y INOX), tanto en disolución (simulando las condiciones de disolución de poro del hormigón), como en hormigón, con el fin de ser seleccionados aquellos metales de cuya respuesta se pudiera extraer una mayor información. Una vez finalizada la fase previa se estudió la respuesta aislada de cada uno de los metales seleccionados (Au, Ag, Ni e INOX), dividiéndose el estudio en 3 fases: ¿ Fase 1. Estudio en disolución: se analizaron los procesos que tienen lugar sobre la superficie del electrodo en disoluciones que simulaban distintas circunstancias que se pueden dar en el hormigón (variación de la disponibilidad de O2, variación del pH y presencia del anión cloro). Los resultados obtenidos se compararon con los encontrados en literatura. ¿ Fase 2. Estudios hechos con el sensor embebido en hormigones convencionales sin adiciones. Se embebieron sensores voltamétricos en hormigones convencionales de distinta relación agua/cemento. Seguidamente, se analizaron las probetas bajo distintas circunstancias que tuvieran influencia en el desencadenamiento y cinética de los procesos de corrosión como son: o Variaciones en la disponibilidad de O2 y H2O. o Carbonatación del hormigón. o Presencia de Cl-. ¿ Fase 3. Se desarrollaron modelos que permitieran identificar variaciones en parámetros relacionados con el deterioro del hormigón armado o estimar y predecir el parámetro de interés. Terminado el estudio de la respuesta aislada de los cuatro sensores, se procedió a evaluar la respuesta cruzada de los sensores siguiendo los protocolos propios de las lenguas electrónicas. Tras analizar y comparar las respuestas aisladas y cruzadas de los sensores, se propuso una rutina de trabajo que en un futuro ayude a optimizar los recursos, tanto operacionales como de fabricación, utilizados en el sistema. Para finalizar, se hizo un estudio inicial para tratar de mejorar la autonomía del sistema, evaluando el efecto producido al simplificar la configuración de celda, reduciendo el número de electrodos de tres a dos. / [CA] En la present tesi doctoral s'exposen els resultats obtinguts en el desenvolupament inicial d'un sistema multisensor, tipus llengua electrònica voltamètrica, pel control de la durabilitat de les estructures de formigó armat (EFA). Encara que l'ús d'aquest tipus de sistema està molt expandit en l'àmbit del medi ambient i de la indústria alimentària, el seu ús en les EFAs és molt nou. Igualment, resulta nova la utilització de sensors voltamètrics, que com és demostra en aquesta tesi, són de gran eficàcia en la determinació de les condicions del formigó armat, millorant-se considerablement els models de durabilitat obtinguts mitjançant sensors potenciomètrics. Tot això, sense augmentar la complexitat electrònica i computacional del sistema d'una forma inabordable. El prototip dissenyat de llengua electrònica és un sistema de sensors híbrids compost per quatre elèctrodes de treball (Au, Ag, Ni i acer inoxidable). Es diu que és híbrid perquè en el sistema de sensors s'utilitzen tècniques voltamètriques i impedimètriques. S'han utilitzat metalls nobles (Au i Ag), metalls no nobles (Ni) i aliatges d'alta durabilitat (acer inoxidable). Amb la finalitat d'obtindre un comportament electroquímic més variat. En la fase prèvia al desenvolupament del sistema, es van seleccionar els metalls a utilitzar en els sensors que formarien part del sistema multisensor. Per a això es va realitzar una quantitat ingent d'assajos amb diferents metalls (Ir, Rh, Pt, Au, Ag, W, Ni i acer inoxidable), tant en dissolució com en formigó, amb l'objectiu de seleccionar aquells metalls dels quals es poguera aconseguir més informació amb la seua resposta. Una vegada finalitzada aquesta fase prèvia, es va estudiar la resposta aïllada de cadascun dels metalls seleccionats (Au, Ag, Ni i acer inoxidable). L'estudi es va dividir en tres fases: ¿ Fase 1. Estudis en dissolució: es van analitzar els processos duts a terme sobre la superfície de l'elèctrode en dissolucions que simulaven diferents circumstàncies que es poden donar en el formigó (variació de la disponibilitat d' O2, variació de pH i presència de l'anió clor). Els resultats obtinguts es van comparar amb els trobats en la literatura. ¿ Fase 2. Estudis fets amb els sensors embeguts en formigó: es van embeure els sensors voltamètrics en formigons convencionals de diferent relació aigua/ciment i sense adicions. A continuació, es van analitzar les provetes sota diferents circumstàncies que tingueren influència en el desencadenament i cinètica dels processos com són: o Variacions en la disponibilitat d' O2 i H2O. o Carbonatació del formigó. o Presencia de Cl-. ¿ Fase 3. Desenvolupament de models que possibiliten identificar variacions en paràmetres relacionats amb el deteriorament del formigó armat o estimar i predir el paràmetre d'interès. Finalitzat l'estudi de la resposta aïllada dels quatre sensors, es va avaluar la resposta creuada mitjançant protocols propis de les llengües electròniques (PCA i PLS). Després d'analitzar i comparar les respostes aïllades i creuades dels sensors, es va proposar una rutina de treball que un futur ajude a optimitzar els recursos, tant operacionals com de fabricació, utilitzats al sistema. Per acabar, es va fer un estudi inicial per a tractar de millorar l'autonomia del sistema, avaluant l'efecte produït al simplificar la configuració de cel·la, reduint el nombre d'elèctrodes de tres a dos. / [EN] In this thesis the results obtained in the development of a multisensor system, known as electronic voltametric tongue, for the reinforcement concrete structures' (RCS) durability control are exposed. Although the use of this multisensor system is widespread in different fields such as: the food industry and environmental control, its use in RCS monitoring is very novel. It is equally novel the use of voltametric sensors, this kind of sensors are very efficient in determining concrete conditions, improving the durability models obtained through potentiometric sensors, all without overly increasing the system's electronic and computational complexity The electronic tongue prototype designed is a hybrid sensor system made up of four working electrodes (Au, Ag, Ni and stainless steel). It has been referred to as hybrid because in the system voltametric and impedimetric electrochemical techniques are used. Noble metals (Au and Ag), non-noble metals (Ni) and high-durability alloys (stainless steel) have also been used with the purpose of achieving a more varied electrochemical behaviour. In the previous development phase of the system, the metals involved in the development of the electronic tongue were selected. In order to do this, a variety of tests with different metals were performed (Ir, Rh, Pt, Au, Ag, W, Ni and SS), in both dissolution (different concrete pore solution conditions were simulated) and hardened concrete. This allowed us to choose the metals which responses contained the most information. The next steps focused on the study of the selected sensors isolated response: ¿ Phase 1: simulation of concrete pore solution in dissolution systems. The results were compared with those already existing in the bibliography. ¿ Phase 2: studies with the sensors embedded in different standard concretes without additions. The samples were tested in different conditions involved in the rebars corrosion kinetics (variations in O2 and humidity availability, concrete carbonation and chlorides presence). ¿ Phase 3: Development of estimation models for the parameters of interest. After finishing the study of the isolated sensors' response, a cross-evaluation of their response was performed using typical protocols used in the electronic tongues (i.e. PCA and PLS). After analysing and comparing the isolated and crossed sensor's response, an optimized multisensory routine work was proposed which could, in the future, help optimize the resources used in the system. Finally, a study was carried out to improve the system's autonomy, in which the repercussion of the cell configuration simplification by means of the removal of the reference electrode was evaluated. / La autora quiere expresar su agradecimiento al Ministerio de Educación, Cultura y Deporte por la beca predoctoral FPU 16/00723 / Martínez Ibernón, A. (2023). Lenguas electrónicas para la evaluación de la durabilidad de estructuras de hormigón armado y el seguimiento de la corrosión [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/192263

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The work presented in this thesis examines the electrochemical behaviour of a number of species, both surface-bound and in the solution phase, in various room-temperature ionic liquids (RTILs), in order to identify systems which show altered reactivities in room-temperature ionic liquids, compared to that in conventional, molecular, aprotic solvents. The fundamentals of electrochemistry are outlined and an introduction to room-temperature ionic liquids is given, after which the results of six original investigations are presented, as follows; The electrochemical response of surface-bound anthraquinonyl films was investigated as a function of RTIL cation size. The reduction of oxygen to superoxide in the [C₂mim][NTf₂] RTIL was studied at different carbon electrodes. The mechanisms of electrodeposition and stripping of Zn(II) onto bulk zinc deposits, on glassy carbon electrodes, in the [C₄mPyrr][NTf₂] RTIL were investigated. A novel and successful method for the fabrication of zinc microdisk electrodes was developed and the electrochemical behaviour of these electrodes was investigated. The mechanisms for the electrochemical reductions of some bromo- and nitrobenzenes at platinum microelectrodes were determined in the [C₄mPyrr][NTf₂] ionic liquid, in order to identify systems which displayed changed reactivities in RTILs compared to those in molecular aprotic solvents. The altered reactivity of 1-bromo-4-nitrobenzene in the [C₄mPyrr][NTf₂] ionic liquid was utilised via electrochemical reduction at zinc microelectrodes in order to form arylzinc compounds. The work presented in this thesis shows that the oft-taken view that the reactivity of a given species in an ionic liquid will mimic that in conventional aprotic solvents is not always the case. Reactivities can be markedly different between RTILs and aprotic solvents and can also be highly dependent on the specific ionic liquid employed.

Στην παρούσα διπλωματική εργασία γίνεται χρήση λεπτών υμενίων TiO2 ως στερεό υπόστρωμα για την ακινητοποίηση πρωτεϊνών με απώτερο σκοπό την ανάπτυξη ενός αμπερομετρικού βιοαισθητήρα με ευαισθησία στο υπεροξείδιο του υδρογόνου (H2O2). Αρχικά περιγράφεται η λειτουργία των βιοαισθητήρων καθώς και οι σημαντικότεροι τύποι βιοαισθητήρων που έχουν κατασκευαστεί μέχρι σήμερα. Σημαντικό ρόλο στην επιτυχή κατασκευή ενός βιοαισθητήρα παίζει η επιλογή του υλικού που θα χρησιμοποιηθεί ως υπόστρωμα / ηλεκτρόδιο (υμένια TiO2) καθώς και ο τρόπος που ακινητοποιείται το βιομόριο πάνω σε αυτό, γι’ αυτό και έχει δοθεί έμφαση στην ανάλυση των παραπάνω πληροφοριών. Επίσης περιγράφεται η δομή και η φυσική λειτουργία της πρωτεΐνης, (κυτόχρωμα c), που χρησιμοποιήθηκε ως το βιομόριο επιλογής για την ανάπτυξη του βιοαισθητήρα. Αναλύθηκαν επίσης οι κρυσταλλικές δομές του διοξειδίου του τιτανίου, οι βασικές φυσικοχημικές τους ιδιότητες και οι λόγοι που επιλέξαμε την ανατάση για τη συγκεκριμένη εργασία. Περιγράφεται η πειραματική διαδικασία εναπόθεσης των υμενίων του TiO2 σε υποστρώματα αγώγιμου υάλου. Στη συνέχεια περιγράφονται οι πειραματικές διατάξεις που χρησιμοποιήθηκαν τόσο για τον χαρακτηρισμό των υμενίων διοξειδίου του τιτανίου (TiO2) όσο και για την αναλυτική μελέτη της ακινητοποίησης του κυτοχρώματος c πάνω σε αυτά. Τέλος περιγράφεται η ηλεκτροχημική κυψελίδα 3 ηλεκτροδίων και η τεχνική της κυκλικής βολταμετρίας που επιλέχθηκαν τόσο για τη μελέτη των ηλεκτροχημικών ιδιοτήτων των υμενίων TiO2 με ή χωρίς ακινητοποιημένη πρωτεΐνη όσο και για την ανάπτυξη ενός αμπερομετρικού βιοαισθητήρα με ευαισθησία στο H2O2. / In the present study, the use of thin nanocrystalline TiO2 films as solid substrates for protein immobilization and for the development of an electrochemical biosensor for hydrogen peroxide (H2O2) are investigated. First of all, a general description of biosensors and their most important types that have been developed to date is given. For the successful development of a biosensor, the choice of material/substrate used as the surface/electrode (thin film of TiO2) for the attachment of the bio-molecule of interest, as well as the manner in which the bio-molecule is immobilized upon it are critical and therefore emphasis is given for the analysis of this information. Furthermore, a description of the structure and basic functions of the bio-molecules (cytochrome c and hemoglobin), used for the immobilization studies and for the development of the biosensor is presented. Additionally, the crystalline structures of titanium dioxide have been analyzed, along with its basic physicochemical properties and the reasons for choosing its anatase structure for the specific project. In the experimental part, the deposition of the colloidal TiO2 paste on conducting glass for the preparation of the thin mesoporous TiO2 films is described in detail. Also described are the experimental techniques used for the characterization of these films as well as a thorough analysis of the binding of cytochrome c upon them and the parameters that influence its adsorption. Finally, description of the 3-elecrode electrochemical cell used in this study of perform of cyclic voltammetry experiments in order to investigate the electrochemical properties of the TiO2 thin films with or without immobilized protein is given. The same setup is also used for the development of an electrochemical biosensor for H2O2.