Los dos baños de cobre más utilizados comercialmente son el baño ácido a base de sulfato y el baño alcalino a base de cianuro. Los baños alcalinos son utilizados principalmente para producir recubrimientos en piezas con geometría compleja y para evitar la deposición galvánica cuando se deposita un metal en un sustrato menos noble. Debido a la toxicidad de los compuestos de cianuro, se han desarrollado baños alternativos usando diferentes agentes complejantes. El punto de partida de la presente investigación es un baño primario sin cianuros para deposición de cobre en sustratos de Zamak desarrollado en el Instituto de Investigaciones Tecnológicas del Estado de Sao Paulo / Brasil. La sustitución de materias primas como el cianuro debe ser económicamente ventajosa y técnicamente viable. De esta manera, la investigación presentada pretendió proponer una alternativa para el tratamiento de residuos líquidos del baño ya mencionado con la finalidad de recuperar de manera simultánea el agua y las materias primas en un sistema cerrado. Se ha estudiado el proceso de separación por membranas de intercambio iónico, la electrodiálisis, usando un sistema en escala de laboratorio y una disolución sintética que simulaba las aguas residuales del baño a base de HEDP. Se ha evaluado la viabilidad del sistema por medio del análisis de los parámetros de operación, como la extracción de iones, la tasa de desmineralización, el porcentaje de concentración, la eficiencia de la intensidad calculada para cada especie y el consumo medio de energía. Debido a que el ácido HEDP es un agente quelante, se ha evaluado el transporte de los quelatos Cu(II) HEDP a través de membranas de intercambio de aniones por medio de métodos electroquímicos. Se han construido curvas cronopotenciométricas y curvas intensidad-potencial para diferentes disoluciones sintéticas que contenían los mismos compuestos que el baño original. Se ha establecido la relación entre la presencia de los quelatos en las disoluciones y los grupos fijos de intercambio de aniones. Por fin, se han realizado las pruebas de deposición usando electrólitos conteniendo los compuestos reciclados y se han evaluado las características de los depósitos obtenidos. Los resultados indicaron que el sistema de electrodiálisis usando membranas de intercambio de aniones con grupos de intercambio de base fuerte ha podido producir disoluciones tratadas y un concentrado conteniendo los iones del baño. Se ha podido añadir el concentrado al baño original para compensar eventuales perdidas del arrastre sin afectar la calidad de los depósitos. Por lo tanto, la aplicación de la electrodiálisis demostró ser una alternativa viable para la recuperación del agua y de las materias primas de la disolución evaluada, reduciendo la generación de residuos líquidos y ahorrando los recursos naturales. / The two most common commercial copper baths are the acid sulfate copper bath and the alkaline cyanide copper bath. Alkaline copper baths are mostly used to coat parts with complex geometry and to avoid galvanic deposition when depositing a metal on a less noble substrate. Because of the toxicity of cyanide compounds, alternative baths have been developed using different complexing agents. The starting point of the present study is a cyanide free strike bath developed for copper plating on Zamak substrates developed by the Institute for Technological Research of the State of São Paulo/ Brazil. The replacement of a raw material such as cyanide must be economically advantageous and technically feasible. Therefore, this study intended to propose an alternative to the treatment of liquid wastes from the mentioned bath, aiming at simultaneous water reclamation and chemicals recovery in a closed system. The electrodialysis membrane separation process was studied, using a laboratory-scale system operating with a synthetic solution simulating the rinsing waters from the HEDP-based bath. The feasibility of the technique was evaluated by analyzing operational parameters such as ion extraction, demineralization rate, concentration rate, current efficiency for each anionic specie and average energy consumption. Because HEDP is a chelating agent, the transport of Cu(II) HEDP chelates through anion exchange membranes was also evaluated by means of electrochemical methods. Chronopotentiometric and current-voltage curves were constructed for different model solutions containing the same compounds as the original bath. A relation between the presence of chelates in the solutions and the fixed ion exchange group could be established. Lastly, deposition tests were performed using electrolytes containing the recycled inputs and the characteristics of the coatings were analyzed. The results showed that an electrodialysis stack using strongly basic anion exchange membranes was suitable to produce treated solutions and a concentrate containing the ions from the bath. The concentrate could be added to the copper bath to compensate eventual drag-out losses without affecting the quality of the coatings. Thus, the application of electrodialysis was shown to be a feasible alternative for recovering water and inputs from the evaluated solution, reducing the wastewater generation and saving natural resources. / Els dos banys de coure més utilitzats comercialment són el bany àcid a base de sulfat i el bany alcalí a base de cianur. Els banys alcalins són utilitzats principalment per a produir recobriments en peces amb geometria complexa i per a evitar la deposició galvànica quan es deposita un metall en un substrat menys noble. A causa de la toxicitat dels compostos de cianur, s'han desenrotllat banys alternatius usant diferents agents complexants. El punt de partida de la present investigació és un bany primari sense cianurs per a deposició de coure en substrats de Zamak desenrotllat en l'Institut d'Investigacions Tecnològiques de l'Estat de Sao Paulo / Brasil. La substitució de matèries primeres com el cianur ha de ser econòmicament avantatjosa i tècnicament viable. D'aquesta manera, la investigació presentada va pretendre proposar una alternativa per al tractament de residus líquids del bany ja mencionat amb la finalitat de recuperar de manera simultània l'aigua i les matèries primeres en un sistema tancat. S'ha estudiat el procés de separació per membranes d'intercanvi iònic, electrodiàlisi, usant un sistema en escala de laboratori i una dissolució sintètica que simulava les aigües residuals del bany a base d'HEDP. S'ha avaluat la viabilitat del sistema per mitjà de l'anàlisi dels paràmetres d'operació, com l'extracció d'ions, la taxa de desmineralització, el percentatge de concentració, l'eficiència de la intensitat calculada per a cada espècie i el consum mitjà d'energia. Pel fet que l'àcid HEDP és un agent quelant, s'ha avaluat el transport dels quelats Cu (II)-HEDP a través de membranes d'intercanvi d'anions per mitjà de mètodes electroquímics. S'han construït corbes cronopotenciomètriques i corbes intensitat-potencial per a diferents dissolucions sintètiques que contenien els mateixos compostos que el bany original. S'ha establit la relació entre la presència dels quelats en les dissolucions i els grups fixos d'intercanvi d'anions. Finalment, s'han realitzat les proves de deposició usant electròlits contenint els compostos reciclats i s'han avaluat les característiques dels depòsits obtinguts. Els resultats van indicar que el sistema d'electrodiàlisi usant membranes d'intercanvi d'anions amb grups d'intercanvi de base forta ha pogut produir dissolucions tractades i un concentrat que conté els ions del bany. S'ha pogut afegir el concentrat al bany original per a compensar eventuals perdudes de l'arrossegament sense afectar la qualitat dels depòsits. Per tant, l'aplicació de l'electrodiàlisi va demostrar ser una alternativa viable per a la recuperació de l'aigua i de les matèries primeres de la dissolució avaluada, reduint la generació de residus líquids i estalviant els recursos naturals. / Scarazzato, T. (2017). Treatment of a cyanide-free copper electroplating solution by electrodialysis: study of ion transport and evaluation of water and inputs recovery [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/98502

This dissertation examines Elizabeth Robinson Montagu's relationships with three men: her husband, Edward Montagu; George Lyttelton, first baron Lyttelton; and William Pulteney, earl of Bath to show how these relationships were structured and how Elizabeth Montagu negotiated them in order to forward her own intellectual interests. Montagu's relationship with her husband Edward and her friendships with Lord Lyttelton and Lord Bath supplied her with important outlets for intellectual and political expression. Scholarly work on Montagu's friendships with other intellectual women has demonstrated how Montagu drew on the support of female friends in her literary ambitions, but at the same time, it has obscured her equally important male relationships. Without discounting the importance of female friendship to Montagu's intellectual life, this study demonstrates that Montagu's relationships with Bath, Lyttleton, and her husband were at least as important to her as those with women, and that her male friendships and relationships offered her entry into the political sphere. Elizabeth Montagu was greatly interested in the political debates of her day and she contributed to the political process in the various ways open to her as an elite woman and female intellectual. Within the context of these male friendships, Montagu had an opportunity to discuss political philosophy as well as practical politics; as a result, she developed her own political positions. It is clear that contemporary gender conventions limited the boundaries of Montagu's intellectual and political concerns and that she felt the need to position her interests and activities in ways that did not appear transgressive in order to follow her own inclinations. Montagu represented her interest in the political realm as an extension of family duty and expression of female tenderness. In this manner, Montagu was able to forward her own opinions without appearing to cross conventional gender boundaries.

The area which today covers the Doric House, the Roman East Bath and the Byzantine East Church at the Karian sanctuary of Zeus at Labraunda in south-western Turkey, was by Swedish archaeologists called the P-building and the R-bath during the early 1950s. The excavations of this area in 1951 and 1953 were documented in three excavation diaries by archaeologist Inge Dahlén, written in Swedish. These diaries have, however, never been published. This thesis therefore focused to analyse Dahlén’s three excavation diaries in terms of three aspects. The first aspect was to understand the archaeological work and documentation methods at Labraunda during the 1951 and 1953 excavations and consequently, determine how the archaeology functioned in practice at the site in the early 1950s. The second aspect was to present in what ways Dahlén’s diaries could contribute to the current and future excavations at the East Bath at Labraunda. The last aspect was to study Dahlén’s own archaeological interpretations which occured in the diaries. In order to present all the three aspects, the analysis and discussion on the diaries were organised into four headings: archaeological work, archaeological finds, stratigraphy and documentation methods. Studying the diaries based on these headings showed that certain improvements occurred in the diaries from 1951 to 1953. Dahlén’s excavation diaries reveal a large amount of archaeological data regarding the progress of the excavations and the numerous discoveries from the excavated areas. They need, therefore, to be taken into consideration for a better understanding of both the early and the new excavations that are being conducted at the same area.

Over the last two centuries, there has been a continual evolution of how occupied rooms are heated, with inventors competing to design new heating devices. In particular, there is a wide range of convector types, which vary in shape, size, design, material, operating medium and application. With approximately 190 million convectors installed in the UK alone, the question arises regarding the dependencies on the efficiency of heat distribution through convector-induced filling flows. A standard approach to evaluate convector performance is based on the convector strength only, the implication being the stronger the convector the better the performance. This work has gone beyond the limits of a stereotypical assessment in pursuit of answers regarding the physics of convector-induced filling and a new objective method to evaluate the efficiency of this transient process. The ultimate goal has been to provide a deep understanding of filling and stratification induced by a convector, in order to heat rooms rapidly and effectively. An experimental facility has been designed that approximates dynamic similarity between the experimental set-up and a real-life room with a convector. In the experiments, a rectangular sectioned water tank represents a room and a saline source rectangular sectioned panel with sintered side walls provides a convector representation. Experiments have been performed in water with a saline solution to ensure high Rayleigh numbers. Diagnostic techniques involve a combination of a shadowgraph method, a dye-attenuation method, direct salinity measurements and a new application of Particle Image Velocimetry (PIV). Interesting insight into convector-induced buoyancy-driven flows has been gained. As a result, new guidelines aimed at heating rooms more rapidly and effectively have been proposed. The key outcome that can be immediately applied is that, for a given convector strength, heat distribution with height can be improved by adjusting the convector position. For instance, faster filling leading to more uniform heat distribution occurs in rooms with convectors detached from side walls, due to large-scale mixing flows in the early period of filling. Also shorter convectors relative to the room height, positioned close to the floor level, promote faster and more uniform filling. An attempt to describe the transient filling has been made and to do so statistical methods, application specific, have been developed. As a result, the empirical equations describing both the filling rates in different stages of filling and the development of stratification have been derived, which rank the governing parameters, based on their importance, as either dominant or subordinate. Two dominant parameters governing filling flows are the non-dimensional accumulation parameter B and the Rayleigh number ΔRa, which are related to the convector strength. The impact of these two parameters is constant throughout the process. The parameters accounting for the system geometry and filling time (T) are subordinate parameters. Their impact, visible in the early period, decreases as filling continues.