Characterization of spontaneous combustuion tendency of dried sewage sludge

The general purpose of this study was the determination of the safety conditions to avoid the presence of explosive atmospheres in the wastewater industry. Eight Spanish plants located in Madrid, Barcelona and Málaga were considered and several sludge samples were taken in different seasons. The base for the assessment of the spontaneous ignition behaviour of dust accumulations is the experimental determination of the self-ignition temperature under isothermal conditions. Self-ignition temperatures at four volumes were obtained for one sample of sewage sludge, allowing their extrapolation to large storage facilities. A simple test method, based also on an isothermal study of samples, is the UN classification of substances liable to spontaneous combustion. Two different samples were so tested, obtaining unlike results if transported in packages of different volumes. By means of thermogravimetric techniques it is possible to analyse the thermal susceptibility of dried sewage sludge. Apparent activation energy can be obtained from the rate of weight loss. It is also applied to the study of self-ignition susceptibility by modifying test conditions when oxygen stream is introduced. As a consequence of this oxidant contribution, sample behaviour can be very different during testing and a step drop or sudden loss of weight is observed at a characteristic temperature for every substance, associated to a rapid combustion. Plotting both the activation energy and the characteristic temperature, a map of self-ignition risk was obtained for 10 samples, showing different risk levels for samples taken in different locations and at different seasons. A prediction of the self-ignition risk level can be also determined.

Estudio de la precisión en la determinación del coeficiente de absorción acústica en tubo de impedancia

El objetivo del presente Trabajo Fin de Máster es estudiar la precisión de los resultados obtenidos en la medición del coeficiente de absorción acústica en tubo de impedancia, según la norma UNE-EN ISO 10534-2 “Determinación del coeficiente de absorción acústica y de la impedancia acústica en tubos de impedancia. Parte 2: Método de la función de transferencia”. En primer lugar, se han estudiado los fundamentos teóricos relacionados con el método de ensayo. A continuación, se ha detallado dicho método y se ha aplicado a un caso práctico con la instrumentación disponible en el laboratorio de Acústica de la Escuela. En relación a la precisión del método se ha analizado si la preparación e instalación de la muestra son causas de imprecisión. Para ello, se han realizado varios ensayos con dos tipos de materiales acústicos, con el fin de estudiar la dispersión entre los resultados que produce tanto el corte de la muestra, realizado en el proceso de confección, como su colocación en el tubo de impedancia. Además, se ha estudiado si desviaciones en la medida de la temperatura y de la distancia entre los micrófonos influyen en los valores del coeficiente de absorción acústica medido y de su incertidumbre asociada. Puesto que el resultado de un ensayo únicamente se halla completo cuando está acompañado de una declaración acerca de la incertidumbre de dicho resultado, en el presente trabajo se ha aplicado a este método de ensayo un procedimiento para estimar la incertidumbre empleando el método de Monte Carlo. ABSTRACT The objective of this project is studying the precision of the measurements of sound absorption coefficient in impedance tube, according to standard UNE-EN ISO 10534-2 “Determination of sound absorption coefficient and impedance in impedance tubes. Part 2: Transfer-function method”. Firstly, theoretical basis related to the test method have been studied. Furthermore, this method has been defined and applied to a particular case with the instrumentation available in the Acoustics laboratory of the College. In relation to the precision of the method, the preparation and installation of the test sample have been analyzed as possible causes of imprecision. For this purpose, two types of acoustic materials have been tested in order to study the deviation between the results produced by the cutting of the test sample and the collocation in impedance tube. In addition, it has been studied if deviations in the measurement of the temperature and distance between microphones may influence the sound absorption coefficient measured and its associated uncertainty. The test result must be accompanied by a statement of the uncertainty of the result. For this reason, in this project a procedure for estimating uncertainty of the result of this test method has been applied using the Monte Carlo method.

Análisis de las causas de dispersión en los resultados de las medidas del coeficiente de absorción acústica en cámara reverberante

El objetivo del presente Trabajo Fin de Máster es llevar a cabo un estudio de las causas de la precisión de los resultados de las medidas del coeficiente de absorción acústica en cámara reverberante, siguiendo el procedimiento descrito en la norma UNE-EN ISO 354 “Medición de la absorción acústica en una cámara reverberante”. En primer lugar, se han estudiado los fundamentos teóricos relacionados con el método de ensayo. A continuación, se ha detallado dicho método y se ha aplicado a un caso práctico con la instrumentación disponible en el laboratorio de Acústica de la Escuela. Puesto que el resultado de un ensayo únicamente se halla completo cuando está acompañado de una declaración acerca de la incertidumbre de dicho resultado, en el presente trabajo se ha aplicado a este método de ensayo, tanto el enfoque clásico de la GUM, como el método de Monte Carlo, para evaluar la incertidumbre y comparar los resultados obtenidos mediante las dos metodologías. Para estudiar la influencia que produce en el campo sonoro de una cámara reverberante la introducción de un material absorbente en su interior, se realizó un estudio mediante trazado de rayos de la cámara reverberante del CEIS. ABSTRACT The objective of this Master's Thesis is to study the causes of accuracy of the measurements results of sound absorption coefficient in a reverberation room, according to the procedure of standard UNE-EN ISO 354 "Measurement of sound absorption in a reverberation room ". Firstly, theoretical basis related to the test method have been studied. Then, this method has been defined and applied to a particular case with the instrumentation available in the Acoustics laboratory of the College. The test result must be accompanied by a statement of the uncertainty of the result. For this reason, Monte Carlo method and GUM uncertainty framework have been applied in this project for estimating uncertainty and comparing the results obtained by these two methodologies. In addition, a study was made in the reverberation room of CEIS, by ray tracing, to study the influence on the sound field produced by the introduction of an absorbent material inside of the room.

Madera termo-tratada de frondosas para uso estructural

La madera termotratada es madera modificada mediante un proceso térmico a elevadas temperaturas que le proporciona mayor estabilidad dimensional y durabilidad sin incorporar productos químicos perjudiciales para el medio ambiente. Hasta el momento se ha aplicado fundamentalmente a madera de coniferas por motivos económicos, siendo su uso más habitual en ambientes exteriores o de elevada humedad, como elementos de revestimiento no estructurales, carpinterías, mobiliario de jardín, etc. En la presente tesis se estudia la viabilidad de la madera termotratada de frondosas para uso estructural, en particular fresno (Fraxinus excelsior L) y haya (Fagus sylvatica L). Con este fin, y considerando que el termotratamiento modifica la estructura interna de la madera resultando en un nuevo material, se realizan estudios experimentales y numéricos para su caracterización. Estos trabajos se desarrollan bajo el enfoque de la Mecánica de Fractura debido a la pérdida de resistencia y aumento de fragilidad que presenta el material, especialmente a tracción perpendicular a las fibras. Así mismo, se lleva a cabo una recopilación de las bases, fundamentos y metodologías de esta teoría aplicados a madera sin tratar y otros materiales debido a la inexistencia de este tipo de estudios en madera termotratada. De igual manera se realiza un programa de caracterización mecánica del material para determinar sus propiedades elásticas considerando un modelo ortótropo, necesarios en la investigación del comportamiento a fractura. El trabajo derivó en el desarrollo de un nuevo método de ensayo para la determinación multiparamétrica a partir de un sólo espécimen, proporcionando resultados mucho más robustos que los obtenidos con la metodología convencional de ensayos. En base a los trabajos realizados, considerando las limitaciones de resistencia y fragilidad, así como la dudosa aplicabilidad de las normativas existentes en madera sin tratar, se aconseja no utilizar tratamientos térmicos intensos en elementos estructurales primarios. Se propone su aplicación en elementos secundarios, de manera que un posible colapso no implique una pérdida de fiabilidad global de la estructura. Se estudia la viabilidad de un panel sandwich innovador y ecológico para fachadas expuesto a cargas de viento, compuesto de madera termotratada en las caras y panel aislante de fibras de madera con función estructural en el alma. Esta investigación se desarrolló dentro del proyecto de investigación Europeo "Holiwood", Holistic implementation of European thermal treated hardwood (TMT) in the sector of construction industry and noise protection by sustainable, knowledge-based and value added products, perteneciente al sexto Programa Marco. ABSTRACT Hcat-trcatcd wood is modified wood by a thermal process at high temperatures which provides greater dimensional stability and durability without adding harmful chemicals to the environment. It has been mainly applied to softwoods due mainly to economical reasons, being its most common use outdoors or in high humidity environments, as non-structural elements, furniture, etc. The present Thesis studies the feasibility of heat-treated hardwoods for structural uses, particularly ash (Fraxinus excelsior L) and beech (Fagus sylvatica L). To this end, and considering that heat treatment modifies the internal structure of the wood resulting in a new material, experimental and numerical studies are performed for its characterization. This investigation is developed under the approach of Fracture Mechanics due to the loss of strength and the increase in brittlcncss of the material, especially in tension perpendicular to the grain. Likewise, it holds a collection of the bases, foundations and methodologies of this theory applied to untreated wood and other materials due to the lack of such studies in heat-treated wood. In addition, studies for the mechanical characterization of the material are performed in order to determine the elastic properties considering an orthotropic model. This work is necessary in the investigation of the fracture behavior. It led to the development of a new test method for multiparameter determination by using just a single specimen, providing much more robust results than those obtained with conventional test methodology. Based on this investigation, and considering the limitations of strength and brittleness, and the questionable applicability of existing standards for untreated wood, it is advised not to use intense heat treatments in primary structural elements. It is proposed the application to secondary elements, so that a possible collapse does not involve a loss of overall reliability of the structure. It is studied the feasibility of an innovative and ecological sandwich panel for facades exposed to wind loads, composed by heat-treated wood faces and insulating wood fiberboard with structural function in the core. This investigación was developed within the European research project "Holiwood", Holistic implementation of European thermal treated hardwood (TMT) in the sector of construction industry and noise protection by sustainable, knowledge-based and value added products, of the Sixth Framework Program.

Estudio sobre la durabilidad de los nuevos tipos de cemento para la evaluación del comportamiento de morteros y hormigones frente a la agresión química de los sulfatos y del agua de mar

Esta investigación ha sido desarrollada para analizar la influencia de las características específicas de los nuevos cementos en el comportamiento expansivo originado durante cinco años por el ataque externo por sulfatos o agua de mar, y para estudiar la validez de diversos métodos de ensayo aplicables para evaluar la resistencia de los conglomerantes a los sulfatos o al agua de mar. Se han determinado las características químicas y mecánicas de los quince cementos seleccionados en el estudio (su contenido de yeso, tipo y cantidad de adiciones, contenidos de C3A y C4AF) para examinar la relación entre estos parámetros y su durabilidad frente al ataque por sulfatos. Se han llevado a cabo ensayos para evaluar la resistencia a sulfatos sobre probetas de mortero fabricadas con los quince cementos comunes seleccionados de muy distintos tipos, la mayoría de ellos resistentes a sulfatos conforme a la norma UNE-EN 197-1. Por cada tipo de cemento se fabricaron probetas de mortero para la realización de ensayos acelerados usando Na2SO4 como medio agresivo según la norma ASTM C 1012 manteniendo esas condiciones de exposición durante dos años. En paralelo se fabricaron otras series de probetas idénticas, que fueron conservadas en agua de mar y en agua saturada en cal (como patrón de un medio no agresivo) durante el mismo plazo. Adicionalmente estos cementos fueron evaluados conforme a los procedimientos de ensayo acelerado de la norma ASTM C 452 y del ensayo de Koch y Steinegger. También se fabricaron otras series de probetas de 40x40x160 mm (adoptando una relación a/c=0,5 y la composición arena:cemento definida en la norma UNE-EN 196-1). Durante cinco años de exposición en las tres condiciones de conservación establecidas (sulfatos, agua de mar y agua patrón) se han efectuado ensayos para determinar la resistencia a compresión y el deterioro superficial de las probetas de mortero. Ninguno de los conglomerantes fue mezclado inicialmente con yeso para acelerar el ataque ni se establecieron otras condiciones no realísticas en la fabricación de los morteros Se ha analizado el comportamiento durable de los cementos tanto frente al ataque por sulfatos como por agua de mar. Para la evaluación se han tomado en consideración las variaciones de contenido en C3A, los tipos y proporciones de los constituyentes (adiciones puzolánicas, escorias de horno alto, caliza …) con el mismo tipo de clínker en algunos casos. Se ha procedido a evaluar la validez de los límites de aceptación establecidos en cada uno de los ensayos acelerados para determinar la resistencia a sulfatos y valorar su idoneidad en los nuevos cementos, y se ha propuesto un método de ensayo acelerado recomendable para discriminar cementos resistentes y no resistentes a sulfatos. A la edad final de los tres tipos de exposición han sido correlacionados los parámetros relativos a la degradación superficial, pérdida de resistencia y expansión lineal de las probetas con las características de los cementos y los productos expansivos analizados mediante difracción de rayos X, con objeto de poder redefinir las características recomendables exigibles a los cementos resistentes a sulfatos o al agua de mar. Experimental research has been performed to relate specific cement characteristics to expansion due to sulfate or sea water attack during five years, and to study different test methods suitability for sulfate and marine resistance. Chemical and mechanical characteristics were studied to determine the variation in properties of selected cements (SO3 content, type and amount of additions, C3A, and C4AF content) and examine relationships between these characteristics and the results of sulfate resistance. Sulfate resistance testing have been performed on mortar specimens prepared from fifteen cement types of statistically diverse chemical composition, most of them with sulfate resistant properties according to European standard EN 197-1 Mortar specimens testing using Na2SO4 as the aggressive medium according to ASTM C 1012 was performed using each cement; identical specimens were also stored in sea water, and in lime saturated water (blank condition), up to two years age. Additionally these cements were tested conforming to ASTM C 452 and Koch and Steinegger test. Mortar specimens of 40x40x160 mm were also moulded (with w/c ratio and cement:sand composition of EN 196-1). Compressive strength of these mortar specimens have been tested during five years of immersion in a sulfate solution and also in seawater (and in lime saturated water, as a blank condition), and external damage and have been analyzed. None of the prepared mortars was blended with gypsum or any other nonrealistic condition. Durability behaviour in sulfate resistant common cements conforming to EN 197-1 exposed to sulfate attack was evaluated, and also the correlation between sulfate resistance and seawater resistance has been studied. Different C3A contents, variable types and proportioning of constituents (limestone, pozzolanic additions, blastfurnace slag ...) with or without the same clinker type were investigated. Recommended acceptance limits for sulfate resistance of cements concerning to each used test method were evaluated in order to explore their suitability. A new accelerated method has been recommended to provide a meaningful discrimination between sulfate resistant or non-sulfate resistant cements. Relationships between cement characteristics, degradation, expansive products obtained by X-ray diffraction techniques, strength loss and maximum expansion after applied storage treatments, were correlated at final age, to redefine cement characteristics for sulfate resistant and marine resistant Portland cement.

Corrosión de armaduras en el hormigón armado en ambiente marino aéreo

La presente tesis doctoral surge ante la necesidad de completar el estudio sobre la corrosión en el hormigón armado expuesto al ambiente marino iniciado por D. Miguel Ángel Bermúdez Odriozola en 2007 con la tesis doctoral con título “Corrosión de las armaduras del hormigón armado en ambiente marino: zona de carrera de mareas y zona sumergida”. Una vez realizado el estudio bibliográfico, se ha planteado un estudio experimental en el que se analizan cuatro muelles de distintas edades y localizados en distintos lugares de la geografía española. Uno de ellos contiene adiciones en el hormigón. Una vez inspeccionados, se extraen testigos de cada uno de ellos con el fin de realizar ensayos de caracterización y se analizan sus resultados en paralelo con los coeficientes de difusión. Uno se los objetivos ha sido comprobar el mejor método de ensayo que permita controlar la durabilidad del hormigón en ambiente IIIa. La tesis que se presenta ha demostrado la efectividad del ensayo de penetración de agua para discriminar los hormigones que presentarán un buen comportamiento frente a la difusión de cloruros y por tanto para predecir la vida útil de la estructura. Asimismo, otro objetivo ha sido valorar el uso de adiciones en el hormigón y cómo afectan a la mejora del comportamiento del hormigón expuesto al ambiente marino. Se han obtenido valores del coeficiente de eficacia de cenizas volantes y humo de sílice frente a la difusión de cloruros, muy superiores a los actualmente considerados en términos de resistencia. El ambiente marino aéreo engloba estructuras situadas en primera línea de costa así como aquellas que se sitúan hasta 5km de distancia de la línea del mar. La investigación realizada ha demostrado la necesidad de establecer una nueva subdivisión en este ambiente introduciendo la zona Spray, siguiendo criterios internacionales, que permita diferenciar la zona más desfavorable del mismo que comprende las estructuras ubicadas sobre el nivel del mar tal como los tableros de pantalanes portuarios estudiados. Se han analizado en profundidad los valores del contenido de cloruros en superficie de hormigón en los diferentes tipos de ambiente marino recogidos por la Instrucción EHE- 08 contrastando los requisitos normativos. Como conclusión se han hecho nuevas propuestas normativas que afectan al ambiente sumergido y al ambiente marino aéreo (zona spray). Asimismo se ha realizado un análisis en profundidad de la concentración crítica de cloruros recogida por la Instrucción EHE-08, a partir de los datos obtenidos en estructuras reales. Se ha evaluado el ensayo de resistividad para estimar el valor del coeficiente de difusión de cloruros. Este ensayo ha demostrado su efectividad para discriminar hormigones con adiciones y con muy baja penetración de agua, si bien no resulta sensible para detectar hormigones con elevada permeabilidad. Finalmente en la tesis se ha obtenido un modelo de difusión de cloruros (a/c-D) en ambiente marino aéreo a fin de poder estimar la difusión de cloruros en el hormigón a partir de un requisito normativo como es la relación a/c. This Thesis is focussed to complete the previous study on the corrosion of reinforced concrete exposed to marine environment, carried out by Dr. Miguel Ángel Bermúdez Odrizola in 2007. That Thesis title was “Corrosion of concrete reinforcement located in marine environment: tidal zone and submerged zone”. After the literature review presented in the State of the Art, an experimental programme was carried out. Four docks of different ages and locations have been studied, one of them was a fly ash concrete. The structures were inspected on site and several cores extracted in order to develop characterization tests and obtain diffusion profiles at the laboratory. One of the objectives has been to check the best laboratory test method to control concrete durability when exposed to atmospheric marine environment. This Thesis has proven the effectiveness of the water penetration test to differentiate concretes well behaved against chloride diffusion and also to predict the structure service life. Another objective has been to study the effect of mineral additions in concrete and how they improve the durability of concrete in this environment. Efficiency factors have been obtained for fly ashes and silica fume, much higher than those consider for strength. According to the Spanish Concrete Code EHE 08, the atmospheric marine environment includes structures located at the cost, from the sea line up to 5km inland. The research conducted has shown the need to consider a spray zone which is the most unfavourable area of the atmospheric environment, affecting structures over the sea level as the decks of the wharves here studied. Surface chloride contents of structures in the different marine environments have been deeply analysed, checking the actual standard limits. As a conclusion, new normative values have been proposed for submerged and atmospheric zone (spray zone). A complete analysis of the chloride threshold concentration from the data obtained in real structures has also been performed. It has been evaluated the resistivity test as a tool to estimate the chloride diffusion coefficient. This test has proven effectiveness to discriminate concrete with mineral additions and low water penetration values, while it is not sensitive to detect concretes with high permeability. Finally, a chloride diffusion model (w/c) has been obtained in atmospheric marine environment in order to estimate the chloride diffusion of the concrete knowing a normative requirement as w/c.

Avaliação do efeito de diferentes concentrações de fotoiniciadores em propriedades mecânicas e na cor de um adesivo dental experimental

O presente trabalho teve por foco prover uma revisão de conceitos relacionados às resinas dentais fotopolimeráveis e, também, analisar como diferentes concentrações de fotoiniciadores de uso comum em odontologia podem influenciar no desempenho mecânico e na cor de resinas dentais. Concentrações de 0,01%, 0,10%, 0,25% 0,50%, 0,75%, 1,00% e 10% em massa de fotoiniciador foram adicionadas em uma matriz polimérica composta por TEGDMA/BisGMA 50%/50% em massa de forma que, fixando variáveis externas referentes à fonte de luz e à preparação das amostras, foi possível avaliar o efeito da concentração de fotoiniciador nas propriedades mecânicas de resistência à fratura por compressão, resistência à fratura pela aplicação de tensão diametral e dureza Barcol. Por fim, o efeito da concentração na cor aferida através do método CIELab foi investigada. Os fotoiniciadores utilizados foram o Irgacure® 819, a 1-fenil-1,2-propanodiona (PPD) e a Canforoquinona a qual foi utilizada juntamente com ocoiniciador Etil-4 dimetilaminobenzoato (EDB) na concentração constante de 1% em massa. Os resultados mecânicos e de cor foram comparados entre as diferentes amostras através de análises estatísticas (ANOVA) e, especificamente para cor, o parâmetro de diferença de cor (ΔE) foi interpretado verificar se as alterações observadas são perceptíveis ao olho humano. Para fundamentar os estudos, análises do espectro de absorção das amostras, do espectro de irradiação da fonte de luz e do grau de conversão das amostras foram realizadas. Os resultados revelaram que, independentemente do fotoiniciador, graus de conversão da mesma ordem de grandeza de um adesivo comercial foram obtidos, porém as velocidades de reação foram diferentes (maior velocidade para as amostras de CQ e menor para PPD). Curvas características foram obtidas para os espectros de absorção e de irradiação confirmando, pela sobreposição das curvas, que a fonte de luz é efetiva para iniciação da polimerização das amostras. As análises de resistência à fratura revelaram que a quebra catastrófica do material ocorrerá preferencialmente quando a força é aplicada ao longo do diâmetro para os corpos de prova preparados. Quanto à dureza, verificou-se que que para a CQ houve um máximo, para Irgacure um comportamento assintótico com aumento da concentração e, para a PPD, não foi possível a obtenção de amostras (verificado que a PPD necessita de tempo de irradiação superior ao convencionalmente utilizado na prática odontológica). Os testes de ANOVA permitiram verificar que o Irgacure é capaz de fornecer resultados mecânicos semelhante em relação à CQ ocasionando, em contrapartida, um menor escurecimento e amarelamento. Analisando o parâmetro ΔE, confirmou-se que a alteração na cor se torna evidente à medida que ocorre o aumento da concentração de fotoiniciador independentemente do fotoiniciador utilizado, porém a alteração é maior para a CQ.

Instantaneous RRMI of iron rods in reduced gravity

Standard upward-burning promoted ignition tests (“Standard Test Method for Determining the Combustion Behavior of Metallic Materials in Oxygen-Enriched Atmospheres,” ASTM G4-124 [1] or “Flammability, Odor, Offgassing, and Compatibility Requirements and Test Procedures for Materials in Environments that Support Combustion,” NASA-STD-6001, NASA Test 17 [2]) were performed on cylindrical iron (99.95% pure) rods in various oxygen purities (95.0–99.98%) in reduced gravity onboard NASA JSC's KC-135 to investigate the effect of gravity on the regression rate of the melting interface. Visual analysis of experiments agrees with previous published observations showing distinct motions of the molten mass attached to the solid rod during testing. Using an ultrasonic technique to record the real-time rod length, comparison of the instantaneous regression rate of the melting interface and visual recording shows a non-steady-state regression rate of the melting interface for the duration of a test. Precessional motion is associated with a higher regression rate of the melting interface than for test periods in which the molten mass does not show lateral motion. The transition between the two types of molten mass motion during a test was accompanied by a reduced regression rate of the melting interface, approximately 15–50% of the average regression rate of the melting interface for the entire test.

Antimicrobial efficacy of copper surfaces against spores and vegetative cells of Clostridium difficile: the germination theory

OBJECTIVES: Persistent contamination of surfaces by spores of Clostridium difficile is a major factor influencing the spread of C. difficile-associated diarrhoea (CDAD) in the clinical setting. In recent years, the antimicrobial efficacy of metal surfaces has been investigated against microorganisms including methicillin-resistant Staphylococcus aureus. This study compared the survival of C. difficile on stainless steel, a metal contact surface widely used in hospitals, and copper surfaces. METHODS: Antimicrobial efficacy was assessed using a carrier test method against dormant spores, germinating spores and vegetative cells of C. difficile (NCTC 11204 and ribotype 027) over a 3 h period in the presence and absence of organic matter. RESULTS: Copper metal eliminated all vegetative cells of C. difficile within 30 min, compared with stainless steel which demonstrated no antimicrobial activity (P < 0.05). Copper significantly reduced the viability of spores of C. difficile exposed to the germinant (sodium taurocholate) in aerobic conditions within 60 min (P < 0.05) while achieving a >or=2.5 log reduction (99.8% reduction) at 3 h. Organic material did not reduce the antimicrobial efficacy of the copper surface (P > 0.05).

The release of nicotine from chewing gum formulations

The first clinically proven nicotine replacement product to obtain regulatory approval was Nicorette® gum. It provides a convenient way of delivering nicotine directly to the buccal cavity, thus, circumventing 'first-pass' elimination following gastrointestinal absorption. Since launch, Nicorette® gum has been investigated in numerous studies (clinical) which are often difficult to compare due to large variations in study design and degree of sophistication. In order to standardise testing, in 2000 the European Pharmacopoeia introduced an apparatus to investigate the in vitro release of drug substances from medical chewing gum. With use of the chewing machine, the main aims of this project were to determine factors that could affect release from Nicorette® gum, to develop an in vitro in vivo correlation and to investigate formulation variables on release of nicotine from gums. A standard in vitro test method was developed. The gum was placed in the chewing chamber with 40 mL of artificial saliva at 37'C and chewed at 60 chews per minute. The chew rate, the type of dissolution medium used, pH, volume, temperature and the ionic strength of the dissolution medium were altered to investigate the effects on release in vitro. It was found that increasing the temperature of the dissolution media and the rate at which the gums were chewed resulted in a greater release of nicotine, whilst increasing the ionic strength of the dissolution medium to 80 mM resulted in a lower release. The addition of 0.1 % sodium Jauryl sulphate to the artificial saliva was found to double the release of nicotine compared to the use of artificial saliva and water alone. Although altering the dissolution volume and the starting pH did not affect the release. The increase in pH may be insufficient to provide optimal conditions for nicotine absorption (since the rate at which nicotine is transported through the buccal membrane was found to be higher at pH values greater than 8.6 where nicotine is predominately unionised). Using a time mapping function, it was also possible to establish a level A in vitro in vivo correlation. 4 mg Nicorette® gum was chewed at various chew rates in vitro and correlated to an in vivo chew-out study. All chew rates used in vitro could be successfully used for IVIVC purposes, however statistically, chew rates of 10 and 20 chews per minute performed better than all other chew rates. Finally a series of nicotine gums was made to investigate the effect of formulation variables on release of nicotine from the gum. Using a directly compressible gum base, in comparison to Nicorette® the gums crumbled when chewed in vitro, resulting in a faster release of nicotine. To investigate the effect of altering the gum base, the concentration of sodium salts, sugar syrup, the form of the active drug, the addition sequence and the incorporation of surfactant into the gum, the traditional manufacturing method was used to make a series of gum formulations. Results showed that the time of addition of the active drug, the incorporation of surfactants and using different gum base all increased the release of nicotine from the gum. In contrast, reducing the concentration of sodium carbonate resulted in a lower release. Using a stronger nicotine ion-exchange resin delayed the release of nicotine from the gum, whilst altering the concentration of sugar syrup had little effect on the release but altered the texture of the gum.

Wear and corrosion of mechanical seals

Mechanical seals are used extensively to seal machinery such as pumps, mixers and agitators in the oil, petrochemical and chemical industries. The performance of such machinery is critically dependent on these devices. Seal failures may result in the escape of dangerous chemicals, possibly causing injury or loss of life. Seal performance is limited by the choice of face materials available. These range from cast iron and stellited stainless steel to cemented and silicon carbides. The main factors that affect seal performance are the wear and corrosion of seal faces. This research investigated the feasibility of applying surface coating/treatments to seal materials, in order to provide improved seal performance. Various surface coating/treatment methods were considered; these included electroless nickel plating, ion plating, plasma nitriding, thermal spraying and high temperature diffusion processes. The best wear resistance, as evaluated by the Pin-on-Disc wear test method, was conferred by the sprayed tungsten carbide/nickel/tungsten-chromium carbide deposit, produced by the high energy plasma spraying (Jet-Kote) process. In general, no correlation was found between hardness and wear resistance or surface finish and friction. This is due primarily to the complexity of the wear and frictional oxidation, plastic deformation, ploughing, fracture and delamination. Corrosion resistance was evaluated by Tafel extrapolation, linear polarisation and anodic potentiodynamic polarisation techniques. The best corrosion performance was exhibited by an electroless nickel/titanium nitride duplex coating due to the passivity of the titanium nitride layer in the acidified salt solution. The surface coating/treatments were ranked using a systematic method, which also considered other properties such as adhesion, internal stress and resistance to thermal cracking. The sealing behaviour of surface coated/treated seals was investigated on an industrial seal testing rig. The best sealing performances were exhibited by the Jet-Kote and electroless nickel silicon carbide composite coated seals. The failure of the electroless nickel and electroless nickel/titanium nitride duplex coated seals was due to inadequate adhesion of the deposits to the substrate. Abrasion of the seal faces was the principal wear mechanism. For operation in an environment similar to the experimental system employed (acidified salt solution) the Jet-Kote deposit appears to be the best compromise.

The effect of catchment characteristics on sewage settling velocity grading

A procedure has been developed which measures the settling velocity distribution of particles within a complete sewage sample. The development of the test method included observations of particle and liquid interaction using both synthetic media and sewage. Comparison studies with two other currently used settling velocity test procedures was undertaken. The method is suitable for use with either DWF or storm sewage. Information relating to the catchment characteristics of 35 No. wastewater treatment works was collected from the privatised water companies in England and Wales. 29 No. of these sites were used in an experimental programme to determine the settling velocity grading of 33 No. sewage samples. The collected data were analysed in an attempt to relate the settling velocity distribution to the characteristics of the contributing catchment. Statistical analysis of the catchment data and the measured settling velocity distributions was undertaken. A curve fitting exercise using an S-shaped curve which had the same physical characteristics as the settling velocity distributions was performed. None of these analyses found evidence that the settling velocity distribution of sewage had a significant relationship with the chosen catchment characteristics. The regression equations produced from the statistical analysis cannot be used to assist in the design of separation devices. However, a grading curve envelope was produced, the limits of which were clearly defined for the measured data set. There was no evidence of a relationship between settling velocity grading and the characteristics of the contributing catchment, particularly the catchment area. The present empirical approach to settling tank design cannot be improved upon at present by considering the variation in catchment parameters. This study has provided a basis for future research into the settling velocity measurement and should be of benefit to future workers within this field.

Efficacy and toxicity of biocides used in handling sterile pharmaceuticals

This thesis has sought to investigate disinfection agents and procedures which may provide sanitisation against bacterial spores. A hard-surface disinfection test method was designed to ascertain which combinations of biocide and application method were most effective against bacterial spores. A combination of spraying and wiping was the most effective method of disinfection against Bacillus spores, with wiping found to play a key role in spore removal. The most efficacious of the biocides investigated was the 6% hydrogen peroxide. Vaporised Hydrogen Peroxide (VHP) gassing was more effective than traditional disinfection. In addition to efficacy, the toxic potential of the biocides to human airway epithelial cells in vitro was evaluated. Toxicity against human bronchial and nasal epithelial cells was assessed by determining cell viability, inflammatory status, protein oxidation and epithelial cell layer integrity. In addition the cell death mechanism following biocide exposure was investigated. There was a decrease in viable cells following exposure to all biocides when applied at practical concentrations. Almost all of the biocides tested elicited a pro-inflammatory response from the cells as measured by IL-8 production. All biocides increased protein oxidation as measured by thiol and carbonyl levels. Measurement of transepithelial electrical resistance and paracellular permeability indicated biocide-dependent decrease in epithelial cell barrier function. The cellular response was biased towards necrotic rather than apoptotic death. The use of biocides, although efficacious to some effects against Bacillus spores, will require careful monitoring for adverse health effects on personnel.

Desenvolvimento de emulsões o/a contendo extrato glicólico de açai e avaliação da atividade fotoprotetora

Sunscreen use is the most common photoprotection alternative used by the population, and so these products should offer improved protection with broad - spectrum, UVA and UVB protection . Vegetal substances have recently been considered as resources for sunscreen formulations due to their UV spectrum absorption and antioxidant properties. The Euterpe oleracea Mart., popularly known as açai, in its che mical composition contain polyphenols compounds, such as anthocyanins and flavonoids , to which antioxidant properties have been attributed . The aim of this work was to develop O/W sunscreens emulsions con taining açai glycolic extract ( AGE) and to evaluate both their physical stability , safety and photoprotective efficacy. The safety of the extract was evaluated by in vitro phototoxicity and cytotoxicity tests. Emulsions containing AGE and sunscreens were formulated using different types and concentrations o f polymeric surfactant (Acrylates/C 10 - 30 Alkyl Acrylate Crosspolymer and Sodium Polyacrylate). The influence of two rheology modifiers (Polyacrylamide (and) C13 - 14/Isoparaffin (and) Laureth - 7 and Carbomer) on the stability was also investigated. Physical stability was evaluated by preliminary and accelerated studies. The macroscopic analyses, pH value and electrical conductivity determinations and rheological behavior were evaluated at different time intervals . The in vivo Sun Protect Factor ( SPF ) was determined according to the International Sun Protection Factor Test Method – 2006 and UVA Protection Factor (FPUVA), wavelength critical and reason SPF/FPUVA were performed according to the method Colipa 2011. The extract did not present cytotoxic ity and phototoxic ity . The stable emulsion containing 5% glycolic extract of açai and 1.0% of sodium poliyacrylate showed pseudoplastic and thixotropic behavior . The sunscreen emulsion containing açai glycolic extract showed a SPF 25.3 and PF - UVA = 14.97. Whe n açai glycolic extract was added in the emulsion sunscreen, no significant increase in the in vivo SPF and FPUVA values were observed. This emulsion showed 1.69 of the SPF/PF - UVA ratio and a critical wavelength value of 378 nm, so may therefore be conside red a sunscreen with UVA and UVB protection.

RELATIONSHIP BETWEEN PHYSICAL AND CHEMICAL PROPERTIES OF STRAIGHT AND RECOVERED ASPHALT BINDERS FROM ONTARIO

Thermal and fatigue cracking are the major pavement distresses that contribute to a drastic reduction of the pavement’s service life and performance in Ontario. Chemical oxidation and hardening of asphalt binders deteriorates its physical properties since physical properties of asphalts depend on its chemical composition. This thesis is aimed to establish a relationship between physical and chemical properties of asphalt binders. A secondary objective is to show the strong correlation between CTOD and temperature. All recovered and straight Ministry of Transportation of Ontario (MTO) samples were investigated using conventional Superpave® test method dynamic shear rheometer (DSR) as well as improved MTO test methods such as extended bending beam rheometer (eBBR) and double-edge-notched tension (DENT) test. DENT test was conducted for all Ontario contract samples at three different temperatures based on their performance grade after three hours of thermal conditioning and compared the results in terms of essential work of fracture, plastic work of fracture and CTOD at different temperatures. Good correlation exists between CTOD and temperature according to the DENT data. X-ray fluorescence (XRF) analysis was conducted to detect the presence of heavy metals such as zinc and molybdenum believed to have originated from waste engine oil. Fourier transform infra-red spectroscopy (FTIR) was performed to determine the abundance of functional groups such as carbonyl, sulfoxides, polyisobutylene, etc. XRF and FTIR analysis confirmed that most of the samples contain waste engine oil and/or oxidized residues, which is believed to be a root cause of premature pavement failures.