Denna avhandling behandlar rökgasutsläpp av persistenta organiska föroreningar, framförallt dioxiner, vid förbränning av fasta biobränslen och torrt hushållsavfall i relativt små anläggningar (5-600 kW) utan avancerad rökgasreningsteknik. Samförbränning av avfall och biobränsle i effektiva mindre biobränslepannor testades som en alternativ strategi till den vanligen förekommande storskaliga hanteringen och förbränningen fast hushållsavfall. Medan storskalig förbränning av avfall ger investeringsmässiga fördelar med rökgasreningsteknik etc. kan små lokala anläggningar ha transportmässiga fördelar och möjligheter till utnyttjande av lokala biobränsletillgångar. Källsorterat, torrt, brännbart hushållsavfall insamlades från hushåll i glesbygd och samförbrändes i brikettform med energigräset rörflen i 150-600 kW biobränslepannor. Endast undantagsvis understeg dioxinemissionerna gällande gränsvärden för avfallsförbränning och nivåerna av väteklorid i rökgas översteg gränsvärdena flerfaldigt. Det bedömdes att någon form av extra rökgasrening är nödvändig för att säkerställa nivågränserna. Dioxiner hittades också i det eldade avfallet, framförallt i textilfraktionen. Dioxinmängderna i rökgaserna var oftast lägre än i det ingående bränslet. Intermittent pelletseldning gav oväntat höga utsläpp av dioxiner med en emissionsfaktor på 28 ng(WHO-TEQ)/kg. Vedeldning i en modern miljömärkt villapanna gav betydligt lägre utsläpp av dioxiner än eldning i en gammal kombipanna och eldning med full lufttillförsel, som kan jämföras med användning av ackumulatortank, resulterade i upp till 90% minskning av utsläpp av dioxiner jämfört med eldning med reducerat lufttillskott (’pyreldning’). Eldning av plastavfall i en vedpanna gav höga utsläpp av dioxiner. Okontrollerad förbränning av trädgårdsavfall och hushålls avfall i tunna eller som öppen eld ’bakgårdsbränning’, gav stora variationer i utsläppsnivåer som bara delvis kunde kopplas till avfallsinnehåll. Resultaten visar att denna typ av förbränning kan vara en betydande källa till dioxiner i miljön, och ett emissionsfaktorintervall på 4-72 ng (WHO-TEQ)/kg föreslås för bedömningar av utsläpp från backgårdsbränning av avfall med låga eller måttliga klorhalter. En sammanfattande slutsats av alla försök är att dioxin utsläpp beror på komplicerade samband mellan bränsleinnehåll och förbränningsbetingelser. Bränslen med mycket höga klorhalter av ger oftast högre utsläpp av dioxiner än bränslen med låga klorhalter medan små skillnader döljs av variationer i förbränningsbetingelser. / This thesis deals with emissions of persistent organic pollutants, primarily dioxins, from the combustion of solid biofuels and dry combustible household waste in relatively small facilities, 5-600 kW, without advanced air pollution controls. Co-combustion of waste and biofuel in effective small boilers was tested as an alternative to prevailing large-scale management and combustion strategies for handling municipal solid waste. This approach includes no advanced air pollution control systems, but offers two advantages: limiting transport and providing scope to use local biofuel resources. Source-sorted, dry, combustible household waste was collected from households in a sparsely populated area and co-combusted as briquettes together with reed canary-grass in 150-600 kW biofuel boilers. Most trials showed difficulties to meet regulative limits for the emissions of dioxins valid for incineration of MSW and the regulated limits for emissions of hydrochloric acid were exceeded manifold. It was concluded that additional flue-gas cleaning will be needed to ensure that emissions are sufficiently low. Dioxins were also found in the waste, especially in the textile fraction. The mass of dioxins in the flue-gas emissions was generally lower than the mass in the fuel input. Intermittent combustion of wood pellets in a residential boiler resulted in an unexpectedly high dioxin emissions factor of 28 ng (WHO-TEQ)/kg fuel. Combustion of wood in a modern environmentally certified boiler yielded considerably lower dioxin emissions than combustion in an old boiler, and combustion with a full air supply, i.e. with use of heat storage tank, resulted in up to 90% reductions in dioxin emission factors compared to combustion with reduced air supply. Combustion of plastic waste in a residential wood boiler resulted in high emissions of dioxins. Tests of uncontrolled combustion of garden and household waste in barrels or open fires, ‘backyard burnings’, resulted in emissions with large variations that could only be partly correlated to the waste constituents. The results imply that this may be an important source of dioxins in the environment and an emission factor range of 4-72 ng (WHO-TEQ)/kg is suggested for estimating emissions from backyard burnings of lightly and moderately chlorine-contaminated waste. A summarized conclusion from all of the experiments is that predicting emission levels from waste contents is not straightforward (except that fuels with very high chlorine levels will usually result in high levels of dioxins in flue-gas emissions). Moderate differences in chlorine levels will usually be masked by the effect of variations in combustion conditions.

[ES] El municipio de Serra se asienta en la vertiente meridional de la Sierra Calderona. El término municipal ocupa una superficie de 5.730 hectáreas de las cuales, el 95 % de su territorio se encuentra dentro del ámbito del Parque Natural de la Sierra Calderona y el 85% del territorio corresponde a Suelo Forestal. La estructura económica del municipio ha tenido, desde 1960, al sector de la construcción como eje principal de la economía, quedando el subsector forestal, como actividad residual. Esto ha provocado un flujo de mano de obra desde el sector primario hacia otros más productivos, teniendo como consecuencia un crecimiento desordenado de la masa forestal, provocando un deterioro del paisaje. Esto ha aumentado considerablemente el riesgo de incendios y plagas y amenaza en definitiva el patrimonio forestal del Parque Natural de la Sierra Calderona. Siguiendo las directrices marcadas por las prioridades de la UE en desarrollo rural se ha puesto en marcha un proyecto de investigación dirigido hacia la creación de empleo local mediante el fomento de actividades sostenibles cuyos resultados se reinviertan en la sociedad local generando una economía circular que constituya la base del desarrollo socio económico local. El proyecto consiste en el aprovechamiento energético sostenible de la biomasa forestal, agrícola y de jardinería y su reconversión a un combustible sólido (pélet) empleado en la calefacción de edificios públicos y por otra parte, comercializando el excedente de pélet, con esto se pretende un ahorro económico energético y de gestión del residuo y un beneficio que podrá ser empleado directamente en la creación de empleo local. El proyecto contribuye además a la protección y mejora de los montes de Serra. La presente Tesis trata de estudiar si un adecuado modelo de gestión de la biomasa en zonas de la interfaz urbano forestal de municipios, como Serra, incluidos en el Parque Natural de la Sierra Calderona puede tener efectos directos positivos en la prevención de incendios forestales y la lucha contra el cambio climático, la Tesis estudia además si estos modelos de gestión pueden ser económica y medioambientalmente sostenibles y su capacidad para contribuir a mejorar el desarrollo socioeconómico de estas poblaciones, fijando su población y ofreciendo un verdadero desarrollo rural basado en el aprovechamiento racional de sus recursos naturales. / [CA] El municipi de Serra s'assenta en el vessant meridional de la Serra Calderona. El terme municipal ocupa una superfície de 5.730 hectàrees de les quals, el 95 % del seu territori es troba dins de l'àmbit del Parc Natural de la Serra Calderona i el 85% del territori correspon a Sòl Forestal. L'estructura econòmica del municipi ha tingut, des de 1960, al sector de la construcció com a eix principal de l'economia, quedant el subsector forestal, com a activitat residual. Açò ha provocat un flux de mà d'obra des del sector primari cap a uns altres més productius, tenint com a conseqüència un creixement desordenat de la massa forestal, provocant una deterioració del paisatge. Açò ha augmentat considerablement el risc d'incendis i plagues i amenaça en definitiva el patrimoni forestal del Parc Natural de la Serra Calderona. Seguint les directrius marcades per les prioritats de la UE en desenvolupament rural s'ha engegat un projecte de recerca dirigit cap a la creació d'ocupació local mitjançant el foment d'activitats sostenibles els resultats de les quals es reinverteixen a la societat local generant una economia circular que constituïsca la base del desenvolupe soci econòmic local. El projecte consisteix en l'aprofitament energètic sostenible de la biomassa forestal, agrícola i de jardineria i la seua reconversió a un combustible sòlid (pélet) emprat en la calefacció d'edificis públics i d'altra banda, comercialitzant l'excedent de pélet, amb açò es pretén un estalvi econòmic energètic i de gestió del residu i un benefici que podrà ser emprat directament en la creació d'ocupació local. El projecte contribueix a més a la protecció i millora de les muntanyes de Serra. La present Tesi tracta d'estudiar si un adequat model de gestió de la biomassa en zones de la interfície urbà forestal de municipis, com Serra, inclosos en el Parc Natural de la Serra Calderona pot tenir efectes directes positius en la prevenció d'incendis forestals i la lluita contra el canvi climàtic, la Tesi estudia a més si aquests models de gestió poden ser econòmica i mediambientalment sostenibles i la seua capacitat per a contribuir a millorar el desenvolupament socioeconòmic d'aquestes poblacions, fixant la seua població i oferint un vertader desenvolupament rural basat en l'aprofitament racional dels seus recursos naturals. / [EN] The municipality of Serra sits on the southern slope of the Sierra Calderona mountains. The municipality occupies an area of 5,730 hectares of which, 95% of its territory is within the Sierra Calderona Natural Park and 85% of the territory corresponds to forest land. The economic structure of the municipality has had, since 1960, the construction sector as the main axis of the economy, leaving the forestry sub-sector as a residual activity. This has caused a labor flow from the primary sector to more productive ones, resulting in a disorderly growth of the forest mass, causing a deterioration of the landscape. This has considerably increased the risk of fire and pests and ultimately threatens the forest heritage of the Sierra Calderona Natural Park. Following the guidelines set by the EU priorities for rural development, a research project aimed at the creation of local jobs has been launched through the promotion of sustainable activities whose results are reinvested in the Local society generating a circular economy that constitutes the basis of the local socio-economic development. The project consists of the sustainable energetic use of forest, agricultural and garden biomass and its conversion to a solid fuel (wood pélet) used in the heating of public buildings and on the other hand, marketing the surplus of this wood pélet, this aims to a saving of energy bills and waste management costs and brings a benefit that can be used directly in the creation of local employment. The project also contributes to the protection and improvement of the Serra Mountains. This thesis aims to study whether an adequate model of management of biomass in the municipal urban forest interface, such as Serra, included in the Natural Park of the Sierra Calderona can have direct positive effects on the prevention of forest fires and the fight against climate change, the thesis also studies whether these management models can be economically and environmentally sustainable and their ability to contribute to improving the socioeconomic development of these populations, setting their Population and offering a true rural development based on the rational use of their natural resources. / Mayans Díaz, JJ. (2021). Gestión integral de la biomasa en la interfaz urbano-forestal, en ámbito supramunicipal y sus efectos en la lucha contra el cambio climático, Red Natura 2000 y prevención de incendios forestales [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/166094

O objetivo do presente trabalho foi desenvolver e avaliar péletes para compor sistema multiparticulado contendo ácido ascórbico, bem como validar metodologia analítica por cromatografia líquida de alta eficiência (CLAE) para aplicação em ensaio de dissolução destas formas farmacêuticas. A técnica de extrusão-esferonização foi utilizada por ser de fácil aplicação a nível laboratorial e industrial obtendo-se péletes matriciais, compostos de Methocel® K4M, Methocel® K100M e Eudragit® L 100, e péletes de liberação convencionais, para revestimento em leito fluidizado com Kollicoat® SR 30 D como agente regulador da liberação do fármaco. O sistema multiparticulado foi preparado na forma de comprimido pela compressão dos péletes com menor nível de revestimento, avaliando-se o nível de força aplicada e a presença da Microcel® 101 como protetor da camada de revestimento. Os péletes obtidos foram caracterizados quanto à esfericidade por análise imagem, friabilidade, dureza e perfil de dissolução comparativo com apresentações comerciais. Os péletes matriciais foram obtidos com grau de dificuldade variável em função do polímero utilizado, porém apresentaram esfericidade e resistência mecânica adequadas. O perfil de dissolução destas formulações demonstrou que não houve controle na liberação do fármaco, mesmo naquelas onde havia maior concentração de polímero. Os péletes revestidos com três níveis de polímero (5,07; 8,26 e 10,35% em relação à massa do pélete) apresentaram boas características granulométricas e o perfil de dissolução daqueles revestidos com 5,07% de polímero demonstrou semelhança com o da apresentação comercial. O perfil de dissolução comparativo entre os péletes isolados e os comprimidos obtidos sem a presença de excipiente mostrou que ocorre dano na camada de revestimento nos maiores níveis de força de compressão aplicada. Para os comprimidos obtidos a partir da mistura de péletes e Microcel® 101 este fato não foi observado, indicando que a presença do excipiente é fundamental para a manutenção da integridade da camada de revestimento além de promover a desintegração parcial dos comprimidos. / The present work aimed to develop and evaluate pellets to compound a multiparticulate system containing ascorbic acid, as well as, validate analytic methodology through high performance liquid chromatography and evaluate the essay of dissolution from these dosage forms. The extrusion-spheronization technique was used for its laboratorial and industrial application to obtain matrix pellets compounds of Methocel® K4M, Methocel® K100M, Eudragit® L 100, and conventional release pellets, for fluid bed coating with Kollicoat® SR 30 O as a regular occurrence release agent for the drug. The multiple system was prepared in tablets through the compression of the pellets with a lower coating levei, evaluating its applied compression force and the presence of Microcel® 101 as a protector of the coating layer. The obtained pellets were characterized according to its roundness through image analysis, friability, hardness and dissolution profile compared with those marketed products. The matrix pellets were obtained on varied difficulty degree due to the polymer utilized, even through they presented adequate spheroid and mechanical properties. The dissolution profile of these formulations didn\'t show any control in the release of the drug even in those, which had a high concentration of the polymer. The pellets coated with three polymers leveis (5,07%, 8,26% and 10,35% related to the pellets mass) presented good sphericity, and the dissolution profile of those pellets coated with 5,07% polymer demonstrated similarity with those ones marketed products. The comparative dissolution profile among isolated pellets and the tablets obtained without excipients presence, showed that damage right occur on the higher compression force levei is applied. This fact is not observed on the tablets obtained from the pellets blend and Microcel®101, which indicates that the presence of the excipients is fundamental for the maintenance and integrity of the coating layer, moreover, it causes the partial disintegration of the tablets.

Matrizes hidrofílicas de diclofenaco sódico e de cetoprofeno foram preparadas por meio de compressão direta ou granulação úmida seguida de compressão, utilizando-se hipromelose para modular a dissolução do fármaco. Foram também obtidos péletes de liberação prolongada de cetoprofeno, mediante extrusão-esferonização e revestimento, em leito fluidizado, com Kollicoat® EMM 30D. Um planejamento fatorial 22 foi usado para elucidar os efeitos de variáveis de formulação sobre os perfis de liberação do fármaco a partir dos sistemas em estudo, determinados empregando-se os métodos da pá e/ou Bio-Dis. No caso dos comprimidos matriciais, os efeitos do grau de viscosidade e concentração de hipromelose foram investigados. Para os péletes, avaliou-se os efeitos da granulometria e ganho de peso em revestimento. A influência do pH sobre a liberação do fármaco a partir dos sistemas preparados foi também estudada, usando-se meios de dissolução com pH 1,2-7,2. Os métodos ANOVA e teste de Tukey (comparação estatística entre porcentuais de fármaco dissolvido e/ou eficiência de dissolução), f1, f2 e Weibull foram usados para caracterizar e comparar os perfis de dissolução. O grau de viscosidade e concentração de hipromelose influenciaram a liberação de diclofenaco sádico e cetoprofeno a partir das matrizes em estudo, sendo a concentração do polímero o fator principal que governou o processo. A granulação alterou os perfis de dissolução de cetoprofeno em relação às matrizes obtidas por compressão direta, diminuindo a velocidade e modificando o mecanismo de liberação. No caso dos péletes, o ganho de peso em revestimento foi o parâmetro que exerceu maior efeito sobre a liberação do cetoprofeno, enquanto a granulometria apenas influenciou os perfis de dissolução dás formulações com maior ganho de peso em revestimento. A liberação do fármaco a partir dos sistemas em estudo aumentou com a elevação do pH, o que ocorreu devido à solubilidade pH-dependente do cetoprofeno e diclofenaco sódico. / Diclofenac sodium and ketoprofen hydrophilic matrices were prepared by direct compression or wet granulation followed by compression, using hypromellose to modulate the drug dissolution. Sustained release ketoprofen pellets were also obtained by extrusion-spheronization and fluidized bed coating with Kollicoat® EMM 30D. A 22 factorial design has been used to elucidate the effects of formulation variables on the drug release profiles from the systems in study, determined using the paddle method and Bio-Dis. In the case of matrix tablets, the effects of the viscosity grade and concentration of hypromellose were investigated. For the pellets, the effects of granulometry and weight gain were evaluated. The influence of the pH value on the drug release from the prepared systems was also studied, using pH 1,2-7,2 dissolution media. ANOVA and Tukey\'s test (statistical comparison between percentages of drug dissolved and/or dissolution efficiency), f1, f2 and Weibull methods were used to characterize and compare the dissolution profiles. The concentration and viscosity grade of hypromellose influenced the ketoprofen and diclofenac sodium release from the studied matrices, being the polymer concentration the main factor that has governed the process. Granulation has modified the dissolution profiles of ketoprofen in relation to the matrices obtained by direct compression, reducing the rate and modifying the mechanism of drug release. In the pellets case, weight gain was the main factor that has influenced the ketoprofen release, while ganulometry has only influenced the dissolution profiles of the formulation with the highest weight gain. Drug release from the systems under study increased with the increase of the pH value of the medium because of the diclofenac sodium and ketoprofen pH-dependent solubility.

A finalidade deste trabalho é estudar a redução carbotérmica de minério hematítico com misturas e pelotas autorredutoras em um forno rotativo experimental. Trabalhou-se com duas temperaturas, a 1673 e 1773 K (1400 a 1500 °C), em fluxo de argônio de 1Nl/min, em um forno rotativo experimental aquecido por resistências, com uma rotação fixa de 5 rpm. Foram realizadas diversas experiências, alterando variáveis como a temperatura, composição e quantidade da escória, tipo de redutor, e tipo de conformação. Foi estudado o tempo de residência das pelotas e misturas autorredutoras dentro do forno e sua interrelação com a inclinação do mesmo. Mediu-se a resistência a compressão de diferentes composições de pelotas. Foi analisada a fração de redução atingida nas experiências com ajuda de um método indireto proposto neste trabalho, atingindo-se frações de redução acima de 98%. Especial atenção foi dada para os casos limites estudados, o primeiro com uma mistura autorredutora de 81% de minério hematítico de baixo teor, 19% de coque de petróleo,+10% cimento ARI, processada a 1773 K (1500 °C) com 33% de escória final, a qual, apesar da grande quantidade de escória, atingiu uma fração de redução de 98,7%; e o segundo, para uma mistura autorredutora de 43,5% de minério hematítico de baixo teor, 56,5% de pó de serragem, processada a 1773 K (1500 °C), a qual atingiu uma fração de redução de 99,2%, provando, com as ressalvas cabíveis, a factibilidade de reduzir diretamente com pó de serragem. Com base nas observações experimentais sugeriram-se modelos do processo de redução-fusão tanto das misturas como das pelotas autorredutoras no forno rotativo. Analisaram-se a composição da escória e a composição da fase metálica obtida. Para comparar o grau de coalescimento entre as amostras, foram levantadas as análises granulométricas de cada uma delas, comparando-se as porcentagens em massa dos nódulos de ferro-carbono com diâmetro superior a 7,93 mm. Atenção especial foi dada ao método de desagregação do produto; pela ausência de normas técnicas especificas para processos autorredutores, foi empregada uma adaptação do método de desagregação por tambor (ASTM E279-95), e validada por moagem manual. Estudou-se o efeito das variáveis: temperatura de processamento, temperatura liquidus da escória, da quantidade de escória de alta temperatura liquidus, da quantidade de voláteis do redutor, da quantidade do redutor, e da ausência de conformação. Entre os resultados destas experiências tem-se que a maior temperatura de processamento leva a maior grau de coalescimento. Na medida em que a escória do sistema não se liquefaz, o processo de coalescimento é prejudicado. Na medida em que a quantidade de escória com alta temperatura liquidus aumenta, o grau de coalescimento decresce. Ao se aumentar a quantidade do redutor acima do necessário para a correta redução, carburação e colaescimento, prejudica-se o processo de formação dos nódulos de ferro-carbono. Ao se comparar o grau de coalescimento obtido entre as misturas e as pelotas autorredutoras, temse que o desempenho das misturas autorredutoras é superior. Para aclarar o efeito da temperatura liquidus da escória no processo de carburação e coalescimento, foram realizadas experiências paralelas para estudar como a temperatura liquidus da escória e a ausência do FeO afetava o coalescimento. Ao estudar o transporte de carbono pelas escórias sem e com a presença de um óxido redutível, tem-se que o transporte do óxido de ferro na escória sem agitação é um fenômeno difusivo. / The purpose of this work is to study the carbothermal reduction of hematite ore as self-reducing mixtures or pellets in an experimental rotary kiln. Two different temperatures were employed, 1673 and 1773 K (1400-1500 ° C) in an experimental rotary kiln heated by resistors, with a fixed rotation of 5 rpm and under an argon flow of 1Nl/min. Several experiments were performed by changing variables such as temperature, composition and quantity of slag, type of carbonaceous material, and type of conformation. The residence time inside the furnace and its interrelation with the slope of the kiln containing self-reducing pellets or mixtures was studied. It was measured the compressive strength of pellets of different compositions. It has been analyzed the fractional reduction achieved in the experiments with the help of an indirect method proposed in this work, reaching fractional reduction above 98%. Special attention was given to some cases, the first one with a self-reducing mixture of 81% low grade ore, 19% petroleum coke, ARI +10%, processed to 1773 K (1500 ° C) with 33% final slag, which despite the large amount of slag reached a fractional reduction of 98.7%, and the second for a self-reducing mixture of 43.5% low-grade ore, 56.5% of sawdust processed to 1773 K (1500 ° C) which reached a fractional reduction of 99.2%, proving, with reasonable exceptions, the feasibility of reducing directly with sawdust. Based on experimental observations, process models of both the reduction-melting of self-reducing mixtures and pellets in the rotary kiln were proposed. The composition of slag and composition of the metallic phase obtained were analyzed. To compare the degree of coalescence between the samples, particle size analysis of each one was performed, comparing the percentages by weight of iron-carbon nuggets with a diameter greater than 7.93 mm. Regarding the method of disintegration of the product, due to the lack of technical standards for specific self-reducing processes, the drum method (ASTM E279-95) was adapted and validated by manual grinding. It was studied the effect of the following parameters: processing temperature, slag liquidus temperature, the amount of high liquidus temperature slag, amount of volatile matter of the reducing agent, the amount of reducing agent, and the absence of conformation. These experiments have shown that the higher the processing temperature, the greater the degree of coalescence, and also that as long as the slag does not melt, the coalescence process is impaired. As the amount of slag with high liquidus temperature increases, the degree of coalescence decreases. Increasing the amount of carbonaceous material above to that necessary to reduction and carburization undermines the process of formation of iron-carbon nuggets. When comparing the degree of coalescence obtained between the self-reducing mixtures and pellets, it has been shown that the performance of self-reducing mixtures is superior. To clarify the effect of the slag liquidus temperature in the carburization and coarsening process, experiments were conducted to study how the liquidus temperature of the slag and the absence of FeO affected the coarsening. By studying the transport of carbon in slags with and without the presence of a reducible oxide, it has been shown that the transport of iron oxide in the slag without agitation is a diffusive phenomenon.

Nenhuma / Neste trabalho foi realizada a modelagem geométrica computacional das Cetapas de prensagem e sinterização da pastilha e da laminação da placa de combustível nuclear contendo microesferas de (Th,25%U)O2 dispersas em matriz de aço inoxidável com o objetivo de avaliar a distribuição destas microesferas nas diversas etapas do processamento. As regras de modelagem foram desenvolvidas baseadas nos parâmetros de cada etapa da fabricação da placa combustível. Para isto foram obtidas placas através do processamento por laminação de molduras de chapas de aço inoxidável, contendo pastilha fabricadas com microesferas de (Th,25%U)O2 com carregamentos de 10, 20 e 40% em peso de combustível disperso em matriz de aço inoxidável. Os dados das placas com carregamentos de 30 e 50% foram obtidos por interpolação da curva. As microesferas, obtidas pelo processo sol-gel, foram previamente secas, reduzidas e sinterizadas a 1700oC, durante 2 horas, sob atmosferas de hidrogênio. As microesferas sinterizadas alcançaram uma densidade de cerca de 98% da densidade teórica, e possuem um diâmetro médio de cerca de 300 mm e uma elevada resistência à fratura, de aproximadamente 40 N/microesfera. As regras implementadas neste modelo foram aplicadas nas coordenadas dos centros das esferas virtuais, que simulam as microesferas combustíveis de (Th,25%U)O2, obtendo-se novas coordenadas espaciais para cada uma delas nas etapas de prensagem e sinterização da pastilha e da laminação da placa combustível. Este modelo foi projetado com o uso de técnicas de análise de sistema estruturada, implementado utilizando a linguagem de programação Delphi e os resultados visualizados através do programa AutoCAD. Os resultados do modelo foram validados comparando-se as frações volumétricas experimentais em cada um dos carregamentos estudados com as frações simuladas. Este trabalho será de grande valia para o estudo do carregamento de microesferas na placa combustível, permitindo obter um combustível de elevado desempenho mecânico, térmico e neutrônico mesmo em mais alto carregamento. / The computational geometric modeling of the pressing, sintering and lamination stages for nuclear fuel plates composed by (Th,25%U)O2, microspheres dispersed into stainless steel matrix has been done in order to investigate the microspheres distribution in the various processing stages. The modeling standards were based on the parameters related to each fuel plate manufacturing stage. Accordingly, the plates were obtained through lamination processing of stainless steel plate frames comprising (Th,25%U)O2 microspheres pellets dispersed into stainless steel powder with loading of 10, 20 and 40% of microspheres dispersed into stainless steel matrix. The data for plates with loading of 30 and 50% have been obtained by linear interpolation. The microspheres produced by the sol-gel method were previously reduced and sintered at 1700 0C during 2 hours at hydrogen atmosphere. These sintered microspheres have reached about 98% of the theoretical density, with a mean diameter of 300 mm and a high resistance to fracture, near to 40 N/microsphere. The implemented standards in this model were applied at the virtual spheres center coordinates, which simulate the (Th,25%U)O2 fuel microspheres, and generate the new spatial coordinates to each of them in the pressing, sintering and lamination stages. This model was developed using structured system analysis techniques and it has been implemented using the Delphi programming language. The results were displayed through the AutoCAD program and validated comparing the experimental volumetric fractions in each of the studied loading, with the simulated fractions. The results indicate that this work could be a powerful tool in the investigation of microspheres loading in the fuel plate, allowing the attainment of a high mechanical and neutronic performance fuel, even for higher level loading.

<p>Relationships between stresses during the drying process, particle structural and functional properties, and particle engineering by the drying process were addressed in this thesis. In the first part, the importance of the drying phase and the effect of the drying rate on the intragranular porosity of microcrystalline cellulose pellets were investigated. Differences in porosities of dried pellets could be explained by liquid-related differences in densification during convective drying rather than by differences in densification during wet agglomeration. An increased drying rate gave more porous pellets with a lower compression shear strength, and thereby stronger tablets. The next part dealt with modulation of solid-state stability and tabletting behaviour of amorphous lactose by incorporation of different polymers by spray drying. Increased content and molecular weight of poly(vinylpyrrolidone) (PVP) resulted in an increased resistance to crystallisation provoked by heat and moisture. The stabilising effect was even more evident after long-term storage. However, the glass transition temperature was almost unaffected and may, therefore, be questioned as a stability indicator for these types of materials. The presence of the polymers resulted in somewhat less deformable particles. Incorporation of PVP increased the compactability, whilst a surfactant decreased it, which could be shown to be related to differences in particle-particle adhesivity between the different particles. This thesis contributes to increased mechanistic understanding in the area of particle engineering that may lead to better prediction and optimisation of the functionality of pharmaceutical particles, which is of the utmost importance in the development and production of solid dosage forms.</p>

<p>This thesis evaluates the use of Fourier Transform Infrared Spectroscopy (FTIR) as an approach to the increasingly difficult air sampling challenges within the field of occupational and environmental hygiene. The application of FTIR is exemplified by the assessment of emissions from and exposures in the sawmill and pellet industries. </p><p>Open path FTIR was applied in the sawsheds and the terpene levels were monitored for several days. Traditional adsorbent sampling was used to evaluate the FTIR measurements. The volatile emissions from wood pellets were investigated in warehouses and in domestic storage rooms. </p><p>The installation of open path FTIR in the harsh sawmill environment proved useful, however, attention must be paid to vibrations, beam blockage and limited sensitivity. Adsorbent sampling showed good agreement with open path FTIR. The uncontrolled airflows in sawsheds caused significant underestimation of emission rates. By the use of FTIR and a tracer gas a more accurate estimate was obtained. The total emission from processing of Scots pine was estimated to 660 g/m³ of roundwood under bark, and can amount to 700 tons annually from a large sawmill.</p><p>Hexanal (111±32 mg/m³) and CO (56±4mg/m³) were recorded in pellet warehouses. Storage of wood pellets constitutes a potential occupational and domestic health hazard. Experiments from kiln drying of lumber show that the emissions of hexanal and carbon monoxide are not limited to wood pellets but are caused by general degradation processes of wood, facilitated by drying at elevated temperature. This is the first published report where low-temperature emission of carbon monoxide from wood materials is described. </p><p>The FTIR method is a significant advancement in measurement technology. The retrieved data offers unparalleled information. It offers robust, convenient and efficient monitoring of gases over extended periods. FTIR spectroscopy should be considered a standard technique within the field of occupational and environmental hygiene.</p>

Relationships between stresses during the drying process, particle structural and functional properties, and particle engineering by the drying process were addressed in this thesis. In the first part, the importance of the drying phase and the effect of the drying rate on the intragranular porosity of microcrystalline cellulose pellets were investigated. Differences in porosities of dried pellets could be explained by liquid-related differences in densification during convective drying rather than by differences in densification during wet agglomeration. An increased drying rate gave more porous pellets with a lower compression shear strength, and thereby stronger tablets. The next part dealt with modulation of solid-state stability and tabletting behaviour of amorphous lactose by incorporation of different polymers by spray drying. Increased content and molecular weight of poly(vinylpyrrolidone) (PVP) resulted in an increased resistance to crystallisation provoked by heat and moisture. The stabilising effect was even more evident after long-term storage. However, the glass transition temperature was almost unaffected and may, therefore, be questioned as a stability indicator for these types of materials. The presence of the polymers resulted in somewhat less deformable particles. Incorporation of PVP increased the compactability, whilst a surfactant decreased it, which could be shown to be related to differences in particle-particle adhesivity between the different particles. This thesis contributes to increased mechanistic understanding in the area of particle engineering that may lead to better prediction and optimisation of the functionality of pharmaceutical particles, which is of the utmost importance in the development and production of solid dosage forms.

This thesis evaluates the use of Fourier Transform Infrared Spectroscopy (FTIR) as an approach to the increasingly difficult air sampling challenges within the field of occupational and environmental hygiene. The application of FTIR is exemplified by the assessment of emissions from and exposures in the sawmill and pellet industries. Open path FTIR was applied in the sawsheds and the terpene levels were monitored for several days. Traditional adsorbent sampling was used to evaluate the FTIR measurements. The volatile emissions from wood pellets were investigated in warehouses and in domestic storage rooms. The installation of open path FTIR in the harsh sawmill environment proved useful, however, attention must be paid to vibrations, beam blockage and limited sensitivity. Adsorbent sampling showed good agreement with open path FTIR. The uncontrolled airflows in sawsheds caused significant underestimation of emission rates. By the use of FTIR and a tracer gas a more accurate estimate was obtained. The total emission from processing of Scots pine was estimated to 660 g/m3 of roundwood under bark, and can amount to 700 tons annually from a large sawmill. Hexanal (111±32 mg/m3) and CO (56±4mg/m3) were recorded in pellet warehouses. Storage of wood pellets constitutes a potential occupational and domestic health hazard. Experiments from kiln drying of lumber show that the emissions of hexanal and carbon monoxide are not limited to wood pellets but are caused by general degradation processes of wood, facilitated by drying at elevated temperature. This is the first published report where low-temperature emission of carbon monoxide from wood materials is described. The FTIR method is a significant advancement in measurement technology. The retrieved data offers unparalleled information. It offers robust, convenient and efficient monitoring of gases over extended periods. FTIR spectroscopy should be considered a standard technique within the field of occupational and environmental hygiene.