977 resultados para Thermal behaviour


Relevância:

60.00% 60.00%

Publicador:

Resumo:

O trabalho aqui apresentado teve como principal propósito o estudo do potencial da suberina como fonte de produtos de química fina e como precursor de novos materiais macromoleculares de origem renovável. O interesse na suberina reside, não só na sua ubiquidade e nas suas propriedades únicas em termos de composição química e hidrofobicidade, mas também no facto de ser um dos principais componentes macromoleculares dos subprodutos da indústria corticeira de Quercus suber L. no Sul da Europa, e da indústria de pasta de papel do Norte da Europa, que utiliza a Betula pendula Roth como matéria-prima. A primeira parte do presente trabalho consistiu no estudo detalhado da composição química da cortiça de Quercus suber L. e respectivos resíduos industriais bem como da casca de Betula pendula Roth recorrendo a diferentes técnicas de caracterização, nomeadamente GC-MS, IV, RMN de 1H e de 13C, DSC, termomicroscopia, TGA e difracção de raios-X. Os resultados mostraram que os produtos de despolimerização da suberina representam tipicamente uma fracção substancial de todas as amostras. Para além da suberina, foram também identificados nas diversas amostras quantidades variáveis de compostos triterpénicos, lenhina, polissacarídeos e matéria inorgânica. Os principais resultados da análise por GC-MS mostraram que todas as amostras de suberina despolimerizada são fontes abundantes de ω-hidroxiácidos e de ácidos dicarboxílicos, bem como dos correspondentes derivados epóxidados. No entanto, as quantidades relativas de cada componente identificado foram significativamente diferentes entre amostras. Por exemplo, em amostras de suberina da casca de Quercus suber L. isoladas por metanólise alcalina o composto maioritário encontrado foi o ácido 22-hidroxidocosanóico, enquanto que a suberina também proveniente da cortiça, mas isolada por hidrólise alcalina era composta maioritariamente pelo ácido 9,10-dihidroxioctadecanóico. Já no caso da amostra de suberina despolimerizada proveniente da casca externa da bétula o composto identificado como mais abundante foi o ácido 9,10-epoxi-18-hidroxioctadecanóico. A caracterização das diversas amostras de suberina despolimerizada por FTIR e RMN de 1H e de 13C foram concordantes com os resultados de GC-MS, evidenciando a sua natureza predominantemente lipofílica. Foi ainda determinada a razão entre os grupos CO2H/OH e CO2CH3/OH por RMN de 1H das amostras convenientemente derivatizadas com isocianato de tricloroacetilo, verificando-se que a suberina despolimerizada possuía quantidades não-estequiométricas destes grupos funcionais. A investigação do comportamento térmico das amostras de suberina despolimerizada, por DSC e termomicroscopia, bem como a análise por difracção de raios-X, permitiu concluir que algumas amostras de suberina despolimerizada possuíam importantes domínios cristalinos e pontos de fusão bem definidos, tipicamente próximos de 70 oC, enquanto outras amostras eram essencialmente amorfa. Factores como a fonte de suberina ou as condições de despolimerização estiveram na origem destas diferenças. iv Neste trabalho estudaram-se também os extractáveis lipofílicos da cortiça e dos seus resíduos industriais, em particular os do pó industrial de cortiça e dos condensados negros, mostrando que os extractáveis lipofílicos são uma fonte abundante de compostos triterpénicos, em particular de ácido betulínico e de friedelina. Foram ainda identificadas fracções abundantes de ω-hidroxiácidos e de ácidos dicarboxílicos no condensado negro. A segunda parte deste trabalho abordou a síntese e a caracterização de novos poliésteres alifáticos derivados de suberina. Estes materiais foram sintetizados utilizando, quer misturas de suberina despolimerizada, quer monómeros modelo estruturalmente análogos aos existentes na suberina. Recorreu-se para o efeito a duas aproximações distintas de polimerização por passos, a policondensação e a politransesterificação. Procurou-se em simultâneo maximizar a eficiência da polimerização em termos de peso molecular e de extensão da reacção e utilizar condições de reacção de química “verdes”. Neste sentido, utilizou-se a policondensação em emulsão utilizando um tensioactivo como catalisador e a policondensação em massa utilizando a lipase B de Candida antarctica. Adicionalmente foram também testado os catalisadores trifluorometanosulfonato de bismuto(III) no caso da policondensação, e ainda os catalisadores clássicos óxido de antimónio(III) e o carbonato de potássio no caso da politransesterificação. Os poliésteres resultantes foram caracterizados através de várias técnicas, tais como IV, RMN (de 1H e de 13C), DSC, DMA, TGA, difracção de raios-X e medidas dos ângulos de contacto. Verificou-se que os catalisadores trifluorometanosulfonato de bismuto (III), óxido de antimónio(III) e carbonato de potássio conduziram aos rendimentos de isolamento dos polímeros resultantes mais elevados. No caso dos poliésteres derivados da suberina os resultados em termos de rendimentos e pesos moleculares sofreram um incremento substancial quando a estequiometria da reacção de polimerização foi adequadamente balanceada (r=1) com a adição de uma quantidade extra de um comonómero. Verificou-se a predominância de diferentes estruturas consoante a amostra de suberina utilizada e as condições de síntese adoptada, predominando as cadeias lineares ou então quantidades substanciais de estruturas reticuladas. Globalmente, este primeiro estudo sistemático da utilização de suberina como um precursor de novos poliésteres alifáticos confirmou o elevado potencial deste recurso abundante e renovável como precursor para preparar materiais macromoleculares.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The domain of thermal therapies applications can be improved with the development of accurate non-invasive timespatial temperature models. These models should represent the non-linear tissue thermal behaviour and be capable of tracking temperature at both time-instant and spatial position. If such estimators exist then efficient controllers for the therapeutic instrumentation could be developed, and the desired safety and effectiveness reached.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The study shows that standard plastics like polypropylene and high density polyethylene can be reinforced by adding nylon short fibres. Compared to the conventional glass reinforced thermoplastics this novel class of reinforced thermoplastics has the major advantage of recyclability. Hence such composites represent a new spectrum of recyclable polymer composites. The fibre length and fibre diameter used for reinforcement are critical parameters While there is a critical fibre length below which no effective reinforcement takes place, the reinforcement improves when the fibre diameter decreases due to increased surface area.While the fibres alone give moderate reinforcement, chemical modification of the matrix can further improve the strength and modulus of the composites. Maleic anhydride grafting in presence of styrene was found to be the most efficient chemical modification. While the fibre addition enhances the viscosity of the melt at lower shear rates, the enhancement at higher shear rate is only marginal. This shows that processing of the composite can be done in a similar way to that of the matrix polymer in high shear operations such as injection moulding. Another significant observation is the decrease in melt viscosity of the composite upon grafting. Thus chemical modification of matrix makes processing of the composite easier in addition to improving the mechanical load bearing capacity.For the development of a useful short fibre composite, selection of proper materials, optimum design with regard to the particular product and choosing proper processing parameters are most essential. Since there is a co-influence of many parameters, analytical solutions are difficult. Hence for selecting proper processing parameters 'rnold flow' software was utilized. The orientation of the fibres, mechanical properties, temperature profile, shrinkage, fill time etc. were determined using the software.Another interesting feature of the nylon fibre/PP and nylon fibre/HDPE composites is their thermal behaviour. Both nylon and PP degrade at the same temperature in single steps and hence the thermal degradation behaviour of the composites is also being predictable. It is observed that the thermal behaviour of the matrix or reinforcement does not affect each other. Almost similar behaviour is observed in the case of nylon fibre/HDPE composites. Another equally significant factor is the nucleating effect of nylon fibre when the composite melt cools down. In the presence of the fibre the onset of crystallization occurs at slightly higher temperature.When the matrix is modified by grafting, the onset of crystallization occurs at still higher temperature. Hence it may be calculated that one reason for the improvement in mechanical behaviour of the composite is the difference in crystallization behaviour of the matrix in presence of the fibre.As mentioned earlier, a major advantage of these composites is their recyclability. Two basic approaches may be employed for recycling namely, low temperature recycling and high temperature recycling. In the low temperature recycling, the recycling is done at a temperature above the melting point of the matrix, but below that of the fibres while in the high temperature route. the recycling is done at a temperature above the melting points of both matrix and fibre. The former is particularly interesting in that the recycled material has equal or even better mechanical properties compared to the initial product. This is possible because the orientation of the fibre can improve with successive recycling. Hence such recycled composites can be used for the same applications for which the original composite was developed. In high temperature recycling, the composite is converted into a blend and hence the properties will be inferior to that of the original composite, but will be higher than that of the matrix material alone.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The main aim of the study was to optimise the reactive extrusion conditions in the conventional modification processes of polyethylenes in a single screw extruder.The optimum conditions for peroxide crosslinking of low density polyethylene (LDPE), linear low density polyethylene (LLDPE) and their blend were determined in a torque rheometer. The actual reactive extrusion was performed in a laboratory single screw extruder using the optimum parameters. The influence of the coagent, triaUyl cyanurate (TAC), on the cross linking of low density polyethylene in the presence of peroxide was also investigated. The peroxide crosslinking was found to improve the mechanical properties and the thermal stability of the polyethylenes. The efficiency of crosslinking was found to be improved by the addition of coagent such as TAC.The optimum conditions for silane grafting viz temperature, shear rate, silane and DCP concentrations were determined on a torque rheometer in the case of LDPE, LLDPE and their blend. Silane grafting of LDPE in the presence of peroxide was performed with and without addition of water. Compounding of such mixtures in the melt at high temperatures caused decomposition of the peroxide and grafting of alkoxy silyl groups to the polyethylene chains.The optimum parameters for maleic anhydride modification of LDPE, LLDPE and their blend were determined. The grafting reaction was confinned by FTIR spectroscopy. Modification of polyethylenes with maleic anhydride in the presence of dicumyl peroxide was found to be useful in improving mechanical properties. The improvement was found to be mainly due to the grafting of carboxyl group and formation of crosslinks between the chains. The cross linking initiated improvements indicate extended property profiles and new application fields for polyethylenes.On the whole the study shows that the optimum conditions for modifying polyethylenes can be determined on a torque rheometer and actual modification can be performed in a single screw extruder by employing the optimum parameters for improved mechanical! thermal behaviour without seriously affecting their processing behaviour.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Thermoaktive Bauteilsysteme sind Bauteile, die als Teil der Raumumschließungsflächen über ein integriertes Rohrsystem mit einem Heiz- oder Kühlmedium beaufschlagt werden können und so die Beheizung oder Kühlung des Raumes ermöglichen. Die Konstruktionenvielfalt reicht nach diesem Verständnis von Heiz, bzw. Kühldecken über Geschoßtrenndecken mit kern-integrierten Rohren bis hin zu den Fußbodenheizungen. Die darin enthaltenen extrem trägen Systeme werden bewußt eingesetzt, um Energieangebot und Raumenergiebedarf unter dem Aspekt der rationellen Energieanwendung zeitlich zu entkoppeln, z. B. aktive Bauteilkühlung in der Nacht, passive Raumkühlung über das kühle Bauteil am Tage. Gebäude- und Anlagenkonzepte, die träge reagierende thermoaktive Bauteilsysteme vorsehen, setzen im kompetenten und verantwortungsvollen Planungsprozeß den Einsatz moderner Gebäudesimulationswerkzeuge voraus, um fundierte Aussagen über Behaglichkeit und Energiebedarf treffen zu können. Die thermoaktiven Bauteilsysteme werden innerhalb dieser Werkzeuge durch Berechnungskomponenten repräsentiert, die auf mathematisch-physikalischen Modellen basieren und zur Lösung des bauteilimmanenten mehrdimensionalen instationären Wärmeleitungsproblems dienen. Bisher standen hierfür zwei unterschiedliche prinzipielle Vorgehensweisen zur Lösung zur Verfügung, die der physikalischen Modellbildung entstammen und Grenzen bzgl. abbildbarer Geometrie oder Rechengeschwindigkeit setzen. Die vorliegende Arbeit dokumentiert eine neue Herangehensweise, die als experimentelle Modellbildung bezeichnet wird. Über den Weg der Systemidentifikation können aus experimentell ermittelten Datenreihen die Parameter für ein kompaktes Black-Box-Modell bestimmt werden, das das Eingangs-Ausgangsverhalten des zugehörigen beliebig aufgebauten thermoaktiven Bauteils mit hinreichender Genauigkeit widergibt. Die Meßdatenreihen lassen sich über hochgenaue Berechnungen generieren, die auf Grund ihrer Detailtreue für den unmittelbaren Einsatz in der Gebäudesimulation ungeeignet wären. Die Anwendung der Systemidentifikation auf das zweidimensionale Wärmeleitungsproblem und der Nachweis ihrer Eignung wird an Hand von sechs sehr unterschiedlichen Aufbauten thermoaktiver Bauteilsysteme durchgeführt und bestätigt sehr geringe Temperatur- und Energiebilanzfehler. Vergleiche zwischen via Systemidentifikation ermittelten Black-Box-Modellen und physikalischen Modellen für zwei Fußbodenkonstruktionen zeigen, daß erstgenannte auch als Referenz für Genauigkeitsabschätzungen herangezogen werden können. Die Praktikabilität des neuen Modellierungsansatzes wird an Fallstudien demonstriert, die Ganzjahressimulationen unter Bauteil- und Betriebsvariationen an einem exemplarischen Büroraum betreffen. Dazu erfolgt die Integration des Black-Box-Modells in das kommerzielle Gebäude- und Anlagensimulationsprogramm CARNOT. Die akzeptablen Rechenzeiten für ein Einzonen-Gebäudemodell in Verbindung mit den hohen Genauigkeiten bescheinigen die Eignung der neuen Modellierungsweise.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Die in dieser Arbeit durchgeführten Untersuchungen zeigen, daß es möglich ist, komplexe thermische Systeme, unter Verwendung der thermisch-, elektrischen Analogien, mit PSpice zu simulieren. Im Mittelpunkt der Untersuchungen standen hierbei Strangkühlkörper zur Kühlung von elektronischen Bauelementen. Es konnte gezeigt werden,daß alle Wärmeübertragungsarten, (Wärmeleitung, Konvektion und Wärmestrahlung) in der Simulation berücksichtigt werden können. Für die Berechnung der Konvektion wurden verschiedene Methoden hergeleitet. Diese gelten zum einen für verschiedene Kühlkörpergeometrien, wie z.B. ebene Flächen und Kühlrippenzwischenräume, andererseits unterscheiden sie sich, je nachdem, ob freie oder erzwungene Konvektion betrachtet wird. Für die Wärmestrahlung zwischen den Kühlrippen wurden verschiedenen Berechnungsmethoden entwickelt. Für die Simulation mit PSpice wurde die Berechnung der Wärmestrahlung zwischen den Kühlrippen vereinfacht. Es konnte gezeigt werden, daß die Fehler, die durch die Vereinfachung entstehen, vernachlässigbar klein sind. Für das thermische Verhalten einer zu kühlenden Wärmequelle wurde ein allgemeines Modell entworfen. Zur Bestimmung der Modellparameter wurden verschiedene Meßverfahren entwickelt. Für eine im Fachgebiet Elektromechanik entwickelte Wärmequelle zum Test von Kühlvorrichtungen wurde mit Hilfe dieser Meßverfahren eine Parameterbestimmung durchgeführt. Die Erstellung des thermischen Modells eines Kühlkörpers für die Simulation in PSpice erfordert die Analyse der Kühlkörpergeometrie. Damit diese Analyse weitestgehend automatisiert werden kann, wurden verschiedene Algorithmen unter Matlab entwickelt. Es wurde ein Algorithmus entwickelt, der es ermöglicht, den Kühlkörper in Elementarzellen zu zerlegen, die für die Erstellung des Simulationsmodells benötigt werden. Desweiteren ist es für die Simulation notwendig zu wissen, welche der Elementarzellen am Rand des Kühlkörpers liegen, welche der Elementarzellen an einem Kühlrippenzwischenraum liegen und welche Kühlkörperkanten schräg verlaufen. Auch zur Lösung dieser Aufgaben wurden verschiedene Algorithmen entwickelt. Diese Algorithmen wurden zu einem Programm zusammengefaßt, das es gestattet, unterschiedliche Strangkühlkörper zu simulieren und die Simulationsergebnisse in Form der Temperaturverteilung auf der Montagefläche des Kühlkörpers grafisch darzustellen. Es können stationäre und transiente Simulationen durchgeführt werden. Desweiteren kann der thermische Widerstand des Kühlkörpers RthK als Funktion der Verlustleistung der Wärmequelle dargestellt werden. Zur Verifikation der Simulationsergebnisse wurden Temperaturmessungen an Kühlkörpern durchgeführt und mit den Simulationsergebnissen verglichen. Diese Vergleiche zeigen, daß die Abweichungen im Bereich der Streuung der Temperaturmessung liegen. Das hier entwickelte Verfahren zur thermischen Simulation von Strangkühlkörpern kann somit als gut bewertet werden.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Debido a la gran cantidad de muestras arqueológicas impregnadas con PEG que se encuentran contaminadas por compuestos insolubles de hierro, se plantea la posible extracción y formación de complejos Fe-L (L=PBTC) y sus efectos en (i) la estructura de la matriz orgánica, (ii) la estructura y propiedades físicas del PEG y (iii) el comportamiento de la muestra en la etapa posterior de almacenamiento. El proyecto analiza la formación de compuestos químicos y posibles modificaciones estructurales en el proceso de extracción del hierro. Consiste en un estudio sistemático de un sistema químico y su influencia en los procesos de precipitación de Fe3+ en medio acuoso. El proyecto se fundamenta en: (1) desarrollar un proceso experimental de optimización para la extracción de las sales contaminantes y (2) encontrar las técnicas analíticas óptimas que permitan apreciar modificaciones estructurales de los diferentes sistemas. Se determina la cantidad de hierro extraído mediante A.A. Las interacciones entre PBTC y PEG se analizan por IR. Las modificaciones de determinadas propiedades físicas se determinan por DSC y las estructurales mediante SEM. En las condiciones termodinámicas óptimas se obtiene una extracción superficial del hierro (30-35%). La disolución del PEG origina modificaciones de la masa y el volumen de la muestra

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Fabric energy storage (FES) systems have gained in popularity in the recent years in response to the demand for energy efficient buildings. The dynamic heat transfer mechanisms of an FES require specialised techniques to predict its thermal performance. This requirement has been one of the barriers to the wider use of FES systems. Based on the research literature, this paper presents a critical review of the published mathematical models of FES systems. The paper discusses the usefulness of these models based on the following criteria: the inputs required; the accuracy of predictions; the ability to link with commercially available simulation software: and the degree of difficulty in using the models. The review found that the currently available mathematical models are either not able to predict the thermal behaviour of a building space with an FES system reliably or the models are too complicated and/or require too much specialised knowledge to make them useful.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Environmental conscious design refers to variety of approaches in architecture design that covers technical, behavioural, and functional aspects (Goulding et al, 1992). These approaches usually include contradictory measures with social indicators (Sykes, 1995; Norton, 1999). The contradiction is magnified in incarceration architecture, which is very specific type of buildings (McConville, 2000). Prison buildings represent the split between the society requirements and the needs for the users, in this case the prisoners, to have comfortable environment. Energy as an ultimate natural resource reflects both the cost to the society, in terms of cooling/ heating load and the need for comfort and rehabilitation of prisoners (Al-Hosany and Elkadi, 2000). Different energy codes tend to control the thermal behaviour of buildings in certain environment in order to maximise their energy efficiency (e.g. CIBSE, 1999). In prison buildings, some of the main variables of such code are not relevant. While energy codes, for example, regulate the use of glass in buildings by either minimise the openings size (prescriptive criteria) or by determine an overall limit of heat transfer (performance criteria), the objective in prison buildings is to minimise glass areas for security purposes. This leads in turn to reduction in visual and comfort levels in prison cells. The aim of this paper is to address the balance between the society requirements of reducing energy consumption in prison buildings and the need for humane and comfortable environment for prisoners in order to maintain sustainability. The paper investigates the possible role of façade technologies to bridge the gap between requirements of both society and prisoners.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The addition of nano-sized ceramic particles to the plastic crystal ethyl-methyl pyrrolidinium bis(trifluoromethane sulfonyl)amide (P12TFSA) has been investigated by means of DSC and conductivity. The thermal behaviour of the plastic crystal as a function of filler content suggests that the filler particles decrease the onset temperature of the melting slightly at high loadings, however they do not decrease the crystallinity of the material. Furthermore, the IV → III transition decreases in intensity, indicating that the addition of filler increases the possibility for the crystal to remain in metastable rotator phases also at lower temperatures. The conductivity shows a more than one order of magnitude increase with the addition of filler, with a filler concentration dependence that levels out above ~ 10 wt.% TiO2.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Novel salts based the pyrrolidinium cation [Cnmpyr]+ (where n denote the number of carbons in the straight alkyl chain) and either the [NPf2] or [CTf3] anions have been synthesized and characterized to determine their thermal behaviour, stability, and conductivity. [C1mpyr][NPf2], [C2mpyr][NPf2], and [C1mpyr][CTf3] exhibit behaviour indicative of a plastic crystal phase. Both [C3mpyr][NPf2] and [C4mpyr][NPf2] are RTILs, while all of the [CTf3]salts, have melting points above 60°C. [C3mpyr][NPf2] exhibited the widest electrochemical window of 5.5 V. The [NPf2]– salt exhibited similar reductive limits to the [NTf2] anion, –3.2 V versus Fc+|Fc, while [CTf3] had lower reductive stability. The [CTf3] salts were more stable towards oxidation, +2.5 V versus Fc+|Fc, compared to the [NPf2] and [NTf2] salts.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The reaction of the group 14 tetrachlorides MCl4 (M = Si, Ge, Sn) with oleum (65 % SO3) at elevated temperatures led to the unique anionic complexes [M(S2O7)3]2– that show the central M atoms in coordination of three chelating S2O72– groups. The mean distances M–O within the complexes increase from 175 pm (M = Si) via 186 pm (M = Ge) up to 200 pm (M = Sn). The charge balance for the [M(S2O7)3]2– anions is achieved by alkaline metal ions A+ (A = Li, Na, K, Rb, Cs) which were implemented in the syntheses in form of their sulfates. The size of the A+ ions, i.e. their coordination requirement causes the crystallographic differences in the crystal structures, while the structure of the complex [M(S2O7)3]2– anions remains essentially unaffected. Furthermore, we were able to characterize the unique germanate Hg2[Ge(S2O7)3]Cl2 which forms when HgCl2 is added as a source for the counter cation. The Hg2+ and the Cl– ions form infinite cationic chains according to 1∞[HgCl2/2]+ which take care for the charge compensation. For selected examples of the compounds the thermal behavior has been monitored by means of thermal analyses and X-ray powder diffraction. For A being an alkaline metal the decomposition product is a mixture of the sulfates A2SO4 and the dioxides MO2, whereas Hg2[Ge(S2O7)3]Cl2 shows a more complicated decomposition. The tris-(disulfato)-silicate Na2[Si(S2O7)3] has additionally been examined by solid state 29Si and 23Na NMR spectroscopic measurements.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

The thermal degradation behaviour of rubber from six new Hevea brasiliensis clones (IAC 40, 56, 300, 301, 302 and 303) from São Paulo State, Brazil was studied by thermogravimetry using the Flynn-Wall-Ozawa approach to assess the kinetic parameters ( reaction order, activation energy and pre-exponential factor) of the decomposition process. This study indicated that the thermal behaviour is a complex multiple step process, which depends on the type of rubber Hevea clones studied. The rubber from these clones can be classified, following the order of decreasing thermal stability, as IAC 303 > 302 > 56 > 40 > 300 > 301.

Relevância:

60.00% 60.00%

Publicador:

Resumo:

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)