Made available in DSpace on 2017-07-21T20:42:36Z (GMT). No. of bitstreams: 1 EDSON JOSE LIMA DA SILVA.pdf: 3364047 bytes, checksum: 8d0d1391435837a4f603477a06c59876 (MD5) Previous issue date: 2011-12-22 / This work describes the preparation of nanoparticles of spinel structure, made from oxides of Manganese, Nickel and Cobalt, via lyophilization process, which was compared to the process of obtaining conventional mixture of oxides, in order to analyze different forms of preparation and its influence on electrical properties (characteristic resistance, temperature coefficient, stability of the thermistor), through the measures obtained by applying a voltage of 5 volts on pads and subjecting them to a temperature range of 20 C to 300 C, measured with a thermocouple type K The microstructures were analyzed by scanning electron microscopy (SEM), the average particle size ranged from 60 to 93 nm. X-ray spectroscopy to determine the phases present in the samples and analysis of infrared to identify in the process, organic waste and the organic phase transitions were completely volatilized during the controlled heating pad on high-temperature furnace (with resistance molybdenum silicide) (Lindenberg). Through the obtained results it was noted a certain advantage at all temperatures of the samples had the composition Ni Mn and Co on the Mn Ni which had only giving larger values between 4335 and 4571 for samples made from the process liofilization. / Este trabalho descreve a preparação de nanoparticulas de estrutura espinélio, feitas a partir de óxidos de Manganês, Níquel e Cobalto, via processo de liofilização, o qual foi comparado ao processo de obtenção convencional, mistura de óxidos, afim de se analisar diferentes formas de preparação e sua influência nas propriedades elétricas (resistência característica, coeficiente de temperatura, estabilidade do termistor), através das medidas obtidas aplicando-se uma tensão de 5 volts nas pastilhas e submetendo-as a uma variação de temperatura de 20C a 300C, aferidos com um termopar tipo K. As Microestruturas foram analisadas por microscopia eletrônica de varredura (MEV), o tamanho médio das partículas ficaram entre 60 a 93 nm. Espectroscopia de raios X para determinação das fases presentes nas amostras e análise de infravermelho para se identificar em que fase do processo os resíduos orgânicos e as transições de fases orgânicas foram totalmente volatilizados ao longo do aquecimento controlado das pastilhas em forno de alta temperatura (com resistência de siliceto de molibdênio) (Lindenberg). Através dos resultados obtidos notou-se uma certa vantagem em todas as temperaturas das amostras que tinham na composição Mn Ni e Co sobre as que tinham apenas Mn Ni dando valores de maiores, entre 4335 e 4571 para as amostras feitas a partir do processo de liofilização.

Submitted by Angela Maria de Oliveira (amolivei@uepg.br) on 2017-12-12T13:03:18Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Eduardo Pagano.pdf: 5564139 bytes, checksum: 41a00843092c58a3dcd62662b42000f1 (MD5) / Made available in DSpace on 2017-12-12T13:03:18Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Eduardo Pagano.pdf: 5564139 bytes, checksum: 41a00843092c58a3dcd62662b42000f1 (MD5) Previous issue date: 2017-08-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste estudo foi realizado a obtenção e caracterização de materiais cerâmicos de alumina com gradiente funcional de porosidade. Foram utilizados como os métodos de processamento a rota de freeze casting em água e a fase de sacrifício utilizando o amido. Os materiais utilizados para a produção das amostras foram a alumina e o amido de milho de pureza analítica. Foram investigadas as características de porosidade quanto a morfologia de poros, distribuição dos poros pela matriz e interferência do processamento na formação destes. Para o estudo da porosidade, os métodos de porosimetria via método de Arquimedes em água e penetração de mercúrio foram aplicados na analise desta porosidade obtida. As propriedades mecânicas, bem como o modo de fratura obtido, também foram investigadas em ensaio de compressão uniaxial em uma máquina de ensaios universal. As imagens obtidas por microscopia eletrônica de varredura auxiliaram a correlacionar os dados obtidos nos ensaios de porosimetrias com a resposta mecânica obtida do material. Os resultados obtidos entre os métodos, quanto à porosidade, revelam diferenças consideráveis na distribuição e quantidade de poros ao se comparar o freeze casting com a fase de sacrifício com amido. Porém quanto a tamanho, os valores se mantiveram bem próximos. A resistência mecânica em compressão é maior nas amostras com amido, porém estas amostras falham de forma catastrófica. As amostras de freeze casting, por sua vez, possuem menor resistência mecânica e tiveram suas fraturas influenciadas por vários fatores durante o processamento. A morfologia de poros e microestrutura apresentada pelos dois métodos aplicados são consequência direta da rota de processamento utilizada. Nas amostras por freeze casting, foram observados canais de poros. Já as amostras com amido como fase de sacrifício, os poros são arredondados e não conectados / In this study, preparation and characterization of alumina ceramic materials with functional porosity gradients were performed. Freeze casting of alumina slurries, using water as the chosen solvent, and sacrificial phase method using corn starch as sacrificial phase, were implemented. The materials used to produce the samples were alumina and analytical purity corn starch. Porosity characteristics were investigated concerning pore morphology, pore distribution in the ceramic matrix and processing route interference in pore formation. The evaluation of porosity was made utilizing porosity determination methods as mercury intrusion and Archimedes method with water as immersion liquid. The mechanical properties, as well as the fracture mode, were investigated during uniaxial compressive test in a universal testing machine. Using the images obtained by scanning electron microscopy (SEM), it was possible to correlate the data obtained in the porosimetry analysis with the mechanical response obtained from the material. In terms of porosity, the results between the processing routes reveal considerable differences in pore distribution and quantity of pores. However, the pore sizes obtained for both methods were pretty close to each other. The mechanical strength during compressive stress was higher in the samples produced via sacrificial phase method, but those samples failed catastrophically. Freeze casting samples, on the other hand, had lower mechanical resistance and their fractures were directly influenced by several factors during their assembly processing. The pore and microstructure morphology presented by both methods were direct consequence of the processing route used. In the samples produced by freeze casting, pore channels were observed. The samples produced via sacrificial phased method using corn starch presented unconnected rounded pores.

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In der vorliegenden Arbeit werden wissenschaftlich-technologische Untersuchungen zur wandabgelösten VGF-Züchtung von Germanium präsentiert. Dazu wurden zwei Varianten mit Hinblick auf die Etablierung und Stabilisierung bestimmter Druckverhältnisse angewendet: (i) Beim passiven dVGF-Verfahren erfolgt die Erzeugung der Druckdifferenz über die thermische Beeinflussung des Inertgases Ar, und (ii) beim erstmals gezeigten aktiven dVGF-Verfahren über eine temperaturkontrollierte, separate Zn-Dampfdruckquelle. Ge-Einkristalle mit einem Durchmesser bis zu 3 Zoll wurden nahezu vollständig ohne Tiegelkontakt gezüchtet. Der Effekt der Wandablösung wird anhand der mikroskopischen Charakterisierung der Kristalloberfläche, der Durchbiegung der Phasengrenze sowie der etch pit density (EPD), ein Maß für die Versetzungsdichte gezeigt. Im Vergleich zu konventionell gezüchteten VGF-Kristallen zeigen die detached gezüchteten Kristalle eine hohe strukturelle Qualität. Dies wird auf reduzierte thermische und thermo-mechanische Spannungen bei der wandabgelösten Züchtung zurückgeführt.

In der vorliegenden Arbeit werden wissenschaftlich-technologische Untersuchungen zur wandabgelösten VGF-Züchtung von Germanium präsentiert. Dazu wurden zwei Varianten mit Hinblick auf die Etablierung und Stabilisierung bestimmter Druckverhältnisse angewendet: (i) Beim passiven dVGF-Verfahren erfolgt die Erzeugung der Druckdifferenz über die thermische Beeinflussung des Inertgases Ar, und (ii) beim erstmals gezeigten aktiven dVGF-Verfahren über eine temperaturkontrollierte, separate Zn-Dampfdruckquelle. Ge-Einkristalle mit einem Durchmesser bis zu 3 Zoll wurden nahezu vollständig ohne Tiegelkontakt gezüchtet. Der Effekt der Wandablösung wird anhand der mikroskopischen Charakterisierung der Kristalloberfläche, der Durchbiegung der Phasengrenze sowie der etch pit density (EPD), ein Maß für die Versetzungsdichte gezeigt. Im Vergleich zu konventionell gezüchteten VGF-Kristallen zeigen die detached gezüchteten Kristalle eine hohe strukturelle Qualität. Dies wird auf reduzierte thermische und thermo-mechanische Spannungen bei der wandabgelösten Züchtung zurückgeführt.

This study aims to validate and develop applications for a novel impedance-based process analytical technology for monitoring the attributes of the product during the entire freeze-drying process (from pre-freezing and annealing to primary and then secondary drying). This measurement approach involves the application of foil electrodes, mounted externally to a conventional glass freeze-drying vial, and coupled to a high-impedance analyser. The location of the electrodes on the outside, rather than the inside of the vial, leads to a description of the technology as a through-vial impedance spectroscopy (TV-IS) technique. The principle observation from this approach is the interfacial-polarization process arising from the composite impedance of the glass wall and product interface. For a conventional glass vial (of wall thickness ~ 1 mm and cross sectional diameter ~ 22 mm) it was shown that the process is manifest within the frequency range 101 to 106 Hz, as a single, broad band peak which spans 2-3 decades of the imaginary part spectrum. Features of the interfacial-relaxation process, characterised by the peak amplitude, C″Peak, and peak frequency, fpeak, of the imaginary capacitance spectra and the equivalent circuit elements that model the impedance spectra (i.e. the solution resistance (R) and solution capacitance (C) were monitored along with the product temperature data during the cycle(s), for a variety of surrogate formulations comprising lactose, sucrose, mannitol or maltodextrin solutions, during the freezing, re-heating, annealing and primary drying stages of freeze drying). It was shown that the parameters, fpeak and R, are strongly coupled to each other and change as a function of the temperature of the solution and its phase state, whereas C″Peak is strongly coupled to the amount of ice that remains during the drying process. Both log fpeak and log R have a linear dependence on the temperature of the solution, provided there was no phase change in the solution. The crystallization process (ice onset, solidification and equilibration to shelf temperature) is characterized well by both log fpeak and log R, whereas the parameter R demonstrates most clearly the formation of eutectic crystallization during freezing. In contrast it was the parameter C which was most sensitive to the detection of the glass transition during re-heating. During primary drying, it was shown that C″peak, is dependent on the amount of ice remaining and therefore provides a convenient assessment of the rate of drying and primary drying end point. The impedance changes during annealing provide a mechanistic basis for the modifications in ice structure which result directly in the observed decrease in primary drying times. The principal observation on annealing of a 10% w/v solution of maltodextrin, was the minimal changes in the glass transition (recorded at ~−16 °C) during the re-heating and cooling step (post-annealing). This result alone appears to indicate that a maximum freeze concentration was achieved during first freezing with no further ice being formed on annealing. The phenomenon of devitrification (and the production of more ice, and hence larger ice crystals) was therefore discounted as the mechanism by which annealing impacts the drying time. Having excluded devitrification from the mechanism of annealing enhanced drying, it was then possible to conclude that the decrease in the electrical resistance (that was observed during the annealing hold time) must necessarily result from the simplified structure of the unfrozen fraction and the improved connectivity of ice crystals that may be the consequence of Ostwald ripening. The application of through vial impedance measurement approach provides a non-invasive, real time monitoring of critical process parameters which subsequently leads to an improved understanding of the mechanisms and effects of different parameters, providing a reliable basis for process optimization, along with improved risk management to ensure optimum quality of the formulation and optimization of the freeze drying process.

The term Nanoceramics is well known in the ceramic field for at least two decades. In this project a detailed study was performed on the synthesis of α-alumina nanopowders. High solids content nanoalumina suspensions were prepared and used to form green bodies using both wet and dry forming routes. The green bodies were then sintered using both conventional single and two-step sintering approaches. Synthesis: Two different synthesis methods, viz. precipitation and hydrothermal treatment, were used to synthesize fine α-alumina powders from aluminium chloride, ammonia solution and TEAH (Tetraethyl ammonium hydroxide). XRD, TEM and FEG-SEM were used to characterise the powders produced. The presence of commercial α-alumina powder as seed particles did not affect the transformation to α-alumina phase during the hydrothermal treatment at 220˚C in either basic or acidic environments. The results obtained from the precipitation route showed that the combined effect of adding α-alumina seeds and surfactants to the precursor solution could lower the transformation temperature of α-alumina from about 1200˚C for unseeded samples to 800˚C, as well as reducing the level of agglomeration in the alumina powders. The difference in transformation temperature mainly resulted from the nucleation process by the α-alumina seeds, which enhanced the θ → α transformation kinetics. The lower level of agglomeration present in the final powders could be due to the surface modifying role of the surfactants preventing the particles from growing together during the synthesis process. By introducing a further high-temperature step for a very short duration (1 minute) to the low-temperature heat treatment route (800˚C/12 h), the unseeded sample with added surfactant transformed into pure α-alumina phase. The newly-added step was shown to be an in-situ seeding step, followed by a conventional nucleation and growth process. The best final powder was compared with a commercial α-alumina nanopowder. Processing of alumina ceramics: The effect of low-molecular weight ammonium dispersants including Dispex-A40, Darvan-C and Dolapix-CE64, on high solids content nanoalumina suspensions was investigated. The nanosuspension prepared using the most suitable dispersant, Dolapix-CE64, was slip cast into ~53% dense, very homogeneous green bodies. This nanosuspension was also spray freeze dried into crushable granules using Freon as a foaming agent. Green compacts with density of ~53.5% were then formed by dry pressing the 2 vol% Freon-added spray freeze dried granules at 40 MPa. Both slip cast and die pressed green bodies were sintered using conventional single-step and two-step routes followed by characterising the density and grain size measurement of final dense compacts. The results have been compared with that of a submicron alumina ceramic prepared using a commercial α-alumina suspension. Highly dense alumina with an average grain size of ~0.6 μm was fabricated by means of spark plasma sintering at 1200˚C. The application of 500 MPa allowed achieving almost fully dense alumina at temperature as low as 1200˚C for 30 minutes with no significant grain growth.

Since the introduction of Portland cement in the early nineteenth century the number of buildings constructed from concrete or using cement mortars and renders has grown exponentially, and cement is one of the most common building materials in use today. Consequently a significant proportion of the built heritage contains cementitious materials. The relative youth of these buildings means that less research has been undertaken to understand how and why they deteriorate than for traditional buildings, and that the development of appropriate conservation methods and techniques is less advanced. The primary aim of this research was to understand the causes and mechanisms of some of the types of deterioration commonly found in historic concrete and cement buildings and structures, with reference to the Second World War reinforced concrete and cement-rendered buildings at East Fortune airfield in East Lothian, Scotland. Additional aims were to investigate the efficacy of the building repairs and maintenance regimes undertaken to date, and to make recommendations for the future conservation of the buildings. East Fortune airfield contains a number of cement-rendered brick masonry buildings and a reinforced concrete air raid shelter. The initial visual survey identified several types of deterioration, from which the blistering and flaking of the render; the cracking and delamination of the render; and the spalling of the concrete in the air raid shelter were selected for further research. The research included time lapse photography, non-destructive testing, environmental monitoring and the physical, chemical and petrographic characterisation of the building materials. Hypotheses regarding the causes of deterioration were tested in the laboratory, for example with linear variable displacement transducer measurements, and modelled using crack propagation theories and models for water transport through porous media. It is demonstrated that the blistering and flaking of the render is caused by shale aggregate particles, which undergo sufficient expansion during freeze-thaw cycles to crack the surrounding render. This phenomenon is termed ‘pop-outs’ in the concrete literature. The more catastrophic cracking and delamination of the renders is also due to freeze-thaw cycling, which is shown to cause significant damage provided the moisture content of the render is above a certain threshold level. This type of deterioration has occurred at an accelerated rate for some of the modern render repairs, due to an inadequate understanding of the properties of the original and repair materials. In particular, the properties of the bricks are critical to the performance of the cement renders, and it is found that the sorptivity of historic bricks may vary considerably depending upon the orientation of the brick. Finally, the diagnosis for the air raid shelter is that the corrosion of the steel reinforcements is caused by high levels of chlorides present within the raw materials used to make the pre-cast concrete sections. The results of the investigations are used to suggest building conservation solutions for this particular site. Furthermore, since the deterioration mechanisms investigated are common for historic cement and concrete, the findings are relevant to many other sites. The over-arching methodology used to investigate the deterioration at the site and the methodologies developed to test particular hypotheses are also applicable for other investigations of historic building materials. There is much about this research that is innovative and new. The work on render cracking compares the results of dilation tests on cementitious and ceramic materials, which has not been done previously, and the pop-outs diagnosed in the work on render flaking have rarely, if ever, been reported for cement renders. The modelling work undertaken to quantify the stresses produced by the pop-outs and to explain the inclined crack formation patterns is entirely original. The use of petrography to diagnose causes of render failure is described in the literature, but this is one of very few case studies to be written up, and the work on the air raid shelter constitutes the only formal investigation of this type of Stanton shelter.

Introduction: Hemostasis is a complex system in the body that maintains blood flow and prevents bleeding. Patients with platelet disorders are at the risk of mucocutaneous bleedings and at Clinical chemistry in Linköping platelet function is measured with flow cytometry. The platelet response to various agonists is measured with fluorescently labeled platelet antibodies. The aim of this study was to evaluate the stability of the frozen reagents used for platelet function testing. Further the durability of platelet antibodies after freezing and freeze-drying was tested.   Method: Platelet antibodies were prepared for freezing/freeze-drying in buffer and were analyzed at three different occasions using blood from 2 to 3 individuals with flow cytometry. Agonists and blood were added on the day of analysis. The reagent stability test was evaluated statistically using one-way ANOVA with Bonferronis post-hoc test. Results: The slight drop in percent positive platelets and median fluorescence intensity (MFI) seen over time in the reagent stability test was not statistically significant (p>0,05). All platelet antibodies could be used after freezing/freeze-drying. The results are showing a declining trend, especially for MFI values. Conclusion: The frozen reagents used for platelet function testing is stabile up to 36 months. The results from the freeze-drying/freezing indicate that all platelet antibodies keep some activity but that some are more sensitive than others. Some antibodies could not be evaluated due to concentration of agonist in the sample being too low to induce activation. Due to individual variations further studies with more participants and more agonists in their optimal concentrations are needed. / Bakgrund: Hemostas är ett komplext system i kroppen som upprätthåller blodflödet och förhindrar blödning. Mukokutana blödningar kan uppstå hos patienter som har problem i den primära hemostasen vilket kan bero på trombocydefekter. På Klinisk kemi i Linköping mäts trombocytfunktion med flödescytometri. Trombocyterna aktiveras med olika agonister och svaret på stimuli mäts genom detektion av fluoroforkonjugerade antikroppar. Syftet med denna studie var att utvärdera långtidsstabiliteten av de frysta reagens som används för trombocytfunktionsutredningen, att testa om nya trombocytantikroppar klarar att frysas och att utvärdera reagensens hållbarhet för frystorkning. Metod: Antikroppar frystorkades/frystes i buffert och analyserades vid tre tillfällen med blod från 2 till 3 personer med flödescytometri. Agonist och blod tillsattes på analysdagen. Långtidsstabilitetstestet utvärderades statistiskt med  one-way ANOVA med Bonferronis post-hoc test. Resultat: En svag nedgång över tid i procent positiva trombocyter och MFI i långtidsstabilitetstestet var inte statistiskt signifikant (p>0,05). Alla antikroppar gav signal efter frysning och frystorkning. Främst för MFI syns en nedåtgående trend över tid. Slutsats: Reagenset för trombocytfunktionsutredningen är stabilt upp till 36 månader. Resultat från frystorkningen tyder på att alla antikroppar klarar att frystorkas/frysas men vissa är känsligare än andra. Vissa antikroppar kunde inte utvärderas p.g.a. för låg agonistkoncentration för att inducera aktivering. Ytterligare försök måste göras med fler individer och fler agonister i optimal koncentration p.g.a. individuella skillnader i svar för agonister. Frystorkningsprocessen kan optimeras.