Através de microscopia ótica utilizando luz polarizada e de metalografia quantitativa, determinou-se a cinética de recristalização a 400 ºC de uma liga de alumínio da série 3000 contendo dispersão de precipitados, para diferentes graus de deformação produzidos por laminação. Mediram-se parâmetros, para vários tempos de recozimento, que permitiram determinar: fração volumétrica recristalizada, quantidade de interfaces por unidade de volume entre regiões recristalizadas e não recristalizadas e, entre regiões recristalizadas, assim como velocidade média de migração de interfaces. Fizeram-se também medidas de microdureza em todas as amostras. Os resultados experimentais mostraram que à medida que se diminui o grau de deformação, a quantidade de interfaces por unidade de volume responsáveis pela recristalização diminui exigindo portanto um crescimento através de distâncias maiores para a recristalização se completar, tornando a cinética de recristalização mais dependente do crescimento. Constatou-se a ocorrência de recuperação, durante a recristalização, das regiões não recristalizadas e consequente diminuição da velocidade média de migração de interfaces com o tempo de recozimento. Com a diminuição da deformação, ocorreram frações não recristalizadas residuais, as quais eram maiores para graus de deformação menores, chegando a atingir mais de 80% para 34,4% de redução em espessura. Os resultados sugerem que, para baixas deformações, a velocidade de crescimento tem um papel importante na cinética de recristalização de ligas com dispersão de precipitados. A comparação entre os resultados de metalografia quantitativa e medidas de microdureza evidenciou algumas limitações desta última técnica para estudo de recristalização. / Using polarized light optical micrsocopy and quantitative metalography, kinetics of recrystallization at 400 ºC of an aluminum alloy of 300 series were determined, for different rolling deformation. Recrystallized volume fraction, amount of interfaces per unit volume, between recrystrallized and unrecrystallized regions and between recrystallized grains, and also mean velocity of interface migration were determined. Microhardness measurements were made in all specimens. The results have shown that with decreading deformation, the amount of interfaces responsible for recrystallization, per unit volume, decreases and so the interfaces must sweep larger distances for complete recrystallization, making kinetics more dependent on growth. Recovery of the unrecrystallized regions was observed, during recrystallization, causing decrease in the average velocity of interface migration with annealing time. With decreasing deformation residual unrecrystallized volumes have been observed, after long time anneals. The fraction of residual unrecrystallized region were large than 80-% for 34,4% thickness reduction. The results suggest that, in alloys with precipitates, the growth velocity has an important role in recrystallization kinetics. Some shortcomings of hardness measurements, as a tool to study recrystallization, were shown by comparison between the quantitative metallography and hardness measurements.

A liga Cu-30%Zn, conhecida como latão 70/30, possui diversas aplicações comerciais, tais como cartuchos para munição e conectores elétricos. Na produção de chapas e barras dessa liga no formato e nas propriedades almejadas para a aplicação final, comumente utiliza-se de tratamento térmicos para restauração das propriedades mecânicas, chamados de recozimento. Em particular, o efeito de solutos em solução sólida é um fator determinante para o comportamento de ligas metálicas durante o recozimento e deve ganhar importância com a tendência industrial de utilização de matéria-prima reciclada, gerando adições inadvertidas de elementos químicos que estarão presentes como solutos em solução sólida. Este trabalho levanta dados referentes a alterações no comportamento do latão 70/30 diante do tratamento de recozimento causados por teores residuais de ferro. Com base na revisão da literatura, propôs-se a metodologia de tratamentos interrompidos em dilatômetro para o estudo do recozimento de três materiais: CuZn-1Fe (0,0126%Fe), CuZn-4Fe (0,0417%Fe) e CuZn-6Fe (0,0599%Fe). Duas taxas de aquecimento foram utilizadas: 10 ºC/min e 1000 ºC/min. As propriedades mecânicas foram avaliadas em termos de microdureza Vickers e a fração recristalizada determinada por metalografia quantitativa. As análises microestruturais mostraram que a recristalização inicia-se preferencialmente em bandas de cisalhamento. A análise conjugada dos resultados mostra a seguinte faixa de temperatura de recristalização: taxa de aquecimento de 10 ºC/min - 295ºC a 345ºC; taxa de 1000 ºC/min - 365ºC a 445ºC, sendo que o teor residual de ferro não causa alterações neste comportamento. A análise das amostras recozidas isotermicamente a 500ºC e a 600ºC mostram uma tendência à formação de uma microestrutura heterogênea, possivelmente pela evolução da microestrutura de recristalização, que dá origem a grãos grosseiros em sua etapa final. A amostra com 599 ppm de Fe não apresentou evolução do tamanho de grão a 500ºC. Resultados de MET não mostraram a formação de partículas dispersas, enquanto análises de DSC revelaram um pico prévio à recristalização, identificado como a formação de uma atmosfera de Cottrell, sendo esta atrasada pela presença de ferro em solução sólida. / The Cu-30%Zn alloy, known as 70/30 brass, has many commercial applications like ammunition cartridge and electronic connectors. To properly produce strips and bars of this material it is necessary to realize a heating treatment called annealing, which aims on recovering the mechanical properties of the material. The effect of solute atoms is a high important factor to determine the material behavior during annealing. This issue is getting even more importance to industrial applications, due to the increase of the recycle of waste products. These wastes often contaminate the molten metal with foreign elements which may be in solid solution after solidification. This work aims to assess changes in behavior of the 70/30 brass during annealing due to iron in residual content. Based on literature, it was proposed a methodology which takes advantages of interrupted annealing in dilatomer and isothermal annealing for three different iron residual content: CuZn- 1Fe (0,0126%Fe), CuZn-4Fe (0,0417%Fe) and CuZn-6Fe (0,0599%Fe). Two heating rates were used: 10 ºC/min e 1000 ºC/min. The mechanical properties were evaluated by Vickers microhardness and the recrystallized fraction was determined by quantitative microscopy. The microstructural analysis showed that the recrystallization starts preferentially on shear bands. The results from different techniques showed that the recrystallization temperature range is 295ºC to 345ºC when the heating rate was 10 ºC/min and 365º to 445ºC for 1000 ºC/min. There were no evidences of changing the brass behavior during annealing with the residual iron content. The isothermal annealed samples demonstrated a tendency for the formation of a heterogeneous microstructure at both 500ºC or 600ºC, which can be due to the recrystallization microstructure evolution. In the final stage, bigger recrystallized grains are formed inside cold worked grains. Also, the material with 599 ppm Fe did not change its grain size during annealing at 500ºC. MET results did not demonstrate the occurrence of dispersed iron particles. DSC analysis showed a peak prior to recrystallization, which was identified as the formation of a Cottrell atmosphere in all samples. The iron solute seems to detain its occurrence.

Este trabalho analisa o efeito da descarbonetação nas perdas magnéticas de aços elétricos semiprocessados, após recozimento final, descarbonetante e/ou não-descarbonetante. Neste trabalho foi utilizado um aço de baixo carbono (600ppm de C) encruado a 4-6% de deformação, tipo COSCORE 55O. Foi notado que o recozimento descarbonetante reduz rapidamente (poucos minutos de tratamento térmico) o teor de carbono do aço a níveis baixos (abaixo de 100ppm de C), reduzindo também as Perdas magnéticas totais (abaixo de 10W/Kg). Verifica-se que recozimentos de 20 e 40 minutos são tempos suficientes para produzir aços com baixas Perdas e baixo teor de C. É mostrado também que recozimento descarbonetante influencia na recristalização de aços carbono encruado. Verificou-se que, durante recozimento descarbonetante, o espaçamento entre as lâminas influenciou a microestrutura e as perdas magnéticas do material. A análise de Textura cristalográfica do material revela que quanto maior o nível de umidade do ensaio, maior a redução da intensidade de fibra Gama, (111)//DN, e aumento da intensidade de textura cristalográfica Goss, ou seja, grãos com orientação cristalográfica, (110)// de grande intensidade é obtido. / This work analyzes the effects of decarburizing annealing on the magnetic, microstructure and texture properties of semiprocessed electrical steels after annealing. A rolles low-carbon electrical steel (0,06%wt/wt Carbon) sheet was used in the experiments. It was verified that decarburizing annealings decrease quickly carbon content (after few minutes of thermal treatment) to levels lower than 100ppm, and after annealing the magnetic losses fastly decreases until below 10W/Kg. It was seen that decarburizing annealings for 20 and 40 minutes are enough to produce low magnetic losses and low carbon content steels. The annealings resulted in low magnetic losses steels whenever microstructure recrystallization has occurred, associated with decarburization. It was noticed that, during decarburizing annealing, the spacing between sheets affected the microstructure and magnetic losses of the material. Crystallographic texture analysis of material reveals that the bigger the annealing humidity, Gama fiber, (111)//DN, decreases and Goss texture, (110)//, increases.

Orientador: Vivaldo Silveira Júnior / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-24T21:16:55Z (GMT). No. of bitstreams: 1 MonzonDavila_LenaSoledad_D.pdf: 2543288 bytes, checksum: a039e70acb94ec045bbf18c3ccde7d06 (MD5) Previous issue date: 2014 / Resumo: A qualidade dos alimentos congelados esta diretamente relacionada ao tamanho e quantidade de cristais de gelo formados após o processo de congelamento. Para a maioria dos alimentos (carne, peixe, frutas e vegetais), a formação de cristais de gelo maiores durante o congelamento ou estocagem tem mostrado resultados de alterações na textura e nas propriedades organolépticas. Assim, fatores como a baixa temperatura mas com uma oscilação de temperatura controlada inadequadamente durante a estocagem, podem resultar no fenômeno de recristalização dos cristais de gelo, o qual consiste na migração da água de pequenos cristais de gelo formados após a etapa de congelamento para cristais de gelo maiores; podendo provocar perda do teor de água do alimento e conseqüentemente uma diminuição na vida útil do produto. Neste trabalho, avalia-se o fenômeno de recristalização de amostras de gel de gelatina 2% (peso/peso) congeladas em diferentes velocidades de congelamento (congelamento médio de 0,007 ºC/s, rápido de 0,060 ºC/s e ultra-rápido de 0,270 ºC/s) e estocadas a -12,0 ± 2,5 °C, -12,0 ± 5,0 °C, -18,0 ± 2,5 °C e -18,0 ± 5,0 °C por um período mínimo de 4 meses. Pequenos e regulares cristais de gelo foram encontrados para o congelamento rápido e ultra-rápido quando comparados ao congelamento médio. Para a mesma flutuação de temperatura, após 4 semanas de estocagem, uma diferença significativa do tamanho do cristal de gelo foi encontrada para o congelamento médio em relação ao congelamento rápido e ultra-rápido. Tanto para o congelamento rápido, como para o ultra-rápido, houve uma grande diferença do tamanho do cristal de gelo após 90 dias de estocagem. Por outro lado, os tamanhos dos cristais de gelo foram significativamente maiores quando as temperaturas e/ou as flutuações de temperatura, durante a estocagem, foram maiores. Este estudo também analisou a hipótese de que altas velocidades de congelamento produzem pequenos cristais de gelo iniciais que, ao longo da estocagem, recristalizam em menor tamanho quando comparadas aos tamanhos dos cristais iniciais de gelo formados por baixas velocidades de congelamento. Foi constatado neste projeto que cristais de gelo iniciais formados por uma velocidade de congelamento rápido, podem recristalizar ao mesmo tamanho que os cristais de gelo recristalizados a partir de um tamanho de cristais maiores gerados por uma velocidade de congelamento médio, ou seja, após uma incorreta estocagem a recristalização afeta ainda mais os alimentos mesmo iniciando-se com um ótimo processo de congelamento / Abstract: The quality of frozen foods is directly related to the size and number of ice crystals formed after the freezing process. For most food (meat, fish, fruits and vegetables), the formation of larger ice crystals during freezing or storage have proved to changes in texture and organoleptic properties. Thus, factors such as low temperature but with an inadequately controlled temperature oscillation during storage can result in the phenomenon of recrystallization of ice crystals, which comprises water migration of small ice crystals formed after the freezing process to larger ice crystals; may cause loss of water content of food and consequently a decrease in the shelf life of the product. In this work, we evaluate the phenomenon of recrystallization of samples of gelatin gel 2% (weight / weight) frozen at different freezing rates (quick freezing of 0.007 ºC/s, rapid freezing of 0.060 ºC/s and ultra-rapid freezing of 0.270 ºC/s) and stored at 12.0 ± 2.5 °C, -12.0 ± 5.0 °C, -18.0 ± 2.5 °C e -18.0 ± 5.0 °C for a minimum period of 4 months. Small and regular ice crystals were found for the rapid freezing and ultra-rapid freezing when compared to the quick freezing. For the same temperature fluctuation, after 4 weeks of storage, a significant difference in the ice crystal size was found for the quick freezing. For the rapid freezing and ultra-rapid freezing, there was a big difference from ice crystal size after 90 days of storage. On the other hand, the size of the ice crystals was significantly greater when temperatures and / or temperature fluctuations during storage were higher. This work also examined the hypothesis that high freezing rates produce small initial ice crystals and during the storage, those ice crystals recristallize in size when compared to the initial ice crystals formed by the low freezing rates. It has been found in this work that smaller initial ice crystals formed by the rapid freezing can recrystallize to the same size of the recrystallized crystals from the larger initial size crystals generated by the quick freezing, or after an incorrect storage the recrystallization affects more the food even starting with a great freezing process / Doutorado / Engenharia de Alimentos / Doutora em Engenharia de Alimentos

Orientadores: Antonio Jose Ramirez Londono, Paulo Roberto Mei / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T04:14:39Z (GMT). No. of bitstreams: 1 Hermenegildo_TahianaFranciscadaConceicao_D.pdf: 6825596 bytes, checksum: 036996ce1577dccad9ce590969e2cfe2 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho chapas do aço ISO 3183 X80M, foram soldadas empregando o processo de soldagem por atrito com pino não consumível, conhecido em inglês como ''Friction Stir Welding'', através de dois passes, sendo um em cada lado da chapa, utilizando ferramentas de NBCP (Nitreto de Boro Cúbico Policristalino). Juntas soldadas com aportes térmicos diferenciados foram processadas para estudo visando entender a influência da velocidade rotacional e de soldagem nas transformações microestruturais e no desempenho mecânico das juntas. Para tal, foram utilizadas as técnicas de microscopias óptica e eletrônica de varredura e transmissão, EBSD (Electron Backscattering Diffraction) e difração de raios-X para caracterização microestrutural. A determinação da história térmica, juntamente com ensaios mecânicos de microdureza, tração, dobramento e tenacidade à fratura (CTOD) complementaram a avaliação das juntas. Pelas análises microestruturais realizadas nas juntas de menor e maior aporte térmico e com o auxílio da história térmica, ficaram evidenciados os efeitos da deformação abaixo e acima da temperatura de não recristalização, da taxa de resfriamento e da recristalização dinâmica e metadinâmica na evolução microestrutural da zona misturada. Ensaios de dureza por microindentação Vickers e de tenacidade à fratura revelaram que a junta produzida com menor aporte térmico apresentou menor dureza e maior tenacidade na zona misturada. Por outro lado, a dureza e a tenacidade da zona afetada pelo calor não foram influenciadas pela variação dos parâmetros adotados neste trabalho. Os ensaios de dobramento não revelaram quaisquer descontinuidades nos corpos de prova, enquanto que nos ensaios de tração as amostras romperam sempre no metal de base, indicando uma alta resistência mecânica da junta soldada quando comparado ao metal de base. Tais resultados combinados validam completamente as juntas soldadas por SAPNC em relação às normas vigentes para a sua aplicação. As características microestruturais corroboram com o desempenho mecânico das juntas avaliadas / Abstract: In this work X80M ISO 3183 steel plates were welded using the Friction Stir Welding process by two passes, one on each side of the plate using PCBN (Polycrystalline Cubic Boron Nitride) tools. To understand the influence of the rotational and welding speed on the microstructural evolution and mechanical performance of the welded joints, samples with different heat inputs were processed. To this end, optical, scanning and transmission electron microscopy, EBSD (Electron Backscattering Diffraction), X-ray diffraction were used for the microstructural characterization. The thermal history registration with the mechanical tests of microhardness, tensile, bending and fracture toughness (CTOD) completed the evaluation of the joints. Based on the microstructural characterization and thermal history analyses of the joints with lower and higher heat input, the effects of deformation below and above the non-recrystallization temperature, cooling rate, and dynamic and metadynamic recrystallization on the microestrutural evolution of the stir zone were evidenced. Vickers microhardness and fracture toughness tests showed that the joint produced with lower heat input has lower hardness and higher toughness within the stir zone. Moreover, the hardness and toughness of the heat affected zone were not influenced by the parameters variation adopted in this work. The bending test did not revealed discontinuities in the specimens, while the tensile test specimens failed within the base metal, indicating a higher resistance of the weld metal when compared to the base metal. Such combined results fully validate the FSW joints regarding its commercial application. The microstructural observations are in agreement with the mechanical performance of the joints / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Orientador: Antonio José Ramirez Londono / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Mecânica / Made available in DSpace on 2018-08-20T13:37:33Z (GMT). No. of bitstreams: 1 TorresLopez_EdwarAndres_D.pdf: 14707024 bytes, checksum: 982b5dbc99d5f7bbef2ea2c34019eea4 (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foram realizadas juntas soldadas dissimilares de aço carbono AISI SAE 1020 e a liga de alumínio AA6063-T5, com 2 mm de espessura, empregando o processo de soldagem por atrito com pino não consumível (SAPNC). As juntas soldadas a topo foram realizadas empregando ferramenta de WC-14Co, com diâmetro de ombro e pino de 25,0 e 5,7 mm, respectivamente, e comprimento de pino de 1,35 mm. Foram empregadas velocidades de rotação e avanço de 300 RPM e 150 mm.min-1, respectivamente, para três deslocamentos da ferramenta: +0,5, +1,0 e +1,5 mm. A caracterização microestrutural foi realizada por meio de microscopia óptica e eletrônica de varredura e de transmissão, difração de elétrons retroespalhados (EBSD), espectrometria de raios X dispersiva em energia (X-EDS) e difração de raios X (DRX). Para relacionar os parâmetros de soldagem com a microestrutura das juntas soldadas, foram elaborados os perfis da história térmica durante a soldagem. Juntas soldadas consolidadas foram obtidas para deslocamentos tangenciais da ferramenta (DT) de +1,0 e +1,5 mm, sendo descartado o DT de +0,5 mm por resultarem em penetração heterogênea ao longo da junta. As juntas realizadas no presente trabalho podem ser consideradas como de baixo aporte térmico. Esta condição evitou a formação da denominada zona de menor dureza na zona termicamente afetada (ZTA) do lado do alumínio e de compostos intermetálicos AlxFey na interface alumínio-aço. Na zona misturada, foram obtidas evidências da presença de dois mecanismos de recristalização dinâmica diferentes. No lado de avanço da zona misturada foi identificado o mecanismo de recristalização dinâmica geométrica, enquanto no lado de retrocesso o mecanismo ativo foi recristalização dinâmica continua / Abstract: In this work dissimilar AISI SAE 1020 mild steel and aluminum alloy AA6063-T5 joints, with 2 mm thickness, were friction stir welded (FSW). The welded joints were conducted employing WC-14Co tools, with shoulder and pin diameter of 25.0 and 5.7 mm respectively, and pin length of 1.35 mm. Rotation and weld speeds of 300 RPM and 150 mm.min-1 were employed, for three tool offsets: 0.5, 1.0 and 1.5 mm. The microstructural characterization was performed through optical, scanning and transmission electron microscopy, electron backscatter diffraction (EBSD), energy dispersive X-ray spectroscopy (X-EDS) and x-ray diffraction (DRX). In order to correlate the welding parameters with the final microstructure of the joints, thermal history profiles were collected during welding. Consolidated welded joints were obtained for tool offsets (DT) of +1.0 and +1.5 mm, being discarded the +0.5 mm offset by to produce heterogeneous penetration along the welded joint. The joints made in this work can be considered as low-heat input. This condition prevented the formation of the so-called low hardness zone in heat affected zone (HAZ) aluminum side, and the formation of intermetallic compounds AlxFey in the aluminum-steel interface. In the stir zone evidences of the presence of two different dynamic recrystallization mechanisms were observed. In the advance side of the stir zone, the geometric dynamic recrystallization was identify as working mechanism, while in retreating side of the stir zone, the active mechanism is the so-called continuous dynamic recrystallization / Doutorado / Materiais e Processos de Fabricação / Doutor em Engenharia Mecânica

Abstract The aim of this work was to study systematically the effects of composition and processing on austenite grain growth and static recrystallization (SRX) kinetics, austenite decomposition under controlled cooling as well as microstructures, mechanical properties and weldability of hot rolled low carbon bainitic (LCB) steels. The results showed that the coarsening of austenite grain structure is influenced by the chemical composition. Steels with Nb-Ti alloying exhibited fine and uniform austenite grain size up to 1125 °C, whereas higher temperatures led to formation of the bimodal grain structures. However, with Nb-Ti-B microalloying, the abnormal grain growth was already observed at 1050 °C. SRX rate at roughing temperatures, determined by the stress relaxation method, was found to be retarded markedly by Mo, Nb and B alloying. For the test conditions investigated, the decomposition of austenite started in the temperature range from 780 °C to below 550 °C. All alloying elements with the exception of Nb (0.04–0.10 wt-%) decreased the phase transformation temperatures and increased the hardness of dilatometric specimens. Detailed microstructural examinations enabled the identification of 4 different ferrite morphologies: polygonal ferrite, quasi-polygonal ferrite (QF), granular bainitic ferrite (GB) and bainitic ferrite (BF), generally as a mixed microstructure consisting of 2–3 types morphologies. Consistent with the microstructures detected in dilatometric experiments, the microstructures of rolled plates comprise various combinations of low C ferrite morphologies. These microstructure types provided the yield strengths from 500 MPa up to 850 MPa in hot rolled condition and from 500 MPa to 950 MPa in heat-treated condition (600 °C/1h). The yield strengths from 500 MPa to 570 MPa were mainly related to QF microstructures in as-rolled condition, while the steels with the yield strength from 570 to 700 MPa had GB-QF microstructures. Steels with the yield strengths above 700 MPa consisted of BF. The most effective alloying element regarding the strength properties is B. Also C, Mn, Cr, Mo and Ni have strong influences, but Nb in the range of 0.05–0.10 wt-% is ineffective. Strengthening with B and Mo was detrimental to toughness. Alloying with Ni and Mn is beneficial to good strength and toughness combination. Mn, Mo, Nb and B contents mainly dictate CGHAZ toughness.

The system of upper high nickel alloying steel seal ring and lower high nickel alloying steel seal ring, installed in the grooves of turbine, can extend out and fit with the wall of valve cage, resulting in forming a good seal under the pressure. In the project, the failure steel seal ring is considered. This situation had threatened the safety of the whole steam turbine system. The purpose of this study is to identify the failure cause of the steel seal ring used in nuclear steam turbines. New high nickel steel alloy seal ring was compared with the failed seal ring. The dimensions of macroscopic ring with clearly plastic deformation were measured using calipers. Surface morphology of ring was observed by optical microscopy through metallographic analysis. There is a lot of precipitation in the grain boundaries of used seal ring, along with smaller grain size than the new seal ring. To explore the composition of precipitation, scanning electron microscopy (SEM) with energy-dispersive spectrometer (EDS) were used. The results indicated that the concentration of titanium (Ti) and molybdenum (Mo) was higher in the precipitation of used seal ring. At the same time, the hardness and elastic modulus of used seal ring were reduced, measured by nanoindentation test. In-situ SEM tensile testing were used to record and analyze the generation of crack source and crack development under applied load. The reasons of the seal ring failure can be answered because of these experimental results at both macroscopic and microscopic scales. The main reason of the seal ring failure is a combination of long-term stress and elevated temperature during turbine operation. Complex work environment caused recrystallization and recovery, resulting in grain refinement and secondary phase precipitation. Further embodiment, recrystallization and recovery caused the elastic modulus and hardness of used seal ring decrease. Moreover, a lot of secondary phase precipitates appeared at grain boundaries during use. The appearance of secondary phase precipitates become the weakest part of used seal ring. The applied load lead to seal ring failure from the formation of microvoids to microvoids aggregated becoming microcracks until to the appearance of cracks at macroscopic scale. These changes of microscopic structure ultimately reflected in critical plastic deformation of used seal ring.

Cryopresevation is the process of cooling biological materials to low sub-zero temperatures for storage purposes. Numerous medical and technical applications, such as hematopoeitic stem cell transplantation and sperm banking, sometimes require the use of cryopreserved cells. Cryopreservation, however, can induce cell injury and reduce the yields of viable functional cells. Ice recrystallization is a mechanism of cryopreservation injury, but is rarely addressd in strategies to optimize cell cryopreservation. The results from this thesis demonstrate an association between the potency of carbohydrate-mediated ice recrystallization inhibition used in the cryopreservation of umbilical cord blood and recovery of viable non-apoptotic cells and hematopoietic progenitor function. Furthermore, increased numbers of apoptotic cells in hematopoeitic stem cell grafts were associated with reduced hematopoietic function and delayed hematopoietic recovery in patients undergoing blood stem cell transplantation. These findings provide a basis for pursuing further studies assessing ice recrystallization inhibition as a strategy for improving cell cryopreservation.

In this thesis computational chemistry has been used to accelerate experimental discovery in the fields of ice recrystallization inhibitors for cryopreservation and ultra-microporous MOFs for carbon dioxide capture and storage. Ice recrystallization is one of the leading contributors to cell damage and death during the freezing process. This occurs when larger ice crystal grains grow at the expense of smaller ones. Naturally occurring biological antifreeze molecules have been discovered but only operate up to -4oC and actually exasperate the problem at temperatures lower than this. Recently, the group of Dr. Robert Ben have been successful in synthesizing small organic molecules which are capable of inhibiting the growth of ice crystals during the freezing process. They have built a library of diverse compounds with varying functionalities and activity. Chemical intuition has been unsuccessful in finding a discernible trend with which to predict activity. Herein we present work where we have utilized a quantitative structure activity relationship (QSAR) model to predict whether a molecule is active or inactive. This was built from a database of 124 structures and was found to have a positive find rate of 82%. Proposed molecules that had yet to be synthesized were predicted to active or inactive using our method and 9/11 structures were indeed active which is strikingly consistent to the 82% find rate. Our efforts to aid in the discovery of these novel molecules will be described here. Metal organic frameworks (MOFs) are a relatively new class of porous materials which have taken the academic community by storm. These three-dimensional crystalline materials are built from a metal node and an organic linker. Depending on the metals and organic linkers used, MOFs can possess a vast range of topologies and properties that can be exploited for specific applications. Ultra-microporous MOFs possess relatively small pores in the range of 3.5 Å to 6 Å in diameter. These MOFs have some structural advantages compared to larger pored MOFs such as molecular sieving, smaller pores which promote strong framework-gas interactions and cooperative effects between guests, and longer shelf-life due to small void volumes and rigid frameworks. Here we present newly synthesized ultra-microporous MOFs based on isonicotnic acid as the organic linker with Ni and Mg as the metal centre. Despite having such small pores, Ni-4PyC exhibits exceptionally high CO2 uptake at high pressures. Furthermore, Mg-4PyC exhibits novel pressure dependent gate-opening behaviour. Computational simulations were employed to investigate the origin of high CO2 uptake, predict high pressure (>10bar) isotherms, quantify CO2 binding site positions and energies, and study uptake-dependent linker dynamics. This work hopes to provide experimentalists with some explanation to these interesting unexplained phenomena and also predict optimal properties for new applications.