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Organisms have evolved a remarkable ability to mineralize complex skeletons and functional biomaterials. These structures are nucleated and grown in close associaiton with macromolecular assemblages of proteins and polysaccharides that are implicated in regulating all stagees of mineralization. Because of this intimate association of organic with inorgaic components, many studies have investigated the effects of particular organic species on mineral morphology, phase, and growth rate. However, the diversity and species-specific nature of the organic assemblages associated with biominerals across a wide variety of taxa, has limited our understanding of how organisms use biomolecules to regulate skeletal formation. It is clear that a mechanistic picture of biomolecular controls on mineralization requires molecular-level investigations of the interplay between organic and inorganic components at all stages of crystallizaiton. This dissertation presents the findings from theoretical and experimental studies of the physical mechanisms that underlie biomolecule controls on mineral formation. Molecular dynamics simulations probe the effects of acidic molecules on the hydration of alkaline earth cations. After first calculating baseline hydration properties for magnesium, calcium, strontium, and barium, I determine the effects of carboxylate-containing molecules on cation hydration state as well as the kinetics and thermodynamics of water exchange. Experimental work utilizes self-assembled monolayers as proxies for matrix macromolecules in order to understand their effects on CaCO3 nucleation kinetics and thermodynamics. Estimates of nucleation rates and barriers are made from optical microscopy data and correlated with measurements of crystal – substrate rupture force from dynamic force microscopy. These investigations show that an important function of biomolecules in directing mineralization lies in their ability to modulate cation hydration. Both chemical functionality and molecular conformation are influential in regulating the kinetics and thermodynamics of mineral nucleation, and these effects may be predicted by the strength of interaction between organic and inorganic components. These findings contribute to a mechanistic understanding of how organic matrices act to regulate biomineral formation. They demonstrate a plausible physical basis for how carboxyl-rich biomolecules accelerate the kinetics of biomineral growth and suggest roles for organic species in the nucleation and pre-nucleation stages of mineralization. / Ph. D.

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Made available in DSpace on 2016-12-08T17:19:24Z (GMT). No. of bitstreams: 1 Elder Gregol dos Santos.pdf: 4072797 bytes, checksum: c4f0d20ac13dce8a35fd04f90bc3545d (MD5) Previous issue date: 2014-11-07 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The carburiser materials have been widely used in the foundry industry, motivated by increasing use of scrap steel and consequent reduction in the use of pig iron. Several factors, besides of recovery of carbon in the metal bath, can be associated with the use of carburisers, including the effect on the levels of silicon, sulfur, nitrogen and degree of nucleation of metal. This paper evaluates the effects of the use of carburisers materials, of the types natural graphite, synthetic graphite, graphite permanent mold residue (used in molds of continuous casting) and synthetic graphite with low sulphur amount. The method of addition was chosen on the surface of the liquid bath, at a medium frequency induction furnace, 2500 kg capacity, tests at three different temperatures. Was observed that there was no incorporation of nitrogen of carburisers to liquid metal, and the sulfur content was altered only when used synthetic carburiser. The increase in temperature caused an increase in the value of carburation efficiency, regardless of the type of carburisers. In general, it was observed an increase 21-32% when the temperature is changed from 1480 to 1545 ° C. Only the special synthetic carburisers showed lower sensitivity to temperature increase, showing an increase of only 5% efficiency. It was found that the ash content of the carburiser is a variable that affects significantly the dissolution process of the carburiser. The results showed that the carburisers with lower ash content, have higher carburation efficiency. This paper proposed the concept of rate of gain of associated carbon, which was effective for predicting the behavior of % C of liquid metal after the addition of the carburiser. It was found that the rate of gain associated initial carbon is favored with increasing temperature and the sulfur content of liquid metal, and impaired with an increase in the percentage of ash in carburiser. As for the value of the combined rate of dissolution, this showed an increase when the temperature of addition is growing. It was noted that the value of maximum rate of efficiency has relation with the value of the combined rate of dissolution, allowing to conclude that the higher the value of the combined dissolution rate, the faster the process reaches its maximum efficiency. The results observed for the residue of graphite mold, in the carburation efficiency, efficiency rate and combined rate of dissolution, showed that this material has the potential to be used as carburante in foudry. Comparing the initial and final conditions of the experiments, it was found that bath treated with synthetic carburiser with low% S, showed a reduction in the degree eutetic supercooling at temperatures of 1485 and 1545 ° C and the chill residue contributed to the reduction of degree eutetic supercooling at temperatures of 1485, 1515 and 1545 ° C. When analyzing the behavior of the degree eutetic supercooling with time after the addition of carburiser, was possible to identify three different behaviors. / Os materiais carburantes têm sido amplamente utilizados na indústria de fundição, em função da crescente utilização de sucata de aço e a consequente redução do uso de ferro gusa. Vários fatores, além da recuperação de carbono no banho metálico, podem ser associados ao uso dos carburantes, entre eles o efeito nos teores de sílicio, enxofre, nitrogênio e no grau de nucleação do metal. Este trabalho apresenta a avaliação dos efeitos do uso de materiais carburantes, dos tipos grafite natural, grafite sintético, resíduo de coquilha de grafite (utilizado em matrizes de fundição contínua) e grafite sintético com baixo teor de enxofre. O método de adição escolhido foi sobre a superfície do banho líquido, em um forno à indução de média frequência, de 2500 Kg de capacidade, realizando testes em três temperaturas distintas. Observou-se que não houve incorporação de nitrogênio do carburante pelo metal líquido, e o teor de enxofre sofreu alteração somente quando usado o carburante sintético. O aumento da temperatura provocou um aumento no valor da eficiência de carburação, independente do tipo de carburante. De maneira geral, observou-se um aumento de 21 32% na eficiência, quando a temperatura é alterada de 1480 a 1545°C. Apenas o carburante sintético especial apresentou menor sensibilidade ao aumento da temperatura, mostrando um aumento de apenas 5% de eficiência. Verificou-se que o teor de cinzas do carburante é uma variável que afeta significativamente o processo de dissolução do carburante. Os resultados evidenciaram que os carburantes com menor teor de cinzas, apresentam maiores valores de eficiência de carburação. Este trabalho propôs o conceito da taxa de ganho de carbono associada, a qual se mostrou efetiva para a previsão do comportamento do % C do banho, após a adição do carburante. Verificou-se que a taxa de ganho de carbono associada inicial, é favorecida com o aumento da temperatura e do teor de enxofre do metal, sendo prejudicada com aumento do percentual de cinzas do carburante. Quanto ao valor da taxa de dissolução combinada, esta mostrou um aumento quando a temperatura de adição é crescente. Notou-se que o valor da taxa de eficiência máxima possui relação com o valor da taxa de dissolução combinada, permitindo concluir que quanto maior o valor da taxa de dissolução combinada, mais rapidamente o processo atinge a sua eficiência máxima. Os resultados observados para o resíduo de coquilha de grafite, na eficiência de carburação, taxa de eficiência e na taxa de dissolução combinada, evidenciaram que este material tem potencial para ser utilizado como carburante. Comparando as condições iniciais e finais dos experimentos, verificou-se que banhos tratados com carburante sintético com baixo %S, apresentaram uma redução no super-resfriamento do eutético, nas temperaturas de 1485 e 1545°C, e o resíduo de coquilha contribuiu para a redução do super-resfriamento do eutético nas temperaturas de 1485, 1515 e 1545°C. Quando analisado o comportamento do grau de super-resfriamento com o tempo, após a adição dos carburantes, foi possível identificar três comportamentos distintos.