Submitted by MAURICIO UMENO WATANABE null (mauriciowatanabe@yahoo.com.br) on 2017-01-31T20:21:29Z No. of bitstreams: 1 TESE Mauricio Umeno Watanabe Doutorado.pdf: 1431193 bytes, checksum: 6559d1f5a8ffe6a615335a16b8dd301c (MD5) / Approved for entry into archive by LUIZA DE MENEZES ROMANETTO (luizamenezes@reitoria.unesp.br) on 2017-02-03T18:53:52Z (GMT) No. of bitstreams: 1 watanake_mu_dr_araca.pdf: 1431193 bytes, checksum: 6559d1f5a8ffe6a615335a16b8dd301c (MD5) / Made available in DSpace on 2017-02-03T18:53:52Z (GMT). No. of bitstreams: 1 watanake_mu_dr_araca.pdf: 1431193 bytes, checksum: 6559d1f5a8ffe6a615335a16b8dd301c (MD5) Previous issue date: 2016-12-19 / Objetivo: Resinas compostas para uso direto têm sido frequentemente usadas pelos profissionais para confecção de restaurações indiretas extensas. O objetivo do presente estudo foi avaliar a resistência à flexão (RF) e o módulo de elasticidade (ME) de diferentes materiais restauradores poliméricos diretos, nos tempos de 30min e 24h sem tratamento térmico (TT); e quando submetidos ou não ao TT, sendo armazenados ou não por 180 dias. Materiais e método: Foram confeccionados 200 corpos de prova divididos nos seguintes grupos de acordo com o material: o ormocer microhíbrido Admira Fusion (ADM), a resina tipo “bulk” nanoparticulada Filtek Bulk Fill (BU), a resina composta convencional nanoparticulada Filtek Z350XT (Z350) e resina composta convencional microhíbrida IPS Empress Direct (EMP). Os grupos foram subdivididos (n=10) nos tempos de 30min sem TT, 24h com e sem TT ou 180 dias com e sem TT. Os corpos de prova (10 mm x 2 mm x 2 mm) foram confeccionados usando-se um molde tripartido de aço inox, no qual o material foi inserido em incremento único e fotoativado por 20s de cada lado. No final do período de 24h da fotoativação, o TT foi realizado por 10min em estufa à temperatura controlada de 170⁰C. O armazenamento das amostras de 180 dias foi em água destilada em ambiente escuro a 37⁰C. O teste de resistência à flexão de 3 pontos foi realizado em uma máquina de ensaio Instron à velocidade de 1,0 mm/min. Resultados: Os resultados foram obtidos em MPa (RF) e GPa (ME), sendo depois submetidos à análise estatística ao nível de significância de 5%. Todos materiais tiveram aumentos significativos do tempo de 30min para o tempo de 24h, tanto para a RF quanto para o ME (p<0,05). A realização do TT promoveu aumento nos valores de RF para as resinas compostas BU e EMP no tempo de 24h e Z350 no tempo de 180 dias (p<0,05). Para a BU sem TT, o armazenamento não influenciou nos resultados de RF. A realização do TT promoveu aumento nos valores de ME para o ADM nos dois tempos de análise, e para as resinas compostas EMP, BU e Z350 no tempo de 24h (p<0,05). Houve diminuição significativa no ME de ADM e EMP após 180 dias em comparação ao tempo de 24h, independente do TT e para BU com TT (p<0,05). Não houve diferença quanto ao ME na comparação entre 180 dias e 24h para a BU sem TT e para a Z350 com TT (p>0,05). Conclusões: Pode-se concluir que a influência do tempo de 30min para o tempo de 24h na RF e no ME independe do material. A influência do armazenamento e do TT na RF e no ME são materiais dependentes. / Purpose: Direct composite resins are often used by professionals for making extensive indirect restorations. The aim of this investigation was to evaluate flexural strength and elastic modulus of different restorative polymeric materials at 30 minutes and 24 hours without heat treatment (HT); and with and without HT at 24 hours and 180 days post cure. Materials and method: 200 samples were prepared and divided according to the material as follows: microhybrid ormocer Admira Fusion (ADM), nanofilled bulk-fill composite resin Fitek Bulk Fill (BU), nanofilled universal composite resin Filtek Supreme Ultra (Z350) and microhybrid universal composite resin IPS Empress Direct (EMP). Groups were subdivided (n=10) at 30 minutes into: without HT (30 min), 24 h with and without HT and 180 days with and without HT. The samples (10 mm x 2 mm x 2 mm) were made in a tri-part stainless steel mold where the material was inserted and light-cured for 20 seconds on each side. At the end of the 24 h period HT at 170⁰C was performed for 10 minutes in a dry heat oven. The 180 day storage samples were placed in destilled water at 37⁰C in the dark. A standard three point bending test was conducted on all samples with a universal testing machine (Instron) at a crosshead speed of 1.0 mm/min. Results: The results were recorded in MPa (flexural strength) and GPa (elastic modulus) and data were analyzed statistically at a significance level of 5%. All the materials had a significant increase in flexural strength and elastic modulus from 30 minutes to 24 hours (p<0.05). HT promoted an increase in flexural strength for BU and EMP at 24 hours and Z350 at 180 days (p<0,05). Storage didn’t influence flexural strength for BU without HT. HT promoted elastic modulus increase for ormocer ADM at both testing times and for EMP, BU and Z350 at 24 hours (p<0.05). With regard to ADM and EMP the elastic modulus decreased significantly after 180 days in comparison to 24 h independent of HT. BU with HT also decreased in modulus after 180 days (p<0.05). There was no significant difference in elastic modulus between 24 hours and 180 days for BU without HT and for Z350 with HT (p>0.05). Conclusions: It can be concluded that the influence of time from 30 minutes to 24 hours in flexural strength and elastic modulus is independent of the material. Storage and HT influence on flexural strength and elastic modulus are material dependent.

O objetivo principal foi investigar se o osso cortical apresenta comportamento bimodular, ou seja, se os valores de módulo de elasticidade (E) dependem do tipo de carregamento que o método utiliza. Para alcançá-lo foi preciso: (1) \"calibrar\" os diferentes métodos em um material conhecidamente unimodular, para afastar a possibilidade de erros ligados à execução de um método. (2) Depurar os métodos já calibrados para torná-los exequíveis em osso cortical. O que foi feito em espécimes de resina composta, que é um material unimodular e com E parecido com o do osso cortical. Foi investigado se o método de medida interfere no valor do E obtido neste material (pois, pelas informações da literatura, existia uma dúvida consistente). Finalmente, (3) foi avaliado se o método de medida, a região anatômica e o indivíduo interferem nos valores de E em espécimes de osso cortical. Adicionalmente, (4) verificou-se a possibilidade de se encontrar e validar uma correlação entre E e dureza Knoop (KH), para medir o E de resinas compostas indiretamente. Espécimes de latão (n = 5) tiveram o seu E calculado por quatro métodos estáticos diferentes (flexão em três pontos; tração; compressão e método de Marshall), que foram calibrados até que todos medissem o valor esperado; os valores de cada método foram comparados por análise de variância de medidas repetidas (o método foi o fator vinculado e o nível de significância foi de 5%). Espécimes (n = 4) de cinco marcas diferentes de resina composta, também foram submetidos aos quatro métodos, fazendo as adaptações pertinentes (depuração), e tiveram o seu E calculado. Estes valores foram submetidos à análise de variância de medidas repetidas (o método foi o fator vinculado e o nível de significância foi de 5 %). Espécimes (n = 48) obtidos em diferentes regiões (periósteo, endósteo e \"transversal\") de fêmures de quatro bois diferentes tiveram seu E calculado através dos métodos devidamente depurados (flexão em três pontos, tração indireta e compressão). Os valores de E foram submetidos a análises de variâncias (nível de significância de 5 %) para avaliar a influência do método, da região e do indivíduo (bois diferentes) sobre os valores de E. O método experimental de tração não foi utilizado para analisar o comportamento bimodular, porque durantes os ensaios com osso cortical, ele apresentou valores com viés. Por isso, os valores de tração foram calculados de forma indireta (Eti) através de uma equação e dos valores experimentais de flexão em três pontos (Eb) e compressão (Ec). Para validar o uso de valores de Eti, eles foram comparados com os respectivos valores de tração experimental (Et) calculados previamente nos espécimes de resinas compostas por análise de variância de medidas repetidas, e não foram achadas diferenças significantes (p > 0,05). Para encontrar e validar a correlação entre E e KH, os valores médios de E em cada espécime de resina (média do E obtido nos 4 métodos em cada espécime) foram submetidos ao teste de correlação de Pearson (nível de significância de 5%) com os respectivos valores experimentais de dureza Knoop (KH) e foi obtida uma equação de regressão linear. Para validar a equação foi confeccionado um segundo grupo de espécimes de resina (de marcas diferentes das utilizadas anteriormente) que teve seu E calculado pelo ensaio de flexão (Eb) e pela equação de regressão proposta previamente (Er); verificou-se então se a correlação entre estes valores (Eb x Er) era significante (nível de significância de 5 %), e se a nova reta de regressão apresentava coeficiente angular não diferente de 1, e coeficiente constante não diferente de zero (critérios de validação). A análise de variância não apontou diferença significante (p > 0,05) entre os valores de E calculados para o metal pelos 4 métodos, e os valores obtidos não diferiram do E conhecido do latão (ao redor de 100 GPa). As depurações necessárias foram realizadas e com elas os diferentes métodos calcularam o E dos espécimes de resina composta de modo consistente: a análise de variância encontrou diferenças significantes (p < 0,05) entre marcas (cujos E médios cobriram a faixa entre 3 e 20 GPa) e não significantes entre os 4 métodos (p > 0,05). Nos espécimes de osso cortical o valor de E foi significantemente dependente (p < 0,05) do método de obtenção (Eti > Eb > Ec). O E dos espécimes obtidos na região \"transversal\" foi menor que o E dos espécimes obtidos na região do endósteo (p < 0,05); no entanto, não houve diferença significante (p > 0,05) entre o E dos espécimes obtidos nas regiões do endósteo e periósteo e entre o E dos espécimes obtidos nas regiões do periósteo e \"transversal\". Ao considerar somente os valores obtidos no ensaio de compressão (Ec), um dos indivíduos apresentou valores de E maiores que os demais (p < 0,05). As médias de E (dos quatro métodos) em cada espécime de resina apresentaram correlação significante com os respectivos valores de KH (p < 0,05) e a equação de regressão linear: E = 0,1602 KH. Também foi significante (p < 0,05) a correlação dos valores de Eb com os respectivos valores de Er (calculados pela regressão E = 0,1602 KH); além disso, a reta de regressão linear desta nova correlação (Eb = 1,0088Er + 0,0475) apresentou coeficiente angular não diferente de 1 e coeficiente constante não diferente de zero. Pode-se concluir que: (1) Quatro métodos de medir o E apresentaram resultados semelhantes em um material metálico. (2) Estes mesmos métodos foram depurados com sucesso para sua utilização em espécimes de osso cortical ao constatar que também não interferiram no valor do E obtido em espécimes semelhantes aos de osso, confeccionados com resinas compostas. (3) Os valores de E de osso cortical dependem do método de medida, o que demonstra seu comportamento bimodular. A região anatômica e o indivíduo também afetam os valores de E dos espécimes de osso cortical (o indivíduo só foi um fator significante ao considerar somente os valores obtidos no ensaio de compressão). (4) Foi encontrada e validada uma correlação entre E e KH em resinas compostas, que permite calcular o E deste material através da regressão E = 0,1602 KH. / The main objective was to investigate whether the cortical bone has a bimodular behavior, that is, if the values of elastic modulus (E) depend on the load type used by the method. To achieve this, it was necessary: (1) \"calibrate\" the different methods in a material with well-known unimodular behavior, for excluding the possibility of systematic errors in the execution of the methods. (2) Depurate the calibrated methods to make them executable in cortical bone. This was made on specimens of composite resin, which is a unimodular material and has an E similar to that of cortical bone. It was also investigated if the method of measuring the E influences the obtained value in this material (because there was a consistent doubt in the literature). Finally (3), we assessed whether the E values in cortical bone are influenced by the measurement method, by the anatomical region and by the individual. Additionally, (4) it was verified if it would be possible suggesting and validating a correlation between E and Knoop hardness (KH), to indirectly measure the E of composite resins. Brass specimens (n = 5) had their E calculated by four different static methods (three point bending, tensile, compression and Marshall\'s method), which were calibrated until all the methods were capable of measuring the expected value; the E values of each method were compared by analysis of variance of repeated measures (the method was the linked factor and the significance level was 5%). Specimens (n = 4) of five different composite resins were also subjected to the four methods, making the relevant adjustments (depuration), and had their E calculated. These values were subjected to analysis of variance of repeated measures (the method was the linked factor and the significance level was 5%); Specimens (n = 48) obtained in different regions (periosteum, endosteum and \"transverse\") of bovine femurs from four different individual had their E calculated using the depurated methods (three point bending, indirect tensile and compression). The E values were subjected to analyzes of variance (significance level of 5%) to evaluate the influence of the method, of the region and of the individual (different cattle) in the E values. The experimental tensile method was not used to analyze the bimodular behavior because during tests on cortical bone, this method showed values with bias. Therefore, the tensile values were indirectly calculated (Eti) by a formula and by the experimental values of E calculated by three point bending (Eb) and compression (Ec). To validate the use of Eti values, they were compared with the corresponding tensile experimental values (Et) previously measured in the composite resins specimens by analysis of variance (repeated measures), and no significant difference was found (p > 0.05). For suggesting and validating the correlation between E and KH, the average values of E of each composite specimen (mean of E obtained considering the values of the four methods in each specimen) were submitted to the Pearson\'s correlation test (significance level of 5 %) with the corresponding experimental KH values and it was obtained the linear regression equation. To validate this equation, it was made a second group of composite resins specimens (with different brands of the previously used) in which the E was calculated by three point bending test (Eb) and by regression equation previously proposed (Er); then it was checked whether the correlation between these values (Eb x Er) was significant (significance level of 5 %), and if the new regression line showed angular coefficient no different from one, and constant coefficient no different from zero (validation criteria). The analysis of variance showed no significant difference (p > 0.05) among the E values calculated for the metal specimens by the four methods; the obtained values did not differ from the known E of the brass (about 100 GPa). The necessary adjustments (depuration) were made and then the different methods calculated the E of the composite resin specimens consistently: the analysis of variance found significant difference (p < 0.05) between composite brands (whose E mean covered the range between 3 and 20 GPa) and no significant difference among the four methods (p> 0.05). In the specimens of cortical bone, the E values were significantly dependent (p < 0.05) of the obtainment method (Eti > Eb> Ec). The E values of the \"transversal\" specimens were lower than the endosteum specimens (p < 0.05); but there was no significant difference (p > 0.05) between the E of endosteum specimens and periosteum specimens and between the E of periosteum specimens and \"transversal\" specimens. When considering just E values of the compression method, one cattle showed higher E values than the others (p < 0.05). The mean of the four methods for each specimen composite resin exhibited a significant correlation with the respective KH values (p < 0.05) and the linear regression equation: E = 0.1602 KH. It was also significant (p < 0.05) the correlation between Eb and the respective Er values (calculated by the regression E = 0.1602 KH); furthermore, the linear regression of this new correlation (Eb = 1.0088Er + 0.0475) presented angular coefficient no different from 1, and constant coefficient no different from zero. It can be concluded that: (1) Four methods of E measuring showed similar results in a metallic material. (2) The same methods were successfully depurated for their execution in cortical bone specimens, since the measurement method did not affect the obtained E value in resin composites (that is a material with E value similar to cortical bone); (3) The E values of cortical bone depend on the measurement method, which demonstrates its bimodular behavior. The anatomical region and the individual also affect the E values of the cortical bone specimens (the individual was a significant factor only when considering just the E values obtained in the compression test). A correlation between E and KH that allows the E estimation by the regression E = 0.1602 KH was suggested and validated in composite resins.

Over the past 50 years, several advancements have been made in the research area of the mechanics of unsaturated soils. These advancements can be categorized into two groups; (i) development (or improvement) of testing techniques (or apparatus) to determine the mechanical properties of unsaturated soils and (ii) development of (numerical, empirical or semi-empirical) models to estimate the variation of mechanical properties of unsaturated soils with respect to suction based on the experimental results. Implementation of the mechanics of unsaturated soils in conventional geotechnical engineering practice, however, has been rather limited. The key reasons for the limited practical applications may be attributed to the lack of simple and reliable methods for (i) measuring soil suction in the field quickly and reliably and (ii) estimating the variation of mechanical properties of unsaturated soils with respect to suction. The main objective of this thesis research is to develop simple and reliable techniques, models or approaches that can be used in geotechnical engineering practice to estimate sol suction and the mechanical properties of unsaturated soils. This research can be categorized into three parts. In the First Part, simple techniques are proposed to estimate the suction values of as-compacted unsaturated fine-grained soils using a pocket penetrometer and a conventional tensiometer. The suction values less than 300 kPa can be estimated using a strong relationship between the compressive strength measured using a pocket penetrometer and matric suction value. The high suction values in the range of 1,200 kPa to 60,000 kPa can be estimated using the unique relationship between the initial tangent of conventional tensiometer response versus time behavior and suction value. In the Second Part, approaches or semi-empirical models are proposed to estimate the variation of mechanical properties of unsaturated soils with respect to suction, which include: - Bearing capacity of unsaturated fine-grained soils - Variation of bearing capacity of unsaturated fine-grained soils with respect to matric suction - Variation of initial tangent elastic modulus of unsaturated soils below shallow foundations with respect to matric suction - Variation of maximum shear modulus with respect to matric suction for unsaturated non-plastic sandy soils (i.e. plasticity index, Ip = 0 %) In the Third Part, approaches (or methodologies) are suggested to simulate the vertically applied stress versus surface settlement behavior of shallow foundations in unsaturated coarse-grained soils assuming elastic-perfectly plastic behavior. These methodologies are extended to simulate the stress versus settlement behavior of both model footings and in-situ plates in unsaturated coarse-grained soils. The results show that there is a reasonably good comparison between the measured values (i.e. soil suction, bearing capacity, elastic and shear modulus) and those estimated using the techniques or models proposed in this thesis research. The models (or methodologies) proposed in this thesis research are promising and encouraging for modeling studies and practicing engineers to estimate the variation of mechanical behavior of unsaturated soils with respect to matric suction.

Chemische und physikalische Eigenschaften von Polymeren können verschiedene Zelltypen unterschiedlich, z. B. hinsichtlich Adhärenz oder Funktionalität, beeinflussen. Die Elastizität eines Polymers beeinflusst vor allem, welche Zugkräfte eine Zelle gegenüber ihrem Substrat entwickeln kann. Das Zellverhalten wird dann über intrazelluläre Rückkopplungsmechanismen reguliert. Die Oberflächenladung und/oder Hydrophilie eines Polymers beeinflusst zunächst die Adsorption von Ionen, Proteinen und anderen Molekülen. Vor allem über die Zusammensetzung, Dichte und Konformation der adsorbierten Komponenten werden anschließend die Wechselwirkungen mit den Zellen vermittelt. Des Weiteren können verschiedene Zelltypen unterschiedliche membranassoziierte Proteine, Zucker und Lipide aufweisen, so dass Polymereigenschaften zellspezifische Effekte bewirken können. Für biotechnologische Anwendungen und für den Einsatz in der regenerativen Medizin gewinnen Polymere, die spezifische Zellreaktionen regulieren können, immer weiter an Bedeutung. Die Isolierung und Kultur von primären Keratinozyten ist noch immer anspruchsvoll und die adäquate Heilung von Hautwunden stellt eine fortwährende medizinische Herausforderung dar. Ein Polymer, das eine bevorzugte Adhärenz von Keratinozyten bei gleichzeitig verminderter Anheftung dermaler Fibroblasten ermöglicht, würde erhebliche Vorteile für den Einsatz in der Keratinozyten-Zellkultur und als Wundauflage bieten. Um den potentiell spezifischen Einfluss bestimmter Polymereigenschaften auf primäre humane Keratinozyten und dermale Fibroblasten zu untersuchen, wurde in der vorliegenden Arbeit ein Zellkultursystem für die Mono- und Cokultur beider Zelltypen entwickelt. Das Testsystem wurde als Screening konzipiert, um den Einfluss unterschiedlicher Polymereigenschaften in mehreren Abstufungen auf die Zellen zu untersuchen. Folgende Parameter wurden untersucht: 1. Vitalität und Dichte adhärenter und nicht-adhärierter Zellen, 2. Schädigung der Zellmembran, 3. selektive Adhärenz von Keratinozyten in Cokultur durch die spezifische immunzytochemische Färbung von Keratin14 und Vimentin. Für die Polymere mit variabler Elastizität wurden zusätzlich die Ablagerung extrazellulärer Matrixkomponenten und die Sekretion löslicher Faktoren durch die Zellen untersucht. Als Modellpolymere für die Variation der Elastizität wurden vernetzte Poly(n-butylacrylate) (cPnBA) verwendet, da deren Elastizität durch den Anteil des Vernetzers eingestellt werden kann. Auf dem weniger elastischen cPnBA zeigte sich in der Cokultur ein doppelt so hohes Verhältnis von Keratinozyten zu Fibroblasten wie auf dem elastischeren cPnBA, so dass ein leichter zellselektiver Effekt angenommen werden kann. Acrylnitril-basierte Copolymere wurden als Modellpolymere für die Variation der Oberflächenladung und Hydrophilie verwendet, da die Eigenschaften durch Art und molaren Anteil des Comonomers eingestellt werden können. Durch Variation des molaren Anteils der Comonomere mit positiver bzw. negativer Ladung, Methacrylsäure-2-aminoethylester-hydrochhlorid (AEMA) und N-3-Aminopropyl-methacrylamid-hydro-chlorid (APMA) bzw. Natriumsalz der 2-Methyl-2-propen-1-sulfonsäure (NaMAS), wurde der Anteil der positiven bzw. negativen Ladung im Copolymer variiert. Durch die Erhöhung des molaren Anteils des hydrophilen Comonomers N-Vinylpyrrolidon (NVP) wurde die Hydrophilie des Copolymers gesteigert. Die Erhöhung des molaren Anteils an positiv geladenem Comonomer AEMA im Copolymer führte tendenziell zu einer höheren Keratinozytendichte, wobei die Fibroblastendichte unverändert blieb. Durch die Erhöhung des molaren Anteils des positiv geladenen Comonomers APMA ergaben sich keine deutlichen Unterschiede in Dichte, Vitalität oder Selektivität der Zellen. Durch die stufenweise Erhöhung des molaren Anteils des negativ geladenen Comonomers NaMAS konnte, wie im Falle von AEMA, eine Tendenz zur verbesserten Keratinozytenadhärenz beobachtet werden. Die Steigerung der Hydrophilie der Copolymere führte sowohl für Keratinozyten als auch für Fibroblasten zu einer reduzierten Adhärenz und Vitalität. In der vorliegenden Doktorarbeit wurde ein Testverfahren etabliert, das die Untersuchung von primären humanen Keratinozyten und primären humanen Fibroblasten in Monokultur und Cokultur auf verschiedenen Polymeren ermöglicht. Die bisherigen Ergebnisse zeigen, dass sich durch die gezielte Modifizierung verschiedener Polymereigenschaften die Adhärenz und Vitalität beider Zelltypen beeinflussen lässt. Die Reduktion der Elastizität sowie die Erhöhung des molaren Anteils geladener Comonomere führten zu einer Zunahme der Keratinozytenadhärenz. Da die Fibroblasten unbeeinflusst blieben, zeigte sich für einige der untersuchten Polymere eine leichte Zellselektivität. Diese könnte durch die weitere Erhöhung der Steifigkeit oder des Anteils geladener Comonomere möglicherweise weiter gesteigert werden. / Chemical and physical properties of polymers can influence various cell types, e.g. concerning adherence and functionality. For instance, the elasticity of a polymer can influence, which pulling force a cell can generate towards a substrate. According to the cell type, its behavior can be controlled by intracellular feedback mechanisms. The surface charge and/or hydrophilicity of a polymer initially influence the adsorption of ions, proteins and other molecules. In particular, the composition, density, and conformation of the adsorbed components mediate the cell-material interactions. Since different cell types present varying cell membrane associated proteins, sugars and lipids, it is assumed that polymer properties can induce cell specific effects. Polymers, which can regulate specific cell reactions, become more and more important for biotechnological uses and applications in the regenerative medicine. The isolation and culture of primary keratinocytes is still challenging and an adequate wound healing remains a clinical task. A polymer, which enables a preferential adherence of keratinocytes and induces a reduced adherence of dermal fibroblasts, would provide enormous advantages for keratinocyte culture systems as well as for wound dressings. To investigate the specific influence of certain polymer properties on primary human keratinocytes and fibroblasts, a cell culture system for mono- and coculture of both cell types was established. The test system was designed as a screening to investigate the influence of polymers with gradations of different properties on the cells. Thereby, the viability and density of adherent and not adhered cells, as well as the impairment of the cell membranes were analyzed in mono- and cocultures, and the selective adherence of keratinocytes in the coculture was evaluated using a specific immunocytochemical staining for keratin14 and vimentin. Furthermore, the deposition of extracellular matrix components and the secretion of soluble factors were analyzed for the elastic polymers. Since the elasticity of crosslinked poly(n-butylacrylate) (cPnBA) networks can be adjusted by the amount of the crosslinker, they were used as model polymers to investigate the influence of varying elasticity to the cells. On the less elastic cPnBA, the ratio of keratinocytes to fibroblasts was increased compared to the more elastic one. From these results, a slight cell selective effect can be assumed. Acrylonitrile-based copolymers were used as model polymers for the variation of surface charge and hydrophilicity, since their properties can be modified by the type and molar ratio of comonomers. By the variation of the molar ratio of positively charged comonomers (Methacrylic acid-2-aminoethylester hydrochloride (AEMA) and N-3-aminopropyl methacrylamide hydrochloride (APMA)), or a negatively charged comonomer (2-methyl-2-propene-1-sulfonic acid sodium salt (NaMAS)), the amount of positive or negative charges was modified. The hydrophilicity was increased by the molar ratio of the hydrophilic comonomer N-vinylpyrrolidone (NVP). With an increased molar ratio of the positively charged comonomer AEMA, a tendency towards a higher density of adherent keratinocytes could be shown, whereby, the density of adherent fibroblasts remained unaffected. With increasing molar ratios of the positively charged comonomer APMA, no differences between cell densities, viability or selectivity were detectable. Comparable to AEMA, a tendency towards improved keratinocyte adhesion could be shown with an increasing molar ratio of the negatively charged comonomer NaMAS. The increase of the hydrophilicity of the copolymers led to a reduced adherence and viability of the keratinocytes, as well as of the fibroblasts. In conclusion, a test system was established, which enables the evaluation of primary human keratinocytes and fibroblasts in contact with different polymers in monoculture, as well as in coculture. Furthermore, the present thesis shows that directed modifications of polymer properties influenced the adherence and viability of both cell types. The decrease of elasticity and the increase of the molar ratio of charged comonomers led to an increased keratinocyte adherence. Since the fibroblasts remained unaffected, slight cell selectivity was shown. By further increasing the stiffness or the amount of charged comonomers, further enhancement of this effect might be possible.

Segmental long spacing (SLS) collagen self-assembly was studied by analyzing aggregates formed from different nucleoside triphosphates at various protonation stages. Triple-negatively charged triphosphate groups were determined to be critical for SLS assembly, electrostatically bridging basic residues between collagen monomers. In the second part of this thesis, the nominal elastic modulus for each of the three forms of Type I collagen aggregate was measured and compared. Fibrous long spacing collagen, often associated with diseased tissues, exhibited lower stiffness in comparison to the other forms, native and SLS, suggesting decreased structural stability in diseased tissues. In the last section, a unidirectional pattern of native fibrils was assembled using mica as a template; the ability to customize and change the surface morphology was also demonstrated. For the first time, collagen monomers deposited on the mica were demonstrated to gain lateral mobility.

Segmental long spacing (SLS) collagen self-assembly was studied by analyzing aggregates formed from different nucleoside triphosphates at various protonation stages. Triple-negatively charged triphosphate groups were determined to be critical for SLS assembly, electrostatically bridging basic residues between collagen monomers. In the second part of this thesis, the nominal elastic modulus for each of the three forms of Type I collagen aggregate was measured and compared. Fibrous long spacing collagen, often associated with diseased tissues, exhibited lower stiffness in comparison to the other forms, native and SLS, suggesting decreased structural stability in diseased tissues. In the last section, a unidirectional pattern of native fibrils was assembled using mica as a template; the ability to customize and change the surface morphology was also demonstrated. For the first time, collagen monomers deposited on the mica were demonstrated to gain lateral mobility.

This thesis describes improvements on newly-discovered high-strength pozzolan-based materials fabricated via a low-cost chemical reaction that takes place between 90 and 115 ℃ for 3 to 24 hours. The reported results focus on pozzolan constituents acquired from Coal Combustion Products (CCPs) such as cenospheres, fly ash C and F, as well as bottom ash. The thesis reports on various types of these materials with specific gravity ranging from 0.5 to 1.6; compressive strength ranging from 300 to 3600 psi, and compressive modulus ranging from 50 to 240 ksi. In addition to their good mechanical properties under compression that are attractive for the building and construction industries, the materials further exhibit great potential for applications as energy absorption cores in sandwich construction that could extend their value in other industries including the automotive and aerospace industries. For example, the load-displacement curve exhibits a short elastic zone followed by a long load-plateau; while the materials crush through a controlled vertical cracking process. Additionally, an attempt was made to further decrease the manufacturing cost of the material by investigating incorporation of chemicals that accelerates dehydration of the mixture. One such successful chemical reported in this thesis is aluminum phosphate; while it is not conclusive how the chemical improves any major property.

In this thesis, the relationship between the elastic modulus of PDMS and the base/agent ratio (the amount of crosslinking) is studied. Reliable macroscopic compression test instrument was developed. Preload method was applied for the nanoindentation flat punch test to develop full contact. In chapter 2, an easy instrument setup for macroscopic compression test is described. A series of PDMS samples with different base/agent ratios were tested using the macroscopic compression method. The relationship between PDMS elastic modulus and its base/agent ratio was established. In chapter 3, PDMS nanoindentation DMA tests provide stable data with different test control models. The storage modulus collected using nanoindenting DMA tests is comparable with elastic modulus collected in PDMS compression test in chapter 2. Nanoindentation experiments with flat punch were also done to test the elastic modulus of PDMS network 5:1. The adhesion force tests with different nanoindentation tips, which are Berkovich tip, conical tip and cube corner tip, show that PDMS's adhesion force is related to the sample's base/agent ratio, the nanoindentating depth and the tip's geometrical shape.

The shear strength, elastic moduli and plastic strain characteristics of scaled-down ballast materials are investigated by use of the parallel gradation technique. Uniformly graded ballast materials chosen for the investigation are limestone, basalt and steel-slag. Steel-slag is a byproduct material of Eregli Iron and Steel Works, which is suitable to meet the durability test requirements as well as the electrical resistivity and the waste contaminants regulatory level. Conventional triaxial testing at a strain rate of 0.4 mm/min is used to obtain these characteristics for the scaled-down materials with a diameter of 100 mm specimen under a confining stress of 35 kPa, 70 kPa and 105 kPa / whereas that of only 35 kPa is used to characterize the accumulated plastic strain. The angle of internal friction, f, and the apparent cohesion, c, may be conservatively taken to be 42o and 35 kPa for all materials. The elastic moduli values for all materials may be predicted within an adequate estimate for the engineering purposes by using the power law parameters, K and n, determined for L-9.5 (D50 = 12.7 mm), the coarsest gradation tested for limestone. K with a reference pressure, pr = 1 kPa and n values for L-9.5, respectively, are 4365 and 0.636 for initial / 8511 and 0.419 for secant / 25704 and 0.430 for unloading-reloading elastic moduli. The unloading-reloading moduli increased, as the number of cycles increased. An increase in unloading-reloading modulus at N = 20 obtained was roughly 15% for scaled-down limestone / 10% for the basalt / and 5% for the steel-slag. The plastic strain after first cycle, &amp / #949 / 1, and the plastic strain coefficient, C can be represented as a function of mean particle size for each material type. For the limestone, basalt and steel-slag prototype size, D50 = 45 mm, &amp / #949 / 1 values of 0.59, 0.43 and 0.75 and C values of 0.54, 1.42 and 0.74 are predicted, respectively.

Made available in DSpace on 2015-05-14T12:56:02Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 1634368 bytes, checksum: 15995bdf9c8fa3e54e6dbaeeb501003d (MD5) Previous issue date: 2014-02-17 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Objectives: To analyze the effect of NaF and TiF4 varnishes on nanohardness (N) and elastic modulus (E) of enamel surface after very short exposure time to simulation of drinking a can of soft drink; and evaluate the thickness and topography of protective layer formed, by atomic force microscopy (AFM). Methods: Thirty blocks of human enamel (4x4 mm) were divided into 3 groups (n=10): control, NaF varnish and TiF4 varnish. The specimens remained in artificial saliva for 24h, and the varnishes were applied only once. After 6h, specimens were submitted to erosive challenge (10 cycles: 5s in cola drink/5s in artificial saliva). The thickness of protective layer formed and the surface topography were evaluated by optical microscope and AFM. The data were subjected to Two-Way ANOVA, Tukey and Student s-t (&#945;=0.05). Results: The values shown for N and E (GPa) before and after erosive challenge differed statistically, only for control and TiF4 groups. After the erosive challenge, NaF group showed statistically higher values for N and E than those found for control and TiF4 groups. However, the thickness and depth of indentation values showed that N and E values found for TiF4 group were related to the protective layer formed. By AFM, both varnishes showed globular protective layer formation, and the thickness of layer was significantly higher for TiF4 than NaF group. Conclusions: NaF varnish was able to protect the nanomechanical properties of enamel after short erosive challenge, and TiF4 varnish showed a thick and homogeneous protective layer formation with nanomechanical properties. Keywords: tooth erosion; elastic modulus; fluorides; microscopy, atomic force / Objetivos: Analisar o efeito dos vernizes de NaF e TiF4 na nanodureza (N) e módulo de elasticidade (E) da superfície do esmalte após um curto tempo de exposição a bebida a base de cola, simulando a ingestão de uma lata de refrigerante, e também avaliar a espessura e topografia da camada protetora formada, por meio de microscópio de força atômica (AFM). Métodos: Trinta blocos de esmalte humano (4x4 mm) foram divididos em 3 grupos (n = 10): controle (sem verniz), verniz de NaF e verniz de TiF4. As amostras permaneceram em saliva artificial durante 24 horas, e os vernizes foram aplicados apenas uma vez. Após 6h os espécimes foram submetidos a desafio erosivo (10 ciclos: 5s em bebida a base de cola/5s em saliva artificial). A espessura da camada protetora formada e a topografia da superfície foram avaliadas por microscopia óptica e AFM. Os dados foram submetidos à ANOVA Two-Way, Tukey e T- Student (&#945; = 0,05). Resultados: Houve diferença estatística dos valores de N e E (GPa), antes e após o desafio erosivo, apenas para os grupos controle e TiF4. Após o desafio erosivo o grupo NaF mostrou estatisticamente maiores valores de N e E que os grupos controle e TiF4. No entanto, os valores da espessura e profundidade da indentação mostraram que os valores encontrados de N e E para o grupo TiF4 estavam relacionados com a camada protetora formada e não com o esmalte erodido. Ambos os vernizes mostraram, por meio de AFM, a formação de uma camada protetora globular, e a espessura da camada formada foi significativamente maior para o grupo TiF4 que NaF. O verniz de NaF foi capaz de proteger as propriedades nanomecânicas de esmalte após curto desafio erosivo e o verniz de TiF4 apresentou formação de camada protetora espessa e homogênea com propriedades nanomecânicas . Conclusões: O verniz de NaF foi capaz de proteger as propriedades nanomecânicas de esmalte após curto desafio erosivo e o verniz de TiF4 apresentou formação de camada protetora espessa e homogênea com propriedades nanomecânicas.