La mise en place, l'étalonnage et l'utilisation d'un nouveau banc expérimental basses températures basé sur une technique photothermique appelée photo pyroélectricité (PPE) sont décrits dans ce manuscrit. Les échantillons que nous avons étudiés en utilisant ce nouvel instrument sont le glycérol, le 1,2 propanediol et leurs mélanges binaires avec l'eau. Ce sont des cryoprotecteurs bien connus (CPAs) utilisés dans la cryoconservation, qui est une technique de préservation des cellules et tissus vivants en les refroidissant à des très basses températures. Le but ultime de la cryoconservation est d'éviter ou de maîtriser la formation de glace et d'atteindre un état vitreux ou amorphe. La vitesse de refroidissement, de chauffage et la concentration des CPAs utilisés sont les paramètres clés qui déterminent la formation de la glace. Par conséquent, l'étude des propriétés thermiques, en particulier près de la transition vitreuse (Tg) des solutions binaires des CPAs avec de l'eau est très importante pour comprendre leur comportement lors du refroidissement. La PPE a été utilisée pour étudier l'effusivité et le temps de relaxation ∝ caractéristique de la transition vitreuse. Le Tg et la fragilité (m) ont été déterminés à partir des données de la PPE en utilisant le modèle d'Havriliak Negami. L'état vitreux présente une très grande viscosité, de l'ordre de 10¹² Pa.s au voisinage du Tg. Le Tg et m peuvent être calculés à partir de l'évolution de la viscosité en fonction de la température ou par calorimétrie différentielle à balayage (DSC). Ainsi, des études à l'aide de ces deux techniques ont été menées et les résultats ont été comparés avec les données de la PPE. / The construction, calibration and application of a new low temperature instrument based on a photothermal technique called photo pyroelectricity (PPE) is described in this manuscript. The samples we studied using the new PPE instrument were glycerol, 1,2 propanediol and their binary mixtures with water. These liquids are well known cryoprotectants (CPAs) used in cryopreservation, which is a technique to preserve the living cells and tissues from biological degradation by cooling to sub zero temperatures. The ultimate goal in cryopreservation is to avoid or control the ice formation and attain a glassy or amorphous state.The rate of cooling and heating and the concentration of the CPAs used are the key parameters that determine the ice formation. Therefore, studying the temperature dependent thermal properties especially near their glass transition temperature (Tg) of the binary solutions of CPAs with water at different concentrations are highly important to understand their behavior while cooling. The PPE technique was used to study the effusity and the ∝ relaxation time near the glass transition phenomenon. The Tg and fragility (m) were determined from the PPE data using the Havriliak Negami model. The glassy state has a characteristic property of very high viscosity, of the order of 10¹² Pa.s at Tg. The Tg and m can be calculated from the temperature evolution of viscosity or from Differential Scanning Calorimetry (DSC) measurements. Therefore, viscosity and DSC studies were conducted on the samples and were compared with PPE data.

O Brasil, à semelhança de outros países, está envelhecendo rapidamente. Os indivíduos com mais de 60 anos compõem hoje o segmento que mais cresce em termos proporcionais, mostrando um incremento da ordem de 500%, em 40 anos. A estimativa para o ano de 2020 é de que o Brasil tenha em torno de 32 milhões de indivíduos idosos, e desta população, uma parcela significativa será parcial ou totalmente desdentada, necessitando de aparelhos protéticos. Apesar da Odontologia apresentar avanços científicos notáveis na reabilitação da saúde bucal, muitos ainda usarão estes aparelhos. Sabe-se que o uso contínuo de próteses pode propiciar o desenvolvimento da estomatite protética, cuja etiologia é multifatorial, destacando-se principalmente a má higiene bucal e da prótese, e geralmente associada à presença de Candida albicans. Desta forma, há necessidade de se propor um método de desinfecção, que se mostre eficaz, que seja seguro quanto à toxicidade, que represente baixo risco ocupacional, que seja de fácil manuseio e que não interfira nas propriedades dos materiais utilizados na confecção destes aparelhos. Portanto, a proposição deste trabalho foi avaliar a influência de dois métodos de desinfecção, nas propriedades das resinas acrílicas empregadas na confecção das próteses.As propriedades avaliadas foram: resistência e módulo de flexão, resistência ao impacto Izod, microdureza Knoop, rugosidade, massa específica e grau de inchamento, grau de conversão do monômero, temperatura de transição vítrea, sorção e solubilidade. Os corpos de prova foram confeccionados de acordo com os requisitos de cada ensaio, tanto para os grupos controle (sem tratamento), quanto para os tratados (submetidos a um dos processos de desinfecção). Os tratamentos de desinfecção consistiram de: a) irradiação com energia de microondas na potência de 840 W, durante 1 minuto; b) imersão em ácido peracético durante 5 minutos. A eficácia da desinfecção foi avaliada através de ensaios microbiológicos que consistiram em verificar o crescimento no meio de cultura e na superfície do corpo de prova de Candida albicans, após a desinfecção dos corpos de prova, previamente contaminados com uma cepa conhecida do fungo (ATCC 10231). Como as resinas acrílicas são materiais muito utilizados em todas as áreas de atuação da Odontologia, o conhecimento das suas propriedades é de interesse do cirurgião-dentista. As resinas acrílicas tipo 1 (de termopolimerização), tipo 2 (quimicamente ativada) e tipo 5 (ativada por microondas) foram avaliadas neste trabalho. Os resultados mostraram que as resinas acrílicas tipo 1 e tipo 5 apresentam valores semelhantes em todas as propriedades analisadas. A resina acrílica tipo 2 apresentou valores inferiores àqueles encontrados nas tipo 1 e 5. O ciclo de polimerização com melhores resultados foi aquele proposto pelo respectivo fabricante daresina acrílica. A presença de fibras de nylon e de corante não influenciou as propriedades da resina acrílica tipo 5. Das técnicas de desinfecção, a imersão em ácido peracético apresentou os melhores resultados para todas as propriedades avaliadas ao longo do tempo de 20 meses. Por outro lado a irradiação de microondas, a longo prazo, apresentou os piores resultados para todas as propriedades avaliadas. Ambas as técnicas de desinfecção foram eficazes do ponto de vista microbiológico. Mas, para o uso prolongado, a técnica de desinfecção com ácido peracético pode ser recomendada com toda a segurança, no que diz respeito às propriedades avaliadas neste trabalho. / Brazil, similar to other countries, is aging quickly. The individuals with more than 60 years old compose today the segment that more grows in proportional terms, showing an increment of about 500% in 40 years. The estimate for 2020 is that Brazil has around 32 million elderly and a significant parcel of them will be partial or totally toothless, needing prosthetic equipments. In spite of notable scientific advance in the rehabilitation of the oral health, many people still will use these equipments. The continuous use of the prosthesis can propitiate the development of denture stomatitis, whose etiology is multifactorial, being generally, associated to the presence of fungus Candida albicans. Bad oral hygiene and prosthesis is still distinguished as factor of risk. Therefore, it very necessary for the elderly a efficient, safe and easy handling method of disinfection with low occupational risk and that doesn’t intervene with the properties of the materials used in the confection of these prosthetic equipments. The aim of this work is to evaluate the influence of two disinfection methods on the properties of acrylic resin used in the confection of dental prosthesis. Samples had been confectioned in accordance with the requirements of each test for the control groups (without treatment), as for the treated (submitted to one of the disinfection process). The evaluated properties had been resistance and module of flexure, Izod impact, Knoop microhardness, rugosity, specific mass and degree of swelling, degree of conversion of monomer, glass transition temperature, sorption and solubility. The treatments of disinfection had consisted of: a) irradiation with energy of microwaves, in the power of 840 W, during 1 min, or b) immersion in peracetic acid during 5 min. The effectiveness of the disinfection was evaluated by means of microbiological tests, in which was verified the occurrence of growth of Candida albicans through of culture and sample surface. For that, the samples were previously contaminated with one type of fungus (known as ATCC 10231) and, after, submitted to one of the two considered processes of disinfection. The work was studied the behavior of three commercial acrylic resins of dental use: acrylic resins of thermal polymerization, self-polymerization and polymerization for energy of microwaves (type 1, 2 and 5 respectively) from two different suppliers The results had shown that the acrylic resins of type 1 and type 5 presented similar values in all the analyzed properties. The acrylic resins of type 2 had also similar values in all the properties, but statistically lower than ones of type 1 and 5. The best polymerization cycle, which did not modify the resin properties, was that one considered by the respective manufacturer of the acrylic resin. The nylon fiber presence and colouring did not influence the properties of the acrylic resin of type 5. The first irradiation with microwaves significantlyincreased the evaluated properties and the first immersion in peracetic acid did not modify these properties, in comparison to the control groups. After 20 months, the immersion in peracetic acid did not modify the properties of the material, while the microwave irradiation showed alterations in some properties. Both disinfection techniques had been efficient of the microbiological point of view. On the basis of these results, can be concluded that the microwave irradiation after the polymerization of the material (first cycle), can be recommended, since it increased all the values of the evaluated properties, specially to the conversion degree monomer/polymer. Nevertheless, for prolonged use, the disinfection by means of the immersion in peracetic acid must be recommended, it is efficient for elimination of fungal microorganism and security, characterized for the maintenance of the properties of the acrylic resin evaluated in this work.

Thin polymer films and their properties have been investigated. The characteristics of crystalline polymers according to film thickness have been improved using polycaprolactone (PCL). The melting enthalpy of PCL has increased when the film thickness decreased and the peak melting temperature showed no significant changes with film thickness. Film thickness variation influenced surface roughness and crystal size. Optical microscope images showed the rougher surface of thicker films. The spinning time has shown no influence on film thickness and no significant changes to surface roughness. Thin films of block copolymers were used in the surface modification study; films studied included poly(styrene-b-butadiene-b-styrene) (SBS) and poly(styrene-b-isoprene-b-styrene) (SIS) and their surface modifications have been controlled using different methods of treatment. Films of SIS heated at different temperatures have shown different surface texture and roughness. Films treated at low temperature (45 °C) had smooth surfaces when compared with films heated at high temperature (120 °C and 160 °C). Phase separation of SIS heated at (120 °C and 160 °C) caused bulges of different sizes to cover the surface. The height and width of the bulges showed variation with film thickness and heating. Substrate interaction with SBS and SIS block copolymer films showed different surface texture when using the same type of substrate and different texture were obtained when SBS solutions were spun onto different substrates. It has been demonstrated that using different solvents in copolymer preparation caused different texture. Thermal and surface property variations with film thickness have been improved using amorphous polymers. Surface roughness of poly(methyl methacrylate) PMMA and disperse red 1-poly(methyl methacrylate) DR1-PMMA, PMMA has improved using thickness variation. Glass transition temperature measurement has increased when film thickness was increased. The glass transition temperature (Tg) and surface roughness of UV15 UV - curable coating polymer has been modified using UV curing and heating methods. Tg variation was observed when curing time and curing intensity were changed causing the optical properties of the polymer to be more variable. A plasma etcher caused wrinkles to occur on the surface of unheated UV15. Tg of UV15 increased when curing time increased. The Fourier Transform Infrared Spectroscopy (FTIR) spectra of cured UV15 film have shown peak variations of the ester and carbon double bond regions over the range of 1850-1700 cm-1. Urethane-Urea (UU) Polymer thin films were used to investigate optical properties and develop an optical waveguide. Absorption and transmission properties of light using non-linear optical (NLO) polymer was investigated and used in optical waveguide fabrication. Refractive indices were measured to examine UU films at two different wavelengths. A UU film of 1 µm thickness caused a maximum absorption at max = 471 nm also obtained at 810 nm wavelength. Many methods of fabrication were used; photolithography, plasma etching in a barrel reactor and thin film deposition using sputtering and evaporation. Etched depths from 1 μm to 100 μm were obtained. An optical waveguide has been prepared using plasma etching of a cured UV15 as a cladding layer on a silicon substrate.

In this study, low temperature cracking of asphalt concrete is investigated based on a laboratory experimental program including the design variables of aggregate type, gradation, asphalt content, binder grading, binder modification, and the experimental variables of cooling rate, and specimen size. The design of experiment is proposed according to the fractional factorial design principles to reduce the required number of test specimens. Mix designs are performed according to the Superpave mix design guidelines using materials obtained from the Turkish General Directorate of High-ways. In the course of this study, a test setup for thermal stress restrained specimen test for asphalt concrete is developed and used successfully to test a number of as-phalt concrete beam specimens. The same setup is also used for measuring the glass transition temperatures to obtain various thermo-volumetric properties of mixtures. Statistical methods are used to identify the effect of experimental variables on frac-ture strength, fracture temperature and other dependent variables obtained from the testing program. Statistical models are also developed to predict the fracture strength, fracture temperature and other thermo-volumetric properties of mixtures. Results of analyses show that aggregate type, binder modification, and asphalt content significantly affect both the fracture strength and fracture temperature of asphalt concrete. While the glass transition temperature is affected by only aggregate type, coefficients of contraction before and after the glass transition temperature are not influenced by any of the experimental variables. The results of this study provide an important basis to prevent low temperature cracking in asphalt concrete pavements.

Abdominal aortic aneurysms are a leading cause of death in the U.S. where 14,000 people die from aneurysm rupture and 178,000 are diagnosed each year. A novel alternative treatment for abdominal aortic aneurysms has been proposed, where a biodegradable polymer scaffold is photopolymerized in situ around the exterior of the aneurysm. This scaffold will mechanically constrain the aneurysm from further expansion, and will deliver a drug, doxycycline, to treat the underlying biological cause of the disease. In order for device development, a suitable polymer must be designed with appropriate mechanical properties, degradation rate, polymerization, and elution rate. Poly(β-amino ester) networks have been proposed as the material of choice; however, many of their structure-property relationships have yet to be determined. Therefore, the overall goal of this work is to determine the structure-property relationships of the poly(β-amino ester) networks in order to advance the design of the treatment, and has been divided into three objectives: (1) understand the structure-property relationships of poly(β-amino ester) networks, specifically the polymerization, degradation rate, and thermo-mechanical properties, (2) determine the impact of doxycycline incorporation on degradation rate and mechanical properties, (3) evaluate the effect of simulated physiological conditions on degradation rate and mechanical properties. In the initial chapters, the fundamental structure-property relationships are established between reactant chemical structure, step-growth polymerization, photopolymerization, thermo-mechanical properties, and degradation rate using a systematic approach of two homologous series of reactants. Further tailoring of degradation rate, water content, and modulus in vitro was performed by using a copolymer network. Doxycycline inhibited photopolymerization due to overlapping absorbance spectra with the photoinitiator, but full network formation occurred by increasing the photoinitiator concentration. Networks displayed varying controlled release rates, and the underlying release mechanism was determined for each network using established methods. In order to increase mechanical properties, a co-monomer, methyl methacrylate, was added to the network to increase the glass transition temperature, toughness, and deformation capacity. These co-networks displayed temporal-control of mechanical properties in simulated physiological conditions, since degradation caused a shift in the glass transition temperature, which changed the mechanical behavior of the network. The temporal-control of mechanical properties was further investigated under degradation conditions in vitro and in vivo. Due to the mechanically active loading environment in vivo, networks displayed a decrease in toughness, yet maintained mechanical properties similar to native biological tissues. These networks establish a multifunctional biomaterials platform with materials that can be easily synthesized, photopolymerized into various geometries, and sustain mechanical properties while undergoing degradation and therapeutic agent release.

O Brasil, à semelhança de outros países, está envelhecendo rapidamente. Os indivíduos com mais de 60 anos compõem hoje o segmento que mais cresce em termos proporcionais, mostrando um incremento da ordem de 500%, em 40 anos. A estimativa para o ano de 2020 é de que o Brasil tenha em torno de 32 milhões de indivíduos idosos, e desta população, uma parcela significativa será parcial ou totalmente desdentada, necessitando de aparelhos protéticos. Apesar da Odontologia apresentar avanços científicos notáveis na reabilitação da saúde bucal, muitos ainda usarão estes aparelhos. Sabe-se que o uso contínuo de próteses pode propiciar o desenvolvimento da estomatite protética, cuja etiologia é multifatorial, destacando-se principalmente a má higiene bucal e da prótese, e geralmente associada à presença de Candida albicans. Desta forma, há necessidade de se propor um método de desinfecção, que se mostre eficaz, que seja seguro quanto à toxicidade, que represente baixo risco ocupacional, que seja de fácil manuseio e que não interfira nas propriedades dos materiais utilizados na confecção destes aparelhos. Portanto, a proposição deste trabalho foi avaliar a influência de dois métodos de desinfecção, nas propriedades das resinas acrílicas empregadas na confecção das próteses.As propriedades avaliadas foram: resistência e módulo de flexão, resistência ao impacto Izod, microdureza Knoop, rugosidade, massa específica e grau de inchamento, grau de conversão do monômero, temperatura de transição vítrea, sorção e solubilidade. Os corpos de prova foram confeccionados de acordo com os requisitos de cada ensaio, tanto para os grupos controle (sem tratamento), quanto para os tratados (submetidos a um dos processos de desinfecção). Os tratamentos de desinfecção consistiram de: a) irradiação com energia de microondas na potência de 840 W, durante 1 minuto; b) imersão em ácido peracético durante 5 minutos. A eficácia da desinfecção foi avaliada através de ensaios microbiológicos que consistiram em verificar o crescimento no meio de cultura e na superfície do corpo de prova de Candida albicans, após a desinfecção dos corpos de prova, previamente contaminados com uma cepa conhecida do fungo (ATCC 10231). Como as resinas acrílicas são materiais muito utilizados em todas as áreas de atuação da Odontologia, o conhecimento das suas propriedades é de interesse do cirurgião-dentista. As resinas acrílicas tipo 1 (de termopolimerização), tipo 2 (quimicamente ativada) e tipo 5 (ativada por microondas) foram avaliadas neste trabalho. Os resultados mostraram que as resinas acrílicas tipo 1 e tipo 5 apresentam valores semelhantes em todas as propriedades analisadas. A resina acrílica tipo 2 apresentou valores inferiores àqueles encontrados nas tipo 1 e 5. O ciclo de polimerização com melhores resultados foi aquele proposto pelo respectivo fabricante daresina acrílica. A presença de fibras de nylon e de corante não influenciou as propriedades da resina acrílica tipo 5. Das técnicas de desinfecção, a imersão em ácido peracético apresentou os melhores resultados para todas as propriedades avaliadas ao longo do tempo de 20 meses. Por outro lado a irradiação de microondas, a longo prazo, apresentou os piores resultados para todas as propriedades avaliadas. Ambas as técnicas de desinfecção foram eficazes do ponto de vista microbiológico. Mas, para o uso prolongado, a técnica de desinfecção com ácido peracético pode ser recomendada com toda a segurança, no que diz respeito às propriedades avaliadas neste trabalho. / Brazil, similar to other countries, is aging quickly. The individuals with more than 60 years old compose today the segment that more grows in proportional terms, showing an increment of about 500% in 40 years. The estimate for 2020 is that Brazil has around 32 million elderly and a significant parcel of them will be partial or totally toothless, needing prosthetic equipments. In spite of notable scientific advance in the rehabilitation of the oral health, many people still will use these equipments. The continuous use of the prosthesis can propitiate the development of denture stomatitis, whose etiology is multifactorial, being generally, associated to the presence of fungus Candida albicans. Bad oral hygiene and prosthesis is still distinguished as factor of risk. Therefore, it very necessary for the elderly a efficient, safe and easy handling method of disinfection with low occupational risk and that doesn’t intervene with the properties of the materials used in the confection of these prosthetic equipments. The aim of this work is to evaluate the influence of two disinfection methods on the properties of acrylic resin used in the confection of dental prosthesis. Samples had been confectioned in accordance with the requirements of each test for the control groups (without treatment), as for the treated (submitted to one of the disinfection process). The evaluated properties had been resistance and module of flexure, Izod impact, Knoop microhardness, rugosity, specific mass and degree of swelling, degree of conversion of monomer, glass transition temperature, sorption and solubility. The treatments of disinfection had consisted of: a) irradiation with energy of microwaves, in the power of 840 W, during 1 min, or b) immersion in peracetic acid during 5 min. The effectiveness of the disinfection was evaluated by means of microbiological tests, in which was verified the occurrence of growth of Candida albicans through of culture and sample surface. For that, the samples were previously contaminated with one type of fungus (known as ATCC 10231) and, after, submitted to one of the two considered processes of disinfection. The work was studied the behavior of three commercial acrylic resins of dental use: acrylic resins of thermal polymerization, self-polymerization and polymerization for energy of microwaves (type 1, 2 and 5 respectively) from two different suppliers The results had shown that the acrylic resins of type 1 and type 5 presented similar values in all the analyzed properties. The acrylic resins of type 2 had also similar values in all the properties, but statistically lower than ones of type 1 and 5. The best polymerization cycle, which did not modify the resin properties, was that one considered by the respective manufacturer of the acrylic resin. The nylon fiber presence and colouring did not influence the properties of the acrylic resin of type 5. The first irradiation with microwaves significantlyincreased the evaluated properties and the first immersion in peracetic acid did not modify these properties, in comparison to the control groups. After 20 months, the immersion in peracetic acid did not modify the properties of the material, while the microwave irradiation showed alterations in some properties. Both disinfection techniques had been efficient of the microbiological point of view. On the basis of these results, can be concluded that the microwave irradiation after the polymerization of the material (first cycle), can be recommended, since it increased all the values of the evaluated properties, specially to the conversion degree monomer/polymer. Nevertheless, for prolonged use, the disinfection by means of the immersion in peracetic acid must be recommended, it is efficient for elimination of fungal microorganism and security, characterized for the maintenance of the properties of the acrylic resin evaluated in this work.

O Brasil, à semelhança de outros países, está envelhecendo rapidamente. Os indivíduos com mais de 60 anos compõem hoje o segmento que mais cresce em termos proporcionais, mostrando um incremento da ordem de 500%, em 40 anos. A estimativa para o ano de 2020 é de que o Brasil tenha em torno de 32 milhões de indivíduos idosos, e desta população, uma parcela significativa será parcial ou totalmente desdentada, necessitando de aparelhos protéticos. Apesar da Odontologia apresentar avanços científicos notáveis na reabilitação da saúde bucal, muitos ainda usarão estes aparelhos. Sabe-se que o uso contínuo de próteses pode propiciar o desenvolvimento da estomatite protética, cuja etiologia é multifatorial, destacando-se principalmente a má higiene bucal e da prótese, e geralmente associada à presença de Candida albicans. Desta forma, há necessidade de se propor um método de desinfecção, que se mostre eficaz, que seja seguro quanto à toxicidade, que represente baixo risco ocupacional, que seja de fácil manuseio e que não interfira nas propriedades dos materiais utilizados na confecção destes aparelhos. Portanto, a proposição deste trabalho foi avaliar a influência de dois métodos de desinfecção, nas propriedades das resinas acrílicas empregadas na confecção das próteses.As propriedades avaliadas foram: resistência e módulo de flexão, resistência ao impacto Izod, microdureza Knoop, rugosidade, massa específica e grau de inchamento, grau de conversão do monômero, temperatura de transição vítrea, sorção e solubilidade. Os corpos de prova foram confeccionados de acordo com os requisitos de cada ensaio, tanto para os grupos controle (sem tratamento), quanto para os tratados (submetidos a um dos processos de desinfecção). Os tratamentos de desinfecção consistiram de: a) irradiação com energia de microondas na potência de 840 W, durante 1 minuto; b) imersão em ácido peracético durante 5 minutos. A eficácia da desinfecção foi avaliada através de ensaios microbiológicos que consistiram em verificar o crescimento no meio de cultura e na superfície do corpo de prova de Candida albicans, após a desinfecção dos corpos de prova, previamente contaminados com uma cepa conhecida do fungo (ATCC 10231). Como as resinas acrílicas são materiais muito utilizados em todas as áreas de atuação da Odontologia, o conhecimento das suas propriedades é de interesse do cirurgião-dentista. As resinas acrílicas tipo 1 (de termopolimerização), tipo 2 (quimicamente ativada) e tipo 5 (ativada por microondas) foram avaliadas neste trabalho. Os resultados mostraram que as resinas acrílicas tipo 1 e tipo 5 apresentam valores semelhantes em todas as propriedades analisadas. A resina acrílica tipo 2 apresentou valores inferiores àqueles encontrados nas tipo 1 e 5. O ciclo de polimerização com melhores resultados foi aquele proposto pelo respectivo fabricante daresina acrílica. A presença de fibras de nylon e de corante não influenciou as propriedades da resina acrílica tipo 5. Das técnicas de desinfecção, a imersão em ácido peracético apresentou os melhores resultados para todas as propriedades avaliadas ao longo do tempo de 20 meses. Por outro lado a irradiação de microondas, a longo prazo, apresentou os piores resultados para todas as propriedades avaliadas. Ambas as técnicas de desinfecção foram eficazes do ponto de vista microbiológico. Mas, para o uso prolongado, a técnica de desinfecção com ácido peracético pode ser recomendada com toda a segurança, no que diz respeito às propriedades avaliadas neste trabalho. / Brazil, similar to other countries, is aging quickly. The individuals with more than 60 years old compose today the segment that more grows in proportional terms, showing an increment of about 500% in 40 years. The estimate for 2020 is that Brazil has around 32 million elderly and a significant parcel of them will be partial or totally toothless, needing prosthetic equipments. In spite of notable scientific advance in the rehabilitation of the oral health, many people still will use these equipments. The continuous use of the prosthesis can propitiate the development of denture stomatitis, whose etiology is multifactorial, being generally, associated to the presence of fungus Candida albicans. Bad oral hygiene and prosthesis is still distinguished as factor of risk. Therefore, it very necessary for the elderly a efficient, safe and easy handling method of disinfection with low occupational risk and that doesn’t intervene with the properties of the materials used in the confection of these prosthetic equipments. The aim of this work is to evaluate the influence of two disinfection methods on the properties of acrylic resin used in the confection of dental prosthesis. Samples had been confectioned in accordance with the requirements of each test for the control groups (without treatment), as for the treated (submitted to one of the disinfection process). The evaluated properties had been resistance and module of flexure, Izod impact, Knoop microhardness, rugosity, specific mass and degree of swelling, degree of conversion of monomer, glass transition temperature, sorption and solubility. The treatments of disinfection had consisted of: a) irradiation with energy of microwaves, in the power of 840 W, during 1 min, or b) immersion in peracetic acid during 5 min. The effectiveness of the disinfection was evaluated by means of microbiological tests, in which was verified the occurrence of growth of Candida albicans through of culture and sample surface. For that, the samples were previously contaminated with one type of fungus (known as ATCC 10231) and, after, submitted to one of the two considered processes of disinfection. The work was studied the behavior of three commercial acrylic resins of dental use: acrylic resins of thermal polymerization, self-polymerization and polymerization for energy of microwaves (type 1, 2 and 5 respectively) from two different suppliers The results had shown that the acrylic resins of type 1 and type 5 presented similar values in all the analyzed properties. The acrylic resins of type 2 had also similar values in all the properties, but statistically lower than ones of type 1 and 5. The best polymerization cycle, which did not modify the resin properties, was that one considered by the respective manufacturer of the acrylic resin. The nylon fiber presence and colouring did not influence the properties of the acrylic resin of type 5. The first irradiation with microwaves significantlyincreased the evaluated properties and the first immersion in peracetic acid did not modify these properties, in comparison to the control groups. After 20 months, the immersion in peracetic acid did not modify the properties of the material, while the microwave irradiation showed alterations in some properties. Both disinfection techniques had been efficient of the microbiological point of view. On the basis of these results, can be concluded that the microwave irradiation after the polymerization of the material (first cycle), can be recommended, since it increased all the values of the evaluated properties, specially to the conversion degree monomer/polymer. Nevertheless, for prolonged use, the disinfection by means of the immersion in peracetic acid must be recommended, it is efficient for elimination of fungal microorganism and security, characterized for the maintenance of the properties of the acrylic resin evaluated in this work.

Orientador: Maria Aparecida Silva / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-07T05:34:31Z (GMT). No. of bitstreams: 1 Katekawa_MarcelEiki_D.pdf: 5613864 bytes, checksum: f3c6dcb950a61ff8698eef8f2ed21fd8 (MD5) Previous issue date: 2006 / Resumo: O processo de secagem de sólidos induz efeitos colaterais no material seco, sendo que a redução de volume é um destes efeitos. O objetivo deste estudo é investigar as características do processo de encolhimento e propor uma estratégia para inclusão destes efeitos na simulação da secagem. Escolheu-se a banana como objeto de estudo devido a sua importância para o Brasil e à existência de alguns estudos sobre o encolhimento desta fruta. Estudou-se inicialmente o processo de encolhimento durante a secagem e os efeitos das condições de processo sobre o comportamento dimensional do material. Fatias de banana encolhem linearmente no início da secagem, mas esse comportamento não é observado para baixos teores de umidade. Como a banana possui uma estrutura potencialmente anisotrópica, o efeito do comportamento dos diferentes tecidos da fruta teve que ser levado em consideração através do estudo da transição vítrea de cada fase durante a secagem. Um dos tecidos, o mesocarpo, possui temperatura de transição vítrea de 46ºC quando seco e pode sofrer transição durante a secagem convectiva e afetar o volume final da amostra seca. Além disso, estudou-se como a umidade é compartimentalizada no interior de cada tecido pela técnica de RMN e a influência sobre o encolhimento da amostra. O mesocarpo é seco mais rapidamente, mesmo possuindo uma quantidade de umidade livre menor que o endocarpo. Finalmente, desenvolveu-se uma resolução de equações de balanço de massa e energia utilizando-se malhas não estruturadas para poder melhor adaptar o encolhimento na modelagem / Abstract: The drying process may induce collateral effects in the dry material, such as the volume reduction. The objectives of this study are to investigate the characteristics of the shrinking process and to consider a strategy for inclusion of these effects in a drying simulation. Banana was chosen as a case study due to its importance in Brazil and to the existence of some studies on the shrinking process of this fruit during drying. Initially the effects of the drying conditions on the dimensional behavior of the material were analyzed. Banana slices shrink linearly in the beginning of the drying process, though some deviation of this behavior is observed for low moisture content. As banana possesses a potentially anisotropic structure, the behavior of the different tissues from the edible fruit had to be taken into consideration through the study of the glass transition of each phase. One of the tissues, the mesocarp, has a glass transition temperature of 46ºC when totally dry and may undergo glass transition during convective drying, which affects the final volume of the dried sample. Moreover, moisture compartmentalization in the interior of each tissue was analyzed and related to the differential behavior during drying. The mesocarp is more easily dried even though it possesses a higher concentration of unbound moisture. Finally, a resolution of mass and energy balance equations using unstructured meshes in order to allow a better inclusion of the shrinkage effects in drying was developed. / Doutorado / Engenharia de Processos / Doutor em Engenharia Química

L´objectif du travail présenté dans ce manuscrit consiste à conserver les bonnes propriétés mécaniques du poly(butadiène) dihydroxytéléchélique (PBHT) tout en améliorant sa stabilité. Un des principaux verrous techniques de cette approche réside dans le fait que les doubles liaisons responsables la flexibilité du matériau sont également la cause de son vieillissement par oxydation. Les solutions proposées reposent sur l´utilisation de la métathèse comme outils de synthèse de polymères insaturés. Deux grandes voix de synthèse ont été étudiées : la polymérisation par ouverture de cycle via métathèse (ROMP) ainsi que la dépolymerisation fonctionnalisante (ADMET). Ces deux approches bien que prometteuses n’ont pas permis de sortir de la relation ciseau existante entre flexibilité et stabilité. Finalement, une solution basée sur le mélange entre deux polymères dihydroxytéléchéliques de basse température de transition vitreuse – poly(butadiene) et poly(isobutylene) a permis de répondre dans une certaine mesure aux cahier des charges. En parallèle a ces parties synthèses, une étude physique des relations structure-propriétés visant à améliorer la stabilité des oligomères a été apporté par mesure rhéologique du temps critique de réticulation. / The work reported in the following document is aiming at maintaining the good mechanical properties of diHydroxyTelechelic PolyButadiene HTPB while improving its stability. The major challenge of this approach is that the unsaturations responsible for the outstanding flexibility of the material are also rather sensitive to oxidation. The solutions presented in this study are based on the use of metathesis reactions as a tool for the design of new difunctional unsaturated oligomers. Two functionalization techniques have been investigated, on the one hand, the Ring Opening Methathesis Polymerisation (ROMP) and, on the other hand, the depolymerisation via Acyclic Diene METathesis (ADMET). Although promising, the latters proved to fall into the vicious circle consisting in simultaneously increasing the stability while losing the flexibility. Finally, a blending concept based on the mixture of two dihydroxytelechelic polymers, namely, poly(isobutylene) and poly(butadiene), could enable us to achieve our initial goal. In addition to the chapters focusing on polymer chemistry and synthesis, a physical study of the parameters influencing the aging of unsaturated oligomers have been set-up and the properties relationship using measurements of the critical time.

Dans le cadre de la recherche sur le conditionnement des déchets nucléaires issus des combustibles usés, de nouvelles formulations vitreuses sont à l’étude. Ces nouvelles matrices doivent être capables d’incorporer une importante teneur en produits de fission et actinides mineurs (PFA) tout en présentant d’excellentes propriétés en termes d’homogénéité, stabilité thermique, comportement à long terme et faisabilité technologique. Cette étude s’intéresse aux verres dits « peralumineux », c’est-à-dire à des verres présentant un excès d’ions aluminium vis-à-vis des ions compensateurs de charges (Na⁺, Li⁺ et Ca²⁺). Une approche par plan d’expériences a été réalisée afin de déterminer les relations entre la composition de systèmes peralumineux simplifiés à sept oxydes (SiO2 – B2O3 – Al2O3 – Na2O – Li2O – CaO – La2O3) et leurs propriétés physico-chimiques : viscosité, température de transition vitreuse et microstructure. Une étude structurale réalisée par spectroscopie RMN a également permis de mieux définir les rôles structuraux de Na⁺, Li⁺ et Ca²⁺ au sein des verres peralumineux ainsi que l’organisation structurale de ces matrices. Par la suite, des verres peralumineux complexes ont été élaborés et caractérisés afin d’une part, de valider la transposition des résultats entre verres simplifiés et verres complexes et d’autre part, de souligner la potentialité des verres peralumineux comme matrice de conditionnement. / Part of the Research and Development program concerning high level nuclear waste conditioning aims to assess new glass formulations able to incorporate a high waste content with enhanced properties in terms of homogeneity, thermal stability, long term behavior and process ability. This study focuses on peraluminous glasses, defined by an excess of aluminum ions Al³⁺ in comparison with modifier elements such as Na⁺, Li⁺ or Ca²⁺. A Design of Experiment approach has been employed to determine relationships between composition of simplified peraluminous glasses (SiO2 – B2O3 – Al2O3 – Na2O – Li2O – CaO – La2O3) and their physical properties such as viscosity, glass transition temperature and glass homogeneity. Moreover, some structural investigation (NMR) was performed in order to better understand the structural role of Na⁺, Li⁺ and Ca²⁺ and the structural organization of peraluminous glasses. Then, physical and chemical properties of fully simulated peraluminous glasses were characterized to evaluate transposition between simplified and fully simulated glasses and also to put forward the potential of peraluminous glasses for nuclear waste containment.