Thesis (M. S.)--Materials Science and Engineering, Georgia Institute of Technology, 2008. / Committee Chair: Kenneth Gall; Committee Member: David Bucknall; Committee Member: Karl Jacob.

Thesis (M.S.)--University of Michigan, 1952.

Thesis (M.S.)--University of Wisconsin--Madison, 1983. / Typescript. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 228-230).

No description available.

Gelatin methacrylate (GelMA) is a ubiquitous biocompatible photopolymer used in tissue engineering and regenerative medicine due to its cost-effective synthesis, tunable mechanical properties, and cellular response. Biotechnology applications utilizing GelMA have ranged from developing cell-laden hydrogel networks to cell encapsulation and additive manufacturing (3D printing). However, extrusion based 3D printing is the most common technique used with GelMA. Mask projection microstereolithography (MPµSL or µSL) is an advanced 3D printing technique that can produce geometries with high resolution, high complexity, and feature sizes unlike extrusion based printing. There are few biomaterials available for µSL applications, so 3D printing GelMA using µSL would not only add to the repertoire materials, but also demonstrate the advantages of µSL over other 3D printing techniques. A novel GelMA resin was tested with µSL to create a porous scaffold with a height and print time that has not been displayed in the literature before for a scaffold of this size. The resin consists of GelMA, deionized water, lithium phenyl-2,4,6-trimethylbenzoylphosphinate (LAP, photoinitiator), and 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid (sulisobenzone, UV blocker) and can be processed at room temperature. Four resins were tested (w/w %) and characterized for µSL printing: 20% GelMA 0.5% UV blocker, 20% GelMA 1.0% UV blocker, 30% GelMA 0.5% UV Blocker, and 30% GelMA 1.0% UV blocker. Swell testing, working curve, photo-rheology, photo-DSC (dynamic scanning calorimetry), 3D printing, and cell culture tests were performed and results showed that 30% GelMA 1.0% UV blocker had the best 3D print fidelity among resin compositions. / Master of Science / Three dimensional (3D) printing is a widely used technology to rapidly produce structures with varying degrees of complexity. 3D printing of biological components is of interest because as the world population increases, there is a lack of donors available to compensate for organ loss and tissue replacement. 3D printing offers a solution to great custom scaffolds and structures that mimic physiological geometry and properties. One printing technique is known as microstereolithography, or µSL, which uses a projector-like system to pattern ultraviolet (UV) light in specific arrangements to generate complex geometries and 3D parts. Gelatin is a material of interest for this technology because gelatin is derived from collagen, which is the most abundant protein found in the body. Gelatin can be modified so that it is reactive with UV light, and can be processed with µSL to generate 3D structures. In this work, gelatin was modified into the form of gelatin methacrylate (GelMA) in order to develop and test resin formulations for use with µSL. Four different resins were tested and characterized and the results indicated that one GelMA resin produced prints with greater fidelity and resolution than other formulations. This resin has been identified for potential applications in tissue engineering and 3D printed organ development.

Environmentally friendly processing of materials is becoming an increasingly important consideration in a wide variety of emerging technologies. Polymer processing,in particular, has benefited tremendously in this venue from numerous advances achievedusing high-pressure carbon dioxide (CO2) as a viscosity modifier, plasticizing agent,foaming agent, and reaction medium. Polymer processing in supercritical fluids has been a major interest for a portfolio of materials processing applications including their impregnation into porous matrices. Also, SCF solvents are being examined as a media for polymerization processes, polymer purification and fractionation, and as environmentally preferable solvents for solution coatings. Pressurized CO2 isinexpensive, sustainable, relatively benign, and versatile due to its gas-like viscosity and liquid-like densities, which can be controllably tuned through appropriate choice of temperature and pressure. Addition of high-pressure CO2 to polymer systems can have a profound impact on their thermodynamic properties and phase behavior, since the number of interacting species increases due to the high-pressures, so that the compressibility also increases, as well as the plasticity effects. Even then, polymers are only sparingly soluble in CO2 unless one uses an entrainer or surfactant. An addition of a liquid monomer co-solvent results in greatly enhanced polymer solubility in the supercritical fluid at rather mild conditions of lower temperatures and reduced pressures.The focus of this research is to measure, evaluate and model the phase behavior of the methyl methacrylate-CO2 and the poly (methyl methacrylate)-CO2-methyl methacrylatesystem, where methyl methacrylate plays role of a co-solvent. Cloud-point data are measured in the temperature range of 30-80ʻC, pressures as high as 300 bar, co-solvent concentrations of 27 and 48.4 wt% MMA, and varying PMMA concentrations of 0.1, 0.2,0.5, and 2.5 wt%. Solubility data is reported for these systems. The experimental results are modeled accurately using the Statistical Associating Fluid Theory (SAFT) for multi component polymer/solvent mixtures. The measured solubility data appears to be significantly different than previously published results by McHugh et al, Fluid Phase Equilibria, 1999. Thorough investigation, re-calibration of the equipment, and repetition of the measurements has proved that the measured data is entirely correct and the reference data is significantly off, which indirectly gives credit to this work and opens room for amendments of those results.

ABSRACT: This research focuses on two hydrophilic polymers that form hydrogels when they sorb water: Poly(2-hydroxyethyl methacrylate) (PHEMA) and Poly(2,3-dihydroxypropyl methacrylate) (PDHPMA). Present work in the field obviated the need to properly characterize the thermal and dielectric properties of these materials.The dielectric permittivity, e', and the loss factor, e", of dry poly(2-hydroxyethyl methacrylate) and poly(2,3-dihydroxypropyl methacrylate) were measured using a dielectric analyzer in the frequency range of 0.1Hz to 100 kHz and between the temperature range of -150 °C to 275°C. The dielectric response of the sub-Tg gamma transition of PHEMA has been widely studied before but little to no DEA data above 50°C is present in the literature. This study is the first to present the full range dielectric spectrum of PHEMA, PDHPMA and their random copolymers up to and above the glass transition region. The electric modulus formalism and several mathematical proofs were used to reveal the gamma, beta, alpha and conductivity relaxations. Dielectric analysis gives insight into the network structure of the polymer; it has been shown through thermal analyses that as the DHPMA content increased in HEMA-DHPMA copolymers the polymer matrix increased in available free volume and facilitated the movement of ions in its matrix. This is of significance as we then investigated the feasibility of using PHEMA, PDHPMA and their random copolymers as materials for a biocompatible coating for an implantable glucose sensor. The biocompatibility of hydrogels can be attributed to the low interfacial tension with biological fluids, high gas permeability, high diffusion of low molecular weight compounds, and reduced mechanical and frictional irritation to surrounding tissue. Once the biocompatibility of the hydrogels was established, the task to coat the polyurethane (PU)/epoxy coated metal glucose sensor was addressed. Plasma polymerization was found to be the most feasible technique for the application of the biocompatible hydrogel as a coating on the implantable glucose sensor. It has also been shown that thermal analysis techniques provide a mode of investigation that can be used to investigate the interfacial interactions of a novel hydroxylated, self-assembled nanoparticle with two functionally different polymers, poly(2-dihydroxyethyl methacrylate) and poly(methyl methacrylate).

Orientador: Marcelo Ferraz Mesquita / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-08-09T19:25:40Z (GMT). No. of bitstreams: 1 Oliveira_LucianaValadares_D.pdf: 36824583 bytes, checksum: 7a4d2a0d063c3cd9180327ea1a830f60 (MD5) Previous issue date: 2007 / Resumo: As distorções oriundas das técnicas de aplicação dos revestimentos estéticos sobre infraestruturas metálicas de próteses fixas podem resultar em margens cervicais desadaptadas. Este trabalho avaliou o efeito do tipo de revestimento estético, da simulação dos ciclos de cocção da porcelana e da eletroerosão sobre o desajuste de infra-estruturas implantossuportadas. Foi utilizada uma matriz metálica simulando um arco mandibular, contendo 5 pilares intermediários do tipo Microunit (Conexão Sistema de Próteses, Brasil). Sobre essa matriz, foram enceradas 40 infra-estruturas, fundidas em liga de CoCr (Remanium 2000, Alemanha). Para cada infra-estrutura, foi confeccionado um index, parafusando-se 5 réplicas em cada uma das infra-estruturas. Esse conjunto foi posicionado em gesso pedra especial com auxílio de delineador, antes da aplicação dos revestimentos estéticos, para avaliar o desajuste provocado apenas pela fase de aplicação dos revestimentos estéticos e ciclo de cocção da porcelana. As infra-estruturas foram separadas aleatoriamente: G1: resina acrílica termopolimerizável (Clássico, Clássico, Brasil); G2: resina fotopolimerizável (Versyo.com, Heraeus Kulzer, Brasil); G3: porcelana (Carmen, Dentaurum, Alemanha); G4: simulação dos ciclos de cocção da porcelana. Antes da aplicação dos revestimentos estéticos, foi realizada a avaliação do desajuste marginal sobre o index, após aperto de 10 Ncm em um único parafuso, correspondente ao implante A. Através desse procedimento, verificou-se a adaptação dos componentes C e E. O procedimento foi repetido no outro implante mais distal (E), para mensuração nos implantes A e C. As leituras foram realizadas utilizando microscópio mensurador (STN ¿ Olympus Optical, Japão). Procedeu-se o processo de eletroerosão (Tel Med Technologies, EUA), e novamente avaliação do desajuste marginal. Os resultados obtidos foram submetidos à Análise de Variância e teste de Tukey (p<0,05). Os valores de desajuste marginal das infra-estruturas antes da aplicação dos revestimentos estéticos não apresentaram diferença estatística significante entre si: G1: 56,97 µm (± 16,86); G2: 43,27 µm (± 16,49); G3: 49,26 µm (± 17,11); G4: 40,66 µm (+ 10,85). A aplicação dos revestimentos estéticos e simulação dos ciclos de cocção da porcelana aumentaram significantemente os valores médios de desajuste marginal para todos os grupos: G1: 170,01 µm (±53,98); G2: 72,32 µm (±27,49); G3: 164,84 µm (±27,67); e G4: 86,28 µm (±20,01). Os grupos G1 e G3 não apresentaram diferença estatisticamente significante entre si, mas apresentaram diferença quando comparados aos G2 e G4. Após eletroerosão, as médias de desajuste marginal apresentaram valores significamente menores para os grupos: Gl: 108, 54 µm (±40,75); G3: 109,61 µm (±24,42); e G4: 59,63 µm (±22,13). A média de desajuste marginal para o grupo de resina fotopolimerizável não apresentou diferença estatística significante: G2: 49,70 µm (±16,65). Como observado anteriormente, os grupos G1 e G3 não apresentaram diferença estatística significante, mas ambos apresentaram diferença dos grupos G2 e G4. Conclui-se que os revestimentos estéticos em resina acrílica e porcelana produzem os maiores valores de desajuste marginal para próteses implantossuportadas, enquanto a resina fotopolimerizável, os menores. A aplicação de porcelana resultou em maiores valores de desajuste marginal que apenas a simulação dos ciclos de cocção. A eletroerosão foi eficaz na redução dos desajustes marginais até os limites considerados clinicamente aceitáveis / Abstract: The demand for a passive fit of frameworks for osseointegrated endousseous implants abutments is well known, because the tightening of an inaccurate framework to the abutments can transmit stress to the bone-metal interface. The purpose of the present study was to evaluate the influence of the veneering application and porcelain firing cycle on the misfit level of implant-supported frameworks. Forty Co-Cr (Remanium 2000, Dentaurum, Germany) alloy frameworks were fabricated from a metallic index containing 5 Branemark type multi unit abutments. Analogs of the abutments were positioned to the framework, to construct an index for each framework. This index allowed the observation of the marginal gaps caused by the application of the veneering material. The frameworks were grouped (n=10): 1) heat acrylic resin (Clássico, Clássico, São Paulo, Brazil); 2) light polymerized resin (Versyo.com, Heraeus Kulzer, Brazil); 3) porcelain application (Carmen, Dentaurum, Germany); 4) simulation of porcelain firing cycle. Marginal refinement with spark erosion was conducted on specific equipment (Tel Med Technologies, U.S.A.). The marginal gap was obtained before and after the veneering materials and the spark erosion procedure, following the single screw test protocol (using a tightening force of 10 Ncm). A traveling microscope (STN ¿ Olympus Optical Co. Ltd Japan (120X) was used, tightening 10N in the titanium screw of the extremity distal implant, measuring the gaps at the central and distal implants. Data were subject Analysis of Variance followed by Tukey test (5%). Marginal gap mean values of the frameworks before the veneering application were not significantly different: G1: 56.97(± 16.86); G2: 43.27(± 16.49); G3: 49.26(± 17.11); G4: 40.66(± 10.85). The application veneering materials and the simulation of porcelain firing cycle increased significantly the misfit mean values of all groups: G1: 170.01 µm (±53.98); G2: 72.32 µm (+±27.49); G3: 164.84 µm (±27.67); e G4: 86.28 µm (±20.01). There were no significant differences between G1 and G3, but they were significantly different from both G2 and G3. After the spark erosion process, marginal gap mean values decreased significantly for the following groups: G1: 108. 54 µm (±40.75); G3: 109.61 µm (±24.42); and G4: 59.63 µm (±22.13). The light curing group decreased the marginal gap mean values, but not significantly after the spark erosion procedure: G2: 49.70 µm (±16.65). As occurred after the application of veneering materials, G1 and G3 groups did not show significant difference, but they both were significantly different from G2 and G4 groups. It can be concluded that heat cured acrylic resin and porcelain produced the highest mean values of marginal gaps, while light cured acrylic resin, the lowest. The application of porcelain produced higher misfit values than the simulation of porcelain firing cycles only. The spark erosion procedure was efficacious in reducing the frameworks marginal gaps to the levels clinically accepted for all groups evaluated. / Doutorado / Protese Dental / Doutor em Clínica Odontológica

Orientadores: Leila Peres, Jose Luiz Trochmann / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-12T03:11:40Z (GMT). No. of bitstreams: 1 Lucente_AnaGlauciaBogalhos_M.pdf: 1102673 bytes, checksum: b3cbcd44fdb8348cba4293d33498fee3 (MD5) Previous issue date: 2008 / Resumo: A redução no uso de compostos orgânicos voláteis (VOC) é uma demanda ambiental constante. Emulsões poliméricas aquosas com baixo conteúdo de surfactantes, produzidas pela síntese de miniemulsão direta são usadas com vantagens como substitutas a emulsões com solventes orgânicos, assim como a emulsões aquosas com altos teores de surfactantes. A água como fase contínua e monômeros orgânicos com baixa solubilidade em água, são usados. Essas emulsões podem ser termodinamicamente ou cineticamente estabilizadas com agentes surfactantes e ou hidrófobos. Na polimerização por radical livre em miniemulsão o sítio orgânico estabilizado atua como um mini-reator, formando uma dispersão polimérica estável. Dependendo da técnica de preparação utilizada e das taxas de conversão, vários diâmetros médios de partículas (Dp) e distribuição de tamanho (DSD) podem ser obtidos. Das várias técnicas de polimerização em emulsão a miniemulsão se destaca, por poder ser estabilizada cineticamente o que permite reduzir o uso de surfactantes em tipo e quantidade aplicadas, onde as gotículas monoméricas podem ser formadas por cisão da fase orgânica ou por fusão de gotículas ainda menores, cineticamente estabilizadas por agentes surfactantes e ou hidrófobos resultando em nanopartículas. O meio aquoso permite altíssimas taxas de transferência de calor e taxas de transferência de massa adequadas para taxas de polimerização moderadas e altas. Nesse trabalho um polímero acrílico com propriedades físicas específicas para o desenvolvimento de materiais aplicados a área odontológica foi a força motriz na obtenção de um copolímero de metacrilato de metila (MMA) e metacrilato de etila (EMA) dada sua razão de reatividade de 1,08 e 0,98 respectivamente, o que teoricamente leva a obtenção de um copolímero estatístico ou aleatório. O efeito da temperatura (50, 60 e 80°C) na conversão global e na cinética da reação, o Dp e a DSD, a temperatura de transição vítrea (Tg) e a temperatura de fusão (Tf) do copolímero obtido foram estudados por meio de análise gravimétrica, espectrometria de espalhamento de laser (LSS) e calorimetria diferencial de varredura (DSC). O material sintetizado a 60ºC foi também caracterizado com as g/mol. Da caracterização realizada (RMN, FTIR e DSC) foi possível concluir que foi obtido como esperado um copolímero, possivelmente do tipo aleatório ou alternado. técnicas de espectrometria de infravermelho, (FTIR), ressonância magnética nuclear (MNR) para a verificação das funções orgânicas e cromatografia de permeação em gel (GPC) na determinação da massa molar média e sua distribuição. A adição de agente hidrófobo e o uso de ultra-som tornaram possível a obtenção de partículas poliméricas tão pequenas quanto 280nm, com polidispersividade de 1,6 e massa molar média de 2,16 x 106 g/mol. Da caracterização realizada (RMN, FTIR e DSC) foi possível concluir que foi obtido como esperado um copolímero, possivelmente do tipo aleatório ou alternado. / Abstract: Reduction of volatile organic compounds (VOC) usage is a constant environmental demand. Polymeric aqueous emulsion of low surfactant contends produced from direct miniemulsion synthesis are used with advantages to replace organic solvents media as well as aqueous emulsions of high surfactant concentration. Water as continuous phase and organic monomers with low solubility in water are used. This emulsion can be thermodynamically or kinetically stabilized by surfactant agents and / or hydrophobic agents. In free radical miniemulsion polymerization the stabilized organic site acts as a reactor, forming a kinetically stable polymeric dispersion. Depending on the emulsion preparation technique and polymerization rates, at the end of polymerization, several mean particle diameters (Dp) and several size particle distributions (DSD) are possible. Among the emulsion polymerization techniques, miniemulsion polymerization stands out, since kinetic stabilization allows to reduce the need for different types and large amounts of surfactants, where the reaction sites are the monomer droplets formed from scission of the monomer phase or by fusion of even smaller droplets, kinetically stabilized by surfactants and hydrophobic agents resulting in nanoparticles. The water media allow outstanding heat transfer rates as well as mass transfer rates that do not interfere in conversion rates from moderate to high. On this work, a methacrylate polymer based with specific physical properties for the development of materials for Dentistry application, drove the choice of the copolymer obtained from methyl methacrylate (MMA) and ethyl methacrylate (EMA) monomers as they reactivity ratios were: 1.08 and 0.98, respectively, which theoretically would allow obtaining a statistical or random copolymer. Polymerization temperature effect (50, 60 and 80oC) on: overall conversion and kinetic reaction, Dp, DSD, glass transition temperature (Tg) and melting temperature (Tf) of the obtained copolymer, were studied using gravimetric analysis, laser spectrometry spreading (LSS) and differential scanning calorimetry (DSC). The synthesized copolymer at 60o C was also characterized by Fast Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance analysis (NMR) for verification of copolymer organic functions, and gel permeation chromatography (GPC) to determine distribution and mean molar mass. The addition of hydrophobic agent and the use of ultrasound, made possible to obtain volumetric particle diameter as low as 280 nm and polydispersity of 1.60 with average molar mass of 2.16 x 106 g/mol. From the polymer characterization (RMN, FTIR e DSC) it was possible to conclude that a random or alternating copolymer was obtained, as expected. / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

In this paper, we discuss the effect of the hydrogen-bonding on the photoluminescent(PL) properties of 1-pyrenecarboxylic acid (PCA)/ poly(methyl methacrylate) (PMMA). Isolated fluorophore can be obtained when PCA molecules were blended and septrated by PMMA, i. e. excimer emission can be more efficiently prevented. With the use of non-solvent, toluene, in the preparation step, excimer emission of PCA can be more effeiciently prevented as compared to the good solvent, tetrahydrofuran(THF). With a high PMMA/PCA ratio of 1000/1, emission spectra show no sign of excimer formation. Intermolecular hydrogen bonding between PMMA and PCA helps to prevent the excimer formation. Solvents used in the preparative state play important role on the final PL properties of the solid film. In the blend, partial carbonyl groups in PMMA band with carboxylic acid group in PCA, this causes the appearance of a stretching band at 1718 cm-1 in infrared spectroscopy. The hydrogen-bond interactions help to the prevention of excimer formation in the PMMA/PCA blending systems.