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The non-reactive Dreiding and the reactive ReaxFF atomic potentials were applied within a family of atom molecular dynamics (MD) simulations to investigate and understand interfacial adhesion in graphene/vinyl ester composites. First, a liquid vinyl ester (VE) resin was equilibrated in the presence of graphene surfaces and then cured, resulting in a gradient in the monomer distribution as a function of distance from the surfaces. Then the chemically realistic relative reactivity volume (RRV) curing algorithm was applied that mimics the known radical addition regiochemistry and monomer reactivity ratios of the VE monomers during three-dimensional chain-growth polymerization. Surface adhesion between the cured VE resin and the graphene reinforcement surfaces was obtained at a series of VE resin “crosslink densities.” Both pristine and oxidized graphite sheets were employed separately in these simulations using a Dreiding potential. The pristine sheets serve as a surrogate for pure carbon fibers while oxidizing the outer graphene sheets serve as a model for oxidized carbon fibers. Hence, the effects of local monomer distribution and temperature on the interphase region formation and surface adhesion can be investigated. Surface adhesion was studied at various curing conversions and as a function of temperature. Uniaxial loading simulations were performed at different curing conversions for both models to predict the composites’ modulus of elasticity, Poisson’s ratio, and yield strength. The same analysis was performed for the neat cured matrix. The glass transition temperature (Tg) for the homogenized composite and neat VE matrix was determined at different degrees of curing. Subsequent MD simulations were performed to predict structural damage evolution and fracture in the neat VE matrix. The ReaxFF potential was used to quantify irreversible damage due to bond breakage in the neat VE matrix for different degrees of cure, stress states, temperatures, and strain rates. The predicted damage mechanisms in the bulk VE thermosetting polymer were directly compared to those for an amorphous polyethylene (PE) thermoplastic polymer.

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The initial objective of this research project was to determine the feasibility of manufacturing carbon fiber-reinforced (CFR) composites with a matrix consisting of a phenylethynyl-terminated version of a thermoplastic poly(etherimide) termed PETU. Successful composite manufacture with 3,000 g/mol (3k) PETU led to a survey of CFR 3kPETU mechanical properties for comparison with other high-performance composites. Encouraging results led to a study of moisture sorption effects on CFR 3kPETU properties. The success of these initial studies spawned the large scale production of 2,500 g/mol (2.5k) PETU. Thermal characterization of neat and CFR 2.5kPETU via differential scanning calorimetry, dynamic mechanical thermal analysis, and parallel plate rheometry resulted in an understanding of the influence of cure time and temperature on reaction progress via both reaction kinetics and monitoring of the glass transition temperature. From the rheological characterization, a two-stage, dual-Arrhenius model was developed to successfully model isothermal complex viscosity over the range of processing temperatures. Neat 2.5kPETU and CFR 2.5kPETU specimens were exposed separately to elevated temperature environments of different moisture and different oxygen concentrations to evaluate the effects of moisture absorption, moisture desorption, and thermal oxidation on material properties. Moisture absorption took place in a 90 °C / 85% relative humidity environment followed by moisture desorption in a 90 °C / 10% relative humidity environment. Thermal-oxidative aging for up to 5000 hours took place at 204 204 °C in environments of four different oxygen partial pressures: 0.0 kPa, 2.84 kPa, 20.2 kPa, and 40.4 kPa. Following exposure to the different aging environments, the specimens were tested for retention of mechanical properties. In addition, moisture sorption properties were measured. Results from the moisture sorption studies on CFR 3kPETU and CFR 2.5kPETU suggest that fully cured composites will withstand moisture absorption and desorption with negligible effects on mechanical properties, whereas, lack of full cure allows moisture sorption to permanently damage the composites. Despite a lack of mass loss or visual evidence of degradation following thermal-oxidative aging, a decline in mechanical properties was observed with the reduction becoming greater with longer aging times and higher oxygen partial pressures. / Ph. D.

Farmaceutická fakulta, Katedra farmaceutické technologie, Hradec Králové, 2014 Vypracovala: Markéta Valentová Školitel: Doc. RNDr. Milan Dittrich, CSc. ABSTRACT STUDY OF POLYESTER DRUG CARRIERS DEGRADATION USING THE DSC METHOD The aim of this work was focused on the study of relations among various parameters of degradation process, such as time-dependent range of glass transition temperature, swelling, erosion, and molar weight decrease. Two model polyesters of two type architectures of polyester molecules were used and monitored during two-week period. In the theoretical part of this diploma thesis are in details described biopolymers with stimulus responsive activity and exploitation of these materials in various biomedical applications in the topic of tissue engineering. The experimental part of this work is directed into the study of molecule degradation parameters, eventually into simulated biodegradation in the in vitro conditions of two different in the type polyesters with the contrast polyester molecule constitution. It was demonstrated that parameter Mn decreases towards the limit values. Between the values of molar weight and glass transition temperature is not Flory-Fox relation in the advanced phase of degradation process. The erosion of the material begins after the lag-time in the dependency...

La grande majorité des résines époxy utilisées aujourd’hui sont issues ou dérivées du bisphénol-A (BPA). Cependant, le BPA est soumis à de très fortes régulations, notamment vis-à-vis de sa récente classification comme substance chimique extrêmement préoccupante par l’agence européenne des produits chimiques (ECHA). Dans un but d’anticiper les évolutions de régulation, ArianeGroup a décidé de remplacer cette substance chimique de ces formulations. Ces travaux de thèse portent donc sur l’élaboration de nouvelles résines époxy biosourcées ayant des propriétés similaires voire supérieures aux références dérivées du bisphénol-A. Pour cela, une bioplatforme de monomères polyépoxydés issus de la vanilline, du méthyl vanillate, du 2,6-diméthoxyphénol et de l’eugénol a été développée. Ces précurseurs biosourcés ont ensuite été utilisés comme précurseurs de réseaux époxyde par réticulation avec des amines. Les réseaux réticulés biosourcés ainsi obtenus ont démontré des propriétés thermomécaniques remarquables bien supérieures à la référence de type DGEBA, notamment en termes de température de transition vitreuse (>300 °C) et taux de coke (>50%). En parallèle de ces travaux, la synthèse de diamines biosourcées, dérivées de la divanilline, et pouvant être utilisées comme agents de réticulation de résines époxy, a été réalisée. Des réseaux époxyde entièrement biosourcés ont ainsi été synthétisés et présentent des propriétés thermomécaniques prometteuses. / Today, most of the epoxy resins produced are derived from bisphenol-A (BPA). However, BPA is subject to strong regulations, particularly because of its recent classification as chemical of very high concern by the European Chemicals Agency (ECHA). In order to anticipate new regulations, ArianeGroup has decided to replace this substance in its applications. The aim of this thesis is to develop new bio-based epoxy thermosets with comparable thermomechanical properties as the ones issued from bisphenol-A-based materials. For this purpose, a bio-platform of epoxy monomers from vanillin, methyl vanillate, 2,6-dimethoxyphenol and eugenol was developed. These precursors were cross-linked with amines used as curing agent to obtain bio-based epoxy networks. The latter demonstrated thermomechanical properties well above the DGEBA-type reference, especially in terms of glass transition temperature (> 300 °C) and char content (> 50%). Finally, the synthesis of bio-based diamines derived from divanillin was developed and enabled the synthesis of fully bio-based epoxy networks with promising thermomechanical properties.

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.