Sub-surface modification using a frequency doubled Ti: Sapphire femtosecond (fs) laser at 1kHz repetition rate, producing 100-fs pulse duration at 400nm, is studied in order to fabricate optical components within non-photosensitised polymethyl methacrylate (PMMA). This thesis explores the feasibility of producing three-dimensional optical devices in bulk polymers and polymer optical fibre (POF) using fs laser direct-writing techniques. For effective and optimal structuring, the laser writing parameters and focusing conditions, such as focusing depth, translation speed, and accumulated fluence are investigated by means of photo-modification thresholds; structural changes in dimensions and morphologies; and the magnitude of the refractive index modulation. The highest refractive index change is 3.2x10^(-3) achieved by using a dry (non-immersion) 0.45-NA objective for a single laser scan. Variations in damage threshold with focusing depths are attributed to a combination of material absorption or surface scattering of light due to contamination or surface imperfections, as well as oxygen diffusion and spherical aberration. Distortion of the laser-induced feature size and shape due to spherical aberrations is controlled and compensated by adjusting the laser power near the damage threshold. Permanent refractive index structures with cross-sectional dimensions of 2μm by 0.9μm and 3μm by 1.4μm are demonstrated at depths of 300μm and 500μm below the surface, resulting in the axial/ lateral ratio of 2.2 and 2.1, respectively. A novel phenomenon relevant to effects of translation speed on the fs laser modification is observed for the first time. As translation speeds reduce from 1.2 to 0.6mm/s, the optical damage threshold power decreases by 6μW, whilst other writing conditions remain constant. However, the damage threshold increases by 74μW with decreasing speeds from 0.6 to 0.35mm/s. This significant increase in threshold power enables inscription of refractive index gratings <5μm below the surface, because irradiation on the surface or near the surface initiates ablation rather than refractive index changes, and this forms a limit for writing useful structures. Compensating for this limit by using appropriate writing parameters highlights the potential of fabricating three-dimensional integrated optical circuits in thin (100μm) polymer substrates. Finally, highly localised fabrication of long period gratings into step-index single mode polymer fibres is demonstrated by removing distortion effects due to the curved surface. The distortion is compensated by sandwiching the fibre with two flat PMMA sheets, between which index-matching oil (n=1.5) is injected. This arrangement enables precise laser micro-structuring with flat interfaces and continuous inner material. The first demonstration of a 250-μm-period fibre grating, resulting in attenuation bands in the visible spectral region at 613, 633, 728, 816, 853, 877 and 900nm, is presented.

Este estudo teve o objetivo de avaliar in vitro a influência da alteração dimensional de resinas acrílicas para base de prótese total submetidas a diferentes formas de processamento sobre a posição da cabeça da mandíbula, buscando estabelecer uma possível relação com a etiologia das disfunções crânio-mandibulares nos pacientes usuários desse tipo de prótese. Foram duas etapas: a primeira parte enfocou o papel do tipo de prensa (Getom ou de cozimento) e da força de prensagem para fechamento da mufla (1000 ou 1500 kgf) utilizados no processamento de duas resinas: Lucitone 550 e QC–20 e somente da força de prensagem para a resina Acron MC. Já a segunda parte do estudo teve o intuito de avaliar a influência dos ciclos de polimerização curtos e longos na alteração dimensional de cinco resinas: as mesmas três da primeira parte, além da Clássico e Ondacryl. As próteses superiores acrilizadas foram remontadas em articulador totalmente ajustável, tendo como referência a posição de máxima intercuspidação (MIC). Nessa posição de maior estabilidade oclusal, foi vazado gesso tipo IV no espaço entre as esferas condilares do articulador e as paredes dos estojos condilares. Após a cristalização, esses corpos-de-prova de gesso foram removidos do estojo condilar e suas dimensões medidas e submetidas à análise estatística por meio de um modelo de análise de variância com medidas repetidas que permitiu concluir que houve variações na posição da “cabeça da mandíbula” em 625 das 630 medidas efetuadas; as médias de movimentação condilar variaram de 0,118 (DP = 0,0968) a 1,956 mm (DP = 0,414) e ocorreram principalmente no sentido posterior do lado esquerdo; na maioria dos casos em que a força de prensagem agiu como fator devariação, os deslocamentos obtidos com 1500 kgf foram menores do que aqueles obtidos com 1000 kgf; nos casos em que o tipo de prensa agiu como fator de variação, ora os menores deslocamentos foram obtidos com a prensa de cozimento, ora com a Getom; o ciclo empregado na polimerização não influenciou significativamente na estabilidade dimensional das próteses totais e a única diferença encontrada envolveu a resina Clássico, que levou aos maiores deslocamentos no sentido posterior do lado esquerdo. / The purpose of this study was to evaluate in vitro the influence of dimensional changes in denture base acrylic resins submitted to different processing methods on the position of the mandibular condyle. This was done to establish a relation between these dimensional changes and the etiology of temporomandibular disorders in complete denture wearers. This research was divided into two parts. The first part focused on the type of press (conventional water bath or Getom), on the pressing force for flask closure (1000 or 1500 kgf) when processing Lucitone 550 and QC-20 resins, and on the pressing force when processing Acron MC resin. The purpose of the second part was to evaluate the influence of polymerization time on the dimensional stability of five resins, namely Lucitone 550, QC-20, Acron MC, Clássico and Ondacryl. The polymerized upper prostheses were remounted on a fully adjustable articulator, using the maximal intercuspal position (MIP) as reference. Type IV dental stone was poured into the space between the condylar spheres and the condylar walls. After the dental stone dried, the samples were removed from the articulator and their dimensions were measured and submitted to analysis of variance with repeated measures. The following conclusions were drawn: 625 from 630 measurements done showed changes in the position of the “mandibular condyle” and mean values for condylar movement ranged from 0.118 (SD = 0.0968) to 1.956 mm (SD = 0.414) and occurred mainly in the posterior direction on the left side; in most cases where the pressing force influenced the condylar position, the changes were smaller in 1500 kgf group than in the 1000 kgf group; in the cases where the type of press influenced the changes in condylar position, the smallest values were found in both groups, sometimes with Getom and other times with conventional water bath press; polymerization time did not significantly affect the dimensional stability of the dentures and the greatest changes occurred in the posterior direction on the left side with Clássico resin.

Indentation hardness, H, has been widely used to characterize the mechanical properties of materials for more than a century because of the following advantages of this technique; (1) it requires small sample and (2) the test is non destructive in nature. Recent technological advances helped in the development of instrumented indentation machines which can record the load, P, vs. displacement, h, data continuously during indentation with excellent load and displacement resolutions. From these, H and the elastic modulus, E, of the indented material can be obtained on the basis of the ‘contact area’ of the indentation at the maximum load. The estimation of true contact area becomes difficult during ‘pile-up’ and ‘sink-in’, commonly observed phenomena while indentation of a low and high strain hardened materials. In order for the better understanding of these phenomena it is important to understand the plastic flow distribution under indenters. It is also important for the prediction of elastic-plastic properties from the P-h data. Recently, there have been considerable theoretical and simulation efforts on this front with a combination of dimensional analysis and finite element simulations. One of the important input parameter for the dimensional analysis is the ‘representative strain’ under the indenter, which is a strong function of the indenter geometry. However there is no comprehensive understanding of the representative strain under the indenter despite several studies till date. One objective of the present thesis is to conduct an experimental analysis of the plastic flow during the sharp indentation. The plastic zone size and shape under conical indenters of different apex angles in a pure and annealed copper were examined by employing the subsurface indentation technique to generate the hardness map. From these isostrain contours are constructed joining the data having similar strain values. The following are the key observations. (1) The plastic strain contours are elliptical in nature, spreading more along the direction of the indenter axis than the lateral direction. (2) The magnitude of the plastic strain in the contact region decreases with increasing the indenter angle. (3) The strain decay in the indentation direction follow a power-law relation with the distance. The estimated representative strains under the indenters, computed as the volume average strain within the elastic-plastic boundary, decreases with increasing indenter angle. We also performed finite element simulations to generate plastic flow distribution under the indenter geometries and compared with the experimental results. The results suggest that the experimental and computed average strains match well. However, the plastic strain contours do not, suggesting that further detailed understanding of the elasto-plastic deformation underneath the sharp indenter is essential before reliable estimates of plastic properties from the P-h curves can be made routinely. The second objective of this thesis is to understand plastic flow in amorphous alloys. It is now well established that plastic deformation in metallic glasses is pressure sensitive, owing to the fundamentally different mechanisms vis-à-vis the dislocation mediated plastic flow in crystalline metals alloys. Early work has shown that the pressure sensitivity of amorphous alloys gets reflected as high constraint factor, C (hardness to yield stress ratio), which sometimes exceed 3.0. In this thesis, we study the temperature dependence of pressure sensitive plastic flow in bulk metallic glasses (BMGs) using C as the proxy for the pressure sensitivity. Experiments on three different BMGs show that C increases with temperature hence the pressure sensitivity. In addition we have carried out finite element simulations to generate P-h curves for different levels of pressure sensitivities and match them with the experimental curves that are obtained at different temperatures. Simulations predict that higher pressure sensitivity index values are required to match the experimental curves at high temperatures confirming that the pressure sensitivity increases with increasing temperature. The fundamental mechanisms responsible for the increase in pressure sensitivity are discussed in detail. Finally we pose a question, is the increase in pressure sensitivity with temperature is common to other amorphous materials such as strong amorphous polymers? In order to answer this question we have chosen PMMA, a strong amorphous polymer. In this study also we have taken C as a proxy to index the pressure sensitivity. Indentation stress-strain curves are constructed at different temperature using spherical indentation experiments. The C values corresponding to different temperatures are determined and plotted as a function of temperature. It is found that C increases with temperature implying that the pressure sensitivity of amorphous polymers also increases with temperature. The micro-mechanisms responsible for the increase in pressure sensitivity are sought.

Orientador: Ana Lucia Machado / Resumo: Devido ao aumento da tolerância dos microrganismos aos antimicrobianos atualmente disponíveis, existe a necessidade de desenvolvimento de métodos alternativos para o controle das infecções. Na primeira etapa dessa pesquisa, óxidos bimetálicos foram sintetizados por meio dos métodos hidrotermal assistido por micro-ondas e co-precipitação, variando-se as condições de síntese, como temperatura, pH, utilização ou não de surfactantes e tipos de solventes. Os diferentes microcristais de tungstato de prata (α-Ag2WO4) e molibdato de prata (β-Ag2MoO4) obtidos foram caracterizados por difração de Raios X (DRX), microscopia eletrônica de varredura por emissão de efeito de campo (MEV-EC), microscopia eletrônica de transmissão (MET), espectroscopia de energia dispersiva de raios-X (EDX), espectroscopia Raman e mensurações de fotoluminescência (PL) e UV-Vis. A atividade antimicrobiana desses compostos contra células planctônicas de Staphylococcus aureus resistente à meticilina - SARM, Escherichia coli (E. coli) e Candida albicans (C. albicans) foi avaliada por meio da determinação das concentrações inibitórias (CIM) e bactericida/fungicida mínimas (CBM/CFM). Além disso, com base nos testes de CIM, CBM e CFM, os compostos que proporcionaram os melhores resultados (α-Ag2WO4 irradiado e α-Ag2WO4 e β-Ag2MoO4, ambos sintetizados em álcool) foram também avaliados quanto à inibição da formação de biofilmes de SARM, E. coli e C. albicans, através de contagem de unidades formadoras de colônias por ... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Due to the increased tolerance of the microrganisms to the available antimicrobial drugs, there is a need of development of alternative methods for infection control. In the first part of this study, bimetallic oxides were synthesized by hydrothermal microwave-assisted and coprecipitation methods, varying synthesis conditions, as presence or absence of surfactants and types of solvents used. The different microcrystals of α-Ag2WO4 and β-Ag2MoO4 obtained were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), energy diffraction spectroscopy (EDS), Raman spectroscopy and photoluminescence measurements (PL) and UV-Vis. Their antimicrobial activity was evaluated against planktonic cells of methicillin - resistant Staphylococcus aureus - MRSA, Escherichia coli (E. coli) and Candida albicans (C. albicans) by the determination of inhibitory concentrations (MIC) and bactericidal/fungicidal concentrations (MBC/MFC). Based on the MIC, MBC and MFC values, the microcrystals that provided the best results (α-Ag2WO4 irradiated and α-Ag2WO4 and β-Ag2MoO4, both synthesized in alcohol) were also evaluated for their ability to inhibit biofilm of MRSA, E. coli and C. albicans, by counting the CFU/mL, dry weight determination, and analysis using confocal laser scanning microscopy (CLSM) and FE-SEM. Other method for infection control evaluated in the second part of this research, was the deposition of SiO2/Ag thi... (Complete abstract click electronic access below) / Doutor

Indiana University-Purdue University Indianapolis (IUPUI) / Background: Interim restoration for a lost anterior tooth is often needed for temporary esthetic and functional purposes. Materials for interim restorations usually have less strength than ceramic or gold and can suffer from fracture. Several approaches have been proposed to reinforce interim restorations, among which fiber reinforcement has been regarded as one of the most effective methods. However, some studies have found that the limitation of this method is the poor polymerization between the fibers and the composite resin, which can cause debonding and failure. 64 Purpose: The purpose of this study was to investigate the effects of different polymerization methods as well as fiber types on the mechanical behavior of fiberreinforced composite resin. Material and Methods: A 0.2-mm thick fiber layer from strip fibers or mesh fibers embedded in uncured monomers w as fabricated with polymerization (two-step method) or without polymerization (one-step method), on top of which a 1.8-mm composite layer was added to make a bar-shape sample, followed by a final polymerization. Seventy-five specimens were fabricated and divided into one control group and four experimental groups (n=15), according to the type of glass fiber (strip or mesh) and polymerization methods (one-step or two-step). Specimens were tested for flexural strength, flexural modulus, and microhardness. The failure modes of specimens were observed by scanning electron microscopy (SEM). Results: The fiber types showed significant effect on the flexural strength of test specimens (F = 469.48; p < 0.05), but the polymerization methods had no significant effect (F = 0.05; p = 0.82). The interaction between these two variables was not significant (F = 1.73; p = 0.19). In addition, both fiber types and polymerization steps affected the flexural modulus of test specimens (F = 9.71; p < 0.05 for fiber type, and F = 12.17; p < 0.05 for polymerization method). However, the interaction between these two variables was not significant (F = 0.40; p = 0.53). Both fiber types and polymerization steps affected the Knoop hardness number of test specimens (F = 5.73; p < 0.05 for polymerization method. and F = 349.99; p < 0.05 for fiber type) and the interaction between these two variables was also significant (F = 5.73; p < 0.05). SEM images revealed the failure mode tended to become repairable while fiber reinforcement was 65 existed. However, different polymerization methods did not change the failure mode. Conclusion: The strip fibers showed better mechanical behavior than mesh fibers and were suggested for use in composite resin reinforcement. However, different polymerization methods did not have significant effect on the strength and the failure mode of fiber-reinforced composite

No / To determine whether Hartmann-Shack wavefront sensing detects differences in optical performance in vivo between poly(methyl methacrylate) (PMMA) and foldable acrylic intraocular lenses (IOLs) and between clear corneal and scleral tunnel incisions and whether optical differences are manifested as differences in visual performance. SETTING: Department of Optometry, University of Bradford, West Yorkshire, United Kingdom. METHODS: This study comprised 74 subjects; 17 were phakic with no ocular pathology, 20 had implantation of a Pharmacia 722C PMMA IOL through a scleral tunnel, 21 had implantation of an Alcon AcrySof IOL through a scleral tunnel, and 16 had implantation of an AcrySof IOL through a corneal incision. Visual acuity and contrast sensitivity testing, ocular optical quality measurement using Hartmann-Shack wavefront sensing, and corneal surface measurement with a videokeratoscope were performed in all cases. RESULTS: There were significant differences between groups in the total root-mean-square (RMS) wavefront aberration over a 6.0 mm pupil (F=3.91; degrees of freedom=3,70; P<.05) mediated at the 4th-order RMS, specifically spherical and tetrafoil aberrations. The PMMA-scleral group had the least aberrations and the AcrySof-corneal group the most. For a 3.5 mm diameter pupil, the total higher-order RMS wavefront aberration was not significantly different between the groups (P>.05). There were no differences between groups in corneal shape, visual acuity, or contrast sensitivity. CONCLUSIONS: Implantation of the spherical PMMA IOL led to a slight reduction in total wavefront aberration compared to phakic eyes. AcrySof IOLs induced more aberrations, especially spherical aberration. Corneal-based incisions for IOL implantation compounded this increase. Studies of the optical performance of IOLs in vivo should use wavefront sensing as the main outcome measure rather than visual measures, which are readily confounded by multiple factors.

Made available in DSpace on 2017-07-24T19:22:01Z (GMT). No. of bitstreams: 1 Rosana Marques Silva Figueroa.pdf: 3807885 bytes, checksum: 3650be97bf0d582c6f9fac01fcff5ea1 (MD5) Previous issue date: 2016-02-12 / Fundação Araucária de Apoio ao Desenvolvimento Científico e Tecnológico do Paraná / The aim of this study was to determine a microwave polymerization cycle that resulted in adequate physicomechanical and biological properties for the denture base acrylic resins polymerized in water bath (Vipi Cril-VC, VIPI®) or processed by microwave energy (Vipi Wave-VW, VIPI®). The evaluated polymerization cycles were: 1) WB (water bath) = (65ºC during 90 min + boiling during 90 min), recommended cycle for the VC resin; 2) M630/25 = 10 min at 270 W + 5 min at 0 W + 10 min at 360 W, recommended cycle for VW resin; 3) M650/5 = 5 min at 650 W; 4) M550/3 = 3 min at 550 W. The following properties were evaluated: degree of conversion (n=6), cytotoxicity (n=9), porosity (n=10), water sorption and solubility (n=10), and surface roughness and color stability (n=5) after immersion in potential colorant beverages and simulated toothbrushing. Data were submitted to analysis of variance ANOVA-2 way followed by Bonferroni’s test for degree of conversion and color stability, ANOVA-2 way for porosity and cytotoxicity, ANOVA-2 way followed by HSD Tukey’s test for water sorption and solubility, and ANOVA-3 way followed by Bonferroni’s test for surface roughness (α=0.05). For VC resin, there was no significant difference among the groups for degree of conversion. For VW resin, the lowest degree of conversion values appeared in the M630/25 and M650/5 cycles (P<0.05). Degree of conversion values ranged from 66.9 to 85.9%. There was no difference between the materials and experimental groups for cytotoxicity and all conditions resulted in non-cytotoxic effects. Porosity mean values below 1.52% with no significant difference among groups for both materials were observed. Resins showed water sorption and solubility values without a significant difference. The highest water sorption (2.43%) and solubility (0.13%) values were obtained for WB and M550/3, respectively (P<0.05). After immersion in coffee, M550/3 and WB groups of VC resin showed the highest and the lowest roughness values, respectively (P<0.05). There was also an increase in roughness of M550/3 group after immersion in wine (P<0.05). For VW resin, M650/5 group presented rougher surface after immersion in coffee (P<0.05). There was no difference in color among cycles for VW resin and VC resin showed more changes (P<0.05). All medium values were classified as acceptable, exception for VW resin (M630/25 group) which presented NBS=4.88 after immersion in wine. Vipi Cril conventional resin can be polymerized in microwave without impairment to the evaluated properties. According to the obtained results, the better experimental condition was the microwave polymerization at 650 W for 5 min for Vipi Cril. / O objetivo deste estudo foi determinar um ciclo de polimerização em micro-ondas que resultasse em propriedades físico-químicas e biológicas satisfatórias para resinas acrílicas termopolimerizáveis para base de prótese processadas em banho de água (Vipi Cril-VC, VIPI®) ou por energia de micro-ondas (Vipi Wave-VW, VIPI®). Os ciclos de polimerização avaliados foram: 1) BA (banho de água) = (65ºC por 90 min + 90 min em ebulição), ciclo recomendado para a resina VC; 2) M630/25 = 10 min a 270 W + 5 min a 0 W + 10 min a 360 W, ciclo recomendado para a resina VW; 3) M650/5 = 5 min a 650 W; 4) M550/3 = 3 min a 550 W. Foram avaliadas as seguintes propriedades: grau de conversão (n=6), citotoxicidade (n=9), porosidade (n=10), sorção de água e solubilidade (n=10) e rugosidade de superfície e estabilidade de cor (n=5) após imersão em líquidos potencialmente corantes e escovação simulada. Os resultados obtidos foram submetidos à análise de variância ANOVA-2 fatores seguida pelo teste de Bonferroni para grau de conversão e estabilidade de cor, ANOVA-2 fatores para porosidade e citotoxicidade, ANOVA-2 fatores seguida pelo teste de Tukey HSD para sorção de água e solubilidade e ANOVA-3 fatores seguida pelo teste de Bonferroni para rugosidade de superfície (α=0,05). Não houve diferença significante entre os grupos para os resultados de grau de conversão da resina VC. Para a resina VW, os valores mais baixos de grau de conversão foram obtidos nos ciclos M630/25 e M650/5 (P<0,05). Os valores médios de grau de conversão foram entre 66,9% e 85,9%. Não houve diferença entre os materiais e os grupos experimentais para os resultados de citotoxicidade e todas as condições resultaram em efeitos não citotóxicos. Foram observados valores médios de porosidade inferiores a 1,52%, sem diferença significante entre os grupos para ambos os materiais. As resinas apresentaram valores de sorção de água e solubilidade sem diferença estatisticamente significante entre elas. Os valores mais altos de sorção de água (2,43%) e de solubilidade (0,13%) foram obtidos nos grupos BA e M550/3, respectivamente (P<0,05). Com a imersão em café, os grupos M550/3 e BA da resina VC apresentaram os maiores e os menores valores de rugosidade de superfície, respectivamente (P<0,05). Também houve aumento da rugosidade do grupo M550/3 após imersão no vinho tinto (P<0,05). Para a resina VW, o grupo M650/5 demonstrou superfície mais rugosa após imersão em café (P<0,05). Não houve diferença de cor entre os ciclos para a resina VW e a resina VC apresentou mais alterações (P<0,05). Todos os valores médios de estabilidade de cor foram classificados como aceitáveis, exceto para a resina VW (grupo M630/25) que apresentou NBS=4,88 após imersão em vinho tinto. A resina Vipi Cril formulada para polimerização convencional pôde ser polimerizada em micro-ondas sem prejuízo às suas propriedades avaliadas. De acordo com os resultados obtidos, a melhor condição experimental foi a polimerização da resina Vipi Cril em micro-ondas a 650 W por 5 min.

Indiana University-Purdue University Indianapolis (IUPUI) / Provisional restorative treatment is an essential part of fixed prosthodontics. Incorporation of adequately constructed provisional restorations will enhance the success rate of definitive restorations. Repairing or replacing failed provisional restorations is a concern for both clinicians and patients. The objective of this investigation was to study the effects of alumina nanofibers reinforcement on the mechanical properties of commercially available provisional fixed partial denture PMMA material. The hypothesis was that the addition of alumina nanofibers to commercially available PMMA resin will significantly increase its flexural strength, fracture toughness, and microhardness. Alumina nanofibers at 0.0 wt %, 0.5 wt %, 1.0 wt %, and 2.5 wt % were added to commercially available provisional fixed partial material (Jet Tooth Shade). A quaternary ammonium acetate dispersant (CC-59, Goldschmidt, Janesville, WI) was added to the acrylic monomer at 0.0 wt %, 1.0 wt %, 2.0 wt % and 5.0 wt % of the nanofiber weight (12 test groups, 1 control). Samples from each group were evaluated for flexural strength, flexural modulus, fracture toughness, and microhardness. The samples were tested after storing in distilled water for 24 hours and 7 days at 37ºC. Two-way analysis of variance (ANOVA) was used to test the effects of storage time and combinations of alumina nanofiber level and quaternary ammonium acetate dispersant level on the flexural strength, fracture toughness, and microhardness of the provisional PMMA resin. Pair-wise comparisons between groups were performed using Tukey’s multiple comparisons procedure to control the overall significance level at 5 percent. Three fracture toughness samples/group were randomly selected for Energy Dispersive Spectrometry (EDS) to qualitatively evaluate the dispersion of the fibers. The data obtained from this study showed that control sample values were in the acceptance range compared with previous research. The experimental samples did not reinforce the provisional resin in the flexural strength, modulus, fracture toughness, or microhardness. There are several factors may attribute to these results, such as poor bonding at the filler/matrix interface. The more homogeneous the mixture of PMMA and fiber, the stronger the acrylic resin. In fact, the presence of poorly bonded fibers, to which little load is transferred, can be almost equivalent to voids. In addition, as seen with EDS images, alumina nanofibers had a tendency to agglomerate. The use of a magnetic stirrer was not effective in physically separating nanofibers agglomerates. Direct dispersion of alumina nanofibers in methyl methacrylate monomer and quaternary ammonium acetate dispersant was not effective in separating the nanofibers into nano-scaled single crystals. The presence of fiber agglomerates acts as a structural defect that detrimentally affects the mechanical properties. Further studies are needed to evaluate the effectiveness of fibers, dispersion techniques, and coupling agents to enhance the mechanical properties of the provisional PMMA resin.

This master´s thesis deals with the properties of gel polymer electrolytes, brief characteristics of other types of electrolytes and materials that are used for preparing polymer electrolytes. The thesis explains the use of the gel electrolytes in practice, the current conduction in the electrolytes and the properties of ionic liquids, and flame retardants. This thesis also focuses on methods of measurement of mechanical properties of gel polymer electrolytes. The practical part is focused on preparation of methacrylate gel electrolytes and their modifications with the use of flame retardant - triethyl phosphate (TEP) and ionic liquid - 1-ethyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (Emim TFSI). In this part there are evaluations of their potential funcionality (potential window) and specific conductance conductivity using the method LSV (linear sweep voltammetry) and impedance spectroscopy. The practical part also includes a thermal analysis of selected samples by TGA, DTA and EGA methods.

La vaste gamme de combinaisons possibles de cations et anions, ainsi que les excellentes propriétés intrinsèques des liquides ioniques (LIs) peuvent être considérées comme les principaux facteurs qui ont conduit au développement d’une recherche utilisant des LIs comme additifs des matériaux polymère. Ainsi, l'objectif principal de ce travail est d'explorer le rôle de la nature du cation et/ou du anion du LI sur les propriétés des matériaux basées de poly (méthacrylate de méthyle) (PMMA). Dans une première partie, des LIs de type imidazolium et ammonium ont été incorporés au PMMA et des caractérisations morphologiques et structurales ont été effectuées afin de comprendre leur impact sur les propriétés thermiques, viscoélastiques et mécaniques des matériaux résultants. Dans la section suivante, la capacité de ces LIs à base d'imidazolium et d'ammonium en tant qu’agents interfaciaux à la surface de la silice a été évaluée. Sub-micro et nanoparticules de silice, ainsi que les LIs, ont été incorporées dans une matrice de PMMA afin de préparer des composites. L'amélioration des propriétés des matériaux ont été discutées en fonction du degré auquel chaque LI influence la compatibilité entre les particules et la matrice polymère. De plus, ces composites ont été exposés au dioxyde de carbone en état supercritique (scCO2) pour utiliser celui-ci comme agent moussant et ainsi produire des matériaux expansés. Le rôle du LI et des particules de silice pour structurer les matériaux expansés a été analysé. Dans la dernière partie de cette étude, le scCO2 est utilisé comme milieu de réaction pour la modification chimique par greffage de la surface des nanoparticules de silice par des LIs de type imidazolium, contenant également des groupes hydrolysables et différentes chaînes alkyles. Le rôle de la pression et la quantité de LI ajoutées au milieu de réaction, ainsi que la longueur de la chaîne alkyle des LIs se sont avérées essentielles pour contrôler le degré de fonctionnalisation des nanoparticules. Enfin, ces nanoparticules modifiées ont été incorporées dans une matrice PMMA. Des analyses de morphologie ont été utilisées pour évaluer la dispersion des particules dans la matrice et les propriétés physico-chimiques de ces matériaux ont été également étudiées. / The large array of cation/anion combinations, and the excellent intrinsic properties of ionic liquids (ILs) open a large range of possibilities in their use as additives to polymer materials. Thus, the main objective of this work is to explore the role of both the cation and anion of a series of ILs on the properties of poly(methyl methacrylate) (PMMA)-based materials. In a first approach, low amounts of imidazolium and ammonium-based ILs were incorporated as additives to PMMA in the molten state. Morphological and structural characterizations were developed in order to understand the impact of the presence of such ILs on the thermal and mechanical properties of the resulting materials. Then, in the following section, the ability of the same imidazolium and ammonium-based ILs as physical modifiers of silica surface was evaluated. In such an approach, ILs were supposed to act as interfacial agents. Sub-micron and nanosize silica particles were used to prepare PMMA composites. Thus, the extents of each IL improve the interfacial interaction between PMMA and silica particles were discussed. In addition, supercritical carbon dioxide (scCO2) was used as foaming agent to produce foamed PMMA-based composites. In such a case, the combined effect of the presence of ILs and silica particles was analyzed regarding the morphology of the foamed structures. In the last section, scCO2 was used as reaction medium, in an environmental friendly approach, to chemically modify silica nanoparticles using a series of imidazolium IL-functionalized silanes (with different alkyl chain lengths). Thermogravimetric analysis (TGA) was used to highlight the effect of the working pressure and the content of such ILs in the reaction medium. The effect of the alkyl chain length on the grafting density of the resulting nanoparticles was also discussed. Finally, novel PMMA-based nanocomposites were prepared by the incorporation of such grafted nanoparticles. Transmission electron microscopy (TEM) and small-angle neutron scattering (SANS) analyses were used to evaluate the state of dispersion of the particles into the polymer matrix. Moreover, the thermal, rheological and mechanical properties of the materials were studied.