The purpose of this study was to assess the decay resistance of wood modified with a variety of chemicals and to attempt to further understand the mechanism by which chemical modification protects wood from decay. Corsican pine (Pinus nigra) sapwood was modified with three cyclic anhydrides; succinic anhydride, alkenyl succinic anhydride (a derivative of succinic anhydride with a 16-18 carbon alkenyl chain) and phthalic anhydride, and with two more widely studied modifying chemicals; acetic anhydride and butyl isocyanate. All reactions were carried out using pyridine as solvent and catalyst. Modified wood was tested against decay fungi in a pure culture test against basidiomycete fungi (Coniophora puteana, Gloeophyllum trabeum, Trametes versicolor and Pycnoporus sanguineus) under different moisture content regimes, an unsterile soil soft rot test, a fungal cellar test and a field trial. Butyl isocyanate proved the most effective modifying chemical at protecting wood from decay, followed by acetic anhydride and then alkenyl succinic anhydride. Uneven distribution of the modifying chemical in wood was evident using each of these three chemicals, particularly in the case of acetic anhydride. Despite its apparent ability to control decay by basidiomycete fungi, alkenyl succinic anhydride was unable to completely protect wood from soft rot fungi. Phthalic and succinic anhydride modifications both proved susceptible to hydrolysis and leaching, and neither were effective as wood protection chemicals. Phthalic anhydride modified wood performed well in the pure culture test, apparently through biocidal action, but was susceptible to decay in unsterile conditions. The approach made in this study to understanding the mechanism of protection was to analyse physical properties of the modified wood cell wall. This involved the measurement of adsorption isotherms, volumetric swell due to water soak, and cell wall pore size (using the solute exclusion technique). Neither the moisture content of modified wood nor its cell wall moisture content (measured as the fibre saturation point from the adsorption analysis) provided a good explanation of decay resistance. In several cases, the relationship between volumetric swell (due to water soak) and weight loss (to a given fungus in pure culture) was found to be consistent between modification types. From this it is concluded that the extent by which water swells modified wood is important to decay resistance. A reduction in cell wall pore volume was measured using the solute exclusion technique, though no further conclusions could be drawn from this test. It is proposed that the mechanism of resistance to decay by basidiomycete fungi involves the blocking of cell wall pores, which restricts the access of degradative agents released by decay fungi. The amount by which wood swells is important in this theory since this will determine by how much transient pores in modified wood can open, and whether enough space is created to bypass this blocking effect. The possibility of the role of site substitution in decay resistance is not discounted, and may contribute to decay resistance, particularly against white rot fungi. Pore blocking is not thought to be the mechanism of protection against soft rot fungi. In this case the substitution and shielding of decay susceptible sites are thought to be more important.

ABSTRACT Objectives: Flowable composites are characterized by lower filler loading and a greater proportion of diluent monomers in their formulation. These composites were traditionally created by retaining the same small particle size of the conventional hybrid composites, but reducing the filler content and allowing the increased resin to reduce the viscosity of the mixture However, their various mechanical properties such as flexural strength and wear resistance have been reported to be generally inferior compared to those of the conventional composites. Dental restorative materials are in continuous contact with fluids and saliva in the patient’s mouth. Consequently, the water sorption and solubility of these materials are of considerable importance. Resin based materials demonstrate water sorption in the oral cavity, which is the amount of water absorbed by the material on the surface and into the body while the restoration is in service. The water intrusion in the dental material can lead in a deterioration of the physical/mechanical properties, decreasing the life of resin composites. Water uptake can promote breakdown causing a filler-matrix debonding. Water sorption affects the physical and mechanical properties of resin composite such as dimensional change, decrease in surface hardness and wear resistance, filler leaching, change in color stability, reduction in elastic modulus, and an increase in creep and a reduction in ultimate strength, fracture strength, fracture toughness, and flexural strength. In addition, penetration of water into the composite may cause release of unreacted monomers (solubility) which may stimulate the growth of bacteria and promote allergic reactions. The effect of water sorption on conventional composites has been extensively studied and reviewed in the dental literature. However , there are no published studies on the water sorption of flowable composites. Water sorption increases as the amount of resin matrix increases and filler content decreases, since the filler particles do not absorb water. Thus, it is of utmost importance to study the water sorption of flowable composite. Hence the aim of this study was to evaluate and compare water sorption and solubility values of different light-activated flowable composite materials in solutions with varying pH values. And, since water filled porosities in the flowable composites may form small incubation chambers, a second related objective was to compare and correlate water sorption values of the various flowables to their ability to form Streptococcus mutans and Streptococcus sanguis single species biofilms in/on their surfaces. Methods: In this study, water sorption and solubility tests were performed according to the ISO standards (International Organization for Standardization specification 4049:07-2009- Dentistry- Polymer Based Restorative Materials [available at http://www.iso.org/iso/home/store.htm]). Three disc-shaped specimens of each flowable composite were made in a jig consisting of a Teflon mold (15 mm in diameter by 1 mm in thickness) compressed between 2 glass slabs with mylar strips used as separating sheets. The flowable resin was inserted in the Teflon mold in a single increment. All specimens were cured with a light-emitting diode curing unit. According to the ISO standard, discs were weighted every day for 35 days using the same balance, with a repeatability of 0.1 mg, until a constant mass (M1) was obtained. Once a constant M1 was obtained, the volume (V) was then calculated in cubic millimeters as follow: V =π(d/2)2h, where π=3.14; d is the mean diameter of the specimen; and h is the mean thickness of the specimen. After M1 was achieved, each flowable composite resin group of 3 discs was placed into buffers of pH = 4.0,5.5 and 7.0. After 24 hrs, specimens were wiped free of excess buffer with absorbent paper and weighed. This cycle was repeated at one week , one month, and six months. When a constant mass was achieved it was designated M2. Mass gain (Mg) was defined as follows: (M2 –M1). Per cent mass gain (%Mg) was defined as follows: (M2-M1/M1). Finally, the specimens were reconditioned to constant mass, once again following the above-mentioned procedure. This constant mass was recorded as M3. Water sorption (Wsp) was calculated in micrograms per cubic millimeter for each of the specimens by using the following equation provided by ISO 4049 standard: Wsp=(M2-M3)/V, where M2 is the mass of the specimens in micrograms after immersion in buffer for 30 days; M3 is the reconditioned mass of the specimen, in micrograms; and V is the volume of the specimen in cubic millimeters. Water solubility (Wsl) was calculated in micrograms per cubic millimeter for each of the specimens, using the following equation, provided by ISO 4049 standard: Wsl=(M1-M3)/V, where M1 is the conditioned mass of the specimen in micrograms before immersion in buffer; M3 is the reconditioned mass of each specimen in micrograms, and V is the volume of the specimen in cubic millimeters. For biofilm experiments, flowable discs were prepared as described above. Each disc was then sectioned into three equal portions using high speed and low speed handpieces , a diamond bur, and sandpaper discs, such that the three samples of each flowable had the same mass to within 0.3 mg. The samples were sterilized by dipping in 1.2% sodium hypochlorite (Chlorox), followed by rinsing with sterile distilled water, and then conditioning to a constant mass as described above, inside a desiccator that was wiped with 1.2 % Chlorox. Biofilm experiments were conducted as follows: three equal mass specimens of each flowable composite were placed in a series of wells of a sterile culture disc. Then sterile BHI broth (2 ml) was added to each well. One well served as control and no growing bacteria were added to it. To the other specimens was added 40 μl log phase S. mutans or S. sanguis cells. The culture dishes were then placed on a rotator at 37C for six hrs. Biofilm formation was measured by staining attached cells with crystal violet, destaining with 30% acetic acid, and measuring the satin spectrophotometically. Results: The pH of the solution influenced the % mass gain, as all samples gained more mass at pH 4.0 as compared to pH 5.5 and 7.0. The flowable resin SureFill showed the least % mass gain at each pH. However, there was no statistical difference in % mass gain based on pH of storage buffer for any of the flowable composites (P=.05) . Time had a significant influence on the % mass gain for the first week for all samples, with minor gains thereafter, and became steady after 1 month. Surefill showed the least water sorption when stored in buffer for 30 days, however it was not significant compared to the other flowables (P= 0.05). Filtek showed the least water solubility, but is not significant compared to the other flowables (P=0.05). The highest significant values (P< 0.05) for water sorption and solubility were observed for Virtuoso. Two trials indicated that strains of S. mutans and S. sanguis form biofilm readily on the surface of the composites, with S. sanguis having a higher predilection to form biofilm on all composites (Figure 6). However, no correlation was found between water sorption and solubility values of the flowable composites and biofilm formation. Conclusions: Within the limitations of this study the following is concluded: Time and storage conditions are important to the % mass gain due to water, with all flowable composites showing more mass gain at low PH. Due to its hydrophilic nature, as well as to the filler characteristics, the flowable composite Virtuoso exhibited significantly higher values of water sorption and water solubility than the other flowable composites that were tested. All flowable composites formed S. sanguis and S. mutans single species biofilm on their surfaces, with S. sanguis forming higher concentrations of biofilm on all samples. There was no clear correlation to water sorption and biofilm formation characteristics of the composites. / Oral Biology

Proton-Exchange Membrane (PEM) fuel cells are extremely attractive for replacing internal combustion engines in the next generation of automobiles. However, two major technical challenges remain to be resolved before PEM fuel cells become commercially successful. The first issue is that CO, produced in trace amounts in fuel reformer, severely limits the performance of the conventional platinum-based PEM fuel cell. A possible solution to the CO poisoning is higher temperature operation, as the CO adsorption and oxidation overpotential decrease considerably with increasing temperature. However, the process temperature is limited in atmospheric fuel cells because water is critical for high conductivity in the standard PEM. An increase in operating pressure allows higher temperature operation, although at the expense of parasitic power for the compressor. Further the conventional PEM, Nafion? is limited to 120°C due to it's low glass transition temperature. Thus, the design of higher temperature PEMs with stable performance under low relative humidity (RH) conditions is considered based on a proton transport model for the PEM and a fuel cell model that have been developed. These predictive models capture the significant aspects of the experimental results with a minimum number of fitted parameters and provides insight into the design of higher temperature PEMs operating at low RH. The design of an efficacious high temperature, low RH, PEM was based on enhancing the acidity and water sorption properties of a conventional PEM by impregnating it with a solid superacid. A systematic investigation of the composite Nafion?inorganic PEMs comprising experiments involving water uptake, ion-exchange capacity (IEC), conductivity and fuel cell polarization is presented in the work. The most promising composite is the nano-structured ZrO2/Nafion?PEM which exhibits an increase in the IEC, a 40% increase in water sorbed and a resulting 24% conductivity enhancement vs. unmodified Nafion?112 at 120°C and at RH < 40%.

Made available in DSpace on 2017-07-10T14:57:28Z (GMT). No. of bitstreams: 1 dissertacao marcal final_ apos defesaIpdf.pdf: 991526 bytes, checksum: 320d4a641b2062d25e7dffaef6de5e29 (MD5) Previous issue date: 2015-02-24 / The aim of this study was evaluate the influence of three techniques of photoactivation, in the sorption (SO) and solubility (SL) of three composite resins Filtek Z350 XT, Tetric N-Ceram and IPS Empress Direct. It was prepared 90 specimen (CP) of 8mm of diameter and 1mm of thickness and divided in 9 groups (n=10). The CP were photoactivated by a LED Bluephase device following these techniques: Convencional (CONV); Soft-Start (SS) and Pulse Delay (PA). They were then placed in a desiccator containing silica gel at 37°C and weighed daily until obtainment of a constant mass m1. Then, they were immerse in deionized water for seven days and weighed (m2). The reconditioning of the CP were accomplished following the procedure of m1 until the obtainment of a constant mass (m3). The values of SO and SL was calculated according to ISO 4049 and submitted to the ANOVA test (two-way) followed by the pos hoc of Turkey, p<0.05. There were no significant statistical differences in SO and SL when compared to the photoactivation techniques for all tested resins. In the analysis of SL, no significant statistical differences between the materials and the photoactivation techniques were observed. As for the composite resin Filtek Z350 XT, statistically higher results to other resins was evaluated. It was concluded that the different forms of photoactivation did not influence in the SO and SL of the tested composite resins. / O objetivo deste estudo foi avaliar a influência de três técnicas de fotoativação, na sorção (SO) e solubilidade (SL) de três resinas compostas Filtek Z350 XT ,Tetric N-Ceram e IPS Empress Direct. Foram confeccionados 90 corpos-de-prova (CP) de 8 mm de diâmetro e 1 mm de espessura e divididos em 9 grupos (n=10). Os CP foram fotoativados com o aparelho de luz LED Bluephase seguindo as seguintes técnicas: Convencional (CONV); Soft-Start (SS) e Pulso Atrasado (PA). Em seguida, foram colocados em um dessecador com sílica gel a 37ºC e pesados diariamente até obtenção de uma massa constante m1. Em seguida, foram imersos em água deionizada por sete dias e pesados novamente (m2). O recondicionamento dos CP foi realizado seguindo o procedimento da m1, até obtenção de uma massa constante (m3). Os valores de SO e SL foram calculados de acordo com a ISO 4049 e submetidos ao teste de ANOVA (two-way), seguido do post hoc de Tukey, p<0,05. Não houve diferenças estatisticamente significantes para SO e SL quando as técnicas de fotoativação foram comparadas, para todas as resinas estudadas. Na análise da SL não foram observadas diferenças estatisticamente significativas entre os materiais e técnicas de fotoativação. Já para SO, a resina composta Filtek Z350 XT apresentou resultados estatisticamente mais elevados às demais resinas compostas avaliadas. Foi possível concluir que as diferentes formas de fotoativação não influenciaram na SO e SL das resinas compostas testadas.

Magister Scientiae Dentium - MSc(Dent) / Resin filled dental composite materials has been introduced into dental practice since mid-1960s as an aesthetic restorative material for anterior teeth (Bowen, 1962 cited in Peutzfeldt, 1997). Since then, they have undergone several developments in order to enhance the longevity and performance of these materials. Resin filled dental composites consist of three main components namely, organic resin matrix which consists of a monomer, an initiator system and a stabilizer system, inorganic filler such as quartz, silica, etc. and coupling agent such as organo-silane coupling agent that chemically bonds the inorganic fillers to the organic resin matrix (Phillips, 1973). The properties and the performance of the resin filled dental composites are basically dependent upon the components of the materials. Some properties are related to the resin matrix, whereas others are related to the inorganic fillers and coupling agent. Furthermore, properties such as polymerization shrinkage and water sorption are dependent on both the inorganic fillers and the organic resin matrix (Asmussen, 1975; Hashinger and Fairhust, 1984; Munksgaard et al., 1987). Aim and objectives: The aim and the objectives of this study was to compare the water sorption and solubility of four bulk-fill dental resin composite materials namely, two conventional viscosity bulk-fill (Surefil bulk fill composite and Tetric N Ceram Bulk Fill) and two low viscosity bulk-fill flowable dental composite materials (Filtek Bulk Fill flowable restorative and Surefil SDR Flow). Materials and methods: Four types of bulk-fill composite restorative materials (2 bulk-fill conventional viscosity (Surefil bulk fill composite and Tetric N Ceram Bulk Fill) and 2 bulk-fill flowable low viscosity (Filtek Bulk Fill flowable restorative and Surefil SDR Flow) were used to analyse the water sorption and solubility for each resin composite type. Thirty specimens for each type of material were prepared, giving the total number of specimens to be 120 (n=120). To standardize this study Vita shade A2 was used for all the material types. All specimens were prepared in a Teflon mould with internal diameter of 15±1mm and thickness of 1±0.1mm in accordance with ISO 4049. The light curing unit used for all specimens was Elipar™ S10, (3M ESPE, Germany) at an output of 1200 mW/cm2 and used according to the manufacturer’s instructions. Prior to curing, the intensity of the light was checked using Cure Rite visible curing light meter (Caulk, USA) to ensure light output consistency between specimens and was found to be 1200 mW/cm2 . All the specimens were first removed from the Teflon mould as prepared and described previously and placed in an oven at 37 ºC until their weights were constant and these weights were recorded as m1 by using an analytic balance (OHAUS, TS400D, USA). Ten specimens of each type of resin filled composite were then immersed individually in glass containers filled with 10 ml distilled water and placed in the oven at 37±1 ºC for 24 hours, 7 days, 14 days respectively. The specimens were removed; surface water was blotted with tissue paper until free from visible moisture and weighed using the analytic balance (OHAUS, TS400D, USA). The resultant weights were recorded as m2. The specimens were then placed in a desiccator containing silica gel (Associated Chemical Enterprises, ZA) and freshly dried for two hours in an oven at 58 ºC and then weighted to obtain m3. According to Oysaed and Ruyter formula (Oysaed and Ruyter, 1986), the water sorption and solubility was calculated using the following equation: i.Water sorption (SP) = m2 -m3 / v., ii.Water solubility (SI) = m1 -m3 / v - where v is the volume of the specimen. For monomer leakage high performance liquid chromatography (HPLC) was used to identify monomers. The water that contained stored specimens was transferred to a refrigerator immediately after the specimens were removed until HPLC analysis was carried out to determine the amount of monomers that leached out of the cured composite specimens. Results: A significant difference between the materials (p<0.05, ANOVA Analysis of Variance) showed that Surefil SDR Flow composite had the lowest overall mean water sorption values (10.191) over the three time intervals (24 hrs, 7 days and 14 days) which was significantly smaller than the other means, followed by Filtek Bulk Fill flowable restorative composite (11.135) and Tetric N Ceram Bulk Fill composite (16.419). The highest water sorption mean value was recorded for Surefil bulk fill composite (21.515). The overall means of water solubility for the two bulk-fill flowables i.e. Filtek Bulk Fill flowable restorative and Surefil SDR Flow were smaller than bulk-fill conventional viscosity Surefil bulk fill and Tetric N Ceram Bulk Fill. However, all the test materials displayed no statistically significant increase in water solubility over the time period (p > 0.05 two way ANOVA test). The amounts of eluted monomers from bulk-fill conventional viscosity materials (Surefil bulk fill and Tetric N Ceram Bulk Fill) were higher than bulk-fill flowable materials (Surefil SDR Flow and Filtek Bulk Fill flowable restorative). Of all the monomers tested UDMA eluted more than Bis-GMA and TEGDMA. Overall UDMA monomer eluted the most, followed by Bis-GMA and the TEGDMA. Conclusion: Within the limitation of this study, the results of this study did not support the null hypothesis that there is no significant difference in the water sorption. The bulk-fill low viscosity flowables showed lower water sorption than the conventional viscosity bulk-fills. Surefil SDR Flow was significantly lower than the other materials followed by Filtek Bulk Fill flowable restorative and Tetric N-Ceram Bulk Fill and the highest overall means were recorded for Surefil bulk fill. For water solubility the overall means for the flowables of Filtek and SDR were smaller than Surefil and Tetric N-Ceram. For monomer elution three monomers were detected of which UDMA monomer eluted the most, followed by Bis-GMA and the TEGDMA. With regards to the elution of monomers, it was found that 3 monomers named UDMA eluted more than Bis-GMA and TEGDMA.

Since resin composites were first presented to dentistry more than half a century ago, the composition of resin composites has developed significantly. One major change was that the reinforcing filler particles were reduced in size to generate materials of a given filler content that display better physical and mechanical properties. Resin composites may absorb water and chemicals from the surrounding environment but at the same time, composites may release constituents to their surroundings. The physical/mechanical properties of a restorative material provide an indication of how the material will function under stress in the oral environment. The aims of this research were to examine the effects of water at 37°C on the physical and mechanical properties, and the effect of food-simulating solvents of a variety of experimental and contemporary resin composites, on the surface properties. Eight representative resin composites were selected (Exp. VT, BL, NCB, TEC, GSO, XB, VDF and CXD). Due to the recent development of bulk fill materials on the market during the course of this research, the post-cure depth of cure of new bulk fill materials was also investigated. Five representative resin composites were selected: TBF, XB, FBF, VBF and SF. Water sorption and solubility were investigated at 37°C for 150 days. Sorption and solubility are affected by the degree of hydrophilicity of the resin matrix. The bulk fill materials examined showed the lowest water sorption and solubility. Laser scan micrometer (LSM) was used to investigate hygroscopic expansion. The extent of the hygroscopic expansion positively correlated with the amount of water sorption. The effect of water on fracture toughness was also examined. A self-adhesive hydrophilic resin matrix decreased in fracture toughness after 7 days of storage at 37°C. By contrast, the least water absorbed bulk fill material increased in fracture toughness over time. The effect of food-simulating solvents (distilled water, 75% ethanol/water and MEK) on surface micro-hardness, colour stability and gloss retention were investigated. The MEK solvent resulted in the lowest micro-hardness and the greatest colour change (ΔE) for most of the examined composites, while the 75% ethanol/water solution caused the greatest loss in gloss for most of the examined composites. A highly filled nano-composite showed the best result over time, regardless of the condition of storage. Surface micro-hardness profiles were used as an indirect method to assess the depth of cure of bulk fill resin composites. The examined bulk fill resin composites can be cured to an acceptable depth (4 mm).

Orientador: Celia Marisa Rizzatti Barbosa / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Odontologia de Piracicaba / Made available in DSpace on 2018-07-31T18:51:13Z (GMT). No. of bitstreams: 1 Nadin_PauloSergio_D.pdf: 3982871 bytes, checksum: 60b40819eee30b6dd20d8ff8604c5f8a (MD5) Previous issue date: 2001 / Resumo: O objetivo deste trabalho foi avaliar a adaptação e a alteração na inclinação dental dos primeiros molares de próteses totais superiores em função do método de polimerização, e da sorção de água apresentada pela resina, frente a alterações de pressão e temperatura de armazenagem das amostras. Foram confeccionadas 60 próteses divididas em 4 grupos: (G I) polimerizadas em água 73 :I: 2 °C / 9 horas e armazenadas em água à 37 :I: 2 °C por 30 dias; (G 11) polimerizadas em água 73 :I: 2 °C / 9 horas e armazenadas em água sob temperatura de 60 :I: 2°C, pressão de 40 Lib/PoF por 1 hora; (G lU) polimerizadas por energia de microondas 500W / 3 minutos e armazenadas em água de 37 :I: 2 °C por 30 dias; (G IV) polimerizadas por energia de microondas 500 W / 3 minutos e armazenadas em água sob temperatura de 60 :I: 2°C, pressão de 40 Lib/PoF por 1 hora. Foi feita a análise da inclinação dental nos períodos de enceramento (TO), de polimerização (TI), polimento (T2) e sorção de água (T3). Para o teste de adaptação, a base foi analisada na região de primeiros molares, em sete pontos pré-estabelecidos. Estes foram feitos nos períodos de polimento (TO) e após a de sorção de água (TI). Os dados obtidos foram submetidos à análise de variância e teste de Tukey ao nível de 5 % de significância. Estes demonstraram que as alterações mais significativas da inclinação dental ocorreram em todos os grupos após o processamento das amostras (TI), sendo de 2,3 °, 0,85 °, 2,54 °, e 3,47° para os grupos I, 11, 111 e IV respectivamente (p<0.05). Conclui-se que: 1) As maiores alterações na inclinação dos dentes ocorreram entre os períodos de enceramento e polimerização, em média 2,29 graus. 2) As alterações na inclinação dental durante o polimento e após o fenômeno de sorção de água não foram estatisticamente significantes. 3) Não houve diferença significativa na inclinação dos dentes entre os métodos de polimerização por energia de microondas e por banho de água convencional. 4) Os métodos de tratamento utilizados para sorção de água influenciaram igualmente as alterações ocorridas. 5) A melhor adaptação ocorreu na região palatina para o grupo 111 sendo em (TO) 0,142 mm e (TI) 0,134 mm. 6) Na região de tlanco observou-se a menor variação na adaptação entre TI e T2 (0,005 mm). 7) De modo geral após a sorção de água houve melhora na adaptação / Abstract: The aim of this work was to evaluate the adaptation and change in dental inclination of the first molars in upper complete dentures in function of the curing method and water sorption shown by the resin, before changes in pressure and temperature of storage of the samples. Sbcty dentures were constructed and divided into 4 groups: (G I) cured in 73° C water/ 9 hours and water sorption of37° C for 30 days; (G 11) cured in 73° C water/ 9 hours and water sorption under a temperature of 60° C, pressure of 40 Libs/inch2 per hour; (G 111) curing by microwave energy 500W/3 minutes and water sorption of 37° C for 30 days; (G IV) cured by microwave energy 500W/ 3 minutes and water sorption under a temperature of 60° C, pressure of 40Libs/inch2 per hour. An analysis was made on the dental inclination in waxing (TO), curing (TI); polishing (T2) and water sorption (T3) periods. For the adaptation test, the base was analyzed in the first molar region, in seven pre-established points. These were made in the polishing period (TO) and after water sorption (TI). The obtained data were submitted to variance analysis and Tukey's test at a 5% significance level. These demonstrated that the most significant changes of dental inclination had occurred in ali groups after the processing of the samples (TI), being of 2,3°, 0,85°, 2,54° and 3,47° for groups I, 11, 111 and IV, respectively (p<0.05). It is concluded that: 1) The biggest changes in dental inclination occurred between the waxing and curing periods, an average of 2,29 degrees. 2) The changes in dental inclination during the polishing and after the phenomenon of water sorption were statistically insignificant. 3) There was no significant difference in tooth inclination between the curing methods by microwave energy and conventional water bath. 4) The methods of treatment used for water sorption influenced equally the occurred changes. 5) The best adaptation occurred in the palatine region for group IH, being in (TO) 0,142 mm and (TI) 0,134 mm. 6) In the flange region, it was observed the least variation in adaptation between TI and T2 (0,005 mm). In a general sense, there was an improvement in adaptation after water sorption / Doutorado / Protese Dental / Doutor em Clínica Odontológica

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La sorption de CO2 et de CH4 dans des charbons a été caractérisée au laboratoire afin d'étudier la faisabilité du stockage géologique de CO2 dans les veines de charbon. La diffusion et la sorption de CO2 et de CH4 sur des charbons du bassin de Lorraine et du bassin de Gardanne ont été étudiées par une méthode gravimétrique jusqu'à une pression de 5 MPa et pour des températures variant de 283 à 333 K. La cinétique de sorption dépend du gaz utilisé, de la granulométrie, de la pression en gaz et de la température. Elle peut être représentée par un modèle unipore basé sur la loi de Fick. Le coefficient de diffusion de CO2 dans le charbon est supérieur à celui du CH4 et est d'environ 10–12 m2 s–1, valeur de diffusion assez faible. A l'équilibre, la température, la pression, le gaz utilisé, la composition des charbons et la teneur en eau sont des paramètres qui influencent la capacité de sorption sur les charbons. Le charbon du bassin de Lorraine possède une plus grande capacité de sorption de CO2 (1,6 mmol g–1, soit ~ 36 m3 t–1) que celle du charbon du bassin de Gardanne. Le modèle de Dubinin-Astakhov basé sur un remplissage volumique des pores, rend mieux compte de la sorption de CO2 et CH4 que les modèles de Dubinin-Radushkevich et de Langmuir. Par ailleurs, les mécanismes de sorption de l'eau sur le charbon ont été mis en évidence, permettant de mieux interpréter l'influence de l'eau sur la capacité de sorption des gaz. A partir de l'ensemble des résultats, une évaluation des possibilités de stockage est discutée. Il en ressort la nécessité d'études complémentaires dans le but d'améliorer la perméabilité de la veine à l'échelle du site de stockage pour permettre une meilleure injectivité du gaz / The CO2 and CH4 sorption onto coals has been characterized in laboratory in order to study the feasibility of CO2 geological storage in coal seams. The diffusion and sorption of CO2 and CH4 on coals of Lorraine and Gardanne basins have been performed from a gravimetric method until a pressure of 5 MPa and for temperatures from 283 to 333 K. The kinetics of sorption depends on the nature of gas, the grain size of coal, the gas pressure and the temperature. It can be represented by a unipore model based on Fick's law. The CO2 diffusion coefficient on coal is higher than that of CH4 and is about 10–12 m2 s–1. At equilibrium, the temperature, pressure, nature of gas, composition of coal and water content are parameters that influence the sorption capacity of coals. The coal of Lorraine basin has a greater capacity for sorption of CO2 (1.6 mmol g–1, ~ 36 m3 t–1) than that of coal of Gardanne basin. The model of Dubinin-Astakhov based on a pore volume filling, has a best fit of sorption data that Dubinin-Radushkevich and Langmuir models. Finally, the different mechanisms of water sorption on coal have been identified and can better interpret the influence of moisture on the gas sorption capacity. From all results, an assessment of capacity storage is discussed. This indicates the need for further studies in order to improve the permeability of the coal seams across the storage site for better gas injectivity

Les élastomères à base d’Ethylène Propylène Diène Monomère (EPDM) sont utilisés dans les accessoires du réseau de distribution d’électricité sous-terrain pour assurer l’isolation des jonctions de câbles. En effet, la structure chimique de ce polymère est apolaire et induit donc l’hydrophobicité désirée pour cette application. Cependant, en conditions de service, la thermo-oxydation provoque l’incorporation d’atomes d’oxygène (formation de fonctions hydrophiles) aux chaines EPDM. Ainsi, l’objectif de cette thèse était d’étudier l’influence du vieillissement thermo-oxydant sur les propriétés de transport d’eau dans les accessoires en EPDM. Trois formulations d’EPDM sans charges (une réticulée au peroxyde et deux autres réticulées au soufre) ainsi que six formulations industrielles (toutes réticulées au soufre) ont subi un vieillissement thermique accéléré en étuve ventilée d’air entre 90 et 190°C. L’analyse multi-échelle (combinant plusieurs techniques expérimentales) a permis de mettre en évidence les modifications structurales dans les matrices EPDM et d’établir des corrélations entre les propriétés physico-chimiques mesurées au cours du vieillissement. Les propriétés de transport d’eau ont ensuite été caractérisées entre 30 et 70°C et entre 10 et 100 % HR à l’état initial et pour différents états d’oxydation. Ces résultats ont permis d’établir des relations structure/propriété entre les propriétés de transport d’eau et l’incorporation d’oxygène, mais aussi de simuler l’influence cruciale des charges. / Ethylene Propylene Diene Monomer (EPDM) based elastomers are used in the accessories of the underground electrical distribution network for guaranteeing the insulation of cable junctions. Indeed, the chemical structure of this apolar polymer gives the desired hydrophobicity for this application. However, in service conditions, thermo-oxidation causes an incorporation of oxygen atoms (formation of hydrophilic function) into EPDM chains. Thus, this PhD thesis aimed at studying the influence of thermal oxidative ageing on the water transport properties into EPDM accessories. Three unfilled formulations (one peroxide crosslinked and two sulfur vulcanized) and six industrial formulations (all vulcanized) were submitted to an accelerated thermal ageing in air-ventilated ovens between 90 and 190 °C. The multi-scale analysis (combining several experimental techniques) allowed highlighting the structural changes in EPDM matrices and establishing correlations between the physico-chemical properties measured during ageing. Then, the water transport properties were characterized between 30 and 70 °C and between 10 and 100 %RH at the initial state and for different oxidation states. These results allowed establishing structure/property relationships between water transport properties and oxygen incorporation, but also to simulate the crucial influence of fillers.