Esta pesquisa objetiva avaliar o emprego de agregados graúdos reciclados (produzidos a partir do entulho de construção e demolição) e o emprego do látex estireno-butadieno (polímero sintético) nas propriedades de concretos estruturais de média resistência. Todos os estudos são conduzidos comparando-se as propriedades de concretos com agregados naturais sem adição de látex, e de concretos com agregados graúdos reciclados com e sem adição de látex. Na primeira fase da pesquisa, são avaliadas propriedades físicas e mecânicas destes concretos. São analisados três traços (com diferentes consumos de cimento) modificados com quatro percentagens de látex e submetidos a quatro formas de cura. Os resultados da primeira fase formam a base para a segunda fase da pesquisa, na qual apenas um dos traços contendo uma determinada porcentagem de látex e sob uma única forma de cura é submetido a ensaios em célula de corrosão acelerada e aderência aço-concreto. Como resultado principal, tem-se que o emprego conjunto de agregados graúdos reciclados e látex estireno-butadieno fornece concretos com resistência mecânica equivalente aos concretos contendo agregados naturais e com desempenho em ambientes agressivos e aderência aço-concreto também semelhantes. Conclui-se, portanto, pela viabilidade do emprego destes concretos como concreto estrutural armado no que tange às propriedades avaliadas. / This research aims at evaluating the use of coarse recycled aggregates (produced from construction and demolition debris) and the use of styrene-butadiene latex (synthetic polymer) in the concrete constitution of medium resistance concrete structures. All studies are carried out comparing the concrete properties with natural aggregates without latex, and concrete with coarse recycled aggregates with or without latex. In the first stage of the research, physical and mechanical properties of these concretes are evaluated (with different cement contents) modified with four percent of latex and submitted to four cure condition. The results of the first stage produce the base for the second stage of the research, where only one of the features containing a determinate percentage of latex and under a sole form of cure condition it is submitted to tests in accelerated corrosive cell and steel-concrete adherence. As a main result, it is believed that the joint usage of coarse recycled aggregates and styrene-butadiene latex provides mechanical resistant concrete equivalent to concrete containing natural aggregates with a similar performance in aggressive environments and with steel-concrete adherence. Due to the its employment feasibility, one can conclude that this concrete is structurally armed in as far as its properties were evaluated.

Esta pesquisa apresenta um estudo de uma argamassa modificada para uso como elemento de ligação entre elementos de concreto pré-moldado. A argamassa utilizada nesta pesquisa é obtida pela introdução de látex estireno-butadieno (SB) e fibras de polipropileno a uma argamassa de cimento e areia. Estas adições modificam suas propriedades mecânicas, proporcionando o aumento da deformabilidade por diminuição do módulo de elasticidade do compósito, conferindo-lhe características favoráveis ao uso como elemento de apoio para elementos pré-moldados de concreto. Foram realizados ensaios de caracterização do compósito por meio da obtenção das resistências à compressão e à tração e, do módulo de elasticidade para corpos-de-prova cilíndricos com 50 mm de diâmetro com 100 mm de altura. Ensaios de capacidade de deformação, capacidade de rotação e capacidade de acomodação de imperfeições e distribuição das tensões foram realizados em almofadas de 150 mm x 150 mm com espessura de 10 mm. Os resultados mostraram que o material possui boa capacidade de se deformar em níveis de tensão da ordem de 10 a 20 MPa mantendo sua resiliência. Valores de rotações entre 0,01 e 0,02 rad foram obtidos nos ensaios, sendo estas maiores que os valores necessários para a maioria dos casos convencionais de projeto. Na acomodação e distribuição das tensões, a presença das almofadas promoveu uma melhora de 25% no desempenho de ligações submetidas à compressão uniforme, com rugosidades de 1,0 mm. / This research presents a study of a mortar modified to use as bearing pad between precast concrete elements. The mortar used in this research is achieved by the introduction of styrene-butadiene latex (SB) and polypropylene fibers into a cement mortar and sand, modifying their mechanical properties, as increase of the potential deformation by decrease of the composite modulus of elasticity, providing favorable characteristics to the use as bearing pad for precast concrete elements. Cylindrical samples of 50 mm of diameter with height of 100 mm were molded and tested to determination the compressive and the tensile strength and also the modulus of elasticity of the composite. Compression tests with cushions of 150 mm x 150 mm of base with thickness of 10 mm were done to determinate the deformation capacity, rotation capacity and capacity of accommodation of imperfections and distribution of the stresses between precast elements. The results showed that the material has a capacity to deform in levels of tension from 10 to 20 MPa maintaining his resilience. Values of rotations among 0,01 and 0,02 rad were obtained, being these larger ones than the necessary values for most of the conventional cases of project. In the accommodation and distribution of the stresses, the presence of the bearing pad promoted an improvement of 25% in the strength of connections subject to uniform compressive stresses, with surface irregularities of 1,0 mm.

O crescimento dos países em desenvolvimento aumentará em várias vezes o consumo de energia, materiais e alimentos. Para suprir essa demanda é necessário o aproveitamento racional dos resíduos gerados por processos industriais, agrícolas e lixo urbano, transformando-os em energia economicamente competitiva com as outras formas de energia, e em materiais com propriedades otimizadas. O objetivo do presente trabalho foi comparar o comportamento da sílica da casca de arroz obtida por pré-hidrólise ácida seguida de calcinação controlada (Sil-PH) com sílicas de casca de arroz comerciais obtidas simplesmente pela queima da casca (Sil-B e Sil-C) e com a sílica comercial obtida da areia quartzítica (Sil-Z), como carga de reforço em borracha de estireno-butadieno (SBR), que é a mais usada na indústria de fabricação de pneus. Estudos foram conduzidos em SBR 1502, preparados conforme norma ASTM 3191-2010. Foram adicionadas à borracha as sílicas em concentrações de 0, 10, 20 e 40 ppcb. Foram conduzidos testes físicos, químicos, mecânicos, reométricos, dinâmico-mecânicos e análise térmica, bem como ensaios de inchamento dos corpos de prova em toluol e análise microestrutural das sílicas e dos compostos por microscopia eletrônica de varredura, com o objetivo de determinar a natureza do reforço. O número de ligações cruzadas foi avaliado e a energia de formação dessas ligações foi calculada. A relação entre as metodologias de cálculo da densidade de ligações cruzadas foi também avaliada, obtendo a caracterização desse tipo de carga de reforço não somente por correlações mecânicas mas também pela energia de formação das ligações. Os resultados mostraram que quanto maior a adição de sílica, maior é sua interação com a borracha. Dentre as sílicas adicionadas, Sil-Z alcançou os maiores valores de propriedades mecânicas dos compostos, e Sil-PH mostrou os melhores resultados dentre as sílicas de casca de arroz. Por avaliação por inchamento em toluol (teste estático) e por testes de tração e testes dinâmicos foi possível afirmar que as densidades de ligações cruzadas estão correlacionadas, Usando os resultados de reometria e as equações de Arrhenius estimou-se uma energia média de ligação, concluindo que esta corresponde a uma ligação do tipo covalente. Pelos valores de tan ? confirmou-se que os compostos com Sil-PH têm maior aderência no chão molhado do que aqueles com Sil-Z. A sílica nos compostos tende a diminuir a temperatura de transição vítrea. Os resultados da análise térmica mostraram elevada estabilidade térmica dos compostos com Sil-PH e Sil-Z. A falta de cominuição adequada da Sil-PH ocasionou uma dispersão irregular da sílica na SBR, uma molhabilidade parcial da sílica pela borracha e pelo agente de acoplamento, com consequente aparecimento de falhas na estrutura do composto. Por esse motivo as propriedades mecânicas dos compostos com Sil-PH foram inferiores às dos compostos com Sil-Z. / Developing countries are increasing by several times their consumption of energy, materials, and food. To attend their demand it is necessary to rationally reuse industrial, agricultural, and municipal solid waste residues, transforming them into economically competitive energy and materials with optimized properties. The objective of this work was to compare the behavior of a rice husk silica obtained by acidic prehydrolysis and controlled calcination (Sil-PH) with commercial amorphous silicas obtained from quartzite sand (Sil-Z) and from simply burned rice husks (Sil-B and Sil-C), as reinforcing filler in styrene-butadiene rubber (SBR) composites, which is the most used rubber in the tire manufacture industry. Studies were conducted on SBR 1502 rubber according to ASTM 3191-2010 in which amorphous silicas obtained from rice husk and quartzite silica were added at concentrations of 0, 10, 20, and 40 phr. Physical, chemical, mechanical, rheometric, dynamic-mechanical tests, thermal analysis, swelling studies in toluol and scanning electron microscopy of the silicas and composite specimens were made with objective to determine the nature of reinforcement. The number of crosslinks was evaluated and the energy of formation of these bonds calculated. The correlation between the methodologies of calculation of crosslink density was also evaluated, getting the characterization of this type of reinforcing filler not only by mechanical correlations but also by the energy of their formation. The results showed that the higher the content of added silica, the greater the interaction with rubber. According to the mechanical properties values Sil-Z achieved the highest properties values but Sil-PH showed better results compared to the other types of rice husk silicas. By evaluation by swelling in toluene (static), tensile tests and dynamic tests it was possible to affirm that the crosslink densities are correlated. By using the rheometry results and the Arrhenius equations the average bound was estimated to be of a covalent type. The silica in the compounds tends to lower the values of the glass transition temperature. The evaluation of tan ? showed that Sil-PH has more stickiness on the wet floor, which is an important property to tire application. Due to the lack of appropriate grinding of the Sil-PH the dispersion of the silica on SBR was irregular; partial wetting of the silica particles by rubber and silane had also occurred. Those facts had caused failures on the compound structural integrity, with a consequent lowering of the mechanical property values as compared to the compounds with Sil-Z addition.

Nesta Dissertação, foram realizadas reações de copolimerização de 1,3-butadieno com diferentes alfa-olefinas (1-hexeno, 1-octeno e 1-dodeceno) utilizando-se um sistema catalítico do tipo Ziegler-Natta ternário constituído por versatato de neodímio, hidreto de diisobutilalumínio e cloreto de t-butila. O sistema catalítico também foi avaliado em reações de homopolimerização com cada alfa-olefina. As condições reacionais, tanto da síntese do catalisador como das reações de polimerização, foram mantidas constantes. Foi estudada a influência de diferentes teores de cada alfa-olefina (1, 3, 5, 10, 20 e 30 % em relação ao 1,3-butadieno) sobre a conversão da polimerização, a microestrutura, a massa molar, as propriedades viscosimétricas e a estabilidade térmica dos polímeros obtidos. Foi avaliada, ainda, a influência do tamanho da cadeia da alfa-olefina sobre as características da polimerização. Os polímeros foram caracterizados por espectroscopia na região do infravermelho (FTIR), cromatografia por exclusão de tamanho (SEC), viscosimetria capilar e termogravimetria (TG). A microestrutura dos polímeros, praticamente, não variou com a adição das alfa-olefinas. A massa molar numérica média (Mn) não sofreu alterações significativas, enquanto que a massa molar ponderal média (Mw) apresentou tendência ao aumento, quanto maior foi a incorporação de comonômero. A viscosidade intrínseca não apresentou uma tendência com a adição da alfa-olefina na reação, permanecendo na faixa de 2,015 a 3,557 dL/g. A estabilidade térmica do copolímero mostrou uma tendência a aumentar com a incorporação das alfa-olefinas / In this work, were performed copolymerization reactions of 1,3-butadiene with different alpha-olefins (1-hexene, 1-octene and 1-dodecene), using a ternary catalytic system of Ziegler-Natta, constituted by neodymium versatate, diisobutylaluminum hydride and t-butyl chloride. The catalytic system was also evaluated in homopolymerization reactions with the alpha-olefins. The reaction conditions, both the catalyst synthesis as the polymerization reactions, were kept constant. The influence of different content of each alpha-olefin (1, 3, 5, 10, 20 and 30% compared to 1,3-butadiene) on the polymerization conversion, the microstructure, molar mass, viscometric properties and thermal stability of polymers was studied. The influence of alpha-olefin chain size on polymerization characteristics was also evaluated. The polymers were characterized by infrared spectroscopy (FTIR), size exclusion chromatography (SEC), capillary viscometry and thermogravimetry (TG). The polymer microstructure, practically, did not change with the addition of alpha-olefins. The number average molecular mass (Mn) has not changed; while the weight average molecular mass (Mw) trended to increase. The intrinsic viscosity did not show a trend with the alpha-olefin addition, remaining in the range from 2.015 to 3.557 dL/g. The copolymer thermal stability showed a tendency to increase with the incorporation of alpha-olefins

<p>Strukturiranje elastomernih kompozita dodavanjem različitih vrsta nanopunila je dovelo do značajnog pobolj&scaron;anja njihovih primenskih svojstava, a samim tim i do povećanja njihove potencijalne primene kao pogodnih materijala za specijalne namene. U ovom radu, dobijene su dve grupe elastomernih hibridnih materijala za specijalne namene (na osnovu stirenbutadienskog elastomera i na osnovu termoplastičnih poliuretana).<br />U prvom delu istraživanja, veliki doprinos u razvoju industrije gume je postignut strukturiranju stirenbutadienskih nanokompozita primenom nanočestica punila silicijum(IV)oksida različitih morfolo&scaron;kih svojstava, dobijenih hidrotermičkom i termičkom obradom, primenom tri eksperimentalno modelovana punila silicijum(IV)oksida (dobijena taloženjem iz Na-vodenog stakla sa sumpornom kiselinom), kao i hibridnog punila (kombinacije čestica aktivne čađi i SiO₂ optimalnih svojstava). Izvr&scaron;ena je analiza uticaja strukture, povr&scaron;ine i povr&scaron;inske aktivnosti nanopunila na ojačanje elastomera, kao i provera koncepata, modela i teorija ojačanja na neumreženim i umreženim sistemima stirenbutadienskih elastomera ojačanih modifikovanim punilima SiO₂. Primenom mnogobrojnih metoda karakterizacije, sveobuhvatno je ispitan uticaj nanopunila na karakteristike me&scaron;anja, reolo&scaron;ka svojstva pripremljenih hibridnih nanokompozita, sposobnost umrežavanja u neumreženom materijalu, kao i na toplotna, dinamičko-mehanička i mehanička svojstva umreženih nanokompozita, radi projektovanja i optimizovanja sastava SBR hibridnih materijala za razvoj modelnog protektora sa optimalnim svojstvima za ekolo&scaron;ke ili &quot;zelene pneumatike&quot;. Drugi deo istraživanja je bio posvećen dobijanju segmentiranih poliuretanskih elastomernih nanokompozita primenom alifatičnih polikarbonatnih diola i nanočestica bentonita, koji nalaze primenu u medicini, građevinarstvu, u industriji name&scaron;taja i sportske opreme. Primenom mnogobrojnih metoda za karakterizaciju, ispitan je složen mehanizam uticaja tvrdih segmenata, termodinamičke nekompatibilnosti i prisustva nanočestica punila bentonita na strukturu i morfologiju, kao i na toplotna i dinamičko-mehanička svojstva pripremljenih poliuretanskih termoplastičnih elastomera. Dobijeni podaci o obrazovanju vodoničnih veza, termičkoj stabilnosti i termičkoj dekompoziciji, kao i o temperaturama prelaska u staklasto stanje i oblasti raskidanja čvorova fizičkih veza, predstavljaju značajan doprinos napretku strukturiranja poliuretanskih elastomera i nanokompozita na osnovu alifatičnih polikarbonatnih diola, i omogućavaju primenu ovih materijala za specijalne namene.</p> / <p>The structuring of elastomeric composites by addition of different nanofillers has led to a significant improvement of their end-use properties, and therefore, to their potential application as suitable materials for special applications. In this work, two types of elastomeric hybrid materials for special purposes were obtained (based on styrene-bustadiene elastomer or on segmented thermoplastic polyurethanes).<br />In the first part of the study, a major contribution to the development of the rubber industry was achieved by structuring styrene-butadiene nanocomposites, applying silica nanoparticles of various morphological properties: prepared by hydrothermal or thermal treatment, three experimentally prepared SiO2 fillers (obtained by precipitation from sodium silicate with sulfuric acid), as well as a hybrid filler (combination of carbon black and SiO2 fillers with optimal properties). The analysis of the influence of the nanoparticles structure, surface and surface activity on the reinforcment of SBR elastomers, as well as the verification of concepts, models and reinforcement theories on non-cross-linked and cross-linked systems of styrene-butadiene nanocomposites was performed. Using the numerous characterization methods, the influence of nanofillers on the mixing characteristics, the rheological properties of the prepared hybrid nanocomposites, as well as the thermal, dynamic-mechanical and mechanical properties of cross-linked SBR nanocomposites was studied, in order to design and optimize the composition of SBR hybrid materials for development of environmental friendly or &quot;green&quot; tyre protector model.<br />The second part of the research was devoted to the preparation of segmented polyurethane elastomeric nanocomposites using aliphatic polycarbonate diols and bentonite nanoparticles, that have found the significant application in the medicine, construction, the furniture and sports equipment industry. Applying numerous characterization methods, a complex mechanism of the influence of the hard segments, thermodynamic incompatibility and the presence of bentonite filler on the structure and morphology, as well as on the thermal and dynamic-mechanical properties of the synthesized thermoplastic elastomers was studied. The obtained data on the hydrogen bonds formation, thermal stability and thermal decomposition, as well as the glass transition temperature and physical crosslink disruption temparature range, makes a significant contribution to the progress in structuring of polycarbonate-based polyurethane elastomers and their hybrid materials, and improves their potential applications for the special purposes.</p>

Es wird eine neue Sequenz von [3,3]-sigmatropen Umlagerungen vorgestellt, die zu 1,2-difunktionalisierten 1,3-Butadienen führt. Dabei werden ausgehend von 3-Butin-1,2-diyl-Derivaten im ersten Umlagerungsschritt 1,2-Butadien-1,4-diyl-Verbindungen erhalten, die anschließend im zweiten Umlagerungsschritt zu den Zielprodukten isomerisieren. Die Anwendungsbreite dieser Synthesemethode wird anhand verschiedener Verbindungsklassen dokumentiert. So gelingt beispielsweise ausgehend von 3-Butinen mit jeweils zwei Imidat-, Thiokohlensäurearylester-, Xantogenat-, Thiocarbamat- sowie Thiobenzoat-Funktionen in 1- und 2-Position die Darstellung der entsprechend 1,2-disubstituierten 1,3-Butadiene, die zwei identische funktionelle Gruppen in Vinylposition tragen. Die geeignete Substitution des Grundgerüstes der 3-Butin-1,2-diyl-Vorläufer zeigt, daß die [3,3]-sigmatropen Isomerisierungen der diastereomeren Edukte stereospezifisch zu den entsprechenden Butadienen führen, die sich bezüglich der Konfiguration der Doppelbindungen unterscheiden. Zur Erklärung dieses Sachverhaltes werden die sterischen Wechselwirkungen diskutiert, die die Konformationen der durchlaufenen Übergangszustände beeinflussen und damit die bevorzugte Bildung bestimmter Konfigurationen der resultierenden Butadiene bedingen. Die Ermittlung der Konfiguration der synthetisierten Diene erfolgt zum einen durch NMR-Spektroskopie, wobei insbesondere die NOE-Differenzspektroskopie ein wertvolles Mittel zur Konfigurationsbestimmung darstellt. Zum anderen werden die unterschiedlichen Reaktivitäten der konfigurationsisomeren Butadiene bei Cycloadditionsreaktionen, speziell Diels-Alder-Reaktionen, zur Aufklärung der Stereochemie der Doppelbindungen genutzt. Gleichzeitig zeigen diese Folgereaktionen exemplarisch das Synthesepotential der Zielprodukte.

The aim of this study was to investigate rubber toughening of resol type phenol-formaldehyde resin. For this purpose, phenolic resin was first modified by only acrylonitrile butadiene rubber, and then by using nitrile rubber together with 3-aminopropyltriethoxysilane. Test specimens were prepared by mixing and casting of liquid phenolic resin in three groups. In the first one, neat phenolic resin specimens were produced. In the second group, phenolic resin was modified with 0.5, 1, 2, and 3 wt.% nitrile rubber, while in the last group modification was carried out by using 0.5 wt.% nitrile rubber together with 1, 2, and 4wt.% amino silane (with respect to nitrile rubber). All specimens were heat cured in the oven. In order to observe behaviors of the specimens, Three-Point Bending, Charpy Impact, Plane-Strain Fracture Toughness, and Dynamic Mechanical Analysis tests were conducted according to the related ISO standards for all specimens groups. Scanning Electron Microscopy was also used for the fractographic analysis of some samples. It can be concluded that, although there were problems in mixing and casting of liquid resol type phenolic resin, its toughness could be improved by using nitrile rubber and amino silane. Modification by using nitrile rubber and amino silane together was much more effective than by using only nitrile rubber. In this synergistic case for instance, Charpy impact strength and fracture toughness values of the neat phenolic specimens were increased 63% and 50%, respectively. SEM studies indicated that the main rubber toughening mechanism was shear yielding observed as deformation lines especially initiated at the domains of nitrile rubber and amino silane.

Dans ce travail de thèse nous décrirons tout d'abord la synthèse de nouveaux composés terpénoïdes par télomérisation de l'éthanolamine avec l'isoprène. Ensuite nous présentons l'utilisation de cette méthode pour la fonctionnalisation des poly-carbohydrates non alimentaires comme le chitosane et une hémicellulose (la gomme de guar) dans l'eau. Avec les substrats bifonctionnels (éthanolamine, chitosane), la réaction de télomérisation des diènes peut avoir lieu avec l'amine ou l'alcool pour conduire à la formation d'éthers ou d'alkylamines fonctionnalisés à longue chaine carbonée. Cette réaction est catalysée par des complexes de palladium-phosphine formés in-situ et est réalisée en présence ou en absence d'une base dans différents solvants (Eau, MeOH, i-PrOH, Eau/iPrOH), y compris en milieu biphasique.L'influence des paramètres réactionnels tels que l'effet du solvant, du précurseur de palladium, de la charge en catalyseur, du rapport Ligand/Palladium, de la nature des ligands phosphines, de la température et du temps réactionnel, de la quantité de diène et de la quantité de la base, a été étudiée. L'activité et la sélectivité de la réaction ont été déterminées en réalisant des analyses de chromatographie gazeuse GC (pour les terpénoïdes), des analyses RMN 1D et 2D (pour les terpénoïdes et les polysaccharides modifiées). Ceci a permis la détermination des conversions, ainsi que des degrés de substitution (DS) des polysaccharides modifiés. Des analyses élémentaires {C, H, N} ont été réalisées pour valider les structures et la pureté des produits obtenus. La stabilité thermique des télomères des carbohydrates (chitosane et gomme de guar) a été étudiée par analyse thermogravimétrique (ATG).Avec l'éthanolamine, le rendement total en terpénoïdes varie de 31% à 81 %, distribués entre des monotélomères (50-80%) et des ditélomères (20-50%). Pour les polysaccharides, des degrés de substitution compris entre 0.03 et 0.61 (DS =0.61 dans l'eau) pour les alkyl-chitosane et 0.01 et 0.31 (dans l'eau) pour la gomme de guar modifiée sont obtenus / In this thesis, we will first describe the synthesis of new terpenoid compounds by telomerization of isoprene with ethanolamine. Then we will present the usage of this method for the functionalization of non-food related poly-carbohydrates such as the hemicellulose (guar gum) and the chitosan in water.With the bifunctional substrates (ethanolamine, chitosan), the reaction of telomerization of the dienes can take place between the amine or the alcohol in order to lead either to the formation of the ethers or to the formation of the functionalized alkylamines with a long carbon chain. This reaction is catalyzed by palladium-phosphine complexes formed in situ, and realized in the presence or in the absence of a base in different solvents (water, MeOH, i-PrOH, water/iPrOH), and in biphasic medium.The influence of reactional parameters such as the effect of the solvent, that of the precursor of palladium, that of the catalyst charge, that of the Ligand/Palladium ratio, that of the nature of the phosphines ligands, that of the temperature and the reaction time, as well as the effect of the quantity of diene and of the base were studied.The activity and the selectivity of the reaction were determined using the gas chromatography analysis (for the terpenoids), and 1D & 2D RMN analyses (for the terpenoids and modified polysaccharides). This allowed us to determine the conversions and the degree of substitution of the modified polysaccharides. Elementary analysis (C, H, N) were also performed to validate the structures and the purity of the products obtained. The thermal stability of the carbohydrates telomeres (chitosan and guar gum) was studied by thermogravimetric analysis.With the ethanolamine, the total yield in terpenoids varied between 31% and 81% and was distributed between monotelomers (50-80%) and ditelomers (20-50%).For the polysaccharides, the degree of substitution obtained varied between 0.03 and 0.61 (DS=0.61 in water) for the alkyl-chitosan and between 0.01 and 0.31 (in water) for the modified guar gum

Cette thèse de doctorat s’intéresse à la fatigue des élastomères, et plus particulièrement des caoutchoucs nitrile hydrogénés (sigle HNBR en anglais). Les HNBR sont des élastomères de haute performance,classiquement utilisés pour des applications industrielles à haute température où une bonne résistance chimique aux hydrocarbures est également requise.La thèse est divisée en trois parties principales.En premier lieu, des améliorations majeures pour les expériences de durée de vie en fatigue des élastomères sont proposées. Une approche expérimentale originale permettant le pilotage des essais en contrainte vraie est détaillée.Grâce à cette méthode, la première « vraie »courbe de Wöhler (contrainte vraie en fonction du nombre de cycles) pour des élastomères est tracée. Ensuite, des outils statistiques, issus de la recherche médicale, permettent une analyse probabiliste des résultats présentant une grande dispersion et des durées de vie censurées.Dans un second temps, ces nouveaux outils sont utilisés pour étudier l'effet de la formulation chimique – les taux d’acrylonitrile et d'hydrogénation notamment - sur la résistance en fatigue du HNBR à 120 oC. Ces résultats sont complétés par des expériences de propagation de fissure de fatigue et par une analyse de l'endommagement. Finalement, l'influence du vieillissement thermique sur la résistance en fatigue du HNBR est étudiée ; deux nouveaux essais sont développés : des essais simultanés de vieillissement et de fatigue, et des expériences de fatigue sur des échantillons préalablement vieillis.De plus, la cristallisation sous tension dans le HNBR est pour la première fois étudiée de manière quantitative / The present PhD thesis is devoted to investigation of fatigue in elastomers, andmore particularly of carbon black-filled hydrogenated nitrile butadiene rubber (HNBR).HNBR is a high performance elastomer classically used for high temperature industrial applications, where high resistance to industrial solvents is also required.The thesis is divided into three main parts.First, major improvements of testing procedures utilized in fatigue life testing ofelastomers are proposed. An original method to prescribe the true stress throughout fatigue experiments is developed; it permits to plot the first “true” Wöhler curve, i.e. true stress vs.number of cycles, for elastomers. Then,statistical tools, widely applied in medical research, are adopted for a comprehensive probabilistic analysis of fatigue life results that exhibit high scatter and censored lifetimes.Second, these novel tools are used to investigate the effect of chemical formulation -acrylonitrile content, percent hydrogenation,and of a composite blend - on fatigue resistance of HNBR at the service temperature of 120 oC. In addition to these fatigue life tests,fatigue crack propagation experiments and microscopic fatigue damage analysis are carried out. Third, the influence of thermal aging on fatigue performances of HNBR is investigated.To this end, two additional fatigue life tests are carried out: simultaneous aging and fatigue experiments, and fatigue experiments on preaged samples.Additionally, strain-induced crystallization in HNBR is studied; for the first time, quantitative relationships between crystallization, strain,and stress are established for unfilled HNBR blends.

Atualmente, o grande apelo mundial às questões ambientais tem forçado cada vez mais as organizações industriais a repensarem o modo de realização de suas atividades. No entanto, a busca por soluções que valorizam a sustentabilidade ambiental não se restringe apenas às fábricas. À sociedade moderna, comprovadamente consumista, cabe a opção de escolher produtos obtidos por tecnologias mais limpas e que, de preferência, sejam de fácil destinação final, não representando risco de acúmulo a posteriori no meio ambiente. Ocorre que, muitas das vezes, a escolha de um produto ecologicamente correto pode não ser a que fornecerá o melhor desempenho mecânico requerido para uma dada aplicação. Nesse sentido, essa Dissertação de Mestrado teve como objetivo mostrar a obtenção de composições à base do copolímero de butadieno-estireno (SBR), com diferentes teores de resíduos elastoméricos de pneus inservíveis gerados por uma empresa recauchutadora, avaliando suas propriedades mecânicas e reológicas. Os resultados obtidos mostraram melhoria na resistência ao rasgamento para composições preparadas com adição de até 120 phr de resíduos de pneus, em comparação com a amostra obtida pela adição somente de negro de fumo como carga, mesmo para frações de resíduos não-peneirados, sugerindo a possibilidade de se empregar esses rejeitos como carga inerte ao sistema polimérico. Os ensaios reológicos demonstraram ser ferramentas essenciais para previsão da homogeneidade das composições, através de testes de varredura de deformação sob freqüência e temperatura constantes. / Currently, the great appeal about the ambiental questions has forced much more companies and industries around the world to search ecological alternatives to their activities. However, the environmental sustainability it is not a task only for the factories. The consumption society must be able to choice products obtained by cleaner technologies and easily disposable. Occurs that the option for correct ecologically articles probably is not the best choice in point of view of mechanical performance. The aim of this M.Sc. Dissertation was to show butadiene-styrene (SBR) compounds filled with varied concentrations of elastomeric wastes from useless tires obtained from recapping factories processes. The samples were submitted to mechanical and rheologycal evaluation. The results showed that samples obtained by addition of up to 120 phr of elastomeric wastes had the best mechanical performance considering tear strength in comparison to sample with only carbon black as filler. Rheological experiments, specially strain sweep tests, showed to be an important tool to predict the homogeneity of compositions and their sensibilities to strain at constant frequency and temperature.