Phosphorus containing monomers, bis(3-aminophenyl)methyl phosphine oxide (m-DAMPO) and bis(3-aminophenyl)phenyl phosphine oxide (m-DAPPO), were synthesized and incorporated into a thermoplastic poly(arylene ether imide) based upon 2,2'-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride and 1,3-phenylene diamine, in order to study their influence on flame resistance and other properties. DAMPO or DAPPO were quantitatively incorporated in concentrations of 25, 50, 75 and 100 mole percent, using the "one pot" ester-acid method. The number average molecular weights of the prepared materials were controlled to 20,000g/mol by off-setting the stoichiomety and endcapping with phthalic anhydride. This strategy enabled one to distinguish the effects of the phosphine oxide incoporation from the influence of molecular weight. The resulting copolymers demonstrated a significant increase in char yield as a function of the phosphine oxide content, thus suggesting improved fire resistance. Glass transition temperatures similar to the control were determined by DSC analysis. Analysis of the mechanical behavior of the DAMPO system at room temperature showed that tensile strength and elongation at failure values were comparable to the control system, while the DAPPO containing copolymers were surprisingly brittle. The influence of the reactive endgroup on the synthesis, cure behavior and network properties of thermosetting polyetherimides was investigated. Reactive phenylacetylene, acetylene and maleimide terminated poly(ether imide) oligomers were prepared and characterized. Optimal reaction conditions were established to produce fully endcapped oligomers with imidized structures and controlled molecular weight. The phenylacetylene endcapped system was synthesized by a conventional ester-acid method. The acetylene endcapped system was prepared via modified ester-acid method and the maleimide endcapped system was fabricated utilizing an amic-acid route. It was determined that phenylethynyl endcapped polymers could be thermally cured at high temperatures (350-380°C) providing good processibility. The networks exhibited thermal stability, chemical resistance and good adhesion strength, ideal as "primary" bonding adhesives. Acetylene and maleimide endcapped systems were prepared for application as "secondary" bonding materials, meaning that they are cured at a lower temperature than that of the Tg of the primary structure. Lap shear test results indicated good adhesion to titanium when cured at 250°C -280°C. The cured materials showed high glass transition temperatures and good thermal and thermo-oxidative stability as determined by DSC, TGA and DMA. Good chemical resistance was demonstrated via solvent extraction measurements. The influence of molecular weight between crosslinks (Mc) on thermal and mechanical behavior was also investigated. Lower molecular weight oligomers exhibited lower Tg and cure temperatures, whereas the cured networks resulting from lower molecular weight oligomers afforded higher Tg and higher gel fractions, but reduced toughness. / Ph. D.

This labor is based on penetration of adhesives into a wood cell walls. It focuses mainly on adhesives that are currently used for construction purposes. It also contains a methodics of selecting adhesives and wood, which will be used for glued joints and summarizes the methods used for detect these adhesives in the wood cell wall. It experimentally verifies the appropriate selection of the dye-solvent combination used in the adhesive.

In this dissertation, four test approaches were developed to characterize the adhesion performance and durability of adhesive bonds for specific applications in areas spanning from structural adhesive joints to popular confectionaries such as chewing gum. In the first chapter, a double cantilever beam (DCB) specimen geometry is proposed for combinatorial fracture studies of structural adhesive bonds. This specimen geometry enabled the characterization of fracture energy vs. bondline thickness trends through fewer tests than those required during a conventional "one at a time" characterization approach, potentially offering a significant reduction in characterization times. The second chapter investigates the adhesive fracture resistance and crack path selection in adhesive joints containing patterns of discreet localized weak interfaces created using physical vapor deposition of copper. In a DCB specimen tested under mode-I conditions, fracture energy within the patterned regions scaled according to a simple rule of mixture, while reverse R-curve and R-curve type trends were observed in the regions surrounding weak interface patterns. Under mixed mode conditions such that bonding surface with patterns is subjected to axial tension, fracture energy did not show R-curve type trends while it was observed that a crack could be made to avoid exceptionally weak interfaces when loaded such that bonding surface with defects is subjected to axial compression. In the third chapter, an adaptation of the probe tack test is proposed to characterize the adhesion behavior of gum cuds. This test method allowed the introduction of substrates with well-defined surface energies and topologies to study their effects on gum cud adhesion. This approach and reported insights could potentially be useful in developing chewing gum formulations that facilitate easy removal of improperly discarded gum cuds from adhering surfaces. In the fourth chapter we highlight a procedure to obtain insights into the long-term performance of silicone sealants designed for load-bearing applications such as solar panel support sealants. Using small strain constitutive tests and time-temperature-superposition principle, thermal shift factors were obtained and successfully used to characterize the creep rupture master curves for specific joint configurations, leading to insights into delayed failures corresponding to three years through experiments carried out in one month. / Ph. D.

As pontes tradicionais de madeira no Brasil, nem sempre atingem as condições plenamente satisfatórias em estradas vicinais, exigem manutenção contínua e a maioria não está adequada ao tráfego pesado usual. As pontes mistas de madeira e concreto destacam-se como alternativa econômica apresenta grande resistência e rigidez além de exigir baixa manutenção. Neste trabalho os estudos dos tabuleiros mistos de madeira e concreto para pontes desenvolveram-se em três fases: estudo da ancoragem de barras de aço coladas em peças estruturais de madeira; estudo dos conectores de cisalhamento formados por barras de aço coladas na madeira em corpos-de-prova mistos de madeira e concreto e, estudos; construções e análises de protótipos de tabuleiros mistos de madeira e concreto. Nos estudos de ancoragens, as barras de aço com superfície deformada, do tipo CA-50 com tensão de escoamento 'F IND.Y,K' = 500 MPa, foram coladas em furos com diâmetros maiores, inclinadas de '0, 45 e 90 GRAUS' em relação às fibras das madeiras. Utilizaram-se quatro tipos de resina epóxi e uma poliuretana, considerando as principais variáveis que influenciam na resistência de ancoragem. Os corpos-de-prova foram construídos com amostragens de madeiras de: Eucalyptus citriodora (ρ 12% = 1000 kg/'M POT.3') e Pinus oocarpa shiede (ρ 12% = 550 kg/'M POT.3'). Os testes de ancoragem apresentam as estimativas das resistências médias obtidas por meio de análise de regressão múltipla e as resistências características, obtidas pelo limite inferior do intervalo de confiança a 90%. Nos estudos dos conectores de cisalhamento utilizaram-se corpos-de-prova mistos, do tipo push out, executados com madeira roliça natural de Eucalyptus citriodora tratada com CCA e concreto armado de média resistência. Os conectores de cisalhamento, em três variações, foram executados com barras de aço do tipo CA-50 ancoradas na madeira, com a resina epóxi SIKADUR 32 fluido e inclinados de '45 GRAUS' em relação às fibras, os resultados apresentam, as resistências últimas médias, as resistências características; os valores médios e os valores característicos dos módulos de deslizamento da conexão. Nos estudos, projetos e execuções de dois tabuleiros mistos, de madeira e concreto, utilizaram-se toras de Eucalyptus citriodora tratadas com CCA, concreto armado de média resistência e conectores de barras de aço coladas com resina epóxi no formato X. Análises estáticas foram realizadas submetendo os tabuleiros às provas de carga, utilizando caminhões. Os deslocamentos na linha central transversal foram medidos e comparados com os valores teóricos calculados usando um modelo de cálculo que considera o tabuleiro misto como uma placa ortotrópica equivalente. Os conectores apresentaram alta resistência; alta rigidez e modo de ruptura uniforme. Os tabuleiros mistos de madeira e concreto apresentaram muito bom desempenho, confirmaram-se as hipóteses fundamentais e o modelo de cálculo proposto. / The traditional timber bridges in secondary roads in Brazil not always meet the requirements of quality, but they also demand continuing maintenance and adequacy to heavy traffic. The mixed wood-concrete deck bridges arise as a viable alternative, because of its low construction cost, low maintenance and its high strength and stiffness. In this thesis the mixed wood concrete deck bridge studies was showed in three phases: the experimental pull out strength results of bonded-in steel rods in wood beams studs; the experimental analysis on shear connectors in mixed wood concrete specimens using bonded-in steel bars and, designs; constructions and statistics tests on log-concrete composed deck bridges was presented too. In the anchorage studies the deformed and reinforced CA-50 steel bars, with the minimum yield strength of 500 Mpa, were bonded in holes drilled at angles of '0, 45 and 90 DEGREES' between the rods and on the direction of grain. Four types of epoxy and one polyurethane adhesive were used regarding the influence of the most significant variables. The specimens were made using Eucalyptus citriodora (ρ 12% = 1000 kg/'M POT.3') and Pinus oocarpa shiede (ρ 12% = 550 kg/'M POT.3') beams. The pull out tests presents the median strength results estimated by multiple regression analysis and the characteristics response estimated by the lower range in 90% of the confidence interval. In the shear connections studies were carried using specimens of push out tests type made of logs of Eucalyptus citriodora treated with CCA and medium strength reinforced concrete. The shear connectors, in three shapes, were made with CA-50 steel bars bonded-in wood with SIKADUR 32 fluid epoxi resin, with '45 DEGREES' angles between the rods and on the direction of grain. The results presents the ultimate limit strength median, the characteristics strength, the slip modulus medians and the characteristics slip modulus. In the studies, designs and executions of two mixed wood-concrete decks bridge were used made of logs of Eucalyptus citriodora treated with CCA, medium strength reinforced concrete, and bonded-in steel CA-50 rods, as shear connectors in X format. Same static loads test on the bridges was carried out using a truck. Deflections in the medium span transversal directions were measured and analytically predicted using an equivalent orthotropic plate model. The shear connectors showed high ultimate strength and stiffness and, uniforms failure mode. The results showed a very good performance to the composed log-concrete deck bridges, it confirms the fundamental hypothesis and calculus model suggested.

Atualmente, as indústrias brasileiras recorrem a normas de outros países para o controle de qualidade para a caracterização de elementos estruturais feitos de Madeira Laminada Colada (MLC) e de LVL (Laminated Veneer Lumber) devido à ausência de especificações nacionais. Este trabalho teve como finalidade a verificação da adequação de alguns métodos de ensaios propostos nos projetos de norma ABNT NBR PN 02:126.10-001-3 e ABNT NBR PN 02:126.10-001-5 para determinar as propriedades dos elementos estruturais de madeira colada para o controle de qualidade da indústria produtora. Para tanto, foram obtidos das indústrias vários grupos de vigas de MLC e grupos de emendas dentadas produzidos com diversas combinações de madeiras e adesivos. Também, foram obtidos grupos de vigas de LVL na posição horizontal e grupos de vigas de LVL na posição de vertical. Foram realizados testes de flexão estática para determinação do módulo de ruptura e de elasticidade de todas as vigas. Além disso, das vigas foram retirados corpos de prova para realização dos ensaios de cisalhamento na linha de cola, delaminação e compressão paralela às fibras, enquanto as emendas dentadas foram analisadas pelo ensaio de tração paralela às fibras. Os procedimentos empregados podem ser considerados adequados para aplicação pelas indústrias no controle de qualidade da produção de elementos estruturais de MLC e de LVL. O ensaio de delaminação para adesivos expostos a ambientes externos, proposto no projeto de norma, pode ser analisado como prático e eficaz. Em relação aos testes de cisalhamento, o número de análises por amostra pode ser reduzido, desde que, priorize o ensaio na região central da seção transversal devido à maior concentração de tensões de cisalhamento. Como era esperado, as emendas dentadas formaram pontos de fragilidade, reduzindo a resistência de algumas vigas e tendo sua ruptura evidenciada por esforço de tração. No LVL, a posição vertical apresentou melhor resistência à flexão e ao cisalhamento do que a horizontal. O projeto de norma é apresentado em anexo nesse trabalho. / Nowadays, the Brazilian industries follow the foreign countries standard regulation to the quality control of characterization of structural elements produced from Glued Laminated Timber (glulam) and Laminated Veneer Lumber (LVL) due to the absence of national specifications. This work has the purpose of verifying the suggested methods of regulation projects, such as ABNT NBR PN 02:126.10-001-3 and ABNT NBR PN 02:126.10-001-5, to determine the properties of glued timber structural elements to quality control of producer industry. Therefore, glulam beams and fingerjoints groups, produced from several combinations of woods and adhesives, were obtained from industries. In addition, it was used flatwise LVL beams groups and edgewise LVL beams groups. It was made the static bending tests to determine strength and stiffness for each beam. Furthermore, from the beams it was extracted samples in order to test shear in the glue line, delamination and parallel grain compression whereas the fingerjoints were analysed by the parallel grain tensile test. The procedures taken on the experimental program can be considered suitable for industrial usage at quality control of production of structural elements from glulam and LVL. The delamination test for adhesive exposed to external environment, proposal in the new standard, can be analysed as practical and effective. In relation to the shear test, the number of analysis by sample can be reduced, whether prioritized the test in the central region of transversal section due to higher shear stress concentration. As expected, the fingerjoints formed fragile points, reducing strength for some beams and by presenting rupture when tensile stressed. In the LVL, the edgewise groups presented better bending and shear resistance than flatwise groups. The new test method is presented in annex in this dissertation.

Submitted by Claudia Rocha (claudia.rocha@udesc.br) on 2017-12-08T13:57:32Z No. of bitstreams: 1 PGEF16MA066.pdf: 1624060 bytes, checksum: 61f98997f35b2a6f9e48ef3f872a39b6 (MD5) / Made available in DSpace on 2017-12-08T13:57:32Z (GMT). No. of bitstreams: 1 PGEF16MA066.pdf: 1624060 bytes, checksum: 61f98997f35b2a6f9e48ef3f872a39b6 (MD5) Previous issue date: 2016-07-29 / UNIEDU / FUMDES / The geometry of finger joint is one of the most important variables when determining the connection strength among timber with structural use purpose. This research aimed to evaluate three finger joint geometries and its correlation with three species of timber from reforestation and three adhesives used for structural purposes. The species were: Eucalyptus grandis, Pinus taeda and Schizolobium parahyba var. amazonicum (known as paricá), and the adhesives: resorcinol formaldehyde, melamine urea formaldehyde and reactive polyurethane. Finger profiles were produced by means of a spindle moulder, glued and pressed in manufacture plant and laboratory. Then, the specimens were flattened obtaining the dimensions as recommended by NBR 7190/1997. The finger joint geometry was measured with a digital caliper, the specimens were tested and the failure modes determined. Statistical analysis was done by evaluating the geometric means by Tukey test with 95% probability. Results showed that E. grandis produced with resorcinol adhesive from geometry B, had the highest tensile strength parallel to the fibers (67,55 MPa). Also, the higher tensile strength values were from the specimens with higher basic density. As for failure modes, 64% of the specimens failed in modes number 3 (14%) and 4 (50%). It was found that all evaluated factors interfered in the results of resistance and, regarding the determination of the best geometry, specie and adhesive, these can not be analyzed separately / A geometria da emenda por entalhes múltiplos é uma das variáveis mais importantes quando se determina a resistência da ligação entre madeiras com finalidade de uso estrutural. O objetivo da pesquisa foi avaliar três geometrias de emendas por entalhes múltiplos e sua correlação com três espécies de madeira de florestas plantadas e três adesivos utilizados para fins estruturais. As espécies foram o Eucalyptus grandis, o Pinus taeda e o Schizolobium parahyba var amazonicum (paricá), e os adesivos: resorcina formaldeído, melamina ureia formaldeído e poliuretano reativo. Os corpos de prova foram fresados, colados e prensados em parque fabril e em laboratório. Posteriormente, eles foram aplainados obtendo-se as dimensões conforme orientação da NBR 7190/1997. Foram medidas as geometrias com paquímetro digital, realizados pré-testes e determinados os modos de ruptura. A análise estatística foi feita avaliando-se as médias de geometria pelo teste de Tukey a 95% de probabilidade. Dos resultados obtidos, destaca-se a espécie E. grandis produzida com o adesivo resorcina da geometria B, que teve a maior resistência à tração paralela às fibras (67,55 MPa). Também, os maiores valores de tensão foram provenientes dos corpos de prova com maior densidade básica. Quanto aos modos de ruptura, 64% dos corpos de prova romperam pelos tipos 3 (14%) e 4 (50%). Verificou-se que todos os fatores avaliados interferiram nos resultados de resistência e, no que se refere à determinação damelhor geometria, melhor espécie e melhor adesivo, não podem ser analisados separadamente

As pontes tradicionais de madeira no Brasil, nem sempre atingem as condições plenamente satisfatórias em estradas vicinais, exigem manutenção contínua e a maioria não está adequada ao tráfego pesado usual. As pontes mistas de madeira e concreto destacam-se como alternativa econômica apresenta grande resistência e rigidez além de exigir baixa manutenção. Neste trabalho os estudos dos tabuleiros mistos de madeira e concreto para pontes desenvolveram-se em três fases: estudo da ancoragem de barras de aço coladas em peças estruturais de madeira; estudo dos conectores de cisalhamento formados por barras de aço coladas na madeira em corpos-de-prova mistos de madeira e concreto e, estudos; construções e análises de protótipos de tabuleiros mistos de madeira e concreto. Nos estudos de ancoragens, as barras de aço com superfície deformada, do tipo CA-50 com tensão de escoamento 'F IND.Y,K' = 500 MPa, foram coladas em furos com diâmetros maiores, inclinadas de '0, 45 e 90 GRAUS' em relação às fibras das madeiras. Utilizaram-se quatro tipos de resina epóxi e uma poliuretana, considerando as principais variáveis que influenciam na resistência de ancoragem. Os corpos-de-prova foram construídos com amostragens de madeiras de: Eucalyptus citriodora (ρ 12% = 1000 kg/'M POT.3') e Pinus oocarpa shiede (ρ 12% = 550 kg/'M POT.3'). Os testes de ancoragem apresentam as estimativas das resistências médias obtidas por meio de análise de regressão múltipla e as resistências características, obtidas pelo limite inferior do intervalo de confiança a 90%. Nos estudos dos conectores de cisalhamento utilizaram-se corpos-de-prova mistos, do tipo push out, executados com madeira roliça natural de Eucalyptus citriodora tratada com CCA e concreto armado de média resistência. Os conectores de cisalhamento, em três variações, foram executados com barras de aço do tipo CA-50 ancoradas na madeira, com a resina epóxi SIKADUR 32 fluido e inclinados de '45 GRAUS' em relação às fibras, os resultados apresentam, as resistências últimas médias, as resistências características; os valores médios e os valores característicos dos módulos de deslizamento da conexão. Nos estudos, projetos e execuções de dois tabuleiros mistos, de madeira e concreto, utilizaram-se toras de Eucalyptus citriodora tratadas com CCA, concreto armado de média resistência e conectores de barras de aço coladas com resina epóxi no formato X. Análises estáticas foram realizadas submetendo os tabuleiros às provas de carga, utilizando caminhões. Os deslocamentos na linha central transversal foram medidos e comparados com os valores teóricos calculados usando um modelo de cálculo que considera o tabuleiro misto como uma placa ortotrópica equivalente. Os conectores apresentaram alta resistência; alta rigidez e modo de ruptura uniforme. Os tabuleiros mistos de madeira e concreto apresentaram muito bom desempenho, confirmaram-se as hipóteses fundamentais e o modelo de cálculo proposto. / The traditional timber bridges in secondary roads in Brazil not always meet the requirements of quality, but they also demand continuing maintenance and adequacy to heavy traffic. The mixed wood-concrete deck bridges arise as a viable alternative, because of its low construction cost, low maintenance and its high strength and stiffness. In this thesis the mixed wood concrete deck bridge studies was showed in three phases: the experimental pull out strength results of bonded-in steel rods in wood beams studs; the experimental analysis on shear connectors in mixed wood concrete specimens using bonded-in steel bars and, designs; constructions and statistics tests on log-concrete composed deck bridges was presented too. In the anchorage studies the deformed and reinforced CA-50 steel bars, with the minimum yield strength of 500 Mpa, were bonded in holes drilled at angles of '0, 45 and 90 DEGREES' between the rods and on the direction of grain. Four types of epoxy and one polyurethane adhesive were used regarding the influence of the most significant variables. The specimens were made using Eucalyptus citriodora (ρ 12% = 1000 kg/'M POT.3') and Pinus oocarpa shiede (ρ 12% = 550 kg/'M POT.3') beams. The pull out tests presents the median strength results estimated by multiple regression analysis and the characteristics response estimated by the lower range in 90% of the confidence interval. In the shear connections studies were carried using specimens of push out tests type made of logs of Eucalyptus citriodora treated with CCA and medium strength reinforced concrete. The shear connectors, in three shapes, were made with CA-50 steel bars bonded-in wood with SIKADUR 32 fluid epoxi resin, with '45 DEGREES' angles between the rods and on the direction of grain. The results presents the ultimate limit strength median, the characteristics strength, the slip modulus medians and the characteristics slip modulus. In the studies, designs and executions of two mixed wood-concrete decks bridge were used made of logs of Eucalyptus citriodora treated with CCA, medium strength reinforced concrete, and bonded-in steel CA-50 rods, as shear connectors in X format. Same static loads test on the bridges was carried out using a truck. Deflections in the medium span transversal directions were measured and analytically predicted using an equivalent orthotropic plate model. The shear connectors showed high ultimate strength and stiffness and, uniforms failure mode. The results showed a very good performance to the composed log-concrete deck bridges, it confirms the fundamental hypothesis and calculus model suggested.

Atualmente, as indústrias brasileiras recorrem a normas de outros países para o controle de qualidade para a caracterização de elementos estruturais feitos de Madeira Laminada Colada (MLC) e de LVL (Laminated Veneer Lumber) devido à ausência de especificações nacionais. Este trabalho teve como finalidade a verificação da adequação de alguns métodos de ensaios propostos nos projetos de norma ABNT NBR PN 02:126.10-001-3 e ABNT NBR PN 02:126.10-001-5 para determinar as propriedades dos elementos estruturais de madeira colada para o controle de qualidade da indústria produtora. Para tanto, foram obtidos das indústrias vários grupos de vigas de MLC e grupos de emendas dentadas produzidos com diversas combinações de madeiras e adesivos. Também, foram obtidos grupos de vigas de LVL na posição horizontal e grupos de vigas de LVL na posição de vertical. Foram realizados testes de flexão estática para determinação do módulo de ruptura e de elasticidade de todas as vigas. Além disso, das vigas foram retirados corpos de prova para realização dos ensaios de cisalhamento na linha de cola, delaminação e compressão paralela às fibras, enquanto as emendas dentadas foram analisadas pelo ensaio de tração paralela às fibras. Os procedimentos empregados podem ser considerados adequados para aplicação pelas indústrias no controle de qualidade da produção de elementos estruturais de MLC e de LVL. O ensaio de delaminação para adesivos expostos a ambientes externos, proposto no projeto de norma, pode ser analisado como prático e eficaz. Em relação aos testes de cisalhamento, o número de análises por amostra pode ser reduzido, desde que, priorize o ensaio na região central da seção transversal devido à maior concentração de tensões de cisalhamento. Como era esperado, as emendas dentadas formaram pontos de fragilidade, reduzindo a resistência de algumas vigas e tendo sua ruptura evidenciada por esforço de tração. No LVL, a posição vertical apresentou melhor resistência à flexão e ao cisalhamento do que a horizontal. O projeto de norma é apresentado em anexo nesse trabalho. / Nowadays, the Brazilian industries follow the foreign countries standard regulation to the quality control of characterization of structural elements produced from Glued Laminated Timber (glulam) and Laminated Veneer Lumber (LVL) due to the absence of national specifications. This work has the purpose of verifying the suggested methods of regulation projects, such as ABNT NBR PN 02:126.10-001-3 and ABNT NBR PN 02:126.10-001-5, to determine the properties of glued timber structural elements to quality control of producer industry. Therefore, glulam beams and fingerjoints groups, produced from several combinations of woods and adhesives, were obtained from industries. In addition, it was used flatwise LVL beams groups and edgewise LVL beams groups. It was made the static bending tests to determine strength and stiffness for each beam. Furthermore, from the beams it was extracted samples in order to test shear in the glue line, delamination and parallel grain compression whereas the fingerjoints were analysed by the parallel grain tensile test. The procedures taken on the experimental program can be considered suitable for industrial usage at quality control of production of structural elements from glulam and LVL. The delamination test for adhesive exposed to external environment, proposal in the new standard, can be analysed as practical and effective. In relation to the shear test, the number of analysis by sample can be reduced, whether prioritized the test in the central region of transversal section due to higher shear stress concentration. As expected, the fingerjoints formed fragile points, reducing strength for some beams and by presenting rupture when tensile stressed. In the LVL, the edgewise groups presented better bending and shear resistance than flatwise groups. The new test method is presented in annex in this dissertation.

La démocratisation des technologies du collage dans le domaine aérospatial amène les industriels à exiger des adhésifs toujours plus performants. L’objectif de cette thèse est d’optimiser les propriétés thermomécaniques d’un adhésif polyépoxyde bi-composant qui devra présenter des propriétés structurales entre -150°C et +150°C, tout en respectant des exigences de mise en oeuvre.L’analyse de la littérature et des expériences préliminaires a permis de sélectionner le système polyépoxyde modèle binaire le plus pertinent en termes de réactivité à l’ambiante et de propriétés sur assemblage collé. Pour optimiser la résistance en température élevée de ce système, deux voies ont été explorées : l’incorporation d’époxydes multi-fonctionnalisés pour augmenter la densité de réticulation, et l’utilisation d’amines cycliques qui accroit la rigidité des segments macromoléculaires. Pour améliorer les propriétés de résistance à la propagation de fissure à basse température, les additifs de renforcement montrent un intérêt certain pour la formulation d’adhésifs structuraux polymérisés à température ambiante. Sur la base de ces résultats, plusieurs formulations complexes ont pu être élaborées. Des phénomènes de synergie et d’inhibition entre les différents éléments des formulations ont été constatés, sans pouvoir être totalement compris ce qui met en lumière la difficulté de prévoir le comportement d’adhésifs complexes, à l’image des formulations commerciales.Ces travaux de thèse ont permis de développer un adhésif structural répondant aux exigences strictes du secteur aérospatial, et de dégager une stratégie de formulation qui pourra être appliquée à d’autres secteurs d’activités. / The democratisation of bonding technologies in aerospace field leads industrials to demand more and more efficient adhesives. The aim of this thesis is to optimise thermomechanical properties of two-component epoxy adhesives which need to preserve structural properties on a large scale of temperature (from -150°C to +150°C) and observing application process requirements.The analysis of scientific literature and preliminary experiments enable to select the most relevant binary epoxy system in terms of reactivity and bonding mechanical properties. To optimise high temperature resistance of this epoxy system, two approaches have been explored: addition of multi-functionalised epoxy resin to extend the crosslink density, and use of cycloaliphatic amines which increase the rigidity of macromolecular segments. To improve crack propagation resistance in low temperature, tougheners reveal an interest to formulate room temperature structural adhesives. On the basis of these results, complex formulations have been developed. Synergy and inhibition phenomenon between the formulation blends have been observed without being able to fully understand them which highlight the difficulty to predict the behaviour of complex adhesives such as commercial formulations.This thesis works allowed to develop a two-component epoxy adhesive formulation which meets aerospace requirements, and to bring about a formulation strategy which could be adapted to others sectors activities.

Le dimensionnement des joints collés est une préoccupation majeure du CNES pour lesapplications spatiales des futurs lanceurs. Pour dimensionner une structure collée, il est nécessaire depouvoir apprécier les caractéristiques mécaniques du joint collé.Dans cette étude, trois adhésifs structuraux ont été sélectionnés (Hysol®EA 9321, Hysol®EA9394 et Hysol EA® 9395). Après leur caractérisation massique, une étude statistique pour mettre enévidence les effets des différents paramètres (vitesse d’essai, géométrie éprouvette, le degré depolymérisation…) a été entreprise.La deuxième étape a pour objectif de fiabiliser l’analyse des essais de fissuration etd’améliorer la compréhension des mécanismes d’endommagement et de propagation de fissure dansles liaisons collées. Trois types d’essai ont été utilisés, à savoir, l’essai Double Cantilever Beam(DCB), pour l’étude du mode I, l’essai End Notched Flexure (ENF), pour le mode II, et l’essai MixedMode Bending (MMB), pour les chargements en mode mixte I/II. Nous avons développé de nouvellesinstrumentations et méthodologies d’analyse. Pour affiner le protocole de test standard, la techniquedite de « backface strain monitoring » a été utilisée. Elle consiste à positionnées des jauges dedéformation sur les surfaces de l’éprouvette de façon à enregistrer l’évolution du signalextensométrique durant la propagation de la fissure. Cette méthode permet une meilleure estimation dela position front de fissure ainsi que l'étude de la répartition des contraintes le long du joint de colle.La corrélation d'images numériques (DIC) a également été utilisée afin de proposer un nouveauprotocole de calibrage de la longueur de fissure et pour comparer un modèle analytique (poutre deTimoshenko sur fondation élastique) avec les résultats expérimentaux. / Adhesive bonding is being strongly considered in space applications CNES as anadvantageous assembly technique for future launchers. Correct design of adhesive joints is of majorconcern. Aerospace adhesives are tough viscoelastic matrices (special epoxy resins) reinforced withnano-, or microparticles. Extended use of adhesive joints in structural applications is limited due to thedifficulties in predicting in-service performance, frequently leading to over-conservative design.Three structural adhesives (Hysol®EA 9321, Hysol®EA 9394 and Hysol®EA 9395) wereselected. After their bulk characterization, statistical studies to highlight effects of different parameterse.g. speed, test piece geometry, degree of polymerization were undertaken.In the second stage, fracture mechanics tests were effected employing: the double cantileverbeam (DCB) configuration (mode I characterisation), the three point bending end-notched flexure(ENF) (mode II) and the mixed-mode bending (MMB) (combined mode I/II loading). Crack growth inbonded joints was investigated in a novel way. To refine standard test protocol, the backface strainmonitoring technique was used. Strain gauges were used to measure the strain on the exposed skin ofthe adherends during crack onset and propagation. This method allows better estimation of the crackfront position as well as fine investigation of the stress distribution along the bondline and in the crackfront vicinity. Digital image correlation (DIC) was also used to compare analytical models, e.g.Timoshenko beam on elastic foundation model with experimental results.