Literature review of processing and toughening of bulk Al2O3 ceramics was performed. Based on performed experiments, optimal technological conditions of infiltration of alumina ceramics by nickel oxide and zirconia dioxide were found. These approaches were used for preparation of toughened alumina. The properties of sintered alumina matrix composites were discussed from the point of view of their hardness, bending strength, microstructure and phase composition.

Neste trabalho foi estudado o processo de tenacificação do poli(ácido lático), PLA, através da produção de blenda com terpolímero randômico (etileno/éster acrílico/glicidil metacrilato), EMA-GMA, como modificador de impacto. Três composições foram estudadas, 90/10, 80/20 e 70/30% em massa, as misturas foram homogeneizadas em extrusora dupla-rosca (melt blending) e corpos de prova foram moldados por injeção. A avaliação do comportamento mecânico e da eficiência da tenacificação foi realizada através de ensaios mecânicos de tração (ATSM D638), resistência ao impacto Izod com entalhe (ASTM D256), flexão (ASTM D790) e dureza Shore D (ASTM 2240). A presença de umidade e a temperatura de degradação foram avaliadas por análise termogravimétrica (TGA), as temperaturas de transição vítrea (Tg), fusão cristalina (Tm) e grau de cristalinidade foram avaliadas por calorimetria exploratória diferencial (DSC) e a morfologia foi analisada por meio de micrografias obtidas por microscopia eletrônica de varredura (MEV). Os resultados dos ensaios mecânicos idicaram que todas as blendas possuem valores de tenacidade superiores ao do PLA. Entretanto, as blendas apresentaram como efeito colateral queda em módulo (obtidos por ensaios de resistência a tração e flexão), resistência a tração no ponto de escoamento e dureza, em função do aumento da concentração de EMA-GMA no PLA. Na composição com 20% de EMA-GMA a distribuição da dispersa ao longo da fase matriz está mais homogênea, e a composição com 30% de EMA-GMA resultou em um material super tenaz (com valores de resistência ao impacto Izod com entalhe acima de 500J/m). / In this work poly(lactic acid), PLA, was toughened by addition a thermoplastic elastomer, the random terpolymer (ethylene / acrylic ester / glycidyl methacrylate), EMA-GMA. Three= compositions were prepared: with concentrations of 10, 20 and 30 wt% of EMA-GMA into PLA. The blends were prepared in a twin-screw extruder and molded by injection molding. The samples were systematically characterized by tensile strength, notched Izod impact strength, flexural properties and Shore hardness (using Shore D scale). The presence of moisture and the degradation temperature of PLA were evaluated by thermogravimetric analysis (TGA), the glass transition temperature (Tg), crystalline melting (Tm) and crystallinity index of PLA and of the blend were evaluated by differential scanning calorimetry (DSC) and the blend morphology was analyzed by scanning electron microscopy (SEM). The results showed that all blends presented a dramatic increase in their toughness, when compared to PLA. However, the moduli (obtained by tensile and flexural tests), tensile strength at yield, and hardness decreased when the dispersed phase content increased. In the 80/20 PLA/EMA-GMA blend, the dispersed phase is more homogeneously dispersed within the matrix, and the composition with 30 wt% of EMA-GMA resulted in a super tough material (notched Izod impact strength exceeding 500 J/m).

Cette étude porte sur la production et à la caractérisation de matériaux composites à base de matrices d’époxy modifiées par incorporation de particules de caoutchouc recyclées et dévulcanisées. Ces matrices sont renforcées par des fibres d'alumine (Al2O3- FA) et/ou par des nanoplaquettes de graphène (GnPs). Principalement, la fabrication, la caractérisation générale des composites ainsi que l’identification des mécanismes de renforcement à l’échelle micro et nano ont été réalisées. En outre, la fabrication de composites multifonctionnels à base de caoutchouc dévulcanisé et d'époxy a été réalisée pour des applications diverses potentielles dans les industries aéronautique et automobile. Dans un premier temps, les propriétés mécaniques et thermomécaniques des composites ont été étudiées de manière approfondie. L’étude mécanique a consisté à mesurer le module d’élasticité, la ténacité et la température de transition vitreuse. / Recycling of rubber is gaining importance across the world in many industries due to shrinking resources, increasing cost of raw materials, growing conscious about sustainable development as well as environmental issues. In the frame of the common research program between Michigan Tech University/USA and Supmeca/Paris-FRANCE, this PhD work is devoted to the design, development and characterization of recycled rubber modified epoxy-based composites . Additionally, alumina (Al2O3) fibers (AFs) and/or graphene nano platelets (GnPs) have been used as the basic reinforcements. A detailed experimental approach was adapted to these multifunctional composites for explaining of toughening mechanisms by means of fracture toughness test methods and scanning electron microscopy (SEM) on the fracture surfaces. Also, different case studies were included at the end of this work for various potential applications in aeronautic and automotive industries.

The structure-property relationships of epoxy nanocomposites with inorganic layer-structure nanofillers have been studied to obtain the fundamental understanding of the role of nanofillers and the physics of polymer nanocomposites in this dissertation. Several polymer nanocomposite systems with modified montmorillonite (MMT) or α-zirconium phosphate (ZrP) nanofillers were prepared with epoxy matrices of different ductility and properties. The successful nanofiller's exfoliations were confirmed with X-ray diffraction and transmision electronic microscopy (TEM). Dynamic mechanical analysis (DMA) on the prepared epoxy nanocomposites revealed the significant increase in rubbery plateau moduli of the epoxy nanocomposite systems above Tg, as high as 4.5 times, and tensile test results showed improved modulus by the nanofiller addition, while the fracture toughenss was not affected or slightly decreased by nanofillers. The brittle epoxy nanocomposite systems were toughened with core shell rubber (CSR) particles and showed remarkable increase in fracture toughness (KIC) value up to 270%. The CSR toughening is more effective at ductile matrices, and TEM observation indicates that major toughening mechanisms induced by the CSR addition involve a large scale CSR cavitation, followed by massive shear deformation of the matrix.

The effects of melt state compounding and addition order of ethylene-butyl acrylate-maleic anhydride (E-BA-MAH), ethylene-glycidyl methacrylate (E-GMA), ethylene-methyl acrylate-glycidyl methacrylate (E-MA-GMA) terpolymer and/or three types of organoclays (Cloisite&reg / 15A, 25A and 30B) on morphology, thermal, mechanical and dynamic mechanical properties of polyamide-6 are investigated. XRD patterns show that the interlayer spacing for Cloisite&reg / 15A remained unchanged / however it increased for the organoclays Cloisite&reg / 25A and Cloisite&reg / 30B in both polyamide-6/organoclay binary nanocomposites and in polyamide-6/organoclay/impact modifier ternary systems. TEM analyses indicate that exfoliated-intercalated nanocomposites are formed. Sizes of elastomeric domains in nanocomposites are larger than the domains in their corresponding blends. The MFI results show that incorporation of elastomer reduces the MFI, due to the formation of graft copolymer. Both storage and loss moduli and complex viscosity of polyamide-6 increase with organoclay addition. In DMA measurements, in rubbery region, all nanocomposites show higher storage modulus than the unfilled counterparts. In general, the organoclays increase tensile and flexural strength, Young&amp / #8217 / s and flexural modulus and elongation at break, but decrease the impact strength, on the contrary, the addition of elastomer has the opposite effect. Generally, Cloisite&reg / 15A containing ternary nanocomposites have higher tensile, flexural and impact strength and Young&amp / #8217 / s and flexural modulus than the ternary nanocomposites prepared with Cloisite&reg / 25A and Cloisite&reg / 30B. In general, nanocomposites processed by adding all the ingredients simultaneously give higher tensile and flexural strength and modulus than the nanocomposites produced by other mixing sequences.

The structure-property relationships of epoxy nanocomposites with inorganic layer-structure nanofillers have been studied to obtain the fundamental understanding of the role of nanofillers and the physics of polymer nanocomposites in this dissertation. Several polymer nanocomposite systems with modified montmorillonite (MMT) or α-zirconium phosphate (ZrP) nanofillers were prepared with epoxy matrices of different ductility and properties. The successful nanofiller's exfoliations were confirmed with X-ray diffraction and transmision electronic microscopy (TEM). Dynamic mechanical analysis (DMA) on the prepared epoxy nanocomposites revealed the significant increase in rubbery plateau moduli of the epoxy nanocomposite systems above Tg, as high as 4.5 times, and tensile test results showed improved modulus by the nanofiller addition, while the fracture toughenss was not affected or slightly decreased by nanofillers. The brittle epoxy nanocomposite systems were toughened with core shell rubber (CSR) particles and showed remarkable increase in fracture toughness (KIC) value up to 270%. The CSR toughening is more effective at ductile matrices, and TEM observation indicates that major toughening mechanisms induced by the CSR addition involve a large scale CSR cavitation, followed by massive shear deformation of the matrix.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Nesta Dissertação foi realizado um estudo sobre a tenacificação do poliestireno com diferentes tipos de polibutadieno (alto cis, baixo cis e copolímeros dibloco e tribloco de estireno e butadieno). Esses materiais (poliestireno de alto impacto HIPS) foram produzidos por processo de mistura física no estado fundido. Foi realizado um estudo sobre a interação entre a fase rígida do poliestireno (PS) e a fase elastomérica do polibutadieno baixo ou alto cis (PBb ou PBa) das misturas poliméricas, bem como, o grau de interação dos copolímeros em bloco de estireno butadiêno (SB ou SBS) quando a elas são adicionados, em uma percentagem de 2,5%, como agente compatibilizante. As misturas foram analisadas em microscópio eletrônico de varredura (SEM), microscópio eletrônico de transmissão (TEM) e microscópio de força atômica (AFM). As propriedades mecânicas determinadas foram: dureza Shore D, resistência ao impacto (método Izod) e resistência à tração. As propriedades térmicas foram avaliadas por calorimetria diferencial de varredura (DSC), termogravimetria (TG) e análise termodinâmico-mecânica (DMTA). A espectroscopia de ressonância magnética nuclear (NMR) de baixo campo também foi empregada para determinação dos tempos de relaxação de próton (T1) a fim de identificar a formação de domínios do material a nível molecular. Os resultados mostraram que todas as misturas apresentaram um comportamento pseudoplástico. As análises morfológicas indicaram uma morfologia bifásica com domínios de polibutadieno em torno de 1 m de diâmetro, distribuídos aleatoriamente na matriz do poliestireno. Os resultados obtidos nas análises mecânicas mostraram uma melhoria nas propriedades das misturas processadas com polibutadieno alto cis e compatibilizadas com 2,5% do copolímero dibloco de estireno-butadieno (SB). O resultado obtido na análise termogravimétrica revelou uma melhoria da estabilidade térmica dos materiais. Os resultados das análises de DMTA mostraram duas transições distintas. Um aumento significativo da Tg foi observado quando foi utilizado o PBa, indicando uma interação entre as fases. O resultado da análise de NMR mostra uma organização molecular similar nas misturas (PS/PB) e indica que o melhor agente compatibilizante é o copolímero dibloco (SB). / This Dissertation describes a study about the toughening of polystyrene with different types of polybutadiene (high-cis, low-cis and styrene - butadiene diblock or triblock copolymers). These materials (High Impact of PolyStyrene HIPS) were performed by melt blending. The mechanical properties (hardness, tensile strength and impact strength); morphology and the rheological behavior of these blends were evaluated. A study about the interaction between the rigid phase of the polystyrene (PS) and the elastomeric phase of the low or high cis polybutadiene (PBl or PBh ) of the polymeric blends was carried out. It was also studied the interaction degree of the block copolymers (SB or SBS) when they were incorporated in the blend using a percentage of 2.5% (mass fraction), as compatibilizer agent. The morphological analyses of the materials were performed in a scanning electron microscope (SEM), transmission electron microscope (TEM) and atomic force microscope (AFM). The mechanical properties were determined by penetration of an indenter (Shore-Durometer Hardness Type D), by tensile test using a universal testing machine and by impact test using a instrumental impact testing machine. The thermal properties were studied by differential scanning calorimetry (DSC), thermogravimetry (TG) and by dynamic-mechanical thermal analysis (DMTA). The low-field nuclear magnetic resonance (NMR) was applied to determine the proton relaxation time in order to identify the heterogeneity (domain formation) of the material at the molecular level. The results showed that all polymer blends presented pseudoplastic behavior. The morphological analysis showed biphasic morphology with domains of polybutadiene dispersed heterogeneously on the PS matrix, with domains diameter around 1μm. The results obtained by the mechanical analysis showed an improvement on the blends processed with high cis polybutadiene and compatibilized with 2.5% of styrene-butadine diblock copolymer (SB). Thermogravimetry showed an improvement on the thermal stability of the blends. It was also observed by dynamic mechanical thermal analysis two distinct transitions. An increase on the Tg was observed when was used PBh, indicating interaction between the phases. The low field NMR results of the blends (PS/PB) presented a similar molecular organization and showed that the best compatibilizer agent was the diblock copolymer (SB).

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Nesta Dissertação foi realizado um estudo sobre a tenacificação do poliestireno com diferentes tipos de polibutadieno (alto cis, baixo cis e copolímeros dibloco e tribloco de estireno e butadieno). Esses materiais (poliestireno de alto impacto HIPS) foram produzidos por processo de mistura física no estado fundido. Foi realizado um estudo sobre a interação entre a fase rígida do poliestireno (PS) e a fase elastomérica do polibutadieno baixo ou alto cis (PBb ou PBa) das misturas poliméricas, bem como, o grau de interação dos copolímeros em bloco de estireno butadiêno (SB ou SBS) quando a elas são adicionados, em uma percentagem de 2,5%, como agente compatibilizante. As misturas foram analisadas em microscópio eletrônico de varredura (SEM), microscópio eletrônico de transmissão (TEM) e microscópio de força atômica (AFM). As propriedades mecânicas determinadas foram: dureza Shore D, resistência ao impacto (método Izod) e resistência à tração. As propriedades térmicas foram avaliadas por calorimetria diferencial de varredura (DSC), termogravimetria (TG) e análise termodinâmico-mecânica (DMTA). A espectroscopia de ressonância magnética nuclear (NMR) de baixo campo também foi empregada para determinação dos tempos de relaxação de próton (T1) a fim de identificar a formação de domínios do material a nível molecular. Os resultados mostraram que todas as misturas apresentaram um comportamento pseudoplástico. As análises morfológicas indicaram uma morfologia bifásica com domínios de polibutadieno em torno de 1 m de diâmetro, distribuídos aleatoriamente na matriz do poliestireno. Os resultados obtidos nas análises mecânicas mostraram uma melhoria nas propriedades das misturas processadas com polibutadieno alto cis e compatibilizadas com 2,5% do copolímero dibloco de estireno-butadieno (SB). O resultado obtido na análise termogravimétrica revelou uma melhoria da estabilidade térmica dos materiais. Os resultados das análises de DMTA mostraram duas transições distintas. Um aumento significativo da Tg foi observado quando foi utilizado o PBa, indicando uma interação entre as fases. O resultado da análise de NMR mostra uma organização molecular similar nas misturas (PS/PB) e indica que o melhor agente compatibilizante é o copolímero dibloco (SB). / This Dissertation describes a study about the toughening of polystyrene with different types of polybutadiene (high-cis, low-cis and styrene - butadiene diblock or triblock copolymers). These materials (High Impact of PolyStyrene HIPS) were performed by melt blending. The mechanical properties (hardness, tensile strength and impact strength); morphology and the rheological behavior of these blends were evaluated. A study about the interaction between the rigid phase of the polystyrene (PS) and the elastomeric phase of the low or high cis polybutadiene (PBl or PBh ) of the polymeric blends was carried out. It was also studied the interaction degree of the block copolymers (SB or SBS) when they were incorporated in the blend using a percentage of 2.5% (mass fraction), as compatibilizer agent. The morphological analyses of the materials were performed in a scanning electron microscope (SEM), transmission electron microscope (TEM) and atomic force microscope (AFM). The mechanical properties were determined by penetration of an indenter (Shore-Durometer Hardness Type D), by tensile test using a universal testing machine and by impact test using a instrumental impact testing machine. The thermal properties were studied by differential scanning calorimetry (DSC), thermogravimetry (TG) and by dynamic-mechanical thermal analysis (DMTA). The low-field nuclear magnetic resonance (NMR) was applied to determine the proton relaxation time in order to identify the heterogeneity (domain formation) of the material at the molecular level. The results showed that all polymer blends presented pseudoplastic behavior. The morphological analysis showed biphasic morphology with domains of polybutadiene dispersed heterogeneously on the PS matrix, with domains diameter around 1μm. The results obtained by the mechanical analysis showed an improvement on the blends processed with high cis polybutadiene and compatibilized with 2.5% of styrene-butadine diblock copolymer (SB). Thermogravimetry showed an improvement on the thermal stability of the blends. It was also observed by dynamic mechanical thermal analysis two distinct transitions. An increase on the Tg was observed when was used PBh, indicating interaction between the phases. The low field NMR results of the blends (PS/PB) presented a similar molecular organization and showed that the best compatibilizer agent was the diblock copolymer (SB).

Neste trabalho foi estudado o processo de tenacificação do poli(ácido lático), PLA, através da produção de blenda com terpolímero randômico (etileno/éster acrílico/glicidil metacrilato), EMA-GMA, como modificador de impacto. Três composições foram estudadas, 90/10, 80/20 e 70/30% em massa, as misturas foram homogeneizadas em extrusora dupla-rosca (melt blending) e corpos de prova foram moldados por injeção. A avaliação do comportamento mecânico e da eficiência da tenacificação foi realizada através de ensaios mecânicos de tração (ATSM D638), resistência ao impacto Izod com entalhe (ASTM D256), flexão (ASTM D790) e dureza Shore D (ASTM 2240). A presença de umidade e a temperatura de degradação foram avaliadas por análise termogravimétrica (TGA), as temperaturas de transição vítrea (Tg), fusão cristalina (Tm) e grau de cristalinidade foram avaliadas por calorimetria exploratória diferencial (DSC) e a morfologia foi analisada por meio de micrografias obtidas por microscopia eletrônica de varredura (MEV). Os resultados dos ensaios mecânicos idicaram que todas as blendas possuem valores de tenacidade superiores ao do PLA. Entretanto, as blendas apresentaram como efeito colateral queda em módulo (obtidos por ensaios de resistência a tração e flexão), resistência a tração no ponto de escoamento e dureza, em função do aumento da concentração de EMA-GMA no PLA. Na composição com 20% de EMA-GMA a distribuição da dispersa ao longo da fase matriz está mais homogênea, e a composição com 30% de EMA-GMA resultou em um material super tenaz (com valores de resistência ao impacto Izod com entalhe acima de 500J/m). / In this work poly(lactic acid), PLA, was toughened by addition a thermoplastic elastomer, the random terpolymer (ethylene / acrylic ester / glycidyl methacrylate), EMA-GMA. Three= compositions were prepared: with concentrations of 10, 20 and 30 wt% of EMA-GMA into PLA. The blends were prepared in a twin-screw extruder and molded by injection molding. The samples were systematically characterized by tensile strength, notched Izod impact strength, flexural properties and Shore hardness (using Shore D scale). The presence of moisture and the degradation temperature of PLA were evaluated by thermogravimetric analysis (TGA), the glass transition temperature (Tg), crystalline melting (Tm) and crystallinity index of PLA and of the blend were evaluated by differential scanning calorimetry (DSC) and the blend morphology was analyzed by scanning electron microscopy (SEM). The results showed that all blends presented a dramatic increase in their toughness, when compared to PLA. However, the moduli (obtained by tensile and flexural tests), tensile strength at yield, and hardness decreased when the dispersed phase content increased. In the 80/20 PLA/EMA-GMA blend, the dispersed phase is more homogeneously dispersed within the matrix, and the composition with 30 wt% of EMA-GMA resulted in a super tough material (notched Izod impact strength exceeding 500 J/m).

The high functionality epoxy resins tetraglycidyl-4,4’-diaminodiphenyl-methane(TGDDM) and triglycidyl-p-aminophenol (TGPAP) are the main components in most aerospace grade epoxy resin formulations. Owing to their high reactivity and high viscosity, TGDDM and TGPAP pose difficulties when used in wet layup composite manufacturing. As such, these resins are often modified to achieve the desired performance both in the liquid and cured states. The main objective of this thesis is to optimise a low viscosity multi-component epoxy resin formulation suitable for use as an aerospace grade composite matrix. The formulation will allow for the addition of high levels of thermoplastic to improve the fracture toughness of the resin whilst also maintaining resin processability. Through the use of thermal analytical techniques this thesis aims to study the effects of varying the TGDDM/TGPAP ratio, incorporation of a low viscosity bi-functional epoxy resin, the diglycidyl ether of bisphenol F (DGEBF) and changes to the stoichiometric ratio (r)between reactive groups of the epoxy resin and amine hardener (4,4’-diaminodiphenylsulphone, DDS) in multi-component epoxy resin formulations. Resin formulations were optimised using factorial experimental design (FED). Results from two FED’s showed curing multi-component resins at a low stoichiometric ratio significantly increased the processing window whilst also increasing the glass transition temperature (Tg) of the cured resin. No apparent benefit could be assigned to the inclusion of TGDDM owing to its poor processability and a Tg similar to TGPAP. Up to 60% DGEBF was incorporated in a multi-component resin formulation whilst still attaining a Tg greater than 220°C. Its inclusion at 60% had the additional benefit of increasing the processing window by 48 minutes over TGPAP, an increase of 62%. Two optimised resin formulations, 100% TGPAP (100T) and a binary mix of 60% DGEBF and 40% TGPAP (60D) were taken forward to study the effects of adding a thermoplastic toughener (polyethersulphone, PES) in incremental amounts up to 50wt%. SEM images showed all toughened 100T resins had a phase separated morphology whilst all 60D resins were homogenous. The phase separation seen in 100T did not improve the matrix fracture toughness when loaded at 10 wt% and 30 wt% PES. Only when 50 wt% PES was added did fracture toughness increase in comparison to the homogenous 60D resins. Through factorial experimental design two epoxy resin formulations which excluded TGDDM were optimised with a low stoichiometric ratio. The optimum aerospace formulation is dependent on the desired processability and fracture toughness of the resin. High DGEBF-containing formulations give the longest processing windows whilst the 100% TGPAP formulation toughened with 50% PES has the highest fracture toughness.