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Yes / The “sliding graft copolymer” (SGC), in which many linear poly-ε-caprolactone (PCL) side chains are bound to cyclodextrin rings of a polyrotaxane (PR), was prepared and employed to toughen brittle polylactide (PLA) with methylene diphenyl diisocyanate (MDI) by reactive blending. The SGC was in situ crosslinked and therefore transformed from a crystallized plastic into a totally amorphous elastomer during reactive blending. Meanwhile, PLA-co-SGC copolymer was formed at interface to greatly improve the compatibility between PLA and SGC, and the chain extension of PLA also occurred, were confirmed by FTIR, GPC, SEM, and TEM. The resulting PLA/SGC/MDI blends displayed super impact toughness, elongation at break and nice biocompatibility. It was inferred from these results the crosslinked SGC (c-SGC) elastomeric particles with sliding crosslinking points performed as stress concentrators and absorbed considerable energy under impact and tension process. / This work was supported by the National Natural Science Foundation of China (50933001, 51221002 and 51320105012).

As a part of a larger effort towards the fundamental understanding of mechanical behaviors of polymers toughened by nanoparticles, this dissertation focuses on the structure-property relationship of epoxies modified with nano-sized poly(ethylene-altpropylene)- b-poly(ethylene oxide) (PEP-PEO) block copolymer (BCP) micelle particles. The amphiphilic BCP toughener was incorporated into a liquid epoxy resin and selfassembled into well-dispersed 15 nm spherical micelle particles. The nano-sized BCP, at 5 wt% loading, can significantly improve the fracture toughness of epoxy (ca. 180% improvement) without reducing modulus at room temperature and exhibits only a slight drop (ca. 5 �C) in glass transition temperature (Tg). The toughening mechanisms were found to be BCP micelle nanoparticle cavitation, followed by matrix shear banding, which mainly accounted for the observed remarkable toughening effect. The unexpected ?nano-cavitation? phenomenon cannot be predicted by existing physical models. The plausible causes for the observed nano-scale cavitation and other mechanical behaviors may include the unique structural characteristics of BCP micelles and the influence from the surrounding epoxy network, which is significantly modified by the epoxy-miscible PEO block. Other mechanisms, such as crack tip blunting, may also play a role in the toughening. Structure-property relationships of this nano-domain modified polymer are discussed. In addition, other important factors, such as strain rate dependence and matrix crosslink density effect on toughening, have been investigated. This BCP toughening approach and conventional rubber toughening techniques are compared. Insights on the decoupling of modulus, toughness, and Tg for designing high performance thermosetting materials with desirable physical and mechanical properties are discussed.

"Learning lessons from nature is the key element in the design of tough and light composites."

Neste trabalho, nanocompósitos de PBT, poli(tereftalato de butileno) e argila brasileira montmorilonita (MMT) modificada organicamente, foram obtidos com e sem agente tenacificante. Sais quaternários de amônio e fosfônio com estruturas químicas diferentes foram utilizados para modificar as argilas. Nanocompósitos de PBT com argilas comerciais, dos Estados Unidos, modificadas com de sais de amônio, foram obtidos para comparação das propriedades. As argilas e os polímeros foram misturados utilizando um misturador e uma extrusora dupla rosca, acoplados a um reômetro de torque. A qualidade da troca catiônica foi avaliada por difração de Raios-X (XRD), inchamento em solventes e análises termogravimétricas (TGA). O estado das argilas modificadas (OMMT) na matriz de PBT foi avaliado por XRD, microscopia ótica e microscopia eletrônica de transmissão (TEM). A dispersão do agente tenacificante foi avaliada por microscopia eletrônica de varredura (SEM). As propriedades mecânicas e de flamabilidade também foram avaliadas. Os resultados de flamabilidade foram explicados com ensaios de (TGA). Os resultados de espaçamento basal obtidos por XRD e inchamento em solventes foram dependentes da arquitetura do sal quaternário utilizado. Os espaçamentos basais ficaram maiores para os sais quaternários de longas cadeias alquílicas. Entretanto, o sal quaternário em excesso não foi eliminado na lavagem. A maior estabilidade térmica foi obtida com sais quaternários de fosfônio. Após a adição ao PBT, foi observado que a adição da argila organofílica na matriz polimérica não contribuiu para a significativa melhora das propriedades mecânicas que, em alguns casos, foram inferiores àquelas do PBT. Entretanto, a retardância a chama apresentou melhores resultados na presença de argila organofílica, sendo ainda melhores apenas na presença de sais quaternários de fosfônio. No sentido de melhorar as propriedades de flamabilidade do PBT sem perder em propriedades mecânicas, utilizou-se o agente tenacificante P(E-co-MA-co-GMA), copolímero etileno acrilato de metila metacrilato de glicidila. Desta forma, foram preservadas as propriedades mecânicas e retardância à chama. / In this work, nanocomposites of PBT, poly (butylene terephthalate) and Brazilian clay montmorillonite (MMT) organically modified were obtained with and without further addition of toughening agent. Quaternary ammonium and phosphonium salts with different chemical structures were used to organically modify the clays. PBT nanocomposites with commercial organoclays were also obtained for comparison. The materials were mixed using a mixer and a twin screw, coupled to a torque rheometer. The efficiency of cation exchange was evaluated by X-ray diffraction (XRD), swelling and thermogravimetric analysis (TGA). The dispersion of PBT with modified clay (OMMT) was evaluated by XRD, optical microscopy and transmission electron microscopy (TEM). The toughness dispersion was evaluated by scanning electron microscopy (SEM). The flammability and mechanical properties were also evaluated. Thermogravimetric analysis (TGA) of the OMMTs and PBT / OMMTs was also studied. The basal spacing obtained from XRD analysis were shown to depend on the architecture of the quaternary salt used and were larger for long alkyl chains. The quaternary salt excess was not removed during the washing step. The highest thermal stability was obtained with quaternary phosphonium salts. After adding the PBT, it was observed that the addition of organoclay to the polymer matrix did not contribute to a significant improvement of mechanical properties and in some cases even resulted in a decrease of mechanical properties. However, the flame retardancy showed best results in the presence of organoclay. The best results for the flammability properties were observed in the presence of only quaternary phosphonium salts. However, these materials were very fragile. In order to improve the flammability properties of PBT maintaining the mechanical properties, a toughening agent P(E-co-MA-co-GMA), copolymer ethylene methyl acrylate glycidyl methacrylate was used. In doing so both the mechanical and flame retardancy were preserved.

This work is mainly focused upon the preparation, processing and evaluation of mechanical and material properties of epoxy/single walled carbon nanotube (SWCNT) nanocomposite thin films. B-staged epoxy/SWCNT nanocomposite thin films at 50% of cure have been prepared for improving conductivity and mechanical performance of laminated composites. The SWCNTs were functionalized by oxidation and subsequent grafting using polyamidoamine generation 0 dendrimers (PAMAM-G0). The epoxy nanocomposites containing SWCNTs were successfully cast into thin films by manipulating degree of cure and viscosity of epoxy. The first section of this study focuses on the covalent oxidation and functionalization of single-walled carbon nanotubes (SWCNTs), which is necessary in order to obtain the full benefit of the SWCNTs inherent properties for reinforcement. In the second section of this work the preparation of B-staged epoxy/SWCNT nanocomposite thin films is discussed and what the purposes of thin films are. Additionally, the morphology as well as mechanical properties is evaluated by numerous means to obtain a clear picture as to the mechanisms of the epoxy/SWCNT nanocomposites. Furthermore, the effects of using sulfanilamide as a more attractive surface modifier for improved dispersion and adhesion and the effects of nylon particles for improved toughening on epoxy/SWCNT nanocomposites are discussed which displays improvements in numerous areas. Finally, based on these findings and previous studies, the B-staged epoxy/SWCNT nanocomposite thin films can be seamlessly integrated into laminated composite systems upon heating, and can serve as interleaves for improving conductivity and mechanical strengths of laminated fiber composite systems.

Neste trabalho, nanocompósitos de PBT, poli(tereftalato de butileno) e argila brasileira montmorilonita (MMT) modificada organicamente, foram obtidos com e sem agente tenacificante. Sais quaternários de amônio e fosfônio com estruturas químicas diferentes foram utilizados para modificar as argilas. Nanocompósitos de PBT com argilas comerciais, dos Estados Unidos, modificadas com de sais de amônio, foram obtidos para comparação das propriedades. As argilas e os polímeros foram misturados utilizando um misturador e uma extrusora dupla rosca, acoplados a um reômetro de torque. A qualidade da troca catiônica foi avaliada por difração de Raios-X (XRD), inchamento em solventes e análises termogravimétricas (TGA). O estado das argilas modificadas (OMMT) na matriz de PBT foi avaliado por XRD, microscopia ótica e microscopia eletrônica de transmissão (TEM). A dispersão do agente tenacificante foi avaliada por microscopia eletrônica de varredura (SEM). As propriedades mecânicas e de flamabilidade também foram avaliadas. Os resultados de flamabilidade foram explicados com ensaios de (TGA). Os resultados de espaçamento basal obtidos por XRD e inchamento em solventes foram dependentes da arquitetura do sal quaternário utilizado. Os espaçamentos basais ficaram maiores para os sais quaternários de longas cadeias alquílicas. Entretanto, o sal quaternário em excesso não foi eliminado na lavagem. A maior estabilidade térmica foi obtida com sais quaternários de fosfônio. Após a adição ao PBT, foi observado que a adição da argila organofílica na matriz polimérica não contribuiu para a significativa melhora das propriedades mecânicas que, em alguns casos, foram inferiores àquelas do PBT. Entretanto, a retardância a chama apresentou melhores resultados na presença de argila organofílica, sendo ainda melhores apenas na presença de sais quaternários de fosfônio. No sentido de melhorar as propriedades de flamabilidade do PBT sem perder em propriedades mecânicas, utilizou-se o agente tenacificante P(E-co-MA-co-GMA), copolímero etileno acrilato de metila metacrilato de glicidila. Desta forma, foram preservadas as propriedades mecânicas e retardância à chama. / In this work, nanocomposites of PBT, poly (butylene terephthalate) and Brazilian clay montmorillonite (MMT) organically modified were obtained with and without further addition of toughening agent. Quaternary ammonium and phosphonium salts with different chemical structures were used to organically modify the clays. PBT nanocomposites with commercial organoclays were also obtained for comparison. The materials were mixed using a mixer and a twin screw, coupled to a torque rheometer. The efficiency of cation exchange was evaluated by X-ray diffraction (XRD), swelling and thermogravimetric analysis (TGA). The dispersion of PBT with modified clay (OMMT) was evaluated by XRD, optical microscopy and transmission electron microscopy (TEM). The toughness dispersion was evaluated by scanning electron microscopy (SEM). The flammability and mechanical properties were also evaluated. Thermogravimetric analysis (TGA) of the OMMTs and PBT / OMMTs was also studied. The basal spacing obtained from XRD analysis were shown to depend on the architecture of the quaternary salt used and were larger for long alkyl chains. The quaternary salt excess was not removed during the washing step. The highest thermal stability was obtained with quaternary phosphonium salts. After adding the PBT, it was observed that the addition of organoclay to the polymer matrix did not contribute to a significant improvement of mechanical properties and in some cases even resulted in a decrease of mechanical properties. However, the flame retardancy showed best results in the presence of organoclay. The best results for the flammability properties were observed in the presence of only quaternary phosphonium salts. However, these materials were very fragile. In order to improve the flammability properties of PBT maintaining the mechanical properties, a toughening agent P(E-co-MA-co-GMA), copolymer ethylene methyl acrylate glycidyl methacrylate was used. In doing so both the mechanical and flame retardancy were preserved.

The industrial demand for high strength-to-weight ratio materials is increasing due to the need for high performance components. Epoxy polymers, although often used in fiber-reinforced polymeric composites, have an inherent low toughness that further decreases with decreasing temperatures. Second-phase additives have been effective in increasing the toughness of epoxies at room temperature; however, the mechanisms at low temperatures are still not understood. In this study, the deformation mechanisms of a DGEBA epoxy modified with MX960 core-shell rubber (CSR) particles were investigated under quasi-static tensile and impact loads at room temperature (RT) and liquid nitrogen (LN2) temperature. Overall, the CSR had little effect on the tensile properties at RT and LN2 temperature. The impact strength decreased from neat to 3 wt% but increased from neat to 5 wt% at RT and LN2 temperature, with a higher impact strength at RT at all CSR loadings. The CSR particles debonded in front of the crack tip, inducing voids into the matrix. It was found that an increase in shear deformation and void growth likely accounted for the higher impact strength at 5 wt% CSR loading at RT while the thermal stress fields due to the coefficient of thermal expansion mismatch between rubber and epoxy and an increase in secondary cracking is likely responsible for the higher impact strength at 5 wt% tested at LN2 temperature. While a large toughening effect was not seen in this study, the mechanisms analyzed herein will likely be of use for further material investigations at cryogenic temperatures.