## Modification of Epoxy Systems for Mechanical Performance Improvement

• Epoxy belongs to a category of high-performance thermosetting polymers which have been used extensively in industrial and consumer applications. Highly cross-linked epoxy polymers offer excellent mechanical properties, adhesion, and chemical resistance. However, unmodified epoxies are prone to brittle fracture and crack propagation due to their highly crosslinked structure. As a result, epoxies are normally toughened to ensure the usability of these materials in practical applications. This research work focuses on the development of novel modified epoxy matrices, with enhanced mechanical, fracture mechanical and thermal properties, suitable to be processed by filament winding technology, to manufacture composite based calender roller covers with improved performance in comparison to commercially available products. In the first stage, a neat epoxy resin (EP) was modified using three different high functionality epoxy resins with two type of hardeners i.e. amine-based (H1) and anhydride-based (H2). Series of hybrid epoxy resins were obtained by systematic variation of high functionality epoxy resin contents with reference epoxy system. The resulting matrices were characterized by their tensile properties and the best system was chosen from each hardener system i.e. amine and anhydride. For tailored amine based system (MEP_H1) 14 % improvement was measured for bulk samples similarly, for tailored anhydride system (MEP_H2) 11 % improvement was measured when tested at 23 °C. Further, tailored epoxy systems (MEP_H1 and MEP_H2) were modified using specially designed block copolymer (BCP), and core-shell rubber nanoparticles (CSR). Series of nanocomposites were obtained by systematic variation of filler contents. The resulting matrices were extensively characterized qualitatively and quantitatively to reveal the effect of each filler on the polymer properties. It was shown that the BCP confer better fracture properties to the epoxy resin at low filler loading without losing the other mechanical properties. These characteristics were accompanied by ductility and temperature stability. All composites were tested at 23 °C and at 80 °C to understand the effect of temperature on the mechanical and fracture properties. Examinations on fractured specimen surfaces provided information about the mechanisms responsible for reinforcement. Nanoparticles generate several energy dissipating mechanisms in the epoxy, e.g. plastic deformation of the matrix, cavitation, void growth, debonding and crack pinning. These were closely related to the microstructure of the materials. The characteristic of the microstructure was verified by microscopy methods (SEM and AFM). The microstructure of neat epoxy hardener system was strongly influenced by the nanoparticles and the resulting interfacial interactions. The interaction of nanoparticles with a different hardener system will result in different morphology which will ultimately influence the mechanical and fracture mechanical properties of the nanocomposites. Hybrid toughening using a combination of the block-copolymer / core-shell rubber nanoparticles and block copolymer / TiO2 nanoparticles has been investigated in the epoxy systems. It was found out that addition of rigid phase with a soft phase recovers the loss of strength in the nanocomposites caused by a softer phase. In order to clarify the relevant relationships, the microstructural and mechanical properties were correlated. The Counto’s, Halpin-Tsai, and Lewis-Nielsen equations were used to calculate the modulus of the composites and predicted modulus fit well with the measured values. Modeling was done to predict the toughening contribution from block copolymers and core-shell rubber nanoparticles. There was good agreement between the predicted values and the experimental values for the fracture energy.

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