The present paper investigates the effect of adding silica nanoparticles to an anhydride-cured epoxy polymer in bulk and when used as the matrix of carbon- and glass-fibre reinforced composites. The formation of ‘hybrid’ epoxy polymers, containing both silica nanoparticles and carboxyl-terminated butadiene-acrylonitrile (CTBN) rubber microparticles, is also discussed. The structure/property relationships are considered, with an emphasis on the toughness and the toughening mechanisms. The fracture energy of the bulk epoxy polymer was increased from 77 to 212 J/m² by the presence of 20 wt% of silica nanoparticles. The observed toughening mechanisms that were operative were (a) plastic shear-yield bands, and (b) debonding of the matrix from the silica nanoparticles, followed by plastic void-growth of the epoxy. The largest increases in toughness observed were for the ‘hybrid’ materials. Here a maximum fracture energy of 965 J/m² was measured for a ‘hybrid’ epoxy polymer containing 9 wt% and 15 wt% of the rubber microparticles and silica nanoparticles, respectively. Most noteworthy was the observation that these increases in the toughness of the bulk polymers were found to be transferred to the fibre composites. Indeed, the interlaminar fracture energies for the fibre-composite materials were increased even further by a fibre-bridging toughening mechanism. The present work also extends an existing model to predict the toughening effect of the nanoparticles in a thermoset polymer. There was excellent agreement between the predictions and the experimental data for the epoxy containing the silica nanoparticles, and for epoxy polymers containing micrometre-sized glass particles. The latter, relatively large, glass particles were investigated to establish whether a ‘nano-effect’, with respect to increasing the toughness of the epoxy bulk polymers, did indeed exist.

Multi-walled carbon nanotubes, with a typical length of 140 μm and a diameter of 120 nm, have been used to modify an anhydride-cured epoxy polymer. The modulus, fracture energy and the fatigue performance of the modified polymers have been investigated. Microscopy showed that these long nanotubes were agglomerated, and that increasing the nanotube content increased the severity of the agglomeration. The addition of nanotubes increased the modulus of the epoxy, but the glass transition temperature was unaffected. The measured fracture energy was also increased, from 133 to 223 J/m² with the addition of 0.5 wt% of nanotubes. The addition of the carbon nanotubes also resulted in an increase in the fatigue performance. The threshold strain-energy release-rate, G _th, increased from 24 J/m² for the unmodified material to 73 J/m² for the epoxy with 0.5 wt% of nanotubes. Electron microscopy of the fracture surfaces showed clear evidence of nanotube debonding and pull-out, plus void growth around the nanotubes, in both the fracture and fatigue tests. The modelling study showed that the modified Halpin–Tsai equation can fit very well with the measured values of the Young’s modulus, when the orientation and agglomeration of the nanotubes are considered. The fracture energy of the nanotube-modified epoxies was predicted, by considering the contributions of the toughening mechanisms of nanotube debonding, nanotube pull-out and plastic void growth of the epoxy. This indicated that debonding and pull-out contribute to the toughening effect, but the contribution of void growth is not significant. There was excellent agreement between the predictions and the experimental results.

An epoxy resin, cured using an anhydride hardener, has been modified by the addition of pre-formed polysiloxane core-shell rubber (S-CSR) particles with a mean diameter of 0.18 μm. The glass transition temperature, Tg, of the cured unmodified epoxy polymer was 148 °C, and this was unchanged after the addition of the S-CSR particles. The polysiloxane rubber particles had a Tg of about −100 °C. Atomic force microscopy showed that the S-CSR particles were well-dispersed in the epoxy polymer. The addition of the S-CSR particles reduced the Young's modulus and tensile strength of the epoxy polymer, but at 20 °C the fracture energy, GIc, increased from 117 J/m2 for the unmodified epoxy to 947 J/m2 when 20 wt% of the S-CSR particles were incorporated. Fracture tests were also performed at −55 °C, −80 °C, and −109 °C. The results showed that the measured fracture energy of the S-CSR-modified epoxy polymers decreased significantly below room temperature. For example, at −109 °C, a fracture energy of 481 J/m2 was measured using 20 wt% of S-CSR particles. Nevertheless, this value of toughness still represented a major increase compared with the unmodified epoxy polymer, which possessed a value of GIc of 174 J/m2 at this very low test temperature. Thus, a clear fact that emerged was that the addition to the epoxy polymer of the S-CSR particles may indeed lead to significant toughening of the epoxy, even at temperatures as low as about −100 °C. The toughening mechanisms induced by the S-CSR particles were identified as (a) localised plastic shear-band yielding around the particles and (b) cavitation of the particles followed by plastic void growth of the epoxy polymer. These mechanisms were modelled using the Hsieh et al. approach [33,49] and the values of GIc of the S-CSR-modified epoxy polymers at the different test temperatures were calculated. Excellent agreement was found between the predictions and the experimentally measured fracture energies. Further, the experimental and modelling results of the present study indicated that the extent of plastic void growth was suppressed at low temperatures for the S-CSR-modified epoxy polymers, but that the localised shear-band yielding mechanism was relatively insensitive to the test temperature