Highly ordered, homogeneous polymer nanocomposites of layered graphene oxide are prepared using a vacuum‐assisted self‐assembly (VASA) technique. In VASA, all components (nanofiller and polymer) are pre‐mixed prior to assembly under a flow, making it compatible with either hydrophilic poly(vinyl alcohol) (PVA) or hydrophobic poly(methyl methacrylate) (PMMA) for the preparation of composites with over 50 wt% filler. This process is complimentary to layer‐by‐layer assembly, where the assembling components are required to interact strongly (e.g., via Coulombic attraction). The nanosheets within the VASA‐assembled composites exhibit a high degree of order with tunable intersheet spacing, depending on the polymer content. Graphene oxide–PVA nanocomposites, prepared from water, exhibit greatly improved modulus values in comparison to films of either pure PVA or pure graphene oxide. Modulus values for graphene oxide–PMMA nanocomposites, prepared from dimethylformamide, are intermediate to those of the pure components. The differences in structure, modulus, and strength can be attributed to the gallery composition, specifically the hydrogen bonding ability of the intercalating species

The thermal and dynamic behavior of epoxy nanocomposites with varying cross-link density was tested via dynamic scanning calorimetry (DSC) in order to determine the influence of cross-link density on the creation of “interphase”, zones of altered polymer properties near polymer−particle interfaces. The results show that the inclusion of nanoparticles creates an increase in the glass transition temperature (T g) at low cross-link density and a decrease in T g at higher cross-link densities. This phenomenon suggests that two mechanisms work in tandem to alter the T g of epoxy systems, with relative magnitudes determined by cross-link density: (1) network disruption at the nanotube−polymer interfaces leading to lower T g and (2) interphase creation leading to retarded dynamics, resulting in higher T g. Results show that as cross-link density increases, the length scale of cooperatively rearranging regions (CRRs) decreases. This decrease hinders communication of the dynamics between adjacent CRRs, thereby reducing interphase penetration into the bulk matrix. Moreover, increasing cross-link density leads to increased network disruption due to the presence of nanoparticle obstacles in an otherwise densely connected network.

Many natural composites, such as nacre or bone, achieve exceptional toughening enhancements through the rupture of noncovalent secondary bonds between chain segments in the organic phase. This "sacrificial bond" rupture dissipates enormous amounts of energy and reveals significant hidden lengths due to unraveling of the highly coiled macromolecules, leaving the structural integrity of their covalent backbones intact to large extensions. In this work, we present the first evidence of similar sacrificial bond mechanisms in the inorganic phase of composites using inexpensive stacked-cup carbon nanofibers (CNF), which are composed of helically coiled graphene sheets with graphitic spacing between adjacent layers. These CNFs are dispersed in a series of high-performance epoxy systems containing trifunctional and tetrafunctional resins, which are traditionally difficult to toughen in light of their highly cross-linked networks. Nonetheless, the addition of only 0.68 wt % CNF yields toughness enhancements of 43-112% for the various blends. Analysis of the relevant toughening mechanisms reveals two heretofore unseen mechanisms using sacrificial bonds that complement the observed crack deflection, rupture, and debonding/pullout that are common to many composite systems. First, embedded nanofibers can splay discretely between adjacent graphitic layers in the side walls; second, crack-bridging nanofibers can unravel continuously. Both of these mechanisms entail the dissipation of the pi-pi interactions between layers in the side walls without compromising the structural integrity of the graphene sheets. Moreover, increases in electrical conductivity of approximately 7-10 orders of magnitude were found, highlighting the multifunctionality of CNFs as reinforcements for the design of tough, inexpensive nanocomposites with improved electrical properties.

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