Crystalline hydrates of swelling clay minerals (smectites) exhibit a strong coupling between their ion exchange and hydration/dehydration reactions. The uptake or removal of water from smectite interlayers as a result of a change in the environmental conditions also leads to the partitioning of cations. Three factors, the solid ion composition, the solid basal spacing/water content, and the aqueous solution composition, are all implicated in controlling the thermodynamics of ion exchange. However, conventional approaches to measuring the exchange free energy cannot separate the influence of each of these individual factors. Here, we explore the energetics of the swelling and ion exchange reactions in montmorillonite using a potential of mean force approach and the thermodynamic integration method within molecular simulations. We investigate the influence of solution and clay composition on the spontaneity of the reactions, focusing on the 2 water-layer hydration state. The swelling simulations provide the equilibrium water content, interlayer water structure, and basal spacings, while thermodynamic integration of sodium–potassium exchange in the aqueous solution and solid phase are combined to calculate ion exchange free energies as a function of solution composition. Results confirm the tendency of the clay to collapse to lower hydration states as the concentration of the solution increases. Changes to the equilibrium water content, even at fixed hydration states, and the composition of the mixed electrolyte solution play a critical role in driving ion exchange and the selectivities of the clay to the exchanged cation, while the composition of the solid phase is shown to be insignificant. These findings underscore the extreme sensitivity of clay swelling and ion exchange thermodynamics to small (tenths of an Angstrom) deviations in layer spacing.

@en

The effectiveness of carbonaceous nanoparticles in arresting and delaying damage in nanocomposites has been attributed to multiscale toughening mechanisms. To explore their application in joined interfaces of composites, this study investigates the use of carbon nanotube (CNT) interleaved films for co-cured joining of composite parts and their consequent effects on the interfacial fracture toughness. Carbon nanotubes dispersed in a thermoset resin into thin films of two discrete thicknesses (200 μ and 500 μ) and three concentrations of CNT dispersion were chosen for this study (0.5% wt., 1% wt., and 2% wt.). The films were semi-cured in the oven before being incorporated as interleaves in the composite laminate interface. Fracture toughness of the interface in mode I loading conditions was determined through double cantilever beam (DCB). Micrographs of the fracture surfaces reveal a slip-and-stick based crack jump and arrest phenomena in mode I when nanoparticles are added to the interleaved interface. The thickness of the interleaves has a more significant effect on mode I toughening mechanisms than the concentration of the nanoparticles. @en

Bonded and co-cured composites are popular alternatives to structures joined with mechanical fasteners in aircraft but the complex and coupled damage mechanisms in the co-cured/bonded region are poorly understood, thus making the evaluation of their strength and durability difficult with current modelling strategies. This study explores the potential of interleaf inclusion in failure-prone, critical regions of co-cured composite specimens in improving the joint strength and interface fracture toughness and strives to advance the understanding of damage initiation in the co-cured region using an atomistic model. A two-pronged approach is pursued here with bench-scale experimental testing and molecular modelling in this study. Experiments are performed for mode I fracture toughness with double cantilever beam (DCB) on composite laminates with an epoxy interleaf layer. Two epoxy resins and three methods for interleaf inclusion are explored in this study; we supplement the results from DCB testing with insights from confocal microscopy on the crack tip and the interleaf layer pre- and post-testing. Molecular dynamic (MD) simulations capture the cohesive interactions at the threephase interface containing the carbon fiber, the prepreg epoxy, and the interleaf epoxy. Results highlight that an interleaf layer made from partially-cured and filmed epoxy, further consolidated in the composite lay-up is the most effective way to suppress void formation, improve dispersion, and maximize cohesive interactions at the interface of co-cured composites. @en

The carbon fiber/polymer matrix interphase region plays an important role in the behavior and failure initiation of polymer matrix composites and accurate modeling techniques are needed to study the effects of this complex region on the composite response. This paper presents a high fidelity multiscale modeling framework integrating a novel molecular interphase model for the analysis of polymer matrix composites. The interphase model, consisting of voids in multiple graphene layers, enables the physical entanglement between the polymer matrix and the carbon fiber surface. The voids in the graphene layers are generated by intentionally removing carbon atoms, which better represents the irregularity of the carbon fiber surface. The molecular dynamics method calculates the interphase mechanical properties at the nanoscale, which are integrated within a high fidelity micromechanics theory. Additionally, progressive damage and failure theories are used at different scales in the modeling framework to capture scale-dependent failure of the composite. Comparisons between the current molecular interphase model and existing interphase models and experiments demonstrate that the current model captures larger stress gradients across the material interphase. These large stress gradients increase the viscoplasticity and damage effects at the interphase which are necessary for improved prediction of the nonlinear response and multiscale damage in composite materials.

@en