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The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs (134Cs, 135Cs, 137Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.

The charged surfaces of micaceous minerals, especially illite, regulate the mobility of the major radioisotopes of Cs (134Cs, 135Cs, 137Cs) in the geosphere. Despite the long history of Cs adsorption studies, the nature of the illite surface sites remains incompletely understood. To address this problem, we present atomistic simulations of Cs competition with Na for three candidate illite adsorption sites - edge, basal plane, and interlayer. Our simulation results are broadly consistent with affinities and selectivities that have been inferred from surface complexation models. Cation exchange on the basal planes is thermodynamically ideal, but exchange on edge surfaces and within interlayers shows complex, thermodynamically non-ideal behavior. The basal planes are weakly Cs-selective, while edges and interlayers have much higher affinity for Cs. The dynamics of NaCs exchange are rapid for both cations on the basal planes, but considerably slower for Cs localized on edge surfaces. In addition to new insights into Cs adsorption and exchange with Na on illite, we report the development of a methodology capable of simulating fully-flexible clay mineral nanoparticles with stable edge surfaces using a well-tested interatomic potential model.

© 2016 American Chemical Society. The mobility of radiocesium in the environment is largely mediated by cation exchange in micaceous clays, in particular Illite - a non-swelling clay mineral that naturally contains interlayer K+and has high affinity for Cs+. Although exchange of interlayer K+for Cs+is nearly thermodynamically nonselective, recent experiments show that direct, anhydrous Cs+-K+exchange is kinetically viable and leads to the formation of phase-separated interlayers through a mechanism that remains unclear. Here, using classical atomistic simulations and density functional theory calculations, we identify a molecular-scale positive feedback mechanism in which exchange of the larger Cs+for the smaller K+significantly lowers the migration barrier of neighboring K+, allowing exchange to propagate rapidly once initiated at the clay edge. Barrier lowering upon slight increase in layer spacing (∼0.7 Å) during Cs+exchange is an example of "chemical-mechanical coupling" that likely explains the observed sharp exchange fronts leading to interstratification. Interestingly, we find that these features are thermodynamically favored even in the absence of a heterogeneous layer charge distribution.

Patterning is a familiar approach for imparting novel functionalities to free surfaces. We extend the patterning paradigm to interfaces between crystalline solids. Many interfaces have non-uniform internal structures comprised of misfit dislocations, which in turn govern interface properties. We develop and validate a computational strategy for designing interfaces with controlled misfit dislocation patterns by tailoring interface crystallography and composition. Our approach relies on a novel method for predicting the internal structure of interfaces: rather than obtaining it from resource-intensive atomistic simulations, we compute it using an efficient reduced order model based on anisotropic elasticity theory. Moreover, our strategy incorporates interface synthesis as a constraint on the design process. As an illustration, we apply our approach to the design of interfaces with rapid, 1-D point defect diffusion. Patterned interfaces may be integrated into the microstructure of composite materials, markedly improving performance., United States. Dept. of Energy. Office of Basic Energy Sciences (Award 2008LANL1026), National Science Foundation (U.S.) (Grant 1150862)

Using atomistic modeling, we show that restructuring of the network of interconnected ligaments causes coarsening in a model of nanoporous gold. The restructuring arises from the collapse of some ligaments onto neighboring ones and is enabled by localized plasticity at ligaments and nodes. This mechanism may explain the occurrence of enclosed voids and reduction in volume in nanoporous metals during their synthesis. An expression is developed for the critical ligament radius below which coarsening by network restructuring may occur spontaneously, setting a lower limit to the ligament dimensions of nanofoams.