Compacted Na-bentonite clay barriers, widely used in the isolation of solid-waste landfills and other contaminated sites, have been proposed for a similar use in the disposal of high-level radioactive waste. Molecular diffusion through the pore space in these barriers plays a key role in their performance, thus motivating recent measurements of the apparent diffusion coefficient tensor of water tracers in compacted, water-saturated Na-bentonites. In the present study, we introduce a conceptual model in which the pore space of water-saturated bentonite is divided into ‘macropore’ and ‘interlayer nanopore’ compartments. With this model we determine quantitatively the relative contributions of pore-network geometry (expressed as a geometric factor) and of the diffusive behavior of water molecules near montmorillonite basal surfaces (expressed as a constrictivity factor) to the apparent diffusion coefficient tensor. Our model predicts, in agreement with experiment, that the mean principal value of the apparent diffusion coefficient tensor follows a single relationship when plotted against the partial montmorillonite dry density (mass of montmorillonite per combined volume of montmorillonite and pore space). Using a single fitted parameter, the mean principal geometric factor, our model successfully describes this relationship for a broad range of bentonite-water systems, from dilute gel to highly-compacted bentonite with 80% of its pore water in interlayer nanopores.

Nanopore science, the study of individual nanoscale pores within thin membranes, is a fast-growing field which presents numerous interesting problems for physicists and applied mathematicians. Nanopores are most commonly applied to resistive pulse sensing (RPS) of individual particles suspended in aqueous electrolyte. The form of a resistive pulse is dependent on an array of experimental variables, including electrolyte characteristics, electrophoretic and convective transport, and (especially) pore and particle geometry. The level of analysis required depends on the application, but any broadly useful approach should be simple and flexible, due to the requirement for high data throughput and variations between different experimental systems and specimens. Here we review analytic methods for interpreting RPS experiments for particles in the approximate range 100 nm to 1 $\def \xmlpi #1{}\def \mathsfbi #1{\boldsymbol {\mathsf {#1}}}\let \le =\leqslant \let \leq =\leqslant \let \ge =\geqslant \let \geq =\geqslant \def \Pr {\mathit {Pr}}\def \Fr {\mathit {Fr}}\def \Rey {\mathit {Re}}\mu $m, focusing on calculation of resistance change as a function of the particle’s position. We detail a recently developed semi-analytical model and compare the modelled electric field with finite element results. The model can also be used to calculate particle motion, so that the experimental current–time history can be reconstructed. This approach is useful for a wide range of pore and particle geometries, and includes consideration of entrance effects. Tunable elastomeric pores with truncated linear cone geometry are used as a model system.

An in situ electron energy loss spectroscopy (EELS) technique has been developed to investigate the dynamic processes associated with electron-beam nanofabrication on thin membranes. In this article, practical applications germane to e-beam nanofabrication are illustrated with a case study of the drilling of nanometer-sized pores in silicon nitride membranes. This technique involves successive acquisitions of the plasmon-loss and the core-level ionization-loss spectra in real time, both of which provide the information regarding the hole-drilling kinetics, including two respective rates for total mass loss, individual nitrogen and silicon element depletion, and the change of the atomic bonding environment. In addition, the in situ EELS also provides an alternative method for endpoint detection with a potentially higher time resolution than by imaging. On the basis of the time evolution of in situ EELS spectra, a qualitative working model combining knock-on sputtering, irradiation-induced mass transport, and phase separation can be proposed.