We report the preparation and characterization of charged nanoporous membranes by self-assembly of “hairy” silica nanoparticles (HNPs) functionalized with polyelectrolyte copolymer brushes. We show that HNP membranes possess high water flux, have well-defined pore sizes, and rejection up to 80% of charged species in solution. The properties of these membranes can be tuned by controlling the length and composition of polymer brushes and the electrolyte concentration in solution. We demonstrate that membrane pore sizes undergo changes of up to 40% in response to changes in the ionic strength of the salt solution. Using MD computer simulations of a coarse-grained model, we link these tunable properties to the conformations of polymer chains in the spaces between randomly packed HNPs. As polymer length increases, the polymers fill the interparticle gaps, and the pore size decreases markedly. On the basis of their straightforward fabrication and tunable properties, HNP membranes may find applications in size- and charge-selective separations, water desalination, and responsive devices.

Percolation theory can be used to study the flow-related properties of various porous systems. In particular, recently developed membranes from silica nanoparticles with surface grafted polymer brushes represent a quintessential hard-sphere soft-shell system for which fluidflow behavior can be illuminated via a percolation framework. However, a critical parameter in membrane design involves the maximum pass-through size of particles. While percolation theory considers path connectedness of a system, little explicit consideration is given to the size of the paths that traverse the space. This paper employs a hard-sphere soft-shell percolation model to investigate maximum particle pass-through size of membranes. A pixelated (as opposed to continuous) representation of the geometry is created, and combined with readily available homology software to analyze percolation behavior. The model is validated against previously published results. For a given sphere volume fraction, the maximum diameter of a percolating path is determined by applying iterative dilations to the spheres until the percolation threshold is reached. A simple approximate relationship between maximum particle size and sphere volume fraction is derived for application to membrane design. Experimental particle cutoff size results for the polymer modified silica nanoparticle membranes were used as a partial verification of the model created in this paper. The presence of a distribution of sphere sizes (naturally created by the manufacturing process) is found to have negligible effect, compared to results for a single sphere size.

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We developed a novel approach to the preparation of nanoporous membranes by the assembly of polymer brush-modified colloidal nanoparticles. Membranes made of uncharged HNPs carrying PHEMA brushes were stable in water, disassembled in organic solvents and could withstand multiple cycles of assemblydisassembly. Their filtration cut-off could be controlled by varying the silica sphere diameter and depends on the polymer brush structure. These membranes can also be recycled and washed from contaminants. Charged HNP membranes containing PSPM-r-PEEMA brushes can be prepared through layered deposition of bare silica and hairy particles. The flux through these membranes responds to the changes in electrolyte concentration. The salt rejection by these membranes is in the moderate to high range (65-80%) and depends on the composition of the polymer brushes and salt concentration.