Spatial pattern and surface-specificity of particle and microorganism deposition and attachment: Modeling, analytic solution and experimental test.

HYPOTHESIS: Understanding microparticle and living cell deposition and attachment on surfaces from a flow is a long-standing surface-science problem, pivotal to developing antifouling strategies. Recent studies indicate a complex non-conservative and surface-specific nature of adhesion and mechanical contact forces that determine attachment kinetics. This requires new models and kinetic data, however, observed deposition rates (e.g., in parallel-plate flow chamber, PPFC) represent a superposition of attachment and bulk transport. Here, we propose to deduce attachment rates (as an appropriate rate constant) from spatial deposition profiles along PPFC and develop an analytical solution for the full problem, suitable for deposition data analysis and parameter fitting. EXPERIMENTS: Analytical solution, validated by numerical simulations, reveals relation between the deposition profile along PPFC and key model parameter B, the ratio of sedimentation and attachment rates. Its use is demonstrated on experimental data obtained in a PPFC for particles and bacteria on various surfaces. FINDINGS: Fitted B values highlight correlation with the particle/substrate nature and consistently explain the observed trends along PPFC, both decreasing and increasing. Thus derived attachment rates will serve as basis for future microscopic modelling that would relate attachment to appropriate surface and contact-mechanical characteristics of particles and substrate and flow conditions.

In Situ Modification of Reverse Osmosis Membrane Elements for Enhanced Removal of Multiple Micropollutants.

Reverse osmosis (RO) membranes are widely used for desalination and water treatment. However, they insufficiently reject some small uncharged micropollutants, such as certain endocrine-disrupting, pharmaceutically active compounds and boric acid, increasingly present in water sources and wastewater. This study examines the feasibility of improving rejection of multiple micropollutants in commercial low-pressure RO membrane elements using concentration polarization- and surfactant-enhanced surface polymerization. Low-pressure membrane elements modified by grafting poly(glycidyl methacrylate) showed enhanced rejection of all tested solutes (model organic micropollutants, boric acid, and NaCl), with permeability somewhat reduced, but comparable with commercial brackish water RO membranes. The study demonstrates the potential and up-scalability of grafting as an in situ method for improving removal of various classes of organic and inorganic micropollutants and tuning performance in RO and other dense composite membranes for water purification.

Facile Modification of Reverse Osmosis Membranes by Surfactant-Assisted Acrylate Grafting for Enhanced Selectivity.

The top polyamide layer of composite reverse osmosis (RO) membranes has a fascinatingly complex structure, yet nanoscale nonuniformities inherently present in polyamide layer may reduce selectivity, e.g., for boron rejection. This study examines improving selectivity by in situ "caulking" such nonuniformities using concentration polarization-enhanced graft-polymerization with a surfactant added to the reactive solution. The surfactant appears to enhance both polarization (via monomer solubilization in surfactant micelles) and adherence of graft-polymer to the membrane surface, which facilitates grafting and reduces monomer consumption. The effect of surfactant was particularly notable for a hydrophobic monomer glycidyl methacrylate combined with a nonionic surfactant Triton X-100. With Triton added at an optimal level, close to critical micellization concentration (CMC), monomer gets solubilized and highly concentrated within micelles, which results in a significantly increased degree of grafting and uniformity of the coating compared to a procedure with no surfactant added. Notably, no improvement was obtained for an anionic surfactant SDS or the cationic surfactant DTAB, in which cases the high CMC of surfactant precludes high monomer concentration within micelles. The modification procedure was also up-scalable to membranes elements and resulted in elements with permeability comparable to commercial brackish water RO elements with superior boric acid rejection.

Surface structure of Nafion in vapor and liquid.

The microstructure of Nafion varies in response to changes in hydration. Thus, it undergoes a transition from tightly packed bundles of inverted micelles with aqueous cores and fused hydrophobic shells ("macaroni bundles") at low hydrations to normal type ("spaghetti") micelles at high hydrations. It was postulated recently that a similar "macaroni-spaghetti" transition, i.e., breakup of surface-aligned macaroni to randomly oriented spaghetti, takes place at the polymer surface when the external medium is changed from vapor to liquid water, which can explain some puzzling features of Nafion and similar microphase-separated ionomers. The resulting (nonequilibrium) structures may remain confined to a few nanometers thick surface region. Here, this picture is corroborated using grazing-incidence small-angle X-ray scattering (GISAXS), contact angle, and atomic force microscopy (AFM). The enhanced alignment of bundles adjacent to the surface in vapor, similar to the effect of biaxial stretching, is elucidated by GISAXS of spin-cast Nafion films. It is inferred from the characteristic change in relative intensities and position of the ionomer peak in the X-Y (in-plane) and Z (out-of-plane) directions with varying X-ray penetration depths into the film. However, contact angle measurements show that the relatively smooth and very hydrophobic surface of Nafion in vapor transforms to a hydrophilic surface, when vapor as the external medium is replaced with liquid water. In addition, AFM indicates that the surface roughness significantly increases in liquid. The results demonstrate that the surface region of Nafion and similar microphase-separated materials may be indeed subject to drastic structural variations, even though the extremely slow relaxation of the solid matrix may preclude propagation of such changes into the bulk. These effects may have a profound effect on the macroscopic characteristics of Nafion membranes, such as hydration and conductivity, as well as their functioning as ion-selective barriers in electrochemical and other applications.