Towards Enhanced Performance Thin-film Composite Membranes via Surface Plasma Modification

Advancing the design of thin-film composite membrane surfaces is one of the most promising pathways to deal with treating varying water qualities and increase their long-term stability and permeability. Although plasma technologies have been explored for surface modification of bulk micro and ultrafiltration membrane materials, the modification of thin film composite membranes is yet to be systematically investigated. Here, the performance of commercial thin-film composite desalination membranes has been significantly enhanced by rapid and facile, low pressure, argon plasma activation. Pressure driven water desalination tests showed that at low power density, flux was improved by 22% without compromising salt rejection. Various plasma durations and excitation powers have been systematically evaluated to assess the impact of plasma glow reactions on the physico-chemical properties of these materials associated with permeability. With increasing power density, plasma treatment enhanced the hydrophilicity of the surfaces, where water contact angles decreasing by 70% were strongly correlated with increased negative charge and smooth uniform surface morphology. These results highlight a versatile chemical modification technique for post-treatment of commercial membrane products that provides uniform morphology and chemically altered surface properties

Determining how polymer-bubble interactions impact algal separation using the novel "Posi"-dissolved air flotation process

The novel dissolved air flotation (DAF) process that uses hydrophobically-modified polymers (HMPs) to generate positively charged bubbles (PosiDAF) has been shown to separate negatively charged algal cells without the need for coagulation-flocculation. Previous research has been limited to HMPs of poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) and, while they were effective at bench-scale, performance at pilot-scale was better using commercial poly(N,N-diallyl-N,N-dimethylammonium chloride) (PDADMAC). Hence, the aim of this research was to compare the effectiveness of PDADMAC modified with aliphatic and aromatic moieties in comparison to previously tested PDMAEMA HMPs in respect to algal cell separation and minimisation of effluent polymer concentration, as well as defining the underlying polymer-bubble interaction mechanisms. Polymer-bubble adhesion properties were measured using atomic force microscopy (AFM) while polymer concentration was monitored via zeta potential and, where possible, assays using fluorescence spectroscopy. Both PDADMAC functionalised with a fluorinated aromatic group (PDADMAC-BCF) and PDMAEMA modified with 1-bromodecane respectively, gave effective cell separation, while the treated effluent zeta potential values at maximum cell removal were lower than the other polymers trialled. The effluent polymer concentration when using PDADMAC-BCF was four times lower in comparison to another aromatically modified PDADMAC polymer. AFM studies indicated that, in contrast to the PDMAEMA-based polymers, the PDADMAC-based polymers did not adsorb closely to the bubble surface. The different polymer-bubble interactions indicate that separation mechanisms will also vary, potentially leading to differences in process effectiveness when explored at pilot scale

Silver metal nano-matrixes as high efficiency and versatile catalytic reactors for environmental remediation

Nano-porous metallic matrixes (NMMs) offer superior surface to volume ratios as well as enhanced optical, photonic, and electronic properties to bulk metallic materials. Such behaviours are correlated to the nano-scale inter-grain metal domains that favour the presence of electronic vacancies. In this work, continuous 3D NMMs were synthesized for the first time through a simple diffusion-reduction process whereby the aerogel matrix was functionalized with (3-Mercaptopropyl)trimethoxysilane. The surface energy of the silica monolith templates was tuned to improve the homogeneity of the reduction process while thiol functionalization facilitated the formation of a high density of seeding points for metal ions to reduce. The diameter of NMMs was between 2 and 1000 nm, corresponding to a silver loading between 1.23 and 41.16 at.%. A rates of catalytic degradation kinetics of these NMMS which is three orders of magnitude higher than those of the non-functionalized silver-silica structures. Furthermore, the enhancement in mechanical stability at nanoscale which was evaluated by Atomic Force Microscopy force measurements, electronic density and chemical inertness was assessed and critically correlated to their catalytic potential. This strategy opens up new avenues for design of complex architectures of either single or multi-metal alloy NMMs with enhanced surface properties for various applications

Characterization of optical properties and surface roughness profiles: The Casimir force between real materials

The Lifshitz theory provides a method to calculate the Casimir force between two flat plates if the frequency dependent dielectric function of the plates is known. In reality any plate is rough and its optical properties are known only to some degree. For high precision experiments the plates must be carefully characterized otherwise the experimental result cannot be compared with the theory or with other experiments. In this chapter we explain why optical properties of interacting materials are important for the Casimir force, how they can be measured, and how one can calculate the force using these properties. The surface roughness can be characterized, for example, with the atomic force microscope images. We introduce the main characteristics of a rough surface that can be extracted from these images, and explain how one can use them to calculate the roughness correction to the force. At small separations this correction becomes large as our experiments show. Finally we discuss the distance upon contact separating two rough surfaces, and explain the importance of this parameter for determination of the absolute separation between bodies.}Comment: 33 pages, 14 figures, to appear in Springer Lecture Notes in Physics, Volume on Casimir Physics, edited by Diego Dalvit, Peter Milonni, David Roberts, and Felipe da Ros

Oscillatory packing and depletion of polyelectrolyte molecules at an oxide water interface

Total internal reflection microscopy (TIRM) has been used to study the interactions between a 5 μm borosilicate glass sphere and a silica slide in the presence of a nonadsorbing polyelectrolyte, sodium (polystyrene sulfonate) (NaPSS). The effect of the polymer concentration, within the dilute solution regime, on the observed interactions was investigated. In all cases, the interactions displayed a short-range electrostatic repulsion followed immediately, at larger separations, by a decaying oscillatory interaction that is attributed to structuring of the polyelectrolyte in solution. The periodicity of the oscillations, as a function of concentration, indicates that at large surface separations the polymer chains are ordered as a nonintermixing, space-filling, latex. At polymer concentrations of between 200 and 1000 ppm, a transition to a system of ordered rods, parallel to the interface was seen for the final layer of polymer molecules

Direct comparison of atomic force microscopic and total internal reflection microscopic measurements in the presence of nonadsorbing polyelectrolytes

We have investigated the structural and depletion forces between silica glass surfaces in aqueous, salt-free solutions of sodium poly(styrene sulfonate). The interaction forces were investigated by two techniques: total internal reflectance microscopy (TIRM) and colloid probe atomic force microscopy (AFM). The TIRM technique measures the potential energy of interaction directly, while the AFM is a force balance. Comparison between the data sets was used to independently calibrate the AFM data since the separation distances cannot be unequivocally determined by this technique. Oscillatory structural forces are excellent for this work since they give multiple reference points against which to analyze. Comparison of the data from the two techniques highlighted significant uncertainties in the AFM data. At low polymer concentrations, a significant uncertainty in the apparent zero separation distance was seen as a result of the AFM cantilever reaching an apparent constant compliance region prior to any real contact between the surfaces. Further complications arising from the number and position of the measured minima were also seen in the dilute polymer concentration regime as a result of hydrodynamic drainage between the approaching surfaces in the AFM perturbing the delicate structural components in the fluid

Dynamic interactions between microbubbles in water

The interaction between moving bubbles, vapor voids in liquid, can arguably represent the simplest dynamical system in continuum mechanics as only a liquid and its vapor phase are involved. Surprisingly, and perhaps because of the ephemeral nature of bubbles, there has been no direct measurement of the time-dependent force between colliding bubbles which probes the effects of surface deformations and hydrodynamic flow on length scales down to nanometers. Using ultrasonically generated microbubbles (∼100 μm size) that have been accurately positioned in an atomic force microscope, we have made direct measurements of the force between two bubbles in water under controlled collision conditions that are similar to Brownian particles in solution. The experimental results together with detailed modeling reveal the nature of hydrodynamic boundary conditions at the air/water interface, the importance of the coupling of hydrodynamic flow, attractive van der Waals–Lifshitz forces, and bubble deformation in determining the conditions and mechanisms that lead to bubble coalescence. The observed behavior differs from intuitions gained from previous studies conducted using rigid particles. These direct force measurements reveal no specific ion effects at high ionic strengths or any special role of thermal fluctuations in film thickness in triggering the onset of bubble coalescence

The hydrophobic force: measurements and methods

The hydrophobic force describes the attraction between water-hating molecules (and surfaces) that draws them together, causing aggregation, phase separation, protein folding and many other inherent physical phenomena. Attempts have been made to isolate the range and magnitude of this interaction between extended surfaces for more than four decades, with wildly varying results. In this perspective, we critically analyse the application of common force-measuring techniques to the hydrophobic force conundrum. In doing so, we highlight possible interferences to these measurements and provide physical rationalisation where possible. By analysing the most recent measurements, new approaches to establishing the form of this force become apparent, and we suggest potential future directions to further refine our understanding of this vital, physical force