Professor Erica Wanless

The potential of poly(acrylic acid)-b-poly(n-butyl acrylate) as a dual flocculant-collector in combined flotation-sedimentation dewatering operations was investigated. The amphiphilic block copolymers were synthesised with consistent hydrophilic chain lengths and varying hydrophobic chain lengths. Various techniques were employed to analyse polymer behaviour at the air¿water interface, being interfacial surface tension and dilational viscoelasticity. Polymer adsorption onto Mg(OH)2 was determined differentially using UV¿Vis spectroscopy. Floc structures were determined using static light scattering, and flocculation-flotation performance was analysed using settling tests and flotation cell material balances. Results showed that longer hydrophobic chains were less surface-active, reducing foamability and water entrainment. The unimer-micellar adsorption transition points were identified through viscoelastic properties and particle adsorption studies. A distinct change in floc density and structure was observed for the largest molecular weight copolymer when the dosed concentration increased into the micellar adsorption region, suggesting a pseudo-bridging flocculation mechanism. Settling rates were significantly higher for particles flocculated with the larger molecular weight polymer, correlating to their larger aggregate sizes, especially over the micellar transition point. The largest molecular weight block copolymer demonstrated superior collection efficiency compared to the traditional surfactant, sodium dodecylsulfate (SDS), below its micellar adsorption transition point. However, beyond this point, the lack of exposed hydrophobic blocks hindered the hydrophobisation of Mg(OH)2 particles, reducing collection efficiency. Comparing flotation cell particle size distributions, it was suggested that recovery may be hydrodynamically hindered by the largest floc sizes, though recovery was observed for particles in the order of < 600 µm.

Hypothesis: Anionic surfactants have been reported to interact with poly(N-isopropyl acrylamide) (PNIPAM), suppressing its thermoresponse. Scattering and NMR studies of the anionic sodium dodecylsulfate (SDS) system propose that the PNIPAM-surfactant interaction is purely hydrophobic. However, prior phenomenological investigations of a range of surfactant identities (anionic, cationic, nonionic) show that only anionic surfactants affect the thermoresponse and conformation of PNIPAM, implying that the hydrophilic head¿group also contributes. Crucially, the phenomenological experiments do not measure the affinity of the tested surfactants to the polymer, only their effect on its behaviour. Experiments: We study the adsorption of six surfactants within a planar PNIPAM brush system, elucidating the polymer conformation, thermoresponse, and surfactant adsorption kinetics using ellipsometry, neutron reflectometry (NR), optical reflectometry and the quartz crystal microbalance technique. NR is used to measure the distribution of surfactants within the brush. Findings: We find that only anionic surfactants modify the structure and thermoresponse of PNIPAM, with the greater affinity of anionic surfactants for PNIPAM (relative to cationic and nonionic surfactants) being the primary reason for this behaviour. These results show that the surfactant head¿group has a more critical role in mediating PNIPAM-surfactant interaction than previously reported. Taking inspiration from prior molecular dynamics work on the PEO-surfactant system, we propose an interaction mechanism for PNIPAM and SDS that reconciles evidence for hydrophobic interaction with the observed head¿group-dependent affinity.

refellips is an open-source analysis package written in Python for modelling variable angle spectroscopic ellipsometry data. The software is designed to be used in Jupyter notebook environments or simple Python scripts, facilitating reproducible research. The modular design of refellips means users can implement simple models (e.g., slabs) or create their own complex mathematical optical models to describe an interface. refellips can read a range of file types from common ellipsometers and utilises the suite of local and global minimisers offered by the scipy package to fit data. refellips allows for the batch processing of large ellipsometry datasets, e.g., from the spatial mapping of surfaces or time-series experiments. Furthermore, as refellips is part of the refnx family, its operation (e.g., model creation) is almost identical to that used by refnx for neutron and X-ray reflectometry analyses, permitting simultaneous co-refinement of ellipsometry, neutron, and X-ray reflectometry data for the first time. This enables superior characterisation of complex interfaces in condensed matter films and oxide surfaces.

Hypothesis: Electrostatic extraction of particles from a bed to a pendent droplet to form liquid marbles has previously been investigated with respect to particle conductivity, size and shape, however, interparticle forces have not been specifically interrogated. If cohesion is the dominant force within the particle bed, then particles will be more readily extracted with reduced surface free energy. Experiments: Glass particles were surface-modified using various alkyltrichlorosilanes. The surface free energy was measured for each sample using colloid probe atomic force microscopy (AFM) and sessile drop measurements on similarly modified glass slides. The ease of electrostatic particle extraction of each particle sample to a pendent droplet was compared by quantifying the electric field force required for successful extraction as a function of the measured surface free energy. Findings: Surface free energy calculated from sessile droplet measurements and AFM were not in agreement, as work of adhesion of a liquid droplet on a planar substrate is not representative of the contact between particles. Ease of electrostatic extraction of particles was observed to generally decrease as a function of AFM-derived surface free energy, confirming this is a critical factor in electrostatic delivery of particles to a pendent droplet. Roughness was also shown to inhibit particle extraction.

The number of women employed in STEM in Australia is increasing, however, they continue to remain underrepresented in most industries. A significant corpus of literature on female underrepresentation has emerged in the past 20 years, however, many of those studies focus on educational access and retention and not many look at the lived experiences of women after they have left higher education. In this article, we take a different stance and explore the heterogeneous experiences of female STEM professionals in regional Australia. Through the qualitative analysis of 25 interviews, we learn what women have endured, accepted, and valued on their individual STEM journeys. While these journeys are often quite different, our interviewees independently reported having experienced similar societal prejudices and possessing similar personality traits. Our data reveals that resilience and determination proved vital for these women, as did a strong early interest in STEM. Our interviews also unearth issues in which women's opinions are fiercely divided, such as whether positive discrimination has been a barrier or an enabler for their careers. Based on what we have learnt from their accounts, we argue that these women have 'survived' their work environments despite structural barriers, only due to their determination, resilience and fervent interest.

We report an unusually large spacing observed between microparticles after delivery to the surface of a pendent water droplet using a DC nonuniform electrostatic field, primarily via dielectrophoresis. The influence of particle properties was investigated using core particles, which were either coated or surface-modified to alter their wettability and conductivity. Particles that exhibited this spacing were both hydrophobic and possessed some dielectric material exposed to the external field, such as a coating or exposed dielectric core. The origin of this behavior is proposed to be the induced dipole-dipole repulsion between particles, which increases with particle size and decreases when the magnitude of the electric field is reduced. When the particles were no longer subjected to an external field, this large interparticle repulsion ceased and the particles settled to the bottom of the droplet under the force of gravity. We derive a simple model to predict this spacing, with the dipole-dipole repulsion balanced against particle weight. The external electric field was calculated using the existing electric field models. The spacing was found to be dependent on particle density and the induced dipole moment as well as the number of particles present on the droplet interface. As the number of particles increased, a decrease in interparticle spacing was observed.

Liquid marbles may be traditionally formed by rolling a droplet on a bed of non-wetting particles resulting in encapsulation and stabilisation. Particles used in this process may range from nanometre to millimetre if handled with sufficient care. This method, however, runs the risk of droplet coalescence and is limited to non-wetting particles. Currently there exist some alternative methods of formulation including using electrostatics to either deliver a particle bed to the droplet or pull the droplet to the particles. The former has shown some promise in potential batch processes but is hindered by interparticle forces. Additional production methods include a form of blender, but this has shown to be unable to produce marbles of a narrow size distribution. Once formed, liquid marbles have demonstrated value as potential blood typing devices, as micro-reaction vessels due to the inherent barrier between the internal phase and the substrate whilst maintaining gas permeability, and as contaminant sensors. Liquid marbles also demonstrate a remarkable level of elasticity under compressive force and reduced evaporation rates when compared to bare water droplets, a function of the size and composition of the stabilising particles. In addition to this, liquid marbles have been proposed as actuators. Locomotion may easily be induced in these structures, using electrostatics, sound, magnetism or light depending on the particle/liquid combinations used in formation, and the environment of deployment. This review seeks to present and summarise recent advances in the field of liquid marble manufacture and methods for actuation. We also aim to highlight potential future avenues of further study within this arena.

Hypothesis: Despite advances in understanding the R5 (SSKKSGSYSGKSGSKRRIL) peptide-driven bio-silica process, there remains significant discrepancies regarding the physicochemical characterization and the self-assembling mechanistic driving forces of the supramolecular R5 template. This paper investigates the self-assembly of R5 as a function of monovalent (sodium chloride) and multivalent salt (phosphate) to determine if assembly is phosphate ion concentration dependent. Additionally, we hypothesize that the assembled R5 aggregates do not resemble a micelle or unimer structure as proposed in current literature. Experiments: R5 peptides were synthesized, and aggregates evaluated for their size, morphology, and association state as a function of salt and ionic strength concentration via dynamic and static light scattering, small angle X-ray and neutron scattering and cryogenic transmission electron microscopy. Furthermore, we compare the proposed R5 template to precipitated silica by scanning electron microscopy. Findings: R5 peptides assemble into large aggregates due to multivalence bridging and the decrease in electrostatic repulsion due to ionic strength. We elucidate the structure of R5 aggregates as mass-fractals composed of small spherical aggregates. Moreover, we discover that phosphate ions not only have a significant role in driving the growth of the R5 scaffold, but additionally in driving the polycondensation of silicic acid during the bio-silification process via electrostatic interactions.

Neutron reflectometry is the foremost technique for in situ determination of the volume fraction profiles of polymer brushes at planar interfaces. However, the subtle features in the reflectometry data produced by these diffuse interfaces challenge data interpretation. Historically, data analyses have used least-squares approaches that do not adequately quantify the uncertainty of the modeled profile and ignore the possibility of other structures that also match the collected data (multimodality). Here, a Bayesian statistical approach is used that permits the structural uncertainty and multimodality to be quantified for polymer brush systems. A free-form model is used to describe the volume fraction profile, minimizing assumptions regarding brush structure, while only allowing physically reasonable profiles to be produced. The model allows the total volume of polymer and the profile monotonicity to be constrained. The rigor of the approach is demonstrated via a round-Trip analysis of a simulated system, before it is applied to real data examining the well characterized collapse of a thermoresponsive brush. It is shown that, while failure to constrain the interfacial volume and consider multimodality may result in erroneous structures being derived, carefully constraining the model allows for robust determination of polymer brush compositional profiles. This work highlights that an appropriate combination of flexibility and constraint must be used with polymer brush systems to ensure the veracity of the analysis. The code used in this analysis is provided, enabling the reproduction of the results and the application of the method to similar problems.

Hypothesis: Grafted poly(ethylene glycol) methyl ether methacrylate (POEGMA) copolymer brushes change conformation in response to temperature ('thermoresponse'). In the presence of different ions the thermoresponse of these coatings is dramatically altered. These effects are complex and poorly understood with no all-inclusive predictive theory of specific ion effects. As natural environments are composed of mixed electrolytes, it is imperative we understand the interplay of different ions for future applications. We hypothesise anion mixtures from the same end of the Hofmeister series (same-type anions) will exhibit non-additive and competitive behaviour. Experiments: The behaviour of POEGMA brushes, synthesised via surface-initiated ARGET-ATRP, in both single and mixed aqueous electrolyte solutions was characterised with ellipsometry and neutron reflectometry as a function of temperature. Findings: In mixed fluoride and chloride aqueous electrolytes (salting-out ions), or mixed thiocyanate and iodide aqueous electrolytes (salting-in ions), a non-monotonic concentration-dependent influence of the two anions on the thermoresponse of the brush was observed. A new term, d, has been defined to quantitively describe synergistic or antagonistic behaviour. This study determined the specific ion effects imparted by salting-out ions are dependent on available solvent molecules, whereas the influence of salting-in ions is dependent on the interactions of the anions and polymer chains.

Life as we know it is dependent upon water, or more specifically salty water. Without dissolved ions, the interactions between biological molecules are insufficiently complex to support life. This complexity is intimately tied to the variation in properties induced by the presence of different ions. These specific ion effects, widely known as Hofmeister effects, have been known for more than 100 years. They are ubiquitous throughout the chemical, biological and physical sciences. The origin of these effects and their relative strengths is still hotly debated. Here we reconsider the origins of specific ion effects through the lens of Coulomb interactions and establish a foundation for anion effects in aqueous and non-aqueous environments. We show that, for anions, the Hofmeister series can be explained and quantified by consideration of site-specific electrostatic interactions. This can simply be approximated by the radial charge density of the anion, which we have calculated for commonly reported ions. This broadly quantifies previously unpredictable specific ion effects, including those known to influence solution properties, virus activities and reaction rates. Furthermore, in non-aqueous solvents, the relative magnitude of the anion series is dependent on the Lewis acidity of the solvent, as measured by the Gutmann Acceptor Number. Analogous SIEs for cations bear limited correlation with their radial charge density, highlighting a fundamental asymmetry in the origins of specific ion effects for anions and cations, due to competing non-Coulombic phenomena. This journal is

Specific particle material properties such as conductivity, cohesion, and density have been neither directly nor thoroughly studied regarding particle behavior in an electrostatic field and the follow-on impact this has on the electrostatic formation of liquid marbles. In this method, an applied electric field drives the extraction of particles from a bed and their transport to a pendent, earthed water droplet. Herein, prior studies of electrostatic formation of particle-stabilized droplets and liquid marbles have been expanded to compare the impact of density using the spherical polystyrene (PS) latex and glass particles of similar shape and size. The addition of thin polymer shells to both samples, which increases the conductivity and cohesion, allows the interplay of these three properties to be examined systematically. Separation distances between the particle bed and the droplet from which particles can initially be extracted increase as the negative applied potential increases. Initial extraction distances of both core particles were found to be similar, ~1.5 mm at 2.0 kV applied potential, despite the greater density, and thus mass of the glass particles. It is demonstrated that this is a result of competitive interactions between particle density, conductivity, and cohesion; PS is less conductive and more cohesive than glass. Introducing a polypyrrole shell increases the separation distance for extraction to approximately 4 mm for PS core particles but has little impact on glass core particles, demonstrating that for particles with constant conductivity and cohesion reducing the density facilitates extraction. Modeling and quantification of extraction threshold forces for each particle type were undertaken, utilizing the measurement of a radially symmetric area of the particle bed from which particles were observed in the initial extraction stages. This measurement highlighted that it is significantly easier to extract PS compared to glass, with particles extracted from a region in the bed up to 5 times the width in the PS case. Particle density is hypothesized to not be the determining factor in the stabilization of the coated liquid droplets; therefore, the interplay of a multitude of physical properties must be considered when determining the suitability of particulate materials for this electrostatic method.

This work presents a computational study based on Discrete Element Method (DEM) to investigate the capture of particles by bubbles in the presence of electrical double layer repulsion. In the DEM model a fully mobile boundary condition was assumed for the gas-liquid (bubble) interface. The forces acting on the particle were gravitational, buoyancy, hydrodynamic, as well as elastic and damping forces if/when the particle penetrated inside the bubble. Surface forces were considered and were evaluated through the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory. A preliminary theoretical analysis of the surface forces was carried out in order to determine the possibility of particle capture. This analysis included the determination of the interaction potential energy. Five different types of interaction energy curves were found. They were characterised by (1) a monotonic increase with distance; (2) the presence of a primary minimum; (3) the presence of an energy barrier and a primary minimum, (4) the presence of an energy barrier and a primary and a secondary minimum, and (5) a monotonic decrease with distance. DEM modelling was conducted to investigate the induction time for a single particle-bubble system. It was found that the induction time decreased with increasing contact angle and decreasing height of the energy barrier. In contrast, the primary minimum had very limited impact on induction time. Additionally, modelling of a more complex system consisting of a single bubble and multiple particles was also carried out. The multiple particle-single bubble simulation results showed that a decrease in induction time considerably enhanced collection efficiency. Finally, the concept of "contactless" flotation, which occurs in the case in which only a primary minimum exists, was also demonstrated through the use of DEM modelling.

We report the manufacture of complex structures of silica, coal or sphalerite particles around a water droplet, driven by an electrostatic field. A particle bed was deposited on an electrically biased substrate and an earthed water drop brought close, such that the particles jumped to the drop. These structures' shape and internal composition were determined by a combination of the particles' wettability and electrical properties, and other attributes such as shape, size and density were also thought to play a role. Hydrophilic particles tend to be internalised by the drop, while hydrophobic ones tend to form a layer or shell on the surface. Thus, one example of these structures was a 'complex liquid marble', with a hydrophilic particle suspension core and a stabilising shell of hydrophobic particles.

Stability of bubbles laden with particles of different densities was investigated. Capillary-held bubbles were produced and coated with particles across the density range of 1.2-3.6 g·cm-3. The materials used were poly(methyl methacrylate) (PMMA), glass, and anatase. The interaction of the bubbles, once brought into contact, was monitored using high-speed video recording. Visual inspection indicated that denser particles were more easily displaced during the contact of the bubbles and therefore the PMMA particles provided a particle barrier more resistant to coalescence. The coalescence events yielded information on the surface properties of the bubble and the detachment of particles. The attached particles commonly dampen the oscillation of the coalesced bubbles through viscous drag and change in the surface properties (e.g., area-exclusion principle). The dampening of the oscillation generally leads to a reduced mass of particles detaching from the bubble surface. It was found that the different materials investigated did not offer clear evidence of the effect of particle detachment on the bubble surface properties in the present systems. On the other hand, the detachment of different particle materials seemed to be consistent with one another when comparing the attachment and detachment forces exerted on the particles based on their density, size, and hydrophobicity. It was concluded that particles of lower density are more effective in stabilizing interfaces, and thus particle density is an important parameter in the selection of materials for the handling of dispersions.

© 2016 The Royal Society of Chemistry.The interactions of two oil droplets grown in the presence of swollen, lightly cross-linked cationic poly(tert-butylamino)ethyl methacrylate (PTBAEMA) microgels was monitored using a high-speed video camera. Three oils (n-dodecane, isopropyl myristate and sunflower oil) were investigated, each in the absence and presence of an oil-soluble cross-linker [tolylene 2,4-diisocyanate-terminated poly(propylene glycol), PPG-TDI]. Adsorption of the swollen microgel particles was confirmed by interfacial tension, interfacial elasticity and dilational viscosity measurements on single pendant oil droplets, and assessment of the oscillatory dynamics for coalescing droplet pairs. Like the analogous bulk emulsions, particle adsorption alone did not prevent coalescence of pairs of giant Pickering emulsion droplets. However, prior addition of surface-active PPG-TDI cross-linker to the oil phase results in the formation of highly stable microgel colloidosomes via reaction with the secondary amine groups on the PTBAEMA chains. Colloidosome stability depended on the age of the oil-water interface. This reflects a balance between the adsorption kinetics of the PPG-TDI cross-linker and the microgel particles, each of which must be present at the interface to form a stable colloidosome. Colloidosome formation was virtually instantaneous in n-dodecane, but took up to 120 s in the case of isopropyl myristate. The impact of an acid-induced latex-to-microgel transition on the interaction of giant colloidosomes (originally prepared at pH 10 using isopropyl myristate) was also studied. This acid challenge did not result in coalescence, which is consistent with a closely-related study (A. J. Morse et al., Langmuir, 2014, 30(42), 12509-12519). No evidence was observed for inter-colloidosome cross-linking, which was attributed to retention of an aqueous film between the adjacent pair of colloidosomes.

We report the first study of the influence of drop and particle size on the electrostatic manufacture and subsequent stability of liquid marbles. It is clear from this study that the 'rules' for electrostatic formation of liquid marbles are quite different for those for conventional direct-contact manufacture. Formation of liquid marbles was observed when an earthed water drop of volume 3¿7¿µL was brought into proximity with a bed of highly-charged polystyrene particles of diameter 22¿153¿µm. Under appropriate conditions the particles jumped to and coated the drop, producing a particle-liquid aggregate that dropped to the bed surface in the form of either a stable liquid marble or a particle-stabilised sessile drop. The subsequent evolution of the physical dimensions of the metastable aggregate was measured as the liquid drained into the bed, and its stability assessed. Formation of stable liquid marbles appeared to occur more easily for smaller drops and larger particles, and some of these considerably exceeded the conventionally-understood limit for the ratio of particle to drop size of stable liquid marbles.

The conformation of a hydrophobic, weak cationic poly(2-diisopropylamino)ethyl methacrylate (PDPA) brush was studied using neutron reflectometry as a function of aqueous solution pH, ionic strength, and anion identity. In pH 4, 10 mM potassium nitrate the brush is highly charged, resulting in an extended, dilute conformation; at pH 9 the uncharged brush collapses to a single, dense layer. The brush response to added salt at constant pH (4.5) for varying concentrations of the potassium salts of acetate, nitrate, and thiocyanate revealed ion-specific conformations of the brush. At low ionic strength (0.1 mM) the brush was collapsed, independent of salt identity, while at higher ionic strengths (up to 500 mM) the conformation was dependent on counterion identity. The brush exhibited extended conformations in the presence of kosmotropic acetate counterions, while collapsed conformations were retained in the presence of strongly chaotropic thiocyanate counterions. The brush showed a richer set of behaviors in the solutions containing the weakly chaotropic nitrate anion, being similar to acetate (swollen) at intermediate concentrations but similar to thiocyanate (collapsed) at high salt concentrations. Numerical self-consistent field (nSCF) simulations indicate that the response of the brush to pH changes is dominated by the hydrophobicity of the polymer at pH values near the pKa. Furthermore, the simulations reveal that the addition of a single Flory-Huggins interaction parameter analogous to the hydrophilicity of the counterion is sufficient to replicate the observed specific anion response of a hydrophobic weak polyelectrolyte brush.

The effect of anion identity and temperature on the internal nanostructure of poly(N-isopropylacrylamide) brushes were investigated using neutron reflectometry (NR), atomic force microscopy (AFM), and quartz crystal microbalance with dissipation monitoring (QCM-D). NR and QCM-D measurements showed that addition of strongly kosmotropic acetate anions shifted the lower critical solution temperature (LCST) to lower temperatures relative to pure D2O/H2O, while strongly chaotropic thiocyanate anions shifted the LCST to higher temperatures. Polymer density profiles derived from NR showed direct evidence of vertical phase separation at temperatures around the LCST in all conditions. Results indicate that the density profiles were not simple modulations of structures observed in D2O to higher or lower temperatures, with both anion identity and ionic strength found to influence the qualitative features of the profiles. In particular, the presence of thiocyanate broadened the LCST transition which is attributed to the ability of the thiocyanate anion to electrosterically stabilize the brush above its LCST. Complementary AFM data showed that the acetate ion induced collapsed structures while a broader transition is observed in the presence of thiocyanate.

Complementary interaction force measurements between an atomic force microscope (AFM) tip or colloid probe and a weak polybasic brush have been shown to yield a number of fundamental characteristics of the brush and its response to the presence of specific anions in aqueous solution. Stretching of the poly(2-diisopropylamino)ethyl methacrylate (PDPA) chains physisorbed to the AFM tip and modeling the resultant force curves allowed the persistence and contour lengths, molecular weight, and thus grafting density of the brush to be determined. In kosmotropic acetate, high osmotic forces associated with the swollen PDPA brush repelled the colloid probe during both approach and retraction. For mildly chaotropic nitrate the behavior was similar, but at high ionic strength and during retraction, the interaction was strongly adhesive partly because of decreased brush solvation. For strongly chaotropic thiocyanate, the interaction was adhesive over the entire concentration range studied. Here, physical contact between the poorly solvated brush and the colloid resulted in an attractive force.

This paper presents a computer simulation analysis of the selective capture of binary particle mixtures by a central bubble, as influenced by the relative strength of the hydrophobic interaction assigned to each type of particle. The analysis was carried out for a quiescent fluid using two different configurations of initial particle positions, namely: spherical (particles released from within a spherical shell surrounding the bubble) and top (particles released from a horizontal plane located above the bubble) distributions. The top distribution was also used to study the effect of fluid velocity (< 0.05 m/s). The results show that in the case of a quiescent fluid the collection efficiency was greater for the top distribution than for the spherical one. In addition, when the strength of the hydrophobic force was less than the net particle weight, particles easily detached from the bubble surface. In the presence of fluid flow the collection efficiency followed an exponential decay with the fluid velocity and a quadratic relationship with an effective cross-section for the particle-bubble collision. The latter closely follows the collision models in the literature. Importantly, we have shown that selective capture only occurs when one type of particle possesses a hydrophobic force magnitude close to or less than the net particle weight, while the hydrophobic force for the second type needs to be much larger than the net weight of the particle. Therefore, we have concluded that selectivity does not depend solely on the hydrophobicity differences, but also requires that one type of particle has to be weakly interacting with the bubble.

The stability of capillary-pinned bubble pairs covered with hydrophobized particles in aqueous solutions of 1-pentanol or methyl isobutyl carbinol (MIBC) was studied using high-speed cinematography. Glass particles were first rendered hydrophobic by covalently bonding a linear alcohol onto the solid interface to achieve a specific hydrophobicity (i.e. contact angle of 43° measured with the captive bubble on a treated wafer) and effectively avoid the presence of any mobile hydrophobizing surfactant. The resistance to coalescence of the bubbles was measured at different frother concentrations and for various initial bubble interfacial areas covered by particles; with particle coverage not exceeding the contact region between the bubbles.Frother molecules were shown to delay the coalescence of bubbles whereas particles were not present in a sufficient quantity at the interface of the bubbles to provide steric stability. However, in some cases in the presence of MIBC, the particles were believed to act as means of transportation for the frother molecules to the surface of the bubbles thus forcing the local relaxation of the interface, which improved bubble stability. The coalescence of two bubbles released energy causing a rapid motion of the interface. This motion was sufficient to expel a fraction of the attached particles from the interface. The addition of frother, and of particles in some cases, increased the dampening of the oscillatory motion generated by bubble coalescence. In general, damped bubble oscillations were associated with a reduced quantity of particles detaching from the bubble. Although particles were observed to dampen the oscillation of the bubble, they were not as effective as the frother molecules in reducing the detachment of particles upon bubble coalescence. This finding is believed be of relevance for industrial applications such as froth flotation.

The interactions between two individual water droplets were investigated in air using a combination of coalescence rig and high speed video camera. This combination allows the visualization of droplet coalescence dynamics with millisecond resolution which provides information on droplet stability. Bare water droplets coalesced rapidly upon contact, while droplet stability was achieved by coating the droplets with polystyrene particles carrying pH-responsive poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS particles) to form liquid marbles. The asymmetric interaction of a water droplet (pH 3 or 10) armoured with the PDEA-PS particles (liquid marble) with a bare droplet at pH 3 exhibited intermediate stability with coalescence observed following an induction time. The induction time was longer for the pH 10 liquid marble, where the PDEA-PS particles have a hydrophobic surface, than in the case of a pH 3 liquid marble, where the PDEA-PS particles have a hydrophilic surface. Furthermore, film formation of PDEA-PS particles on the liquid marble surface with toluene vapour confirmed capsule formation which prevented coalescence with the neighbouring water droplet instead wetting the capsule upon contact within 3 milliseconds. This study illuminates the stability of individual particle-stabilized droplets and has potential impact on processes and formulations which involve their interaction.

Particle-stabilised foams (or froths) form the fundamental framework of industrial processes like froth flotation. This review provides an overview of the effects of particles on bubble surfaces. The characteristics of the particles have a profound effect on the stability of the bubbles although the stabilisation mechanisms may differ. It is well known that layers of particles may provide a steric barrier between two interfaces, which prevents the coalescence of bubbles. Although perhaps considered of lesser importance, it is interesting to note that particles may affect the bubble surface and momentarily suppress coalescence despite being absent from the film separating two bubbles.Foams are at best metastable and coalescence occurs to achieve a state of minimum energy. Despite this, particles have been reported to stabilise bubbles for significant periods of time. Bubble coalescence is accompanied by a release of energy triggered by the sudden change in surface area. This produces a distinctive oscillation of the bubble surface, which may be influenced by the presence of incompressible particles yielding unique surface properties. A survey of the literature shows that the properties of these composite materials are greatly affected by the physicochemical characteristics of the particles such as hydrophobicity and size.The intense energy released during the coalescence of bubbles may be sufficient to expel particles from the bubble surface. It is noted that the detachment of particles may preferentially occur from specific locations on the bubble surface. Examination of the research accounts again reveals that the properties of the particles may affect their detachment upon the oscillation of the bubble surface. However, it is believed that most parameters affecting the detachment of particles are in fact modifying the dynamics of the three-phase line of contact. Both the oscillation of a coalescing bubble and the resulting detachment of particles are highly dynamic processes. They would greatly benefit from computer simulation studies.

Millimeter- and centimeter-sized "liquid marbles" were readily prepared by rolling water droplets on a powder bed of dried submicrometer-sized polystyrene latex particles carrying poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS). Scanning electron microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable spherical liquid marbles. The liquid marbles were deformed as a result of water evaporation to adopt a deflated spherical geometry, and the rate of water evaporation decreased with increasing atmospheric relative humidity. Conversely, liquid marbles formed using saturated aqueous LiCl solution led to atmospheric water absorption by the liquid marbles and a consequent mass increase. The liquid marbles can be transformed into polymeric capsules containing water by exposure to solvent vapor: the PDEA-PS particles were plasticized with the solvent vapor to form a polymer film at the air-water interface of the liquid marbles. The polymeric capsules with aqueous volumes of 250 ÎL or less kept their oblate ellipsoid/near spherical shape even after complete water evaporation, which confirmed that a rigid polymeric capsule was successfully formed. Both the rate of water evaporation from the pure water liquid marbles and the rate of water adsorption into the aqueous LiCl liquid marbles were reduced with an increase of solvent vapor treatment time. This suggests that the number and size of pores within the polymer particles/flocs on the liquid marble surface decreased due to film formation during exposure to organic solvent vapor. In addition, organic-inorganic composite capsules and colloidal crystal capsules were fabricated from liquid marbles containing aqueous SiO2 dispersions. © 2014 American Chemical Society.