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When monoclonal antibodies are exposed to an air-water interface, they form aggregates, which negatively impacts their performance. Until now, the detection and characterization of interfacial aggregation have been difficult. Here, we exploit the mechanical response imparted by interfacial adsorption by measuring the interfacial shear rheology of a model antibody, anti-streptavidin immunoglobulin-1 (AS-IgG1), at the air-water interface. Strong viscoelastic layers of AS-IgG1 form when the protein is adsorbed from the bulk solution. Creep experiments correlate the compliance of the interfacial protein layer with the subphase solution pH and bulk concentration. These, along with oscillatory strain amplitude and frequency sweeps, show that the viscoelastic behavior of the adsorbed layers is that of a soft glass with interfacial shear moduli on the order of 10 -3 Pa m. Shifting the creep compliance curves under different applied stresses forms master curves consistent with stress-time superposition of soft interfacial glasses. The interfacial rheology results are discussed in the context of the interface-mediated aggregation of AS-IgG1.

Foams can resist destabilizaton in ways that appear similar on a macroscopic scale, but the microscopic origins of the stability and the loss thereof can be quite diverse. Here, we compare both the macroscopic drainage and ultimate collapse of aqueous foams stabilized by either a partially hydrolyzed poly(vinyl alcohol) (PVA) or a nonionic low-molecular-weight surfactant (BrijO10) with the dynamics of individual thin films at the microscale. From this comparison, we gain significant insight regarding the effect of both surface stresses and intermolecular forces on macroscopic foam stability. Distinct regimes in the lifetime of the foams were observed. Drainage at early stages is controlled by the different stress-boundary conditions at the surfaces of the bubbles between the polymer and the surfactant. The stress-carrying capacity of PVA-stabilized interfaces is a result of the mutual contribution of Marangoni stresses and surface shear viscosity. In contrast, surface shear inviscidity and much weaker Marangoni stresses were observed for the nonionic surfactant surfaces, resulting in faster drainage times, both at the level of the single film and the macroscopic foam. At longer times, the PVA foams present a regime of homogeneous coalescence where isolated coalescence events are observed. This regime, which is observed only for PVA foams, occurs when the capillary pressure reaches the maximum disjoining pressure. A final regime is then observed for both systems where a fast coalescence front propagates from the top to the bottom of the foams. The critical liquid fractions and capillary pressures at which this regime is obtained are similar for both PVA and BrijO10 foams, which most likely indicates that collapse is related to a universal mechanism that seems unrelated to the stabilizer interfacial dynamics.

In multiphase materials, structured fluid-fluid interfaces can provide mechanical resistance against destabilization. Coarsening, coalescence, and significant deformation can be stalled with appropriate interfacial rheology and thus preserve interface integrity. Often, interfacial "strength" is generated by dense, packed surface populations, which are challenging to achieve through gradual, equilibrium-limited adsorption. Recent efforts have focused on developing new methods to produce kinetically trapped interfacial structures that possess desirable viscoelasticity or viscoplasticity, sometimes even with sparse populations. In creating these interfaces, we should recognize that the processing history is deterministic and offers alternative handles to engineer useful rheology. In this Perspective, we consider what can be achieved by designing not only the intrinsic qualities of surface-active species but also the process that brings them to the interface. We contrast different classes of processing history through a somewhat historical lens: after creating an interface ("divide"), what ("conquering") strategies exist for populating it with agents that ensure stabilization? Navigating the delicate interplay among property, structure, and processing history is required to improve material and energy use and to realize unique multiphase materials.

Asphaltenes have been suggested to play an important role in the remarkable stability of some water-in-crude oil emulsions, although the precise mechanisms by which they act are not yet fully understood. Being one of the more polar fractions in crude oils, asphaltenes are surface active and strongly adsorb at the oil/water interface, and as the interface becomes densely packed, solid-like mechanical properties emerge, which influence many typical interfacial experiments. The present work focuses on purposefully measuring the rheology in the limit of an insoluble, spread Langmuir monolayer in the absence of adsorption/desorption phenomena. Moreover, the changes in surface tension are deconvoluted from the purely mechanical contribution to the surface stress by experiments with precise interfacial kinematics. Compression "isotherms" are combined with the measurement of both shear and dilatational rheological properties to evaluate the relative contributions of mechanical versus thermodynamic aspects, i.e., to evaluate the "interfacial rheological" versus the standard interfacial activity. The experimental results suggest that asphaltene nanoaggregates are not very efficient in lowering interfacial tension but rather impart significant mechanical stresses. Interestingly, physical aging effects are not observed in the spread layers, contrary to results for adsorbed layers. By further studying asphaltene fractions of different polarity, we investigate whether mere packing effects or strong interactions determine the mechanical response of the dense asphaltene systems as either soft glassy or gel-like responses have been reported. The compressional and rheological data reflect the dense packing, and the behavior is captured well by the soft glassy rheology model, but a more complicated multilayer structure may develop as coverage is increased. Potential implications of the experimental observations on these model and insoluble interfaces for water-in-crude oil emulsion stability are briefly discussed.

Wet processing of graphene sheets is a potentially interesting route for the economically viable creation of graphene-based composites. In the present work, flow dichroism and small-angle light scattering are used to investigate the dispersion of functionalized graphene sheets in a suspension and their response to shear flow. In line with expectations from scaling theory at rest, the functionalized graphene sheets are present as Brownian flat sheets, and there is no evidence of significant crumpling. More surprisingly, we find that the rate-dependent orientation of these molecularly thin sheets can be described by numerical predictions for hard spheroidal sheets, making quantitative predictions of the flow-induced orientation possible. Further comparison of the flow-induced orientation of thick gold decahedra with the thin graphene sheets shows that, except for effects of polydispersity, the flow-induced orientation is predicted well quantitatively. Adequate prediction of the effects of flow on the orientation of graphene sheets makes it possible to design wet processed graphene-based composite materials.

In food-grade emulsions, particles with an appropriate surface modification can be used to replace surfactants and potentially enhance the stability of emulsions. During the life cycle of products based on such emulsions, they can be exposed to a broad range of pH conditions and hence it is crucial to understand how pH changes affect stability of emulsions stabilized by particles. Here, we report on a comprehensive study of the stability, microstructure, and macroscopic behavior of pH-controlled oil-in-water emulsions containing silica nanoparticles modified with chitosan, a food-grade polycation. We found that the modified colloidal particles used as stabilizers behave differently depending on the pH, resulting in unique emulsion structures at multiple length scales. Our findings are rationalized in terms of the different emulsion stabilization mechanisms involved, which are determined by the pH-dependent charges and interactions between the colloidal building blocks of the system. At pH 4, the silica particles are partially hydrophobized through chitosan modification, favoring their adsorption at the oil-water interface and the formation of Pickering emulsions. At pH 5.5, the particles become attractive and the emulsion is stabilized by a network of agglomerated particles formed between the droplets. Finally, chitosan aggregates form at pH 9 and these act as the emulsion stabilizers under alkaline conditions. These insights have important implications for the processing and use of particle-stabilized emulsions. On one hand, changes in pH can lead to undesired macroscopic phase separation or coalescence of oil droplets. On the other hand, the pH effect on emulsion behavior can be harnessed in industrial processing, either to tune their flow response by altering the pH between processing stages or to produce pH-responsive emulsions that enhance the functionality of the emulsified end products.

Capacitance measurements provide unique insights into the thickness, compressibility, and composition of large-area membrane bilayers and are used here in addition to demonstrate the successful incorporation of model ion channels. The simultaneous ability to control the bilayer size, manipulate tension, and optically monitor and electrically stimulate freestanding membranes enables precise determination of their specific capacitance and thickness across a wide range of areas. We confirm that membranes formed by this recently developed technique have capacitive properties similar to those formed by existing protocols, including solvent-free approaches, and discuss the effect using either hexadecane or squalene as the oil solvent. The results obtained here are relevant for other methods where lipid membranes are reconstituted from a bulk oil solvent. Because biological membranes have a diverse phospholipid profile, we show that the technique can successfully reconstitute membranes with binary composition mixtures. As an outlook, we show the capability of model membrane proteins, specifically α-hemolysin and alamethicin, to be incorporated into the formed bilayers and measure ion transport.

Particle-laden interfaces can be used to stabilize a variety of high-interface systems, from foams over emulsions to polymer blends. The relation between the particle interactions, the structure and rheology of the interface, and the stability of the system remains unclear. In the present work, we experimentally investigate how micron-sized, near-hard-sphere-like particles affect the mechanical properties of liquid interfaces. In particular, by comparing dried and undried samples, we investigate the effect of aggregation state on the properties of the particle-laden liquid interface and its relation to the stability of the corresponding Pickering emulsions. Partially aggregated suspensions give rise to a soft-solid-like response under shear, whereas for stable PMMA particulate layers a liquid-like behavior is observed. For interfacial creep-recovery measurements, we present an empirical method to correct for the combined effect of the subphase drag and the compliance of the double-wall ring geometry, which makes a significant contribution to the apparent elasticity of weak interfaces. We further demonstrate that both undried and dried PMMA particles can stabilize emulsions for months, dispelling the notion that particle aggregation, in bulk or at the interface, is required to create stable Pickering emulsions. Our results indicate that shear rheology is a sensitive probe of colloidal interactions but is not necessarily a predictor of the stability of interfaces, e.g., in quiescent Pickering emulsions, as in the latter the response to dilatational deformations can be of prime importance.

The adsorption of particles at liquid-liquid interfaces is of great scientific and technological importance. In particular, for nonspherical particles, the capillary forces that drive adsorption vary with position and orientation, and complex adsorption pathways have been predicted by simulations. On the basis of the latter, it has been suggested that the timescales of adsorption are determined by a balance between capillary and viscous forces. However, several recent experimental results point out the role of contact line pinning in the adsorption of particles to interfaces and even suggest that the adsorption dynamics and pathways are completely determined by the latter, with the timescales of adsorption being determined solely by particle characteristics. In the present work, the adsorption trajectories of model ellipsoidal particles are investigated experimentally using cryo-SEM and by monitoring the altitudinal orientation angle using high-speed confocal microscopy. By varying the viscosity and the viscosity jump across the interfaces, we specifically interrogate the role of viscous forces.

Semifluorinated alkanes form monolayers with interesting properties at the air-water interface due to their pronounced amphi-solvophobic nature and the stiffness of the fluorocarbons. In the present work, using a combination of structural and dynamic probes, we investigated how small molecular changes can be used to control the properties of such an interface, in particular its organization, rheology, and reversibility during compression-expansion cycles. Starting from a reference system perfluor(dodecyl)dodecane, we first retained the linear structure but changed the linkage groups between the alkyl chains and the fluorocarbons, by introducing either a phenyl group or two oxygens. Next, the molecular structure was changed from linear to branched, with four side chains (two fluorocarbons and two hydrocarbons) connected to extended aromatic cores. Neutron reflectivity at the air-water interface and scanning force microscopy on deposited films show how the changes in the molecular structure affect molecular arrangement relative to the interface. Rheological and compression-expansion measurements demonstrate the significant consequences of these changes in molecular structure and interactions on the interfacial properties. Remarkably, even with these simple molecules, a wide range of surface rheological behaviors can be engineered, from viscous over viscoelastic to brittle solids, for very similar values of the surface pressure.

The sorption and rheological properties of an acidic polyaromatic compound (C5PeC11), which can be used to further our understanding of the behavior of asphaltenes, are determined experimentally. The results show that C5PeC11 exhibits the type of pH-dependent surface activity and interfacial shear rheology observed in C6-asphaltenes with a decrease in the interfacial tension concomitant with the elastic modulus when the pH increases. Surface pressure-area (Π-A) isotherms show evidence of aggregation behavior and π-π stacking at both the air/water and oil/water interfaces. Similarly, interactions between adsorbed C5PeC11 compounds are evidenced through desorption experiments at the oil/water interface. Contrary to indigenous asphaltenes, adsorption is reversible, but desorption is slower than for noninteracting species. The reversibility enables us to create layers reproducibly, whereas the presence of interactions between the compounds enables us to mimic the key aspects of interfacial activity in asphaltenes. Shear and dilatational rheology show that C5PeC11 forms a predominantly elastic film both at the liquid/air and the liquid/liquid interfaces. Furthermore, a soft glassy rheology model (SGR) fits the data obtained at the liquid/liquid interface. However, it is shown that the effective noise temperature determined from the SGR model for C5PeC11 is higher than for indigenous asphaltenes measured under similar conditions. Finally, from a colloidal and rheological standpoint, the results highlight the importance of adequately addressing the distinction between the material functions and true elasticity extracted from a shear measurement and the apparent elasticity measured in dilatational-pendant drop setups.

The synthesis of nanoparticle clusters, also referred to as colloidal clusters or colloidal molecules, is being studied intensively as a model system for small molecule interactions as well as for the directed self-assembly of advanced materials. This paper describes a technique for the interfacial assembly of planar colloidal clusters using a combination of top-down lithographic surface modification and bottom-up Langmuir-Blodgett deposition. Micrometer sized polystyrene latex particles were deposited onto a chemically modified substrate from a decane-water interface with Langmuir-Blodgett deposition. The surface of the substrate contained hydrophilic domains of various size, spacing, and shape, while the remainder of the substrate was hydrophobic. Particles selectively deposited onto hydrophilic regions from the decane-water interface. The number of deposited particles depended on the size of each patch, thereby demonstrating that tuning cluster size is possible by engineering patch geometry. Following deposition, the clusters were permanently bonded with temperature annealing and then removed from the substrate via sonication. The permanently bonded planar colloidal clusters were stable in an aqueous environment and at a decane-water interface laden with isotropic colloidal particles. The method is a simple and fast way to synthesize colloidal clusters with few limitations on particle chemistry, composition, and shape.

The drying of sessile droplets represents an intriguing problem, being a simple experiment to perform but displaying complexities that are archetypical for many free surface and coating flows. Drying can leave behind distinct deposits of initially well dispersed colloidal matter. For example, in the case of the coffee ring effect, particles are left in a well-defined macroscopic pattern with particles accumulating at the edge, controlled by the internal flow in the droplet. Recent studies indicate that the addition of surfactants strongly influences this internal flow field, even reversing it and suppressing the coffee ring effect. In this work, we explore the behavior of droplets at high surfactant loadings and observe unexpected outward fingering instabilities. The experiments start out with droplets with a pinned contact line, and fast confocal microscopy is used to quantify a radially outward surfactant-driven Marangoni flow, in line with earlier observations. However, the Marangoni flows are observed to become unstable, and local vortex cells are now observed in a direction along the contact line. The occurrence of these vortices cannot be explained on the basis of the effects of surfactants alone. Thermal imaging shows that thermocapillary effects are superimposed on the surfactant-driven flows. These local vortex cells acts as little pumps and push the fluid outward in a fingering instability, rather than an expected inward retraction of the drying droplet. This leads to a deposition of colloids in a macroscopical flower-shaped pattern. A scaling analysis is used to rationalize the observed wavelengths and velocities, and practical implications are briefly discussed.

The wetting of anisotropic colloidal particles is of great importance in several applications, including Pickering emulsions, filled foams, and membrane transduction by particles. However, the combined effect of shape and surface chemistry on the three-phase contact angle of anisotropic micrometer and submicrometer colloids has been poorly investigated to date, due to the lack of a suitable experimental technique to resolve individual particles. In the present work, we investigate the variation of the contact angle of prolate ellipsoidal colloids at a liquid-liquid interface as a function of surface chemistry and aspect ratio using freeze-fracture shadow-casting cryo-SEM. The method, initially demonstrated for spherical colloids, is extended here to the more general case of ellipsoids. The prolate ellipsoidal particles are prepared from polystyrene and poly(methyl methacrylate) spheres using a film stretching technique, in which cleaning steps are needed to remove all film material from the particle surface. The effects of the preparation protocol are reported, and wrinkling of the three-phase contact line is observed when the particle surface is insufficiently cleaned. For identically prepared ellipsoids, the cosine of the measured contact angle is, in a first approximation, a linearly decreasing function of the contact line length and thus a decreasing function of the aspect ratio. Such a trend violates Young-Laplace's equation and can be rationalized by adding a correction term to the ideal Young-Laplace contact angle that expresses the relative importance of line effects relative to surface effects. From this term the contribution of an effective line tension can be extracted. This contribution includes the effects that both surface chemical and topographical heterogeneities have on the contact line and which become increasingly more important for ellipsoids with higher aspect ratios, where the contact line length to contact area ratio increases.

The two-particle interaction between 3.1-μm-diameter polystyrene latex particles at a decane-water interface was measured with time-shared optical tweezers. The water subphase contained either 0.103 mM RbCl or 0.0342 mM MgCl2, which have hydrated cations of different size but identical anions. The choice of both the anion and the concentrations makes a comparison with published data on NaCl possible and also isolates the effect of the nature of the cation on the electrostatic interaction. The measured magnitude of the dipolar force and the relative changes as a function of electrolyte were in quantitative agreement with predictions from a recently published model that uses the Langevin-Poisson-Boltzmann equation including steric effects and the polarization saturation of the medium to predict the dipolar interaction (Frydel, D.; Oettel, M. Phys. Chem. Chem. Phys. 2011, 13, 4109-4118). These results support the hypothesis that a condensed layer of counterions contributes to the electrostatic interaction between colloidal particles at an oil-water interface. Although it has been suggested that the electrostatic interactions between particles at liquid interfaces could serve as a sensitive probe of the structural details of the electric double layer, both the model predictions and experimental measurements showed a maximum change of only ~25% in the magnitude of the interaction with a change in electrolyte under the conditions tested. The ability to resolve this small change was confounded by the heterogeneous nature of the interaction. Thus, despite the apparent importance of the choice of electrolyte, the subtlety of competing effects makes it unlikely that colloidal force measurements could be used to probe the fine structure of the electric double layer.

The effect of using a viscoelastic suspending medium on the in-plane hydrodynamic interaction between two equally sized spheres in shear flow is studied experimentally to understand flow-induced assembly behavior (i.e., string formation). A counterrotating device equipped with a Couette geometry is used together with quantitative videomicroscopy. To evaluate the effects of differences in rheological properties of the suspending media, fluids have been selected that highlight specific constitutive features. These include a reference Newtonian fluid (N), a constant-viscosity, high-elasticity Boger fluid (BF), a wormlike micellar surfactant solution with a single dominant relaxation time (WMS), and a broad spectrum shear-thinning elastic polymer solution (ST). As expected, the trajectories are symmetric in the Newtonian fluid. In the BF, the midpoints of the spheres are observed to remain in the same plane before and after the interaction, as in the Newtonian fluid, although the path lines are in this case no longer symmetric. Interactions in the ST and WMS are highly asymmetric. Two fundamentally different kinds of path lines are observed in the WMS and ST: reversing and open trajectories. The type of trajectory depends on the initial configuration of the spheres with respect to each other and on the shear rate. On the basis of the obtained results, shear-thinning of the viscosity seems to be the key rheological parameter that determines the overall nature of the interactions, rather than the relative magnitude of the normal stress differences.

The hydrophilic nature of graphene oxide sheets can be tailored by varying the carbon to oxygen ratio. Depending on this ratio, the particles can be deposited at either a water-air or a water-oil interface. Upon compression of thus-created Langmuir monolayers, the sheets cover the entire interface, assembling into a strong, compact layer of tiled graphene oxide sheets. With further compression, the particle layer forms wrinkles that are reversible upon expansion, resembling the behavior of an elastic membrane. In the present work, we investigate under which conditions the structure and properties of the interfacial layer are such that free-standing films can be obtained. The interfacial rheological properties of these films are investigated using both compressional experiments and shear rheometry. The role of surface rheology in potential applications of such tiled films is explored. The rheological properties are shown to be responsible for the efficiency of such layers in stabilizing water-oil emulsions. Moreover, because of the mechanical integrity, large-area monolayers can be deposited by, for example, Langmuir-Blodgett techniques using aqueous subphases. These films can be turned into transparent conductive films upon subsequent chemical reduction.

Several technological applications, consumer products, and biological systems derive their functioning from the presence of a complex fluid interface with viscoelastic interfacial rheological properties. Measurements of the "excess" rheological properties of such an interface are complicated by the intimate coupling of the bulk and interfacial flows. In the present work, analytical, numerical, and experimental results of the interfacial flow fields in a magnetic rod interfacial stress rheometer (ISR) are presented. Mathematical solutions are required to correct the experimentally determined apparent interfacial shear moduli and phase angles for the drag exerted by the surrounding phases, especially at low Boussinesq numbers. Starting from the Navier-Stokes equations and using the generalized Boussinesq-Scriven equation as a suitable boundary condition, the problem is solved both analytically and numerically. In addition, experimental data of the interfacial flow field are reported, obtained by following the trajectories of tracer particles at the interface with time. Good agreement is found between the three methods, indicating that both the analytical solution and the numerical simulations give an adequate description of the flow field and the resulting local interfacial shear rate at the rod. Based on these results, an algorithm to correct the experimental data of the ISR is proposed and evaluated, which can be extended to different types of interfacial shear rheometers and geometries. An increased accuracy is obtained and the measurement range of the ISR is expanded toward viscosities and elastic moduli of smaller magnitude.

Ordering induced by shear flow can be used to direct the assembly of particles in suspensions. Flow-induced ordering is determined by the balance between a range of forces, such as direct interparticle, Brownian, and hydrodynamic forces. The latter are modified when dealing with viscoelastic rather than Newtonian matrices. In particular, 1D stringlike structures of spherical particles have been observed to form along the flow direction in shear thinning viscoelastic fluids, a phenomenon not observed in Newtonian fluids at similar particle volume fractions. Here we report on the formation of freestanding crystalline patches in planes parallel to the shearing surfaces. The novel microstructure is formed when particles are suspended in viscoelastic, wormlike micellar solutions and only when the applied shear rate exceeds a critical value. In spite of the very low volume fraction (less than 0.01), particles arrange themselves in 2D crystalline patches along the flow direction. This is a bulk phenomenon because 2D crystals form throughout the whole gap between plates, with the gap thickness being much larger than the particle size. Shear flow may hence be an easy method to drive particles into crystalline order in suspensions with viscoelastic properties. The crystalline structure reported here could be used to design new materials with special mechanical, optical, thermal, or electric properties.

Colloidal particles confined at liquid interfaces have important applications, for example in the stabilization of emulsions and foams. Also the self-assembly of particles at interfaces offers potential for novel applications and structured particle films. As the colloidal interactions of colloidal particles at interfaces differ from those in bulk, colloidal microstructures can be achieved at an interface which cannot be produced in bulk. In the present work the particle shape, surface charge, and wetting properties are varied, and the resulting self-assembly of particles at a fluid interface is studied. Model monodisperse micrometer-sized ellipsoidal particles were prepared by a mechanical stretching method. These particles were chosen to be well-suited for investigation by optical microscopy. When deposited at an interface between two fluids, shape-induced capillary interactions compete with the electrostatic repulsion. Changing the surface charge and the position at the interface can be used to manipulate the experimentally observed self-assembly process. The initial microstructure of charged ellipsoids at a decane-water interface consists of individual ellipsoids coexisting with linear chains of ellipsoids, connected at their tips. The aggregation behavior in these monolayers was investigated by optical microscopy combined with quantitative image analysis and a dominant tip-tip aggregation was observed. Microstructural information was quantified by calculating the pair-distribution and orientation-distribution functions, as a function of time. Compared to particles at an oil-water interface, particles of the same surface chemistry and charge at an air-water interface seem to have weaker electrostatic interactions, and they also have a different equilibrium position at the interface. The latter leads to differences in the capillary forces. The subsequent change in the balance between electrostatic and capillary forces gave rise to very dense networks having as a typical building block ellipsoids connected at their tips in triangular or flower-like configuration. These networks were very stable and did not evolve in time. The resulting monolayers responded elastically and buckled under compression. Furthermore, the mechanical properties of these monolayers, as measured by surface shear rheology, showed that the monolayer of ellipsoids exhibit a substantial surface modulus even at low surface coverage and can be used to create more elastic monolayers compared to aggregate networks of spheres of the same size and surface properties.

The synthesis and selected macroscopic properties of a new model system consisting of poly(N-isopropylacrylamide) (PNIPAM)-coated rod-like fd virus particles are presented. The sticky rod-like colloids can be used to study effect of particle shape on gelation transition, the structure and viscoelasticity of isotropic and nematic gels, and to make both open isotropic as well as ordered nematic particle networks. This model system of rod-like colloids, for which the strength of attraction between the particles is tunable, is obtained by chemically grafting highly monodisperse rod-like fd virus particles with thermoresponsive polymers, e.g. PNIPAM. At room temperature, suspensions of the resulting hybrid PNIPAM-fd are fluid sols which are in isotropic or liquid crystalline phases, depending on the particle concentration and ionic strength. During heating/cooling, the suspensions change reversibly between sol and gel state near a critical temperature of approximately 32 degrees C, close to the lower critical solution temperature of free PNIPAM. The so-called nematic gel, which exhibits a cholesteric feature, can therefore be easily obtained. The gelation behavior of PNIPAM-fd system and the structure of the nematic gel have been characterized by rheology, optical microscopy and small-angle X-ray scattering.

Flow can change the rate at which solutes adsorb on surfaces by changing mass transfer to the surface, but moreover, flow can induce changes in the conformation of macromolecules in solution by providing sufficient stresses to perturb the segmental distribution function. However, there are few studies where the effect of flow on macromolecules has been shown to alter the structure of macromolecules adsorbed on surfaces. We have studied how the local energy dissipation alters the adsorption of gelatin onto polystyrene nanoparticles ( r = 85 nm). The change in the nature of the adsorbed layer is manifest in the change in the ability of the nanoparticles to resist aggregation. Circular dichroism spectroscopy was used to assess conformational changes in gelatin, and dynamic light scattering was used to assess the colloid stability. Experiments were conducted in a vortex jet mixer where energy density and mixing times have been quantified; mixing of the gelatin and unstable nanoparticles occurs on the order of milliseconds. The adsorption of the gelatin provides steric stabilization to the nanoparticles. We found that the stability of the gelatin-adsorbed nanoparticles increased with increasing mixing velocities: when the mixing velocities were changed from 0.9 to 550 m/s, the radius of the nanoclusters (aggregates) formed 12 h after the mixing decreased from 2620 to 600 nm. Increasing temperature also gave rise to similar trends in the stability behavior with increasing temperature, leading to increasing colloid stability. Linear flow birefringence studies also suggested that the velocity fields in the mixer are sufficiently strong to produce conformational changes in the gelatin. These results suggest that the energy dissipation produced by mixing can activate conformational changes in gelatin to alter its adsorption on the surfaces of nanoparticles. Understanding how such conformational changes in gelatin can be driven by local fluid mechanics and how these changes are related to the adsorption behavior of gelatin is very important both industrially and scientifically.

The forces between colloidal particles at a decane-water interface, in the presence of low concentrations of a monovalent salt (NaCl) and the surfactant sodium dodecyl sulfate (SDS) in the aqueous subphase, have been studied using laser tweezers. In the absence of electrolyte and surfactant, particle interactions exhibit a long-range repulsion, yet the variation of the interaction for different particle pairs is found to be considerable. Averaging over several particle pairs was hence found to be necessary to obtain a reliable assessment of the effects of salt and surfactant. It has previously been suggested that the repulsion is consistent with electrostatic interactions between a small number of dissociated charges in the oil phase, leading to a decay with distance to the power -4 and an absence of any effect of electrolyte concentration. However, the present work demonstrates that increasing the electrolyte concentration does yield, on average, a reduction of the magnitude of the interaction force with electrolyte concentration. This implies that charges on the water side also contribute significantly to the electrostatic interactions. An increase in the concentration of SDS leads to a similar decrease of the interaction force. Moreover, the repulsion at fixed SDS concentrations decreases over longer times. Finally, measurements of three-body interactions provide insight into the anisotropic nature of the interactions. The unique time-dependent and anisotropic interactions between particles at the oil-water interface allow tailoring of the aggregation kinetics and structure of the suspension structure.

The controlled generation of 2D aggregate networks is studied experimentally using micrometer-sized polystyrene latex particles attached to the oil-water interface. Starting from an initially crystalline monolayer, appropriate combinations of carefully added electrolyte and surfactant enable control over both the fractal dimension and the kinetics of aggregation. Remarkably, the colloidal crystals formed upon first spreading remain stable, even for days, when substantial amounts of electrolyte are added to the aqueous phase. Pressure-area isotherms reveal a slow time evolution of the electrostatic dipole-dipole interaction. When the electrostatic interaction has been sufficiently weakened, aggregation proceeds in well-defined, reproducible manner. The aggregation process is analyzed using quantitative video microscopy. The evolution of the cluster size distribution and its moments is characterized, and static and dynamic scaling exponents are derived to identify the nature of the aggregation process. In the range of concentrations studied here, the kinetics all agree with a "fast", diffusion-limited cluster type of aggregation. However, the fractal dimension strongly depends on the composition of the aqueous subphase. Rather dense structures are found when only electrolyte is used, whereas more open structures are obtained when even small amounts of surfactant are added. It is suggested that this structural dependency is related to the effect of surfactant on the contact angle and its consequences for the anisotropic nature of the capillary interactions.

The behavior of a colloidal suspension of rodlike fd viruses in the nematic phase, subjected to steady state and transient shear flows, is studied. The monodisperse nature of these rods combined with relatively small textural contribution to the overall stress make this a suitable model system to investigate the effects of flow on the nonequilibrium phase diagram. Transient rheological experiments are used to determine the critical shear rates at which director tumbling, wagging, and flow-aligning occurs. The present model system enables us to study the effect of rod concentration on these transitions. The results are in quantitatively agreement with the Doi-Edwards-Hess model. Moreover, we observe that there is a strong connection between the dynamic transitions and structure formation, which is not incorporated in theory.