Atomic force microscopy of emulsion droplets: probing droplet-droplet interactions

A method has been developed for attaching oil (tetradecane) droplets to the end of an atomic force microscopy (AFM) cantilever and for immobilizing droplets on a glass substrate. This approach has permitted the monitoring of droplet-droplet interactions in aqueous solution as a function of interdroplet separation. Coating the droplet surfaces with added proteins or surfactants has allowed the production of model emulsions. We demonstrate that AFM measurements of droplet deformability are sensitive to interfacial rheology by modifying the interfacial film on a pair of droplets in situ. For droplets coated with the anionic surfactant sodium dodecyl sulfate, screening of the double layer has been found to facilitate coalescence. Direct imaging of the droplets has revealed the presence of regularly spaced concentric rings on the droplet surfaces. Careful experimental studies suggest that these structures may be imaging artifacts and are not perturbations of the droplet surface determined by the composition of the interface.     

Influence of poly(ethylene oxide) brushes on the rheological properties of MgO colloidal suspensions in water

A combined experimental and multiscale simulation study of the influence of polymer brush modification on interactions of colloidal particles and rheological properties of dense colloidal suspensions has been conducted. Our colloidal suspension is comprised of polydisperse MgO colloidal particles modified with poly(ethylene oxide) (PEO) brushes in water. The shear stress as a function of shear rate was determined experimentally and from multiscale simulations for a suspension of 0.48 volume fraction colloids at room temperature for both bare and PEO-modified MgO colloids. Bare MgO particles exhibited strong shear thinning behavior and a yield stress on the order of several Pascals in both experiments and simulations. In contrast, simulations of PEO-modified colloids revealed no significant yielding or shear thinning and viscosity only a few times larger than solvent viscosity. This behavior is inconsistent with results obtained from experiments where modification of colloids with PEO brushes formed by adsorption of PEO-based comb-branched chains resulted in relatively little change in suspension rheology compared to bare colloids over the range of concentration of comb-branch additives investigated. We attribute this discrepancy in rheological properties between simulation and experiment for PEO-modified colloidal suspensions to heterogeneous adsorption of the comb-branch polymers.     

Block copolymers at interfaces: Interactions with physiological media

Triblock copolymers (also known as Pluronics or poloxamers) are biocompatible molecules composed of hydrophobic and hydrophilic blocks with different lengths. They have received much attention recently owing to their applicability for targeted delivery of hydrophobic compounds. Their unique molecular structure facilitates the formation of dynamic aggregates which are able to transport lipid soluble compounds. However, these structures can be unstable and tend to solubilize within the blood stream. The use of nanoemulsions as carriers for the lipid soluble compounds appears as a new alternative with improved protection against physiological media. The interfacial behavior of block copolymers is directly related to their peculiar molecular structure and further knowledge could provide a rational use in the design of poloxamer-stabilized nanoemulsions. This review aims to combine the new insights gained recently into the interfacial properties of block copolymers and their performance in nanoemulsions. Direct studies dealing with the interactions with physiological media are also reviewed in order to address issues relating metabolism degradation profiles. A better understanding of the physico-chemical and interfacial properties of block copolymers will allow their manipulation to modulate lipolysis, hence allowing the rational design of nanocarriers with efficient controlled release.     

XPCS: Nanoscale motion and rheology

X-ray photon correlation spectroscopy (XPCS) has emerged as a powerful technique for investigating slow, nanometer-scale structural dynamics in materials. This paper reviews major directions of recent XPCS research on complex fluids where significant information relevant to their rheological behavior has been obtained. The review focuses on three topics: block-copolymer phases, colloidal glasses and gels, and polymer thin-film surfaces and interfaces. The paper also discusses important anticipated developments for XPCS in the near future and describes some particularly promising directions for the technique in advancing understanding of complex-fluid rheology, including the application of XPCS to microrheology.     

Effect of counterion substitution on the viscosity anomaly in AOT microemulsions

AOT-based water-in-oil microemulsions display an anomalous maximum in the viscosity with X, the water to surfactant ratio. Several explanations for this phenomenon have been offered. In this work, we investigate viscosity and droplet interactions in Ca(AOT)(2)/water/n-decane and KAOT/water/n-decane microemulsions and compare our results with the commonly studied NaAOT/water/oil system. The Ca(AOT)(2) system demonstrates a maximum in relative viscosity and droplet attraction near X=15, similar to the NaAOT system, although the maximum occurs at a higher value of X in the Ca(AOT)(2) system. By contrast, the viscosity and interparticle interactions in the KAOT system do not strongly depend on the amount of water in the system. We attribute the differences in behavior between the two systems to different hydration characteristics of the counterion, and we believe that our results are consistent with a previously proposed model that attributes interdroplet attractions to charge fluctuations and surfactant exchange. Our findings support the connection between the viscosity anomaly and interparticle interactions.     

Microrheology of aggregated emulsion droplet networks, studied with AFM-CSLM

We studied the mechanical behavior of densely packed (up to approximately 30% v/v), sedimented layers of (1 microm) water-in-oil W/O emulsion droplets, upon indentation with a (10 microm) large spherical probe. In the presence of attractive forces, the droplets form solid like networks which can resist deformation. Adding a polymer to the oil phase was used to control droplet attraction. The droplet layers were assembled via normal gravity settling. Considering that both the network structure and the droplet interactions play a key role, we used a combination of atomic force microscopy (AFM) and confocal scanning laser microscopy (CSLM) to characterize the mechanical behavior. Here the AFM was used both as indentation tool and as force sensor. Indentation experiments were performed via a protocol consisting of approach, waiting, and retract stages. CSLM was used to observe the network structure at micron resolution in real time. Use of refractive index matched fluorescent droplets allowed the visualization of the entire layer. Upon compression with the probe, a markedly nonhomogeneous deformation occurred, evidenced by the formation of a dense corona (containing practically all of the displaced droplets) in the direct vicinity of the probe, as well as more subtle deformations of force-chains at larger distances. Upon decompression, both the imprint of the indenter and the corona remained, even long after the load was released. The force-distance curves recorded with the AFM correspond well to these observations. For each deformation cycle performed on fresh material, the retract curve was much steeper than the approach curve, thus corroborating the occurrence of irreversible compaction. Contrary to classic linear viscoelastic materials, this hysteresis did not show any dependence on the deformation speed. Our force-indentation approach curves were seen to scale roughly as F approximately delta(3/2). The pre-factor was found to increase with the polymer concentration and with the density of the network. These findings suggest that this new AFM-CSLM method could be used for rheological characterization of small volumes of "granular networks" in liquid. Our hypothesis that the mechanical resistance of the networks originates from interdroplet friction forces, which in turn are set by the interdroplet potential forces, is supported by the predictions from a new mechanical model in which the interdroplet bonds are represented by stick-slip elements.     

Nanoemulsions prepared by a two-step low-energy process

A simple low-energy two-step dilution process has been applied in oil/surfactant/water systems with pentaoxyethylene lauryl ether (C12E5), dodecyldimethylammonium bromide, sodium bis(2-ethylhexyl)sulfosuccinate, sodium n-dodecyl sulfate-pentanol, and hexadecyltrimethylammonium bromide-pentanol. Appropriate formulations were chosen for the concentrate to be diluted with water to generate oil-in-water (O/W) emulsions or nanoemulsions. For the system of decane/C12E5/water, bluish, transparent nanoemulsions having droplet radii of the order of 15 nm were formed, only when the initial concentrate was a bicontinuous microemulsion, whereas opaque emulsions were generated if the concentrate began in an emulsion-phase region. Nanoemulsions generated in the system decane/C12E5/water have been investigated both by dynamic light scattering (DLS) and contrast-variation small-angle neutron scattering (SANS). The SANS profiles show that nanodroplets exist as spherical core-shell (decane-C12E5) particles, which suffer essentially no structural change on dilution with water, at least for volume fractions phi down to 0.060. These results suggest that the nanoemulsion droplet structure is mainly controlled by the phase behavior of the initial concentrate and is largely independent of dilution. A discrepancy between apparent nanoemulsion droplet sizes was observed by comparing DLS and SANS data, which is consistent with long-range droplet interactions occurring outside of the SANS sensitivity range. These combined phase behavior, SANS, and DLS results suggest a different reason for the stability/instability of nanoemulsions compared with earlier studies, and here it is proposed that a general mechanism for nanoemulsion formation is homogeneous nucleation of oil droplets during the emulsification.     

Tunable rheology of dense soft deformable colloids

In the last two decades, advances in synthetic, experimental and modeling/simulation methodologies have considerably enhanced our understanding of colloidal suspension rheology and put the field at the forefront of soft matter research. Recent accomplishments include the ability to tailor the flow of colloidal materials via controlled changes of particle microstructure and interactions. Whereas hard sphere suspensions have been the most widely studied colloidal system, there is no richer type of particles than soft colloids in this respect. Yet, despite the remarkable progress in the field, many outstanding challenges remain in our quest to link particle microstructure to macroscopic properties and eventually design appropriate soft composites. Addressing them will provide the route towards novel responsive systems with hierarchical structures and multiple functionalities. Here we discuss the key structural and rheological parameters which determine the tunable rheology of dense soft deformable colloids. We restrict our discussion to non-crystallizing suspensions of spherical particles without electrostatic or enthalpic interactions.     

How to prepare and stabilize very small nanoemulsions

Practical and theoretical considerations that apply when aiming to formulate by ultrasonication very small nanoemulsions (particle diameter up to 150 nm) with very high stability are presented and discussed. The droplet size evolution during sonication can be described by a monoexponential function of the sonication time, the characteristic time scale depending essentially on the applied power. A unique master curve is obtained when plotting the mean diameter size evolution as a function of sonication energy. We then show that Ostwald ripening remains the main destabilization mechanism whereas coalescence can be easily prevented due to the nanometric size of droplets. The incorporation of "trapped species" within the droplet interior is able to counteract Ostwald ripening, and this concept can be extended to the membrane compartment. We finally clarify that nanoemulsions are not thermodynamically stable systems, even in the case where their composition lies very close to the demixing line of a thermodynamically stable microemulsion domain. However, as exemplified in the present work, nanoemulsion systems can present very long-term kinetic stability.     

Energy of interaction in colloids and its implications in rheological modeling

This work deals with the problem of deriving theoretical connections between rheology and interparticle forces in colloidal suspensions. The nature of interparticle forces determines the colloidal structure (crystalline order due to long range repulsive forces, flocculation due to attractive forces, etc.) and hence, the flow behavior of suspensions. The aim of this article is to discuss how these interactions enter the modeling of rheometric functions, in particular, the shear viscosity. In this sense, the main interactions commonly appearing in colloids are reviewed, as well as the role they play in phase transition behavior. Then, a series of approaches relating the interaction potential to viscosity is examined. The results of applying these models to experimental data are also discussed. Finally, examples of viscosity modeling for different interaction potentials are given, by using the structural model proposed previously by the authors. The possibility of relating the flow behavior of colloidal suspensions to the interaction between particles offers new perspectives for the study and technical applications of these systems.     

Active colloidal particles at fluid-fluid interfaces

This review explores the intersection between two important fields of colloid and interface science – that of active colloidal particles and of (passive) particles at fluid-fluid interfaces. The former uses energy input at the particle level to propel particle motions and direct dynamic assemblies. The latter relies on the spontaneous adsorption of particles at fluid interfaces to modify the interfacial energy, rheology, and permeability of biphasic materials. Here, we address two key questions that connect these otherwise distinct fields of study. How do liquid interfaces influence the dynamics of active or driven colloidal particles? How can particle activity influence the dynamics of liquid interfaces? These questions motivate the pursuit of active particle surfactants that move and organize at fluid interfaces to perform useful functions such as enhancing mass transport or modulating interfacial properties. Drawing examples from the literature, we discuss how fluid interfaces can provide a unique environment for the study of active colloids, how surface tension can be harnessed to propel particle motions, and how capillary interactions can be activated to achieve dynamically tunable emulsions and foams. We highlight opportunities for the future study and application of active particles at liquid interfaces.     

Colloid probe AFM investigation of the influence of cross-linking on the interaction behavior and nano-rheology of colloidal droplets

The repulsive forces between a glass sphere and immobilized colloidal droplets of poly(dimethylsiloxane) (PDMS) (with various levels of internal cross-linking) have been determined in aqueous solution using colloid probe atomic force microscopy. On initial surface approach, droplet deformation is negligible and interaction forces resemble those expected for electrical double layer interaction of rigid spheres. Upon further approach, droplet flattening results in forces that deviate below rigid body electrical double layer interaction. The extent of droplet deformation has been determined in terms of the deviation from hard-sphere interaction. Droplet deformability is strongly dependent on the droplet cross-linking level and hence controlled by some combination of the bulk rheological and interfacial properties of the droplets. Droplet nano-rheology has been determined from the extent of force curve hysteresis. For liquidlike droplets, with low levels of cross-linking, no force curve hysteresis is observed and the elastic deformation may be described by a single spring constant, which is controlled by the interfacial properties. For highly cross-linked droplets, the extent of deformation is controlled by the droplet's bulk rheology rather than the interfacial properties. Upon retraction of the surfaces, force curve hysteresis is observed and is due to the viscoelastic response of the PDMS. The extent of hysteresis is dependent on the rate of approach/retraction and the loading force and has been theoretically analyzed to determine nano-rheological parameters that describe droplet relaxation processes. Elastic moduli and relaxation times of the PDMS droplets vary over several orders of magnitude as a function of cross-linking.     

Interactions,Structure, and Microscopic Response: Complex Fluid Rheology Using Laser Tweezers

Optical trapping techniques are emerging as significant research tools in complex fluids, offering the ability to probe nano‐ and microscopic interactions, structures, and responses that govern the rheology of complex fluids. In combination with real‐space imaging, microstructural response of these fluids can be directly and quantitatively correlated to imposed microscopic stresses and strains. Thus, laser tweezers are enabling us to bridge multiple length scales in colloid and polymer rheology and should be highly useful for investigating the mechanisms of linear and nonlinear rheology. In this article, we briefly review the theory and practice of using optical traps in complex fluids. We discuss the characteristics of the gradient force trap, practical concerns in trapping experiments, and applications, including measurements of micromechanics and microrheology in colloid and polymer gels.     

Janus and multiblock colloidal particles

We review recent developments in the synthesis and self-assembly of Janus and multiblock colloidal particles, highlighting new opportunities for colloid science and technology that are enabled by encoding orientational order between particles as they self-assemble. Emphasizing the concepts of molecular colloids and colloid valence unique to such colloids, we describe their rational self-assembly into colloidal clusters, taking monodisperse tetrahedra as an example. We also introduce a simple method to lock clusters into permanent shapes. Extending this to 2D lattices, we also review recent progress in assembling new open colloidal networks including the kagome lattice. In each application, areas of opportunity are emphasized.     

Some aspects of colloids in photography

The principles of colloid and interface science underlie the successful formulation and manufacture of photographic products. The colour-forming components are usually delivered in colloidal form. Rapid and stable manufacture depends on the dynamic surface properties and the rheology of the coated fluids.     

Interfacial interactions and colloid retention under steady flows in a capillary channel

Colloidal interfacial interactions in a capillary channel under different chemical and flow conditions were studied using confocal microscopy. Fluorescent latex microspheres (1.1 microm) were employed as model colloids and the effects of ionic strength and flow conditions on colloidal retention at air-water interface (AWI) and contact line were examined in static and dynamic (flow) experiments. Colloids were preferentially attached to and accumulated at AWI, but their transport with bulk solution was non-negligible. Changing solution ionic strength in the range 1-100 mM had a marginal effect on colloidal accumulation, indicating forces other than electrostatic are involved. Flow through the open channel resembled Poiseuille flow with AWI acting as a non-stress-free boundary, which resulted in near stagnation of AWI and consequently promoted colloid accumulation. Retention on contact line was likely dominated by film-straining and was more significant in flow relative to static experiments due to hydrodynamic driving force. Modeling and dimensionless analysis of the flow behavior in the capillary channel clearly indicate the important role of apparent surface viscosity and surface tension in colloidal interfacial retention at the pore scale, providing insight that could improve understanding of colloid fate and transport in natural unsaturated porous media.     

Effect of ethoxylated nonyl-phenols on interfacial rheological properties of oil/water systems

 Interfacial rheological properties of different Hungarian crude oil/water systems were determined in wide temperature and shear rate range and in presence of ethoxylated nonyl-phenols with ethoxy group number between 10 and 40. The fundamental conclusion of the experimental results is that the interfacial viscosity, the non-Newtonian flow behavior and the activation energy of the viscous flow drastically decrease in presence of non-ionic surfactants. Modification of these interfacial rheological properties increase with decreasing ethoxy group number and increasing tenside concentration and temperature. The most radical change was observed in presence of NPEO₁₀. As a summary it was evidenced that the interfacial rheology is an efficient and powerful detection technique, which may enhance our knowledge on formation, structure, properties and behavior of interfacial layers formed in oil/water systems. Thus, similar studies will probably accelerate the progress significantly not only in oil recovery but also in all areas of colloid science and technology. Received: 10 August 1996 Accepted: 29 November 1996     

蛋白质膜界面流变行为研究进展

随着界面流变测量技术以及相关的光学辅助仪器的发展,近10年来界面流变学在食品、化妆品、医药等领域发挥了重要作用。本文介绍了近年来蛋白质膜界面流变行为的研究进展,着重介绍了蛋白质界面流变学在泡沫和乳液方面的研究。本文主要分为3个部分,内容包括:蛋白质膜界面流变学行为与泡沫、乳液稳定性的相互关系,蛋白质-多聚糖的界面流变行为研究,蛋白质-表面活性物质的界面流变行为研究。界面流变学在泡沫和乳液方面取得的较快研究进展不仅促进了人们对蛋白质膜界面流变行为更为深刻的理解,而且为更好地开发和应用蛋白质及其混合物作为表面活性物质和胶体稳定剂而提供重要的理论依据和指导。     

Characteristics of pickering emulsion gels formed by droplet bridging

We experimentally characterize the microstructure and rheology of a carefully designed mixture of immiscible fluids and near-neutral-wetting colloidal particles. Particle bridging across two fluid interfaces provides a route to highly stable gel-like emulsions at volume fractions of the dispersed phase well below the random close-packing limit for spheres. We investigate the microstructural origins of this behavior by confocal microscopy and reveal a percolating network of colloidal particles that serves as a cohesive scaffold, bridging together droplets of the dispersed phase. Remarkably, the mixture's salient rheological characteristics are governed predominantly by the solids loading and can be tailored irrespective of the droplet volume fraction. The identification of this rheological hallmark could provide a means toward the improved design of modern products that utilize solid-stabilized interfaces.