Active colloids on fluid interfaces

We review recent work on active colloids at interfaces, including self-propelled colloids that move by generating a propulsive force, and driven colloids that move under external fields. Features unique to fluid interfaces alter the flows generated at interfaces by active colloid motion, and hydrodynamic interactions with these layers. We emphasize recent observations of natural swimmers, like bacteria, and bio-mimetic colloids including self-propelled phoretic and Marangoni swimmers, and magnetically driven colloids. We discuss active colloid interaction with boundaries and with each other. We conclude with a discussion of open issues and opportunities to design active colloids as active surface agents that manipulate interfacial properties and the transport in the vicinity of interfaces.     

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.     

Active colloids: Progress and challenges towards realising autonomous applications

Active colloids are small scale materials capable of producing enhanced motion within fluid environments. The field of active colloids has grown rapidly over the last ten years and is approaching maturity where viable applications are within reach. In this review, recent advances are surveyed with a strong emphasis on developments that can enable autonomous applications, where colloids execute useful tasks without external interventions. These applications are likely to prove transformative as the resulting technologies will be significantly less complex than current methods. A survey of the requirements to achieve autonomous applications is provided, considering guidance, solution compatibilities, manufacture and function; with reference to recent developments in these capacities. Following on from this, progress towards applications in environmental remediation, lab-on-a-chip microfluidics and in vivo drug delivery is highlighted.     

Dynamic Coupling at Low Reynolds Number

Collective and emergent behaviors of active colloids provide useful insights into the statistical physics of out‐of‐equilibrium systems. Colloidal suspensions containing microscopic active swimmers have been intensively studied to understand the principles of energy transfer at low Reynolds number conditions. Studies on active enzymes and Ångström‐sized organometallic catalysts have demonstrated that energy can even be transferred by molecules to their surroundings, thereby influencing the overall dynamics of the systems substantially. By monitoring the diffusion of non‐reacting tracers in active solutions, it has been shown that the nature of energy transfer in systems containing different swimmers is surprisingly similar—irrespective of their size, modes of energy transduction, and propulsion strategies. This Review discusses research results obtained so far in this direction, highlighting the common features observed in the dynamic coupling of swimmers with their surroundings.     

Alignment of particles in sheared viscoelastic fluids

We investigate the shear-induced structure formation of colloidal particles dissolved in non-Newtonian fluids by means of computer simulations. The two investigated visco-elastic fluids are a semi-dilute polymer solution and a worm-like micellar solution. Both shear-thinning fluids contain long flexible chains whose entanglements appear and disappear continually as a result of Brownian motion and the applied shear flow. To reach sufficiently large time and length scales in three-dimensional simulations with up to 96 spherical colloids, we employ the responsive particle dynamics simulation method of modeling each chain as a single soft Brownian particle with slowly evolving inter-particle degrees of freedom accounting for the entanglements. Parameters in the model are chosen such that the simulated rheological properties of the fluids, i.e., the storage and loss moduli and the shear viscosities, are in reasonable agreement with experimental values. Spherical colloids dispersed in both quiescent fluids mix homogeneously. Under shear flow, however, the colloids in the micellar solution align to form strings in the flow direction, whereas the colloids in the polymer solution remain randomly distributed. These observations agree with recent experimental studies of colloids in the bulk of these two liquids.     

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.     

在介观尺度研究多相复杂流体——四辊流变仪及其应用

研究多相复杂流体的流变学需要介观尺度下基本力学过程的信息.四辊流变仪可以产生旋转、剪切、拉伸等多种流场,且在流场中心形成一个停滞点,适于实时观察和测量介观尺度范围内与基质不相容的液滴的形变、破裂和聚并,或纤维、固体粒子、液晶等与液体组成的多相复杂流体的流变性质,还可以和多种仪器联用进一步扩展应用范围.本文综述了四辊流变仪的发展、主要部件、理论基础、用途以及应用四辊流变仪所做的主要研究,最后与其它流变仪器加以比较并总结了它的优缺点.     

Dynamical and rheological properties of soft colloid suspensions

Soft colloids comprise a wide class of materials, ranging from linear polymers over polymeric assemblies, such as star polymers and dendrimers, to vesicles, capsules, and even cells. Suspensions of such colloids exhibit remarkable responses to imposed flow fields. This is related to their ability to undergo conformational changes and elastic deformations, and the adaptation of their dynamical behavior. The rational design of soft particles for targeted applications or the unraveling of their biological function requires an understanding of the relation between their microscopic properties and their macroscopic response. Here, mesoscale computer simulations provide an invaluable tool to tackle the broad range of length and time scales. In this article, we discuss recent theoretical and simulation results on the rheological behavior of ultrasoft polymeric colloids, vesicles, capsules, and cells. The properties of both, individual particles and semi-dilute suspensions, are addressed.     

A Study of the Influence of Nanoparticles on the Properties of Drilling Fluids

The effect of nanoparticles with different compositions and sizes on the rheological properties, filtration losses, and lubricating ability of drilling fluids has been experimentally studied. Nanoparticles of silicon, aluminum, and titanium oxides have been examined, while an aqueous bentonite suspension with a solid phase mass fraction of 5% has been used as a basic model of a drilling fluid. The concentrations and sizes of nanoparticles in the drilling fluids have been varied from 0.25 to 2 wt % and from 5 to 100 nm, respectively. It has been shown that the addition of nanoparticles substantially changes the properties of the drilling fluids. In contrast to suspensions of particles with macro- and microscopic sizes, the rheological parameters, filtration losses, and lubricating and sticking abilities of the suspensions containing nanoparticles depend on the size and nature of the latter and vary markedly already at low nanoparticle concentrations.     

Two-fluid model for the simultaneous flow of colloids and fluids in porous media

To describe the velocities of particles such as ions, protein molecules and colloids dispersed or dissolved in a fluid, it is important to also describe the forces acting on the fluid, including pressure gradients and friction of the fluid with the particles and with the porous media through which the fluid flows. To account for this problem, the use of a two-fluid model is described, familiar in the field of fluid mechanics, extended to include osmotic effects. We show how familiar relationships follow in various situations and give examples of combined fluid/particle transport in neutral and charged membranes driven by a combination of electrostatic, diffusional and pressure forces. The analysis shows how the same modeling framework can be generally used both for multidimensional electrokinetic flow through macroscopic channels and around macroscopic objects, as well as for mean-field modeling of transport through porous media such as gels and membranes.     

Bubble dynamics for broadband microrheology of complex fluids

Bubbles in complex fluids are often desirable, and sometimes simply inevitable, in the processing of formulated products. Bubbles can rise by buoyancy, grow or dissolve by mass transfer, and readily respond to changes in pressure, thereby applying a deformation to the surrounding complex fluid. The deformation field around a stationary, spherical bubble undergoing a change in radius is simple and localized, thus making it suitable for rheological measurements. This article reviews emerging approaches to extract information on the rheology of complex fluids by analysing bubble dynamics. The focus is on three phenomena: changes in radius by mass transfer, harmonic oscillations driven by an acoustic wave, and bubble collapse. These phenomena cover a broad range of deformation frequencies, from 10⁻⁴–10⁶ Hz, thus paving the way to broadband microrheology using bubbles as active probes. The outstanding challenges that need to be overcome to achieve a robust technique are also discussed.     

Self-organization in the flow of complex fluids (colloid and polymer systems). Part 2: Theoretical models

Flow induced transitions in complex fluids are usually accompanied by changes in the internal media structure and the flow symmetry. In this review paper, we discuss the theoretical models and approaches that have been used for the analysis of different types of flow instabilities and flow patterns. The main attention is focused on the basic fluid models which reveal vortex and banding flow structures at high shear rates. The Oldroyd-B fluid is one of such models. The Reynolds and the Weissenberg (or Deborah) numbers are the parameters governing its flow behavior. For this model, the secondary flow patterns arising in viscometric flows of different geometries at the bifurcation point are described. Complex fluids which are able to exist in multiple states can form coexisting bands of different structures with different rheological properties and flowing with different shear rates at the same shear stress. Shear banding is typical for fluids demonstrating non-monotonous flow curves described by such models as the diffusive Johnson-Segalman fluid model, for example. Recent progress in exploring this phenomenon is discussed.     

Arrested chain growth during magnetic directed particle assembly in yield stress matrix fluids

The process of assembling particles into organized functional structures is influenced by the rheological properties of the matrix fluid in which the assembly takes place. Therefore, tuning these properties represents a viable and as yet unexplored approach for controlling particle assembly. In this Letter, we examine the effect of the matrix fluid yield stress on the directed assembly of polarizable particles into linear chains under a uniform external magnetic field. Using particle-level simulations with a simple yield stress model, we find that chain growth follows the same trajectory as in Newtonian matrix fluids up to a critical time that depends on the balance between the yield stress and the strength of magnetic interactions between particles; subsequently, the system undergoes structural arrest. Appropriate dimensionless groups for characterizing the arresting behavior are determined and relationships between these groups and the resulting structural properties are presented. Since field-induced structures can be indefinitely stabilized by the matrix fluid yield stress and "frozen" into place as desired, this approach may facilitate the assembly of more complex and sophisticated structures.     

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.     

New Approach to Enhance the Yield Stress of Electro‐Rheological Fluids by Polyaniline‐Coated Layered Silicate Nanocomposites

We synthesized new polyaniline (PANI)/organoclay (aminosilane surface‐treated) nanocomposite particles and prepared electro‐rheological (ER) fluids by dispersing the particles in silicone oil. A distinct enhancement in yield stress was observed due to the presence of PANI‐coated clay particles. The effects of delaminated clay on the ER yield stress were investigated and compared with other ER fluid systems, which use PANI particles only or a simply intercalated PANI/clay nanocomposite.     

Static Retention of Dynamic Chiral Arrangements for Achiral Shear Thinning Metal–Organic Colloids

Chiral compounds are known to be important not only because they are the fundamental components of living organisms, but also for their unique chiroptical properties. In recent years, scientists have fabricated several chiral organic supramolecular aggregates by using chiral physical fields, such as vortex flow. Herein, the relationship between dynamic chiroptical properties and rheological nature is discussed, suggesting the shear thinning properties of non-Newtonian fluids might help colloidal particles adopt a chiral arrangement in vortices. Furthermore, the storage modulus of colloids could be increased by adding a linking agent, which successfully kept the dynamic chiroptical properties in the static state. Moreover, the salt effect on the host–guest interaction involved in the colloids was studied, the results suggested a significant enhancement of the transferred dynamic circular dichroism for the achiral guest molecule.     

Effect of polymerization temperature on polyaniline based electrorheological suspensions

As one of the intrinsically polarizable materials used in electrorheological (ER) fluid, polyaniline was synthesized by the chemical oxidation of aniline with ammonium peroxysulfate. ER fluids were prepared by dispersing polyaniline particles in silicone oil, and their rheological properties were measured. The effect of the polymerization temperature of polyaniline on its ER characteristics was investigated. ER fluids with polyaniline particles synthesized at −10°C (PA-10) showed the best ER performance (yield stress) compared with those synthesized at higher temperatures. A difference in the flow behavior of the ER fluids was also investigated through the dielectric spectra of ER fluids. Received: 24 March 1988 Accepted: 3 August 1998     

Experiments with active and driven synthetic colloids in complex fluids

In this review, we focus on recent experimental research involving active colloidal particles of non-biological origin evolving in non-Newtonian fluids. This includes self-propelling active particles and particles driven by external fields. We present different propulsion strategies that are either enabled, or strongly modified, by the presence of a complex medium. This paves the way for novel mechanisms of active transport in biofluids or in other non-Newnotian fluids. When considering the medium, we differentiate between disordered complex fluids, such as diluted polymer solutions, and liquid crystals. While the latter are also viscoelastic fluids, the ability to control their molecular orientation results in distinct colloidal driving and steering mechanisms, and enables new types of active soft matter in the form of active quasi-particles.     

Partitioning of clay colloids at air-water interfaces

Colloid sorption onto air-water interfaces in a variety of natural environments has been previously recognized, but better quantification and understanding is still needed. Affinities of clay colloids for the air-water interface were measured using a bubble-column method and reported as partition coefficients (K). Four types of dilute clay suspensions were measured in NaCl solutions under varying pH and ionic strength conditions: kaolinite KGa-1, illite IMt-2, montmorillonite SWy-2, and bentonite. The K values of three types of polystyrene latex particles with different surface-charge properties were also measured for comparison. Kaolinite exhibited extremely high affinity to the air-water interface at pH values below 7. Illite has lower affinity to air-water interfaces than kaolinite, but has similar pH dependence. Na-montmorillonite and bentonite clay were found excluded from the air-water interface at any given pH and ionic strength. Positively and negatively charged latex particles exhibited sorption and exclusion, respectively, at the air-water interface. These results show the importance of electrostatic interactions between the air-water interface and colloids, especially the influence of pH-dependent edge charges, and influence of particle shape.