The Origin of Thermal Gradient-Induced Voltage in Polyelectrolytes.

Ionic thermoelectric materials can generate large thermal voltages under temperature gradients while also being low-cost and environmentally friendly. Many electrolytes with large Seebeck coefficients are reported in recent years, however, the mechanism of the thermal voltage is remained elusive. In this work, three types of polyelectrolytes are studied with different cations and identified a significant contribution to their thermal voltage originating from a concentration gradient. This conclusion is based on studies of the loss and gain of water upon temperature changes, variations in conductivity with water content and temperature, and the voltages induced by changes in water content. The results are analyzed by the "hopping mode" dynamics of charge transport in electrolytes. The hydration of different cations influences the water concentration gradient, which affects the barrier height and ion-induced potential in the electrodes. This work shows that the hydro-voltage in ionic thermoelectric devices can be one order of magnitude larger than the contribution from thermodiffusion-induced potentials, and becomes the main contributor to energy harvesting when implemented into ionic thermoelectric supercapacitors. Together with the rationalized theoretical discussion, this work clarifies the mechanism of thermal voltages in electrolytes and provides a new path for the development of ionic thermoelectric materials.

Electroviscous drag on squeezing motion in sphere-plane geometry.

Theoretically and experimentally, we study electroviscous phenomena resulting from charge-flow coupling in a nanoscale capillary. Our theoretical approach relies on Poisson-Boltzmann mean-field theory and on coupled linear relations for charge and hydrodynamic flows, including electro-osmosis and charge advection. With respect to the unperturbed Poiseuille flow, we define an electroviscous coupling parameter ξ, which turns out to be maximum where the film height h_{0} is comparable to the Debye screening length λ. We also present dynamic atomic force microscopy data for the viscoelastic response of a confined water film in sphere-plane geometry; our theory provides a quantitative description for the electroviscous drag coefficient and the electrostatic repulsion as a function of the film height, with the surface charge density as the only free parameter. Charge regulation sets in at even smaller distances.

Unconventional Thermoelectric Materials for Energy Harvesting and Sensing Applications.

Heat is an abundant but often wasted source of energy. Thus, harvesting just a portion of this tremendous amount of energy holds significant promise for a more sustainable society. While traditional solid-state inorganic semiconductors have dominated the research stage on thermal-to-electrical energy conversion, carbon-based semiconductors have recently attracted a great deal of attention as potential thermoelectric materials for low-temperature energy harvesting, primarily driven by the high abundance of their atomic elements, ease of processing/manufacturing, and intrinsically low thermal conductivity. This quest for new materials has resulted in the discovery of several new kinds of thermoelectric materials and concepts capable of converting a heat flux into an electrical current by means of various types of particles transporting the electric charge: (i) electrons, (ii) ions, and (iii) redox molecules. This has contributed to expanding the applications envisaged for thermoelectric materials far beyond simple conversion of heat into electricity. This is the motivation behind this review. This work is divided in three sections. In the first section, we present the basic principle of the thermoelectric effects when the particles transporting the electric charge are electrons, ions, and redox molecules and describe the conceptual differences between the three thermodiffusion phenomena. In the second section, we review the efforts made on developing devices exploiting these three effects and give a thorough understanding of what limits their performance. In the third section, we review the state-of-the-art thermoelectric materials investigated so far and provide a comprehensive understanding of what limits charge and energy transport in each of these classes of materials.

Non-equilibrium properties of an active nanoparticle in a harmonic potential.

Active particles break out of thermodynamic equilibrium thanks to their directed motion, which leads to complex and interesting behaviors in the presence of confining potentials. When dealing with active nanoparticles, however, the overwhelming presence of rotational diffusion hinders directed motion, leading to an increase of their effective temperature, but otherwise masking the effects of self-propulsion. Here, we demonstrate an experimental system where an active nanoparticle immersed in a critical solution and held in an optical harmonic potential features far-from-equilibrium behavior beyond an increase of its effective temperature. When increasing the laser power, we observe a cross-over from a Boltzmann distribution to a non-equilibrium state, where the particle performs fast orbital rotations about the beam axis. These findings are rationalized by solving the Fokker-Planck equation for the particle's position and orientation in terms of a moment expansion. The proposed self-propulsion mechanism results from the particle's non-sphericity and the lower critical point of the solution.

Motion and trapping of micro- and millimeter-sized particles on the air-paramagnetic-liquid interface.

Understanding the motion of particles on an air-liquid interface can impact a wide range of scientific fields and applications. Diamagnetic particles floating on an air-paramagnetic-liquid interface are previously known to have a repulsive motion from a magnet. Here, we show a motion mechanism where the diamagnetic particles floating on the air-paramagnetic-liquid interface are attracted and eventually trapped at an off-center distance from the magnet. The behavior of magnetic particles has been also studied and the motion mechanisms are theorized in a unified framework, revealing that the motion of particles on an air-paramagnetic-liquid interface is governed not only by magnetic energy, but as an interplay of the curvature of the interface deformation created by the nonuniform magnetic field, the gravitational potential, and the magnetic energy from the particle and the liquid. The attractive motion mechanism has been applied in directed self-assembly and robotic particle guiding.

Thermoelectric Ratchet Effect for Charge Carriers with Hopping Dynamics.

We show that the huge Seebeck coefficients observed recently for ionic conductors arise from a ratchet effect where activated jumps between neighbor sites are rectified by a temperature gradient, thus driving mobile ions toward the cold. For complex systems with mobile molecules like water or polyethylene glycol, there is an even more efficient diffusiophoretic transport mechanism, proportional to the thermally induced concentration gradient of the molecular component. Without free parameters, our model describes experiments on the ionic liquid EMIM-TFSI and hydrated NaPSS, and it qualitatively accounts for polymer electrolyte membranes with Seebeck coefficients of hundreds of k_{B}/e.

Hydrodynamic self-assembly of active colloids: chiral spinners and dynamic crystals.

Active colloids self-organise into a variety of collective states, ranging from highly motile "molecules" to complex 2D structures. Using large-scale simulations, we show that hydrodynamic interactions, together with a gravity-like aligning field, lead to tunable self-assembly of active colloidal spheres near a surface. The observed structures depend on the hydrodynamic characteristics: particles driven at the front, pullers, form small chiral spinners consisting of two or three particles, whereas those driven at the rear, pushers, assemble into large dynamic aggregates. The rotational motion of the puller spinners, arises from spontaneous breaking of the internal chirality. Our results show that the fluid flow mediates chiral transfer between neighbouring spinners. Finally we show that the chirality of the individual spinners controls the topology of the self-assembly in solution: homochiral samples assemble into a hexagonally symmetric 2D crystal lattice while racemic mixtures show reduced hexatic order with diffusion-like dynamics.

Erratum: Polarization of active Janus particles [Phys. Rev. E 89, 050303(R) (2014)].

This corrects the article DOI: 10.1103/PhysRevE.89.050303.

Hydrodynamic interaction of a self-propelling particle with a wall : Comparison between an active Janus particle and a squirmer model.

Using lattice Boltzmann simulations we study the hydrodynamics of an active spherical particle near a no-slip wall. We develop a computational model for an active Janus particle, by considering different and independent mobilities on the two hemispheres and compare the behaviour to a standard squirmer model. We show that the topology of the far-field hydrodynamic nature of the active Janus particle is similar to the standard squirmer model, but in the near-field the hydrodynamics differ. In order to study how the near-field effects affect the interaction between the particle and a flat wall, we compare the behaviour of a Janus swimmer and a squirmer near a no-slip surface via extensive numerical simulations. Our results show generally a good agreement between these two models, but they reveal some key differences especially with low magnitudes of the squirming parameter [Formula: see text]. Notably the affinity of the particles to be trapped at a surface is increased for the active Janus particles when compared to standard squirmers. Finally, we find that when the particle is trapped on the surface, the velocity parallel to the surface exceeds the bulk swimming speed and scales linearly with [Formula: see text].

Hydrodynamic interactions in DNA thermophoresis.

We theoretically study the molecular-weight dependence of DNA thermophoresis, which arises from mutual advection of the n repeat units of the molecular chain. As a main result we find that the dominant driving forces, i.e., the thermally induced permittivity gradient and the electrolyte Seebeck effect, result in characteristic hydrodynamic screening. In comparison with recent experimental data on single-stranded DNA (2 ≤ n ≤ 80), our theory provides a good description for the increase of the drift velocity up to n = 30; the slowing-down of longer molecules is well accounted for by a simple model for counterion condensation. It turns out that thermophoresis may change sign as a function of n: for an appropriate choice of the salt-specific Seebeck coefficient, short molecules move to the cold and long ones to the hot; this could be used for separating DNA by molecular weight.

Janus Colloids Actively Rotating on the Surface of Water.

Biological or artificial microswimmers move performing trajectories of different kinds such as rectilinear, circular, or spiral ones. Here, we report on circular trajectories observed for active Janus colloids trapped at the air-water interface. Circular motion is due to asymmetric and nonuniform surface properties of the particles caused by fabrication. Motion persistence is enhanced by the partial wetted state of the Janus particles actively moving in two dimensions at the air-water interface. The slowing down of in-plane and out-of-plane rotational diffusions is described and discussed.

Playing with Emulsion Formulation to Control the Perforation of a Freely Expanding Liquid Sheet.

A single-drop experiment based on the collision of one drop of liquid on a small solid target is used to produce liquid sheets that are visualized with a fast camera. Upon impact, the drop flattens into a sheet that is bounded by a thicker rim and radially expanding in air. Emulsion-based liquid sheets are destabilized through the nucleation of holes that perforate the sheet during its expansion. The holes grow until they merge together and form a web of ligaments, which are then destabilized into drops. We propose the perforation mechanism as a sequence of two necessary steps. The emulsion oil droplets first enter the air/water interface, and then spread at the interface. We show that the formulation of the emulsion is a critical parameter to control the perforation as the addition of salt or amphiphilic copolymers can trigger or completely inhibit the perforation mechanism. We demonstrate that the entering of the droplets at the air/water interface is the limiting step of the mechanism. Thin-film forces such as electrostatic or steric repulsion forces stabilize the thin film formed between the interface and the approaching oil droplets, thus preventing the entering of droplets at the interface and in turn inhibiting the perforation process. We theoretically rationalize the successive steps in the approach and entering of an oil droplet at the film interface and the role of salt and amphiphilic polymer in the different steps.

Thermo-Osmotic Flow in Thin Films.

We report on the first microscale observation of the velocity field imposed by a nonuniform heat content along the solid-liquid boundary. We determine both radial and vertical velocity components of this thermo-osmotic flow field by tracking single tracer nanoparticles. The measured flow profiles are compared to an approximate analytical theory and to numerical calculations. From the measured slip velocity we deduce the thermo-osmotic coefficient for both bare glass and Pluronic F-127 covered surfaces. The value for Pluronic F-127 agrees well with Soret data for polyethylene glycol, whereas that for glass differs from literature values and indicates the complex boundary layer thermodynamics of glass-water interfaces.

Hydrodynamic Boundary Effects on Thermophoresis of Confined Colloids.

We study hydrodynamic slowing down of a particle moving in a temperature gradient perpendicular to a wall. At distances much smaller than the particle radius, h≪a, the lubrication approximation leads to the reduced velocity u/u_{0}=3(h/a)[ln(a/h)-9/4], where u_{0} is the velocity in the bulk. With Brenner's result for confined diffusion, we find that the trapping efficiency, or effective Soret coefficient, increases logarithmically as the particle gets very close to the wall. Our results provide a quantitative explanation for the recently observed enhancement of thermophoretic trapping at short distances. Our discussion of parallel and perpendicular thermophoresis in a capillary reveals a good agreement with experiments on charged polystyrene particles, and sheds some light on a controversy concerning the size dependence and the nonequilibrium nature of the Soret effect.

Comment on "Curvature capillary migration of microspheres" by N. Sharifi-Mood, I. B. Liu, K. J. Stebe, Soft Matter, 2015, 11, 6768.

In a recent paper, Sharifi-Mood et al. studied colloidal particles trapped at a liquid interface with opposite principal curvatures c1 = -c2. In the theory part, they claim that the trapping energy vanishes at second order in Δc = c1 - c2, which would invalidate our previous result [Phys. Rev. E: Stat., Nonlinear, Soft Matter Phys., 2006, 74, 041402]. Here we show that this claim arises from an improper treatment of the outer boundary condition on the deformation field. For both pinned and moving contact lines, we find that the outer boundary is irrelevant, which confirms our previous work. More generally, we show that the trapping energy is determined by the deformation close to the particle and does not depend on the far-field.

Self-Diffusiophoresis of Janus Particles in Near-Critical Mixtures.

We theoretically study the self-propulsion of a laser-heated Janus particle in a near-critical water-lutidine mixture, and we relate its velocity v_{p} and squirmer parameter ß to the wetting properties of its two hemispheres. For nonionic surface forces, the particle moves the active cap at the front, whereas a charged hydrophilic cap leads to backward motion, in agreement with the experiment. Both v_{p} and ß show nonmonotonic dependencies on the heating power, and they may even change sign. The variation of ß is expected to strongly affect the collective behavior of dense squirmer systems.

Polarization of active Janus particles.

We theoretically study the motion of surface-active Janus particles, driven by an effective slip velocity due to a nonuniform temperature or concentration field ψ. With parameters realized in thermal traps, we find that the torque exerted by the gradient ∇ψ inhibits rotational diffusion and favors alignment of the particle axes. In a swarm of active particles, this polarization adds a novel term to the drift velocity and modifies the collective behavior. Self-polarization in a nonuniform laser beam could be used for guiding hot particles along a given trajectory.

Do thermal diffusion and Dufour coefficients satisfy Onsager's reciprocity relation?

It is commonly admitted that in liquids the thermal diffusion and Dufour coefficients D(T) and D(F) satisfy Onsager's reciprocity. From their relation to the cross-coefficients of the phenomenological equations, we are led to the conclusion that this is not the case in general. As illustrative and physically relevant examples, we discuss micellar solutions and colloidal suspensions, where D(T) arises from chemical reactions or viscous effects but is not related to the Dufour coefficient D(F). The situation is less clear for binary molecular mixtures; available experimental and simulation data do not settle the question whether D(T) and DF are reciprocal coefficients.

Trapping of single nano-objects in dynamic temperature fields.

In this article we explore the dynamics of a Brownian particle in a feedback-free dynamic thermophoretic trap. The trap contains a focused laser beam heating a circular gold structure locally and creating a repulsive thermal potential for a Brownian particle. In order to confine a particle the heating beam is steered along the circumference of the gold structure leading to a non-trivial motion of the particle. We theoretically find a stability condition by switching to a rotating frame, where the laser beam is at rest. Particle trajectories and stable points are calculated as a function of the laser rotation frequency and are experimentally confirmed. Additionally, the effect of Brownian motion is considered. The present study complements the dynamic thermophoretic trapping with a theoretical basis and will enhance the applicability in micro- and nanofluidic devices.

Specific salt effects on thermophoresis of charged colloids.

We study the Soret effect of charged polystyrene particles as a function of temperature and electrolyte composition. As a main result we find that the Soret coefficient is determined by charge effects, and that non-ionic contributions are small. In view of the well-known electric-double layer interactions, our thermal field-flow fractionation data lead us to the conclusion that the Soret effect originates to a large extent from diffusiophoresis in the salt gradient and from the electrolyte Seebeck effect, both of which show strong specific-ion effects. Moreover, we find that thermophoresis of polystyrene beads is fundamentally different from proteins and aqueous polymer solutions, which show a strong non-ionic contribution.