Vapor Nanobubbles around Heated Nanoparticles: Wetting Dependence of the Local Fluid Thermodynamics and Kinetics of Nucleation.

Plasmonic nanobubbles are composite objects resulting from the interaction between light and metallic nanoparticles immersed in a fluid. Plasmonic nanobubbles have applications in photothermal therapies, drug delivery, microfluidic manipulations, and solar energy conversion. Their early formation is, however, barely characterized due to the short time and length scales relevant to the process. Here, we investigate, using molecular dynamics (MD) simulations, the effect of nanoparticle wettability on both the local fluid thermodynamics and the kinetics of nanobubble generation in water. We first show that the local onset temperature of vapor nucleation decreases with the nanoparticle/water interfacial energy and may be 100 K below the water spinodal temperature in the case of weak nanoparticle/water interactions. Second, we demonstrate that vapor nucleation may be slower in the case of weak water/nanoparticle interactions. This result, which is qualitatively at odds with the predictions of isothermal classical nucleation theory, may be explained by the competition between two antagonist effects: while, classically, hydrophobicity increases the vapor nucleation rate, it also penalizes interfacial thermal transfer, slowing down kinetics. The kinetics of heat transfer from the nanoparticle to water is controlled by the interfacial thermal conductance. This quantity turns out not only to decrease with the nanoparticle hydrophobicity but also drops down prior to phase change, yielding even longer nucleation times. Such conclusions were reached by considering the comparison between MD and continuous heat transfer models. These results put forward the role of nanoparticle wettability in the generation of plasmonic nanobubbles observed experimentally and open the path to the control of boiling using nanopatterned surfaces.

Electron-phonon effects on the photoacoustic response of gold core-silica shell nanoparticles: From the linear regime to nanocavitation.

Coating gold nanostructures with a silica shell has been long considered for biomedical applications, including photoacoustic imaging. Recent experimental and modeling investigations reported contradicting results concerning the effect of coating on the photoacoustic response of gold nanostructures. Enhanced photoacoustic response is generally attributed to facilitated heat transfer at the gold/silica/water system. Here, we examine the photoacoustic response of gold core-silica shell nanoparticles immersed in water using a combination of the two temperature model and hydrodynamic phase field simulations. Here, of particular interest is the role of the interfacial coupling between the gold electrons and silica shell phonons. We demonstrate that as compared to uncoated nanoparticles, photoacoustic response is enhanced for very thin silica shells (5 nm) and short laser pulses, but for thicker coatings, the photoacoustic performance are generally deteriorated. We extend the study to the regime of nanocavitation and show that the generation of nanobubbles may also play a role in the enhanced acoustic response of core-shell nanoparticles. Our modeling effort may serve as guides for the optimization of the photoacoustic response of heterogeneous metal-dielectric nanoparticles.

Interacting Cracks Obey a Multiscale Attractive to Repulsive Transition.

The observed repulsive behavior of two initially collinear cracks growing towards each other and leading to a hook-shaped path questioned recently the validity of the principle of local symmetry within linear elastic fracture mechanics theory. Our theoretical and numerical work solves this dilemma, providing the precise geometric conditions for the existence of this repulsive phase. We moreover reveal a multiscale behavior of the repulsive-attractive transition, explaining its ubiquitous occurrence, but also the difficulty to predict the final cracks' paths.

Ballistic heat transport in laser generated nano-bubbles.

Nanobubbles generated by laser heated plasmonic nanoparticles are of interest for biomedical and energy harvesting applications. Of utmost importance is the maximal size of these transient bubbles. Here, we report hydrodynamic phase field simulations of the dynamics of laser induced nanobubbles, with the aim to understand which physical processes govern their maximal size. We show that the nanobubble maximal size and lifetime are to a large extent controlled by the ballistic thermal flux which is present inside the bubble. Taking into account this thermal flux, we can reproduce the fluence dependence of the maximal nanobubble radius as reported experimentally. We also discuss the influence of the laser pulse duration on the number of nanobubbles generated and their maximal size. These studies represent a significant step toward the optimization of the nanobubble size, which is of crucial importance for photothermal cancer therapy applications.

Phase field modelling of strain induced crystal growth in an elastic matrix.

When a crystal phase grows in an amorphous matrix, such as a crystallisable elastomer, containing cross-links and/or entanglements, these "topological constraints" need to be pushed away from the crystal phase to allow further crystallization. The accumulation of these topological constraints in the vicinity of the crystal interface may store elastic energy and affect the phase transition. To evaluate the consequences of such mechanism, we introduce a phase field model based on the Flory theory of entropic elasticity. We show that the growth process is indeed sensibly affected, in particular, an exponential increase of the surface energy with the displacement of the interface is induced. This explains the formation of stable nano-crystallites as it is observed in the Strain Induced Crystallization (SIC) of natural rubber. Although simple, the model developed here is able to account for many interesting features of SIC, for instance, the crystallite shapes and their sizes which depend on the applied deformation.

Nanobubbles around plasmonic nanoparticles: Thermodynamic analysis.

We describe the dynamics of vapor nanobubbles in water, on the basis of simulations of a hydrodynamics phase-field model. This situation is relevant to recent experiments, where a water nanobubble is generated around a nanoparticle immersed in water, and heated by an intense laser pulse. We emphasize the importance of nanoscale effects in the dynamics of the nanobubble. We first analyze the evolution of the temperature inside the bubble. We show that the temperature drops by hundredths of kelvins in a few picoseconds, just after nanobubble formation. This is the result of the huge drop of the thermal boundary conductance between the nanoparticle and the fluid accompanying vaporization. Subsequently, the temperature inside the vapor is almost homogeneous and the temperature gradient is concentrated in the liquid, whose thermodynamic state locally follows the saturation line. We discuss also the evolution of the pressure inside the vapor nanobubble. We show that nanobubble generation is accompanied by a pressure wave propagating in the liquid at a velocity close to the liquid speed of sound. The internal pressure inside the vapor just after its formation largely exceeds Laplace pressure and quickly relaxes as a result of the damping generated by the viscous forces. All these considerations shed light on the thermodynamics of the nanobubbles generated experimentally.

Kinetics of nanobubble generation around overheated nanoparticles.

We report on the formation and growth of nanobubbles around laser-heated gold nanoparticles in water. Using a hydrodynamic free-energy model, we show that the temporal evolution of the nanobubble radius is asymmetrical: the expansion is found to be adiabatic, while the collapse is best described by an isothermal evolution. We unveil the critical role of the thermal boundary resistance in the kinetics of formation of the nanobubbles: close to the vapor production threshold, nanobubble generation is very long, yielding optimal conditions for laser-energy conversion. Furthermore, the long appearance times allow nanoparticle melting before the onset of vaporization.

Activated drying in hydrophobic nanopores and the line tension of water.

We study the slow dynamics of water evaporation out of hydrophobic cavities by using model porous silica materials grafted with octylsilanes. The cylindrical pores are monodisperse, with a radius in the range of 1-2 nm. Liquid water penetrates in the nanopores at high pressure and empties the pores when the pressure is lowered. The drying pressure exhibits a logarithmic growth as a function of the driving rate over more than three decades, showing the thermally activated nucleation of vapor bubbles. We find that the slow dynamics and the critical volume of the vapor nucleus are quantitatively described by the classical theory of capillarity without adjustable parameter. However, classical capillarity utterly overestimates the critical bubble energy. We discuss the possible influence of surface heterogeneities, long-range interactions, and high-curvature effects, and we show that a classical theory can describe vapor nucleation provided that a negative line tension is taken into account. The drying pressure then provides a determination of this line tension with much higher precision than currently available methods. We find consistent values of the order of -30 pN in a variety of hydrophobic materials.

Three-dimensional vesicles under shear flow: numerical study of dynamics and phase diagram.

The study of vesicles under flow, a model system for red blood cells (RBCs), is an essential step in understanding various intricate dynamics exhibited by RBCs in vivo and in vitro. Quantitative three-dimensional analyses of vesicles under flow are presented. The regions of parameters to produce tumbling (TB), tank-treating, vacillating-breathing (VB), and even kayaking (or spinning) modes are determined. New qualitative features are found: (i) a significant widening of the VB mode region in parameter space upon increasing shear rate γ and (ii) a robustness of normalized period of TB and VB with γ. Analytical support is also provided. We make a comparison with existing experimental results. In particular, we find that the phase diagram of the various dynamics depends on three dimensionless control parameters, while a recent experimental work reported that only two are sufficient.

Transport, phase transitions, and wetting in micro/nanochannels: a phase field/DDFT approach.

While the flow of a liquid in a macroscopic channel is usually described using hydrodynamics with no-slip boundary conditions at the walls of the channel, transport phenomena in microchannels involve physics at many different scales due to the interplay between the micrometric section of the channel and the micro- or nanometric roughness of the boundaries. Roughness can have many different effects such as increasing the friction between the liquid and the walls (leading to the macroscopic no-slip boundary condition) or on the contrary reduce it thanks to the Wenzel-Cassie-Baxter wetting transition induced by capillarity. Here we detail a phase-field/dynamic density functional theory model able to account for the wetting transitions, the resulting friction between the wall and the fluid, and compressible hydrodynamics at high viscosity contrast.

Analytical progress in the theory of vesicles under linear flow.

Vesicles are becoming a quite popular model for the study of red blood cells. This is a free boundary problem which is rather difficult to handle theoretically. Quantitative computational approaches constitute also a challenge. In addition, with numerical studies, it is not easy to scan within a reasonable time the whole parameter space. Therefore, having quantitative analytical results is an essential advance that provides deeper understanding of observed features and can be used to accompany and possibly guide further numerical development. In this paper, shape evolution equations for a vesicle in a shear flow are derived analytically with precision being cubic (which is quadratic in previous theories) with regard to the deformation of the vesicle relative to a spherical shape. The phase diagram distinguishing regions of parameters where different types of motion (tank treading, tumbling, and vacillating breathing) are manifested is presented. This theory reveals unsuspected features: including higher order terms and harmonics (even if they are not directly excited by the shear flow) is necessary, whatever the shape is close to a sphere. Not only does this theory cure a quite large quantitative discrepancy between previous theories and recent experiments and numerical studies, but also it reveals a phenomenon: the VB mode band in parameter space, which is believed to saturate after a moderate shear rate, exhibits a striking widening beyond a critical shear rate. The widening results from excitation of fourth-order harmonic. The obtained phase diagram is in a remarkably good agreement with recent three-dimensional numerical simulations based on the boundary integral formulation. Comparison of our results with experiments is systematically made.

Dynamics and rheology of a dilute suspension of vesicles: higher-order theory.

Vesicles under shear flow exhibit various dynamics: tank treading (TT), tumbling (TB), and vacillating breathing (VB). The VB mode consists in a motion where the long axis of the vesicle oscillates about the flow direction, while the shape undergoes a breathing dynamics. We extend here the original small deformation theory [C. Misbah, Phys. Rev. Lett. 96, 028104 (2006)] to the next order in a consistent manner. The consistent higher order theory reveals a direct bifurcation from TT to TB if Ca identical with taugamma is small enough-typically below 0.5, but this value is sensitive to the available excess area from a sphere (tau=vesicle relaxation time towards equilibrium shape, gamma=shear rate). At larger Ca the TB is preceded by the VB mode. For Ca1 we recover the leading order original calculation, where the VB mode coexists with TB. The consistent calculation reveals several quantitative discrepancies with recent works, and points to new features. We briefly analyze rheology and find that the effective viscosity exhibits a minimum in the vicinity of the TT-TB and TT-VB bifurcation points. At small Ca the minimum corresponds to a cusp singularity and is at the TT-TB threshold, while at high enough Ca the cusp is smeared out, and is located in the vicinity of the VB mode but in the TT regime.

Phase-field approach to three-dimensional vesicle dynamics.

We extend our recent phase-field [T. Biben and C. Misbah, Phys. Rev. E 67, 031908 (2003)] approach to 3D vesicle dynamics. Unlike the boundary-integral formulations, based on the use of the Oseen tensor in the small Reynolds number limit, this method offers several important flexibilities. First, there is no need to track the membrane position; rather this is automatically encoded in dynamics of the phase field to which we assign a finite width representing the membrane extent. Secondly, this method allows naturally for any topology change, like vesicle budding, for example. Thirdly, any non-Newtonian constitutive law, that is generically nonlinear, can be naturally accounted for, a fact which is precluded by the boundary integral formulation. The phase-field approach raises, however, a complication due to the local membrane incompressibility, which, unlike usual interfacial problems, imposes a nontrivial constraint on the membrane. This problem is solved by introducing dynamics of a tension field. The first purpose of this paper is to show how to write adequately the advected-field model for 3D vesicles. We shall then perform a singular expansion of the phase field equation to show that they reduce, in the limit of a vanishing membrane extent, to the sharp boundary equations. Then, we present some results obtained by the phase-field model. We consider two examples; (i) kinetics towards equilibrium shapes and (ii) tanktreading and tumbling. We find a very good agreement between the two methods. We also discuss briefly how effects, such as the membrane shear elasticity and stretching elasticity, and the relative sliding of monolayers, can be accounted for in the phase-field approach.

Dynamics of Bio-Polymeric Brushes Growing from a Cellular Membrane: Tentative Modelling of the Actin Turnover within an Adhesion Unit; the Podosome.

Podosomes are involved in the adhesion process of various cells to a solid substrate. They have been proven to consist of a dense actin core surrounded by an actin cloud. The podosomes, which nucleate when the cell comes in the vicinity of a substrate, contribute to link the membrane to the solid surface, but rather than frozen links, collective dynamical behaviors are experimentally observed. Depending on the differentiation stage, podosomes assemble and form clusters, rings or belts. Considering the dynamics of a polymeric brush, we design a simple model aiming at the description of a single podosome, the basic unit of these complex adhesion-structures and compare our theoretical conclusions to recent experimental results. Particularly, we explain, by solving the diffusion problem around the podosome, why the structure is likely to have a finite life-span.