The excitation of localized surface plasmon resonances in Au and Ag colloids can be used to drive the synthesis of complex nanostructures, such as anisotropic prisms, bipyramids, and core@shell ...nanoparticles. Yet, after two decades of research, it is challenging to paint a complete picture of the mechanisms driving such light-induced chemical transformations. In particular, whereas the injection of hot charge carriers from the metal nanoparticles is usually proposed as the dominant mechanism, the contribution of plasmon-induced heating can often not be neglected. Here, we tackle this uncertainty and quantify the contribution of different activation mechanisms using a temperature-sensitive synthesis of Au@Ag core@shell nanoparticles. We compare the rate of Ag shell growth in the dark at different temperatures with the one under plasmon excitation with varying laser intensities. Our controlled illumination geometry, coupled to numerical modeling of light propagation and heat diffusion in the reaction volume, allows us to quantify both localized and collective heating effects and determine their contribution to the total growth rate of the nanoparticles. We find that nonthermal effects can be dominant, and their relative contribution depends on the fraction of nanoparticle suspension under irradiation. Understanding the mechanism of plasmon-activated chemistry at the surface of metal nanoparticles is of paramount importance for a wide range of applications, from the rational design of novel light-assisted nanoparticle syntheses to the development of plasmonic nanostructures for catalytic and therapeutic purposes.
The evening transition is investigated in an idealized model for the nocturnal boundary layer. From earlier studies it is known that the nocturnal boundary layer may manifest itself in two distinct ...regimes, depending on the ambient synoptic conditions: strong-wind or overcast conditions typically lead to weakly stable, turbulent nights; clear-sky and weak-wind conditions, on the other hand, lead to very stable, weakly turbulent conditions. Previously, the dynamical behaviour near the transition between these regimes was investigated in an idealized setting, relying on Monin–Obukhov (MO) similarity to describe turbulent transport. Here, we investigate a similar set-up, using direct numerical simulation; in contrast to MO-based models, this type of simulation does not need to rely on turbulence closure assumptions. We show that previous predictions are verified, but now independent of turbulence parametrizations. Also, it appears that a regime shift to the very stable state is signaled in advance by specific changes in the dynamics of the turbulent boundary layer. Here, we show how these changes may be used to infer a quantitative estimate of the transition point from the weakly stable boundary layer to the very stable boundary layer. In addition, it is shown that the idealized, nocturnal boundary-layer system shares important similarities with generic non-linear dynamical systems that exhibit critical transitions. Therefore, the presence of other, generic early warning signals is tested as well. Indeed, indications are found that such signals are present in stably stratified turbulent flows.
The hydrodynamic force exerted by a fluid on small isolated rigid spherical particles are usually well described by the Maxey–Riley (MR) equation. The most time-consuming contribution in the MR ...equation is the Basset history force which is a well-known problem for many-particle simulations in turbulence. In this paper a novel numerical approach is proposed for the computation of the Basset history force based on the use of exponential functions to approximate the tail of the Basset force kernel. Typically, this approach not only decreases the cpu time and memory requirements for the Basset force computation by more than an order of magnitude, but also increases the accuracy by an order of magnitude. The method has a temporal accuracy of O(Δt2) which is a substantial improvement compared to methods available in the literature. Furthermore, the method is partially implicit in order to increase stability of the computation. Traditional methods for the calculation of the Basset history force can influence statistical properties of the particles in isotropic turbulence, which is due to the error made by approximating the Basset force and the limited number of particles that can be tracked with classical methods. The new method turns out to provide more reliable statistical data.
We perform three-dimensional particle tracking measurements on droplets in a turbulent airflow. The droplets display the well-known preferential concentration of inertial particles, with an ...additional extreme clustering at the smallest scales. We explain this additional clustering phenomenon theoretically based on a Stokes-flow description of two spheres including their mutual hydrodynamic interaction and a perturbative small-inertia expansion.
The force balance of rotating Rayleigh–Bénard convection regimes is investigated using direct numerical simulation on a laterally periodic domain, vertically bounded by no-slip walls. We provide a ...comprehensive view of the interplay between governing forces both in the bulk and near the walls. We observe, as in other prior studies, regimes of cells, convective Taylor columns, plumes, large-scale vortices (LSVs) and rotation-affected convection. Regimes of rapidly rotating convection are dominated by geostrophy, the balance between Coriolis and pressure-gradient forces. The higher-order interplay between inertial, viscous and buoyancy forces defines a subdominant balance that distinguishes the geostrophic states. It consists of viscous and buoyancy forces for cells and columns, inertial, viscous and buoyancy forces for plumes, and inertial forces for LSVs. In rotation-affected convection, inertial and pressure-gradient forces constitute the dominant balance; Coriolis, viscous and buoyancy forces form the subdominant balance. Near the walls, in geostrophic regimes, force magnitudes are larger than in the bulk; buoyancy contributes little to the subdominant balance of cells, columns and plumes. Increased force magnitudes denote increased ageostrophy near the walls. Nonetheless, the flow is geostrophic as the bulk. Inertia becomes increasingly more important compared with the bulk, and enters the subdominant balance of columns. As the bulk, the near-wall flow loses rotational constraint in rotation-affected convection. Consequently, kinetic boundary layers deviate from the expected behaviour from linear Ekman boundary layer theory. Our findings elucidate the dynamical balances of rotating thermal convection under realistic top/bottom boundary conditions, relevant to laboratory settings and large-scale natural flows.
The cause of persistent cyanobacteria scum formation in lakes is an unresolved subject. Scum refers to the event in which cyanobacteria are at the water surface of a lake. Factors like low turbulence ...levels, long day-light, high water temperatures and the buoyant capacity of cyanobacterial cells play a role in the occurrence of scums. However, they do not explain why scums are observed at periods during the day when according to theory they should have disappeared into the deeper water layers. In this study, we present an alternative explanation. The hypothesis we present here is that irreversible buoyancy of cyanobacteria colonies is created by the growth of gas bubbles on or within the mucilage of the colonies. These bubbles grow under oxygen super-saturated conditions. At low wind speed and high chlorophyll levels, the dissolved oxygen (DO) produced during photosynthesis by cyanobacteria, cannot escape sufficiently fast to the atmosphere hence a DO supersaturated condition arises in the water. At this stage, growth of oxygen bubbles may occur inside or attached to the mucilage. We present results of compression experiments to support our hypothesis. In a chamber, the pressure on lake water containing a natural cyanobacteria population is increased. At 3×105 and 4×105Pa the cyanobacteria colonies were not able to float anymore and sank. This pressure is lower than the 106Pa needed to collapse all gas vacuoles inside the cyanobacteria cells (Walsby, 1994). The observed change from floating to sinking colonies due to increased water pressure suggests that gas bubbles were present inside the colonies. In lakes, these gas bubbles may lead to permanent buoyancy, i.e. a persistent scum.
We study the competition between domain coarsening in a symmetric binary mixture below critical temperature and turbulent fluctuations. We find that the coarsening process is arrested in the presence ...of turbulence. The physics of the process shares remarkable similarities with the behavior of diluted turbulent emulsions and the arrest length scale can be estimated with an argument similar to the one proposed by Kolmogorov and Hinze for the maximal stability diameter of droplets in turbulence. Although, in the absence of flow, the microscopic diffusion constant is negative, turbulence does effectively arrest the inverse cascade of concentration fluctuations by making the low wavelength diffusion constant positive for scales above the Hinze length.
We perform direct numerical simulations of rotating Rayleigh-Bénard convection (RRBC) of fluids with low (Pr = 0.1) and high (Pr ≈ 5) Prandtl numbers in a horizontally periodic layer with no-slip ...bottom and top boundaries. No-slip boundaries are known to actively promote the formation of plumelike vertical disturbances, through so-called Ekman pumping, that control the ambient flow at sufficiently high rotation rates. At both Prandtl numbers, we demonstrate the presence of competing large-scale vortices (LSVs) in the bulk. Strong buoyant forcing and rotation foster the quasi-two-dimensional turbulent state of the flow that leads to the upscale transfer of kinetic energy that forms the domain-filling LSV condensate. The Ekman plumes from the boundary layers are sheared apart by the large-scale flow, yet we find that their energy feeds the upscale transfer. Our results of RRBC simulations substantiate the emergence of large-scale flows in nature regardless of the specific details of the boundary conditions.
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Anisotropic particles are present in many natural and industrial flows. Here we perform direct numerical simulation (DNS) of turbulent pipe flows with dispersed finite-size prolate spheroids ...simulated by means of the lattice Boltzmann method (LBM). We consider three different particle shapes: spheroidal (aspect ratio 2 and 3) and spherical. These three simulations are complemented with a reference simulation of a single-phase flow. For the sake of comparison, all simulations, laden or unladen have the same energy input. The flow geometry used is a straight pipe with length eight times its radius where the fluid is randomly seeded with 256 finite-size particles. The volume fraction of particles in the flow has been kept fixed at 0.48% by varying the major and minor axis of each particle such that their volume remains the same. We studied the effect of different particle shapes on particle dynamics and orientation, as well as on the flow modulation. We show that the local accumulation of spheres close to the wall decreases for spheroids with increasing aspect ratio. These spheroidal particles rotate slower than spheres near to the wall and tend to stay with their major axes aligned to the flow streamwise direction. Despite the lower rotation rates, a higher intermittency in the rotational rates was observed for spheroids and this increase at increasing the aspect ratio. The drag reduction observed for particles with higher aspect ratio have also been investigated using the one-dimensional energy and dissipation spectra. These results point to the relevance of particle shapes on their dynamics and their influence on the turbulent flow.
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