We analyze the heat transfer between two nanoparticles separated by a distance lying in the near-field domain in which energy interchange is due to Coulomb interactions. The thermal conductance is computed by assuming that the particles have charge distributions characterized by fluctuating multipole moments in equilibrium with heat baths at two different temperatures. This quantity follows from the fluctuation-dissipation theorem (FDT) for the fluctuations of the multipolar moments. We compare the behavior of the conductance as a function of the distance between the particles with the result obtained by means of molecular dynamics simulations. The formalism proposed enables us to provide a comprehensive explanation of the marked growth of the conductance when decreasing the distance between the nanoparticles.
We compute the thermal conductance between two nanoparticles in contact based on the Molecular Dynamics technique. The contact is generated by letting both particles stick together under van der Waals attractions. The thermal conductance is derived from the fluctuation-dissipation theorem and the time fluctuations of the exchanged power. We show that the conductance is proportional to the atoms involved in the thermal interaction. In the case of silica, the atomic contribution to the thermal conductance is in the range of 0.5 to 3 nW.K-1. This result fits to theoretical predictions based on ch…
Heat transfer from irradiated metallic nanoparticles is relevant to a broad array of applications ranging from water desalination to photoacoustics. The efficacy of such processes relies on the ability of these nanoparticles to absorb the pulsed illuminating light and to quickly transfer energy to the environment. Here we show that compared to homogeneous gold nanoparticles having the same size, gold-silica core-shell nanoparticles enable heat transfers to liquid water that are faster. We reach this conclusion by considering both analytical and numerical calculations. The key factor explaining…
We have studied conductance ($\it{g}$) of butanedithiol-linked gold nanoparticle films across a percolation insulator-to-metal transition. As the transition proceeds, electrons become itinerant (i.e. Coulomb charging and kinetic effects are both significant), and films exhibit a previously unobserved zero-bias conductance peak (ZBCP). The peak is much more pronounced and easily observed using electromigration-induced break junction (BJ) contacts rather than macroscopic 4-probe electrodes. We attribute this ZBCP to quantum correlations amongst electrons, in view of other temperature- ($\it{T}$-…
The final performance of a molecular electronic device is determined by the chemical structure of the molecular wires used in its assembly. Molecular place-exchange was used to incorporate di-thioacetate terminated molecules into ordered arrays of dodecanethiol capped gold nanoparticles. X-ray photoelectron spectroscopy confirmed successful molecular replacement. Room-temperature molecular conductance of a statistically large number of devices reveals that conductance is enhanced by up to two orders of magnitude for the di-thioacetate terminated molecules. Density functional theory transport c…
The radiative heat transfer between gold nanoparticle layers is presented using the coupled dipole method. Gold nanoparticles are modelled as effective electric and magnetic dipoles interacting via electromagnetic fluctuations. The effect of higher-order multipoles is implemented in the expression of electric polarizability to calculate the interactions at short distances. Our findings show that the near-field radiation reduces as the radius of the nanoparticles is increased. Also, the magnetic dipole contribution to the heat exchange becomes more important for larger particles. When one layer…
To evaluate the self-heating effects of FeCo magnetic nanoparticles, the surface oxidized FeCo nanoparticles were synthesized by co-precipitation method with the reduction reaction without any post treatments. As-synthesized FeCo nanoparticles exhibited the mean diameter of about 39 nm with the oxidized shell thickness of about 4-5 nm. The saturation magnetization and coercivity were obtained 172 emu/g and 268 Oe at 300 K, respectively. The heat elevation of the FeCo magnetic colloid was measured under alternating magnetic fields of 76, 102, and 127 Oe with selectable frequencies of 190, 250 a…
We show that the effect of size dependence of the melting temperature of nanocrystals may be used to govern anomalies of thermodynamic properties of nanocrystals in the premelting range. For example, if temperature of nanocrystals is near the melting point, their mechanical contact should result in a change of the temperature and release of some heat. We discuss fundamental possibility of construction of a "heat pump" to extract thermal energy from a low-temperature medium.
We investigate the problem of heat conduction across a molecular junction connecting two nanoparticles, both in vacuum and in a liquid environment, using classical molecular dynamics simulations. In vacuum, the well-known result of a length independent conductance is recovered; its precise value, however, is found to depend sensitively on the overlap between the vibrational spectrum of the junction and the density of states of the nanoparticles that act as thermal contacts. In a liquid environment, the conductance is constant up to a crossover length, above which a standard Fourier regime is r…
We present a theoretical study of heat transport in electrically insulating ferromagnetic wires containing a domain wall. In the regime of validity of continuum micromagnetism a domain wall is found to have no effect on the heat conductance. However, spin waves are found to be reflected by domain walls with widths of a few lattice spacings, which is associated with emergence of an additional spin wave bound state. The resulting domain wall heat conductance should be significant for thin films of Yttrium Iron Garnet with sharply defined magnetic domains.
We study heat transfer from a heated nanoparticle into surrounding fluid, using molecular dynamics simulations. We show that the fluid next to the nanoparticle can be heated well above its boiling point without a phase change. Under increasing nanoparticle temperature, the heat flux saturates which is in sharp contrast with the case of flat interfaces, where a critical heat flux is observed followed by development of a vapor layer and heat flux drop. These differences in heat transfer are explained by the curvature induced pressure close to the nanoparticle, which inhibits boiling. When the na…
The performance of magnetic nanoparticles is intimately entwined with their structure, mean size and magnetic anisotropy. Besides, ensembles offer a unique way of engineering the magnetic response by modifying the strength of the dipolar interactions between particles. Here we report on an experimental and theoretical analysis of magnetic hyperthermia, a rapidly developing technique in medical research and oncology. Experimentally, we demonstrate that single-domain cubic iron oxide particles resembling bacterial magnetosomes have superior magnetic heating efficiency compared to spherical parti…
Understanding high-field amplitude electromagnetic heat loss phenomena is of great importance, in particular in the biomedical field, since the heat-delivery treatment plans might rely on analytical models that are only valid at low field amplitudes. Here, we develop a nonlinear response model valid for single- domain nanoparticles of larger particle sizes and higher field amplitudes in comparison to linear response theory. A nonlinear magnetization expression and a generalized heat loss power equation are obtained and compared with the exact solution of the stochastic Landau-Lifshitz-Gilbert …
We theoretically investigate equilibrium behaviors and photothermal effects of a flexible plasmonic metamaterial composed of aramid nanofibers and gold nanoparticles. The fiber matrix is considered as an external field to reconfigure a nanoparticle assembly. We find that the heating process tunes particle-particle and fiber-particle interactions, which alter adsorption of nanoparticles on fiber surfaces or clustering in pore spaces. Thus, it is possible to control the nanoparticle self-assembly by laser illumination. Gold nanoparticles strongly absorb radiations and efficiently dissipate absor…
We theoretically analyzed transport properties of a molecular network constructed of gold nanoparticles linked with oligophenylenevinulene (OPV) molecules. We showed that the conductance of such system was strongly reduced when trinitrotoluene (TNT) became attached to the OPV linkers in the network. The reported results are based on the ab inicio electronic structure calculations. These results corroborate and elucidate experiments which revealed significant drops in the conductance the network while the latter was exposed to TNT vapors. The results suggest that the detected sensitivity of tra…
We have calculated heat capacity of TiO2 nanoparticles in three stable polymorphs by applying size and surface effects on heat capacity of the bulk structure. The size and surface corrections were imposed on the acoustic and optical bulk phonons, separately. The model used in the present work is a simple modification of the model proposed by Wang et al. We applied the modified model to obtain the specific heat capacity of 10-100 nm TiO2 nanoparticles. A very good consistency is observed between the computational and experimental data. Based on the modified model, particles with sizes larger th…
Heat transfer between a silver nanoparticle and surrounding water has been studied using molecular dynamics (MD) simulations. The thermal conductance (Kapitza conductance) at the interface between a nanoparticle and surrounding water has been calculated using four different approaches: transient with/without temperature gradient (internal thermal resistance) in the nanoparticle, steady-state non-equilibrium and finally equilibrium simulations. The results of steady-state non-equilibrium and equilibrium are in agreement but differ from the transient approach results. MD simulations results also…
Nanocrystalline bulk materials are desirable for many applications as they combine mechanical strength and specific electronic transport properties. Our bottom up approach starts with tailored nanoparticles. Compaction and thermal treatment are crucial, but usually the final stage sintering is accompanied by rapid grain growth which spoils nanocristallinity. For electrically conducting nanoparticles, field activated sintering techniques overcome this problem. Small grain sizes have been maintained in spite of consolidation. Nevertheless, the underlying principles, which are of high practical i…
Near-field radiative heat transfer is investigated in composite media including nanoparticles. By modeling pair interactions only, the effective thermal conductivity due to near field radiation is calculated based on a thermal nodes model. We highlight the onset of a Near-Field percolation occurring much earlier than the mechanical percolation at critical volume fraction f=0.033. This 15 mechanism drastically increases the thermal conductivity even at low volume fractions. It also indicates a simple experimental protocol to prove Near-Field contact.
We theoretically investigate photothermal heating of ultra-flexible metamaterials, which are obtained by randomly mixing TiN nanoparticles in polydimethylsiloxane (PDMS). Due to the plasmonic properties of TiN nanoparticles, incident light is perfectly absorbed in a broadband range (300-3000 nm) to generate heat within these metamaterials. Under irradiation of an 808 nm near-infrared laser with different intensities, our predicted temperature rises as a function of time agree well with recent experimental data. For a given laser intensity, the temperature rise varies non-monotonically with con…
Magnetic nanoparticles constitute potential nanomedicine tools based on the possibility to obtain different responses triggered by safe remote stimulus. However, such richness can be detrimental if the different performances are not accurately differentiated (and controlled). An example of this is the reorientation of magnetic nanoparticles under the influence of AC fields, which can be exploited for either magneto-mechanical actuation (MMA) at low frequencies (tens of Hz); or heat release at large ones (MHz range). While it is clear that Brownian rotation is responsible for MMA, its heating r…
Relaxation dynamics of embedded metal nanoparticles after ultrafast laser pulse excitation is driven by thermal phenomena of different origins the accurate description of which is crucial for interpreting experimental results: hot electron gas generation, electron-phonon coupling, heat transfer to the particle environment and heat propagation in the latter. Regardingthis last mechanism, it is well known that heat transport in nanoscale structures and/or at ultrashort timescales may deviate from the predictions of the Fourier law. In these cases heat transport may rather be described by the Bol…
Ba0.6Sr0.4TiO3 nanoparticles were synthesized by the sol-gel method. The effects of the heat treatment conditions, ethylene glycol (EG) and deionized water (DW) on their phase structure and formation of the undesirable barium carbonate (BaCO3) phase were investigated. It was found that increasing the temperature of the samples caused an increase in the peak intensities of perovskite structures, and a decrease in the intensities of the BaCO3 peaks. Moreover, omitting EG, the sol stabilizer, and water, the solvent, decreased the peak intensities of BaCO3. Decreasing the heating rate caused bette…
We present a general study of frequency and magnetic field dependence of the specific heat power produced during field-driven hysteresis cycles in magnetic nanoparticles with relevance to hyperthermia applications in biomedicine. Employing a kinetic Monte-Carlo method with natural time scales allows us to go beyond the assumptions of small driving field amplitudes and negligible inter-particle interactions, which are fundamental to applicability of the standard approach based on linear response theory. The method captures the superparamagnetic and fully hysteretic regimes and the transition be…
In this contribution, we study situations in which nanoparticles in a fluid are strongly heated, generating high heat fluxes. This situation is relevant to experiments in which a fluid is locally heated using selective absorption of radiation by solid particles. We first study this situation for different types of molecular interactions, using models for gold particles suspended in octane and in water. As already reported in experiments, very high heat fluxes and temperature elevations (leading eventually to particle destruction) can be observed in such situations. We show that a very simple m…
Selective hysteretic heating of multiple collocated sets of single domain magnetic nanoparticles (SDMNPs) by alternating magnetic fields (AMFs) may offer a useful tool for biomedical applications. The possibility of magnetothermal multiplexing has not yet been realized, in part due to prevalent use of linear response theory to model SDMNP heating in AMFs. Predictive successes of dynamic hysteresis (DH), a more generalized model for heat dissipation by SDMNPs, are observed experimentally with detailed calorimetry measurements performed at varied AMF amplitudes and frequencies. The DH model sugg…
We compute atomistically the heat conductance for ultra-thin pristine silicon nanowires (SiNWs) with diameters ranging from 1 to 5 nm. The room temperature thermal conductance is found to be highly anisotropic: wires oriented along the <110> direction have 50-75% larger conductance than wires oriented along the <100> and <111> directions. We show that the anisotropies can be qualitatively understood and reproduced from the bulk phonon band structure. Ab initio density functional theory (DFT) is used to study the thinnest wires, but becomes computationally prohibitive for larger diameters, wher…
We propose a theoretical approach to describe quantitatively the heating process in aqueous solutions of dispersed TiN nanoparticles under solar illumination. The temperature gradients of solution with different concentrations of TiN nanoparticles are calculated when confinement effects of the container on the solar absorption are taken into account. We find that the average penetration of solar radiation into the solution is significantly reduced with increasing the nanoparticle concentration. At high concentrations, our numerical results show that photons are localized near the surface of th…
The cooling dynamics of glass-embedded noble metal nanoparticles with diameters ranging from 4 to 26 nm were studied using ultrafast pump-probe spectroscopy. Measurements were performed probing away from the surface plasmon resonance of the nanoparticles to avoid spurious effects due to glass heating around the particle. In these conditions, the time-domain data reflect the cooling kinetics of the nanoparticle. Cooling dynamics are shown to be controlled by both thermal resistance at the nanoparticule?glass interface, and heat diffusion in the glass matrix. Moreover, the interface conductances…
We present a numerical model allowing to determine the electron and lattice temperature dynamics in a gold nanoparticle under subpicosecond pulsed excitation, as well as that of the surrounding medium. For this, we have used the electron-phonon coupling equation in the particle with a source term linked with the laser pulse, and the ballistic-diffusive equations for heat conduction in the host medium. Our results show that the heat transfer rate from the particle to the matrix is significantly smaller than the prediction of Fourier's law. Consequently, the particle temperature rise is much lar…
We present a study on the magnetic properties of naked and silica-coated Fe3O4 nanoparticles with sizes between 5 and 110 nm. Their efficiency as heating agents was assessed through specific power absorption (SPA) measurements as a function of particle size and shape. The results show a strong dependence of the SPA with the particle size, with a maximum around 30 nm, as expected for a Neel relaxation mechanism in single-domain particles. The SiO2 shell thickness was found to play an important role in the SPA mechanism by hindering the heat outflow, thus decreasing the heating efficiency. It is…
The influence of a transverse static magnetic field on the magnetic hyperthermia properties is studied on a system of large-losses ferromagnetic FeCo nanoparticles. The simultaneous measurement of the high-frequency hysteresis loops and of the temperature rise provides an interesting insight into the losses and heating mechanisms. A static magnetic field of only 40 mT is enough to cancel the heating properties of the nanoparticles, a result reproduced using numerical simulations of hysteresis loops. These results cast doubt on the possibility to perform someday magnetic hyperthermia inside a m…
We describe a low-cost and simple setup for hyperthermia measurements on colloidal solutions of magnetic nanoparticles (ferrofluids) with a frequency-adjustable magnetic field in the range 5-500 kHz produced by an electromagnet. By optimizing the general conception and each component (nature of the wires, design of the electromagnet), a highly efficient setup is obtained. For instance, in a useful gap of 1.1 cm, a magnetic field of 4.8 mT is generated at 100 kHz and 500 kHz with an output power of 3.4 W and 75 W, respectively. A maximum magnetic field of 30 mT is obtained at 100 kHz. The tempe…
Graphene, as a passivation layer, can be used to protect the black phosphorus from the chemical reaction with surrounding oxygen and water. However, black phosphorus and graphene heterostructures have low efficiency of heat dissipation due to its intrinsic high thermal resistance at the interfaces. The accumulated energy from Joule heat has to be removed efficiently to avoid the malfunction of the devices. Therefore, it is of significance to investigate the interfacial thermal dissipation properties and manipulate the properties by interfacial engineering on demand. In this work, the interfaci…
Microparticles including paraffin are currently used for textiles coating in order to deaden thermal shocks. We will show that polymer nanoparticles embedded in those microsized capsules allow for decreasing the thermal conductivity of the coating and enhance the protection in the stationary regime. A reasonable volume fraction of polymer nanoparticles reduces the conductivity more than predicted by Maxwell mixing rules. Besides, measurements prove that the polymer nanoparticles do not affect the latent heat and even improve the phase change behaviour as well as the mechanical properties.
Gold nanoparticles (AuNPs) are increasingly used for their thermoplasmonic properties, i.e. their ability to convert light into heat upon plasmon resonance. However, measuring temperature gradients generated at the microscale by assemblies of AuNPs remains challenging, especially when they are randomly distributed in three dimensions. Here, we introduce a label-free thermometry approach, combining optical wavefront microscopy and numerical simulations, to infer the heating power dissipated by a three-dimensional model system consisting in emulsion microdroplets loaded with AuNPs. This approach…
The proper design and synthesis of molecular junctions for the purpose of establishing percolative networks of conductive nanoparticles represent an opportunity to develop more efficient thermally-conductive nanocomposites, with several potential applications in heat management. In this work, theoretical classical molecular dynamics simulations were conducted to design and evaluate thermal conductance of various molecules serving as thermal bridges between graphene nanosheets. A wide range of molecular junctions was studied, with a focus on the chemical structures that are viable to synthesize…
