A setup to measure the temperature-dependent heating power of magnetically heated nanoparticles up to high temperature.

Magnetic heating, namely, the use of heat released by magnetic nanoparticles (MNPs) excited with a high-frequency magnetic field, has so far been mainly used for biological applications. More recently, it has been shown that this heat can be used to catalyze chemical reactions, some of them occurring at temperatures up to 700 °C. The full exploitation of MNP heating properties requires the knowledge of the temperature dependence of their heating power up to high temperatures. Here, a setup to perform such measurements is described based on the use of a pyrometer for high-temperature measurements and on a protocol based on the acquisition of cooling curves, which allows us to take into account calorimeter losses. We demonstrate that the setup permits to perform measurements under a controlled atmosphere on solid state samples up to 550 °C. It should in principle be able to perform measurements up to 900 °C. The method, uncertainties, and possible artifacts are described and analyzed in detail. The influence on losses of putting under vacuum different parts of the calorimeter is measured. To illustrate the setup possibilities, the temperature dependence of heating power is measured on four samples displaying very different behaviors. Their heating power increases or decreases with temperature, displaying temperature sensibilities ranging from -2.5 to +4.4% K-1. This setup is useful to characterize the MNPs for magnetically heated catalysis applications and to produce data that will be used to test models permitting to predict the temperature dependence of MNP heating power.

Silica coated iron nanoparticles: synthesis, interface control, magnetic and hyperthermia properties.

This work provides a detailed study on the synthesis and characterization of silica coated iron nanoparticles (NPs) by coupling Transmission Electronic Microscopy (TEM), X-ray Photoelectron Spectroscopy (XPS) and magnetic measurements. Remarkably, iron NPs (of 9 nm of mean diameter) have been embedded in silica without any alteration of the magnetization of the iron cores, thanks to an original protocol of silica coating in non alcoholic medium. Tuning the synthesis parameters (concentration of reactants and choice of solvent), different sizes of Fe@SiO2 composites can be obtained with different thicknesses of silica. The magnetization of these objects is fully preserved after 24 h of water exposure thanks to a thick (14 nm) silica layer, opening thus new perspectives for biomedical applications. Hyperthermia measurements have been compared between Fe and Fe@SiO2 NPs, evidencing the self-organization of the free Fe NPs when a large amplitude magnetic field is applied. This phenomenon induces an increase of heating power which is precluded when the Fe cores are immobilised in silica. High-frequency hysteresis loop measurements allowed us to observe for the first time the increase of the ferrofluid susceptibility and remanence which are the signature of the formation of Fe NPs chains.

Effects of inter- and intra-aggregate magnetic dipolar interactions on the magnetic heating efficiency of iron oxide nanoparticles.

Iron oxide nanoparticles have found an increasing number of biomedical applications as sensing or trapping platforms and therapeutic and/or diagnostic agents. Most of these applications are based on their magnetic properties, which may vary depending on the nanoparticle aggregation state and/or concentration. In this work, we assess the effect of the inter- and intra-aggregate magnetic dipolar interactions on the heat dissipation power and AC hysteresis loops upon increasing the nanoparticle concentration and the hydrodynamic aggregate size. We observe different effects produced by inter- (long distance) and intra-aggregate (short distance) interactions, resulting in magnetizing and demagnetizing effects, respectively. Consequently, the heat dissipation power under alternating magnetic fields strongly reflects such different interacting phenomena. The intra-aggregate interaction results were successfully modeled by numerical simulations. A better understanding of magnetic dipolar interactions is mandatory for achieving a reliable magnetic hyperthermia response when nanoparticles are located into biological matrices.

An air-cooled Litz wire coil for measuring the high frequency hysteresis loops of magnetic samples--a useful setup for magnetic hyperthermia applications.

A setup for measuring the high-frequency hysteresis loops of magnetic samples is described. An alternating magnetic field in the range 6-100 kHz with amplitude up to 80 mT is produced by a Litz wire coil. The latter is air-cooled using a forced-air approach so no water flow is required to run the setup. High-frequency hysteresis loops are measured using a system of pick-up coils and numerical integration of signals. Reproducible measurements are obtained in the frequency range of 6-56 kHz. Measurement examples on ferrite cylinders and on iron oxide nanoparticle ferrofluids are shown. Comparison with other measurement methods of the hysteresis loop area (complex susceptibility, quasi-static hysteresis loops, and calorific measurements) is provided and shows the coherency of the results obtained with this setup. This setup is well adapted to the magnetic characterization of colloidal solutions of magnetic nanoparticles for magnetic hyperthermia applications.

Tuning deposition of magnetic metallic nanoparticles from periodic pattern to thin film entrainment by dip coating method.

In this work, we report on the self-assembly of bimetallic CoFe carbide magnetic nanoparticles (MNPs) stabilized by a mixture of long chain surfactants. A dedicated setup, coupling dip coating and sputtering chamber, enables control of the self-assembly of MNPs from regular stripe to continuous thin films under inert atmosphere. The effects of experimental parameters, MNP concentration, withdrawal speed, amount, and nature of surfactants, as well as the surface state of the substrates are discussed. Magnetic measurements revealed that the assembled particles were not oxidized, confirming the high potentiality of our approach for the controlled deposition of highly sensitive MNPs.

A frequency-adjustable electromagnet for hyperthermia measurements on magnetic nanoparticles.

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 of 5-500 kHz produced by an electromagnet. By optimizing the general conception and each component (nature of the wires, design of the electromagnet, etc.), 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 and 500 kHz with output powers of 3.4 and 75 W, respectively. A maximum magnetic field of 30 mT is obtained at 100 kHz. The temperature of the colloidal solution is measured using optical fiber sensors. To remove contributions due to heating of the electromagnet, a differential measurement is used. In this configuration the sensitivity is better than 1.5 mW at 100 kHz and 19.3 mT. This setup allows one to measure weak heating powers on highly diluted colloidal solutions. The hyperthermia characteristics of a solution of Fe nanoparticles are described, where both the magnetic field and the frequency dependence of heating power have been measured.

Magnetic configurations of 30 nm iron nanocubes studied by electron holography.

Ferromagnetic nanomaterials exhibit unique magnetic properties common to materials with dimensions approaching the atomic scale and have potential applications in magnetic data storage. Technological applications, however, require that the detailed magnetic behaviors and configurations of individual and interacting magnetic nano-objects be clarified. We determined the magnetic remnant configurations in single crystalline 30 nm Fe nanocubes and groups of nanocubes using off-axis electron holography in a transmission electron microscope. Our measurements on an isolated cube reveal a vortex state whose core size has been determined. Two neighboring nanocubes with adjacent {100} surfaces exhibit a ferromagnetic dipolar coupling, while similar magnetic interactions between four cubes in a square arrangement induce a bending of the magnetic induction, i.e., a magnetic flux closure state. The various configurations were successfully simulated by micromagnetic calculations.

Magnetic relaxation of interacting co clusters: crossover from two- to three-dimensional lattices.

The influence that dipole-dipole interactions exert on the dynamics of the magnetization of nanometer-sized Co clusters has been studied by means of ac and dc susceptibility experiments. These clusters grow in a quasiordered layered structure, where all relevant parameters can be tailored and measured independently. Our data show without ambiguity that the magnetic relaxation becomes slower as the degree of interaction increases. The effective activation energy increases linearly with the number of nearest neighbor clusters, evolving from the value for a 2D layer to the fully 3D behavior, which is nearly reached for five layers. The experimental results agree quantitatively with the predictions of a simple model.

Growth of Au clusters on amorphous Al2O3: evidence of cluster mobility above a critical size.

We study the 3D growth of clusters during the deposition of Au atoms on amorphous Al2O3. By comparing transmission electron microscopy images of the growth with Monte Carlo simulations, we show that nucleation takes place on substrate defects, but that further stages of growth imply that clusters leave the defects after they have reached a given critical size, and diffuse. An interesting consequence of this property is that, in contrast to intuition, and in a certain range of size, larger clusters are more mobile than smaller ones in this system.