J. Carrey

Simple models for dynamic hysteresis loop calculations of magnetic single-domain nanoparticles: Application to magnetic hyperthermia optimization

To optimize the heating properties of magnetic nanoparticles (MNPs) in magnetic hyperthermia applications, it is necessary to calculate the area of their hysteresis loops in an alternating magnetic field. The separation between “relaxation losses” and “hysteresis losses” presented in several articles is artificial and criticized here. The three types of theories suitable for describing hysteresis loops of MNPs are presented and compared to numerical simulations: equilibrium functions, Stoner–Wohlfarth model based theories (SWMBTs), and a linear response theory (LRT) using the Neel–Brown relaxation time. The configuration where the easy axis of the MNPs is aligned with respect to the magnetic field and the configuration of a random orientation of the easy axis are both studied. Suitable formulas to calculate the hysteresis areas of major cycles are deduced from SWMBTs and from numerical simulations; the domain of validity of the analytical formula is explicitly studied. In the case of minor cycles, the hysteresis area calculations are based on the LRT. A perfect agreement between the LRT and numerical simulations of hysteresis loops is obtained. The domain of validity of the LRT is explicitly studied. Formulas are proposed to calculate the hysteresis area at low field that are valid for any anisotropy of the MNP. The magnetic field dependence of the area is studied using numerical simulations: it follows power laws with a large range of exponents. Then analytical expressions derived from the LRT and SWMBTs are used in their domains of validity for a theoretical study of magnetic hyperthermia. It is shown that LRT is only pertinent for MNPs with strong anisotropy and that SWMBTs should be used for weakly anisotropic MNPs. The optimum volume of MNPs for magnetic hyperthermia is derived as a function of material and experimental parameters. Formulas are proposed to allow to the calculation of the optimum volume for any anisotropy. The maximum achievable specific absorption rate (SAR) is calculated as a function of the MNP anisotropy. It is shown that an optimum anisotropy increases the SAR and reduces the detrimental effects of the size distribution of the MNPs. The optimum anisotropy is simple to calculate; it depends only on the magnetic field used in the hyperthermia experiments and the MNP magnetization. The theoretical optimum parameters are compared to those of several magnetic materials. A brief review of experimental results as well as a method to analyze them is proposed. This study helps in the determination of suitable and unsuitable materials for magnetic hyperthermia and provides accurate formulas to analyze experimental data. It is also aimed at providing a better understanding of magnetic hyperthermia to researchers working on this subject.To optimize the heating properties of magnetic nanoparticles (MNPs) in magnetic hyperthermia applications, it is necessary to calculate the area of their hysteresis loops in an alternating magnetic field. The three types of theories suitable for describing the hysteresis loops of MNPs are presented and compared to numerical simulations: equilibrium functions, Stoner-Wohlfarth model based theories (SWMBTs) and linear response theory (LRT). Suitable formulas to calculate the hysteresis area of major cycles are deduced from SWMBTs and from numerical simulations; the domain of validity of the analytical formula is explicitly studied. In the case of minor cycles, the hysteresis area calculations are based on the LRT. A perfect agreement between LRT and numerical simulations of hysteresis loops is obtained. The domain of validity of the LRT is explicitly studied. Formulas to calculate the hysteresis area at low field valid for any anisotropy of the MNP are proposed. Numerical simulations of the magnetic field dependence of the area show it follows power-laws with a large range of exponents. Then, analytical expressions derived from LRT and SWMBTs are used for a theoretical study of magnetic hyperthermia. It is shown that LRT is only pertinent for MNPs with strong anisotropy and that SWMBTs should be used for weak anisotropy MNPs. The optimum volume of MNPs for magnetic hyperthermia as function of material and experimental parameters is derived. The maximum specific absorption rate (SAR) achievable is calculated versus the MNP anisotropy. It is shown that an optimum anisotropy increases the SAR and reduces the detrimental effects of size distribution. The optimum anisotropy is simple to calculate and depends on the magnetic field used in the hyperthermia experiments and on the MNP magnetization only. The theoretical optimum parameters are compared to the one of several magnetic materials.

A Simple Chemical Route toward Monodisperse Iron Carbide Nanoparticles Displaying Tunable Magnetic and Unprecedented Hyperthermia Properties

We report a tunable organometallic synthesis of monodisperse iron carbide and core/shell iron/iron carbide nanoparticles displaying a high magnetization and good air-stability. This process based on the decomposition of Fe(CO)(5) on Fe(0) seeds allows the control of the amount of carbon diffused and therefore the tuning of nanoparticles magnetic anisotropy. This results in unprecedented hyperthermia properties at moderate magnetic fields, in the range of medical treatments.

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 hyperthermia in single-domain monodisperse FeCo nanoparticles: Evidences for Stoner–Wohlfarth behavior and large losses

We report on hyperthermia measurements on a colloidal solution of 14.2±1.5 nm monodisperse FeCo nanoparticles (NPs). Losses as a function of the magnetic field display a sharp increase followed by a plateau, which is what is expected for losses of ferromagnetic single-domain NPs. The frequency dependence of the coercive field is deduced from hyperthermia measurement and is in quantitative agreement with a simple model of noninteracting NPs. The measured losses (1.5 mJ/g) compare to the highest of the literature, although the saturation magnetization of the NPs is well below the bulk one.

Increase of magnetic hyperthermia efficiency due to dipolar interactions in low-anisotropy magnetic nanoparticles: Theoretical and experimental results

When magnetic nanoparticles (MNPs) are single-domain and magnetically independent, their magnetic properties and the conditions to optimize their efficiency in magnetic hyperthermia applications are now well-understood. However, the influence of magnetic interactions on magnetic hyperthermia properties is still unclear. Here, we report hyperthermia and high-frequency hysteresis loop measurements on a model system consisting of MNPs with the same size but a varying anisotropy, which is an interesting way to tune the relative strength of magnetic interactions. A clear correlation between the MNP anisotropy and the squareness of their hysteresis loop in colloidal solution is observed : the larger the anisotropy, the smaller the squareness. Since low anisotropy MNPs display a squareness higher than the one of magnetically independent nanoparticles, magnetic interactions enhance their heating power in this case. Hysteresis loop calculations of independent and coupled MNPs are compared to experimental results. It is shown that the observed features are a natural consequence of the formation of chains and columns of MNPs during hyperthermia experiments: in these structures, when the MNP magnetocristalline anisotropy is small enough to be dominated by magnetic interactions, the hysteresis loop shape tends to be rectangular, which enhance their efficiency. On the contrary, when MNPs do not form chains and columns, magnetic interactions reduces the hysteresis loop squareness and the efficiency of MNPs compared to independent ones. The present work should improve the understanding and interpretation of magnetic hyperthermia experiments.

Nano-electromanipulation of Spin Crossover Nanorods: Towards Switchable Nanoelectronic Devices

The nanoscale manipulation and charge transport properties of the [Fe(Htrz)2(trz)](BF4) spin-crossover compound is demonstrated. Such 1D spin-crossover nanostructures are attractive building blocks for nanoelectronic switching and memory devices.

Tunnel magnetoresistance in nanojunctions based on Sr2FeMoO6

We report on the observation of magnetoresistance in a Sr2FeMoO6 (SFMO)-based tunnel junction. This result is obtained by combining a three-step process for the growth of the Sr2FeMoO6 layer by pulsed laser deposition with a technology allowing the definition of nanometer-sized junctions. A clear positive magnetoresistive signal of 50% is obtained at low temperature in a Sr2FeMoO6/SrTiO3/Co junction. Since the SrTiO3/Co interface is known to have a negative spin polarization of about 20%, this result yields a negative spin polarization of SFMO, which we find to amount to more than 85% in our film. This confirms the half-metallic character of this compound, predicted by band structure calculations.

Large specific absorption rates in the magnetic hyperthermia properties of metallic iron nanocubes

We report on the magnetic hyperthermia properties of chemically synthesized ferromagnetic 11 and 16 nm Fe(0) nanoparticles of cubic shape displaying the saturation magnetization of bulk iron. The specific absorption rate measured on 16 nm nanocubes is 1690±160 W/g at 300 kHz and 66 mT. This corresponds to specific losses-per-cycle of 5.6 mJ/g, largely exceeding the ones reported in other systems. A way to quantify the degree of optimization of any system with respect to hyperthermia applications is proposed. Applied here, this method shows that our nanoparticles are not fully optimized, probably due to the strong influence of magnetic interactions on their magnetic response. Once protected from oxidation and further optimized, such nano-objects could constitute efficient magnetic cores for biomedical applications requiring very large heating power.

Spark-eroded particles: Influence of processing parameters

Ni particles were prepared by spark erosion in a fixed-gap apparatus, and in the usual “shaker-pot” assembly, in an investigation of the influence of various processing parameters on the particles’ properties. The sizes of the particles were studied as functions of spark energies ranging from 10 μJ to 1 J, and a scaling relation derived from a simple model was verified. Several different static and rotating electrode configurations were compared with respect to their suitability for producing significant yields of small particles. The advantages of stirring the dielectric with the fixed-gap apparatus and of rotating the electrodes were demonstrated. Water, kerosene, and liquid argon and nitrogen were used as dielectric liquids. When compounds were formed, the reaction with the dielectric proceeded inversely with particle size. Spark erosion in kerosene at low spark energies, followed by annealing, proved to be an effective method to produce fine nickel particles.

Influence of a transverse static magnetic field on the magnetic hyperthermia properties and high-frequency hysteresis loops of ferromagnetic FeCo nanoparticles

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 magnetic resonance imaging setup.