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.

Silica nanoparticles separation from water: aggregation by cetyltrimethylammonium bromide (CTAB).

Nanoparticles will inevitably be found in industrial and domestic wastes in the near future and as a consequence soon in water resources. Due to their ultra-small size, nanoparticles may not only have new hazards for environment and human health, but also cause low separation efficiency by classical water treatments processes. Thus, it would be an important challenge to develop a specific treatment with suitable additives for recovery of nanoparticles from waters. For this propose, this paper presents aggregation of silica nanoparticles (Klebosol 30R50 (75nm) and 30R25 (30nm)) by cationic surfactant cetyltrimethylammonium bromide (CTAB). Different mechanisms such as charge neutralization, "depletion flocculation" or "volume-restriction", and "hydrophobic effect" between hydrocarbon tails of CTAB have been proposed to explicate aggregation results. One important finding is that for different volume concentrations between 0.05% and 0.51% of 30R50 suspensions, the same critical coagulation concentration was observed at CTAB=0.1mM, suggesting the optimized quantity of CTAB during the separation process for nanoparticles of about 75nm. Furthermore, very small quantities of CTAB (0.01mM) can make 30R25 nanosilica aggregated due to the "hydrophobic effect". It is then possible to minimize the sludge and allow the separation process as "greener" as possible by studying this case. It has also shown that aggregation mechanisms can be different for very small particles so that a special attention has to be paid to the treatment of nanoparticles contained in water and wastewaters.

Iron under pressure: "Kohn tweezers" and remnant magnetism.

In this work we investigate the magnetic and structural properties of bulk Fe and Fe nanoparticles under pressure with x-ray absorption and emission spectroscopies providing answers to two fundamental questions: (a) the chicken-or-egg problem for the magnetic and structural transitions and (b) magnetism in the high pressure hcp phase. The two transitions, inextricably linked in the bulk, are clearly decoupled in the nanoparticles, with the magnetic collapse preceding the structural transition. Ultrafast x-ray emission spectroscopy detects remnant magnetism, probably antiferromagnetic fluctuations, up to pressures of about 40 GPa in the hcp phase. This could be of direct relevance to the superconductivity in ϵ-Fe [K. Shimizu et al., Nature (London) 412, 316 (2001)] through the existence of a quantum critical point and associated magnetic fluctuations.

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.