Elucidating Individual Magnetic Contributions in Bi-Magnetic Fe3 O4 /Mn3 O4 Core/Shell Nanoparticles by Polarized Powder Neutron Diffraction.

Heterogeneous bi-magnetic nanostructured systems have had a sustained interest during the last decades owing to their unique magnetic properties and the wide range of derived potential applications. However, elucidating the details of their magnetic properties can be rather complex. Here, a comprehensive study of Fe3 O4 /Mn3 O4 core/shell nanoparticles using polarized neutron powder diffraction, which allows disentangling the magnetic contributions of each of the components, is presented. The results show that while at low fields the Fe3 O4 and Mn3 O4 magnetic moments averaged over the unit cell are antiferromagnetically coupled, at high fields, they orient parallel to each other. This magnetic reorientation of the Mn3 O4 shell moments is associated with a gradual evolution with the applied field of the local magnetic susceptibility from anisotropic to isotropic. Additionally, the magnetic coherence length of the Fe3 O4 cores shows some unusual field dependence due to the competition between the antiferromagnetic interface interaction and the Zeeman energies. The results demonstrate the great potential of the quantitative analysis of polarized neutron powder diffraction for the study of complex multiphase magnetic materials.

'Phantom' atoms and thermal motion in fullerene C60revealed by x-ray and neutron diffraction.

The additional atomic occupancy in the octahedral and the tetrahedral voids of the face-centered cubic lattice (fcc) of fullerene C60was detected by neutron and x-ray powder diffraction. The observed occupancy exactly tracks the rearrangement of the orientation order with temperature decreases and results from the large atomic vibrations of the carbon atoms constituting the fullerene molecules. This motion assumes a small but finite probability to find the carbon atoms in the fcc interstitial voids, which is modeled by the detected 'phantom' occupancies.

Neutron diffraction study of the (BiFeO3)1-x(PbTiO3)x solid solution: nanostructured multiferroic system.

Neutron diffraction studies performed on the solid solution of (BiFeO(3))(1-x)(PbTiO(3))(x) reveal a mixture of two nanoscale phases with different crystal structures: a rhombohedral BiFeO(3)-based phase and a tetragonal PbTiO3-based phase. The ratio of Fe(3)+ and Ti(4)+ ions in the two phases is practically constant; only the proportion of the phases changes. The magnetic moments in the BiFeO(3)-based phase, in contrast to BiFeO(3), deviate from the basal plane. The temperature evolutions of the spin components along the hexagonal axis and within the perpendicular plane are different, leading to a spin re-orientation transition. The antiferromagnetic order in the PbTiO(3)-based phase corresponds to a simple structure with the propagation vector (1/2, 1/2, 1/2). The temperature dependence of the antiferromagnetic moment in the tetragonal phase at x = 0.5 indicates a canted antiferromagnetic order and a net ferromagnetic moment. A strong magnetic coupling between the two constituting phases due to the nanoscale character of the phases and well-developed interface between nanoparticles has been observed. The system of (BiFeO(3))(1-x)(PbTiO(3))(x) demonstrates an interesting scenario, where the proximity effects in the unstable system play a crucial role in the appearance of the unusual magnetic properties.

Robust antiferromagnetic coupling in hard-soft bi-magnetic core/shell nanoparticles.

The growing miniaturization demand of magnetic devices is fuelling the recent interest in bi-magnetic nanoparticles as ultimate small components. One of the main goals has been to reproduce practical magnetic properties observed so far in layered systems. In this context, although useful effects such as exchange bias or spring magnets have been demonstrated in core/shell nanoparticles, other interesting key properties for devices remain elusive. Here we show a robust antiferromagnetic (AFM) coupling in core/shell nanoparticles which, in turn, leads to the foremost elucidation of positive exchange bias in bi-magnetic hard-soft systems and the remarkable regulation of the resonance field and amplitude. The AFM coupling in iron oxide-manganese oxide based, soft/hard and hard/soft, core/shell nanoparticles is demonstrated by magnetometry, ferromagnetic resonance and X-ray magnetic circular dichroism. Monte Carlo simulations prove the consistency of the AFM coupling. This unique coupling could give rise to more advanced applications of bi-magnetic core/shell nanoparticles.

Strongly exchange coupled inverse ferrimagnetic soft/hard, Mn(x)Fe(3-x)O4/Fe(x)Mn(3-x)O4, core/shell heterostructured nanoparticles.

Inverted soft/hard, in contrast to conventional hard/soft, bi-magnetic core/shell nanoparticles of Mn(x)Fe(3-x)O(4)/Fe(x)Mn(3-x)O(4) with two different core sizes (7.5 and 11.5 nm) and fixed shell thickness (∼0.6 nm) have been synthesized. The structural characterization suggests that the particles have an interface with a graded composition. The magnetic characterization confirms the inverted soft/hard structure and evidences a strong exchange coupling between the core and the shell. Moreover, larger soft core sizes exhibit smaller coercivities and loop shifts, but larger blocking temperatures, as expected from spring-magnet or graded anisotropy structures. The results indicate that, similar to thin film systems, the magnetic properties of soft/hard core/shell nanoparticles can be fine tuned to match specific applications.

Magnetic proximity effect features in antiferromagnetic/ferrimagnetic core-shell nanoparticles.

A study of "inverted" core-shell, MnO/gamma-Mn(2)O(3), nanoparticles is presented. Crystal and magnetic structures and characteristic sizes have been determined by neutron diffraction for the antiferromagnetic core (MnO) and the ferrimagnetic shell (gamma-Mn(2)O(3)). Remarkably, while the MnO core is found to have a T_{N} not far from its bulk value, the magnetic order of the gamma-Mn(2)O(3) shell is stable far above T_{C}, exhibiting two characteristic temperatures, at T approximately 40 K [T_{C}(gamma-Mn(2)O(3))] and at T approximately 120 K [ approximately T_{N}(MnO)]. Magnetization measurements are consistent with these results. The stabilization of the shell moment up to T_{N} of the core can be tentatively attributed to core-shell exchange interactions, hinting at a possible magnetic proximity effect.

Temperature evolution of sodium nitrite structure in a restricted geometry.

The NaNO2 nanocomposite ferroelectric material in porous glass was studied by neutron diffraction. For the first time, the details of the crystal structure including positions and anisotropic thermal parameters were determined for the solid material, embedded in a porous matrix, in ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with bulk data, but above transition temperature the giant growth of amplitudes of thermal vibrations is observed, resulting in the formation of a "premelted state." Such a conclusion is in good agreement with the results of dielectric measurements published earlier.

Magnetic ordering and phase transition in MnO embedded in a porous glass.

We present the results of a neutron diffraction study of the antiferromagnet MnO embedded in a porous glass. The type of magnetic ordering and the structural distortion are similar to those of the bulk, but the ordered magnetic moment of 3.84(4)muB/ion is strongly reduced and the Néel temperature is enhanced. The magnetic transition is second order, in contrast to the first order transition of the bulk. The size of the magnetic region is smaller than the average size of the nanoparticles. The reasons for this behavior are discussed.