National Institute Of Materials Physics - Romania

Herein we report on novel multiferroic core shell nanostructures of cobalt ferrite (CoFe2O4) bismuth, sodium titanate doped with barium titanate (BNT-BT0.08), prepared by a two step wet chemical procedure, using the sol gel technique. The fraction of CoFe2O4 was varied from 1:0.5 to 1:1.5 = BNT-BT0.08/CoFe2O4 (molar ratio). X-ray diffraction confirmed the presence of both the spinel CoFe2O4 and the perovskite Bi0.5Na0.5TiO3 phases. Scanning electron microscopy analysis indicated that the diameter of the core shell nanoparticles was between 15 and 40 nm. Transmission electron microscopy data showed two phase composite nanostructures consisting of a BNT-BT0.08 core surrounded by a CoFe2O4 shell with an average thickness of 4-7 nm. Cole-Cole plots reveal the presence of grains and grain boundary effects in the BNT-BT0.08/CoFe2O4 composite. Moreover, the values of the dc conductivity were found to increase with the amount of CoFe2O4 semiconductive phase. Both X-ray photoelectron spectroscopy (XPS) and Mossbauer measurements have shown no change in the valence of the Fe3+, Co2+, Bi3+ and Ti4+ cations. This study provides a detailed insight into the magnetoelectric coupling of the multiferroic BNT-BT0.08/CoFe2O4 core shell composite potentially suitable for magnetoelectric applications.

Superconductors are key materials for shielding quasi-static magnetic fields. In this work, we investigated the shielding properties of an MgB2 cup-shaped shield with small aspect-ratio of height/outer radius. Shape and aspect-ratio were chosen in order to address practical requirements of both high shielding factors (SFs) and space-saving solutions. To obtain large critical current densities (J(c)), which are crucial for achieving high magnetic-mitigation performance, a high-purity starting MgB2 powder was selected. Then, processing of the starting MgB2 powder into high density bulks was performed by spark plasma sintering. The as-obtained material is fully machinable and was shaped into a cup-shield. Assessment of the material by scaling of the pinning force showed a non-trivial pinning behaviour. The MgB2 powder selection was decisive in enlarging the range of external fields where efficient shielding occurs. The shield's properties were measured in both axial- and transverse-field configurations using Hall probes. Despite a height/outer radius aspect ratio of 2.2, shielding factors higher than 10(4) at T = 20 K up to a threshold field of 1.8 T were measured in axial-field geometry at a distance of 1 mm from the closed extremity of the cup, while SFs > 10(2) occurred in the inner half of the cup. As expected, this threshold field decreased with increased temperature, but SFs still exceeding the above mentioned values were found up to 0.35 T at 35 K. The shield's shape limits the SF values achievable in transverse-field configuration. Nevertheless, the in-field J(c) of the sample supported SFs over 40 at T = 20 K up to a field of 0.8 T, 1 mm away from the cup closure.

A complex investigation of the morpho-structural, magnetic, magneto-optical and magneto-transport properties of amorphous Fe-Gd thin films crossing the magnetization compensation point is reported and the unexpected observed magneto-functionalities are discussed. A tendency of magnetic domain formation with increasing the Fe content over the compensation concentration is observed. The switch from a reversed Magneto-optical Kerr Effect loop to a direct loop when increasing the Fe content over the compensation point is explained via the specific contribution to the rotation of the polarization vector from each magnetic sublattice, belonging to Fe and Gd, respectively. Local atomic configurations and magnetic interactions ascertained the amorphous character and revealed an out-ofplane orientation of the magnetic moment of Fe above the compensation point. The thermomagnetic curves prove a concentration dependent behavior, explained by weakly coupled magnetization relaxation processes of the two magnetic sub-lattices. On the other hand, the magnetic hysteresis loops gave evidence of two exchange coupled magnetic phases with different coercive fields. According to structural and Fe-57 Mossbauer Spectroscopy results, the two phases correspond to definite nanosized volumes of two different average concentrations (one of them closer to the compensation point) which are randomly distributed in the film. The unexpected single step-like behavior of the magneto-resistivity curves was explained by dissimilar switching of the spins in these two magnetic phases distributed in nano-sized volumes.

We explore the cross coupling between the ferroelectric and ferromagnetic phases in Ni/BaTiO3(001) heterostructures and demonstrate the modulation of the magnetism and incidence of exchange bias in the ultrathin metallic Ni overlayer, depending on the ferroelectric state of the bottom layer. We establish that 5-nm-thick monocrystalline Ni film deposited on BaTiO3 with ferroelectric polarization pointing towards the surface (P+) favors the organization of Ni into uniform ferromagnetic domains. Ni grown on BaTiO3 with opposite ferroelectric polarization is featured by emerging exchange-bias coupling between the ferromagnetic Ni top layers and the antiferromagnetic reacted interface, as theoretically explained by first-principles calculations. We explicitly obtain the morphology of the magnetic domains of the crystalline Ni layer in atomic and magnetic force microscopy measurements (AFM/MFM). The resemblance of AFM and MFM images indicate that, although with radically different morphologies, in both cases all spins orient in the Ni plane. Consequently, the distinct signature of the ferroelectric-ferromagnetic coupling extracted from the magneto-optical Kerr effect measurements encodes all the information of sample magnetism. The peculiar magnetic coupling depending on the ferroelectric state indicates new ways of engineering the functionality of metal/ferroelectric interfaces.

Matrix-assisted pulsed laser evaporation (MAPLE) was used to deposit hybrid nanocomposite thin films based on cobalt phthalocyanine (CoPc), C60 fullerene and ZnO nanoparticles. The inorganic nanoparticles, with a size of about 20 nm, having the structural and optical properties characteristic of ZnO, were chemically synthesized by a simple precipitation method. Furthermore, ZnO nanoparticles were dispersed in a dimethyl sulfoxide solution in which CoPc and C60 had been dissolved, ready for the freezing MAPLE target. The effect of the concentration of ZnO nanoparticles on the structural, morphological, optical and electrical properties of the CoPc:C60:ZnO hybrid nanocomposite layers deposited by MAPLE was evaluated. The infrared spectra of the hybrid nanocomposite films confirm that the CoPc and C60 preserve their chemical structure during the laser deposition process. The CoPc optical signature is recognized in the ultraviolet-visible (UV-Vis) spectra of the obtained layers, these being dominated by the absorption bands associated to this organic compound while the ZnO optical fingerprint is identified in the photoluminescence spectra of the prepared layers, these disclosing the emission bands linked to this inorganic semiconductor. The hybrid nanocomposite layers exhibit globular morphology, which is typical for the thin films deposited by MAPLE. Current-voltage (J-V) characteristics of the structures developed on CoPc:C60:ZnO layers reveal that the addition of an appropriate amount of ZnO nanoparticles in the CoPc:C60 mixture leads to a more efficient charge transfer between the organic and inorganic components. Due to their photovoltaic effect, structures featuring such hybrid nanocomposite thin films deposited by MAPLE can have potential applications in the field of photovoltaic devices.

A facile and cheap surfactant-assisted hydrothermal method was used to prepare mesoporous cobalt ferrite nanosystems with BET surface area up to 151 m(2)/g. These mesostructures with high BET surface areas and pore sizes are made from assemblies of nanoparticles (NPs) with average sizes between 7.8 and 9.6 nm depending on the initial pH conditions. The pH proved to be the key factor for controlling not only NP size, but also the phase purity and the porosity properties of the mesostructures. At pH values lower than 7, a parasite hematite phase begins to form. The sample obtained at pH = 7.3 has magnetization at saturation M-s = 38 emu/g at 300 K (54.3 emu/g at 10 K) and BET surface area S-BET = 151 m(2)/g, whereas the one obtained at pH = 8.3 has M-s = 68 emu/g at 300 K (83.6 emu/g at 10 K) and S-BET = 101 m(2)/g. The magnetic coercive field values at 10 K are high at up to 12,780 Oe, with a maximum coercive field reached for the sample obtained at pH = 8.3. Decreased magnetic performances are obtained at pH values higher than 9. The iron occupancies of the tetrahedral and octahedral sites belonging to the cobalt ferrite spinel structure were extracted through decomposition of the Mossbauer patterns in spectral components. The magnetic anisotropy constants of the investigated NPs were estimated from the temperature dependence of the hyperfine magnetic field. Taking into consideration the high values of BET surface area and the magnetic anisotropy constants as well as the significant magnetizations for saturation at ambient temperature, and the fact that all parameters can be adjusted through the initial pH conditions, these materials are very promising as recyclable anti-polluting agents, magnetically separable catalysts, and targeted drug delivery vehicles.

We propose a concept of hybrid nanoelectronic-magnetic device made of magnetic Fe-C core-shell nanoparticles deposited onto prepatterned Si (111) substrate with basic circuitry made of metallic conductive lines. The synthesis of magnetic material and the creation of nanoelectronic prepatterned interdigitated die are reported and to prove the effectiveness in devices, their magnetotransport properties are investigated. Magnetic Fe/FeC nanoparticles, 11 nm diameter, with a core-shell structure have been prepared by laser pyrolysis. Two different layouts of prepatterned interdigitated die, have been conceived using e-beam lithography, with various geometries. A range of microscopy techniques, transmission electron, scanning and optical, were employed for morphological characterization of the as-obtained structures. Magnetic and magnetotransport characterization using SQUID magnetometry has been performed onto both the core-shell nanoparticles and onto the hybrid device obtained by depositing centrifugated and dispersed core-shell nanoparticles from liquid carrier solutions. From magnetotransport measurements, it has been revealed that the hybrid device made of Fe/FeC nanosized materials on prepatterned interdigitated die exhibit a large giant magnetoresistive (GMR) effect of about 8% at 300 K. This result is promising in view of the use of such devices as arrays of nanosensors and in spintronic applications.

Nanocomposites of polyvinylidene fluoride loaded with various amounts of gamma-Fe2O nanoparticles, with an average size ranging between 20 and 40 nm, have been obtained by melt mixing and investigated using various experimental techniques [Superconducting Quantum Interference Device, Mossbauer, and Thermogravimetric Analysis]. Magnetic and Mossbauer measurements confirmed the presence of maghemite and a trace of a paramagnetic iron compound. Magnetic data are consistent with a blocking temperature close to room temperature (RT), showing a decrease in the coercive field as the temperature is increased. A weak exchange bias was noticed in all nanocomposites investigated at all temperatures and tentatively ascribed to surface spin disorder. The temperature dependence of the coercive field obeys the Kneller law. The nanocomposites exhibit superparamagnetic behavior near RT. Most magnetic measurements have been performed below the blocking temperature, revealing thus a complex behavior. The dependence of the mass loss derivative versus temperature, as obtained by thermogravimetric analysis, exhibits a single peak due to the thermal degradation of the polymeric matrix. A weak increase in the thermal stability of the polymeric matrix upon loading with maghemite is reported.

The particle reinforcement of fusion-relevant tungsten through the incorporation of tungsten sub-carbide W2C particles at the grain boundaries is demonstrated as an effective way of eliminating the harmful W oxide, enhancing densification and stabilising the composite's microstructure and flexural strength at room and high temperatures. The W2C particles are formed in situ during the sintering by carbon diffusion from WC nano-particles added as a precursor to the W matrix. Even in an extremely fast sintering process using Field-Assisted Sintering Technology (FAST, 1900 degrees C, 5 min), the added WC completely transforms to W2C, resulting in a W-W2C composite. While at least 5 vol % of WC nanoparticles are needed to eliminate the oxide, approximately 10 vol % result in a W-W2C composite with favourable characteristics: high density, high flexural strength at RT (>1200 MPa) as well as at elevated temperatures, and high thermal conductivity, which remains above 100 W/mK up to 1000 degrees C.

Magnetic Fe@Y composites (carbon-coated magnetic iron nanoparticles incorporated in zeolite Y) with 5-8 wt % Fe were synthesized and characterized. Overall acidity of the samples ranged between 2.0 and 2.47 mmol/g and is mostly attributed to Lewis acid sites. The obtained materials were proven to catalyze the hydrolysis of the marine sulfated polysaccharide ulvan with high conversion rates. The distribution of the reaction products depended on the reaction conditions and the concentration of ulvan. The catalytic property catalytic performance correlations clearly showed that the acid zeolite Y is the active phase for the hydrolysis of ulvan, while the iron nanoparticles enable the catalyst separation in a magnetic field. Under oxygen pressure, the selectivity was completely changed to favor succinic acid production. All Fe@Y composites were recycled 10 times with no change in their catalytic performance after recovery via a simple magnetic separation and washing with water.