Dr. Gabriel SCHINTEIE

A methodology for the quantitative estimation of the drug loading of iron oxide-based magnetic nanoparticles by corroborating magnetometry and M & ouml;ssbauer spectroscopy investigations is reported. The proposed methodology is exemplified in the case of two series of nanoparticles, namely Fe3O4 nanoparticles covered with citric acid molecules and further functionalized with doxorubicin, and Fe3O4 nanoparticles covered with L-Cysteine molecules and further functionalized with doxorubicin. The general idea of the proposed methodology is to probe the real magnetic structure of the magnetic core via low-temperature M & ouml;ssbauer spectroscopy for the correct estimation of the spontaneous magnetization of the magnetic core. It subsequently uses the ratio between the spontaneous magnetization of the covered nanoparticles and that of the magnetic core for the reliable and nondestructive evaluation of the nanoparticle loading by organic molecules. Although the methodology is exemplified in the case of magnetite-based nanoparticles, it can be successfully considered for a large class of medicine-loaded Fe-containing magnetic nanoparticles where 57Fe M & ouml;ssbauer spectroscopy can be applied.

Fabrication and extensive characterization of hard-soft nanocomposites composed of hard magnetic low-temperature phase LTP-MnBi and amorphous Fe70Si10B20 soft magnetic phase for bulk magnets are reported. Samples with compositions Mn55Bi45 + x center dot(Fe70Si10B20) (x = 0, 3, 5, 10, 20 wt.%) were prepared by spark plasma sintering of powder mixtures. Characterization has been performed by X-ray diffraction, scanning and transmission electron microscopy, magnetometry and Fe-57 Mossbauer spectroscopy. It was shown that samples contain crystallized and nanometric LTP-MnBi phases with various elemental compositions depending on the degree of Bi clustering. Complex correlations between starting compositions, processes during fabrication, and functional magnetic characteristics were observed. Unexpected special situations of the relation between microstructure and magnetic coupling mechanisms are discovered. Exchange spring effects of different strengths occur, being very sensitive to morpho-structural and compositional features, which in turn are controlled by processing conditions. An in-depth analysis of related microscopic characteristics is provided. Results of this work suggest that fabrication by powder metallurgy routes, such as spark plasma sintering of hard and soft magnetic powder mixtures, of MnBi-based composites with exchange spring phenomena have a high potential in designing and optimization of suitable materials with tunable magnetic properties towards rare-earth-free permanent magnet applications.

We report on the Matrix Assisted Pulsed Laser Evaporation, laser technology for depositing biocompatible, antimicrobial, hydrophilic, and biodegradable complex hybrid polymeric system loaded with essential cypress-oil and magnetite nanoparticles as resorbable implants, capable of targeting possible hyperthermia applications, an anticancer moderate field heating therapy. Magnetite nanoparticles based on iron oxide (Fe3O4) coated with Cypress essential oil (denoted: Fe3O4- Cypress) and embedded in PLGA (poly(lactic-co-glycolic acid) (denoted: PLGA-Fe3O4- Cypress-) and PLGA - poly(3,4ethylene dioxythiophene) doped with poly(styrene sulfonate) anions) (PEDOT: PSS) mixture (denoted: PLGA-Fe3O4- Cypress- PEDOT: PSS) were used as MAPLE targets. The controlled drug delivery of the active Cypress oil, an antimicrobial therapeutic agent from Fe3O4- Cypress nanoparticles could be possible by applying an external radio frequency (RF) magnetic field. The Fe3O4-Cypress-based powders as well as the final hybrid coatings have been characterized in terms of stoichiometry, morphology, magnetic, antimicrobial properties, biocompatibility, and response to external physical stimuli. FTIR analyses confirmed the quasi-stoichiometric laser transfer of organic compounds while the XRD evidenced the semicrystalline structure of deposited thin films. SEM and AFM images evidence that conductive polymer addition led to the films' relief flattening and a decrease in the coatings' thickness and roughness by changing the polymeric packaging. The samples containing conductive polymer exhibited 3 times higher current and corrosion rate values. All coatings are hydrophilic and revealed enhanced cellular viability when cultured with osteoblast-like MG-63 cells. The composite structures exhibited significant antimicrobial activity against Gram-positive (Staphylococcus aureus), and Gram -negative (Escherichia coli ) bacteria, as well as to the opportunistic yeast Candida albicans.

Nano-logic magnetic structures are of great interest for spintronic applications. While the methods used for developing arrays of magnetic L1(0)-phase dots are, in most cases, based on deposition followed by annealing at high temperatures, usually around 700 degrees C, we demonstrate here a technique where a much lower annealing temperature (i.e., 400 degrees C) is needed in order to promote fully the disorder-order phase transformation and achievement of highly coercive L1(0)-phase dots. In order to develop building blocks based on arrays of L1(0)-phase FePt dots for further spintronic applications, an engraving technique using electron beam lithography is employed. This paper describes the fabrication, as well as the morphological and magnetic characterization, of regularly placed FePt dots of various shapes, as pre-requisites for integration into nano-logic devices. As a proof of concept, regular arrays of FePt circular dots were devised and their structural characterization, using X-ray diffraction (XRD) and transmission electron microscopy (TEM), was performed. It has been shown that annealing at only 400 degrees C for 30 min proved the occurrence of the tetragonal L1(0) phase. Moreover, structural characterization showed that the disorder-order phase transformation was complete with only the L1(0) phase detected in high resolution TEM. The magnetic characterization provided more insight into the potential of such arrays of magnetic devices with convenient values of magnetic coercivity, remanent and saturation magnetization. These findings show good potential for developing regular arrays of uniformly shaped magnetic entities with encouraging magnetic performances in view of various applications.

AuxFe1-x nanophase thin films of different compositions and thicknesses were prepared by co-deposition magnetron sputtering. Complex morpho-structural and magnetic investigations of the films were performed by X-ray Diffraction, cross-section Transmission Electron Microscopy, Selected Area Electron Diffraction, Magneto Optical Kerr Effect, Superconducting Quantum Interference Device magnetometry and Conversion Electron Mossbauer Spectroscopy. It was proven that depending on the preparation conditions, different configurations of defect alpha-Fe magnetic clusters, i.e., randomly distributed or auto-assembled in lamellar or filiform configurations, can be formed in the Au matrix. A close relationship between the Fe clustering process and the type of the crystalline structure of the Au matrix was underlined, with the stabilization of a hexagonal phase at a composition close to 70 at. % of Au and at optimal thickness. Due to different types of inter-cluster magnetic interactions and spin anisotropies, different types of magnetic order from 2D Ising type to 3D Heisenberg type, as well as superparamagnetic behavior of non-interacting Fe clusters of similar average size, were evidenced.

The manipulation of magnetic anisotropy represents the fundamental prerequisite for the application of magnetic materials. Here we present the vectorial magnetic properties of nanostructured systems and thin films of Fe and FeCo prepared on linearly trenched Mo templates with thermally controlled periodicity. The magnetic properties of the nanosystems are engineered by tuning the shape, size, thickness, and composition parameters of the thin films. Thus, we control coercivity, magnetization, orientation of the easy axis of magnetization, and the long-range magnetic order of the system in the function of the temperature. We distinguish magnetic components that emerge from the complex morpho-structural features of the undulating Fe or FeCo nanostructured films on trenched Mo templates: (i) assembly of magnetic nanowires and (ii) assembly of magnetic islands/clusters. Uniaxial anisotropy at room temperature was proven, characterized, and explained in the case of all systems. Our work contributes to the understanding of magnetic properties necessary for possible further applications of linear systems and undulated thin films.

Fe-Gd amorphous thin films of different compositions and thicknesses were analyzed with respect to their magnetic and magneto-optical behavior. By preparing samples with the same Fe/Gd elemental ratio at different thicknesses, and of various Fe/Gd ratios at constant thickness, respectively, we were able to show the influences of these two parameters on the interconnected behavior of the two magnetic sub-lattices, one of Fe and the other of Gd, which are antiferromagnetically coupled. Magneto-Optical Kerr Effect (MOKE) measurements revealed reversed hysteresis loops for sample compositions crossing the magnetic compensation point. Temperature dependent magnetization curves highlighted the variation of the overall net contribution of the two magnetic sub-lattices by changing either the Fe/Gd elemental ratio or the film thickness. Fe-57 Conversion Electron Mossbauer (CEM) spectra give additional support to the specific magnetic behavior evidenced by temperature and field dependent Superconducting Quantum Interference Device (SQUID) magnetometry.

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.

Mononuclear Mn(II) coordination compound, [Mn(H2L)Cl-2] (1), was synthesized by the reaction of H2L and MnCl2 center dot 4H(2)O in methanol where H2L is tridentate ONO-donor hydrazone ligand [H2L = (E)-N'-(2-hydroxy-5-iodobenzylidene)isonicotinohydrazide]. The reaction of H2L with MnCl2 center dot 4H(2)O in the presence of excess amount of NaN3 in methanol gave an azido bridged dinuclear Mn(III) coordination compound, [Mn-2(L)(mu-N-3)(2)(CH3OH)(2)] (2), whereas in the presence of low amount of NaN3, a phenolate bridged dinuclear Mn(II) coordination compound, [Mn-2(HL)(2)(CH3OH)(2)Cl-2]center dot CH3OH (3), was obtained. These compounds were characterized by elemental analysis, spectroscopic methods, single crystal X-ray analysis and magnetic measurements. The structural studies indicated that the ligand is coordinated as ONO-donor ligand in 1-3 and behave as a neutral, dianionic and monoanionic ligand in compounds 1, 2 and 3, respectively. There is a good agreement between spectroscopic properties and structures of the compounds. Several synthetic attempts indicated that the azide anion has considerable effect on the formation of phenolate bridged dinuclear Mn(II) coordination compound which attributed to its general basic properties. Magnetic measurements indicate the formation of dinuclear molecules with ferromagnetic intramolecular couplings in the case of 2 and 3 as well as with much weaker and distributed antiferromagnetic interactions among the dinuclear units of these compounds. (C) 2020 Elsevier Ltd. All rights reserved.

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.

Structural and magnetic properties of Fe oxide nanoparticles prepared by laser pyrolysis and annealed in high pressure hydrogen atmosphere were investigated. The annealing treatments were performed at 200 degrees C (sample A200C) and 300 degrees C (sample A300C). The as prepared sample, A, consists of nanoparticles with similar to 4 nm mean particle size and contains C (similar to 11 at.%), Fe and O. The Fe/O ratio is between gamma-Fe2O3 and Fe3O4 stoichiometric ratios. A change in the oxidation state, crystallinity and particle size is evidenced for the nanoparticles in sample A200C. The Fe oxide nanoparticles are completely reduced in sample A300C to alpha-Fe single phase. The blocking temperature increases from 106 K in A to 110 K in A200C and above room temperature in A300C, where strong inter-particle interactions are evidenced. Magnetic parameters, of interest for applications, have been considerably varied by the specific hydrogenation treatments, in direct connection to the induced specific changes of particle size, crystallinity and phase composition. For the A and A200C samples, a field cooling dependent unidirectional anisotropy was observed especially at low temperatures, supporting the presence of nanoparticles with core-shell-like structures. Surprisingly high M-S values, almost 50% higher than for bulk metallic Fe, were evidenced in sample A300C.

Temperature dependent interfacial coupling mechanisms in SRO/BFO/Fe layered structures were investigated. The BFO/Fe heterostructures were prepared by PLD and sputtering, respectively, on the STO(0 0 1) substrate with a 20 nm SRO buffer layer. An annealing treatment in external magnetic field was further applied. Complex characterizations with X-ray diffraction, atomic force microscopy, Transmission Electron Microscopy, Mossbauer spectroscopy, magneto-optic Kerr effect and SQUID magnetometry were performed. Before annealing, the films show good crystallization and epitaxy of the SRO and BFO layers with smooth interfaces. Two coupling mechanisms of the ferromagnetic layers (top Fe and bottom SRO, respectively) to the epitaxial BFO film with mainly antiferromagnetic structure were evidenced in the as deposited samples at low temperatures. Negative exchange bias fields of up to 67(10) Oe and 37(5) Oe at low temperatures were observed for the two ferromagnetic components, respectively, depending on the thickness of the Fe layer. The field annealing treatments induce a specific morphology and magnetic spin structure at both interfaces of the BFO spacer layer, giving rise to a long range magnetostatic coupling between the two ferromagnetic films, in addition to the interfacial couplings. Moreover, the experimentally evidenced Fe clusters penetrating the BFO/Fe interface toward the BFO layer give support for this interaction. As an additional consequence, a considerable enhancement of both uniaxial and unidirectional anisotropies as well as an increased blocking temperature of exchange bias were obtained. The involved exchange coupling mechanisms were discussed in detail. (C) 2018 Elsevier B.V. All rights reserved.

Among the rare-earth-free systems that are currently investigated in search for novel permanent magnet solutions for various applications, with special emphasis on the magnets required to operate in extreme conditions, the FePt binary system, where the tetragonal hard magnetic L1(0) phase can be formed by suitable microstructure processing via annealing, has been extensively studied. A variation of this system, the ternary FeMnPt system, has been also recently shown to exhibit good permanent magnet behavior due to the suitable formation of the L1(0) phase. In addition to be likely to form the L1(0) phase as its parent binary system, the ternary FeMnPt benefits from the reduced costs due to the reduced amount of Pt and may exhibit particular magnetic structure due to the influence of the antiferromagnetic Mn. In the present work, we have employed a mixed sputtering technique, based on the use of both elemental and compound target for developing L1(0) FeMnPt thin films with specific structural features that triggers better magnetic performances in terms of coercivity and maximum energy products. The as-obtained films have been thermally annealed and characterized by means of transmission electron microscopy, X-ray diffraction, Mossbauer spectroscopy, magneto-optic Kerr effect (MORE) and SQUID magnetometry. The aim is to correlate the Mn induced microstructural and lattice changes with the magnetic properties and to optimize the microstructure for an early formation of the ordered L1(0) phase and increased coercivity compared to the as-prepared, structurally disordered, face centred cubic initial state of the films.

The reaction of manganese(II) chloride tetrahydrate with sodium azide and ONO-donor hydrazone ligand, (H2L = (E)-3-hydroxy-N'-((2)-4-hydroxy-4-phenylbut-3-en-2-ylidene)-2-naphthohydrazide), in methanol gives rise to the formation of red crystals which are stable out of the solvent. The red crystals slowly transform to brown crystals in the methanolic solution. In the last case, the rate of the transformation from red to brown crystals mainly depends on the presence of molecular oxygen and reaction temperature. Both compounds are characterized by elemental analysis, spectroscopic methods and single crystal X-ray diffraction studies. The X-ray analysis indicates that the red crystals consist of a tetranuclear Mn(II) complex molecules, [Mn-4(H0.5L)(4) (mu(1.3)-N-3)(2)(CH3OH)(4)] (1), while the brown crystals consist of dinucelar Mn(III), [Mn2L2(mu(1.1)-OCH3)(1.5)(mu(1.1)-N-3)(0.5)] (2) molecules. In complex 1 with molecules of D2 (222) point symmetry, four Mn(II) ions are connected together by four ONO-donor hydrazone ligands and two end-to-end (EE) bridging azide anions. In complex 2 two Mn(III) ions are connected together by azide or methoxy bridging groups. Magnetic susceptibility measurements on complex 1 reveal the occurrence of antiferromagnetic couplings through azide ligands and enolate oxygen atom of the ligand in which the magnetic coupling constants have been determined. (C) 2018 Elsevier Ltd. All rights reserved.

Arrays of Ni submicron wires surrounded by poly (vinylidene fluoride) (PVDF) submicron tubes were prepared via solution-processed polymer and Ni electrodeposition into anodic aluminum oxide template. The PVDF solution was filtered in vacuum through the template and the resulting dried structure was used for the electrodeposition of Ni wires. The obtained core-shell submicron wire structure consists of a metallic magnetic nanowire core of about 50 mu m in length and about 300 nm diameter surrounded by a polymer tube shell with thickness less than 10 nm. The specific ferroelectric beta-phase of the polymer was obtained whereas the magnetic behavior of the Ni-cores was proven to be specific to an array of ferromagnetic Ni cylindrical wires (about 0.62 mu(B)/Ni atom) with magnetization reversal mechanisms dominated by dipolar interactions and domain wall displacements. No significant differences of the magnetization reversal mechanism were observed in case of Ni submicron wires surrounded by PVDF tubes and similar Ni wires without PVDF shell, suggesting that magneto-coupling effects in such systems might be observed only by measuring the perturbation of the electric state of the polymer shell under a magnetic excitation of the Ni cores.

Local atomic configuration, phase composition and atomic intermixing in Fe-rich Fe1-xCrx and Fe1-xMox ribbons (x = 0.05, 0.10, 0.15), of potential interest for high-temperature applications and nuclear devices, are investigated in this study in relation to specific processing and annealing routes. The Fe-based thin ribbons have been prepared by induction melting, followed by melt spinning and further annealed in He at temperatures up to 1250 degrees C. The complex structural, compositional and atomic configuration characterisation has been performed by means of X-ray diffraction (XRD), transmission Mossbauer spectroscopy and differential scanning calorimetry (TG-DSC). The XRD analysis indicates the formation of the desired solid solutions with body-centred cubic (bcc) structure in the as-quenched state. The Mossbauer spectroscopy results have been analysed in terms of the two-shell model. The distribution of Cr/Mo atoms in the first two coordination spheres is not homogeneous, especially after annealing, as supported by the short-range order parameters. In addition, high-temperature annealing treatments give rise to oxidation of Fe (to haematite, maghemite and magnetite) at the surface of the ribbons. Fe1-xCrx alloys are structurally more stable than the Mo counterpart under annealing at 700 degrees C. Annealing at 1250 degrees C in He enhances drastically the Cr clustering around Fe nuclei.

Amorphous hematite synthesized by a simple and fast microwave route was used to obtain Fe16N2 fine particles by reducing in 5% H-2/Ar gas flow, followed by long time nitridation in ammonia gas flow at temperatures below 200 degrees C. Depending on nitridation temperature, various amounts of metallic iron were present along with the alpha" -Fe16N2 main phase. A small amount of iron oxide was observed by Mossbauer spectroscopy, but it was undetected by X-ray diffraction due to its high degree of amorphization. Increased amounts of Fe3N and Fe4N phases were observed at a nitridation temperature above 150 degrees C, which had a detrimental effect on the magnetic properties. Structural information and phase composition were extracted from Rietveld refinement of the XRD data. Values of the magnetization at saturation measured at 40 kOe and 25 degrees C of 222 emu/g for alpha"-Fe16N2 and 192 emu/g for metallic iron were obtained via magnetic measurements, Rietveld, and Mossbauer analysis.

Reduced-activation steels such as Eurofer alloys are candidates for supporting plasma facing components into kamak-like nuclear fusion reactors. In order to investigate the impact of hydrogen/deuterium insertion in their crystalline lattice, annealing treatments in hydrogen atmosphere have been applied on Eurofer slabs. The resulting samples have been analyzed with respect to local structure and atomic configuration both before and after successive annealing treatments, by X-ray diffractometry (XRD), scanning electron microscopy and energy dispersive spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The corroborated data point out for a bcc type structure of the non-hydrogenated alloy, with an average alloy composition approaching Fe0.9Cr0.1 along a depth of about 100 nm. EDS elemental maps do not indicate surface inhomogeneities in concentration whereas the Mossbauer spectra prove significant deviations from a homogeneous alloying. The hydrogenation increases the expulsion of the Cr atoms toward the surface layer and decreases their oxidation, with considerable influence on the surface properties of the steel. The hydrogenation treatment is therefore proposed as a potential alternative for a convenient engineering of the surface of different Fe-Cr based alloys.(C) 2017 Elsevier B.V. All rights reserved.

Magnetic nanoparticles embedded in the active layer of the Organic Light Emitting Diodes (OLEDs) significantly increases the electroluminescence and the charge transport without influencing the transparency of these devices. A brief comparison was done in order to identify which parameter influences these properties, by comparing the CoFe2O4 magnetic nanoparticles with CoFe2 metallic magnetic nanoparticles, the latter one being obtained by thermal reduction in hydrogen of cobalt ferrite nanoparticles. CoFe2 have shown a better efficiency of the metallic nanoparticles where probably the main advantage is the higher magnetization property instead of the coercive field. Concerning the charge transport across the OLEDs, these nanoparticles reduce the electron injection, acting as filling traps, which directly increases the electroluminescence and the current at the same voltage.

A comparative study of morpho-structural, magnetic and magneto-transport properties of two Fe-Au granular films with different concentrations of Fe nanoclusters of almost similar size is reported. Different organizations of the Fe clusters, i.e. in lamellar-like or random-like configuration, were obtained by varying the amount of Fe in the Fe-Au films. The specific magnetic behaviour was investigated with respect to local structure and morpho-structural aspects by combining magneto-optic Kerr effect and superconducting quantum interference device magnetometry, Fe-57 conversion electron Mossbauer spectroscopy and a wide range of electron microscopy techniques. A strong in-plane magnetic texture with uniaxial anisotropy was observed in the case of the lamellar-like organization of the clusters (specific to the Fe-Au film with higher Fe concentration) whereas a superparamagnetic behaviour was evidenced in the case of random distribution of the clusters (specific to the Fe-Au film with lower Fe concentration), despite the similar average size of the clusters in the two samples. Specific magnetoresistance effects were investigated with respect to both the involved magnetic configurations and magnetic interactions of the Fe clusters.

TiO2 nanoparticles, undoped and doped with Fe, have been prepared by laser pyrolysis and further investigated with respect to morphological, structural and magnetic aspects by transmission electron microscopy, diffractometry, Mossbauer spectroscopy, and magnetometry. The obtained nanoparticles, consisting of mainly anatase phase, agglomerate in clusters of tenths of units and present a large size distribution in the range from 5 to 40 nm. The anatase to rutile weight ratio (about 9) and the morphology of particles is similar in all analyzed samples (doped by up to 12 0,0 at. % Fe). Only Fe3+ ions in high spin-configuration were observed mainly at the, surface of TiO2 nanoparticles, either distributed or forming fine clusters of Fe oxide.;:Both a paramagnetic phase and a superparamagnetic one with blocking temperature lower than 50 K are superposed over a long-range ferromagnetic phase specific to diluted magnetic oxide systems. The influence of doping Fe ions on the magnetic behavior of each phase is discussed in detail. Evidences for interface exchange couplings (with unidirectional anisotropy in specific conditions) between the long-range ferromagnetic phase and the fine clusters (antiferromagnetic in nature), which become frozen below temperature of 50, K, are provided. The specificity of the processing route and the physical mechanisms responsible observed relevant magnetic features, which can be tailored for suitable applications, are discussed.

Be/W and W/Be bilayers, of interest in regard to the specific behavior of plasma facing components (PFCs) were deposited on Si substrates by thermionic vacuum arc, with Fe, Fe-Cr and Fe-Cr-Al interlayers. The interlayers, with compositions approaching the one of the reduced activation steels used in supporting PFCs, were subsequently annealed in hydrogen atmosphere. The multilayers were characterized with respect to morphologic, structural, diffusional and atomic intermixing aspects via XRD, XRR, X-ray photoemission spectroscopy and Mossbauer spectroscopy. All as-prepared samples present partially amorphous structures. A main alpha-Fe phase is observed, as well as (superparamagnetic) secondary Fe oxides, metallic Fe with Si, Cr, W and Be neighbors, Be-rich Fe-Be and Fe-Si phases. High amounts of tungsten and tungsten oxides were also evidenced in the Fe layer. The strong atomic intermixing of W and Be layers was indirectly supported by the unusual densities of Wand Be layers and Fe-57 Mossbauer spectroscopy results. (C) 2016 Elsevier B.V. All rights reserved.

Fe16N2 fine particles were prepared by reduction in 5% H-2/Ar gas mixture flow, starting from goethite or hematite precursors, followed by nitridation in ammonia gas flow. Small amounts of metallic iron and iron oxide are present besides the main phase which is an ordered iron nitride having martensite structure (alpha''-Fe16N2) as revealed by Mossbauer spectroscopy measurements. However, X-ray diffraction data do not show any traces of oxides due to their high degree of amorphization. When nitridation is performed at about 150 C-0, Fe4N phase begins to form and its presence deteriorates the magnetic properties. The samples prepared by nitridation of goethite present better magnetic properties compared to those obtained by nitridation of hematite. Magnetic and Mossbauer measurements performed at ambient temperature were corroborated in order to extract the magnetization at saturation value for each phase which occurs in the obtained samples. The corresponding values are 226 emu/g for Fe16N2 and 198 emu/g for metallic iron contained in the prepared powders.

A quantitative treatment of the effects of magnetic mutual interactions on the specific absorption rate of a superparamagnetic system of iron oxide nanoparticles coated with oleic acid is reported. The nanoparticle concentration of the considered ferrofluid samples varied from a very low (0.005) to a medium (0.16) value of the volume fraction, whereas the amplitude of the exciting AC magnetic field ranged from 14-35 kA m(-1). It was proved that a direct effect of the interparticle interactions resides in the regime of the modified superparamagnetism, dealing, besides the usual increase in the anisotropy energy barrier per nanoparticle, with the decrease in the specific time constant tau(0) of the relaxation law, usually considered as a material constant. Consequently, the increase in the specific absorption rate versus the volume fraction is significantly diminished in the presence of the interparticle interactions compared to the case of non-interacting superparamagnetic nanoparticles, with direct influence on the magnetic hyperthermia efficiency.

Atomic intermixing processes in relation to structural aspects and phase formation in Be based thin films subjected to different annealing treatments simulating the case of re-deposited layered structures on plasma facing components in nuclear fusion devices are reported. Accordingly, bilayers of Be/W and Be/C have been deposited on Si(001) substrates with Fe buffer layers. The Fe films have been prepared by radiofrequency sputtering and further processed by annealing in hydrogen atmosphere at 300 degrees C, for 90 min, at a pressure of 10 bars of H-2. After the Be/W and Be/C bilayer deposition by means of thermionic vacuum arc method, annealing in vacuum at 600 degrees C, for 10 min has been applied to the complex structures. The influence of annealing on the phase composition and atomic intermixing processes in the complex structures has been studied by means of X-ray photoelectron spectroscopy (XPS) and conversion electron Mossbauer spectroscopy (CEMS). The layered structures present an oxidation gradient with oxide phases in the uppermost layers and non-oxidized phases in the lower layers, as observed from the XPS data. The CEMS results revealed that the as-deposited structures contain a main metallic Fe phase and secondary superparamagnetic Fe oxide phases at the Fe/Be interface, while annealed samples present a large contribution of Fe-Be and Fe-C mixtures. The annealing treatment induces considerable atomic interdiffusion, strongly dependent on the nature of the upper layer. In the case of Be/W system, the annealing provides a much rougher Be/W interface, while in case of the Be/C structure, the annealing treatment only homogenize the structure over the whole depth. (C) 2014 Elsevier B.V. All rights reserved.

The content of defects in Bi4Ge3O12 (BGO) glass-ceramic materials together with their ordering during crystallization induces ferromagnetic behaviours in these materials. The observed ferromagnetism has to be associated strictly with the GeO4 related defects in the atypical amorphous phase. The photoluminescence of BGO glass-ceramic materials can give useful information about the nature of defects, especially the oxygen vacancies from the GeO4 tetrahedra and Bi4Ge3O12 cubic structures. The concentration of these defects depends on annealing between 600 degrees C and 700 degrees C where orthorhombic and cubic phases coexist. The magnetization at saturation is higher in the samples dominated by the amorphous phase and the strength of the exchange interaction is higher in the samples dominated by the cubic phase, obtained over 700 degrees C, when the GeO4 tetrahedra are rearranged during crystallization together with their oxygen vacancies. (C) 2014 Elsevier B.V. All rights reserved.

Homogeneous hybrids in which iron oxide nanoparticles are entrapped within polymer structure are of interest for their potential applications in biomedical field, such as diagnostic, therapeutic and theranostic purposes. For this reason, hybrid nanomaterials based on branched polyethyleneimine (PEI) and iron oxide with different ratios were synthesized in a single step by hydrothermal procedure at high pressure and low temperature. Iron oxide is formed in the presence of branched PEI and the interaction between them takes place in the reaction medium. The influence of synthesis parameters on the hybrid formation, as well as chemical and structural properties was studied by means of FTIR, DSC-TG, HRTEM, electron paramagnetic resonance (EPR), magnetic measurements (SQUID) and Fe-57 Mossbauer analyses. It has been shown that synthesis parameters influence thermal stability and morphology of the hybrids. FeO(OH) crystallites of 2-5 nm are formed. Iron oxyhydroxide nanoparticles strongly entrapped in PEI structure are obtained. The low and distributed values of the specific spontaneous magnetisation in samples prepared under the same pressure conditions support the presence of very fine FeO(OH) nanoparticles, which formation and magnetic properties are depending on the mass ratio between iron oxide and PEI. (C) 2015 Elsevier B.V. All rights reserved.

Thermionic vacuum arc was successfully used to prepare high quality nanostructure thin films with different fields of applicability. One advantage of this deposition technique was the ability to have a controlled range of thicknesses starting from few nanometers to hundreds of nanometers. The purity of the thin films was insured by a high vacuum pressure and a lack of any kind of buffer gas inside the coating chamber. The aim of this work was to obtain significant magnetic response and to compare the MR to the structures obtained for two different granular combinatorial structures. The samples were investigated using scaning and transmision electron mycroscopy while SEM and The magnetic properties were first studied by measuring the electrical resistance behavior for a magnetic field of 0.3 T, at different values of the sample temperature and using a non-destructive optical method called Magneto-Optical Kerr Effect (MOKE). The magnetoresistive effect obtained for the studied samples varied from 0.6% to 19% in respect sample structure and temperature for a constant magnetic field.

Previous studies have shown that the magnetic parameters of the Romanian loess/paleosol sequences have recorded Quaternary glacial/interglacial cycles over the last 600 kyr. Previous rock magnetic investigations pointed out that the magnetic enhancement in Romanian loess sequences is mainly due to pedogenic magnetite close to superparamagnetic/stable single domain boundary. We report the first reconstruction of grain size distribution (GSD) of the superparamagnetic (SP) particles for two Romanian loess deposits, Costinesti and Mircea Voda, located in the Dobrogea Plateau between the Danube River and the Black Sea. The GSDs were obtained using both the wide-band frequency spectrum of magnetic susceptibility (FSMS) method and low temperature Mossbauer spectroscopy. The FSMS method shows that the SP particles are present both in loess and paleosols. The GSDs in loess are shifted to slightly higher diameters with respect to paleosols. The concentration of SP particles has an opposite trend. The largest value is reached in the forest paleosol and the lowest in the loess samples. Both loess and paleosols indicated almost the same dominant grain size (about 17 nm in paleosols and 18 nm in loess samples). However the GSD shapes in loess are different than those found in paleosols. in the paleosols, the shape of GSDs seems to be independent of climate and degree of pedogenesis. These factors control only the concentration of SP particles present in each paleosol. Temperature dependent Mossbauer spectroscopy also supports the presence of SP particles both in loess and paleosol with a mean diameter around 13-14 nm. Dispersion of the diameters in the case of Mossbauer spectroscopy varies from sample to sample being probably affected by random surface defects. (C) 2015 Elsevier B.V. All rights reserved.

A new methodology for the accurate determination of the specific absorption rate of ferrofluids with magnetite nanoparticles of average size of about 10 nm subjected to alternative current magnetic fields is proposed. A simple numerical compensation of the heating rates by the cooling rates obtained at similar temperatures is employed. Comparisons of the as-obtained adiabatic heating curves with theoretical evaluations are discussed.

Fe-Ni graded films have been prepared by co-sputtering permalloy and Fe targets at different time-power sequences. Morpho-structural and magnetic investigations have been performed by transmission electron microscopy, Xray reflectometry, conversion electron Mossbauer spectroscopy and magneto-optic Kerr effect vector magnetometry, proving the thickness dependence of the properties. A magnetization reversal involving the displacement of Bloch-type walls is characteristic for a 115 nm thick Fe-Ni graded film whereas an in-plane coherent rotation of the spins, according to a Stoner-Wohlfarth mechanism was evidence for a 23 nm thick Fe-Ni graded film.

The aim of this paper is to present a reliable procedure for the experimental determination of the specific absorption rate (SAR) in case of superparamagnetic Fe oxide nanoparticles dispersed in liquid environments. It is based on the acquisition of consecutive steps of time-temperature dependences along of both heating and cooling processes. Linear fitting of these recorded steps provides the heating and cooling speeds at different temperatures, which finally allow the determination of the heating profile in adiabatic-like conditions over a broad temperature range. The presented methodology represents on one hand, a useful alternative tool for the experimental evaluation of the heating capability of nanoparticulate systems for magnetic hyperthermia applications and on the other hand, gives support for a more accurate modeling of bio-heat transfer phenomena.

Finite size effects and interfacial interactions as well as their influence on the magnetic properties of nanosized systems are discussed by starting from very basic principles of magnetism. Some preparation and subsequent processing tools for a proper engineering of the properties of such magnetic nanosized systems are introduced together with specific characterization tools. A summary of the most important technological applications related to size effects and interfacial interactions, with exemplifications starting from bio-medical applications of magnetic fluids to magnetoresitive multilayers for sensor applications are also provided.

In order to study specific phenomena at ferromagnetic/semiconducting interfaces, of potentially high interest in spintronics and information technology, structural aspects and magnetic properties of Fe thin films grown on Si(001) substrates by RF sputtering have been investigated using Fe-57 conversion electron Mossbauer spectroscopy (CEMS) and magneto-optic Keer effect (MOKE). Films of different thicknesses have been deposited either directly on crystalline Si substrates or on Cu buffer layers. An inherent Fe oxide layer is observed in all as prepared films, with a relative thickness decreasing drastically with the deposition time. The Cu buffer layer does not diminish either the interfacial diffusion or the oxidation process. An efficient method to prepare sharper oxygen- and silicon-free interfaces for an improved spin injection, via thermal treatment in hydrogen atmosphere, is proposed. Accordingly, the hydrogenation treatments are very efficient in the modification of the ferromagnetic film structure, phase composition, magnetic properties and interfacial mixing. (C) 2013 Elsevier B.V. All rights reserved.

Ferrofluid samples consisting of magnetite nanoparticles (NPs) coated with oleic acid and dispersed in a non-polar organic solvent have been synthesized by chemical routes. Different volume fractions, phi, of magnetic NPs were considered. The overall structural characterization of NPs has been performed by x-ray diffractometry, with lattice parameters and average coherence lengths evaluated via Rietveld refinements. The magnetic properties of different samples have been analysed by SQUID magnetometry and temperature-dependent Mossbauer spectroscopy and finally explained by adequate magnetic relaxation mechanisms. Zero field cooling-field cooling protocols provided useful information about specific volume fraction dependent magnetic relaxation and de-freezing processes, the lack of the Verwey transition and stronger dipolar interactions at higher volume fractions. Anisotropy energies as obtained by both temperature dependent Mossbauer spectroscopy and magnetometry data are compared and a new procedure for a quantitative characterization of the dipolar interactions is proposed.

New nanometric systems were produced by using specific parameters of the laser pyrolysis process. Relevant results related to the magnetic behavior of the samples were obtained via SQUID magnetometry and Mossbauer spectroscopy, the data being corroborated with those previously obtained from X-ray diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy. The formed nanocomposites contain iron carbides, iron oxides and metallic iron nanoparticles which relative content and average size depend strongly on experimental specific parameters of the pyrolysis process. The magnetic properties and the local interaction mechanisms were explained by adequate magnetic relaxation and static models. (C) 2013 Elsevier B.V. All rights reserved.

Structural aspects and atomic intermixing processes in Be/W bilayers deposited on Si(0 0 1) substrates with Fe buffer layers enriched in the (57)Fe Mossbauer isotope have been studied via atomic force microscopy, grazing incidence X-ray diffractometry, X-ray reflectometry, X-ray photoelectron spectroscopy and conversion electron Mossbauer spectroscopy. The mentioned investigations allowed a full sequential characterization of the involved interfaces. Various ionic configurations appeared for Fe or W, while an amorphous state was observed in the case of Be. It has been proven that the Be layer has a negative influence on the roughness of the whole structure, which however presents an oxidation gradient from more oxidized elements at the surface towards more reduced elements in deeper layers. A strong diffusion of the W atoms inside the Be layer, induced by the deposition method, as well as of the Fe atoms inside the Be layer, induced by thermal annealing, has been evidenced. (C) 2011 Elsevier B.V. All rights reserved.

Magnetite alternating copolymers divinylbenzene-maleic anhydride (DVB-MA) composites were prepared by dispersion polymerization. Because magnetite is used as a complex with oleic acid (Fe(3)O(4)OLA), the final hybrids show good dispersion of inorganic nanofillers in the polymer matrix. The obtained composites were analyzed by infrared absorption spectrometry, diffuse reflectance in visible light, thermogravimetry, X-ray fluorescence, X-ray diffraction, dynamic light scattering, scanning electron microscopy and vibrating sample magnetometry. The obtained results indicate the successful preparation of magnetite nanoparticles with an average size of about 23 nm dispersed in micrometer size copolymer spherical particles, which relative content can be controlled via the processing parameters. A relationship between the relative content of magnetite nanoparticles and the size of the polymer particles, with direct influence on the diffuse reflectance in the visible domain, was observed. A superparamagnetic behavior was evidenced at room temperature with a blocking temperature lower than as expected from the bulk anisotropy constant and the average size of the magnetite nanoparticles. Both the unexpected low blocking temperature and the observed low specific magnetizations were explained by a defected and poor crystalline structure of the magnetite nanoparticles, giving rise to spin disorder and diminished crystalline anisotropy constant. (C) 2012 Elsevier Ltd. All rights reserved.

The results of the electric and magnetic measurements performed on PbZr0.2Ti0.8O3-BiFeO3 symmetric structures, deposited on Pt/Si wafers, were compared for different number of layers in order to analyse the effect of interfaces over the macroscopic properties. It was found that the shape and magnitude of the capacitance-voltage characteristic, as well as the shape and parameters of the ferroelectric and magnetic hysteresis, depend on the number of interfaces in the intended multilayer structure. A temperature induced gradual transition from a magnetically disordered spin glass like phase of low temperature to an uncompensated antiferromagnetic phase at room temperature takes place in the BiFeO3 films, under low applied magnetic fields. A partial ferromagnetic like order can be obtained at low temperatures by increasing the field. The observed changes in the electric and magnetic behaviour of the systems were related to an increased degree of disorder for electric dipoles and magnetic moments, due to the increased number of layers and crystallization treatments. (C) 2011 Elsevier B.V. All rights reserved.

Multilayer spin valve structures of type AF/F/Cu/F and AF/F/MgO/F (AF=antiferromagnetic layer and F=ferromagnetic layer) have been prepared by sputtering in radiofrequence. The samples were investigated at room temperature by magneto-optic Kerr effect and conversion electron Mossbauer spectroscopy, before and after thermal hydrogenation. Additional magnetic peculiarities were observed at low temperatures via SQUID magnetometry. The effect of the thermal hydrogenation on the magnetic properties of the systems was discussed with respect to the changes in the local spin configuration, observed by Mssbauer spectroscopy.

The article reports the preparation and complex characterization of iron-containing phosphate glasses considered to be ecological materials, as they contain nontoxic compounds related to environment. The oxide system Li2O-MgO-(CaO)-Al2O3-P2O5-(FeO/Fe2O3) was investigated in respect to its structural changes caused by MgO replacement with CaO and by the iron addition. UV-vis-NIR (ultraviolet-visible-near infrared) spectroscopy as well as thermo-gravimetric (TG) measurements, differential thermo-analysis (DTA), X-ray diffraction (XRD) analysis, electronic paramagnetic resonance (EPR), and Mossbauer (nuclear gamma resonance) spectroscopy have been used to investigate redox states and coordination symmetry of iron, together with vitreous network changes during the heat treatment up to 1000 degrees C. UV-vis-NIR transmission spectroscopy revealed no structural modifications when MgO was substituted by CaO, but noteworthy absorption bands attributed to Fe2+/Fe3+ species. TG analysis made in the 20-1000 degrees C range shows low weight loss accompanied by several thermal effects, as evidenced by DTA. XRD patterns for the glass samples heat treated at about 700 degrees C revealed the presence of different phosphate crystalline phases containing Mg, Al, and Fe ions. EPR spectroscopy revealed the presence of paramagnetic Fe3+ ions and the change of the first coordination symmetry, when the samples are heated below the vitreous transition temperature. Mossbauer spectroscopy has evidenced two paramagnetic species, Fe2+ and Fe3+, both in octahedral coordination symmetry and a clustering process supported by only Fe3+ ions.

A designed experimental configuration for the simultaneous study of magnetization reversal and giant magnetoresistance effects in layered systems is reported. The suitability of the device, designed mainly for didactical purposes, to prove giant magneto-resistance effects is exemplified in case of exchange coupled spin valve structures. The multilayer structures were prepared by theromo-ionic vacuum arc methods and initially characterized by X-ray diffractometry and energy dispersive Xray spectroscopy. According to the performed experiments, it has been clearly proven the presence of magnetoresistance maxima ever ranges of applied fields inducing antiparallel magnetizations of the two ferromagnetic layers interfacing a thin conductive layer.

Simple Fe-Co ferromagnetic films and Fe-Mn antiferromagnetic films of different compositions were grown on epitaxial Si substrates with Ta buffer layers via thermo-ionic vacuum arc method. Fe-Co/Fe-Mn bilayer structures were obtained by following similar growing conditions as for the simple films. The magnetic behavior concerning easy axis distribution, anisotropy energy and coercive field of the Fe-Co films exchange coupled to the antiferromagnetic layers were discussed with respect to the magnetic behavior of the simple, uncoupled, ferromagnetic films. The composition of the antiferromagnetic films has a sensible influence on the magnetic parameters of the exchange coupled ferromagnetic films. The largest coupling and the narrowest easy axis distribution are induced in the bilayer system with equatomic composition of the Fe-Mn antiferromagnetic layer. (C) 2010 Elsevier B.V. All rights reserved.

The influence of different crystallization conditions on the microstructure and magnetic hardening of RE-Fe-B amorphous ribbons with different Fe concentrations and Pr and Nd as rare earth elements was analyzed. The microalloying effects of Zr and Ti substitution on the evolution of crystallization process and the magnetic hardening was also discussed. The final aim of this experimental study was to obtain performing exchange spring magnets with as much as lower content of the expensive RE material.

Exchange bias AF/Fe and spin valve AF/Fe/Cu/Fe (AF=Fe50Mn50 and Ir50Mn50) multilayer systems have been prepared by molecular beam epitaxy. Thin tracer layers enriched in the Fe-57 isotope were artificially grown at the AF/Fe interface and the phase composition of the ferromagnetic layer, as well as the interfacial atomic diffusion were observed via Fe-57 conversion electron Mossbauer spectroscopy. The dependence of the magnetization reversal process on training and temperature associated effects was studied by low temperature vibrating sample magnetometry, whereas the interlayer magnetic coupling was analyzed via longitudinal magneto-optic Kerr effect.

Spin valve like AF/Fe/Cu/Fe (AF = Fe50Mn50 and Ir50Mn50) multilayer systems have been prepared by molecular beam epitaxy. Thin tracer layers enriched in the Fe-57 isotope were artificially grown at the AF/Fe and Fe/Cu interfaces and the interfacial atomic diffusion was observed via Fe-57 conversion electron Mossbauer spectroscopy. The results show that the atomic interdiffusion at all involved interfaces is lower in the IrMn based structures as compared to the FeMn based ones. (C) 2010 Elsevier B.V. All rights reserved

The difficulty to stabilize a definite crystalline structure or phase, due to a large gradient of defects along the particle diameter, is unfortunately specific to particles of nanometer size. Therefore, atypical spin configurations and magnetic anisotropies as well as enhanced magnetic relaxations via thermal excitations are expected in systems of fine nano-particles. The actual work reports on various possibilities for a comprehensive characterization of the magnetic configuration and magnetic relaxation mechanisms of nano-particles, by corroborating the powerful method of Mossbauer spectroscopy with complementary magnetic and structural techniques. The capabilities of temperature and field dependent Mossbauer spectroscopy to provide valuable information about spin blocking temperatures, effective anisotropy constants, amount of uncompensated spins inside of particle and magnetic phase composition are critically discussed for both powder like systems and nano-particles dispersed in different solvents.

Six tetranuclear complexes [Fe(III)(3)Ln(mu(3)-O)(2)(CCl3COO)(8)(H2O)(THF)(3)]center dot THF center dot C7H16 [Ln=Gd(III) (1), Tb(III) (2), Dy(III) (3), Ho(III) (4), Y(III) (5), and Lu(III) (6)] have been studied by magnetic susceptibility and Moumlssbauer spectroscopy. These isostructural molecules have a "butterfly" structure core consisting of two Fe(2)Ln(mu(3)-O) triangular "wings" which share a common Ln-Fe "body"; the dihedral angle between the wings is ca. 148 degrees. The coordination spheres of the iron ions are essentially distorted octahedral. The lanthanides are eight-coordinate with coordination polyhedra that may be described as distorted tetragonal bipyramids. Variable-temperature solid-state magnetic susceptibility in the temperature range 1.8-300 K and magnetization at 1.8 K for compounds 1-6 were measured. The spin state of Fe is S=5/2 in all cases. In compounds 5 and 6, where Ln(III) (Y and Lu, respectively) is diamagnetic, the three Fe atoms form an obtuse isosceles triangle with antiferromagnetic interactions J(Fe-Fe)=-50 K between the wing-tip Fe-w and body Fe-b atoms, and negligible interaction between the Fe-w's, resulting in a ground state of effective spin S=5/2 per cluster. In the complexes with paramagnetic lanthanide ions, the interaction between the Fe-3 triangle and the Ln(III) center is described by an effective exchange constant which is antiferromagnetic and 1 order of magnitude weaker. Besides, at 3 K incipient spin blocking, characteristic of single molecule magnets, was found to occur in the out-of-phase component of the ac susceptibility in {Fe3TbO2}, {Fe3DyO2}, and {Fe3HoO2}. The activation energy of a Debye process describing the magnetization reversal has been determined to be, E-a approximate to 8, 9, and 10 K for the Ln=Tb, Dy, and Ho, respectively, and the prefactor tau(0)approximate to 10(-7) s. The high spin states of the Fe(III) centers were confirmed by the Moumlssbauer spectra, in which two distinguishable Fe sites could be resolved above 80 K, corresponding to the Fe-w and Fe-b sites, respectively. Relatively larger values of the quadrupole splitting of the Moumlssbauer spectra were observed for the Fe-w pair as compared with that for the Fe-b, and both quadrupole splittings diminished with increasing temperature. At 3 K the Moumlssbauer spectra showed a state with blocked spins (sextets) for the {Fe3TbO2} and {Fe3DyO2} cases. From the E-a and tau(0), determined in the ac susceptibility, the relaxation time at 3 K is estimated as tau approximate to 10(-5)-10(-6) s much longer than the time window of Moumlssbauer spectroscopy and compatible with the single molecule magnet behavior. In the presence of a strong magnetic field the moments of the Ln(III) cation and the Fe-3 triangle are polarized. For some compounds at low temperature a magnetic pattern (sextet) for each of the three Fe sites appeared, and the antiferromagnetic coupling within the Fe-3 cluster was directly proved by the opposite trend of the field dependence of the two Fe-w sextets as compared with the Fe-b third one.

Exchange bias and spin valve structures with Fe as ferromagnetic layers selectively enriched in Fe-57 and Ir-Mn of different compositions as antiferromagnetic pinning layers have been prepared by r.f. sputtering. Conversion Electron Mossbauer Spectroscopy and Magneto Optic Kerr Effect have shown that the local structure and interactions in the whole ferromagnetic layers, with direct influence on their magnetic reversal processes, depend on growing order of the layers and composition of the AF layer. Interfacial atomic diffusion is the main reason of perturbing the local structure of the ferromagnet. Mossbauer Spectroscopy is a powerfool tool which allows a detailed analysis of local configurations, in order to optimize the magnetic and giant magnetoresistive parameters of such multilayers of important technological applications.

Mossbauer spectroscopy studies of Fe-Co/MgO catalysts proved that a high dispersion degree of Fe may be achieved for catalysts containing Fe/Co in a ratio close to 1. During materials processing. the presence of hydrogen at high temperatures, even for short time, induced an increased particle size of the catalytic Fe. The evaluation of various iron species from their areas in the Mossbauer spectra revealed the dependence of the nanotube amount on (FeCo alloy + Fe2+) content in the catalyst, in good agreement with literature mechanisms. The Raman spectra show that carbon nanotubes synthesized from ethanol in argon flow on 4.5%Fe:4.5%Co/MgO are richer in low diameter (0.7-1.0nm) tubes than those obtained at low ethanol pressure, in agreement with the effects of hydrogen reported in literature. The close similarity with the Raman spectra of Aldrich double-walled carbon nanotubes and from literature, recommends the syntheses in argon flow as better conditions for double-walled carbon nanotube growth.

The laser pyrolysis became a useful tool, providing various ways, in production of nano materials. The iron Mossbauer spectroscopy is one very accurate method in evidencing the physical properties and related processes in the nano scale compounds. The effect of pressure, laser spot area and induced combustion, of gas mixture and laser power on the phase composition and inside particle distribution, grain size as well as the related phenomena were investigated by temperature dependent Mossbauer spectroscopy. A selection of most relevant properties is presented and discussed in details.

Samples of LaNi5-xFex were prepared by arc melting and subsequent melt spinning procedure. Structural, magnetic and Mossbauer investigations were performed for physical characterization while the hydrogen storage properties were carefully analyzed. Detailed discussions concerning the sample's quality, the site assignment, the effect of temperature and applied fields on hyperfine parameters and the related Debye temperatures were provided. (C) 2008 Elsevier B.V. All rights reserved.

The laser pyrolysis became a useful tool, providing various ways, in production of nano materials. The iron Mossbauer spectroscopy is one very accurate method in evidencing the physical properties and related processes in the nano scale compounds. The effect of pressure, laser spot area and induced combustion, of gas mixture and laser power on the phase composition and inside particle distribution, grain size as well as the related phenomena were investigated by temperature dependent Mossbauer spectroscopy. A selection of most relevant properties is presented and discussed in details.

Exchange bias and spin valve systems with Fe-Mn antiferromagnetic layers of different Fe concentrations were obtained by the thermo-ionic vacuum arc method. The adherence of the multilayer system to the Si substrate depends on the Fe-Mn composition. The overall roughness depends on the growing order of the antiferromagnetic/ferromagnetic layers. Very low blocking temperatures for exchange bias were observed for the considered compositions of the Fe-Mn layer. The coercive forces of both the pinned and the free layers of spin valve structures can be considerably modified along a large set of samples simultaneously prepared. (C) 2008 Elsevier B.V. All rights reserved.

Four Fe-Mn-Si alloys, Fe(62)Mn(32)Si(6), Fe(62)Mn(20)Si(5)Cr(8)Ni(5), Fe(62)Mn(16)Si(5)Cr(12)Ni(5) and Fe(65)Mn(9)Si(7)Cr(10)Ni(9), were obtained by the melt-spinning method. The samples were structurally, magnetic and shape memory effect (SME) investigated, both ''as quenched'' and thermally treated. The Mn-rich compositions show different phase, magnetic behavior and SME in comparison with Mn-poor compositions. The thermal treatments generate transformation between the two existing majority phases (alpha and gamma), related magnetization and SME behavior. The features are derived from the corroboration of structural, magnetic interaction and magnitude of SME data. (c) 2008 Elsevier B.V. All rights reserved.

Co-MgO granular films presenting TMR effects were prepared by thermo-ionic vacuum arc (TVA) method with the simultaneous ignition of plasma in Co and MgO vapors, respectively. The processing method is suitable for the simultaneous preparation of films of different relative content of Co in the MgO insulating matrix. Morphologic, structural and magnetic behaviors were analyzed in as prepared and annealed samples. The influence of the Co content on the magnetic properties of the prepared films was analyzed, in correlation with tunneling magneto-resistance effects. The tunneling magneto-resistance effect is maximal for certain Co content. This behavior was interpreted by the contrary effects of decreasing the average size of the magnetic grains, and hence the average inter-grains distance at higher Co relative content, and the enhanced magnetic disorder in very fine grains dispersed in the insulating matrix. This mechanism was suggested by the comportment of as prepared and thermally annealed samples.

The effects of heating-induced crystallization on the structural and mechanical properties of Mg-Ni-Fe amorphous ribbons were studied by anelastic spectroscopy, differential scanning calorimetry (DSC) and X-ray diffraction. DSC results show that the crystallization occurs through several non-reversible steps, which correspond to significant changes in the Young's modulus and concomitant irreversible elastic energy loss peaks. Moreover, an anelastic peak is found at 215 K, which for the first time indicates the presence of some dynamical process related to the simultaneous presence of different phases. The formation of a metastable Mg(6)Ni phase is detected, which transforms into Mg and Mg(2)Ni stable phases. A quantitative analysis of the different phases present at the different steps was also carried out. (C) 2007 Elsevier B.V. All rights reserved.

Various samples of ferrofluids consisting of colloidal suspensions of surfacted cobalt ferrite or magnetite nanoparticles in water were studied by x-ray diffraction and temperature dependent Mossbauer spectroscopy. Information about the particle mean size, the size dispersion and the effective magnetic anisotropy energy was obtained for each sample. The results are consistent with the formation of a magnetic dead layer at the particle surface, whose thickness depends on the surfactant - ferrite combination. The magnetic relaxation processes are faster in the colloidal suspensions of magnetite particles as compared with the suspensions of cobalt ferrite particles. The type of the surfactant also influences the magnetic relaxation behaviour, and hence the macroscopic properties of the ferrofluid at ambient temperature.

Co-MgO granular films presenting TMR effects were prepared by thermo-ionic vacuum arc method with the simultaneous ignition of plasma in Co and MgO vapors. Morphologic, structural and magnetic behaviors were analyzed in as prepared and annealed samples. The influence of the Co content on the magnetic properties of the prepared films was analyzed, in correlation with tunneling magneto-resistance effects. The tunneling magneto-resistance effect is maximal for certain Co content. This behavior was interpreted by the contrary effects of decreasing the average size of the magnetic grains, and hence the average inter-grains distance at higher Co relative content, and the enhanced magnetic disorder in very fine grains dispersed in the insulating matrix.

Mg-Ni-Fe magnesium-rich intermetallic compounds were prepared following two distinct routes. A Mg88Ni11Fe1 sample (A) was prepared by melt spinning Mg-Ni-Fe pellets and then by high-energy ball milling for 6 h the obtained ribbons. A (MgH2)(88)Ni11Fe1 sample (B) was obtained by high-energy ball milling for 20 h a mixture of Ni, Fe and MgH2 powders in the due proportions. A SPEX8000 shaker mill with a 10:1 ball to powder ratio was used for milling in argon atmosphere. The samples were submitted to repeated hydrogen absorption/desorption cycles in a Sievert type gas-solid reaction controller at temperatures in the range 520 divided by 590 K and a maximum pressure of 2.5 MPa during absorption. The samples were analysed before and after the hydrogen absorption/desorption cycles by X-ray diffraction and Mossbauer spectroscopy. The results concerning the hydrogen storage properties of the studied compounds are discussed in connection with the micro-structural characteristics found by means of the used analytical techniques. The improved kinetics of hydrogen desorption for sample A, in comparison to sample B, has been ascribed to the different behaviour of iron atoms in the two cases, as proved by Mossbauer spectroscopy. In fact, iron results homogeneously distributed in sample A, partly at the Mg2Ni grain boundaries, with catalytic effect on the gas-solid reaction; in sample B, instead, iron is dispersed inside the hydride powder as metallic iron or superparamagnetic iron.

Magnesium-rich Mg-Ni-Fe intermetallic compounds have been prepared by two different routes: (a) short time ball milling of ribbons obtained by melt spinning; (b) long time ball milling of a mixture of MgH2, Ni and Fe powders. The first type of samples displays an hydrogen desorption kinetics better than the second one. Pressure composition isotherm measurements exhibit for both type of samples two plateaux, the lower and wider corresponding to the MgH2 phase and the upper and shorter corresponding to the Mg2NiH4 phase. The presence of the two types of hydrides is confirmed by X-ray diffraction analysis. Mossbauer spectroscopy shows that in melt spun and subsequently milled samples iron is mainly in a disordered structure and segregates after hydrogenation, while in directly milled powders remains mainly unalloyed. After multiple hydrogen absorption/desorption cycles the main part of iron is in metallic state in samples of both types, those of first type preserving better hydrogen desorption kinetics. (c) 2005 Elsevier B.V. All rights reserved.

The ability of the Fe-57 Mossbauer technique to reveal the spin structures in exchange coupled magnetic phases containing iron is emphasized. Experimental results obtained on layered exchange-bias systems are presented. The influence of the ferromagnetic top layer on the out-of-plane spin component of the pinning antiferromagnetic-like layer, in both Fe/FeSn2 and Fe/Fe-Gd-B exchange bias systems, is discussed.

Giant magnetoresistive (GMR) coatings on silicon, glass and Kapton were prepared by simultaneous thermionic vacuum are (TVA) discharges in high vacuum conditions. The magnetic metal or alloy (Fe, Co, Ni, Permalloy) together with the noble non magnetic metal were deposited on substrates having different positions relative to the discharges. Local magnetic interactions and Fe-phase composition were obtained by Mossbauer spectroscopy whereas the magnetoresistance effects were measured by a dc method using a four-point configuration with perpendicular to plane magnetic fields up to 0.8 T. The surface morphology of the coatings was characterized by atomic force microscopy (AFM) in contact mode.

Fe-Ni-Co-Ti shape memory alloys were prepared by various techniques. A comparison between samples prepared by classical metallurgy and by melt spinning technique is performed in respect to the microscopic mechanisms responding for the shape memory effects. X-ray diffraction, thermomagnetic measurements and Mossbauer spectroscopy were applied for a complete structural and magnetic characterization. Only samples supporting an aging treatment gave evidence for shape memory effects and correlated structural transformations.

Local magnetic interactions and spin configurations in alpha-Fe/Nd2Fe14B composite exchange-spring magnets have been investigated by Mossbauer spectroscopy and the magnetic behaviour was analysed by magnetometry. A new method for the evaluation of the coupling strength between soft and hard magnetic phases is proposed. (C) 2003 Elsevier B.V. All rights reserved.

The gamma-Fe2O3 nanoparticles with different surface states are investigated by X-ray Diffraction, Electron Microscopy, Differential Thermal Analysis and magnetic: measurements in low applied field. The influence of the adsorbed species (H2O and sulphate complexes) on the inter-particle magnetic interactions is analysed in relation to both the magnetic states of the surface and the inter-particle distance.