Dr. Alina CRISAN

Recent achievements in ultrafast spin physics have enabled the use of heterostructures composed of ferromagnetic (FM)/non-magnetic (NM) thin layers for terahertz (THz) generation. The mechanism of THz emission from FM/NM multilayers has been typically ascribed to the inverse spin Hall effect (ISHE). In this work, we probe the mechanism of the ISHE by inserting a second ferromagnetic layer in the form of an alloy between the FM/NM system. In particular, by utilizing the co-sputtering technique, we fabricate Fe/L1(0)-FePt/Pt ultra-thin heterostructures. We successfully grow the tetragonal phase of FePt (L1(0)-phase) as revealed by X-ray diffraction and reflection techniques. We show the strong magnetic coupling between Fe and L1(0)-FePt using magneto-optical and Superconducting Quantum Interference Device (SQUID) magnetometry. Subsequently, by utilizing THz time domain spectroscopy technique, we record the THz emission and thus we the reveal the efficiency of spin-to-charge conversion in Fe/L1(0)-FePt/Pt. We establish that Fe/L1(0)-FePt/Pt configuration is significantly superior to the Fe/Pt bilayer structure, regarding THz emission amplitude. The unique trilayer structure opens new perspectives in terms of material choices for the future spintronic THz sources.

Terahertz (THz) spintronic emitters represent a novel class of heterostructures composed of ferromagnetic (FM) and non-magnetic (NM) metallic layers that strongly emit terahertz (THz) radiation upon femtosecond laser pulse excitation. The optimal geometric configuration to maximize the strength of the emission is currently considered a trilayer structure, NM1/FM/NM2, where the FM layer is confined between two NM layers with opposite spin Hall angles. To investigate this, ultrathin Ta/Fe/Pt trilayers are fabricated and their THz emission profiles are analyzed. These results show that the highest THz emission is achieved for the sample of Ta (1.5 nm)/Fe (2 nm)/Pt (2 nm), demonstrating a significant enhancement compared to standard FM/NM bilayers. Furthermore, the thickness dependence of the THz emission is modeled in Ta (t1 nm)/Fe (2 nm)/Pt (t2 nm), varying t1 and t2 from 1 nm to 3 nm. From this analysis, spin diffusion lengths of lambda Pt = 1.2 nm and lambda Ta = 0.85 nm are extracted. The structure-property relationship is assessed via transmission electron microscopy, revealing that an epitaxial single-crystalline Ta layer covers the MgO surface with Ta adopting a high-resistivity fcc allotropic phase with a lattice parameter of a = 0.436 nm. This phase, together with the prerequisite for low Ta+Pt thickness, emerges as a key factor in achieving high THz emission from trilayer structures.

In view of their potential applicability in technology fields where magnets are required to operate at higher temperatures, the class of nanocomposite magnets with little or no rare earth (RE) content has been widely researched in the last two decades. Among these nanocomposite magnets, the subclass of magnetic binary systems exhibiting the formation of L10 tetragonal phases is the most illustrious. Some of the most interesting systems are represented by the Mn-based alloys, with addition of Al, Bi, Ga, Ge. Such alloys are interesting as they are less costly than RE magnets and they show promising magnetic properties. The paper tackles the case of MnGa binary alloys with various compositions around the Mn3Ga stoichiometry. Four MnGa magnetic alloys, with Mn content ranging from 70 at% to 75 at% were produced using rapid solidification to form the melt. By combining structural information arising from X-ray diffractometry and transmission electron microscopy with magnetic properties determined by vibrating sample magnetometry, we are able to document the nature and properties of the structural phases formed in the alloys in their as-cast state and upon annealing, the evolution of the phase structure after annealing and its influence on the magnetic behavior of the MnGa alloys. After annealing at 400 degrees C and 500 degrees C, MnGa alloys are showing a multiple-phase microstructure, consisting of co-existing crystallites of L10 and D022 tetragonal phase. As a consequence of these structurally and magnetically different phases, co-existing within the microstructure, promising magnetic features are obtained, with both coercive fields and saturation magnetization exceeding values previously reported for both alloys and layers of MnGa.

In order to develop the building blocks for future biosensing and spintronic applications, an engraving technique using electron beam lithography is employed in order to develop nanomagnetic pre-patterned structures with logic potential. The paper describes the realization and morphological and magnetic characterization of potentially logic-conditioned substrates, a building block to be further used as an integration platform upon which nanodevices, such as magnetic wires, or various geometrical shapes, circles, triangles, can be considered as pre-requisite for full integration into logic devices. As a proof of concept, regular arrays of FePt circles or magnetic dots were devised and structural characterization by X-ray diffraction and transmission electron microscopy proved the occurrence of the tetragonal L1(0) phase. Moreover, the magnetic characterization provided more insight into the potential of such arrays of magnetic devices as the hysteresis provided good 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 potential applications in various applications.

In the quest for novel rare earth (RE)-free magnetic materials, which also exhibit other additional properties such as good corrosion resistance and potential to operate at higher temperatures, an alloy deriving from the binary FePt system, with Mo and B addition, has been synthesized for the first time, using the out-of-equilibrium method of rapid solidification form the melt. The alloy with the composition Fe49Pt26Mo2B23 has been subjected to thermal analysis through differential scanning calorimetry in order to detect the structural disorder - order phase transformation as well as to study the crystallization processes. For the stabilization of the formed hard magnetic phase, the sample has been annealed at 600 degrees C and further structurally and magnetically characterized by means of X-ray diffraction, transmission electron microscopy, Fe-57 Mossbauer spectrometry as well as magnetometry experiments. It has been proven that after annealing at 600 degrees C the tetragonal hard magnetic L1(0) phase emerges via crystallization from a disordered cubic precursor and becomes the predominant phase in terms of relative abundance. Moreover, it has been revealed by quantitative analysis via Mossbauer spectroscopy that the annealed sample exhibits a complex phase structure, where the L1(0) hard magnetic phase is accompanied by few other soft magnetic phases, in minority abundance: the cubic A1, orthorhombic Fe2B and residual intergranular region. The magnetic parameters have been derived from 300 K hysteresis loops. It was shown that, contrary to the as-cast sample which behaves as a typical soft magnet, the annealed sample presents strong coercivity and high remanent magnetization, accompanied by a large saturation magnetization. These findings offers good insight into the potential developing of novel class of RE-free permanent magnets, based on Fe-Pt-Mo-B, where the magnetic performance emerges from the co-existence of hard and soft magnetic phases in controlled and tunable proportions, capable of finding good applicability in fields requiring good catalytic properties and strong corrosion resistance.

Rare-earth-free permanent magnets with the L1(0) phase are actively researched for their potential as a future class of magnetic materials, capable of operating at higher temperatures and in challenging corrosion environments such as renewable energy applications. Among these classes, MnGa shows potential, being cost effective and having interesting magnetic properties. A MnGa magnetic alloy, with composition Mn73.6Ga26.4 in atomic percent, was produced via the out-of-equilibrium method, and its structural and magnetic properties were assessed using X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and extended magnetic characterization. We show that the MnGa alloy submitted to thermal annealing in optimal conditions exhibits a two-phase microstructure, where small nanocrystals of tetragonal L1(0)/D0(22) magnetic phase are embedded within a D0(19) MnGa matrix of a non-collinear antiferromagnetic nature. These co-existing, magnetically different phases produce an optimal set of promising magnetic properties, larger than the values reported in the literature for single-phase MnGa alloys and thin films. Such large values are explained by the exchange coupling between competing non-collinear magnetic sublattices of the D0(19) MnGa with the net moment of the small magnetic nanocrystals of tetragonal symmetry.

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.

Intermetallic Cr-Al-C thin films from the 211 class of MAX phases were fabricated via ion beam deposition and structural investigations were undertaken to obtain information about morpho-structural effects propelled by carbon excess in the stoichiometry of the films. In order to promote the occurrence of the Cr2AlC MAX phase, the stoichiometric thin films were subsequently annealed at two temperature values: 650 degrees C and 700 degrees C in UHV conditions for 30 min. The morpho-structural effects in both as-deposited and annealed films were monitored using scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. XRD analysis showed that the as-deposited sample was almost completely crystallized in the hexagonal Cr2AlC structure, with a remaining amorphous fraction of about 17%, most probably rich in carbon. Raman analysis allowed the identification of three spectral regions, two of them encompassing the Raman optical modes belonging to the Cr2AlC 211 MAX phase, while the third one gave strong evidence of highly intense and large D- and G-bands of carbon. Structural parameters such as the crystal lattice parameters as well as the volume of the crystal unit cell were found to decrease upon annealing; this decrease is attributed to the grain growth. The average crystallite dimension was proven to increase after annealing, while the lattice micro-strain lowered to approximately 63% in the annealed thin film compared to the as-deposited one. Well-formed and intense Raman peaks attributed to D- and G-bands of carbon were also observed and, corroborated with the structural data, seemed to indicate an overall increased level of crystal ordering as well as potential carbon nanoclustering after thermal treatments with thin Cr2AlC films. This observed phenomenon concords with previously documented reports on ab initio modelling of possible Cr2AlC structures with carbon excess.

A quaternary Fe-Pt-Nb-B alloy has been fabricated by the melt spinning method with the purpose of the formation of crystallographically coherent multiple magnetic phases, emerging from the same metastable precursor, as well as to investigate the phase interactions and the influence of their coupling on magnetic performances. For this purpose, extended structural and magnetic investigations were undertaken by making use of X-ray diffraction, transmission electron microscopy, and Fe-57 Mossbauer spectroscopy, as well as magnetic measurements using SQUID magnetometry. It was documented that intermediate metastable phases formed during primary crystallization, in intermediate stages of annealing, and a growth-dominated mode was encountered for the secondary crystallization stage upon annealing at 700 degrees C and 800 degrees C where fcc Fe3Pt and fct Fe2B polycrystalline were formed. The Mossbauer investigations have documented rigorously the hyperfine parameters of each of the observed phases. The fcc A1 FePt phase was shown to exhibit a peculiar ferromagnetic transition, and this transition has been proven to occur gradually between 300 K and 77 K. The magnetic measurements allowed us to identify the annealing at 700 degrees C as optimal for obtaining good magnetic features. Coercive field dependence shows similarities to the random anisotropy model for samples annealed at 500 degrees C to 700 degrees C which are nanocrystalline. These results show good perspectives for use in applications where different magnetic states are required at different operating temperatures.

The microcrystallization effects induced by the real-time laser annealing in Cr-Al-C ion-sputtered films with an off-stoichiometric composition are studied. The laser annealing has been performed during Raman experiments with tunable laser power densities. Morphostructural changes induced during laser annealing were investigated by scanning electron microscopy. It has been proven that real-time laser annealing in the high-laser-power-density mode promotes quite clearly the formation of nanograins through surface microcrystallization. Detailed Raman analysis allowed for the observation of the optical modes that unequivocally identifies the low-symmetry 211 MAX phase in both low- and high-power-density modes. Such findings confirming the microcrystallization as well as the stabilization of the grain boundaries by carbon nanoclustering are confirmed by X-ray diffraction results, where the single-phase hexagonal 211 was unequivocally proven to form in the high-laser-power-density mode. The microcrystallization via laser annealing was also found to be beneficial for the elastic behavior, as the hardness values between 16 and 26 GPa were found after laser annealing, accompanied by a significantly high Young's bulk modulus. Such large values, larger than those in bulk compounds, are explicable by the nanometric grain sizes accompanied by the increase of the grain boundary regions.

Alloys possessing nominal compositions Mn53Al45C2 and Mn52Al46C2 were prepared by the melt spinning method and were subjected to complex structural, morphological and magnetic investigations. As these alloys can exhibit tetragonal L1(0)-type and tau phase, they have good potential as rare earth (RE)-free magnets. It is, therefore, important to monitor the epsilon-tau phase transformation and the stability and the magnetic features of the tetragonal phase in an entire temperature interval. By using synchrotron X-ray diffraction, it has been proven that the epsilon-tau phase transformation occurs gradually, with the tau phase becoming predominant only after 450 & DEG;C. Moreover, this phase has been proven to be quite stable without any grain growth even at the highest temperature investigated at 800 & DEG;C. Low temperature behavior was thoroughly investigated by using a complex combination of major and minor hysteresis loops combined with the zero field cooled-field cooled magnetization protocols (ZFC-FC). Two different regimes, blocking and superparamagnetic, were documented. A spin reorientation transition was proven to occur at 55 K while a maximum magnetization observed in ZFC-FC curves proved that at about 75 K, a transition from ferro to superparamagnetic state occurs. The existence of a blocking regime below 55 K that is characteristic to nanogranular systems with superparamagnetic behavior has shown further development towards obtaining RE-free magnets.

In order to prove the usefulness of having a structurally disordered precursor to the formation of FePt L1(0) phase and to facilitate the co-existence of exchange coupled hard and soft magnetic phases with optimized magnetic properties in various conditions of annealing, a Fe-Pt-Zr-B melt spun alloy has been synthesized and detailed structural and magnetic investigations have been undertaken to probe its phase evolution during annealing. The dynamics of formation of the hard magnetic L1(0) phase during the gradual disorder-order phase transformation has been monitored by using a complex combination of X-ray diffraction methods and Fe-57 Mossbauer spectroscopy methods, over a wide range of annealing temperatures. Multiple phases co-existing in the annealed sample microstructures, observed in XRD, have been reconfirmed by the Mossbauer spectra analysis and, moreover, accurate quantitative data have been acquired in what concerns the relative abundance of each of the observed crystalline phases in every stage of annealing. It is shown that the formation of the hard magnetic phase, emerging from the chemically disordered precursor, is gradual and occurs via complex mechanisms, involving the presence of a disordered Fe-Zr-B-rich intergranular region which contributes to an increase in the abundance of the L1(0) phase for higher annealing temperatures. Magnetic measurements have confirmed the good performances of these alloys in terms of coercivity and remanence. These results contribute to the development of these alloys as the next generation of rare earth, free permanent magnets.

Melt spun ribbons of Mn53Al45C2 and Mn52Al46C2 have been synthesized by rapid quenching of the melt with the purpose of monitoring the epsilon-tau phase transformation to show technologically feasible ways to increase magnetic parameters and to illustrate the viability of these alloys as the next generation of rare earth (RE)-free magnets. By differential scanning calorimetry (DSC), activation energies and temperatures of onset of the epsilon-tau phase transformation were obtained. Structural analysis was performed using X-ray diffraction (XRD) and the resulting XRD patterns were quantitatively assessed using full profile Rietveld-type analysis. Appropriate annealing was performed in order to enable the epsilon-tau phase transformation. While hcp epsilon-phase was found to be predominant in the as-cast samples, after appropriate annealing, the tetragonal tau-phase, the one that furnishes the relevant magnetic response, was found to be predominant with an abundance of about 90%. The data suggested a mechanism of hcp epsilon-phase decomposition controlled by the segregation towards the interfacial regions, having the rate of transformation governed by antiphase boundary diffusion processes. Magnetic measurements of annealed sample Mn53Al45C2, consisting of predominant tetragonal tau-phase, showed high values of magnetization and increased coercivity, consistent with an energy product of about 10 MGOe, similar with previously reported magnetization measurements, providing further insight into the realization of future class of RE-free low-cost permanent magnets.

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.

Magnetic nanoscale materials exhibiting the L1(0)tetragonal phase such as FePt or ternary alloys derived from FePt show most promising magnetic properties as a novel class of rare earth free permanent magnets with high operating temperature. A granular alloy derived from binary FePt with low Pt content and the addition of Mn with the nominal composition Fe(57)Mn(8)Pt(35)has been synthesized in the shape of melt-spun ribbons and subsequently annealed at 600 degrees C and 700 degrees C for promoting the formation of single phase, L1(0)tetragonal, hard magnetic phase. Proton-induced X-ray emission spectroscopy PIXE has been utilized for checking the compositional effect of Mn addition. Structural properties were analyzed using X-ray diffraction and diffractograms were analyzed using full profile Rietveld-type analysis with MAUD (Materials Analysis Using Diffraction) software. By using temperature-dependent synchrotron X-ray diffraction, the disorder-order phase transformation and the stability of the hard magnetic L1(0)phase were monitored over a large temperature range (50-800 degrees C). A large interval of structural stability of the L1(0)phase was observed and this stability was interpreted in terms of higher ordering of the L1(0)phase promoted by the Mn addition. It was moreover found that both crystal growth and unit cell expansion are inhibited, up to the highest temperature investigated (800 degrees C), proving thus that the Mn addition stabilizes the formed L1(0)structure further. Magnetic hysteresis loops confirmed structural data, revealing a strong coercive field for a sample wherein single phase, hard, magnetic tetragonal L1(0)exists. These findings open good perspectives for use as nanocomposite, rare earth free magnets, working in extreme operation conditions.

This work reports the effect of the Mn substitution, rapid solidification technique and heat treatments on the martensitic transformation, magnetic and magnetostrictive properties on the Fe70-xPd30Mnx (x = 1, 3) ferromagnetic shape memory ribbons. The samples were investigated by X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, magnetic and magnetostrictive measurements. The thermal treatments induce significant changes in the microstructure and magnetocrystalline anisotropy of the martensitic phase, for Fe67Pd30Mn3 compared to Fe69Pd30Mn1. The competition between the magnetization orientation and twin boundary motion within martensitic variants under magnetic field evidenced in the magnetic-strain curves was discussed and correlated with the magnetic data.

With the aim of demonstrating phase coexistence of two magnetic phases in an intermediate annealing regime and obtaining highly coercive FePt nanocomposite magnets, two alloys of slightly off-equiatomic composition of a binary Fe-Pt system were prepared by dynamic rotation switching and ball milling. The alloys, with a composition Fe(53)Pt(47)and Fe55Pt45, were subsequently annealed at 400 degrees C and 550 degrees C and structurally and magnetically characterized by means of X-ray diffraction,Fe-57 Mossbauer spectrometry and Superconducting Quantum Interference Device (SQUID) magnetometry measurements. Gradual disorder-order phase transformation and temperature-dependent evolution of the phase structure were monitored using X-ray diffraction of synchrotron radiation. It was shown that for annealing temperatures as low as 400 degrees C, a predominant, highly ordered L1(0)phase is formed in both alloys, coexisting with a cubic L1(2)soft magnetic FePt phase. The coexistence of the two phases is evidenced through all the investigating techniques that we employed. SQUID magnetometry hysteresis loops of samples annealed at 400 degrees C exhibit inflection points that witness the coexistence of the soft and hard magnetic phases and high values of coercivity and remanence are obtained. For the samples annealed at 500 degrees C, the hysteresis loops are continuous, without inflection points, witnessing complete exchange coupling of the hard and soft magnetic phases and further enhancement of the coercive field. Maximum energy products comparable with values of current permanent magnets are found for both samples for annealing temperatures as low as 500 degrees C. These findings demonstrate an interesting method to obtain rare earth-free permanent nanocomposite magnets with hard-soft exchange-coupled magnetic phases.

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 influence of the Gd3+ co-dopant on the structure, morphology and up-conversion luminescence/magnetic properties of the LiYF4:Gd3+/Yb3+/Er3+ nanocrystals was investigated and compared to those of Gd-free samples. Electron microscopy has indicated an inhibiting effect of the agglomeration and collapsing process of the nanocrystals compared to the Gd-free powder samples. The surface analysis of nanocrystals have not shown oxygen-metal bonds related to the metal oxidation within the surface nanometric layer. The paramagnetic properties are related to the magnetic moment of the Gd3+ ions. The up-conversion luminescence of the LiYF4:Gd3+/Yb3+/Er3+ nanocrystals is about six times stronger than in LiYF4:Yb3+/Er3+ nanocrystals; the enhancement effect is most probably due to the lattice distortion induced by the Gd co-doping.

We report on the formation of the Ti3SiC2 nanolaminate phase in the Ti-Si-C thin film system, using a UHV magnetron sputtering technique with top mounted sample holder, from elemental and compound targets. The formation of the Ti3SiC2 (or 312 phase) has been evidenced by detailed X-ray diffraction analysis followed by full-profile quantitative analysis of the obtained diffractograms. It has been proven that for deposition temperatures as low as 500 degrees C, there is a significant amount of 312 phase obtained in the deposited films, in co-existence with the majority TiC phase. This amount increased to about 21% when the deposition temperature was raised to 650 degrees C. The ternary 312 phase becomes predominant at around 60% relative abundance for slight off-stoichiometric, Si increased, content of the alloy, for temperatures as low as 650 degrees C. The conditions for improving the relative abundance of the 312 phase within our experimental setup are pointed out and explained in terms of a nucleation and growth model of nanostructure formation from the amorphous precursor (?).

A novel class of quaternary intermetallic alloys based on CoPt is investigated in view of their interesting magnetic properties induced by the presence of hard magnetic L1(0) phase. A Co48Pt28Ag6B18 alloy has been prepared by rapid solidification from the melt and subjected to various isothermal annealing procedures. The structure and magnetism of both as-cast and annealed samples as well as the phase evolution with temperature are investigated by means of thermal analysis, X-ray, and selected area electron diffraction, scanning and high-resolution electron microscopy, and magnetic measurements. The X-ray diffraction (XRD) analysis shows that both the as-cast alloy and the sample annealed at 400 degrees C (673 K) have a nanocrystalline structure where fcc CoPt phase predominates. Annealing at 473 degrees C promotes the formation of L1(0) phase triggered by the disorder-order phase transformation as documented in the differential scanning calorimetry results. The sample annealed at 670 degrees C (943 K) shows full formation of L1(0) CoPt as revealed by XRD. Magnetic measurements showed coercivity values ten times increased compared to the as-cast state. This confirms the full formation of L1(0) CoPt in the annealed samples. Moreover, detailed atomic resolution HREM images and SAED patterns show the occurrence of the rarely seen (003) superlattice peaks, which translated into a high ordering of the L1(0) CoPt superlattice. Such results spur more interest in finding novel classes of nanocomposite magnets based on L1(0) phase.

We have undertaken a temperature-dependent, investigation of the thermodynamics, structure, morphology and magnetism of two MnAl nanocomposite alloys (Mn60Al40 and Mn55Al45). Differential scanning calorimetry (DSC) studies allowed the determination of the exo-effects occurring in the structural phase transformation of MnAI, while by using temperature-dependent X-ray diffraction of synchrotron radiation we were able to monitor the phase transformation effects and the evolution with temperature of various structural phases occurring in the samples. We have shown that slight changes in stoichiometry (5 at.%) give rise to different phase structure in the as-cast state. While in Mn60Al40 only hcp epsilon phase can be found, in Mn55Al45 as-cast alloy, there is a quite complex phase structure with a mixture of gamma(2) (Al8Mn5) and epsilon as well as ferromagnetic MnAI T-phase. Activation energies of about 165 kJ/mol and 290 kJ/mol have been calculated from the Ozawa-Flynn-Wall analysis of DSC experimental data. These findings are in good agreement with the results obtained from XRD. For the Mn55Al45 as cast alloy, we have confirmed by temperature-dependent synchrotron XRD that the hcp e phase decomposes through the migration of interphase interfaces with the transformation rate controlled by boundary diffusion processes. High-resolution transmission electron microscopy have confirmed the phase structure obtained by XRD, while magnetic properties, obtained for the as-cast alloys are consistent with the multiphase character of the samples and in good agreement with previously reported results. The magnetization does not saturate for the maximum applied field of about 4 x 10(6) A/m and a marked coercivity of about 160 kA/m is obtained for the Mn55Al45 as-cast alloy.

Ceramic-metallic MAX phase of chromium aluminium carbide ternary compounds was successfully obtained through deposition by DC sputtering onto Si substrates. A study of the influence of substrate temperature and in-air post-annealing on the film crystallinity and oxidation was undertaken. Scanning electron microscopy (SEM), wavelength-dispersive X-ray analysis (WDSX), and X-ray diffraction (XRD) were used for film characterization. It is shown that, at substrate temperature of about 450 degrees C, as-deposited films are amorphous with small nanocrystals. Subsequent annealing in air at 700 degrees C leads to film crystallization and partial oxidation. WDSX spectroscopy shows that the films oxidise to a depth of around 120 nm, or 5% of total film thickness which amounts at around 2.68 mu m. As a novelty, this demonstrates the possibility of in-air crystallization of Cr2AlC films without significant oxidation. Materials Analysis Using Diffraction (MAUD) software package for a full-profile analysis of the XRD patterns (Rietveld-type) was used to determine that, as a result of annealing, the average crystallite size changes from 7 to 34 nm, while microstrain decreases from 0.79% to 0.24%. A slight tendency of preferential growth along the (10 (1) over bar0) direction has been observed. Such texturing of the microstructure has the potential of inducing beneficial anisotropic fracture behaviour in the coatings, potentially interesting for several industrial applications in load-bearing devices.

The elastic and structural properties of thermal barrier coatings of Cr2AlC DC sputtered from elemental targets onto Si(100) substrate at 200 degrees C are studied. The material was subsequently submitted to re-crystallization procedure by annealing the film at 650 degrees C and 700 degrees C in high vacuum and in air for 30 min. As-deposited and annealed films are shown to be homogeneous and dense over large areas. The re-crystallization process was monitored using X-ray diffraction and Raman spectroscopy. As-deposited films have an amorphous-like Cr-C-Al solid solution structure and annealed samples crystallize into single-phase hexagonal Cr2AlC. While XRD analysis and Raman spectroscopy of samples annealed in-air show the presence of 5% Cr2O3, the high vacuum samples annealed at 650 degrees C and 700 degrees C are fully crystallized and comprise only single-phase Cr2AlC hexagonal structure. Oxygen presence in the in-air annealed sample is shown to cause an elongation of the hexagonal unit cell along the c axis which coincides with the direction of stacking of Cr6C octahedral building blocks with alternate Al layers. Whereas the average grain size is shown to increase upon annealing, lattice microstrain, calculated using the integral breadth method, is seen to decrease by almost 70% in the annealed films. Raman spectra of as-deposited films show characteristic MAX-phase bands with broad, overlapping peaks in the region of 120-400 cm(-1) but also peaks in the range of 550-900 cm(-1), attributed to other Raman-active modes of the Cr2AlC structure. After annealing, the Raman peaks corresponding to Cr2AlC single-phase are narrower, more intense and better defined than in the as-deposited case. The occurrence of the disorder-induced D carbon band is observed in the Raman spectrum of the as-deposited film while, after high vacuum annealing, a sharp and relatively intense peak attributed to the carbon G band is observed that suggests that there may be carbon nanoclustering in the coatings upon annealing. This observation is consistent with and comes as a confirmation of previously reported ab initio modelling of possible Cr2AlC off-stoichiometric structures.

In melt-spun FePtB-based ribbons, the addition of Ag has been proven to decrease the temperature of phase transformation from the A1 fcc FePt phase to the hard magnetic tetragonal L1(0) phase. Alloys with 6 and 9 at.% Ag added to the initial FePtB have been synthesized by rapid solidification from the melt. The samples have been laser irradiated and submitted to nitriding procedure. This procedure has been proven beneficial for inducing complete transformation of A1 to L1(0) phase and a strong (001) texturing. Ag segregation combined to mechanisms of creation of vacancies and diffusion of N give rise to the formation of an intergranular disordered region and due to an improved interfacial coupling between FePt grains, enhanced coercivity and two-phase magnetic behavior is obtained.

The double-perovskite Sr2FeMoO6 has been obtained by solid state method at low temperature (1060 degrees C) and a very short time of synthesis (up to 4h). Both, X-ray diffraction and scanning electron microscopy (SEM) confirmed the formation of Sr2FeMoO6 oxide with grain sizes around 160 mm, and a small amount of SrMoO4 as an impurity. Mossbauer spectroscopy revealed a mixed site population with Fe and Mo ions generating a structure type with population inversion. This structure has a critical influence on the magnetic properties, as confirmed by the magnetization and TC values, i.e 3.56 mu(B)/f.u and 415 K, respectively. The Sr2FeMoO6 behavior was interpreted in terms of ferrimagnetic couplings generated by the various distributions of local interactions between Fe and Mo neighbors while comparing the ideal structure should show antiferromagnetic coupling between the two sublattices.

FePt-based alloys are currently under scrutiny for their possible use as materials for perpendicular magnetic recording. Another possible application is in the field of permanent magnets without rare-earths, magnets that may operate at higher temperatures than the classic Nd-Fe-B magnets. Within this study, FeCoPt alloys prepared by rapid solidification from the melt are structurally and magnetically characterized. In the as-cast FeCoPt ribbons, a three-phase structure comprising well-ordered CoFePt and CoPt L1(0) phases embedded in a disordered fcc FePt matrix was evidenced by XRD, HREM and SAED. Extended transmission electron microscopy analysis demonstrates the incipient formation of ordered L1(0) phases. X-ray diffraction was used to characterize the phase structure and to obtain the structural parameters of interest for L1(0) ordering. In the as-cast state, the co-existence of hard magnetic CoFePt and CoPt L1(0) tetragonal phases with the soft fcc FePt phase is obtained within a refined microstructure made of alternatively disposed grains (grain sizes from 1 to 7 nm). Following a thermal treatment of 1 h at 670 degrees C, the soft magnetic fcc matrix phase transforms to tetragonal L1(0) phases (disorder-order transition). The resulting CoPt and CoFePt L1(0) phases have grains of around 5-20 nm in size. In the as-cast state, magnetic measurements show a quite large remanence (0.75 T), close to the value of the parent L1(0) FePt phase. Coercive fields of about 200 kA/m at 5 K were obtained, comparable with those reported for some FePt-based bulk alloys. Upon annealing both remanence and coercivity are increased and values of up to 254 kA/m at 300 K are obtained. The polycrystalline structure of the annealed FeCoPt samples, as well as the formation of multiple c-axis domains in different CoPt and CoFePt regions (which leads to a reduction of the magneto-crystalline anisotropy) may account for the observed coercive fields that are lower than in the case of very thin FeCoPt films. A Curie temperature of about 820 K (close to 550 degrees C) is reported for the Fe35Co15Pt50 alloy which opens wide possibilities for the use of such magnets in high operating temperature industrial applications. The present results indicate that ternary FeCoPt alloys hold a great potential as a novel class of rare earth free exchange-spring coupled nanocomposite magnets. (C) 2015 Elsevier B.V. All rights reserved.

The influence of the heat treatments on the martensitic transformation, magnetic properties and thermo- and magnetic induced strain on Ni50Fe20Ga27Cu3 ferromagnetic shape memory alloy prepared as ribbons by melt spinning technique are investigated. The degree of atomic order as effect of different thermal treatments produces important changes in the magneto-crystalline anisotropy of the martensite phase. The anomalies evidenced in the thermo-and magnetic-strain curves are discussed and correlated with the thermo-magnetic data. The transformation-induced strains with and without magnetic field have been measured, the results setting out the influence of the pre-martensitic transformation. Copyright (C) 2016 The Authors. Published by Elsevier B.V.

The effect of "in situ" thermal treatments (by DSC measurements) on the martensitic transformation in two representative Ni-Fe-Ga and Ni-Mn-Ga alloys has been studied and discussed by correlating the structural and magnetic properties. The alloys were prepared from high purity elements, by arc melting under argon protective atmosphere as bulk and also as melt-spun ribbons - an alternative preparation route that also allows to assess the influences of grains size and strain induced by this processing method. All samples presented reversible thermo-elastic transformations. The thermal treatments promote a reduction of the martensitic transformation temperatures in the Ni-Fe-Ga investigated samples, as opposed to the stoichiometric Ni2MnGa where the temperatures increase with increasing the annealing temperatures. Interestingly however, the off-stoichiometric Ni-Mn-Ga with increased Ni content recovers the behaviour with reduction of transformation temperatures by thermal treatments. The precipitation of the secondary FCC (gamma) phase is inherently found in Ni-Fe-Ga alloys with Ga <= 27% at, and also-although in lower amounts- in the off-stoichiometric Ni-Mn-Ga. The gamma phase is considered to contribute to the decrease of the MT temperatures (via valence electrons concentration depletion of the main matrix) and of the transformation heat as well as to the final structural degradation if the temperature of the thermal treatments is further increased. In addition, this phase, located mainly at the grain boundaries, is responsible for the improved ductility of Ni-Fe-Ga based alloys. Changes in the transformation heat due to thermal treatments are observed and discussed in both types of alloys, the maxima of the transformation heat being associated with the highest atomic order. Thermo-magnetic measurements show that Ni-Fe-Ga alloys have close magnetic and structural transitions temperatures, with promising applications for magnetic refrigeration. Copyright (C) 2016 The Authors. Published by Elsevier B.V.

Influence of Nd substitution for Ni on the magnetic properties and the martensitic transformation (MT) characteristics are investigated on Ni57-xNdxFe18Ga25 (x=0 divided by 4) ferromagnetic shape memory alloys (FSMAs) in bulk and also in ribbons prepared by melt spinning method and subjected to different thermal treatments. Increasing the Nd content induces a decrease of both the Curie and the MT temperatures. (C) 2015 The Authors. Published by Elsevier Ltd.

Nano-composite magnets with L1(0) structure derived from binary FePt alloys and prepared as melt-spun ribbons are of current interest due to their higher operating temperature and the ability to be cast as a two-phase magnet with exchange spring magnetic properties, as both soft and hard magnetic phase may emerge from the same metastable precursor, i.e. the disordered cubic A1 phase. The present paper studies the effect of Mn addition on the thermal stability and phase structure, on the abundance of the hard magnetic phase and relative proportion of the soft ones, on the microstructure of the alloy as a function of temperature and on the overall magnetic properties. The interplay of the various magnetic sublattices in the ordering of the L1(0) phases as a consequence of introducing antiferromagnetically coupled Mn atoms in the alloy composition is discussed and interpreted in terms of microstructural changes induced by this addition as revealed by high resolution transmission electron microscopy and Xray diffraction. The temperature evolution of the phase composition and structural parameters is monitored using synchrotron radiation powder diffraction, while the compositional aspects are investigated using proton-induced X-ray emission and energy dispersive X-ray spectroscopy. Magnetic measurements reveal the magnetic parameters of interest (coercivity, remanence, Curie temperature, saturation magnetization), as well as the exchange-coupled two-phase nature of these magnets and provide information that hints at possible spin reorientation transitions in the Mn-containing planes of the L1(0) superlattice. (C) 2015 Elsevier Ltd. All rights reserved.

Rare-earth free (RE-free) exchange coupling nanocomposite magnets are intensively studied nowadays due to their potential use in applications demanding stable high-temperature operation and corrosion resistance. In this respect, the FePt alloy system is one of the most actively addressed potential permanent magnet solutions. In FePt alloys, promising magnetic features arise from the co-existence of hard magnetic L1(0) FePt and soft magnetic L1(2) Fe3Pt phases emerged from the same metastable precursor. The present work deals with an in-situ temperature-resolved synchrotron radiation study of the thermal stability, thermal expansion and microstructure evolution in exchange-coupled FePtAgB alloys. The as-cast microstructural state as well as the optimized magnetic behavior are given as reference and correlated to the observed microstructural evolution with temperature. The melt-spun Fe48Pt28Ag6B18 alloy ribbons were examined in situ by synchrotron X-ray powder diffraction from ambient temperature up to 600 degrees C. The FePt-Fe3Pt exchange-coupled microstructure achieved by rapid solidification is not significantly altered during the high temperature exposure. The thermal expansion of the FePt L1(0) unit cell has been found to be strongly anisotropic, being essentially an in-plane expansion which may be seen as an anisotropic invar effect. For the FePt L1(0) phase, a significant deviation from linear thermal expansion is observed at the Curie temperature T-C = 477 degrees C. This non-linear behavior above T-C is tentatively linked to a diffusion/segregation mechanism of Ag. The promising hard magnetic properties as well as the direct formation of the L1(0) phase from the as-cast state are directly related to the presence of Ag in the intergranular regions. (C) 2014 Elsevier B.V. All rights reserved.

The effect of thermal treatments on the martensitic transformation in three representative Ni-Fe-Ga alloys with or without Co substitutions has been studied by calorimetry, X-ray diffractometry, scanning electron microscopy and magnetometry. The alloys were prepared as ribbons, by the melt spinning technique. The thermal treatments promote a reduction of the martensitic transformation temperature in all investigated samples, with the most pronounced decrease for the alloys with lower Ga content. Three different mechanisms induced by specific thermal treatments and responsible for the characteristic behaviour of the martensitic transformation, with respect to temperature and heat of transition, were observed and discussed in details. (C) 2015 Elsevier B.V. All rights reserved.

The functionality of the ferromagnetic shape memory alloys is related to the martensitic and magnetic order-disorder transformations, both of which may be tailored by doping with other elements or by suitable thermal treatments, so that alloys with concomitant (or sequential but close) structural and magnetic phase transitions may be obtained. Concerning the magnetocaloric applications, it is assumed that the thin melt-spun ribbons assure a more efficient heat transfer. In the present work we investigate the influence of Co and Al substitutions on magnetocaloric effect characteristics of NiFeGa in bulk and also in ribbons prepared by melt spinning method and subjected to different thermal treatments. X-ray diffraction, differential scanning calorimetry, magnetocaloric and magnetoresistive characterizations have been performed. The results highlight the differences between the bulk and the ribbons (both as prepared and annealed) and the role of substitutions.

The FePt system has important perspectives as high-temperature corrosion-resistant magnets. In the form of rapidly solidified melt-spun ribbons, FePt-based magnets may exhibit in certain cases a two-phase hard-soft magnetic behaviour. The present paper deals with a microstructural and magnetic study of FePtAgB alloys with increasing Ag content. The aim is to identify and confirm the effect of Ag addition in decreasing the temperature of the FePt disorder-order structural phase transformation. A detailed high-resolution transmission electron microscopy study is employed, and the alternative disposal of hard and soft regions within the two-phase microstructure is observed and interpreted with respect to the X-ray diffraction results. In the as-cast Ag-containing samples, it is shown that there is an optimum of the Ag content for which best magnetic properties are obtained. Ag addition creates a nonlinear behaviour of the coercive field and the ordering parameter, similar to the RKKY interaction-induced interlayer exchange coupling (IEC) observed in magnetic layers separated by non-magnetic spacer layers. Direct formation of the L1(0) phase from the as-cast state in the FePtAgB alloys is reported with magnetic parameters compatible to other exchange spring permanent nanomagnets. These findings open novel perspectives into utilization of such alloys in applications requiring magnets operating in high-temperature industrial environments.

The growth of submonolayer metallic or molecular nanostructures via ion beam sputtering onto reconstructed semiconductor surfaces followed by in situ scanning probe imaging of the formed nanostructures provides an interesting basis for future development of new molecular multifunctional nanoarchitectured materials for various applications. The observed growth modes, structure and topology of pentacene, which is one of the most important candidates in the field of organic thin film electronic molecules, and Au metallic nanostructures deposited in the submonolayer regime onto reconstructed InP (0 0 1) surface, are discussed. During the initial stages of growth, a uniaxial diffusion channel dominates, and long pentacene molecular chains self-organise parallel to the [110] crystallographic direction on the InP surface. The study is performed by in situ non-contact atomic force microscopy (AFM) investigations with atomic resolution. It is shown that self-assembling of molecular structures onto flat terraces is dependent on the flatness and orientation of the terraces reconstructed onto the semiconductor surface. Moreover, it is possible to create functional molecular nanoarchitectures by nanomanipulation of single molecules with the AFM tip. This procedure may have large impact for technological applications such as organic thin film transistors and molecular nanowires.

Phase transformation behavior of Ti50Ni30Cu20 shape memory alloys prepared by powder metallurgy is analyzed with respect to the duration of mechanical alloying. The processed blends were studied by differential scanning calorimetry and room temperature X-ray diffraction. The martensitic transformations evidenced by thermal scans are discussed in correlation with the relative phase content obtained from the refinement of the X-ray diffraction patterns. (c) 2011 Elsevier B.V. All rights reserved.

A novel nanocomposite FePt-based exchange-coupled magnet has been synthesized and structurally and magnetically characterized. We report for the first time the direct formation of the L1(0) FePt phase without the need for post-synthesis annealing procedures in Fe-Pt-based melt-spun ribbons, obtained by a conventional melt spinning method. The structure and magnetic properties are investigated and the occurrence of the L1(0) ordered phase in the as-cast state of Fe-Pt-Ag-B melt-spun ribbons is confirmed by XRD and magnetic measurements. A microstructure consisting of fine, uniformly dispersed, 22-24 nm FePt grains dispersed within a soft magnetic matrix is observed by scanning transmission electron microscopy imaging. Coercive fields as high as 727 kAm(-1), saturation magnetization of about 1.2 T and energy product around 87 kJm(-3) are determined from 270 K hysteresis loops of the as-cast ribbons, making one of the best FePt-based nanocomposite magnet ribbons even without further annealing treatments.

Nanostructured powders processed by ball milling of a mixture of Fe and Fe3O4 at room temperature are shown to undergo an incomplete redox reaction with formation of FeO during the milling process. This reaction is favored by the high energy introduced during the mechano-alloying process. Concurrent effects of milling such as grain refinement down to the nanometre scale lead at the end of the milling processes to a mixed multiphase powder of nanograins, with Fe and Fe oxide grains inter-dispersed. We show that in the as-milled Fe/Fe3O4 powder, during milling process, wustite (FeO) is formed as a consequence of the redox reaction. Moreover, with increasing temperature, the system undergoes an inverse phase transformation towards the initial Fe and Fe3O4 phases until about 450 degrees C. Above this temperature the reduction reaction Fe + Fe3O4 = 4FeO is reinitiated, resulting in sharp decrease of Fe and Fe3O4 content from about 550 degrees C and almost complete disappearance of these phases at about 900 degrees C. This transformation was investigated via an energy-dispersive in situ X-ray diffraction experiment using the synchrotron radiation. This study allows direct collection of X-ray patterns after few minutes exposure, at selected temperatures, ranging between 20 degrees C and 1000 degrees C. The structural and magnetic characterizations of the nanograin powders, as-milled and annealed at several temperatures, are studied using XRD, SEM and magnetic measurements. Such ferromagnetic-antiferromagnetic composites are extensively studied as they exhibit exchange bias effect, with a large impact in technological applications. The magnetic behaviour and intrinsic mechanisms leading to the occurrence of exchange bias effects are discussed and related to the samples microstructural features. A significant exchange bias effect, related to FeO content, is observed for as-milled sample, the effect being less pronounced upon annealing the nanograin powder. (C) 2011 Elsevier B.V. All rights reserved.

In core-shell systems with non-magnetic core and magnetic shell the electron transport and magnetic properties are expected to show enhanced behavior due to the particular morpho structural features of the conductive and magnetic regions This may lead to novel advanced GMR materials and spin valves This is the case of core-shell Ag-Co colloidal nanoscale particles that organize into regular arrays An insight on the structure and morphology of the newly synthesized Ag-Co nanoparticles deposited on different substrates will be presented The influence of the substrate on different morphologies and organization dynamics is discussed It is shown that the magnetic behavior of the Ag-Co nanoparticles is highly influenced by the corona-like morphology of Co shell chemical environment of the magnetic atoms and by the fact that they exhibit strongly reduced coordination due to the surface states (C) 2010 Elsevier Masson SAS All rights reserved

A simple and novel method for production of metal clusters as building blocks for nanoscale devices is presented. With this procedure, called the gas / cluster aggregation method, a wide range of clusters may be synthesised and, more important, these clusters may be subsequently modified and functionalized in-situ by adding atoms/molecules of different nature, on the surface of readily formed clusters. The cluster size is extremely well controlled by the vapour pressure of the picked-up species. Moreover, the method is versatile, since it allows multiple pick-up processes within the same rare gas cluster for producing, for example, core-shell nanoparticles with metal core and non-metallic shell or vice-versa, nano-onions, with different species successively attached to the surface of the initial picked-up cluster, and so on. Initial formation of Fe gas-stabilised clusters and core-shell nanoparticles with Fe core and Fe oxide shell, as well as their structure and morphology, are presented and discussed. The core-shell nanoparticles show incipient self-organization into hexagonal cluster superlattice. Structural, magnetic and Mossbauer spectroscopy investigations have been performed on the Fe cluster samples. The magnetic properties of supported Fe clusters show marked differences compared to the bulk. A small hysteresis is observed in the parallel applied field while in the perpendicular case, lack of saturation at the highest applied field is noticed. Such behaviour has been also observed in FeRh [1] and AgCo [2] bimetallic nanoparticles. This behaviour marks the occurrence of a strong planar magnetic anisotropy in the sample and may also be a consequence of increased surface spin disorder and finite size effects, which are typical for nanoparticles in the reported size range.

The FePtNbB alloys are of interest as a new class of exchange spring magnets. In strictly defined compositional range and after proper conditions of annealing, they develop a microstructure made of small nanograins of hard and soft magnetic phases alternatively disposed and coupled through exchange interactions. Taking advantage of the high uniaxial aniosotropy of the tetragonal hard magnetic FePt phase and high saturation magnetization of the cubic soft magnetic FePt phases, an exchange coupled nanocomposite magnet can be derived. A compositional study of FePtNbB alloys is provided in order to understand the role of each additional element. The possibility of casting alloys where two or more magnetic phases can be obtained is discussed in terms of the eutectic point of the FePt phase diagram. Also, the formation and evolution of the magnetic phases is studied by differential scanning calorimetry (DSC) and detailed analysis of these DSC scans is provided. Activation energy determined from DSC scans provides essential informations about crystallization and disorder-order phase transformation in these alloys.

A FePt-based hard-magnetic nanocomposite of exchange spring type was prepared by isothermal annealing of melt-spun Fe52Pt28Nb2B18 (atomic percent) ribbons. The relationship between microstructure and magnetic properties was investigated by qualitative and quantitative structural analysis based on the x-ray diffraction, transmission electron microscopy, and Fe-57 Mossbauer spectrometry on one hand and the superconducting quantum interference device magnetometry on the other hand. The microstructure consists of L1(0)-FePt hard-magnetic grains (15-45 nm in diameter) dispersed in a soft magnetic medium composed by A1 FePt, Fe2B, and boron-rich (FeB)PtNb remainder phase. The ribbons annealed at 700 degrees C for 1 h exhibit promising hard-magnetic properties at room temperature: M-r/M-s=0.69; H-c=820 kA/m and (BH)(max)=70 kJ/m(3). Strong exchange coupling between hard and soft magnetic phases was demonstrated by a smooth demagnetizing curve and positive delta M-peak in the Henkel plot. The magnetic properties measured from 5 to 750 K reveals that the hard characteristics remains rather stable up to 550 K, indicating a good prospect for the use of these permanent magnets in a wide temperature range. (C) 2010 American Institute of Physics. [doi:10.1063/1.3504245]

Fe / Fe3O4 (magnetite) powders obtained by ball milling at room temperature, undergo an incomplete redox reaction with formation of FeO. This reaction is favoured due to the high energy developed during the milling and alloying. Concurrent effects of the milling, such as grain refinement down to the nanometric scale lead at the end of the milling processes to a mixed multiphased nanopowder, with a homogeneous dispersion of Fe and Fe oxide grains. Such ferromagnetic - antiferromagnetic systems are extensively studied due to their exchange bias properties, extremely useful in technological applications. We study the phase transformation that leads to a multiphased metal / oxide microstructure with an energy-dispersive in-situ X-ray diffraction experiment using the synchrotron radiation. This study allows direct collection of X-ray spectra after few minutes exposure, at selected temperatures, ranging between 20 degrees C and 1000 degrees C. Magnetic behavior has been studied for as-milled and annealed samples and the obtained magnetic parameters are correlated to the microstructure and phase composition at each stage of annealing. A significant exchange bias effect, related to FeO content, is observed for as-milled sample, the effect being less pronounced upon annealing the nanogranular powder.

Fe-Pt alloys have gained much interest for the occurrence of permanent magnetic features resulting from the L1(0) ordered face-centred-tetragonal FePt phase with very high magnetic crystalline anisotropy (7x10(6) J/m(3)). An amorphous melt spun ribbons of the composition Fe51Pt27Nb2B20 has been synthesized by the rapid solidification technique and its microstructure and magnetic properties were studied. After appropriate annealing, an ordered face-centred-tetragonal (f.c.t.) L1(0) phase is formed. X-ray analysis revealed a structural phase transformation from the body-centered-cubic Al to f.c.t. L1(0) phase and this produce magnetic hardening of the alloy, upon appropriate annealing conditions. Extremely performant magnetic properties, typical for exchange spring magnets, are obtained.

Fe-Pt system is nowadays widely studied due to its potential applications as magnetic recording media. The hard magnetic FePt L1(0) phase has extremely promising potential as permanent magnet with high magnetocrystalline anisotropy. Of recent interest is also the developing of the hard magnetic phase from an amorphous precursor by appropriate crystallization processes. The melt-spun amorphous Fe68Pt13Nb2B17 alloy has been submitted to dynamical annealing and its phase transformation during the process has been monitored by differential scanning calorimetry and in situ energy-dispersive X-ray diffraction of the synchrotron radiation. In the first stage of crystallization, alpha-Fe and cubic FePt phases are formed from the amorphous precursor. At around 600 degrees C superlattice Bragg reflections corresponding to tetragonal FePt are indexed in the XRD spectra and a-Fe phase diminishes drastically. Finally, between 900 degrees C and 975 degrees C the tetragonal superlattice peaks disappear and cubic FePt phase is formed again. This reversible order-disorder transformation is accompanied by a strong uniaxial lattice expansion of the cubic FePt unit cell. The system show promising features for the co-existence of hard and soft exchange coupled magnetic phases crystallized from FePt-based amorphous precursors. (c) 2006 Elsevier B.V. All rights reserved.

The Fe-Pt-rich alloys has recently attracted a lot of interest for their potential development of the hard magnetic L1(0) (also denoted gamma(1)) FePt phase with high magnetocrystalline anisotropy. An alloy with the nominal composition Fe65Pt25Nb2B8 has been synthesised by rapid quenching of the melt. The phase evolution in the as-cast ribbons was monitored by energy dispersive X-ray diffraction of the synchrotron radiation. It is shown that the Fe65Pt25Nb2B8 alloy is completely crystallized in the as-cast state. With increasing temperature a partial disorder-order phase transformation with occurrence of hard magnetic L1(0) phase is observed. This transformation is directly related to thermal and pressure effects in the sample. With applying pressure, the phase transformation between cubic and tetragonal FePt symmetry is more pronounced and is accompanied by a strong uniaxial lattice expansion. The results are extremely promising for the direct formation from the melt of an exchange coupled hard-soft magnetic alloy with initial formation of the tetragonal hard magnetic L1(0) FePt phase. (C) 2006 Elsevier B.V. All rights reserved.

Intermetallic Fe-Pt-Nb-B alloys with 3 different compositions have been synthesized by rapid solidification technique and their phase structure was characterized by means of X-ray diffraction and Mossbauer spectrometry. It is shown that Fe68Pt21Nb2B9 and Fe65Pt25Nb2B8 as-east samples consist mainly of A1 soft magnetic f.c.c. Fe-Pt phase, while the Fe68Pt13Nb2B17 as-cast sample exhibits topological short-range order, typical for amorphous ribbons. Crystallization processes in the amorphous sample and phase evolution with the temperature have been studied using differential scanning calorimetry (DSC). The occurrence of exothermic peaks is related to structural transformations in the alloys and the crystallization process is shown to be highly dependent upon the heating rate in the DSC process. (C) 2006 Elsevier B.V. All rights reserved.

The crystallization processes that occur in amorphous melt-spun ribbons of nominal composition Fe73.5Cu1Nb3Si13.5B9 with Gd addition in different concentrations are studied by differential scanning calorimetry (DSC). The aim of Gd addition is to study the changes induced in the calorimetric behavior of Finemet alloys, the crystallization sequences at intermediate stages of annealing as well as the nature of obtained crystallization products. The nature and structural properties of the phases formed at the end of the calorimetric process are investigated using X-ray diffraction (XRD) and Mossbauer spectrometry (MS). The crystallization sequence and also the phase composition at different stages of annealing were investigated for the Fe68.5Gd5Cu1Nb3Si13.5B9 alloy. Structure and magnetic properties of resulting crystallized samples have been thoroughly investigated. It is shown that in the above-mentioned composition, the decomposition at around 690 degrees C of the metastable Gd3Fe62B14 phase formed at incipient stages of crystallization leads to the co-existence of Gd2Fe14B, Fe2B and alpha-Fe(Si) phases. Magnetic measurements of as-cast and annealed samples are in good agreement with the XRD and MS results and with the proposed crystallization sequences and decomposition of intermediate metastable phases. (c) 2005 Elsevier B.V. All rights reserved.

The magnetic properties of FINEMET-type nanocrystalline alloys and isolated ferromagnetic AgCo nanoparticles are investigated both experimentally and numerically. Theoretical models of spins that simulate ideal nanocrystalline alloys and isolated nanoparticles are considered while their magnetic properties are derived from Monte Carlo simulation of low-temperature spin ordering. Interesting features such as magnetic polarization of the matrix due to penetrating fields arising from nanograins and the role played by the crystalline fraction in the overall L magnetic behaviour, in the case of nanocrystalline alloys are investigated. For isolated nanoparticles it is shown that the competition between surface and bulk anisotropy gives rise to surface spin disorder that, together with finite-size effects, is responsible for the experimentally observed lack of saturation of the magnetization in high applied fields. These simulation results are confirmed by experimental data obtained on FINEMET nanocrystalline alloys and isolated ferromagnetic AgCo colloidal nanoparticles.

Colloidal solutions of magnetic nanoparticles are regularly dispersed onto patterned substrates in order to form novel magnetic nanostructures. The morphology of these nanostructures is investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM) and their structure is correlated with magnetic properties. It is shown that, depending on the nature of the substrate, different nanoparticle growth modes are identified during the colloidal crystallization. (C) 2003 Elsevier B.V. All rights reserved.

The effect of rare earth addition in the structure and magnetism of melt spun nanocrystalline Finemet-type alloys devitrified from amorphous precursor ribbons is discussed. Starting with the initial composition Fe73.5Cu1Nb3Si13.5B9 an amount of 5 at% Gd is introduced into the primary alloy. The purpose is to enable after appropriate recrystallization the occurrence of hard and soft magnetic, suitably dispersed, exchange-coupled nanograins and to determine the transformation sequences of the crystallization process and the obtained crystallization products. (C) 2003 Elsevier B.V. All rights reserved.

The melt spun nanocrystalline alloys such as Fe73.5Cu1Nb3Si13.5B9 (FINEMET) have attracted great deal of interest in recent years due to their excellent soft magnetic properties mostly related to the exchange coupling between nanograins, through the amorphous matrix. The microstructural evolution of both nanocrystalline and amorphous residual phases during annealing of the ribbons give rise to crystallization products that determine the expected magnetic properties for specific applications. Upon addition of the rare earth (RE), the evolution of the crystalline phases which emerge from metastable precursors during annealing is investigated. It is expected that the RE presence should strongly modify both the phase structure via new ternary metastable precursors and the magnetic properties of the ribbons by inducing enhanced exchange correlation due to novel ternary crystalline phases.

Mossbauer spectrometry and magnetic measurements are employed to experimentally investigate the magnetic behavior of nanocrystalline Fe73.5Cu1Nb3Si13.5B9 ribbons obtained by appropriate annealing of the amorphous precursor. A detailed analysis of the correlation between the microstructure of annealed samples and their magnetic properties is provided. Thermomagnetic data allow the Curie temperatures of both amorphous residual matrix and nanocrystalline phase to be estimated. The differences between Curie temperatures of amorphous residual matrix and amorphous precursor are investigated and explained in terms of magnetic polarization of the matrix by exchange fields arising from the nanocrystalline grains. Theoretical systems of spins consisting of a single ferromagnetic nanocrystalline grain immersed in weakly ferromagnetic environment, quite similar to our real samples, are considered and their magnetic behavior is investigated by Monte Carlo simulation of low temperature spin ordering, with emphasize on the matrix-nanocrystalline grain interface which is shown to exhibit peculiar magnetic behavior. The magnetic features of the matrix-nanocrystalline grain interface are studied, as depending on matrix-nanocrystalline grain exchange coupling as well as crystalline fraction of the nanocrystalline systems.

Recent developments of lithographic techniques as well as improved chemical synthesis methods allow researchers to engineer novel nanostructured materials consisting of arrays of self-organized nanocrystals and multilayers grown as patterns on different substrates. In our case, the magnetic nanostructures consist either of multilayers directly deposited on pre-patterned substrates to form regular arrays of stripes and grooves or colloidal solutions of self-organized bimetallic Ag/Co nanoparticles on patterned and nonpatterned substrates. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed in order to study the surface morphology of the 2D patterning arrays and the 3D nanostructures. The development of periodic arrays of magnetic patterns of micrometer size is strongly dependent on technological parameters such as: film, thickness, distances, size and shape of the patterns. Moreover, it is shown that the substrate morphology significantly affects the colloidal crystallization of magnetic nanoparticles and leads to different growth modes. This will ultimately affect the overall magnetic behavior of the nanostructures. Consequently, the combination of self-assembly and patterning allows for the controlled fabrication of the novel magnetic nanostructures at a macroscopic level and the study of fundamental aspects in magnetism such as quantum tunneling magnetization and magneto-transport properties along well-defined nanosized patterns. (C) 2003 Elsevier B.V. All rights reserved.