National Institute Of Materials Physics - Romania

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.

Distribution of magnetic relaxation time using Mossbauer spectroscopy has been observed for CoFe2-xCrxO4 (0.1 <= x <= 0.4) annealed at lower temperature (<= 400 degrees C). The estimated cation distribution over A and B sites observed by Mossbauer spectroscopy is consistent with that obtained by the Rietveld analysis of the X-ray diffraction patterns. Saturation magnetization and magnetocrystalline anisotropy constant increase up to 20% of Cr (x = 0.2) substitution and, decrease with further increase of x. However, the coercive field as well as the Neel temperature decreases with increase in Cr3+ concentration, i.e., a crossover from the hard magnetic to soft magnetic nature by Cr substitution at the Fe site of CoFe2O4 has been observed. This behavior is attributed to the competition between strain induced magnetism and superexchange interaction between cations. (C) 2018 Elsevier B.V. All rights reserved.

Four Ge-based organometallic (OM = C6H10 Ge2O7) polymers with similar chemical composition were used as additions for MgB2. MgB2 (OM) 0.0014 dense samples with a relative density higher than 97% were obtained by ex situ spark plasma sintering. The critical current density and the irreversibility magnetic field of the added samples are slightly improved at high magnetic fields by repagermanium (Alfa Aesar) addition when compared to the pristine reference sample. Addition of Ge-straight-chain polymer shows some improvement of the maximum volume pinning force, F-p (max). There is no significant Ge substitution in the crystal lattice of MgB2, while C substitutes for B. Pinning mechanism is mainly of a point pinning type, with the grain boundary pinning mechanism strengthening at lower temperatures and when additives are not used. A relatively high amount of carbon in the samples washes out the Ge effects on pinning-force-related parameters. The structure and morphology of the polymer additive play an important role in dispersion when mixing, impacting the quality of the superconducting properties. The nanosize dimension of the pristine MgB2 powder shows also some drawbacks in mixing and sintering.

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.

New magneto-optical vitreous materials were obtained by melting-quenching technique comprising wet route raw materials preparation. The glass has the following composition in oxide mol. % 10 Li2O, 9 Al2O3, 5 ZnO, (35; 20; 50) B2O3,,(35; 50; 20) P2O5, 3 Bi2O3, 3 PbO, phosphorus and boron oxide being the vitreous network formers. It was also prepared a similar reference glass composition but without Bi2O3 and PbO. Optical and structural characterization by ultraviolet-visible (UV-Vis), Fourier Transform Infrared (FTIR) and Raman Spectroscopy of the bulk glasses showed a transmission over 90%, metaphosphate structure of glass together with Q(2) boron oxide units and P-O-B bonds. The mechanical parameters, hardness (H), Youngs modulus (E) and fracture toughness (KO of boron phosphate glasses, evaluated by micro- and nanoindentation techniques, demonstrated mostly higher values in comparison with those for alumino-phosphate glasses due to mixed borophosphate network. Thermal behavior was investigated by Differential Scanning Calorimetry (DSC) putting in evidence the vitreous transition temperature which decreases with about 45 degrees C when Bi and Pb oxides were added and two crystallization effects. The diamagnetic character of a highly transparent Bi and Pb oxide co doped boron phosphate glass was confirmed by ellipsometry, and the glass presented high magneto-optical properties at the top of the commercial bulk products.

Four batches of cerium oxide powders (with nanocrystallite size of 6.9 nm-572 nm) were prepared from four precursor nanopowders by thermal decomposition of Ce-propionate and annealing in air between 250 degrees C-1200 degrees C for 10 min-240 min. Ceria formation reactions, structure, vibrational, luminescence and magnetic properties were investigated by differential scanning calorimetry, x-ray diffraction, electron microscopy, infrared spectroscopy, photoluminescence and SQUID. All the samples exhibit room temperature ferromagnetism, RTFM, (with coercivity, H-c, of 8 Oe - 121 Oe and saturation magnetization, M-s, of up to 6.7*10(-3) emu/g) and a broad defect-related photoluminescence, PL, emission in the visible range. The samples derived from the same precursor show M-s proportional to the peak area of defect-related PL emission whereas this is not valid for the samples derived from the different precursors. An improvement of ferromagnetism and intensity of defect-related PL emission was observed when annealing the products in which nanocrystalline cerium oxide coexists with Ce - oxicarbonate traces, Ce2O2CO3. The experimental results were explained based on the following considerations: room temperature ferromagnetism was induced by the defective ceria with high concentration of oxygen vacancies generated by decomposition of Ce-propionate; oxygen vacancies of the starting precursor nanopowders could be redistributed (at the surfaces/grain boundaries, GBs) upon heating under conditions that promote an inert local environment; the decomposition of Ce2O2CO3 residues can provide an excess of oxygen vacancies at the nanoparticles surfaces or GBs, which can induce or enhance ferromagnetism; surfaces/GBs rather than bulk defects appear responsible for RTFM - this can explain the (often reported in literature) inconsistency between oxygen vacancies concentration and M-s. (C) 2018 Elsevier B.V. All rights reserved.

Small samples of 12.5 mm in diameter made from pure tungsten were exposed to a dense plasma jet produced by a coaxial plasma gun operated at 2 kJ. The surface of the samples was analyzed using a scanning electron microscope (SEM) before and after applying consecutive plasma shots. Cracks and craters were produced in the surface due to surface tensions during plasma heating. Nanodroplets and micron size droplets could be observed on the samples surface. An energy-dispersive spectroscopy (EDS) analysis revealed that the composition of these droplets coincided with that of the gun electrode material. Four types of samples were prepared by spark plasma sintering from powders with the average particle size ranging from 70 nanometers up to 80 mu m. The plasma power load to the sample surface was estimated to be 4.7 MJ m(-2) s(-1/2) per shot. The electron temperature and density in the plasma jet had peak values 17 eV and 1.6 x 10(22) m(-3), respectively. (C) 2017 National Institute for Laser, Plasma, and Radiation Physics (INFLPR). Published by Elsevier B.V. All rights reserved.

Synthesis and characterization of iron oxide nanoparticles coated with a large molar weight dextran for environmental applications are reported. The first experiments involved the synthesis of iron oxide nanoparticles which were coated with dextran at different concentrations. The synthesis was performed by a co-precipitation technique, while the coating of iron oxide nanoparticles was carried out in solution. The obtained nanoparticles were characterized by using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction spectrometry, Fourier transform infrared spectroscopy and superconducting quantum interference device magnetometry. The results demonstrated a successful coating of iron oxide nanoparticles with large molar weight dextran, of which agglomeration tendency depended on the amount of dextran in the coating solution. SEM and TEM observations have shown that the iron oxide nanoparticles are of about 7 nm in size.