A study of the influence of crystallite size on the electrical and magnetic properties of CuFe2O4

An attempt has been made to clarify the fundamental assumption that the properties of materials change as the crystallite size of the material is reduced below 100 nm. CuFe₂O₄ samples of different crystallite sizes were prepared by the sol–gel and combustion methods and then analyzed by X-ray diffraction (XRD), thermal analyses (TGA/DTG) and scanning electron microscopy (SEM) techniques. The magnetic properties were studied by measuring the AC magnetic susceptibility (χ) and the Mössbauer spectroscopy. The DC electrical resistivity, dielectric constant, dielectric loss tangent, Curie temperature and hyperfine splitting of the samples change with the crystallite size. The change in the electrical properties is attributed to the formation of discrete energy levels instead of the bands. However, the magnetic parameters change due to the existence of non magnetic surface layers. The isomer shift and the hyperfine splitting show gradual increase with the increase in crystallite sizes.     

Synthesis, structure and magnetic properties of a new iron phosphonate-oxalate with 3D framework: [Fe(O3PCH3)(C2O4)0.5(H2O)]

A new iron phosphonate-oxalate [Fe(O₃PCH₃)(C₂O₄)_0.5(H₂O)] (1), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction studies reveal that 1 consists of layers of vertex-linked FeO₆ octahedra and O₃PC tetrahedra, which are further connected by bis-chelate oxalate bridges, giving to a 3D structure with 10-membered channels. Crystal data: monoclinic, P2₁/n (no. 14), a = 4.851(2) Å, b = 16.803(7) Å, c = 7.941(4) Å, β = 107.516(6)°, V = 617.2(5) Å³, Z = 4, R₁ = 0.0337 and wR₂=0.0874 for 1251 reflections [I > 2σ(I)]. Mössbauer spectroscopy measurement confirms the existence of high-spin Fe(III) in 1. Magnetic studies show that 1 exhibits weak ferromagnetism with T_N = 30 K due to a weak spin canting.     

Phase transformation and the mechanism of combustion synthesis of ZnFe2O4 ferrite powders

The reaction mechanism of combustion synthesis of zinc ferrite, which belongs to the complex oxide combustion reaction was investigated using a combustion front quenching method (CFQM). Phase transformation and microstructural evolution of the quenched samples were observed by XRD, SEM, and Mössbauer spectroscopy. The results showed that the combustion proceeded by a dissolution-precipitation mechanism, viz the iron was burned to form Fe₂O₃ in an oxygen atmosphere and melting of the Fe₂O₃ led to the dissolving of the ZnO particles, then ZnFe₂O₄ precipitated out. In addition, a model of the mechanism was drawn.     

Nanocrystallization kinetics of amorphous Fe81B13.5Si3.5C2 magnetic ribbons

The kinetics of the nanocrystallization of amorphous Fe₈₁B_13.5Si_3.5C₂ ribbon is studied. The changes in the microstructures and magnetic properties of ribbons annealed at 425 and 495 °C for 0.5-10 h were investigated using an X-ray diffractometer (XRD), Mössbauer spectroscopy (MS), differential scanning calorimeter (DSC) and vibrating sample magnetometer (VSM). The changes in the surface morphology were observed by a changed atomic force microscope (AFM). The XRD patterns and the Mössbauer spectrums show the formation of nanocrystallites of α-Fe(Si), Fe-B, Fe₃C and Fe₃Si of different grain sizes when annealed at different temperatures. The nanocrystallization kinetics of the Fe₈₁B_13.5Si_3.5C₂ ribbon are described by an Avrami growth curve with an exponent values of 1.34 and 1.01 for the isothermal annealing at 425 and 495 °C, respectively. AFM topography pictures and surface image show that the density of the microstructure and the size of the grain increase as higher annealing temperatures are used.     

Iron-stabilized nanocrystalline ZrO2 solid solutions: Synthesis by combustion and thermal stability

The synthesis of Fe³⁺-stabilized zirconia by the nitrate/urea combustion route was investigated. Using several characterization techniques, including X-ray diffraction, field-emission-gun scanning electron microscopy and notably Mössbauer spectroscopy, it was possible to determine the appropriate amount of urea that allows to obtain a totally stabilized Zr_0.9Fe_0.1O_1.95 solid solution. The nanocrystalline zirconia solid solution is mostly tetragonal, but the presence of the cubic phase could not be ruled out. An in-depth study of the thermal stability in air showed that the Fe³⁺ solubility in the stabilized solid solution starts to decrease at about 875 °C which results in the formation of hematite (possibly containing some Zr⁴⁺) at the surface of the zirconia grains and further provokes the progressive transformation into the monoclinic zirconia phase.     

Structural characterization, thermal, spectroscopic and magnetic studies of the (C3H12N2)0.75[Mn1.50Fe1.50(AsO4)F6] and (C3H12N2)0.75[Co1.50Fe1.50(AsO4)F6] compounds

The (C₃H₁₂N₂)_0.94[Mn_1.50Fe_1.50^III(AsO₄)F₆] and (C₃H₁₂N₂)_0.75[Co_1.50Fe_1.50^III(AsO₄)F₆] compounds 1 and 2 have been synthesized using mild hydrothermal conditions. These phases are isostructural with (C₃H₁₂N₂)_0.75[Fe_1.5^IIFe_1.5^III(AsO₄)F₆]. The compounds crystallize in the orthorhombic Imam space group. The unit cell parameters calculated by using the patterns matching routine of the FULPROOF program, starting from the cell parameters of the iron(II),(III) phase, are: a = 7.727(1) Å, b = 11.047(1) Å, c = 13.412(1) Å for 1 and a = 7.560(1) Å, b = 11.012(1) Å, c = 13.206(1) Å for 2, being Z = 8 in both compounds. The crystal structure consists of a three-dimensional framework constructed from edge-sharing [M^II(1)₂O₂F₈] (M = Mn, Co) dimeric octahedra linked to [Fe^III(2)O₂F₄] octahedra through the F(1) anions and to the [AsO₄] tetrahedra by the O(1) vertex. This network gives rise two kinds of chains, which are extended in perpendicular directions. Chain 1 is extended along the a-axis and chain 2 runs along the c-axis. These chains are linked by the F(1) and O(1) atoms and establish cavities delimited by eight or six polyhedra along the [1 0 0] and [0 0 1] directions, respectively. The propanediammonium cations are located inside these cavities. The thermal study indicates that the structures collapse with the calcination of the organic dication at 255 and 285 °C for 1 and 2, respectively. The Mössbauer spectra in the paramagnetic state indicate the existence of two crystallographically independent positions for the iron(III) cations and a small proportion of this cation in the positions of the divalent Mn(II) and Co(II) ones. The IR spectrum shows the protonated bands of the H₂N- groups of the propanediamine molecule and the characteristic bands of the [AsO₄]³⁻ arsenate oxoanions. In the diffuse reflectance spectra, it can be observed the bands characteristic of trivalent iron(III) cation and divalent Mn(II) and Co(II) ones in a distorted octahedral symmetry. The calculated Dq and B-Racah parameters for the cobalt(II) phase are 710 and 925 cm⁻¹, respectively. The ESR spectra of compound 1 maintain isotropic with variation in temperature, being g = 1.99. Magnetic measurements for both compounds indicate that the main magnetic interactions are antiferromagnetic in nature. However, at low temperatures small ferromagnetic components are detected, which are probably due to a spin decompensation of the two different metallic cations. The hysteresis loops give values of the remnant magnetization and coercive field of 84.5, 255 emu/mol and 0.01, 0.225 T for phases 1 and 2, respectively.     

Mössbauer and magnetic studies of Mg1+2xSbxFe2−3xO4 spinel ferrites

Spinel-related Mg_1+2xSb_xFe_2−3xO₄ samples (x = 0.0, 0.05, 0.10, 0.15, 0.20, and 0.30) prepared using the conventional double sintering technique were investigated using ⁵⁷Fe Mössbauer spectroscopy and magnetic measurements. Mössbauer spectra favor a cationic distribution of the form (Mg_δFe_1−δ)^A[Mg_1+2x−δSb_xFe_1+δ−3x]^BO₄ among the tetrahedral-A and octahedral-B sites of the spinel structure. The cation distribution parameter (δ) was found to vary with the Sb⁵⁺ concentration (x). The Mössbauer hyperfine magnetic fields at both sites and the Curie temperatures of the ferrites decrease as x increases. This was attributed to gradual weakening in the magnetic exchange interaction as more Fe³⁺ ions are substituted by diamagnetic Sb⁵⁺ and Mg²⁺ ones. The sample with x = 0.30 exhibits short range magnetic order due to cationic clustering and/or superparamagnetism. The magnetization of all samples was found to be temperature-dependent implying that δ depends on temperature in addition to x. At low temperatures the substituted ferrites (x ≠ 0.0) unexpectedly exhibit higher magnetization values relative to that of the pure ferrite MgFe₂O₄. This behavior, while at variance with the Néel's model for ferrimagnetism, is explicable in terms of the spin canting mechanism proposed in the Yafet–Kittel model.     

Hydrothermal synthesis, characterization and magnetic properties of NaVGe2O6 and LiVGe2O6

Supercritical fluids are shown to be an excellent reaction media for the synthesis of novel solid state phases at intermediate temperatures. LiVGe₂O₆ and NaVGe₂O₆ have the common pyroxene structure composed of VO₆ linear chains. NaVGe₂O₆ crystallizes in the monoclinic space group C2/c with four formula units having cell dimensions a = 9.960(4) Å, b = 8.853(10) Å, c = 5.4861(10) Å, β = 106.403(3)°. The structure was refined until R = 0.0290 and R_w = 0.0370. For LiVGe₂O₆ in space group P2₁/c: a = 9.8508(7) Å, b = 8.754(3) Å, c = 5.3948(13) Å, β = 108(3)°, R = 0.0240 and R_w = 0.0250. The compounds contain edge-shared VO₆ octahedral chains and corner-shared GeO₄ tetrahedral chains. The presence of these VO₆ chains results in spin-Peierls distortion. Structural and physical characterization of the compounds are reported.     

Study on properties of CaO-SiO2-B2O3 system glass-ceramic

Low temperature co-fired ceramic (LTCC) is prepared by sintering a glass selected from CaO-SiO₂-B₂O₃ system, and its sintered bodies are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). It is found that the optimal sintering temperature for this glass-ceramic is 820 °C for 15 min, and the major phases of this material are CaSiO₃, CaB₂O₄ and SiO₂. The glass-ceramic possesses excellent dielectric properties: ?_r = 6.5, tan δ < 2 × 10⁻³ at 10 MHz, temperature coefficient of dielectric constant about −51 × 10⁻⁶ °C⁻¹ and coefficient of thermal expansion about 8 × 10⁻⁶ °C⁻¹ at 20-400 °C. Thus, this material is supposed to be suitable for the tape casting process and be compatible with Ag electrode, which could be used as the LTCC materials for the application in wireless communications.     

Structural, thermal, magnetic and electrical studies of the iron oxophosphate Rb7Fe7(PO4)8O2·2H2O

A new iron oxophosphate of composition Rb₇Fe₇(PO₄)₈O₂·2H₂O has been synthesized and studied by X-ray diffraction, TG and DTA analysis, magnetic susceptibility, neutron diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic system with the P2₁/c space group and the unit cell parameters a = 8.224(8) Å, b = 22.162(6) Å, c = 9.962(6) Å and β = 109.41(8)°. Its structure is built up from Fe₇O₃₂ clusters of edge- and corner-sharing FeO₅ and FeO₆ polyhedra. Neighboring clusters are connected by the phosphate tetrahedra to form a three-dimensional framework. The Rb⁺ cations and the water molecules are occupying intersecting tunnels parallel to a and c. The presence of water molecules was confirmed by TG and DTA analysis. The magnetic susceptibility measurements have shown the existence of antiferromagnetic ordering below 22 K with a weak ferromagnetic component. Additionally, these measurements show evidence for a strong magnetic frustration characterized by |θ/T_N| ≈ 12. Powder neutron diffraction study confirms the presence of a long range antiferromagnetic order coupled to a weak ferromagnetic component along the b-axis. The strongly reduced magnetic moments extracted from the refinement support the existence of a magnetically frustrated ground state. The Mössbauer spectroscopy results confirmed the presence of only Fe³⁺ ions in both five and six coordination. The ionic conductivity measurements led to activation energy of 0.81 eV, a value that agrees with the obtained for other rubidium phosphates.     

Temperature-dependent oxygen release, intercalation behaviour and catalytic properties of V2O5·xNb2O5 compounds

In order to investigate the catalytic properties, V_2,38Nb_10,7O_32,7, VNb₉O₂₅ and solid solutions of V₂O₅ in TT-Nb₂O₅ were prepared by thermal decomposition of freeze-dried oxalate precursors. The samples were characterised by X-ray diffraction and surface area determination. The crystalline samples are capable of the intercalation of sodium and lithium ions from solution. Above a temperature of about 500 °C, in dependence on the oxygen partial pressure a reversible release and uptake of oxygen without a structural variation takes place. The catalytic properties have been evaluated for the oxidative dehydrogenation (ODH) of propane and propene. There are only small differences in the catalytic activity of the different crystalline samples. Because of the relative high starting temperature, a selective catalytic oxidation of propane to propene is hardly observed.     

Influence of structural transformations on functional properties of Fe75Ni2Si8B13C2 amorphous alloy

The influence of thermal treatment on functional properties of Fe₇₅Ni₂Si₈B₁₃C₂ amorphous alloy was investigated, showing the change that resulted from thermally induced structural transformations. Thermal history of the sample was found to have a significant effect on magnetic properties. Structural transformations were identified using DSC and thermomagnetic curve and characterized using Mössbauer spectroscopy and X-ray diffraction. Further investigation of magnetic and electrical properties of the alloy showed that structural relaxation prior to crystallization affected both magnetic susceptibility and electrical resistivity of the alloy, leading to an increase in both. This was caused by a confluence of stress relieving and a decrease in number of defects and an increase in free volume in the alloy sample, not only enabling greater mobility of magnetic domain walls, but also decreasing electron density of states at the Fermi level. Annealing at temperatures below crystallization caused an increase in magnetic susceptibility of the alloy at room temperature, however, a shift in Curie temperature was not observed. The alloy also exhibits a wide supercooled liquid region before crystallization, where its functional properties remained relatively constant, exhibiting the low values of both magnetic susceptibility and electrical conductivity.     

Synthesis by an ionic liquid-assisted method and optical properties of nanoflower Y2O3

Flower-like Y₂O₃ nano-/microstructured phosphors without metal activators have successfully been fabricated by an ionic liquid (IL)-assisted method involving temperature (600 °C) annealing. In this paper, the effect of IL concentration on the morphology of the product has been investigated. The IL plays a crucial role in the formation of various morphologies of Y₂O₃. The structural and morphological features of the obtained samples have been characterized by means of X-ray powder diffraction (XRD) analysis, photoluminescence spectra (PL), Fourier-transform infrared (FT-IR) spectra and X-ray photoelectron spectra (XPS). The photoluminescence spectra of the products exhibit an intense bluish-white emission (ranging from 405 to 430 nm and centered at 418 nm). The luminescent mechanisms have been ascribed to the carbon impurities in the Y₂O₃ host. The effect of the ILs cation and the counter anions on the Y₂O₃ morphology of these nanostructures was studied experimentally. It was observed that Y₂O₃ morphology and PL of these nanostructures were strongly influenced by the type of cation and anion. As the length of the subsidiary chain of cation section of IL (imidaziole ione) reduces, the thickness of the nano-sheets increases. It is expected that the present method may easily be extended to similar nano-/microstructures of other oxide materials. Such investigations are currently underway.     

Structural and magnetic characterization of LiMn1.825Cr0.175O4 spinel obtained by ultrasonic spray pyrolysis

Quaternary spinel oxide LiMn_1.825Cr_0.175O₄ powder was synthesized by using an ultrasonic spray pyrolysis method, without additional annealing. The crystal structure of the as-prepared powder was revealed by X-ray powder diffraction and identified as a single spinel phase with Fd3m space group. The powders had a spherical morphology with extremely smooth surface appearance and densely congested interior structure. Transmission electron microscopy confirmed that the particle consisted by the cohesion of the primary particles. Magnetic measurements performed in DC field in both zero-field-cooled and field-cooled regimes, as well as AC susceptibility experiments, show that system undergoes spin-glass transition at the freezing temperature T_f = 20 K. The value of the effective magnetic moment μ_eff = 4.34 μ_B obtained from the Curie-Weiss fit in the high temperature region confirms the substitution of Mn³⁺ ions with Cr³⁺ ions.     

Fine Fe16N2 powder prepared by low-temperature nitridation

α-Fe was prepared by reduction of a fine γ-Fe₂O₃ powder under hydrogen at 500 °C for 8 h. The α-Fe fine powder, about 100 nm in crystallite size, was then nitrided under an ammonia flow at 130 °C for 100 h. X-ray single-phase Fe₁₆N₂ was obtained with a magnetization value of 225 emu/g at room temperature under a magnetic field of 15 kOe. The Mössbauer spectrum at room temperature could be resolved into three sets of hyperfine fields with an average magnetic moment of 2.52 μ_B. An additional paramagnetic component was present in the spectrum with an area ratio of 19%.     

Structural properties of Al2O3-La2O3 binary oxides prepared by sol-gel

The structural properties of La₂O₃ and Al₂O₃-La₂O₃ binary oxides prepared by sol-gel were studied by XRD, HRTEM and UV-vis. The binary oxides with high lanthana contents show an amorphous structure after calcination at 650 °C. At calcination temperatures higher than 1000 °C there is a phase transformation from the amorphous state to the crystalline LaAlO₃ with a perovskite structure. The structure of La₂O₃ is consistent with the hexagonal system; however, some crystalline microdomains with a monoclinic structure were detected by HRTEM. Islands of La₂O₃ and LaAl₁₁O₁₈ phases were detected at high lanthana concentration in the binary oxide. The modification in the coordination shell of the Al³⁺ cations due to the interaction with La³⁺ cations confirms the formation of phases with a perovskite structure and the presence of islands of the LaAl₁₁O₁₈ phase.     

Structural and magnetic properties of LaFe0.5Cr0.5O3 studied by neutron diffraction, electron diffraction and magnetometry

The structural and magnetic properties of the perovskite type compound LaFe_0.5Cr_0.5O₃ have been studied by temperature dependent neutron powder diffraction and magnetization measurements. Rietveld refinement of the neutron diffraction data shows that the compound crystallizes in an orthorhombic perovskite structure with a random positioning of the Fe and Cr cations at the B sublattice. The magnetic structure at 10 K is a collinear antiferromagnetic one with the magnetic moment per site being equal to 2.79(4) μ_B. Magnetisation measurements confirm the overall antiferromagnetic behaviour. Moreover, it indicates a weak uncompensated magnetic moment close to the transition temperature T_N ≈ 265 K. This moment can be described by a magnetic cluster state, which remains up to 550 K. Electron diffraction patterns along with high-resolution transmission electron microscopy images reveal that the crystallites are composed by domains of different orientation, which share the same cubic perovskite sub-cell reflections.     

Synthesis and properties of solid solutions of hexagonal YCu0.5Ti0.5O3 with YMO3 (M = Mn, Cr, Fe, Al, Ga, and In)

Solid solutions of the type Y(Cu_0.5Ti_0.5)_1−xM_xO₃ with a hexagonal structure were prepared for M = Mn, Fe, Cr, Al, Ga, and In. A complete solid solution could be obtained only in the case of M = Mn. The green color of YCu_0.5Ti_0.5O₃ was found to be enhanced by small substitutions of Al, Ga, and In. All compositions containing Mn were black in color. Suppression of magnetic transitions is observed upon co-doping of Cu/Ti into YMnO₃. Measurements of dielectric constant suggest some magneto-electric coupling may be present in the Y(Cu_0.5Ti_0.5)_1−xMn_xO₃ solid solution.     

Study on the structures and magnetic properties of Ni, Co-Al2O3 electrodeposited nanowire arrays

We report on the direct electrodeposition of nickel and cobalt nanowire arrays within the nanopores of ordered porous alumina films prepared by a two-step anodization. SEM and TEM images reveal that the pore arrays are regularly arranged throughout the alumina film. X-ray diffraction and TEM analysis show that the nickel and cobalt nanowires are single crystalline with highly preferential orientation. The aspect ratio of nanowires is over 300. M-H hysteresis loops determined by VSM indicate that the nanowire arrays obtained possess obvious magnetic anisotropy. Because of proper square ratio and coercivity the nanowire arrays of nickel seem to be more suitable candidates for perpendicular magnetic recording medium than those of cobalt.     

Electronic characterization of alkali ruthenium hollandites: KRu4O8, RbRu4O8 and Cs0.8Li0.2Ru4O8

Transport, specific heat, and magnetic measurements have been performed on three alkali hollandites: KRu₄O₈, RbRu₄O₈, and a newly synthesized Cs analog, Cs_0.8Li_0.2Ru₄O₈, which was determined to have space group I4/m (#87) and lattice parameters, a = 10.0850(4) and c = 3.12180(20). In contrast to the ruthenium perovskites, which display a wide range of electrical and magnetic behavior, the alkali hollandites are simple paramagnetic metals.