Hyperfine field and magnetic moment of V and Cr in iron

The hyperfine fields of ⁵¹V and ⁵³Cr in diluted alloys V_xFe_1?x and Cr_xFe_1?x have been measured by NMR. No concentration dependence is found for x<2%. Therefore we conclude that the magnetic moments of the impurities are constant in contrast to recent neutron scattering results.     

Xanes (X-ray absorption near edge structure) of V in vanadium-iron phosphate glasses

The X-ray Absorption Near-Edge Structure (XANES) of V in vanadium-iron glasses (50P₂O₅ + (50?x)FeO + xV₂O₅) have been measured. The effective charge of V ions in glasses has been determined. At low V₂O₅ concentration (x ～ 5) only V⁴⁺ with 6-fold coordination is present on the contrary a static mixed valence state (V⁴⁺, V⁵⁺) has been found at high concentrations 20?x?50. The results explain the electron hopping conductivity effects at high V₂O₅ concentration (x ～ 50) involving V⁴⁺ ? V⁵⁺ pairs and at low V₂O₅ concentration (x?10) involving V⁴⁺ ? Fe³⁺ pairs.     

Thermodynamic study of lithium insertion in V6O13 and Li1+xV3O8

The enthalpies of Li⁺ insertion into two V oxides of interest as cathodes for secondary Li batteries, i.e. V₆O₁₃ and Li_1+xV₃O₈ have been directly measured by solution calorimetry. By comparing the integral molar enthalpies ΔH⁰/x with the corresponding ΔG⁰/x values, ΔS⁰/x higher than expected have been found for Li_1+xV₃O₈. This has been correlated to a reorganization of its distorted structure induced by the initial Li⁺ insertion. Two other cathode materials, having the same variation of the potential with Li⁺ content, i.e. MoO₃ and (Mo_0.3V_0.7)₂O₅, show even higher ΔS⁰/x values. The entropic values stemming from structural reorganizations add to the configurational entropies of inserted ions in determining the initial profile of E as a function of Li⁺.     

An investigation of lithium transport properties in V6O13 single crystals

Lithium has been incorporated into single crystals of V₆O₁₃ by coulometric titration in solid state electrochemical cells. A single phase region was identified for Li_xV₆O₁₃ between x=0 and x=0.17 at 120°C. The lithium chemical diffusion coefficient, self-diffusion coefficient, ionic conductivity and partial molar entropy have been estimated at intervals over this composition range in two specific crystallographic directions. The chemical diffusion coefficients were found to be constant in a particular crystal direction with values of 3.5 × 10^-8 cm² s^-1 and 4.9 × 10^-9 cm² s^-1 perpendicular to the (0 1 0) and (0 0 1) planes respectively.     

Magnetic behaviour and site occupation of YFe12-x V x (x=2,3,4)

The effects of vanadium substitution on the iron magnetism in YFe_12-x V _x compounds (x～2–4) have been studied by⁵⁷Fe Mössbauer spectroscopy. The preference of vanadium atoms for the 8i site of these ThMn₁₂-structure type compounds is confirmed. The rapid collapse of the iron sublattice magnetization with increasing vanadium concentration is analysed in terms of the ‘magnetic valence’ model.     

Magnetic clusters in Fe3−x V x Al alloys with DO3 type structure forx≤1.1

Polycrystalline Fe_3?x V _x Al alloys with the DO₃ type structure were investigated by magnetostatic and Mössbauer methods. In alloys with 0.2<x<0.5 the ferro- and superpara-magnetic phases coexist. For alloys withx≥0.5 these investigations showed that in spite of the lack of magnetic order, they are characterized by strong nonlinear variations of the magnetization in a magnetic field over a wide temperature range. This indicates the presence of magnetic clusters of Fe atoms with very large magnetic moments. Analysis of the magnetization isotherms indicates that in these alloys a distribution of magnetic moments of clusters (μ_c) from 10 μ_B to 10⁴ μ_B exists.     

Raman studies of (Fe,V)3S4 solid solution

Raman scattering of Fe_xV_3-xS₄ with 0?x?2 has been studied. The observed spectra of V₃S₄, one of the end members of this solid solution, have been assigned to the Raman active lattice modes based on the C_2h³ space group symmetry. On the basis of the results obtained for V₃S₄, the nature of the metal-metal interactions and the site distributions of Fe atoms in (Fe, V)₃S₄ have been discussed.     

7Li and 51V NMR study on Li+ ionic diffusion in lithium intercalated LixV2O5

Li_xV₂O₅ (0.4 < x < 1.4) prepared by solid-state reaction were studied by ⁷Li and ⁵¹V NMR spectroscopy. ⁷Li NMR spectra showed a narrowing of the line width in relation to Li⁺ionic diffusion. Analysis of Li_xV₂O₅ using a Debye-type relaxation model showed a low activation energy ∼0.07 eV in the sample of x = 0.4 below room temperature, and revealed a Li⁺ionic diffusion with larger activation energy ∼0.5 eV above 450 K in lithium-rich samples. The latter is ascribed to the existence of a multi-phase system comprising stable ɛ- and γ-phases, resulting from complicated phase transitions at high temperature. These shapes and shifts enable the classification of the β-, ɛ-, δ-, and γ-phases. The ionic diffusion of Li⁺ ions is discussed in relation to the complicated phase transitions.     

Synthesis, structure and luminescence properties of Y(V,P)O4:Eu,Bi phosphors

YVO₄:Eu³⁺-based red-emitting phosphors with the compositions of Y_0.95−xVO₄:0.05Eu³⁺,xBi³⁺ (x=0.01, 0.03, 0.05, 0.07 and 0.09) and Y_0.90(V_1−zP_z)O₄:0.05Eu³⁺,0.05Bi³⁺ (z=0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were synthesized by the high temperature solid-state method. The as-prepared phosphors have the similar tetragonal phase structure and their morphologies varied with the relative content ratio of V to P. The photoluminescence spectra for the as-synthesized phosphors show that a dominant red emission line at around 619 nm, which is due to the Eu³⁺ electric dipole transition of ⁵D₀-⁷F₂, is observed under different excitation wavelengths (254 and 365 nm). Further, the emission intensities of ⁵D₀-⁷F₂ transition upon 365 nm excitation increase sharply owing to the Bi³⁺ doping. Energy transfer process, luminescent lifetime and quantum efficiency for the selected Y_0.90(V_1−yP_y)O₄:0.05Eu³⁺,xBi³⁺phosphors were also studied in detail.     

EPR and optical absorption studies of V O ions in L-asparagine monohydrate

Electron paramagnetic resonance (EPR) studies of V O²⁺ ions in L-asparagine monohydrate single crystals are reported at room temperature. It is found that the V O²⁺ ion takes up an interstitial site. The angular variations of the EPR spectra in three mutually perpendicular planes are used to determine the principal g and A values and their direction cosines. The values of g and A parameters are: g_x=1.9011, g_y=2.1008, g_z=1.9891 and A_x=100, A_y=78, A_z=126 (×10⁻⁴) cm⁻¹. The optical absorption spectrum of V O²⁺ ions in L-asparagine monohydrate is also studied at room temperature. The band positions are calculated using the energy expressions and compared with the observed band positions to confirm the transitions. The best-fit values of the crystal field (Dq) and tetragonal (Ds and Dt) parameters are evaluated from the observed band positions.     

Influence of V2O5 ion addition on the conductivity and grain growth of Ni–Zn–Cu ferrites

Polycrystalline nickel–zinc–copper ferrites with chemical formula Ni_0.6+xZn_0.2Cu_0.2V_xFe_2−2xO₄,(0.0 ⩽ x ⩽ 0.25) were prepared by the ceramic route. The X-ray diffraction (XRD) analysis of the samples results confirms single-phase spinel structure. Scanning electron microscopy (SEM) of the prepared ferrites reveal that vanadium addition resulted in a rapid grain growth with large pores trapped inside the grains as the vanadium concentration increases. The ac conductivity σ_ac has been studied as a function of frequency and temperature over the temperature range (300–600 K). The results obtained for these materials reveal a semiconductor – to semimetal transition as V⁵⁺ content increases. All studies composition exhibit a transition with change in the slope of conductivity. The obtained temperature T_c is found to be decrease with the increasing vanadium content. The hopping of electrons between Fe³⁺ and Fe²⁺ as well as the hole hopping between Ni³⁺ and Ni²⁺ are found to responsible for the conduction mechanism. The relation of the universal exponent s with temperature gives evidence for the presence of the correlation barrier hopping (CHB) mechanism in these compounds. The impedance technique has been used to study effect of grain and grain boundary on the electrical properties. The analysis data show only one semi-circle for all samples except for sample with x = 0.05. The results suggested that the conduction mechanism takes place predominantly through the grain in the studied samples.     

Paramagnetic resonance of V in tetragonal GeO2

Anisotropic g and A tensors are found for V⁴⁺ in single crystal tetragonal GeO₂. The orbital mixing parameter λ, normalized radial average 〈1/r³〉/N and core polarization x/N are calculated, and λ is not anomalously low as reported from polycrystalline measurements.     

Electrical transport and crystallization in Cu+ ion substituted AgI–Ag2O–V2O5 glassy superionic system

A new glassy solid electrolyte system Cu_xAg_1 − xI–Ag₂O–V₂O₅ has been synthesized. The structural, thermal and electrical properties of the samples have been investigated. The glassy nature of the samples is confirmed by X-Ray diffraction and Differential Scanning Calorimetry studies. The electrical conductivity of these samples increases with CuI content and approaches a maximum value of ∼ 10⁻² Ω^− 1 cm^− 1 for x = 0.35 at room temperature. Ionic mobility measurements suggest that enhancement in the conductivity with Cu⁺ ion substitution may be attributed to increase in the mobility of Ag⁺ ions. The electrical conductivity versus temperature cycles carried out at well-controlled heating rate above T_g and T_c reveal interesting thermal properties. For lower CuI content samples conductivity exhibits anomalous rise above T_g and subsequent fall at T_c. It is also found that CuI addition into AgI–Ag₂O–V₂O₅ matrix reduces the extent of crystallization.     

Stabilizing the triclinic structure of Mn2V2O7 via isovalent cationic substitution

The thermal expansion of Mn₂V₂O₇ in the temperature range of ?190 to 1030°C is studied. The volumetric thermal expansion coefficients for triclinic (α) and monoclinic (β) modifications are 2.57 × 10^?5 and 3.86 × 10^?5 1/deg, respectively. It is shown that as the Ni²⁺ concentration in Mn_2?2x Ni_2x V₂O₇ rises, the point of the α → β phase transition point moves from room temperature for Mn₂V₂O₇ to 155 ° 5°C for Mn_1.46Ni_0.54V₂O₇ (27 mol % Ni₂V₂O₇).     

Momentum matrix elements in III–V semiconductor alloys

The composition dependence of P², the square of the principal interband matrix element, is investigated. P² is calculated in a virtual crystal approximation within the empirical pseudopotential method. In all the alloys studied, the variation of P² with x is found to be nearly linear. The results are compared with experimental values, obtained from a five-band $\text{K}$, $\text{K}$ analysis of the conduction electron Landé factor and effective mass data. The agreement is good in Ga_1?xIn_xAs and Ga_1?xAl_xAs, but not in In_1?xGa_xSb, which shows a disorder induced deviation.     

Ionic conductivity properties and 19F NMR investigation of Pb1−xCrxF2+x solid solutions with fluorite-type structure

The F⁻ ion transport and diffusion properties inside the solid solution Pb_1−xCr_xF_2+x (0≤x≤0.12) with fluorite-type structure have been determined by impedance spectroscopy and ¹⁹F NMR investigation. The various electrical parameters of Pb_1−xCr_xF_2+x are compared with those of Pb_1−xAl_xF_2+x (0≤x≤0.12) whose structure derives also from the fluorite-type. The Cr³⁺ substitutional cation is of a slightly larger size than the Al³⁺ cation but both cations offer the same usual coordination (CN=6) in ternary fluorides. Comparison of ¹⁹F NMR spectra of some compositions Pb_1−xM_x′F_2+x (M′=Al, Cr) at different temperatures has been realized in order to discover whether the clustering process proposed in Pb_1−xAl_xF_2+x can be extended to Pb_1−xCr_xF_2+x.     

X-Band ESR and51V NMR study of the Haldane system PbNi2−xMgxV2O8

The temperature and angular dependence of the X-band electron spin resonance (ESR) and⁵¹V nuclear magnetic resonance (NMR) spectra have been measured in a recently discovered Haldenegap system, PbNi_2-xMg_xV₂O₈ (0≤x≤0.24). The angular dependence of the ESR signal suggests that both the spin diffusion as well as the magnetic anisotropy determine the electronic spin correlation functions. However, in doped samples the magnetic anisotropy increasingly dominates the spin dynamics on cooling. The huge broadening of the⁵¹V NMR spectra in doped samples at low temperatures provides evidence for localized magnetic moments in the vicinity of the Mg impurities. Locally distorted structure around each Mg impurity may slightly modify the magnetic interactions and be potentially responsible for the antiferromagnetic ordering (belowT _N≈ 3.5K) in doped compositions.     

Superconducting transition temperatures of the system V1−xTixHy

T_c measurements for V_1?xTi_xH_y show that a decrease in T_c always occurs upon hydrogenation, but with slopes ($\text{?T}{}_{\mathrm{c}}\text{?y}\text{)}{}_{\mathrm{x}}$ that change with x. A phenomenological model is suggested, associating the T_c decrease in most of the range of x to changes in nominal number of conducting electrons and in the volume induced by the hydrogenation. The model roughly accounts for the variations in T_c in the V-rich alloys. It fails to explain the T_c variation at the Ti end.     

Magnetic annealing effect in amorphous Fe100-xBx and Co100-xBx binary alloys

The uniaxial magnetic anisotropy induced by magnetic annealing was studied for rapidly quenched amorphous Fe_100-xB_x (12?x?25) and Co_100-xB_x (17?x?30) alloys. The value of induced uniaxial anisotropy constant K_ui increased with increasing B content from 1 x 10³ erg/cm³ at x = 12 to about 4 x 10³ erg/cm³ at x = 25 in Fe_100-xB_x alloy s exhibiting an inflection around x=20. While the value of K_ui in Co_100-xB_x alloys exhibits a maximum of about 6 x 10³ erg/cm³ aro round x=20. The compositional dependence of K_ui for both alloy systems can be explained roughly by the model of the directiona; occupation of B atom between ferromagnetic atoms.     

Creation of ferromagnetic properties of V–Fe and Zr–Fe alloys by hydrogen absorption

The results of investigations of V_1?y Fe _y H _x and Zr_1?y Fe _y H _x alloys by ⁵⁷Fe Mössbauer spectroscopy are presented and discussed in view of hydrogen ability to create ferromagnetic properties of the alloy. The results indicate two different possibilities of hydrogen influence on the hyperfine magnetic field. Hydrogen absorption causes the ferromagnetic behaviour of the alloys at significant lower iron concentration compared to the concentration of magnetic transition in binary alloys. The main reason for such behaviour is the anisotropic lattice expansion in hydrogenated V–Fe and Zr–Fe alloys as well as the decomposition of paramagnetic Zr-rich intermetallic compounds in the aftermath of the strong electron affinity of hydrogen for zirconium. These trends give rise to growth of magnetic clusters of Fe atoms so strong that they can participate in the overall magnetic properties of the system under investigation.