Structural characterization and magnetic properties of the spinel compound CoIn0.5Cr1.5S4

Single crystals of the magnetic semiconductor CoIn_0.5Cr_1.5S₄, belong to the system CoIn_(2‐2X)Cr_(2X)S₄ with x = 0.75, was grown by the chemical transport method. X‐ray powder diffraction characterization by the Rietveld method indicated that CoIn_0.5Cr_1.5S₄ crystallizes in the space group Fd‐3m, Z = 8, with a = 10.0700(6) Å and V = 1021.2(1) ų, in a normal spinel structure. The temperature dependence of the DC magnetization suggests that the studied compound presents a ferromagnetic behavior with a Curie temperature Tc = 220 K. Sharp spin‐glass like behavior was found also. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical and magnetic properties of first-row transition metal ions in lead-silicate glass

First-row transition metal ions in lead-silicate glasses of composition: 37.9% mol PbO, 61.8% mol SiO₂ have been studied with regard to the oxidation state and the coordination by means of optical and magnetic measurements. Optical spectra have been recorded at 300 and 77 K. All the observed bands are assigned as being due to d-d transitions in T_d and/or O_h fields. Magnetic moments are of the order of the spin-only values. By ESR measurements we reveal and quantify titanium, vanadium and manganese oxidation states not detectable by the other techniques.It turns out that the various metal ions have the following oxidation states: Ti³⁺ and Ti⁴⁺, V⁴⁺ and V⁵⁺, Cr³⁺ and Cr⁶⁺, Mn²⁺ and Mn³⁺, Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺. The coordination is 4-fold for Ti⁴⁺ and V⁵⁺ and 6-fold for Mn³⁺ and Cu²⁺. Moreover it has been found that Fe³⁺, Co²⁺ and Ni²⁺ are both 4-fold and 6-fold coordinated and that Cr³⁺ and Cr⁶⁺ oxidation states coexist in the same sample.     

Growth,structure, and magnetic properties of CuFeTe<Subscript>2</Subscript> single crystals

CuFeTe₂ single crystals were grown and the temperature dependence of their magnetic susceptibility in the temperature range 1.8–400 K was investigated. It is found that the magnetic susceptibility shows anomalies at temperatures T _s = 65 and T _N = 125 K. At T > 125 K, the crystal is in the paramagnetic state controlled by Fe²⁺ and Cu²⁺ ions with an effective magnetic moment of 1.44 μB.     

Crystal structure and magnetic properties of the LaCo0.5Fe0.5O3 perovskite

The magnetic and crystal structures of the LaCo_0.5Fe_0.5O₃ perovskite are investigated. It is established that the unit cell of this compound at room temperature is characterized by rhombohedral distortions. As the temperature decreases, the compound undergoes a structural phase transition from the rhombohedral phase to the orthorhombic phase in the temperature range 200–300 K. The LaCo_0.5Fe_0.5O₃ perovskite has an antiferromagnetic structure with the G _z spatial orientation of the antiferromagnetic vector. The magnetic properties of the LaCo_0.5Fe_0.5O₃ perovskite are interpreted within a model according to which the ground state of Co³⁺ ions is a low-spin state and the existence of the weak ferromagnetic component is associated with the exchange interactions between the Fe³⁺ ions.     

EPR spectra of Cr3+-doped LuNbO4 crystals

Ferroelastic LuNbO₄ single crystals containing 0.3 at. % Cr³⁺ ions have been grown by the floating zone technique, and their EPR spectra have been studied at a frequency of 9.8 GHz at room temperature. The lines on the spectra are due to the transitions caused by three paramagnetic centers formed as a result of the replacement of one isovalent position of a Lu₃₊ ion and two nonisovalent positions of Nb₅₊ions by Cr₃₊-ions. As a result of twinning, the line number is doubled and four principal directions arise along which the same spectra are obtained. The spectra of these centers were described by a spin Hamiltonian with S = 3/2, the D and E parameters ranging from 0.024 to 0.17 cm^?1, and the g-factors g ∥ = 1.75–2.20 and g ⊥ = 1.90–2.13.     

A Highly Selective Rhodamine Based Colorimetric Sensor Toward Cu2+

A probe for recognition of Cu²⁺ was developed based on rhodamine B. The probe was synthesized by condensation between rhodamine B and quinoline-2-carbaldehyde. The probe exhibits highly selectivity toward Cu²⁺ detection. It binds Cu²⁺ in a 1:1 stoichiometry in acetonitrile solution. Distinct color change can be observed upon the addition of Cu²⁺ and little interference with other biologically relevant metal ions. Only Fe³⁺ addition shows a little disturbance in absorption enhancement. In addition, the limit of detection toward Cu²⁺ is about 235 times lower than the World Health Organization (WHO) recommended level in drinking water.     

Absorption,emission and absorption saturation of Cr4+ ions in calcium aluminate glass

Absorption, luminescence and absorption saturation of Cr ions in a calcium aluminate glass are studied. In the absorption spectrum, the absorption bands of Cr³⁺, Cr⁴⁺ and Cr⁶⁺ ions are revealed. The emission spectrum presents luminescence of Cr³⁺ ions centered at 0.82 μm and that of Cr⁴⁺ ions at 1.3 μm. The luminescence signal demonstrates short decay times of 120 ± 10 ns and 300 ± 20 ns for Cr³⁺ and Cr⁴⁺ ions, respectively. Absorption saturation measurements allowed an estimate of the ground-state absorption cross-sections for Cr⁴⁺ ions at 1.06 μm of 0.7 × 10⁻¹⁸ cm² and at 0.69 μm of 1.5 × 10⁻¹⁸ cm².     

Spectroscopy studies of pure and chromium-doped calcium gallogermanate crystals, Ca3Ga2Ge4O14

Absorption spectra, the spectra of circular dichroism and magnetic circular dichroism of pure and Cr-doped Ca₃Ga₂Ge₄O₁₄ crystals have been studied. The crystal-field parameters and the transition frequencies of Cr³⁺ ions are calculated. The location of Cr³⁺ and Cr⁴⁺ ions in oxygen octahedra and tetrahedra is confirmed. The spectra of circular dichroism show the maxima due to Cr³⁺ ions and growth-induced defects.     

Influence of the temperature and the oxygen partial pressure on the phase formation in the system Cu – Fe – O

Copper iron oxides, Cu_1‐xFe_2+xO₄ (0 ≤ x ≤ 0.5), have been synthesized by thermal oxidation of copper ‐ iron mixtures. In this process, the phase formation and the phase stability were investigated as function of the temperature (800°C – 1200°C) and the oxygen partial pressure (1.013 x 10¹ – 1.013 x 10⁵ Pa). The phase formation starts with the reaction of the metallic components to simple oxides (Fe₃O₄, Fe₂O₃, CuO). From these simple oxides, the formation of complex oxides requires a minimum temperature of 800°C. The synthesis of single phase spinel compounds Cu²⁺_1‐2x Cu¹⁺_xFe_2+xO_4±δ is realized for 0.1 ≤ x ≤ 0.5, using specific temperature – p(O₂) – conditions for a given value of x. Remarkably, to achieve our goal, we found that the increase of x implies that of the reaction temperature and/or a decrease of the p(O₂) in the reaction gas stream. Besides, a single phase spinel CuFe₂O₄ does not exist in the temperature / p(O₂)‐field investigated. Using the results of XRD ‐ phase analysis, T ‐ p(O₂) – x – diagrams were constructed. These diagrams allow the prediction of phase compositions expected for different synthesis conditions. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Recharging processes of Cr ions in Mg2SiO4 and Y3Al5O12 crystals under influence of annealing and γ ‐ irradiation

Recharging processes of chromium ions were investigated for Mg₂SiO₄:Mg, Cr single crystals using annealing in O₂ and in air and γ‐irradiation, as compare to YAG :Ca, Cr single crystals. The formation of tetravalent Cr ions in the Mg₂SiO₄ :Mg, Cr is related not only to the initial Cr content in the melt, oxygen partial pressure and O₂‐ vacancy existing in the crystal, but also to the external field such as γ‐irradiation. The additional absorption after γ‐irradiation shows the decrease in intensity of the absorption of Cr³⁺ and Cr⁴⁺ ions in some part of the spectrum and increase in the other giving evidence on recharging effects between Cr³⁺ and Cr⁴⁺. There arises also color centers observed between 380 nm and 570 nm that may participate in energy transfer of any excitation to Cr⁴⁺ giving rise to Cr⁴⁺ emission. Opposite to forsterite crystal, absorption spectrum of YAG:Ca, Cr crystal after γ‐irradiation reveals only increase in the absorption of the Cr bands. The observed behavior of the absorption spectrum of YAG:Ca, Cr crystal under influence of γ‐irradiation suggests that γ‐irradiation ionizes only Cr ions. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Spectroscopic properties of Cr3+ ions in nanocrystalline glass–ceramic composites

Luminescence properties of Cr³⁺ ions in a silica-based precursor glass, and in fabricated optically transparent glass-based nanocrystalline composites, have been investigated. The luminescence spectra of the precursor glass revealed a wide range of crystal fields and showed the ⁴T₂–⁴A₂ broadband emission of Cr³⁺ ions in a weak crystal field, combined with ²E–⁴A₂ emission characteristic for Cr³⁺ ions in a strong crystal field. Glass–ceramic nanocomposites, with gallium oxide nanocrystals nucleated in a host glass matrix, indicated the prevailing contribution of the crystal-like ²E–⁴A₂ emissions (R-lines) of Cr³⁺ ions in a strong crystal field. The low-temperature studies demonstrated that the fluorescence of Cr³⁺ ions could be altered from sharp R-lines of the ²E–⁴A₂ transition, below 70 K, to a combination of R-lines and their sidebands, above 70 K. Our results indicate that, in the developed glass–ceramic nanocomposites, most of the Cr³⁺ ions have migrated from the host glass matrix to the nucleated gallium oxide nanocrystalline phase.     

X‐ray powder diffraction study of the semiconducting alloy Cu2Cd0.5Mn0.5GeSe4

The structure of the semiconducting alloy Cu₂Cd_0.5Mn_0.5GeSe₄ was refined from an X‐ray powder diffraction pattern using the Rietveld method. The present alloy crystallizes in the wurtz‐stannite structure, space group Pmn2₁ (N^o 31), and unit cell parameters values of a = 8.0253(2) Å, b = 6.8591(2) Å, c = 6.5734(2) Å and V = 361.84(2) ų. The structure exhibits a three‐dimensional arrangement of slightly distorted CuSe₄, Cd(Mn)Se₄ and GeSe₄ tetrahedras connected by corners. © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

The investigation of the magnetic interaction between Cu2+ and V4+ ions in x(CuO·2V2O5)(1 − x)[2B2O3·K2O] glasses

EPR and magnetic susceptibility measurements have been performed on (CuO·2V₂O₅)(1?x)[2B₂O₃·K_2O] glasses with 0 ? x ? 40 mol. %.For x < 10 mol.%, both Cu²⁺ and V⁴⁺ ions are present mostly as the isolated species. The values of MO coefficients indicate a high covalent degree of the transition metal (TM)-oxygen bonds. Also, the EPR parameters suggest the presence of strong (TM)-oxygen bonds along the 0_z axis, which lead to an octahedral (Oh) symmetry component at TM ions sites.In the case of 10 ? x ? 40 mol.%, the dipole-dipole and superexchange interactions occur between transition metal ions, which determine a broad resonance line at $\text{g ? 2}$. The strong interactions between Cu²⁺ and V⁴⁺ ions give rise to the exchange coupled Cu²⁺ V⁴⁺ pairs in the studied glasses with x > 10 mol.% (y > 3.9 mol.%).     

Cation distribution in the structure of titanium-containing ludwigite

The crystal structure of natural titanium-containing ludwigite has been refined. The unit-cell parameters are a = 9.260 ± 0.002 Å, b = 12.294± 0.002 Å, c = 3.0236± 0.0005 Å, sp. gr. Pbam, and R = 0.0288. The observed cation distribution over the M1-M4 positions corresponds to the structural formula (Mg_0.5)(Mg_1.0)(Mg_0.338Fe _0.162 ²⁺ )(Fe _0.47 ³⁺ Ti _0.21 ⁴⁺ Mg _0.15 ²⁺ Al _0.10 ³⁺ Fe _0.07 ²⁺ (BO₃)O₂. Highly charged titanium ions in the M4 position are balanced mainly with magnesium and not with divalent iron ions.     

Synthesis and crystal structure of new phosphate NaFe 4 2+ Fe 3 3+ [PO4]6

New sodium iron orthophosphate NaFe ₄ ²⁺ Fe ₃ ³⁺ [PO₄]₆ was synthesized by the hydrothermal method. The crystal structure (sp. gr. $P\bar 1$ ) was established by the heavy-atom method, with the exact chemical formula of the compound being unknown; R _hkl = 0.0492, R _whkl = 0.0544, S = 0.52. The new compound is analogous to iron phosphate Fe ₃ ²⁺ Fe ₄ ³⁺ [PO₄]₆ studied earlier. However, these two compounds differ in the Fe²⁺ and Fe³⁺ contents, because Na⁺ ions in the new compound are located at the centers of symmetry not occupied earlier.     

Nuclear57Fe relaxation in Fe2+-containing NiFe2O4 and CoFe2O4 single crystals

Spin-lattice (T ₁) and spin-spin (T ₂) relaxation times of ⁵⁷Fe nuclei in the single-crystal NiFe₂O₄ and CoFe₂O₄ ferrites containing Fe²⁺ ions have been studied in the temperature range of 4.2–100 K by a spin-echo technique. The peaks of relaxation rates T ₁ ^?1 and T ₂ ^?1 caused by the presence of Fe²⁺ ions were observed for both ferrites in the ranges 38–42 and 28–32 K, respectively. The analysis of the results obtained with invocation of the data on ferromagnetic resonance and the measurements of the temperature dependence of resistivity shows that the mechanism of nuclear relaxation responsible for “impurity” peaks and is a slow relaxation process caused by electron exchange Fe²⁺ ? Fe³⁺, characterized by a low activation energy.     

Magnetic resonance study of the crystallization behavior of InF3-based glasses doped with Cu2+, Mn2+ and Gd3+

The crystallization of fluoroindate glasses doped with Gd³⁺, Mn²⁺ and Cu²⁺ heat treated at different temperatures, ranging from the glass transition temperature (T_g) to the crystallization temperature (T_c), are investigated by electron paramagnetic resonance (EPR) and ¹⁹F nuclear magnetic resonance (NMR). The EPR spectra indicate that the Cu²⁺ ions in the glass are located in axially distorted octahedral sites. In the crystallized glass, the g-values agreed with those reported for Ba₂ZnF₆, which correspond to Cu²⁺ in a tetragonal compressed F⁻ octahedron and to Cu²⁺ on interstitial sites with a square-planar F⁻ co-ordination. The EPR spectra of the Mn²⁺ doped glasses exhibit a sextet structure due to the Mn²⁺ hyperfine interaction. These spectra suggest a highly ordered environment for the Mn²⁺ ions (close to octahedral symmetry) in the glass. The EPR spectra of the recrystallized sample exhibit resonances at the same position, suggesting that the Mn²⁺ ions are located in sites of highly symmetric crystalline field. The increase of the line intensity of the sextet and the decrease of the background line in the thermal treated samples suggest that the Mn²⁺ ions move to the highly ordered sites which contribute to the sextet structure. The EPR spectra of the Gd³⁺ doped glasses exhibit the typical U-spectrum of a s-state ion in a low symmetry site in disordered systems. The EPR of the crystallized glasses, in contrast, have shown a strong resonance in g ≈ 2.0, suggesting Gd³⁺ ions in environment close to cubic symmetry. The ¹⁹F NMR spin–lattice relaxation rates were also strongly influenced by the crystallization process that takes over in samples annealed above T_c. For the glass samples (doped or undoped) the ¹⁹F magnetization recoveries were found to be adjusted by an exponential function and the spin–lattice relaxation was characterized by a single relaxation time. In contrast, for the samples treated above T_c, the ¹⁹F magnetization-recovery becomes non-exponential. A remarkable feature of our results is that the changes in the Cu²⁺, Mn²⁺, Gd³⁺ EPR spectra and NMR relaxation, are always observed for the samples annealed above T_c.     

Structural and magnetic properties of nanometric Zn0.5Co0.5Fe2O4 prepared by hydrothermal method

ABSTRACT

The study of the structural, morphology and magnetic properties of Zn_0.5Co_0.5Fe₂O₄ ferrite is the objective of this work. The sample was prepared by hydrothermal method and was characterized by X-ray diffraction (XRD), (SEM) and (TEM) micrographs and magnetization measurements.

The magnetic hysteresis loops, field cooling (FC) and zero field cooling (ZFC) curves, in temperature range (0-400K), were measured using XL-SQUID magnetometer and the values of blocking temperatures (T_B) were determined. The results indicated that Zn_0.5Co_0.5Fe₂O₄ sample were formed in a single spinel phase and gives the value for the lattice parameter (8.3952 Å) and nanosizes of particles (13.8 nm) were compared with these obtained from ZnFe₂O₄ sample prepared also by synthesis method (8.4261 Å and 14 nm). Although, the superparamagnetic behaviour for Co-Zn ferrite has observed at 350K with a blocking temperature (T_B = 300K), that is maximum at the value obtained in the case of Zn-ferrite (T_B = 12K).     

Magnetic interactions in frustrated Mn3Fe4(VO4)6

Magnetic interactions in a site-disordered multicomponent vanadate Mn₃Fe₄(VO₄)₆ are studied using DC magnetization and multifrequency Electron Paramagnetic Resonance (EPR). The static magnetic susceptibility χ shows antiferromagnetic interactions between Fe³⁺ and Mn²⁺ spins with a Curie–Weiss temperature Θ = ?165(5) K. EPR measurements indicate a strong dependence of χ on the frequency and temperature. The EPR spectra due to iron and manganese ions are observed in the X-band. It is mostly manganese ions that are observed at 80 GHz while two kinds of magnetic centers are identified at frequencies above 160 GHz. The observed shifts of the resonance lines for Fe³⁺ ions at low frequencies differ from those at high frequencies. The observed features may be due to different magnetic sublattices which modify the magnetic ground state, while competing magnetic interactions may lead to magnetic frustration. It appears that the very high magnetic fields employed in our high-frequency EPR measurements may affect the spin-flop transitions anticipated below Neel temperature T_N.     

Spectroscopy and crystal-field analysis of Cr4+-doped transparent silicate glass-ceramics

We report transparent Cr⁴⁺-doped SiO₂–Al₂O₃–ZnO–Li₂O–K₂O glass-ceramics with broadband infrared luminescence. After heart-treatment, Li₂ZnSiO₄ crystallite was precipitated in the glasses, and its average size increased with increasing heat-treatment temperature. Racah parameters of Cr⁴⁺–Li₂ZnSiO₄ glass-ceramics have been calculated, and it was confirmed from absorption spectra that the energy levels of Cr⁴⁺-doped glass-ceramics are close to the cross point ¹E and ³T states. No infrared emission was detected in the as-made glass samples, but the broadband infrared emission centered at 1210 nm with the full width at half maximum (FWHM) of more than 250 nm was observed by exciting the glass-ceramics with excitation of an 808 nm laser diode. In order to analyze the located crystal field of Cr⁴⁺ ions, the emission spectra are fitted by multi-peak Gauss fitting. It is seen that the fluorescence spectra are fitted into two Gaussian bands at around 1195 and 1263 nm with band widths of 208 and 278 nm, respectively. The two Gaussian bands at around 1195 and 1263 nm have about the same decay rate, and hence they would probably originate from the same luminescent centers. The observed infrared emission could be attributed to Cr⁴⁺ ions at low-field sites in Li₂ZnSiO₄ glass-ceramics.