Electrical and magnetic properties of pseudo-one-dimensional calcium iridium oxide Ca5Ir3O12

The electrical and magnetic properties of one-dimensional calcium iridium oxide Ca₅Ir₃O₁₂ are investigated. A weak ferromagnetic transition has been found at 7.5 K through magnetic susceptibility measurements. At the same temperature, a λ-type specific heat anomaly has been observed. The effective magnetic moments in the paramagnetic temperature range and the magnetic entropy due to the magnetic transition indicates that the tetravalent and pentavalent Ir ions exist in the ratio of 1:2. Another λ-type anomaly has been observed at 105 K in the temperature dependence of the specific heat. The electrical conductivity shows one-dimensional Mott variable-range hopping conduction behavior.     

Transport properties of lead phosphate glass doped by cobalt,vanadium and chromium oxides

The electrical transport properties were investigated of a glass system of basic composition 50?mol. % Pb₃O₄–50?mol. % P₂O₅ containing CoO, Cr₂O₃ or V₂O₅ dopanys. The ac conductivity and the thermoelectric power were measured as a function of temperature. Properties such as dielectric constant, loss factor tangent and electrical conductivity are reported in the frequency range 200?Hz–100?kHz and temperature range 300–450?K. The variation in electrical conductivity with temperature was found to depend on the types of transition metal ions involved. The temperature dependence of the frequency exponent, s, was analyzed using different theoretical models. The variation of the thermoelectric power with temperature indicated the presence of more than one conduction mechanism for the investigated samples. This result was confirmed with the results of the dielectric properties at different frequencies. The introduction of cobalt ions in glass formers improves the electrical properties of non-crystalline ionic conductors.     

Magnetic properties of partially devitrified B2O3-MnFe2O4 glass

Crystallization processes of partially devitrifled glass obtained by rapid quenching of 0·17₅ MnO + 0·17₅. Fe₂O₃ + 0·65 B₂O₃ melt were studied by DTA and X-ray analyses and the temperature regions of nucleation, crystallization and decompozition of the spinel phase were established. The magnetization curves measured between 4·2 and 250 K in magnetic fields up to 42 kOe divided the samples into two groups: the original as cast glass and those annealed below the crystallization temperature, as well as above the decomposition temperature showed essentially paramagnetic behaviour, whereas those annealed closely above the crystallization temperature displayed a spontaneous magnetic moment. The former ones could not be classified as superparamagnetic but the temperature dependence of their susceptibility could be explained by interactions of the antiferromagnetic type. The comparison of lattice parameter and Curie temperature of the latter one with crystalline Mn _x Fe_3-x O₄, system indicated pronounced iron enrichment of the spinel phase formed during heat treatment.Based on a paper presented at the Conference of Socialist Countries on Magnetic Oxides and Compounds; Reinhardsbrunn bei Friedrichroda, GDR, October 22nd–27th, 1972.The authors thank Mrs. A.Hadincová for the help with the evaluation of the results.     

Synthesis and laser patterning of Bi-doped Y3Fe5O12 crystals in germanosilicate glasses

New germanosilicate glasses giving the crystallization of yttrium iron garnet Y₃Fe₅O₁₂ (YIG) and Bi-doped YIG, 23Na₂O-xBi₂O₃-(12−x)Y₂O₃-25Fe₂O₃-20SiO₂-20GeO₂ (mol%), are developed, and the laser-induced crystallization technique is applied to the glasses to pattern YIG and Bi-doped YIG crystals on the glass surface. It is clarified from the Mössbauer effect measurements that iron ions in the glasses are present mainly as Fe³⁺. It is suggested from the X-ray diffraction analyses and magnetization measurements that Si⁴⁺ ions are incorporated into YIG crystals formed in the crystallization of glasses. The irradiations (laser power: 32-60 mW and laser scanning speed: 7 μm/s) of continuous wave Yb:YVO₄ fiber laser (wavelength: 1080 nm) are found to induce YIG and Bi-doped YIG crystals, indicating that Fe³⁺ ions in the glasses act as suitable transition metal ions for the laser-induced crystallization. It is suggested that YIG and Bi-doped YIG crystals in the laser irradiated part might orient. The present study will be a first step for the patterning of magnetic crystals containing iron ions in glasses.     

Crystallization kinetics of Li2O-PbO-V2O5 glasses

Lead vanadate glasses of the system 5Li₂O−(45−x) PbO−(50+x) V₂O₅, with x=0, 5, 10, and 15 mol% have been prepared and studied by differential scanning calorimetry (DSC). The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC using continuous-heating techniques. In addition, from dependence of the glass-transition temperature (T_g) on the heating rate, the activation energy for the glass transition was derived. Similarly the activation energy of the crystallization process was determined and the crystallization mechanism was characterized. The results reveal the increase of the activation energy for glass transition which was attributed to the increase in the rigidity, the cross-link density and the packing density of these glasses. The phases into which the glass crystallizes have been identified by X-ray diffraction. Diffractograms of the transformed material indicate the presence of microcrystallites of Li_0.30V₂O₅, Li_0.67O₅V₂, LiV₆O₁₅, Li₄O₄Pb, and O₇Pb₂V₂ in a remaining amorphous matrix.     

Crystallization-dependent magnetic properties of Mn1.56Co0.96Ni0.48O4 thin films

The effects of magnetic property dependence of the Mn_1.56Co_0.96Ni_0.48O₄ (MCN) films on crystallization are investigated in the growth temperature of 450-750 °C. With the growth temperature increase, both the crystalline quality and the grain size improve. The MCN films exhibit paramagnetic to ferromagnetic transition and the paramagnetic parts fit to the modified Curie-Weiss law. The ferromagnetic couplings of the magnetic ions in the MCN films enhance at elevated growth temperature. The saturation magnetization at 5 K increases with increasing growth temperature, but coercive field decreases monotonously. The magnetic properties of the MCN films strongly depend on their microstructures.     

Elaboration and structural characterization of glasses inside the ternary SrO-TiO2-P2O5 system

The glasses in the SrO-TiO₂-P₂O₅ system were prepared by the conventional quenching route. The amorphous state of samples was verified by X-ray diffraction (XRD). Density, molar volume, micro-hardness, glass transition temperature (T_g), and crystallization temperature (T_c) parameters are determined for each glass. The results show that they depend strongly on the chemical compositions. The structure approach of the glasses is determined by using Infrared spectroscopy (IR). This investigation highlights that the glassy-matrix contains various phosphate structural units. The crystallization of the glasses by heat-treatments is performed and the crystallized phases Sr₃P₄O₁₃, TiP₂O₇, Sr(PO₃)₂ are identified by XRD. The overall results are correlated to the glass structure and the nature of chemical bonds constituting the glass network.     

Excited state absorption and energy-transfer mechanisms of up-conversion luminescence in Er-doped oxyfluoride glass ceramics at different temperatures

Oxyfluoride silicate glass SiO₂-Al₂O₃-Na₂CO₃-NaF-LaF₃-ErF₃ was synthesized. The glass transition and crystallization temperatures were determined by differential thermal analysis. Glass ceramics containing LaF₃:Er³⁺ crystallites of size ∼20 nm were formed in the glass matrix after the heat treatment of the precursor glass in the vicinity of the crystallization temperature. Up-conversion luminescence, excitation spectra as well as time-resolved up-conversion luminescence of the glass and glass ceramics were studied at different temperatures. The up-conversion transients showed that at room temperature the dominant mechanism of the up-conversion luminescence in the glass ceramics is excited state absorption while at lower temperatures energy-transfer mechanism prevails. The origins of these differences are discussed in terms of the transitions between Stark manifolds of ⁴I_15/2, ⁴I_11/2 and ⁴F_7/2 states in Er³⁺ ions.     

Muon spin relaxation investigation of frustrated antiferromagnetic pyrochlores A2B2O7

In a system where magnetic ions occupy the vertices of edge or corner sharing triangular units, the natural antiferromagnetic coupling between ions is geometrically frustrated. A wide variety of interesting magnetic behaviour has been observed in pyrochlores, where magnetic ions form a network of corner sharing tetrahedra. The low temperature spin dynamics of a number of pyrochlores A₂B₂O₇ have been investigated using the technique of μ SR. For example, Y₂Mo₂O₇ shows a transition to a disordered magnetic state similar to a spin glass at T_F=22 K. However, unlike conventional metallic spin glasses, a non‐zero muon spin depolarization rate is observed to persist well below 0.1\ T_F. These results suggest that there is a finite density of states for magnetic excitations in this system near zero energy. This revised version was published online in July 2006 with corrections to the Cover Date.     

Magnetic properties of disordered ferrite and ilmenite-hematite thin films

We have synthesized thin films of disordered zinc ferrite (ZnFe₂O₄) and ilmenite-hematite (FeTiO₃-Fe₂O₃) solid solution, the former and the latter of which are interesting from the viewpoints of magnetooptics and spintronics, respectively, by utilizing sputtering and pulsed laser deposition methods, and have explored their magnetic, magnetooptical, and electrical properties. Although ZnFe₂O₄ possesses a normal spinel structure as its stable phase, some of the Fe³⁺ ions occupy the tetrahedral as well as the octahedral sites in ZnFe₂O₄ of which the sputtered thin film is composed. Consequently, the as-deposited thin film manifests large magnetization even at room temperature although the magnetic phase transition temperature of the stable phase of ZnFe₂O₄ is as low as 10 K. Also, the thin film exhibits a cluster spin glass transition at a temperature as high as 325 K. Furthermore, the ZnFe₂O₄ thin films exhibit large Faraday effects at a wavelength of 400 nm or so. The ilmenite-hematite solid solution is one of the ferrimagnetic semiconductors. Most of the compositions possess Curie temperatures higher than room temperature, and the type of carrier can be tuned only by changing the composition. We have succeeded in synthesizing solid-solution thin films of various compositions grown epitaxially on sapphire substrates with a (0 0 0 1) plane, and have shown that the thin films are ferrimagnetic semiconductors.     

Laser patterning and magnetic properties of perovskite-type La0.7Sr0.3MnO3 crystals on the glass surface

The laser-induced crystallization technique has been applied to 10La₂O₃-35SrO-25MnO₂-30B₂O₃ glass (mol%) in order to examine the possibility of the formation and morphology control of perovskite-type La_1?xSr_xMnO₃ crystals on the glass surface. It is found from X-ray diffraction analyses that La_0.7Sr_0.3MnO₃ crystals are formed in the sample obtained by continuous wave Y b:Y V O₄ fiber laser (wavelength: 1080 nm) irradiations (power: 350 mW, scanning speed: 10 μm/s). La_0.7Sr_0.3MnO₃ manganites in the laser-irradiated samples are proposed to be ferromagnetic crystals having a Curie temperature of ～315 K from magnetization measurements and the Arrott plot. The surface morphology of laser-irradiated parts is not smooth, and La_0.7Sr_0.3MnO₃ crystals are present randomly without any orientations. It is clarified that Mn⁴⁺ ions in the glass act as suitable transition metal ions for the laser-induced crystallization.     

An anomalous enhancement in the electrical conductivity of Li2O : B2O3 : Al2O3 glasses

The study of electrical conductivity of 27.5 Li₂O : (72.5 − x) B₂O₃ : x Al₂O₃ glass samples has been carried out. It has been observed that the conductivity exhibits Arrhenius behavior for all samples up to glass transition temperature T_g. Beyond T_g, an anomalous enhancement followed by decrease in conductivity has been observed. The results have been explained by dividing the temperature range into two regions. In region-I, it has been observed that the conductivity variation exhibits a maximum at 2.5 mol% Al₂O₃, which has been explained on the basis of Mixed Glass Former Effect (MGFE). An anomalous enhancement in the conductivity observed in region-II has been attributed to the nucleation in the glass. The subsequent decrease in the conductivity has been attributed to the crystallization of the glass samples.     

Thermal features and physical properties of sulfur modified barium vanadate glasses

Differential scanning calorimetry (DSC) and XRD were used to investigate the role of sulfur in the network of V₂O₅–Fe₂O₃–BaO glasses. The crystallization kinetics of the glasses were investigated under non-isothermal conditions applying the formal theory of transformations for heterogeneous nucleation to the experimental data obtained by DSC. The activation energy for the glass transition (E _g) was derived from dependence of the glass-transition temperature (T _g) on the heating rate. Similarly the activation energy of the crystallization (E _c) and the frequency factor (K ₀) were determined. The results reveal the increase of the activation energy for glass transition was attributed to the increase in the rigidity and the cross-link density of these composites. The evaluated thermal stability decreases with increasing sulfur content. The phases of BaFe₂O₄, V₂O₅ and FeVO₄ micro-crystallites in the remaining amorphous matrix have been identified by X-ray diffraction.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

Control of Crystallization Kinetics and Study of the Thermal, Structural and Morphological Properties of an Li2O–B2O3–Al2O3 Vitreous System

A glass matrix with nominal composition 50Li₂O·45B₂O₃·5Al₂O₃ (mol%) was synthesized, and its physical properties were investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), and atomic force microscopy (AFM). The glass transition temperature T _g, the crystallization-onset temperature T _x,, the crystallization peak temperatures T _c1 and T _c2, and the fusion peak temperatures T _m1 and T _m2 were determined from at least two glass matrix phases to be approximately 382, 457, 486, 574, 761, and 787?°C, respectively, at 5?°C/min heating rate. Heat treatments at 450?°C for an increasing sequence of time intervals allowed control over the amount of crystallization. Additional information on the crystallization kinetics for the LBA glass matrix was gathered from AFM images, DTA thermograms, and XRD diffractograms. The latter technique showed that LiBO₂ (ICDD-16568) and Li₃AlB₂O₆ (ICDD-51754) phases are formed in the glass?Cceramic system. Debye?CScherrer analysis of the XRD peaks revealed a competition between the evolutions of crystal phases during heat treatment. Activation energies for crystallization, obtained from theoretical models applied to the DTA data showed that the crystallization is heterogeneous. The AFM images demonstrated that this heterogeneous crystallization starts at the surface of the LBA glass matrix and identified crystal sizes in agreement with the results of the Debye?CScherrer analysis. Our study shows that thermal and structural characterization techniques can be combined with theoretical results drawn from well-tested models to offer a unified view of crystallization in a glass?Cceramics system.     

Crystallization process of Bi(Pb)-Sr-Ca-Cu-O glass

A crystallization study has been carried out for rapidly solidified Bi₂Pb_0.5Sr₂Ca₄Cu₅O_x glass. Glass transition temperature T _g, crystallized superconducting phases and microstructural changes were measured and analysed by differential thermal analysis (DTA), X-ray diffraction (XRD), and scanning electron microscopy (SEM). The crystallization mechanism of the three superconducting phases — (2201) 20 K phase, (2212) 80 K phase, and (2223) 110 K phase — has been discussed, and a time-temperature-transformation diagram for the glass has been constructed.     

Induced crystallization and the physical properties of PbO–Sb2O3–As2O3: MoO3 glass system

PbO–Sb₂O₃–As₂O₃ glasses mixed with different concentrations of MoO₃ (ranging from 0 to 1.0 mol%) were crystallized. The samples were characterized by X-ray diffraction, scanning electron microscopy and differential thermal analysis techniques. The X-ray diffraction and the scanning electron microscopic studies have revealed the presence of Pb₅Sb₂O₈, PbSb₂O₆, SbAsO₄, Sb₂MoO₆, Sb₄Mo₁₀O₃₁, As₄Mo₃O₁₅, Pb₅Sb₄O₁₁ crystalline phases in these samples. The differential thermal analysis indicated that the surface crystallization prevails over the bulk crystallization as the concentration of the crystallizing agent is increased. The infrared (IR) spectral studies exhibit bands due to MoO₄ structural units in addition to the conventional bands due to various antimonate and arsenate structural groups. The studies on PbO–Sb₂O₃–As₂O₃: MoO₃ glass-ceramics with respect to various physical properties viz., dielectric properties over a range of frequency and temperature, optical absorption, electron spin resonance (ESR) and magnetic susceptibility at room temperature have also been reported. The optical absorption, ESR and magnetic susceptibility studies indicated that the molybdenum ions exist in Mo⁵⁺ state in addition to Mo⁶⁺ state in these samples. The redox ratio found to increase as the concentration of the MoO₃ is increased. The variations observed in all these properties with the concentration of the crystallizing agent have been analyzed in the light of different oxidation states and environment of molybdenum ions in the glass ceramic network.     

Effect of mixed glass formers on the crystallization kinetics in AgI–Ag<Subscript>2</Subscript>O–V<Subscript>2</Subscript>O<Subscript>5</Subscript>–MoO<Subscript>3</Subscript> glassy superionic system

The crystallization and glass transition kinetics using differential scanning calorimetry (DSC) in 50AgI–33.33Ag₂O–16.67[(V₂O₅)_1−x –(MoO₃) _x ] superionic glassy system is discussed. Thermal stability of glass, studied using various criteria, does not vary significantly with glass former variation. However, the activation energies for structural relaxation (E _s) at glass transition temperature and crystallization (E _c) obtained using Moynihan and Kissinger, Matusita-Sakka formulations found to exhibit interesting trends with MoO₃ substitution in the glass matrix. It is noticed that the electrical conductivity (σ)–temperature (T) cycles obtained at a typical heating rate of 1 °C/min do exhibit significant thermal events. The conductivity after first heating cycle at room temperature is found to be increasing with MoO₃ content and maximum for x = 0.3 (~10⁻³ Ω⁻¹ cm⁻¹ at 30 °C) which is comparable to that of the host 50AgI–33.33Ag₂O–16.67V₂O₅ glassy system. The parameters obtained from σ–T plots and DSC scans do complement each other in a particular range of composition.     

Copper Defects and Conductivity in Bi—Pb—Sr—Ca—Cu—O Glasses

Glass ceramics of the composition (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O₈ prepared by the melt quenching technique and the crystalline phases produced by the rapid thermal annealing have been studied by electrical resistivity and electron paramagnetic resonance (EPR) measurements in the temperature range from liquid helium up to room temperature. The concentration of the EPR active Cu^2? paramagnetic centers decreases as conductivity increases for the glass ceramics and disappears after crystallization and the growth of superconducting phases, similar to bulk high-T_c superconductors. The KPR spectra of both glass and crystallized ceramics after short-time annealing indicate the coexistence of Cu^2? paramagnetic ions and the exchange coupled clusters.     

Electrical conductivity improvement of strontium titanate doped lead vanadate glasses by nanocrystallization

The structural and electrical conductivity (σ) of annealed SrTiO₃–PbO₂–V₂O₅ glasses were studied. The annealing of initially glass samples leads to formation of nanocrystalline grains embedded in the glassy matrix. XRD patterns of the glass–ceramic samples show that nanocrystals were embedded in the glassy matrix with an average grain size of 32 nm. The glass–ceramic nanocrystals obtained by annealing at temperatures close to the crystallization temperature T_c exhibit enhancement of electrical conductivity up to four orders of magnitude than initially glasses. The enhancement of the electrical conductivity due to annealing was attributed to two interdependent factors: (i) an increase of concentration of V⁴⁺–V⁵⁺ pairs; and (ii) formation of defective, well-conducting regions along the glass–crystallites interfaces. From the conductivity temperature relation, it was found that small polaron hopping model was applicable at temperature above θ_D/2 (θ_D, the Debye temperature). The electrical conduction at T >θ_D/2 was due to non-adiabatic small polaron hopping (SPH) of electrons between vanadium ions. The parameters obtained from the fits of the experimental data to this model appear reasonable and are consistent with glass composition.