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.     

Pitfalls in the Use of Common Luminescent Probes for Oxidative and Nitrosative Stress

Lucigenin (LC²⁺, bis-N-methylacridinium) and 2,7-dichlorofluorescin (DCFH₂) are widely used as chemiluminescent or fluorescent probes for cellular oxidative stress, to reflect levels of superoxide (O₂ ^·–) and hydrogen peroxide, respectively. We report mechanistic studies that add to the growing evidence for the unsuitability of either probe except in very well-defined circumstances. The ability for lucigenin to generate superoxide via reduction of LC²⁺ to LC^·+ and redox cycling with oxygen depends on the reduction potential of the LC²⁺/LC^·+ couple. Redox equilibrium between LC^·+ and the redox indicator benzyl viologen is established in microseconds after generation of the radicals by pulse radiolysis and indicated E(LC²⁺/LC^·+) –0.28 V vs. NHE. Reaction of LC^·+ with O₂ to generate O₂ ^·– was also observed directly similarly, occurring in milliseconds, with a rate constant k 3 × 10⁶ M ^–1 s^–1. Quinones act as redox mediators in LC^·+/O₂ redox cycling. Oxidation of DCFH₂ to fluorescent DCF is not achieved by O₂ ^·– or H₂O₂, but NO₂ ^·) reacts rapidly: k 1 × 10⁷ M ^–1 s^–1. Oxidation by H₂O₂ requires a catalyst: cytochrome c (released into the cytosol in apoptosis) is very effective (even 10 nM). Fluorescence reflects catalyst level as much as O₂ ^·–) production.     

Substrate temperature influenced structural, electrical and optical properties of dc magnetron sputtered MoO3 films

Molybdenum oxide (MoO₃) films were deposited on glass and (1 1 1) silicon substrates by sputtering of metallic molybdenum target in an oxygen partial pressure of 2 × 10⁻⁴ mbar and different substrate temperatures in the range 303-623 K using dc magnetron sputtering technique. X-ray photoelectron spectrum of the films formed at 303 K showed asymmetric Mo 3d_5/2 and Mo 3d_3/2 peaks due to the presence of mixed oxidation states of Mo⁵⁺ and Mo⁶⁺ while those deposited at substrate temperatures ≥473 K were in Mo⁶⁺ oxidation state of MoO₃. The films formed at substrate temperatures ≥473 K were polycrystalline in nature with orthorhombic α-phase MoO₃. Fourier transform infrared spectra of the films showed an absorption band at 1000 cm⁻¹ correspond to the stretching vibration of MoO, the characteristic of the α-MoO₃ phase. The electrical resistivity increased from 3.3 × 10³ to 8.3 × 10⁴ Ω cm with the increase of substrate temperature from 303 to 473 K respectively due to improvement in the crystallinity of the films. Optical band gap of the films increased from 3.03 to 3.22 eV with the increase of substrate temperature from 303 to 523 K.     

Effect of temperature of annealing on optical, structural and electrochromic properties of sol-gel dip coated molybdenum oxide films

The sol-gel dip-coating method is used for the preparation of MoO₃ thin films. The 6 layered MoO₃ films were prepared and annealed at various temperatures in the range of 200-350 °C. The band gap value for MoO₃ films were calculated from optical absorption measurements and it is in the range of 3.55-3.73 eV. XRD spectrum reveals (0 2 0) is the major diffraction plane for the films prepared above 250 °C, which reveals the formation of MoO₃ in α-orthorhombic phase. The films prepared at 200 °C and 250 °C exhibits amorphous nature. The FTIR spectrum confirms the presence of Mo-O-Mo and MoO bonds. Nanorods were observed in the SEM images in the case of MoO₃ films prepared above 250 °C. The films prepared at 250 °C exhibit maximum anodic diffusion coefficient of 9.61 × 10⁻¹¹ cm²/s. The same film exhibits the change in optical transmission of 58.4% at 630 nm with the optical density of 0.80.     

Nuclear orientation study of the decay of204BiFe

The decay of²⁰⁴Bi nuclei (I =6⁺, T_1/2=11·22 h) oriented in an iron host was investigated on the JINR low-temperature nuclear orientation facility SPIN. The orientation parameterB ₂=1·17 (6) was obtained from the analysis of six prominent E1 gamma-transitions. From the measured normalized intensities of the gamma-rays observed some 70 values of multipole mixing ratios for the gamma-transitions in²⁰⁴Pb nucleus were determined for the first time. The spins 6, 6, 5 and 4 could be uniquely assigned to the²⁰⁴Pb negative parity levels at 3891·5 keV, 3768·4 keV, 3301·5 keV and 2338·2 keV, respectively. The spin-parity assignments of the levels at 4183·8 keV, 4094·2 keV, 3782·0 keV, 2506·9 keV and 2065·1 keV were confirmed as 6^–, 6^–, 5^–, 5^– and 5⁺, respectively. For the level at 3105·1 keV spin-parity 5^– was suggested and spinparity 7^– of the level at 2696·4 keV was called in question. The possible placements of the gammatransitions 3 1351·7 keV and 1353·4 keV in the decay scheme is discussed. The reorientation parameters for the long-living levels at 2264·2 keV (T _1/2=0·45 s) and 1273·9 keV (T _1/2= =265 ns) were determined asG ₂=0·41 (14) andG ₂=0·60 (17), respectively. For the isomeric level at 2185·7 keV (T _1/2=67·2 min) the value ofG ₂=0·88 (49) was proposed.The authors would like to express their thanks to T. I. Kracíková and M. Trhlík for the valuable discussions in the course of the evaluation of the experimental data.     

Thermally stimulated depolarization of a phosphate glass

Thermally stimulated depolarization (TSD) of phosphate glass of the composition 72·9% P₂O₅, 8·5% Al₂O₃, 18·6% CaO, 0·23% MnO has confirmed the existence of two types of slow relaxation. Migration polarization leads to TSD maximum near 0 °C, while the high temperature TSD maximum at 113 °C probably corresponds to space charge polarization. An analysis of the high temperature maximum shows that it is formed by a spectrum of relaxations with a single activation energy 1·0 eV, distributed over the dipole frequency factors with the most probable value ₀ 10¹⁰ sec^–1. Strong dispersion of permittivity points to the space charge polarization, though it is found that the effect is linear and independent of the sample geometry.The authors thank Dr. A.Bohun for the samples and for valuable advice.     

Study of molybdenum coordination state and crystallization behavior in MoO3-La2O3-B2O3 glasses by Raman spectroscopy

The ternary MoO₃-La₂O₃-B₂O₃ glasses containing a large amount of MoO₃ (10-50 mol%) are prepared, and their structure and crystallization behavior are examined from the Raman scattering spectrum measurements and X-ray diffraction analyses. It is found that the glass transition and crystallization temperatures and the thermal stability against crystallization decrease with increasing MoO₃ content. It is suggested that the main coordination state of Mo⁶⁺ ions in the glasses is isolated (MoO₄)²⁻ tetrahedral units giving strong Raman bands at 830-860 and 930 cm⁻¹. It is found that the crystalline phases in the crystallized glasses are mainly LaMoBO₆ and LaB₃O₆, and the main crystallization mechanism in MoO₃-La₂O₃-B₂O₃ glasses is surface crystallization. LaMoBO₆ crystals are found to give strong Raman bands at 810-830 and ∼910 cm⁻¹.     

Van Vleck paramagnetism of the trivalent Eu ions

Magnetic susceptibilities of Eu₂O₃, EuF₃ and EuBO₃ have been measured over the wide temperature range 5-650 K. The Van Vleck paramagnetism, with the ground state of ⁷F₀ (S=3, L=3), has been investigated comprehensively. The temperature independent paramagnetism emerges manifestly below approximately 100 K. The variation of the susceptibility with temperature for EuBO₃ is in satisfactory agreement with the coupling constant , where the spin-orbit interaction is λL·S for the Russell-Saunders coupling on the basis of Van Vleck theory with one parameter λ. The value of can fit the susceptibility data of EuF₃. The deviation from the theory arises in Eu₂O₃. This discrepancy originates mainly from the influence of the crystalline field. Susceptibility of Gd₂O₃, having the ground state of ⁸S_7/2 (S=7/2, L=0), is also presented as a magnetic standard compound in comparison with these results.     

Epitaxial MoOx nanostructures on TiO2(1 1 0) obtained using thermal decomposition of Mo(CO)6

Stoichiometric and highly-defective TiO₂(1 1 0) surfaces (called as yellow and blue, respectively) were exposed to Mo(CO)₆ vapours in UHV and in a reactive O₂ atmosphere. In the case of yellow-TiO₂, an O₂ reactive atmosphere was necessary to obtain the Mo(CO)₆ decomposition at 450 °C with deposition of MoO_x nanostructures where, according to core level photoemission data, the Mo⁺⁴ state is predominant. In the case of blue-TiO₂ it was possible to obtain Mo deposition both in UHV and in an O₂ atmosphere. A high dose of Mo(CO)₆ in UHV on blue-TiO₂ allowed the deposition of a thick metallic Mo layer. An air treatment of this sample at 580 °C led to the elimination of Mo as MoO₃ and to the formation of a transformed layer of stoichiometry of Ti_(1−x)Mo_xO₂ (where x is close to 0.1) which, according to photoelectron diffraction data, can be described as a substitutional near-surface alloy, where Mo⁺⁴ ions are embedded into the titania lattice. This embedding procedure results in a stabilization of the Mo⁺⁴ ions, which are capable to survive to air exposure for a rather long period of time. After exposure of the blue-TiO₂(1 1 0) substrate to Mo(CO)₆ vapours at 450 °C in an O₂ atmosphere it was possible to obtain a MoO₂ epitaxial ultrathin layer, whose photoelectron diffraction data demonstrate that is pseudomorphic to the substrate.     

Judd-Ofelt parameters of Er in transparent TeO2-based nanocrystallized glasses

Transparent Er³⁺-doped bulk nanocrystallized (size of nanocrystals: ∼40 nm) glasses of 15K₂O·15Nb₂O₅·70TeO₂·0.5Er₂O₃ and 10BaO·10Gd₂O₃·80TeO₂·0.5Er₂O₃ are prepared, and the Judd-Ofelt parameters, (t=2, 4, 6), of Er³⁺ are evaluated from optical absorption spectra. The change in the molar polarizability due to the nanocrystallization is small in both samples, but a clear decrease in the mean atomic volume due to the nanocrystallization, i.e. more close atom packing, is observed. In both systems, a large decrease is observed in the parameter due to the nanocrystallization, indicating that the degree of the site symmetry of Er³⁺ ions in nanocrystallized glasses is much higher than that in the precursor glasses. The decrease in the and parameters due to the crystallization is small, suggesting that the covalency of Er³⁺-O bonds in nanocrystals is not so different from that in the precursor glasses.     

Temperature‐dependent Raman spectroscopic studies of microstructure present in dipotassium molybdate crystals and their melts

Temperature‐dependent Raman spectra of K₂Mo_nO_3n+1 (n = 1, 2, 3) crystals up to and above their melting points were recorded, and their vibration modes in solid and molten states were assigned. Basic structural units and the corresponding cluster forms in molten dipotassium monomolybdates, dimolybdates, and trimolybdates were studied by in situ high‐temperature Raman spectroscopic studies together with theoretical calculations, including density functional theory and quantum chemistry ab initio calculation. Anion units of [MoO₄]²⁻, [Mo₂O₇]²⁻, and [Mo₃O₁₀]²⁻ were shown to principally exist in molten K₂MoO₄, K₂Mo₂O₇, and K₂Mo₃O₁₀, respectively. The mechanisms of the microstructural evolution of K₂Mo_nO_3n+1 (n = 1, 2, 3) crystals while being melted are schematically illustrated. Copyright © 2016 John Wiley & Sons, Ltd.     

Laser- and gamma-ray induced crystallization of IR-transmitting calcium gallate glass

Ar⁺-laser (=488 nm) irradiation of calcium gallate (CG) glass with the composition of 60CaO·39Ga₂O₃·Fe₂O₃ resulted in a distinct decrease in the IR transmittance (T) due to the formation of crystalline CaGa₂O₄ and CaGa₄O₉ phases. The Mössbauer spectrum of non-irradiated glass comprised a broad doublet due to distorted Fe³⁺(T_d) with, , and of 0.20, 1.33, and 1.00 mm s^–1, respectively. An additional doublet due to Fe³⁺(T_d) was observed in the Ar⁺-irradiated glass and, , and were 0.17, 1.32, and 0.75 mm s^–1, respectively. A decrease inT was also observed after the⁶⁰Co -ray irradiation with doses 10⁵Gy, and the precipitation of CaO, Ga₂O₃, and CaGa₄O₇ phases was confirmed by X-ray diffraction.     

Lack of oxygen substitution in the chevrel compound Mo6S8

We present results from x-ray powder diffraction and lithium intercalation cells on samples of nominal composition “Cu₂Mo₆S₆O₂” and “Mo₆S₆O₂”. Our results show that it is not possible to prepare these materials with any significant fraction of the sulfur substituted by oxygen as claimed by Umarji et al.¹ Instead, the high temperature (1250°C) products from starting materials of CuO, Cu, S, MoO₂ and/or Mo are MoO₂, Mo and Cu_yMo₆S₈ with y>2.     

Pressure‐induced structural transformations in In2‐xYx(MoO4)3 systems

In this work, we report results of high‐pressure Raman experiments (P < 8 GPa) on In_2‐xY_xMo₃O₁₂ for x = 0.0 and 0.5. A crystalline to crystalline structural phase transition and pressure‐induced amorphization (PIA) have been identified. The structural phase transition takes place at 1.5 and 1.0 GPa for In₂(MoO₄)₃ and In_1.5Y_0.5(MoO₄)₃, respectively, resulting in the change of structure from monoclinic P2₁/a to a more denser structure. The PIA started at 5 and 3.4 GPa for In₂Mo₃O₁₂ and In_1.5Y_0.5Mo₃O₁₂, respectively. The amorphization process takes place in two stages in the case of In_1.5Y_0.5Mo₃O₁₂ phase, while for In₂Mo₃O₁₂, it is not complete until the pressure is as high as 7 GPa. Our results also suggest that with increase of ionic size of the A³⁺ ions, the octahedral distortion increases and consequently larger local structural disorder is introduced in the A₂(MoO₄)₃ system, where A is a trivalent ion (In, Y³⁺, Sc³⁺, Fe³⁺, etc.). Copyright © 2015 John Wiley & Sons, Ltd.     

X‐Ray Luminescence of Thin Oxide Films Containing Lead and Bismuth

We obtained thin films of the Bi₄Ge₃O₁₂, Bi₄Si₂O₁₂, PbWO₄, and Bi₂WO₆ scintillators and investigated their luminescence properties on xray excitation. We measured the xray luminescence spectra and established the linear character for the dependence of the luminescence intensity on the power of the dose of xray irradiation within the limits of up to 3·10^–3 A/kg. We investigated the radiation stability of the films obtained. The possibility of their application for detecting ionizing radiation is investigated. The films based on Bi₄Ge₃O₁₂ with an admixture of the Ge and Si or Mn activator of up to 1.5 mol.% are most suitable.     

Optical,photoelectric and electric properties of single-crystalline Sb2Se3

Measurements of absorption coefficient in the region of the absorption edge, of spectral distribution of photoconductivity and dependence of electrical conductivity upon temperature on Sb₂Se₃ single crystals are given. The absorption of light was proved to correspond to indirect forbidden transitions. The value of optical gapE _g ^opt =(1·11±0·02) eV forE a andE c was determined. From photoconductivity and conductivity measurements the values of the gaps areE _g ^opt =1·11 eV andE _g ^el =1·04 eV. The anisotropy of the electrical conductivity parallel and perpendicular to the cleavage plane is 2·2.     

Resistivity changes of evaporated Ti films caused by sorption of O2, CO2 and H2

Resistivity changes of Ti films evaporated in UHV were measured during sorption of O₂, CO₂ and H₂ at very low pressures (p 1·6×10^–6–1·6×10^–5Pa). During the sorption process the pressure was kept constant. For O₂ and CO₂ an increase of the resistivity with a tendency to saturation was observed. For H₂ anomalous curves with a resistivity maximum and a subsequent decrease of the resistivity were obtained. Possible mechanisms of the processes are discussed. For the Ti/O₂ interaction a simple model describing the time dependence of the resistivity changes is proposed.We are indebted to dr. L. Pátý for consultations in vacuum technology and his permanent help in the experimental work and to dr. Z. Knor for a valuable discussion and for kindly extending us many references.     

Properties of MOS-structures based on anode-oxidized CdSnAs2

The properties of metal (Al, Au)-anodic oxide-CdSnAs₂ monocrystal structures are studied. It is established that MOS-structures using undoped CdSnAs₂ crystals show a high positive fixed charge in the anodic oxide (N_S 5·10¹² cm^–2) and high surface state density on the oxide-CdSnAs₂ boundary surface (N_SS 2·10¹³ cm^–2·eV^–1). In MOS-structures using diffusion-doped (copper) crystals the sign of the fixed charge is negative (N_S 10¹¹ cm^–2, N_SS 2·10¹² cm^–2·eV^–1). The latter structures show a definite photosensitivity and photomemory. The possibility of effective control of the fixed charge value within the oxide by illumination is shown. The surface state distribution over energy, time constant, and capture section is determined.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 90–93, September, 1982.     

The magnetic anisotropy of manganate ferrites

The anisotropy constants K₁ for systems Mn_xFe_3–xO₄, with 1x 1·8, are calculated on the basis of the one-ion model and it is shown that the anomalous temperature dependence of the constant K₁ can be explained by the presence of Mn³⁺ ions in octahedral positions. The influence of the spin order on the magnetic anisotropy and the uniaxial anisotropy in systems Mn_xFe_3–xO₄ are discussed.