Heats of solution/substitution and of fusion of Cs(1−x)KxCl compositions 0<x<0.57 by differential scanning calorimetry

Measurements of the change in heat (enthalpy) of solid-solid transition ΔH_t and of fusion ΔH_fus in crystalline CsCl effected by the presence of guest ion K⁺ up to 56.5 mol% using differential scanning calorimetry are reported. The range of K⁺ solubility is found to be higher and at variance with the subsolidus region described in earlier reports. Novel features of ΔH_t and ΔH_fus dependence on solute composition are in contrast to parallel binary systems, viz. CsNO₃-RbNO₃, CsNO₃-TlNO₃ and RbNO₃-TlNO₃. Some fundamental solution quantities are calculated from heat of transition, viz. slope ΔH_t/x or and χ-apparent partial molar heat of solution and partial molar heat of solution at infinite dilution, respectively.     

Theoretical study of local crystal structure in KZnF3:Fe system

An analysis of the relationship between the EPR trigonal-field parameters and the local crystal structure of KZnF₃:Fe³⁺system is presented by diagonalizing the complete energy matrices for a d⁵ configuration ion in a trigonal crystal field. We propose a two-layer-ligand model, in which the ligands consist of six nearest-neighbor F⁻ ions in the first layer and eight next nearest-neighbor K⁺ ions in the second layer. The calculation indicates that the local structure distortion of KZnF₃:Fe³⁺system is due to the displacement of a K⁺ ion along C₃ axis towards the Fe³⁺ ion, which leads to the shift of the F⁻ ions away from C₃ axis. By simulating the EPR low-symmetry parameters D and (a−F), the distorted angles between the Fe³⁺-F⁻ bonds and C₃ axis are determined, Δθ₁=2.58°, Δθ₂=−1.4° at room temperature (300 K) and Δθ₁=2.84°, Δθ₂=−1.4° at low temperature (77 K). Those results are in good agreement with the experimental findings Δθ₁=2.8±0.3°and Δθ₂=−1.1±0.3°.     

Study of ethylene adsorption on zeolite NaY modified with group I metal ions

The adsorption of ethylene by zeolite NaY and zeolite NaY modified by cation exchange with potassium, rubidium, and cesium ions was studied. Cation exchanges were carried out using KNO₃, RbNO₃, and CsNO₃ in the concentration ranges of 0.2-10 mM. XRD patterns and specific surface areas illustrated that modification of NaY zeolite by very dilute solutions containing K⁺, Rb⁺ and Cs⁺ did not lead to significant changes in the crystallinity. Analysis of metals content (ICP-OES) showed that Cs⁺ can replace Na⁺ better than Rb⁺ and K⁺. Particle analysis indicated slight decreases in surface area but pore volumes and pore diameters remained unchanged. Ethylene adsorption isotherms indicated that Na-Y zeolite which was modified by 5.0 mM KNO₃, 0.5 mM RbNO₃ and 1.0 mM CsNO₃ could adsorb ethylene better than zeolite Na-Y. K-NaY zeolite adsorbed up to 102.45 cm³/g ethylene, while Rb-NaY and Cs-NaY zeolites adsorbed up to 98.50 cm³/g and 90.15 cm³/g ethylene, respectively. Ethylene adsorption capacities depended on number of adsorption sites and surface interactions.     

Effects of excess oxygen content on the hole-carrying CuO2-layers in Tl2(Ba1−xSrx)2Ca2Cu3Oy superconducting oxides

The effects of oxygen doping on the hole-carrying CuO₂-layers in Tl₂(Ba_1−xSr_x)₂Ca₂Cu₃O_y were studied by combined chemical and valence analysis, T_c measurements and neutron diffraction. The highest T_c is characterized by an optimal excess oxygen content, Δy, dichotomizing the under- and over-doped regions for each Sr concentration. While the average Tl valence is close to 3.0 and independent of Δy, the average Cu valence shows a linear dependence with Δy. An increase of the flatness of the CuO₂ plane, characterized by the O(2)-Cu(2)-O(2) bond angle of ∼176°, was observed at the optimal Δy.     

Phase transition and freezing of ionic disorder in CsNO2 and TINO2 crystals2

The heat capacities of CsNO₂ and TlNO₂ have been measured in the temperature region between 13 and 350 K. The phase transitions of CsNO₂ and TlNO₂ were found at (209.16 ± 0.10)K and (282.4 ± 0.1)K. The enthalpy and entropy of the phase transition were (3.45 ± 0.20) kJ mol^?1 and (17.2 ± 1.0) JK^?1 mol^?1 for the former, and (6.44 ± 0.31) kJ mol^?1 and (23.8 ± 1.1) JK^?1 mol^?1 for the latter. The glass transitions were found around 42 K in CsNO₂ and around 60 K for TlNO₂, respectively. The corresponding dielectric relaxations were observed between 58 and 130 K for CsNO₂ in the frequency range between 10² and 10⁵ Hz and between 80 and 180 K for TlNO₂ in the frequency range between 2 × 10² and 10⁵ Hz. The calorimetric and dielectric relaxation times yielded a straight line in the Arrhenius plot over a wide time scale ranging from 10^?6 to 10⁵ sec. The slope gave the activation enthalpy of 13.8 kJ mol^?1 and 19.5 kJ mol^?1 for CsNO₂ and TlNO₂, respectively. The transition entropy supplemented by a residual entropy R ln 3 for CsNO₂ and R ln 2 for TlNO₂ gave (26.3 ± 1.0) JK^?1 mol^?1 and (29.6 ± 1.1) JK^?1 mol^?1 for the orientational entropy of the NO₂^? ion in the high-temperature phase. Based on the packing and symmetry considerations, these entropies were interpreted by the model which included two different sets of orientations of the NO₂^? ions parallel to [110] and [111] in the CsCl type unit cell. The existence of the different sets of orientation was proved by the doublet (Δv ~ 10 cm^?1) of the Raman spectrum of the bending mode of the NO₂^? ion in the cubic phase of the CsNO₂ crystal. The band narrowed to an ordinary singlet with increasing temperature. This observation was accounted for as the motional narrowing in which the NO₂^? ion felt an averaged field of the two different sets owing to the increased rate of jumping as the temperature increased.     

Orientational and positional disorder of ions and its freezing in the CsNO2-TlNO2 system2

The heat capacities of Cs_0.695Tl_0.305NO₂ (Specimen I) and Cs_0.385Tl_0.615NO₂ (Specimen II) have been measured between 14 and 350 K. Specimen I underwent a phase transition at (197.7 ± 0.1) K, with ΔS = (19.2 ± 1.5) JK^?mol^?, and specimen II at (214.5 ± 0.2) K, with ΔS = (5.4 ± 1.0) JK^?1mol^?1, respectively. Above the phase transition, an exothermic temperature drift due to phase separation was observed. Annealing of the sample at 203 K for 300 hr brought about complete phase separation. The solid solution system annealed at 203 K gave two heat capacity peaks at (203.3 ± 0.1) K, with ΔS = (13.8 ± 0.8) JK^?1 mol^?1, and (242.4 ± 0.2) K, with ΔS = (10.6 ± 1.3) JK^?1 for Specimen I, and at (203.0 ± 0.1) K with ΔS = (6.7 ± 0.5) JK^?1 mol^?1, and (257.5 ± 0.2) K with ΔS = (17.9 ± 1.7) JK^?1 mol^?1 for Specimen II. The phase diagram of the CsNO₂-TlNO₂ binary system was constructed on the basis of DTA, heat capacity and dielectric measurements. In the metastable phase, the existence of a residual entropy due to the freezing of a random distribution of Cs⁺₁ and Tl⁺ cations in addition to the orientational disorder of the NO₂^?1 ion was confirmed by a comparison of entropies of the stable and the metastable phases.     

Effects of protons and acceptor substitution on the electrical conductivity of La6WO12

Transport properties and non-stoichiometry of La_1−xCa_xW_1/6O₂ and La_1−yW_1/6O₂ (x=0, 0.005, 0.05; y=0.05, 0.1) have been characterized by means of impedance spectroscopy, the EMF-technique, H⁺/D⁺ isotope exchange, and thermogravimetry in the temperature range 300-1200 °C as a function of oxygen partial pressure and water vapor partial pressure. The materials exhibit mixed ionic and electronic conductivities; n- and p-type electronic conduction predominate at high temperatures under reducing and oxidizing conditions, respectively. Protons are the major ionic charge carrier under wet conditions and predominates the conductivity below ∼750 °C. The maximum in proton conductivity is observed for LaW_1/6O₂ with values reaching 3×10⁻³ S/cm at approximately 800 °C. The high proton conductivity for the undoped material is explained by assuming interaction between water vapor and intrinsic (anti-Frenkel) oxygen vacancies.     

α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

Raman scattering studies of the GeS2-Ga2S3-CsCl glassy system

Room temperature Raman spectra of samples on four serials within GeS₂-Ga₂S₃-CsCl glassy system have been investigated systematically. Based on the analysis of the local coordination surroundings of Cs⁺ ions, the similarities and changes of Raman spectra for glass Ga₂S₃-2CsCl and bridged molecular GaCl₃ were explained successfully. With a profound consideration of the effect of Cs⁺ ions on mixed anion units (GaS_4−xCl_x) and bridged units (Ga₂S_6−xCl_x) and the corresponding micro-structural model, the Raman spectral evolution of the samples within GeS₂-Ga₂S₃-CsCl glassy system was reasonably elucidated.     

High electric-field-induced strain of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals in multilayer actuators

An optimum composition range (29%≤x≤31%) of 〈001〉 oriented (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃(PMNT) crystals was ascertained for multilayer actuator applications, which exhibited high-strain and low-hysteresis behavior. A −1.5 kV/cm negative E-field can be applied to PMNT ferroelectric samples with low hysteresis. Forty layer actuators with individual element sizes of 7×7×0.7 mm³ were fabricated under identical processing conditions using two different materials: (1) single crystal PMNT and (2) commercial PZT-SF ceramics. Under free-load conditions, 48 μm displacements can been achieved in PMNT actuators at electric fields ranging from −1.5 to 10 kV/cm, which is more than twice the displacement of the PZT-SF actuators driven from −10 to 10 kV/cm. Under 4 kg loading, the displacements in PMNT stain actuators are decreased to 42.5 μm.     

The ν5 and 2ν9 bands of the N isotopic species of nitric acid (H15NO3): Line positions and intensities

Nitric acid (HNO₃) plays an important role in the Earth’s atmosphere as a reservoir molecule of NO_x species. It has a strong infrared signature at 11 μm which is one of the most commonly used for the infrared retrieval of this species in the atmosphere since this spectral region coincides with an atmospheric window. It is therefore essential to have high quality spectral parameters in this spectral region. For the H¹⁴NO₃ (main) isotopic species, the 11 μm bands were already the subject of numerous extensive studies which involve not only the ν₅ and 2ν₉ cold bands but also the first hot bands. The present work is the first high resolution Fourier transform analysis of the 11 μm bands for H¹⁵NO₃, which is the second most abundant isotopomer of nitric acid [a ≅ 0.00365(7)]. In this way, the analysis of the ν₅ and 2ν₉ cold bands centered at 871.0955 and 893.4518 cm⁻¹ was performed, and as for H¹⁴NO₃, these bands are significantly perturbed since rather strong resonances couple the 5¹ and 9² rotational levels. The theoretical model that we used to compute the line positions and line intensities is directly issued from the one which we used recently for H¹⁴NO₃ [A. Perrin, J. Orphal, J.-M. Flaud, S. Klee, G. Mellau, H. Mäder, D. Walbrodt, M. Winnewisser, J. Mol. Spectrosc. 228 (2004) 375-391]. Actually, for the H¹⁵NO₃ line positions, the Hamiltonian matrix accounts for the rather strong Fermi and the weaker Coriolis interactions linking the 5¹⇔9² rotational levels. Using this model which accounts correctly for the strong mixing of the 5¹ and 9² upper state energy levels, the ν₅ and 2ν₉ line intensities for H¹⁵NO₃ were satisfactorily computed using the ν₅ and 2ν₉ transition moment operators achieved previously for the ¹⁴N (main) isotopic species. In this way, the transfer of intensities from the ν₅ fundamental (and presumably strong) band to the 2ν₉ overtone (and presumably weak) band could be explained for H¹⁵NO₃ as it was done previously for the ¹⁴N (main) isotopic species. Finally, the position of the H¹⁵NO₃ν₅ + ν₉ − ν₉ hot band was identified at 875.245 cm⁻¹.     

Anomalous behavior of ultrasonic properties near 50 K in Rb0.30MoO3 and Rb0.30(Mo1−xVx)O3

Depending on the temperature, the charge density wave (CDW) nonlinear conductivity of the blue bronzes A_0.30MoO₃ (A=K, Rb) shows two different regimes: a strongly damped motion above ∼50 K and motion with almost no damping below ∼50 K. In a search for an elastic signature of this CDW behaviour, we performed ultrasonic measurements on Rb_0.30MoO₃ and Rb_0.30(Mo_1−xV_x)O₃ single crystals between 4 K and 300 K. In Rb_0.30MoO₃, at T∼50 K, upon cooling, a large increase of the sound velocity is observed. The ultrasonic attenuation coefficient shows an increase down to 50 K followed by a plateau. In Rb_0.30(Mo_1−xV_x)O₃ (x=0.4 at%) the anomaly broadens and is shifted towards higher temperatures. The results are discussed in terms of CDW glass.     

Photoluminescence properties of Eu in Y(PO3)3 under VUV excitation

The photoluminescence properties of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) are investigated. The excitation spectrum of Y_0.85(PO₃)₃:0.15Eu₃⁺ shows that both the (PO₃)₃³⁻ groups and the CT bands of O²⁻-Y³⁺ can efficiently absorb the excitation energy in the region of 120-250 nm. Under 147 nm excitation, the optimal emissive intensity of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) is about 36% of the commercial phosphor (Y,Gd)BO₃:Eu³⁺, which hints that the absorbed energy by the host matrix could be efficiently transferred to Eu³⁺. We try to study the concentration quenching mechanism of Y_1−x(PO₃)₃:xEu³⁺ (0<x≤0.2) under 147 and 172 nm excitation.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Synthesis and characterization of a new monophosphate [2,5-(CH3)2C6H3NH3]H2PO4

Chemical preparation, calorimetric studies, crystal structure and spectroscopic investigations are given for a new noncentrosymmetric organic cation monophosphate [2,5-(CH₃)₂C₆H₃NH₃]H₂PO₄. This compound is orthorhombic P2₁2₁2₁ with the following unit-cell parameters: a=5.872(4), b=20.984(3), c=8.465(1) Å, Z=4, V=1043.0(5) Å³ and D_x=1.396 g cm⁻³. Crystal structure has been solved and refined to R=0.048 using 2526 independent reflections. Structure can be described as an inorganic layer parallel to (a,b) planes between which organic groups [2,5-(CH₃)₂C₆H₃NH₃]⁺ are located. Multiple hydrogen bonds connecting the different entities of compound thrust upon three-dimensional network a noncentrosymmetric configuration.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

EPR theoretical study of local lattice structure in Al2O3:Fe system

By analyzing the EPR spectrum of transition-metal ion Fe³⁺ in Al₂O₃:Fe³⁺ system, the local lattice structure around impurity Fe³⁺ ion in the crystal has been studied by means of the diagonalization of the energy matrices of the electron-electron repulsion, the ligand-field and the spin-orbit coupling for a d⁵ configuration ion in a trigonal ligand-field. Both the second-order and fourth-order EPR parameters D and (a−F) are taken simultaneously in the structural investigation. The results indicate that the two three-edge-pyramids elongated obviously along C₃ axis. The two distortion angles Δθ₁=−1.1±0.1°,Δθ₂=−1.8° as well as the two Fe-O bond lengths R₁=2.016 A, R₂=1.907 A are determined, respectively.     

Luminescence investigation of red phosphors Ca0.54Sr0.34−1.5xEu0.08Smx(MoO4)y (WO4)1−y for UV-white LED device

Ca_0.54Sr_0.34−1.5xEu_0.08Sm_x(MoO₄)_y (WO₄)_1−y red phosphors were prepared by solid-state reaction using Na⁺ as a charge compensator for light-emitting diodes (LED). The effects of Na⁺ concentration, synthesis temperature, reaction time and Eu³⁺ concentration were studied for the properties of luminescence and crystal structure of red phosphors. The results show that the optimum reaction condition is 6%, 900 °C, 2 h and 8%. The photoluminescence spectra show that red phosphors are effectively excited at 616 nm by 292, 395 and 465 nm. The wavelengths of 465 nm nicely match the widely applied emission wavelengths of blue LED chips.