Pressure derivatives of the elastic moduli of strontium,barium and lead nitrate

The pressure derivatives of the elastic moduli of Sr(NO₃)₂, Ba(NO₃)₂ and Pb(NO₃)₂ single crystal, have been measured by the ultrasonic pulse superposition method. The results for Sr(NO₃)₂ and Pb(NO₃)₂ are similar in magnitude and character, while the ones for Ba(NO₃)₂ differ strongly, $\text{?c}{}_{11}\text{?P}$ and $\text{?c}{}_{12}\text{?P}$ even From the measured pressure derivatives, the mode Grüneisen gammas and the Grüneisen constant as a function of temperature have been determined, and the latter is correlated with the experimental values, deduced from thermal expansion. The explicit temperature dependence of the elastic moduli is calculated, and found to be always negative, increasing in absolute value from Sr(NO₃)₂ to Pb(NO₃)₂.     

Angular dependence of the207Pb NMR linewidth in Pb(NO3)2 due to14N—207Pb direct dipole-dipole interaction

NMR signals of²⁰⁷Pb²⁺ have been measured in a single crystal of Pb(NO₃)₂. For rotation axes perpendicular to the static magnetic field and perpendicular to the (100) or (011) plane the linewidths of these signals vary by a factor 2 for different rotation angles of the single crystal. This dependence of the linewidth on the orientation has been explained by a¹⁴N —²⁰⁷Pb direct dipole-dipole coupling and it has been used to assign the different Pb²⁺ NMR signals to the different Pb²⁺ sites in the cubic unit cell of Pb(NO₃)₂.     

Nuclear magnetic shielding tensors of207Pb2+ in Pb(NO3)2

The NMR signals of²⁰⁷Pb were observed in a single crystal of Pb(NO₃)₂ and could be assigned to the four different Pb²⁺ sites by the dependence of the linewidths on the orientation. Four different nuclear magnetic shielding tensors with equal principal values but with different characteristic vectors could be determined. The symmetry of the shielding tensors is in agreement with the symmetry at the Pb²⁺ sites. It is shown, that intermolecular contributions can not account for the anisotropy of the nuclear magnetic shielding, which is 3 of the isotropic absolute magnetic shielding.     

Effects of divalent alkaline earth ions on the magnetic and transport features of La0.65A0.35Mn0.95Fe0.05O3 (A = Ca, Sr, Pb, Ba) compounds

We have studied the magnetic and transport properties of Fe doped La_0.65A_0.35Mn_0.95Fe_0.05O₃ (A = Ca, Sr, Pb, Ba) manganites. All the compositions show ferromagnetic/metal to paramagnetic/insulator transition (T_C) except the Pb doped sample which is insulating and ferromagnetic (FM) in the entire temperature range. The magnetization and T_C are decreased by decreasing the cation size on La site. The transition temperature and magnetic moment at 77 K is a maximum for Sr doped sample and is decreasing if we increase or decrease the cation size from Sr size. The maximum value of T_C and magnetic moment for Sr based sample is most likely due to the closer ionic sizes of La and Sr as compared to the other dopants (Ca, Pb, and Ba). We observed a spin freezing type effect in the Pb doped sample below 120 K in resistivity, ac susceptibility and in magnetization. This suggests that the AFM interactions introduced by the Fe are most effective in the Pb doped composition leading to increased competition between the FM and AFM interactions. This FM and AFM interaction generates some degree of frustration leading to the appearance of spin glass like phase whose typical magnetic behavior is studied for small ion when the metallic like behavior is lost.     

Paramagnetic resonance in irradiated Sr(NO3)2 single crystal

Paramagnetic resonance absorption of centres with spin 1/2 centered aboutg=2 is reported in gamma-irradiated single crystals of Sr(NO₃)₂. At room temperature four centres are detected which appear to exhibit axial symmetry about the [111] crystal direction. Two of the observed centres have a resolved hyperfine structure of N¹⁴. This hyperfine structure and axial symmetry of the centres indicate that they could be irradiation products of the nitrate ion. To find the number of trapped electrons, a simplified calculation of the molecular orbitals of planar and pyramidal NO₃ is carried out. Centres with a resolved hyperfine structure are then identified as pyramidal NO ₃ ^? and a NO₂ molecule rotating about the [111] direction. Two centres without hyperfine structure are not identified exactly.     

Flower-like Ni3(NO3)2(OH)4@Zr-metal organic framework (UiO-66) composites as electrode materials for high performance pseudocapacitors

Zr-metal organic frameworks (Zr-MOFs, UIO-66) as a kind of crystalline porous material possess controllable porous structure and strong thermal stability up to 753 K. In this paper, we synthesized Ni₃(NO₃)₂(OH)₄, Zr-MOF with high specific surface area (1073 m² g⁻¹) and Ni₃(NO₃)₂(OH)₄@Zr-MOF composite for pseudocapacitor material. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were taken to characterize the structure and morphology of Ni₃(NO₃)₂(OH)₄, Zr-MOF, and Ni₃(NO₃)₂(OH)₄@Zr-MOF. The porous structure of Zr-MOF favors the utilization of the active material Ni₃(NO₃)₂(OH)₄ and interfacial charge transport and provides short diffusion paths for ions, which results in a high specific capacitance. Electrochemical properties are evaluated by cyclic voltammetry (CV) and galvanostatic charge/discharge measurement. A maximum specific capacitance (SC) of 992 F/g was obtained from CV at a scan rate of 5 mVs⁻¹, which is higher than Zr-MOF (∼134 F g⁻¹) and Ni₃(NO₃)₂(OH)₄ (∼753 F g⁻¹). Meanwhile, the Ni₃(NO₃)₂(OH)₄@Zr-MOF composite electrode exhibits a good cycling stability over 3000 cycles.

     

Anomalous magnetic susceptibilities of the alkaline earth hexammines

The magnetic susceptibility of the metallic compounds Ca(NH₃)₆, Sr(NH₃)₆ and Ba(NH₃)₆ has been measured by the Faraday method in the range 2–200 K. The susceptibility of Ca(NH₃)₆ is strongly dependent on temperature and exhibits a broad minimum near 120 K and a peak near 10 K. In contrast to Ca(NH₃)₆, the susceptibilities of Sr(NH₃)₆ and Ba(NH₃)₆ are diamagnetic and decrease rapidly as the temperature is lowered. At low temperatures Ba(NH₃)₆ has the largest mass susceptibility of any nonsuperconducting metal.     

Strontium diffusion in Sr3−3x La2x □x(VO4)2 solid solutions

Layer-by-layer radiometric analysis in the temperature range 800–950 °C was used to measure the diffusion coefficients of ⁹⁰Sr, ⁴⁵Ca, ¹³³Ba radionuclides in Sr_3−3x La_2x □_x(VO₄)₂ (x=0,0.1,0.15,0.2,0.25) solid solutions. It was established that D _Ca ^* >D _Sr ^* >D _Ba ^* . An increase in the concentrations of vacancies (□) in the strontium sublattice leads to increased coefficients of diffusion of rare-earth metal cations. The activation energies for radionuclide diffusion were determined. It was shown that M²⁺ cations migrate via Sr(2) positions. Fiz. Tverd. Tela (St. Petersburg) 40, 223–226 (February 1998)     

Dielectric and leakage current properties of Li doped (Ba,Sr)TiO3 thick film interdigital capacitors on the alumina substrates

Li doped (Ba,Sr)TiO₃ thick films were fabricated by employing the screen printing method on the alumina (Al₂O₃) substrates. Interdigital capacitor patterns with seven fingers of 200 μm gap, 250 μm length were designed and screen printed on the alumina substrates. Ba_0.5Sr_0.5TiO₃ materials, paraelectric state at the room temperature, have been chosen for the microwave devices due to high dielectric permittivity and low loss tangent, however, the sintering temperature of (Ba,Sr)TiO₃ is over 1350 °C. In order to lower the sintering temperature, Li (3 wt%) was added to the (Ba,Sr)TiO₃ materials. Li doped (Ba,Sr)TiO₃ thick films screen printed on the alumina (Al₂O₃) substrates were sintered at 900 °C for 1.5 h. The structural feature was analyzed with X-ray diffraction method. Temperature dependent dielectric properties were characterized from 303 to 403 K at 1 MHz. Within the ±100 V of bias voltage, current-voltage characteristics of Li doped (Ba,Sr)TiO₃ films were investigated from 303 to 403 K. Through the current-voltage characteristics, the resistivity of Li doped (Ba,Sr)TiO₃ films were calculated.In this paper, the significant negative temperature coefficient of resistance (NTCR) of Li doped (Ba,Sr)TiO₃ films will be presented through the activation energy fitting. Measured activation energy is approximately 0.366 eV.     

IR Spectral Analysis of the Mixed Crystal System of AgNO3 and Sr(NO3)2

IR spectroscopy is utilized to analyse the mixed crystal system of AgNO₃ and Sr(NO₃)₂ in the ordered phase II and disordered phases of silver nitrate. The study aims mainly to clearify the change and the affect of partial replacement of Ag⁺ ion by Sr⁺⁺ ion in the mixed crystal system of the two metal nitrates. The change in the rotational energy barrier of the nitrate group was also checked.     

Preparation of porous (Ba,Sr)TiO3 by adding corn-starch

A new method of preparing porous (Ba,Sr)TiO₃ ceramics has been introduced, using an ordinary ceramics processing technique. The effect of corn-starch on the positive temperature coefficient of resistivity characteristics and microstructure of the porous (Ba,Sr)TiO₃ ceramics has been investigated. When the corn-starch addition was 1-20 wt%, the PTCR jump was over 10⁶ and 1-2 orders higher than that of samples without corn-starch. Also, it was found that the (Ba,Sr)TiO₃ ceramics had porous microstructure by the addition of corn-starch. The porosity of the ceramics with 20 wt% corn-starch was 44%. The electrical properties of the (Ba,Sr)TiO₃ ceramics have been discussed, based on the microstructure, resistivity of grain boundaries, donor concentration of grains and the electrical potential barrier of grain boundaries.     

The structure and magnetotransport properties of La2/3Sr1/3MnO3/Ba(La)TiO3 composites

The effect of Ba(La)TiO₃ doping on the structure and magnetotransport properties of La_2/3Sr_1/3MnO₃(LSMO)/xBa(La)TiO₃ (x=0.0, 1.0, 5.0 mol%) have been investigated. The X-ray diffraction patterns and microstructural analysis show that BaTiO₃ and LSMO phases exist independently in BaTiO₃-doped composites. The metal-insulator transition temperature (T_MI) decreases whereas the maximum resistivity increases very quickly by the increase of BaTiO₃ doping level. The partial substitution of Ba by La(0.35 mol%) results in a decrease in resistivity of LSMO/xBa(La)TiO₃ composites. Magnetoresistance of BaTiO₃-doped composites decreases monotonously in the temperature range 200-400 K in a magnetic field of 5 T, which is completely different from that of LSMO compound. The value of MR decreases at low field (H<1 T) and increases at high fields (H>1 T) with increasing the BaTiO₃ doping level at low temperatures below 280 K. These investigations reveal that the magnetotransport properties of LSMO/xBa(La)TiO₃ composites are dominated by spin-dependent scattering and tunneling effect at the LSMO/BaTiO₃/LSMO magnetic tunnel junction.     

Comparitive study of structure changes with temperature in univalent and divalent ionic nitrate crystals

The temperature dependence of the d.c. resistivity and dielectric constant of polycrystalline samples of Pb(NO₃)₂, Ba(NO₃)₂ and Sr(NO₃)₂ were found to show anomalies in the high temperature region. In addition, sharp peaks were obtained in both differential thermal analysis (DTA) and thermomechanical analysis (TMA) curves in the same temperature range. The observed anomalies were attributed to orientational disorder of the nitrate group leading to an order-disorder phase transition which is reported here for the first time. A comparison is made between the role of NO₃^?ions in both the divalent and univalent nitrates, taking NaNO₃ as representative. The TMA curve for Sr(NO₃)₂ showed a pronounced peak at 325°C. This peak was related to a sudden increase in the expansion coefficient associated with the rotation of the NO₃^? group leading to a solid state phase transformation. Energy diagrams describing the conduction mechanism and showing a fractionization of energy barriers in the case of divalent nitrates are introduced.     

Exploring the electronic structure of Pb2+ ions containing material Pb16(OH)16(NO3)16

A theoretical band structure calculation for lead nitrate hydroxide Pb₁₆(OH)₁₆(NO₃)₁₆ single crystal was performed based on the experimental crystallographic data obtained by Chang et al. Calculations exhibit that the conduction band minimum (CBM) is situated at Γ the center of the Brillouin zone (BZ) while the valence band maximum (VBM) is located between Γ and Y points of the BZ, resulting in an indirect energy band gap of about 3.70 eV in close agreement to the measured one (3.78 eV). The angular momentum resolved projected density of states reveals the existence of the strong hybridization between the orbitals and the VBM is originated from Pb-6s/6p and O-2p orbitals while the CBM from N-2p and Pb-6p orbitals. The calculated valence electronic charge density distribution explore the bond characters and the dominancy of the covalent bonding between Pb–O of PbO_n ployhedra and N–O of [NO₃]⁻ triangle. The calculated bond lengths and angles show good agreement with the experimental data.     

Phase equilibria in the La-Me-Co-O (Me=Ca, Sr, Ba) systems

The phase equilibria of the La-Me-Co-O systems (Me = Ca, Sr and Ba) were studied in air at 1100 °C. Two types of solid solution of general composition La_1−xMe_xCoO_3−δ and (La_1−y Me_y)₂CoO₄ were found to exist in the systems. The limiting composition of La_1−xMe_xCoO_3−δ lies at x=0.8 for Me = Sr, Ba and between 0.3–0.5 for Me = Ca. It is shown that the rhombohedral distortion of the perovskite type La_1−xMe_xCoO_3−y decreases while x increases. La_1−xMe_xCoO_3−δ (Me = Sr, Ba) shows an ideal cubic structure at x=0.5. The stability range of (La_1−yMe_y)₂CoO₄ was found to be 0.25≤y≤0.35 for Me = Ca, 0.3≤y≤0.55 for Me = Sr and 0.3≤y≤0.375 for Me = Ba. All phases have tetragonal K₂NiF₄-type crystal structure. Based on the XRD and neutron diffraction patterns of quenched samples, the phase diagrams (Gibbs triangles) are constructed for all systems. The phase equilibrium at low oxygen pressure is shown for the example of the La-Sr-Co-O system. The decomposition mechanism of La_1−xSr_xCoO_3−δ at 1100 °C for the samples with 0.5<x<0.8 within the oxygen pressure range −0.678>log(Po₂)>−2.25 can be written as follows: La_1−x′ Sr_x′CoO_3−δ′=n La_1−x″Sr_x″CoO_3−δ″+m SrCoO_2.5+q/2 O₂ where x′>x″. The decomposition mechanism of La_1−xSr_xCoO_3−δ for the samples with x < 0.5 within the oxygen pressure range −2.25>log(Po₂)>−3.55 changes and can be written as follows: La_1−xSr_xCoO_3−δ′=r La_1−x′Sr_x′CoO_3−δ″+w (La_1−y′Sr_y′)₂CoO₄+v CoO+f/2 O₂. The results are shown in “logPo₂-composition” diagrams. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Dielectric and impedance measurements on (1−x)Ba(Fe1/2Ta1/2)O3-xBa(Zn1/3Ta2/3)O3 ceramics

In this work, ((1−x)Ba(Fe_1/2Ta_1/2)O₃-xBa(Zn_1/3Ta_2/3)O₃), ((1−x)BFT-xBZT) ceramics with x = 0.00–0.12 were synthesized by the solid–state reaction method. X-ray diffraction data revealed that both the powders and ceramics were of a pure-phase cubic perovskite structure. All ceramics showed large dielectric constants. For the x = 0.12 sample, a very high dielectric constant (>20,600) was observed. A lowering in the dielectric loss compared to pure BFT ceramics was observed with the BZT addition. The impedance measurements indicated that BZT has a strong effect on the bulk grain and grain boundary resistance of BFT ceramics. These results are in agreement with the measured dielectric properties. Based on dielectric and impedance results, (1−x)BFT-xBZT ceramics could be of great interest for high performance dielectric materials applications due their giant dielectric constant behavior.     

20-Hz operation of an eye-safe cascade Raman laser with a Ba(NO3)2 crystal

Operation of a 1.598-μm eye-safe third-Stokes Raman laser with a Ba(NO₃)₂ crystal pumped by a 1.064-μm Nd:YAG laser is described. We observed a substantial decrease in the output energy during the first 50 s of the continuous operation at 20 Hz. The energy drop is ∼76% of the initial third-Stokes output. We confirmed negative thermal lensing and thermally induced birefringence in the crystal. With a concave cavity mirror at a matched curvature to the thermal lensing, we obtained an output energy of 11 mJ at 20 Hz. TEM₀₀ output was also obtained with a smaller pump-beam diameter with a highest conversion efficiency of 15.5% for a pumping power of only 45 MW/cm² (0.9 J/cm²). Received: 20 November 2001 / Revised version: 20 February 2002 / Published online: 2 May 2002     

Catalytic effect of water,water dimer,water trimer,HCOOH, H2SO4, CH3CH2COOH and HN(NO2)2 on the isomerisation of HN(NO2)2 to O2NNN(O)OH: a mechanism study

In this article, the isomerisation mechanisms of HN(NO₂)₂ to O₂NNN(O)OH without and with catalyst X (X = H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄, CH₃CH₂COOH and HN(NO₂)₂) have been investigated theoretically at the CBS-QB3 level of theory. Our results show that the catalyst X (X = H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄ and CH₃CH₂COOH) shows different positive catalytic effects on reducing the apparent activation energy of the isomerisation reaction processes. Such different catalytic effects are mainly related to the number of hydrogen bonds and the size of the ring structure in X (X = H₂O, (H₂O)₂ and (H₂O)₃)-assisted transition states, as well as different values of pK_a for H₂SO₄, HCOOH and CH₃CH₂COOH. Very interesting is also the fact that H₂SO₄-assisted reaction is the most favourable for the hydrogen transfer from HN(NO₂)₂ to O₂NNN(O)OH, due to the smallest pK_a (?3.0) value of H₂SO₄ than H₂O, HCOOH, H₂SO₄ and CH₃CH₂COOH, and also because of the largest ∠X???H???Y (the angle between the hydrogen bond donor and acceptor) involved in H₂SO₄-assisted transition state. Compared to the self-catalysis of the isomerisation mechanisms of HN(NO₂)₂ to O₂NNN(O)OH, the apparent activation energy of H₂SO₄-assisted channel also reduces by 9.6 kcal?mol^?1, indicating that H₂SO₄ can affect the isomerisation of HN(NO₂)₂ to O₂NNN(O)OH, most obvious among all the catalysts H₂O, (H₂O)₂, (H₂O)₃, HCOOH, H₂SO₄, CH₃CH₂COOH and HN(NO₂)₂.     

Z-Scan studies of KYW, KYbW, KGW, and Ba(NO3)2 crystals

We present the studies of nonlinear refraction and nonlinear absorption in promising crystals which are extensively used in Raman lasers or as solid-state laser host materials: Ba(NO₃)₂, KGW, KYW, and KYbW. The single-beam z-scan technique with 1 ps laser pulses at 790 and 395 nm has been applied for the study. Nonlinear refraction-index intensity-coefficients and two-photon absorption coefficients have been determined for the crystals. The considerable enhancement of nonlinear refraction is observed in the crystals at 395 nm.     

Crystal structures and phonon modes of Ba(Ca1/2W1/2)O3, Ba(Ca1/2Mo1/2)O3 and Ba(Sr1/2W1/2)O3 complex perovskites investigated by Raman scattering

This work investigates the crystal structures and phonon modes of Ba(Ca_1/2W_1/2)O₃, Ba(Ca_1/2Mo_1/2)O₃ and Ba(Sr_1/2W_1/2)O₃ perovskites by Raman spectroscopy. The samples were produced by conventional solid‐state processing at 1200 °C. X‐ray diffraction showed that single‐phase homogeneous materials were produced, which are cubic or pseudo‐cubic in symmetry. The existing controversies in the literature for these complex perovskites were investigated by comparing experimental Raman data with group‐theory analysis. Ceramics with Ca and W or Mo were found to be cubic, space group Fm3 m. For these materials, four Raman‐active bands were observed and the fitting parameters showed that the Ba(Ca_1/2Mo_1/2)O₃ ceramic presents bands at lower wavenumbers if compared with the Ba(Ca_1/2W_1/2)O₃ sample. For the Ba(Sr_1/2W_1/2)O₃ material, two hypotheses were investigated for monoclinic or triclinic structures. The experimental results showed 12 Raman‐active modes for this ceramic, which is in perfect agreement with the theoretical predictions for a monoclinic (I2/m) structure. Copyright © 2009 John Wiley & Sons, Ltd.