Soft chemistry synthesis and characterizations of fully oxidized and reduced NdBaCo2O5+δ phases δ = 0, 1

The double ordered perovskites NdBaCo₂O₅ and NdBaCo₂O₆ were prepared by soft chemistry. The samples were characterized from a structural and chemical point of view, concomitantly with their physical properties. Upon reduction, NdBaCo₂O₅ is formed with a tetragonal unit cell (a = b = 3.94 Å, c = 7.57 Å) and presents an antiferromagnetic behavior. Upon oxidation, a complete stoichiometric ordered phase NdBaCo₂O₆ with a tetragonal unit cell (a = b = 3.88 Å, c = 7.63 Å) could be obtained with a ferromagnetic and a metallic behavior. Finally it is shown that these phases are able to reversibly catch and release oxygen, suggesting a high anionic conductivity.     

Structural and magnetic properties of the double perovskite Sr2MnWO6

The nuclear and magnetic structure and the magnetic properties of the polycrystalline double perovskite Sr₂MnWO₆ have been studied. Rietveld analysis of neutron powder diffraction (NPD) data at T=295 K shows that the sample is tetragonal (space group P4₂/n, a=8.0119(4) Å, c=8.0141(8) Å). Some additional magnetic diffraction peaks were found in the NPD pattern at 10 K, which can be accounted for by antiferromagnetic ordering of spins at the Mn sites. The magnetic unit cell is doubled in all three unit axes directions (a=b=15.9984(8) Å, c=16.012(2) Å) and the manganese moments are coupled antiferromagnetically along the unit cell axes. The total magnetic moment of Mn²⁺ is found to be 2.27(7) μ_B. The antiferromagnetic behaviour was confirmed from magnetisation measurements. The transition from a paramagnetic to an antiferromagnetic state takes place at 13.0±0.1 K.     

Structural changes in ab-plane of Zn doped Bi-2212 HTSC single crystals

Single crystals of undoped and 1% Zn-doped Bi-2212 are grown by self-flux slow cooling method under similar growth conditions. T_c(ΔT_c) are found to be 84 K (2 K) and 82 K (8 K) for undoped and doped samples respectively. Effect of Zn doping on structure and modulation is studied. Different change in the value of a- and b-axes are observed resulting in a transformation of structure from tetragonal to orthorhombic one. However, no effective change in modulation is there. Distortions are compared in c- and b-axes for undoped and doped samples. The asymmetry in position and intensity of satellite peaks has been discussed. The value of a in excess of b has been reported for the first time. These results are discussed in terms of valancy, coordinates and position of occupancy of Zn ions vis-à-vis those of Cu⁻ ions in Cu–O plane of the structure.     

Magnetoresistance hysteresis of bulk textured Bi1.8Pb0.3Sr1.9Ca2Cu3Ox + Ag ceramics and its anisotropy

Magnetoresistance of bulk textured Bi_1.8Pb_0.3Sr_1.9Ca₂Cu₃O_x + Ag ceramics has been studied in the magnetic fields applied parallel and perpendicular to a–b planes of Bi2223 crystallites. Besides well known anisotropy of magnetoresistance of textured superconductors (R_H || c > R_H || a–b), anisotropic hysteresis of R(H) dependences was investigated. Parameters characterizing hysteretic R(H) curves differ for the cases H || c and H || a–b. This behavior is explained within the model of a granular superconductor where the total magnetic induction in the intercrystallite boundaries is superposition of the external field and the magnetic field induced by dipole magnetic moments of neighbor crystallites.     

Crystal growth and characterization of a new co-ordination complex—barium tetrakis(maleate) dihydrate

Crystals of barium tetrakis(maleate) dihydrate [Ba₄(C₄H₂O₄)₄]^?2H₂O are grown in gelated hydrosilica matrix. Single crystal X-ray diffraction studies show that the crystal system is monoclinic with space group P2₁/c. The unit cell dimensions are a=9.3721(2)  Å, b=20.5880(7)  Å, c=14.0744(4) Å, α=γ=90°, β=90.289(2)°. Powder XRD studies confirmed the single phase nature of the grown crystals. The FTIR data is in conformity with the XRD results. The TG–DTA curves of the material indicate a three-step thermal decomposition. The response of the dielectric properties in the temperature range 30 °C to 500 °C is correlated with the TG–DTA results.     

Synthesis,growth and characterization of a semiorganic nonlinear optical single crystal: L-Valine cadmium bromide

A semiorganic nonlinear optical material L-valine cadmium bromide was synthesized and single crystal grown from an aqueous solution by the method of slow evaporation technique at room temperature. The grown crystal was characterized by Powder X-ray diffraction and FT IR studies. The LVCB crystallizes in monoclinic system with cell parameters a = 10.144(2) Å, b = 5.54(1) Å, c = 12.07(2) Å, β = 109.115(2)° with space group P₂₁. Thermal behavior and stability of crystal were studied using thermogravimetric analyses (TGA) and differential thermal analysis (DTA) techniques. The suitability of this material for NLO application was studied by optical absorption studies and second harmonic generation (SHG) efficiency measurement by Kurtz–Perry powder method.     

Synthesis,crystal growth and characterization of a semiorganic material: Calcium dibromide bis(glycine) tetrahydrate

Single crystals of semiorganic material calcium dibromide bis(glycine) tetrahydrate were grown from aqueous solution. The crystal belongs to monoclinic system, with a = 13.261(5) Å, b = 6.792(2) Å, c = 15.671(9) Å and β = 91.68(4)°. The presence of the elements in the title compound was confirmed by energy dispersive X-ray analysis. The solubility and metastable zone width were found. The grown crystals were tested by powder XRD, FTIR, Thermo Gravimetric and Differential Thermal Analysis, UV–vis–NIR analysis, dielectrical and mechanical studies. The transmittance of calcium dibromide bis(glycine) tetrahydrate crystal has been used to calculate the refractive index n, the extinction coefficient K and both the real ɛ_r and imaginary ɛ_i components of the dielectric constant as functions of wavelength. The optical band gap of calcium dibromide bis(glycine) tetrahydrate is 3.23 eV.     

Optical and dielectric studies of solution grown glycinium maleate single crystal

Bulk single crystals of glycinium maleate have been grown from aqueous solution by slow evaporation method by optimizing the growth parameters within a period of 15 days. From X-ray diffraction analysis, the crystal was found to crystallize in monoclinic structure (space group C_2/c) with a = 17.866 Å, b = 5.684 Å, c = 17.408 Å and β = 112.65°. Presence of characteristic functional groups was confirmed in FTIR analysis. UV–Vis spectral analysis has revealed the absence of any high absorbance region between the wavelengths ranging from 300 to 900 nm. The optical band gap was calculated and found to be 3.91 eV. The activation energy for conduction at different frequencies was calculated and found to decrease from 0.54 eV to 0.41 eV as frequency increased from 100 Hz to 2 MHz. The dielectric behavior, conduction mechanism and the optical characterization of the glycinium maleate single crystals are being reported for the first time.     

Stishovite and post-stishovite polymorphs of silica in the shergotty meteorite: their nature,petrographic settings versus theoretical predictions and relevance to Earth's mantle

The Shergotty meteorite contains three dense silica polymorphs in distinct petrographic settings: (1) two post-stishovite SiO₂ polymorphs in individual multiphase grains coexisting with glass with nearly labradorite composition, and (2) large individual stishovite grains in shock-melt pockets which also contain the new CAS phase (Calcium-aluminosilicate; CaAl₄Si₂O₁₁; [Phys Earth Planet Interiors 97 (1996) 97; Geophys Abstract 5(2003)] and hollandite structured plagioclase composition. Prismatic and wedge-shaped grains of the original accessory tridymite (or cristobalite) in the Shergotty meteorite were densified during a major impact event on the Shergottite–Nakhlite–Chaissingite (SNC) parent body and inverted either to (1) multiphase assemblages of several post-stishovite polymorphs depicting prominent tweed pattern or to (2) Large homogeneous stishovite grains in melt pockets. In the first setting we identified an orthorhombic and a monoclinic post-stishovite silica polymorph, respectively. TEM investigations of a grain containing the orthorhombic polymorph revealed an α-PbO₂ like phase that could be assigned to either Pnc2 (with the cell parameters: a=4.55±0.01 Å, b=4.16±0.03 Å, c=5.11±0,04 Å), or Pbcn space group and dense SiO₂ glass. The X-ray diffraction pattern from a second grain revealed a polymorph with a monoclinic lattice with the space group P21/c, that is related to the baddeleyite (ZrO₂) structure with the cell parameters: a=4.375(1) Å, b=4.584(1) Å, c=4.708(1) Å, β=99.97(3), ρ=4.30(2) g/cm³. TEM-SAED pattern of this grain revealed the presence of the α-PbO₂-like SiO₂ polymorph, stishovite, secondary cristobalite, and dense silica glass. The coexistence of several high-density polymorphs and dense silica glass in the same grain suggests that several post-stishovite phases were formed during the shock event in Shergotty. Some of these polymorphs were highly unstable and vitrified, presumably in the decompression stage. Based on diamond anvil experiments on cristobalite a peak shock pressure in excess of 40 GPa could be deduced. The petrographic setting and texture of the single stishovite grains in the melt pockets is different. The mono-phase individual grains occur exclusively as large (>10 μm) rounded objects inside melt pockets together with hollandite structured plagioclase composition and the new CAS phase [1]. Stishovite in melt pockets is barren of any sign of a tweed pattern and contains no silica glass. This suggests that the mechanisms of phase transitions were different in the two lithologies. Stishovite in the melt pockets probably did not form by a retrograde transformation from a post-stishovite polymorph.     

Stabilization of ErFeAsO-based superconductor by hydrogen doping under high pressure

Here we report on the successful synthesis of ErFeAsO-based superconductor by hydrogen doping using high-pressure (HP) synthesis technique. The ErFeAsO_1?y target pellets were sandwiched between LaFeAsO_0.8H_0.8 pellets, which act as a hydrogen source. Hydrogen released from the hydrogen source soaks into the target pellets during HP synthesis and the target pellets crystallizes with the tetragonal crystal structure with the lattice constants a = 3.8219 Å and c = 8.2807 Å. The hydrogen doped sample ErFeAsO_1?y(H) thus obtained shows superconducting critical temperatures (T_c) of 44.5 K and 42.5 K determined by onsets of resistive and diamagnetic transitions, respectively.     

Experimental and theoretical studies on bis(glycine) lithium nitrate (BGLiN): A physico-chemical approach

Good quality and bulk size single crystal (size: 20×13×8 mm³) of bis(glycine) lithium nitrate (BGLiN) was grown by a slow evaporation solution technique from the aqueous solutions at constant temperature i.e. 27 °C using synthesized materials. Crystal system and lattice parameters were determined by single crystals as well as powder X-ray diffraction analysis. The lattice parameters of the titled compound are a=10.0223 Å, b=5.0343 Å, c=17.0510 Å, and V=860.312 Å³ and it crystallized in an orthorhombic system with space group Pca2₁ obtained by single crystal XRD. Elemental composition was confirmed by energy dispersive X-ray spectroscopic analysis. Optical absorption spectrum was recorded and various optical parameters such as optical transmission (~60%), and optical band gap (4.998 eV) were calculated. Photoluminescence study shows that the grown crystal is free from major defects. Crystalline perfection of the grown crystal was assessed and found good. Ground state optimized geometry has been obtained by using DFT with 6-31G(d,p) basis set. HOMO and LUMO energy gap was found to be 6.01 eV and dipole moment was 1.65 D.     

Crystal chemistry and physical properties of the ternary compounds RE5B4C5 (RE=Ce,Pr, Nd)

The ternary rare-earth metal boride carbides RE₅B₄C₅ (RE=Ce, Pr, Nd) were prepared by arc melting the mixtures of the pure elements and subsequent annealing at 1270 K. Their crystal structures were determined from single crystal X-ray diffraction data. They crystallize in the Ce₅B₄C₅ type of structure (space group Pna2₁, Z=8). Two new compounds were found, Pr₅B₄C₅: a=24.592(2) Å, b=8.4563(5) Å, c=8.4918(5) Å, R₁=0.043 (wR₂=0.076) for 2871 reflections with I_o?2σ(I_o)); for Nd₅B₄C₅: a=24.301(1) Å, b=8.3126(5) Å, c=8.3545(4) Å, R₁=0.035 (wR₂=0.069) for 3707 reflections with I_o?2σ(I_o)). Its structural arrangement consists of a three-dimensional framework of rare-earth atoms resulting from the stacking of slightly corrugated two-dimensional square nets, leading to voids filled with B₄C₄, B₃C₃, BC₂ finite chains and isolated carbon atoms. Ce₅B₄C₅ is an antiferromagnet at 5 K followed by a metamagnetic transition in elevated external fields. Pr₅B₄C₅ and Nd₅B₄C₅ are ferromagnets below T_C=12 and 15 K, respectively.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

The layered iron phosphate KMgFe(PO4)2: Crystal structure,Mössbauer spectroscopy and ionic conductivity

A new iron phosphate, KMgFe(PO₄)₂ has been synthesized and investigated by X-ray diffraction, Mössbauer spectroscopy and ionic conductivity. This compound crystallizes in the monoclinic space group C2/c with the parameters a = 18.529(7) Å, b = 5.402(3) Å, c = 9.374(9) Å, β = 120.64(5)° and Z = 4. Its original structure can be described as the stacking along the [101] direction of [MgFe(PO₄)^?₂]_∞ layers of corner-sharing MO₄ (M = 0.5 Fe + 0.5 Mg) and PO₄ tetrahedra. The K⁺ ions are occupying the inter-layer space. The Mössbauer spectroscopy confirms the occurrence of only tetrahedral Fe³⁺ ions and gives a definitive proof of the disordered character of their distribution. Ionic conductivity results obtained by the impedance spectroscopy technique show that this material is a two-dimensional ionic conductor, with low activation energy, 0.51 eV, that is interpreted on the basis of two-dimensional pathways.     

Studies on the optical and mechanical properties of non-linear optical 3-aminophenol orthophosphoric acid (3-amphph) single crystal

Single crystals of semiorganic material 3-aminophenol orthophosphoric acid (denoted as 3-amphph) of size 29 × 17 × 4 mm³ have been grown by the slow evaporation of an aqueous solution of deionized water at 50 °C. The crystal belongs to orthorhombic system with the non centrosymmetric space group P2₁2₁2₁. The lattice parameter values of 3-amphph crystal are a = 4.481(2) Å, b = 9.782(4) Å and c = 18.326(4) Å. The grown crystals are subjected to single crystal XRD studies to identify its morphology and structure. Optical transmittance and second harmonic generation of the grown crystals have been studied by UV–Vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of 3-amphph crystal has been used to calculate the refractive index n, the extinction coefficient k, reflectance R and both the real (?_r) and imaginary (?_i) components of the dielectric constant as a function of wavelength. The optical band gap of 3-amphph is 4.05 eV with direct transition. The anisotropic mechanical behavior of 3-amphph has been analyzed using Vickers microhardness test. The mechanism of growth is revealed by carrying out chemical etching using water as etchant.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Ionic conductivity and phase transition in Pb4.8Bi1.6Na3.6(PO4)6, an apatite-type compound

Bismuth sodium lead phosphate, Pb_4.8Bi_1.6Na_3.6(PO₄)₆, a compound having an apatite structure, was obtained via a solid-state reaction. Determination of the structure by X-ray diffraction on a single crystal gave the following results: hexagonal, P6₃/m, a = 9.6545(11) Å, c = 7.1457(5) Å, R = 0.03 and R_w = 0.09. The presence of Bi³⁺ and Pb²⁺ ions, carrying a lone electron pair, at (6h) sites helped to stabilize the apatite structure in spite of the anionic vacancies in the center of the tunnel. The compound was characterized by chemical analysis, differential thermal analysis, thermal expansion of the cell, and infrared, impedance and ²³Na NMR spectroscopy. The thermal behavior revealed two breaks attributed to order–disorder transitions. One of them was ascribed to a reordering of cations from the (6h) site to the center of the tunnel. Conductivity was dominated by hopping mechanisms.     

Interfacial reactions of Ba2YCu3O6+z with coated conductor buffer layer,LaMnO3

Chemical interactions between the Ba₂YCu₃O_6+x superconductor and the LaMnO₃ buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba₂YCu₃O_6+x–LaMnO₃ system. The Ba₂YCu₃O_6+x–LaMnO₃ join within the BaO–(Y₂O₃–La₂O₃)–MnO₂–CuO_x multi-component system is non-binary. At 810 °C (p_O2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba_2?x(La_1+x?yY_y)Cu₃O_6+z, Ba(Y_2?xLa_x)CuO₅, (La_1?xY_x)MnO₃, (La,Y)Mn₂O₅. The crystal chemistry and crystallography of Ba(Y_2?xLa_x)CuO₅ and (La_1?xY_x)Mn₂O₅ were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y_2?xLa_x)CuO₅ are Ba(Y_1.8La_0.2)CuO₅ and Ba(Y_0.1La_1.9)CuO₅, respectively. The structure of Ba(Y_1.8La_0.2)CuO₅ is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å³, and D_x = 6.29 g cm^?3. YMn₂O₅ and LaMn₂O₅ do not form solid solution at 810 °C (p_O2 = 100 Pa) or at 950 °C (in air). The structure of YMn₂O₅ was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å³. A reference X-ray pattern was prepared for YMn₂O₅.     

Synthesis and structure determination of a chain-like aluminophosphate obtained with 1,2-diaminopropane as the structure-directing agent

Colorless plate-like crystals (AlPO-1,2DAP) crystallize from a clear ‘AlPO₄-1,2-diaminopropane’ reaction system. The results of elemental, thermal and FTIR analyses give the following chemical formula: (NH₄⁺)(1,2-H₂DAP)²⁺(AlP₂O₈)³⁻, confirmed also by single crystal structure determination. The X-ray diffraction data collected at 150 K reveal the space group Pc2₁n with a=8.2788(2), b=16.7882(3), c=8.6608(2) Å, and V=1203.73(5) Å³. The AlPO-1,2DAP has a chain structure related to the aluminophosphate AlPO-enA structure. Two occluded cations, NH₄⁺ and doubly protonated diamine, balance the negative charge and interact with the chain oxygen atoms via hydrogen bond network.     

Structural reinvestigation of Li3FeN2: Evidence of cationic disorder through XRD,solid-state NMR and Mössbauer spectroscopy

A significant cationic disorder is evidenced on Li₃FeN₂ prepared through solid-state reaction under controlled atmosphere. This derivative anti fluorite type structure (orthorhombic, space group Ibam, a=4.870(1) Å, b=9.652(1) Å and c=4.789(1) Å), solved first through single crystal X-ray diffraction [7], is usually described by Li⁺ and Fe⁺³ ordered distribution in tetrahedral sites formed by the nitrogen network, leading to [FeN_4/2]³⁻ edge-sharing tetrahedral chains. From ⁷Li/⁶Li Nuclear Magnetic Resonance spectroscopy, ⁵⁷Fe Mössbauer spectroscopy and powder X-ray and neutron diffraction, we demonstrate that about 4% of lithium sites are filled by iron and about 11% of iron sites are occupied by Li, which can explain the discrepancy within the Gudat's model observed on larger scale solid-state synthesis samples.