Structural phase transitions at high-temperature in double perovskite Sr2GdRuO6

The crystal structure evolution of the Sr₂GdRuO₆ complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K≤T≤1273 K. Powder X-ray diffraction measurements at room temperature and Rietveld analysis show that this compounds crystallizes in a monoclinic perovskite-type structure with P2₁/n (#14) space group and the 1:1 ordered arrangement of Ru⁵⁺ and Gd³⁺ cations over the six-coordinate M sites, with lattice parameters a=5.81032(8) Å, b=5.82341(4) Å, c=8.21939(7) Å, V=278.11(6) Å³ and angle β=90.311(2)^o. The high-temperature analysis shows that this material suffers two-phase transitions. At 373 K it adopts a monoclinic perovskite structure with I2/m space group, and lattice parameters a=5.81383(2) Å, b=5.82526(4) Å, c=8.22486(1) Å, V=278.56(2) Å³ and angle β=90.28(2)^o. Above of 773 K, it suffers a phase transition from monoclinic I2/m to tetragonal I4/m, with lattice parameters a=5.84779(1) Å, c=8.27261(1) Å, V=282.89(5) Å³ and angle β=90.02(9)^o. The high-temperature phase transition from monoclinic I2/m to tetragonal I4/m is characterized by strongly anisotropic displacements of the anions.     

Structure and high pressure behaviour of organic crystals based on aromatically substituted 1,3,4-oxadiazoles

The crystalline structure of a new compound containing the 1,3,4-oxadiazole moiety, 4-(5-methyl-1,3,4-oxadiazole-2yl-)-N,N′-dimethyl-phenylamine (MODPA) was determined. It shows a monoclinic structure with space group P2₁/c and lattice parameters: a=1.02997(6), b=0.64840(4), c=1.58117(10) nm and β=99.4820(10)°. To study the intermolecular interactions in oxadiazole containing organic crystals, X-ray studies on MODPA and 2,5-diphenyl-1,3,4-oxadiazole (DPO) were performed up to 5 GPa at room temperature. The Murnaghan equation of state is used to describe the compression behaviour of both substances. From these results, the bulk modulus and its pressure derivative were determined. The values obtained are: K₀=6.3 GPa and K′₀=6.8 for MODPA and K₀=7.3 GPa and K′₀=6.7 for DPO. Additionally, measurements under increasing temperature at ambient pressure were carried out to evaluate the thermal expansion coefficient: α=1.8×10⁻⁴ K⁻¹ for MODPA and α=1.9×10⁻⁴ K⁻¹ for DPO.     

Crystal and magnetic structures of Y2CrS4

Chromium(II) sulfide, Y₂CrS₄, prepared by a solid-state reaction of Y₂S₃ and CrS, showed an antiferromagnetic transition at 65 K. The neutron diffraction patterns at 10 and 90 K were both well refined with the space group Pca2₁. At 90 K, cell parameters were a=12.5518(13) Å, b=7.5245(8) Å, and c=12.4918(13) Å. At 10 K, magnetic peaks were observed, which could be indexed on the same unit cell. Magnetic moments of chromium ions were parallel to the b-axis and antiferromagnetically ordered in each set of the 4a sites.     

First-principle study of structural and electronic properties of ternary layered Ta2AlC

The structural and electronic properties of ternary layered Ta₂AlC ceramics have been studied using the first-principle method based on the density-functional theory. We have obtained the equilibrium lattice parameters and the equilibrium atomic positions in the unit cell. The equilibrium lattice parameters are computed to be a=b=3.15 Å and c=13.95 Å. The internal coordinates of Ta are determined to be (1/3, 2/3, 0.092). The band structure and density of states reveal that Ta₂AlC is an electronic conductor. The charge density distribution shows that the Ta and C atoms form a strong Ta-C-Ta covalently bonded chain.     

Optical,thermal and mechanical characterization of Al(III)/Sb(III)-doped tris(thiourea)zinc(II) sulphate crystals

The influence of Al(III)/Sb(III)-doping on the properties of tris(thiourea)zinc(II) sulphate (ZTS) crystals grown by slow evaporation solution growth technique is reported. The as-grown crystals belong to orthorhombic system and cell parameters are, a = 7.77 Å, b = 11.13 Å, c = 15.47 Å, V = 1338 Å³ (Al(III)-doped) and a = 11.1996 Å, b = 7.770 Å, c = 15.5598 Å, V = 1368.3 Å³ (Sb(III)-doped). The structure and the crystallinity of the materials are further confirmed by powder X-ray diffraction analysis. The modes of vibrations of different functional groups present are identified by Fourier transform infrared studies. Thermogravimetric/differential thermal analysis studies reveal the purity of the materials and no decomposition is observed up to the melting point. Surface morphological changes due to doping are observed by scanning electron microscopy. Microhardness study was carried out to elucidate the mechanistic behavior microhardness studies were carried out to elucidate the mechanistic behavior. Second harmonic generation activity is much better in the case of Sb(III)-doping. The specimen is also characterized by dielectric studies.     

Synthesis, growth, and characterization of a non-linear optical crystal-glycine lithium chloride

A new non-linear optical material, glycine lithium chloride, was synthesized and single crystals were grown by slow evaporation solution growth technique at constant temperature from its aqueous solution. Transparent and well-crystallized hexagonal prisms were obtained by controlled evaporation at a constant temperature of 45 °C. The grown crystals were characterized by X-ray diffraction methods, Fourier transforms infrared spectroscopy, and optical absorption spectrum. Single crystal X-ray diffraction analysis revealed that the crystal lattice of glycine lithium chloride is hexagonal with unit cell a = b = 7.023 Å, c = 5.478 Å, α = β = 90°, γ = 120°, V = 234 Å³. The dielectric response of the crystal with varying frequencies was studied. The second harmonic generation efficiency of the crystal was studied and is found to be larger than KDP.     

Calorimetric and single crystal X-ray study of the phase transition of (PyH)2PdCl4

Polymorphic transition of pyridinium tetrachloropalladate(II) was investigated by heat capacity measurements and by single crystal X-ray structural analysis. A large λ-type anomaly was detected at 240 K in the temperature dependence of the heat capacity. The low-temperature phase (LTP) belongs to the triclinic space group with a=6.856(1), b=7.293(1), c=7.721(1) Å, α=75.180(2)°, β=71.081(2)°, γ=81.109(3)° at 100 K, and the high-temperature phase (HTP) to the same space group with a=7.217(2), b=7.470(2), c=7.880(2) Å, α=73.438(3)°, β=65.195(3)°, γ=82.727(4)° at 293 K. The pyridinium cations are ordered antiferroelectrically in LTP. In HTP, however, an orientational disorder of the cation was observed. The energy difference between potential wells for the reorientation of pyridinium ion in HTP is discussed referring to the results of the present single crystal X-ray and heat capacity as well as the previous ¹H NMR measurements. A five-site disorder model is shown to be consistent with both of the observations of ¹H NMR and X-ray study.     

Synthesis and characterization of Co7(OH)12(C2H4S2O6)(H2O)2—a single crystal structural study of a ferrimagnetic layered cobalt hydroxide

A novel layered hydrotalcite-like material, Co₇(H₂O)₂(OH)₁₂(C₂H₄S₂O₆), has been prepared hydrothermally and the structure determined using single crystal X-ray diffraction (a=6.2752(19) Å, b=8.361(3) Å, c=9.642(3) Å, α=96.613(5)°, β=98.230(5)°, γ=100.673(5)°, R1=0.0551). The structure consists of brucite-like sheets where 1/6 of the octahedral sites are replaced by two tetrahedrally coordinated Co(II) above and below the plane of the layer. Ethanedisulfonate anions occupy the space between layers and provide charge balance for the positively charged layers. The compound is ferrimagnetic, with a Curie temperature of 33 K, Curie-Weiss θ of −31 K, and a coercive field of 881 Oe at 5 K.     

Synthesis and hydrolysis of octacalcium phosphate and its characterization by electron microscopy and X-ray diffraction

Octacalcium phosphate (OCP) powder was produced by precipitating 250 mL Ca(CH₃COO)₂ 0.04 M into 750 L of phosphate solution (5 mmol Na₂HPO₄ and 5 mmol NaH₂PO₄) at a constant temperature of 60 °C and pH 5, which resulted in a dry white powder. X-ray diffraction (XRD), transmission electron microscopy (TEM) analysis, and the electron diffraction pattern (SAED) all showed only OCP. Hydroxyapatite (HAP) was directly obtained through hydrolysis of the powder. The total transformation of OCP into HAP was registered over a period of 6 h. During the first 30 min of hydrolysis both phases coexisted. The two phases and the OCP-HAP interface were structurally analyzed through XRD and TEM. OCP parameters (calculated by the Rietveld method) are a=19.70, b=9.50, c=6.85 Å; α=90.03°, β=92.48°, γ=108.32° (triclinic P-1) with average crystal size of 13.5±0.2 nm, while HAP parameters were a=9.45, c=6.87 Å (hexagonal P6₃/m) with average crystal size of 16.9±0.2 nm.     

A new sodium samarium borate Na3Sm2(BO3)3

A new sodium samarium borate with composition Na₃Sm₂(BO₃)₃ (NSBO) has been synthesized by high temperature solid state reaction. The yellowish transparent single crystals of Na₃Sm₂(BO₃)₃ have been grown from the Na₂CO₃-H₃BO₃ flux system using the top-seeded solution growth (TSSG) method. X-ray diffraction analysis demonstrated that the NSBO crystals belong to orthorhombic systems and lattice parameters are a=5.0585 Å, b=11.0421 Å, c=7.0316 Å. The measurement of the infrared spectrum indicated that the basic anionic groups are the BO³⁻₃ groups. Furthermore, Na₃Sm₂(BO₃)₃ exhibits an optical second harmonic generation effect which is close to that of KDP (KH₂PO₄).     

Intermediate-temperature polymorphic phase transition in KH2PO4: A synchrotron X-ray diffraction study

We have used synchrotron X-ray diffraction to investigate the structural and chemical changes undergone by polycrystalline KH₂PO₄ (KDP) upon heating within the 30-250 °C temperature interval. Our data show evidence of a polymorphic transition at T∼190 °C from the room-temperature tetragonal KDP phase to a new intermediate-temperature monoclinic KDP modification (spacegroup P2₁/m and lattice parameters a=7.590, b=6.209, c=4.530 Å, and β=107.36°). The monoclinic RDP polymorph remains stable upon further heating to 235 °C, and is isomorphic to its RbH₂PO₄ and CsH₂PO₄ counterparts.     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Growth and physical properties of an organic crystal for NLO applications: Guanidinium phenyl arsonate (GPA)

Single crystals of organic material guanidinium phenyl arsonate (GPA) of size 28 × 14 × 10 mm³ were grown from propanol–water mixed solvent by slow solvent evaporation technique. The crystal belongs to monoclinic system with noncentrosymmetric space group Cc. The lattice parameter values of GPA crystals are a = 18.453 Å, b = 7.609 Å, c = 12.592 Å and β = 121.856°. The grown crystal was subjected to X-ray diffraction (XRD) study to identify its morphology and structure. Chemical etching study using propanol–water as etchant reveals the mechanism of growth. The formation of synthesized compound was confirmed by Fourier transform infrared (FT-IR) spectroscopy analysis. Optical transmittance and second harmonic generation (SHG) of the grown crystals were studied by UV–vis–NIR spectrum and Kurtz powder technique respectively. The transmittance of GPA has been used to calculate the refractive index ‘n’ and the extinction coefficient ‘k’. The laser induced surface damage threshold for the grown crystal was determined using Nd:YAG laser. The mechanical behavior of GPA was analyzed using Vickers microhardness test.     

Electrical properties of SrBi2(Nb0.5Ta0.5)2O9 ceramics

Aurivillius SrBi₂(Nb_0.5Ta_0.5)₂O₉ (SBNT 50/50) ceramics were prepared using the conventional solid-state reaction method. Scanning electron microscopy was applied to investigate the grain structure. The XRD studies revealed an orthorhombic structure in the SBNT 50/50 with lattice parameters a=5.522 Å, b=5.511 Å and c=25.114 Å. The dielectric properties were determined by impedance spectroscopy measurements. A strong low frequency dielectric dispersion was found to exist in this material. Its occurrence was ascribed to the presence of ionized space charge carriers such as oxygen vacancies. The dielectric relaxation was defined on the basis of an equivalent circuit. The temperature dependence of various electrical properties was determined and discussed. The thermal activation energy for the grain electric conductivity was lower in the high temperature region (T>303.6 °C, E_a−ht=0.47 eV) and higher in the low temperature region (T<303.6 °C, E_a−lt=1.18 eV).     

A new quasi-one-dimensional molecular solid based on Ni(mnt)2 anion: Crystal structure and spin-gap transition

A new molecular solid, [1-(4′-bromo-2′-fluorobenzyl)-4-dimetylaminopyridinium]-bis(maleonitriledithiolato)nickel(III), (BrFBzPyN(CH₃)₂(Ni(mnt)₂)(1), has been prepared and characterized by elemental analyses, IR, ESI-MS spectra, single crystal X-ray diffraction and magnetic measurements. Compound 1 crystallizes in the orthorhombic space group Pnma, a=20.579(4) Å, b=7.078(1) Å, c=17.942(4) Å, α=β=γ=90°, V=2613.3(9) Å³, Z=4. The Ni(III) ions of 1 form a quasi-one-dimensional Zigzag magnetic chain within a Ni(mnt)₂⁻ column through Ni?S, S?S, Ni?Ni, or π?π interactions with an Ni?Ni distance of 4.227 Å. Magnetic susceptibility measurements in the temperature range 2-300 K show that 1 exhibits a spin-gap transition around 200 K, and antiferromagnetic interaction in the high-temperature phase (HT) and spin gap in the low-temperature phase (LT). The transition for 1 is second-order phase transition as determined by DSC analyses.     

Structural, dielectric, optical and ferroelectric property of urea succinic acid crystals grown in aqueous solution containing maleic acid

Urea-succinic acid crystals have been grown at room temperature from aqueous solution in the presence of maleic acid by a slow evaporation technique. The structural parameters were determined using powder X-ray diffraction (XRD) and found to have monoclinic symmetry (space group P2₁/m) with a=9.902, b=17.510, c=5.555 Å and α=γ=90°, β=96.46°. The transparency and optical analysis were carried out using UV-vis analysis. The optical band gap is found to be 4.71 eV. The presence of various functional groups was confirmed by FTIR analysis. The samples have shown piezoelectric behavior with a fairly good piezoelectric charge coefficient (d₃₃) of 5 pC/N, when it is poled at 7 kV/cm. The hysteresis loop was plotted and the remnant polarization and coercive field were found to be 2.8 μC/cm² and 4 kV/cm, respectively. The dielectric analysis was carried out as a function of temperature at various frequencies and the results were also discussed.     

Crystal structure and thermal behavior of two new organic monosulfates NH3(CH2)5NH3SO4 1.5H2O and NH3(CH2)9NH3SO4 H2O

The chemical preparation, the calorimetric studies and the crystal structure are given for two new organic sulfates NH₃(CH₂)₅NH₃SO₄ 1.5H₂O (DAP-S) and NH₃(CH₂)₉NH₃SO₄·H₂O (DAN-S). DAP-S is monoclinic P2₁/n with unit cell dimensions: a=11.9330(2) Å; b=10.9290(2) Å; c=17.5260(2) Å; β=101.873(1)°; V=2236.77(6) Å³; and Z=8. Its atomic arrangement is described as inorganic layers of units and water molecules separated by organic chains. DAN-S is monoclinic P2₁/c with unit cell parameters: a=5.768(2) Å; b=25.890(10) Å; c=11.177(5) Å; β=115.70(4)°; V=1504.0(11) Å³ and Z=4. Its structure exhibits infinite chains, parallel to the [100] direction where the organic cations are interconnected. In both structures a network of strong and weak hydrogen bonds connects the different components in the building of the crystal.     

The structure and optical properties of AlN nanocrystals prepared by Schlenk techniques at atmospheric pressure and low temperature

AlN nanocrystals were prepared in organic solvent at atmospheric pressure and low temperature by the Schlenk technique. Both hexagonal and cubic AlN nanocrystals were obtained. The hexagonal nano-AlN powder possessed a wurtzite structure with a=3.124 Å, c=5.024 Å, the average grain size was about 2 nm. The lattice constant of the cubic nano-AlN was a=9.171 Å, the average grain size was about 4 nm. The structural and optical properties of the obtained AlN were analyzed. The emission related to deep-level defects was investigated by using temperature-dependent photoluminescence.     

Crystallographic study of the phase transition in (Me4P)2ZnBr4

The compound (Me₄P)₂ZnBr₄, a member of the β-K₂SO₄ structure class, undergoes a phase transition at 84°C from the room temperature space group P12₁/c1 to the parent Pmcn structure. The room temperature structure corresponds to a ferrodistortive transition of B_1g symmetry at the zone center. At room temperature, the compound has lattice constants a=9.501(1), b=16.055(2), c=13.127(2) Å and β=90.43(1)°. For the high temperature phase, the orthorhombic cell has dimensions a=9.466(2), b=16.351(3) and c=13.284(2) Å. The structures consist of two crystallographically independent Me₄P⁺ cations and the ZnBr₄²⁻ anions. In the room temperature phase, all three ionic species show substantial displacement from the mirror plane perpendicular to the a-axis that exists in the high temperature phase, as well as rotations out of that plane. The thermal parameters of the cations are indicative of substantial librational motion. Measurements of lattice parameters have been made at 2-5°C intervals over the temperature range 40-140°C. The changes in the lattice constants appear continuous at T_c (within experimental limits) indicating that the phase transition is likely second-order. The a lattice constant shows an anomalous shortening as T_c is approached. Thermal expansion coefficients are calculated from this data. An application of Landau theory is used to derive the temperature dependencies of spontaneous shear strain and corresponding elastic stiffness constants associated with the primary order parameter.     

Magnetic properties and EPR spectra of [Cu(L-arginine)2](NO3)2·3H2O

Magnetic and EPR data have been collected for complex [Cu(L-Arg)₂](NO₃)₂·3H₂O (Arg=arginine). Magnetic susceptibility χ in the temperature range 2-160 K, and a magnetization isotherm at T=2.29(1) K with magnetic fields between 0 and 9 T were measured. The observed variation of χT with T indicates predominant antiferromagnetic interactions between Cu(II) ions coupled in 1D chains along the b axis. Fitting a molecular field model to the susceptibility data allows to evaluate g=2.10(1) for the average g-factor and J=−0.42(6) cm⁻¹ for the nearest neighbor exchange coupling (defined as H_ex=-∑J_ijS_i·S_j). This coupling is assigned to syn-anti equatorial-apical carboxylate bridges connecting Cu(II) ion neighbors at 5.682 Å, with a total bond length of 6.989 Å and is consistent with the magnetization isotherm results. It is discussed and compared with couplings observed in other compounds with similar exchange bridges. EPR spectra at 9.77 were obtained in powder samples and at 9.77 and at 34.1 GHz in the three orthogonal planes of single crystals. At both microwave frequencies, and for all magnetic field orientations a single signal arising from the collapse due to exchange interaction of resonances corresponding to two rotated Cu(II) sites is observed. From the EPR results the molecular g-tensors corresponding to the two copper sites in the unit cell were evaluated, allowing an estimated lower limit |J |>0.1 cm⁻¹ for the exchange interaction between Cu(II) neighbors, consistent with the magnetic measurements. The observed angular variation of the line width is attributed to dipolar coupling between Cu(II) ions in the lattice.