Crystal structure and spectroscopic studies of NaGd(PO3)4

Single crystals of gadolinium–sodium polyphosphate NaGd(PO₃)₄ were grown for the first time using a flux method and characterized by X-ray diffraction. This phosphate crystallizes in a monoclinic system with P2₁/n space group and with the following unit-cell dimensions: a = 9.767(3) Å, b = 13.017(1) Å, c = 7.160(2) Å, β = 90.564(5)°, V = 910.3(4) Å³ and Z = 4. The crystal structure was solved from 3451 X-ray independent reflections with final R(F²) = 0.0219 and R_w(F²) = 0.056 refined with 164 parameters (). The atomic arrangement can be described as a long chain polyphosphate organization. Two infinite (PO₃)∝ chains with a period of eight tetrahedra run along the [0 1 1] direction. The structure of NaGd(PO₃)₄ consists of GdO₈ polyhedra sharing oxygen atoms with phosphoric group PO₄. Each Na⁺ ion is bonded to eight oxygen atoms.     

Synthesis, structure refinement and characterization of tetrahydrated acid gadolinium diphosphate HGdP2O7·4H2O

Synthesis and single crystal structure are reported for a new gadolinium acid diphosphate tetrahydrate HGdP₂O₇·4H₂O. This salt crystallizes in the monoclinic system, space group P2₁/n, with the following unit-cell parameters: a = 6.6137(2) Å, b = 11.4954(4) Å, c = 11.377(4) Å, β = 87.53(2)° and Z = 4. Its crystal structure was refined to R = 0.0333 using 1783 reflections. The corresponding atomic arrangement can be described as an alternation of corrugated layers of monohydrogendiphosphate groups and GdO₈ polyhedra parallel to the () plane. The cohesion between the different diphosphoric groups is provided by strong hydrogen bonding involving the W4 water molecule.

IR and Raman spectra of HGdP₂O₇·4H₂O confirm the existence of the characteristic bands of diphosphate group in 980–700 cm⁻¹ area. The IR spectrum reveals also the characteristic bands of water molecules vibration (3600–3230 cm⁻¹) and acidic hydrogen ones (2340 cm⁻¹). TG and DTA investigations show that the dehydration of this salt occurs between 79 and 900 °C. It decomposes after dehydration into an amorphous phase. Gadolinium diphosphate Gd₄(P₂O₇)₃ was obtained by heating HGdP₂O₇·4H₂O in a static air furnace at 850 °C for 48 h.     

Pyroelectric properties of BST/PLT composite thick films with addition of xPbO–(1 − x)B2O3 glass

The Ba_xSr_1−xTiO₃ (BST)/Pb_1−xLa_xTiO₃ (PLT) composite thick films (20 μm) with 12 mol% amount of xPbO–(1 − x)B₂O₃ glass additives (x = 0.2, 0.35, 0.5, 0.65 and 0.8) have been prepared by screen-printing the paste onto the alumina substrates with silver bottom electrode. X-ray diffraction (XRD), scanning electron microscope (SEM) and an impedance analyzer and an electrometer were used to analyze the phase structures, morphologies and dielectric and pyroelectric properties of the composite thick films, respectively. The wetting and infiltration of the liquid phase on the particles results in the densification of the composite thick films sintered at 750 °C. Nice porous structure formed in the composite thick films with xPbO–(1 − x)B₂O₃ glass as the PbO content (x) is 0.5 ≥ x ≥ 0.35, while dense structure formed in these thick films as the PbO content (x) is 0.8 ≥ x ≥ 0.65. The volatilization of the PbO in PLT and the interdiffusion between the PLT and the glass lead to the reduction of the c-axis of the PLT phase. The operating temperature range of our composite thick films is 0–200 °C. At room temperature (20 °C), the BST/PLT composite thick films with 0.35PbO–0.65B₂O₃ glass additives provided low heat capacity and good pyroelectric figure-of-merit because of their porous structure. The pyroelectric coefficient and figure-of-merit F_D are 364 μC/(m² K) and 14.3 μPa^−1/2, respectively. These good pyroelectric properties as well as being able to produce low-cost devices make this kind of thick films a promising candidate for high-performance pyroelectric applications.     

Synthesis and crystal structure of [2-NH2-5-CH3C5H4N]4P4O12·6H2O

Chemical preparation, crystal structure, IR absorption and thermal analysis of a new cyclotetraphosphate [2-NH₂-5-CH₃C₅H₄N]₄P₄O₁₂·6H₂O are reported. This compound is triclinic P-1 with unit-cell parameters: a = 10.206(5), b = 11.778(1), c = 9.991(4) Å,  = 110.40(6), β = 117.74(6), γ = 86.41(3)°, V = 989.1(8) Å³, Z = 1, D_x = 1.445 g cm⁻³. The structure has been determined and refined to R = 0.034 and R_w = 0.044, using 3663 independent reflections. The ring anions and water molecules form layers spreading around (a, b + c) planes via OHO hydrogen bonds. Between them are anchored 2-amino-5-methylpyridium cations, which establish H-bonds to interconnect the different adjacent layers and so contribute to the cohesion of the three-dimensional network. Tautomerization of (C₆H₉N₂)⁺ groups was evidenced in the present structure.     

Frequency dependent electrical conductivity and dielectric relaxation behavior in amorphous (90V2O5–10Bi2O3) oxide semiconductors doped with SrTiO3

We report on the experimental results of frequency dependent a.c. conductivity and dielectric constant of SrTiO₃ doped 90V₂O₅–10Bi₂O₃ semiconducting oxide glasses for wide ranges of frequency (500–10⁴ Hz) and temperature (80–400 K). These glasses show very large dielectric constants (10²–10⁴) compared with that of the pure base glass (≈10²) without SrTiO₃ and exhibit Debye-type dielectric relaxation behavior. The increase in dielectric constant is considered to be due to the formation of microcrystals of SrTiO₃ and TiO₂ in the glass matrix. These glasses are n-type semiconductors as observed from the measurements of the thermoelectric power. Unlike many vanadate glasses, Long's overlapping large polaron tunnelling (OLPT) model is found to be most appropriate for fitting the experimental conductivity data, while for the undoped V₂O₅–Bi₂O₃ glasses, correlated barrier hopping conduction mechanism is valid. This is due to the change of glass network structure caused by doping base glass with SrTiO₃. The power law behavior (σ_ac=A(ω^s) with s<1) is, however, followed by both the doped and undoped glassy systems. The model parameters calculated are reasonable and consistent with the change of concentrations (x).     

An electron diffraction study of the ZnIn2Se4 crystal structure: A novel phase

A novel layered-structure ZnIn₂Se₄ phase has been obtained. Texture electron diffraction patterns aid in the identification of a crystal structure with lattice parameters a = 4.045 Å and c = 52.29 Å, space group R m, and z = 4.5. Crystal electron diffraction patterns displayed superstructural reflection, thus indicating a √3-fold increase in the a parameter. The similirity of reflection locations and intensities both on the crystal rotation electron diffraction pattern and on texture electron diffraction patterns showed that no phase transition occurred on specimen pounding. Electrophysical and optical parameters (E_g = 1.68 eV; N = 8 × 10²² m^-3; = 0.1Ωm) are studied at 300 K. The Hall coefficient is constant (R_H = 7.2 × 10^-5m³C^-1, mobility μ = 8 × 10^-3m²V^-1s^-1 at 200–300 K.     

Reaction between the tetragonal tungsten bronze niobate K2Sr4Nb10O30 and the perovskite Pb(Mg1/3Nb2/3)O3

The search for dielectric materials with a high dielectric constant and ′_r = ƒ(T) curves with a flat profile fitting the X7R specification is still ongoing. Promising results were obtained by mixing compounds with closely related structures, such as the tetragonal tungsten bronze (TTB) niobate K₂Sr₄Nb₁₀O₃₀ and the perovskite Pb(Mg_1/3Nb_2/3)O₃ (PMN). The present study, based on three methods of synthesis, explores the origin of the spreading out of the dielectric curves ′_r = ƒ(T). For the composition 10x K_0.2Sr_0.4NbO₃ (KSN) + (1 − x)Pb(Mg_1/3Nb_2/3)O₃ (PMN) with x = 0.3–0.6, the three synthesis methods provided similar characteristics and for the highest perovskite ratio (x = 0.3), the ′_r = ƒ(T) curve exhibits a flat profile. When lithium is used as a sintering agent, ′_r = ƒ(T) curves present a linear dependency with the temperature. These materials are also characterized by a structural and a microstructural inhomogeneity. Two phases TTB and perovskite type, different from KSN and PMN, are present after calcination and sintering, but not evenly distributed. The PbO loss during sintering also contributes to the evolution of the properties of the material.     

Photoinduced changes in the optical constants of Ge–Se–AgI thin films

The photoinduced changes in the complex refractive index n=n − ik of thin films from the Ge–Se–AgI system with constant ratio Ge/Se=1/4 and concentrations of AgI of 0, 5 and 10 mol% are studied by real time measurements of reflectance (R) and transmittance (T) of the films. The phase delay (δ) between the components of the transmitted wave, which is proportional to the birefringence of the film, is measured in real time as well. The changes in the average value of the refractive index (Δn), and in the average value of the absorption index (Δk) in the imaginary part of n as well as the induced optical anisotropy are estimated by solving the inverse optical problem. It is found that involving small quantities of AgI into a Ge–Se matrix increases the sensitivity of the films, but the anisotropic effects are comparatively weakly in them. The maximum values of changes in the average refractive index (Δn=0.025) and in the average absorption index (Δk=−0.03) are obtained in the films, containing 5 and 10 mol% AgI, respectively. Considerable values of the photoinduced anisotropy – birefringence (Δn_a≈−0.002) and dichroism (ΔD≈0.05, which corresponds to Δk_a≈0.035) are observed in films without addition of AgI (“pure” Ge–Se film).     

Microstructure and strength of brazed joints of Ti3Al-base alloy with NiCrSiB

Brazing of Ti₃Al alloys with the filler metal NiCrSiB was carried out at 1273–1373 K for 60–1800 s. The relationship of brazing parameters and shear strength of the joints was discussed, and the optimum brazing parameters were obtained. When products are brazed, the optimum brazing parameters are as follows: brazing temperature is 1323–1373 K, brazing time is 250–300 s. The maximum shear strength of the joint is 240–250 MPa. Three kinds of reaction products were observed to have formed during the brazing of Ti₃Al alloys with the filler metal NiCrSiB, namely, TiAl₃ (TiB₂) intermetallic compounds formed close to the Ti₃Al alloy. TiAl₃+AlNi₂Ti (TiB₂) intermetallic compounds layer formed between TiAl₃ (TiB₂) intermetallic compounds and the filler metal and a Ni[s,s] solid solution formed in the middle of the joint. The interfacial structure of brazed Ti₃Al alloy joints with the filler metal NiCrSiB is Ti₃Al/TiAl₃ (TiB₂)/TiAl₃+AlNi₂Ti (TiB₂)/Ni[s,s] solid solution/TiAl₃+AlNi₂Ti (TiB₂)/TiAl₃ (TiB₂)/Ti₃Al, and this structure will not change with brazing time once it forms. The formation of over many intermetallic compounds TiAl₃+AlNi₂Ti (TiB₂) results in embrittlement of the joint and poor joint properties. The thickness of TiAl₃+AlNi₂Ti (TiB₂) intermetallic compounds increases with brazing time according to a parabolic law. The activation energy Q and the growth velocity K₀ of the reaction layer TiAl₃+AlNi₂Ti (TiB₂) in the brazed joints of Ti₃Al alloys with the filler metal NiCrSiB are 349 kJ/mol and 24.02 mm²/s, respectively, and the growth formula was y²=24.04exp(−41977.39/T)t. Careful control of the growth of the reaction layer TiAl₃+AlNi₂Ti (TiB₂) can influence the final joint strength.     

Temperature-independent electron tunneling injection in tris (8-hydroxyquinoline) aluminum thin film from high-work-function gold electrode

We fabricated electron-only tris (8-hydroxyquinoline) aluminum (Alq₃) single-layer devices with a device structure of glass substrate/MgAg anode (100 nm)/Alq₃ layer (100 nm)/metal cathode (100 nm), and systematically varied the work functions (WF) of the metal cathodes from WF = − 1.9 (Cs) to − 2.9 (Ca), − 3.8 (Mg), − 4.4 (Al), − 4.6 (Ag), and − 5.2 eV (Au) to investigate how electron injection barriers at the cathode/Alq₃ interfaces influence their current density–voltage (J–V) characteristics. We found that current densities at a certain driving voltage decrease and the temperature dependence of J–V characteristics of the devices gradually becomes weaker as the work functions of the metal cathodes are decreased. The device with the highest-work-function Au cathode exhibited virtually temperature-independent J–V characteristics, suggesting that a current flow mechanism of this device is mainly controlled by electron tunneling injection at the Au/Alq₃ interface.     

Thermal nonlinear refraction in the dye-doped sol–gel xTiO2 · (100 − x)SiO2 system

The build-up time of the thermal lens effect induced by a Gaussian beam in the DO3-doped sol–gel system xTiO₂ · (100 − x)SiO₂ at different compositions, both in the liquid and gel phases has been measured in a Z-scan geometry. While the pure titania samples show a minimum of the thermal diffusivity, a maximum is found for x ≈ 30. The sol to gel transformation leads to an increase of the build-up times at all compositions.     

Crystal structure, thermal analysis and IR spectroscopic investigation of (C6H9N2)H2XO4 (X = As, P)

Crystals of 2-amino-4-methylpyridinium dihydrogenmonoarsenate (C₆H₉N₂)H₂AsO₄ and 2-amino-4-methylpyridinium dihydrogenmonophosphate (C₆H₉N₂)H₂PO₄ have been prepared and grown at room temperature. These materials are isotypic with the following unit cell dimensions (C₆H₉N₂)H₂AsO₄: a = 12.4415(5) Å, b = 6.8224(3) Å, c = 11.3524(5) Å, Z = 4, V = 963.60(6) Å³; (C₆H₉N₂)H₂PO₄: a = 12.4410(9) Å, b = 6.7165(3) Å, c = 11.3417(5) Å, Z = 4, V = 925.09(10) Å³. The common space group is Pnma. The structure of these compounds has been determined by X-ray data collection on single crystals of (C₆H₉N₂)H₂AsO₄ and (C₆H₉N₂)H₂PO₄. Due to the strong hydrogen-bond network connecting the H₂XO₄ groups, the anionic arrangement must be described as a linear organization. The chains composed by the macroanion spread along the b-direction, approximately centered by x = 0 and 1/2. All atoms of the structure, except one oxygen atom, are located in the mirror planes situated at y = 1/4 and 3/4, imparting an internal mirror symmetry to the anionic and the cationic entities. The linear macroanions are crossed by organic cations lying in mirrors perpendicular to the b-direction; this atomic arrangement is then described by a three-dimensional network of hydrogen bonds, built up by two types, O–HO bonds inside the chains and N–HO bonds linking adjacent chains. The thermal properties of both compounds are investigated as well as the IR properties supported by group theoretical analyses.     

Rietveld refinement and spectroscopic studies of sodium lead fluoroapatite lacunaire synthesized by hydrothermal method

The structure of NaPb₉(PO₄)₆F(H₂O)_0.33, isostructural with apatite, was determined by X-ray powder diffraction methods and the result of Rietveld refinement is P6₃/m, a = 9.76396(8) Å and c = 7.27520(9) Å. The final refinement led to R_F = 5.4%, R_B = 6.6%. In the tunnel, the water molecule (O_w) and F⁻ ions appear to be located in 2b and 4e sites, with occupancies of 0.028(6) and 0.075(8), respectively. In the M(1) and M(2) sites the occupancies of Pb and Na are 0.282(3)/0.051(3) and 0.467(5)/0.033(5), respectively. The formula assigned to the compound is [Pb_3.38(4)Na_0.62(4)](1)[Pb_5.60(6)Na_0.40(6)](2)(PO₄)₆F_0.90(10)(H₂O)_0.33(7)□_0.77(17), where □ = vacancy. The assignment of the observed frequencies in the Raman and infrared spectra is discussed on the basis of a unit-cell group analysis and by comparison with fluor and chloroapatite analogs. The result of ³¹P and ²³Na magic angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies confirmed the structural results.     

Crystal structure and characterization of [2,5-(CH3O)2C6H3NH3]4P4O12·2H2O

The preparation, crystal structure, TG–DTA analysis and spectroscopy investigation are reported for the 2,5-dimethoxy phenyl ammonium cyclotetraphosphate dihydrate [2,5-(CH₃O)₂C₆H₃NH₃]₄P₄O₁₂·2H₂O. This new compound is triclinic P with unit cell dimensions: a = 7.438(5) Å, b = 11.841(7) Å, c = 12.354(4) Å,  = 96.61(4)°, β = 98.35(4)°, γ = 102.60(6)°, Z = 1 and V = 1038.0(1) Å³. Its crystal structure has been determined and refined to R = 0.049, with 5128 independant reflections. The structure can be described by rows of P₄O₁₂ ring anions along the a axis; between these rows are located the organic groups, connected to them by hydrogen bonds.     

Effects of growth conditions on the domain structure and dielectric properties of (1 − x)Pb(Sc1/2Nb1/2)O3–xPbTiO3 single crystals

The studies of the (1 − x)Pb(Sc_1/2Nb_1/2)O₃–xPbTiO₃ (PSN–PT) single crystals reveal that the chemical and physical properties of the materials are affected by the growth conditions. By the measurements of the dielectric constant as a function of temperature upon cooling, it is found that crystals grown from the same charged stoichiometric composition (x = 0.425), but under different flux environments (i.e. the composition of flux and the flux to PSN–PT ratios are varied), show anomalies (i.e. phase transitions) at different temperatures. This phenomenon is attributed to the complex local chemical structure of the PSN–PT solid solution single crystals with B-site random occupancy of three different cations (Sc³⁺, Nb⁵⁺ and Ti⁴⁺). The dielectric and domain structure of the PSN–PT crystals with composition near the morphotropic phase boundary (MPB) are investigated, showing much more complex situations compared with Pb(Sc_1/2Nb_1/2)O₃.     

Polar nanodomains and relaxor behaviour in (1 − x)Pb(Mg1/3Nb2/3)O3–xPbTiO3 crystals with x = 0.3–0.5

Phase transitions and dielectric properties of the (1 − x)Pb(Mg_1/3Nb_2/3)O₃–xPbTiO₃ crystals with x = 0.3–0.5 are studied. The solid solutions in this composition range are shown to be relaxor ferroelectrics. The crystals with low x demonstrate a diffused maximum in the temperature dependences of the dielectric permittivity at T_m. T_m varies with frequency according to the Vogel–Fulcher law. The polarizing microscopy investigations reveal a first-order phase transition from the relaxor phase to the low-temperature ferroelectric phase at T_C, which is several degrees below T_m. The permittivity peak in the crystals with x = 0.5 is sharp, and T_m is equal to T_C and does not depend on frequency, as is typical of the transition from a ferroelectric to an ordinary paraelectric phase. Nevertheless, the relaxor, but not the paraelectric, phase is observed at T > T_m. This conclusion is confirmed by the observation of the temperature behaviour of complex dielectric permittivity at T > T_m, which is typical of relaxors and related to the existence of polar nanodomains.     

Structure, magnetic and thermal properties of Gd2MnTiO6

A new perovskite compound Gd₂MnTiO₆ was synthesized and its crystal structure, magnetic and thermal properties have been investigated. The XRD patterns were refined by the Rietveld method and the refined lattice parameters with the monoclinic space group P2₁/n (No. 14) were a=0.5398 (2), b=0.5704 (2), c=0.7767 (2) nm and β=89.68 (2)°. The antiferromagnetic behavior was observed below 16.0 K and λ-type heat capacity was measured near this temperature.     

Quantum chemical modelling of point defects in KNbO3 perovskite crystals

We present results of semi-empirical quantum chemical calculations for several perovskite KNb_xTa_1−xO₃ (KTN) solid solutions, as well as point intrinsic defects – F centers and hole polarons bound to K vacancy – in KNbO₃. Method of the intermediate neglect of the differential overlap (INDO) was combined with typically 320-atom supercells and atomic geometry optimization. Analysis of the optimized atomic and electronic structure has clearly demonstrated that several nearest Nb atoms substituting for Ta in KTaO₃ – unlike Ta impurities in KNbO₃ – reveal the self-ordering effect, which probably triggers the ferroelectricity observed in KTN. We predict co-existence of one-site (atomic) and two-site (molecular) polarons with close absorption energies (≈1 eV). When available, the INDO results are compared with ab initio calculations. The relevant experimental data are discussed.     

Powder X-ray diffraction, infrared and conductivity studies of AgSbMP3O12 (M = Al, Ga, Fe and Cr)

New Nasicon type of compounds of composition AgSbMP₃O₁₂ (M = Al, Ga, Fe and Cr) are synthesized by solid-state method. All the compounds crystallize in the hexagonal lattice with space group . The infrared spectra of these compounds show characteristic bands due to PO₄ group. The frequency independent conductivity of these compounds shows Arrhenius type behavior and the activation energy for conduction is in the range 0.40–0.55 eV. Frequency independent conductivity (σ_dc) studies and frequency dependent (σ_ac) impedance measurements correlate well. The Cole–Cole plots do not show any spikes on the lower frequency side indicating negligible electrode effects. The activation energies obtained from the plots of log σ_dcT versus 1/T, log σ_ac(0) versus 1/T and log τ versus 1/T are approximately the same. The peak width at half height for electric modulus (M″) plot is 1.24 decades for all samples, which is close to 1.14 decades observed for Debye solid. The height of electric modulus (M″) obtained from the experimental plots are close to that of M″ (max) = C₀/2C indicating the Debye nature of the samples.     

Mechanical characterization of Ni1−xZnxFe2O4 prepared by non-conventional methods

The mechanical properties like hardness, H_v and compressive strength, σ of Ni_1−xZn_xFe₂O₄ (x = 0.2, 0.3, 0.4 and 0.5) prepared by the non-conventional flash combustion and citrate-gel decomposition techniques are studied and reported. It is observed that there is an increase in hardness with zinc content as well as sintering temperature. The hardness in the order of 2.0–3.63 GPa and compressive strength in the order of 150–240 MPa are obtained for Ni–Zn ferrites prepared by these non-conventional techniques. The influence of density, porosity and microstructure on hardness and compressive strength of Ni–Zn ferrites with respect to sintering temperature was studied.