Preparation and structures of the La1−xKxCo1−xNbxO3 (x = 0–l) system

The La_1−xK_xCo_1−xNb_xO₃ system was performed by conventional solid state reaction technique using metal oxides. By DSC analysis, the activation energy of crystallization of the powders with x = 0.3 is 388.4 kJ/mol. The crystal structure of the compound reveals a transition from rhombohedral to cubic, and then to orthorhombic structure as the amount of the potassium niobate (KNbO₃) increases. It is found that the structure of the samples with x < 0.3 is similar to that of lanthanum cobaltate (LaCoO₃), while at the compositions with 0.7 ≥ x ≥ 0.3, the structure transforms to cubic. Finally, with x ≥ 0.7, the structures were similar to that of KNbO₃. According to the results of selected-area-diffraction (SAD) patterns and X-ray diffraction (XRD) identifications, the lattice parameters were calculated. The direction of superlattice structure along [2 1 0] was found for x = 0.5 as identified from SAD patterns. The dielectric constants were measured with cubic structure. Dielectric constant (K) decreases with increasing x.     

Subsolidus phase relation and crystal structure of the PrBa2−xSrxCu3O7±δ system

The PrBa_2−xSr_xCu₃O_7±δ solid solution was investigated by means of X-ray powder diffraction in combination with Rietveld analysis. The Sr-doped Pr123 single phase could be synthesized at 950 °C in air. The solubility of PrBa_2−xSr_xCu₃O_7±δ solid solution is 0.2≤x≤0.6. The structure of PrBa_2−xSr_xCu₃O_7±δ is orthorhombic for x=0.2. The structure transforms into tetragonal for 0.3≤x≤0.6. In the PrBa_2−xSr_xCu₃O_7±δ structure, Sr ions can replace Ba ions, the highest value is x=0.6 under our experimental condition. But Sr ions could not replace Pr ions. Furthermore Pr ions could not occupy the sites of Ba ions in the PrBa_2−xSr_xCu₃O_7±δ system. Both ionic radii and chemical properties play an important role in the mutual substitution of Pr, Ba and Sr ions in the Pr123 structure of the PrBa_2−xSr_xCu₃O_7±δ system.     

Synthesis and characterization of new pyrochlore solid solution Bi1.5Sb1.5Cu1−xMnxO7

A new pyrochlore solid solution with formula Bi_1.5Sb_1.5Cu_1−xMn_xO₇ has been synthesized using ceramic method at 1000 °C. The cell parameter decreases linearly with increasing manganese concentration. Rietveld refinements for (B_1.5Mn_0.5)(Sb_1.5Mn_0.5)O₇ compound using X-ray powder diffraction data confirmed an overall A₂B₂O₇ cubic pyrochlore structure with a = 10.42749 (4) Å and Fd-3m symmetry. The reliability factors are R_wp = 3.48%; R_p = 2.37%; R_exp = 1.65% and R_Bragg = 1.58%. The magnetic susceptibility measurements achieved between 4 and 300 K indicate a paramagnetic behaviour with an oxidation state “2+” of the manganese ion. The electric resistance measured using complex impedance spectroscopy method put in evidence a decrease of the electric resistance with the temperature, which reached 5 × 10² Ω at 675 K. Dielectric properties depend on the variation of frequency and temperature, results indicate a conductive compound.     

Power factor of La1−xSrxFeO3 and LaFe1−yNiyO3

The electrical conductivity (σ), Seebeck coefficient (S), and power factor (σS²) of perovskite-type LaFeO₃, La_1−xSr_xFeO₃ [0.1 ≤ x ≤ 0.4] and LaFe_1−yNi_yO₃ [0.1 ≤ y ≤ 0.6] were investigated in the temperature range of 300–1100 K to explore their possibility as thermoelectric materials. The electrical conductivity of LaFeO₃ showed semiconducting behavior, and its Seebeck coefficient changed from positive to negative around 650 K with increasing temperature. The electrical conductivity of LaFeO₃ increased with the substitutions of Sr and Ni atoms, while its Seebeck coefficient decreased. The Seebeck coefficient of La_1−xSr_xFeO₃ was positive, whereas that of LaFe_1−yNi_yO₃ changed from positive to negative with increasing Ni content. The substitutions of Sr and Ni were effective in increasing the power factor of LaFeO₃; 0.0053 × 10⁻⁴ Wm⁻¹ K⁻² for LaFeO₃ (1050 K), 1.1 × 10⁻⁴ Wm⁻¹ K⁻² for La_1−xSr_xFeO₃ (x = 0.1 at 1100 K) and 0.63 × 10⁻⁴ Wm⁻¹ K⁻² for LaFe_1−yNi_yO₃ (y = 0.1 at 1100 K).     

EXAFS and Te spectroscopy study of the Yb1−xEuxTe, Pb1−xEuxTe and Yb1−xGdxTe solid solutions

We report EXAFS (Extended X-Ray Absorption Fine Structure) measurements on three solid solutions of rare-earth monotelluride in order to measure the x-dependence of the cation-anion distance and Debye-Waller factor. We find Yb_1−xEu_xTe is an ideal solid solution with a bimodal distribution of distances, accommodated by the Te sublattice, at contrast with the two other solid solutions Pb_1−xEu_xTe and Yb_1−xGd_xTe. The anomalous behaviour of the EXAFS parameters in the last system is related to the shallow nature of the Gd donor.     

Phase relations and hydrogenation behavior of Sr(Al1−xMgx)2

The phase relations and hydrogenation behavior of Sr(Al_1−xMg_x)₂ alloys were studied. The pseudobinary C36-type Laves phase Sr(Al,Mg)₂ was found as a structural intermediate between the Zintl phase and the C14 Laves phase. The single-phase regions for the Zintl phase, C36 phase and C14 phase, were determined to be x=0–0.10, 0.45–0.68 and 0.80–1, respectively. The Mg-substituted Zintl phase Sr(Al_0.95Mg_0.05)₂ can be hydrogenated to Sr(Al,Mg)₂H₂ at about 473 K. However, the Sr(Al,Mg)₂H₂ directly decomposes into SrH₂ and Sr(Al,Mg)₄ starting at 513 K. When the temperature is 573 K, the C36 Laves phase Sr(Al_0.5Mg_0.5)₂ can be hydrogenated into SrMgH₄ and Al, while the C14 Laves phase Sr(Al_0.1Mg_0.9)₂ is hydrogenated into SrMgH₄, Mg₁₇Al₁₂ and Mg.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Crystal fields in (La1−xGdx)OCl:Eu solid solutions

The formation of cation solid solution in the (La_1−xGd_x)OCl:Eu³⁺ (0≤x_Gd≤1; Δx_Gd=0.1) series was studied by photoluminescence spectroscopy. The luminescence from the ⁵D_0–2 to the ⁷F_0–4 levels of the Eu³⁺ ion in the (La_1−xGd_x)OCl series was recorded at 77 K by using argon ion laser excitation (457.9 nm). The interpretation of the spectra according to the C_4v site symmetry of the Eu³⁺ ion in the tetragonal PbFCl-type structure yielded nearly complete sets (18 to 19 levels) for the ⁷F_0–4 levels. Simulations of the Stark level schemes were carried out with the aid of a phenomenological c.f. theory utilizing the five non-zero c.f. B_q^k parameters (B₀², B₀⁴, B₄⁴, B₀⁶ and B₄⁶) allowed for the C_4v site symmetry. By using the calculated c.f. parameter sets a quantitative measure was obtained to monitor the formation of cation solid solutions. The strength of the c.f. effect was estimated with the c.f. strength parameters S and S^k (k=2, 4 and 6). The c.f. parameter sets reproduced the experimental ⁷F_J (J=0–4) energy level schemes with the rms deviations between 4 and 11 cm⁻¹. The individual parameters as well as the c.f. strength parameters were found to evolve in a smooth manner indicating complete solid solubility in the (La_1−xGd_x)OCl series. Some local distortions from the C_4v symmetry — probably of long range—leading to the splitting of the ⁷F₁ doubly degenerate E level were observed, however.     

Studies on structural and electrical properties of Co1−xNixFe1.9Mn0.1O4 ferrite

Nickel-doped iron-deficient cobalt ferrite with small amount of manganese having the chemical composition Co_1−xNi_xFe_1.9Mn_0.1O₄, with x = 0.2, 0.4, 0.6 and 0.8, were prepared by standard double sintering ceramic method. The spinel phase formation was confirmed by X-ray diffraction (XRD). The DC resistivity measurements with temperature indicate a semiconducting behavior showing a linear decrease with increasing temperature and the doping of Ni enhances the resistivity. Maximum resistivity of the order of 10⁹ Ω cm was found for composition x = 0.8. Room temperature dielectric constant measurements with frequency (100 Hz to 1 MHz), show usual dielectric dispersion. Also, the variation of room temperature AC conductivity as a function of frequency were studied and explained by using Maxwell–Wagner two-layer model. The studies on dielectric constant (′), loss tangent (tan δ) and AC conductivity (σ_AC), at four different frequencies (viz., 1, 10, 100 kHz and 1 MHz), with temperature were made.     

Synthesis, crystal structure, oxygen stoichiometry, and electrical conductivity of La1−aCaaCr0.8Ti0.2O3−δ solid solutions

Series of perovskite-type compounds La_1−aCa_aCr_0.8Ti_0.2O_3−δ (a=0–1.0) were synthesized by the ceramic technique in air (final heating 1350 °C). The crystal structure of the compounds after cooling in air to room temperature was characterized as orthorhombic in space group Pbnm. Analysis of the lattice constants shows a noticeable decrease with increasing Ca content. All compounds prepared were stable in air and in a stream of Ar/1 Pa O₂ at 20–1400 °C, as also in Ar/5% H₂ (pH₂O/pH₂=0.01) at 850–1000 °C. Oxygen stoichiometry and electrical conductivity of the solid solutions with a=0.0–1.0 are investigated. Increasing Ca contents decrease the stability of the oxides in respect to the thermal dissociation of oxygen. All compounds are p-type semiconductors in the temperature range 20–1000 °C at oxygen partial pressures of 10⁻¹⁵ to 0.21×10⁵ Pa. A maximum conductivity of about 30 S/cm in air at 1000 °C is observed for the composition with a=0.6 corresponding to a ratio of Cr³⁺/Cr⁴⁺=1 at an oxygen stoichiometry near 3.0, and oxidation states of La, Ca, Ti, and O ions of 3+, 2+, 4+, and 2−, respectively.     

Formation and properties of BaxFe3−xO4 with spinel structure by mechanochemical reaction of α-Fe2O3 and BaCO3

Magnetic Ba_xFe_3−xO₄ (x  0.23) with spinel structure was fabricated by ball milling of mixture of BaCO₃ and nonmagnetic α-Fe₂O₃ powders, and the molar ratio of BaCO₃ and α-Fe₂O₃ is 1:6. In the milling process, a mechanochemical reaction took place between BaCO₃ and α-Fe₂O₃, and Ba cation incorporated into α-Fe₂O₃ with rhombohedral structure to form a α-(Fe,Ba)₂O₃ solid solution. The Ba content in the α-(Fe,Ba)₂O₃ increased with increasing milling time, when the Ba content exceeded a limited solubility, the α-(Fe,Ba)₂O₃ transformed into a phase of Ba_xFe_3−xO₄ with spinel structure, where the Ba cation occupied an octahedral site or tetrahedral site. The product obtained in the balling process was different from that prepared in the annealing process at atmospheric pressure, which was BaFe₂O₄ with orthorhombic structure. Accompanying the crystal structure transition from α-(Fe,Ba)₂O₃ to Ba_xFe_3−xO₄, the magnetic properties also changed from nonmagnetism into ferromagnetism. The saturation magnetization was 53.3 emu/g and coercivity was 113.7 Oe. The mechanism of transitions of the crystal structure was discussed in the present work.     

Hydrogen-induced decomposition in Pr(Co1−xCux)5 intermetallic compounds

Quasi-binary Pr(Co_1−xCu_x)₅ intermetallics with 0≤x≤1 were hydrogenated at elevated temperatures to precipitate Co and Cu and to study their mutual solubility. Low temperature hydrogenation was found to form a CaCu₅-type hydride containing about 1.6 hydrogen atoms per formula unit. Above 500 °C, the samples decompose into PrH_2.6, Cu and h.c.p.-Co. In the temperature range 330–450 °C, the CaCu₅-type hydrides coexist with the decomposed phases. Structural and magnetic measurements indicate that no solid solution are formed in Co-Cu decomposed phases. The magnetoresistance on both parent and hydrogenated samples does not exceed 0.5%.     

Synthesis and properties of Ba3NaRu2O9−δ and Ba3(Na, R)Ru2O9−δ (R=rare earth) crystals

Crystals of Ba₃NaRu₂O_9−δ (δ≈0.5) and Ba₃(Na, R)Ru₂O_9−δ (R=Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb) were grown by an electrochemical method, and their crystallographic, magnetic, and electric properties were studied. All crystals have a hexagonal structure of space group P6₃mmc. Ba₃NaRu₂O_9−δ and Ba₃(Na, R)Ru₂O_9−δ (except Ce) have a negative asymptotic Curie temperature suggesting the existence of an antiferromagnetic order; however, they are paramagnetic at temperatures above 1.7 K. Ba₃NaRu₂O_9−δ has an effective magnetic moment P_eff of 0.91 μ_B, while P_eff of Ba₃(Na, R)Ru₂O_9−δ (except Ce) reflects the large free-ion moment of the rare earth ions. Ba₃(Na, Ce)Ru₂O_9−δ shows peculiar magnetic behavior that differs from the magnetism of other Ba₃(Na, R)Ru₂O_9−δ crystals. The resistivity of all crystals exhibits an activation-type temperature dependence with an activation energy in the range of 0.10.2 eV.     

Investigation of structural and electrical properties of (1 − x) Bi0.5Mg0.5TiO3–(x) PbTiO3 ceramic system

A 3 V cathode material for lithium ion batteries, Li_0.33MnO₂, was synthesized by solid-state reaction. Two Mn crystallographic positions, Mn₍₁₎ and Mn₍₂₎, were determined by X-ray diffraction analysis. The [Mn₍₂₎O₆] octahedron had a lower symmetrical degree than that of [Mn₍₁₎O₆], which was attributed to the geometrical effects of the non-symmetrical environment around Mn₍₂₎. Li_0.33MnO₂ delivered a reversible discharge capacity 140 mA h g⁻¹. In situ synchrotron diffraction clearly showed a reversible phase transition of Li_0.33MnO₂ during electrochemical process. The analysis of X-ray absorption near edge spectroscopy observed the conversion of Mn⁴⁺ to Mn³⁺ with Li⁺ intercalation into Li_0.33MnO₂, accompanied by the formation of more severely distorted [MnO₆] octahedron.     

Crystal structure of the new ternary aluminide CeRu3−xAl10+x (x = 0.17)

A large and transparent Yb³⁺:GdYCOB crystal with dimensions up to 30 mm× 58 mm have been grown by the Czochralski method. The spectral properties of Yb³⁺:GdYCOB crystal has been investigated. The absorption cross-section (σ_a) is 1.65 × 10⁻²⁰ cm² at 977 nm. The emission cross-section (σ_e) is 0.25 × 10⁻²⁰ cm² with an FWHM of 37.2 nm at 1020 nm. The fluorescence lifetime is 3.00 ms.     

Studies on structural and thermal expansion properties of Ho2−xLnxMo4O15 (Ln = Er, Sm and Ce) solid solutions

Three new series of Ho_2−xEr_xMo₄O₁₅ (x = 0.0–2.0), Ho_2−xSm_xMo₄O₁₅ (x = 0.0–0.6) and Ho_2−xCe_xMo₄O₁₅ (x = 0.0–0.25) solid solutions have been prepared successfully by solid-state reaction and studied by powder X-ray diffraction. All the XRD patterns of these molybdates can be indexed in monoclinic space group P2₁/c. Lattice parameters a, b and c of Ho_2−xLn_xMo₄O₁₅ decrease linearly with increasing erbium content and increase with increasing samarium or cerium content. Thermal expansion behaviors of Ho_2−xLn_xMo₄O₁₅ have been investigated in the 25–500 °C temperature range with high-temperature X-ray diffraction. The temperature dependence of Mo(2)–O14 interaction looks like to be responsible for their thermal expansion behaviors.     

Structural, electrical and magnetic properties of Cu1−xZnxFe2O4 ferrites (0 ≤ x ≤ 1)

Copper–zinc ferrites bearing chemical formula Cu_1−xZn_xFe₂O₄ for x ranging from 0.0 to 1.0 with the step increment of 0.2 were prepared by the standard solid-state technique. The variation of Zn substitution has a significant effect on the structural, electrical and magnetic properties. Lattice parameters ‘a’ increased from 8.370 to 8.520 Å. Dielectric constant decreased up to 311 with the increase in frequency from 80 Hz to 1 MHz at room temperature. All the samples follow the Maxwell–Wagner's interfacial polarization. Saturation magnetization, magnetic moment and Yafet–Kittel angles were also determined. The possible reasons responsible for the change in density related, electrical and magnetic properties with the increase in Zn concentration are undertaken.     

Structure and magnetic properties of Gd3(Fe1−xTix)29 (x=0.011–0.034)

Single-phase compounds Gd₃(Fe_1−xTi_x)₂₉ (x=0.0110.034) have been synthesized. Gd₃(Fe_1−xTi_x)₂₉ crystallises in a monoclinic lattice with space group P2₁/c, and the crystal structure is refined by the Rietveld technique based on X-ray powder diffraction data. Thermomagnetic analysis indicates that the Curie temperature of the compounds ranges from 517 K to 538 K. The saturation magnetizations of the Gd₃(Fe_1−xTi_x)₂₉ (x=0.011, 0.022, 0.034) at 1.5 K are 103.6, 102.0 and 94.3 Am²/kg, and the anisotropy fields at 1.5 K are 6.0, 6.2 and 6.4T, respectively.     

Characterization of hydrothermally prepared BaTi1−xZrxO3

BaTiO₃ (BTO) and BaTi_0.8Zr_0.2O₃ (BZT) powders were prepared using the hydrothermal method, starting from BaO, TiO₂ and Zr(NO₃)₂, 7H₂O. X-ray diffraction analysis showed that the cubic phase is stable at room-temperature and the pure perovskite phase is obtained after heating the powders for 2 h at 1280 °C. The temperature dependence of the dielectric constant points to ferroelectric behavior. This ferroelectric behavior can likely be due to the presence of a possible quadraticity gradient in the grains since the cubic phase may not be ferroelectric. The diffuse character of the transition is attributed to this quadraticity gradient, to grain size distribution and (for BZT) to spatial fluctuations in the concentrations of the substituted ion (Zr) leading to the coexistence of regions of different Curie temperatures.     

Monoclinic phases and stress-relief conditions in (1 − x)Pb(Mg1/3Nb2/3)TiO3–xPbTiO3 solid solutions

A comparative study on heterophase states in perovskite-type solid solutions of (1 − x)Pb(Mg_1/3Nb_2/3)TiO₃–xPbTiO₃ is carried out for compositions near the morphotropic phase boundary. The conditions for mechanical stress relief at elastic matching of phases are analysed at x = const in a wide temperature range. The heterophase states concerned with the presence of the intermediate monoclinic phase are interpreted using the domain state–interface diagrams calculated for x = 0.28, 0.32 and 0.34. It is shown that optimum volume fraction parameters of the domains in the monoclinic phase of the B type are varied in relatively wide ranges and promote complete stress relief with cubic–monoclinic phase coexistence. Two scenarios of stress relief at x = 0.32 are considered in connection with different heterophase states (either tetragonal–monoclinic of the B type or tetragonal–monoclinic of the C type) in a wide temperature range. Possibilities of elastic matching of two polydomain phases (tetragonal–monoclinic of the B type) with almost equal relative widths of the domains in these phases are shown for x = 0.34. The active role of domains of the monoclinic phases in stress relief and forming the planar unstrained interfaces is discussed.