Photoluminescence of Ga<Subscript>2</Subscript>S<Subscript>3</Subscript>:Eu nanocrystals

The photoluminescence (PL) of Ga₂S₃-5 mol % Eu₂O₃ nanocrystals prepared by mechanical comminution of the initial compound has been studied in the temperature range from 77 to 300 K. It is established that the PL spectrum of nanocrystals, in comparison to that of a massive sample, extends over a broader wavelength interval (430–620 nm) and has two maxima (at 507 and 556 nm) instead of one. The intensity of emission from nanocrystals is significantly higher than that from the massive crystal. The halfwidth in both cases varies with the temperature in proportion to T ^1/2. The intensity of emission at 556 nm for nanocrystals depends on the temperature as lgI ～ 1/T, this dependence having three linear portions corresponding to an activation energy of 0.04, 0.16, and 0.43 eV. The PL bands with maxima at 507 and 556 nm are assigned to the intracenter 4f ⁶5d4f ⁷ transitions in Eu²⁺ ions.     

Compounds WAl<Subscript>4</Subscript>, WAl<Subscript>3</Subscript>, W<Subscript>3</Subscript>Al<Subscript>7</Subscript>, and WAl<Subscript>2</Subscript> and Al-W-N combustion products

X-ray diffraction data are presented for combustion products in the Al-W-N system. New, nonequilibrium intermetallic compounds have been identified, their diffraction patterns have been indexed, and their unit-cell parameters have been determined. The phases α-and β-WAl₄ are shown to exist in three isomorphous forms, differing in unit-cell centering. The phases α′-, α″-, and α?-WAl₄ are monoclinic, with a ₀ = 5.272 Å, b ₀ = 17.770 Å, c ₀ = 5.218 Å, β = 100.10°; point groups C12/c1, A12/n1, I12/a1, respectively. The phases β′-, β″-, and β?-WAl₄ are monoclinic, with a ₀ = 5.465 Å, b ₀ = 12.814 Å, c ₀ = 5.428 Å, β = 105.92°; point groups A112/m, B112/m, I112/m, respectively. The compounds WAl₂ and W₃Al₇, identified each in two isomorphous forms, differ in cell metrics (doubling) but possess the same point group: P222. WAl ₂ ^′ : orthorhombic, a ₀ = 5.793 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. WAl ₂ ^″ : orthorhombic, a ₀ = 11.586 Å, b ₀ = 3.740 Å, c ₀ = 6.852 Å. W₃Al ₇ ^′ : orthorhombic, Pmm2, a ₀ = 6.225 Å, b ₀ = 4.806 Å, c ₀ = 4.437 Å. W₃Al ₇ ^″ : orthorhombic, Pmm2, a ₀ = 12.500 Å, b ₀ = 4.806 Å, c ₀ = 8.874 Å. The new phase WAl₃: triclinic, P1, a ₀ = 8.642 Å, b ₀ = 10.872 Å, c ₀ = 5.478 Å, α = 104.02°, β = 64.90°, γ = 107.15°.     

The magnetic properties of BiY<Subscript>2</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> nanoparticles doped with Cr ions

BiY₂Cr _x Fe_5?x O₁₂ (x = 0, 0.05, 0.1, 0.2, 0.3) nanocrystals were synthesized by using a sol-gel method. Samples were characterized by the powder X-ray diffraction (XRD), the thermal gravity analysis (TGA) and the differential thermal analysis (DTA), the vibrating sample magnetometer(VSM) and Mössbauer spectrums. The average sizes of the particles were determined by the Scherrer’s formula. The special Ms and Mössbauer spectra of BiY₂Cr _x Fe_5?x O₁₂ nanocrystals are researched at room temperature. It is seen that the special Mss of samples are initially increased with increasing Cr³⁺ content (x < 0.1), and decreased with increasing content of Cr³⁺ ions (x > 0.1).     

Crystal structures of Ln<Subscript>2</Subscript>TiO<Subscript>5</Subscript> (Ln = Gd,Dy) polymorphs

Single crystals of four Ln₂TiO₅ polymorphs have been grown, and their structures have been determined: orthorhombic (Gd₂TiO₅, a = 10.460(5), b = 11.317(6), c = 3.750(3) Å, Pnam, Z = 4), hexagonal (Gd_1.8Lu_0.2TiO₅, a = 3.663(3), c = 11.98(1) Å, P6₃/mmc, Z = 1.2), cubic (Dy₂TiO₅, a = 10.28(1) Å, Fd3m, Z = 10.4), and monoclinic (Dy₂TiO₅, a = 10.33(1), b = 3.653(5), c = 7.306(6) Å, β = 90.00(7)°, B2/m, Z = 2.4). The last polymorph has been identified for the first time.     

High-temperature heat capacity and thermodynamic properties of Tb<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Tb₂Sn₂O₇ has been prepared by solid-state reaction in air at 1473 K over a period of 200 h and its isobaric heat capacity has been studied experimentally in the range 350–1073 K. The C _p(T) data for this compound have no extrema and are well represented by the classic Maier–Kelley equation. The experimental C _p(T) data have been used to evaluate the thermodynamic properties of terbium stannate (pyrochlore structure): enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(Т).     

Synthesis and high-temperature heat capacity of Gd<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

Gd₂Sn₂O₇ gadolinium stannate with the pyrochlore structure has been prepared by solid-state reaction and its high-temperature heat capacity has been determined by differential scanning calorimetry in the temperature range 350–1020 K. The C_p(T) data are shown to be well represented by the classic Maier–Kelley equation. The experimental C_p(T) data have been used to evaluate the thermodynamic functions of gadolinium stannate: enthalpy increment H°(T)–H°(339 K), entropy change S°(T)–S°(339 K), and reduced Gibbs energy Ф°(Т).     

New,thermally stable Gd<Subscript>11</Subscript>(GeO<Subscript>4</Subscript>)(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>O<Subscript>10</Subscript>-based upconversion phosphors

A series of Gd_11–x–y Yb _x Er _y GeP₃O₂₆ germanate phosphates differing in the ratio of the Yb³⁺ and Er³⁺ active ions have been synthesized, and their luminescence spectra have been measured. According to X-ray diffraction characterization results, all of the synthesized germanate phosphates are single-phase and have a triclinic structure (sp. gr. P1). We have measured upconversion luminescence spectra due to the Er^{3+ 2}H_11/2, ⁴S_3/2 → ⁴I_15/2 and ⁴F_9/2 → ⁴I_15/2 radiative transitions in the synthesized gadolinium ytterbium erbium germanate phosphates and determined the luminescence upconversion energy yield (B _en) in Gd_11–x–y Yb _x Er _y GeP₃O₂₆. The effects of the concentrations and ratio of the dopants in the Gd₁₁(GeO₄)(PO₄)₃O₁₀ germanate phosphate host on B _en and the ratio of the luminescence intensities in the red and green spectral regions (R/G) have been assessed.     

Solid-state reactions in the system Li<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Na<Subscript>2</Subscript>CO<Subscript>3</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>

The formation mechanisms of Li _x Na_{1 ?x} Ta _y Nb_{1 ? y} O₃ perovskite solid solutions in the Li₂CO₃-Na₂CO₃-Nb₂O₅-Ta₂O₅ system have been studied by x-ray diffraction, differential thermal analysis, thermogravimetry, IR spectroscopy, and mass spectrometry at temperatures from 300 to 1100°C. The results indicate that the synthesis of Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions involves a complex sequence of consecutive and parallel solid-state reactions. An optimized synthesis procedure for Li _x Na_{1 ? x} Ta _y Nb_{1 ? y} O₃ solid solutions is proposed.     

Synthesis and High-Temperature Heat Capacity of Dy<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript> and Ho<Subscript>2</Subscript>Ge<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates have been prepared by solid-state reactions in several sequential firing steps in the temperature range 1237–1473 K using stoichiometric mixtures of Dy₂O₃ (or Ho₂O₃) and GeO₂. The heat capacity of the synthesized germanates has been determined as a function of temperature by differential scanning calorimetry in the range 350–1000 K. The experimentally determined C _p (T) curves of the dysprosium and holmium germanates have no anomalies and are well represented by the Maier–Kelley equation. The experimental C _p (T) data have been used to evaluate the thermodynamic functions of the Dy₂Ge₂O₇ and Ho₂Ge₂O₇ pyrogermanates: enthalpy increment H°(T)–H°(350 K), entropy change S°(T)–S°(350 K), and reduced Gibbs energy Ф°(T).     

Synthesis and structure of the CsSmP<Subscript>4</Subscript>O<Subscript>12</Subscript> cyclotetraphosphate (cubic CsNdP<Subscript>4</Subscript>O<Subscript>12</Subscript> structure)

CsSmP₄O₁₂ crystals have been prepared at 300°C in molten polyphosphoric acids containing Cs, Mg, and Sm cations, and their crystal structure has been determined: sp. gr. I \(\bar 4\) 3d, a = 15.1225(8) Å, Z = 12, CsNdP₄O₁₂ structure.     

Study of Magnetic Entropy Change in Nd<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.98</Subscript>Fe<Subscript>0.02</Subscript>O<Subscript>3</Subscript> by Means of Theoretical Models

Magnetic entropy change (?ΔS _M ) of Nd_0.67 Ba_0.33Mn_0.98Fe_0.02O₃ perovskite have been analyzed by means of theoretical models. An excellent agreement has been found between the (ΔS_M) values estimated by Landau theory and those obtained using the classical Maxwell relation. In order to estimate the spontaneous magnetization M _{s pont}(T), we used the mean-field theory to analyses the (ΔS_M) vs. M ² data. The obtained M _{s pont}(T) values are in good agreement with those found from the classical extrapolation from the Arrott plots(H/M vs. M ²), confirming that the magnetic entropy is a valid approach to estimate the spontaneous magnetization in our system. At a relatively low magnetic field, a phenomenological model has been used to estimate the values of the magnetic entropy change. The results are in good agreement with those obtained from the experimental data using Maxwell relation.     

Structural and dielectric properties of PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions synthesized at high pressures and temperatures

(1 ? x)PbMg_1/3Nb_2/3O₃ · xPbZrO₃ (1 ? x)PMN · xPZ) solid solutions have been synthesized at a pressure of 5 GPa and temperatures from 1300 to 1700 K, and their structural and dielectric properties have been studied. The composition dependences of the average unit-cell parameter and dielectric permittivity for the solid solutions indicate that the PMN-PZ system has a morphotropic phase boundary near x = 0.65. The solid solutions have a cubic structure for x < 0.65, a rhombohedral structure in the range 0.65 < x < 0.9, and an orthorhombic structure (similar to that of PbZrO₃) for x > 0.9. The temperature and frequency dependences of dielectric permittivity suggest that the (1 ? x)PMN · xPZ samples with x < 0.65 consist of two ferroelectric phases: a relaxor with antipolar dipole order and a normal ferroelectric with a diffuse phase transition. The effect of annealing temperature on the ferroelectric state of the samples with x < 0.65 is examined. In the composition range 0.65 < x < 0.9, the samples have normal ferroelectric properties, independent of annealing temperature.     

Critical Behavior of La<Subscript>0.67</Subscript>Ba<Subscript>0.33</Subscript>Mn<Subscript>0.95</Subscript>Fe<Subscript>0.05</Subscript>O<Subscript>3</Subscript> Manganite

The critical behavior of perovskite manganite La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ at the ferromagnetic–paramagnetic has been analyzed. The results show that the sample exhibited the second-order magnetic phase transition. The estimated critical exponents derived from the magnetic data using various such as modified d’Arrott plot Kouvel–Fisher method and critical magnetization M(T _C, H). The critical exponents values for the La_0.67Ba_0.33Mn_0.95Fe_0.05O₃ are close to those expected from the mean field model β = 0.504 ± 0.01 with T _C = 275661 ± 0.447 (from the temperature dependence of the spontaneous magnetization below T _C ), γ = 1.013 ± 0.017 with T _C = 276132 ± 0.452 (from the temperature dependence of the inverse initial susceptibility above T _C ), and δ = 3.0403 ± 0.0003. Moreover, the critical exponents also obey the single scaling equation of M(H, ε) = |ε| ^β f _±(H/|ε| ^β+γ ).     

Rare-earth-doped PbTiO<Subscript>3</Subscript>-PbZrO<Subscript>3</Subscript> solid solutions

(Pb_{1 ? x} Ln _x )(Zr_0.53Ti_0.47)O₃ and (Pb_{1 ? x} Ln _x )(Zr_0.65Ti_0.35)O₃ (x = 0.02, 0.06; Ln = La, Pr, Gd, Yb) solid solutions have been prepared by modified solid-state synthesis using organic-ligand precursors. The solid solutions have been characterized by thermal analysis, IR spectroscopy, x-ray powder diffraction, and atomic force microscopy. All of them have a rhombohedrally distorted perovskite structure (sp. gr. R3c).     

Investigation of Magnetic,Magnetocaloric, and Critical Properties of La<Subscript>0.5</Subscript>Ba<Subscript>0.5</Subscript>MnO<Subscript>3</Subscript> Manganite

We present an extensive study of the magnetic properties of a novel La_0.5Ba_0.5MnO₃ perovskite material prepared by the hydrothermal method. The explored sample was structurally studied by the x-ray diffraction (XRD) method which confirms the formation of a pure cubic phase of a perovskite structure with Pm3m space group. The magnetic properties were probed by employing temperature M (T) and external magnetic field M (μ_oH) dependence of magnetization measurements. A magnetic phase transition from ferromagnetic to paramagnetic phase occurs at 339 K in this sample. The maximum magnetic entropy change (\(\left | {{\Delta } S}_{M}^{\max } \right |\)) took a value of 1.4 J kg^??1 K^??1 at the applied magnetic field of 4.0 T for the explored sample and has also been found to occur at Curie temperature (T_C). This large entropy change might be instigated from the abrupt reduction of magnetization at T_C. The magnetocaloric effect (MCE) is maximum at T_C as represented by M (μ_oH) isotherms. The relative cooling power (RCP) is 243.2 J kg^??1 at μ_oH =?4.0 T. Moreover, the critical properties near T_C have been probed from magnetic data. The critical exponents δ, β, and γ with values 3.82, 0.42, and 1.2 are close to the values predicted by the 3D Ising model. Additionally, the authenticity of the critical exponents has been confirmed by the scaling equation of state and all data fall on two separate branches, one for T < T_C and the other for T > T_C, signifying that the critical exponents obtained in this work are accurate.     

Phenomenological Model of Magnetocaloric Effect in La<Subscript>0.7</Subscript>Ca<Subscript>0.2</Subscript>Ba<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> Manganite Around Room Temperature

In this work, we studied in detail the magnetic and magnetocaloric properties of the La_0.7Ca_0.2Ba_0.1MnO₃ compound according to the phenomenological model. Based on this model, the magnetocaloric parameters such as the maximum of the magnetic entropy change ΔS _M and the relative cooling power (RCP) have been determined from the magnetization data as a function of temperature at several magnetic fields. The theoretical predictions are found to closely agree with the experimental measurements, which make our sample a suitable candidate for refrigeration near room temperature. In addition, field dependences of \({{\Delta } S}_{\mathrm {M}}^{\max }\) and RCP can be expressed by the power laws \({\Delta S}_{\mathrm {M}}^{\max }\approx a\)(μ ₀ H) ⁿ and RCP ≈b(μ ₀ H) ^m , where a and b are coefficients and n and m are the field exponents, respectively. Moreover, phenomenological universal curves of entropy change confirm the second-order phase transition.     

Peculiarities of phase transitions in polytypes of monoclinic TlInS<Subscript>2</Subscript>

The existence of two polytypes at room temperatures, C-TlInS₂ and 2C-TlInS₂, with different monoclinic cell parameters, c and 2c, has been revealed. Significant differences in crystal lattice dynamics of these polytypes have been found. In particular, two phase transitions (PTs) have been detected for the polytype C-TlInS₂ as the temperature varies: a second-order PT from paraphase to incommensurate phase at T _i = 215 K and a first-order ferroelectric PT accompanied by a quadrupling of the parameter c at T _c = 197 K. No PT accompanied by an increase in unit cell parameter c has been found in the polytype 2C-TlInS₂, but a global temperature hysteresis characteristic of crystals with an incommensurately modulated structure has been detected at T = 180–230 K.     

High-temperature heat capacity and vibrational spectra of Eu<Subscript>2</Subscript>Sn<Subscript>2</Subscript>O<Subscript>7</Subscript>

The Eu₂Sn₂O₇ compound has been prepared by solid-state reaction (by sequentially firing a stoichiometric mixture of Eu₂O₃ and SnO₂ in air at 1273 and 1473 K) and its heat capacity has been determined by differential scanning calorimetry in the temperature range 370–1000 K. The heat capacity data have been used to evaluate the thermodynamic properties of europium stannate: enthalpy increment H°(T)–H°(370 K), entropy change S°(T)–S°(370 K), and reduced Gibbs energy Ф°(T). Raman spectra of Eu₂Sn₂O₇ polycrystals with the pyrochlore structure have been measured in the range 200–1200 cm^–1.     

Interaction of hydrogen with the intermetallic compound Nd<Subscript>2</Subscript>Fe<Subscript>17</Subscript> studied by calorimetry

Interaction of hydrogen with the intermetallic compound Nd₂Fe₁₇ has been studied for the first time by calorimetry using a differential heat conduction calorimeter coupled to a Sieverts apparatus. Hydrogen absorption and desorption reactions were run at 200°C, and two types of data were obtained: p–C–T and ΔH–C–T (where p is the equilibrium hydrogen pressure, C = H/Nd₂Fe₁₇, ΔH is the reaction enthalpy, and T is the measurement temperature). The p–C–T curves obtained for the hydrogen absorption and desorption processes have no plateau or two-phase region, in contrast to what is characteristic of the formation of a hydride phase. At the same time, the ΔH(C) curves have a few portions where the enthalpy of reaction between hydrogen and the intermetallic compound remains constant: 0 < C < 2.0, with ΔH _abs =–85.05 ± 0.65 kJ/mol H ₂; 2.0 < C < 2.7, with ΔH _abs =–80.64 ± 1.00 kJ/mol H₂; and 1.9 < C < 2.7, with ΔH _des = 76.48 ± 0.85 kJ/mol H₂. The data obtained in this study suggest that positions 9e and 18g in the intermetallic compound are occupied by hydrogen in a particular order.     

Synthesis and x-ray diffraction study of solid solutions in the Zn<Subscript>2</Subscript>SnO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>TiO<Subscript>4</Subscript>-Zn<Subscript>2</Subscript>ZrO<Subscript>4</Subscript> system

The multicomponent refractory oxide system Zn₂(Ti_aSn_b)_{1 ? x} Zr_xO₄ (a + b = 1; a: b = 1: 5, 1: 4, 1: 3, 1: 2, 1: 1, 1: 0, 2: 1, 3: 1, 4: 1; x = 0?1.0; Δx = 0.05) has been studied by x-ray diffraction, using samples prepared by melting appropriate oxide mixtures in a low-temperature hydrogen-oxygen plasma. Two phases, both with wide homogeneity ranges, have been identified: α-phase, with a cubic inverse spinel structure, and β-phase, with a tetragonal spinel structure. The phase boundaries in the system have been determined. Structural data are presented for about 100 solid solutions of different compositions.