Phase diagrams of binary systems: AgNO3KNO3 and AgNO3 -@#@ NaNO3

AgNO₃-KNO₃ and AgNO₃-NaNO₃ phase diagrams were drawn using a simultaneous thermal analysis technique in the range 373 to 623 K. The apparatus is described briefly. Figure 1 shows a continuous solid solution in equilibrium with the liquid phase. It exhibits a eutectoid mixture (20 mol% NaNO₃) at 380.7 K. Figure 2 shows a eutectic mixture (45 mol % KNO₃) at 413 K, a eutectoid mixture (20 mol % KNO₃) at 409 K, and a continuous invariant at 404 K.     

Thermodynamic evaluation of phase equilibria in NaNO3-KNO3 system

The binary phase diagram of NaNO₃-KNO₃ was studied by differential scanning calorimetry (DSC) and high-temperature x-ray diffractometry. The solid solutions in the intermediate concentration phase appeared to be a mixture of the NaNO₃-based solid solutions and KNO₃-based solid solutions. This behavior below the solidus suggests that NaNO₃-KNO₃ might well be regarded as a system with limited solid solubilities instead of a continuous series of solid solutions. The temperatures for the solidus and liquidus have been determined with consideration of limited terminal solid solutions. Two models, the Henrian solution and regular solution theory for NaNO₃-based phase and the KNO₃-based phase, respectively, were used to reproduce the solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for the NaNO₃-based and KNO₃-based solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent. Thus, the limited solid solution model seems to be more consistent with the phase diagram obtained by DSC than the continuous solid solution model.     

The influence of moisture on the oxidation rate of iron in NaNO3 and KNO3 melts

The open circuit potential (E_corr) and oxidation rate (I_corr) of iron were measured in dry and wet NaNO₃ and KNO₃ melts at 340 °C. A shift of E_corr in the positive direction and a higher oxidation rate were observed in wet melts in comparison with dry melts. The oxidation rate was almost 55% higher in KNO₃ melts than in NaNO₃ melts. To ascertain the effect of moisture on the cathodic reaction, a cyclic voltammetry study was carried out on platinum surface in dry and wet conditions of the melt. An increase of cathodic current in the presence of moisture in the melt is in good agreement with the increased oxidation rate of iron. A proportionate increase of oxidation rate was also noted in wet NaNO₃ and KNO₃ melts to those in their dry melts.     

Solubility of YbTe in Sb2Te3 and thermodynamic properties of the solid solution

The solubility of YbTe in Sb₂Te₃ is investigated by a combination of DTA, XRD, SEM, and EMF methods. The fragment of the T-x phase diagram of the YbTe-Sb₂Te₃ system is constructed for 0-25 mol.% YbTe. It is shown that the solubility limit for YbTe in Sb₂Te₃ is achieved at 15 mol.% YbTe at 300 K and at 17.5 mol.% YbTe at 855 K. From the EMF measurements with an YbTe electrode the partial thermodynamic functions of the YbTe pseudo-component are calculated for the alloys of different compositions. Also, the standard integral thermodynamic functions of the YbTe dissolution in Sb₂Te₃ as well as the standard thermodynamic functions of formation and the standard entropy of the solid solution are calculated from the experimental data.     

Formation of nanoparticles and nanorods via UV irradiation of AgNO3 solutions

The synthesis of silver nanoparticles via UV irradiation of AgNO₃ solutions was controlled by using UV–vis absorption spectra and TEM (transmission electron microscope) images. The UV–vis absorption method is good enough for the general control of synthesis process, and TEM images give us information about size of formed species. For investigated solutions of silver nitrate in ethanol and water, we observed formation of large nanoparticles (size about 100 nm) and nanorods (100 nm in length). Moreover, there was effort to confirm evidence of formation of these particles by using TOF mass spectrometer. Due to laser desorption/ionization process there is only evidence of small silver nanoparticles Ag_x, x ≤ 4 (clusters), and variety of silver compounds Ag_xN_yO_z (x ≤ 5, y ≤ 2, z ≤ 3).     

Phase diagram of the quasi-binary system TlInSe2-SnSe2

The TlInSe₂-SnSe₂ quasibinary system was investigated using differential thermal and X-ray phase analysis methods. The phase diagram is of eutectic type (V type of the Rozeboom classification). The solid solution range of the ternary compound in the TlInSe₂-SnSe₂ system extends to 28 mol.% SnSe₂ at 670 K. The eutectic point coordinates are 63 mol.% SnSe₂ and 788 K.     

Optical properties of thermally evaporated Bi2Se3 thin films treated with AgNO3 solution

Bismuth selenide (Bi₂Se₃) thin films have been prepared onto clean glass substrates by the thermal evaporation technique. The deposited films were then immersed in silver nitrate solution for different periods of time, followed by annealing in Argon atmosphere at 473 K for 1 h, to obtain Ag/Bi₂Se₃ samples. The prepared films have been examined by X-ray and transmission electron microscopy for structural determination. The optical transmission and reflection spectra of the deposited films have been recorded within the wavelength range 400-2500 nm. The variation of the optical parameters of the prepared films, such as refractive index, n, and the optical band gap, E_g as a function of the immersion duration times has been determined. The refractive index dispersion in the transmission and low absorption region is adequately described by the well-known Sellmeier dispersion relation, whereby the values of the oscillator strength, oscillator position, the high-frequency dielectric constant, ε_∞ as well as the carrier concentration to the effective mass ratio, N/m* were calculated as a function of the immersion duration time.     

Thermodynamic evaluation of phase equilibria in NaNO3-KNO3 system

The binary phase diagram of NaNO₃-KNO₃ was studied by differential scanning calorimetry (DSC) and high-temperature x-ray diffractometry. The solid solutions in the intermediate concentration phase appeared to be a mixture of the NaNO₃-based solid solutions and KNO₃-based solid solutions. This behavior below the solidus suggests that NaNO₃-KNO₃ might well be regarded as a system with limited solid solubilities instead of a continuous series of solid solutions. The temperatures for the solidus and liquidus have been determined with consideration of limited terminal solid solutions. Two models, the Henrian solution and regular solution theory for NaNO₃-based phase and the KNO₃-based phase, respectively, were used to reproduce the solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for the NaNO₃-based and KNO₃-based solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent. Thus, the limited solid solution model seems to be more consistent with the phase diagram obtained by DSC than the continuous solid solution model.     

Electrical and electrochemical properties of γ-Li2CuZrO4

The γ-Li₂CuZrO₄ with a double rock-salt structure, as a lithium-ion compound, has never been reported on their physical and physicochemical properties. The γ-Li₂CuZrO₄ was prepared by a solid-state reaction process. X-ray diffraction was used to analyze the structure of the products. Its electrical properties were characterized by both DC and AC measurements in the temperature range from 133 to 1273 K. Cyclic voltammetry and galvanostatic cell cycling were also employed to evaluate its electrochemical performance. It is found to be a pure electronic semiconductor with a fairly high conductivity (10⁻⁵ S/cm at 133 K, 10⁻² S/cm at 300 K and 10⁻¹ S/cm at 1173 K). The average activation temperature is 14.4 kJ/mol. When increasing the temperature above 1073 K, a phase transition from γ to β takes place. When reacting with lithium in an electrochemical cell, γ-Li₂CuZrO₄ decomposes into three phases during the initial discharge process, and possesses a reversible capacity of about 70 mAh/g.     

电渣重熔中TiO2对低氟CaF2-CaO-Al2O3-MgO-Li2O渣黏度和结构的影响

本文研究了连续冷却条件下电渣重熔中TiO₂对低氟CaF₂-CaO-Al₂O₃-MgO-Li₂O渣黏度的影响,并利用傅里叶变换红外光谱和拉曼光谱分析水淬渣和对应结构的关系。结果表明,渣的黏度随着TiO₂的增加而降低,当TiO₂含量达到13.1%,随着温度从1743K, 1793K, 1843K 增加至1893K时, 对应黏度从0.067 Pa?s, 0.059 Pa?s, 0.056 Pa?s 降低到0.054 Pa?s;当温度达到1843K或之上时,TiO₂的加入对降低黏度有较小的影响。随着TiO₂含量从0,4.3%,8.7%增加至13.1%,黏流活化能从58.0 kJ/mol,47.7 kJ/mol,42.8 kJ/mol降低到38.6 kJ/mol。此外,红外光谱结果表明,随着TiO₂的加入,渣中[AlOnF_4-n]-四面体络合物和[AlO₄]-四面体网状结构被解聚,但[AlO₆]-八面体结构没有发现;同时,拉曼光谱分析表明,TiO₂加入可解聚[AlO₄]-四面体网状结构中Al-O-Al键, 并且Q^₄单元转化为Q^₂单元,同时形成O-Ti-O和Ti-O-Ti键。这些结果都表明TiO₂可降低渣的聚合度,并且有利于渣的结构简单化。最终,黏度变化与渣的对应结构有很好的一致性。     

Microstructure evolution of the Si3N4/Si3N4 joints brazed using Au-Ni-V filler alloys with different V content

Au-Ni-V filler alloys with different vanadium contents were designed to braze Si₃N₄ ceramic at 1373 K for 30 min, and the microstructures of brazing seams were investigated by SEM and TEM. When the Au-Ni-V filler alloy contains 5 at.% V, round-like Ni[Si, V, Au] precipitates form in the Au[Ni] solid solution matrix and a VN reaction layer with 0.5 μm thickness appears on Si₃N₄ interface. When the V content increases to 10 at.%, a new polygonal Ni₂SiV₃ phase occurs in the seam, and the Ni[Si, V, Au] precipitate coarsens and VN layer thickens. With increase of V contents to 15 and 20 at.%, laminar Ni[Au] and polygonal Ni₃V precipitates form. With 25 at.% V content in the filler alloy, the Ni₂SiV₃ and Ni₃V precipitates distribute homogenously in the brazing seam. These microstructure evolutions were attributed to the reaction between Si₃N₄ and vanadium, which forms VN reaction layer and releases Si into the molten alloy.     

Phase diagram of Ni3V-Co3V pseudobinary system

A phase diagram of Ni₃V-Co₃V pseudobinary system is proposed based on x-ray diffraction and differential thermal analysis. Four invariant reactions are located in the phase diagram—two eutectoid and two peritectoid reactions. Six kinds of geometrically close-packed phases are encountered. The stability of these close-packed phases correlate well with the electron concentration.     

Magnetic property of the low temperature phase of α-(BEDT-TTF)2KHg(SCN)4

The low temperature phase of the organic conductor, α-(BEDT-TTF)₂KHg(SCN)₄, has been investigated by EPR measurements. The spin susceptibility determined by the EPR intensity is 3 × 10⁻⁴ emu/mol at room temperature, in agreement with the static susceptibility measurement. It decreases slightly with decreasing temperature down to 10 K, below which a rapid drop of the intensity is observed for all directions of the applied field. This temperature is close to the one which the resistivity anomaly was observed at. At temperatures below 20 K, the EPR signal was found to split into two or three lines depending on the external field direction. We discuss the possible origin of the splitting.     

Colossal and constant magnetoresistance over a large temperature range between 230 and 4.2 K in La0.8Li0.2MnO3 prepared by a partial melting technique

La_0.8Li_0.2MnO₃ was prepared by a partial melting technique. The Li-doped LaMnO₃ compound has a rhombohedral perovskite structure and shows a wide semiconductor-to-metal transition between 230 and 175 K in resistance versus temperature. Nearly constant magnetoresistance, Δρ/ρ₀, above 20–60% was achieved with application of magnetic fields from 1 to 8 Tesla (T) over a very large temperature range from the ferromagnetic transition at 230–4.2 K. As a comparison, a partial melted La_0.7Ca_0.3MnO₃ shows a very narrow ferromagnetic transition around 230 K which is the same as that of single crystals and epitaxy thin films.     

Magnetic and neutron diffraction studies on potassium uranate KUO3

The magnetic properties of KUO₃ with the cubic perovskite structure have been studied. It shows an antiferromagnetic-type of transition at ca. 17 K in the magnetic susceptibility vs. temperature curve. Magnetic hysteresis is observed at 4.5 K, but not observed at 20 K. Neutron diffraction measurements have been performed on the powdered KUO₃ below and above the transition temperature. The neutron diffraction pattern measured at 10 K shows no appreciable difference from that measured at 50 K. A small ordered magnetic moment of U⁵⁺ ion will make it very difficult to observe magnetic diffractions, even if a magnetic ordering occurs. If the magnetic spin alignment occurs in a small domain, no magnetic diffraction will be found in the neutron experiments. On the other hand, the magnetic phenomena of KUO₃ have been analyzed on the basis of an octahedral crystal field model.     

Corrosion inhibition of zinc in tetra-n-butylammonium bromide aerated aqueous solution by benzotriazole and Na3PO4

The effect of benzotriazole (BTA), Na₃PO₄ and their mixture on the corrosion of zinc in 17 wt.% (0.534 mol l⁻¹) tetra-n-butylammonium bromide (TBAB) aerated aqueous solution has been investigated by means of weight-loss test, potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS) and SEM/EDX techniques. The experimental results showed that BTA or Na₃PO₄ or inhibitor mixture could protect zinc in aqueous TBAB solution. The inhibitor combinations led to higher efficiencies compared to those obtained when added individually. An inhibition efficiency of an inhibitor mixture consisting of 0.5 g l⁻¹ BTA and 1 g l⁻¹ Na₃PO₄ was more than 97%.     

A-site-disorder-dependent magnetocaloric properties in the mono-valent-metal doped La0.7Ca0.3MnO3 manganites

The influence of mono-valence-metal (Li, Na, and K) doping effect on the structural, resistivity, magnetic and magnetocaloric properties of La_0.7Ca_0.3MnO₃ polycrystalline samples is studied for a fixed (5% at Ca site) dopant concentration. All the samples crystallize in orthorhombic structure and the lattice parameters increase continuously as the dopant atoms changes from Li to Na and then K. Paramagnetic-ferromagnetic phase transition at T_C and insulator-metal phase transition at T_p are observed for all studied samples. The transition temperature decreases as Ca atoms is replaced by Li, while the transition temperature shifts to higher values as Ca is substituted by Na or K. In addition, the maximum magnetic entropy change of the K-doped sample is much smaller than that of the free- and Na-doped samples. The results are discussed according to the change of A-site-disorder effect caused by the systematic variations of A-site average ionic radius 〈r_A〉 and A-site-cation mismatch σ².     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Phase Relations in the Systems SrO-Y2O3-CuO-O2 and CaO-Y2O3-CuO-O2 at 1173 K

Phase relations in the systems SrO-Y₂O₃-CuO-O₂ and CaO-Y₂O₃-CuO-O₂ at 1173 K were estab-lished by equilibrating different compositions in flowing oxygen gas at a pressure of 1.01 × 10⁵ Pa. The quenched samples were examined by optical microscopy, X-ray diffraction (XRD), energy dis-persive analysis of X-rays (EDAX), and electron spin resonance (ESR). In the system SrO-Y₂O₃-CuO-O₂, except for the limited substitution of Y₃+ for Sr₂+ ions in the ternary oxide Sr₁₄ Cu₂₄O₄₁, no new quaternary phase was found to be stable. The compositions corresponding to the solid solution Sr_14-xY_xCu₂₄O₄₁ and the compound SrCuO₂+δ lie above the plane containing SrO, Y₂O₃, and CuO, displaced towards the oxygen apex. However, in the system CaO-Y₂O₃-CuO-O₂ at 1173 K, all the condensed phases lie on the plane containing CaO, Y₂O₃, and CuO, and a new quaternary oxide YCa₂Cu₃O_6.5 is present. The quaternary phase has a composition that lies at the center of the non-stoichiometric field of the analogous phase YBa₂Cu₃O_7-δ in the BaO-Y₂O₃-CuO-O₂ system. The com-pound YCa₂Cu₃O_6.5 has the tetragonal structure and does not become superconducting at low temperature. Surprisingly, phase relations in the three systems CaO-Y₂O₃-CuO-O₂, SrO-Y₂O₃-CuO-O₂, and BaO-Y₂O₃-CuO-O₂ are found to be quite different.