Synthesis of nanostructured Pt<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Ni/C and Pt<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Co/C catalysts and their activity in the reaction of oxygen electroreduction

Nanostructured Pt _x Ni/C and Pt _x Co/C catalysts (1 ≤ x ≤ 3) containing from 27 to 40 wt % of metal with the average size of metal (alloy) particles from 2.6 to 4.7 nm are obtained using the methods of liquid-phase synthesis. Addition of a doping component is found to yield a decrease in the average nanoparticle sizes and an improved activity of materials in oxygen electroreduction reactions. The obtained catalysts are characterized by high specific activity as compared to commercial Pt/C materials. The stability of electrocatalysts to selective dissolution of the doping component is evaluated.     

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.     

Influence of hydrogen on the thermoelectric voltage signal in a Pt/WO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/6<Emphasis Type="Italic">H</Emphasis>-SiC/Ni/Pt layered structure

The possibility of detecting H₂ by registering the thermal electromotive force signal, which arises between the surfaces of 6H-SiC plates with a thickness of 400 μm, is established. The working surface of the plates is modified by deposition of a WO _x film and catalytic Pt. An ohmic contact (Ni/Pt) is created on the rear surface of the plate, and this surface is maintained at a stabilized temperature of 350°C. The temperature gradient through the plate thickness arises due to the cooling of the working surface with the air medium. The delivery of H₂ into this medium up to a concentration of 2% gives rise to a 15-fold increase in the electric signal, which considerably exceeds the Pt/WO _x /SiC/Ni/Pt system’s response registered in the usual way by measuring the current–voltage dependence. In this case, an additional power source for the registration of the thermal electromotive force is not required.     

Metastable phases in the Ni<Subscript>75</Subscript>Nb<Subscript>12</Subscript>B<Subscript>13</Subscript> alloy prepared under nonequilibrium conditions

The structure of Ni₇₅Nb₁₂B₁₃ alloys prepared by liquid quenching (LQ) and mechanical alloying (MA) has been studied by x-ray diffraction. The alloy prepared by LQ at a cooling rate of ～10⁶ K/s is shown to be fully amorphous, while MA yields an amorphous-crystalline material in which the predominant phase is an fcc Ni〈Nb,B〉 solid solution. The thermal stability of the alloys and their structural transformations on heating have been studied by differential scanning calorimetry. The amorphous phase obtained by LQ is shown to crystallize at 490°C. After heating to 720°C, the alloy consists of two equilibrium phases: Ni₂₁Nb₂B₆ (τ) and Ni₅Nb₃B₂ (z). Heating the MA alloy to 720°C leads to the formation of a stable τ-phase, while the Ni-based fcc solid solution remains supersaturated and, hence, metastable. Increasing the milling time leads to the formation of nanocrystalline τ and Ni₃B phases, in addition to the Ni-based fcc solid solution, which corresponds to the equilibrium phase composition of the Ni₇₅Nb₁₂B₁₃ alloy in the Ni-Nb-B phase diagram. The effect of high-energy milling on the phase composition of the alloy is similar to that of heat treatment.     

Phases and morphotropic regions in the PbNb<Subscript>2/3</Subscript> Mg<Subscript>1/3</Subscript>O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> system

Ceramic samples of solid solutions (1 ? x) PbNb_2/3Mg_1/3O₃ · xPbTiO₃ (0 ≤ x ≤ 1.0, Δx = 0.0025–0.05) are prepared by the columbite method. A detailed x?T phase diagram of the system is constructed (isothermal join at 25°C), and dielectric, piezoelectric, and elastic properties are investigated. It is established that the region of the morphotropic phase transition is positioned in the range 0.28 < x ≤ 0.43 and consists of a series of narrower regions. Inside one phase (cubic, rhombohedral, tetragonal), regions are found in which a qualitative and quantitative difference in structural and electrical parameters is observed. An interpretation of the observed effects in the context of the defect structure of the objects is suggested.     

Properties of fluorine-doped PbMg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>O<Subscript>3</Subscript> ceramics

We report the first fluorine doping of lead magnesium niobate in the PbMg _{(1 + x)/3}Nb_{(2 ? x)/3}O_{3 ? x} F _x system in a wide composition range, x = 0.025 to 0.625. The fluorine content of the samples is shown to be substantially lower than the intended one because of the fluorine volatilization in the form of HF during synthesis and sintering in air. The ceramics consist of magnesium and lead oxides undetectable by x-ray diffraction, and a perovskite phase whose composition can be represented by the formula PbMg_{(1 + m)/3}Nb_{(2 ? m)/3}O_{3 ? m} F _m , where the fluorine content after sintering is m ≤ 0.12. The PbO and MgO contents of the ceramics depend on the starting mixture composition (x) and heat-treatment conditions (hydrogen fluoride and lead oxide volatilization). As a result of the low fluorine content, the diffraction patterns of the samples show no superlattice reflections, and their lattice parameter varies insignificantly with x. Data are presented on the temperaturedependent dielectric permittivity of ceramic samples sintered and annealed under different conditions.     

Effect of Ni Doping at Pd Site in Nb<Subscript>2</Subscript>PdS<Subscript>5</Subscript> Superconductor

The superconducting properties of Nb₂PdS₅ superconductor have been investigated with Ni doping at Pd site All the bulk polycrystalline Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.10) samples are crystallized in singlephase monoclinic structure. The electrical resistivity and magnetic measurements of Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.15) were carried out to study the variation of superconducting critical parameters with Ni doping. Superconductivity in Nb₂PdS₅ sample completely disappears for x ≥ 0.15. We observed that the ratio of upper critical field to transition temperature decreases with increasing Ni concentration. Also, the magnetization study of Nb₂Pd_1?xNi_x S ₅ (0 = x ≤ 0.15) samples shows similar superconducting behaviour. In summary, the superconductivity in Nb₂PdS₅ sample is slightly varying with partial doping of Ni at Pd site in Nb₂PdS₅ superconductor.     

Preparation and electrical properties of Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>-PbTiO<Subscript>3</Subscript> solid solutions

Ceramic samples of lead magnesium niobate (PMN) and (1 ? x)Pb(Mg_1/3Nb_2/3)O₃?xPbTiO₃ (PMN-PT) solid solutions with x = 0, 0.05, 0.10, and 0.30 have been prepared by solid-state reactions, and their structural, electrical, and piezoelectric properties have been studied using x-ray diffraction, Rietveld profile analysis, impedance spectroscopy, and the resonance/antiresonance method. The results indicate that the use of nonstoichiometric columbite niobates enables the synthesis of phase-pure PMN and PMN-PT.     

Growth and properties of LiCu<Subscript>2</Subscript>O<Subscript>2</Subscript>-NaCu<Subscript>2</Subscript>O<Subscript>2</Subscript> crystals

Platelike Li_{1 ? x} Na _x Cu₂O₂ single crystals up to 2 × 10 × 10 mm in dimensions have been grown by slowly cooling (1 ? x)Li₂CO₃·xNa₂O₂·4CuO melts in alundum crucibles in air. Li_{1 ? x} Na _x Cu₂O₂ solid solutions in the LiCu₂O₂-NaCu₂O₂ system have been shown to exist in the composition range 0.78 < x < 1. The temperature stability ranges of NaCu₂O₂ and LiCu₂O₂ are 780–930 and 890–1050°C, respectively. The Mössbauer spectra and electrical conductivity of the crystals have been measured.     

Composition and Structure of (Zr<Subscript>0.37</Subscript>Ti<Subscript>0.63</Subscript>)<Subscript>3</Subscript>AlC<Subscript>2</Subscript> MAX Phase Crystals Prepared by Self-Propagating High-Temperature Synthesis

A (Zr_0.37Ti_0.63)₃AlC₂ MAX phase has been prepared by self-propagating high-temperature synthesis. The composition of its crystals has been determined by comparing X-ray structure analysis results with structural data for (Zr_xTi_1–x)₃AlC₂ (0 < x < 1) crystals prepared by other methods. Comparison of X-ray structure analysis data with density functional theory calculation results indicates that the arrangement of the Zr and Ti atoms in the metal–carbon layer is disordered.     

Strong up-conversion luminescence and electrical properties of SrBi<Subscript>4</Subscript>Ti<Subscript>4</Subscript>O<Subscript>15</Subscript> multifunctional ceramics by Er<Superscript>3+</Superscript> doping

Novel green-emitting piezoelectric ceramics of SrBi_4?x Er _x Ti₄O₁₅ (SBT-xEr) were prepared. Strong up-conversion with bright green (524 and 548 nm) and a relatively weak red (660 nm) emission bands were obtained under 980 nm excitation at room temperature, which is attributed to the intra 4f–4f electronic transition of (²H_11/2, ⁴S_3/2)–⁴I_15/2 and the transition from ⁴F_9/2 to ⁴I_15/2 of Er³⁺ ions, respectively. Simultaneously, Er³⁺ doping promotes the electrical properties. At 0.8 mol%Er, the optimal electric properties with high Curie temperature of T _c?~527?°C, large remanent polarization of 2P _r?~14.92 μC/cm² and piezoelectric constant of d ₃₃?~17 pC/N was achieved. As a multifunctional material, Er³⁺ doped SBT showed a great potential to be used in 3D-display, bio-imaging, solid state laser and optical temperature sensor.     

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.     

New NaSrPO<Subscript>4</Subscript>:Sm<Superscript>3+</Superscript> phosphor as orange-red emitting material

Sm³⁺-activated NaSrPO₄ phosphors could be efficiently excited at 403 nm, and exhibited a bright red emission mainly including four wavelength peaks of 565, 600, 646 and 710 nm. The highest emission intensity was found for NaSr _1?x PO₄: xSm³⁺ with a composition of x = 0.007. Concentration quenching was observed as the composition of x exceeds 0.007. The decay time values of NaSr_1?x PO ₄ : xSm³⁺ phosphors range from around 2.55 to 3.49 ms. NaSr_1?x PO₄: xSm³⁺ phosphor shows a higher thermally stable luminescence and its thermal quenching temperature T ₅₀ was found to be 350°C, which is higher than that of commercial YAG:Ce³⁺ phosphor and ZnS:(Al, Ag) phosphor. Because NaSr_1?x PO₄: xSm³⁺ phosphor features a high colour-rendering index and chemical stability, it is potentially useful as a new scintillation material for white light-emitting diodes.     

Electrical Conductivity and Electrochemical Characteristics of Na<Subscript>3</Subscript>V<Subscript>2</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-Based NASICON-Type Materials

NASICON-type materials with the compositions Na₃V_2–xAl_x(PO₄)₃, Na₃V_{2 - x}Fe_x(PO₄)₃, Na_{3 + x}V_2–xNi_x(PO₄)₃, and Na₃V_{2 - x}Cr_x(PO₄)₃ (x = 0, 0.03, 0.05, and 0.1) have been prepared and characterized by X-ray diffraction analysis, electron microscopy, and impedance spectroscopy. The results demonstrate that the highest electrical conductivity among the samples studied is offered by the material doped with 5% Fe: Na₃V_1.9Fe_0.1(PO₄)₃. The activation energy for low-temperature conduction in the doped materials decreases from 84 ± 2 to 54 ± 1 kJ/mol and that for high-temperature conduction is ~33 kJ/mol. The discharge capacity of Na₃V_1.9Fe_0.1(PO₄)₃/C under typical working conditions of cathodes of sodium ion batteries has been shown to exceed that of Na₃V₂(PO₄)₃/C. The capacity of the more porous material prepared by the Pechini process (Na₃V_1.9Fe_0.1(PO₄)₃/C-{II}) approaches the theoretical one at a low charge–discharge rate and retains its high level as the charge rate is raised (its discharge capacity was 117.6, 108.8, and 82.6 mAh/g at a discharge rate of 0.1C, 2C, and 8C, respectively).     

Structure and electrical properties of MnO doped (Ba<Subscript>0.96</Subscript>Ca<Subscript>0.04</Subscript>)(Ti<Subscript>0.92</Subscript>Sn<Subscript>0.08</Subscript>)O<Subscript>3</Subscript> lead free ceramics

In this work, (Ba_0.96Ca_0.04)(Ti_0.92Sn_0.08)O₃–xmol MnO (BCTS–xMn) lead-free piezoelectric ceramics were fabricated by the conventional solid-state technique. The composition dependence (0 ≤ x ≤ 3.0 %) of the microstructure, phase structure, and electrical properties was systematically investigated. An O–T phase structure was obtained in all ceramics, and the sintering behavior of the BCTS ceramics was gradually improved by doping MnO content. In addition, the relationship between poling temperature and piezoelectric activity was discussed. The ceramics with x = 1.5 % sintering at temperature of 1330 °C demonstrated an optimum electrical behavior: d ₃₃ ~ 475 pC/N, k _p ~ 50 %, ε _r ~ 4060, tanδ ~ 0.4 %, P _r ~ 10.3 μC/cm², E _c ~ 1.35 kV/mm, T _C ~ 82 °C, strain ~0.114 % and \(d_{33}^{*}\) ~ 525 pm/V. As a result, we achieved a preferable electric performance in BaTiO₃-based ceramics with lower sintering temperature, suggesting that the BCTS–xMn material system is a promising candidate for lead-free piezoelectric ceramics.     

Ultralow thermal conductivity of cerium-doped Nd<Subscript>2</Subscript>Zr<Subscript>2</Subscript>O<Subscript>7</Subscript> over a wide doping range

In this paper, we report an ultralow thermal conductivity and a high-temperature phase stability of the (Nd_1?x Ce _x )₂Zr₂O_7+x system over the temperature range from room temperature to 1600 °C and over a wide composition range (0.2 ≤ x ≤ 0.8), and the (Nd_1?x Ce _x )₂Zr₂O_7+x system is therefore considered a strong candidate material for the fabrication of next-generation high-temperature thermal barrier coatings. The observed thermal conductivities (0.65–1.0 W/mK) are about 60–40% lower than those of undoped Nd₂Zr₂O₇ over the same temperature range (100–700 °C) and indicate a glass-like behavior. For comparison, the variation in the thermal conductivity with the temperature of the (Gd_1?x Ce _x )₂Zr₂O_7+x system with similar point defects was also measured, and the observed behavior was almost the same as that of undoped Gd₂Zr₂O₇ and was mostly determined by phonon–phonon scattering (λ ∝ 1/T). The effect of point defect scattering and strong phonon scattering sources (rattlers) on the thermal conductivity is also discussed in this paper. The results of this study suggest that the ultralow thermal conductivity of (Nd_1?x Ce _x )₂Zr₂O_7+x can be attributed to the presence of rattlers because of the large difference between the ionic radii of the Nd³⁺ and Ce⁴⁺ ions.     

Magnetization reversal and tunable exchange bias behavior in Mn-substituted NiCr<Subscript>2</Subscript>O<Subscript>4</Subscript>

Single phase samples of Ni(Cr_1?xMn _x )₂O₄ (x = 0–0.50) were synthesized by using sol–gel route. Investigation of structural, magnetic, exchange bias and magnetization reversal properties was carried out in the bulk samples of Ni(Cr_1?xMn _x )₂O₄. Rietveld refinement of the X-ray diffraction patterns recorded at room temperature reveals the tetragonal structure for x = 0 sample with I4₁/amd space group and cubic structure for x ≥ 0.05 samples with \( {\text{Fd}\bar{3}\text{m}} \) space group. Magnetization measurements show that all samples exhibit ferrimagnetic behavior, and the transition temperature (T_C) is found to increase from 73 K for x = 0 to 138 K for x = 0.50. Mn substitution induces magnetization reversal behavior especially for 30 at% of Mn in NiCr₂O₄ system with a magnetic compensation temperature of 45 K. This magnetization reversal is explained in terms of different site occupation of Mn ions and the different temperature dependence of the magnetic moments of different sublattices. Study of exchange bias behavior in x = 0.10 and 0.30 samples reveals that they exhibit negative and tunable positive and negative exchange bias behavior, respectively. The magnitudes of maximum exchange bias field of these samples are found to be 640 and 5306 Oe, respectively. Exchange bias in x = 0.10 sample originates from the anisotropic exchange interaction between the ferrimagnetic and the antiferromagnetic components of magnetic moment. The tunable exchange bias behavior in x = 0.30 sample is explained in terms of change in domination of one sublattice moment over the other as the temperature is varied.     

Preparation of Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript> through reduction of titanium dioxide with silicon carbide

This paper describes the reduction of titanium dioxide with a mixture of silicon carbide and silicon powders at a temperature of 1550°C under vacuum. It has been shown that the use of the combined reductant enables the preparation of the ternary phase Ti₃SiC₂ through concurrent carboand silicothermic processes. The optimal compositions for Ti₃SiC₂ formation are TiO₂ + (1.5–x)SiC + 2xSi with x = 0.4–0.5. The Ti₃SiC₂ yield then reaches 96 wt %.     

Comparative Magnetic and Structural Properties Study of Micro- and Nanopowders of Nd<Subscript>2</Subscript>Fe<Subscript>14</Subscript>B Doped with Ni

Micropowders of melted and heat-treated Nd₁₆(Fe_76?x Ni _x )B₈ alloys system, with x = 0, 10, 20, and 25 (size distribution under 20 μm), were studied and compared with the study of nanopowders obtained, from the previous ones, by surfactant-assisted ball-milling process during 2 h. By XRD, a majority of Nd₂Fe₁₄B hard phase and a minority of α-Fe, Nd_1.1Fe₄B₄ and NdNi₂ phases were detected. The last one increases with Ni content. The crystallite size of the hard phase, in both types of samples, is not affected by the Ni content; however, the grains in micropowders are oblate, with a mean size of 37 nm, while those of the nanopowders are symmetric, with a mean size of 35 nm. Mössbauer spectra were fitted with seven sextets, which correspond to the six ferromagnetic sites of the hard phase and that of the α-Fe, and a doublet corresponding to the paramagnetic Nd_1.1Fe₄B₄ phase. The mean hyperfine magnetic field, for both types of samples, decreases with Ni content. The hysteresis loops of both types of samples show a hard magnetic character, however, the coercive field and the M _r/M _s values for nanopowders are greater than those obtained for micropowders for all the Ni contents. Values of H _c = 2 kOe and M _r/ M _s = 0.54 were obtained for nanopowders with 10 at.% Ni. From the hysteresis loops, which include the initial magnetization curve, Henkel plots for all the samples were obtained. These plots show that for micropowders, the predominant magnetic interaction is of dipolar type, while for nanopowders, the ferromagnetic exchange is the predominant one, which favored the magnetization.     

Structural,Thermal and Magnetic Properties of Nanocrystalline Co<Subscript>80</Subscript>Ni<Subscript>20</Subscript> Alloy Prepared by Mechanical Alloying

Co₈₀Ni₂₀ powder mixture was mechanically alloyed by high-energy planetary ball milling, starting from elemental Co and Ni metal powders. The morphological, microstructural, thermal and magnetic properties of the milled powders were characterised respectively by scanning electron microscopy, X-ray diffraction, differential scanning calorimetry and vibratory sample magnetometry. In addition to a highly disordered phase, two face-centred cubic (FCC) and hexagonal close-packed (HCP), solid solutions, FCC Co(Ni), FCC Ni(Co) and HCP Co(Ni), are observed after 3 h of milling. Their grain sizes decrease with increase in milling time attaining, at 48 h of milling, 12 nm, 25 nm and 10 nm, respectively. Beyond a certain milling time, no further refinement of the microstructure occurs and the morphological equilibrium is usually given by a bimodal particle size distribution. Magnetic measurements of the milled Co₈₀Ni₂₀ alloy powder exhibit a soft ferromagnetic character where the magnetic parameters are sensitive to the milling time mainly due to the particle size refinement as well as the formation of Co(Ni) and Ni(Co) solid solutions. Both the saturation magnetisation ( M _s) and coercivity ( H _c) were found to decrease with milling time, attaining the values of M _s = 126 emu/g and H _c = 60 Oe after 48 h of milling.