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The influence of the calcination process on the physicochemical properties and catalytic behavior of the Co/Mg/La catalysts for ammonia synthesis has been investigated. The catalysts were prepared using the different thermal pre-treatment methods prior to the activation, i.e., drying and calcination, and the respective activities for ammonia synthesis were assessed. It was found out that changing from air calcination prior to activation to direct activation of the co-precipitated species led to the different catalytic performances. The most favorable catalytic performance was achieved with Co/Mg/La prepared by calcination in air. Detailed characterization methods, employing e.g., XRPD, H2-TPD, N2-TPD, CO2-TPD, SEM, and TEM, showed that the superior catalytic behavior of this catalyst was attributed to its strong basicity and favorable adsorption properties toward hydrogen and nitrogen.

Reversible oxidation-reduction of cerium ions in a monoclinic Ce4Al2O9 aluminate was studied by XRD, TEM, temperature programmed reduction-oxidation and magnetic methods. It has been shown that nanocrystalline Ce4Al2O9 reacts with gaseous oxygen, undergoing at 20–300 °C transformation into a new, oxidized phase described in the same P21/c space group, but with 10% smaller unit cell volume. Magnetic measurements revealed that the oxidized Ce4Al2O9 still contains ~20% of paramagnetic Ce3+ ions. The oxidized Ce aluminate may be reduced back to Ce4Al2O9 by heating in H2 atmosphere to 1000 °C. The reversibility of the oxidation-reduction process of Ce4Al2O9 aluminate bears resemblance to the behaviour of fluorite type CeO2, and may be of interest for applications (e.g., in catalytic high-temperature oxidation reactions).

Analysis of bipolar thermal conductivity might be very useful in preliminary stages of thermoelectric materials discovery. Using its product---mobility ratio between electrons and holes---it is possible to choose the most promising compound from the series and pave the correct direction of doping. Current work presents positive verification of this approach for $\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}$, which is anticipated to show superior mobility when tuned towards n-type behavior. In agreement with expectation, the mobility increases by an order of magnitude due to rising tellurium content in the ${\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}}_{1\ensuremath{-}x}{\mathrm{Te}}_{x}$ series. The effect is most likely driven by change of the dominant charge carriers' scattering mechanism from ionized impurity influence to point defect and acoustic phonon interaction. Simultaneously, due to a highly anisotropic conduction band, the effective mass of the carriers rises towards the n-type regime. These two effects lead to an improved thermoelectric power factor of electron-doped samples, up to $40\phantom{\rule{0.2em}{0ex}}\ensuremath{\mu}{\mathrm{WK}}^{\ensuremath{-}2}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ at 740 K for ${\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}}_{0.85}{\mathrm{Te}}_{0.15}$. Based on this result, we suggest n-type doping for other rare-earth-based half-Heusler compounds. Representatives of this group exhibit the smallest lattice thermal conductivity in the pristine form among any half-Heusler thermoelectrics, and are anticipated to show comparably good electrical properties to ScNiSb due to their high mobility ratio in favor of electrons.

Made available in DSpace on 2021-06-25T10:51:07Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 New materials discovery is the driving force for progress in solid state physics and chemistry. Here we solve the crystal structure and comprehensively study physical properties of ZnVSb in the polycrystalline form. Synchrotron x-ray diffraction reveals that the compound attains a layered ZrSiS-type structure (P4/nmm, a = 4.09021(2) Å, c = 6.42027(4) Å). The unit cell is composed of a 2D vanadium network separated by Zn-Sb blocks that are slightly distorted from the ideal cubic arrangement. A considerable amount of vacancies were observed on the vanadium and antimony positions; the experimental composition is ZnV0.91Sb0.96. Low-temperature x-ray diffraction shows very subtle discontinuity in the lattice parameters around 175 K. Bonding V-V distance is below the critical separation of 2.97 Å known from the literature, which allows for V-V orbital overlap and subsequent metallic conductivity. From ab initio calculations, we found that ZnVSb is a pseudogap material with an expected dominant vanadium contribution to the density of states at the Fermi level. The energy difference between the antiferromagnetic and nonordered magnetic configurations is rather small (0.34 eV/f.u.). X-ray photoelectron spectroscopy fully corroborates the results of the band structure calculations. Magnetic susceptibility uncovered that, in ZnVSb, itinerant charge carriers coexist with a small, localized magnetic moment of ca. 0.25 μB. The itinerant electrons arise from the ordered part of the vanadium lattice. Fractional localization, in turn, was attributed to V atoms neighboring vacancies, which hinder full V-V orbital overlap. Furthermore, the susceptibility and electrical resistivity showed a large hysteresis between 120 K and 160 K. The effect is not sensitive to magnetic fields up to 9 T. Curie-Weiss fitting revealed that the amount of itinerant charge carriers in ZnVSb drops with decreasing temperature below 160 K, which is accompanied by a concurrent rise in the localized magnetic moment. This observation together with the overall shape of the hysteresis in the resistivity allows for suggesting a plausible origin of the effect as a charge-transfer metal-insulator transition. Ab initio phonon calculations show the formation of a collective phonon mode at 2.8 THz (134 K). The experimental heat capacity reflected this feature by a boson peak with Einstein temperature of 116 K. Analysis of the heat capacity with both an ab initio perspective and Debye-Einstein model revealed a sizable anharmonic contribution to heat capacity, in line with disordered nature of the material. Further investigation of the electron and phonon properties for ZnVSb is likely to provide valuable insight into the relation between structural disorder and the physical properties of transition-metal-bearing compounds. Physics Department Colorado School of Mines Institute of Low Temperature and Structure Research Polish Academy of Sciences University of Illinois at Urbana-Champaign Instituto de Física Teórica São Paulo State University (UNESP) University of California Santa Barbara Max Planck Institute for Chemical Physics of Solids Department of Chemistry and Biochemistry The Ohio State University National Synchrotron Radiation Research Center (NSRRC) Instituto de Física Teórica São Paulo State University (UNESP)

Deeper understanding of electrical and thermal transport is critical for further development of thermoelectric materials. Here we describe the thermoelectric performance of a group of rare-earth-bearing half-Heusler phases determined in a wide temperature range. Polycrystalline samples of $\mathrm{Sc}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Dy}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Er}\mathrm{Ni}\mathrm{Sb}$, $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$, and $\mathrm{Lu}\mathrm{Ni}\mathrm{Sb}$ are synthesized by arc melting and densified by spark plasma sintering. They are characterized by powder x-ray diffraction and scanning electron microscopy. The physical properties are studied by means of heat-capacity and Hall-effect measurements performed in the temperature range from 2 to 300 K, as well as electrical-resistivity, Seebeck-coefficient, and thermal-conductivity measurements performed in the temperature range from 2 to 950 K. All the materials except $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$ are found to be narrow-gap intrinsic $p$-type semiconductors with rather light charge carriers. In $\mathrm{Tm}\mathrm{Ni}\mathrm{Sb}$, the presence of heavy holes with large weighted mobility is evidenced by the highest power factor among the series ($17\phantom{\rule{0.2em}{0ex}}\ensuremath{\mu}\mathrm{W}\phantom{\rule{0.2em}{0ex}}{\mathrm{K}}^{\ensuremath{-}2}\phantom{\rule{0.2em}{0ex}}{\mathrm{cm}}^{\ensuremath{-}1}$ at 700 K). The experimental electronic relaxation time calculated with the parabolic band formalism is found to range from $0.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}14}$ to $2.8\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}14}$ s. In all the materials studied, the thermal conductivity is between 3 and $6\phantom{\rule{0.2em}{0ex}}{\mathrm{W m}}^{\ensuremath{-}1}\phantom{\rule{0.2em}{0ex}}{\mathrm{K}}^{\ensuremath{-}1}$ near room temperature (i.e., smaller than in other pristine $d$-electron half-Heusler phases reported in the literature). The experimental observation of the reduced thermal conductivity appears fully consistent with the estimated low sound velocity as well as strong point-defect scattering revealed by Debye-Callaway modeling. Furthermore, analysis of the bipolar contribution to the measured thermal conductivity yields abnormally large differences between the mobilities of $n$-type and $p$-type carriers. The latter feature makes the compounds examined excellent candidates for further optimization of their thermoelectric performance via electron doping.

Ni-rich layered oxides, i.e., LiNi0.6Mn0.2Co0.2O2 (NMC622) and LiNiO2 (LNO), were prepared using the two-step calcination procedure. The samples obtained at different calcination temperatures (750&ndash, 950 &deg, C for the NMC622 and 650&ndash, 850 &deg, C for the LNO cathode materials) were characterized using nitrogen physisorption, PXRD, SEM and DLS methods. The correlation of the calcination temperature, structural properties and electrochemical performance of the studied Ni-rich layered cathode materials was thoroughly investigated and discussed. It was determined that the optimal calcination temperature is dependent on the chemical composition of the cathode materials. With increasing nickel content, the optimal calcination temperature shifts towards lower temperatures. The NMC-900 calcined at 900 &deg, C and the LNO-700 calcined at 700 &deg, C showed the most favorable electrochemical performances. Despite their well-ordered structure, the materials calcined at higher temperatures were characterized by a stronger sintering effect, adverse particle growth, and higher Ni2+/Li+ cation mixing, thus deteriorating their electrochemical properties. The importance of a careful selection of the heat treatment (calcination) temperature for each individual cathode material was emphasized.

In the present study, a nanoapatite-mediated delivery system for imatinib has been proposed. Nanohydroxyapatite (nHAp) was obtained by co-precipitation method, and its physicochemical properties in combination with imatinib (IM) were studied by means of XRPD (X-ray Powder Diffraction), SEM-EDS (Scanning Electron Microscopy-Energy Dispersive X-ray Spectroscopy), FT-IR (Fourier-Transform Infrared Spectroscopy), absorption spectroscopy as well as DLS (Dynamic Light Scattering) techniques. The obtained hydroxyapatite was defined as nanosized rod-shaped particles with high crystallinity. The amorphous imatinib was obtained by conversion of its crystalline form. The beneficial effects of amorphous pharmaceutical agents have been manifested in the higher dissolution rate in body fluids improving their bioavailability. Imatinib-to-hydroxyapatite interactions on the surface were confirmed by SEM images as well as absorption and FT-IR spectroscopy. The cytotoxicity of the system was tested on NI-1, L929, and D17 cell lines. The effectiveness of imatinib was not affected by nHAp modification. The calculated IC50 values for drug-modified nHAp were similar to those for the drug itself. However, higher cytotoxicity was observed at higher concentrations of imatinib, in comparison with the drug alone.

The Y 2-x Te 4 O 11 (x = 0.1, 0.5, 1.0, 2.0 and 5.0 at%) microcrystalline powders were successfully synthesized by a conventional solid state reaction method. Optical absorption (300 K) and fluorescence spectra (300 K) as well as fluorescence decay curves (300 K) of the emitting levels of Tm 3+ ion in Y 2 Te 4 O 11 powders are presented and analyzed in details. The Judd-Ofelt theory was applied to analyze experimental data for the quantitative determination of phenomenological Ω λ ( λ = 2, 4, 6) parameters, radiative transition probabilities ( A ), branching ratios ( β ) of luminescence and radiative lifetimes ( τ rad ) of the 1 D 2 , 1 G 4 , 3 H 4 and 3 F 4 levels. The observed non-exponential decays nature and concentration quenching of the 1 G 4 and 3 H 4 states have been attributed to cross-relaxation processes and this phenomena has been analyzed by Inokuti-Hirayama model. The stimulated emission cross-section for the 3 F 4 → 3 H 6 transition equals to 1.12 × 10 −20 cm 2 at 1809 nm was calculated using the Fuchtbauer-Ladenburg method and compared with the corresponding values of other Tm 3+ -doped laser hosts. From obtained results, follow that the Tm 3+ :Y 2 Te 4 O 11 is a potential candidate for a solid-state laser host operating at 1.8 µm.

The effects of heat treatment temperature, time and isostatic pressure on the grain connectivity and superconducting properties of Mg11B2 wires prepared using nano-amorphous isotopic boron powder (11B) have been investigated. The article presents detailed studies of the Mg11B2 material structure of the wires using scanning electron microscope (SEM). Heat treatment at low and high temperature for different annealing time and isostatic pressure does not create an internal macro-defect that disrupts connectivity in the Mg11B2 superconducting wires. Our study shows that dense longitudinal superconducting layers are formed at high annealing temperature of 800 °C for 60 min. Formation of dense longitudinal superconducting layers under high isostatic pressure (HIP) allow improved grain connectivity and high density of pinning centers and as a result, high engineering critical current density, Jec, at 4.2 K has been achieved. Also, high upper critical field (Bc2) and high irreversible magnetic field (Birr) were obtained using HIP process while superconducting transition temperature (Tc) was not significantly affected. Better grain connectivity obtained using high annealing temperature and long annealing time under low isotopic pressure leads to Jec enhancement at high magnetic fields at 20 K. Our results show that the annealing temperature of 800 °C for 60 min under isostatic pressure of 1 GPa yields the required Jec of 25 A/mm2 and 50 A/mm2 for ITER applications in magnetic fields of 8 T and 7 T, respectively. The promising results obtained in this work could pave the way for designing low activation superconducting Mg11B2 wires to be considered for next generation fusion magnets.

In this paper, some spectroscopic properties of Y2Te4O11 microcrystalline powders, doped with Nd3+ ions are presented. The samples were successfully synthesized by the solid state reaction method. Absorption (300 K) and fluorescence (at 77 and 300 K) spectra as well as the fluorescence decay curves (300 K) of the 4F3/2 state are presented and analyzed. The phenomenological Ωλ (λ=2, 4, 6) Judd-Ofelt parameters were evaluated in order to determine radiative probabilities (A), branching ratios (β), the radiative lifetime (τR) of the 4F3/2 level and the stimulated emission cross-section (σem) for the 4F3/2 → 4IJ/2 (J=9 and 11) transitions of the Nd3+ ion. The fluorescence decay curves were single exponential for 0.01–5.0 at% of Nd3+ and became evidently non-exponential for higher Nd3+ ion concentration. With increasing activator concentration from 0.01 to 10.0 at%, the experimental lifetime of the emitting level decreases from 95 to 33 μs. The non-exponential fluorescence decay curve has been fitted by the Yokota-Tanimoto model, indicating that the energy migration process via a diffusion limited relaxation, plays a important role in the depopulation of the 4F3/2 level of Nd3+ ions doped in the Y2Te4O11 microcrystalline powder. The calculated absorption value (1.135×10–19 cm2 at 807.5 nm) of the 4I9/2 → 4F5/2 transition as well as the value of the stimulated emission cross-section (1.196×10–19 cm2 at 1063.5 nm) for that of 4F3/2 → 4I11/2 were compared with the corresponding values of other laser hosts. For the first time a very high σem value of the 4F3/2 → 4I11/2 transition for TeO2-based compounds, has been observed. From the presented spectroscopic properties follows that the Nd3+:Y2Te4O11 powder is a potential candidate for a random laser host, operating at 1.06 μm.

In this paper, the optical properties of Y 2 Te 4 O 11 microcrystalline powders doped with Dy 3+ ions, ranging between 0.01 and 5.0 at%, are reported. The powders were successfully synthesized by the solid state reaction method. Absorption (300 K), excitation (300 K) and fluorescence spectra (at 11.6 and 300 K) as well as fluorescence decay curves recorded at room temperature are presented and analyzed in details. Oscillator strengths, phenomenological Ω λ ( λ =2, 4, 6) Judd-Ofelt parameters, radiative transition probabilities, branching ratios, the radiative lifetime of the 4 F 9/2 level as well as the stimulated emission cross-section for the 4 F 9/2 → 6 H 13/2 transition have been determined. The observed non-exponential decay nature and concentration quenching of the 4 F 9/2 emitting level of the Dy 3+ ion, have been attributed to cross-relaxation processes. The high value of the stimulated emission cross-section for the 4 F 9/2 → 6 H 13/2 transition at 576.6 nm, equal to 0.756×10 −20 cm 2 , indicates that Y 2 Te 4 O 11 activated by trivalent dysprosium ions is an attractive candidate for a solid-sate laser.

Among a wide variety of solid state materials, alkali lanthanide double phosphates are the subject of extensive spectroscopic investigations for their application as laser active materials. The edge of absorption in this compound is at rather high energies, which makes them suitable as efficient host for luminescent materials. Spectroscopic properties of Sm3+-doped K3Y(PO4)2 are reported basing on the high resolution absorption and emission spectra for various temperatures mainly at 4, 10, and 293 K from UV to IR range. The effects of concentration and temperature on intensities and shape of the observed bands were studied. Radiative transition probabilities were calculated from absorption spectra and Judd–Ofelt parameters evaluated. The excited state dynamics will be discussed based on the decay time measurement.

Half-Heusler phase HoPtSb was studied by means of powder X-ray diffraction, scanning electron microscopy with energy-dispersive X-ray spectrometry, high-resolution transmission electron microscopy (HRTEM), heat capacity, magnetization, electrical resistivity and magnetoresistance. Measurements were performed in temperature range 2–300 K and magnetic fields up to 14 T. The results revealed significant atomic disorder in the crystal structure of this compound, and indicated that the electrical transport in HoPtSb is noticeably affected by scattering conduction electrons on structural inhomogeneities. Due to large value of the resistivity accompanied by small overall change of resistivity with changing temperature the high-temperature behavior was attributed to disorder-induced violation of the Matthiessen’s rule. In turn, at low temperatures, strong magnetic field of 14 T disclosed resistivity upturn reminiscent of Altshuler-Aronov quantum correction observed in disordered metallic systems.

The relaxation processes of the adiabatic temperature changes (ΔTad) at the phase transitions in Ni45Mn43CoSn11, Ni50Mn36.5In13.5, and Ni50Mn35In14.25B0.75 Heusler alloys with different magnetic structures have been studied using a direct extraction method in magnetic fields up to 14 T. It has been found that ΔTad exhibits short relaxation times (less than 10−1 (s)) in the vicinity of the second order phase transitions at the Curie temperatures. The relaxation times of the first order martensitic transitions strongly depend on the latent heat of the transition and can be characterized by a logarithmic law.