Solid state sintering of lime in presence of La<Subscript>2</Subscript>O<Subscript>3</Subscript> and CeO<Subscript>2</Subscript>

The sintering of lime by double calcination process from natural limestone has been conducted with La₂O₃ and CeO₂ additive up to 4 wt.% in the temperature range 1500–1650° C. The results show that the additives enhanced the densification and hydration resistance of sintered lime. Densification is achieved up to 98.5% of the theoretical value with La₂O₃ and CeO₂ addition in lime. Grain growth is substantial when additives are incorporated in lime. The grain size of sintered CaO (1600°C) with 4 wt.% La₂O₃ addition is 82 μm and that for CeO₂ addition is 50 μm. The grains of sintered CaO in presence of additive are angular with pores distributed throughout the matrix. EDX analysis shows that the solid solubility of La₂O₃ and CeO₂ in CaO grain is 2.9 and 1.7 weight %, respectively. The cell dimension of CaO lattice is 4.803 %C. This value decreases with incorporation of La₂O₃ and CeO₂. The better hydration resistance of La₂O₃ added sintered lime compared to that of CeO₂ added one, is related to the bigger grain size of the lime in former case.     

Synthesis of orthorhombic and cubic PbF<Subscript>2</Subscript> by hydrothermal method

Orthorhombic (α-) and cubic (β-) PbF₂ have been successfully synthesized via a simple hydrothermal process at 200 °C for 8 h using Pb(C₂H₃O)₂ and NH₄F as the raw reaction materials. The crystal structure, morphology, and optical properties of the as-synthesized samples were characterized by X-ray powder diffraction, scanning electron microscopy, and photoluminescence spectroscopy. XRD and SEM results show that the uniform β-PbF₂ microspheres and porous-microspheres with the average diameter about 3 and 5 μm, respectively, were synthesized assisting with citric acid and α-PbF₂ microrods and microtubes with a diameter about 15 and 10 μm, respectively, were synthesized assisting with acetic acid. The reaction conditions influencing the synthesis of these PbF₂ microstructures, such as reaction time, the amount of CTAB, and the molar ratio of F/Pb were investigated. On the basis of a series of observations, phenomenological elucidation of a mechanism for the growth of the β-PbF₂ microspheres and multispheres has been presented. Room-temperature photoluminescence measurements indicated that the as-prepared α-PbF₂ microrods exhibit a strong green emission.     

Mechanical properties and electronic structures of compressed C<Subscript>60</Subscript>, C<Subscript>180</Subscript> and C<Subscript>60</Subscript>@C<Subscript>180</Subscript> fullerene molecules

Molecular dynamics simulations were performed for compressed C₆₀, C₁₈₀ and C₆₀@C₁₈₀ fullerene molecules, and the semi-empirical PM3 calculations were carried out to obtain the electronic structure of the compressed fullerenes. According to the obtained results, the differences of mechanical properties between these compressed fullerenes, as well as the changes of their FMO (Frontier molecular orbital) energy-levels during compression, were discussed. It is shown that (1) the C₆₀ molecule has much higher load-support and energy-absorbing capability than the C₁₈₀ and C₆₀@C₁₈₀ molecules, and the C₆₀@C₁₈₀ is only slightly superior to the C₁₈₀, (2) of the three molecules, the C₆₀ molecule has the best chemical-stability, and the C₆₀@C₁₈₀ molecule has the worst one, (3) with the increase of compressive strain, both the C₆₀ and C₆₀@C₁₈₀ molecules become more chemically active, and (4) when the compressed C₁₈₀ molecule caves in at the loading position(s), its chemical-stability decreases abruptly.     

Mass spectrometry of carbon nitride C<Subscript>3</Subscript>N<Subscript>4</Subscript>

Carbon nitride has been synthesized in macroscopic amounts by means of the original method based on an ecologically safe technology using inorganic initial compounds. The product has been characterized by mass spectrometry (MS), X-ray diffraction, and quantitative chemical analysis. The MS and thermochemical data show that stoichiometry of the samples of carbon nitride obtained using the proposed method corresponds to the empirical formula C₃N₄.     

Core electron level structure in C<Subscript>60</Subscript>F<Subscript>18</Subscript> and C<Subscript>60</Subscript>F<Subscript>36</Subscript> fluorinated fullerenes

The structure of C1s and F1s core electron levels in C₆₀F₁₈ and C₆₀F₃₆ fluorinated fullerenes has been studied by X-ray photoelectron spectroscopy using synchrotron radiation. It is established that C1s levels of carbon atoms not bound to fluorine in these compounds are shifted down by 1.0 and 1.6 eV relative to the C1s level in the usual C₆₀ fullerene, so that the binding energies of the core electron levels in C₆₀F₁₈ and C₆₀F₃₆ amount to E _b (C1s, C-C) = 285.7 and 286.3 eV, respectively. These values are characteristic and can be used for the identification of both homogeneous fluorinated fullerenes and combined materials comprising a mixture of various fluorinated fullerenes with each other and with different carbon-containing based materials.     

Development of Fe<Subscript>3</Subscript>C,SiC and Al<Subscript>4</Subscript>C<Subscript>3</Subscript> compounds during mechanical alloying

Mechanical alloying process, as a solid-state technique, is a very useful method for fabrication of high melting point compounds like metal carbides and nitrides, which additionally have nanocrystalline structure with improved properties. In this work the development of several carbides including iron, aluminium and silicon carbides by the mechanical alloying process and the effect of subsequent heat treatment were investigated. Mixtures of elemental powders of Fe–C, Si–C and Al–C were mechanically alloyed, nominally at room temperature using a laboratory planetary ball mill. Structural changes of samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results showed that the aluminium carbide (Al₄C₃) could not be synthesized by mechanical alloying process alone, even after long milling times. A suitable subsequent heat treatment was required to allow Al–C reaction to take place kinetically. In contrast mechanical alloying of Fe–C as well as Si–C systems directly led to the formation of Fe₃C and SiC carbides after sufficient milling time. In all cases the end product had a nanosized structure.     

Refractive index of Al<Subscript>3</Subscript>C<Subscript>2</Subscript>B<Subscript>48</Subscript> aluminum borocarbide crystals

Aluminum borocarbide single crystals have been grown from an Al-based solution melt. The crystal lattice parameters have been determined, the dispersion of the refractive index in a 0.55–1.3 μm wavelength interval has been studied, and the temperature coefficient of the refractive index in a 300–600 K range has been measured. The crystals are characterized by a high refractive index in the visible spectral range in combination with at a high hardness, which makes them of interest for jewelry, as well as for both traditional and X-ray optics.     

Melting behavior of the Nowotny phase Mo<Subscript>4.8</Subscript>Si<Subscript>3</Subscript>C<Subscript>0.6</Subscript>

Mixtures of the Mo₅Si₃ silicide with 1.1–2.4 wt % carbon were melted after reaction sintering and the formation of the Nowotny phase (Mo_4.8Si₃C_0.6), and the effect of various heat treatments on the phase composition of the samples was studied. The crystallization of the melted samples leads to a reduction of the volume fraction of the Nowotny phase relative to that after reaction sintering, but subsequent annealing below the liquid phase formation temperature allows the volume fraction of Mo_4.8Si₃C_0.6 to be again raised. We discuss possible causes of the observed phase transformations.     

Liquid-phase epitaxy of NdAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> and Yb-doped YAl<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript>

Epitaxial layers of NaAl₃(BO₃)₄ (NAB) and YAl₃(BO₃)₄〈Yb〉 (YAB〈Yb〉) containing up to 10 at % Yb have been grown by liquid-phase epitaxy on YAB substrates. Their growth kinetics have been studied at relative supersaturations of the high-temperature solution from 2 × 10^?2 to 16 × 10^?2. The ytterbium concentration in YAB〈Yb〉 has been shown to vary little during the epitaxial process. Near the edges of the substrate, the surface morphology of the layers is complicated by vicinals, which have a spiral form in the case of YAB〈Yb〉. On \(\{ 10\overline 1 1\} \) YAB substrates, homogeneous single-crystal NAB films have been grown.     

Effect of complexation on crystallization of plutonium(IV) oxalate in the system Pu(NO<Subscript>3</Subscript>)<Subscript>4</Subscript>-HNO<Subscript>3</Subscript>-H<Subscript>2</Subscript>C<Subscript>2</Subscript>O<Subscript>4</Subscript>

The published data on complexation in the system Pu(NO₃)₄-HNO₃-H₂C₂O₄ were treated on the basis of a unified approach to determination of the oxalate ion concentration. Because of discrepancies between results published by different researchers, additional experiments on crystallization of Pu(IV) oxalate were carried out at widely varied excess and deficiency of oxalic acid. These experiments confirmed high stability of the complex cations PuC₂O ₄ ²⁺ . The upper boundary of the field of metastable supersaturated solutions of Pu oxalate at the initial Pu concentration of 15–50 g l^?1 was determined.     

Enhancing both selectivity and coking-resistance of a single-atom Pd<Subscript>1</Subscript>/C<Subscript>3</Subscript>N<Subscript>4</Subscript> catalyst for acetylene hydrogenation

Selective hydrogenation is an important industrial catalytic process in chemical upgrading,where Pd-based catalysts are widely used because of their high hydrogenation activities.However,poor selectivity and short catalyst lifetime because of heavy coke formation have been major concerns.In this work,atomically dispersed Pd atoms were successfully synthesized on graphitic carbon nitride (g-C3N4) using atomic layer deposition.Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) confirmed the dominant presence of isolated Pd atoms without Pd nanoparticle (NP) formation.During selective hydrogenation of acetylene in excess ethylene,the g-C3N4-supported Pd NP catalysts had strikingly higher ethylene selectivities than the conventional Pd/A12O3 and Pd/SiO2 catalysts.In-situ X-ray photoemission spectroscopy revealed that the considerable charge transfer from the Pd NPs to g-C3N4 likely plays an important role in the catalytic performance enhancement.More impressively,the single-atom Pd1/C3N4 catalyst exhibited both higher ethylene selectivity and higher coking resistance.Our work demonstrates that the single-atom Pd catalyst is a promising candidate for improving both selectivity and coking-resistance in hydrogenation reactions.     

Preparation and properties of orthorhombic TlInS<Subscript>2</Subscript>

A procedure is described for crystal growth of orthorhombic TlInS₂. The lattice parameters of the grown crystals are a = 6.88 Å, b = 14.04 Å, and c = 4.02 Å (sp. gr. P222₁, Z = 4, _x = 6.59 g/cm³). The dielectric permittivity of the crystals is measured from 170 to 300 K. The spectral dependence of the 300-K photocurrent through the crystals indicates that orthorhombic TlInS₂ is a wide-gap semiconductor. Its band gap, E _g = 2.52 ± 0.01 eV, slightly exceeds that of monoclinic TlInS₂.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 138–142.Original Russian Text Copyright © 2005 by Nadjafov, Alekperov, Guseinov.     

On possible synthesis and crystalline structure of nanodisperse C<Subscript>3</Subscript>N<Subscript>4</Subscript> carbon nitride

Nanodisperse crystalline carbon nitride (C₃N₄) can be obtained by the method of dynamic synthesis in a hypersonic jet of electric-discharge carbon plasma in nitrogen atmosphere. The data of high-resolution transmission electron microscopy show that the crystalline structure of the synthesized material is close to a theoretical structural model of the α phase of C₃N₄. Flattened C₃N₄ nanocrystals possess a unique structure and appear as quasi-two-dimensional multilayer particles without any known analogs.     

Formation of superhard phases in the C<Subscript>diam</Subscript>-AlB<Subscript>12</Subscript> and C<Subscript>diam</Subscript>-AlB<Subscript>2</Subscript> systems at high pressures and temperatures

A chemical interaction of diamond and aluminum borides to form ternary compounds in the diamond-diamond intergranular spaces has been considered.     

Determination of CaCO<Subscript>3</Subscript> and SiO<Subscript>2</Subscript> content in the binders of historic lime mortars

The binders of historic mortars composed of small grain sized silica (SiO₂) and carbonated lime (CaCO₃) are considered as the main part that give hydraulic character and high strength to the mortar. In this study, FTIR, SEM–EDS, LIBS and XRD spectroscopy were used to find out the weight ratios of CaCO₃ to SiO₂ in the binders of historic lime mortars. For this purpose, a series of pure calcium carbonate and silica mixture were prepared in ten combinations in varying ratios from 0.5 to 5. Calibration curve was prepared for each analysis by plotting the peak area or intensity ratios of CaCO₃ to SiO₂ versus the weight ratios of CaCO₃ to SiO₂. A good linear correlation coefficient was obtained for each analysis respectively. The analyses were then tested on the binder of the Roman mortar samples. The results indicated that FTIR, SEM–EDS and LIBS spectroscopy are convenient tools to determine the weight ratios of CaCO₃ to SiO₂ in the binders of mortars. But XRD spectroscopy is not convenient for quantitative analysis of binders due to the presence of varied amounts of amorphous or poor crystalline silica in their compositions.     

Graphite intercalation in the graphite-H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-R (R = H<Subscript>2</Subscript>O,C<Subscript>2</Subscript>H<Subscript>5</Subscript>OH,C<Subscript>2</Subscript>H<Subscript>5</Subscript>COOH) systems

The electrochemical behavior of graphite in polar solvent-H₂SO₄ electrolytes is studied in a wide range of H₂SO₄ concentrations. The results demonstrate that, with decreasing H₂SO₄ concentration, the charging curves become smoother and shift to higher potentials, the stage index increases, and intercalation compounds are more difficult to obtain. At H₂SO₄ concentrations of 50% and lower, graphite polarization is accompanied by a significant overoxidation, as evidenced by the anomalously small intercalate layer thicknesses: 7.75–7.85 Å. Anodic polarization of graphite in electrolytes consisting of H₂SO₄ and a polar solvent (H₂O and C₂H₅OH) follows the same mechanism as in the case of the formation of graphite bisulfate. In going from water to C₂H₅OH, a less polar solvent, the intercalation threshold increases from 30 to 70% H₂SO₄. It is shown using a set of characterization techniques that, in the graphite-H₂SO₄-R (R = H₂O, C₂H₅OH) systems, the solvent is not intercalated into graphite. Stage I–III ternary graphite intercalation compounds (TGICs) are synthesized for the first time in the graphite-H₂SO₄-C₂H₅COOH system: stage I TGICs at H₂SO₄ concentrations above 70%, stage II in the range 30–70% H₂SO₄, and stage III at H₂SO₄ concentrations down to 10%. The intercalate layer thickness in the TGICs is 7.94 Å. The mechanism of TGIC formation in this system is shown to differ from those in mixtures of H₂SO₄ and other organic acids. Thermal analysis in combination with spectroscopic analysis of gaseous products provides clear evidence for intercalation of propionic acid into the TGIC and indicates that the thermal stability of this compound is lower than that of graphite bisulfate.Translated from Neorganicheskie Materialy, Vol. 41, No. 2, 2005, pp. 162–169.Original Russian Text Copyright © 2005 by Shornikova, Sorokina, Maksimova, Avdeev.     

Thermodynamic properties of fullerite C<Subscript>70</Subscript>

A new expression for the isochoric heat capacity and the equation of state of fullerite C₇₀ are obtained in the framework of a quantum-statistical method. Analogs of the Debye law and Dulong–Petit law for this fullerite are formulated. Fullerene C₇₀ molecules are modeled by isotropic quantum oscillators under the assumption that their nonsphericity weakly influences the thermodynamic properties of the condensed phase. The intramolecular oscillations of carbon atoms are described using the Debye theory and the cold contribution to the free energy of fullerite is calculated using the Lennard-Jones pair potential for fullerene molecules. A comparison of the proposed theory to experiment shows good agreement.     

The photoluminescence of amorphous carbon in a-C:C<Subscript>60</Subscript> films obtained by fullerene C<Subscript>60</Subscript> deposition

The results of experimental investigations of the carbon deposits obtained in the course of fullerene C₆₀ sublimation are presented. It is shown that the films formed at a high deposition rate possess a composite structure representing a mixture of fullerenes and an amorphous carbon phase with a graphitelike short-range order. The films containing amorphous nonhydrogenated carbon possess photoluminescent properties analogous to those of hydrogenated amorphous carbon films with a high hydrogen content. The possible mechanism of photoluminescence of the composite carbon films is discussed.     

Crystal structure of a complex of Pu(VI) nitrate with triphenylphosphine oxide, [PuO<Subscript>2</Subscript>(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>(OP(C<Subscript>6</Subscript>H<Subscript>5</Subscript>)<Subscript>3</Subscript>)<Subscript>2</Subscript>]

Single crystals of [PuO₂(NO₃)₂(TPPO)₂] (TPPO = OPPh₃) isostructural to the related compounds of uranyl and neptunyl were isolated, and the structure of this complex was determined. Contrary to the complexes [AnO₂(TPPO)₄](ClO₄)₂ studied previously, the interatomic distances and volumes of coordination polyhedra of An in these compounds somewhat decrease in the series U-Np-Pu. This difference was attributed to a change in the number of TPPO ligands in the compounds and weakening of their interaction with oxygen atoms of the AnO ₂ ²⁺ groups in passing from [AnO₂(TPPO)₂](ClO₄)₂ to [AnO₂(No₃)₂(TPPO)₂].