Fusion-Cast High-Chrome Refractories Synthesized in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - SiO<Subscript>2</Subscript> System

The synthesis and comprehensive study of fusion-cast refractories based on the Cr₂O₃ - MgO - SiO₂ system containing more than 60% Cr₂O₃ are reported. Analyzed by x-ray diffractometry and petrography, the synthesized materials display a phase composition represented by a complex spinel and escolaite. Tested for stability by molten alkali-free borosilicate E-glass, the synthesized refractories are shown to be not inferior in corrosion resistance to a chromium oxide-based ceramic refractory. __________ Translated from Novye Ogneupory, No. 10, pp. 68 – 74, October, 2005.     

Mechanism of reaction-front propagation in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> + 2Al mixture

Results of a combustion study of a powder mixture of Cr₂O₃ and Al burnt in an argon flow are reported. The combustion process is affected by a pressure difference along the filler by evacuating one end of the reaction cell. Effects of the initial density, gasifiable additive (borax or sodium carbonate), and pressure difference on specific features of the combustion process are examined. The data obtained were interpreted within the convective-conductive combustion theory of heterogeneous condensed systems.     

A method for determining the charge state of chromium in Cr-doped Bi<Subscript>12</Subscript>SiO<Subscript>20</Subscript> and Bi<Subscript>12</Subscript>TiO<Subscript>20</Subscript> materials

A chemical method for determination of the charge state of chromium in B₂O₃-based materials (Bi₁₂SiO₂₀ and Bi₁₂TiO₂₀ single crystals) in a wide Cr concentration range (1 × 10^–5 – 2 × 10^–2 wt.%)is proposed. The method is based on a color reaction between Cr⁶⁺ and diphenylcarbazide in an acid medium.Translated from Novye Ogneupory, No. 8, pp. 61 – 63, August, 2004.     

Effects of adding B<Subscript>2</Subscript>O<Subscript>3</Subscript> as a flux on phosphorescent properties in synthesis of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: (Eu<Superscript>2+</Superscript>, DY<Superscript>3+</Superscript> phosphor

SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was prepared by solid state reaction. B₂O₅ as a flux was added in SrAl₂O₄:(Eu ²⁺, Dy³⁺) in order to accelerate a solid state reaction. In this paper, the effects of B₂O₃ on the crystal structure and the phosphorescent properties of the material have been evaluated. The synthesized phosphor exhibited a broad band emission spectrum peaking at 520 nm, and the spectrum peak showed little effect by the B₂O₃ contents. The maximum afterglow intensity of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was obtained at the B₂O₃ content of 5%. Adding the B₂O₃ caused uniform distortion to the crystal structure of the phosphor and resulted in reducing the lengths of a and c axes and Β angle of the SrAl₂O₄ crystal. The uniform distortion was accompanied with crystal defects which can trap the holes generated by the excitation of Eu²⁺ ions. The afterglow characteristic of the SrAl₂O₄: (Eu²⁺, Dy³⁺) phosphor was thus enhanced.     

Volumetric nucleation of crystals catalyzed by Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> in glass based on furnace slags

The features of the volumetric nucleation of crystals in glass obtained by melting furnace slags with the additive of SiO₂, chromium sesquioxide Cr₂O₃, are studied by the methods of differential thermal and Xray phase analysis and optical microscopy. Upon the introduction of Cr₂O₃ as the catalytic additive, two phases are sequentially formed in the glass: magnesiochromite (MgO · Cr₂O₃) and diopside (CaO · MgO · 2SiO₂). The characteristics of homogeneous and heterogeneous crystallization are determined: the stationary nucleation rate, nonstationary nucleation time, crystal growth rate, and their temperature dependences are obtained. Practical recommendations on the use of the obtained glass are given.     

The Structure of Fusion-Cast High-Chrome Oxide Refractories in the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> - MgO - Al<Subscript>2</Subscript>O<Subscript>3</Subscript> System

The phase composition and structure of fusion-cast refractories composed of 57.0 – 84.2% Cr₂O₃, 4.3 – 36.1% MgO, 2.0 – 9.7% Al₂O₃, and 2.4 – 6.9% SiO₂ have been studied by petrographic and x-ray spectral microprobe analysis methods. Refractories high in MgO with modulus M = (Cr₂O₃ +Al₂O₃)/MgO = 1.64 – 3.1 are shown to consist of spinel phase Mg(Cr, Al)₂O₄ and silicate glass. Refractory materials (80.8 – 84.2% Cr₂O₃, 4.3 – 4.7% MgO, 2.0 – 9.7% Al₂O₃, and 2.7 – 6.9% SiO₂ with M = 18.7 – 20.2) are three-phase systems composed of spinel, escolaite, and glass phase. These materials, owing to their high corrosion resistance, have promising potentiality for practical applications.__________Translated from Novye Ogneupory, No. 12, pp. 69 – 74, December, 2004.     

Synthesis and properties of binary spinels in a NiO–CuO–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The conditions for the formation of a spinel structure from a NiO–CuO–Fe₂O₃–Cr₂O₃ oxide mixture using several technological approaches have been examined. Addition of KCl is accompanied with the formation of two spinel-like phases, whereas in the absence of KCl just one solid solution of nickel–copper ferrite–chromite with the structure of a cubic spinel is formed. At the temperature of thermal treatment of 900°C, the presence of an admixture phase of the delafossite (CuCrO₂) type was established. The conditions for the fabrication of samples containing two spinel phases (cubic and tetragonal) characterized with the most developed surface and manifesting = increased catalytic activity in the reaction of the decomposition of an organic substance by hydrogen peroxide have been formulated. The studied features of spinel synthesis can be of interest for developing materials with an active surface promising for application as adsorbents of catalysts and sensors.     

Electrochemical performance of La<Subscript>0.75</Subscript>Sr<Subscript>0.25</Subscript>Cr<Subscript>0.9</Subscript>M<Subscript>0.1</Subscript>O<Subscript>3</Subscript> perovskites as SOFC anodes in CO/CO<Subscript>2</Subscript> mixtures

The performance of La_0.75Sr_0.25Cr_0.9M_0.1O₃ (M = Mn, Fe, Co, and Ni) perovskitic materials as anodes was studied for a CO-fueled solid oxide fuel cell. The electrocatalytic performance and the tolerance to carbon deposition were investigated, while electrochemical characterization was carried out via AC impedance spectroscopy and cyclic voltammetry. The La_0.75Sr_0.25Cr_0.9Fe_0.1O₃ perovskite showed the best anode performance at temperatures above 900 °C; while at temperatures below 900 °C, the best performance was achieved with the La_0.75Sr_0.25Cr_0.9Co_0.1O₃ material. AC impedance spectroscopy was used for a semi-quantitative analysis of the LSC-M_0.1 anodes performance in view of total cell and charge transfer resistance. All anode materials exhibit high electronic conductivity and presumably do not substantially contribute to the overall cell resistance and concomitant ohmic losses.     

Combustion of a Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Al-C Powder Mixture in the SHS Regime and the Structure of the Combustion Products

The combustion of pressed specimens of a stoichiometric Fe₂O₃-TiO₂-Al-C powder mixture burning in the SHS regime is studied. It is found that the final product has the same shape and size as the initial specimen. The composition and structure of the final product, which is highly porous high-melting Al₂O₃-TiC-Fe(Ti) composite ceramics, are studied. The mechanism of phase and structure formation in the examined system is proposed.__________Translated from Fizika Goreniya i Vzryva, Vol. 41, No. 4, pp. 60–66, July–August, 2005.     

Combustion synthesis of some compounds in the Li<Subscript>2</Subscript>O-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

At least four compounds, viz. LiAlO₂, LiAl₅O₈, Li₅AlO₄ and Li₂Al₄O₇, are known in the Li₂O-Al₂O₃ system. These compounds are important for several technological applications. Combustion synthesis of these compounds using urea as a fuel was attempted. LiAlO₂ and LiAl₅O₈ could be successfully prepared by choosing the starting materials in required stoichiometric ratios. Li₂Al₄O₇ was not obtained as a pure phase; γ-LiAlO₂ was formed as an impurity phase. Li₅AlO₄ could not be prepared by combustion process. Some phosphors based on these aluminates could also be prepared. Activation of these aluminates with Fe³⁺, Mn⁴⁺, Cu⁺, etc. was successfully achieved. Excitation and emission spectra for LiAl₅O₈: Fe³⁺, LiAl₅O₈: Mn²⁺, and Li₂Al₄O₇: Cu⁺ are reported.     

(Ti<Subscript>0.8</Subscript>Cr<Subscript>0.2</Subscript>)B<Subscript>2</Subscript>–CrB–<Emphasis Type="Italic">x</Emphasis>TiN composites by pressure-assisted SHS

Explored was the feasibility of preparing (Ti_0.8Cr_0.2)B₂–CrB–TiN ceramics by pressure-assisted SHS from reactive powder compacts containing TiN nanopowder as an inert modifier of product structure. The combustion products obtained under optimized conditions exhibited a uniform structure with a porosity of 1–3% and a Vickers hardness of 22.5 GPa.     

SHS of metal-oxide systems in a DC magnetic field: Part 1. TRXRD and thermal imaging studies of the Fe-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The effect of a 0.2 T external magnetic field on the heterogeneous combustion of a mixture of iron metal and oxide (Fe₂O₃) system with solid oxidizer (NaClO₄) was studied. Time-resolved X-ray diffraction (TRXRD) was used to study the kinetics of intermediate product formation and thermal imaging experiments to measure the reaction temperature and velocity. Metastable fcc iron phase formation was discovered as an intermediate predominantly in applied field reactions.     

Combustion of Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript>/Al thermit mixtures in steel tubes

Explored was the combustion of Fe₂O₃/TiO₂/Al thermit mixtures in steel tubes upon variation in green composition and with special emphasis on the dependence of combustion temperature T _c and burning velocity U on reaction heat Q. Special attention was given to incompleteness of combustion for compositions with low Q.     

Roles of doping ions in persistent luminescence of SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>: Eu<Superscript>2+</Superscript>,<Emphasis Type="Italic">RE</Emphasis><Superscript>3+</Superscript> phosphors

The polycrystalline Eu²⁺ and Dy³⁺ codoped strontium aluminates SrAl₂O₄: Eu²⁺,Dy³⁺ were prepared by a solid-state reaction. The UV-excited photoluminescence, persistent luminescence, and thermoluminescence of the SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors with different compositions and ion doping was studied and compared. The results showed that the Eu²⁺ ion doped in SrAl₂O₄: Eu²⁺,Dy³⁺ phosphors is not only the UV-excited luminescent center but also the persistent luminescent center. The Dy³⁺ ion introduced into SrAl₂O₄: Eu²⁺ crystal matrix can hardly yield any luminescence under UV excitation but acts as an electron trap with a suitable depth for persistent luminescence. The Dy³⁺ codoping would effectively enhance the persistent luminescence and thermoluminescence. Different codoping RE ³⁺ ions have a different effect on persistent luminescence. Only the RE ³⁺ ions (for example, Dy³⁺ and Nd³⁺), which have suitable optical electronegativity, can form suitable electron traps and effectively improve the persistent luminescence of SrAl₂O₄: Eu²⁺. Based on the above observations, a persistent luminescence mechanism, electron transfer model, was proposed and illustrated. The text was submitted by the authors in English.     

Synthesis of spinel Ni<Subscript>0.75</Subscript>Zn<Subscript>0.25</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> and the properties of a coating obtained by gas-flame spraying

Ferrite Ni_0.75Zn_0.25Fe₂O₄ was prepared by the solid-state synthesis and thermal decomposition of the complex oxalate Ni_0.75Zn_0.25Fe₂(C₂O₄)₃ · 6H₂O. The oxalate precursor and the products obtained at different stages of the thermal decomposition were identified by differential thermal analysis and X-ray and X-ray photoelectron spectroscopy. The properties of a ferromagnetic coating deposited on a substrate by gasflame coating were studied. The magnetic properties of the Ni-Zn ferrite product and the ferromagnetic coating were also investigated.     

Formation of the complex oxide NaNdTiO<Subscript>4</Subscript>

The processes of phase formation in the Na₂CO₃-TiO₂ and Na₂CO₃-TiO₂-Nd₂O₃ systems are investigated in the temperature range 600–900°C. The high-temperature solid-phase reactions underlying the process of formation of complex oxide NaNdTiO4 are studied. It is established that the synthesis of the NaNdTiO₄ compound occurs through the reaction of the intermediate product Na₈Ti₅O₁₄ with neodymium oxide in the temperature range 720–780°C. The optimum method is proposed for synthesizing NaNdTiO₄, which makes it possible to reduce the temperature of the synthesis, to avoid the formation of impurities, and to obtain the product in a finely dispersed state.     

Mechanism of formation of the complex oxide Na<Subscript>2</Subscript>Nd<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript>

The processes of phase formation in the Nd₂O₃-TiO₂-Na₂CO₃ system have been investigated in the temperature range 500–1100°C. The mechanism of the high-temperature solid-phase reaction of formation of the complex oxide Na₂Nd₂Ti₃O₁₀ has been studied. It has been established that the Na₂Nd₂Ti₃O₁₀ compound is formed from the intermediate product Na_0.5Nd_0.5TiO₃ with a perovskite structure in the temperature range 830–890°C and from the NaNdTiO₄ oxide with a perovskite-like layered structure in the temperature range 960–1100°C.     

A Resumable Fluorescent Probe BHN-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Hybrid Nanostructure for Fe<Superscript>3+</Superscript> and its Application in Bioimaging

A multifunctional fluorescent probe BHN-Fe₃O₄@SiO₂ nanostructure for Fe³⁺ was designed and developed. It has a good selective response to Fe³⁺ with fluorescence quenching and can be recycled using an external magnetic field. With adding EDTA (2.5?×?10^?5 M) to the consequent product Fe³⁺-BHN-Fe₃O₄@SiO₂, Fe³⁺ can be removed from the complex, and its fluorescence probing ability recovers, which means that this constituted on-off type fluorescence probe could be reversed and reused. At the same time, the probe has been successfully applied for quantitatively detecting Fe³⁺ in a linear mode with a low limit of detection 1.25?×?10^?8 M. Furthermore, the BHN-Fe₃O₄@SiO₂ nanostructure probe is successfully used to detect Fe³⁺ in living HeLa cells, which shows its great potential in bioimaging detection.     

Phase cooperation of V<Subscript>2</Subscript>O<Subscript>5</Subscript> and Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> in the selective oxidation of H<Subscript>2</Subscript>S containing ammonia and water

The selective oxidation of hydrogen sulfide containing excess water and ammonia was studied over vanadium oxide-based catalysts. The investigation was focused on the role of V₂O₅, and phase cooperation between V₂O₅ and Bi₂O₃ in this reaction. The conversion of H₂S continued to decrease since V₂O₅ was gradually reduced by treatment with H₂S. The activity of V₂O₅ was recovered by contact with oxygen. A strong synergistic phenomenon in catalytic activity was observed for the mechanically mixed catalysts of V₂O₅ and Bi₂O₃. Temperature-programmed reduction (TPR) and oxidation (TPO) and two bed reaction tests were performed to explain this synergistic effect by the reoxidation ability of Bi₂O₃. This paper is dedicated to Professor Wha Young Lee on the occasion of his retirement from Seoul National University.     

Structural characterization and superconducting properties of MgB<Subscript>2</Subscript> prepared by SHS-method

Self-propagating high-temperature synthesis (SHS) of bulk MgB₂ superconductor from Mg-2B powder blend is reported. This reaction proceeds violently at 100 A under a protective atmosphere. Since the heat of reaction of Mg and B was not enough for chain reaction, then (Ti + C) mixed powders were used as the ignition agent to assist the reaction (Mg + 2B). In this case, the combustion front moved without any difficulty. The diffraction lines of the product can be indexed to a hexagonal MgB₂ phase, with lattice constants a = 3.0845 Å, and c = 3.5259 Å. For comparison, the direct synthesis of (Mg + 2B) mixture was carried out at (800°C–1000°C). It can be found, that high-temperature sintering (1000°C) will induce the formation of impurities. The MgB₂ grains are fine, well compacted and more homogenous. The structure of materials was studied using XRD, FESEM and EDX. M-H curvatures were measured under the magnetic fields between ?80 kOe and 80 kOe. J _c was calculated from width of magnetization hysteresis loops based on the extended Bean Model.