Synthesis and properties of flux-cast refractories in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

Details are given of the synthesis and testing of flux-cast refractory materials in the alumina-rich region of the Al₂O₃-MgO-B₂O₃ system; XRD and petrography indicate that the main structure-forming phases are corundum and magnesian spinel. In subordinate amounts there are the boroaluminate 9Al₂O₃·2B₂O₃ and the previously unknown compound 4Al₂O₃·MgO·2B₂O₃, whose composition has been established by microprobe analysis. Corrosion tests showed that three-component systems containing magnesium and boron oxides at levels of 5–10% do not increase the corrosion resistance of refractories in molten sodium-calcium-silicate glass and electrovacuum borosilicate glass. __________ Translated from Novye Ogneupory, No. 3, pp. 161–163, March, 2008.     

Glass formation region and order of formation of crystalline phases in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The glass formation region in the SrO-B₂O₃-SiO₂ system has been refined. The order of formation of crystalline phases in the system has been investigated at SrO contents of 50–75 mol %. It has been demonstrated that, at low temperatures, the 2SrO · SiO₂ and 3SrO · B₂O₃ phases crystallize first irrespective of the composition. The congruent melting temperature of the 3SrO · B₂O₃ · SiO₂ compound is determined to be 1180 ± 10°C. The triangulation previously performed for the SrO-B₂O₃-SiO₂ system in the concentration range 50–75 mol % SrO has been confirmed.     

Crystallization of glasses in the SrO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> system

The crystallization of strontium borate glasses containing 16.7–43.0 mol % SrO is investigated. New crystalline compounds of the hypothetical compositions 2SrO · 3B₂O₃ (metastable) and SrO · 5B₂O₃ (stable below 750°C), as well as the metastable diborate modification β-SrO · 2B₂O₃, are revealed, and their X-ray powder diffraction data are obtained. It is demonstrated that, with a deficit of strontium oxide, the 4SrO · 7B₂O₃ compound forms solid solutions. Strontium triborate SrO · 3B₂O₃, which was previously prepared only through the dehydration of crystal hydrates, is produced using crystallization of glasses. The thermal stability of this compound is studied. The influence of the dispersity on the stability of different crystalline phases is discussed. Variants of the phase diagram for the SrO · B₂O₃-B₂O₃ system in the case of monolithic and dispersed samples are proposed from analyzing the experimental results and the data available in the literature.     

The system SiC–W<Subscript>2</Subscript>B<Subscript>5</Subscript>–LaB<Subscript>6</Subscript>

Experiments and calculations have been applied to the structure of the triple eutectic system SiC–W₂B₅–LaB₆(T _eu = 1900 ± 40°C), composition in mol.%: 10 LaB₆, 44 SiC, 46 W₂B₅, error ±2–3%, which opens up prospects for making ceramic materials for various purposes.     

Structure and crystallization of ZnO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Structure and crystalline behavior of the ternary system ZnO-B₂O₃-P₂O₅ glasses were investigated by means of X-ray diffraction (XRD) and infrared Raman spectra. The research showed that number of the planar [BO₃] units increases with the increase of B₂O₃ content. When the B₂O₃ content is above ≥10 mol %, the relative content of planar [BO₃] units increases rapidly and causes weakening of the glass structure and decrease in the chemical stability. In the crystallized glasses the predominant crystal phase Zn₂P₂O₇ decreases with the increase of B₂O₃ content, while the crystal phase BPO₄ increases with it, which cause the declining of chemical stability and the decrease of thermal coefficients of expansion.     

Refractive index and compressibility of the KAlSi<Subscript>3</Subscript>O<Subscript>8</Subscript> glass at pressures up to 6.0 GPa

The refractive index of potassium aluminosilicate glass of the KAlSi₃O₈ composition in the pressure range up to 6.0 GPa has been measured using a polarizing interference microscope and an apparatus with diamond anvils. The changes in the relative density, which characterize the compressibility of the K₂O · Al₂O₃ · 6SiO₂ glass, have been estimated in the pressure range under investigation from the measured refractive indices within the framework of the theory of photoelasticity. The results have been compared with the data previously obtained for the Na₂O · Al₂O₃ · 6SiO₂ glass. Although the molar contents of Al₂O₃ and M ₂O (where M = K or Na) are identical in these glasses, the KAlSi₃O₈ glass exhibits a higher compressibility, which agrees with the lower degree of depolymerization of this glass as compared to that observed in the NaAlSi₃O₈ glass. The pressure derivative of the bulk modulus K′ _t , which is calculated from the Birch-Murnaghan equation for the KAlSi₃O₈ glass (K′ _t = 7–9), is higher than that for the NaAlSi₃O₈ glass (K′ _t = 5.5–6.0). An increase in the pressure derivative of the bulk modulus K′ _t upon replacement of the Na⁺ cations by the K⁺ cations is explained by the inhibition of compression of the large K⁺ cations, which are located in cavities and have a considerably larger orbital radius than the Na+ cations. This manifests itself in the fact that the curves describing the dependences of the change in the relative density (d − d0)/d (compressibility) on the pressure P for the KAlSi₃O₈ and NaAlSi₃O₈ glasses converge at pressures above 4.0 GPa.     

Temperature programmed desorption of oxygen from Pd films interfaced with Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-doped ZrO<Subscript>2</Subscript>

The origin of the effect of non-faradaic electrochemical modification of catalytic activity (NEMCA) or Electrochemical Promotion was investigated via temperature-programmed-desorption (TPD) of oxygen, from polycrystalline Pd films deposited on 8 mol%Y₂O₃–stabilized–ZrO₂ (YSZ), an O²⁻ conductor, under high-vacuum conditions and temperatures between 50 and 250 °C. Oxygen was adsorbed both via the gas phase and electrochemically, as O²⁻, via electrical current application between the Pd catalyst film and a Au counter electrode. Gaseous oxygen adsorption gives two adsorbed atomic oxygen species desorbing at about 300 °C (state β₁) and 340–500 °C (state β₂). The creation of the low temperature peak is favored at high exposure times (exposure >1 kL) and low adsorption temperatures (T_ads < 200 °C). The decrease of the open circuit potential (or catalyst work function) during the adsorption at high exposure times, indicates the formation of subsurface oxygen species which desorbs at higher temperatures (above 450 °C). The desorption peak of this subsurface oxygen is not clear due to the wide peaks of the TPD spectra. The TPD spectra after electrochemical O²⁻ pumping to the Pd catalyst film show two peaks (at 350 and 430 °C) corresponding to spillover O_ads and according to the reaction:

Oxygen permeability and structural stability of La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>Co<Subscript>0.2</Subscript>Fe<Subscript>0.8</Subscript>O<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript> membrane

La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ oxides were synthesized by citrate method and hydrothermal method. The oxides prepared by citrate method are perovskite type structure, while the oxides by hydrothermal method have a small amount of secondary phase in the powder. Pyrex glass seal and Ag melting seal provided reliable gas-tight sealing of disk type dense membrane in the range of operation temperature, but commercial ceramic binder could not be removed from the support tube without damage to the tube or membrane. Though the degree of gas tightness increases in the order of glass>Ag>ceramic binder, in the case of glass seal, the undesired spreading of glass leads to an interfacial reaction between it and the membrane and reduction of effective permeation area. The oxygen flux of La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ membrane increases with increasing temperature and decreasing thickness, and the oxygen permeation flux through 1.0 mm membrane exposed to flowing air (P _h =0.21 atm) and helium (P₁=0.037 atm) is ca. 0.33 ml/cm²·min at 950 °C. X-ray diffraction analysis for the membrane after permeation test over 160 h revealed that La₂O₃ and unknown compound were formed on the surface of membrane. The segregation compounds of surface elements formed on both surfaces of membrane irrespective of spreading of glass sealing material. This paper was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

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.     

Synthetic spinels of the system MgO-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>

Synthetic spinels of the system MgO-Cr₂O₃-Al₂O₃-Fe₂O₃ are considered and the desirability of organizing their production for the refractory industry is demonstrated. Translated from Novye Ogneupory, No. 6, pp. 32–35, June 2008.     

Research of mica/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> pearlescent pigment by co-precipitation

Experiments on preparation of mica/Fe₃O₄ pearlescent pigment were performed to discuss influences of several crucial parameters on final products. The samples were characterized by XRD, HRSEM, FTIR and color measurement, the content of Fe₃O₄ on the mica surface was also analyzed by XPS. It was found that the smoothness, compactness and colour deepness of the coating were influenced by different pH values and temperatures. The optimum preparation parameters of mica/Fe₃O₄ pearlescent pigment were obtained: the value of pH ≥ 9.2; the concentration of sodium hydroxide was 0.5 mol/l; the concentration ratio of Fe³⁺ to Fe²⁺ was 1.6 : 1; the velocity of magnetic stirring was 138 ≤ v ≤ 151 r/min; reaction temperature was 70–80°C; calcination temperature was 350°C and calcination time was 3 h.     

Thermal and neutron shielding properties of <Superscript>10</Superscript>B<Subscript>2</Subscript>O<Subscript>3</Subscript>/polyimide hybrid materials

In this study, ¹⁰B₂O₃/polyimide (PI) hybrid materials were synthesized with the aim to improve their thermal stability and neutron shielding properties. 3,3′-Diaminodiphenyl sulfone (DADPS) reacted with 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA) in N-methyl-2-pyrrolidone (NMP) and mixed with amine functionalized ¹⁰B₂O₃ to prepare a series of poly (amic acid), meanwhile, corresponding PIs were obtained via the thermal imidization procedures. The morphologies and structures of the prepared hybrid materials were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The thermooxidative and flame retardancy properties of the PI films were examined by thermogravimetric analysis (TGA) and limiting oxygen ındex (LOI). The experimental results showed that as the amount of functionalized ¹⁰B₂O₃ was increased, flame retardant properties of the hybrid films were increased. Hybrid materials were also irradiated with thermal neutrons. The neutron shielding properties increasing depends on the amount and the distribution of the ¹⁰B isotope.     

Effect of the relative volume of the conducting phase on the electroconductivity of glasses in the Na<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system

The effect of the relative volume of the conducting phase on the electroconductivity of phase-separated glasses in the ternary system Na₂O–B₂O₃–SiO₂, whose compositions are on the same glass transition isotherm at 550°C, is investigated. It is demonstrated that the electroconductivity of phase-separated sodium borosilicate glasses does not depend on the relative volume of the conducting phase (within the limits from 0.3 to 0.9) under the condition that its composition invariable.     

On the structure of glasses in the BaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The structure of single-phase glasses in the BaO-B₂O₃-SiO₂ system has been studied by the large- and small-angle X-ray scattering techniques. The glasses containing 40 mol % BaO upon equimolar replacement of B₂O₃ by SiO₂ have been investigated. It has been demonstrated that the incorporation of barium ions into structural groupings fixes their position and provides ordering in the distribution of barium ions at interatomic distances up to at least 5 Å. The glasses under investigation are homogeneous, and their inhomogeneity is determined by thermal density fluctuations and fluctuations of the concentration of a part of barium ions distributed in a statistically random manner in the volume of the glass. The observed ordering in the distribution of barium ions is not reduced to the formation of local clusters with an increased concentration of barium ions but is most likely a characteristic feature of the bulk glass structure. The glass structure is consistent with the model of ideal associated solutions.     

Synthesis and properties of the composite ceramics from nanocrystalline Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-30% Y<Subscript>0.1</Subscript>Zr<Subscript>0.9</Subscript>O<Subscript>2</Subscript> prepared from a water-alcohol solution

The hydrogel of the mixed oxide Al₂O₃-30% Y_0.1Zr_0.9O₂ was prepared by precipitation of ammonia from a water-alcohol mixture (1 : 5). The Al₂O₃-30% Y_0.1Zr_0.9O₂ compound thus synthesized was characterized using differential scanning calorimetry, transmission electron microscopy, and the BET adsorption method. The obtained sample consisted of spherical particles with an average size of 16–20 nm and a specific surface area of 167 m²/g. The Al₂O₃-30% Y_0.1Zr_0.9O₂ powder was pressed at 300 MPa and then calcinated at 1600°C for 2 h in air. The topographic and structural features of the prepared ceramics were determined using atomic force microscopy and X-ray electron probe microanalysis. The porosity, the Vickers microhardness, and the tensile strength were determined by mercury porometry.     

Local crystallization of glasses in the La<Subscript>2</Subscript>O<Subscript>3</Subscript>-B<Subscript>2</Subscript>O<Subscript>3</Subscript>-GeO<Subscript>2</Subscript> system under laser irradiation

A method is proposed for local crystallization of glasses under laser irradiation. This method makes it possible to nucleate and grow microcrystals with a size distribution similar to a monodisperse distribution for several fractions of a second in any glass region chosen in advance. It is demonstrated using glasses in the La₂O₃-B₂O₃-GeO₂ system as an example that the crystallization of the stillwellite-like phase LaBGeO₅ with the composition close to the composition of the initial glass is observed in the glass under irradiation with the copper vapor laser operating in the high-speed pulse modulation mode. Strips (up to ～300 μm) produced at a specified depth from the glass surface contain extended regions consisting of uniformly distributed crystals, which have almost identical sizes, exhibit a pronounced faceting, and are identified using X-ray diffraction. The size and the number of crystals can be changed over a wide range by varying laser treatment conditions. This opens up the way to the design of new glass-ceramic materials in which the location of the crystalline phase in the glass bulk is controlled by a developer.     

Preparation of surface-crystallized optical glass-ceramics SrO · 2B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The physicochemical features of the phase formation upon crystallization of monolithic glasses of the strontium diborate stoichiometric composition are investigated. It is demonstrated that the first phase crystallizing on the surface of the SrO · 2B₂O₃ glass is the strontium borate Sr₄B₁₄O₂₅, which plays the role of a precursor for the subsequent crystallization of the SrB₄O₇ borate. The temperature corresponding to the maximum crystal nucleation rate on the surface and the time of complete “operation” of nuclei are determined using differential thermal analysis. The optical glass-ceramics prepared by the two-stage crystallization are surface-crystallized glasses in which the filling density of the surface is approximately equal to 30% and the content of the main phase SrB₄O₇ is as high as ∼ 70%. No second harmonic generation of neodymium laser radiation in the glass-ceramics is observed because of both the absence of the preferred orientation of SrB₄O₇ nonlinear optical crystals and the small crystal sizes (considerably smaller than the coherence length of the SrB₄O₇ crystal) in the direction perpendicular to the glass surface.     

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.     

Initiation of combustion of a CH<Subscript>4</Subscript>-O<Subscript>2</Subscript> mixture in a supersonic flow with excitation of O<Subscript>2</Subscript> molecules by an electric discharge

The possibility of intensification of ignition of a methane-oxygen mixture in a supersonic flow behind the front of an oblique shock wave by means of excitation of O₂ molecules to the states a ¹Δ_g and b ¹Σ_g⁺ in an electric discharge is discussed. Through numerical simulations, activation of O₂ molecules by an electric discharge is demonstrated to speed up chain reactions in the CH₄-O₂ mixture and to reduce the induction-zone length. Even a small amount of energy input to O₂ molecules in the discharge (≈3·0⁻² J/cm³) can reduce the ignition-delay length by a factor of hundreds and initiate combustion at distances of ≈1 m from the discharge zone at comparatively low temperatures of the gas behind the front (≈1000 K) and moderate pressures (≈10⁵ Pa). Excitation of O₂ molecules by an electric discharge is much more efficient than simple heating of the mixture. __________ Translated from Fizika Goreniya i Vzryva, Vol. 44, No. 3, pp. 3–16, May–June, 2008.     

An investigation into the conversion of In<Subscript>2</Subscript>O<Subscript>3</Subscript> into InN nanowires

Straight In₂O₃ nanowires (NWs) with diameters of 50 nm and lengths ≥2 μm have been grown on Si(001) via the wet oxidation of In at 850°C using Au as a catalyst. These exhibited clear peaks in the X-ray diffraction corresponding to the body centred cubic crystal structure of In₂O₃ while the photoluminescence (PL) spectrum at 300 K consisted of two broad peaks, centred around 400 and 550 nm. The post-growth nitridation of In₂O₃ NWs was systematically investigated by varying the nitridation temperature between 500 and 900°C, flow of NH₃ and nitridation times between 1 and 6 h. The NWs are eliminated above 600°C while long nitridation times at 500 and 600°C did not result into the efficient conversion of In₂O₃ to InN. We find that the nitridation of In₂O₃ is effective by using NH₃ and H₂ or a two-step temperature nitridation process using just NH₃ and slower ramp rates. We discuss the nitridation mechanism and its effect on the PL.