Preparation of nanodisperse solid solutions based on ZrO<Subscript>2</Subscript> and HfO<Subscript>2</Subscript> from hydroperoxides

A procedure for preparing solid solutions based on zirconium and hafnium hydroperoxides is developed. This procedure is based on the coprecipitation of components in the presence of hydrogen peroxide. Amorphous nanopowders (S _sp = 80–90 m²/g, d _mean = 2–3 nm) without any indication of the agglomeration of particles are synthesized. After the decomposition of complex hydroperoxides at a temperature of 500°C, the compacted powders undergo an active sintering at a temperature of 1450°C. The particle size after heat treatment does not exceed 50 nm. As follows from the electrical and physical characteristics obtained for these materials, they can be recommended for the use as solid electrolytes and sensors of oxygen partial pressure.     

ZrO<Subscript>2</Subscript>-and HfO<Subscript>2</Subscript>-based electrochemical sensors intended for investigation of glass-forming oxide melts

A theoretical analysis was made of the possible use of solid electrolytes with oxygen-ion conductivity for investigation of the relative basicity of silicate melts, and the optimum design of the electrochemical cell was chosen. Glasses in the SiO₂-Na₂O system were synthesized, and ceramic sensory membranes based on the cubic solid solution (ZrO₂)_0.92(Y₂O₃)_0.08 were prepared. An electrochemical cell based on ZrO₂ and HfO₂ and intended for investigation of glass-forming melts with the use of a platinum electrode and a reference electrode with oxygen-ion conductivity was designed and fabricated. The concentration dependence of the electromotive force of the electrochemical cells was examined for melts in the SiO₂-Na₂O system containing alkali oxide in different concentrations. A mathematical treatment of the obtained dependence of the electromotive force on the Na₂O concentration in this system was performed. The results obtained were used to calculate the relative oxygen ion activities and the corresponding pO values for alkali silicate melts under investigation.     

Enhanced functionalization of Mn<Subscript>2</Subscript>O<Subscript>3</Subscript>@SiO<Subscript>2</Subscript> core-shell nanostructures

Core-shell nanostructures of Mn₂O₃@SiO₂, Mn₂O₃@amino-functionalized silica, Mn₂O₃@vinyl-functionalized silica, and Mn₂O₃@allyl-functionalized silica were synthesized using the hydrolysis of the respective organosilane precursor over Mn₂O₃ nanoparticles dispersed using colloidal solutions of Tergitol and cyclohexane. The synthetic methodology used is an improvement over the commonly used post-grafting or co-condensation method as it ensures a high density of functional groups over the core-shell nanostructures. The high density of functional groups can be useful in immobilization of biomolecules and drugs and thus can be used in targeted drug delivery. The high density of functional groups can be used for extraction of elements present in trace amounts. These functionalized core-shell nanostructures were characterized using TEM, IR, and zeta potential studies. The zeta potential study shows that the hydrolysis of organosilane to form the shell results in more number of functional groups on it as compared to the shell formed using post-grafting method. The amino-functionalized core-shell nanostructures were used for the immobilization of glucose and L -methionine and were characterized by zeta potential studies.     

Synthesis and crystal structure of a new oxohalide CdPb<Subscript>2</Subscript>O<Subscript>2</Subscript>Cl<Subscript>2</Subscript>

A new compound, CdPb₂O₂Cl₂, is synthesized by the method of solid-phase reactions. The compound has monoclinic symmetry, space group C2/m, a = 12.392(8) Å, b = 3.8040(14) Å, c = 7.658(5) Å, β = 122.64(5)°, and V = 304.0(3) ų. The structure contains one symmetrically independent position of the Pb²⁺ cation coordinated by three O^2? anions (Pb²⁺-O^2? = 2.29–2.34 Å) and five Cl^? anions (Pb²⁺-Cl^? = 3.35–3.57 Å). The Cd²⁺ cation has a symmetric coordination with the formation of two bonds Cd-O = 2.15 Å and four bonds Cd-Cl = 2.73 Å. The oxygen atom is tetrahedrally coordinated by three Pb²⁺ cations and one Cd²⁺ cation, which leads to the formation of oxo-centered heterometallic OPb₃Cd tetrahedra. The tetrahedra are linked together into chains through common Pb atoms and into layered complexes due to sharing of the equatorial Cd atoms. The chlorine atoms are located above the cavities of the oxo-centered layer.     

Synthesis and study of novel catalysts based on hollandite K<Subscript>2</Subscript>Ga<Subscript>2</Subscript>Ti<Subscript>6</Subscript>O<Subscript>16</Subscript>

The results of experimental studies of synthesis of the hollandite phase K₂Ga₂Ti₆O₁₆ using initial mixtures of different dispersion compositions obtained by two methods, i.e., mechanical dispersion (MD) (followed by solid-phase sintering) and sol-gel method (Pechini method, MP), are reported. The catalytic properties of the obtained materials in the reactions of carbon monoxide (CO) and hydrogen (H₂) oxidation have been determined. It has been demonstrated that an increase in the catalytic activity in the CO oxidation reaction is observed on the samples obtained using the sol-gel method, in which the hollandite phase content is higher and crystallization is more complete. The samples obtained using the MD method are characterized by a low porosity and activity in comparison with those produced by the Pechini method.     

Separation characteristics of tetrapropylammoniumbromide templating silica/alumina composite membrane in CO<Subscript>2</Subscript>/N<Subscript>2</Subscript>, CO<Subscript>2</Subscript>/H<Subscript>2</Subscript> and CH<Subscript>4</Subscript>/H<Subscript>2</Subscript> systems

Nanoporous silica membrane without any pinholes and cracks was synthesized by organic templating method. The tetrapropylammoniumbromide (TPABr)-templating silica sols were coated on tubular alumina composite support ( γ-Al₂O₃/ α-Al₂O₃ composite) by dip coating and then heat-treated at 550 °C. By using the prepared TPABr templating silica/alumina composite membrane, adsorption and membrane transport experiments were performed on the CO₂/N₂, CO₂/H₂ and CH₄/H₂ systems. Adsorption and permeation by using single gas and binary mixtures were measured in order to examine the transport mechanism in the membrane. In the single gas systems, adsorption characteristics on the α-Al₂O₃ support and nanoporous unsupport (TPABr templating SiO₂/ γ-Al₂O₃ composite layer without α-Al₂O₃ support) were investigated at 20–40 °C conditions and 0.0–1.0 atm pressure range. The experimental adsorption equilibrium was well fitted with Langmuir or/and Langmuir-Freundlich isotherm models. The α-Al₂O₃ support had a little adsorption capacity compared to the unsupport which had relatively larger adsorption capacity for CO₂ and CH₄. While the adsorption rates in the unsupport showed in the order of H₂> CO₂> N₂> CH₄ at low pressure range, the permeate flux in the membrane was in the order of H₂≫N₂> CH₄> CO₂. Separation properties of the unsupport could be confirmed by the separation experiments of adsorbable/non-adsorbable mixed gases, such as CO₂/H₂ and CH₄/H₂ systems. Although light and non-adsorbable molecules, such as H₂, showed the highest permeation in the single gas permeate experiments, heavier and strongly adsorbable molecules, such as CO₂ and CH₄, showed a higher separation factor (CO₂/H₂=5-7, CH₄/H₂=4-9). These results might be caused by the surface diffusion or/and blocking effects of adsorbed molecules in the unsupport. And these results could be explained by surface diffusion. This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

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.     

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.     

Optical Properties of CeO<Subscript>2</Subscript> Doped SiO<Subscript>2</Subscript>-Na<Subscript>2</Subscript>O-CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript> Glasses

Cerium oxide is one of the most important rare earth elements that is introduced into glass compositions due to its great effects on the optical properties. CeO₂ was introduced in Hench’s patented SiO₂-Na₂O-CaO-P₂O₅ glasses with different concentrations in order to study its effect on the optical behavior of this glass including optical band gap, transmittance, reflectance and refractive index and to give a complete view for the optical properties on cerium oxide-doped silicate glasses.     

Low-temperature anti-icing reagents in the Ca(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-Mg(NO<Subscript>3</Subscript>)<Subscript>2</Subscript>-CO(NH<Subscript>2</Subscript>)<Subscript>2</Subscript>-H<Subscript>2</Subscript>O system and their properties

The polytherms of ice melting in sections of the Ca(NO₃)₂-Mg(NO₃)₂-CO(NH₂)₂-H₂O system with different component ratios were studied in the temperature interval from 0 to −40°C. A series of nitrate and nitrate-carbonate reagents that are promising for the creation of anti-acing reagents were found, which form eutectics with ice at temperatures from −25 to −39°C. Their properties, viz., melting properties with respect to ice and corrosiveness on metals and alloys, were determined. An effective corrosion inhibitor was selected.     

Effect of ion implantation energy for the synthesis of Ge nanocrystals in SiN films with HfO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> stack tunnel dielectrics for memory application

Ge nanocrystals (Ge-NCs) embedded in SiN dielectrics with HfO₂/SiO₂ stack tunnel dielectrics were synthesized by utilizing low-energy (≤5 keV) ion implantation method followed by conventional thermal annealing at 800°C, the key variable being Ge⁺ ion implantation energy. Two different energies (3 and 5 keV) have been chosen for the evolution of Ge-NCs, which have been found to possess significant changes in structural and chemical properties of the Ge⁺-implanted dielectric films, and well reflected in the charge storage properties of the Al/SiN/Ge-NC + SiN/HfO₂/SiO₂/Si metal-insulator-semiconductor (MIS) memory structures. No Ge-NC was detected with a lower implantation energy of 3 keV at a dose of 1.5 × 10¹⁶ cm^-2, whereas a well-defined 2D-array of nearly spherical and well-separated Ge-NCs within the SiN matrix was observed for the higher-energy-implanted (5 keV) sample for the same implanted dose. The MIS memory structures implanted with 5 keV exhibits better charge storage and retention characteristics compared to the low-energy-implanted sample, indicating that the charge storage is predominantly in Ge-NCs in the memory capacitor. A significant memory window of 3.95 V has been observed under the low operating voltage of ± 6 V with good retention properties, indicating the feasibility of these stack structures for low operating voltage, non-volatile memory devices.     

Porous TiO<Subscript>2</Subscript> nanostructures synthesized from peroxotitanic acid-derived anatase

Abstract  

Titania/titanate nanotubes and nanoplates were prepared by an alkali hydrothermal method using the powder and the sol of peroxotitanic acid-derived anatase, respectively, as precursors. XRD patterns and Raman spectra showed that both nanotubes and nanoplates are of titanate structure with the latter involving a slight part of anatase phase. These nanotubes and nanoplates are highly mesoporous based on nitrogen adsorption measurement. After calcination at 823 K, nanotubes were transformed into nanorods, and nanoplates into spherical particles, both of which are pure anatase-type titania. The nanorod material exhibits an enhanced photocatalytic activity in comparison with the spherical particles.     

Morphology Tailored Synthesis of C-WO<Subscript>3</Subscript> nanostructures and its Photocatalytic Application

Photocatalytic degradation is an ambitious and cost effective technique used for decontamination and sanitization of the waste polluted water of environment. Hydrothermal method is used to synthesis the carbon coupled WO₃ nanoparticles with different concentrations of carbon (0.0, 0.2, 0.5, 1.0 and 2.0%) from precursor Na₂WO₄·2H₂O with glucose and nitric acid. Synthesized nanoparticles were characterized by SEM, EDX, XRD, UV–Vis, and PL to study morphology, and particle size, composition, structural and optical properties, respectively. SEM revealed that morphology of the carbon coupled WO₃ nanoparticles becomes spherical by increasing amount of coupled carbon atoms. The average grain size of the carbon doped nanoparticles is found to be 15–20 nm. Furthermore, size of nanoparticles affect the band gap of synthesized nanoparticles as well. It has also been observed that carbon coupled WO₃ nanoparticles effectively take part in photo degradation due to reduction of electron–hole recombination rate.     

Synthesis and investigation of the structure of ceramic nanopowders in the ZrO<Subscript>2</Subscript>-CeO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system

A new technological scheme has been developed for synthesizing nanocrystalline powders in the ZrO₂-CeO₂-Al₂O₃ system. The powders have been used for preparing nanoceramic materials with an open porosity of ∼1%. The physicochemical properties of these ceramic materials have been investigated.     

Li<Subscript>2</Subscript>Cu<Subscript>2</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> + SiO<Subscript>2</Subscript>/Ti compositions for the catalytic afterburning of diesel soot

Two methods were used to obtain a catalytically active oxide coating on the surface of titanium for the catalytic afterburning of diesel soot: plasma electrochemical formation of an oxide film on the surface of titanium and extraction pyrolytic deposition of the Li₂Cu₂(MoO₄)₃ compound. The Li₂Cu₂(MoO₄)₃/TiO₂ + SiO₂/Ti compositions synthesized by the single-step extraction pyrolytic treatment of the oxidized surface of titanium ensured a high burning rate of soot of ∼300°C. The subsequent deposition of Li₂Cu₂(MoO₄)₃ lowers the activity of the catalyst, due probably to the growth of molybdate phase crystallites and the filling of open oxide film pores. Double lithium-copper molybdate is able to reduce appreciably the concentration of CO in the oxidation products of soot. The advantages of these methods are the possibility of forming high-cohesion durable coatings on surfaces of any complexity, the simplicity of their implementation, and high productivity and low cost. The obtained results can be recommended for use in developing methods for creating composite coatings on catalytic soot filters.     

Synthesis of a New Layered Rb<Subscript>2</Subscript>Nd<Subscript>2</Subscript>Ti<Subscript>3</Subscript>O<Subscript>10</Subscript> Oxide,Its Hydration and Protonation

A new perovskite-like oxide (Rb₂Nd₂Ti₃O₁₀) is synthesized by the ceramic method. Its stability in a humid atmosphere and aqueous solutions of different acidities is investigated. Under these conditions, the formation of hydrated and protonated compounds is revealed. The parameters of the unit cell of the Rb₂Nd₂Ti₃O₁₀ oxide and its derivatives and the degree of rubidium substitution by protons for the obtained protonated phases are determined.     

Electrical conductivity and structure of glasses in the Na<Subscript>2</Subscript>O-Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>O<Subscript>5</Subscript> and Na<Subscript>2</Subscript>S-P<Subscript>2</Subscript>S<Subscript>5</Subscript> systems

The glasses, in which oxygen was partially replaced with sulfur, have been synthesized in the Na₂O-P₂O₅-Na₂S system. The chemical and chromatographic analyses of the glasses synthesized have been performed. The temperature-concentration dependences of electrical conductivity of the glasses have been studied over a wide temperature range; the glass transition temperatures and the nature of charge carriers have been determined. The IR spectra and Raman spectra have been recorded at room temperature; the density and microhardness of the glasses and ultrasound velocity have been measured. A comparison of the electrical conductivities of the investigated glasses with those of the earlier studied glasses in the Na₂O-P₂O₅ system has shown their fair coincidence. The introduction of sodium sulfide into the Na₂O-P₂O₅ system is accompanied by an approximately threefold increase in electrical conductivity, although the concentrations of charge carriers (sodium ions) in the glasses amount to ∼17 and ∼26 mmol/cm³, respectively. The rise in electrical conductivity has been assumed to be caused by the increase in the degree of dissociation of polar structural chemical units including sulfide ions and by the higher mobility of sodium ions in the oxygen-free matrix.     

Synthesis and characterization of zeolite mazzite analogue in Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Piperazine–H<Subscript>2</Subscript>O

Zeolite Mazzite (MAZ) analogue was synthesized directly using piperazine as a structure directing agent. The reactive gel composition used was (5.0–7.0) piperazine:(6.0–7.0) Na₂O:Al₂O₃:20.0SiO₂:400H₂O. Using this composition, the reaction time was shortened greatly to 4 days and the crystallization time was reduced as well. The DTA data showed that piperazine, in as-synthesized zeolite omega decomposed easily. The decomposition of the piperazine occurred at 400–480°C. NH₃-TPD analysis proved that zeolite H-omega from piperazine had strong surface acidity with ammonia desorption temperature up to 590°C.