Synthesis and study of mesoporous xerogels and nanopowders of a metastable solid solution 97ZrO<Subscript>2</Subscript>–3Y<Subscript>2</Subscript>O<Subscript>3</Subscript> for the fabrication of catalyst substrates

The—technology of the liquid-phase synthesis of metastable phases in the ZrO₂–Y₂O₃ system has been developed. Mesoporous xerogels with the specific surface area of ~350 m²/g and monophase nanopowders (5–10 nm) of the tetragonal solid solution (ZrO₂)_0.97(Y₂O₃)_0.03 have been obtained and their structural peculiarities have been revealed. The efficiency of the suggested technology and good prospects of the synthesized ZrO₂-based precursors in creating catalysts’ substrates have been demonstrated.     

Synthesis and physicochemical properties of a solid oxide nanocomposite based on a ZrO<Subscript>2</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–Gd<Subscript>2</Subscript>O<Subscript>3</Subscript>–MgO system

A highly dispersive powder with a (ZrO₂)_0.92(Y₂O₃)_0.03(Gd₂O₃)_0.03(MgO)_0.02 composition and specific surface area of 150 m²/g has been synthesized via a method of coprecipitation of hydroxides with the subsequent cryochemical treatment of the gel. Nanoceramics based on the cubic modification of zirconium dioxide with the grain size of ~40–45 nm have been obtained. The temperature dependence of the specific electrical conductance of the nanoceramics within a temperature range of 350–870°C in air has been studied, and the ratio of the ionic and electronic parts of the conductance has been determined. Recommendations for the use of the obtained oxide nanocomposite as an electrolyte for a high-temperature fuel cell have been given.     

Vapor–Liquid Equilibrium of Binary Components of the BrCF<Subscript>2</Subscript>COOCH<Subscript>3</Subscript>–CF<Subscript>3</Subscript>COOH–BrCF<Subscript>2</Subscript>COOH–CF<Subscript>3</Subscript>COOCH<Subscript>3</Subscript> Quaternary System

Vapor–liquid equilibria of binary components of the BrCF₂COOCH₃–CF₃COOH–BrCF₂COOH–CF₃COOCH₃ quaternary system have been studied experimentally at constant pressure. The experiments have been carried out on a modified Sventoslavskii ebulliometer. Using the Aspen Plus software package, the appropriate models have been selected and the vapor–liquid equilibria for six binary systems have been simulated.     

3-Hydroxybenzoic acid as AISI 316L stainless steel corrosion inhibitor in a H<Subscript>2</Subscript>SO<Subscript>4</Subscript>–HF–H<Subscript>2</Subscript>O<Subscript>2</Subscript> pickling solution

3-Hydroxybenzoic acid (3-HBA) was studied for possible use as a AISI 316L stainless steel (SS) corrosion inhibitor in an environmental-friendly aqueous pickling solution of 75 g l^–1 sulphuric acid (H₂SO₄), 25 g l^–1 hydrofluoric acid (HF) and 30 g l^–1 hydrogen peroxide (H₂O₂). 3-HBA was tested in concentrations from 5 × 10^–5 to 5 × 10^–1 M at 298 and 313 K temperature. Inhibition efficiency increased with the 3-HBA concentration. The inhibitor mechanism is discussed in terms of the properties of the isotherm equations of Frumkin, Hill-de Boer and Kastening–Holleck mainly. The shape, the trend of the slopes along the curve and the existence of inflection points, were analysed as the characteristics that differentiate one adsorption equation from another. The best fit was obtained using the Frumkin isotherm model. The projected molecular area of 3-HBA was calculated as a structural parameter to elucidate its optimal inhibition mechanism.     

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.     

Photon interaction parameters for some ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Some photon interaction parameters such as mass attenuation coefficient, effective atomic number, half value layer, mean free path and electron density for 15ZnO–(17.5–x)Al₂O₃–xFe₂O₃–67.5P₂O₅ glass system (x = 0, 7.5, 12.5, 17.5) and 15ZnO–(25–x)Al₂O₃–xFe₂O₃–60P₂O₅ glass system (x = 0, 25) have been investigated in the photon energy range of 1 keV to 100 GeV. It has been observed that all the photon interaction parameters for the selected glass systems vary with the photon energy. Among the selected glass systems, the sample 15ZnO–25Fe₂O₃–60P₂O₅ glass system shows maximum values for mass attenuation coefficients, effective atomic numbers, electron densities and minimum values for mean free path and half value layer in the entire energy grid.     

Mechanical,Structural and Thermal Properties of Transparent Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–TeO<Subscript>2</Subscript> Glass System

Oxide based optical glass materials has important potential material in many applications from fiber optic to sensor due to the high transparency and amourphous structures. The objective of this study is to synthesize the novel optical glass materials based on the bismuth and aluminum contents to be able to determine the physical, chemical and mechanical properties by considering the systematic experimental steps. In this study, Bi₂O₃–Al₂O₃ based tellurite optical glasses have been prepared by using conventional melt quenching method as a function of the both Bi₂O₃ and Al₂O₃ compositions. There is a strong interactions between the glass former and modifier ions that might effect on the structure and mechanical properties. During the experimental steps, thermal, structural and mechanical properties of the prepared glass materials have been determined considering the DTA/DSC, FT-IR spectroscopy, SEM and Vicker’s hardness techniques, respectively. Thermal parameters, like glass transition, T_g, onset, T_x, crystallization, T_p, and melting, T_m, temperatures were obtained by using DTA scan.     

Hydroisomerization of Benzene-Containing Gasoline Fraction on Pt/B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pt/WO<Subscript>3</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Catalysts

The effect of the hydroisomerization conditions of the benzene-containing fraction of catalytic reforming gasoline on the yield and composition of products is studied on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts. These catalysts allow benzene to be completely removed from the raw material. At the same time, the greatest yields of liquid products are obtained with minimal losses of the octane number at 2 MPa, a mass feedstock hourly space velocity (MFHSV) of 2 h^?1, and 325°C: 96.3 and 95.4 wt % on Pt/B₂O₃–Al₂O₃ and Pt/WO₃–Al₂O₃ catalysts, respectively. The activity of the catalysts is maintained for 100 h during their operation.     

Esterification of stearic acid with methanol over mesoporous ordered sulfated ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> mixed oxide aerogel catalyst

Aerogel sulfated ZrO₂–SiO₂ mixed oxide solid acid catalyst was prepared by sol–gel method followed by supercritical drying (SCD) in n-propanol solvent, which resulted into higher surface area (170 m²/g), pore volume (0.31 cm³/g) and pore diameter (7.2 nm) having ordered mesoporous structure as well as more number of Brönsted and Lewis acid sites available on larger surface area. The catalyst exhibited 91 % yield of methyl stearate at 60 °C in 7 h, which increased from 71 to 91 % with an increase in the Zr to Si ratio from 1:2 to 2:1 due to increase in acid site concentration. The reaction followed pseudo-first order kinetics under the optimized reaction conditions with a reaction rate of 1.15 mmol h^?1, rate constant of 2.7 × 10^?1 h^?1 and turn over frequency of 9.68 h^?1. The catalyst displayed higher activity (91 %) compared to ion exchange resins (44–68 %), Nafion (58 %), acid clay (61 %) and pure sulfated zirconia (78 %), and was slightly lower as compared to H₂SO₄ (97 %). The study clearly reveals the improved structural, textural and acidic properties of ZrO₂–SiO₂ mixed oxide aerogel prepared via SCD technique.     

Structural heterogeneity of SiO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glass

It is shown that the phase heterogeneity of SiO₂–Na₂O–Al₂O₃ glass has a liquation and crystallization nature, the balance between which is determined by the conditions of their synthesis. An increase in the aluminum oxide content decreases the number of liquation and crystallization sites, and also the linear sizes of the crystalline formations without eliminating the phase separation due to the liquation. The area of metastable immiscibility in the SiO₂–Na₂O–Al₂O₃ system, which is determined by scanning electron microscopy, is probably wider than the area detected by the optical methods.     

Bimetallic Pd–Cu/ZnO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Pd–Cu/ZrO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for methanol synthesis

Monometallic copper and bimetallic palladium-copper catalysts supported on ZnO–Al₂O₃ and ZrO₂–Al₂O₃ were prepared by conventional impregnation method and tested in methanol synthesis reaction under elevated pressure (3.5 MPa) in gradientless reactor at 220°C. The physicochemical properties of prepared catalytic systems were studied using BET, X-ray, TPR-H₂, TPD-NH₃ techniques. The promotion effect of palladium on catalytic activity and selectivity of copper supported catalyst in methanol synthesis reaction was proven. The highest activity of this system is explained by the Pd–Cu alloy formation.     

Physicomechanical properties of refractory Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Si<Subscript>3</Subscript>N<Subscript>4</Subscript>–C materials with ACPC

A study has been made on the effects of the amount of silicon nitride and graphite on the physicomechanical properties of Al₂O₃–Si₃N₄–C composites for lining purposes. Adding 2.5–5.0 wt.% silicon nitride and 0.5 wt.% reactive alumina improves the properties, raises their apparent density, and increases the mechanical strength, while reducing the open porosity. Optimized compositions have been determined for refractory materials of Al₂O₃–Si₃N₄–C composition, and it has been found that to attain the higher values of physicomechanical properties the amount of graphite should constitute 5–10 wt.%.     

Synthesis of low-melting eutectic of the CaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system in a solid phase

Results are provided for a physicochemical study of processes that occur during synthesis of eutectic composition of the CaO–B₂O₃–SiO₂ system in a solid phase, and the possibility of their activation by using starting calcium-containing components with different chemical and thermal prehistory. It is established that independent of the form of starting components, in all cases there is formation of a crystalline eutectic phase, and the sequence of physicochemical processes that occur is determined by the reaction capacity of the calcium compound introduced.     

Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>–Au and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>–Au Hybrid Nanorods: Layer-by-Layer Assembly Synthesis and Their Magnetic and Optical Properties

A layer-by-layer technique has been developed to synthesize FeOOH–Au hybrid nanorods that can be transformed into Fe₂O₃–Au and Fe₃O₄–Au hybrid nanorods via controllable annealing process. The homogenous deposition of Au nanoparticles onto the surface of FeOOH nanorods can be attributed to the strong electrostatic attraction between metal ions and polyelectrolyte-modified FeOOH nanorods. The annealing atmosphere controls the phase transformation from FeOOH–Au to Fe₃O₄–Au and α-Fe₂O₃–Au. Moreover, the magnetic and optical properties of as-synthesized Fe₂O₃–Au and Fe₃O₄–Au hybrid nanorods have been investigated.     

Thermal investigation of ammonioborite (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>[B<Subscript>15</Subscript>O<Subscript>20</Subscript>(OH)<Subscript>8</Subscript>] · 4H<Subscript>2</Subscript>O

The thermal behavior of ammonioborite (NH₄)₃[B₁₅O₂₀(OH)₈] · 4H₂O is investigated using thermal X-ray diffraction, differential thermal analysis (DTA) in air and vacuum, and thermogravimetry. It is shown that the decomposition of the mineral (dehydration, dehydroxylation, deammoniation) proceeds in several stages, and the dehydration is accompanied by the amorphization. The thermal expansion of ammonioborite is sharply anisotropic. As in the case of other hydrous pentaborates, the thermal expansion is maximum in the direction in which pentaborate groups alternate with ammonium cations.     

Porous ceramics based on the ZrO<Subscript>2</Subscript>(Y<Subscript>2</Subscript>O<Subscript>3</Subscript>)–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> system for filtration membranes

The results of the studies of the process of fabricating ceramic filtration membranes in the system ZrO₂(Y₂O₃)–Al₂O₃ are presented. The phase compositions of the precursor powders and sintered ceramics have been investigated and their porous structures have been determined. Two stages of the implementation of the technology were demonstrated: fabrication of substrates with an open porosity ranging from 20 to 47% and pore sizes in the 100–300 nm range, as well as the deposition of nanocrystalline aluminum oxide layers on them. It has been established that the pore size distribution in the membrane layer of α-Al₂O₃ is unimodal (from 30 to 100 nm).     

Crystallization and Luminescence Properties of Sm<Superscript>3+</Superscript>-Doped SrO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> Glass-Ceramics

Sm³⁺-doped SrO–Al₂O₃–SiO₂ glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated. The results indicate that the crystal phase in this system is monocelsian (SrAl₂Si₂O₈). Under the excitation with blue light (475 nm) the Sm³⁺-doped SrO–Al₂O₃–SiO₂ glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm, which can be assigned to the ⁴G_5/2 → ⁶H_J/2 (J = 5, 7, 9, 11) electron transitions in Sm³⁺ ions, respectively. With the increase of nucleation/crystallization temperature, the crystallite part rises from 66 to 79%. Besides, by increasing crystallization temperature or concentration of Sm³⁺, the samples emission located at 565, 605 and 650 nm is intensified significantly. We envision that, by fine controlling and combining of these three (green, orange and red) lights in an appropriate proportion, the Sm³⁺-doped glass-ceramics are promising luminescence materials for white light-emitting diodes devices.