Vol 54, No 5 (2018)

Approaches are developed for controlling the size effect in the absorption and photoluminescence properties of colloidal CdS and Zn_0.5Cd_0.5S quantum dots (QDs) in a gelatin matrix and thioglycolic acid. We analyze spectroscopic manifestations of dark Ostwald ripening and size-selective photoetching and demonstrate that the illumination of molten colloidal CdS and Zn_0.5Cd_0.5S QD solutions at a wavelength lying at the optical absorption edge in the presence of hydrogen peroxide as a catalyst for photoetching leads to a blue shift of the optical absorption and photoluminescence spectra of the QDs. Analysis of TEM images of QD samples leads us to conclude that photoetching reduces the average QD size as a consequence of the photodissolution of the CdS and Zn_0.5Cd_0.5S compounds. We demonstrate that, by contrast, heat treatment of the synthesized CdS and Zn_0.5Cd_0.5S QD sols at a temperature between 75 and 90°C leads to an increase in nanocrystal size through recrystallization, which shows up as a redshift of the optical absorption and photoluminescence spectra of the corresponding samples.

Tungsten- and nickel-containing coatings have been produced on the surface of synthetic diamond crystals by rotary chemical vapor deposition (RCVD) using tungsten hexacarbonyl, W(CO)₆, and nickelocene, Ni(C₅H₅)₂, as gaseous precursors. The thickness, composition, and morphology of the coatings have been shown to depend on the RCVD process duration and reactant concentrations in the vapor phase. The synthetic diamond microcrystals with tungsten- and nickel-containing coatings have been used to produce copper–diamond heat-conducting composites. Powder mixtures containing 50 vol % diamond with a particle size of 50, 100, or 200 μm have been consolidated by spark plasma sintering or hot pressing. It has been shown that the highest relative density (97%) and thermal conductivity (340 W/(m K)) are offered by the composites produced by spark plasma sintering using tungsten carbide-coated 50-μm diamond crystals.

Using an arc physical vapor deposition process, we have produced nanostructured Mo–Si–Al–Ti–Ni–N coatings with a multilayer architecture formed by Mo₂N, AlN–Si₃N₄, and TiN–Ni and a crystallite size on the order of 6–10 nm. We have studied the physicomechanical properties of the coatings and their functional characteristics: wear resistance, adhesion to their substrates, and heat resistance. According to high-temperature (550°C) wear testing and air oxidation (600°C) results, the coatings studied here are wearand heat-resistant under appropriate temperature conditions. Their properties are compared to those of Mo–Si–Al–N coatings.

We have studied phase formation in calcium-modified Al₂O₃–ZrO₂–CeO₂ nanopowders during sol–gel synthesis. The results demonstrate that heat treatment of the nanopowders first leads to the formation of a zirconium dioxide-based solid solution stabilized with cerium cations. Raising the heat treatment temperature helps the crystallization of corundum, a stable phase of aluminum oxide, to reach completion. In the temperature range 1400–1550°C, we observe the formation of a second aluminum-containing phase: calcium cerium hexaaluminate consisting of long prismatic grains.

The structure–composition relationship for polished sections of individual platelike ferrospheres in the–0.04 + 0.032 mm size fraction isolated from fly ash from the combustion of brown coal has been studied systematically by scanning electron microscopy and energy dispersive X-ray spectroscopy. We have identified groups of globules whose overall composition, as well as the composition of local areas on their polished sections, can be represented by general equations for component concentrations: CaO = f(FeO) and SiO₂ = f(FeO). Analysis of the structure–composition relationship for the globules leads us to conclude that their structure is determined by transformations that occur in the CaO–Fe_xO_y system in response to an increase in its oxidation potential. It has been shown that the platelike globules containing 68–73 wt % FeO are made up of Ca₂Fe₂O₅ and CaFe₂O₄ crystallites resulting from the oxidative transformation of Fe, Ca, and Mg complex humates in the parent brown coal. The ferrospheres containing 79–90 wt % FeO have a fragmentary core–shell structure, where the platelike shell consists of Ca₂Fe₂O₅ and CaFe₂O₄ crystallites, and the core consists of Fe₂O₃ and a Ca-, Mg-, and Al-promoted magnetite. Precursors for the formation of this type of globule are pyrite associates with complex humates. It has also been demonstrated that the low concentration of aluminum and silicon oxides in the composition of the globules and the viscosity of their melt have no effect on the structure of the platelike ferrospheres.

We have developed a model for the formation of silica-containing synthetic functional materials with a hierarchical pore structure and a large specific surface area under self-assembly conditions of sol–gel processes. The model includes the formation of a three-dimensional core (of a cristobalite type) of sol particles consisting of joined polymorphoids in the form of n-membered rings and a continuous transition between fractal aggregate growth mechanisms, from diffusion-limited to cluster–cluster aggregation, followed by evolution culminating in spinodal decomposition. Hierarchical structures have been studied using three-dimensional simulation with Autodesk 3ds Max software.

This paper considers the distillation refining of a material containing highly volatile and low-volatile impurities and demonstrates the possibility of evaluating the fraction of residue, g_r, during the removal of the highly volatile impurity and the degree of subsequent distillation, g_c, necessary for achieving a predetermined decrease in impurity concentrations at a predetermined product yield and known separation factors. Examples are presented for the distillation in real host–impurity systems: Ga–(Pb,Al), Be–(Al,Fe), and Cr–(Si,Fe).

Bi₂Ca₂Co_xO_y (x = 0.5, 1.7, 2.8) ceramics have been prepared by solid-state reactions and their thermophysical, electrical-transport, and thermoelectric (functional) properties have been studied. The results demonstrate that increasing the cobalt oxide concentration in the ceramics leads to an increase in their thermal conductivity, electrical conductivity, and thermal diffusivity and a reduction in their apparent density. The largest Seebeck coefficient is offered by a single-phase ceramic with the composition Bi2Ca2Co1.7Oy, which in addition has the highest power factor (P₃₀₀ = 26.0 μW/(m K²)) and thermoelectric figure of merit (ZT₁₀₀₀ = 0.019) and the smallest linear thermal expansion coefficient (α = 9.72 × 10^–6 K^–1).