S. M. Zharkov

Formation of bimetallic Au-Pd and Au-Pt nanoparticles under hydrothermal conditions and microwave irradiation.

The reduction of chlorocomplexes of gold(III) from muriatic solutions by nanocrystal powders of palladium and platinum at 110 and 130 °C under hydrothermal conditions and the action of microwave irradiation has been investigated. The structure and composition of the solid phase have been characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and chemical methods. Bimetallic particles with a core-shell structure have been revealed. The obtained particles are established to have a core of the metal reductant covered with a substitutional solid (Au, Pd) solution in case of palladium, and isolated by a gold layer in the case of platinum. The main reason for such a difference is the ratio between the rates of aggregation and reduction. It has been shown by the example of the Au-Pd system that the use of microwave irradiation allows us not only to accelerate the synthesis of particles but also to obtain more homogeneous materials in comparison with conventional heating.

Formation of NiAl Shape Memory Alloy Thin Films by a Solid-State Reaction

NiAl shape memory alloy thin films have been fabricated by a solid-state reaction in Al/Ni bilayer films. Two kinds of synthesis have been used. The first one consists in heating an Al/Ni bilayer film system to temperatures above 480 K. The second one implies the successive deposition of nickel and aluminum films onto a substrate with a temperature above 480 K. Regardless of a kind of the solid-state synthesis, the films obtained reveal a two-way shape memory effect. It is supposed that the solid-state reaction in Al/Ni bilayers starts at a temperature AS of the reverse of the martensitic transition in NiAl alloy. This indicates that the NiAl shape memory alloy thin films can be formed directly during the synthesis without need for lengthy heat treatment.

Structural and magnetic resonance investigations of CuCr2S4 nanoclusters and nanocrystals

Nanoclusters and nanocrystals of the room temperature magnetic spinel CuCr2S4 synthesized using a facile solution-based method have been examined by transmission electron microscopy, magnetic measurements, and magnetic resonance over a wide frequency range 9.6–80 GHz and at temperatures down to 4.2 K. Decreasing of the resonance field and broadening of the resonance lines below 50 K for both samples are due to the freezing of magnetic moments of nanocubes and nanocrystalline particles constituting nanoclusters. The effective fields of averaged magnetic anisotropy ⟨HA⟩≅ 2.4 kOe are similar for both nanopowder samples as estimated from resonance measurements at T = 4.2 K. An additional blocking temperature Tb ≅ 300 K appears in nanoclusters due to freezing of the magnetic moment of the entire cluster as a whole. Below this blocking temperature, the magnetic dipolar field acting in boundary areas of interacting constituent nanocrystals is responsible for the additional low-field resonance line observed in th...

Study of solid-state reactions and order-disorder transitions in Pd/α-Fe(001) thin films

The formation of the hard-magnetic ordered L10-FePd phase in thin bilayer Pd/α-Fe(001) films has been experimentally studied. Solid-state reactions initiated by thermal heating in bilayer Pd/α-Fe(001) films with a thickness of 50–60 nm (the atomic ratio Pd: Fe ≈ 50: 50) separated from the substrate have been studied using the in situ electron diffraction methods. It has been shown that the solid-state reaction between the palladium and iron layers in Pd/α-Fe(001) starts at 400°C with the formation of the disordered Fe-Pd phase. At 480°C, the ordered L10-FePd phase is formed. The order-disorder phase transition has been studied. It has been established that the transition of the ordered L10-FePd phase to the disordered FePd phase starts at 725°C. At 740°C, only the disordered FePd phase is present over the whole volume of the film. The observed temperature of the order-disorder phase transition is shifted from the equilibrium value by 35°C to higher temperatures. This effect is assumingly associated with the higher concentration of palladium atoms at the boundaries of the Fe-Pd crystal grains owing to the grain-boundary adsorption.

Preparation and characterization of colloidal copper xanthate nanoparticles

Despite the important role of metal xanthates in a number of industrial processes and emerging applications, no attempts have been made to prepare the metal xanthate nanoparticles and to study colloidal solutions of insoluble heavy metal xanthates. Here, we examined the formation of colloidal copper xanthate particles during the reactions of aqueous solutions of cupric sulfate and various potassium xanthates, which occur in flotation and water treatment slurries and can be used to manufacture nanoparticles for materials science (e.g., as precursors for copper sulfide nanoparticles and biomedicine). The products were characterized using UV-vis absorption, dynamic light scattering, zeta potential measurements, transmission electron microscopy (TEM), electron diffraction, Fourier transform infrared spectroscopy, thermogravimetry, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy (XANES). Colloidal copper xanthates with compositions of ROCSSCu (R = ethyl, isopropyl, butyl, isobutyl, and amyl groups), disordered structures and average diameters of 20–80 nm easily formed and aggregated and were stable for at least several hours, especially if excessive xanthate was used. The hydrodynamic diameters of the nanoparticles were smaller at lower temperatures. Dixanthogens, which were produced in the reactions along with ROCSSCu, seemed to promote nanoparticle aggregation and precipitated with the copper xanthate, affecting their thermal decomposition. The TEM micrographs and S K- and Cu K-edge XANES spectra revealed core/shell particle morphologies, likely with Cu(I) bonded to four S atoms in the core and reduced copper coordination in the shell.

Ultrafine particles derived from mineral processing: A case study of the Pb-Zn sulfide ore with emphasis on lead-bearing colloids.

Although mining and mineral processing industry is a vast source of heavy metal pollutants, the formation and behavior of micrometer- and nanometer-sized particles and their aqueous colloids entered the environment from the technological media has received insufficient attention to date. Here, the yield and characteristics of ultrafine mineral entities produced by routine grinding of the Pb-Zn sulfide ore (Gorevskoe ore deposit, Russia) were studied using laser diffraction analysis (LDA), dynamic light scattering (DLS) and zeta potential measurement, microscopy, X-ray photoelectron spectroscopy, with most attention given to toxic lead species. It was revealed, in particular, that the fraction of particles less that 1 μm in the ground ore typical reaches 0.4 vol. %. The aquatic particles in supernatants were micrometer size aggregates with increased content of zinc, sulfur, calcium as compared with the bulk ore concentrations. The hydrodynamic diameter of the colloidal species decreased with time, with their zeta potentials remaining about -12 mV. The colloids produced from galena were composed of 20-50 nm PbS nanoparticles associated with lead sulfate and thiosulfate, while the surface oxidation products at precipitated galena were largely lead oxyhydroxides. The size and zeta potential of the lead-bearing colloids decreased with time down to about 100 nm and from -15 mV to -30 mV, respectively. And, conversely, lead sulfide nanoparticles were mobilized before the aggregates during redispersion of the precipitates in fresh portions of water. The potential environmental impact of the metal-bearing colloids, which is due to the large-scale production and relative stability, is discussed.

Solid-State Reactions in Fe/Si Multilayer Nanofilms

Solid-state reaction processes in Fe/Si multilayer nanofilms have been studied in situ by the methods of transmission electron microscopy and electron diffraction in the process of heating from room temperature up to 900ºС at a heating rate of 8-10ºС/min. The solid-state reaction between the nanolayers of iron and silicon has been established to begin at 350-450ºС increasing with the thickness of the iron layer.

Formation of the atomically ordered L 1 0 structure with the [001] orientation during the solid-state reaction in Fe/Pd bilayer thin films

The formation of the atomically ordered L10-FePd structure during the solid-state reaction in Fe/Pd bilayer thin films is in situ investigated by electron microscopy and electron diffraction analysis. The initial iron and palladium layers were mainly coherently oriented crystallites with the orientation relationship α-Fe (001)[110] || Pd(001)[100]. It is established that the solid-state reaction between the iron and palladium layers upon heating at a rate of 4–8°C/min starts with the formation of the FePd solid solution at 390°C; at 430°C, the formation of the atomically ordered L10-FePd structure is observed. It is shown that at the low heating rate (4–8°C/min), the L10-FePd structure with the [001] orientation relative to the film plane forms, while at the high heating rate (50°C/min) it forms with the [100], [010], and [001] orientations.

Formation of Phases and Microstructure of ZnO and TiO2 Based Ceramic

Nanopowders of zinc and titanium oxides were used to obtain samples of Zn2TiO4–ZnO ceramic. Phase formation as well as the microstructure and elemental composition of the phases formed were studied by means of electron microscopy. The density and porosity were calculated, and the sizes of grains and pores in the ceramic were determined. The temperature at the zinc titanate forms was determined. It was shown that it corresponds to the sintering temperature of electrocontact materials with this composition. It is proposed that zinc titanate and oxide be used as arc-suppressing and dispersion-hardening additional additives in copper-based electrocontact materials.

Analysis of the structure and magnetic properties of an interface in multilayered (Fe/Si)N nanostructures with the surface-sensitive XMCD method

The structural and magnetic properties of (Fe/Si)N nanostructures obtained by successive deposition on the SiO2/Si(100) surface at a temperature of the substrate of 300 K have been studied. The thicknesses of all Fe and Si layers have been determined by transmission electron microscopy measurements. The magnetic properties have been studied by the X-ray magnetic circular dichroism (XMCD) method near the Fe L3, 2 absorption edges. The orbital (ml) and spin (mS) contributions to the total magnetic moment of iron have been separated. The thicknesses of magnetic and nonmagnetic iron silicide on the Si/Fe and Fe/Si interfaces have been determined with the surface sensitivity of the XMCD method and the model of the interface between the nonmagnetic and weakened magnetic phases.