V. V. Voronov

Coprecipitation from aqueous solutions to prepare binary fluorides

The synthesis of binary fluoride phases, specifically nanofluorides, by coprecipitation from aqueous solutions is considered in terms of phase equilibria. Phases have been precipitated in NaF-RF3 systems (where R stands for a rare-earth element), MF2-YF3 systems (where M = Ca, Sr, Ba), BaF2-ScF3, and CaF2-BaF2 systems. In the MF2-YF3 systems, unordered metastable congruently soluble phases are precipitated instead of ordered fluorite-like phases. In the BaF2-ScF3 system, the congruently soluble compound Ba3Sc2F12 is precipitated. In the NaF-RF3 systems, incongruently soluble metastable phases with a fluorite-like structure (for R = Er, Lu, Y) and the gagarinite structure (NaGdF4) are formed. In the CaF2-BaF2 system, intermediate phases have not been formed.

Synthesis of Ba4R3F17 (R stands for rare-earth elements) powders and transparent compacts on their base

Single-phase samples of Ba4R3F17 · nH2O (R = La, Ce, Pr, Nd, Eu, Gd, Y, Er, or Yb; n = 2.5−3.2) were prepared by coprecipitation from nitrate solutions using hydrofluoric acid. The phases crystallize in a fluorite-type face-centered cubic lattice. The dried precipitates are transparent. Scanning electron and atomic-force microscopy and X-ray diffraction line broadening show a hierarchic structure in the samples: primary nanoparticles join into agglomerates with characteristic sizes of about 150–200 nm, these agglomerates being self-packed into parallel layers with a thickness on the order of 500 nm.

Preparation of MgO nanoparticles

MgO nanoparticles have been prepared via hydroxide precipitation from aqueous solutions, followed by the thermal decomposition of the hydroxide. The nanoparticles inherit the platelike shape from the hydroxide and break into isometric particles upon significant superheating. The particle size of the synthesized magnesium oxide powders varies from 30 to 75 nm, depending on the annealing temperature.

Soft chemical synthesis of NaYF4 nanopowders

Hydrated NaYF4 powders dominated by the metastable high-temperature cubic phase were precipitated with a fivefold NaF excess from acid solutions of yttrium nitrate. Transformation into the stable hexagonal phase (a = 5.969(2), c = 3.503(1) Å) occurs under heating with an exotherm at ∼400°C.

Preparation of nanopowdered M1−x R x F2+x (M = Ca, Sr, Ba; R = Ce, Nd, Er, Yb) Solid Solutions

The synthesis procedure has been worked out, and nanopowders of fluoride solid solutions (ss) Ca1−xRxF2+x (R = Er, Yb), Sr1−xNdxF2+x, and Ba1−xCexF2+x have been manufactured by coprecipitation from aqueous solutions. The powders consist of rounded particles with sizes from 50 to 150 nm. The particles with sizes of about 150 nm are aggregates of adhered nanoparticles. The nanoparticles are highly reactive and sinter at low temperatures (T < 0.35Tm).

Coprecipitation of barium-bismuth fluorides from aqueous solutions: Nanochemical effects

The BaF2-BiF3 system was studied by the method of coprecipitation from aqueous solutions. The region of precipitation of single-phase nonoxygen powders was revealed (the atomic fraction of Bi in the initial solution was 0.35–0.43). The composition of the cubic fluorite-type phase is BaBiF5 according to an energy-dispersive X-ray spectroscopy analysis. Samples prepared from solutions with high Bi concentrations contain oxygen. This indicates that the hydrolysis temperature of BiF3 decreases when compared with that of the bulk samples and that this process takes place at room temperature. The coherent intergrowth of nanoparticles with the formation of single crystals with nonfaceted complex forms was shown by scanning electron microscopy and transmission electron microscopy.

Yttrium oxide nanopowders from carbonate precursors

Reactions of solutions of yttrium oxide in nitric acid with a 1.67 M NH4HCO3 solution were studied by direct and back titration. When the concentration of the reacting solution was within 0.031–0.052 mol/L (as Y2O3), yttrium carbonate Y2(CO3)3 · nH2O (n ≈ 2.5) of fibrous or spherulitic morphology precipitated. When the concentration was decreased to 0.022 mol/L, a new phase of platy morphology appeared. Heating these precipitates to 650–680°C yielded yttrium oxide having coherent scattering domain sizes of 40–80 nm. Y2O3 particles retain the precursor morphology.

Synthesis and luminescent characteristics of submicron powders on the basis of sodium and yttrium fluorides doped with rare earth elements

Submicron powders of solid solutions on the basis of cubic and hexagonal phases existing in a NaF-YF3 system have been synthesized with the precipitation method from aqueous solutions at room temperature. The conditions for the preparation of single-phase samples have been determined. The upconversion luminescence spectra were investigated. The most promising composition is revealed (Na0.414Ca0.183Y0.215Yb0.094Er0.094F1.989), which demonstrates an upconversion luminescence quantum yield of 1.9% with a 3-W pump power at a 974-nm wavelength.

Evolution of yttria nanoparticle ensembles

The formation of Y2O3 nanoparticles in precipitation from acidic nitrate aqueous solutions, which was done by regulating pH at the expense of their titration with an ammonium hydroxide aqueous solution, was studied. The jellylike precipitates of a (Y2(OH)5NO3 · nH2O, n = 2, 3) precursor lose their volatile components under heating and drying in several stages. Their chemical decomposition terminates at 500–550°C with the formation of the cubic modification of yttria. Yttria particles inherit the platelike morphology of the particles of their precursor. Under further heating, Y2O3 particles lose their nonequilibrium shape due to the decomposition of plates into roundish nanoparticles with the relief of mechanical stresses. The isothermal exposure of nanoparticles formed in this way leads to their stepped agglomeration with a sequential increase in the size of particles by an order of magnitude. The sintering of Y2O3 powders with the formation of ceramics was investigated.

Synthesis of scandium orthoborate powders

Two polymorphs of scandium orthoborate, ScBO3, are synthesized by adding aqueous ammonia to aqueous solutions of scandium nitrate and boric acids and calcining the resulting precipitates. Dehydration of the precipitates reaches completion below 300°C, and further heating leads to highly exothermic crystallization near 750°C. The synthesized ScBO3 powders consist of submicron-sized particles.