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A route for production of fine Bi4Ge3O12 (BGO) powder is sought after to lower the cost of scintillation devices and make their shapes more versatile. A systematic study of highly dispersed BGO crystallization under the hydrothermal-microwave (HTMW) conditions was carried out in the present work. Anionic, cationic and non-ionic surfactants, chelating agents and polyols were used to modify the synthesis and their respective effects on phase composition and morphology were determined. It was shown that chelating agents or other additives that are capable of forming complexes with the bismuth ions allow the production of smaller, non-aggregated particles and have the procedure be scaleable. BGO powders of various morphology were synthesized and study of the optical properties of the product discovered their advantages over traditional single-crystal material. The BGO powders obtained in optimal HTMW conditions are characterized by the presence of a single intense fast scintillation component with a flash time of about 11 ns which is by an order of magnitude less than that observed in single-crystal BGO (327 ns). This suggests the suitability of these powders for the production of scintillation materials with improved properties. This material is promising for creating highly sensitive composite detectors with a high rate of counting events.

A comparative analysis has been made for the dielectric and electrorheological properties of suspensions of highly dispersed powders of bismuth ferrites BiFeO3 and Bi2Fe4O9 in polydimethylsiloxane PMS-300. Dielectric characteristics (dielectric constant, dielectric loss tangent) for the suspensions in frequency range 2.5–106 Hz have been determined and non-Debye character of relaxation processes in these systems has been revealed. The measured values of dielectric constant for the disperse bismuth ferrites at zero and infinite frequency (e0 and e∞) are 150 and 59 for BiFeO3, 22 000 and 14 for Bi2Fe4O9, respectively. Electrorheological properties of bismuth ferrite suspensions in static electric field (up to 5 kV) in tension, compression, and shear modes have been analyzed. It has been found that the values of electrorheological effect for BiFeO3 suspensions in polydimethylsiloxane PMS-300 are small even at high concentrations of disperse phase (60 wt %). On the contrary, the suspensions of highly disperse Bi2Fe4O9 exhibit distinct electrorheological effect. For 80 wt % Bi2Fe4O9 suspension, the tensile yield point reached ~7 kPa in electric field of 5 kV, while compressive stress was 12 kPa.

We have developed a process for the synthesis of fine bismuth orthogermanate, Bi4Ge3O12 (BGO), powders in a NaCl/KCl melt and examined the effect of synthesis conditions on the phase composition and morphology of the powders. Our results demonstrate that the synthesized materials compare well in scintillation performance with single-crystal BGO: their scintillation efficiency is 90% relative to single-crystal BGO, with a decay time of 300 ns.

Reactions of nitric acid solutions of bismuth with alkalis have been studied. The effect caused by coprecipitation conditions in the presence of additional agents (EG, PEG 400, or PEG 8000) and without on the phase composition and morphology of α- and γ-Bi2O3 has been determined.

In this work, Bi1-xPrxGeSbO6 (x = 0–0.5) solid solutions were synthesized, and the corresponding properties were compared to those of La1-xPrxGa0.5Sb1·5O6. The lattice parameters of the La1-xPrxGa0.5Sb1·5O6 solid solutions decrease linearly as the activator concentration increases. This linear reduction is only observed for the a parameter for Bi1-xPrxGeSbO6. Parameter c shows non-linear growth, which is related to the structural features of BiGeSbO6. Increasing the activator content leads to a decrease in the particle size, which is 0.5–8 μm for Bi1-xPrxGeSbO6. The influence of the host composition on the spectral-luminescent properties of the solid solutions was determined. The difference in the phonon frequencies of BiGeSbO6 and LaGa0.5Sb1·5O6 leads to different luminescence quenching processes for Pr3+ ions. Interactions between Pr3+ ions and Bi3+ were observed for Bi1-xPrxGeSbO6 solid solutions. These processes give rise to changes in the ratios of the luminescence bands of these ions. All the bismuth-containing solid solutions are characterized by the appearance of an additional band in the spectrum related to the luminescence of the bismuth centres of the BiGeSbO6 host. An evaluation of the colour coordinates (CIE 1931) of the Bi1-xPrxGeSbO6 luminescence showed that the colour of the radiation depends on the praseodymium content: as the praseodymium content increases, the luminescence changes from orange (x = 0.005, 0.01) to yellow-green (x = 0.05–0.5). Broadband thermal emission is observed for Bi0.5Pr0.5GeSbO6 under laser excitation with λ = 457 nm and a power density of J = 6 kW/cm2.

The Bi–La–Fe–Sb–O, Pr–Fe–Sb–O, and Bi–Pr–Fe–Sb–O systems have been shown to contain pyrochlore solid solutions. We have determined the limits of the Pr2–xFe1 + xSbO7 and Bi2–xLnxFeSbO7 (Ln = La, Pr) solid solutions and shown that there is no compound corresponding to the “ideal” composition Pr2FeSbO7. Analysis of the magnetic properties of the synthesized compounds indicates that rare earth substitution for bismuth ions has no effect on the spin glass transition and that the spin glass state is only determined by the interaction between the Fe3+ spins on the octahedral site. The Pr3+ paramagnetic ion in Pr2–xFe1 + xSbO7 does not participate in the formation of the spin glass state but makes a paramagnetic contribution to the total magnetic susceptibility, which is especially significant at low temperatures.

It was shown that it is possible to obtain by coprecipitation a complex ternary oxide containing elements dissimilar in their chemical nature. The interaction of acidic solutions of bismuth, iron, and antimony with monoethanolamine and ammonia was studied, and the effect of the coprecipitation conditions on the phase composition and morphology of the reaction products was determined. Samples of nanocrystalline pyrochlore containing bismuth, iron, and antimony were produced for the first time.

Single crystals of a new compound, Ba2Bi3B25O44, were grown by cooling a melt of non- stoichiometric composition. The crystal structure was solved by direct methods and refined to R ¼ 0.030

A physicochemical study of glasses based on the MO-Bi2O3-B2O3 and SrO-Bi2O3-B2O3 systems was performed. Glass formation regions were found. The structural and optical properties, as well as the thermal behavior of the glasses, were studied.

Three-dimensional opal-matrix nanocomposites containing various bismuth selenides and tellurides with a particle size from 25 to 150 nm have been produced by reducing oxygen-containing compounds with supercritical isopropanol. The bismuth: chalcogen ratio in the reduction products has been shown to correlate with that in the starting mixtures, indicating that targeted synthesis in opal pores can be used to controllably fabricate nanocomposites.

The 600°C (subsolidus) section of the CaO-Bi2O3-B2O3 phase diagram has been studied by x-ray diffraction and differential thermal analysis. A new calcium bismuth borate of composition CaBi2B4O10 has been identified, and the existence of CaBi2B2O7 has been confirmed. According to T-x phase diagram data, these compounds form peritectically at 700±5 and 783±5°C, respectively.

The crystal structure of a new bismuth aluminoborate Bi0.96Al2.37(B4O10)O is studied by single-crystal X-ray diffraction. The Bi0.96Al2.37(B4O10)O single crystals are hexagonal (space group $$P\bar 6$$ 2m). The unit cell parameters are as follows: a = b = 4.587(4) A, c = 2.253(9) A, α = β = 90°, γ = 120°, V = 168.60 A3, Z = 1.

Phase equilibria in the BaO-Bi2O3-B2O3 system have been investigated by X-ray powder diffraction analysis and DTA. Quasi-binary sections have been determined, and an isothermal section of the system in the subsolidus region has been constructed. The BaO-Bi2O3-B2O3 ternary system has been divided into 22 triangles of coexisting phases. It has been found that four bismuth barium borates exist, namely, Ba3BiB3O9, BaBi2B4O10, BaBiB11O19, and BaBiBO4. Ba3BiB3O9 undergoes a phase transition at 850°C and exists up to 885°C, where it decomposes in the solid state. BaBiB11O19 and BaBi2B4O10 melt congruently at 807 and 730°C, respectively. BaBiBO4 melts incongruently at 780°C. X-ray powder diffraction data for the low-temperature polymorph of Ba3BiB3O9 are presented.

The phase equilibria in the concentration triangle Bi2O3-BaB2O4-B2O3 of the BaO-Bi2O3-B2O3 system have been investigated by X-ray powder diffraction and DTA. Barium bismuth borates of the composition BaBi2B4O10 and BaBiB11O19 have been found to exist. These borates melt at 730 and 807°C, respectively. The quasi-binary sections have been determined. It has been shown that the isothermal section of the Bi2O3-BaB2O4-B2O3 in the subsolidus region at 600°C is characterized by 13 triangles of coexisting phases.

Single crystals of Bi 2 Ga 4 O 9 are grown from a solution in a bismuth oxide melt. The structure (orthorhombic, space group Pbam , a = 7.918(2) A, b = 8.299(2) A, c = 5.894(2) A, Z = 2) is refined to R = 0.052 in the anisotropic approximation based on single-crystal X-ray diffraction data. The structure is a framework. The bismuth(III) atoms are sixfold coordinated; gallium(III) exists in both tetrahedral and octahedral coordina- tions. The thermal expansion of Bi 2 Ga 4 O 9 is studied by high-temperature X-ray powder diffraction method and is found to be sharply anisotropic. A structural interpretation of the anisotropy is proposed. Chemical distortion in the Bi 2 M 4O9 compounds with M = Fe(III), Al, or Ga is analyzed and compared with the thermal expansion of Bi2Ga4O9.

The vibrational spectra of crystals of bismuth borates Bi24B2O39, Bi4B2O9, BiBO3, and Bi2B8O15 were obtained for the first time, and the spectra of Bi3B5O12 and BiB3O6 crystals measured in the range 30–1600 cm−1 at room temperature were refined. The lines observed were assigned to the corresponding vibrational transitions on the basis of the theoretical group analysis and comparison of the obtained results with the vibrational spectra of borates of different composition. The complication of the structure of bismuth borates with increasing content of B2O3 was traced by the example of vibrational spectra.

The photoinduced absorption in a Ca-doped bismuth titanate crystal is measured as a function of temperature in the red (660 nm), yellow (570 nm), and green (505 nm) spectral regions.

Evidence that local ordered magnetic fields from 30 to 250 G exist in bismuth-based diamagnetic compounds comprising neither d- nor f-elements was given by 209Bi NQR spectroscopy and supported by SQUID measurements of α-Bi2O3. The NQR experiments involved a study of the zero-field line shapes, analysis of the Zeeman-perturbed patterns, and examination of the zero-field spin-echo envelopes in single crystals and powders. The results of the experiments followed by computer modeling of the observed spectra were interpreted assuming that ordered magnetic fields are located at the bismuth sites in α-Bi2O3, Bi3O4Br, Bi2Al4O9, Bi4Ge3O12, Bi2Ge3O9 and perhaps in Bi3B5O12. A survey of the related 209Bi NQR data is here presented.

Results of investigations into the dynamics of light-induced absorption in bismuth titanium oxide crystals doped with calcium (Bi12TiO20:Ca) illuminated with quasimonochromatic light of semiconductor light-emitting diodes at two wavelengths from the set λ = 870, 660, and 525 nm are presented. Based on an analysis of the experimental data, a model of charge transfer by defect centers describing the observed phenomena is suggested.

It was earlier found from nuclear quadrupole resonance (NQR) measurements and computer modeling that α-Bi2O3, Bi3O4Br and mixed oxides Bi2O3· 2Al2O3, Bi2O3· 2Ga2O3, Bi2O3· 3GeO2, and 2Bi2O3· 3GeO2exhibit local ordered magnetic fields from 30 to 200 G. It thus follows that these compounds are not diamagnets in a conventional sence of the word. With the aim of revealing previously unknown magnetic properties in bismuth(III) oxide-based Main Group element compounds, the mixed bismuth–boron oxides 2Bi2O3· B2O3, 3Bi2O3· 5B2O3, and Bi2O3· 3B2O3were prepared and studied using 209Bi NQR. The quadrupole interactions of the 209Bi nuclei and their electronic environment were studied, the crystallochemical features of the compounds were discussed, and the conformity of the 209Bi results to the X-ray structure data was verified. The preliminary tests in the field of a permanent magnet showed that the resonance intensities increase in external magnetic fields, indicating that a magnetism of unknown nature develops in the titled compounds. It was found reasonable to continue studies of the magnetic properties of these compounds using single-crystal 209Bi NQR in external magnetic fields.

Evidence that local ordered magnetic fields from 30 to 250 G exist in bismuth-based diamagnetic compounds comprising neither d- nor f-elements was given by 209Bi NQR spectroscopy and supported by SQUID measurements of a-Bi2O3. The NQR experiments involved a study of the zero-field line shapes, analysis of the Zeeman-perturbed patterns, and examination of the zero-field spin-echo envelopes in single crystals and powders. The results of the experiments followed by computer modeling of the observed spectra were interpreted assuming that ordered magnetic fields are located at the bismuth sites in a-Bi2O3, Bi3O4Br, Bi2Al4O9, Bi4Ge3O12, Bi2Ge3O9 and perhaps in Bi3B5O12. A survey of the related 209Bi NQR data is here presented.

We demonstrate experimentally that time evolution of light-induced absorption in Bi12TiO20 crystals exhibits complicated behavior at their sequential irradiation by incoherent light from two light-emitting diodes with the wavelengths of 660 and 505 nm. To interpret our results we propose a novel two-center model of light-induced changes in absorption considering a two-level structure for each defect center and the in-center transitions between inherent levels. Comparison of the experimental results with the theoretical model for Bi12TiO20 crystals with different stoichiometry leads us to the conclusion that the titanium vacancies may be considered as trap centers, which provide light-induced absorption.

Bi12TiO20 single crystals were grown from the various melt compositions (5.0-10.0 mol.% TiO2). The stoichiometric dependence of optical and photoconductive properties of Bi12TiO20 crystals is studied. It was observed that the lattice constant value depends on TiO2-concentration in the melt. The melt composition dependencies of absorption coefficient and circular dichroism value have linear character in spectral range 410- 500 nm. The bismuth-richer melt-grown crystals performed the higher values of absorption coefficient and intensities of the band in the circular dichroism spectrum. It is shown that photoconductivity is more sensitive characteristic to melt composition. The crystal grown from the bismuth- poorest melt exhibits the photoconductivity which is two order of magnitude higher, than in crystal grown from the bismuth-richer melt, over studied spectral range. The crystal grown from 9 mol.% TiO2 melt composition performs the maximal values of photocurrent and photoinduced absorption. Based on these optical and electrical results, the nature of the local centers in Bi12TiO20 crystals is discussed.© (2001) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.