Single crystals of the fluorite nonstoichiometric phase Eu 0.9162+ Eu 0.0843+ F2.084 (conductivity, transmission, and hardness)

The nonstoichiometric phase EuF_2+x has been obtained via the partial reduction of EuF₃ by elementary Si at 900–1100°C. Eu_0.916²⁺Eu_0.084³⁺F_2.084 (EuF_2.084) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF₂ structure type (sp. gr. Fm $ \bar 3 $ \bar 3 m) with the cubic lattice parameter a = 5.8287(2) ?, are transparent in the spectral range of 0.5–11.3 μm, and have microhardness H _μ = 3.12 ± 0.13 GPa and ionic conductivity σ = 1.4 × 10⁻⁵ S/cm at 400°C with the ion transport activation energy E _a = 1.10 ± 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF₂ − EuF₃ systems are similar to those of the phases in the SrF₂ − EuF₃ and SrF₂ − GdF₃ systems due to the similar lattice parameters of the EuF₂ and SrF₂ components. Europium difluoride supplements the list of fluorite components MF₂ (M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M _{1 − x} R _x F_{2 + x} (R are rare earth elements).     

Cluster self-organization of intermetallic systems: Quasi-spherical nanocluster precursors with internal Friauf polyhedra (A-172) and icosahedra (B-137) in the Li19Na8Ba15 (hP842) crystal structure

A combinatorial and topological analysis of Li₁₉Na₈Ba₁₅ (hP842, a = 20 ?, c = 93 ?, V = 33552 ?³, P $ \bar 3 $ \bar 3 ) has been performed using computer methods (the TOPOS program package). Two types of crystal-forming quasi-spherical nanoclusters about 20 ? in diameter with internal Friauf polyhedra (A-172) and icosahedra (B-137) have been established by the complete decomposition of the 3D factor graph of the structure into cluster substructures. Each type of nanoclusters forms close-packed 2D layers 3⁶, which alternate along the c axis. The B-137 and A-172 nanoclusters are composed of three layers and have shell compositions (1 + 12 + 32 + 92) and (1 + 16 + 59 + 103) with local symmetries 3 and $ \bar 3 $ \bar 3 , respectively; they were revealed for the first time in crystal structures as cluster precursors. The icosahedral B-137 nanocluster contains a 104-atom quasicrystal approximant (Samson cluster).     

The structure of the scandium iodide complex with antipyrine (AP) and its comparison with the structure of nonisostructural analogues (Compounds [Ln(AP)6]I3 (Ln = La, Y, or Eu))

An X-ray diffraction study of the scandium iodide complex with antipyrine [Sc(AP)₆]I₃ (AP is antipyrine, i.e., 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one) (I), which is not isostructural to the analogous compounds of Y, La, and Eu (II), is performed. Crystals I are trigonal; a = 24.911 ? and c = 10.140 ?; Z = 3, space group P $ \bar 3 $ \bar 3 . Crystal I is built of [Sc(AP)₆]³⁺ complex cations of two types and I⁻ anions. In both cations, the Sc atom is octahedrally coordinated by six O atoms of six AP ligands (Sc-O, 2.054–2.078 ?). Complexes I differ from II by the absence of π-π stacking interactions between AP molecules, resulting in a supramolecular cation. Complex cations I of both types form combined layers. All I⁻ anions are located in the interlayer space, being statistically disordered within a flat area limited by eight complex cations of Sc1 and Sc2.     

Ionic conductivity of congruently melting Ca0.6Sr0.4F2 and Ca1 ? x ? ySryRxF2 + x (R = La, Ce, Pr, Nd) single crystals with fluorite structure

Single crystals of congruently melting compositions of the Ca_0.6Sr_0.4F₂ and Ca_{1 − x − y} Sr _y R _x F_{2 + x} (R = La, Ce, Pr, Nd; x = 0.16–0.21; y = 0.07–0.16) solid solutions with fluorite structure have been grown by the Bridgman-Stockbarger method. Their electrical properties have been investigated in the range from 473 to 823 K, and it is shown that they are ionic conductors. For Ca_0.6Sr_0.4F₂ crystals, the ionic conductivity σ = 2 × 10⁻⁶ S/cm at 673 K, and the ion transport activation energy E _a = 1.1 eV. For Ca_0.77Sr_0.07La_0.16F_2.16, Ca_0.70Sr_0.11Ce_0.19F_2.19, Ca_0.65Sr_0.15Pr_0.20F_2.20, and Ca_0.58Sr_0.21Nd_0.21F_2.21 crystals, the values of σ lie in the range from 9 × 10⁻⁷ to 2 × 10⁻⁶ S/cm at 500 K, and the activation energy E _a is 0.88–0.93 eV. The concentration and mobility of ionic charge carriers in Ca_{1 − x − y} Sr _y R _x F_{2 + x} crystals have been calculated. Original Russian Text ? N.I. Sorokin, D.N. Karimov, E.A. Krivandina, Z.I. Zhmurova, O.N. Komar’kova, 2008, published in Kristallografiya, 2008, Vol. 53, No. 2, pp. 297–303.     

Nanostructured crystals of fluorite phases Sr1 ? xRxF2 + x (R are rare-earth elements) and their ordering: IV. Study of the optical transmission spectra in the 2–17-μm wavelength range

Transmission spectra of two-component crystals of Sr_1−x R _x F_2+x (R = Y, La-Lu; 0 ≤ x ≤ 0.5) in the 1–17-μm wavelength range were studied. The spectral characteristics of these crystals and of single-component crystals of MF₂ (M = Ca, Sr, or Ba) and RF₃ (R = La-Nd) were compared. The transmission cutoff of Sr_1−x R _x F_2+x crystals is shifted to shorter wavelengths with increasing x. The same tendency is observed with the increasing atomic number R of rare-earth elements for two isoconcentration series of Sr_1−x R _x F_2+x (x ∼ 0.10 and 0.28). This tendency is pronounced at large x. The transmission cutoff of Sr_1−x R _x F_2+x crystals can be varied in the range of from 10.7 to 12.2 μm by changing their qualitative (R) and quantitative (x) composition. Hence, these crystals can be assigned to multicomponent fluoride optical materials with controlled optical characteristics. The Sr_1−x R _x F_2+x crystals, where R = Ce-Sm, were shown to be promising materials for the design of selective optical filters in the 2–10-μm spectral range.     

Defect structure and ionic conductivity of Ca1 ? xScxF2 + x (0.02 ≤ x ≤ 0.15) single crystals

Single crystals of the Ca_{1 − x} Sc _x F_{2 + x} (x = 0.106, 0.132, 0.156) solid solutions (CaF₂ structure type, space group Fm m) are investigated using X-ray diffraction. It is revealed that the crystals under investigation contain vacancies in the 8c positions and interstitial fluorine ions in the 48i positions. The coordination number of Sc³⁺ ions in the structure of the Ca_{1 −x} Sc _x F_{2 + x} solid solutions is equal to eight. The specific features of the concentration dependences of the ionic conductivity and the activation energy of ion transfer for the Ca_{1 − x} Sc _x F_{2 + x} (0.02 ≤ x ≤ 0.15) solid solutions are explained in the framework of the percolation model of conducting “defect regions.” The percolation threshold equal to 3–5 mol % ScF₃ corresponds to the model of [Ca_{14 − n} Sc _n F₆₈] octacubic clusters containing fluorine ions in the 48i positions. The ionic conductivity of the Ca_{1 − x} Sc _x F_{2 + x} solid solutions is analyzed in comparison with the change in this characteristic for the series of Ca_0.8 R _0.2F_2.2 crystals with rare-earth elements. Original Russian Text ? E.A. Sulyanova, V.N. Molchanov, N.I. Sorokin, D.N. Karimov, S.N. Sulyanov, B.P. Sobolev, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 612–622.     

Synthesis and X-ray diffraction study of (Cs0.5Ba0.25)[UO2(CH3COO)3] and Ba0.5[UO2(CH3COO)3]

Uranyl triacetate complexes (Cs_0.5Ba_0.25)[UO₂(CH₃COO)₃] (I) and Ba_0.5[UO₂(CH₃COO)₃] (II) are synthesized for the first time and their structures are determined by X-ray diffraction. Both compounds crystallize in the cubic crystal system. The crystal data are as follows: a = 17.3289(7) ?, V = 5203.7(4) ?³, space group I2₁3 and Z = 16 (I); a = 17.0515(8)?, V = 4957.8(4) ?³, space group I $ \bar 4 $ \bar 4 3d, and Z = 16 (II). In I and II, as in all uranyl triacetates studied earlier, the coordination polyhedron of the uranium atom is a hexagonal bipyramid whose vertices are occupied by the oxygen atoms of the uranyl and three acetate groups. The uranium-containing group belongs to the AB ₃⁰¹ (A = UO₂²⁺, B ⁰¹ = CH₃COO⁻) crystal chemical group of uranyl complexes. It was found that compound II is isostructural to the (Rb_0.50Ba_0.25)[UO₂(CH₃COO)₃] studied earlier.     

The growth and defect structure of CdF2 and nonstoichiometric Cd1 ? xRxF2 + x phases (R are rare earth elements or in): Part VI. The optical properties of Cd0.9R0.1F2.1 crystals

The optical properties of the isoconcentration series of Cd_0.9 R _0.1F_2.1 crystals (R = Y, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, or Lu) grown from a melt by the Bridgman method have been investigated. The crystals have an anomalous birefringence (∼10⁻⁶) nonuniformly distributed over the sample diameter; the dichroism in them does not exceed 10⁻⁹. Scanning using a spectral modulator showed the nonuniform distribution of rare earth elements over the crystal diameter. The refractive indices n have been measured at wave-lengths of 0.436, 0.546, and 0.589 μm. The character of change in n along the rare-earth series is nonuniform and similar to the change in n in Sr_0.9 R _0.1F_2.1 crystals. It is shown that the refractive indices in Cd_{1 − x} R _x F_{2 + x} crystals, depending on the RF₃ content, can be estimated using the method of molecular refraction additivity. Original Russian Text ? A.F. Konstantinova, T.M. Glushkova, I.I. Buchinskaya, E.A. Krivandina, B.P. Sobolev, 2009, published in Kristallografiya, 2009, Vol. 54, No. 4, pp. 648–651.     

Growth and defect crystal structure of CdF2 and nonstoichiometric Cd1?xRxF2+x phases (R = rare earth and In). Part 3. Crystal structure of as-grown Cd0.90R0.10F2.10 (R = Sm-Lu, Y) single crystals

The structures of as-grown Cd_0.90 R _0.10F_2.10 (R = Sm-Lu and Y) crystals are determined and related to the CaF₂ structure type. It is assumed that in all the crystals R ³⁺ and Cd²⁺ ions form clusters with the tetrahedral configuration of the [Cd₂ R ₂F₂₆] and [CdR ₃F₂₆] cations. The concentration of [Cd₂ R ₂F₂₆] cations in crystals with R = Er-Lu and Y is considerably higher that in crystals with R = Sm-Ho. The tendency to a decrease in the coordination number of R ³⁺ toward the end of the rare earth series manifests itself in the fact that the Yb³⁺ ions in Cd_0.90Yb_0.10F_2.10 occupy both tetrahedral (c.n. 10) and octahedral (c.n. 8) clusters. The Yb³⁺ ions in tetrahedral clusters are displaced from their basic positions by 0.15 Å along the 〈100〉 directions. In Cd_1−x R _x F_2+x the relaxation of the anion sublattice of the fluorite matrix around clusters is much more pronounced than in the Ca_1−x R _x F_2+x phases having similar geometry. __________ Translated from Kristallografiya, Vol. 50, No. 2, 2005, pp. 235–248. Original Russian Text Copyright ? 2005 by Sul’yanova, Shcherbakov, Molchanov, Simonov, Sobolev.     

Mechanochemical synthesis of nonstoichiometric fluorite Ca1?xLaxF2+x nanocrystals from CaF2 and LaF3 single crystals

The nonstoichiometric Ca_1−x La_xF_2+x phase (x ≥ 0.1) is obtained by mechanochemical synthesis from CaF₂ and LaF₃ single crystals. This phase is the first representative of fluorite fluorides obtained by mechanochemical synthesis in the MF_m-RF_n systems (m < n ≤ 4). The average grain size ranges within 10–30 nm. The temperature dependence of ionic conductivity of the mechanochemically synthesized phase pressurized at 600 MPa (at its high-temperature portion at temperatures exceeding 200–250°C) coincides with the conductivity of the single crystals of the same composition (Ca_0.8La_0.2F_2.2). The activation energy of ionic conductivity (0.95 eV) corresponds to migration of interstitial fluoride ions in the crystal bulk. Mechanochemical synthesis of a multicomponent fluoride material with nanometer grains opens a new chapter in the chemistry of inorganic fluorides. A decrease of the sintering temperature of the powders with nanometer grains is very important for preparing dense fluoride ceramics of complicated compositions and other polycrystalline forms of fluoride materials. __________ Translated from Kristallografiya, Vol. 50, No. 3, 2005, pp. 524–531. Original Russian Text Copyright ? 2005 by Sobolev, Sviridov, Fadeeva, Sul’yanov, Sorokin, Zhmurova, Herrero, Landa-Canovas, Rojas.     

Crystal structure (Pb4.8Na1.2)[Si8(Si1.2B0.8)O25] with a new double tetrahedral layer and its comparison with hyttsjoeite, barisilite, benitoite, and langasite

A new lead-sodium borosilicate (Pb_4.8Na_1.2)[Si₈(Si_1.2B_0.8)O₂₅] (a = 9.5752 and c = 42.565 ?; space group R $ \bar 3 $ \bar 3 c) is synthesized under hydrothermal conditions, and its crystal structure is determined without preliminary knowledge of the chemical formula. The anionic radical of a new type is a double layer in which one of the three independent Si-tetrahedra contains an isomorphous boron admixture. Its topological relationship with the radicals in the structures of benitoite and langasite, as well as in the structures of lead silicates barisilite and hyttsjoeite, is found based on the block consisting of an octahedron and six tetrahedra. This allows one to consider that the new layer is derived from the hyttsjoeite layer by the replacement of the octahedron with two tetrahedra and the increase of the silicon fraction. Although lead atoms are located between the layers in the intersheet space, they form relatively strong bonds with silicon-oxygen layers. This structural type is a collector of heavy metals.     

Synthesis and X-ray structural investigation of K2(H5O2)[UO2(C2O4)2(HSeO3)]

The synthesis and X-ray diffraction analysis of K₂(H₅O₂)[UO₂(C₂O₄)₂(HSeO₃)] single crystals have been performed. This compound crystallizes in the triclinic system with the unit-cell parameters a = 6.7665(4) ?, b = 8.8850(4) ?, c = 12.3147(7) ?, α = 94.73°, β = 90.16°, γ = 92.11°, sp. gr. P[`1]P\bar 1, Z = 2, and R = 0.019. The basic structural units are island [UO₂(C₂O₄)₂(HSeO₃)]³⁻ groups, which belong to the AB ₂⁰¹ M ¹ crystallochemical group of uranyl complexes (A = UO₂²⁺, B ⁰¹ = C₂O₄²⁻, and M ₁ = HSeO₃⁻). Uraniumcontaining complexes are linked through K⁺ and H₅O₂⁺ ions and via a system of hydrogen bonds with the participation of oxonium hydrogen atoms in this structure.     

Investigation of the structural conditionality for changes in physical properties of K<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript> crystals

With the aim of elucidating the nature of anomalies in the physical properties of K₃H(SO₄)₂ crystals that arise as the temperature grows, the dielectric and optical properties of the crystals are studied, an X-ray diffraction analysis of single-crystal and polycrystalline specimens are performed, and the morphology and chemical composition are studied by scanning electron microscopy and energy-dispersive X-ray spectroscopy. As a result of the studies performed, a phase transition from the phase with the monoclinic symmetry (space group C2/c) to the phase with the trigonal symmetry (space group R $ \bar 3 $ \bar 3 m) is found in a number of K₃H(SO₄)₂ specimens at a temperature of ≈457 K, the responsibility of the dynamically disordered hydrogen-bond system for the rise of high proton conductivity in the high-temperature phases of the crystals of this family is confirmed, and data on the solid-phase reactions proceeding at high temperatures are obtained.     

Effect of high-energy electron irradiation in an electron microscope column on fluorides of alkaline earth elements (CaF2, SrF2, and BaF2)

The effect of high-energy (150 eV) electron irradiation in an electron microscope column on crystals of fluorides of alkaline earth elements CaF₂, SrF₂, and BaF₂ is studied. During structural investigations by electron diffraction and electron microscopy, the electron irradiation causes chemical changes in MF₂ crystals such as the desorption of fluorine and the accumulation of oxygen in the irradiated area with the formation of oxide MO. The fluorine desorption rate increases significantly when the electron-beam density exceeds the threshold value of ∼2 × 10³ pA/cm²). In BaF₂ samples, the transformation of BaO into Ba(OH)₂ was observed when irradiation stopped. The renewal of irradiation is accompanied by the inverse transformation of Ba(OH)₂ into BaO. In the initial stage of irradiation of all MF₂ compounds, the oxide phase is in the single-crystal state with a lattice highly matched with the MF₂ matrix. When the irradiation dose is increased, the oxide phase passes to the polycrystalline phase. Gaseous products of MF₂ destruction (in the form of bubbles several nanometers in diameter) form a rectangular array with a period of ∼20 nm in the sample.     

Mechanochemical synthesis of nonstoichiometric nanocrystals La1 ? yCayF3 ? y with a tysonite structure and nanoceramic materials from CaF2 and LaF3 crystals

The nonstoichiometric phases La_{1 − y} Ca _y F_{3 − y} (y = 0.15, 0.20) with a tysonite (LaF₃) structure have been prepared for the first time by the mechanochemical synthesis from CaF₂ and LaF₃ crystals. The average size of coherent scattering regions is approximately equal to 10–30 nm. It has been shown that the compositions of the phases prepared by the mechanochemical synthesis are inconsistent with the phase diagram of the CaF₂-LaF₃ system. The “mechanohydrolysis” of the La_{1 − y} Ca _y F_{3 − y} phase has been observed for the first time. Under these conditions, the La_{1 − y} Ca _y F_{3 − y} phase partially transforms into lanthanum calcium oxyfluoride for a milling time of 180 min with intermediate sampling. The La_{1 − y} Ca _y F_{3 − y} nanoceramic materials have been prepared from a powder of the mechanochemical synthesis product by pressing under a pressure of (2–6) × 10⁸ Pa at room temperature. The electrical conductivity of the synthesized materials at a temperature of 200°C is equal to 4.9(6) × 10⁻⁴ S/cm, and the activation energy of electrical conduction is 0.46(2) eV. These data for the nanoceramic materials coincide with those obtained for migration of fluorine vacancies in single-crystal tysonite fluoride materials. Original Russian Text ? B.P. Sobolev, I.A. Sviridov, V.I. Fadeeva, S.N. Sul’yanov, N.I. Sorokin, Z.I. Zhmurova, I.I. Khodos, A.S. Avilov, M.A. Zaporozhets, 2008, published in Kristallografiya, 2008, Vol. 53, No. 5, pp. 919–929.     

Synthesis and crystal structure of (NH4)3[UO2(CH3COO)3]2[UO2(CH3COO)(NCS)2(H2O)]

Single crystals of the compound (NH₄)₃[UO₂(CH₃COO)₃]₂[UO₂(CH₃COO)(NCS)₂(H₂O)] (I) are synthesized, and their structure is investigated using X-ray diffraction. Compound I crystallizes in the monoclinic system with the unit cell parameters a = 18.3414(6) ?, b = 16.3858(7) ?, c = 12.4183(5) ?, β = 92.992(1)°, space group C2/c, Z = 4, V = 3727.1(3) ?³, and R = 0.0253. The uranium-containing structural units of crystals I are mononuclear complexes of two types with an island structure, i.e., the [UO₂(CH₃COO)₃]⁻ anionic complexes belonging to the crystal-chemical group (AB ₃⁰¹ = UO₂²⁺, B ⁰¹ = CH₃COO⁻) of the uranyl complexes and the [UO₂(CH₃COO)(NCS)₂(H₂O)]⁻ anionic complexes belonging to the crystal-chemical group AB ⁰¹M₃¹ (A = UO₂²⁺, B ⁰¹ = CH₃COO⁻, M ¹ = NCS⁻ or H₂O).     

Nanostructured crystals of Sr1?xRxF2+x fluorite phases and their ordering: 6. Microindentation analysis of crystals

Hardness, crack resistance, brittleness, and effective fracture energy have been studied for crystals of 24 fluorite phases Sr_{1 − x} R _x F_{2 + x} (R are 14 rare earth elements (REEs); 0 < x ≤ 0.5) and SrF2 grown by the Bridgman method from a melt. These characteristics change nonlinearly with an increase in the REE content for Sr_{1 − x} R _x F_{2 + x} (0 < x ≤ 0.5) with R = La, Nd, Sm, Gd, and Lu; it is maximum in the range x < 0.1 for all REEs. The changes in a number of REEs have been traced for an isoconcentration series of Sr_0.90 R _0.10F_2.10 crystals (R = La, Nd, Sm, Gd, Ho, Er-Lu, or Y) and crystals (similar in composition) with R = Tb and Dy. The hardness of Sr_{1 − x} R _x F_{2 + x} crystals is higher by a factor of ∼2–3 than that of SrF2. The effect of decrease in microstresses in SrF₂ crystals is confirmed by the isomorphic introduction of R ³⁺ ions into this crystalline matrix.     

Growth and defect structure of CdF2 and nonstoichiometric Cd1?xRxF2 + x phases (R = rare earth elements and In). I. Growth of Cd1?xRxF2 + x single crystals (R = La-Lu, Y)

This article begins a series of publications on growth of single crystals of nonstoichiometric Cd_{1− x} R _x F_{2 + x} phases (R = La-Lu, Y, In) with the defect CaF₂-type structure, their crystal structures, and some properties. The present article is dedicated to the phase diagrams of the CdF₂-RF₃ systems in the region of Cd_1−x R _x F_{2 + x} formation. Their analysis shows that it is possible to synthesize homogeneous Cd_0.9 R _0.1F_2.1 crystals. The dependence of the defect structure of the crystals on the type and concentration of rare earth elements is studied on specially grown Cd_0.9 R _0.1F_2.1 (R = La-Lu) and Cd_1−x Y_xF_{2 + x} (x = 0.1, 0.15, 0.20) crystals. It is shown that, despite the fact that all the Cd_0.9 R _0.1F_2.1 crystals melted congruently, irrespectively of the rare earth elements used, they were rather homogeneous. The chemical compositions of the Cd_1−x R _x F_{2 + x} phases (R = Sm, Gd, Tb, Ho, and Lu) determined by the method of inductively coupled plasma atomic emission spectroscopy (ICP-AES) turned out to be close to Cd_0.9 R _0.1F_2.1. __________ Translated from Kristallografiya, Vol. 49, No. 3, 2004, pp. 566–574. Original Russian Text Copyright ? 2004 by Buchinskaya, Ryzhova, Marychev, Sobolev.     

Resonant diffraction of synchrotron radiation in rubidium dihydrophosphate crystals

Purely resonant Bragg reflections 006, 5$ \bar 5 $ \bar 5 0, and 666 in a rubidium dihydrophosphate (RbH₂PO₄) crystal at the K edge of rubidium have been experimentally and theoretically investigated. These reflections remain forbidden when the resonant dipole-dipole (E1E1) contribution to the resonant atomic factor is taken into account; they may be due to the dipole-quadrupole (E1E2) transitions as well as to the anisotropy atomic factor, which is caused by thermal atomic displacements (thermally induced contribution) and/or local jumps of hydrogen atoms. A numerical simulation showed that, at room temperature (experimental conditions), the thermally induced contribution to the “forbidden” reflections is dominant.