Magnetic susceptibility of sodium rare-earth fluorites Na0.5 − x R 0.5 + x F2 + 2x (R = Dy, Ho, Er, Tm, Yb) and some ordered phases

Magnetic properties of the nonstoichiometric phases with the fluorite-type “defect” structure Na_0.4 R _0.6F_2.2 (R = Ho, Er, Tm, Yb) and Na_0.35Dy_0.65F_2.3 have been studied as well as some ordered phases with different distortions of the initial fluorite lattice (NaHo₂F₇, Na₇Tm₁₃F₄₆, NaYb₂F₇, and Na₇Yb₁₃F₄₆) and Na_1.5Dy_1.5F₆ with the gagarinite-type structure (NaCaYF₆). Magnetic susceptibility χ was measured with the aid of the Faraday balance in the temperature range from 20 to 300 K. The crystals with R= Dy, Ho, Er, Tm are paramagnetic; their temperature dependence χ is described by the Curie-Weiss law. It is shown that in the temperature range studied, magnetic susceptibility does not depend on the degree of order of Dy, Ho, Er, and Tm ions in the structure. Below 80 K, the temperature dependence of magnetic susceptibility of the the Yb³⁺-containing phases differs from the analogous dependence χ of an ideal paramagnetic crystal, which is assumed to be caused by the interaction of the crystalline field with Yb³⁺ ions.     

Crystal electric field in RAgSb2 (R = Ho, Er, Tm) intermetallic compounds

The magnetic scattering spectra of RAgSb₂ (R = Ho, Er, Tm) intermetallic compounds are measured and their crystal electric field parameters are determined using inelastic neutron scattering. It is revealed that the ground state is a nonmagnetic singlet for the HoAgSb₂ compound, a Kramers doublet with a strongly anisotropic g factor for the ErAgSb₂ compound, and a quasi-doublet (random doublet) characterized by an extremely anisotropic g factor for the TmAgSb₂ compound. The exchange interaction is estimated in the molecular field approximation. The magnetic properties of the RAgSb₂ compounds are analyzed in terms of the energy level schemes and eigenfunctions determined in this study. The calculated anisotropic magnetic susceptibilities for all compounds are in good agreement with the experimental data obtained for single crystals.     

Growth of R 1 − y Sr y F3 − y crystals with rare earth elements of the cerium subgroup (R = La, Ce, Pr, or Nd; 0 ≤ y ≤ 0.16) and the dependence of their density and optical characteristics on composition

Crystals of the R _{1 ? y} Sr _y F_{3 ? y} phases (R = La, Ce, Pr, or Nd; 0 ≤ y ≤ 0.16) with tysonite (LaF₃) structure are grown by the Bridgman method. A linear dependence of the crystal density on the SrF₂ concentration has been revealed for each series of solid solutions. A scheme of heterovalent isomorphous substitution in the tysonite structure, R ³⁺ + F^1? → M ²⁺ + V _F, with compensation of the difference in the cation charges due to the formation of anion vacancies, is confirmed experimentally. The optical transmission spectra are measured in the wavelength range λ = 2.18–22.22 μm. It is shown that the 50%-transmission edge in the IR range is 10.5 μm for all crystals. The refractive index and the polarizability of crystals decrease with decreasing SrF₂ content according to a linear law. The melting curves of the R _{1 ? y} Sr _y F_{3 ? y} phases studied have a maximum; therefore, these phases can be recommended for use as crystals with a high homogeneity and different optical properties in comparison with the corresponding RF₃ crystals.     

Dielectric and pyroelectric studies of an antiferroelectric liquid crystal

Polymorphism and polar properties of an antiferroelectric (R)-2-methylheptyloxycarbonylphenyl-4-[(4-decyloxy-3-fluoro)benzoyloxy]benzoate liquid crystal are studied. The phases are identified, and the phase transition points are determined. Dielectric constant, dielectric losses, and pyroelectric properties are studied for the orthogonal smectic SmA and tilted smectic, SmC _α ^* , SmC ^*, SmC _γ ^* , and SmC _A ^* phases. The temperature dependence of spontaneous polarization is measured by the repolarization current technique and integration of the pyroelectric constant.     

Synthesis,Crystal Structure,and Topology–Symmetry Analysis of a New Modification of NaIn[IO<Subscript>3</Subscript>]<Subscript>4</Subscript>

Crystals of new iodate NaIn[IO₃]₄ were prepared by the hydrothermal synthesis. The unit cell parameters are a = 7.2672(2) Å, b = 15.2572(6) Å, c = 15.0208(6) Å, β = 101.517(3)°, sp. gr. P2₁/c. The formula was determined during the structure determination and refinement of a twinned crystal based on a set of reflections from the atomic planes of the major individual. The refinement with anisotropic displacement parameters was performed for both twin components to the final R factor of 0.050. The In and Na atoms are in octahedral coordination formed by oxygen atoms. The oxygen octahedra are arranged into columns by sharing edges, and the columns are connected by isolated umbrella-like [IO₃]^– groups to form layers. The new structure is most similar to the isoformular iodate NaIn[IO₃]₄, which crystallizes in the same sp. gr. P2₁/c and is structurally similar, but has a twice smaller unit cell and is characterized by another direction of the monoclinic axis. The structural similarity and difference between the two phases were studied by topologysymmetry analysis. The formation of these phases is related to different combinations of identical one-dimensional infinite chains of octahedra.     

Structural features of compounds of the sillenite family

It is shown that the real composition and structure of phases belonging to the sillenite family can be determined using a complex of techniques (diffraction methods, vibrational and X-ray absorption spectroscopy, and electron probe X-ray microanalysis) with a subsequent crystal-chemical analysis of the data. Refined compositions are presented for phases of nominal composition Bi₂₄ M ₂O₄₀ with M = Zn²⁺, Al³⁺, Ga³⁺, Fe³⁺, Si⁴⁺, Ti⁴⁺, Mn⁴⁺, and P⁵⁺, which demonstrate types and concentrations of point defects as functions of the M type.     

Identification of nematic lymoesophases with discotic and cylindrical micelles in lyotropic amphiphilic systems

Nematic lyomesophases with discotic (N _D) and cylindrical (N _C) micelles in complex multicomponent lyotropic systems based on alkyltrimethylammonium bromide detergents have been identified by the ¹H-²H-, and ¹³C-NMR methods and polarizationoptical microscopy. The difference in the structures of the N _D and N _C nematic phases is especially pronounced in the ¹³C-NMR spectra. Addition of chiral dopants to the lyomixture facilitates formation of the Ch _D and Ch _C cholesteric phases. According to the ¹³C-NMR spectra, the micellar mobility in the cholesteric lyomesophases decreases in comparison with the nematic ones. The alignment of lyocholesterics under the action of an external magnetic field is found.     

Structural aspects of the giant oxygen isotope effect in perovskite manganese oxides

The structure of manganites R _1?x A _x MnO₃ (R = La, Sm, or a mixture of rare earth cations; A = Ca, Sr; x = 0.3, 0.5) has been studied by neutron diffraction to find out the reasons for the giant oxygen isotope effect—the transition from a low-temperature metallic state to an insulating state as a result of replacement of ¹⁶O with ¹⁸O. It is shown that this effect is observed in compositions in which the two phases P1 and P2 coexist at low temperatures. They have the same crystal symmetry (sp. gr. Pnma) but different types of Jahn-Teller distortions of oxygen octahedra and different magnetic structure. Phase P1 has a conductivity of the metallic type, weakly distorted MnO₆ octahedra, and a ferromagnetic structure. Phase P2 is insulating, with MnO₆ octahedra extended or compressed in the apical direction and the moments of Mn ions forming an antiferromagnetic structure. The relative volume of phases P1 and P2 in samples depends on the average radius of the A cation and changes occurring upon replacement of ¹⁶O with ¹⁸O. The percolation transition from the metallic to insulating state upon substitution of ¹⁶O with ¹⁸O is caused by the sharp decrease in the volume of the ferromagnetic metallic phase in favor of the insulating antiferromagnetic phase. An effect of the sample microstructure on the formation of the two-phase state is found.     

Study of microdefects in GaAs:Si single crystals grown by the vertical gradient freeze method

Microdefects in Si-doped GaAs single crystals grown by the vertical gradient freeze method have been studied with X-ray diffuse scattering. In the case of doping to majority carrier concentrations n ～ 1 × 10¹⁸ cm^?3, large microdefects with positive dilatation that accompany the initial stage of arsenic precipitation at high temperatures were observed. It is shown that GaAs samples heavily doped with silicon (n ～ 3 × 10¹⁸ cm^?3) contain large (several micrometers) interstitial microdefects, which can play the role of nucleation regions for new SiAs and SiAs₂ phases.     

Lamellar polymorphism in multicomponent lyotropic amphiphilic systems based on alkyltrimethylammonium bromide detergents

Lamellar polymorphism in multicomponent lyotropic systems based on alkyltrimethylammonium bromide detergents has been studied by polarization microscopy and ¹H-, ²H-, and ¹³C-NMR spectroscopy. The L _α1, L _α1?h , and L _αh lamellar phases are revealed, identified, and characterized. The alignment of the L _α1?h lamellar phase in high magnetic fields is established.     

Nonstoichiometry in inorganic fluorides: I. Nonstoichiometry in MF m -RF n (m < n ≤ 4) systems

The manifestation of gross nonstoichiometry in MF _m -RF _n systems (m < n ?? 4) has been studied. Fluorides of 34 elements, in the systems of which phases of practical interest are formed, are chosen. To search for new phases of complex composition, a program for studying the phase diagrams of the condensed state (??200 systems) has been carried out at the Institute of Crystallography, Russian Academy of Sciences. The main products of high-temperature interactions of the fluorides of elements with different valences (m ?? n) are grossly nonstoichiometric phases of two structural types: fluorite (CaF₂) and tysonite (LaF₃). Systems of fluorides of 27 elements (M ¹⁺ = Na, K; M ²⁺ = Ca, Sr, Ba, Cd, Pb; R ³⁺ = Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; R ⁴⁺ = Zr, Hf, Th, U) are selected; nonstoichiometric M _{1 ? x} R _x F _{m(1 ? x) + nx} phases, which are of greatest practical interest, are formed in these systems. The gross nonstoichiometry in inorganic fluorides is most pronounced in 80 MF₂ ? RF₃ systems (M = Ca, Sr, Ba, Cd, Pb; R are rare earth elements). The problems related to the growth of single crystals of nonstoichiometric phases and basic fields of their application as new fluoride multicomponent materials, the properties of which are controlled by the defect structure, are considered.     

Magnetic, magnetocaloric, and lattice properties of the La(Fe x Si1 − x )13 ferromagnets

The magnetic and lattice properties of a sample of La(Fe_0.86Si_0.14)₁₃ ferromagnet have been measured. The influence that neutron irradiation has on the physical properties of this ferromagnet is studied. It is shown that the irradiation of this sample by a fluence of 3 × 10¹⁹ n/cm² increases the lattice constant a and the Curie temperature (T _C ) as the volume magnetostriction decreases. A model of ferromagnet is proposed which satisfactorily describes the dependence a(T) of the initial and irradiated samples and their magnetic properties. The temperature dependence of the change in entropy when switching the magnetic field on and off is calculated. It is established that the change in both the magnetic and lattice parts of the total entropy at the magnetic phase transition must be taken into account for La(Fe _x Si_{1 ? x} )₁₃ compounds.     

Spectroscopic and Transport Properties of (NH4)2CuCl4 · 2 H2O Single Crystal

Electron paramagnetic resonance (EPR), Optical absorption and Transport properties of (NH₄)₂CuCl₄ 2 H₂O single crystals have been studied. An anisotropic g tensor was observed with gl = 2.241 and g∥ = 2.081 by EPR method. The spin orbit coupling constant is found to be 540 cm⁻¹. The optical absorption in UV region are characterized by charge transfer band, in the visible and near infrared region at 13,333, 4,480, 4,336, and 3,998 cm⁻¹ attributed to the transitions between the (d-d) stark energy levels of the copper (II) ion in an extended octahedral crystal field. Dc electrical conductivity measurements with temperature reveal an anisotropic characteristic of a two-dimensional layered structure, and exhibits two first order structural phase transitions at about 383 K and 413 K. These transitions are attributed to loss of the two water inolecules of hydration and free rotation of NH⁺₄ ion from a state of torsional oscillation.     

Structural and magnetic phase transformations in La<Subscript>0.88</Subscript>MnO<Subscript>3 − <Emphasis Type="Italic">x</Emphasis></Subscript> crystals

The crystal structure and elastic, magnetic, and transport properties of the La_0.88MnO_{3 ? x} system are studied. It is established that, depending on the oxygen content at x > 0.13, the system is orbitally ordered by the LaMnO₃ type and consists of a mixture of orbitally ordered and disordered orthorhombic phases (0.11 ≤ x ≤ 0.13); at x < 0.11, the system is monoclinically distorted. The orbitally ordered samples show properties inherent in both antiferro-and ferromagnetics, whereas the orbitally disordered samples are ferromagnetics and possess extremely high magnetic resistance. Analysis of the structure and properties of the samples showed that no oxygen vacancies are formed in the La_0.88MnO_{3 ? x} system. It is assumed that the excessive Mn³⁺ is incorporated into interstitials in the vicinity of lanthanum vacancies.     

Piezoelectricity in crystallizing ferroelectric polymers: Poly(vinylidene fluoride) and its copolymers (A review)

The piezoelectricity observed in poly(vinylidene fluoride) (PVDF) and its copolymers involves three components that are associated with the presence of at least two phases (crystalline and amorphous) in the polymer structure. The main contributions to the phenomenon observed are made by the size effect and electrostriction, which are related to each other. These contributions manifest themselves through the mechanism of strain-induced reversible transformations of a number of domains of the anisotropic amorphous phase into the crystalline state under the action of mechanical or electrical fields. With due regard for different packings of chains in the amorphous and crystalline phases, this mechanism accounts for the large Poisson ratios μ₃₁ obtained for textured films of flexible-chain crystallizing polymers. The dependence of the piezoelectric coefficient d ₃₂ on the static stress in textured films is governed by the change in the fraction of the crystalline phase due to strong anisotropy of the elastic constants in the film plane. It is shown that the shear deformations of polymers are characterized by a strong piezoelectric response. The specific features revealed in the piezoelectric effect under bending deformations are described for films with an inhomogeneous distribution of polarization over the cross section. The general regularities of the electrostriction in the polymers and inorganic relaxor ferroelectrics studied are considered.     

Trap-limited diffusion of hydrogen in precursor derived amorphous Si–B–C–N-ceramics

The tracer diffusion of hydrogen is studied in precursor derived amorphous Si–C–N and Si–B–C–N ceramics using deuterium as a tracer and secondary ion mass spectrometry (SIMS). Since the amorphous ceramics are separated in carbon rich phases (amorphous carbon and amorphous C(BN)_x, respectively) and silicon rich phases (amorphous Si₃N₄ and amorphous Si_3+(1/4)xC_xN_4−x, respectively) we additionally measured the diffusivities of hydrogen in amorphous carbon, in amorphous SiC and in amorphous C–B–N films. The silicon rich phases are identified as diffusion paths for hydrogen in the precursor derived ceramics. Diffusion of hydrogen in these materials is explained with a trap limited diffusion mechanism with a single trap level. We found activation enthalpies of about 2 eV for the precursor derived ceramics, where the activation enthalpy is the sum of a migration enthalpy and a binding enthalpy. The low values for the pre-exponential factors of less than 10⁻⁷ m²/s can be explained with an appropriate expression for the entropy factor.     

Dielectric Anisotropy and the Order Parameter of HXBBA

Abstract

Measurements of dielectric anisotropy (Δ?), refractive indices (n _e , n _o), birefringence (Δn) and density (ρ) have been made in the nematic and smectic phases of N(-p-hexyloxybenzylidene)-p-butylaniline (HXBBA). The results indicate that the various transitions are of the first order type except smectic B-smectic G, which may be a second order transition. The order parameter S has been determined using the isotropic internal field model (Vuks approach) and the anisotropic internal field model (Neugebauer's approach) and both the values agree fairly well. The dielectric anisotropy (Δ?) increases strongly in the smectic phases whle S increases only slowly. It is interpreted by an increase of dipole-dipole correlations.     

Displacements in the cationic motif of nonstoichiometric fluorite phases Ba1 − x R x F2 + x as a result of the formation of {Ba8[R 6F68–69]} clusters: I. The Ba0.78Tm0.22F2.22 crystals

The displacements of Ba²⁺ cations in the cationic motif of Ba_0.78Tm_0.22F_2.22 crystals, which are representatives of nonstoichiometric fluorite phases Ba_{1 ? x} R _x F_{2 + x} , are proved for the first time with the use of precision investigations of the fine atomic structure. It is shown that the cation displacements, like the previously revealed displacements in the anionic motif, reflect the formation of {Ba₈[R ₆F_68–69]} superclusters of structural defects with nanometer linear sizes. The Ba ²⁺ cations are displaced from the fluorite crystallographic positions 4a (space group Fm $ \bar 3 The displacements of Ba²⁺ cations in the cationic motif of Ba_0.78Tm_0.22F_2.22 crystals, which are representatives of nonstoichiometric fluorite phases Ba_{1 − x} R _x F_{2 + x} , are proved for the first time with the use of precision investigations of the fine atomic structure. It is shown that the cation displacements, like the previously revealed displacements in the anionic motif, reflect the formation of {Ba₈[R ₆F_68–69]} superclusters of structural defects with nanometer linear sizes. The Ba ²⁺ cations are displaced from the fluorite crystallographic positions 4a (space group Fm m) to the positions 32f. The static nature of the cation displacements is confirmed by the fact that these displacements are retained at a temperature of 110 K. The correctness of the interpretation of the correlation between the cation displacements and the formation of superclusters of structural defects is supported by the coincidence of the intercationic distances determined in the disordered phase Ba_0.78Tm_0.22F_2.22 with those found in the previously studied ordered phases Ba₄ R ₃F₁₇ (R = Y, Yb). The model with splitting of cationic positions is appropriate for testing in structural investigations of crystals of the fluorite phases M _{1 − x} R _x F_{2 + x} at room temperature. Original Russian Text ? A.M. Golubev, L.P. Otroshchenko, V.N. Molchanov, B.P. Sobolev, 2008, published in Kristallografiya, 2008, Vol. 53, No. 6, pp. 1023–1030.     

Ordering of calcium and vacancies in calcium catapleiite CaZr[Si<Subscript>3</Subscript>O<Subscript>9</Subscript>] • 2H<Subscript>2</Subscript>O

A sample of holotypic calcium catapleiite from the Burpala alkaline massif (Northern Baikal, Russia) is studied by single crystal X-ray analysis at 120 K and IR spectroscopy. The empirical formula of calcium catapleiite is Ca_0.97Na_0.02Zr_1.01Si₃O₉ ? 2H₂O (Z = 4). The X-ray diffraction study confirms the orthorhombic unit cell with the following parameters: a = 7.406(1), b = 12.687(1), and c = 10.112(1) Å; V = 950.1(2) ų; space group Pbnn. The crystal structure is refined in the anisotropic approximation of atomic displacement parameters using 1177 reflections with I > 2σ(I) to the final R = 2.91%. The structure of calcium catapleiite under study is based on the microporous heteropolyhedral framework formed by ZrO₆ octahedra and threemembered silicon–oxygen rings [Si₃O₉]. It is on the whole analogous to the structures of the samples studied earlier, but differs from them by a high degree of ordering of calcium and vacancies at extraframework positions. The distribution of calcium over Ca1 and Ca2 positions in the calcium catapleiite structure leads to the formation of zigzag chains of the …Сa1–Zr–Ca1–Zr… and …Сa2–h–Ca2–□… types. Low occupancy of the Ca2 position and its alternation with the vacancy are prerequisites for potential Ca²⁺ cationic conduction.     

State of Fe3+ ion and Fe3+ −F− interaction in calcium fluorosilicate glasses

The state of Fe³⁺ ions and Fe³⁺ ?F^? interaction in calcium fluorosilicate glasses xCaF₂·(1- x)CaO·SiO₂) (0 ≤ x ≤ 0.3) containing a small amount of iron were investigated by ESR spectroscopy. Two resonances observed near g = 2.0 and g = 4.3 were assigned to dipole-dipole interacted Fe³⁺ ions and Fe³⁺ ions in a rhombic crystal field, respectively. The fraction of Fe³⁺ ions in a rhombic crystal field decreased and that of dipole-dipole interacted Fe³⁺ ions increased with increasing Fe₂O₃ content. It was found that the quantity of dipole-dipole interacted Fe³⁺ ions depends on the negative partial charge of fluorine ions and shows a maximum at 10 mol% CaF₂ (x = 0.2). The maximum is attributed to the largest difference between absolute values of the ionic potentials of ferric and fluorine ions which is caused by the smallest negative partial charge of flourine at 10 mol% CaF₂.