Disorder-order phase transformations and electrical resistivity of nonstoichiometric titanium carbide

Phase transformations of the disorder-order type in the homogeneity region of nonstoichiometric titanium carbide TiC_y (0.5<y<1.0) have been studied. It has been established that, depending on the actual composition of TiC_y, there may form in it for T<980–1000 K a cubic or a trigonal ordered Ti₂C phase (space groups Fd3m and , respectively) and a rhombic ordered Ti₃C₂ phase (space group C222₁). The effect of ordering on the electrical resistivity of the nonstoichiometric carbide TiC_y was studied, and the temperatures of the reversible disorder-order equilibrium transitions determined. The ordering in titanium carbide is shown to be a first-order phase transition. Fiz. Tverd. Tela (St. Petersburg) 40, 1332–1340 (July 1998)     

Effect of ordering on the structure and specific heat of nonstoichiometric titanium carbide

The experimental results on the change in the crystal structure and specific heat of nonstoichiometric titanium carbide TiC_y (0.5<y<0.65) near disorder-order phase transitions are reported. It is established that at temperatures below 1000 K the ordered phases Ti₂C with cubic and trigonal symmetry and an orthorhombic ordered phase Ti₃C₂ form in titanium carbide by a close-to-first-order phase transition mechanism. The temperatures and heats of order-disorder phase transformations are determined. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 9, 631–637 (10 May 1999)     

Effect of nonstoichiometry and ordering on the period of the basis structure of cubic titanium carbide

We have examined the influence of nonstoichiometry and order-disorder phase transformations on the basis period (of type B1) of the structure of titanium carbide TiC_y (0.5<y<1.0). We found that ordering of titanium carbide TiC_y with formation of superstructures of the type Ti Ti₂C and Ti₃C₂ leads to growth of the period of the basis crystal lattice in comparison with the disordered carbide. Taking the change in the lattice period into account, we discuss the question of the directions of the static displacements of atoms near a vacancy. Fiz. Tverd. Tela (St. Petersburg) 41, 1134–1141 (July 1999)     

The influence of a metalloid on ordered structure in titanium carbide

X-ray and neutron diffraction were used to investigate the effect of oxygen and nitrogen atoms on the formation of the intermediate δ′-cubic (sp. gr. Fd3m) and δ″-tetragonal (sp. gr. P3₁21) ordered structures in titanium carbide. In TiC_0.545O_0.08, TiC_0.545N_0.09 samples that were investigated, the metal atoms were shifted from ideal positions in the direction from vacancies to metalloid atoms. In the intermediate cubic phase (δ′), the free-parameter values of titanium atoms in the two samples are the same, but are different from their analogous value in titanium carbide. Fiz. Tverd. Tela (St. Petersburg) 39, 2207–2209 (December 1997)     

Dependence of the superconducting transition parameters on the solid-solution composition and Te excess in Sn1−z PbzTe:In

A low-temperature (0.4–4.2 K) measurement of the temperature dependences of the resistivity of two series of samples, SnTe_1+y and Sn_0.8Pb_0.2Te_1+y solid solution, doped with 5 at.% In, is reported. The parameters of the superconducting transition, namely, the critical temperatures T _c and the second critical magnetic field H _c2, and their dependences on tellurium excess (0⩽y⩽0.06) have been determined. The observed variation of the critical parameters with increasing tellurium excess in the samples is associated with a change in the filling by holes of the indium-impurity resonance states. Fiz. Tverd. Tela (St. Petersburg) 41, 2132–2134 (December 1999)     

Electron transport in Chevrel phase superconductors,Cu1.8Mo6S8−y Se y , 0⩽y⩽8 and Cu1.8Mo6S8−y Te y , 0⩽y⩽4—Fit to Cote-Meisel theory

Normal state electrical resistivity of the Chevrel phase compounds of the type Cu_1.8Mo₆S_8−y Se _y , 0⩽y⩽8 and Cu_1.8Mo₆S_8−y Te _y , 0⩽y⩽4 is analysed on the basis of the generalized diffraction model which incorporates a postulate on electron-phonon interaction,viz phonons with wavelength exceeding the electron mean-free path are ineffective electron scatterers. Fit obtained by this model was found to be superior to other models based on the interbands-d scattering of electrons.     

Order-disorder phase transformations and specific heat of nonstoichiometric vanadium carbide

AbstractA study has been made of the order-disorder phase transformations in the homogeneity region of the VC_y nonstoichiometric cubic vanadium carbide (0.66<y<0.88). It has been established that an ordered V₆C₅ phase with monoclinic (space group C2/m) or trigonal (P3₁) symmetry, and a cubic (space group P4₃32) ordered V₈C₇ phase can form in the VC_y carbide below 1450 K, depending on the actual composition. The effect of off-stoichiometry and structural vacancy ordering on the specific heat of the VC_y carbide has been investigated. The temperatures and heats of the reversible order-disorder equilibrium transitions have been determined. The ordering in the VC_y carbide is shown to be a first-order phase transition. An equilibrium diagram of the V-C system taking into account ordering in the nonstoichiometric vanadium carbide has been constructed. Fiz. Tverd. Tela (St. Petersburg) 41, 529–536 (March 1999)     

Effect of constant-energy surface anisotropy on the thermoelectric figure-of-merit of the n-Bi2 (Te,Se,S)3 solid solutions

A study is reported of the thermoelectric and galvanomagnetic properties of n-Bi₂Te_3−x−y Se_xSe_y solid solutions for 0.12⩽x⩽0.36 and 0.12⩽y⩽0.21 within the 80–300 K temperature region. The thermoelectric figure-of-merit Z has been found to correlate with the parameters of the many-valley energy-band model including anisotropic carrier scattering. It is shown that a decrease in the constant-energy surface anisotropy and scattering anisotropy results in a growth of Z for optimum carrier concentrations in the solid solution. Fiz. Tverd. Tela (St. Petersburg) 41, 187–192 (February 1999)     

Identification of structural vacancies in carbides,oxides, and sulfides by Doppler broadening of the gamma-ray line

A method has been developed to identify the sublattices of a crystal structure in which there are atomic vacancies. This method is based on determining the chemical environment of vacancies and is implemented using the method of the positron annihilation by measuring the momentum distribution of core electrons. To determine the characteristic momentum distribution of electrons, a special two-detector spectroscopy is used, which ensures measurements of Doppler broadening of the annihilation gamma-ray line with a high (up to 10⁶) signal-to-noise ratio. To test the method, vacancies in irradiated silicon carbide (6H-SiC), sintered nonstoichiometric titanium carbides (TiC _y ) and titanium monoxides (TiO _y ), and chemically deposited lead and cadmium sulfides (PbS and CdS) have been identified. Vacancies in the carbon and silicon sublattices have been identified in silicon carbide after irradiation by low- and high-energy electrons, respectively. Vacancies in the nonmetal sublattice have been identified in TiC _y . Vacancies in the metal sublattice have been identified in TiC _y , as well as in PbS and CdS.     

Direct observation of phase separation in La1−x CaxMnO3

In a study of the infrared optical absorption spectra of polycrystalline La_1−x Ca_xMnO₃ (0.1⩽x⩽0.8), a contribution from free charge carriers is observed below the Curie temperature for compositions with x⩽0.4. The existence of this contribution for samples with a high resistivity is a direct proof of the existence of “metallic” drops in an insulating matrix. The relative volume of the “metallic” phase is estimated. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 1, 89–92 (10 July 1998)     

Synthesis of nanocrystalline multiphase titanium oxycarbide (TiC<Subscript>x</Subscript>O<Subscript>y</Subscript>) thin films by UNU/ICTP and NX2 plasma focus devices

Nanocrystalline multiphase titanium oxycarbide (TiC_xO_y) thin films composed of TiC₂, TiO_0.325, Ti₂O₃ and graphitic carbon have been deposited on titanium substrates, using energetic carbon ions delivered by the UNU/ICTP and the NX2 plasma focus devices operated at different repetition rates. X-ray diffraction (XRD) patterns of the nanocomposite films reveal the relative transformation of various oxide and carbide phases accompanied by the suppression of the TiC₂ phase when the energy flux of the ion beam and the repetition rate are increased. A field emission scanning electron microscope (FESEM) with an energy dispersive X-ray spectroscopy (EDS) attachment reveals a non-porous microcrack-free nanocrystalline granular surface morphology of the composite films with uniform carbon distribution. X-ray photoelectron spectroscopy (XPS) confirms the formation of oxycarbides (TiC_xO_y) along with significant carbon adsorbate. Raman studies of the films also verify the relative phase transformation in the TiC_xO_y nanocomposite by tuning the deposition parameters. The Vickers microhardness of the sample surface is improved more than 400%. PACS 52.59.Hq; 52.77.Dq; 68.55.Jk; 81.15.-z; 81.65.Lp     

Effect of carbon vacancies on the electric resistivity of nonstoichiometric VC<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> vanadium carbide

The influence of the temperature, concentration, and distribution of structure vacancies of the carbon sublattice on the electric resistivity ρ of nonstoichiometric VC _y vanadium carbide (0.66 ≤ y ≤ 0.875) has been studied in the temperature range of 300–1200 K. The symmetry and structure characteristics of the ordered V₆C₅ and V₈C₇ phases formed owing to low-temperature annealing on various sections of the homogeneity region of the VC _y carbide. The dependence of the residual electric resistivity on the content of the disordered vanadium carbide is explained by the atom-vacancy interaction and the change in the carrier concentration in the homogeneity region of VC _y .     

Iron garnet films with enhanced thermal stability of their magnetic parameters

The ferromagnetic resonance in Y₃Fe_5−x Ga_xO₁₂ (0⩽x⩽0.63), iron garnet films obtained by liquid phase epitaxy on substrates of gadolinium gallium garnet is studied at temperatures of 213–353 K. It is found that in the case of liquid phase epitaxy the distribution coefficient of the gallium in the films varies from 2.2 to 4.0, depending on the composition and growth conditions. It is found that the resonance magnetic fields can be temperature stabilized through temperature-induced changes in the saturation magnetization and anisotropy field. Zh. Tekh. Fiz. 68, 46–50 (September 1998)     

Atomic-vacancy ordering and magnetic susceptibility of nonstoichiometric hafnium carbide

Experimental data on the magnetic susceptibility of nonstoichiometric hafnium carbide HfC_y(0.6< y<1.0) are presented. Anomalies are found in the temperature dependences of the magnetic susceptibility of the carbides HfC_0.71, HfC_0.78, and HfC_0.83 in the temperature range 870–930 K. These anomalies are due to the formation of a superstructural short-range order in their nonmetallic sublattice. It is shown that the short-range order in the carbides HfC_0.71 and HfC_0.78 corresponds to the ordered phase Hf₃C₂, while in the carbide HfC_0.83 it corresponds to the ordered phase Hf₆C₅. It is found that the magnetic susceptibility of the carbide HfC_0.78 in the temperature interval 910–980 K is zero. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 4, 296–301 (25 February 1999)     

New line of thermodynamic phase transitions on the x-T diagram of a dilute Heisenberg system with short-range interactions Li0.5Fe2.5−x GaxO4

It is established on the basis of an investigation of the temperature dependences of the saturation magnetization σ_S(T) and the magnetic contribution to the specific heat C _m(T) that in the reentrant region of the x-T diagram (0.9⩽x⩽1.5) of dilute iron spinels Li_0.5Fe_{2.5− x} Ga_xO₄ there exists between the line of Curie points T _C(x) and the line of freezing temperatures T _f(x) another line of first-order phase transitions T ₁(x) to a noncollinear ferrimagnetic phase: T _C(x)⩽T ₁(x)⩽T _f(x). Pis’ma Zh. éksp. Teor. Fiz. 67, No. 5, 329–333 (10 March 1998)     

Transport properties of antiferromagnetic fcc-iron alloys

A study is reported of the electrical resistance and thermopower of Fe_xNi_80−x Cr₂₀ fcc alloys within the 44⩽x⩽70 at. % range. It is shown that, at low temperatures, they typically exhibit minima in the temperature dependences of electrical resistance. The appearance of these anomalies is attributed to the formation of a gap in the conduction electron spectrum due to the onset of long-or short-range antiferromagnetic order in the alloys. The effect of magnetic field on the magnetic states appearing in frustrated antiferromagnetic alloys has been studied, and an H-T magnetic phase diagram constructed. Fiz. Tverd. Tela (St. Petersburg) 40, 101–105 (January 1998)     

Near-ordering structural transitions in amorphous metal alloys

The temperature variations in the modulus of elasticity (Young’s modulus) E and internal friction Q ⁻¹ of the amorphous metal alloys Ti₅₀Cu_50−x Ni_x (5⩽x⩽20) are studied at temperatures of 300–800 K. There is an anomalous increase in E(T) at temperatures above T _x (which varies from 440 to 525 K, depending on the composition). When the amount of nickel in the alloy is high (x>12 at. %), a small peak shows up in Q ⁻¹(T). These effects are related to structural transitions in near-ordering regions (clusters). A model for structural relaxation of near ordering in amorphous alloys is proposed on the basis of these experiments. Fiz. Tverd. Tela (St. Petersburg) 40, 389–392 (March 1998)     

Influence of structural deformations on the magnetic properties of Jahn-Teller complexes of divalent copper in CaxSr1−x F2 mixed crystals

Crystals of variable constituency Ca_xSr_1−x F₂:Cu (0⩽x⩽0.05, x≅0.5, 1.0⩾x⩾0.95) are investigated by EPR and x-ray structural analysis. The electron-Zeeman, intrinsic hyperfine, and ligand hyperfine interaction parameters are determined; they characterize the magnetic properties of the copper paramagnetic complexes formed in the crystals. Models of the molecular structures of these complexes are discussed, along with the influence of structural deformations and vibronic interactions on their magnetic properties. Fiz. Tverd. Tela (St. Petersburg) 40, 445–451 (March 1998)     

Characteristics of magnetic order in perovskite manganites La1−x CaxMnO3

Solid solutions of the system La_1−x Ca_xMnO₃ are synthesized, and their magnetic and electrical properties are investigated. As x is increased, the crystal lattice changes symmetrically from an orthorhombic (x=0 and x=0.8) to a cubic structure (0<x⩽0.6 and x=1). Nonstoichiometric LaMnO₃ and compositions with a low Ca content (0<x<0.4) are collinear ferromagnets. A metal-insulator transition is observed in them near the Curie temperature. Compositions with 0.6⩽x⩽0.9 exhibit a semiconductor-type conductivity and an unusual temperature behavior of the magnetization and the susceptibility with very distinct Curie and Néel temperatures. The magnetic properties of the solid solutions are explained on the basis of the model of ferro-antiferromagnetic phase separation. Zh. éksp. Teor. Fiz. 116, 1664–1675 (November 1999)     

Anomalous absorption of ultrasound in gadolinium in a magnetic field

The absorption coefficient α _k for longitudinal ultrasonic (15 MHz) waves propagating transverse to the direction of a magnetic field H is measured in single crystal gadolinium. It is found that in fields H⩽600 Oe, the peak in α _k is shifted toward lower temperatures, while the absolute magnitude of the absorption rises with increasing H. It is shown on the basis of dynamic scaling that the anomalous behavior of α _k in fields H⩽600 Oe can be explained by introducing a magnetic field analog of the Landau-Khalatnikov relaxation mechanism. Fiz. Tverd. Tela (St. Petersburg) 39, 339–340 (February 1997)