Thermal vibrations and the structure of quasi-two-dimensional R 2CuO4 crystals (R=La, Pr, Nd, Sm, Eu, and Gd)

Thermal vibrations of ions in R ₂CuO₄ crystals (R=La, Pr, Nd, Sm, Eu, Gd) were studied by x-ray diffractometry. A comparative analysis of thermal displacements of the copper and rare-earth ions permitted a conclusion as to the main interactions responsible for the structural state of the CuO₂ sheets and of a crystal as a whole. The structural properties were found to correlate with the magnitude of the ionic radius and with the ground state of the rare-earth ions.     

Paramagnetische Resonanz des dreiwertigen Gadoliniums in YPO4, YVO4 und YAsO4

The EPR spectra of Gd³⁺-doped isostructural single crystals of YPO₄, YVO₄, and YAsO₄ have been measured in X-band at room temperature and at nitrogen and helium temperatures. The zero-field splitting can be described by the five crystal-field parametersb ₂ ⁰ ,b ₄ ⁰ ,b _6/0,b ₄ ⁴ , and b ₆ ⁴ fitted to a tetragonal spin-Hamiltonian corresponding to the point symmetry D_2d of the Gd³⁺ site. The values ofg and b ₂ ⁰ vary significantly with host lattice and with temperature.     

EPR studies of Gd3+-doped Ce2(SO4)3.8H2O and La2(SO4)3.9H2O single crystals

EPR spectra of Gd³⁺-doped Ce₂(SO₄)₃.8H₂O and La₂(SO₄)₃.9H₂O single crystals have been measured with an X-band spectrometer at room and low temperatures. The absolute signs of spin Hamiltonian parameters have been determined for the La₂(SO₄)₃.9H₂O host from intensities of lines at liquid helium temperature; for the Ce₂(SO₄).8H₂O host the lines broaden considerably below 60 K, not permitting the determination of absolute signs of spin Hamiltonian parameters. The data are analysed using a rigourous least-squares procedure, fitting simultaneously all lines obtained for several orientations of the external magnetic field. The zero-field splittings have been computed for both the hosts. The characteristics of EPR spectra of Gd³⁺ in these hosts are compared with those obtained in other rare-earth trisulphate octahydrate hosts.     

Magnetic properties of R3Co29Si4B10 (R=La, Ce, Pr, Nd, Sm, Gd and Dy) borides

The crystal structure and magnetic properties of quaternary rare-earth intermetallic borides R₃Co₂₉Si₄B₁₀ with R=La, Ce, Pr, Nd, Sm, Gd and Dy have been studied by X-ray powder diffraction and magnetization measurements. All compounds crystallize in a tetragonal crystal structure with the space group P4/nmm. Compounds with R=La, Ce, Pr, Nd and Sm are ferromagnets, while ferrimagnetic behavior is observed for R=Gd and Dy. The Curie temperatures vary between 149 K and 210 K. The Curie temperatures in R₃Co₂₉Si₄B₁₀ (R=Ce, Pr, Nd, Sm, Gd, Dy) compounds are roughly proportional to the de Gennes factors.     

Nuclear quadrupole interactions of 111In/Cd solute atoms in a series of rare-earth palladium alloys

Nuclear quadrupole interactions were measured at ¹¹¹In/Cd probe atoms in rare-earth palladium phases RPd₃ having the L1₂ structure using the technique of perturbed angular correlation of gamma rays (PAC). Measurements were made for pairs of samples having compositions of the Pd-poorer and Pd-rich boundaries of the RPd₃ phase fields, typically 75 and 78 at.% Pd. Two signals were detected in most phases, corresponding to probe atoms on cubic R- and non-cubic Pd-sublattices. Site preferences of parent In-probe atoms were characterized by site-fractions of probes on the R- and Pd-sublattices. For all Pd-rich samples, probes exclusively occupied the R-sublattice, consistent with a heuristic rule that solute atoms tend to occupy the sublattice of an element in which there is a deficiency. For Pd-poorer alloys with R = Tb, Er, Yb, Lu, Y and Sc, probes exclusively occupied the Pd-sublattice. For Pd-poorer alloys with R = Ce, Pr, Nd, Sm and Eu, probes occupied both sublattices, with site fractions varying as a function of temperature. In contrast, probes only occupied the R-sublattice in Pd-poorer LaPd₃. Jump frequencies on the Pd-sublattice of daughter Cd-probes were determined from nuclear relaxation caused by fluctuating electric field gradients. Activation enthalpies for diffusional jumps were determined from temperature dependences and found to increase linearly as the lattice parameter decreases along the series Pr, Nd, Eu and Sm. Jump frequencies are believed to have been even higher in CePd₃ than in PrPd₃, but were too low to be detectable in Tb, Er, Yb, Lu, Y and Sc palladides. A correlation between site preferences and jump frequencies is noted and discussed. This paper provides a complete account of measurements of jump frequencies of Cd-probe atoms and comparisons with similar measurements made on other series of L1₂ phases.     

Positron annihilation studies in high-Tc superconductors RBa2Cu3Oy,R: La,Nd, Sm,Eu, Gd,Dy, Ho,Y, Er

Positron lifetime and Doppler broadening of the annihilation line measurements have been performed at room temperature in high-T_c superconductors RBa₂Cu₃O_y, where R: La, Nd, Sm, Eu, Gd, Dy, Ho, Y, Er and 6.9 < y ≤ 7. Doppler broadening of the annihilation line measurements have also been performed in high-T_c superconducting samples R RBa₂Cu₃O_y, where R: Nd, Sm, Eu, Ho, Y, Er as a function of temperature between 14 K and 293 K. It was observed that the positron lifetime and the S parameter values at room temperature have no obvious trend in their variation from the yttrium substitution by a rare-earth element. It was also observed that the temperature dependence of the positron annihilation parameters is similar in the high-T_c superconducting samples.     

Antiferromagnetic resonance and dielectric properties of rare-earth ferroborates in the submillimeter frequency range

The magnetoresonance and dielectric properties of a number of crystals of a new family of multiferroics, namely, rare-earth ferroborates RFe₃(BO₃)₄ (R = Y, Eu, Pr, Tb, Tb_0.25Er_0.75), are studied in the sub-millimeter frequency range (ν = 3–20 cm⁻¹). Ferroborates with R = Y, Tb, and Eu exhibit permittivity jumps at temperatures of 375, 198, and 58 K, respectively, which are caused by the R32 → P3₁21 phase transition. Antiferromagnetic resonance (AFMR) modes in the subsystem of Fe³⁺ ions are detected in the range of anti-ferromagnetic ordering (T < T _N = 30–40 K) in all ferroborates that have either an easy-plane (Y, Eu) or easy-axis (Pr, Tb, Tb_0.25Er_0.75) magnetic structure. The AFMR frequencies are found to depend strongly on the magnetic anisotropy of a rare-earth ion and its exchange interaction with the Fe subsystem, which determine the type of magnetic structure and the sign and magnitude of an effective anisotropy constant. The basic parameters of the magnetic interactions in these ferroborates are found, and the magnetoelectric contribution to AFMR is analyzed.     

Spin and temperature dependence of the magnetic hyperfine field of Cd in the rare earth-aluminum Lavesphase compounds RAl2

Perturbed angular correlation spectroscopy has been used to investigate the combined magnetic and electric hyperfine interaction of the probe nucleus ¹¹¹Cd in ferromagnetically ordered rare earth (R)-dialuminides RAl₂ as a function of temperature for the rare earth constituents R=Pr, Nd, Sm, Eu, Tb, Dy, Ho and Er. In compounds with two magnetically non-equivalent Al sites (R=Sm, Tb, Ho, Er), the magnetic hyperfine field was found to be strongly anisotropic. This anisotropy is much greater than the anisotropic dipolar fields, suggesting a contribution of the anisotropic 4f-electron density to magnetic hyperfine field at the closed-shell probe nucleus. The spin dependence of the magnetic hyperfine field reflects a decrease of the effective exchange parameter of the indirect coupling with increasing R atomic number. For the compounds with the R constituents R=Pr, Nd, Tb, Dy and Ho the parameters B₄, B₆ of the interaction of the crystal field interaction have been determined from the temperature dependence of the magnetic hyperfine field. The ¹¹¹Cd PAC spectrum of EuAl₂ at 9 K confirms the antiferromagnetic structure of this compound.     

Mean-square displacements of metal and boron atoms in crystal lattices of rare-earth hexaborides

The intensities of the I₄₁₀ and I₄₁₁ reflections of nine rare-earth hexaborides MB₆ (M=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy) are experimentally studied in the temperature range 4.2–300 K. The mean-square displacements of metal and boron atoms are calculated from the temperature dependences of the intensities I₄₁₀(T) and I₄₁₁(T). The characteristic temperatures of the metal (θ_M) and boron (θ_B) sublattices of rare-earth hexaborides are determined in the Debye approximation. It is found that the characteristic temperatures decrease with an increase in the atomic number of the metal.     

The effects of elements doping on transport and thermoelectric properties of Sr3Ti2O7

The Ruddlesden–Popper (RP) phase compounds (Sr_0.95R_0.05)₃Ti₂O₇ (R=Er, Y, Dy, Gd, Eu, Sm, Nd and La) were prepared, and their transport and thermoelectric properties were investigated. The results indicate that high-T electrical resistivity ρ (300 K<T<1000 K) increases monotonically with temperature and basically has a relation ρ∝T^M, with M varying from 0.91 to 1.92 at temperatures T>~650 K, suggesting acoustic phonon scattering is dominant. At low temperatures (5 K<T<300 K), ρ for (Sr_0.95R_0.05)₃Ti₂O₇ (R=Nd and La) decreases monotonously with decreasing temperature, whereas ρ for (Sr_0.95R_0.05)₃Ti₂O₇ (R=Er, Y, Dy, Gd, Eu and Sm) decreases first, and then increases instead as T decreases to a critical temperature T_c. Moreover, electrical conductivity σ∝T^1/2 holds at lower temperatures, indicating that the electron–electron interaction caused by the presence of disorder dominates the transport process at the low temperatures. Besides, experiments show that at T<~400 K the lattice thermal conductivity of the doped compounds basically decreases with increase of the atomic mass of dopants. Generally, the figure of merit (ZT) at 1000 K increases first, and then decreases with the increase of the dopants' ionic radius, and the largest ZT is achieved in (Sr_0.95Gd_0.05)₃Ti₂O₇ mainly owing to its lower lattice thermal conductivity.     

Synthesis,Characterization, and Antibacterial Activity of RE(III) Complexes with L-Isoleucine and 1,10-Phenanthroline

Six new ternary rare-earth (La, Eu, Sm, Nd, Y, Yb) complexes with L-isoleucine and 1,10-phenanthroline have been synthesized. Their compositions were characterized as RE(Ile)₃PhenCl₃ · 4H₂O (RE = La, Eu, Sm, Nd, Y, Yb; Ile = L-isoleucine; phen = 1,10-phenanthroline) by elemental analysis, EDTA titration, molar conductance measurement, UV spectra, FT-IR spectra, and TG-DTA. The average diameters of growth inhibition area and the minimal inhibitory concentration (MIC) of the complexes were studied by disc diffusion method and dilution method in nutrient broth. The results showed that the ternary rare-earth complexes strongly exhibited the antibacterial activity against Escherichia coli and Staphylococcus aureus and that their antibacterial effects were better than those of rare-earth chlorides, L-isoleucine, and 1,10-phenanthroline.     

Magnetic and superconducting properties of Tl(Sr1.5R0.5)CaCu2O7−δ compounds

DC magnetic susceptibility and resistivity measurements have been performed on 14 Tl(Sr_1.5R_0.5)CaCu₂O_7−δ compounds with R=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. All samples except the Ce-doped compound show superconducting phase transition temperature around 80–90 K. The rare-earth atoms behave as local moments above the superconducting transition temperature of these compounds. Mechanism of filling of holes in the CuO₂ plane can be employed to interpret the suppression or enhancement of superconductivity by rare-earth ions in Tl(Sr_1.5R_0.5)CaCu₂O_7−δ.     

151,153Eu electron paramagnetic resonance in SrMoO4 and determination of signs of spin Hamiltonian parameters at different temperatures

The electron paramagnetic resonance (EPR) spectra of Eu²⁺ impurity centers in SrMoO₄ crystals have been studied in the temperature range of 1.8, 100–300 K. A hyperfine structure has been simulated for ^151,153Eu of different EPR transitions observed experimentally at different temperatures and external magnetic field orientations. A unique set of all parameters of the spin Hamiltonian for the known sign of the hyperfine interaction parameters A _i has been determined. It has been found that the diagonal parameters |b _n ⁰ | of the spin Hamiltonian decrease with increasing temperature; however, the parameter b ₄ ⁴ increases. The results of the study have demonstrated that |b ₂ ⁰ (T)/P ₂ ⁰ (T)| ～ const for ^151,153Eu in this single crystal.     

Effect of a Rare-Earth Ion on the Structural Instability in RFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> Crystals

The dynamics of the crystal lattice of RFe₃(BO₃)₄ (R = Pr, Nd, Sm, Gd, Tb, Dy, and Ho) compounds in the high-symmetry R32 phase has been calculated. Significant changes in spectra of compounds with various rare-earth ions have been obtained only near the edge Λ point of the Brillouin zone (qΛ = 1/3(?2b₁ + b₂ + b₃, where b₁, b₂, and b₃ are the reciprocal lattice vectors) for acoustic oscillation branches. A decrease in the frequency of an acoustic mode at the point Λ has been revealed in all studied compounds. This frequency depends on the type of rare-earth ion and decreases from a compound with Pr to a compound with Ho down to imaginary values. Such a behavior of the frequency of the unstable acoustic mode is in good agreement with experimental data on the dependence of the temperature of the R32 → P3₁21 structural phase transition on the type of rare-earth ion in ferroborates.     

EXAFS study of intermetallics of the type RGe2 (R=La,Ce, Pr,Nd, Sm,Gd, Tb,Dy, Ho,Er and Y) Part I: Determination of Ge-Ge distances

A study of theEXAFS associated with theK x-ray absorption discontinuity of germanium in pure germanium and in the rare-earth germanides RGe₂ (where R=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Y) has been carried out. The Ge-Ge distances have been obtained in these compounds. Considering the phase to the RGe₂ system, the bond lengths in these compounds have been determined. The values obtained by us for the RGe₂ compounds (R=La, Ce, Pr, Nd, Sm, Gd, Dy and Y) agree with those obtained earlier by crystallographic methods. The bond lengths for the compounds TbGe₂, HoGe₂ and ErGe₂ are also being reported.     

A novel strategy to improve the sensitivity of aerosol phosphor thermometry using co-doped phosphors

A novel strategy is presented to improve the temperature sensitivity and potentially extend the temperature range of aerosol phosphor thermometry (APT) by co-doping host materials with two rare-earth ions. The ratio of the emission bands from each ion are measured and calibrated versus temperature to utilize the high sensitivity of thermographic phosphor absolute signal levels. The potential of the technique is illustrated using trivalent cerium (Ce³⁺) and praseodymium (Pr³⁺) co-doped into yttrium aluminum garnet (Ce,Pr:YAG). The measured fractional sensitivity of this phosphor from 300–450 K was 0.004–0.006 K⁻¹, a factor of 1.5–2 better than previously observed for Eu:BAM. Additionally, the single-shot precision (1σ) was between 9 and 25 K over the range of temperatures measured, illustrating the utility of this co-doping strategy. The level of temperature sensitivity and single-shot precision observed here should be achievable over different temperature ranges by doping Ce³⁺ and Pr³⁺ into different hosts. This new strategy should provide a pathway to ultimately extend the high-temperature single-shot measurement limit for APT to temperatures greater than 1000 K and push forward the state-of-the-art for planar temperature diagnostics in combustion applications.     

Spin dynamics and structural phase transitions in quasi-2D antiferromagnets R2CuO4 (R=Pr, Sm, and Eu)

Spin and lattice dynamics of R₂CuO₄ (R=Pr, Sm, and Eu) crystals were studied over the frequency and temperature ranges 20–250 GHz and 5–350 K, respectively. The absorption coefficients of the R₂CuO₄ crystals (R=Pr, Sm, and Eu) were found to change dramatically at temperatures of, respectively, 20, 80, and 150 K over a broad frequency range above 120 GHz. The absorption jumps were caused by the structural phase transitions. Broad spin-wave bands were observed in the high-temperature phases of all crystals studied. Absorption lines due to lattice dynamics were observed near the temperatures of structural phase transition over a broad frequency range, including the frequencies corresponding to the spin-wave bands.     

Components of the low-temperature heat capacity of rare-earth hexaborides

The temperature dependence of heat capacity C _p(T) was studied for nine rare-earth hexaborides MB₆(M=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, and Dy) at temperatures of 5–300 K. Using the correspondence principle for lattice heat capacities of isostructural compounds, the lattice contribution C ₁(T) and the excess contribution ΔC(T) to the heat capacity of the hexaborides were determined. The lattice heat capacity C ₁(T) is represented as the sum of the Debye contributions of the metal and boron sublattices: C ₁(T)=C _M (T)+6C _B(T). The Debye temperatures π_M and π_B of the metal and boron sublattices were determined. The anomalies in the excess heat capacity ΔC(T)=C _p (T)?C ₁(T) are related to the magnetic ordering effects, the Schottky contribution, and the Jahn-Teller effect.     

Rare-earth valence-state studies of the series RIn3 and RSn3 derived from quadrupole coupling constants

Time-differential perturbed angular correlation was applied to measure the quadrupole coupling constants of¹¹¹Cd (247 keV) at the In and Sn sites for rare-earth compounds of the series RIn₃ and RSn₃ that have the AuCu₃ structure. Definitive evidence was found for Yb and Eu having lower valence states relative to the assumed value of +3 for the other rare earths. Measurements at liquid helium temperatures and pressures to 18.5 kbar indicate that the room temperature valencies of CeSn₃, YbSn₃, and YbIn₃ have not changed.Work done under the auspices of the US Energy Research and Development Administration     

Spin dynamics and phase transitions in quasi-2D antiferromagnets <Emphasis Type="Italic">R</Emphasis><Subscript>2</Subscript>CuO<Subscript>4</Subscript> (<Emphasis Type="Italic">R</Emphasis>=Pr,Nd, Sm,Eu, Gd)

The spin and lattice dynamics of the R₂CuO₄ quasi-2D antiferromagnetic crystals (R=Pr, Nd, Sm, Eu, Gd) were studied in the millimeter-range electromagnetic wave band. Strong variations of the absorption coefficient were observed to occur at temperatures T≈T₀. Absorption lines of electrical nature due to lattice dynamics were also revealed near the T₀ temperatures. The observed anomalies are assumed to originate from phase transitions at T≈T₀, which entail changes in the structural and magnetic properties.