Elastic and brittle properties of the B2-MgRE (RE = Sc,Y, Ce,Pr, Nd,Gd, Tb,Dy, Ho,Er) intermetallics

The brittle and elastic properties of the B2-MgRE (RE = Sc, Y, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er) intermetallics have been investigated using first-principles density functional calculations. The calculated equilibrium lattice constants and enthalpies of formation are in overall agreement with the available experiment and theoretical results. The related physical properties of those compounds are compared with that of ductile YCu. The Fermi energy occurs above a peak in the DOS for B2-MgRE intermetallics, whereas for ductile YCu the Fermi energy occurs near a minimum in the DOS. For B2-YCu, the partial density of states of d-states at the Fermi energy is low, while for B2-MgRE the RE d-states are partially occupied, indicating their important roles in the directional bonding for this material. The Cauchy pressure (C₁₂-C₄₄) and the ratio of bulk to shear modulus B/G are used to assess the brittle/ductile behavior of B2-MgRE and YCu compounds. It can be concluded that the B2-MgRE alloys have brittle behavior. MgSc is the most brittle, and MgHo is the least brittle amongst those alloys.     

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.     

Magnetic properties of RE2Au compounds (RE = Pr,Nd, Gd,Tb, Dy,Ho, Er,Tm and Y)

Magnetic properties of nine RE₂Au compounds have been studied in fields of up to 19 kOe in the temperature range 4.2K–300K. It has been found that all compounds are paramagnetic at room temperature except Gd₂Au. The compounds with Pr, Nd, Ho, Er and Tm exhibit Curie-Weiss behaviour with paramagnetic moments in close agreement with those expected for the free RE³⁺ ion. The moment of gold was found to be zero. The compounds with Pr, Nd, Tb, Dy, Er and Tm are antiferromagnetic at low temperatures. It appears that Ho₂Au is ferromagnetically ordered below 4.5 K. No evidence for magnetic ordering was found for Y₂Au. The compound with Tb exhibits metamagnetic behaviour.     

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

The extended x-ray absorption fine structure (EXAFS) associated with the GeK x-ray absorption discontinuity in pure germanium and in the intermetallics RGe₂ (R=La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er and Y) has been studied. The Ge-R distances in these compounds have been determined by comparing the experimental phase shifts with the theoretical ones. The Ge-R distances in the compounds TbGe₂, HoGe₂ and ErGe₂ are being reported for the first time in this work.     

Magnetic studies of RCo12B6 compounds (R=Y,Ce, Pr,Nd, Sm,Gd and Dy)

Magnetization of the RCo₁₂B₆ borides (R=Y, Ce, Pr, Nd, Sm, Gd and Dy), which crystallize in a rhombohedral structure of the SrNi₁₂B₆-type, has been measured in the temperature range 4.2–300 K. All compounds were found to order magnetically with Curie temperatures ranging from 154 to 177 K. Saturation moments at 4.2 K were found to be 6.5, 5.4, 8.4, 8.8, 6.8, 2.1 and 5.9μ_B/f.u. for R=Y, Ce, Pr, Nd, Sm, Gd and Dy, respectively. These results imply a ferromagnetic coupling of Co and rare earth moments for light rare earths and an antiferrimagnetic coupling for heavy rare earths in these compounds. A spin-compensation effect is observed in GdCo₁₂B₆ alloys at T_comp=46 and 72 K, respectively. Results suggest that in CeCo₁₂B₆ the Ce ion exists in the quadripositive state. It is clear that RCo₁₂B₆ materials are not of interest for permanent magnet applications.     

Properties of hexagonal Al2Ge2RE (RE=Y,La,Ce,Nd,Eu,Gd,Tb,Y b and Lu) : A first-principles study

In this work, we present a study of the structural, elastic and electronic properties of the Al₂Ge₂RE (RE=Y, La, Ce, Nd, Eu, Gd, Tb, Yb and Lu) through the approaches of generalized gradient approximation (GGA) and local spin density approximation with the Hubbard energy (LSDA+U) based on density-functional theory. For most of the compounds (RE=Y, La, Ce, Nd, Eu, Yb and Lu), the results of the structural constants calculated from the approach of LSDA+U are in good agreement with the reported experimental data. Both the approaches of GGA and LSDA+U have been used to calculate DOS. Compared with the results of the GGA approach, the LSDA+U is more credible because it can show the influence of RE-f states and the RE-f states play an important role in the compound. The magnetic property has been investigated according to the result of DOS and it shows that the Al₂Ge₂Y, Al₂Ge₂La, Al₂Ge₂Y b and Al₂Ge₂Lu do not exhibit obvious magnetic property, while the other five ternary compounds are magnetic. The Voigt-Reuss-Hill (VRH) approach is used to calculate the elastic properties including bulk and shear moduli. The results of the calculated Poisson’s ratio ν and the B/G ratio demonstrate that all the Al₂Ge₂RE ternary compounds are brittle materials. The compounds, i.e. Al₂Ge₂Nd, Al₂Ge₂Eu, Al₂Ge₂Gd and Al₂Ge₂Tb which are mechanically unstable, display differences with the other five in the elastic properties.     

Crystal chemistry and physical properties of the ternary compounds RE5B4C5 (RE=Ce,Pr, Nd)

The ternary rare-earth metal boride carbides RE₅B₄C₅ (RE=Ce, Pr, Nd) were prepared by arc melting the mixtures of the pure elements and subsequent annealing at 1270 K. Their crystal structures were determined from single crystal X-ray diffraction data. They crystallize in the Ce₅B₄C₅ type of structure (space group Pna2₁, Z=8). Two new compounds were found, Pr₅B₄C₅: a=24.592(2) Å, b=8.4563(5) Å, c=8.4918(5) Å, R₁=0.043 (wR₂=0.076) for 2871 reflections with I_o?2σ(I_o)); for Nd₅B₄C₅: a=24.301(1) Å, b=8.3126(5) Å, c=8.3545(4) Å, R₁=0.035 (wR₂=0.069) for 3707 reflections with I_o?2σ(I_o)). Its structural arrangement consists of a three-dimensional framework of rare-earth atoms resulting from the stacking of slightly corrugated two-dimensional square nets, leading to voids filled with B₄C₄, B₃C₃, BC₂ finite chains and isolated carbon atoms. Ce₅B₄C₅ is an antiferromagnet at 5 K followed by a metamagnetic transition in elevated external fields. Pr₅B₄C₅ and Nd₅B₄C₅ are ferromagnets below T_C=12 and 15 K, respectively.     

119Sn Mössbauer spectra of RMnSn2 intermetallics (R = La,Ce, Pr,Nd, Sm)

The ternary stannide series of RMnSn₂ compounds crystallize in the defect orthorhombic CeNiSi₂-type structure. They order magnetically close to room temperature. Isomer shifts are approximately 1.9 and 2.8 mm/s at the two tin sites, and there are transferred hyperfine fields of 3–6 T at 15 K, which depend on the rare-earth partner, especially at Sn₂ sites. The magnitude of the transferred hyperfine field per manganese neighbour is 4T.     

Magnetic anisotropy and spin-reorientation transitions in RFe11Ti (R = Nd, Tb, Dy, Er) rare-earth intermetallics

RFe₁₁Ti rare-earth intermetallics (R = Nd, Tb, Dy, Er) which show temperature-induced spin-reorientation transitions (SRT) were investigated. The temperature dependences of the rare-earth anisotropy constants were calculated using the single-ion model. By fitting the experimental data a set of crystal-field and exchange-field parameters for R³⁺ ions wassb deduced. The temperature dependence of the first-order magnetization process fields was calculated for NdFe₁₁Ti and ErFe₁₁Ti within the model. The calculated spin-reorientation transition in NdFe₁₁Ti observed at T_s = 189 K is of first order with a discontinuous jump of the magnetization angle. Present calculations show that a first-order transition occurs in DyFe₁₁Ti at low temperatures. A second-order SRT from ‘easy axis’ to ‘easy cone’ exists in ErFe₁₁Ti. A first-order SRT ‘easy axis’-‘easy plane’ is predicted theoretically in TbFe₁₁Ti. The calculated curves of the temperature dependence of the anisotropy fields and the critical fields of the first-order magnetization processes for RFe₁₁Ti using the fitted crystal- and exchange-field parameters are in good agreement with the experimental data over a wide temperature range.     

Crystal field in RPdIn (R=Ce, Pr, Nd) compounds

The RPdIn compounds (R = rare earth) crystallise in the hexagonal ZrNiAl-type crystal structure. The compounds from this family exhibit a great variety of interesting magnetic properties including heavy fermion behaviour. In order to get a deeper insight into nature of magnetism of RPdIn with light rare earths elements (La–Nd) an inelastic neutron scattering experiment was performed. For compounds with Pr and Nd excitations due to crystal field were clearly distinguished. On the other hand, interesting behaviour for the CePdIn sample was observed. The sample exhibits no signs of crystal field excitations, likely due to highly delocalised Ce 4f states leading to its heavy fermion behaviour.     

Spontaneous magnetostriction in R2Fe14B (R=Y,Nd, Gd,Tb, Er)

Thermal expansion anomalies of R₂Fe₁₄B (R=Y, Nd, Gd, Tb, Er) stoichiometric compounds were studied by X-ray diffraction with high-energy synchrotron radiation using a Debye–Scherrer geometry in temperature range of ∼10–1000 K. A large invar effect with a corresponding large temperature dependence of lattice parameters ∼10–15 K above their Curie temperatures (T_c) are observed. The a-axes show a larger invar effect than the c-axes in all compounds. The spontaneous magnetostrain of the lattices and bonds are calculated. The iron sublattice is shown to dominate the volumetric spontaneous magnetostriction of the compounds and the contribution from the rare-earth sublattice is roughly proportional to the spin magnetic moment of the rare earths. The bond-length changes are consistent with the theoretical spin-density calculation. The average bonds magnetostrain around Fe sites is approximately proportional to their magnetic moments.     

Transport properties and mangetoresistance of (RE,Sr)2NiO4 (RE=Pr,Nd, Sm and Eu)

We report on the crystal growth and the measurements of resistivity, magnetoresistance and photoemission spectroscopy of (RE,Sr)₂NiO₄ in the heavily Sr-doped region. Although the in-plane resistivity of the heavily Sr-doped crystals was rather small at room temperature, it increased for several orders of magnitude with decreasing temperature. A large negative magnetoresistance was observed for NdSrNiO₄ at low temperature, while only small magnetoresistance was observed for the single crystals of RE=Pr, Sm and Eu. Photoemission spectroscopy measurements revealed a significant influence of the RE 4f states to the electronic structure at relatively low binding energies in PrSrNiO₄ and NdSrNiO₄.     

ELECTRONIC STRUCTURE AND CRYSTALLINE ELECTRIC FIELD IN Rco5(R= Y,La, Ce,Pr, Nd,Sm, Gd,and Tb)

Self consistent charge and spin polarized local spin-density approximation functional theory calculations based on the discrete variational method have been performed for RCo₅(R=Y, La, Ce, Pr, Nd, Sm, Gd, and Tb) compounds. The partial density of states of the Pr atom in the PrCo₆Co₁₂ cluster is established to be strikingly similar to that of the Ce atom in the CeCo₆Co₁₂ cluster, supporting the suggestion that the Pr atom is valence fluctuating. The radii ＜r_4f＞ and ＜r₄f²＞ of the 4f electrons of the R atom from La to Tb, except Ce, show the lanthanide contraction. The crystalline electric field (CEF) parameter A⁰₂ at the R site is calculated using a real charge distribution ρ(R) in the cluster, except for Pr and Nd, and is in agreement with that evalu ated based on the single-ion model. This result shows that the CEF parameter A⁰₂ is mainly determined by the near electronic structure. There exists a hybridization in a certain degree between the light rare-earth R-4f and Co-3d orbitals in some single-electron-molecular-orbitals, which are n ear the Fermi energy level and occupied by electrons. For light rare-earths the R-4f electrons in R Co₆Co₁₂(R=Y, La, Ce, Pr, Nd, and Sm) clu sters are not localized entirely and a small amount of the R-4f electrons have itinerant properties.     

FORMATION AND MAGNETIC PROPERTIES OF NEW COMPOUNDS R3Fe29-xCrx(R=Y,Ce,Nd,Sm,Gd,Tb,and Dy)

A systematic investigation of structure and magnetic properties of the new R₃Fe_29-xCr_x compounds(R=Y,Ce,Nd,Sm,Gd, Tb,and Dy)has been performed. The Curie temperature of R₃Fe_29-xCr_x increased with increasing atomic number fromR=Ce to Gd and de creased from Gd to Dy. The saturation magnetization of R₃Fe_29-xCr_x at 4.2 K decreased gradually with increasing atomic number from R=Y to Dy,except for Ce. The spin reorientations of the easy magnetization d irection were observed at around 230 K for Nd₃Fe_24.5Cr_4.5 and 180 K for Tb₃Fe_28.0Cr_1.0,and the magnetohistory effects were obser ved for Nd₃Fe_24.5Cr_4.5 and Sm₃Fe_24.0Cr_5.0 in a low field of about 0.04 T. First order magnetization process occurs in magnetic field of around 2.3 T at room temperature for Tb₃Fe_28.0Cr_1.0. The saturation magnetization of Y₃Fe_27.2Cr_1.8 at 4.2 K is 52.2μ_B/f.u., which corresponds to an average magnetic moment of 1.92μ_B per each Fe atom.     

Mössbauer study of amorphous Fe2RE (RE=Ce,Er) alloys

Among amorphous Fe₂RE (RE=Er, Ce, Gd, La, Pr, Sm, Dy, Ho) alloys, Fe₂Ce exhibits a tendency toward short range order, while the other Fe₂RE compounds show clustering. However, we have almost no information about environments around Fe atoms. Using Mössbauer spectroscopy we have determined the quadrupole splitting distributionsP(QS) of two representative amorphous Fe₂RE (RE=Ce, Er) alloys, leading to local environments of Fe atoms. The analysis of the mixed magnetic dipole and quadrupole interactions in Fe₂Er shows two kinds of electrical field gradients (EFT) with the positive and negative signs in the sample, indicating a random packing of Fe atoms. Furthermore, the analyzed quadrupole splitting distributionP(QS) of Fe₂Er also supports random packing in this amorphous alloy. On the other hand, the amorphous Fe₂Ce alloy shows two kinds of distributions of quadrupole splitting; the major component indicating random packing and the minor component Ce-rich Ce-Fe clusters.     

Theoretical study on the structure for R2Co17 (R=Y, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er) and R2Co17T (T=Be, C)

The structural stability of the intermetallic compounds R₂Co₁₇ and R₂Co₁₇T (T=Be, C) is tested by many means including random atom shifts, global deformations and high temperature disturbances under the control of the pair potentials. The structure type and crystal constants of R₂Co₁₇ and R₂Co₁₇Be are close to experimental results. The addition of Be and C in the interstice of R₂Co₁₇ causes a decrease of the cohesive energy, and Be and C only occupies the 9e interstitial site with the Th₂Zn₁₇-type structure or the 6h interstitial site with the Th₂Ni₁₇-type structure. All the above results indicate that the potentials are valid for studying the structural properties of these kinds of anisotropy materials.