Mn substitution in the topological metal Zr2Te2P.

Results are reported for Mn intercalated Zr2Te2P, where x-ray diffraction , energy dispersive spectroscopy, and transmission electron microscopy measurements reveal that the van der Waals bonded Te-Te layers are partially filled by Zr and Mn ions. This leads to the chemical formulas Zr0.07Zr2Te2P and Mn0.06Zr0.03Zr2Te2P for the parent and substituted compounds, respectively. The impact of the Mn ions is seen in the anisotropic magnetic susceptibility, where Curie-Weiss fits to the data indicate that the Mn ions are in the divalent state. Heat capacity and electrical transport measurements reveal metallic behavior, but the electronic coefficient of the heat capacity (γMn≈ 36.6 mJ (mol·K2)-1) is enhanced by comparison to that of the parent compound. Magnetic ordering is seen atTM≈4 K, where heat capacity measurements additionally show that the phase transition is broad, likely due to the disordered Mn distribution. This transition also strongly reduces the electronic scattering seen in the normalized electrical resistance. These results show that Mn substitution simultaneously introduces magnetic interactions and tunes the electronic state, which improves prospects for inducing novel behavior in Zr2Te2P and the broader family of ternary tetradymites.

Electronic and magnetic properties of EuNi2-δ Sb2 structural variants.

X-ray diffraction, magnetic susceptibility, magnetization, heat capacity and electrical resistivity results are reported for single crystals of two structural variants of EuNi2-δ Sb2 that crystallize in the CaBe2Ge2 and ThCr2Si2-type structures. While the former occurs with a stoichiometric ratio, the latter exhibits a Ni site vacancy (δ = 0.36). Both systems exhibit similar magnetic behavior at elevated temperatures, where there is an isotropic Curie-Weiss temperature dependence that indicates an antiferromagnetic exchange interaction between divalent europium ions, although it is stronger for the CaBe2Ge2-variant. At low temperatures, the differing structural environments that surround the Eu ions result in distinct ordering behavior. The CaBe2Ge2-variant orders antiferromagnetically near T N1 = 6.9 K and then undergoes a first order phase transition at T M = 4.6 K. The ThCr2Si2-variant exhibits simpler behavior, with antiferromagnetic ordering at T N2 = 5.6 K. For both compounds, an applied magnetic field suppresses the ordering temperatures and induce metamagnetic phase transitions, while applied pressure causes the ordering temperatures to increase. From these results, EuNi2-δ Sb2 emerges as a useful system in which to study the impact of structural variation on magnetism in a Eu-based metal.

Superconductivity in a uranium containing high entropy alloy.

High entropy alloys (HEA) are an unusual class of materials where mixtures of elements are stochastically arrayed on a simple crystalline lattice. These systems exhibit remarkable functionality, often along several distinct axes: e.g., the examples [TaNb]1-x(TiZrHf)x are high strength and damage resistant refractory metals that also exhibit superconductivity with large upper critical fields. Here we report the discovery of an f-electron containing HEA, [TaNb]0.31(TiUHf)0.69, which is the first to include an actinide ion. Similar to the Zr-analogue, this material crystallizes in a body-centered cubic lattice with the lattice constant a = 3.41(1) Å and exhibits phonon mediated superconductivity with a transition temperatures Tc ≈ 3.2 K and upper critical fields Hc2 ≈ 6.4 T. These results expand this class of materials to include actinide elements, shows that superconductivity is robust in this sub-group, and opens the path towards leveraging HEAs as functional waste forms for a variety of radioisotopes.

Gd(1.33)Pt(3)(Al,Si)(8) and Gd(0.67)Pt(2)(Al,Si)(5): two structures containing a disordered Gd/Al layer grown in liquid aluminum.

Gd(1.33)Pt(3)Al(8) was synthesized by the combination of Gd and Pt in excess liquid aluminum. Addition of silicon resulted in the incorporation of a small amount of this element into the material to form the isostructural Gd(1.33)Pt(3)Al(7)Si. Both compounds grow as rodlike crystals with hexagonal cross section. The structures were refined in the rhombohedral space group R(-)3m, with cell parameters a = 4.3359(6) A and c = 38.702(8) A for the ternary and a = 4.3280(8) A and c = 38.62(1) A for the quaternary compound. The structure is comprised of stuffed arsenic-like PtAl(2) layers and disordered Gd/Al layers. Analysis of the hk0 zone reflections indicate the presence of an a = radical 3a supercell, but the structure is not ordered along c, as revealed by the highly diffuse reflections in the 0kl zone photos. Therefore, the compounds are disordered variants of the Gd(4)Pt(9)Al(24) type. Magnetic susceptibility studies reveal antiferromagnetic transitions at 15 K for the ternary and 7 K for the quaternary compound. Variation of the reactant ratio produces a different structure comprised of the same structural blocks, including the disordered Gd/Al layer. Gd(0.67)Pt(2)Al(5) and its quaternary analogue Gd(0.67)Pt(2)Al(4)Si form in the hexagonal system P6(3)/mmc with cell parameters a = 4.2907(3) A and c = 16.388(2) A for the ternary and a = 4.2485(6) A and c = 16.156(3) A for the quaternary compound.

Siting of antimony dopants and gallium in Ba(8)Ga(16)Ge(30) clathrates grown from gallium flux.

A series of antimony-doped Ba(8)Ga(16)Ge(30) clathrates was grown as large crystals from gallium flux. These compounds form in the cubic space group Pm(-)3n, with the unit cell parameter varying from 10.784(5) to 10.9008(6) A as the amount of GaSb substituting for germanium atoms in the framework is increased. It was found that more antimony than extra gallium was incorporated into the material and that a specific site (the 24k Wyckoff site) was favored by this element. (71)Ga NMR was carried out to determine the siting of gallium; it fills the 6c site preferentially.

Chemiluminescence detection of hydrazine vapor.

An efficient, real-time chemiluminescence detector for hydrazine vapor, N(2)H(4)(g), is described, capable of monitoring sub part-per-billion levels of hydrazine in air. The catalytic oxidation of hydrazine by colloidal platinum forms an intermediate, oxidizing agent (e.g. OH or OOH) which subsequently oxidizes luminol, generating a chemiluminescence signal that is proportional to the hydrazine concentration. Major components of the instrument include a photomultiplier tube (PMT), a short length of glass tubing coiled directly in front of the PMT cathode surface, a vacuum pump for sampling the air, and a peristaltic pump for circulating the liquid reagent. The liquid reagent, a basic solution (pH 13) of luminol and colloidal platinum, is continuously recycled. The detection sequence is initiated by pumping the hydrazine vapor through a short length of teflon tubing that is concurrently transporting the liquid reagent. The liquid is separated from the gas stream in an impinger and quickly pumped to the PMT. We have evaluated the effect of solution pH, luminol and platinum concentrations, and air and liquid flow rates on the analytical characteristics of this system. A linear, dynamic detection range for hydrazine has been obtained from 1 to 2000 ppb in air, with an instrument response that is fully reversible and achieves plateau response in less than 2 min.