Tau-borides (Mnx{Ru,Os,Ir}1-x)23B6: X-ray single crystal and TEM data, physical properties

Abstract

Investigation (electron microprobe and X-ray powder and single crystal diffraction analyses) of the phase relations in the Mn-rich corner (> 45 at% Mn) of the systems Mn-{Ru,Os,Ir}-B, prompted in all three systems a ternary compound with formula (Mnx{Ru,Os,Ir}1-x)23B6. For the systems Mn-Ru-B, Mn-Ir-B phase equilibria have been determined at 950°C (Ru), 900°C (Ir) revealing in both cases a small homogeneity region at constant B-content (Mn1-xRux)23B6 (0.29 < x < 0.37); (Mn1-xOsx)23B6 (0.33 < x < 0.37), as well as (Mn1-xIrx)23B6 (0.29 < x < 0.34). The crystal structure of the three compounds was determined from single crystal and X-ray powder intensity data analyses to be isotypic with the Cr23B6-type (so-called tau-phase, space group Fm3¯m, No. 225). In all cases Mn atoms fully occupy the 4a site (0,0,0) at the origin of the unit cell. For the 8c site (¼,¼,¼) we observed a random distribution of Mn1-x(PM)x with decreasing PM content (PM stands for a platinum group metal atom) going from Ru to Os and Ir, where Mn atoms fully occupy 8c. Whereas the remaining sites (48h, 32f) show various ratios of the two metal species, boron atoms fully occupy the centers (24e site) of the Archimedean metal atom antiprisms. A transmission electron microscopic study confirms the absence of superstructures related to these metal atom disorder, thus Mn and PM atoms randomly share their sites. The latter is well reflected in the behavior of the electrical resistivity of these compounds, which is dominated by disorder scattering. For (Mn0.6{Ru,Os}0.4)23B6, temperature dependent dc magnetization studies reveal distinct antiferromagnetic-like anomalies at TN ≅ 72 K and 114 K, respectively. Low field dc and ac magnetic susceptibility data of (Mn0.7Ir0.3)23B6 display a distinct ferromagnetic-like transition at TC = 280 K, consistent with a pronounced specific heat anomaly and a rather continuous temperature dependent evolution of magnetic anisotropy effects. Mechanical properties (hardness) characterize the tau phases among rather hard and brittle intermetallics (about 5–6 GPa).