, the enthalpy of formation of LiNi x Mn x Co 1-2x O 2 from the elements becomes more exothermic, implying increased energetic stability. This conclusion is in agreement with the literature results showing improved structural stability and cycling performance of Ni/Mn-rich LiNi x Mn x Co 1-2x O 2 compounds cycled to higher cut-off voltages.

The complete Cd-Pr equilibrium phase diagram was investigated with a combination of powder-XRD, SEM and DTA. All intermetallic compounds within this system, already reported in literature, could be confirmed: CdPr, Cd2Pr, Cd3Pr, Cd45Pr11, Cd58Pr13, Cd6Pr and Cd11Pr. The corresponding phase boundaries were determined at distinct temperatures. The homogeneity range of the high-temperature allotropic modification of Pr could be determined precisely and a limited solubility of 22.1 at.% Cd was derived. Additionally, single-crystal X-ray diffraction was employed to investigate structural details of Cd2Pr; it is isotypic to the AlB2-type structure with a z value of the Cd site of 0.5. DTA results of alloys located in the adjacent two-phase fields of Cd2Pr suggested a phase transformation between 893 and 930°C. For the phase Cd3Pr it was found that the lattice parameter a changes linearly with increasing Cd content, following Vegard’s rule. The corresponding defect mechanism could be evaluated from structural data collected with single-crystal XRD. Introduction of a significant amount of vacancies on the Pr site and the reduction in symmetry of one Cd position (8c to 32f) resulted in a noticeable decrease of all R-values.

Vapor pressure measurements, in terms of a (non-)isothermal isopiestic method, were carried out in the system Cd-Pr between 749 K and 1067 K (476°C and 794°C). Thermodynamic activities of cadmium as a function of temperature were obtained directly for the composition ranging from 50.0 to 85.7 at. pct Cd. From these results, partial molar enthalpies of mixing of Cd were derived for the corresponding composition range. The activity values of Cd were converted to an average sample temperature of 823 K (550°C) by applying an integrated form of the Gibbs-Helmholtz equation. These data indicate that Cd 2 Pr and Cd 58 Pr 13 are probably the most stable intermetallic compounds in this system. Using an activity value of Pr from the literature as integration constant, Gibbs-Duhem integration was performed, and integral Gibbs energies are presented at 823 K (550°C), referred to Cd(l) and a-Pr(s). Gibbs energies of formation at the stoichiometric compositions of the phases Cd 6 Pr, Cd 58 Pr 13 , Cd 45 Pr 11 , Cd 3 Pr, and Cd 2 Pr were determined to be about À18.8, À23.5, À24.8, À28.7, and À33.8 kJ g-atom À1 at 823 K (550°C), respectively.

The ternary phase diagram Al–Ge–Ni was investigated between 0 and 50 at.% Ni by a combination of differential thermal analysis (DTA), powder- and single-crystal X-ray diffraction (XRD), metallography and electron probe microanalysis (EPMA). Ternary phase equilibria and accurate phase compositions of the equilibrium phases were determined within two partial isothermal sections at 400 and 700 °C, respectively. The two binary intermediate phases AlNi and Al3Ni2 were found to form extended solid solutions with Ge in the ternary. Three new ternary phases were found to exist in the Ni-poor part of the phase diagram which were designated as τ1 (oC24, CoGe2-type), τ2 (at approximately Al67.5Ge18.0Ni14.5) and τ3 (cF12, CaF2-type). The ternary phases show only small homogeneity ranges. While τ1 was investigated by single crystal X-ray diffraction, τ2 and τ3 were identified from their powder diffraction pattern.Ternary phase reactions and melting behaviour were studied by means of DTA. A total number of eleven invariant reactions could be derived from these data, which are one ternary eutectic reaction, six transition reactions, three ternary peritectic reactions and one maximum. Based on the measured DTA values three vertical sections at 10, 20 and 35 at.% Ni were constructed. Additionally, all experimental results were combined to a ternary reaction scheme (Scheil diagram) and a liquidus surface projection.