Clathrate formation in the systems Sr-Cu-Ge and {Ba,Sr}-Cu-Ge

In the ternary system Sr-Cu-Ge, a clathrate type-I phase, Sr8Cu5.3Ge40.7 (a = 1.06311(3), exists close to the Zintl limit in a small temperature interval. Sr8Cu5.3Ge40.7 decomposes eutectoidally on cooling at 730{\deg}C into (Ge), SrGe2 and tau1-SrCu2-xGe2+x. Phase equilibria at 700{\deg}C have been established for the Ge rich part and are characterized by the appearance of only one ternary compound, tau1-SrCu2-xGe2+x, which crystallizes with the ThCr2Si2 structure type and forms a homogeneity range up to x=0.4 (a = 0.42850(4), c = 1.0370(1) nm). Additionally, the extent of the clathrate type-I solid solution Ba8-xSrxCuyGe46-y (5.2 < y < 5.4) has been studied at various temperatures. The clathrate type-I crystal structure (space group ) has been proven by X-ray single crystal diffraction on two single crystals with composition Sr8Cu5.3Ge40.7 (a = 1.06368(2) nm) and Ba4.9Sr3.1Cu5.3Ge40.7 (a = 1.06748(2) nm) measured at 300, 200 and 100 K. From the temperature dependency of the lattice parameters and the atomic displacement parameters, the thermal expansion coefficients, the Debye- and Einstein-temperatures and the speed of sound have been determined. From heat capacity measurements of Sr8Cu5.3Ge40.7 at low temperatures, the Sommerfeld coefficient and the Debye temperature have been extracted, whereas from a detailed analysis of these data at higher temperatures, Einstein branches of the phonon dispersion relation have been derived and compared with those obtained from the atomic displacement parameters. Electrical resistivity measurements of Sr8Cu5.3Ge40.7 reveal a rather metallic behaviour in the low temperature range (< 300 K).