High resolution and in situ neutron powder diffraction study of the crystal structure and the stability of Ba4CaCu3O8+δ

The crystal structure and stability of Ba4CaCu3O8+δ have been investigated by neutron powder diffraction, differential thermal analysis and thermogravimetry. It is found that the phase is not stable below 1065 K in p(O2)=1 bar and decomposes according to the eutectoid reaction Ba4CaCu3O8+δ+x O2⇒Ba2CuO3.4+CaO+2BaCuO2. However, the equilibrium with the outer gas is not reached for sintered ceramics so that Ba4CaCu3O8+δ can be obtained in a metastable state after normal cooling conditions. In this case, the crystal structure is cubic (Im-3m  , a=8.1452(1)Å, δ=0.68δ=0.68, Z=2Z=2, Rwp=2.5%Rwp=2.5%, RBragg=5.4%RBragg=5.4%) as reported in the literature. In reduced oxygen partial pressure (p(O2)<10−6 bar), Ba4CaCu3O8+δ is stable down to room temperature and has a tetragonal structure with a significant lower oxygen content (P4/mmm  , a=8.1976(3)Å, c=8.0709(3)Å, δ=-0.81δ=-0.81, Z=2Z=2, Rwp=2.8%Rwp=2.8%, RBragg=5.1%RBragg=5.1%). The difference between the two crystal structures is discussed in terms of oxygen content, copper formal valence and cation coordination. The influence of the oxygen pressure on the stability of Ba4CaCu3O8+δ is also discussed.

Schematic representation of the structure of tetragonal Ba4CaCu3O8+δ. Cu atoms and CuOz coordination polyhedra: Dark grey; CaO6 octahedra and Ba atoms: light grey.Figure optionsDownload as PowerPoint slide