Infrared furnace for in situ neutron single-crystal diffraction studies in controlled gas atmospheres at high temperatures

Abstract

To understand oxygen diffusion mechanisms in non-stoichiometric oxides, the possibility to explore structural changes as a function of the oxygen partial pressure with temperature and related oxygen bulk stoichiometry is mandatory. This article reports on the realization of a high-temperature furnace, suitable for single-crystal neutron diffraction, working continuously at temperatures of up to 1000°C at different and adjustable partial gas pressures of up to 2 bar (1 bar = 100 kPa). This allows exploration of the phase diagrams of non-stoichiometric oxides under in situ conditions and controlled oxygen partial pressure. As a pilot study, the structural changes of Pr2NiO4+δ were explored at room temperature (δ ≃ 0.24) and at 900°C under 1 bar P(O2) (δ ≃ 0.13) as well as under secondary vacuum (approximately 10−5 mbar) conditions yielding a δ close to zero. The strong anharmonic displacements of the apical oxygen atoms along the [110] shallow diffusion pathway, which were previously observed at room temperature and 400°C, become more isotropic at 900°C. The study shows that the anisotropic oxygen displacements, here related to lattice instabilities, play a major role in understanding oxygen diffusion pathways and related activation energies at moderate temperatures. This also shows the importance of the availability of reaction cells for single-crystal neutron diffraction to explore the phase diagram and associated structural changes of non-stoichiometric oxygen ion conductors and respective diffusion mechanisms.