Failure Mechanisms of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ Membranes after Pilot Module Operation

The step from the testing of oxygen transport membranes on a lab scale to long-term operation on a large scale is a challenge. In a previous study, membrane failure was observed at defined positions of one end of the cooled tubular Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3-δ membranes after an emergency shutdown. To understand the failure mechanisms, strength degradation and transient stress distribution were investigated by brittle-ring tests and finite element simulations, respectively. A 15% decrease in the characteristic strength of 162 MPa was proven after aging at 850 °C and was attributed to grain coarsening. The reduction in characteristic strength after thermal shock ranged from 5 to 90% depending on the cooling rates, and from 5 to 40% after the first and 20th soft thermal cycling. Simulations indicated the chemical strains induced by a 10-bar feed air and 50 mbar permeate pressure, which caused tensile stresses of up to 70 MPa at the outer surface. These stresses relaxed to 43 MPa by creep within a 1000 h operation. A remaining local stress maximum seemed to be responsible for the fracture. It evolved near the experimentally observed fracture position during a 1000 h permeation and exceeded the temperature and time-dependent strength. The maximum stress was formed by a chemical strain at temperatures above 500 °C but effective creep relaxation needed temperatures above 750 °C.