Oxygen Transport Membranes

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The focus of this research was to develop new membrane materials by synthesizing different compounds and determining their defect structures, crystallographic structures and electrical properties. In addition to measuring electrical conductivity, oxygen vacancy concentration was also evaluated using thermogravimetry, Neutron diffraction and Moessbauer Spectroscopy. The reducing conditions (CO{sub 2}/CO/H{sub 2} gas mixtures with steam) as encountered in a reactor environment can be expected to have significant influence on the mechanical properties of the oxides membranes. Various La based materials with and without Ti were selected as candidate membrane materials for OTM. The maximum electrical conductivity of LSF in air as ... continued below

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Bandopadhyay, S. August 30, 2008.

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The focus of this research was to develop new membrane materials by synthesizing different compounds and determining their defect structures, crystallographic structures and electrical properties. In addition to measuring electrical conductivity, oxygen vacancy concentration was also evaluated using thermogravimetry, Neutron diffraction and Moessbauer Spectroscopy. The reducing conditions (CO{sub 2}/CO/H{sub 2} gas mixtures with steam) as encountered in a reactor environment can be expected to have significant influence on the mechanical properties of the oxides membranes. Various La based materials with and without Ti were selected as candidate membrane materials for OTM. The maximum electrical conductivity of LSF in air as a function of temperature was achieved at < 600 C and depends on the concentration of Sr (acceptor dopant). Oxygen occupancy in LSF was estimated using Neutron diffractometry and Moessbauer Spectroscopy by measuring magnetic moment changes depending on the Fe{sup 3+} and Fe{sup 4+} ratio. After extensive studies of candidate materials, lanthanum ferrites (LSF and LSFT) were selected as the favored materials for the oxygen transport membrane (OTM). LSF is a very good material for an OTM because of its high electronic and oxygen ionic conductivity if long term stability and mechanical strength are improved. LSFT not only exhibits p-type behavior in the high oxygen activity regime, but also has n-type conduction in reducing atmospheres. Higher concentrations of oxygen vacancies in the low oxygen activity regime may improve the performance of LSFT as an OTM. The hole concentration is related to the difference in the acceptor and donor concentration by the relation p = [Sr'{sub La}]-[Ti{sm_bullet}{sub Fe}]. The chemical formulation predicts that the hole concentration is, p = 0.8-0.45 or 0.35. Experimental measurements indicated that p is about {approx} 0.35. The activation energy of conduction is 0.2 eV which implies that LSCF conducts via the small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume dominated the fracture origins and the overall fracture was purely transgranular. The dual phase membranes have been evaluated for structural properties. An increasing crack growth resistance was observed for the membranes heat-treated at 1000 C in air and N{sub 2} with increasing crack length. The combined effect of thermal and elastic mismatch stresses on the crack path was studied and the fracture behavior of the dual phase composite at the test conditions was analyzed. Ceramic/metal (C/M) seals are needed to form a leak-tight interface between the OTM and a nickel-base super alloy. It was concluded that Ni-based brazing alloys provided the best option in terms of brazing temperature and final operating conditions after analyzing several possible brazing systems. A mechanical testing procedure has been developed. This model was tested with model ceramic/metal systems but it is expected to be useful for testing concentric perovskite/metal seals.

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  • Report No.: None
  • Grant Number: FC26-99FT40054
  • DOI: 10.2172/940905 | External Link
  • Office of Scientific & Technical Information Report Number: 940905
  • Archival Resource Key: ark:/67531/metadc892991

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  • August 30, 2008

Added to The UNT Digital Library

  • Sept. 27, 2016, 1:39 a.m.

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  • Nov. 30, 2016, 3:15 p.m.

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Bandopadhyay, S. Oxygen Transport Membranes, report, August 30, 2008; United States. (digital.library.unt.edu/ark:/67531/metadc892991/: accessed October 22, 2018), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.