The mitigation of greenhouse gas emissions on the environment led to the development of non-polluting hydrogen fuel cell use in automobiles. Syngas produced from coal gasification is converted to H2 and CO2 gasses by the water shift reaction. Metallic membranes are used to separate H 2 from CO2 and other gasses obtained from the water shift reaction of coal-derived syngas. Commercial crystalline Pd-Ag membranes are widely used for this purpose; however, Pd is an expensive strategic metal. Thus, inexpensive Ni-Nb-Zr alloys are studied.The permeation property of amorphous membranes are known, however, the mechanism of permeation and the nature of the local atomic order of the amorphous membranes was not fully understood.
In this study, atom dynamics studied by synchrotron x-ray photon correlation spectroscopy (XPCS) showed the movement of heavier elements such as Ni, Nb, and Zr, at room temperature and 373K. The addition of hydrogen significantly accentuates the motion of atoms as the hydrogen occupies the tetrahedral sites within the icosahedra leading to expansion and short-range diffusion, and no long-range diffusion is observed estimated to be ∼10-22 m2/s. Vacuum removal of hydrogen from these membranes showed a contraction of the icosahedra and approached to its original position. This suggests that the process reversible due to the pressure gradient. The XPCS results did not reveal the specific position of hydrogen atoms in the icosahedra; hydrogen goes into the tetrahedral sites of Zr4 and distorted Nb4 sites as determined by neutron vibrational spectroscopy. Total neutron scattering and DFT-MD simulation determine the short-range order of up to 1.8 nm and the nearest neighbor bond distances. Determination of cluster formation was first attempted by using small neutron scattering, but it did not have appropriate “Q” range. Thus atom probe tomography (APT) was attempted. This APT study revealed Nb-rich and Zr-rich clusters embedded in Ni-rich matrix, whose compositions are reported. DFT-MD simulation reveals interconnected icosahedra in the metal matrix. The atom dynamics (NVS and XPCS), atom probe tomography, total neutron scattering studies are discussed which have implication in the mechanisms of hydrogen permeation in amorphous metallic membranes.
|Commitee:||Chen, Wein-Ming, Daemen, Jaak, Jiang, Yanyao, Li, Bin|
|School:||University of Nevada, Reno|
|Department:||Materials Science and Engineering|
|School Location:||United States -- Nevada|
|Source:||DAI-B 79/03(E), Dissertation Abstracts International|
|Keywords:||Amorphous materials, Hydrogen separation membrane, Metallic glass structure, Neutron scattering, Synchrotron x-ray spectroscopy, Xpcs|
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