Isothermal nucleation and growth kinetics of Pd/Ag alloy phase via in situ time-resolved high-temperature X-ray diffraction (HTXRD) analysis

M. Engin Ayturk, E. A. Payzant, S. A. Speakman, Y. H. Ma

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Abstract

Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex situ studies carried out by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in situ time-resolved high-temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 °C, 550 °C and 600 °C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500 °C, 550 °C and 600 °C, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. Indeed, the cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 kJ/mol and 185.6 kJ/mol and in excellent agreement with the literature values (183-239.5 kJ/mol). Finally, the in situ annealing of the 15.6 μm thick composite Pd/Ag/PSS membrane at 550 °C in hydrogen atmosphere indicated that the Pd/Ag alloy phase formation was not complete even after 500 h. According to the Avrami model, the increase in the hydrogen permeance from 7.1 m3/m2 h atm0.5 to 21.3 m3/m2 h atm0.5 at 550 °C over a period of 500 h corresponded to an ∼83% Pd/Ag alloy phase formation.

Original languageEnglish
Pages (from-to)97-111
Number of pages15
JournalJournal of Membrane Science
Volume316
Issue number1-2
DOIs
StatePublished - May 15 2008

Funding

The authors gratefully acknowledge the financial support provided by Shell International Exploration & Production Inc. and Shell Hydrogen. Research activities at ORNL were sponsored by the Assistant Secretary for Energy Efficiency and Renewable Energy, Office of FreedomCAR and Vehicle Technologies, as part of the High Temperature Materials Laboratory User Program, Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the US. Department of Energy under contract number DE-AC05-00OR22725.

FundersFunder number
Office of FreedomCar
Secretary for Energy Efficiency and Renewable Energy
Shell Hydrogen
Shell International Exploration & Production Inc.
U.S. Department of EnergyDE-AC05-00OR22725
Oak Ridge National Laboratory

    Keywords

    • Composite Pd/Ag alloy membranes
    • Electroless plating
    • H separation
    • In situ time-resolved high-temperature X-ray diffraction
    • Isothermal annealing

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