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Mass Transport Enhancement in Copper Electrodeposition due to Gas Co-Evolution

Gonzalez-Pena, Omar Israel
http://orcid.org/0000-0001-7327-6145
http://rave.ohiolink.edu/etdc/view?acc_num=case1439826379

Abstract Details

2015, Doctor of Philosophy, Case Western Reserve University, Chemical Engineering.
Metal electrodeposition is often associated with simultaneous hydrogen co-evolution. The presence of bubbles complicates the design and control of electrodeposition processes. This is particularly relevant to the electrodeposition from aqueous electrolytes of numerous metals with standard potentials that are negative to hydrogen. As shown in this study, hydrogen co-evolution enhances the transport rates of the metal deposition reaction beyond those predicted by the classical, steady-state mass transport model. Available models addressing transport in the presence of gas co-evolution are based on free convection that is enhanced by the rising bubble cloud. However, there are no models that address mass transfer enhancement by bubbles under forced convection, such as analyzed here for the commonly used, facing-down rotating disk electrode (RDE). This study characterizes experimentally the phenomenon and introduces a model for quantifying it. Experimental data was collected in plating copper at high cathodic overpotentials (-0.4 to -1.0V vs SHE) from acidified copper sulfate on a RDE. The transport enhancement (~2-6 fold) was determined by measuring the copper deposition by gravimetry. Pulse experiments, where the current decay was measured following a short bubble generation confirmed the linkage between the current enhancement and the presence of bubbles. A model based on fresh electrolyte replenishing the volume vacated by the translating bubbles and thus subjecting regions of the electrode to enhanced transient currents has been derived. The model correlates the experimental data indicating higher transport enhancement with increasing cathodic polarization and dependence of the enhancement on the rotation rate and on the bulk copper concentration.
Uziel Landau (Committee Chair)
Rohan Akolkar (Committee Member)
Donald Feke (Committee Member)
Daniel Scherson (Committee Member)
Mohan Sankaran (Committee Member)
185 p.
Applied Mathematics; Chemical Engineering; Chemistry; Engineering; Materials Science; Mechanical Engineering; Physics; Technology
surface renewal, copper electrodeposition, mass transfer enhancement, limiting current density, Levich, penetration model, hydrogen co-evolution, von Karman velocities, Rotating Disk Electrode, electrode area correction, surface roughness, bubbles

Recommended Citations

Citations

  • Gonzalez-Pena, O. I. (2015). Mass Transport Enhancement in Copper Electrodeposition due to Gas Co-Evolution [Doctoral dissertation, Case Western Reserve University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=case1439826379

    APA Style (7th edition)

  • Gonzalez-Pena, Omar. Mass Transport Enhancement in Copper Electrodeposition due to Gas Co-Evolution. 2015. Case Western Reserve University, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=case1439826379.

    MLA Style (8th edition)

  • Gonzalez-Pena, Omar. "Mass Transport Enhancement in Copper Electrodeposition due to Gas Co-Evolution." Doctoral dissertation, Case Western Reserve University, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=case1439826379

    Chicago Manual of Style (17th edition)

case1439826379
575
© 2015, all rights reserved.
This open access ETD is published by Case Western Reserve University School of Graduate Studies and OhioLINK.