Electrodeposition
of metals is relevant to much of materials research including catalysis,
batteries, antifouling, and anticorrosion coatings. The sacrificial
characteristics of zinc used as a protection for ferrous substrates
is a central corrosion protection strategy used in automotive, aviation,
and DIY industries. Zinc layers are often used for protection by application
to a base metal in a hot dip galvanizing step; however, there is a
significant interest in less energy and material intense electroplating
strategies for zinc. At present, large-scale electroplating is mostly
done from acidic zinc solutions, which contain potentially toxic and
harmful additives. Alkaline electroplating of zinc offers a route
to using environment-friendly green additives. Within the scope of
this study an electrolyte containing soluble zinc hydroxide compound
and a polyquarternium polymer as additive were studied during zinc
deposition on gold model surfaces. Cyclic voltammetry experiments
and in-situ electrochemical quartz crystal microbalance with dissipation
(QCM-D) measurements were combined to provide a detailed understanding
of fundamental steps that occur during polymer-mediated alkaline zinc
electroplating. Data indicate that a zincate-loaded polymer can adsorb
within the inner sphere of the electric double layer, which lowers
the electrostatic penalty of the zincate approach to a negatively
charged surface. X-ray photoelectron spectroscopy also supports the
assertion that the zincate-loaded polymer is brought tightly to the
surface. We also find an initial polymer depletion followed by an
active deposition moderation via control of the zincate diffusion
through the adsorbed polymer.
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