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Stabilization of Undercooled Metals via Passivating Oxide Layers
Author(s) -
Martin Andrew,
Chang Boyce S.,
Pauls Alana M.,
Du Chuanshen,
Thuo Martin
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013489
Subject(s) - supercooling , nucleation , oxide , passivation , surface tension , chemical physics , materials science , chemical engineering , activation energy , thermodynamics , metal , chemistry , layer (electronics) , nanotechnology , metallurgy , physics , engineering
Undercooling metals relies on frustration of liquid–solid transition mainly by an increase in activation energy. Passivating oxide layers are a way to isolate the core from heterogenous nucleants (physical barrier) while also raising the activation energy (thermodynamic/kinetic barrier) needed for solidification. The latter is due to composition gradients (speciation) that establishes a sharp chemical potential gradient across the thin (0.7–5 nm) oxide shell, slowing homogeneous nucleation. When this speciation is properly tuned, the oxide layer presents a previously unaccounted for interfacial tension in the overall energy landscape of the relaxing material. We demonstrate that 1) the integrity of the passivation oxide is critical in stabilizing undercooled particle, a key tenet in developing heat‐free solders, 2) inductive effects play a critical role in undercooling, and 3) the magnitude of the influence of the passivating oxide can be larger than size effects in undercooling.