(Digital Presentation) Advances in Cryo-Atom Probe Tomography Studies on Formation of Nanoporous Metals By Dealloying
Authors: El-Zoka Ayman A. , Kim Se-Ho , Khanchandani Heena , Stephenson Leigh T. , Gault Baptiste 
Published: July 2022

The selective removal of a less noble (more chemically active) metal from a mixture of 2–3 metals can yield a bicontinuous, open-pore, 3D nanoporous metal (NPM), that is rich in the more noble metal(s)1. NPMs have been successfully developed by the intelligent use of the conventionally-undesired dealloying corrosion. The excellent properties of NPMs are attributed to the surface area-to-volume ratio, and high curvature of nanoligament surfaces 2,3
.

Experimental work on NPMs revealed the formation of uniformly nanoporous structure by dealloying AgAu alloy in nitric acid, a method still widely used until today for making nanoporous gold (NPG). This dealloying process is complex: the selective dissolution of the less-noble element should lead to the creation of surface vacancies or adatoms, which migrate across the surface to form surface roughening features, and thus assisting the migration of the residual more-noble atoms, leading to island growth4.
Ex-situ characterization cannot fully explain some intricate details at the dealloying interface and at the surface of the formed nanoligaments. Gaining insight into initial stages of dealloying, and the inherent competition between surface roughening from the dissolution of silver atoms, and surface smoothening from surface diffusion of gold atoms5, can only be done effectively by monitoring the changes occurring at the surfaces of alloys in-situ. Several notable in-situ methods were used to characterize formation of NPMs, such as TEM 6, often limited by the 2D nature of the analysis. Also, synchrotron-based methods such as X-ray nanotomography 7 and neutron scattering 8 were limited by resolution and lack of compositional contrast. APT is a powerful technique that provides 3D characterization9 and near-atomic-scale compositional analysis of materials, and could complement the abovementioned suite of techniques, yet the analysis of nanoporous structure comes with challenges.
Aiming to develop a universal method for probing corrosion systems by APT, the concept of embedding frozen solutions in corroded systems was developed and reported in a recent reporting 10 of analyzing NPMs along with frozen water-based solutions. This involved the joint use of an ensemble of equipment and techniques that connect the frozen liquid to the atom probe, including a plasma-focused ion beam (PFIB) where the preparation of APT specimens uses a cryostage, and transfer of the frozen sample through ultra-high-vacuum suitcase11. This paved the way for many advances in characterization of corrosion processes, as the possibility of freezing corrosion reactions for APT (now known as cryo-APT) arises. Here, we further develop cryo-APT to probe into the mechanisms of dealloying in AgAu and how that leads to the formation of NPG using our in-situ approach. Nanoligament structure will be correlated with dealloying conditions by making observations at the solid-liquid interface in 3D.

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