A percolation theory for designing corrosion-resistant alloys.

Iron-chromium and nickel-chromium binary alloys containing sufficient quantities of chromium serve as the prototypical corrosion-resistant metals owing to the presence of a nanometre-thick protective passive oxide film1-8. Should this film be compromised by a scratch or abrasive wear, it reforms with little accompanying metal dissolution, a key criterion for good passive behaviour. This is a principal reason that stainless steels and other chromium-containing alloys are used in critical applications ranging from biomedical implants to nuclear reactor components9,10. Unravelling the compositional dependence of this electrochemical behaviour is a long-standing unanswered question in corrosion science. Herein, we develop a percolation theory of alloy passivation based on two-dimensional to three-dimensional crossover effects that accounts for selective dissolution and the quantity of metal dissolved during the initial stage of passive film formation. We validate this theory both experimentally and by kinetic Monte Carlo simulation. Our results reveal a path forward for the design of corrosion-resistant metallic alloys.

Potential-dependent dynamic fracture of nanoporous gold.

When metallic alloys are exposed to a corrosive environment, porous nanoscale morphologies spontaneously form that can adversely affect the mechanical integrity of engineered structures. This form of stress-corrosion cracking is responsible for the well-known 'season cracking' of brass and stainless steel components in nuclear power generating stations. One explanation for this is that a high-speed crack is nucleated within the porous layer, which subsequently injects into non-porous parent-phase material. We study the static and dynamic fracture properties of free-standing monolithic nanoporous gold as a function electrochemical potential using high-speed photography and digital image correlation. The experiments reveal that at electrochemical potentials typical of porosity formation these structures are capable of supporting dislocation-mediated plastic fracture at crack velocities of 200 m s(-1). Our results identify the important role of high-speed fracture in stress-corrosion cracking and are directly applicable to the behaviour of monolithic dealloyed materials at present being considered for a variety of applications.

Dealloying of noble-metal alloy nanoparticles.

Dealloying is currently used to tailor the morphology and composition of nanoparticles and bulk solids for a variety of applications including catalysis, energy storage, sensing, actuation, supercapacitors, and radiation damage resistant materials. The known morphologies, which evolve on dealloying of nanoparticles, include core-shell, hollow core-shell, and porous nanoparticles. Here we present results examining the fixed voltage dealloying of AgAu alloy particles in the size range of 2-6 and 20-55 nm. High-angle annular dark-field scanning transmission electron microcopy, energy dispersive, and electron energy loss spectroscopy are used to characterize the size, morphology, and composition of the dealloyed nanoparticles. Our results demonstrate that above the potential corresponding to Ag(+)/Ag equilibrium only core-shell structures evolve in the 2-6 nm diameter particles. Dealloying of the 20-55 nm particles results and in the formation of porous structures analogous to the behavior observed for the corresponding bulk alloy. A statistical analysis that includes the composition and particle size distributions characterizing the larger particles demonstrates that the formation of porous nanoparticles occurs at a well-defined thermodynamic critical potential.

Spontaneous evolution of bicontinuous nanostructures in dealloyed Li-based systems.

Dealloying, the selective dissolution of one or more of the elemental components of an alloy, is an important corrosion mechanism and a technologically relevant process used to fabricate nanoporous metals for a variety of applications including catalysis, sensing, actuation, supercapacitors and radiation-damage-resistant materials. In noble-metal alloy systems for which the ambient-temperature solid-state diffusivity is minuscule, dealloying occurs at a composition-dependent critical potential above which bicontinuous nanoporous structures evolve and below which a full-coverage layer of the more-noble component forms causing the alloy surface to become passive. In contrast, for alloy systems exhibiting significant solid-state diffusive transport, our understanding of dealloying-induced morphologies and the electrochemical parameters controlling this are largely unexplored. Here, we examine dealloying of Li from Li-Sn alloys and show that depending on alloy composition, particle size and dealloying rate, all known dealloyed morphologies evolve including bicontinuous nanoporous structures and hollow core-shell particles. Furthermore, we elucidate the role of bulk diffusion in morphology evolution using chronopotentiometry and linear sweep voltammetry. Our results may have implications for lithium-ion battery development while significantly broadening the spectrum of strategies for obtaining new nanoporous materials through dealloying.

Electrochemical stability of elemental metal nanoparticles.

The corrosion behavior of nanometer-scale solids is important in applications ranging from sensing to catalysis. Here we present a general thermodynamic analysis of this for the case of elemental metals and use the analysis to demonstrate the construction of a particle-size-dependent potential-pH diagram for the case of platinum. We discuss the data set required for the construction of such diagrams in general and describe how some parameters are accessible via experiment while others can only be reliably determined from first-principles-based electronic structure calculations. In the case of Pt, our analysis predicts that particles of diameter less than approximately 4 nm dissolve via the direct electrochemical dissolution pathway, Pt --> Pt(2+) + 2e(-), while larger particles form an oxide. As an extension of previously published work by our group, electrochemical scanning tunneling microscopy is used to examine the stability of individual Pt-black particles with diameters ranging from 1 to 10 nm. Our experimental results confirm the thermodynamic predictions, suggesting that our analysis provides a general framework for the assessment of the electrochemical stability of nanoscale elemental metals.

Superhard nanobuttons: constraining crystal plasticity and dealing with extrinsic effects at the nanoscale.

The compressive plastic strength of nanosized single-crystal metallic pillars is known to depend on their diameter D. Herein, the role of pillar height h is analyzed instead, and the suppression of the generalized crystal plasticity below a critical value h(CR) is observed. Novel in situ compression tests on regular pillars as well as nanobuttons, that is, pillars with h < h(CR), show that the latter are much harder, withstanding stresses >2 GPa. A statistical model that holds for both pillars and buttons is formulated. Owing to their superhard nature, the nanobuttons examined here underline with unprecedented resolution the extrinsic effects-often overlooked-that naturally arise during testing when the Saint-Venant assumption ceases to be accurate. The bias related to such effects is identified in the test data and removed when possible. Finally, continuous hardening is observed to occur under increasing stress level, in analogy to reports on nanoparticles. From a metrological standpoint the results expose some difficulties in nanoscale testing related to current methodology and technology. The implications of the analysis of extrinsic effects go beyond nanobuttons and extend to nano-/microelectromechanical system design and nanomechanics in general.

Electrochemical stability of nanometer-scale Pt particles in acidic environments.

Understanding and controlling the electrochemical stability or corrosion behavior of nanometer-scale solids is vitally important in a variety of applications such as nanoscale electronics, sensing, and catalysis. For many applications, the increased surface to volume ratio achieved by particle size reduction leads to lower materials cost and higher efficiency, but there are questions as to whether the intrinsic stability of materials also decreases with particle size. An important example of this relates to the stability of Pt catalysts in, for example, proton exchange fuel cells. In this Article, we use electrochemical scanning tunneling microscopy to, for the first time, directly examine the stability of individual Pt nanoparticles as a function of applied potential. We combine this experimental study with ab initio computations to determine the stability, passivation, and dissolution behavior of Pt as a function of particle size and potential. Both approaches clearly show that smaller Pt particles dissolve well below the bulk dissolution potential and through a different mechanism. Pt dissolution from a nanoparticle occurs by direct electro-oxidation of Pt to soluble Pt(2+) cations, unlike bulk Pt, which dissolves from the oxide. These results have important implications for understanding the stability of Pt and Pt alloy catalysts in fuel cell architectures, and for the stability of nanoparticles in general.

Synthesis and characterization of large colloidal cobalt particles.

Large colloidal environmentally stable silica-coated cobalt particles were synthesized by combining the sodium borohydride reduction in aqueous solution and the Stöber method. Low size polydisperse cobalt spheres with an average size of 95 nm were synthesized by using a borohydride reduction method and were subsequently coated with a thin layer of silica by means of hydrolysis and condensation of tetraethylorothosilicate (TEOS) in an aqueous/ethanolic solution. The large uniform cobalt spheres consist of smaller metallic Co clusters, explaining the superparamagnetic behavior of the spheres. The particles were investigated by transmission electron microscopy (TEM) and vibrating sample magnetometry (VSM).