Maria Jazmin Duarte

Element-Resolved Corrosion Analysis of Stainless-Type Glass-Forming Steels

Rust Resistance The rusting of iron and steel can be prevented through the addition of 11% or more chromium. The addition of molybdenum can enhance the corrosion resistance, with a complex interplay between the Cr and Mo atoms. However, if chemical variations exist, corrosion can still occur in localized regions or if the surface layer is mechanically abraded. Duarte et al. (p. 372) studied the corrosive failure of an iron-based glassy alloy. A combination of atom probe tomography, electron microscopy, and x-ray diffraction was used to build up a near atomistic picture of local variations in the metal as it was heated and allowed to crystallize, and the impact these processes have on the corrosion resistance. Measurements of the local composition of a steel alloy are correlated with the corrosion resistance. Ultrathin passive films effectively prevent the chemical attack of stainless steel grades in corrosive environments; their stability depends on the interplay between structure and chemistry of the constituents iron, chromium, and molybdenum (Fe-Cr-Mo). Carbon (C), and eventually boron (B), are also important constituents of steels, although in small quantities. In particular, nanoscale inhomogeneities along the surface can have an impact on material failure but are still poorly understood. Addressing a stainless-type glass-forming Fe50Cr15Mo14C15B6 alloy and using a combination of complementary high-resolution analytical techniques, we relate near-atomistic insights into increasingly inhomogeneous nanostructures with time- and element-resolved dissolution behavior. The progressive elemental partitioning on the nanoscale determines the degree of passivation. A detrimental transition from Cr-controlled passivity to Mo-controlled breakdown is dissected atom by atom, demonstrating the importance of nanoscale knowledge for understanding corrosion.

Structural and functional characterization of enamel pigmentation in shrews.

Pigmented tooth enamel occurs in several vertebrate clades, ranging from mammals to fish. Although an iron compound is associated with this orange to red colored pigmentation, its chemical and structural organization within the enamel is unknown. To determine the nature of the iron compound, we investigated heavily pigmented teeth of the northern short-tailed shrew Blarina brevicauda using combined characterization techniques such as scanning and transmission electron microscopy and synchrotron X-ray diffraction. We found that the pigmentation of the enamel with an iron content of around 8wt% results from a close to amorphous magnetite phase deposited around the nm-sized enamel crystals. Furthermore, the influence of the pigmentation on the enamel hardness was determined by nanoindentation measurements. Finally, the biomechanical function and biological context are discussed in light of the obtained results.

Star-Shaped Crystallographic Cracking of Localized Nanoporous Defects

On self-assembled monolayer-covered Cu-Au substrates, localized volume shrinkage at initial dealloying sites leads to cracks within the attacked regions. It is started from well-controlled surface structures to gain fundamental insights in the driving mechanisms of localized corrosion and crack formation. Both the crack density and the crack morphology are critically dependent on surface orientation, crystallography, and inhibitor molecule species.

Self‐Assembled Monolayers: Star‐Shaped Crystallographic Cracking of Localized Nanoporous Defects (Adv. Mater. 33/2015)

On page 4877, F. U. Renner, A. Bashir, M. Valtiner, and co-workers describe a star-like dealloying corrosion morphology that appears during the localized attack of smooth well-prepared Cu-Au surfaces. The surfaces are initially protected by thiol or selenol inhibitior films. Localized dealloying of Cu-Au produces nanoporous gold under stress and crystallographic cracks - thereby opening a new approach combining surface science with nanoscale mechanical testing.