Strategies for Preparing and Analyzing Thin Passive Films With Atom Probe Tomography.

Atom probe tomography (APT) provides a unique, three-dimensional map of elemental and isotopic distributions over a wide range of materials with near-atomic scale resolution and is particularly strong at analyzing buried interfaces within materials. However, it is much more difficult to apply atom probe to the analysis of nanoscale surface films, such as those formed during alloy passivation, where unique challenges persist for sample preparation and data collection. Here, we present sample preparation strategies involving the deposition of a <100 nm capping layer that enables reliable characterization of thin passive films ∼2-5 nm thick formed on binary and multiprincipal element alloys via APT.

Spatial mapping of the localized corrosion behavior of a magnesium alloy AZ31B tungsten inert gas weld.

Sections of a magnesium alloy, AZ31B, joined with tungsten inert gas (TIG) welding, were examined with scanning electrochemical microscopy (SECM) and scanning Kelvin probe force microscopy (SKPFM) to investigate corrosion mechanisms by correlating observed corrosion behavior with weld-affected microstructural variations. Insight into the changing nature of the galvanic couples between weld zones and at localized microgalvanic sites were investigated using SECM and SKPFM to map both electrochemically active regions and Volta potential differences across the weld-affected zones. The formation of an Al-Zn solidification network in the fusion zone (FZ) at and near the TIG weld epicenter differs from the outer heat-affected zone (HAZ), where intermetallic particles (IMPs) are the notable secondary phase from the magnesium matrix.

Wavebreakers in excitable systems and possible applications for corrosion mitigation.

Traveling waves of excitation arise from the spatial coupling of local nonlinear events by transport processes. In corrosion systems, these electro-dissolution waves relay local perturbations across large portions of the metal surface, significantly amplifying overall damage. For the example of the magnesium alloy AZ31B exposed to sodium chloride solution, we report experimental results suggesting the existence of a vulnerable zone in the wake of corrosion waves where local perturbations can induce a unidirectional wave pulse or segment.

Morphogenic Modeling of Corrosion Reveals Complex Effects of Intermetallic Particles.

Corrosion processes are often discussed as stochastic events. Here, it is shown that some of these seemingly random processes are not driven by nanoscopic fluctuations but rather by the spatial distribution of micrometer-scale heterogeneities that trigger fast reactions associated with corrosion. Using a novel excitable reaction-diffusion model, corrosion waves traveling over the metal surface and the associated material loss are described.

One dimensional wormhole corrosion in metals.

Corrosion is a ubiquitous failure mode of materials. Often, the progression of localized corrosion is accompanied by the evolution of porosity in materials previously reported to be either three-dimensional or two-dimensional. However, using new tools and analysis techniques, we have realized that a more localized form of corrosion, which we call 1D wormhole corrosion, has previously been miscategorized in some situations.

Recent Advances in Corrosion Science Applicable To Disposal of High-Level Nuclear Waste.

High-level radioactive waste is accumulating at temporary storage locations around the world and will eventually be placed in deep geological repositories. The waste forms and containers will be constructed from glass, crystalline ceramic, and metallic materials, which will eventually come into contact with water, considering that the period of performance required to allow sufficient decay of dangerous radionuclides is on the order of 10-10 years. Corrosion of the containers and waste forms in the aqueous repository environment is therefore a concern.

Electrochemical metrics for corrosion resistant alloys.

Corrosion is an electrochemical phenomenon. It can occur via different modes of attack, each having its own mechanisms, and therefore there are multiple metrics for evaluating corrosion resistance. In corrosion resistant alloys (CRAs), the rate of localized corrosion can exceed that of uniform corrosion by orders of magnitude.

The pervasive threat of lead (Pb) in drinking water: Unmasking and pursuing scientific factors that govern lead release.

The Flint water crisis raised questions about the factors resulting in unacceptable soluble lead concentrations in the city's drinking water. Although water treatment strategies, failure to follow regulations, and unethical behavior were all factors, knowledge deficits at the intersection of several scientific fields also contributed to the crisis. Pursuit of opportunities to address unresolved scientific questions can help avert future lead poisoning disasters.

Nonequilibrium Solute Capture in Passivating Oxide Films.

We report experimental results on the composition and crystallography of oxides formed on NiCrMo alloys during both high-temperature oxidation and aqueous corrosion experiments. Detailed characterization using transmission electron microscopy and diffraction, aberration-corrected chemical analysis, and atom probe tomography shows unexpected combinations of composition and crystallography, far outside thermodynamic solubility limits. The results are explained using a theory for nonequilibrium solute capture that combines thermodynamic, kinetic, and density functional theory analyses.

Time-dependent Enhanced Corrosion of Ti6Al4V in the Presence of HO and Albumin.

There is increasing concern regarding the biological consequences of metal release from implants. However, the mechanisms underpinning implant surface degradation, especially in the absence of wear, are often poorly understood. Here the synergistic effect of albumin and HO on corrosion of Ti6Al4V in physiological saline is studied with electrochemical methods.

Laser irradiation of Mg-Al-Zn alloy: Reduced electrochemical kinetics and enhanced performance in simulated body fluid.

As a lightweight metal with mechanical properties similar to natural bone, Mg and its alloys are great prospects for biodegradable, load bearing implants. However, rapid degradation and H gas production in physiological media has prevented widespread use of Mg alloys. Surface heterogeneities in the form of intermetallic particles dominate the corrosion response.

The effect of absorbed hydrogen on the dissolution of steel.

Atomic hydrogen (H) was introduced into steel (AISI 1018 mild steel) by controlled cathodic pre-charging. The resultant steel sample, comprising about 1 ppmw diffusible H, and a reference uncharged sample, were studied using atomic emission spectroelectrochemistry (AESEC). AESEC involved potentiodynamic polarisation in a flowing non-passivating electrolyte (0.

Corrosion chemistry closing comments: opportunities in corrosion science facilitated by operando experimental characterization combined with multi-scale computational modelling.

Recent advances in characterization tools, computational capabilities, and theories have created opportunities for advancement in understanding of solid-fluid interfaces at the nanoscale in corroding metallic systems. The Faraday Discussion on Corrosion Chemistry in 2015 highlighted some of the current needs, gaps and opportunities in corrosion science. Themes were organized into several hierarchical categories that provide an organizational framework for corrosion.

Revisiting the electrochemical impedance spectroscopy of magnesium with online inductively coupled plasma atomic emission spectroscopy.

The electrochemical impedance of reactive metals such as magnesium is often complicated by an obvious inductive loop with decreasing frequency of the AC polarising signal. The characterisation and ensuing explanation of this phenomenon has been lacking in the literature to date, being either ignored or speculated. Herein, we couple electrochemical impedance spectroscopy (EIS) with online atomic emission spectroelectrochemistry (AESEC) to simultaneously measure Mg-ion concentration and electrochemical impedance spectra during Mg corrosion, in real time.