Quantitative 3D Characterization for Kinetics of Corrosion Initiation and Propagation in Additively Manufactured Austenitic Stainless Steel.

In situ X-ray computed tomography (X-ray CT) is used to investigate the effects of characteristic microstructural features on the pitting initiation and propagation in austenitic stainless steel specimens prepared with laser powder bed fusion (LPBF) additive manufacturing. In situ X-ray CT in probing the mechanism and kinetics of localized corrosion is demonstrated by immersing two LPBF specimens with different porosities in an aggressive ferric chloride solution for the evaluation of corrosion. X-ray CT images are acquired from the specimens after every 8 hours of immersion over an extended period of time (216 hours). Corrosion pit growth is then quantitatively analyzed with a data-constrained modeling method. The pitting growth mechanism of LPBF stainless steel is found to be different from that of conventional stainless steels. More specifically, the mechanism of corrosion pit initiation is closely correlated with the original lack of fusion porosity (LOF) distribution on the surface of the specimens and preferential pit propagation through the LOF pores inside the specimens. Pit growth kinetics are derived from pit volume changes determined through 3D data analysis. The pit growth kinetics in LPBF specimens are found to vary in the initial pit formation, competitive pit propagation, and the dominant pit growth stages.

Observations on the Early Stages of Corrosion on AA2099-T83.

An Al­Cu­Li aerospace alloy has been investigated to determine the order in which corrosion at different types of sites occurs in AA2099-T83. Specifically, the sequence of galvanic attack on intermetallic (IM) particles and other sites of AA2099-T83 was determined as a function of time, in 0.1 M NaCl, through the use of scanning electron microscopy and electron backscatter diffraction characterization techniques. The earliest attack occurred at isolated grains and grain boundaries and on Li-containing dispersoids. Similarly, some constituent IM particles showed evidence of trenching in the surrounding alloy matrix. These IM particles included Al7Cu2Fe and another group of unidentified particles which displayed complete trenching within the first 10 min of exposure. Al13(Fe, Mn)4 were next most active followed by Al37Fe12Cu2 with Al6(Fe,Mn) and large TiB2 particles being the least active.

Investigation of the Internal Structure of a Modern Seafloor Hydrothermal Chimney With a Combination of EBSD, EPMA, and XRD.

Samples from the sphalerite-dominated zone of a seafloor massive sulfide chimney, the Satanic Mills Chimney of the PACMANUS hydrothermal field, have been investigated to determine the internal macrostructure and microstructure of this zone, the phases present, and the distribution of metals. A combination of electron probe microanalysis, electron backscattered diffraction, and x-ray diffraction has been used. At the macroscale, this zone of the chimney wall is heavily porous and is comprised primarily of sphalerite, enclosing minor chalcopyrite, pyrite, and wurtzite. A Pb­As sulfosalt layer of possible microbial origins is present at the outer edge of the sphalerite matrix, next to a pore. The sphalerite has grown in globules on the order of 300 µm in diameter. At the microscale, the sphalerite features a colloform texture and a duplex-type grain structure consisting of either fine-grain regions in the center surrounded by coarse-grained regions or radiating coarse grains only. Pb- and As-rich bands have been detected in the colloform sphalerite, and growth twins have been observed in both the sphalerite and chalcopyrite crystals. A qualitative description of the growth of a typical globule is given, including nucleation, crystal growth, and solute redistribution.

Leaching Behavior and Corrosion Inhibition of a Rare Earth Carboxylate Incorporated Epoxy Coating System.

While paint coatings act as important barriers to corrosion, defects can lead to localized, rapid metal loss. The addition of corrosion inhibitors that are capable of leaching from a coating to protect the metal surface at a defect can prevent this type of corrosion. This work investigates the release and corrosion protection capabilities of two rare earth (RE) carboxylate inhibitors from an epoxy coating as an initial step to understanding their leaching behavior and interaction with the coating system. Leaching experiments were performed via inductively coupled plasma mass spectroscopy (ICP-MS) analyses of the solutions in which free-standing coatings loaded with varying concentrations of inhibitor compounds had been immersed. Inhibitor release from the epoxy coating was observed to be dependent on initial inhibitor concentration, inhibitor chemistry, and solution pH conditions. The coating systems with greater initial inhibitor loadings showed higher leaching rates, particularly in acidic environments. Following immersion, the absence of characteristic inhibitor peaks in the FTIR spectra of the coatings also confirmed leaching had taken place. Cross-sectional views of the coatings after exposure to the pH 1 environment presented a chloride infusion zone at the coating/solution interface where the inhibitor had leached out. The RE active inhibition provided by the leached RE carboxylate inhibitors was verified by exposure of a coating defect to a chloride contaminated environment.

An Examination of the Composition and Microstructure of Coarse Intermetallic Particles in AA2099-T8, Including Li Detection.

Electron and proton microprobes, along with electron backscatter diffraction (EBSD) analysis were used to study the microstructure of the contemporary Al-Cu-Li alloy AA2099-T8. In electron probe microanalysis, wavelength and energy dispersive X-ray spectrometry were used in parallel with soft X-ray emission spectroscopy (SXES) to characterize the microstructure of AA2099-T8. The electron microprobe was able to identify five unique compositions for constituent intermetallic (IM) particles containing combinations of Al, Cu, Fe, Mn, and Zn. A sixth IM type was found to be rich in Ti and B (suggesting TiB2), and a seventh IM type contained Si. EBSD patterns for the five constituent IM particles containing Al, Cu, Fe, Mn, and Zn indicated that they were isomorphous with four phases in the 2xxx series aluminium alloys including Al6(Fe, Mn), Al13(Fe, Mn)4 (two slightly different compositions), Al37Cu2Fe12 and Al7Cu2Fe. SXES revealed that Li was present in some constituent IM particles. Al SXES mapping revealed an Al-enriched (i.e., Cu, Li-depleted) zone in the grain boundary network. From the EBSD analysis, the kernel average misorientation map showed higher levels of localized misorientation in this region, suggesting greater deformation or stored energy. Proton-induced X-ray emission revealed banding of the TiB2 IM particles and Cu inter-band enrichment.

Atom probe tomography study of the nanoscale heterostructure around an Al20Mn3Cu2 dispersoid in aluminum alloy 2024.

Atom probe tomography (APT) has been used to investigate the surface and sub-surface microstructures of aluminum alloy 2024 (AA2024) in the T3 condition (solution heat treated, cold worked, and naturally aged to a substantially stable condition). This study revealed surface Cu enrichment on the alloy matrix, local chemical structure around a dispersoid Al20Mn3Cu2 particle including a Cu-rich particle and S-phase particle on its external surface. Moreover, there was a significant level of hydrogen within the dispersoid, indicating that it is a hydrogen sink. These observations of the nanoscale structure around the dispersoid particle have considerable implications for understanding both corrosion and hydrogen embrittlement in high-strength aluminum alloys.

Reducing ZnO nanoparticle cytotoxicity by surface modification.

Nanoparticulate zinc oxide (ZnO) is one of the most widely used engineered nanomaterials and its toxicology has gained considerable recent attention. A key aspect for controlling biological interactions at the nanoscale is understanding the relevant nanoparticle surface chemistry. In this study, we have determined the disposition of ZnO nanoparticles within human immune cells by measurement of total Zn, as well as the proportions of extra- and intracellular dissolved Zn as a function of dose and surface coating. From this mass balance, the intracellular soluble Zn levels showed little difference in regard to dose above a certain minimal level or to different surface coatings. PEGylation of ZnO NPs reduced their cytotoxicity as a result of decreased cellular uptake arising from a minimal protein corona. We conclude that the key role of the surface properties of ZnO NPs in controlling cytotoxicity is to regulate cellular nanoparticle uptake rather than altering either intracellular or extracellular Zn dissolution.

Electron-beam-induced carbon contamination on silicon: characterization using Raman spectroscopy and atomic force microscopy.

Electron-beam-induced carbon film deposition has long been recognized as a side effect of scanning electron microscopy. To characterize the nature of this type of contamination, silicon wafers were subjected to prolonged exposure to 15 kV electron beam energy with a probe current of 300 pA. Using Raman spectroscopy, the deposited coating was identified as an amorphous carbon film with an estimated crystallite size of 125 A. Using atomic force microscopy, the cross-sectional profile of the coating was found to be raised and textured, indicative of the beam raster pattern. A map of the Raman intensity across the coating showed increased intensity along the edges and at the corner of the film. The intensity profile was in excess of that which could be explained by thickness alone. The enhancement was found to correspond with a modeled local field enhancement induced by the coating boundary and showed that the deposited carbon coating generated a localized disturbance in the opto-electrical properties of the substrate, which is compared and contrasted with Raman edge enhancement that is produced by surface structure in silicon.