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Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn

Additive manufacturing of metallic components – Process, structure and properties

The halogen bond occurs when there is evidence of a net attractive interaction between an electrophilic region associated with a halogen atom in a molecular entity and a nucleophilic region in another, or the same, molecular entity. In this fairly extensive review, after a brief history of the interaction, we will provide the reader with a snapshot of where the research on the halogen bond is now, and, perhaps, where it is going. The specific advantages brought up by a design based on the use of the halogen bond will be demonstrated in quite different fields spanning from material sciences to biomolecular recognition and drug design.

The Halogen Bond

This article presents an overview of the developments in stainless steels made since the 1990s. Some of the new applications that involve the use of stainless steel are also introduced. A brief introduction to the various classes of stainless steels, their precipitate phases and the status quo of their production around the globe is given first. The advances in a variety of subject areas that have been made recently will then be presented. These recent advances include (1) new findings on the various precipitate phases (the new J phase, new orientation relationships, new phase diagram for the Fe–Cr system, etc.); (2) new suggestions for the prevention/mitigation of the different problems and new methods for their detection/measurement and (3) new techniques for surface/bulk property enhancement (such as laser shot peening, grain boundary engineering and grain refinement). Recent developments in topics like phase prediction, stacking fault energy, superplasticity, metadynamic recrystallisation and the calculation of mechanical properties are introduced, too. In the end of this article, several new applications that involve the use of stainless steels are presented. Some of these are the use of austenitic stainless steels for signature authentication (magnetic recording), the utilisation of the cryogenic magnetic transition of the sigma phase for hot spot detection (the Sigmaplugs), the new Pt-enhanced radiopaque stainless steel (PERSS) coronary stents and stainless steel stents that may be used for magnetic drug targeting. Besides recent developments in conventional stainless steels, those in the high-nitrogen, low-Ni (or Ni-free) varieties are also introduced. These recent developments include new methods for attaining very high nitrogen contents, new guidelines for alloy design, the merits/demerits associated with high nitrogen contents, etc.

Recent developments in stainless steels

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Speciation of uranium in cultures of Clostridium sp. by X-ray absorption near-edge spectroscopy (XANES) at the National Synchrotron Light Source and by X-ray photoelectron spectroscopy (XPS) showed that U(VI) was reduced to U(IV). In addition to U(IV), a lower oxidation state of uranium, most probably U(III), was detected by XANES in the bacterial cultures. Reduction of uranium occurred only in the presence of growing or resting cells. Organic acid metabolites, the extracellular components of the culture medium, and heat-killed cells failed to reduce uranium under anaerobic conditions. The addition of uranyl acetate or uranyl nitrate (>210[mu]M U) to the culture medium retarded the growth of the bacteria as evidenced by an increase in the lag period before resumption of growth, by decreases in turbidity, and in the total production of gas and organic acid metabolites. These results show that uranium in wastes can be stabilized by the action of anaerobic bacteria. 31 refs., 2 figs., 3 tabs.

XPS and XANES Studies of Uranium Reduction by Clostridium sp.

Additive manufacturing (AM) of metal alloys to produce complex part designs via powder bed fusion methods such as laser melting promises to be a transformative technology for advanced materials processing. However, effective implementation of AM processes requires a clear understanding of the processing–structure–properties–performance relationships in fabricated components. In this study, we report on the formation of micro and nanoscale structures in 316L stainless steel samples printed by laser AM and their implications for general corrosion resistance. A variety of techniques including x-ray diffraction, optical, scanning and transmission electron microscopy, x-ray fluorescence, and energy dispersive x-ray spectroscopy were employed to characterize the microstructure and chemistry of the laser additively manufactured 316L stainless steel, which are compared with wrought 316L coupons via electrochemical polarization. Apparent segregation of Mo has been found to contribute to a loss of passivity and an increased anodic current density. While porosity will also likely impact the environmental performance (e.g., facilitating crevice corrosion) of AM alloys, this work demonstrates the critical influence of microstructure and heterogeneous solute distributions on the corrosion resistance of laser additively manufactured 316L stainless steel.

Microstructure and Corrosion Resistance of Laser Additively Manufactured 316L Stainless Steel

Polylactic acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR) spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning electron microscopy (SEM) and differential scanning calorimetry (DSC) were used to characterize morphology, cold crystallinity, and the glass transition and melting temperatures following printing. Analysis revealed calcium carbonate-based additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro- and submicron-scale roughness that will also impact potential applications.

Impact of the Fused Deposition (FDM) Printing Process on Polylactic Acid (PLA) Chemistry and Structure

Decontamination of metal surfaces contaminated with low levels of radionuclides is a major concern at Department of Energy facilities. The development of an environmentally friendly and cost-effective decontamination process requires an understanding of their association with the corroding surfaces. We investigated the association of uranium with the amorphous and crystalline forms of iron oxides commonly formed on corroding steel surfaces. Uranium was incorporated with the oxide by addition during the formation of ferrihydrite, goethite, green rust II, lepidocrocite, maghemite, and magnetite. X-ray diffraction confirmed the mineralogical form of the oxide. EXAFS analysis at the U L(III) edge showed that uranium was present in hexavalent form as a uranyl oxyhydroxide species with goethite, maghemite, and magnetite and as a bidentate inner-sphere complex with ferrihydrite and lepidocrocite. Iron was present in the ferric form with ferrihydrite, goethite, lepidocrocite, and maghemite; whereas with magnetite and green rust II, both ferrous and ferric forms were present with characteristic ferrous:total iron ratios of 0.65 and 0.73, respectively. In the presence of the uranyl ion, green rust II was converted to magnetite with concomitantreduction of uranium to its tetravalent form. The rate and extent of uranium dissolution in dilute HCl depended on its association with the oxide: uranium present as oxyhydroxide species underwent rapid dissolution followed by a slow dissolution of iron; whereas uranium present as an inner-sphere complex with iron resulted in concomitant dissolution of the uranium and iron.

Association of uranium with iron oxides typically formed on corroding steel surfaces

Cr spectra obtained by x‐ray photoelectron spectroscopy (XPS) of corrosion product layers is critically examined for evidence of photoreduction of hexavalent species. Tetravalent and trivalent decomposition products are identified, and methods of curve fitting and analysis are discussed. Disagreement between x‐ray absorption near end structure and XPS data, and between thermodynamic analysis and XPS data lead to the acceptance of a model for photoreduction of Cr6+based primarily upon core photoemission.

Gary P. Halada

Papers

XPS and XANES Studies of Uranium Reduction by Clostridium sp.

Microstructure and Corrosion Resistance of Laser Additively Manufactured 316L Stainless Steel

Impact of the Fused Deposition (FDM) Printing Process on Polylactic Acid (PLA) Chemistry and Structure

Association of uranium with iron oxides typically formed on corroding steel surfaces

Photoreduction of Hexavalent Chromium during X‐Ray Photoelectron Spectroscopy Analysis of Electrochemical and Thermal Films