An in-situ synchrotron XAS methodology for surface analysis under high temperature, pressure and shear

The complex tribochemical nature of lubricated tribological contacts is inaccessible in real time without altering their initial state. To overcome this issue, a new design of a pin-on-disc tribological apparatus was developed and combined with synchrotron X-ray absorption spectroscopy (XAS). Using the designed apparatus, it is possible to study in situ the transient decomposition reactions of various oil additives on different surfaces under a wide range of realistic operating conditions of contact pressure (1.0–3.0 GPa), temperature (25–120 °C), and sliding speed (30–3000 rpm or 0.15–15 m/s). To test the apparatus, several tribological tests were performed at different shearing times ranging from 2.5 to 60 min. These tests were carried out under helium atmosphere at a temperature of 80  °C, contact pressure of 2.2 GPa, and sliding speed of 50 rpm. The XAS experiments indicate that the zinc dialkyldithiophosphate antiwear additive decomposes in the oil to form a tribofilm on the iron surface at different reaction kinetics from the ones of the thermal film. The tribofilm composition evolves much faster than the one of the thermal film, which confirms that the formation of the tribofilm is a thermally activated process similar to the one of the thermal film but accelerated by shear. Furthermore, the results indicate that the sulfur of the formed film, whether a tribofilm or a thermal film, appears initially in the form of sulfate, with some sulfide, which under heat or shear is reduced into mainly sulfide

Binding mechanism of arsenate on rutile (110) and (001) planes studied using grazing-incidence EXAFS measurement and DFT calculation

Characterization of contaminant molecules on different exposed crystal planes is required to conclusively describe its behavior on mineral surfaces. Here, the structural properties and relative stability of arsenate adsorbed on rutile TiO2 (110) and (001) surfaces were investigated using grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) spectra and periodic density functional theory (DFT) calculation. The combined results indicated that arsenate mainly formed inner-sphere bidentate binuclear (BB) and monodentate mononuclear (MM) complexes on both surfaces, but the orientational polar angles of arsenate on the (110) surface were commonly smaller than that on the (001) surface for the two adsorption modes. The DFT calculation showed that the (110) plane had a higher affinity toward arsenate than the (001) plane, suggesting that, for a given adsorption mode (i.e., MM or BB structure), a small polar angle was more favorable for arsenate stabilized on the rutile surfaces

Structure and stability of arsenate adsorbed on α-Al2O3 single-crystal surfaces investigated using grazing-incidence EXAFS measurement and DFT calculation

Direct characterization of contaminants on single-crystal planes is required because the specific adsorption characteristics on different exposed crystal planes constitute their actual behavior at water–mineral interfaces in aquifers. Here, the structure and stability of arsenate on α-Al2O3 (0001) and (View the MathML source112¯0) surfaces were characterized by using a combination of grazing-incidence extended X-ray absorption fine structure (GI-EXAFS) spectra and periodic density functional theory (DFT) calculation. The combined results indicated that arsenate was mainly adsorbed as inner-sphere monodentate and bidentate complexes on both surfaces, but the orientational polar angles on the (0001) surface were commonly 10–20° greater than that on the (View the MathML source112¯0) surface. The DFT calculation showed that the large polar angle was more favorable for arsenate stabilized on the alumina surfaces. Based on the spectroscopic and computational data, the dominant bonding modes of arsenate on the two crystal planes of α-Al2O3 were identified as bidentate binuclear structures, and the (0001) surface displayed a stronger affinity toward arsenate

Application of the high-resolution grazing-emission x-ray fluorescence method for impurities control in semiconductor nanotechnology

We report on the application of synchrotron radiation based high-resolution grazing-emission x-ray fluorescence (GEXRF) method to measure low-level impurities on silicon wafers. The presented high-resolution GEXRF technique leads to direct detection limits of about 10¹²  atoms/cm². The latter can be presumably further improved down to 10⁷  atoms/cm² by combining the synchrotron radiation-based GEXRF method with the vapor phase decomposition preconcentration technique. The capability of the high-resolution GEXRF method to perform surface-sensitive elemental mappings with a lateral resolution of several tens of micrometers was probed

FIB-FESEM and EMPA results on Antoninianus silver coins for manufacturing and corrosion processes

[EN] A set of ancient Antoninianus silver coins, dating back between 249 and 274¿A.D. and minted in Rome, Galliae, Orient and Ticinum, have been characterized. We use, for the first time, a combination of nano-invasive (focused ion beam-field emission scanning electron microscopy-X-ray microanalysis (FIB-FESEM-EDX), voltammetry of microparticles (VIMP)) and destructive techniques (scanning electron microscopy (SEM-EDX) and electron microprobe analysis (EMPA)) along with non-invasive, i.e., micro-Raman spectroscopy. The results revealed that, contrary to the extended belief, a complex Ag-Cu-Pb-Sn alloy was used. The use of alloys was common in the flourishing years of the Roman Empire. In the prosperous periods, Romans produced Ag-Cu alloys with relatively high silver content for the manufacture of both the external layers and inner nucleus of coins. This study also revealed that, although surface silvering processes were applied in different periods of crisis under the reign of Antoninii, even during crisis, Romans produced Antoninianus of high quality. Moreover, a first attempt to improve the silvering procedure using Hg-Ag amalgam has been identified.Financial support was provided by Sapienza University of Rome (Ateneo funding, 2014 15) and Spanish projects CTQ2014-53736-C3-1-P and CTQ2014-53736-C3-2-P, which are supported with Ministerio de Economía, Industria y Competitividad (MINECO) and Fondo Europeo de Desarrollo Regional (ERDF) funds, as well as project CTQ2017-85317-C2-1-P supported with funds from, MINECO, ERDF and Agencia Estatal de Investigación (AEI). PhD grants of the Department of Earth Sciences, Sapienza University of Rome, are gratefully acknowledgedDomenech Carbo, MT.; Di Turo, F.; Montoya, N.; Catalli, F.; Doménech Carbó, A.; De Vito, C. (2018). FIB-FESEM and EMPA results on Antoninianus silver coins for manufacturing and corrosion processes. Scientific Reports. 8. https://doi.org/10.1038/s41598-018-28990-xS8Doménech-Carbó, A., del Hoyo-Meléndez, J. M., Doménech-Carbó, M. T. & Piquero-Cilla, J. Electrochemical analysis of the first Polish coins using voltammetry of immobilized particles. Microchem. J. 130, 47–55 (2017).Di Turo, F. et al. Archaeometric analysis of Roman bronze coins from the Magna Mater temple using solid-state voltammetry and electrochemical impedance spectroscopy. Anal. Chim. Acta 955, 36–47 (2017).Doménech-Carbó, A., Doménech-Carbó, M. T. & Peiró-Ronda, M. A. Dating Archeological Lead Artifacts from Measurement of the Corrosion Content Using the Voltammetry of Microparticles. Anal. Chem. 83, 5639–5644 (2011).Giumlia-Mair, A. et al. Surface characterisation techniques in the study and conservation of art and archaeological artefacts: a review. Materials Technology 25(5), 245–261 (2010).Robbiola, L. & Portier, R. A global approach to the authentication of ancient bronzes based on the characterization of the alloy–patina–environment system. Journal of Cultural Heritage 7, 1–12 (2006).Campbell, W. Greek and Roman plated coins, Numismatics Notes and Monographs 57, American Numismatic Society, New York (1933).Kallithrakas-Kontos, N., Katsanos, A. A. & Touratsoglou, J. Trace element analysis of Alexander the Great’s silver tetradrachms minted in Macedonia, Nuclear Instruments and Methods in Physics. Research B 171, 342–349 (2000).Catalli, F. Numismatica greca e romana. (Libreria dello Stato, 2003).Cope, L. H. The Metallurgical development of the Roman Imperial Coinage during the first five centuries. (Liverpool, 1974).Scriptores Historiae Augustae. Historia Augusta. (The Perfect Library, 2014).Vlachou-Mogire, C., Stern, B. & McDonnell, J. G. The application of LA-ICP-MS in the examination of the thin plating layers found in late Roman coins. Nucl. Instruments Methods Phys. Res. Sect. B Beam Interact. with Mater. Atoms 265, 558–568 (2007).Keturakis, C. J. et al. Analysis of corrosion layers in ancient Roman silver coins with high resolution surface spectroscopic techniques. Appl. Surf. Sci. 376, 241–251 (2016).Ingo, G. M. et al. Roman sophisticated surface modification methods to manufacture silver counterfeited coins. Appl. Surf. Sci. 1–11, https://doi.org/10.1016/j.apsusc.2017.01.101 (2017).La Niece, S. In: La Niece S. & Craddock, P. (Eds), Metal, Plating and Platination, Butterworth–Heinemann, London, 1993, p. 201.Anheuser, K. & France, P. Silver plating technology of the late 3rd century Roman coinage. Historical Metallurgy 36(1), 17–23 (2002).Anheuser, K. & Northover, P. Silver plating on Roman and Celtic coins from Britain– A technical study. The British Numismatic Journal 64, 22–32 (1994).Anheuser, K. Where is all the amalgam silvering? Materials Issues1996 in Art and Archaeology - V proceedings, Boston.Beck, L. et al. In NIM 269, 2011 and in Counterfeit coinage of the Holy Roman Empire in the 16th century: silvering process and archaeometallurgical replications, Archaeometallurgy in Europe III.Deraisme, A., Beck, L., Pilon, F. & Barrandon, J. N. A study of the silvering process of the Gallo-Roman coins forged during the third century AD. Archaeometry 48, 469–480 (2006).Giumlia-Mair, A. On surface analysis and archaeometallurgy. Nucl. Instruments Methods Phys. Res. Sect. B Beam Interact. with Mater. Atoms 239, 35–43 (2005).Tate, J. Some problems in analysing museum material by nondestructive surface sensitive techniques. Nuclear Inst. and Methods in Physics Research, B, 14 (1), pp. 20–23 (1986).Beck, L., Bosonnet, S., Réveillon, S., Eliot, D. & Pilon, F. Silver surface enrichment of silver-copper alloys: A limitation for the analysis of ancient silver coins by surface techniques. Nucl. Instruments Methods Phys. Res. Sect. B Beam Interact. with Mater. Atoms 226, 153–162 (2004).Pardini, L. et al. X-ray fluorescence and laser-induced breakdown spectroscopy analysis of Roman silver denarii. Spectrochim. Acta - Part B At. Spectrosc. 74–75, 156–161 (2012).Klockenkämper, R., Bubert, H. & Hasler, K. Detection of near-surface silver enrichment on Roman imperial silver coins by x-ray spectral analysis. Archaeometry 41, 311–320 (1999).Ponting, M., Evans, J. A. & Pashley, V. Fingerprinting of roman mints using laser-amblation MC-ICP-MS lead isotope analysis.Del Hoyo-Meléndez, J. M. et al. Micro-XRF analysis of silver coins from medieval Poland. Nucl. Instruments Methods Phys. Res. Sect. B Beam Interact. with Mater. Atoms 349, 6–16 (2015).Cesare Brandi. Il restauro. Teoria e pratica (1939–1986). (Editori Riuniti, 2009).Barberio, M., Veltri, S., Scisciò, M. & Antici, P. Laser-Accelerated Proton Beams as Diagnostics for Cultural Heritage. Sci. Rep. 7, 40415 (2017).Linke, R., Sehreiner, M., Demortier, G., Alram, M. & Winter, H. Non-Destructive Microanalysis of Cultural Heritage Materials. Comprehensive Analytical Chemistry 42, (Elsevier, 2004).Łojewska, J. et al. Recognizing ancient papyri by a combination of spectroscopic, diffractional and chromatographic analytical tools. Sci. Rep. 7, 46236 (2017).Meulebroeck, W., Wouters, H., Nys, K. & Thienpont, H. Authenticity screening of stained glass windows using optical spectroscopy. Nat. Sci. Reports 6 37726, 1–10 (2016).Martina, I., Wiesinger, R. & Schreiner, M. Micro-Raman Characterisation of Silver Corrosion Products: Instrumental Set Up and Reference. e-Preservation. Sci. Rep 9, 1–8 (2012).Rizzo, F. et al. Non-destructive determination of the silver content in Roman coins (nummi), dated to 308–311 A. D., by the combined use of PIXE-alpha, XRF and DPAA techniques. Microchem. J. 97, 286–290 (2011).Carl, M. & Young, M. L. Complementary analytical methods for analysis of Ag-plated cultural heritage objects. Microchem. J. 126, 307–315 (2016).Cepriá, G., Abadías, O., Pérez-Arantegui, J. & Castillo, J. R. Electrochemical Behavior of Silver-Copper Alloys in Voltammetry of Microparticles: A Simple Method for Screening Purposes. Electroanalysis 13, 477–483 (2001).Capelo, S., Homem, P. M., Cavalheiro, J. & Fonseca, I. T. E. Linear sweep voltammetry: a cheap and powerful technique for the identification of the silver tarnish layer constituents. J. Solid State Electrochem. 17, 223–234 (2013).Doménech-Carbó, A. et al. Detection of archaeological forgeries of Iberian lead plates using nanoelectrochemical techniques. The lot of fake plates from Bugarra (Spain). Forensic Sci. Int. 247, 79–88 (2015).Doménech-Carbó, A., Doménech-Carbó, M. T. & Peiró-Ronda, M. A. ‘One-Touch’ Voltammetry of Microparticles for the Identification of Corrosion Products in Archaeological Lead. Electroanalysis 23, 1391–1400 (2011).Doménech-Carbó, A., Doménech-Carbó, M. T., Montagna, E., Álvarez-Romero, C. & Lee, Y. Electrochemical discrimination of mints: The last Chinese emperors Kuang Hsü and Hsüan T’ung monetary unification. Talanta1 69, 50–56 (2017).Ager, F. J. et al. Combining XRF and GRT for the analysis of ancient silver coins. Microchem. J. 126, 149–154 (2016).Fawcett, T., Blanton, J., Blanton, T., Arias, L. & Suscavage, T. Non-destructive evaluation of Roman coin patinas from the 3rd and 4th century. Powder Diffraction, 1–10.Salvemini, F. et al. Neutron tomographic analysis: Material characterization of silver and electrum coins from the 6th and 5th centuries B.C. Mater. Charact. 118, 175–185 (2016).Ashkenazi, D., Gitler, H., Stern, A. & Tal, O. Metallurgical investigation on fourth century BCE silver jewellery of two hoards from Samaria. Sci. Rep. 7, 40659 (2017).Romano, F. P., Garraffo, S., Pappalardo, L. & Rizzo, F. In situ investigation of the surface silvering of late Roman coins by combined use of high energy broad-beam and low energy micro-beam X-ray fluorescence techniques. Spectrochim. Acta - Part B At. Spectrosc. 73, 13–19 (2012).Ingo, G. M. et al. Ancient Mercury-Based Plating Methods: Combined Use of Surface Analytical Techniques for the Study of Manufacturing Process and Degradation Phenomena. Accounts of Chemical Research 46(11), 2365–2375.Pouchou, J. L. & Pichoir, F.¨PAP¨ (ϕ–ρ–Z) procedure for improved quantitative microanalysis, in: Armstrong, J. T. (Ed.), Microbeam Analysis, San Francisco Press, San Francisco, pp. 104–106 (1985)

Minimally-destructive atmospheric ionisation mass spectrometry authenticates authorship of historical manuscripts

Authentic historic manuscripts fetch high sums, but establishing their authenticity is challenging, relies on a host of stylistic clues and requires expert knowledge. High resolution mass spectrometry has not, until now, been applied to guide the authentication of historic manuscripts. Robert Burns is a well-known Scottish poet, whose fame, and the eponymous ‘Burns Night’ are celebrated world-wide. Authenticity of his works is complicated by the ‘industrial’ production of fakes by Alexander Smith in the 1890s, many of which were of good quality and capable of fooling experts. This study represents the first analysis of the inks and paper used in Burns poetry, in a minimally destructive manner that could find application in many areas. Applying direct infusion mass spectrometry to a panel of selected authenticated Burns and Smith manuscripts, we have produced a Support Vector Machine classifier that distinguishes Burns from Smith with a 0.77 AUC. Using contemporary recipes for inks, we were also able to match features of each to the inks used to produce some of Burns’ original manuscripts. We anticipate the method and classifier having broad application in authentication of manuscripts, and our analysis of contemporary inks to provide insights into the production of written works of art