title: Toward Three-Dimensional Chemical Imaging of Ternary Cu-Sn-Pb Alloys Using Femtosecond Laser Ablation/Ionization Mass Spectrometry.
abstract: Femtosecond laser ablation/ionization mass spectrometry (LIMS) has been applied to probe the spatial element composition of three ternary Cu-Sn-Pb model bronze alloys (lead bronzes: CuSn10Pb10, CuSn7Pb15, and CuSn5Pb20), which were recently identified as high-performance cathode materials in the context of electro-organic synthesis (dehalogenation, deoxygenation) of pharmaceutically relevant building blocks. The quantitative and spatially resolved element analysis of such cathode materials will help in understanding the observed profound differences in their electrochemical reactivity and stability. For that purpose, we developed a measurement procedure using the LIMS technique which allows analyzing the element composition of these ternary alloys in all three spatial dimensions. Their chemical composition was determined spotwise, by ablating material from various surface locations on a 4 × 4 raster array (50 μm pitch distance, ablation crater diameter of ∼20 μm). The element analyses show significant chemical inhomogeneities in all three ternary bronze alloys with profound local deviations from their nominal bulk compositions and indicate further differences in the nature and origin of these compositional inhomogeneities. In addition, the element analyses showed specific compositional correlations among the major elements (Cu, Sn, and Pb) in these alloys. On selected sample positions minor (Ni, Zn, Ag, and Sb) and trace elements (C, P, Fe, and As) were quantified. These results are in agreement with inductively coupled plasma collision/reaction interface mass spectrometry (ICP-CRI-MS) and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) reference measurements, thus proving the LIMS depth profiling technique as a powerful alternative methodology to conventional quantification techniques with the advantage, however, of a highly localized measurement capability.
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, 3012 Bern, Switzerland.
authors.forename: Valentine
authors.initials: V
authors.lastname: Grimaudo
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, 3012 Bern, Switzerland.
authors.forename: Pavel
authors.initials: P
authors.lastname: Moreno-García
authors.affiliation: Physics Institute, University of Bern , Sidlerstrasse 5, 3012 Bern, Switzerland.
authors.forename: Andreas
authors.identifier: 0000-0001-9007-5791
authors.initials: A
authors.lastname: Riedo
authors.affiliation: Physics Institute, University of Bern , Sidlerstrasse 5, 3012 Bern, Switzerland.
authors.forename: Stefan
authors.initials: S
authors.lastname: Meyer
authors.affiliation: Physics Institute, University of Bern , Sidlerstrasse 5, 3012 Bern, Switzerland.
authors.forename: Marek
authors.initials: M
authors.lastname: Tulej
authors.affiliation: Physics Institute, University of Bern , Sidlerstrasse 5, 3012 Bern, Switzerland.
authors.forename: Maike B
authors.initials: MB
authors.lastname: Neuland
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, 3012 Bern, Switzerland.
authors.forename: Miklós
authors.initials: M
authors.lastname: Mohos
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg University Mainz , Duesbergweg 10-14, 55128 Mainz, Germany.
authors.forename: Christoph
authors.initials: C
authors.lastname: Gütz
authors.affiliation: Institute of Organic Chemistry, Johannes Gutenberg University Mainz , Duesbergweg 10-14, 55128 Mainz, Germany.
authors.forename: Siegfried R
authors.identifier: 0000-0002-7949-9638
authors.initials: SR
authors.lastname: Waldvogel
authors.affiliation: Physics Institute, University of Bern , Sidlerstrasse 5, 3012 Bern, Switzerland.
authors.forename: Peter
authors.initials: P
authors.lastname: Wurz
authors.affiliation: Department of Chemistry and Biochemistry, University of Bern , Freiestrasse 3, 3012 Bern, Switzerland.
authors.forename: Peter
authors.initials: P
authors.lastname: Broekmann