TY - JOUR A1 - Schmid, Thomas A1 - Dariz, P. T1 - Raman Microspectroscopic Imaging of Binder Remnants in Historical Mortars Reveals Processing Conditions N2 - Binder remnants in historical mortars represent a record of the connection between the raw materials that enter the kiln, the process parameters, and the end product of the calcination. Raman microspectroscopy combines high structural sensitivity with micrometre to sub-micrometre spatial resolution and compatibility with conventional thin-sectional samples in an almost unique fashion, making it an interesting complementary extension of the existing methodological arsenal for mortar analysis. Raman spectra are vibrational fingerprints of crystalline and amorphous compounds, and contain marker bands that are specific for minerals and their polymorphic forms. Relative intensities of bands that are related to the same crystalline species change according to crystal orientations, and band shifts can be caused by the incorporation of foreign ions into crystal lattices, as well as stoichiometric changes within solid solution series. Finally, variations in crystallinity affect band widths. These effects are demonstrated based on the analysis of three historical mortar samples: micrometric distribution maps of phases and polymorphs, crystal orientations, and compositional variations of solid solution series of unreacted clinker grains in the Portland cement mortars of two 19th century castings, and the crystallinities of thermal anhydrite clusters in a high-fired medieval gypsum mortar as a measure for the applied burning temperature were successfully acquired. KW - Cement clinker remnants KW - High-fired gypsum KW - Thermal anhydrite KW - Spectroscopic imaging KW - Raman microscopy PY - 2019 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-515038 DO - https://doi.org/10.3390/heritage2020102 VL - 2 IS - 2 SP - 1662 EP - 1683 PB - MDPI CY - Basel AN - OPUS4-51503 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmid, Thomas A1 - Hodoroaba, Vasile-Dan T1 - Correlative Analysis by Raman and other Micro & Nanospectroscopic Imaging Techniques N2 - In the present talk the basics of the Raman spectroscopy and particularly of Raman microscopy are explained. Advantages and disadvantages of the method are highlighted through selected case studies. In the second part of the lecture examples of correlative imaging with electron, X-ray, ion and optical microscopies from micro- to the nanoscale are highlighted. T2 - Charisma School on Raman Harmonisation CY - Turin, Italy DA - 19.10.2022 KW - Raman KW - Correlative Imaging KW - Microscopy KW - Hyperspectral imaging PY - 2022 UR - https://amdgroup.inrim.it/events/vamas-sc-meeting-47/program-sc47 AN - OPUS4-56094 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Martins, Ines A1 - Al-Sabbagh, Dominik A1 - Bentrup, U. A1 - Marquardt, Julien A1 - Schmid, Thomas A1 - Scoppola, E. A1 - Kraus, Werner A1 - Stawski, Tomasz A1 - de Oliveira Guilherme Buzanich, Ana A1 - Yusenko, Kirill A1 - Weidner, Steffen A1 - Emmerling, Franziska T1 - Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate N2 - A new hetero-bimetallic polyoxometalate (POM) nano-ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH4)16[(BiPMo11O39)4] ⋅ 22 H2O; (P4Bi4Mo44) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry mass spectrometry (TG-DSC-MS). The formation of the nano-ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo−K and the Bi−L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi−Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure. KW - Bismuth KW - In situ EXAFS KW - In situ SAXS/WAXS KW - Lacunary Keggin ion KW - Polyoxometalates KW - Self-assembly PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546823 DO - https://doi.org/10.1002/chem.202200079 SN - 0947-6539 VL - 28 IS - 27 SP - 1 EP - 7 PB - Wiley-VCH CY - Weinheim AN - OPUS4-54682 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bhattacharya, Biswajit A1 - Michalchuk, Adam A1 - Silbernagl, Dorothee A1 - Rautenberg, Max A1 - Schmid, Thomas A1 - Feiler, Torvid A1 - Reimann, K. A1 - Ghalgaoui, A. A1 - Sturm, Heinz A1 - Paulus, B. A1 - Emmerling, Franziska T1 - A Mechanistic Perspective on Plastically Flexible Coordination Polymers N2 - Mechanical flexibility in single crystals of covalently bound materials is a fascinating and poorly understood phenomenon. We present here the first example of a plastically flexible one-dimensional (1D) coordination polymer. The compound [Zn(m-Cl)2(3,5-dichloropyridine)2]n is flexible over two crystallographic faces. Remarkably, the single crystal remains intact when bent to 1808. A combination of microscopy, diffraction, and spectroscopic studies have been used to probe the structural response of the crystal lattice to mechanical bending. Deformation of the covalent polymer chains does not appear to be responsible for the observed macroscopic bending. Instead, our results suggest that mechanical bending occurs by displacement of the coordination polymer chains. Based on experimental and theoretical evidence, we propose a new model for mechanical flexibility in 1D coordination polymers. Moreover, our calculations propose a cause of the different mechanical properties of this compound and a structurally similar elastic material KW - Coordination polymer KW - Flexible crystals KW - Mechanical properties KW - Plastic deformation PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-504755 DO - https://doi.org/10.1002/anie.201914798 VL - 59 IS - 14 SP - 5557 EP - 5561 PB - Wiley-VCH AN - OPUS4-50475 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -