TY - GEN A1 - Dengiz, Nizametin A1 - Fuchs, Martin A1 - Gaal, Mate A1 - Gautzsch, Tobias A1 - Herzog, Thomas A1 - Kornely, Mike A1 - Littner, Linus A1 - Marhenke, Torben A1 - Schmid, Simon A1 - Sommerhuber, Ryan A1 - Steinhausen, Ralf A1 - Szewieczek, Artur A1 - Wachter, Luis A1 - Waschkies, Thomas A1 - Wunderl, Stefan T1 - Leitfaden zur Durchführung von luftgekoppelter Ultraschallprüfung N2 - Die Anwendungsgebiete der luftgekoppelten Ultraschallprüfung (ACUT) können sehr vielfältig sein und weichen häufig stark von den Einsatzgebieten der klassischen Ultraschallprüfung ab. Vielmehr ist die ACUT eine eigenständige Methode, welche sich häufig eher mit Röntgen oder Thermografie überschneidet oder Prüfungen ermöglicht, die bis heute gar nicht verlässlich zerstörungsfrei durchgeführt werden können. Obwohl die luftgekoppelte Ultraschallprüfung mittlerweile keine neue Technologie ist, bleibt sie im Vergleich zu anderen Verfahren der ZfP ein Randgebiet unter den Methoden. Dies kommt nicht zuletzt dadurch zustande, dass es an Normen, Fachbüchern und Ausbildungsmöglichkeiten für interessierte Prüfer und Prüfaufsichten mangelt. Dies schafft für viele Anwendungsgebiete eine Einstiegshürde, welche die häufigere Anwendung verhindert. Aus diesen Gründen haben sich Experten aus Forschungseinrichtungen und aus der Industrie entschieden, einen Unterausschuss „Luftgekoppelte Ultraschallprüfung“ (ACUT) als Teil des Fachausschusses Ultraschallprüfung der DGZfP einzurichten und dort diese Themen zu bearbeiten. Es wurde beschlossen, einen Leitfaden zu erarbeiten, der interessierten Anwendern den Einstieg in ACUT erleichtert und eine Hilfestellung bei der Spezifikation und Umsetzung von solchen Prüfungen gibt. Das vorliegende Dokument ist das Ergebnis dieser Zusammenarbeit. KW - Luftgekoppelter Ultraschall KW - Ultraschallprüfung KW - Leitfaden PY - 2025 UR - https://publikationen.dgzfp.de/shop/leitfaden-zur-durchfuehrung-von-luftgekoppelter-ultraschallpruefung/ SN - 978-3-947971-45-9 VL - Richtlinie ACUT SP - 1 EP - 28 PB - Deutsche Gesellschaft für Zerstörungsfreie Prüfung (DGZfP) CY - Berlin ET - Ausgabe Januar 2025 AN - OPUS4-62491 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - GEN A1 - Dengiz, Nizamettin A1 - Fuchs, Martin A1 - Gaal, Mate A1 - Gautzsch, Tobias A1 - Herzog, Thomas A1 - Kornely, Mike A1 - Littner, Linus A1 - Marhenke, Torben A1 - Schmid, Simon A1 - Sommerhuber, Ryan A1 - Steinhausen, Ralf A1 - Szewieczek, Artur A1 - Wachter, Luis A1 - Waschkies, Thomas A1 - Wunderl, Stefan ED - Gaal, Mate T1 - Guideline to performing air-coupled ultrasonic testing N2 - The areas of application of air-coupled ultrasonic testing (ACUT) can be very diverse and often differ greatly from the areas of application of classic ultrasonic testing. In fact, ACUT is an independent method that often overlaps with X-ray or thermography or enables tests that cannot yet be reliably performed non-destructively. Although air-coupled ultrasonic testing is not a new technology, it remains a rarely used method compared to other NDT methods. This is not least due to the lack of standards, specialised books and training opportunities for interested inspectors and inspection supervisors. This creates a barrier to entry for many areas of application, which prevents more frequent use. For these reasons, experts from research institutes and industry have decided to set up an "Air-Coupled Ultrasonic Testing" (ACUT) sub-committee as part of the DGZfP's Ultrasonic Testing Technical Committee to work on these topics. It was decided to draw up a guideline to make it easier for interested users to get started with ACUT and to provide assistance with the specification and implementation of such tests. This document is the result of this co-operation. KW - air-coupled ultrasound KW - guideline KW - non-destructive testing PY - 2025 SP - 1 EP - 28 CY - Berlin AN - OPUS4-64847 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Maiwald, Michael A1 - Schmid, Thomas T1 - Möglichkeiten zur Sonderprobenanalytik - Gemeinsame Aktivitäten mit dem Salsa-Applikationslabor der Humboldt Universität zu Berlin N2 - Troubleshooting Samples Analytics: Impurities in products: unexpected & unwanted occurrence, unknown identity, analytical method unclear, often various analytical methods, necessary, short response time important (< 1 d), benefits: allocation of its source within hours safes cost • Investigations planned, coordinated and documented by TSA team • Variety of analytical methods available T2 - 3. Analytic-City-Forum Berlin Adlershof CY - Berlin, Germany DA - 08.10.2015 KW - Troubleshooting Samples Analytics KW - TSA KW - Sonderprobenanalytik KW - Salsa KW - Applikationslabor PY - 2015 AN - OPUS4-36139 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Schäfer, N. A1 - Levcenko, S. A1 - Rissom, T. A1 - Abou-Ras, D. T1 - Orientation-distribution mapping of polycrystalline materials by Raman microspectroscopy N2 - Raman microspectroscopy provides the means to obtain local orientations on polycrystalline materials at the submicrometer level. The present work demonstrates how orientation-distribution maps composed of Raman intensity distributions can be acquired on large areas of several hundreds of square micrometers. A polycrystalline CuInSe2 thin film was used as a model system. The orientation distributions are evidenced by corresponding measurements using electron backscatter diffraction (EBSD) on the same identical specimen positions. The quantitative, local orientation information obtained by means of EBSD was used to calculate the theoretical Raman intensities for specific grain orientations, which agree well with the experimental values. The presented approach establishes new horizons for Raman microspectroscopy as a tool for quantitative, microstructural analysis at submicrometer resolution. PY - 2015 DO - https://doi.org/10.1038/srep18410 SN - 2045-2322 VL - 5 SP - Article 18410, 1 EP - 7 PB - Nature Publishing Group CY - London AN - OPUS4-35224 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Spurenbestandteile in frühmittelalterlichem Ägyptisch Blau als Informationsträger N2 - Naturwissenschaftliche Belege für die Verwendung von Ägyptisch Blau, dem klassischen Blaupigment der römischen Antike, an frühmittelalterlichen Wandmalereien in Mittel- und Südeuropa sind bisher nur vereinzelt greifbar. Das hier diskutierte monochrom blaue Fragment einer Freskomalerei auf Tünche gehört zum zweiten Kirchenbau von St. Peter ob Gratsch (Südtirol, Norditalien); zumindest der Putzmörtel ist gemäß Radiocarbondatierung im 5. oder 6. Jahrhundert n. Chr. zu verorten. Das flächendeckende Abrastern der Probenoberfläche mittels Ramanmikrospektroskopie vermochte neben dem farbgebenden Cuprorivait (und Pflanzenschwarz aus der Untermalung) 26 begleitende Mineralien bis in den Spurenbereich nachzuweisen. Diese erstaunliche Vielfalt ist nur durch mikrospektroskopische Bildgebung in hoher Ortsauflösung zugänglich, ein solch vertiefter Einblick in die Mineralogie der zugrundeliegenden Rohstoffe als auch Umwandlungsreaktionen während Herstellung, Applikation und Alterung des künstlichen Blaupigmentes also an die Weiterentwicklung der analytischen Verfahren gebunden. Insbesondere die natürlichen Verunreinigungen des Quarzsandes liefern Indizien auf die Produktionsstätte: die beiden Klinopyroxene Augit und Aegirin deuten beispielsweise auf magmatischen Aktivitäten ausgesetzte Ablagerungen (oder auf vulkanische Aktivität bereits im Liefergebiet). Zusammen mit Diopsid und Feldspaten, einschließlich des seltenen Celsian, sind sie der Literatur zufolge charakteristischer Bestandteil von vom Fluss Volturno in den Golf von Gaeta transportierten carbonathaltigen Sedimenten. Im Verein mit der archäologischen Evidenz für die Erzeugung von Ägyptisch Blau in Cumae und Liternum und den übereinstimmenden Ausführungen der beiden römischen Fachschriftsteller Vitruv und Plinius der Ältere spricht dies für ein Fabrikat aus dem Golf von Pozzuoli. Als Kupferquelle wurde angesichts des Nachweises von Chalkosin (und Chalkopyrit) vermutlich ein sulfidisches Kupfererz nach Rosten zu Kupferoxid eingesetzt, als schmelzpunktsenkendes Flussmittel wohl ein gemischt-alkalisches, das heißt eine Mischung von Natrium- und Kaliumsalzen in Form von Pflanzenasche. Zum Teil mit Cuprorivait verwachsene, nicht gänzlich umgesetzte Quarzkristalle bei nur geringsten Spuren von Silikatglas lassen auf eine überwiegende Festkörperreaktion (Festphasensintern) schließen; das Aufschmelzen der Rohstoffe zu Glas dürfte bei der Pigmentsynthese eher eine untergeordnete Rolle gespielt haben. KW - Ägyptisch Blau KW - Ramanmikrospektroskopie KW - Spektroskopische Bildgebung KW - Cuprorivait KW - Amorpher Kohlenstoff PY - 2021 VL - 34 SP - 109 EP - 122 PB - Wernersche Verlagsgeselltschaft CY - Worms AN - OPUS4-53758 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Trace compounds in Early Medieval Egyptian blue carry information on provenance, manufacture, application, and ageing N2 - Only a few scientific evidences for the use of Egyptian blue in Early Medieval wall paintings in Central and Southern Europe have been reported so far. The monochrome blue fragment discussed here belongs to the second church building of St. Peter above Gratsch (South Tyrol, Northern Italy, fifth/ sixth century A.D.). Beyond cuprorivaite and carbon black (underpainting), 26 accessory minerals down to trace levels were detected by means of Raman microspectroscopy, providing unprecedented insights into the raw materials blend and conversion reactions during preparation, application, and ageing of the pigment. In conjunction with archaeological evidences for the manufacture of Egyptian blue in Cumae and Liternum and the concordant statements of the antique Roman writers Vitruvius and Pliny the Elder, natural impurities of the quartz sand speak for a pigment produced at the northern Phlegrean Fields (Campania, Southern Italy). Chalcocite (and chalcopyrite) suggest the use of a sulphidic copper ore, and water-insoluble salts a mixed-alkaline flux in the form of plant ash. Not fully reacted quartz crystals partly intergrown with cuprorivaite and only minimal traces of silicate glass portend solid-state reactions predominating the chemical reactions during synthesis, while the melting of the raw materials into glass most likely played a negligible role. KW - Egyptian blue KW - Raman microspectroscopy KW - Spectoscopic imaging KW - Cuprorivaite KW - Amorphous carbon PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537591 DO - https://doi.org/10.1038/s41598-021-90759-6 VL - 11 SP - 1 EP - 12 PB - Nature Portfolio AN - OPUS4-53759 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Kraft, Ronja A1 - Dariz, P. T1 - Shedding light onto the spectra of lime - Part 2: Raman spectra of Ca and Mg carbonates and the role of d-block element luminescence N2 - We previously described the observation of a characteristic narrowband red luminescence emission of burnt lime (CaO), whose reason was unknown so far. This study presents Raman spectra of Mg5 CO3)4(OH)2∙4H2O, Mg5(CO3)4(OH)2, MgCO3, CaMgCO3 and CaCO3 (in limestone powder) as well as luminescence spectra of their calcination products. Comparison of the latter revealed MgO:Cr3+ as the source of the red lime luminescence in all studied samples, containing magnesium oxide as major component, minor component or trace. Spectral characteristics and theoretical background of the luminescence emission of d-block elements integrated in crystal lattices are discussed with the aim of sharpening the awareness for this effect in the Raman community and promoting its application in materials analysis. The latter is demonstrated by the Raman microspectroscopic imaging of the distributions of both Raman-active and Raman-inactive phases in clinker remnants in a 19th-century meso Portland cement mortar sample, which contain relatively high amounts of free lime detected in the form of both luminescing CaO and Raman-scattering Ca(OH)2, owing to exposure of the surface of the thin section to humid air. A combination of light and Raman spectroscopy revealed a calcium–magnesium–iron sulphide phase, indicating sulphurous raw materials and/or solid fuels employed in the calcination process, which in contrast to previously described morphologies of sulphides in cement clinker form extensive greenish black layers on free lime crystals. KW - Calcium carbonates KW - Raman spectroscopy KW - Luminescence KW - Magnesium carbonates KW - Meso Portland cement PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537611 DO - https://doi.org/10.1002/jrs.6174 SN - 0377-0486 VL - 52 IS - 8 SP - 1462 EP - 1472 PB - Wiley Analytical Science AN - OPUS4-53761 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Hidde, Julia A1 - Grünier, Sophie A1 - Jungnickel, Robert A1 - Dariz, P. A1 - Riedel, Jens A1 - Neuhaus, B. T1 - Ageing effects in mountig media of microscope slide samples from natural history collections: A case study with Canada balsam and Permount™ N2 - Microscope slide collections represent extremely valuable depositories of research material in a natural history, forensic, veterinary, and medical context. Unfortunately, most mounting media of these slides deteriorate over time, with the reason for this not yet understood at all. In this study, Raman spectroscopy, ultraviolet–visible (UV–Vis) spectroscopy, and different types of light microscopy were used to investigate the ageing behaviour of naturally aged slides from museum collections and the experimentally aged media of Canada balsam and Permount™, representing a natural and a synthetic resin, respectively, with both being based on mixtures of various terpenes. Whereas Canada balsam clearly revealed chemical ageing processes, visible as increasing colouration, Permount™ showed physical deterioration recognisable by the increasing number of cracks, which even often impacted a mounted specimen. Noticeable changes to the chemical and physical properties of these mounting media take decades in the case of Canada balsam but just a few years in the case of Permount™. Our results question whether or not Canada balsam should really be regarded as a mounting medium that lasts for centuries, if its increasing degree of polymerisation can lead to a mount which is no longer restorable. KW - Deterioration KW - Microscope slides KW - Mounting media KW - Raman spectroscopy KW - UV–Vis spectroscopy PY - 2021 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-537632 DO - https://doi.org/10.3390/polym13132112 VL - 13 IS - 13 SP - 1 EP - 27 PB - MDPI CY - Basel AN - OPUS4-53763 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Wortmann, U. G. A1 - Vogl, Jochen A1 - Schmid, Thomas T1 - Beautiful Pietàs in South Tyrol (Northern Italy): local or imported works of art? N2 - The study, dedicated to Beautiful Pietàs conserved in South Tyrol (Northern Italy), aims to establish, for the first time, a connection between Austroalpine raw materials and the high-fired gypsum mortars constituting the Gothic figure groups in question. The origin and chronology of this stylistically and qualitatively differing ensemble have been subject of art historical debate for nearly a century. The discourse is dominated by three main hypotheses: itinerary of an Austrian artist versus itinerary of the work of art created in an artist’s workshop in Austria versus itinerary of the stylistic vocabulary via graphical or three-dimensional models. The comparison of the δ34S values and the 87Sr/86Sr ratios of the gypsum mortars and Austroalpine sulphate deposits (in a compilation of own reference samples and literature data) points to the exploitation of sediments in the Salzkammergut and possibly also in the evaporite district of the Eastern Calcareous Alps, thus evidencing the import of the sculptures and not the activities of local South Tyrolean or itinerant artists. Two geochronological units are distinguishable: The Pietà in the Church St. Martin in Göflan can be assigned to Upper Permian raw material, whereas the metrologically consistent sculptures in the Church of Our Lady of the Benedictine Abbey Marienberg and in the Chapel St. Ann in Mölten correlate with deposits of the Early Triassic (or the Lower-Middle Triassic transition). The medieval gypsum mortars also differ in their mineralogical characteristics, i.e. in their geologically related minor components, as in the first case, characterised by a significant proportion of primary anhydrite, natural carbonate impurities mainly consist of calcite (partly converted to lime-lump-like aggregates), whereas in the second group dolomite (or rather its hydration products after pyrometamorphic decomposition) predominates, accompanied by celestine, quartz and potassium feldspar. The Pietà in the Cathedral Maria Himmelfahrt in Bozen turned out to be made of Breitenbrunn calcareous sandstone (Leitha Mountains, Burgenland, Austria), which is why the sample is not considered in the geochemical analysis. KW - High-fired gypsum mortar KW - Sulphur isotope KW - Strontium isotope KW - Polarised light microscopy KW - Raman microspectroscopy PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-545610 DO - https://doi.org/10.1186/s40494-022-00678-6 SN - 2050-7445 VL - 10 IS - 1 SP - 1 EP - 17 PB - Springer Nature AN - OPUS4-54561 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Schmid, Thomas T1 - Raman microspectroscopy elucidates Early Medieval art technology: high-fired gypsum mortar and Egyptian blue from the church St. Peter above Gratsch (South Tyrol, Northern Italy) N2 - Raman microspectroscopy enables imaging of the distributions of mineral phases as well as physical properties of materials, such as crystal orientations and crystallinities, with down to sub-micrometre resolution. In a combination with other spectroscopic and microscopic techniques, this approach was applied to the analysis and elucidation of ancient production technologies of stucco fragments made of high-fired gypsum mortar and Egyptian blue pigment discovered on a monochrome wall painting fragment originating from the Early Medieval (5th/6th century AD) construction phase of the church St. Peter above Gratsch in South Tyrol (Northern Italy). T2 - Analytica Conference 2022 CY - Munich, Germany DA - 21.06.2022 KW - Raman microspectroscopy KW - Gypsum KW - Pigments PY - 2022 AN - OPUS4-55896 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Raman focal point on Roman Egyptian blue elucidates disordered cuprorivaite, green glass phase and trace compounds N2 - The discussed comparative analyses of Roman Imperial pigment balls and fragmentary murals unearthed in the ancient cities of Aventicum and Augusta Raurica (Switzerland) by means of Raman microspectroscopy pertain to a predecessor study on trace compounds in Early Medieval Egyptian blue (St. Peter, Gratsch, South Tyrol, Northern Italy). The plethora of newly detected associated minerals of the raw materials surviving the synthesis procedure validate the use of quartz sand matching the composition of sediments transported by the Volturno river into the Gulf of Gaeta (Campania, Southern Italy) with a roasted sulphidic copper ore and a mixed-alkaline plant ash as fluxing agent. Thus, the results corroborate a monopolised pigment production site located in the northern Phlegrean Fields persisting over the first centuries A.D., this in line with statements of the antique Roman writers Vitruvius and Pliny the Elder and recent archaeological evidences. Beyond that, Raman spectra reveal through gradual peak shifts and changes of band width locally divergent process conditions and compositional inhomogeneities provoking crystal lattice disorder in the chromophoric cuprorivaite as well as the formation of a copper-bearing green glass phase, the latter probably in dependency of the concentration of alkali flux, notwithstanding that otherwise solid-state reactions predominate the synthesis. KW - Raman microspectroscopy KW - Egyptian blue KW - Cuprorivaite PY - 2022 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559028 DO - https://doi.org/10.1038/s41598-022-19923-w SN - 2045-2322 VL - 12 IS - 1 SP - 1 EP - 12 PB - Nature Publishing Group CY - London AN - OPUS4-55902 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Jungnickel, R. A1 - Neuhaus, B. A1 - Riedel, Jens A1 - Kneipp, Janina A1 - Lüter, C. T1 - Raman spectroscopy as a tool for the collection management of microscope slides N2 - Throughout the history of preparation of biological samples for microscopy the choice of the mounting medium was sometimes dictated merely by availability of the used media. Thus, a plethora of resins and other organic polymers as well as complex mixtures are found to serve as mounting agents in microscope slide collections of museums of natural history, impeding the work for both curators and conservators. Dramatically, in some cases the used mounting media can already be observed to have undergone crystallization and other decomposition processes within few years of mounting demanding immediate action in restoring as well as an imminent precaution in conservation. Therefore, an unambiguous chemical identification of the used agent as well as its current aging stage is of great interest for the biologist community. The technical demands on the analytical approach to obtain this information can be straightforwardly identified. Any used technique has to be non-destructive, yield in molecular information allowing for a chemical identification of the used mounting agents and allow for a spatially well-defined interrogation in a thin sample slice, typically through a transparent cover slip. In this contribution we present a thorough study of the applicability of Raman spectroscopy for the described task. The obtained results clearly demonstrate the successful feasibility of the chosen method for a) a clear distinction between different media, b) the elucidation of the chemical composition of a multicomponent medium and c) an unambiguous identification of real unknown samples by a distinct assignment to a previously recorded spectral library. This library database was built up by recording pure mounting agents and will be provided to the general public. In combination with a Raman spectrometer, it can be an invaluable tool for future curation and conservation endeavors devoted to microscope slide collections at natural history museums. KW - Taxonomy KW - Mounting medium KW - Coverslip seal PY - 2016 DO - https://doi.org/10.1016/j.jcz.2016.07.002 SN - 0044-5231 VL - 265 SP - 178 EP - 190 PB - Elsevier AN - OPUS4-38210 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schmid, Thomas A1 - Dariz, P. T1 - Chemical imaging of historical mortars by Raman microscopy N2 - Raman microspectroscopic imaging was just recently introduced into the analysis of cement stone. Here, we demonstrate this approach on 19th-century Roman and Portland cement mortars and extend it to gypsum-based samples originating from a medieval stucco sculpture (high-burnt gypsum) and a stucco ornament prefabricated at the beginning of the 20th century (plaster of Paris). Furthermore, the distributions of dolomite and Calcite were mapped in an accessory mineral grain with approx. 500 nm lateral Resolution demonstrating the ability for studying alteration processes such as dedolomitisation. As we would like to make this approach accessible to other researchers, we discuss its present status, advantages, limitations and pitfalls. KW - Raman microscopy KW - Chemical imaging KW - Cement clinker KW - Gypsum KW - Dedolomite PY - 2016 DO - https://doi.org/10.1016/j.conbuildmat.2016.03.153 SN - 0950-0618 VL - 114 SP - 506 EP - 516 PB - Elsevier Science CY - Oxford, UK AN - OPUS4-36661 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Granulierte Hochofenschlacke als Mörtelzuschlag im 19. Jahrhundert in der Schweiz N2 - Als schweizweit einziger Hersteller produzierte die Gesellschaft der Ludwig von Roll'schen Eisenwerke seit den 1870er Jahren granulierte Hochofenschlacke. Im Blashochofen von Choindez im Schweizer Jura wird bis Mitte der 1920er Jahre Bohnerz aus dem Delsberger Becken, das kontemporär publizierten Analysen zufolge als Spuren- bzw. Schwermetalle Titan, Chrom, Blei und Vanadium enthält, zu grauem Roheisen verhüttet. In zementgebundenen Mörtelmischungen des 19. und frühen 20. Jahrhunderts aus verschiedenen Regionen der Schweiz finden sich neben reliktischen Hüttensandsplittern vereinzelt bis zu fünfhundert Mikrometer große scharze Kugeln mit grünlichem Schimmer, wohl nicht gemahlener Schlackensand. Deren mittels Ramanmikroskopie (Phasenbestand) und energiedispersiver Röntgenspektroskopie am Rasterelektronenmikroskop (Elementanalytik) ermittelte Mineralogie ergibt in Form von Plattnerit PbO2, Rutil TiO2 und vermitlich Chromit Fe(II)Cr2O4 bzw. Nichromit (Ni,Co,Fe(II))(Cr,Fe(III),Al)2)4 Übereinstimmungen mit den nur die Elementzusammensetzung berücksichtigenden historischen Resultaten. Ebenfalls im Zusammenhang mit dem das Bohnerz begleitenden Boluston samt Huppererde zu sehen sind die Minerale Coelestin SrSO4 und Zirkon ZrSiO4, des Weiteren der Siliciumcarbidpolymorph Moissanit SiC als Reaktionsprodukt von Quarzsand und Brennstoff. Die Kohärenz zwischen um die Jahrhundertwende durchgeführten Analysen von Rohmaterial als auch Ofenbruch aus dem in Choindez betriebenen Hochofen und den in diesem Beitrag diskutierten Resultaten moderner analytischer Methoden spricht für den Gebrauch von granulierter Schlacke aus dem Hause Ludwig von Roll als Mörtelzuschlag. Die Hüttensandkörner, eigentlich latent hydraulisch, sind aufgrund der fehlenden Aufbereitung zu grob für eine effektive Hydratation und deshalb trotz reaktiver Glasphase und Klinkermineralien (Belit Ca2SiO4 und Monocalciumaluminat CaAl2O4) intakt in der Bindemittelmatrix erhalten. N2 - From the 1870s the Ludwig von Roll ironworks produced granulated blast furnace slag in Choindez (Jura, Switzerland) as a by-product of the smelting of bean ore excavated until 1926 in the Delsberg Basin. According to historical analyses, this iron ore deposit contais heavy and trace metals such as titanium, chromium, lead and vanadium. In mortar samples from different regions of Switzerland originating from the 19th and early 20th centuries, residues of granulated blast furnace slag are observable as angular glassy particles in the binder matrix. In addition, black spherical grains with greenish lustre (up to 500 micrometres in diameter), probably not ground granulated blast furnace slag, can be distinguished sporadically in thin sections. Raman microscopy as well as scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM-EDX) measurements have revealed, inter alia, the presence of the crystalline components plattnerite PbO2, rutile TiO2 and presumably chromite Fe(II)Cr2O4 or nichromite (Ni,Co,Fe(II))(Cr,Fe(III),Al)2O4. These findings are consistent with historical analyses, which were restricted to the determination of the elemental (not phase) composition of the raw material processed by the Ludwig von Roll ironworks. Furthermore the minerals celestine SrSO4 and zircon ZrSiO4 can be linked to bean ore and bole from Delsberg, and likewise the silicon carbide moissanite SiC, which is a reaction product of quartz sand and coke. The coherence if the results of historical chemical analyses and of modern microscopic imaging and spectroscopy methods described here pinpoints the Ludwig von Roll ironworks as the most probable supplier of the granulated blast furnace slag that was added to the mortars under investigation. The unreacted remnants exhibit defined boundaries; no hydration rims are observable despite the glassy nature of the latent hydraulic aggregate, which contains cement clinker minerals (belite and calcium aluminate) as crystalline components. Not finely ground, the spheroids are too coarse for an effective hydration reaction and act as inert filler. KW - Granulierte Hochofenschlacke KW - Raman Mikroskopie KW - REM-EDX KW - Granulated blast furnace slag KW - Raman microscopy KW - SEM-EDX PY - 2015 VL - 29 IS - 2 SP - 293 EP - 304 PB - Wernersche Verlagsgesellschaft mbH CY - Worms AN - OPUS4-36651 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Álvarez-García, J. A1 - Izquierdo-Roca, V. A1 - Pistor, P. A1 - Schmid, Thomas A1 - Pérez-Rodríguez, A. ED - Abou-Ras, D. ED - Kirchartz, T. ED - Rau, U. T1 - Raman spectroscopy on thin films for solar cells N2 - In the present chapter, the capabilities of Raman spectroscopy for the advanced characterisation of thin films for solar cells are reviewed. Raman spectroscopy is an optical, nondestructive technique based on the inelastic scattering of photons with elemental vibrational excitations in the material. The line shape and position of the Raman bands are determined by the crystalline structure and chemical composition of the measured samples, being sensitive to the presence of crystalline defects, impurities and strain. Presence of peaks characteristic of different phases also allows for the identification of secondary phases that are strongly related to the growth and process conditions of the films. All these aspects account for a strong interest in the analysis of the Raman spectra, providing a powerful nondestructive analytical tool for the structural and chemical assessment of the films. In addition, the combination of a Raman spectrometer with an optical microscope also allows for achieving a high spatial resolutions (of below 1 µm) when mapping surfaces and analyzing depth-resolved phase distributions in thin films. The present chapter is divided into four main sections: The two first ones are devoted to a revision of the Fundamentals of Raman spectroscopy (Section 17.2) and Vibrational modes in crystalline materials (Section 17.3). Section 17.4 deals with the main experimental considerations involved in the design and implementation of a Raman scattering setup. This is followed by a detailed description of the application of Raman scattering for the structural and chemico-physical analysis of thin film photovoltaic materials (Section 17.5), with the identification of crystalline structure and secondary phases, evaluation of film crystallinity, analysis of chemical composition of semiconductor alloys, characterisation of nanocrystalline and amorphous layers, stress effects and crystal orientations. This includes the description of corresponding state of the art and recent case examples that illustrate the capabilities of the Raman technique for the advanced characterisation of layers and process monitoring in thin-film photovoltaic technologies. KW - Thin-film solar cells KW - Polycrystalline materials KW - Raman spectroscopy KW - Raman microscopy PY - 2016 UR - http://eu.wiley.com/WileyCDA/WileyTitle/productCd-3527339922.html SN - 978-3-527-33992-1 SP - 469 EP - 499 PB - Wiley & Sons, Ltd. CY - Oxford, UK AN - OPUS4-37451 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Schäfer, N. A1 - Wilkinson, A. J. A1 - Schmid, Thomas A1 - Winkelmann, Aimo A1 - Chahine, G. A. A1 - Schülli, T. U. A1 - Rissom, T. A1 - Marquardt, J. A1 - Schorr, S. A1 - Abou-Ras, D. T1 - Microstrain distribution mapping on CuInSe2 thin films by means of electron backscatter diffraction, X-ray diffraction, and Raman microspectroscopy N2 - The investigation of the microstructure in functional, polycrystalline thin films is an important contribution to the enhanced understanding of structure–property relationships in corresponding devices. Linear and planar defects within individual grains may affect substantially the performance of the device. These defects are closely related to strain distributions. The present work compares electron and X-ray diffraction as well as Raman microspectroscopy, which provide access to microstrain distributions within individual grains. CuInSe₂ thin films or solar cells are used as a modelsystem. High-resolution electron backscatter diffraction and X-ray microdiffraction as well as Ramanmicrospectroscopy were applied for this comparison. Consistently, microstrain values were determined of the order of 10⁻⁴ by these three techniques. However,only electron backscatter diffraction, X-ray microdiffraction exhibit sensitivities appropriate for mapping local strain changes at the submicrometer level within individual grains in polycrystalline materials. KW - Microstrain KW - Thin film KW - X-ray microdiffraction KW - EBSD KW - Raman microspectroscopy PY - 2016 DO - https://doi.org/10.1016/j.ultramic.2016.07.001 SN - 0304-3991 SN - 1879-2723 VL - 169 SP - 89 EP - 97 PB - Elsevier B.V. AN - OPUS4-37453 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CONF A1 - Rühlmann, Madlen A1 - Büchele, Dominique A1 - Schmid, Thomas A1 - Ostermann, Markus T1 - Development of an online-analysis technique for the determination of plant essential nutrients in soils using XRF and LIBS N2 - Currently, there is almost no comprehensive mapping of agricultural cropland because of the lack of fast and affordable mapping methods for important soil properties. Arable land of some hectares in size show a broad range of different nutrient compositions. Because of this heterogeneity wrong fertilization can occur and can cause environmental pollution or lead to smaller harvests and this is simply a waste of resources. The goal of I4S (intelligence for soil) is to develop an integrated system for site-specific soil fertility management. The I4S consortium consists of 10 different institutions, which are testing various sensors for their suitability for the requested applications. Besides the preparation of reference materials, the main task of the Federal Institute for Materials Research and Testing (BAM) in this project is the method development for online-XRF (x-ray fluorescence spectroscopy) and for online-LIBS (laser-induced breakdown spectroscopy) sensor systems. Both methods have the advantage that there is no or only little sample preparation necessary. Each method provides a fast and simultaneous multi-element analysis. Both measurement setups can be utilized for a mobile application which is fundamental for reaching the goals of I4S. Having finally a set of some reference materials, further work will focus on the online-XRF and online-LIBS methods in order to obtain useable calibration models. The calibration models will then be tested using stationary and moving samples. T2 - 12. Kolloquium Prozessanalytik CY - Berlin, Germany DA - 28.11.2016 KW - RFA KW - LIBS KW - Soil KW - Agricultural KW - Online KW - Sensor system PY - 2016 SP - P12, 63 EP - 65 AN - OPUS4-38377 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Ostermann, Markus A1 - Schmid, Thomas A1 - Büchele, Dominique A1 - Rühlmann, Madlen T1 - In Echtzeit durch's Periodensystem N2 - Per Online-RFA und -LIBS Elementgehalte in Böden bestimmen. Die ortsspezifische Steuerung der Bodenfruchtbarkeit durch angepasste Düngung und andere Maßnahmen hilft die Bodenfunktionen zu verbessern und Umweltbelastungen zu vermindern. Dabei zeigt das Beispiel die hohe Relevanz schneller, robuster Vor-Ort-Analysen für viele umweltrelevante Fragestellungen. KW - RFA KW - LIBS KW - Online-Analytik KW - Boden PY - 2016 UR - https://files.vogel.de/vogelonline/vogelonline/issues/lp/7680.pdf SN - 0344-1733 VL - 40 IS - LP 12 SP - 22 EP - 24 PB - Vogel Business Media GmbH & Co. KG CY - Würzburg AN - OPUS4-38700 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Wäsche, Rolf A1 - Brandt, Guido A1 - Ehrke, Roman A1 - Nolze, Gert A1 - Schmid, Thomas A1 - Sasaki, S. A1 - Woydt, Mathias T1 - Wear behaviour of alpha-alumina in hot steam at high contact pressure N2 - The work examines the wear behaviour of α-aluminium oxide by combining thermodynamic modelling with advanced wear testing as well as analytical methods to get a better understanding of this structural ceramic material wear behavior and its possible use in high temperature steam environment. KW - Aluminium oxide KW - Temperature KW - Hot steam KW - Diaspore KW - Ceramic KW - Wear PY - 2018 DO - https://doi.org/10.1016/j.wear.2018.02.012 SN - 0043-1648 SN - 1873-2577 VL - 404-405 SP - 22 EP - 30 PB - Elsevier B.V. AN - OPUS4-44449 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Jakob, C. A1 - Ectors, D. A1 - Neubauer, J. A1 - Schmid, Thomas T1 - Measuring the Burning Temperatures of Anhydrite Micrograins in a High-Fired Medieval Gypsum Mortar N2 - Typical feature of high-fired medieval gypsum mortars is a compact microstructure of squat gypsum crystals containing firing products as remains of the calcination process. So far, the burning history of the binder is estimated based on morphological characteristics of the latter. A novel Raman microspectroscopy approach provides access to the calcination temperatures of individual anhydrite grains based on quantifiable spectroscopic changes appearing due to gradual variations of crystallinity, as independently confirmed by X-ray diffraction analysis of anhydrites synthesised at temperatures between 500°C and 900°C. The approach was successfully applied to the high-fired gypsum mortar of a South Tyrolean stucco sculpture of a pieta dated around 1420. Microparticles of burned anhydrite II with firing temperatures scattered around 650°C and clusters of thermally damaged natural anhydrite II crystals from the raw material were identified and imaged. KW - Analytical methods KW - Gypsum technology KW - High-fired gypsum mortar KW - Raman microspectroscopy KW - Thermal anhydrite PY - 2017 DO - https://doi.org/10.1002/slct.201701260 VL - 2 IS - 28 SP - 9153 EP - 9156 PB - Wiley VCH Verlag AN - OPUS4-42458 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Dariz, P. A1 - Schmid, Thomas T1 - Temperaturindikatoren in mittelalterlichen Hochbrandgipsen: Eine Ramanmikrospektroskopische Studie N2 - Infolge der beschränkten Kontrollmöglichkeiten über die in einem Meiler oder Feldofen herrschenden Parameter konstituiert mittelalterliche Hochbrandgipse ein Gemisch aus verschiedenen Anhydritstufen. Basierend auf modernen Versuchsbränden dienen in der gealterten Gipsmatrix nicht oder nur teilweise hydratisiert erhaltene Brenngutkörner üblicherweise anhand der morphologischen Eigenschaften der Anhydritkristalle der groben Einschätzung der zumindest lokal im Ofen bzw. im stückigen Brenngut erreichten Temperaturwerte. Die bildgebende Ramanmikroskopie ermöglicht die kornspezifische Bestimmung der Hitzeeinwirkung über den Grad der sich im Ramanspektrum abbildenden thermischen Beeinträchtigung der Thermoanhydritphasen, als auch deren Unterscheidung von primärem Anhydrit aus der Gipslagerstätte, da diesen eine höhere Kristallinität kennzeichnet. Hier beispielhaft diskutierte Ramananalysen an zwei reliktischen Brenngutkörnern lassen auf Brenntemperaturen von 650°C bzw. 800°C schließen. Pyrometamorphe Phasenneubildungen der natürlichen Verunreinigungen des Rohgipses liefern aufgrund ihres Bildungs- und Stabilitätsbereiches zusätzliche Hinweise. Im Beitrag erörtert werden die an die Dehydratation von magnesiumreichem Chlorit korrelierte Genese von Forsterit sowie die Zersetzung von Dolomit zu Calcit und Periklas, welcher beim Anmachen des Mörtels zu Brucit gelöscht wird und im Laufe der Zeit in der Gipsmatrix zu Magnesit carbonatisiert; beide pyrometamorphen Reaktionen erfordern Temperaturen von über 800°C. KW - Ramanmikrospektroskopie KW - Mineralthermometer KW - Gips PY - 2018 SN - 0931-7198 VL - 32 IS - 1 SP - 69 EP - 78 PB - Wernersche Verlagsgesellschaft mbH CY - Worms AN - OPUS4-47041 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -