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Eingeladener Vortrag
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Shedding light onto the spectra of lime: Raman and luminescence bands of CaO, Ca(OH)2 and CaCO3
(2015)
In microscopy studies of 19th-century cement stone, we found free lime in the form of darkened spherical structures, as they were described in the literature already. When trying to determine their phase composition by Raman spectroscopy, we encountered contradictive assignments in literature spectra of the lime phases CaO, Ca(OH)2 and CaCO3 and observed strong spectral features that have been ignored or erroneously assigned so far. In this study we present Raman spectra of pure lime phases and of a naturally grown calcite crystal, burnt limestone (quick lime, mainly CaO), aged slaked lime putty (mainly Ca(OH)2), and carbonated lime putty (mainly CaCO3). Based on the results, we shed light mainly onto these two questions: (1) Does CaO have a Raman spectrum? (2) Which features in the spectra are luminescence bands that could be (and already have been) misinterpreted as Raman bands? We proof our assignment of luminescence bands in lime phases by using three different laser wavelengths for excitation, and give hypotheses on the origin of the luminescence as well as practical advices on how to identify these misleading features in Raman spectra. This article is mainly addressed to users of Raman spectroscopy in different fields of material analysis who might not be aware of the presence of interfering bands in their spectra.
Characterization of Cu (In x, Ga y) (S m, Se n) 2 thin-film solar cell materials by Raman microscopy
(2014)
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.
The improved Monte-Carlo (MC) method for standard-less analysis in laser induced breakdown spectroscopy (LIBS) is presented. Concentrations in MC LIBS are found by fitting model-generated synthetic spectra to experimental spectra. The current version of MC LIBS is based on the graphic processing unit (GPU) computation and reduces the analysis time down to several seconds per spectrum/sample. The previous version of MC LIBS which was based on the central processing unit (CPU) computation requested unacceptably long analysis times of 10's minutes per spectrum/sample. The reduction of the computational time is achieved through the massively parallel computing on the GPU which embeds thousands of co-processors. It is shown that the number of iterations on the GPU exceeds that on the CPU by a factor > 1000 for the 5-dimentional parameter space and yet requires > 10-fold shorter computational time. The improved GPU-MC LIBS outperforms the CPU-MS LIBS in terms of accuracy, precision, and analysis time. The performance is tested on LIBS-spectra obtained from pelletized powders of metal oxides consisting of CaO, Fe2O3, MgO, and TiO2 that simulated by-products of steel industry, steel slags. It is demonstrated that GPU-based MC LIBS is capable of rapid multi-element analysis with relative error between 1 and 10's percent that is sufficient for industrial applications (e.g. steel slag analysis). The results of the improved GPU-based MC LIBS are positively compared to that of the CPU-based MC LIBS as well as to the results of the standard calibration-free (CF) LIBS based on the Boltzmann plot method.
The increasing pollution of terrestrial and aquatic ecosystems with plastic debris, which leads to the accumulation of microscopic plastic particles of still unknown fate, is an upcoming problem of our time. In order to monitor the degree of contamination and to understand the underlying processes of degradation and internalization of plastic debris, analytical methods are urgently needed, which help to identify and quantify microplastics. Currently, expensive collected and purified materials enriched on filters are investigated by (micro) infrared spectroscopy (FTIR). Few studies using micro-Raman spectroscopy have been published as well. In contrast to FTIR, Raman spectroscopy can handle wet samples, but it suffers from interference of fluorescent materials. Both micro-FTIR- and micro-Raman, always include time consuming scanning and mapping procedures followed by the manual inspection and measurement of selected particles.
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.
Measuring the Burning Temperatures of Anhydrite Micrograins in a High-Fired Medieval Gypsum Mortar
(2017)
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.
A wide range of aspects concerning microscope slides, their preparation, long-time storage, curatorial measures in collections, deterioration, restoration, and study is summarized based on our own data and by analyzing more than 600 references from the 19th century until 2016, 15 patents, and about 100 Materials Safety Data Sheets. Information from systematic zoology, conservation sciences, chemistry, forensic sciences, pathology, paleopathology, applied sciences like food industry, and most recent advances in digital imaging are put together in order to obtain a better understanding of which and possibly why mounting media and coverslip seals deteriorate, how slides can be salvaged, which studies may be necessary to identify a range of ideal mounting media, and how microscope studies can benefit from improvements in developmental biology and related fields. We also elaborate on confusing usage of concepts like that of maceration and of clearing.
The chemical ingredients of a range of mounting media and coverslip seals are identified as much as possible from published data, but this information suffers in so far as the composition of a medium is often proprietary of the manufacturer and may vary over time. Advantages, disadvantages, and signs of deterioration are documented extensively for these media both from references and from our own observations. It turns out that many media degrade within a few years, or decades at the latest, except Canada balsam with a documented life-time of 150 years, Euparal with a documented life-time of 50 years, and glycerol-paraffin mounts sealed with Glyceel, which represents almost the only non-deteriorating and easily reversible mount. Deterioration reveals itself as a yellowing in natural resins and as cracking, crystallization, shrinkage on drying or possibly on loss of a plasticizer, detachment of the coverslip, segregation of the ingredients in synthetic polymers, as well as continued maceration of a specimen to a degree that the specimen virtually disappears. Confusingly, decay does not always appear equally within a collection of slides mounted at the same time in the same medium. The reasons for the deteriorative processes have been discussed but are controversial especially for gum-chloral media. Comparing data from conservation sciences, chemical handbooks, and documented ingredients, we discuss here how far chemical and physical deterioration probably are inherent to many media and are caused by the chemical and physical properties of their components and by chemicals dragged along from previous preparation steps like fixation, chemical maceration, and physical clearing. Some recipes even contain a macerating agent, which proceeds with its destructive work. We provide permeability data for oxygen and water vapor of several polymers contained in mounting media and coverslip seals. Calculation of the penetration rate of moisture in one example reveals that water molecules reach a specimen within a few days up to about a month; this lays to rest extensive discussions about the permanent protection of a mounted specimen by a mounting medium and a coverslip seal.
Based on the ever growing evidence of the unsuitable composition and application of many, and possibly almost all, mounting media, we strongly encourage changing the perspective on microscope slides from immediate usability and convenience of preparation towards durability and reversibility, concepts taken from conservation sciences. Such a change has already been suggested by Upton (1993) more than 20 years ago for gum-chloral media, but these media are still encouraged nowadays by scientists. Without a new perspective, taxonomic biology will certainly lose a large amount of its specimen basis for its research within the next few decades. Modern non-invasive techniques like Raman spectroscopy may help to identify mounting media and coverslip seals on a given slide as well as to understand ageing of the media. An outlook is given on potential future studies.
In order to improve the situation of existing collections of microscope slides, we transfer concepts as per the Smithsonian Collections Standards and Profiling System, developed for insect collections more than 25 years ago, to collections of slides. We describe historical and current properties and usage of glass slides, coverslips, labels, and adhesives under conservational aspects. In addition, we summarize and argue from published and our own experimental information about restorative procedures, including re-hydration of dried-up specimens previously mounted in a fluid medium. Alternatives to microscope slides are considered. We also extract practical suggestions from the literature concerning microscope equipment, cleaning of optical surfaces, health risks of immersion oil, and recent improvements of temporary observation media especially in connection with new developments in digital software.
Temperaturindikatoren in mittelalterlichen Hochbrandgipsen: Eine Ramanmikrospektroskopische Studie
(2018)
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.
The mechanism of action of zirconium permanent modifiers on graphite surfaces was investigated in order to understand its influence on the analytical signal in atomic and molecular absorption spectrometry (AAS/MAS). For this, the molecule formation of CaF was studied, which is used for the indirect analytical determination of fluorine in high-resolution continuum source graphite furnace molecular absorption spectrometry (HR-CS-GFMAS). The kinetics of this reaction was established by monitoring its molecular spectrum at different atomisation temperatures. An Arrhenius plot showed a pseudo-first order reaction with respect to fluorine (n = 1). An intermediate state was isolated, and its structure was elucidated by spectroscopic methods: scanning electron microscopy with energy dispersive X-ray spectroscopy (SEMEDX), X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XANES and EXAFS), and Raman microspectroscopy. We propose here a mechanism, where ZrO2 acts as a heterogeneous catalyst: after a pyrolytic step, an intermediate state of ZrO(OCaF) is activated, and at higher temperatures, CaF(g) is released from the zirconium-coated graphite surface. No evidence of the formation of zirconium carbide was found. Consequently, as the CaF formation is catalysed by a heterogeneous catalyst, surface modifications with ZrO2 nanoparticles and ZrO xerogels were investigated in order to increase the surface area. Their influence was evaluated in the molecule formation of CaF, CaCl, CaBr, and CaI. Graphite furnace modification with zirconium oxide nanoparticles proves to be the best choice for fluorine analysis with a signal enhancement of more than eleven times with respect a non-coated graphite furnace. However, the influence of zirconium modifications in the analytical signals of Cl, and I is lower than the F signals or even negative in case of the Br. Understanding zirconium modifiers as heterogeneous catalysts offers a new perspective to AAS and MAS, and reveals the potential of surface analytical methods for development of improved permanent modifiers and graphite furnace coatings.
We present a versatile and simple method using electrochemistry for the exclusive functionalization of the edge of a graphene monolayer with metal nanoparticles or polymeric amino groups. The attachment of metal nanoparticles allows us to exploit surface-enhanced Raman scattering to characterize the chemistry of both the pristine and the functionalized graphene edge. For the pristine patterned graphene edge, we observe the typical edge-related modes, while for the functionalized graphene edge we identify the chemical structure of the functional layer by vibrational fingerprinting. The ability to obtain single selectively functionalized graphene edges routinely on an insulating substrate opens an avenue for exploring the effect of edge chemistry on graphene properties systematically.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2019)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
Self-mated magnesia stabilized zirconia (Mg-PSZ) ceramic sliding couples have been investigated at 100 N load (P0max= 1324 MPa) in oscillating sliding conditions in different humidity conditions in air and in hot steam. Temperatures have been varied up to 400 °C and pressures up to 6 bars. The results show that the wear behavior of MgO-ZrO2 under high Hertzian contact pressures is strongly dependent on temperature and is similar for both dry oscillating and oscillating in hot steam. However, although the evolution in wear rates on temperature is similar and the wear rates of MgO-ZrO2 plunged above 300 °C in hot steam and air by nearly three orders of magnitude, SEM micrographs revealed in hot steam at 400 °C smooth wear tracks. In contrast, hot steam enhanced the tribochemistry of self-mated alumina couples and reduced wear rates. Hot steam decreased the coefficients of friction of MgO-ZrO2 with increasing temperature, but not the wear rates.
Früh- bis spätmittelalterliche Stuckausstattungen bilden ein regionales, da an Gips-vorkommen korreliertes kunsttechnologisches Spezifikum. Aufgrund der beschränkten Kontrollmöglichkeiten über die in einem Meiler oder Feldofen herrschenden Parameter charakterisiert mittelalterliche Hochbrandgipse ein Phasengemisch aus Calciumsulfat-Hydratstufen und thermisch mehr oder weniger stark geschädigten Nebenbestandteilen aus der Gipslagerstätte. Die Analyse mittelalterlicher Hochbrandgipse erfordert die genaue Kenntnis der Bildungs- und Stabilitätsbereiche der Phasen im System CaSO4–H2O. Gips CaSO4 x 2 H2O entwässert beim Brennen über Halbhydrat CaSO4 x 0.5 H2O zu Anhydrit III CaSO4, welches schließlich in den für mittelalterliche Hochbrandgipse relevanten Anhydrit II (AII) übergeht. Für diesen wurden aufgrund der Abbindeeigenschaften drei bis vor kurzem nicht spektroskopisch unterscheidbare Sub-Phasen postuliert: Anhydrit II schwerlöslich (300-500°C, AII-s), unlöslich (500-700°C, AII-u) und Estrichgips (> 700°C, AII-E). Anhydrit I ist nur über 1180°C stabil.
Mittels strukturanalytischer Methoden wie Röntgenbeugung (XRD) und Raman-Spektroskopie lassen sich nur die verschiedenen Hydratstufen sowie AIII, AII und AI eindeutig aufgrund unterschiedlicher Kristallstrukturen identifizieren. Ein neues auf Raman-mikrospektroskopischer Bildgebung basierendes Verfahren ermöglicht den Nachweis verschiedener Brenntemperaturen aufgrund der Auswertung von Raman-Bandenbreiten von AII, welche ein Maß für die mit steigender Brenntemperatur zunehmende Kristallinität der Anhydritkörner sind.
Die Anwendung dieser Methode sowie der Nachweis pyrometamorpher Umwandlun-gen von Begleitmineralien aus dem Gipsstein als Mineralthermometer zur Bestimmung von Brenntemperaturen wird anhand von Proben früh- und spätmittelalterlicher Skulpturen und Stuckdekorationen aus Südtirol diskutiert. Außerdem wird gezeigt, wie die Analyse solch komplexer Materialien Rückkopplungen in die Analytische Chemie erzeugen kann, da zur erfolgreichen Analytik eine Möglichkeit zur reproduzierbaren Bestimmung von Ramanbandenbreiten und der Korrektur instrumentenabhängiger Verbreiterung gefunden und optimiert werden musste.
Damit sollten überzeugende Belege dafür erbracht werden können, dass die Komplexität des monomineralischen Bindemittels Gips bezüglich der je nach Brandbedingungen unterschiedlichen Eigenschaften und insbesondere bezüglich der Herausforderungen an die Analytische Chemie häufig unterschätzt wird.
The use of high-fired gypsum as binder for masonry and joint mortars or stuccowork in Central Europe in the Early and High Middle Ages was a regional specific as it depended on local gypsum deposits. The calcination technology possible at the time resulted in an assemblage of calcium sulphate phases dehydrated to different degrees and partly thermally damaged accessory minerals of the raw gypsum. Not hydrated clusters of firing products preserved in the binder matrix are a typical feature of such mortars. A novel Raman microspectroscopic approach, providing access to the burning history of individual anhydrite grains, was applied to samples from medieval South Tyrolean stucco decorations and sculptures. Beyond that, Raman microspectroscopy was employed for tracing and visualising pyrometamorphic reactions in natural impurities of the kiln run. In the discussed examples mineral thermometry indicates process temperatures above 800°C: the breakdown of magnesium-rich chlorite led to the formation of forsterite Mg2SiO4, while the thermal decomposition of dolomite CaMg(CO3)2 to periclase MgO and lime CaO yielded – after hydration and carbonation – magnesite MgCO3, CaCO3 polymorphs and magnesian calcite. Hydration of periclase in the mixed gypsum paste containing sulphate ions also resulted in magnesium sulphate hydrates, here identified in the form of hexahydrite MgSO4·6H2O. Lower burning temperatures left the accessory minerals in their pristine form, but can be traced by measuring the spectra of individual anhydrite crystals in grains of firing products and evaluating Raman band widths. Throughout the present study, calcination temperatures ranging from approx. 600°C to 900°C were determined.
The quantification of the elemental content in soils with laser-induced breakdown spectroscopy (LIBS) is challenging because of matrix effects strongly influencing the plasma formation and LIBS signal. Furthermore, soil heterogeneity at the micrometre scale can affect the accuracy of analytical results. In this paper, the impact of univariate and multivariate data evaluation approaches on the quantification of nutrients in soil is discussed. Exemplarily, results for calcium are shown, which reflect trends also observed for other elements like magnesium, silicon and iron. For the calibration models, 16 certified reference soils were used. With univariate and multivariate approaches, the calcium mass fractions in 60 soils from different testing grounds in Germany were calculated. The latter approach consisted of a principal component analysis (PCA) of adequately pre-treated data for classification and identification of outliers, followed by partial least squares regression (PLSR) for quantification. For validation, the soils were also characterised with inductively coupled plasma optical emission spectroscopy (ICP OES) and X-ray fluorescence (XRF) analysis. Deviations between the LIBS quantification results and the reference analytical results are discussed.
Raman microscopic imaging was just recently introduced into the analysis of residual Roman and Portland cement grains in 19th century cement stone, displaying evidence of the experimental adaptation of contemporary technological knowledge and practice to local circumstance. Beyond calcium ferrites, this study deals with ferruginous clinker phases that are atypical compared to present-day commercial conditions of manufacture, such as iron oxides, clinopyroxenes or pyroxenoids. Analog, microtexture, mineralogy and chemical composition of pulverized ferrosilicate slag used in the course of the 19th century as mineral additive in lime mortar reflect local resource utilization, recording the melting history within the furnace and the effectiveness of the reduction process of a single smelting event. In the case of the discussed example, chemical imaging by Raman microscopy allowed deducing a lime-rich, low-silica melt exposed to fairly reducing conditions because of the detection of the pyrometallurgic phases fayalite (Fe2SiO4), kirschsteinite (CaFeSiO4) and calcioolivine (Ca2SiO4) in zoned olivine laths and (with the melilite gehlenite, Ca2Al2SiO7) in the Interstitial matrix, cross-cut by dendritic wuestite (FeO). The presented analytical approach faces the high spatial complexity of such mortar samples by microspectroscopic imaging with micrometer lateral resolution and their chemical complexity by extracting the rich chemical information content from Raman spectra. Intensity maps of marker bands provide spatial phase distributions. Furthermore, maps of peak positions can give access to the dissemination of spectroscopically similar phases of solid solution series (e.g., olivine and calcium Aluminate ferrite) as well as varying amounts of incorporated foreign cations (e.g., in hematite).
Ramanmikroskopie kombiniert den chemischen Informationsgehalt von Ramanspektren mit einer Ortsauflösung im Mikrometer- bis Sub-Mikrometerbereich und eignet sich daher hervorragend zur Analyse mikrostrukturell und chemisch komplexer Materialien.
Zemente des 19. Jahrhunderts sind chemisch wie mikrostrukturell wesentlich komplexer als die heute aus definierten Rohmaterialien unter optimalen Bedingungen erbrannten Mörtelbinder. Der erstmalige Einsatz bildgebender Ramanmikroskopie im Bereich zementbasierter Materialien zeigte das Potential dieser Analytik auf. Gezieltes, flächendeckendes Abrastern von Klinkerrelikten in der hydratisierten Zementmatrix ermöglicht die Bestimmung von Silikaten, Aluminaten, Ferriten und anderer Phasen inklusive polymorpher Formen und Änderungen der Zusammen-setzung innerhalb von Mischkristallreihen und aufgrund des Einbaus von Fremdionen, wobei auch mikropartikuläre Bestandteile erfasst werden, deren Konzentrationen unter der Nachweisgrenze makroskopischer Analyseverfahren liegen. So lassen sich Rückschlüsse auf die verwendeten Rohmaterialien und die Herstellungsbedingungen ziehen, was die Bestimmung des verwendeten Zementtyps zulässt und damit Auswirkungen auf die Auswahl von Restaurierungsmaterialien hat. Möglichkeiten zur quantitativen Verteilungsanalyse von Kristallorientierungen und mechanischer Spannungen zeigten sich bei der Untersuchung von Dünnschicht-Solarzellen-Absorbern wie Cu(In,Ga)Se2 und daraus abgeleiteter Materialien. Die direkte Kompatibilität mit Lichtmikroskopie-Proben und die hohe chemisch-strukturelle Spezifizität von Ramanspektren kamen der Untersuchung naturhistorischer Mikroskopiepräparate aus Museumssammlungen zugute. Sowohl das Eindeckmedium und seine aktuelle Zusammensetzung (z.B. bezüglich leichtflüchtiger Bestandteile) als auch durch Alterung entstandene Schäden lassen sich mit der Technik zerstörungsfrei erfassen. Damit können in Zukunft Beiträge zum Erhalt der weltweit mehrere Millionen Proben umfassenden naturhistorischen Sammlungen geleistet werden.
Die in der Forschung gesammelte Erfahrung fließt in der BAM direkt in die Sonder-probenanalytik für Industriekunden ein, wo Ramanbildgebung, eingebettet in ein Arsenal komplementärer Methoden, ebenfalls häufig eine zentrale Rolle spielt.
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
This overview article provides insight into how to apply Raman spectroscopy in combination with a confocal, optical microscope setup on polycrystalline material systems, in order to obtain quantitative information on phase distribution, grain sizes, crystal orientations and microstrain. Although the present work uses Cu(In,Ga)(S,Se)₂ absorber layers in corresponding thin-film solar cells as a model system to demonstrate the capabilities of Raman microspectroscopy, the approaches discussed may be applied to any organic or inorganic, polycrystalline materials system.
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.
In the second half of the 19th century, Roman and Portland cements played an essential role as active hydraulic binder material in building construction and façade ornamentation. Size and heterogeneous phase assemblage of unhydrated cement clinker remnants in historical cement stone differ significantly from those of remnants occurring in modern Portland cement clinker burnt in rotary kilns due to limitations of the production technology available in the 19th century (e.g., comminution and homogeneity of the feedstock, burning temperature and regime in the intermittently operated shaft kilns, grinding machinery). In the common analytical approach, thin sections and fracture surfaces of historical Roman and Portland cement mortars are characterised regarding their mineralogical composition and microstructure using optical and electron microscopic imaging techniques. Raman microspectroscopy can be additionally employed for petrographic examination, overcoming some limitations of the methods used so far. The determination of the phase content of residual cement clinker grains in the hydrated matrix allows for the differentiation of Roman and Portland cement binders. As marker phases, we propose the calcium aluminates CA, C12A7, C2AS and C3A – besides the commonly used calcium silicates C2S and C3S – because of their different formation temperatures and stability fields. This study focuses on the identification of different calcium aluminate and aluminoferrite phases in clinker remnants in samples of cast ornaments of three buildings in Switzerland raised between 1875 and 1893; the obtained Raman spectra are compared with fingerprint spectra of the corresponding pure, synthesised clinker phases collected with the same instrument for an unambiguous data interpretation. In addition to these phases, mainly minerals showing no hydraulic activity, such as, wollastonite CS, rankinite C3S2, free lime, portlandite, iron oxides, garnets, augite, albite and feldspathoids have been identified in the sampled historical cement stones by Raman microspectroscopy. As there is a strong relationship between coexisting clinker phases and the chemical composition of the raw meal as well as the burning and cooling history during clinkering, the results can help in understanding the physical and mechanical characteristics of historical cement mortars. This knowledge is fundamental for the choice and the formulation of appropriate repair materials with tailored properties employed in the field of restoration and preservation of the architectural heritage of the 19th and early 20th centuries.
Laser-induced breakdown spectroscopy (LIBS) is a fast and versatile technique for (semi) quantitative element analysis of solids, liquids, gases, and particulate matter. The LIBS method is used for optical sensing in various branches of industrial production. In the contribution we review some of our recent results on LIBS analysis of slags from secondary metallurgy in industrial steel making. Major oxides in steel slags are measured at-line and after homogenization using a calibration-free (CF) method. Two approaches for CF analysis based on the Boltzmann plot method and on the calculation of synthetic spectra are compared for the analysis of quaternary oxides. We also present the research in cooperation with our industrial partners in the process-analytical chemistry network PAC.
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.
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.
Tomography of a laser-induced plasma in air is performed by inverse Radon transform of angle-resolved plasma images. Plasmas were induced by single laser pulses (SP), double pulses (DP) in collinear geometry, and by a combination of single laser pulses with pulsed arc discharges (SP-AD). Images of plasmas on metallurgical steel slags were taken at delay times suitable for calibration-free laser-induced breakdown spectroscopy (CFLIBS). Delays ranged from few microseconds for SP and DP up to tens of microseconds for SP-AD excitation. The white-light and the spectrally resolved emissivity ε(x,y,z) was reconstructed for the three plasma excitation schemes. The electron number density Ne(x,y,z) and plasma temperature Te(x,y,z) were determined from Mg and Mn emission lines in reconstructed spectra employing the Saha-Boltzmann plot method. The SP plasma revealed strongly inhomogeneous emissivity and plasma temperature. Re-excitation of plasma by a second laser pulse (DP) and by an arc discharge (SP-AD) homogenized the plasma and reduced the spatial variation of ε and Te. The homogenization of a plasma is a promising approach to increase the accuracy of calibration-free LIBS analysis of complex materials.
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.
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.
Microstrain distributions were acquired in functional thin films by high-resolution X-ray microdiffraction measurements, using polycrystalline CuInSe2 thin films as a model system. This technique not only provides spatial resolutions at the submicrometre scale but also allows for analysis of thin films buried within a complete solar-cell stack. The microstrain values within individual CuInSe2 grains were determined to be of the order of 10^-4. These values confirmed corresponding microstrain distribution maps obtained on the same CuInSe2 layer by electron backscatter diffraction and Raman microspectroscopy.
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.
Bildgebende Phasenbestimmung mittels Ramanmikroskopie- Grundlagen und Anwendungen an Zementstein
(2015)
Raman band widths of anhydrite II reveal the burning history of high‐fired medieval gypsum mortars
(2019)
When used as a mineral binder, gypsum is thermally dehydrated and mixed with water, resulting in a paste hardening in the backreaction to calcium sulphate dihydrate (CaSO4 · 2 H2O). Although nowadays mainly hemihydratebased (CaSO4 · ½ H2O) binders are employed, higher firing temperatures in medieval kilns yielded anhydrite II (CaSO4). Except for the discrimination of the metastable phases anhydrite III and I due to different crystal structures, variations within the production temperature range of anhydrite II (approximately 300 to 1180°C) were not analytically accessible until recently. This study describes the development of an analytical technique, which is based on steady changes of band widths in room‐temperature Raman spectra of anhydrite II as a function of burning temperature. Raman microspectroscopic mapping experiments enable to pinpoint individual unreacted grains of thermal anhydrite in mortars and to discriminate them from natural anhydrites originating from the raw gypsum. The determination of band full widths at half maximum of down to 3 cm−1 and differences between them of a few tenths of wavenumbers is not a trivial task. Thus, a focus of this work is on peak fitting and strategies for correction of instrument‐dependent band broadening, which is often neglected also beyond the field of mortar analysis. Including other potential influences on band widths, burning temperatures of 400 to 900°C can be retraced in high‐fired medieval gypsum mortars with an uncertainty of approximately ± 50 K, as demonstrated with sample material of a stucco sculpture dated around 1400.
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.
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.
Raman spectroscopy provides vibrational fingerprints of chemical compounds enabling their unambiguous identification. The assignment of Raman spectra to minerals is straightforward, if appropriate reference data is accessible. Modern couplings of Raman spectroscopy with microscopy (Raman microspectroscopy) merge the high structural specificity with down to sub-micrometre spatial resolution. This analytical tool has high potential not only in the identification of minerals from natural sources but also for studying the complex microstructure and mineral distribution of both ancient and modern man-made materials. In addition to the chemical identity of minerals, Raman spectra are affected by crystal orientations (varying relative Raman band intensities); (sub)stoichiometric compositional changes (e.g., in solid solution series), traces of foreign ions, strain (the latter three shifting Raman bands); and crystallinity (changing Raman band widths), enabling a comprehensive physico-chemical characterisation of minerals. Thus, Raman spectroscopy – including its in situ measurement capabilities – provides possibilities to study mineral paragenesis in both, natural and man-made samples at the micrometre scale. While in 1928 the first experimental evidence for inelastic light scattering was provided by C. V. Raman and K. S. Krishnan by using sunlight for excitation, filters for selecting the inelastically scattered light, and their eyes for detection (later, photographic plates for acquisition of spectra were employed), modern Raman spectrometers make use of laser excitation, dispersive spectrographs and charge coupled device (CCD) detection. This Special Issue includes technological developments and applications in the field of modern Raman spectroscopy of minerals in a broad sense, from natural mineral deposits and archaeological objects to inorganic phases in man-made materials. The studied minerals include fossil resins, typical rock-forming minerals (calcite, quartz, forsterite), iron-sulphur species (e.g., mackinawite), a range of sulphates (gypsum, bassanite, anhydrite III, anhydrite II, celestine, barite, ternesite), as well as silicate minerals like garnets (e.g., almandine).
Even though being the subject of natural scientific research for many decades, the system CaSO4–H2O, consisting of the five crystalline phases gypsum, bassanite, and the anhydrites III, II, and I, has left many open questions for research. Raman spectroscopy was used because of its structural sensitivity and in situ measurement capability to obtain further insight by studying phase transitions in both ex situ and in situ experiments. The findings include significant contributions to the completeness and understanding of Raman spectroscopic data of the system. The dehydration path gypsum–bassanite–anhydrite III was shown to have strong parallels to a physical drying process, which depends on many parameters beyond the burning temperature. Raman band width determination was demonstrated to enable the quantitative discrimination of α-bassanite and β-bassanite as well as the postulated three sub-forms of anhydrite II (AII), which are all based on differences in crystallinity. In the latter case, the observed continuous structural variations over increasing burning temperatures were elucidated as a combination of decreasing surface areas and healing of crystal lattice defects. We propose an only two-fold sub-division of AII into reactive “disordered AII” and much less reactive “crystalline AII” with a transition temperature of 650°C ± 50 K.
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
Spatial heterodyne spectroscopy (SHS) is a novel spectral analysis technique that is being applied for Raman spectroscopy of minerals. This paper presents the theoretical basis of SHS and its application for Raman measurements of calcite, quartz and forsterite in marble, copper ore and nickel ore, respectively. The SHS measurements are done using a broadband (518–686 nm) and resolving power R ≈ 3000 instrument. The spectra obtained using SHS are compared to those obtained by benchtop and modular dispersive spectrometers. It is found that SHRS performance in terms of resolution is comparable to that of the benchtop spectrometer and better than the modular dispersive spectrometer, while the sensitivity of SHRS is worse than that of a benchtop spectrometer, but better than that of a modular dispersive spectrometer. When considered that SHS components are small and can be packaged into a handheld device, there is interest in developing an SHS-based Instrument for mobile Raman spectroscopy. This paper evaluates the possibility of such an application.
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.
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.
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.
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.
Electrochemical methods offer great promise in meeting the demand for user-friendly on-site devices for Monitoring important parameters. The food industry often runs own lab procedures, for example, for mycotoxin analysis, but it is a major goal to simplify analysis, linking analytical methods with smart technologies. Enzyme-linked immunosorbent assays, with photometric detection of 3,3’,5,5’-tetramethylbenzidine (TMB),form a good basis for sensitive detection. To provide a straightforward approach for the miniaturization of the detectionstep, we have studied the pitfalls of the electrochemical TMB detection. By cyclic voltammetry it was found that the TMB electrochemistry is strongly dependent on the pH and the electrode material. A stable electrode response to TMB could be achieved at pH 1 on gold electrodes. We created a smartphonebased, electrochemical, immunomagnetic assay for the detection of ochratoxin A in real samples, providing a solid basis forsensing of further analytes.
Raman band widths of anhydrite II reveal the burning history of high-fired medieval gypsum mortars
(2019)
The use of high-fired gypsum as binder for masonry and joint mortars or stuccowork in Central Europe in the Early and High Middle Ages was a regional specific as it depended on local gypsum deposits. The calcination technology possible at the time resulted in an assemblage of calcium sulphate phases dehydrated to different degrees and partly thermally damaged accessory minerals of the raw gypsum. Because of the absence of medieval textbooks, the observation of high-temperature, low-pressure mineral transformations and the correlation of phases coexisting in not hydrated binder relicts in the gypsum matrix to the mineralogy of the raw material and the burning conditions constitute the only source to the historical technological know-how.
The CaSO4–H2O system consists of five crystalline phases, which can be discriminated by structural analysis methods, such as Raman spectroscopy, due to obvious differences in their spectroscopic data: gypsum (CaSO4 ⋅ 2 H2O), bassanite (hemihydrate, CaSO4 ⋅ ½ H2O), anhydrite III (CaSO4), anhydrite II (CaSO4), and anhydrite I (CaSO4). Only recently, it was possible to demonstrate that small spectroscopic variations exist also within the relatively large stability range of anhydrite II from approx. 180°C to 1180°C: all Raman bands narrow with increasing burning temperature applied in the synthesis from gypsum powder. The determination of band widths of down to 3 cm-1 and differences between them of a few tenths of a wavenumber is not a trivial task. Thus, this contribution discusses peak fitting and strategies for correction of instrument-dependent band broadening.
Raman maps of polished thin sections of gypsum mortars provide access to the burning histories of individual remnant thermal anhydrite grains and enable the discrimination of natural anhydrite originating from the gypsum deposit. This novel analytical method was applied to samples from medieval South Tyrolean stucco decorations and sculptures. Beyond that, Raman microspectroscopy was employed for following pyrometamorphic reactions in natural impurities of the raw material. In the presented examples mineral thermometry indicates process temperatures above 800°C: the breakdown of magnesium-rich chlorite led to the formation of forsterite Mg2SiO4, while the thermal decomposition of dolomite CaMg(CO3)2 yielded – after hydration and carbonation – magnesite MgCO3, CaCO3 polymorphs and magnesian calcite. Lower burning temperatures, which leave the accessory minerals in their pristine form, can be traced by measuring the spectra of anhydrite crystalites in grains of firing products and evaluating Raman band widths. Throughout the applications of this analytical method so far, calcination temperatures ranging from approx. 600°C to 900°C were determined.
Research in the SALSA Application Lab – Shedding light onto high-fired medieval gypsum mortars
(2019)
After an introduction into the SALSA lab building and the ideas and sources of inspiration for building up the Application Lab as a spectroscopy lab with a strong focus on imaging and microspectroscopy, a very successful example of an interdisciplinary collaboration between the fields of art technology and analytical sciences is presented.
Raman band widths of anhydrite II reveal the burning history of high‐fired medieval gypsum mortars
(2019)
An interdisciplinary collaboration between art technology and analytical sciences yielded an approach based on Raman microspectroscopy for the determination of the burning temperatures applied during the production process of high-fired medieval gypsum mortars. Analytical challenges and applications of the approach to examples from the cultural heritage of South Tyrol are presented.
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).
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.
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.
Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate
(2022)
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.