Search Results (10)

A series (n = 22) of glasses from the site Kapucinski vrt (garden of the Capuchin monastery, 5th–17th c. CE) in Koper (Capodistria), a port town in the northern Adriatic, was measured using a combined PIXE and PIGE method. Koper has been continuously populated since the late Roman period, with a rich medieval history, thus offering an opportunity to study Early Medieval glass. Stemmed goblet fragments, in the original publication dated between the 6th–9th centuries CE, and several other vessel types (beakers and flasks or bottles and lamps) were selected for analysis. The measurements were expected to show the trends in glass production and consumption from Late Antiquity until the Middle Ages, notably the transition between natron to plant ash glass and the supply of fresh glass. Among the set of 22 glass vessel fragments, both natron and plant ash glass were identified. For finer classification, we relied on a newly developed method of Euclidean distances with respect to major concentrations. Natron glass of the types Foy 2.1 (9 examples), Magby (2 examples), and Levantine I (Apollonia; 2 examples) was found. Two glasses remain undetermined but testify to an Egyptian origin. Most natron glasses show signs of recycling. Among the three unrecycled glasses (about 20% of the whole set), there are two examples of Levantine glass and a Magby glass lamp; this may indicate a modest supply of fresh glass during the period. Plant ash glass may be attributed to the Early or High Middle Ages, exploiting the purified alkalis of the Levantine coasts (known as alume catino in later Venetian glassmaking), and the admixture of impurities in the siliceous sands suggests the circulation and consumption of glass that was produced and traded in the eastern Mediterranean since the 10th century CE. Full article

The initial nucleus of gemstones at the Natural History Museum of the University of Florence (Italy) is linked to the significant collection of the Medici family, who began it as early as the 15th century. The present research aims to study this collection in order to (1) comprehensively review the archival and catalogue information available; (2) identify the mineralogical species correctly; and (3) gather information on the potential provenance of the gem deposits. To address these objectives, fifty gems were investigated using entirely non-invasive methods, ensuring the preservation of the collection’s precious and historical value. All specimens underwent autoptic observation and micro-Raman analysis, while a selection was further examined using PIXE-PIGE to characterise their chemical composition, including trace elements. The gems were attributed to seven mineral species: emerald, topaz, grossular, cordierite, quartz, orthoclase, and tourmaline. One gem was identified as a fake, made of glass and likely produced in the 17th century. Twenty-nine of the historical attributions in the catalogue were found to be incorrect and were subsequently revised. In some cases, the trace elements and mineral inclusions identified in the gems enabled the determination of potential provenance deposits, which were then compared with the available archival information. Full article

The first experimental results obtained by the ion beam-induced luminescence technique from the ceramic bodies of ancient tiles are reported in this work. The photon emission from the ceramic bodies is related to the starting minerals and the manufacturing conditions, particularly the firing temperature and cooling processes. Moreover, the results indicate that this non-destructive technique, performed under a helium-rich atmosphere instead of an in-vacuum setup and with acquisition times of only a few seconds, presents a promising alternative to traditional, often destructive, compositional characterisation methods. Additionally, by adding other ion beam-based techniques such as PIXE (Particle-Induced X-ray Emission) and PIGE (Particle-Induced Gamma-ray Emission), compositional information from light elements such as Na can also be inferred, helping to also identify the raw materials used. Full article

This study aimed to use an in-air micro-particle-induced X-ray/gamma emission (in-air µPIXE/PIGE) system to evaluate tooth-bound fluoride (T-F) in dentin following the application of fluoride-containing tooth-coating materials. Three fluoride-containing coating materials (PRG Barrier Coat, Clinpro XT varnish, and Fuji IX EXTRA) and a control were applied to the root dentin surface of human molars (n = 6, total 48 samples). Samples were stored in a remineralizing solution (pH 7.0) for 7 or 28 days and then sectioned into two adjacent slices. One slice of each sample was immersed in 1M potassium hydroxide (KOH) solution for 24 h and rinsed with water for 5 min for the T-F analysis. The other slice did not undergo KOH treatment and was used to analyze the total fluoride content (W-F). The fluoride and calcium distributions were measured in all the slices using an in-air µPIXE/PIGE. Additionally, the amount of fluoride released from each material was measured. Clinpro XT varnish demonstrated the highest fluoride release among all the materials and tended to show high W-F and T-F and lower T-F/W-F ratios. Our study demonstrates that a high fluoride-releasing material shows high fluoride distribution into the tooth structure and low conversion from fluoride uptake by tooth-bound fluoride. Full article

Ion beam analysis (IBA) methods refer to a set of analytical techniques based on the interactions of energetic ions, produced by a particle accelerator, with matter. The result of such interactions is the emission of characteristic radiation, X and gamma rays, and charged particles, which, upon detection, provide valuable information on the absolute concentration and depth distribution of the elements in the bombarded material. Moreover, IBA techniques can be performed while maintaining the object to be investigated at atmospheric pressure, without placing it in vacuum, in an analysis chamber, with the impinging ion beam extracted from the in-vacuum beamline of the accelerator, avoiding the need of invasive sampling and greatly easing the object positioning, thus allowing precious and big or large artefacts to be studied. This feature has opened the way for applications of IBA techniques for compositional analysis in cultural heritage studies, providing detailed and complete information about elemental compositions and depth distributions of analysed materials that are otherwise difficult or impossible for other analytical techniques. In this paper, the basic principles of the main IBA techniques applied to cultural heritage, namely, particle induced X-ray emission (PIXE), particle induced Gamma-ray emission (PIGE), and Rutherford or elastic backscattering spectrometry (RBS/EBS), will be recalled, and specific and practical details on how these techniques can be used for analysing cultural heritage objects with external beam set-ups will be provided. Full article

Several desensitizers routinely used clinically for dentin hypersensitivity are expected to inhibit demineralization. This study aimed to evaluate the effectiveness of sealing materials in inhibiting demineralization and increasing fluorine (F) uptake by acid-treated root surfaces. Five noncarious extracted human teeth were used to produce specimens. Three different fluoride-containing materials, namely “MS Coat F” (MS), “MS Coat Hys Block Gel” (HS), and CTX2 Varnish (FV), were used herein. Each material was applied to the demineralized root surface. Single sections were obtained from each specimen. All surfaces of each specimen, except the polished surface, were covered with wax and immersed in an automatic pH cycling system for 2 weeks. Fluorine and calcium distributions in the carious lesions of each specimen were evaluated using proton-induced gamma emission (PIGE) and X-ray (PIXE) techniques, respectively. Dentin demineralization was analyzed using transverse microradiography (TMR) before and after pH cycling. µPIXE/PIGE analysis demonstrated that all sample groups showed increased fluoride uptake on the root surface. TMR analysis revealed that both HS and FV showed significantly lower integrated mineral loss values than the control group. All three samples demonstrated a tendency towards increased fluoride uptake from fluoride-containing hypersensitivity desensitizers and a demineralization inhibition effect on root dentin. Full article

In this paper, we focus on the industrial production of porcelain in the Bordeaux area (France) in the 19th century. Our main objective is to assess the evolution of production technology of the same manufactory over a period of more than 40 years. A multi-analytical approach was used to investigate glazes and bodies of thirty-four sherds of biscuit and porcelain found in an archaeological context. The microstructural, chemical, and mineralogical characterization was performed using a combination of scanning electron microscopy, coupled with energy dispersive spectroscopy (SEM-EDS), particles induced X-ray and gamma emission (PIXE-PIGE), and X-ray diffraction (XRD). Results obtained on the characterization of the ceramic production technologies and on the chemical modification over time contributes to investigate this industrial production, which is not well documented by the written archives. The examination of the biscuits, rare artifacts, showed that the porcelain bodies were produced by mixing kaolinitic clays, quartz, and potassium feldspars. The mineralogical analysis of the ceramic supports allowed hypotheses to be put forward on the temperatures of the biscuit firing (around 950 °C) and the second firing (over 1200 °C). Furthermore, the treatment of the compositional data, including both glazes and bodies, using multivariate statistical analysis, revealed different types of production corresponding to the different chronological periods of production at Bordeaux throughout the 19th century. These results will enable us to consider the possibility of authenticating non-stamped and undecorated pieces. Full article

The analysis of material composition by ion-beam analysis (IBA) is becoming a standard method, similar to electron microscopy. A pool of IBA methods exists, from which the combination of particle-induced-X-ray emission (PIXE), particle induced gamma-ray analysis (PIGE), nuclear-reaction-analysis (NRA), and Rutherford-backscattering-spectrometry (RBS) provides the most complete analysis over the whole periodic table in a single measurement. Yet, for a highly resolved and accurate IBA analysis, a sophisticated technical setup is required integrating the detectors, beam optics, and sample arrangement. A new end-station developed and installed in Forschungszentrum Jülich provides these capabilities in combination with high sample throughput and result accuracy. Mechanical tolerances limit the device accuracy to 3% for RBS. Continuous pumping enables 5 × 10⁻⁸ mbar base pressure with vibration amplitudes < 0.1 µm. The beam optics achieves a demagnification of 24–34, suitable for µ-beam analysis. An in-vacuum manipulator enables scanning 50 × 50 mm² sample areas with 10 nm accuracy. The setup features the above-mentioned IBA detectors, enabling a broad range of analysis applications such as the operando analysis of batteries or the post-mortem analysis of plasma-exposed samples with up to 3000 discrete points per day. Custom apertures and energy resolutions down to 11 keV enable separation of Fe and Cr in RBS. This work presents the technical solutions together with the quantification of these challenges and their success in the form of a technical reference. Full article

This study provides an overview of the few archaeometric analyses of European white earthenwares from England, France, Italy, Slovenia, and Switzerland. White earthenwares were an extremely successful mass-product between ca. 1750 and 1900. They became “the porcelain of the poor man” and replaced the older traditional pottery such as faïence. The invention of this new ceramic type took place simultaneously in England and France shortly before 1750. Contemporary recipes can be compared to the analytical results of these products. The ceramic bodies are, according to the chemical (X-ray fluorescence (XRF), scanning electron microscope-energy-dispersive X-ray spectroscopy (SEM-EDS), particle-induced X-ray emission-proton-induced X-ray emission (PIXE-PIGE) and microscopic analyses (scanning electron microscope-back scatter detector (SEM-BSE), artificial mixtures of clay + quartz + flux. Various techniques can be recognized. In England, a blend of a CaO-poor clay (with illite flux) + calcined flint is typical of the so-called creamware, whereas supplementary fluxes (Cornish stone) resulted in the Queen’s ware. In France and Central Europe, CaO-poor clays were mixed with grog (Paris) or with calcined flint/quartz pebbles/sand or with carbonates + Alk-/Pb-frits (Lorraine). Swiss CaO-rich bodies may contain bone ash or dolomite as flux. The products of the individual factories can be differentiated on the basis of their chemical composition. Micromorphological and chemical analyses revealed intensive physico-chemical reactions between the glaze and the body. Full article

The distribution and chemical composition of inorganic components of a corrosion-inhibiting primer based on polyurethane is determined using a range of characterisation techniques. The primer consists of a Li₂CO₃ inhibitor phase, along with other inorganic phases including TiO₂, BaSO₄ and Mg-(hydr)oxide. The characterisation techniques included particle induced X-ray and γ-ray emission spectroscopies (PIXE and PIGE, respectively) on a nuclear microprobe, as well as SEM/EDS hyperspectral mapping. Of the techniques used, only PIGE was able to directly map the Li distribution, although the distribution of Li₂CO₃ particles could be inferred from SEM through using backscatter contrast and EDS. Characterisation was also performed on a primer coating that had undergone leaching in a neutral salt spray test for 500 h. Overall, it was found that Li₂CO₃ leaching resulted in a uniform depletion zone near the surface, but also much deeper local depletion, which is thought to be due to the dissolution of clusters of Li₂CO₃ particles that were connected to the external surface/electrolyte interface. Full article