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In many advanced materials production processes, the analysis must be non-invasive, rapid, and, if possible, operando. The Raman signal of the various forms of alumina, especially transition alumina, is very weak due to the highly ionic nature of the Al-O bond, which requires long exposure times that are incompatible with monitoring transitions. Here, we explore the use of the fluorescence signal of chromium, a natural impurity in alumina, and the Rayleigh wing to follow the crystallization process up to alpha alumina. To clarify the assignment of the fluorescence components, we compare the transformation of beta alumina single crystals into transition (gamma and theta) alumina and then into alpha alumina with the transformation of optically transparent alumina xerogel and glass, obtained by very slow hydrolysis-polycondensation of aluminum sec-butoxide, into alpha alumina. Vibrational modes are better resolved in thermally treated single crystals than in thermally treated xerogels. Measurements of the Rayleigh wing, the Boson peak, and the fluorescence signal are easier than those of vibrational modes for studying the evolution from amorphous to alpha alumina phases. The fluorescence spectra allow almost instantaneous (<1 s) quantitative control of the phases present.

The birth of Chemistry can be found in two main practices: (i) the Arts du feu (ceramic and glass, metallurgy, i.e., inorganic and solid state chemistry) and (ii) the preparation of remedies, alcohols and perfumes, dyes, i.e., organic and liquid state chemistry). After a brief survey of the history of (glazed) pottery and (enameled) glass artifacts, the development of destructive and non-destructive analytical techniques during the last few centuries is reviewed. Emphasis is put on mobile non-destructive Raman microspectroscopy of pigments and their glass/glaze host matrices for chronological/technological expertise. The techniques of white opacification, blue, yellow, green, red, and black coloring, are used as examples to point out the interest of pigments as chronological/technological markers.

Comprehensive studies of Famille rose porcelains, particularly ruby-back pieces, are rare and have generally not addressed the vibrational signatures arising from gold nanoparticles. Due to the high cultural and material value of these artifacts, a strictly non-invasive approach combining X-ray fluorescence (XRF) and Raman (micro-)spectrometry must be employed. If the conservation of porcelain does not pose any difficulties, fakes exist and they must be identified. Preliminary studies show that the presence of metal nanoparticles generates plasmon-related fluorescence. Our results confirm that plasmon fluorescence is more effective than pXRF for detecting colloidal gold, whereas pXRF efficiently identifies associated elements such as arsenic, tin, and, newly observed, antimony; the presence of iron is difficult to demonstrate due to its ubiquitous occurrence. Yellow and green hues, distinct from those produced by Cu2+ ions alone, are mainly due to simple tin yellow (PbSnO3), while the cobalt used originates from a mixture of European smalt (rich in arsenic and potassium) and Asian ores (rich in manganese). Minimal variability was observed among egg-shell porcelains with similar decorations and dimensions, suggesting a common workshop or standardized raw materials and procedures. Two other egg-shell plates employ a different gold preparation technique (addition of Sn and Sb rather than As), which is visually evident in the ruby color.

This study investigates the comparison of the Raman signatures of different phases used in underglaze, inglaze and overglaze decors of selected European, Chinese and Japanese porcelains and enameled metalworks, which are particularly representative of technological developments in enameling. Specifically, the article deals with the main structural types or host networks (corundum/hematite, spinels, zircon, cassiterite, pyrochlore, apatite, sphene, etc.) used for colored enamels on porcelain, earthenware or metal rather than considering all types of pigments and opacifiers. According to the results, Raman microspectroscopy allows identifying of the fingerprint spectra of milestone technologies and represents a simple and rapid tool for detecting copies. Particular attention is paid to the information deduced from the examination of the associated ‘background’ and signatures from electronic transitions induced by uncontrolled traces or voluntary addition of rare earths (luminescence). The relationship between the grinding procedure and Raman signature is also discussed.

Recent archaeological sites dating to the late 19th and early 20th centuries have rarely been studied to date. Among the 500 “glassy” beads excavated from Dohouan (Côte d’Ivoire), elemental analyses reveal that fewer than half contain abnormally high alumina contents, associated with a soda–potash–lime flux (three compositional groups). The remaining beads are typical lead-based glass. The Raman spectra of the alumina-rich beads are quite complex due to their glass–ceramic nature, combining features similar to the vitreous phase of porcelain glaze with the presence of various crystalline phases (quartz, wollastonite, calcium phosphate, calcite). Organic residues are also observed. Colors are primarily produced by transition metal ions, although some specific pigments have also been identified. These characteristics suggest that the alumina-rich beads were manufactured by pressing followed by sintering, as described in patents by Richard Prosser (1840, UK) and Jean Félix Bapterosse (1844, France). A comparison is made with beads from scrap piles at the site of the former Bapterosse factory in Briare, France. This process represents one of the earliest examples of replacing traditional glassmaking with a ceramic process to enhance productivity and reduce costs.

Six rare porcelains of the Qing Dynasty, in particular, dishes ordered respectively for Philibert Orry, the Duke of Penthièvre and a tureen from the service of Louis XV, with royal coat-of-arms, were analyzed non-invasively by Raman microspectrometry. A coffee pot with a rare decoration attributed to Cornelius Pronk was also analyzed as well as two plates, one decorated with an Imari-style pattern and the second post-decorated in the Low-Countries/Holland. The enamel types and coloring or opacifying agents were identified on the basis of combined Raman and SEM-EDXS analysis previously published as well as new section and surface analysis of five plate samples representative of different technologies (blue-and-white, Famille rose). The use of lead oxide for the preparation of overglaze is demonstrated. For the first time, the use of borax in the blue overglaze according to the recipe from the 1753 manuscripts of French chemist Jean Hellot is demonstrated on Chinese porcelain. This fact, like the use of cobalt free of manganese, demonstrates the use of European ingredients and/or recipes for ceramics exported from China to Europe. The highlighting of the use of different recipes or raw materials for porcelain from the same period can therefore be the signature of different workshops. For instance, three different Raman signatures of red decoration were identified from the hematite vibration modes: very narrow modes for Pronk’ coffee pot and Louis XV tureen, broad for Orry’ dish and intermediate for the others. Three workshops are thus expected. It is interesting to note that the use of arsenic for the realization of white enamels corresponds to the latest objects, made after 1738. China was therefore in the 18th century both an importer of European know-how, design and an exporter of enameled products made with imported technologies to Europe.

The production of Japanese enamels for porcelain decoration was thought to have originated from the direct and exclusive influence of Chinese potters who moved to Japan during the chaotic Ming to Qing dynastic change in 1644. Recent systematic studies have identified, for the first time, the crucial influence of Jesuit missionaries on pigment and enamel production in Japan from the late 16th-century. In particular, such first encounter laid the foundation for the continued influence exerted by European technology on Japanese art throughout the centuries. The present study has further identified European enamels used for the decoration of polychrome wares fired in Arita, the porcelain production center of Japan. This continued exchange not only marked the Edo period, but also extended into the twentieth century. For the first time, the lack of written records regarding the use of western pigments for enamel production caused by the persecutions of European and Japanese Christians has been overcome in the work herein presented. The nature of the imported materials has been firmly identified and characterized. The analytical results (EDXRF and Raman) have finally revealed how western technology and materials not only kept influencing Japanese art during the isolation (sakoku) period, but also accompanied the strong westernization process that marked Japanese history from the late nineteenth century. Moreover, the significant reverse influence of Japanese-made enamels on Chinese polychrome porcelain production in the late Qing and twentieth century has been fully identified for the first time. Furthermore, results show that the shift of the Pb mode of lead antimonate (Naples Yellow) is affected by the firing temperature for enamel decoration, and that this characteristic, along with the chemical composition, enables the identification of the origin and manufacture period of the yellow enamel.

Nine glazed porcelain artifacts bearing the coat of arms of France, from King Louis XV tableware orders, were analysed at the laboratory or in their conservation secure room. Based on the experience acquired in the study of 18th century European and Chinese porcelain using mobile XRF (pXRF) and Raman microspectroscopy, a comparison of the impurities in the paste (Y, Rb, and Sr), the elements associated with cobalt in the blue overglaze (Bi, Mn, Zn, and As) and those present in the tin yellow and Naples yellow pigments (Sn, Sb, and Zn) highlights the use of different raw materials for some of these objects. Differences regarding the Ag content in the gold decorations also provide information. Raman identification of the different types of yellow pigment confirms the categorization. The results obtained on the Louis XV tableware are compared to those of “Chine de commande”, attributed to the same places and periods of production or recognized copies. The clustering of the quantitative comparison pXRF signals of the abovementioned elements and a consideration of the Raman parameters of the yellow pigments appear to be effective tools for object categorization to confirm or refute questions about the authenticity of objects.

The authentication and dating of rare ceramics is generally carried out using subjective criteria, mainly based on visual interpretation. However, the scientific study and evaluation of the materials used could contribute objectively. The analytical data relating to the major and minor elements of the coloring agents of the decoration or the base marks, and the characteristics of the raw materials (related to geology and ore processing), can be obtained on the conservation site non-invasively using a pXRF instrument and the phases formed may be identified using Raman microspectroscopy. This approach is applied to 28 objects assigned to the production of the Meissen Factory, from the collection of the Musée National de Céramique, Cité de la Céramique, Sèvres. They have polychromic or blue-and-white decorations and are supposed to have been produced in the 18th and 19th centuries. Some have a production date that has been perfectly established, others may have been produced using an earlier mold, or even have been decorated on an unknown date different from that of the firing of the biscuit. The combination of several classification criteria concerning the type of glaze, previously identified in the study of French and Chinese 17th and 18th centuries productions, i.e., the elements associated with cobalt present in the mark or the blue decoration and the relative levels of impurities of the glaze matrix, both characteristic of the raw materials and giving a strong XRF signal, leads to the identification of groups of homogeneous objects (respectively, counting seven, three, two and two objects for which at least four out of five criteria are identical); the other objects present too many differences to be considered as having been produced with the same raw materials. The first group brings together almost all the objects with a reliable pedigree made before ~1750, but includes two objects with decoration types closer to those of the 1800s. The comparison of the pXRF signals confirms the possibility of identifying the use of European ingredients for the production of painted enamels in the Qing dynasty.

The invention of European hard porcelain, which aims at imitating kaolin-containing white paste of Chinese porcelain, had been started by the development of the technology of “red porcelain”, so-called “Jaspisporzellan” by Johann Friedrich Böttger in the early-eighteenth century at Meissen (Saxony). The visual features of the earlier Böttger red stoneware were rather similar to the one produced in Yixing, China. The prominence of Böttger productions allowed the manufacturing to be expanded across Europe to different countries (Holland, England, France, etc.). In this study, the chemical characteristics of nine European unglazed objects produced in England, France, Russia, and Holland from the 17th to 19th century and 10 Chinese (unglazed or enameled) red stoneware have been studied by using an on-site characterization technique pXRF. The results were compared with the previous studies carried out on 25 unglazed, polished, and non-polished Böttger artefacts. This non-invasive, speedy technique allows a methodology to be created for distinguishing the technological differences related to the provenance and authenticity of the artefacts. The elemental measurements explicitly show the significant discrepancy of Dutch objects from the main group, which involves other European and Chinese ones. Both a Lambertus van Eenhoorn (Delft) statue and an Ary de Milde (Delft) teapot are distinguishable from other European red stoneware by the high content of iron and calcium and high content of titanium and potassium, respectively, found in their body compositions. An overall comparison was made between the measurements made at different times in order to evaluate the error range arising from the measurement procedure (e.g., energy resolution of other series of the same instrument model).