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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.

Japanese art tradition, contrary to the case of China, is characterized by an efficient and continued, although mostly undocumented, use of smalt from the late 16th century onward. Recent studies have successfully identified this pigment, the cobalt-colored glass that spread throughout the Old Continent during the Renaissance period, as the coloring agent employed for overglaze-blue enameling on Japanese porcelains produced at the kilns of Arita (the porcelain production center of Japan) from the early 1640s until the 20th century. Fragmentary evidence of the use of smalt in Japanese sacred art has also been reported, yet its earliest incorporation into such a type of traditional art form could not be identified. In order to resolve this crucial issue, portable EDXRF was employed for the non-destructive analyses of Japanese porcelains and sacred images bearing blue decoration. Scientific analysis allowed, for the first time ever, to establish a clear timeline of smalt use. Furthermore, this evidence and the literature data both agree, leading to the identification of the origin of the blue material used on both art productions.

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.

Chinese porcelain with an optically clear colored glaze, imported to Europe from the Kangxi period (1662–1722, Qing Dynasty) onwards was highly collected by the French Elite of the 18th century. The bright colors with a clear, shiny glaze were unlike anything produced in Europe at that time. The colors of enamelled artifacts (on biscuits or already glazed porcelain) can be fully monochrome or consist of associations of large monochromatic areas with or without application of gilding. Non-invasive portable XRF and mobile Raman analyses have previously shown their effectiveness in the characterization of (colored) glassy silicates. In this study, we compare the Raman signatures of twenty-one Chinese artifacts fully—or with major monochrome area (sancai)—decorated with blue, turquoise (or celectian blue), honey-yellow, green, eggplant, and red color. Different types of glazes are identified and confirmed by pXRF: lead-rich, lead-poor-alkali, lead-doped alkali, and alkali-based compositions. However, an unexpected low level of lead is observed in the turquoise glazes, likely to optimize the gloss. Raman spectroscopy appears more reliable to compare the Pb content than pXRF. This work presents Raman spectral signatures of glazes that can potentially be used for non-invasive object classification and counterfeit detection.

On-site pXRF analysis in various French collections (Musée du Louvre, Musée national des Arts asiatiques-Guimet, Paris) of porcelains decorated with painted enamels from the Qing Dynasty, in particular porcelains bearing an imperial mark, identifies the types of enamels/glazes, the ions and coloring phases or the opacifier. The study of the elements associated with cobalt (nickel, manganese, arsenic, etc.) and of the impurities of the silicate matrix (yttrium, rubidium and strontium) differentiates the use of ‘Chinese/Asian’ raw materials from ones imported from Europe by the initiative of the European missionaries (chiefly Jesuits) present at the Court (Beijing). Particular attention is paid to the analysis of the blue color of the marks and to the elements associated with the use of gold or copper nanoparticles as well as to the compositions of the pyrochlore phases (tin yellow, Naples yellow). The comparison is extended to pXRF and Raman microspectroscopy measurements previously made on other Qing imperial porcelains as well as on Cantonese productions (on porcelain or metal) from different Swiss and French museums and blue-and-white wares of the Ming and Yuan Dynasties (archaeological and private collections).

The study of rare objects requires the use of mobile non-invasive methods such as a portable X-ray fluorescence instrument (pXRF), but this involves an analysis from the outer surface, while the depth analyzed depends on the element measured and, in addition, the material can be very heterogeneous at different scales. The concept of elemental composition, therefore, has no “absolute” meaning for painted enamel decorations. This work evaluates this concept by comparing the pXRF measurements made with different configuration procedures, allowing to evaluate the consequences on the variability of the XRF signals, and discusses the contents of certain chemical elements. For this, two shards from the Qianlong period are analyzed, a shard of blue and white (underglazed) porcelain and a fragment of an ‘imperial’ bowl with painted enamel decoration (huafalang). The variability of measurements is compared for visually appearing homogeneous or heterogeneous areas.

In a noninvasive determination, Raman and XRF analyses showed the possibility of identifying specific phases and elements characteristic of the use of recipes and ingredients imported from Europe, according to the information documented in Chinese and European archives. Two sets of objects, supposed to have been produced during the Qing Dynasty (1662–1912) at the Forbidden City (‘imperial bowls’ of the Baur Foundation, Geneva) and in the customs district of Guangzhou (Musée Ariana, Geneva), were analyzed with pXRF and also for some objects with Raman microspectroscopy also on-site. The heterogeneity of the colored zones, in three spatial directions, requires the development of a new methodology. We focused particular attention on the cobalt used in the colored areas and marks, drawn either on the body layer (standard underglaze) or on the glaze itself (overglaze). Comparison is made with previous data on Chinese and Vietnamese porcelains from the Yuan (1271–1368) and Ming Dynasty (1368–1644) periods. Combined data for objects attributed to Guangzhou from the Kangxi and Yongzheng periods indicates the use of the same raw materials containing cobalt, associated with arsenic, nickel, zinc, copper and bismuth, according to the European sources. Similarity of the glaze composition and impurities promotes the production of the glazed body with the same raw materials as those used at Jingdezhen. A consistent shift in data for Qianlong style items, which are significantly richer in manganese, is compatible with their partial mixing with Asian cobalt. The deliberate selection of conflicting objects—namely, examples belonging to the other places of production or different periods—are well-observed outside the ‘Guangzhou’ cluster. Some artifacts have anachronistic purity characteristics that support a production after ca. 1850. For instance, two objects on which certain attributions had been made concerning the stylistic analysis are definitive examples of ceramics using a refined ‘cobalt’, and therefore now may be assigned to the later production period of the first half of the 19th century.

Representative ‘Blue speckled’ (13–16th centuries) and ‘Brown speckled’ (13–21st century) wares recovered from the excavations in Qalhât or collected around Bahlâ city (Sultanate of Oman) were characterized by XRPD, SEM-EDS, Raman/optical microspectroscopy, and thermal expansion. Minerals present in the body (quartz, augite and albite as major phases, calcite, dolomite, rutile, anatase, phosphate, hematite and magnetite as minor phases) were identified by XRPD and/or Raman spectroscopy. SEM-EDXS microanalysis was performed on the glazes in order to compare their composition, especially the type of flux. The firing temperatures measured from the thermal expansion curves range between 1080 °C and 1150 °C. This preliminary study confirms that the first differentiation can be made by considering non-invasive Raman technique and thermal expansion measurement is sufficient to get an extensive comparison of the wares. A local place of production is likely for the body of all samples but importation of the glazes of ‘Blue speckled’ wares is questioned. Modern Bahlâ productions cannot be considered to have inherited the Qalhât ones. Ba-rich, cassiterite-opacified glaze corresponding to the Late Islamic Arabic Period appears as a new technology without a connection to the ancient one. Resumen: Las mercancías representativas ‘moteadas de azul’ (siglos XIII-XVI) y ‘moteadas de marrón’ (siglos XIII-XXI) recuperadas de las excavaciones en Qalhât o recolectadas alrededor de la ciudad de Bahlâ (Sultanato de Omán) se caracterizaron por microscopía XRPD, SEM-EDS, Raman, microscopía y expansión térmica. Los minerales presentes en el cuerpo (cuarzo, augita y albita como fases principales, calcita, dolomita, rutilo, anatasa, fosfato, hematita y magnetita como fases menores) se identificaron mediante espectroscopía XRPD y/o Raman. Se realizó un microanálisis SEM-EDXS en los esmaltes para comparar su composición, especialmente el tipo de flujo. Las temperaturas de cocción medidas a partir de las curvas de expansión térmica oscilan entre 1080° C y 1150° C. Este estudio preliminar confirma que la primera diferenciación se puede hacer considerando la técnica Raman no invasiva y la medición de la expansión térmica es suficiente para obtener una comparación extensa de las mercancías. Es probable que haya un lugar de producción local para el cuerpo de todas las muestras, pero se cuestiona la importación de los esmaltes de las mercancías “moteadas de azul”. No se puede considerar que las producciones modernas de Bahlâ hayan heredado las de Qalhât. El esmalte opacificado con casiterita, rico en Ba correspondiente al último período árabe islámico, aparece como una nueva tecnología sin conexión con la antigua.

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 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).

Raw materials significantly determine the final composition and properties of a fired ceramic. Raman analysis which characterizes micro- and nanostructures of (coloured) glazes, opacified or not, was applied to shards mostly collected before the 1960s, currently at the Louvre Museum, originated in Anatolia, the Caucasus, Iran and Central Asia, which are, for most of them, characterized by the use of black lines to separate coloured areas, and dated to the period between the 12th and 19th centuries. Measurements were carried out in the laboratory with a blue laser excitation and/or on the conservation site with a mobile device (green laser). Three types of glazes were identified by their nanostructure of the silicate network: (i) a lead-rich glaze analogous to that of Byzantine, Zirid to Hafsid and al-Andalus productions, (ii) a lead-alkali glaze typical of the Ottoman productions of Iznik-Kütahya, and (iii) a mixed (poor lead/lead-free)-alkali glaze typical of Safavid productions. The colour determines the precise composition of the glaze. The identification is not only based on the signature of the stretching mode of the SiO4 tetrahedron (position of the wavenumber of the component(s)) but also on the position and shape of the continuous luminescence of the Raman background, characteristic of the raw materials used. Lead-tin yellow, Fe-rich, Mn-rich and Cr-rich black pigments and opacifiers made of cassiterite and wollastonite were also identified. The results (type of glaze and deduced processing temperature) were discussed in the light of the ternary phase diagrams visualizing elemental composition determined in previous works and the microstructure examination on the polished section (defining single or multistep firing cycles). Continuity was highlighted on the one hand between the tiles of Bursa, Edirne and Istanbul (Ottoman Iznik-like production) and on the other hand between those of Samarkand area (Timurid) and Iran. The procedure was then applied in the study of three objects (two dishes and a bowl) which are very representative of the productions of the Turkish-Persian cultural areas: a polychrome mina’i cup with decoration representing a rider, an Ottoman Iznik fritware with polychrome floral decoration, and a blue-and-white Safavid ceramic with a decoration representing a shrub.

In the late 19th century, ancient tombs were discovered near the village of Vohemar at the northeastern point of Madagascar, and subsequent excavations during the French period (1896–1945) revealed the presence of a major necropolis active from ~13th to 18th centuries. Some artefacts (Chinese ceramic shards and glass trade beads) recovered from these excavations was sent to France and now in part belong to the collection of the Musée d’Histoire Naturelle, Nimes. Carnelian and glass trade beads were analyzed with a mobile Raman spectrometer, which identified different materials (soda-lime glass, quartz/moganite, carnelian/citrine, chalcedony) and coloring agents (Naples yellow, cassiterite, amber chromophore, transition metal ions, etc.). The results are compared with those obtained on beads excavated at different sites of Southern Africa and at Mayotte Island, and it appears that (most of) the beads come from southern Asia and Europe. The results confirmed the role that northern Madagascar played within the maritime networks of the Western Indian Ocean during the 15th–16th century.

Porcelain stone used at the early kilns of Arita, Japan, has never been identified due to the lack of written records. Ryumon and Shirakawa deposits are considered to have possibly been exploited before Izumiyama was discovered in the early 1630s, but there are no records or any previous scientific research aimed at resolving such crucial issue. This work presents the first systematic scientific study of clays from the three deposits and shards excavated at early kiln sites. Portable ED-XRF and SEM-EDS were used to identify the chemical compositions of bodies, glazes, and geochemical characteristics of clays. XRD, TG-DSC, and FTIR-ATR spectroscopy were also used for the mineralogical characterization of clay bodies. Results show that the earliest production was marked by the mineralogical characteristics of the available raw materials. A gradual improvement in material selection and processing will lead to the development of the nigoshide (milky-white) body in the mid-17th century.

The aim of this study is to estimate the uncertainty of a portable X-ray fluorescence (p-XRF) instrument for the (semi-quantitative) analyses of tiles with underglaze decoration. Before starting the campaign of on-site measurements, the optimum acquisition time and the most accurate calibration mode were selected. For this purpose, the elemental composition of two glass standards of NIST (SRM610 and SRM612) and a Corning A standard were measured with varied times (5–360 s) and in different calibration modes (Mining, Mining Light Elements, Soil, and Rare Earth Elements). Afterwards, a set of blue-and-white tiles that was unearthed at Iznik Tile Kilns Excavation between the dig seasons of 2015 and 2019 was examined with p-XRF by selecting ten points of measure from each layer (body, transparent glaze, and blue coloured areas). The elemental composition of different layers was evaluated by means of the intragroup and intergroup data. They were also compared to the previous studies and found that the corrosion-free, homogeneous, and non-porous surfaces decrease the relative standard deviation (RSD) by increasing the consistency of the compositional data. The major elements found in the matrix of each layer (Al and Si for the body, Pb and Sn for the glaze) have the lowest value of RSD, as expected. However, the comparison of the data with the analysis of the reference materials showed that the content of Mg and also Si, which belong to the low-Z elements group, is shifted relatively towards the higher compositional values. The impossibility of measuring the elemental composition of sodium does not hinder the classification of the samples. Although the transition metals have very low concentrations, p-XRF measurements appear rather consistent and the intrinsic scattering of the data observed for a single artefact is largely smaller than those observed for the tiles of different historical buildings. Thus, it allows the classification to be made related to the different techniques used.

Chemically and thermally stable ceramics are required for many applications. Many characteristics (electrochemical stability, high thermomechanical properties, etc.) directly or indirectly imply the use of refractory materials. Many devices require the association of different materials with variable melting/decomposition temperatures, which requires their co-firing at a common temperature, far from being the most efficient for materials prepared by conventional routes (materials having the stability lowest temperature determines the maximal firing temperature). We review here the different strategies that can be implemented to lower the sintering temperature by means of chemical preparation routes of oxides, (oxy)carbides, and (oxy)nitrides: wet chemical and sol–gel process, metal-organic precursors, control of heterogeneity and composition, transient liquid phase at the grain boundaries, microwave sintering, etc. Examples are chosen from fibers and ceramic matrix composites (CMCs), (opto-)ferroelectric, electrolytes and electrode materials for energy storage and production devices (beta alumina, ferrites, zirconia, ceria, zirconates, phosphates, and Na superionic conductor (NASICON)) which have specific requirements due to multivalent composition and non-stoichiometry.

A selection of 15 Chinese painted enameled porcelains from the 18th century (Qing dynasty) was analyzed on-site by mobile Raman and XRF microspectroscopy. The highly prized artifacts are present in the collections of the Musée du Louvre in Paris and Musée Chinois at Fontainebleau Castle in France. In the painted enamels, pigments such as Naples yellow lead pyrochlore, hematite, manganese oxide and carbon and opacifiers such as lead arsenates were detected. The glassy matrices of the enamels mainly belonged to lead-rich and lead-alkali glass types according to the Raman spectra obtained. The glaze and body phases of the porcelain artifacts were also analyzed. The detection of lead arsenate apatite in some of the blue enamels was significant, indicating the use of arsenic-rich European cobalt ores (smalt) and possibly mixing with Asian cobalt. This characteristic phase has also been identified in French soft-paste porcelains and glass decor and high-quality Limoges enamels from the same period. Based on the shape of the Raman scattering background, the presence of colloidal gold (Au° nanoparticles) was identified in red, orange and pink enamels. Different types of Naples yellow pigments were also detected with Sb-rich, Sn-rich and mixed Sb–Sn–(Zn, Fe?) compositions in the yellow enamels. The results were compared to previous data obtained on Chinese cloisonné and painted enameled metalware and Limoges enamels as well as French enameled watches.

Abstract 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.

Out of a total of 56 paintings in the collection of the Lazar Vozarević Gallery in Sremska Mitrovica, only one Lazar Vozarević painting from 1961, titled “Untitled”, has been subject to atypical degradation that has resulted in damage of completely atypical appearance. Such a problem had never before been noticed in Yugoslavian paintings of the 20th century. Discolored areas were found in various locations on the paint layer of the painting “Untitled” (especially on the lower and central parts of the painting), which disturbed the visual experience of the artistic work. To discover the cause of this discoloration, the composition of the paint layer was investigated, with the assumption that the true cause of degradation was hidden therein. Moreover, this painting belongs to a specific period in Vozarević’s activity, characterized by the use of non-traditional painting materials. To identify pigments from the highly degraded painting “Untitled”, scanning electron microscopy coupled with energy dispersive X-ray spectrometry (SEM/EDS) and micro-Raman spectroscopy were applied. Lithol red, a synthetic organic pigment known to give paintings a red tone, was identified as the main reason for the painting’s degradation. Lithol red is not only highly light-sensitive but is also chemically unstable, toxic, and sensitive to heat.

Glass beads have been produced and traded for millennia all over the world for use as everyday items of adornment, ceremonial costumes or objects of barter. The preservation of glass beads is good and large hoards have been found in archaeological sites across the world. The variety of shape, size and colour as well as the composition and production technologies of glass beads led to the motivation to use them as markers of exchange pathways covering the Indian Ocean, Africa, Asia, Middle East, the Mediterranean world, Europe and America and also as chronological milestones. This review addresses the history of glass production, the methodology of identification (morphology, colour, elemental composition, glass nanostructure, colouring and opacifying agents and secondary phases) by means of laboratory based instruments (LA-ICP-MS, SEM-EDS, XRF, NAA, Raman microspectroscopy) as well as the mobile instruments (pXRF, Raman) used to study glass beads excavated from sub-Saharan African sites. Attention is paid to the problems neglected such as the heterogeneity of glass (recycled and locally reprocessed glass). The review addresses the potential information that could be extracted using advanced portable methods of analysis.

The combined use of non-invasive on-site portable techniques, Raman microscopy, and X-ray fluorescence spectroscopy on seven imperial bowls and two decorated dishes, attributed to the reigns of the Kangxi, Yongzheng, Qianlong, and Daoguang emperors (Qing Dynasty), allows the identification of the coloring agents/opacifiers and composition types of the glazes and painted enamels. Particular attention is paid to the analysis of the elements used in the (blue) marks and those found in the blue, yellow, red, and honey/gilded backgrounds on which, or in reserve, a floral motif is principally drawn. The honey-colored background is made with gold nanoparticles associated with a lead- and arsenic-based flux. One of the red backgrounds is also based on gold nanoparticles, the second containing copper nanoparticles, both in lead-based silicate enamels like the blue and yellow backgrounds. Tin and arsenic are observed, but cassiterite (SnO2) is clearly observed in one of the painted decors (dish) and in A676 yellow, whereas lead (calcium/potassium) arsenate is identified in most of the enamels. Yellow color is achieved with Pb-Sn-Sb pyrochlore (Naples yellow) with various Sb contents, although green color is mainly based on lead-tin oxide mixed with blue enamel. The technical solutions appear very different from one object to another, which leads one to think that each bowl is really a unique object and not an item produced in small series. The visual examination of some marks shows that they were made in overglaze (A608, A616, A630, A672). It is obvious that different types of cobalt sources were used for the imprinting of the marks: cobalt rich in manganese for bowl A615 (Yongzheng reign), cobalt rich in arsenic for bowl A613 (but not the blue mark), cobalt with copper (A616), and cobalt rich in arsenic and copper (A672). Thus, we have a variety of cobalt sources/mixtures. The high purity of cobalt used for A677 bowl indicates a production after ~1830–1850.

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.

Two masterpieces of the Qing Dynasty (1644–1912 CE), one in gilded brass (incense burner) decorated with cloisonné enamels stylistically attributed to the end of the Kangxi Emperor’s reign, the other in gold (ewer offered by Napoleon III to the Empress as a birthday present), decorated with both cloisonné and painted enamels bearing the mark of the Qianlong Emperor, were non-invasively studied by optical microscopy, Raman microspectroscopy and X-ray microfluorescence spectroscopy (point measurements and mapping) implemented on-site with mobile instruments. The elemental compositions of the metal substrates and enamels are compared. XRF point measurements and mappings support the identification of the coloring phases and elements obtained by Raman microspectroscopy. Attention was paid to the white (opacifier), blue, yellow, green, and red areas. The demonstration of arsenic-based phases (e.g., lead arsenate apatite) in the blue areas of the ewer, free of manganese, proves the use of cobalt imported from Europe. The high level of potassium confirms the use of smalt as the cobalt source. On the other hand, the significant manganese level indicates the use of Asian cobalt ores for the enamels of the incense burner. The very limited use of the lead pyrochlore pigment (European Naples yellow recipes) in the yellow and soft green cloisonné enamels of the Kangxi incense burner, as well as the use of traditional Chinese recipes for other colors (white, turquoise, dark green, red), reinforces the pioneering character of this object in technical terms at the 17th–18th century turn. The low level of lead in the cloisonné enamels of the incense burner may also be related to the use of European recipes. On the contrary, the Qianlong ewer displays all the enameling techniques imported from Europe to obtain a painted decoration of exceptional quality with the use of complex lead pyrochlore pigments, with or without addition of zinc, as well as cassiterite opacifier.

Minerals able to colour in blue (and green in combination with yellow pigments) are limited in number and geologically. After presenting a short history of the use of cobalt as a colouring agent of glass, glaze and enamel in the Western/Mediterranean, Islamic and Asian worlds since Antiquity, we will present the different forms (dissolved ions, natural and synthetic crystalline phases/pigments) of cobalt and associated elements regarding primary (transition metals) and secondary geological deposits (transition metals and/or arsenic, bismuth, silver). Attempts to identify the origin of cobalt have been made by many authors considering the associated elements but without considering the important modifications due to different processing of the raw materials (extraction/purification/formulation). We review the information available in the ancient reports and present literature on the use of cobalt, its extraction and production from the ores, the different geological sources and their relationship with associated elements (transition metals, bismuth, arsenic, and silver) and with technological/aesthetic requirements. (Partial) substitution of cobalt with lapis lazuli is also addressed. The relative application of non-invasive mobile Raman and pXRF analytical instruments, to detect mineral phases and elements associated with/replacing cobalt is addressed, with emphasis on Mamluk, Ottoman, Chinese, Vietnamese and Japanese productions. The efficiency of Ni-Zn-As diagram proposed by Gratuze et al. as a classification tool is confirmed but additionally, CoO-Fe2O3−MnO and CoO-NiO-Cr2O3 diagrams are also found as very efficient tools in this research. The relationship between the compositional data obtained from the artefacts and historical questions on the origin and date of their production are discussed in order to obtain a global historical view. The need of a better knowledge of (ancient) deposits of cobalt ores and the evolution of cobalt ore processing with time and place is obvious.

Asbestos-containing pottery shards collected in the northeast of Corsica (Cap Corse) and dating from the 19th century, or earlier, have been analyzed by SEM-EDS, XRPD, FTIR and Raman microspectroscopy. Blue (crocidolite) and white (chrysotile) asbestos fiber bundles are observed in cross-sections. Most of the asbestos is partly or totally dehydroxylated, and some transformation to forsterite is observed to occur, indicative of a firing above 800 °C. Examination of freshly fractured pieces shows a nonbrittle fracture with fiber pull-out, consistent with a composite material behavior, which makes these ceramics the oldest fiber-reinforced ceramic matrix composite. Residues indicate the use of this pottery as a crucible for gold extraction using cyanide.

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.

(FT) Raman spectroscopy is used for the first time to identify pigments used in 19th & 20th century Japanese and Vietnamese Lacquerwares. IR spectroscopy is used to assess the Lacquer matrix. Different operative conditions and parameters were experimented with on a limited number of lacquerwares in order to determine the optimal procedure for the identification of pigments/dyes as potential chronological or technological markers. The test was then performed in the collector’s rooms with a mobile Raman set-up. Different pigments (vermilion, Prussian Blue, Naples Yellow, Phtalocyanine Blue, anatase, rutile, chalk, carbon black) were identified despite a strong fluorescence and a rapid degradation of both pigments and binder under increasing laser power. Better spectra were obtained on older lacquerwares.

Recent interest in environmentally friendly technology has promoted research on green house gas-free devices such as water steam electrolyzers, fuel cells and CO2/syngas converters. In such applications, proton conducting perovskite ceramics appear especially promising as electrolyte membranes. Prior to a successful industrial application, it is necessary to determine/understand their complex physical and chemical behavior, especially that related to proton incorporation mechanism, content and nature of bulk protonic species. Based on the results of quasi-elastic neutron scattering (QNS), thermogravimetric analysis (TGA), Raman and IR measurements we will show the complexity of the protonation process and the importance of differentiation between the protonic species adsorbed on a membrane surface and the bulk protons. The bulk proton content is very low, with a doping limit (~1–5 × 10−3 mole/mole), but sufficient to guarantee proton conduction below 600 °C. The bulk protons posses an ionic, covalent bond free nature and may occupy an interstitial site in the host perovskite structure.

Outstanding electrical properties of solids are often due to the composition heterogeneity and/or the competition between two or more sublattices. This is true for superionic and superprotonic conductors and supraconductors, as well as for many ferroelectric materials. As in PLZT ferroelectric materials, the exceptional ferro- and piezoelectric properties of the PMN-PT ((1−x)PbMg1/3Nb2/3O3−xPbTiO3) solid solutions arise from the coexistence of different symmetries with long and short scales in the morphotropic phase boundary (MPB) region. This complex physical behavior requires the use of experimental techniques able to probe the local structure at the nanoregion scale. Since both Raman signature and thermal expansion behavior depend on the chemical bond anharmonicity, these techniques are very efficient to detect and then to analyze the subtitle structural modifications with an efficiency comparable to neutron scattering. Using the example of poled (field cooling or room temperature) and unpoled PMN-PT single crystal and textured ceramic, we show how the competition between the different sublattices with competing degrees of freedom, namely the Pb-Pb dominated by the Coulombian interactions and those built of covalent bonded entities (NbO6 and TiO6), determine the short range arrangement and the outstanding ferro- and piezoelectric properties.

Nowadays the technological progresses provide portable analytical devices allowing measurements out of the laboratory. This paper reviews the contribution of Raman and infrared spectroscopies, which provide non (or weakly) invasive analyses, as often required for studying Cultural Heritage materials/artefacts. The potentialities and limits of such portable analytical techniques are presented and discussed, underlining the analytical strategies offered to enlarge the field of possible studies from laboratories to sites.

This report highlights the promising applications of modern analysis techniques such as Scanning Electron Microsopy, X-ray fluorescence, X-ray diffraction, Raman scattering spectroscopy, and thermal expansion measurement in searching back the ancient art ceramics technologies.