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Elemental analyses of a group of glazed terracotta angels from the Italian Renaissance

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Abstract

A group of Italian glazed terracotta sculptures, attributed to the della Robbia workshop of Florence, is partly displayed in the Louvre Museum. Analyses of the apparently homogeneous sculptures by techniques such as PIXE, SEM, ICP/AES and ICP/MS have identified differences in the materials used. The data provide a subdivision of the sculptures, which is compatible with what is known from historical documents and artistic considerations, and suggest a date for this ensemble at the end of the 15th century, when the della Robbia family was involved in the decoration of the San Frediano church in Florence.

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... He explains that the use of very high tin oxide content in the early period of Italian maiolica production reflects a lack of understanding of the amount of tin oxide necessary to achieve adequate opacity and whiteness. High tin oxide content, 14e20 wt% SnO 2 extending up to 24 wt%, higher than the tin oxide content of Renaissance maiolica glazes, is also characteristic for the white glaze of della Robbia sculptures and panels produced in the 15th and 16th centuries (Fig. 9, Barbour and Olson, 2011;Gianoncelli et al., 2008;Kingery and Aronson, 1990;Tite, 2009;Zucchiatti et al., 2003;Zucchiatti and Bouquillon, 2011). The glaze composition was deliberately modified by the della Robbia workshop to produce sculptural ceramics of high artistic quality. ...
... The less than 1 K 2 O/Na 2 O ratio and the presence of chlorine are evidence of the use of common salt in the preparation of the ceramic colours of samples 1 and 2, while the more than 1 K 2 O/Na 2 O ratio indicates the use of a higher amount of K-bearing flux for the colours of sample 6. Table 2) compared with the white glaze of the Archaic, Early and Late Renaissance Italian maiolica (data from Amato et al., 2010;Tite, 2009;Viti et al., 2003) and the white glaze of della Robbia sculptural ceramics (data from Barbour and Olson, 2011;Gianoncelli et al., 2008;Kingery and Aronson, 1990;Tite, 2009;Zucchiatti et al., 2003). The chemical compositions as measured by SEM-EDS analyses for maiolica glaze, and SEM-EDS, microprobe and portable XRF analyses for della Robbia glaze, respectively. ...
... In the blue glaze of Renaissance sculptural ceramics arsenic appears around 1520, whereas arsenic is absent (i.e. below detection limit, <0.1 wt% As 2 O 3 for PIXE) in blue glaze produced before 1520 (Padeletti et al., 2006;Pappalardo et al., 2004;Zucchiatti et al., 2006). The arsenic content of the pigment is separated from the cobalt and typically present in the form of newly-formed calciume lead arsenate crystals in the vitreous matrix (e.g. ...
Article
The paper presents the first results of a long-term project aiming to reconstruct the production technology of the Anabaptist (Hutterite) tin-glazed ceramics produced in Eastern-Central Europe. Microanalytical investigations were performed on 17th-century faience artefacts (six samples) excavated at Sárospatak, North-East-Hungary. The results are compared with analytical data on the direct or indirect precursor, Italian maiolica. The studied Hutterite faience artefacts reveal similarities with Italian maiolica. Calcareous clay with 14 to 22 wt% CaO was used for the buff-coloured ceramic body. Up to about 400 μm thick, tin-opacified white and blue lead-alkali glaze was applied on the biscuit-fired body. The glaze suspension contained sand admixture and a significant amount of common salt and was not fritted before application. The colorants used for the ceramic colours are lead antimonate for yellow, cobalt with arsenic, nickel and iron for blue, copper for green and manganese with minor iron for black. The ceramic colours were applied on the unfired glaze and maturing occurred during the second firing. The main technological difference when compared with the Italian Renaissance maiolica is the deliberate use of a high amount of tin oxide (17 to 20 wt% SnO2) together with 18 to 28 wt% PbO content for white glaze of the studied Hutterite faience.
... phed works and the elusive documentation regarding commissions and provenance create the need for a variety of research investigations into the materials and techniques used by the Della Robbia family. Elemental analyses of Della Robbia glazed terracottas have been performed using various techniques: particle-induced X-ray emission (PIXE) analysis (Zucchiatti et al . 2003;Pappalardo et al . 2004), X-ray fluorescence (XRF) spectroscopy (Pappalardo et al . 2004), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) (Zucchiatti et al . 2003), inductively coupled plasma combined with mass spectroscopy (ICP-MS) (Zucchiatti et al . 2003;Bouquillon 2004) and inductively coupled plasma comb ...
... a family. Elemental analyses of Della Robbia glazed terracottas have been performed using various techniques: particle-induced X-ray emission (PIXE) analysis (Zucchiatti et al . 2003;Pappalardo et al . 2004), X-ray fluorescence (XRF) spectroscopy (Pappalardo et al . 2004), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) (Zucchiatti et al . 2003), inductively coupled plasma combined with mass spectroscopy (ICP-MS) (Zucchiatti et al . 2003;Bouquillon 2004) and inductively coupled plasma combined with atomic emission spectroscopy (ICP-AES) (Zucchiatti et al . 2003;Bouquillon 2004). Molecular analysis of the Della Robbia yellow from the majolica altar conserved at St Mary of the An ...
... us techniques: particle-induced X-ray emission (PIXE) analysis (Zucchiatti et al . 2003;Pappalardo et al . 2004), X-ray fluorescence (XRF) spectroscopy (Pappalardo et al . 2004), scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDS) (Zucchiatti et al . 2003), inductively coupled plasma combined with mass spectroscopy (ICP-MS) (Zucchiatti et al . 2003;Bouquillon 2004) and inductively coupled plasma combined with atomic emission spectroscopy (ICP-AES) (Zucchiatti et al . 2003;Bouquillon 2004). Molecular analysis of the Della Robbia yellow from the majolica altar conserved at St Mary of the Angels in Assisi (Perugia, Italy), dated to 1490, has been carried out with micro-Raman spectrosc ...
Article
Micro-Raman spectroscopy and the laser-induced transformation technique were used for systematic study of five coloured glazes on Saint John the Baptist (29 inch tondo), a majolica terracotta relief attributed to Luca Della Robbia and on permanent exhibit in The John and Mable Ringling Museum of Art. We suggest that ions in a lead silicate matrix, called ‘lead ultramarine’, could contribute to the famous Della Robbia blue colour, in addition to the effect of Co atoms as suggested previously by Pappalardo et al. (2004). The original yellow glaze contains lead(II) antimonate. The green is a mixture of the yellow and blue pigments, the brown contains hematite, and the white glaze contains tin dioxide as an opacifier. The use of lead oxide as a main fluxing agent is confirmed by laser-induced micro-crystallization.
... Sca13 corresponds to an analysis region in the five-angel row separating the lower and upper sections of the 'Virgen de la Granada'; the low SnO 2 concentration (Table 4) does not correspond to the average values for the Della Robbia production. 1,8,9 Such a conclusion applies also for parts of the blue background (Sca35: PbO 28%, SnO 2 3%) in the upper section (Fig. 1); this section is made of a large number of blue tiles. The blue in other parts of the background (Sca11, Sca12, Sca34, Sca16 and Sca20) of the different sections, as well as the pot at the bottom of the left pillar (Sca31), has lead and tin compositions close to those of Della Robbia. ...
... The average elemental compositions for the two Seville works are gathered in Tables 5 and 6; only the data corresponding to ancient glazes have been kept to calculate the average values. For the purpose of comparisons, Tables 5 and 6 include results from the literature, 1,8,9 which have been obtained by scanning electron microscopy (SEM-EDX) and by PIXE. 7 For the white glazes, Table 5 includes also results of two small fragments collected at the left bottom of the 'Virgen de la Granada' that were analysed by SEM-EDX. ...
... The two glazes are rich in particles (quartz, feldspar) that did not melt during the firing, and SnO 2 concentrations are below the average (Table 5); this could be attributed to the production of Buglioni. 9,10 This could correspond to minor parts of the 'Virgen de la Granada' (Sca10 and Sca14, Table 3) since the (Fig. 1), has concentrations typical of the Della Robbia productions (Tables 2 and 5). ...
Article
A portable XRF spectrometer has been developed at the Centre de Recherche et de Restauration des Musées de France (C2RMF), in Paris. The instrument has been successfully used on many occasions to analyse qualitatively various important works of art. In the present study, it has been utilised for the analysis of two glazed sculptures located in the cathedral of Seville (Spain) and attributed to the Della Robbia workshop. The aim was to perform a quantitative analysis in order to determine the elemental composition of the glazes. The results are compared with those previously obtained with particle induced x-ray emission (PIXE) and µ-PIXE techniques at the C2RMF on other Della Robbia wares located at the Louvre museum. The data provide information on the two sculptures, which is discussed in relation with what is known on the Florentine production at the Renaissance. Copyright © 2006 John Wiley & Sons, Ltd.
... Italian majolica). [4][5][6][7][8]14,16,31,[39][40][41][42][43] The glaze elemental composition used in every production centre is expected to depend on raw materials and workshop recipes, however, in blue-decorated ceramics from Teruel tin-opacified glazes were produced using high content of lead (25-35% PbO), the type called lead-alkali glaze, 23 like all the Iberian production and Italian majolica. [4][5][6][7][8][9]15,16,22,24,30,31,[39][40][41][42][43][44][45] About the use of the blue pigment, Teruel workshops utilised a cobalt pigment characterised by the association Co-Cu-Fe-Ni in the 15th century until the first half of 16th century. ...
... [4][5][6][7][8]14,16,31,[39][40][41][42][43] The glaze elemental composition used in every production centre is expected to depend on raw materials and workshop recipes, however, in blue-decorated ceramics from Teruel tin-opacified glazes were produced using high content of lead (25-35% PbO), the type called lead-alkali glaze, 23 like all the Iberian production and Italian majolica. [4][5][6][7][8][9]15,16,22,24,30,31,[39][40][41][42][43][44][45] About the use of the blue pigment, Teruel workshops utilised a cobalt pigment characterised by the association Co-Cu-Fe-Ni in the 15th century until the first half of 16th century. This feature also appears in Valencia ceramics produced during the 14th and 15th centuries. ...
... 48 In the 16th century Aragonese ceramic workshops modified the way to decorate white opacified glazes with blue designs and the pigments were applied on the glaze. This type of decorating tin-opacified glazes appears as a general feature of Iberian and Italian majolica since the 16th century, [6][7][8][9]30,31,[39][40][41][42][43][44][45] although there are some differences in the blue pigment used. The previously stated fact that As content in blue pigments increases since the 16th century AD in the Aragonese pottery, like in other Iberian centres, 13,27,30,39 is also present in Italian majolica. ...
Article
Full-text available
Cobalt-blue-decorated ceramics with tin glazes have been produced in the Iberian Peninsula since the 14th century AD and in Aragon region since the 15th century until the present time. An important ceramic trade was developed and relations with potters of other important production centres were established. Representative objects from archaeological findings could help in drawing conclusions on the technology used in the manufacture of blue-decoration ceramics. In this work, the composition of bodies and glazes of more than fifty samples of blue-decorated ceramics from Aragon was determined by ICPAES and EDX–Scanning Electron Microscopy (SEM). Based on this information, different ceramic groups could be appreciated and reference values valuable for the subsequent study of the blue decorations by means of other techniques, such as laser ablation (LA)–ICPMS, were also obtained. In particular, the data obtained permitted to unequivocally establish the use of three different types of cobalt pigments, with clear changes between areas and periods. Moreover, it is demonstrated that this evolution in the nature of the blue pigments was related to a different procedure when decorating the object, namely the application of the pigments and the drawing the designs before (under glaze) or after (on glaze) covering the ceramic with the tin glaze.
... During the firing, on-glaze materials melt with the vitreou coating of the ceramic, becoming one with it. Numerous scholars have dealt with archaeometric analysis of the works of Luca dell Robbia [5][6][7][8][9][10][11][12][13][14]. Many of these works were focused mainly on the characterization of glaze Numerous scholars have dealt with archaeometric analysis of the works of Luca della Robbia [5][6][7][8][9][10][11][12][13][14]. ...
... Numerous scholars have dealt with archaeometric analysis of the works of Luca dell Robbia [5][6][7][8][9][10][11][12][13][14]. Many of these works were focused mainly on the characterization of glaze Numerous scholars have dealt with archaeometric analysis of the works of Luca della Robbia [5][6][7][8][9][10][11][12][13][14]. Many of these works were focused mainly on the characterization of glazes and raw materials such as the terracotta body, but no archaeometric study was previously performed on the artist's production, characterised by this experimental technique of gilding. ...
Article
Full-text available
The present work comprises the application of a multi-analytical strategy based on the combination of several non-destructive and micro-invasive methodologies for the examination of the glazed tiles from the tomb of Benozzo Federighi made by Luca della Robbia. The marble tomb is framed by flat glazed terracotta tiles, each ornamented with naturalistically depicted flowers. The tiles are assembled like an “opus sectile” and their background is gilded. The leaf is incorporated on the top of the glaze, differently by traditional gilding technique as in previous glazed works of della Robbia. The identification methodology integrates the results from spot analyses such as UV-vis reflectance spectroscopy and X-ray fluorescence, with those obtained on tiny samples by X-ray diffraction, electron microscopic observations, laser ablation inductively coupled plasma mass spectrometry and firing temperature analysis. The adopted analytical protocol allowed us to clarify peculiarities of the artist’s technique and of the manufacturing technology used to create the terracotta and gilded glazed tiles. The terracotta body shows main phases related with Ca-rich ceramic body and the glaze results Pb-based and additioned with Sn as an opacifier. Co, Pb-Sb and Cu were identified as glazes colouring agents. The hypothesis on the use of the “third firing” technique for gilding tiles is explored in the text.
... A possible way to distinguish between della Robbia and Buglioni works is the comparison of trace element (including REE) pattern of their ceramic bodies. Zucchiatti et al. [5] measured the major, minor and trace element (including REE) compositions of the bodies of ten della Robbia glazed terracotta sculptures, although they did not publish the trace (REE) element concentration values. Recently Dias et al. [24] measured the chemical composition (mainly REEs) of eleven glazed medallions displayed in Portuguese museums and attributed to the della Robbia workshop ( Table 1). ...
... According to our knowledge, the 'coloured glaze on white glaze' technique was not described earlier, therefore it seems to be a new characteristic of Renaissance glazed terracotta sculptures. [2,[5][6][7][9][10][11]15]). Chemical compositions were measured by SEM-EDS, electron microprobe, PIXE and portable XRF analyses for della Robbia and Buglioni glazes. ...
Article
A glazed terracotta statue depicting the Virgin and the Child, dated to the turn of the 15th and 16th centuries, is a prominent object of the Collection of Sculpture before 1800 of the Museum of Fine Arts, Budapest. The provenance of the statue is unknown, it may stem from the place of its 19th-century purchase, Florence or its environs. This paper presents the material analysis and TL dating of the statue and compares the technological features to the glazed sculptural ceramics produced by the della Robbia and Buglioni workshops in the Renaissance Florence. The yellowish ceramic body was made from highly calcareous clay (25 wt% CaO content) and its mineralogical composition indicates an apparent firing temperature of ∼900–950 ̊C. The white tin glaze is of lead-alkali type with 19.2–20.7 wt% SnO2, 26–31 wt% PbO and 4.7–7.4 wt% Na2O + K2O content. Tiny green spots occur sporadically in the white glaze, where the colour is due to the presence of dissolved copper. In these spots, newly-formed potassium-aluminium silicate, calcium-tin silicate and calcium silicate crystals occur at the body-glaze interface and in the glaze. The violet-coloured glaze on the base of the statue contains a lower amount of tin oxide and a higher amount of lead oxide (11.8 wt% SnO2, 40 wt% PbO) compared to the white glaze covering the statue. The colour was achieved by addition of manganese, and the violet-coloured glaze was applied on a white glaze covering the body of the base. Based on the TL dating, the statue is unambiguously authentic with an age of 0.58 ± 0.06 ka.
... It can be due to the fact that tileworks might have been manufactured in a region and have been exported to other regions in order to be applied in architectural facades (Mason, 2003). To determine the origin of unknown products, a numerous provenance studies derived from quantitative elemental analysis, such as Neutron Activation Analysis (NAA) (Buko, 1984;Neff et al., 1988;Cogswell et al., 1996Cogswell et al., , 1998Mainfort et al., 1997;Arnold et al., 1999Arnold et al., , 2000García-Heras et al., 2001;Neff, 2002;Glascock et al., 2004;Ben-Shlomo, 2008;Descantes et al., 2008;Iñañez et al., 2008;Partha Sarathi et al., 2008), Particle-Induced X-ray Emission (PIXE) (Zucchiatti et al., 1998(Zucchiatti et al., , 2003Ruvalcaba-Sil et al., 1999;Robertson et al., 2002), and various techniques of atomic spectroscopy and spectrometry (ICP-MS, LA-ICP-MS, ICP-AES, etc.) (Mallory-Greenough et al., 1998;Kennett et al., 2002;Robertson et al., 2002;Neff, 2003;Zucchiatti et al., 2003;Klein et al., 2004;Li et al., 2005;Tiequan et al., 2010) have been carried out on ceramic bodies. These studies have always been accompanied by statistical methods of data handling to attribute one type of ceramic product to a specific zone. ...
... It can be due to the fact that tileworks might have been manufactured in a region and have been exported to other regions in order to be applied in architectural facades (Mason, 2003). To determine the origin of unknown products, a numerous provenance studies derived from quantitative elemental analysis, such as Neutron Activation Analysis (NAA) (Buko, 1984;Neff et al., 1988;Cogswell et al., 1996Cogswell et al., , 1998Mainfort et al., 1997;Arnold et al., 1999Arnold et al., , 2000García-Heras et al., 2001;Neff, 2002;Glascock et al., 2004;Ben-Shlomo, 2008;Descantes et al., 2008;Iñañez et al., 2008;Partha Sarathi et al., 2008), Particle-Induced X-ray Emission (PIXE) (Zucchiatti et al., 1998(Zucchiatti et al., , 2003Ruvalcaba-Sil et al., 1999;Robertson et al., 2002), and various techniques of atomic spectroscopy and spectrometry (ICP-MS, LA-ICP-MS, ICP-AES, etc.) (Mallory-Greenough et al., 1998;Kennett et al., 2002;Robertson et al., 2002;Neff, 2003;Zucchiatti et al., 2003;Klein et al., 2004;Li et al., 2005;Tiequan et al., 2010) have been carried out on ceramic bodies. These studies have always been accompanied by statistical methods of data handling to attribute one type of ceramic product to a specific zone. ...
... While the artistic study of the della Robbias has produced the master works of Marquand (1925) and Gentilini (1992), the instrumental investigation of their artefacts, and the understanding of their techniques through microscopic inspection, have been undertaken in great detail only in recent years (Kingery and Aronson 1990;Agosti et al . 1997;Zucchiatti et al. 2000Zucchiatti et al. , 2002Zucchiatti et al. , 2003Bouquillon et al. 2001a,b;Olson and Barbour 2001;Pappalardo et al . 2004). ...
... mand 2002) of French Robbiane , and the specimens were submitted to both scanning electron microscopy (SEM) and particle-induced X-ray emission (PIXE): • For polished glaze sections, which were available in several cases, SEM-EDS was performed for analysis of major and minor elements, and for chemical characterization of the microscopic structures (Zucchiatti et al . 2003). The micro-elemental information explains the nature of the formed crystals and aggregates, which in turn discloses the technical details of the manufacturing process. The categorical kind of information (e.g., large or small bubbles, coarse or fine grinding, good or poor fusion, thin or thick interface, etc.) also allows estimation of ...
Article
The morphologies and elemental compositions of cobalt blue glazes are studied in 56 dated and undated terracotta sculptures from the Florentine della Robbia school. The data allow tracing of the pigments through correlations amongst elements that are known to be constituents of the cobalt minerals. The supply of such minerals from the Erzgebirge region in Renaissance times is compatible with our data. A substantial change in the materials is marked by the presence of arsenic and bismuth in the glaze, and by reduced amounts of iron and nickel just before 1520. We speculate that this is due to procedures introduced to industrialize the production of the blue pigment. The exploitation of different cobalt minerals in association with different production procedures may explain the variability of compositions that we observe in this unique ensemble.
... Analytical procedures have already been described and published in various papers [6,7]. ...
... Glazes on Della Robbia sculptures may contain 1−3 wt % of potassium and up to 0.7 wt % of chlorine. 52,53,56 Although leaching of potassium from glasses is known 57 and can lead to the alteration of hydrocerussite, 58 given that the lead chlorides formed in unglazed areas, it is doubtful that the glazes themselves, which are in stable condition, are the source of either potassium or chloride ions that led to the formation of challacolloite in the paint. ...
Article
Materials in the paint layers of an early sixteenth-century painted and glazed terracotta sculpture by Giovanni della Robbia, Pietà were identified. The presence of the rare lead chloride salts, cotunnite (PbCl2) and challacolloite (KPb2Cl5), were confirmed using Raman spectroscopy and electron back scatter diffraction. Well-formed habit of large crystals of challacolloite indicates slow growth from solution. The stability and potential pathways for the in-situ formation of lead chloride compounds are discussed. The presence of lead chloride phases in the Pietà indicates conditions of high chloride ion concentrations (i.e., activities) and/or low pH led to the alteration of the pigment lead white (hydrocerussite, 2PbCO3·Pb(OH)2). This work highlights the role of ion transport in alteration of artists’ materials and emphasizes the importance of considering the role of treatments and envi-ronmental factors in changes in materials, and reinforces our awareness of the on-going chemistry occurring in works of art.
... If the sculptures or taken samples are studied only by portable X-ray fluorescence (e.g., Križnar et al., 2009or Colombo et al., 2011b or, in addition, by spectroscopic methods (e.g., Amadori et al., 2013or Colombo et al., 2011b, nothing can be deduced about the source of the clay materials. Potentially very promising is the information provided by Zucchiatti et al. (2003), who analysed clay bodies of a group of Italian Renaissance glazed terracotta angels by ICP-MS and a total of 53 chemical elements including the trace elements were identified. Unfortunately, only ten major components are listed in the results. ...
Article
In the Baroque European painting technology, various coloured clays had been used to prime canvases. These clays are generally considered to be carefully selected in terms of colour and other technological properties (adhesiveness, ductility etc.), as the painting represented the most delicate field of fine art. However, it seems that the availability of the material at a given place as well as its price often played a much more significant role than previously thought. It led to the usage of highly heterogeneous cheap pottery clays in painting, even though they often had to be additionally coloured. For the first time, a clear evidence is provided that a very similar pottery clay material was applied in three different technological ways: i) as a clay body of an unfired terracotta statue created in Florence or Bologna at the end of 16th century, ii) as a secondary putty on the Renaissance painting by Antonello da Saliba (1466–1535), and iii) as a preparation layer – ground – of an oil-on-canvas paintings attributed to Italian Caravaggists (17th century) or also to Carlo Maratta or workshop (1655–1713). The identity of the material was confirmed by mineralogical analyses as well as description of nannofossils, which enable to date the clay to Eocene – Oligocene.
... The SEM images, only a subset of which are included here (Fig. 3) and in the online Supporting Information (Fig. S3), show that the glaze thicknesses are generally about 100 μm, with thinner regions in a few cases, but occasionally revealing thicker glaze regions (340 μm; see Fig. 3). Glaze thicknesses of about 100 μm are common in ancient ceramics (Molera et al. 1997;Zucchiatti et al. 2003). The glazes appear quite homogeneous except for one observation of a bubble (Fig. 3) and one observation of quartz or feldspar inclusions in a chip from CMA 1986.55. ...
Article
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Chemical analyses of a group of Pb silicate–glazed decorative objets d'art showing scenes of the French royal family (Louis XIII and Henri IV), and biblical and classical figures, have been analysed and compared with other similar heritage ceramics and with the rustiques figulines of Bernard Palissy (1510–90) and his followers and imitators. In particular, non-destructive ion-beam chemical analyses (PIXE and PIGE) have been performed on 11 ceramic artefacts from the Cleveland Museum of Art (CMA) and a like number from several French museums; results for 13 objects are described in detail in this paper. SEM–EDX has been performed on chips (‘microsamples’) taken from small unobtrusive defective regions on the CMA ceramics. The results of the ion-beam and SEM–EDX techniques are in good agreement. All the decorative ceramics included uniform non-opacified glazes. None of these objects can be of 16th century production; all must date from the 17th to the 19th centuries.
... The glaze elemental composition is expected to depend on raw materials and workshop recipes; the precise determination of minor and trace-elements can be particularly important to differentiate [2] or to aggregate [3] groups of objects that are stylistically related, to possibly establish the provenance of the artefact and the origin of pigments as well as to monitor the time evolution of materials and techniques. Since a few years, the polychrome glazes of the Robbiane have been extensively investigated on potsherds, whole sculptures and polished sections [1]. ...
Article
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"In situ" non-destructive characterization of the blue pigments present in the ceramic glazes of Della Robbia sculptures have been carried out at the Bargello museum in Florence. PIXE and XRF portable systems have been used to determine the matrix composition and the trace-elements, respectively. The results indicate that the arsenic is present as trace-element only after 1520. (C) 2004 Elsevier SAS. All rights reserved.
... The presence of kaolin in the white pigment of genuine terracotta contrasts with the absence of organic binders in the fakes (Bordignon et al. 2007). Among the terracottas collected by Campana, some attributed to Della Robbia are also pastiches, identified by the composition of the clays and glazes (Zucchiatti et al. 2003(Zucchiatti et al. , 2006Sendova et al. 2007); and TL dating has also separated modern from Renaissance items (Fleming and Stoneham 1973b). ...
Article
Artefacts and works of art kept in museum collections originated in many cases from ancient private collections. In such cases, a partial or total absence of historical information may create additional problems concerning their authenticity. The study of museum collections and their preservation requires the use of analytical techniques but also combined examination techniques not commonly necessary for the study of archaeological objects. This paper gives an overview of the importance of museum items for the understanding of the past, the difficulties relating to their authentication and the significant advances brought about by science-based techniques, in particular those cases discussed in Archaeometry during the past 50 years.
... Analytical procedures have already been described and published in various papers [6,7]. ...
Article
Analyses of the productions of della Robbia and Palissy, two masters of Renaissance ceramics in France and in Italy, have enlightened their contributions to the improvement of the glazed terracotta technique. Della Robbia used very homogeneous materials: marly clay for the bodies, and tin-opacified coloured glazes. The technique is here very robust and very mastered. Palissy used different types of clay with different colours and physical properties, associated with specific productions. So far, we have identified seven pastes. Concerning the glazes, he played with transparency and opacity, with lead glazes and with tin-opacified lead glazes. He added traditional colouring oxides as well as specific pigments (lead–tin yellow, haematite, etc.). The mixed-earth technique is specific to his palette. So, the materials used by both artists are completely different and illustrate their different philosophical approaches. To perform the different analyses, new methodologies have been developed: ICP/AES-MS, petrography and X-ray diffractometry for the bodies, PIXE and micro-PIXE, SEM coupled with EDS and Raman spectrometry for the glazes.
... The glaze and body compositions observed for this particular late 15th century AD Andrea della Robbia panel are consistent with other published data for della Robbia sculptural ceramics (Kingery and Aronson, 1990b;Agosti et al., 1997;Olson and Barbour, 2001;Zucchiatti et al., 2003Zucchiatti et al., , 2006Bouquillon et al., 2004;Bouquillon and Zucchiatti, 2009). First, the lead contents of the della Robbia glazes consistently extend up to about 40 wt% PbO, and are therefore higher than those observed for the majority of maiolica glazes (Table 4). ...
Article
Full-text available
Analytical scanning electron microscopy was used to determine the microstructures and chemical compositions of some fifty Italian maiolica ceramics, together with a della Robbia terracotta panel, spanning the period from 13th to early 17th century AD, and thus establish the changes in the production technology that occurred during this period. The glaze and body compositions of Archaic maiolica (13th–14th centuries AD), as compared to those for contemporary Islamic ceramics, suggest that the production technology for Archaic maiolica could have been introduced into Italy either from Spain or north Africa. The observed microstructures and compositions of the glazes, colorants and bodies of Renaissance maiolica (15th to early 17th centuries AD) are fully consistent with description of its production technology given by Piccolpasso in his treatise, “The Three Books of the Potter's Art”, written in c. 1557 AD. Consideration of the reasons for the use of calcareous clays for the Italian maiolica bodies, the use of lead-alkali glazes, the addition of further sand to the glazing mixture, the variable tin contents of the glazes, and the application of a transparent coperta layer over the painted decoration strongly suggests that these technological choices were made in order to facilitate production and enhance the quality of the final product.
Article
Nine decorated lead-tin glazed earthenwares, colloquially termed ‘delftware’, produced in c. 1770 in Bristol, Lancaster and Liverpool, England, have been analysed non-invasively by Raman spectroscopy and electron microscopy. The body paste used to manufacture these west coast wares was attained by the blending of highly dolomitic [CaMg(CO3)2] “blue” clay sourced from Carrickfergus, County Antrim, Ireland, with locally sourced clays. Thus, the resulting body fabric of these wares contains significant MgO enabling them to be differentiated from MgO-free London manufactured delftware. The glazes employed all contain arsenic, obtained as a cobalt impurity or by deliberate addition. The presence of this unvolatilised arsenic in the glaze has then reacted with the lead during firing at temperatures approaching 1000°C and then further reacted with calcium and magnesium to form needle-like crystals of lead arsenates in the form of mimetite [Pb5(AsO4)(Cl,OH)], schulténite [Pb(AsO3OH)], β-roselite [Ca2Co(AsO4)2.2H2O], hedyphane [Ca2Pb3(AsO4)3Cl], wendwilsonite [Ca2Mg(AsO4)2.2H2O] and/or adelite [CaMgAsO4(OH)] during high temperature firing.
Article
Artistic and historical examination of high-quality glazed terracotta sculptures displayed in various Portuguese museums point to their production in della Robbia workshop of Florence (Italy). A multitechnique analytical approach is applied for the first time to these sculptures, aiming to confirm their origin. Materials were analyzed using Instrumental Neutron Activation Analysis, Prompt Gamma Activation Analysis and X-ray Diffraction. The compositional results are similar to other della Robbia sculptures, suggesting a common origin for the raw material that was identified as carbonate rich marine origin marly clay. The applied firing temperatures was proved to be around 900 °C. The differences found within each sculpture are explained by the production technique of assembling separate parts to produce these huge sculptures, and the clay pit heterogeneity.
Conference Paper
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The examination of the microstructure of metal artefacts allows a great deal of information to be obtained about the quality of the material used for manufacturing as well as information related to the technology of fabrication. Unfortunately accessing this information normally requires an invasive intervention on the artefact: a small fragment needs to be detached from the artefact, and mounted as a crosssection by an embedding procedure followed by observation under a metallographic microscope. This method is not always acceptable: museum curators are often reluctant to allow extraction of fragments from their artefacts, making a metallurgical study of these objects an impossible feat. In attempt to circumvent this difficulty, the authors are proposing to turn to a more benign method, that of ‘in-situ’ metallographic examination.
Article
This chapter contains two main parts. In the first part a literature survey is proposed about the problem of phosphorus pollution in the ceramic archaeological materials buried in the ground. The second part is a very significant example of research on highly polluted Neolithic pottery.Phosphorus is not an important component of ceramic clays, but in the oldest archaeological pottery very high percentages of this element, up to more than 10% P2O5, are frequent and these contents are commonly interpreted as an effect of contamination.. The sources of phosphorous can be different, for example the bones usually discharged in archaeological sites along with pottery, the foods contained in the vessels during their use, or the agricultural fertilizers. The minced bones, or bone ashes, voluntarily added into the clay paste by the ancient potter are an internal source. The circulating water, the temperature variations and the alternation of wet-dry periods favor the mobilization of phosphorus and then its fixation in the porous ceramic structure. Even the "time factor" is very important, since the solubility of phosphorus is extremely low. The pottery from the Neolithic site of Sammardenchia (Udine, northern Italy) are characterized by high concentrations of phosphorus (exceeding 10% P2O5) and very large macro-pores, often with a geometric shape, produced by the dissolution of calcite inclusions. The SEM/EDS analysis showed that the phosphorus is correlated together with iron and aluminum. It is therefore inferred that the phosphorus is present mainly as iron and/or aluminum phosphate in the amorphous state, because no crystalline phase was detected by the X-ray diffraction analysis. A phosphorous content of about 10% P2O5 would correspond to an amount around 35% of Fe3(PO4)2.8H2O (vivianite). This means that the phosphates largely fill the pores, including those deriving from the dissolution of the calcite inclusions, conferring a good mechanical resistance to the ceramic shards.
Article
“In situ” non-destructive characterization of the blue pigments present in the ceramic glazes of Della Robbia sculptures have been carried out at the Bargello museum in Florence. PIXE and XRF portable systems have been used to determine the matrix composition and the trace-elements, respectively. The results indicate that the arsenic is present as trace-element only after 1520.
Article
PIXE has been used to extract the elemental composition of cobalt blue glazes in 55 dated and undated terracotta sculptures from the Florentine della Robbia school. The data, consistently with previous work, show a rapid change in the composition of blue glazes and locate it just before 1520. The change is marked essentially by the presence of arsenic and bismuth in the glaze and by reduced amounts of iron and nickel after 1520. We speculate that this is due to procedures introduced to industrialise the blue pigments production more than to exploitation of different families of cobalt minerals. We observe in this unique ensemble more variability of products than was known before.
Article
An outstanding style of Persian tilework, which emerged from the north-eastern Iran in the 15th century, was extensively used for decorating architectural facades during the Safavid period (from the 16th through the 18th century). This type of tilework, the so-called haft rang, technically comprises of forming a clay body and firing two glazed layers on top of the body. In the present paper, the first analytical data concerning haft rang tiles is provided. To do so, forty three samples of Safavid haft rang bodies were analysed by wavelength dispersive x-ray fluorescence (WDXRF) and the obtained data were handled by principal component analysis (PCA). The results showed that the 17th century haft rang tiles wherever found are local products; that is, Safavid tile-makers have used local clay sources to make the bodies of haft rang tiles. The analytical data also showed that old tileworks, in general sense, can be simply replaced by newly manufactured tiles or, at least, all tilework revetments in an individual edifice might not have been produced in an identical workshop. Moreover, WDXRF was used as an accurate and precise method to determine the chemical composition and to support compositional classification in provenance studies and can be considered as a reliable alternative for studying the provenance of archaeological ceramics.
Article
Micro-Raman temperature study and X-ray fluorescence (XRF) spectroscopy were used for characterization of the blue glaze on Saint John the Baptist—majolica terracotta relief attributed to Andrea Della Robbia and Saint John the Baptist with Cross—majolica terracotta statue attributed to Giovanni Della Robbia. Both objects are on permanent exhibition in the John and Mable Ringling Museum of Art in Sarasota, FL. This study proves that the detection of the 548 cm−1 Raman band alone cannot serve as evidence for presence of lazurite crystallites in the pigment in the glaze. It was established that the famous Della Robbia blue is due to the combined effect of CoNiCuZn atoms and S3− ions embedded in a lead silicate matrix. It is proposed that the Della Robbia family used Co-containing sulfide ores as a source for manufacturing their blue pigments. Copyright © 2009 John Wiley & Sons, Ltd.
Article
Whitewares are among the most significant finds from Erlitou, China’s earliest state (c. 1900–1500 BC). They were primarily discovered in small numbers from elite tombs of a few sites, leading to the hypothesis that they were made at only a few places and then circulated as prestige items. Recent archaeological work indicates Nanwa may be a whiteware production site. To facilitate determining provenances, we compare the ICP-MS trace elements and TIMS Sr isotopes of Nanwa whitewares with those from Tang dynasty (618–907 AD) Gongxian kilns and Song dynasty (960–1279 AD) Ding kilns. Although all were made of white-firing kaolinic clays, each of the three groups shows a different chemical composition. Furthermore, samples from Nanwa are chemically consistent and restricted in a way analogous to those from Gongxian and Ding, implying that Nanwa whiteware was probably produced in situ. In addition, Gongxian and Ding samples define two separate linear arrays in their 87Rb/86Sr versus 87Sr/86Sr ratios, demonstrating that the clays for these samples are respectively related geochemically. Nanwa samples fall out of the linear arrays of both Gongxian and Ding, indicating that Nanwa whiteware clays were not derived from the same source rock as Gongxian clays, although the two sites are only some 25.5 km apart. In sum, beyond the general similarity of kaolinic clays used at Nanwa, Gongxian and Ding and the geographical proximity of those sites, finer distinctions of elemental and Sr isotopic contents indicate relatively unique chemical characteristics for each group. These traits provide valuable criteria to source traded ceramics of uncertain origins.
Article
For more than 14 years, an IBA facility has been operated in the Louvre for the study of works of art and archaeology. The choice of this equipment derives from the non-destructive character of IBA techniques which has been further strengthened by designing an external beam line permitting the in-air analysis of large or fragile works of art without sampling. Successive improvements have markedly extended the analytical capability of the set-up. The measurements were originally restricted to PIXE–PIGE combination using an external millimetre-sized-beam. By adding a focusing system and an ultra-thin exit window we were able to obtain external beams of protons and alpha particles of respectively 10 and 50 μm in diameter, with low energy straggling. These features have permitted to apply in external beam mode other IBA techniques including RBS, NRA and more recently ERDA. Moreover, elemental maps can be drawn in PIXE and PIGE modes by mechanically scanning the sample under the fixed beam within a lateral range much larger than conventional nuclear microprobes. This facility is used for both short investigations at the request of museum curators and extensive research works in art history and archaeology. Several examples are given to highlight the impact of this tool on cultural heritage.
Article
This paper gives an overview of research in or associated with the pan-European network COST Action G8, which aims at achieving a better preservation and conservation of our cultural heritage by increasing the knowledge of art and archaeological objects through advanced chemical and physical analyses. The paper is focussed on the use of various analytical techniques for the examination of cultural heritage materials and includes research examples on painted works of art, ceramics, glasses, glazes and metals. In addition attention is drawn to advances in analytical instrumentation, for example the development of portable techniques to perform analyses on site, and to the need for collaboration between people directly involved in the field of cultural heritage and analytical scientists.
Article
Full-text available
In a preceding paper dealing with the sourcing of cobalt, we were proposing a trade model for the french glass industry. Since we have extended our study to ceramic glaze. The result we present here are devoted to a selection of sample of broad geographical and chronological origins. These first results confirm those obtained for glass and allow us to spread our model to the whole occidental part of the mediterranean basin. For the oriental part of the Ancient World, they allow some interesting new research projects.
Article
The surface of ceramics is known to be very sensitive to particle beam irradiation, and visible brownish stains are created under bombardment. The cause of the visible damage is probably due to atomic displacements in the material. Whichever the reason, it is important to operationally define under which conditions of irradiation such materials can be safely analysed by ion beams for compositional characterisation. An extensive investigation of this problem has been performed at the external beam PIXE facility of the KN3000 Van de Graaff accelerator in Florence. Both modern materials, prepared according to the ancient tradition, and fragments of original works dating from Renaissance have been employed for the study. The induced damage effects have been measured as a function of beam current, accumulated charge, sample temperature during irradiation. The damage recovery after irradiation has also been studied. Even at room temperature, the induced stain progressively fades out and heating the samples at higher temperatures can eliminate the problem even in a very short time.To be made quantitative, these studies have utilised a preliminary definition of “damage”. This has been assumed as the difference in the measured colour coordinates of the induced stain with respect to the surrounding un-irradiated surface.
Article
The application of Ion Beam Analysis, associated to Scanning Electron Microscopy is examined in connection with an extensive program on structural and chemical analyses of glazed terracotta's from the Italian Renaissance, launched by a French-Italian collaboration in the framework of the European COST-G1 scientific action. The objectives of the collaboration are reviewed. The compatibility of data from different specimen and various laboratories are discussed. Examples of the PIXE and statistical analyses on some artefacts of the "Robbiesche" type, supplied by the Louvre Museum of Paris and the Opificio delle Pietre Dure of Florence, are given to illustrate the performances of IBA in this particular field.
Article
The recently introduced modified Gaussian φ(ϱz) approach is compared with three other correction procedures for quantitative electronprobe microanalysis. On the basis of results obtained for 441 published microanalysis data it is concluded that the modified Φ(ϱz) approach and the Love-Scott correction model perform equally well and are both superior to the Ruste and ZAF correction models. Special attention has been paid to the new atomic number correction proposed by Love et al. It was found to be only marginally better than that of the Φ(ϱz) approach.
Article
An improved correction model for quantitative electron probe microanalysis, based on modifications of the Gaussian ϕ(ϱ) approach, originally introduced by Packwood and Brown, is presented. The improvements consist of better equations for the input parameters of this model which have been obtained by fitting to experimental ϕ(ϱ) data. The new program has been tested on 627 measurements for medium to heavy elements (Z>11) and on 117 carbon measurements with excellent results: an r.m.s. value of 2.99% in the former case and 4.1% in the latter. Finally the new program has been compared to five other current correction programs which were found to perform less satisfactorily.
Article
A series of PIXE analyses has been performed on glazes from terracotta sculptures of the Italian Renaissance and on reference standards. The problems related to the investigation of such heterogeneous materials are discussed and the experimental uncertainties are evaluated, for each element, from the PIXE analysis of standard glasses. Some examples from artefacts coming from Italian collections are given. This research has been conducted in the framework of the COST-G1 European action. (C) 2002 Published by Elsevier Science B.V.
Article
The external beam line of our facility has been recently equipped with the focusing system previously mounted on a classical nuclear microprobe. When using a 0.1 μm thick Si3N4 foil for the exit window and flowing helium on the sample under analysis, a beam spot as small as 10 μm is attainable at a distance of 3 mm from the window. Elemental micromapping is performed by mechanical scanning. An electronic device has been designed which allows XY scanning by moving the sample under the beam by steps down to 0.1 μm. Beam monitoring is carried out by means of the weak X-ray signal emitted by the exit foil and detected by a specially designed Si(Li) detector cooled by Peltier effect. The characteristics of external beams of protons and alpha particles are evaluated by means of resonance scanning and elemental mapping of a grid. An example of application is presented, dealing with elemental micro-mapping of inclusions in gemstones.
Article
The use of an extracted proton micro-beam for the PIXE analysis of glazes is discussed in the context of the growing interest in the creation of an analytical database on Italian Renaissance glazed terracotta sculptures. Some results concerning the frieze of an altarpiece of the Louvre museum, featuring white angels and cherubs heads, are presented.
Article
A second X-ray production database is introduced into GUPIX to complement the existing theoretical (ECPSSR–DHS) database and to provide some estimate of analytical uncertainty due to this aspect of GUPIX; it is based on published compilations and analyses of large numbers of measured K and L subshell X-ray production cross-sections. The two databases are compared through analysis of single-element standards and standard reference materials. Good agreement is observed for the case of K X-rays. In contrast, neither the theoretical nor the “reference” database appears to be entirely satisfactory in the case of L X-rays. New work is required on L subshell X-ray production cross-sections using protons. The tools in GUPIX for film thickness determination are expanded, and tested using the two alternative databases.
Article
The first full account of the Guelph software for fitting PIXE spectra and deriving elemental concentrations is presented. The entire data base has been updated since the program was first reported. Some of the less standard procedures used are discussed in detail; these include the approach to error estimation, the ability to define an element in a thick specimen as a bulk or surface constituent, the ability to redefine the principal line of an element's X-ray spectrum and safeguards against premature elimination from the fit of elements having low concentration. In addition to peak areas, element concentrations and corresponding errors, the program provides limits of detection and a measure of the depth analysed for each element.
The Guelph PIXE software package II, Nuclear Instruments and Methods in
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Les della Robbia, sculptures en terre cuite émaillée de la Renaissance italienne
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Una pala in terracotta invetriata di produzione robbiana: metodi integrati di indagine e restauro
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Study of Italian Renaissance sculptures using an external beam nuclear microprobe
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L’analyse des glacures archeologiques
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Una pala in terracotta invetriata di produzione robbiana: metodi integrati di indagine e restauro
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