The altarpieces of Della Robbia atelier in Marche region: investigations on technology and provenance

Dissemination of Della Robbia glazed terracotta in the Marche (Italy) region started from the third decade of the 16th century. Numerous altarpieces, some of which no longer exist, document this artistic production. The protagonists of this diffusion phase were two of Andrea Della Robbia’s sons, Marco (Fra Mattia) and Francesco (Fra Ambrogio). This paper shows the results of the scientific investigations carried out on constitutive materials of different altarpieces located in South Marche belonging to the Fra Mattia’s production: the Coronation of Virgin between Saints Rocco, Sebastian, Peter martyr and Antonio abbot, dated back to 1527–1530, located in the collegiate church of S. Maria Assunta in Montecassiano; the Annunciation, dated back to 1520, placed in the church of S. Maria del Soccorso in Arcevia; the fragmentary Crowned Madonna and saints altarpiece, probably realized after 1531, today preserved in Civic Museum of Ripatransone. The first altarpiece was made in Montecassiano using two different assembling or production techniques: the external part of the lunette and the pillar strips are made of glazed polychrome terracotta, while the altar step and the internal part are an interesting and uncommon example of polychrome painted terracotta. The provenance of the glazed Arcevia altarpiece is not clear yet: some historians hypothesize a local manufacture of Fra Mattia and some others a Roman or Florentine production. The remaining parts of Ripatransone altarpiece are partially glazed and partially not coated perhaps because they were unfinished and not yet painted. Clay body samples collected from the above mentioned altarpieces were investigated using different analytical techniques (OM, XRD, XRF, PIXE) to point out differences in chemical and mineralogical composition and to determine if the altarpieces were made by using local raw clay materials or other clays from Tuscany or Campania as in the Della Robbia previous production. A comparison has also been made with literature data on the Della Robbia terracotta masterpieces. From the chemical point of view, the clay bodies show a good compositional homogeneity and result calcium and iron-rich according with the raw local materials. The presence of gehlenite, pyroxenes, and hematite and the incomplete decomposition of clay minerals indicate that firing for all different terracotta parts occurred in a thermal range between 800 and 950 °C, mostly in oxidizing conditions.     

Variations in the IR spectra of yellow ochre due to mixing with binding medium and drying

ATR-FTIR spectroscopy is used to analyze the interaction of yellow ochre with a binding medium (linseed oil) and other pigments (orpiment and azurite). Spectra of four different samples of ochre are compared. Variations in the IR spectra of ochre resulting from drying it on various substrates are detected. Changes in spectra of the linseed oil upon its drying are analyzed.     

Analysis of mural paintings using in situ non‐invasive XRF,FTIR spectroscopy and optical microscopy

An analytical protocol consisting of X‐ray fluorescence spectroscopy, optical microscopy and Fourier transform infrared spectroscopy was used to study the origin and the nature of the materials (pigments, binders and coating preparation) of the Fundenii Doamnei church mural paint from Bucharest. The main interest of the present study consisted in the original votive paint from narthex, painted in 1757 in a secco technique. During analysis, an unexpected pigment in the votive paint could be detected by the combined analytical techniques: ultramarine blue. Along with this pigment, the presence of gypsum binder based on egg and flax seed oil could also be evidenced. These results demonstrated a secco execution technique of the votive paint and also the presence of a restoration treatment. Moreover, during the present study, the components of the preparation layer and the constitutive pigments from both 1699 and 1757 years mural paints have been analyzed. Hence, the following pigments could be identified: vermilion, azurite, cinnabar, lead white, ochre, natural umber and gold, by using the combination of the analytical techniques. The novelty of our results consists in detecting the composition of the materials used in this church painting (fresco and a secco) during these 254 years since its first restoration. The results of these investigations pointed to the suitability of the non‐destructive and semi‐destructive analytical techniques in the complex characterization of the paints realized in different techniques, at different periods. Copyright © 2013 John Wiley & Sons, Ltd.     

Heaven and Earth – ‘Madonne col Bambino’ and ‘Rustiques figulines’

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. PACS 82.80.-d; 81.05.Je; 61.43.Fs     

Raman Characterization of Pigments in Painted Beams and a Wall Painting Discovered in the San Francisco Church in Santiago,Chile

A material characterization of two artworks discovered in the San Francisco Church, Santiago, Chile, was performed using micro-Raman spectroscopy. Structural painted beams and a wall painting that belong to the same time period, between the end of the 17th and 19th centuries, were analyzed. The cross-section samples of both artworks were characterized and animal protein was identified in the ground layer in both cases. The supporting material of the beams was identified as cypress wood, and a rag paper layer was used as a base for the paint layer, which is composed mainly of a white ground layer on which the color was subsequently added; the yellow pigments are orpiment and chrome yellow; the green color probably arises from a mixture of orpiment, red lead, ultramarine blue, and calcite. A complete analysis of the materials using complementary techniques such as microchemistry and optical microscopy indicates that the mural was painted using a mixed technique and that organic and inorganic pigments were used. The identification of the synthetic pigment ultramarine blue in some blue areas of the wall revealed a modification of the wall painting in the 19th century; dark blue areas resulted from a mixture of indigo, palygorskite, and lazurite.     

Analytical study of polychromy on exterior sculpted stone

A complete study on the remnants of the polychromy in the main entrance portal of Saint Paul's church (16th century, Úbeda, Spain) has been carried out using Raman microspectroscopy in combination with optical microscopy and scanning electron microscopy with energy dispersive X‐ray spectroscopy (SEM‐EDX). The polychromy in red areas showed the superposition of two well‐defined pictorial layers. The first one (probably original) was composed of cinnabar, red lead and hematite over a preparation coating containing calcite, gypsum and lead white. The second red pictorial layer was mainly constituted by cinnabar and was over a thicker preparation coating. Green samples showed a single pictorial layer over the weathered stone. The high fluorescence background made the examination of the latter samples extremely difficult by means of Raman microspectroscopy. SEM‐EDX detected abundance of copper and chlorine, and a detailed inspection of Raman spectra revealed the presence of a copper hydroxychloride, analogous to the naturally occurring mineral atacamite. Azurite remnants of the original polychromy were only found in the cracks of mortar joints. Alteration products like calcium and copper oxalates were also widely distributed in this layer. Copyright © 2009 John Wiley & Sons, Ltd.     

Non‐invasive approach in the study of polychrome terracotta sculptures: employment of the portable XRF to investigate complex stratigraphy

In the field of conservation science, in situ non‐invasive analytical techniques are widely used to investigate polychrome surfaces as frescoes, mural or easel paintings. Indeed, these techniques allow achieving information on materials composition and they often reduce the micro‐sampling. In this work, in situ non‐invasive techniques have been used to study a complex system, terracotta polychrome sculptures. The presence of the priming, the numerous painted layers and the ground layer spread on a porous material substrate are the main features of these sculptures; therefore, their study requires a scientific approach based on results obtained by different analytical techniques. In order to evaluate potentialities and limitations of the non‐invasive approach to this complex case, the results of energy‐dispersive X‐ray fluorescence (EDXRF), spectrophotometry and optical microscopy have been compared with the data achieved by laboratory analytical investigation as optical and scanning electron microscopy, energy‐dispersive X‐ray microanalysis and Raman spectroscopy. In particular, XRF data collected on several polychrome terracotta are here re‐examined on the basis of the results obtained by laboratory techniques. Even if, in some cases, portable XRF may induce to a wrong interpretation of the stratigraphy, it can be considered a suitable instrument for a preliminary diagnostic campaign of terracotta polychrome sculptures. Copyright © 2011 John Wiley & Sons, Ltd.     

北京故宫养心殿燕喜堂及西围房建筑彩画的分析研究——一种检测颜料和胶结物的集成检测方法

北京故宫是现存规模最大、保存最完整的木结构古建筑群。2015年底,故宫养心殿启动研究性保护修缮工程,燕喜堂是养心殿的后殿西耳房,是此次维修的重点对象之一。彩画是古建筑的重要组成部分,不仅具有美化装饰的作用,更有对木材的防腐保护功能。为了能更好地辅助燕喜堂及西围房建筑彩画的保护与修复,需要对彩画原始材料以及工艺进行检测研究。使用一套集成检测方法：包括样品横截面分析、扫描电子显微镜背散射及能谱技术、拉曼光谱技术、荧光染色法、酶联免疫法、免疫荧光法以及热裂解气相色谱法,分析了故宫养心殿燕喜堂及西围房建筑彩画样品的颜料、沥粉、胶结材料的成分,以及结构关系。结果表明燕喜堂西围房使用的颜料有朱砂、铁红、群青、石青、石绿以及副氯铜矿型铜绿;沥粉的无机组成为石英、滑石、白垩或白云石。胶结材料检测结果发现彩画地仗层中普遍掺加了桐油,颜料层中掺加了动物胶。梁上彩画除了表面图案,地仗层底部还有一层朱砂颜料,同时地仗层内部也不规则地发现朱砂颜料。此外,表层红色颜料通常由两层颜料组成,内层的显色成分是铁红和朱砂,颜料颗粒直径1 μm左右,外层颜料由朱砂组成,颜料颗粒大小不一,直径1～30 μm范围内。上述检测结果不仅可以部分看出燕喜堂及西围房建筑彩画的工艺特征,也表明该集成检测方法可行、所需样品量少,是一种经济实用的彩画文物检测方法。     

Della Robbia blue glaze: micro‐Raman temperature study and X‐ray fluorescence spectroscopy characterization

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 Co Ni Cu Zn 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.     

西藏拉萨大昭寺转经廊壁画颜料的拉曼光谱分析

利用显微激光拉曼光谱仪对大昭寺转经廊壁画颜料进行了分析。结果表明,壁画使用的红、黄、蓝、绿和白色颜料有朱砂、铅丹、甲苯胺红、雌黄、铅铬黄、铁黄、石青、群青、石绿、水胆矾、巴黎绿、菱镁矿、立德粉和方解石。首次发现壁画中使用了合成有机颜料甲苯胺红。检测分析结果提供了准确可靠的资料,有助于清晰认识不同时期壁画绘制和修复所使用颜料成分。     

唐代苏同家族墓天王俑彩绘的光谱分析

天王俑是中原地区的达官贵人墓葬的镇墓俑,是唐墓葬冥器中重要的一种神煞俑。为探究天王俑彩绘颜料的组成元素以及彩绘工艺,使用X射线荧光光谱分析了陕西省咸阳市渭城区苏同家族墓KTJ-2019-019M2、 KTJ-2019-019M3坑出土的天王俑彩绘区域的元素组成。分析结果表明陶俑表面金色贴片主要为金箔(Au);红色颜料的组成元素则是Hg、 S以及少量的Pb、 P;蓝色颜料和绿色颜料的组成元素均为Cu,白色颜料的组成元素为P、 S、 Pb。使用拉曼光谱对彩绘颜料层的鉴定物相,使用拉曼光谱分析技术对彩绘层分析结果确定了红色颜料的主要组成物相为朱砂(HgS)和铅丹(Pb₃O₄)的混合颜料;蓝色颜料的主要组成物相为石青;绿色颜料的主要组成物相为石绿;白色颜料的组成物相可能为铅白。进一步使用XRF面扫描技术分析了天王俑的彩绘工艺,解析金、红、蓝、绿色区域的组成元素位置,发现陶块样品中的M₂-1金色陶块、 M₃-1白色陶块、 M₃-2红色陶块、 M₃-3蓝色陶块、 M<...     

A critical analysis of the application of EDXRF spectrometry on complex stratigraphies

In this work, the potentialities and limits of the investigation by portable energy‐dispersive X‐ray fluorescence (XRF) of complex polychrome stratigraphies are discussed. Data are affected by the mutual influence effects of the chemical elements that characterize mineral pigments, by the sequence and the thickness of the paint layers in the stratigraphies and by the size of pigment grains. Sequences of pictorial layers, which produce the typical stratigraphy of cold‐painted terracotta and wooden sculptures, have been prepared and then analysed by means of two portable X‐ray spectrometers: Innov X Systems Alpha 4000 (Tantalum X‐ray tube, 40 kV and 7 µA) and Assing Lithos 3000 (Molybdenum X‐ray tube, 25 kV and 300 µA). For each layer of pigment, the XRF spectrum was acquired and the areas of K and L peaks of characterizing elements were calculated. Moreover, the thickness of the layers was determined using XRF data following an algorithm already shown and the values have been compared with those measured on polished cross sections observed by optical microscope in reflected light. Copyright © 2011 John Wiley & Sons, Ltd.     

唐卡主色矿物颜料光谱分析

唐卡作为一件艺术品,具有较高的历史价值和艺术价值。对唐卡的矿物颜料进行鉴别分析,对唐卡的鉴定、修复、数字化存档、再现等具有非常重要的意义。该研究对唐卡主色矿物颜料进行体系性的光谱分析,选用唐卡绘制过程中5种主色常用的矿物颜料,深入分析矿物颜料的可见光、近红外、短波红外光谱特征产生机理,总结了不同色系矿物颜料可见光、近红外、短波红外谱段光谱特征。通过分析同一矿物颜料粉末、调和骨胶颜料以及颜料上布色卡光谱特征,发现粉状颜料调和骨胶后,反射率整体下降,在1 447和1 928 nm附近出现两个水的强吸收特征。而当骨胶溶物涂绘上布后,随着膏状颜料中水分的减少,上述两个吸收特征均变弱,个别颜料在1 447 nm处的吸收特征甚至消失。因此,矿物颜料粉末和颜料上布色卡光谱极为接近,可以在后期的唐卡颜料分析中直接利用唐卡矿物颜料粉末光谱进行匹配分析。唐卡红色矿物颜料为朱砂,矿物成分主要为HgS,其光谱在可见光波段先降后升,500 nm附近形成一个较深的吸收特征,且吸收峰较宽（430～530 nm）,红光谱段附近反射率急速升高,近红外波段反射率变化较为平直,在1 940和2 250 nm附近有弱吸收特征。唐卡黄色矿物颜料主要有三种：土黄（雄黄、雌黄）,赭石及金箔,主要成分分别为硫化砷、氧化铁及金。其特征光谱在可见光谱段集中在400～500 nm之间,不同颜料的吸收特征位置和吸收深度均不同。赭石在近红外波段的反射率整体较低,且860 nm附近还出现了吸收特征;而雄黄、雌黄和土黄则在近红外和短波红外谱段表现出反射率较高且波形平直,在1 890和2 230 nm附近有弱吸收特征;金箔在可见光波段的吸收特征窄浅,可作为区分的依据。唐卡蓝色矿物颜料为石青,主要矿物成分为蓝铜矿,其光谱在500～1 000,1 500,2 040,2 285和2 350 nm附近均有较强吸收特征,而在1 885和1 980 nm处有弱吸收特征。唐卡绿色矿物颜料为石绿,主要矿物成分为孔雀石,其光谱在550～1 000 nm有较强的宽吸收特征,在2 270和2 350 nm有明显吸收特征。尽管石青和石绿主要矿物成分皆为碳酸铜,但石绿在900～1 900 nm红-近红外谱段反射率增加较缓,1 500 nm无吸收特征,可以作为区分石青和石绿的依据。唐卡白色矿物颜料为砗磲和白土,主要矿物成分分别为碳酸钙和高岭土。在可见光谱段范围,砗磲在370 nm有弱吸收特征,而白土则在370和730 nm处有两个明显的吸收特征,可作为区分。在短波红外和近红外谱段,白土在1 425,1 930和2 230 nm均具有明显吸收特征,砗磲则在1 930和2 320 nm有明显吸收特征,1 440 nm处吸收特征较弱。且同种矿物颜料粉末,矿物粉末颗粒越大,颜料颜色越深,其光谱特征反射率越低。     

An investigation of a unique group of painted silk banners from a Polish collection

Historic textiles represent a very important part of our cultural heritage. This research focused on the evaluation of a group of unique 16th century banners painted on silk. The banners were examined by Raman spectroscopy and X‐ray fluorescence spectrometry. The measurements were performed to characterize the pigments and materials used, in order to establish the most adequate display methods. Pigments typical of the Renaissance period such as azurite, lead tin yellow, yellow ochre, vermilion, red lead, red ochre, lead white and charcoal were found. Because some of the detected pigments are sensitive to anoxic atmospheres, a microclimate display system was selected as the most adequate option for the safety exhibition. Copyright © 2017 John Wiley & Sons, Ltd.     

Portable XRF study of pigments applied in Juan Hispalense’s 15th century panel painting

Several medieval paintings and polychrome sculptures have been analysed in the frame of a collaboration between the Fine Arts Museum of Seville and the National Centre of Accelerators, dedicated to a non‐destructive study of artworks that belong to the wide museum’s collection. Among the oldest artworks in the collection is the panel painting Archangel St. Michael attributed to Juan Hispalense, one of the first painters in the 15th‐century Seville known by name. The panel was analysed by a portable X‐ray fluorescence (XRF) to get more information about the pigments applied and to identify possible later interventions. The results showed that the pigments were those commonly used in that period. Lead white was found in the preparation of the painting and in colour layers. For yellow colour, yellow ochre was used, while for the red one, the painter usually mixed red earth and vermillion. Blue pigment is azurite, while the copper‐based green one could not be determined more specifically by XRF. Brown colour is made with yellow ochre and organic black or, in some cases, umbra. Black pigment is probably bone or ivory black. Many decorative parts of the panel are gilded, which were confirmed by Au peaks. Later interventions were carried out on the base of Ti–Zn white mixed with earth pigments, while for green areas such as Archangel's wings also chrome green was applied. The research is part of a larger study which is still going on, whose aim is to gain more knowledge about the 15th‐ and 16th‐century Spanish painting and polychromy. Copyright © 2011 John Wiley & Sons, Ltd.     

“钟离君柏”墓出土彩绘陶器颜料的光谱分析

利用拉曼光谱结合X射线衍射物相检测方法,对安徽蚌埠双墩春秋中晚期“钟离君柏”墓出土彩绘陶器颜料的物相结构进行了分析测定。结果表明,陶器表面的红色、黄色和黑色颜料皆保存较好,未发生明显变化,分别是无机矿物朱砂(HgS)和针铁矿(α-FeO(OH))及炭黑。同时,拉曼光谱与X射线衍射分析的结果都显示红色颜料朱砂的组成物相单一,不含天然朱砂的伴生矿物石英,且其晶粒尺寸可能在纳米范围,应是由人工合成或经过古人的加工、纯化处理。针铁矿的发现表明春秋时期该矿物己被用作黄色颜料,这是目前己知的针铁矿作为黄颜料使用的最早的实例。     

A multi-analytical approach for the study of the pigments used in the wall paintings from a building complex on the Caelian Hill (Rome)

In the present study, shards from Roman wall paintings (from the end of the first century to the fourth century A.D.) decorating the domus below the Basilica of SS. John and Paul on the Caelian Hill (Rome), were analyzed in order to identify the pigments used. The analytical techniques employed for the characterization of the pigments were the scanning electron microscope coupled with an energy dispersive spectrometer (SEM-EDS) and infrared spectroscopy (ATR and micro ATR). While SEM-EDS allowed to perform a qualitative analysis of the material, by FT-IR chemical species have been identified. The pigments identified were those mentioned in the literature for the Imperial Roman fresco painting: different types of ochre (yellow and red), mixtures containing lead, green earths and precious pigments such as cinnabar and Egyptian blue. They were often used as mixtures and the use of the most valuable pigments (cinnabar and Egyptian blue) were found in the most ancient rooms.     

Klimt artwork (Part II): material investigation by backscattering Fe-57 Mössbauer- and Raman- spectroscopy,SEM and p-XRF

In a rediscovered Klimt-artwork “Trompetender Putto” material tests have been conducted. We report studies on different points of the painting. The spots are of different colors, mainly taken in spots of the painting not restaurated. MIMOS II Fe-57 Mössbauer spectroscopy revealed mainly haematite and nano particle oxides in red and red/brown colors. Brown colors also contain crystallized goethite. In brown/ochre colors the same pigments as in brown colors are observed, but there is less quantity of goethite and more quantity of haematite. The green colors show Fe-rich clays, like celadonite or glauconite and or lepidocrocite as main component. Raman spectroscopy revealed cinnabar in red colors of the Scarf; and massicot in brown/ochre points, i.e. in the Left Wing of the “Putto”. With scanning electron microscopy, various layers of the original and of overpainting could be recognized. The investigations of sample 1 show three layers of colored materials, which were identified as zinc-white, cinnabar and galena as well as carbon compounds. In sample 2 four layers could be detected. These are identified (bottom to top) as gypsum and lead-white (layer 1), zinc-white (layer 2), lead-white and cinnabar (layer 3) and titanium-white (layer 4). The elementary composition was examined with the portable X-ray-fluorescence analysis for qualitative manner at different points.