A study of smalt and red lead discolouration in Antiphonitis wall paintings in Cyprus

The present analytical study focuses on the degradation phenomena observed in fifteenth century wall paintings of the Christ Antiphonitis monastery in Cyprus. Examination of ten fragments by means of optical microscopy (OM), scanning electron microscopy (SEM/EDS), μRaman and FTIR spectroscopy revealed smalt discolouration and loss, and transformation of red lead from orange Pb₃O₄ to black PbO₂. The chromatic changes have affected the aesthetic effect of the paintings insofar as these pigments were extensively used. The mechanisms of smalt weathering, i.e. leaching of alkali and formation of micro-cracks, are interpreted in relation to its chemical composition and to the aggressive environmental conditions. In addition, it is assumed that red lead degradation may have been induced not only by the effect of temperature, light and humidity but also by the presence of chlorine salts. These phenomena of pigment alteration and loss underline the unsuitability of smalt and minium on wall paintings, regardless of the painting technique (fresco, fresco-secco, secco).     

Mechanisms of CVD diamond nucleation and growth on mechanically scratched Si(100) surfaces

The diamond nucleation has been studied on scratched Si(100) both by surface analyses (XPS, AES, ELS) and microstructural probes (AFM, SEM). Two pathways for diamond formation and growth are detected: A seeding pathway occurs by direct growth from part of diamond seeds left by the mechanical pretreatment. Not all of these seeds however are prone to diamond growth as they can be either dissolved or carburized. A nucleation pathway occurs through a stepwise process including the formation of extrinsic (pretreatment) or intrinsic (in situ) nucleation sites, followed by formation of carbon-based precursors. It is believed that nucleation sites could be either grooves of scratching lines or protrusions produced by etching-redeposition. The size of these protrusions is not larger than 100 nm. On top of these protrusions as well as on the bare substrate, a thin layer of silicon carbide rapidly forms and DLC carbon likely. This complex process on top of protrusions may constitute carbon-based embryos for further diamond nucleation. Received 21 December 1998     

X射线光谱在文物无损分析中的研究进展

文物遗存是人们认识历史发展的重要依据,通过对它们的相关研究可以了解古人的生存方式、生产技能、人与自然的关系等。X射线光谱（X射线荧光光谱和X射线吸收精细结构谱）作为重要的无损分析方法,可以用来研究物质内部元素组成和特定元素近邻结构等信息,为文物的保护研究和价值认知等提供支撑,目前被广泛应用于各种古代物质遗存的研究工作中。对近些年X射线光谱在不同类型文物研究中的应用情况进行简要的总结和介绍。总的来看,X射线荧光光谱技术在古陶瓷、油画、青铜器的断源断代研究方面发挥了重要作用,而基于X射线荧光光谱的成分数据库建设和X射线吸收精细结构谱在文物研究相关问题的深度介入是应用实践中的难点,也应是未来研究工作中的重要课题。     

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。     

广元千佛崖石窟石刻彩妆颜料的分析

四川省广元千佛崖石窟是四川境内最大的石窟寺和摩崖造像群,承载着古代社会的历史信息,对研究当时的政治、文化和社会生活意义重大。千佛崖石窟在自然环境因素的长期作用下,目前受到多种严重病害的侵蚀,亟待保护。为了获取石刻彩妆的成分与工艺信息以支撑彩妆的保护工作,应用X射线衍射分析、剖面显微分析、扫描电镜能谱分析、激光拉曼光谱分析等方法,对广元千佛崖8处洞窟的已脱落彩妆颜料层样品进行了分析。X射线衍射分析鉴定出了铁红(Fe₂O₃)、朱砂 (HgS)、铅丹(Pb₃O₄)、炭黑等颜料成分,以及铅白 (PbSO₄)、石膏(CaSO₄·2H₂O)、长石、二氧化硅等打底层和岩体的组分,验证了样品脱落的原因是岩体的劣化。剖面显微分析和扫描电镜能谱分析表明,不同洞窟的彩妆制作工艺有区别,有的颜料直接施加在岩体表面,有的则在颜料层和岩体间有一层主要为硫酸铅的打底层;样品表面蓝绿色颜料的含量很少,仅通过激光共聚焦显微拉曼光谱成功地识别出来,其鉴定结果为蓝铜矾[Cu₄SO₄(OH)₆·2H₂O]。蓝铜矾作为颜料使用的报道很少。由于其矿物含量较少但分布广泛,古代一般不将其分离出来单独使用,而人工合成的碱式硫酸铜类颜料布勒门绿（Bremen green）出现于18世纪-19世纪,如果有纯碱式硫酸铜单独使用的情况出现,就意味着有近现代重绘的可能性,将有助于彩绘类文物保存历史的判断。该研究不仅为千佛崖石刻彩妆的保护提供了依据,丰富了文化遗产中使用蓝铜矾颜料的案例,更对彩妆的保存历史研究有潜在价值。     

Degradation of azurite in mural paintings: distribution of copper carbonate, chlorides and oxalates by SRFTIR

This article illustrates the analysis by synchrotron micro-analytical techniques of an azurite painting presenting greenish chromatic degradation. The challenge of the experiments was to obtain the spatial distribution of the degradation products of azurite. Copper hydroxychlorides, carbonates and copper oxalates have been mapped by SR FTIR imaging of cross sections in transmission mode. To complement the information, Py/GC/MS and GC/MS techniques were applied in order to characterize the binding media and organic materials present as well as their degradation products. Results contribute to a better understanding of the decay of blue areas in ancient paintings not only from the particular point of view of azurite weathering, but also by adding information regarding the oxalates’ formation and their distribution in painting samples. Synchrotron radiation demonstrates its capability for the mapping in painting cross sections.     

Electrochemical deposition of cerium on porous silicon to improve photoluminescence properties

In this work, we present results for Cerium (Ce) doping effects on photoluminescence (PL) properties of porous silicon (PS). Cerium was deposited using electrochemical deposition on porous silicon prepared by electrochemical anodization of P-type (100) Si. From the photoluminescence spectroscopy, it was shown that porous silicon treated with cerium can lead to an increase of photoluminescence when they are irradiated by light compared to the porous silicon layer without cerium. In order to understand the contribution of cerium to the enhanced photoluminescence, energy dispersive X-ray (EDX) spectroscopy, Fourier transmission infrared spectroscopy (FTIR), X-ray diffraction (XRD) and atomic force microscopy (AFM) were performed, and it was shown that the improved photoluminescence may be attributed to the change of Si–H bonds into Si–O–Ce bonds and to a newly formed PS layer during electrochemical Ce coating.     

Study of two large-dimension Murillo's paintings by means of macro X-ray fluorescence imaging,point X-ray fluorescence analysis,and stratigraphic studies

During the recent restoration of two large-dimension paintings by Murillo, entitled “Miracle of the loaves and fishes” and “Moses and the water from the rock of Horeb,” several studies about the materials employed for their execution were carried out. Macro X-ray fluorescence scanning technique was performed on both works complemented by point X-ray fluorescence and stratigraphic analyses, in order to characterize the different components of the paintings (i.e., ground layer, pigments, and binders). The results allowed us to better elucidate Murillo painting technique and his creative process. Ground layer was prepared in the usual fashion of the artist, using earths, calcium carbonate, iron oxide pigments, and white lead. The polichromy is composed of lead white mixed with various pigments, depending on the colour tone to be obtained in the pictorial composition: Red and yellow ochres, vermilion, azurite, smalt, and lead-tin yellow were the main pigments identified during our study. Finally, the presence of previous conservation treatments was evidenced by detecting pigments (zinc white, Prussian blue, etc.) not coeval with the artist palette.     

Classification of lead white pigments using synchrotron radiation micro X-ray diffraction

Lead white pigment was used and synthesised for cosmetic and artistic purposes since the antiquity. Ancient texts describe the various recipes, and preparation processes as well as locations of production. In this study, we describe the results achieved on several paint samples taken from Matthias Grünewald’s works. Grünewald, who was active between 1503 and 1524, was a major painter at the beginning of the German Renaissance. Thanks to X-ray diffraction analysis using synchrotron radiation, it is possible to associate the composition of the paint samples with the masters ancient recipes. Different approaches were used, in reflection and transmission modes, directly on minute samples or on paint cross-sections embedded in resin. Characterisation of lead white pigments reveals variations in terms of composition, graininess and proportion of mineral phases. The present work enlightens the presence of lead white as differentiable main composition groups, which could be specific of a period, a know-how or a geographical origin. In this way, we aim at understanding the choices and the trading of pigments used to realise paintings during northern European Renaissance. PACS 61.10.Nz; 07.85.Qe; 61.43.Gt     

Pigment analysis of Portuguese portrait miniatures of 17th and 18th centuries by Raman Microscopy and SEM‐EDS

Seventeen Portuguese miniature portraits on copper support from the Évora Museum collection (Portugal) were analyzed in situ and nondestructively by Raman microscopy (RM), SEM‐EDS, and stereomicroscopy. This work constitutes a great breakthrough in the study of miniature paintings from the 17^th and 18^th centuries, since the chemical information known about this unique kind of paintings are still scarce, and in particular, this exclusive collection was never been subjected to any physicochemical study. In this work, each portrait was examined in detail in order to characterize the pigments palette used by the miniaturists. The μ‐Raman analysis, in particular, guaranteed an exceptional visualization and good individual identification of small grains of pigments and other constituents of the pictorial layer. Using this technique, 19 compounds were identified, including bluish black covellite, a pigment rarely found in oil paintings. SEM‐EDS was used as an important complementary technique to confirm the chemical nature of some pigments and to identify shell gold (gold dust) in some portraits. Overall, the pigments identified in this large set of old paintings are broadly consistent with those mentioned in the painting treatises of that time or reported in other more modern bibliographic sources. Copyright © 2014 John Wiley & Sons, Ltd.     

Copper blue in an ancient glass bead: a XANES study

The blue colour in ancient soda-lime glasses has been attributed to the presence of copper and/or cobalt but the origin of different shades is not yet fully interpreted. As a contribution to this question, a non-destructive X-ray absorption study at [ _Cu]K-edge was undertaken on the blue (turquoise) layer from a “Nueva Cadiz” type tubular glass bead dated pre-XVII century where copper is the unique colouring agent. Minerals configuring two distinct blue tonalities due to Cu (2+) in similar square coordination were selected as basic model compounds: azurite, which is a classical navy-blue pigment used in ancient wall paintings over plaster, and chalcanthite, displaying exactly the same turquoise-blue tonality of tubular glass beads manufactured since the Egyptian Antiquity. Theoretical modelling of the XAFS spectra was undertaken using the FEFF code. The IFEFFIT software package was used for fitting the calculated spectra to experimental data. EXAFS results are discussed in view of the crystal structures of copper minerals chosen to model the speciation state and structural situation of that element prevailing in the turquoise-blue archaeological glass. Special attention is focused on the difficulties in theoretical modelling [ _Cu]K-XANES spectra of ancient glasses with different colourings. PACS 61.43.Fs; 61.46.+w; 41.60.Ap; 61.10.Ht.     

太平天国侍王府壁画表面修复材料的原位无损FTIR分析

太平天国侍王府壁画是中国南方壁画的典型代表,具有重要的历史、文化和艺术价值。历史上曾对多幅壁画进行过化学保护,部分壁画表面形成了一定厚度的有机物涂层,分析研究壁画保护修复材料成分对于文物保护具有重要的理论和现实意义。由于文物的珍贵性与不可再生性,原位无损分析技术的研究和应用是未来文物分析的发展趋势,基于便携红外光谱仪的反射红外光谱技术是对文物表面材质较为理想的无损分析手段。利用反射傅里叶变换红外(FTIR)光谱对侍王府壁画的地仗层和表面修复材料涂层进行了现场原位无损分析,这在我国古代壁画及其保护修复材料分析中属首次。首先测试了无涂层壁画白色背景位置反射FTIR光谱,并与标准无机矿物光谱比对确定了壁画地仗层成分主要为方解石和生石膏。在此基础上,分析了无涂层和有涂层壁画表面的红外反射特性及地仗层化学成分对表面涂层反射FTIR光谱测试的影响,探讨了应用Kramers-Kronig(K-K)变换处理数据的可行性,确定了K-K变换的应用范围,分析了壁画涂层K-K变换后反射光谱与衰减全反射(ATR)光谱的差异,并通过显微ATR FTIR光谱和热裂解气相色谱质谱联用(Py-GC/MS)技术分析验证了原位反射FTIR光谱测试结果的可靠性,扫描电子显微镜(SEM)测量了涂层厚度,证明不同厚度涂层均能得到可解析的高质量反射FTIR光谱。最终确定侍王府壁画曾使用过聚醋酸乙烯酯、聚二甲基硅氧烷和三甲树脂三种高分子材料进行过表面加固,并得出壁画保存现状和修复材料及涂层厚度有较大关系。证明了基于反射模式的FTIR光谱技术能准确有效地获取文物表面有机物和部分无机物成分信息。该方法对表面有机涂层尤为敏感,是壁画类文物较为理想的无损分析方法,在壁画保护研究领域具有十分广阔的应用前景。同时,该研究弥补了我国壁画类文物表面有机物原位无损分析的不足,为该领域研究提供了一条新思路。     

Superhydrophobic alumina surface based on stearic acid modification

A novel superhydrophobic alumina surface is fabricated by grafting stearic acid layer onto the porous and roughened aluminum film. The chemical and phase structure, morphology, and the chemical state of the atoms at the superhydrophobic surface were investigated by techniques as FTIR, XRD, FE-SEM, and XPS, respectively. Results show that a super water-repellent surface with a contact angle of 154.2° is generated. The superhydrophobic alumina surface takes on an uneven flowerlike structure with many nanometer-scale hollows distribute in the nipple-shaped protrusions, and which is composed of boehmite crystal and γ-Al₂O₃. Furthermore, the roughened and porous alumina surface is coated with a layer of hydrophobic alkyl chains which come from stearic acid molecules. Therefore, both the roughened structure and the hydrophobic layer endue the alumina surface with the superhydrophobic behavior.     

Joaquin Sorolla's pigment characterisation of the paintings ‘Vision of Spain’ by means of EDXRF portable system

In this work, portable energy dispersive X‐ray fluorescence (EDXRF) spectrometry was employed to the characterisation of the palette used by the Spanish artist Joaquín Sorolla (1863–1923) in the paintings ‘Vision of Spain’, a set of 14 oils on canvas painted by Sorolla between 1911 and 1919 by order of Mr Archer Huntington to decorate the library of the Hispanic Society of America (HSA) in New York. The analyses, sponsored by BANCAJA and provided by the HSA, were carried out in situ, prior to the cleaning and restoration process, while the paintings hanging on the walls of the library of the HSA. The results revealed that the paintings were made over different priming layers containing, respectively, lead white, zinc and barium compounds, lead white mixed with zinc white or lead white mixed with zinc and barium compounds. The EDXRF analyses of coloured zones identified up to 29 inorganic pigments and, in some cases, the probable use of organic pigments. Sorolla used traditional pigments as earth pigments, lead white, vermillion, etc., and modern pigments as cadmium yellow, zinc white, cobalt‐based blue, chromium‐based green, manganese‐based violet, etc. These results provide valuable information about the Sorolla's palette during the last stage of his life. Copyright © 2011 John Wiley & Sons, Ltd.     

Recent applications and current trends in Cultural Heritage Science using synchrotron-based Fourier transform infrared micro-spectroscopy

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-FTIR) is one of the emerging techniques increasingly employed for Cultural Heritage analytical science. Such a technique combines the assets of FTIR spectroscopy (namely, the identification of molecular groups in various environments: organic/inorganic, crystallized/amorphous, solid/liquid/gas), with the extra potential of chemical imaging (localization of components + easier data treatment thanks to geographical correlations) and the properties of the synchrotron source (namely, high brightness, offering high data quality even with reduced dwell time and reduced spot size).This technique can be applied to nearly all kind of materials found in museum objects, going from hard materials, like metals, to soft materials, like paper, and passing through hybrid materials such as paintings and bones. The purpose is usually the identification of complex compositions in tiny, heterogeneous samples.Recent applications are reviewed in this article, together with the fundamental aspects of the infrared synchrotron source which are leading to such improvements in analytical capabilities. A recent example from the ancient Buddhist paintings from Bamiyan is detailed. Emphasis is made on the true potential offered at such large scale facilities in combining SR-FTIR microscopy with other synchrotron-based micro-imaging techniques. To cite this article: M. Cotte et al., C. R. Physique 10 (2009).     

Mössbauer study of rock paintings from minas gerais (Brazil)

Four samples of a wall containing rock paintings have been studied by Mössbauer spectroscopy in combination with optical microscopy analysis and X-ray diffraction. Hematite and goethite were identified as the pigments responsible for the colors and the mineral tinsleyite, as the principal component of a light pink layer that is present in some parts of the wall.     

Nanoindentation and the micromechanics of Van Gogh oil paints

Understanding the mechanical properties of ancient paintings is a major issue for conservation and restoration. One strategy is to measure the mechanical properties of reconstructed paints: however, the aging process is poorly known, so it is also desirable to measure mechanical properties directly on ancient paint samples. Using nanoindentation, we have characterized submillimetric samples recovered from restoration of two Van Gogh paintings and compared the results with reconstructed paint samples. We demonstrate that the reduced modulus and hardness of historical paints can be measured at a very local scale, even differentiating between each paint layer. Our reconstructed paint samples exhibit elastic moduli comparable to values of the literature, but the values measured on the two 19th century paint samples are found to be significantly larger. Similarly, the compositional dependence of the elastic modulus is consistent with literature results for our reconstructed samples while our preliminary results for ancient samples do not readily fall into the same pattern. These results all point out to a significant impact of long term aging, in a manner which is difficult to predict in our present state of understanding. They demonstrate that nanoindentation is a very adequate tool to improve our knowledge of art paint mechanics and aging.     

故宫奉先殿清初彩画颜料成分分析

故宫奉先殿是明清两代皇帝祭祀祖先的家庙,地位仅次于太庙。奉先殿始建于明成祖时期,现存建筑主要建于康熙时期,其上保留了为数不多的清初彩画,是研究清初彩画的珍贵实物。利用显微观察、扫描电子显微镜能谱和激光拉曼光谱分析,对取自奉先殿的彩画颜料进行分析鉴定。结果表明,奉先殿彩画中部分红色和蓝色颜料层存在分层现象,表层颜色鲜艳明亮,中层和下层颜色偏浅,每层所用颜料配方不同。红色颜料有朱砂、铅丹和铁红,绿色颜料均为氯铜矿,蓝色颜料均为石青,用铅白打底。浅色颜料由主显色矿物颜料加入以铅白为主的白色颜料混合调制而成。其中浅红色由铅丹与铅白调和而成,浅绿色由氯铜矿与铅白调和而成。浅蓝色颜料中未发现铅白,但含有大量Al元素和Si元素,推测含有高岭土。浅蓝色颜料有可能是由石青与高岭土调制而成。奉先殿彩画中未发现清晚彩画常用的合成群青、巴黎绿等颜料,反映出奉先殿彩画的绘制年代很有可能就是档案记载的康熙年间,之后未有大修。高岭土作为白色颜料调配浅色颜料在彩画制作中比较少见,奉先殿彩画中高岭土的发现丰富了清代早期彩画颜料制作的资料,具有一定的学术意义。