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.     

Micro-analytical study of interactions between oil and lead compounds in paintings

Oil paintings are complex hybrid materials, made of organic binders associated with inorganic minerals, susceptible to evolving over centuries. In particular, interactions of oil with lead compounds may give rise to the formation of lead soap aggregates, so-called protrusions. This phenomenon is studied here via X-ray and FTIR micro-analysis of an ancient painting dated from 1610. In complement, the synthesis of modern preparations, reconstructed from ancient recipes was assessed. Molecular and atomic images are obtained by combining synchrotron-based FTIR and X-ray fluorescence microscopies. Protrusions are identified in both ancient and modern samples, more particularly, in the ground layer of the paintings, below the colored layer. These observations imply that lead oxide, introduced as a siccative and not as a pigment, may be the element mainly responsible for the protrusions formation, and that this degradation may appear very rapidly on paintings. PACS 87.64.Je; 82.80.Gk; 82.40.Bj     

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。     

European research platform IPANEMA at the SOLEIL synchrotron for ancient and historical materials

IPANEMA, a research platform devoted to ancient and historical materials (archaeology, cultural heritage, palaeontology and past environments), is currently being set up at the synchrotron facility SOLEIL (Saint‐Aubin, France; SOLEIL opened to users in January 2008). The new platform is open to French, European and international users. The activities of the platform are centred on two main fields: increased support to synchrotron projects on ancient materials and methodological research. The IPANEMA team currently occupies temporary premises at SOLEIL, but the platform comprises construction of a new building that will comply with conservation and environmental standards and of a hard X‐ray imaging beamline today in its conceptual design phase, named PUMA. Since 2008, the team has supported synchrotron works at SOLEIL and at European synchrotron facilities on a range of topics including pigment degradation in paintings, composition of musical instrument varnishes, and provenancing of medieval archaeological ferrous artefacts. Once the platform is fully operational, user support will primarily take place within medium‐term research projects for `hosted' scientists, PhDs and post‐docs. IPANEMA methodological research is focused on advanced two‐dimensional/three‐dimensional imaging and spectroscopy and statistical image analysis, both optimized for ancient materials.     

中国古画矿物颜料光谱混合模型初探-以石青和石绿为例

高光谱遥感技术对文物完全无损,适于对中国古画等文物进行颜料的鉴别与分析,但是中国古画中混合颜料不同成分的定量分析仍然是文物颜料分析领域中的难点。针对中国古画中经常出现的混合颜料现象,以石青、石绿两种典型的矿物颜料为例,选用粒度大小相同的两种矿物颜料粉末,按照不同的体积比例精确配比获取颜料样本,然后精确控制实验条件获取其光谱。对混合光谱分别用全约束最小二乘法进行全波段光谱解混,用比值导数解混算法进行单波段光谱解混,然后评定解混精度并对解混结果进行对比分析,探讨这两种矿物颜料的光谱混合模型。实验结果表明,石青、石绿两种矿物颜料的光谱混合从总体上来说非线性混合特征较强,但是在局部某些波段又基本符合线性混合模型,利用这些波段采用比值导数法解混,可以得到远高于全波段解混精度的定量分析结果。     

中国古代艺术品常用矿物颜料的拉曼光谱

拉曼光谱技术在艺术品文物和考古学领域的应用正变得日益重要, 其中对艺术品文物中所使用的颜料的分析是这方面应用的一个重要研究课题, 本文讨论了有关的实验技术, 测量了一些在中国古代艺术品中经常使用的红色、黄色和白色颜料的拉曼光谱, 介绍了相关的背景知识, 并对这些光谱进行了解析, 这些基础数据对于进一步开展对古代壁画、彩塑、雕刻、陶瓷等的拉曼光谱分析有着重要的基础参考价值。     

A prototype for high resolution infrared reflectography of paintings

A new scanner for infrared reflectography of ancient paintings is described. The system is based on an InGaAs focal plane array which automatically scans the image plane of a lens for wide format photography. The device is compact, portable and fast for use in situ.     

Laser cleaning in conservation of stone,metal, and painted artifacts: state of the art and new insights on the use of the Nd:YAG lasers

In the present work the application of laser cleaning in the conservation of cultural assets is reviewed and some further developments on the interpretation of the associated laser-material interaction regimes are reported. Both the state of the art and new insights mainly focus on systematic approaches addressed to the solution of representative cleaning problems, including stone and metal artifacts along with wall and easel paintings. The innovative part is entirely dedicated to the extension of the application perspective of the Nd:YAG lasers by exploiting the significant versatility provided by their different pulse durations. Besides extensively discussing the specific conservation and physical problems involved in stone and metal cleaning, a significant effort was also made to explore the application potential for wall and easel paintings. The study of the latter was confined to preliminary irradiation tests carried out on prepared samples. We characterized the ablation phenomenology, optical properties, and photomechanical generation associated with the irradiation of optically absorbing varnishes using pulse durations of 10 and 120 ns. Further results concern the nature of the well-known problem of the yellowish appearance in stone cleaning, removal of biological growths and graffiti from stones, cleaning of bronze and iron artifacts and related aspects of laser conversion of unstable minerals, removal of calcareous stratification from wall paintings, and other features.     

Multispectral imaging of paintings by optical scanning

In the last few years, there has been a growing interest on multi-spectral imaging as non-destructive technique for painting diagnostics. Providing spectral and colorimetric characterization of the whole paint layer, such a technique is suitable to document the conservation state of an artwork. In this work we present a scanning system for multi-spectral imaging of paintings in the 380–800 nm spectral region, specifically developed to overcome most of the problems related to traditional detection systems based on CCD or Vidicon camera. The device is composed of a spectrometer for contact-less single-point spectral measurements, moved by two orthogonally mounted translation stages. It scans an area of 1 m² with 16 dots/mm² spatial resolution and 10 nm spectral resolution. Spectral reflection factor and tristimulus value measurements were carried out on coloured ceramic tiles and the results were compared to the corresponding certified values. We also present the first application to an ancient painting.     

拉曼微区分析技术在古颜料研究中的应用

拉曼微区分析技术可进行空间分辨的原位无损检测,为其他现代分析技术所不及,文章介绍了这一分析技术在古代文稿、油画、水彩画、壁画、陶等颜料分析中的应用。     

The use of model probes for assessing in depth modifications induced during laser cleaning of modern paintings

The cleaning of over-paint layers is a usual requirement to be met in the conservation of modern paintings. In most cases, acrylics or other related compounds must be removed without affecting the original painting. The elucidation of the extent of any photochemical or structural modification induced to the substrate following laser irradiation is a crucial challenge for the broader implementation of such laser cleaning strategies into the conservation practice. To achieve this, a methodology based on the use of a sensitive photochemical and photomechanical model system is introduced. A probe consisting of a polymeric material (e.g., Paraloid B72) doped with aromatic photo-sensitizers (e.g., POPOP) of known photochemistry and coated with uniform acrylic layer effectively simulates the real case scenario. Following laser irradiation, a variety of spectroscopic techniques including single or multiphoton laser-induced fluorescence and third-harmonic generation are employed for the assessment of any photochemical and structural modification induced in the bulk material. Practical issues related to the laser parameters employed will be presented, and the potential for a more general applicability of this methodology in the laser cleaning of modern paintings will be discussed.     

The use of combined synchrotron radiation micro FT-IR and XRD for the characterization of Romanesque wall paintings

The high analytical sensitivity and high spatial resolution of synchrotron radiation-based techniques, in particular SR-XRD and SR-FT-IR, allows the identification of complex micrometric mixtures of compounds that constitute the different layers of ancient paintings. The reliability of the measurements even with an extremely small amount of sampled material is very high, and this is particularly important when analyzing art works. Furthermore, the micro size (10×10μm for FT-IR and 30 to 50 μm squared spot size for XRD) of the beam enables one to obtain detailed compositional profiles from the different chromatic and preparation layers. The sensitivity of the techniques is high enough for the determination of minor and trace compounds, such as reaction and weathering compounds. We report here the identification of pigments in the Romanesque wall paintings found in situ in the church of Saint Eulàlia of Unha place in the Aran valley (central Pyrenees). During the first centuries of the second millennium numerous religious buildings were built in Western Europe in the Romanesque style. In particular, a great number of churches were built in the Pyrenees, most of which were decorated with wall paintings. Although only a few of these paintings have survived, they represent one of the most important collections of Romanesque art, both for their quantity and quality. A full identification of the pigments, binder, supports, and reaction and weathering compounds has been obtained. The results obtained, in particular aerinite as a pigment, indicate a clear connection between the paintings found in this Occitanian church and the Catalan Romanesque paintings from the south bound of the Pyrenees. PACS 61.10.Nz; 07.85.Qe; 82.80.Gk     

拉曼光谱在考古中的应用

拉曼光谱分析是一种无损快速分析技术,随着显微拉曼光谱仪的不断改进和FT—显微拉曼光谱仪的使用,它已经用于珍贵艺术品、手稿、颜料、古陶瓷和壁画等领域的考古和鉴定研究。本文对这些应用进行了简单概述。     

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。     

Degradation study of XVIII century graffiti on the walls of Chiaramonte Palace (Palermo, Italy)

A systematic investigation of the original materials and the degradation phenomena induced by soluble salts on the wall matrix and on the graffiti of the Inquisition jails of Chiaramonte Palace in Palermo (Italy) was carried out. Built in the XIV century, Chiaramonte Palace was used as Inquisition court during the XV–XVI centuries. The ancient graffiti, recently discovered, represent a unique historical witness of the prisoners that lived during that terrible period. In order to study the nature, the amount and the distribution of the salts in the masonry, stone materials sampled at different depth from the wall matrix and saline efflorescences were analysed. Different physical techniques were used, such as X-ray Photoelectron Spectroscopy, X-ray Fluorescence, Laser Induced Breakdown Spectroscopy, X-ray Diffraction and Ionic Chromatography. Results of the chemical and physical characterisation showed that the main cause of the degradation of graffiti and wall paintings was the presence of soluble salts, such as nitrates, chlorides and sulphates. Traces of oxalates, coming from a previous conservation treatment, were also found. The results obtained by the stratigraphical characterisation of soluble salts in the wall matrix can be used to recommend a procedure based on air humidification at high relative humidity values in order to avoid salt crystallisation and to prevent the crumbling process of the graffiti.     

基于可见光谱的古代壁画颜料无损鉴别方法

矿物颜料是古代壁画显色的物质基础,其可见光谱反映自身物质和物理属性。不同颜料对可见光吸收特性的差异导致光谱曲线形状不同,同一种颜料因粒径等级差异引起光谱曲线幅值的规律性变化。依据矿物颜料上述特性,提出一种基于可见光谱的古代壁画颜料无损鉴别方法,通过光谱归一化方法实现不同粒径等级的同一颜料光谱曲线叠合,去除颜料粒径等级对光谱曲线幅值变化的影响,然后提取表征光谱曲线在各波段增减性和凹凸性的一阶与二阶导数特征,与光谱曲线组合得到颜料物质属性鉴别的光谱组合特征空间,以光谱角和欧式距离为基础构建评价指标,计算待鉴别颜料与数据库参考样本在光谱特征空间中的匹配误差(ME),实现颜料物质属性的鉴别。通过构建矿物颜料平均粒径大小和光谱反射率均值之间关系函数,实现颜料平均粒径大小的鉴别。基于构建的古代壁画常用颜料光谱数据库,以莫高窟壁画为对象,通过非接触式原位无损测量方法测量获得壁画颜料的可见光谱数据,对本文方法进行了验证,并以石绿和青金石颜料的鉴别结果为例,对古代壁画颜料使用技法、不同朝代颜料使用的差异性及原因进行了探讨。该方法将为更加全面深入研究和保护古代壁画提供有效的理论与方法支撑。     

Three fabricated pigments (Han purple,indigo and emerald green) in ancient Chinese artifacts studied by Raman microscopy,energy‐dispersive X‐ray spectrometry and polarized light microscopy

In this study, we analyzed three fabricated pigments from ancient artifacts in China. The purple pigment was obtained from a painted pottery figurine unearthed from the Chu Tombs group of the Western Han dynasty in Xuzhou, Jiangsu Province. The dark blue dye was from silk textiles in the Palace Museum. The green pigment was from decorative paintings on ancient architectures in the Palace Museum. These pigments were analyzed with Raman microscopy (RM), energy‐dispersive X‐ray (EDX) analytic spectroscopy and polarized light microscopy (PLM). By comparing their Raman spectra with standard samples, the primary ingredients of the purple pigment and the dark blue dye were found to be Han purple and indigo, respectively. However, the green pigment could not be identified by RM because of strong fluorescence. It was then confirmed to be emerald green by using EDX analytic microscopy and PLM. We also describe the traditional manufacturing methods of these pigments and their applications on artifacts in Chinese history. Copyright © 2007 John Wiley & Sons, Ltd.     

High-resolution non-invasive 3D imaging of paint microstructure by synchrotron-based X-ray laminography

The characterisation of the microstructure and micromechanical behaviour of paint is key to a range of problems related to the conservation or technical art history of paintings. Synchrotron-based X-ray laminography is demonstrated in this paper to image the local sub-surface microstructure in paintings in a non-invasive and non-destructive way. Based on absorption and phase contrast, the method can provide high-resolution 3D maps of the paint stratigraphy, including the substrate, and visualise small features, such as pigment particles, voids, cracks, wood cells, canvas fibres etc. Reconstructions may be indicative of local density or chemical composition due to increased attenuation of X-rays by elements of higher atomic number. The paint layers and their interfaces can be distinguished via variations in morphology or composition. Results of feasibility tests on a painting mockup (oak panel, chalk ground, vermilion and lead white paint) are shown, where lateral and depth resolution of up to a few micrometres is demonstrated. The method is well adapted to study the temporal evolution of the stratigraphy in test specimens and offers an alternative to destructive sampling of original works of art.