Micro‐Raman spectroscopy analysis of 16th century Portuguese Ferreirim Masters oil paintings

In the present work a set of eight altarpieces of the 16th century (1532–1534), attributed to the Ferreirim Masters (Gregório Lopes, Garcia Fernandes and Cristóvão de Figueiredo), from the Santo António de Ferreirim Monastery (North of Portugal), were analysed by micro‐Raman spectroscopy. For this purpose some samples were taken from the paintings to characterise its artist's ‘school’. It was found that the preparation was made with chalk and gypsum and the palette composed mainly of lamp black, azurite, lead white (mixed with other pigments), lead–tin yellow type I, goethite (the main constituent of yellow ochre), red lead (as under painting), haematite (the main constituent of red ochre) and vermilion. Indigo was detected in one sample. Some derivatives and degradation products were found mainly in the panels subjected to high temperatures during a fire occurred in 1954: a degradation product from massicot or red lead, lead carbonate (dehydrated derivative of lead white), bassanite and anhydrite (hemi‐ and dehydrated forms of gypsum). These results are compared with those of previous total reflection X‐ray fluorescence spectroscopy (TXRF) analyses. Copyright © 2009 John Wiley & Sons, Ltd.     

古壁画、陶彩颜料的拉曼光谱分析

本文利用拉曼光谱对河南班村遗址出土的仰韶彩陶陶彩以及河北磁县湾漳东魏北齐大型壁画墓中的壁画颜料进行了分析,成功的测定出陶彩及壁画颜料的成分。这一研究工作表明,拉曼光谱作为现代技术非常适合于易损和不允许取样的珍贵艺术品颜料的无损分析     

XRF study on the gilding technique of the fresco ‘Crocifissione con Santi’ by Beato Angelico in the San Marco monastery in Florence

This study focused on the gildings of a famous Italian fresco, the Crocifissione con Santi by Beato Angelico, exploiting the XRF spectrometer developed at the LABEC laboratory. This can be considered the first scientific study on the gilding technique on frescoes of Beato Angelico. In order to characterise the original gilding technique and identify restored parts, more than 30 points were analysed in different areas of the wall painting, mostly in halos and decorations. In particular, the main goal was to verify whether Beato Angelico used the composite tin–gold foil, the most common gilding technique during the Italian Renaissance. This study allowed discriminating the original from the restored gildings, and to characterise the layers in both cases, by means of iron Kα/Kβ ratio. Copyright © 2015 John Wiley & Sons, Ltd.     

Interpreting technical evidence from spectral imaging of paintings by Édouard Manet in the Courtauld Gallery

The paintings by Édouard Manet in The Courtauld Gallery Déjeuner sur l'herbe (1863–68), Marguerite de Conflans en Toilette de Bal (1870–1880), Banks of the Seine at Argenteuil (1874), and A Bar at the Folies–Bergère (1882) were investigated for the first time using a range of non-invasive in situ analyses. The aims of the study were to investigate the painting techniques and materials used for this group of works and to critically evaluate the technical evidence derived from the integrated use of imaging techniques and portable spectroscopic methods in this context. The paintings were investigated by means of macro X-ray fluorescence (MA-XRF), reflection spectral imaging, portable UV–Vis–NIR spectroscopy, portable Raman spectroscopy, and reflection FTIR. MA-XRF and reflection spectral imaging allowed visualising elements in the compositions that were not visible using traditional methods of technical study. For example, MA-XRF analysis of Déjeuner sur l'herbe revealed elements of the development of the composition that provided new evidence to consider its relationship to other versions of the composition. The study also highlighted questions about the interpretation of elemental distribution maps and spectral images that did not correspond to the reworking visible in X-radiographs. For example, in A Bar at the Folies–Bergère Manet made numerous changes during painting, which were not clearly visualised with any of the techniques used. The research has wider implications for the study of Impressionist paintings, as the results will support technical studies of works by other artists of the period who used similar materials and painting methods.     

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).     

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.     

Characterisation of ancient Roman wall-painting fragments using non-destructive IBA and MA-XRF techniques

Scientific investigation is very important in studies addressing issues of archaeological and historical objects. Ion beam analysis (IBA) and macro X-ray fluorescence (MA-XRF) spectroscopy are remarkable tools to obtain information about elemental composition and imaging of historical artefacts with a non-invasive character. These investigation techniques were employed in the framework of a project aimed at supporting the characterization of materials and techniques related with the Roman wall painting. The archaeological excavations at Villa della Piscina in Rome have revealed a luxury building with a large pool (about 50 m long) and thermal baths and numerous fragments of plaster, coming from intentional demolitions referable to two distinct architectural contexts of the Villa during the imperial age, have been found. This work deals with studying the interesting wall pictorial apparatus of great cultural value of the heritage inherited from the Roman age in the area of the ancient city of Rome. The colour palette of the pigments investigated, in particular, by MA-XRF and particle-induced X-ray emission (PIXE) and has revealed Fe, Cu, Pb, Si and Hg as main elements. Traces of other constituents uncover the choice of the different colours chosen by the artists who had embellished the rooms of the Villa.     

Rembrandt's Old Woman Praying, 1629/30: A look below the surface using X-ray fluorescence mapping

Rembrandt's painting Old Woman Praying, 1629/30, is the most valuable and exceptional work of art of the Residenzgalerie Salzburg (RGS). It is painted on a gilded copper plate with dimensions of only approximately 15 × 12 cm. The painting probably belongs to a series of three small-scale tronies, all executed on gilded copper plates. This particular picture preparation, which represents a special feature in Rembrandt's work, is quite unusual in the history of art. Previous investigations on the comparable paintings The Laughing Man, 1629/30, in the Mauritshuis, The Hague and the Self Portrait, 1630, in the National Museum, Stockholm showed that the gilding of the copper plate was applied over a lead white ground. To characterize the painting in the RGS, X-ray fluorescence (XRF) mapping was performed in a collaboration between the Research Office Residenzgalerie, Land Salzburg, the XGLab S.R.L, Milan, and the Conservation Science Department of the Kunsthistorische Museum Vienna (KHM). The results indicate a different structure for this painting than that used for The Laughing Man and the Self Portrait. The gilding was applied directly onto the copper plate, but with three areas with the gilding missing. It seems likely that in these sections, the gold was purposely removed to provide a different darker effect. XRF mapping yielded valuable insights into the structure of the painting and its technique as well as the principal pigments used for its composition.     

In‐situ and laboratory Raman analysis in the field of cultural heritage: the case of a mural painting

The present work exemplifies, over a mural painting from the 14th century, the advantages of an initial exhaustive research using latest generation hand‐held spectrometers (Raman mainly) in order to perform the characterization of valuable objects of cultural heritage. These in‐situ techniques (meaning on‐site and non‐destructive) are very useful to study the pigments and materials, to identify the nature and causes of some of the main sources of deterioration and to examine past repaints. In addition, the in‐situ measurements are of great importance in the selection of micro‐samples for the laboratory analyses. In this particular case, the combination of these results with the chemical imaging analyses in the laboratory (such as Raman and energy dispersive X‐ray spectrometry imaging) allowed the characterization of the mural painting, including, the identification of all restoration works applied in the past. Copyright © 2014 John Wiley & Sons, Ltd.     

Unilateral NMR study of a XVI century wall painted

Wall paintings in the XVI century Serra Chapel in the "Chiesa di Nostra Signora del Sacro Cuore" Rome, have been studied using unilateral NMR. In order to map the distribution of moisture content in the wall painted, a large number of Hahn echo measurements, covering large areas of the wall painting were performed. Because the intensity of the Hahn echo is proportional to the amount of moisture in the area under study, the experimental data were transformed into 2D gradient colour maps which allowed an easy visualization of the moisture content of the wall. The state of conservation of the wall painting was monitored using T2 measurements specially with regards to outcropping salt.     

西藏扎什伦布寺壁画的科学研究

壁画是寺院建筑的重要装饰元素,也是藏传佛教艺术的重要组成部分。扎什伦布寺始建于明正统12年（公元1447年）,作为后藏最大的寺院,寺内保存了大量精美壁画,这些壁画对研究藏传佛教及佛教艺术具有重要意义。扎什伦布寺自建寺起一直为传播佛教文化服务,经历了频繁的大规模修建。为了解扎什伦布寺壁画的制作材料与工艺,为今后壁画的保护及修复提供重要的参考及科学支撑,选取寺内强巴佛殿四层北壁、吉康扎仓南殿西侧的典型壁画,共采集8个样品。采用超景深三维视频显微镜观察壁画的制作结构,显微激光拉曼光谱仪对有机与无机颜料的成分信息进行表征,偏光显微镜根据晶体的光学信息鉴别拉曼光谱相似的颜料颗粒,X射线衍射仪用于测定地仗成分,扫描电镜/能谱仪则对微观数据进行确认和补充。通过分析研究,壁画由地仗层、准备层、颜料层构成。颜料包括矿物及人工合成颜料,其中红色颜料为朱砂与颜料红14,绿色颜料为块铜矾、酞菁绿,黑色颜料为碳黑,黄色颜料为雌黄,蓝色颜料为合成群青。颜料红14与酞菁绿为有机合成颜料,合成群青则为无机合成颜料。块铜矾作为矿物颜料,在欧洲曾用于架上画、壁画、手稿等艺术作品中,但在国内还未曾发现其使用历史,这一发现扩展了对绿色颜料的认识。壁画的地仗层依据藏式壁画制作传统使用了阿嘎土,准备层则由黄土制备。研究结果表明,壁画制作时以阿嘎土打底,刷一层黄土找平壁面,以胶调和颜料绘制于黄土层之上。壁画除了使用一些常见的传统藏式壁画材料,还发现了一些近代人工合成材料,说明扎什伦布寺强巴佛殿四层北壁及吉康扎仓南殿西侧壁画曾经历过重绘或补绘。该研究结果不仅弥补了扎什伦布寺壁画的研究空缺,也为扎什伦布寺修缮历史的补充及完善提供了重要证据。     

Non-destructive synchrotron X-ray diffraction mapping of a Roman painting

The history and the properties of materials are deduced not only from their elemental and molecular signatures, but also from their exact phase compositions, and from the structures and the defects of their constituents. Here we implement a non-destructive synchrotron X-ray based method, which combines both the quantitative structural content of diffraction and the imaging mode. As a demonstration case, the pigments of a Roman wall painting are examined. The joined elemental and mineral maps mimic the major features of the painting. Different structural phases made of common atomic elements are differentiated. Textures and graininess are measured and related to the artist’s know-how. PACS 07.85.Qe; 61.10.Nz; 83.85.Hf     

Theoretical study of the temperature dependence of the width of magnetic domain walls

The temperature dependence of magnetic domain walls in ferromagnetic systems with strong exchange coupling and weak lattice anisotropy is studied assuming that the thermal influence results mainly from the temperature dependence of the magnetization. We obtain that in lattices with an uniaxial symmetry like Co the wall width increases with temperature, but stays finite up to the Curie temperature T_c. In contrary, for a cubic lattice like Fe the wall width diverges for T → T_c, if only the lattice anisotropy is taken into account. The shape of the domain walls is not conserved, since at T_c the wall is determined only by the lowest order of anisotropy. In addition, the temperature dependence of a domain wall width for a thin magnetic film is determined. Using a special symmetry, we obtain a diverging wall width at a temperature markedly lower than T_c. However, the consideration of additional domain wall modes should modify this result.     

颜料层微观形貌对古代壁画褪色及显现影响

文物壁画在自然环境下产生褪色现象具有复杂性,严格意义上讲,人们无法重现自然环境下这种褪色发生的条件,但这并不妨碍人们研究其褪色原因的可能性和途径。通过实验来验证所提出机制的合理性,这也符合自然科学普遍采用的研究方法。提出颜料层微观形貌变化是引起壁画褪色的一种重要原因。胶料作为颜料层的连续相,当胶料分解时,颜料层微观形貌必然产生变化,为证明这种变化会引起颜料层褪色,而非颜料变化所致。建立了以具有较高热稳定性的赭石为颜料,以明胶作为粘接剂制成模拟的壁画颜料层。然后通过加热处理使胶料发生氧化分解,从而造成颜料层微观形貌发生变化,但赭石颜料依然稳定,期望证明在颜料赭石不发生变化时,由于颜料层微观形貌变化也可引起颜料褪色。实验通过煅烧壁画颜料层模拟样获得胶料降解的壁画模型,分别以SEM及多角度反射率光谱等技术,考察模拟样胶料降解前后表面微观形貌和光学性质变化。结果表明：壁画模拟样煅烧后,颜料层表面产生空隙结构,样品表面多角度反射率光谱表明煅烧后样品颜料层对可见光的反射增加而吸收降低,并观察到模拟样颜色淡化。以无色,难挥发,且不与颜料层发生化学反应的离子液体涂覆褪色样品表面,以上述技术表征涂覆处理前后颜料层表面微观形貌和表面光学性质变化,结果表明：离子液体填充了褪色样品表面颗粒间空隙,检测到样品表面对可见光的反射降低而吸收增加,观察到褪色样品的颜色加深。以上实验结果证明了推测合理性,即微观形貌变化确实会引起颜色变化。依据此原理以唐代墓室褪色壁画为例,进行了显现修复应用研究,其颜色显现效果显著。     

New insights into René Magritte's early surrealist painting La salle d'armes

Painted in 1925 or 1926, over an older composition, La salle d'armes, is among the first Magritte's surrealist paintings. It is also one of the only four Magritte's using enamels reported in the René Magritte Catalog Raisonné. This paper presents the material and technical study conducted on this double painting. The complementary imaging and analytical methods applied for this purpose provided substantial information on both, the visible image and the hidden one. Concerning the latter, for instance, the obtained results permitted to identify a cubo-futurist oil painting from the very early 1920s.     

分子极性对类胡萝卜素共振拉曼光谱的影响

测量了非极性分子β胡萝卜素和极性分子角黄素, 在非极性溶剂CS₂和极性溶 剂1,2二氯乙烷中243–293 K的温度范围内的共振拉曼光谱. 结果表明, 溶质和溶剂的极性对拉曼光谱影响很大. 非极性分子β胡萝卜素在非极性溶剂CS₂中的拉曼散射截面最大, 线宽最窄, 而极性分子角黄素在极性溶剂1,2二氯乙烷中的拉曼散射截面最小, 线宽最大. 用溶剂效应及线性多烯分子的“相干弱阻尼电子-晶格振动”, “有效共轭长度”模型给予了解释.     

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<...