中国古代艺术品常用矿物颜料的拉曼光谱(二)

在本刊前一篇文章中,我们讨论了拉曼光谱在艺术品分析和考古学应用方面的实验技术并报道了一些中国古代艺术品中经常使用的红色、黄色和白色矿物颜料的拉曼光谱。本文延续前文工作,测量了一些中国古代艺术品中常用的蓝色、绿色和黑色矿物颜料的拉曼光谱,介绍了相关的背景知识,并对这些光谱进行了解析,我们相信,一套比较全面的颜料拉曼光谱数据,对于拉曼光谱技术在考古学和艺术品分析方面的应用将会起到重要的参考价值。     

Characterization of pigments used in painting by means of laser-induced plasma and attenuated total reflectance FTIR spectroscopy

The study of pigments which are found in the works of art is one of the most important tasks in the examination of historic, artistic and archaeological materials since it can provide information about their source, the pictorial technique used or the presence of restoration works.In some studies, the historical, artistic and technical characterization of the artefact is not the final goal but its restoration. In those cases, the knowledge about the chemical composition inferred from the analysis of the artwork is crucial for conservators and restorers in order to ensure that the same pigments that were used in the original work are employed for the restoration.In this work, the analytical characterization of a range of different pigments commonly used in art has been carried out using laser-induced plasma (LIBS) and attenuated total reflectance (ATR)-FTIR spectroscopy. The main purpose of this study is to provide a preliminary database of LIBS and ATR-FTIR spectra in order to supply both elemental and molecular information, respectively.     

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。     

Lifetime measurements of ultrashort-lived excited states in Be-like ions

We propose to measure the lifetime of short-lived excited states in highly charged ions by pump-probe experiments. Utilizing two synchronized and delayed Femtosecond pulses allows accessing these lifetimes with Femtosecond precision. Such measurements could provide sensitive tests of state-of-the art atomic structure calculations beyond the capabilities of established methods.     

Phthalocyanine identification in paintings by reflectance spectroscopy. A laboratory and in situ study

The importance of identifying pigments using non invasive (n.i.) analyses has gained increasing importance in the field of spectroscopy applied to art conservation and art studies. Among the large set of pigments synthesized and marketed during 20th century, surely phthalocyanine blue and green pigments occupy an important role in the field of painting (including restoration) and printing, thanks to their characteristics like brightness and fastness. This research focused on the most used phthalocyanine blue (PB15:1 and PB15:3) and green pigments (PG7), and on the possibility to identify these organic compounds using a methodology like reflectance spectroscopy in the UV, visible and near IR range (UV-vis-NIR RS), performed easily through portable instruments. Laboratory tests and three examples carried out on real paintings are discussed.     

Colour and art: A brief history of pigments

Human beings have had an inherent urge to leave their mark in the form of works of art since prehistoric times. This has driven the quest for new and better pigments with which to make paints. This paper describes the origins and composition of earliest earth pigments used by primitive man to decorate the walls of caves through to the synthetic pigments developed in more recent times. Despite modern technology, the artist's palette remains a mixture of the pigments used by cave artists, natural pigments used in the middle ages, and modern organic compounds.     

Application of field portable EDXRF spectrometry to analysis of pigments of Levantine rock art

The results of the analyses of elemental composition of red and black pigments of Levantine rock art from La Saltadora rock shelters (Valltorta gorge, Castellón, Spain) are presented in this paper. Nondestructive analyses were carried out using a portable energy dispersive X‐ray fluorescence (EDXRF) spectrometer developed for in situ analysis. The results revealed the strong presence of calcium in all the analyzed locations due to the contribution of the underlying calcareous bedrock and the overlying crust. Iron is the main element detected in red pigments and manganese in black pigments. Iron and calcium ratios have been found indicative of the degree of preservation of the pictorial layer. Trace elements detected in the pigment composition confirm the use of different raw materials. Therefore, this work illustrates the potential of the portable EDXRF spectrometers for in situ analysis of rock art paintings. Copyright © 2010 John Wiley & Sons, Ltd.     

Computational models for pigments analysis

The main objective of this study is to develop computational models and algorithms for automated image-based characterization of the types of pigments used in watercolours. Pigments constitute the main element of watercolours and such studies can provide important information related to the non-destructive examination of works of art. Semi-transparent pigments are very difficult to discriminate with non-destructive methods due to the reflective properties of the substrate; computer vision techniques can complement such traditional diagnostic methods by computing models and interpreting the visual properties of the pigments used. PACS 07.05.Pj; 42.30.Tz; 42.30.Va; 42.40.My; 89.20.Cf     

The use of Raman microscopy and laser desorption ionization mass spectrometry in the examination of synthetic organic pigments in modern works of art

Synthetic organic pigments are widely used in modern and contemporary works of art. They have been examined by a variety of techniques including spectroscopic methods such as Fourier transform infrared spectroscopy, Raman, and X‐ray powder diffraction as well as chromatographic or mass spectrometric techniques such as pyrolysis‐gas chromatography/mass spectrometry and laser desorption ionization mass spectrometry (LDI–MS). Often, a combination of techniques has been used to examine these pigments. This paper describes use of Raman spectroscopy to create a database of colorants including two pigments not previously reported, PO1 and PO2. Then, using Raman spectroscopy in combination with LDI–MS, samples from modern works of art by artists including Mark Rothko, Barnett Newman, and José de Rivera were examined in order to identify the pigments present. One finding was that Rothko used a variety of red pigments over the course of his career including PR11 which has not been previously reported in artwork, and PO2 found with its positional isomer PR1. Knowledge of the colorants serves to inform conservators about display and treatment decisions. Published 2014. This article is a U.S. Government work and is in the public domain in the USA.     

紫细菌Rb.Sphaeroides 601外周捕光天线(LH2) B800吸收带的超快动力学研究

利用从紫细菌Rb.sphaeroides 601 所提取出的外周捕光天线LH2以及其不同pH值酸化样品(部分和全部去除B800分子LH2)并采用不同波长下的飞秒单色抽运探测技术详细研究了LH2中B800吸收带内的激发态动力学过程.通过对野生型与部分/完全去B800分子LH2的比较研究，分析了B800吸收带激发后所表现出的丰富变化的动力学过程，研究结果表明激发B800带的动力学过程中包含着B850上激子带的直接激发而产生的对激发态动力学的贡献. 关键词： 紫细菌外周捕光天线LH2 部分和全部去除B800分子LH2 激发态动力学的演变 飞秒抽运探测     

The first Raman spectroscopic study of San rock art in the Ukhahlamba Drakensberg Park,South Africa

San rock art sites are found throughout southern Africa; unfortunately this unique heritage is rapidly being lost through natural weathering processes, which have been the focus of various studies conducted in the uKhahlamba Drakensberg Park since 1992. It has recently been shown that the ability of Raman spectroscopy to identify salts on rock faces on a micro, as well as nano scale, can make a contribution to these projects. In order to test the feasibility of undertaking on‐site analyses, a small rock fragment with red and white pigments still attached, which had weathered off the rock face, was analysed with Raman spectroscopy under laboratory conditions, using a Dilor XY Raman instrument and a DeltaNu Inspector Raman portable instrument. A small sample of black pigment (<1 mm²), collected from a badly deteriorated painting and a few relevant samples collected on site, were analysed as well. It was possible to identify most of the inorganic pigments and minerals detected with previous XRD and EDX measurements including whewellite and weddellite coatings, which could be a tool for carbon dating purposes. Two carotenoid pigments were detected for the first time in San rock art pigments. Animal fat was also observed for the first time on both red and white pigments, on the rock face adjacent to the paintings and in highest concentrations on the back of the rock fragment. The spectra quality makes successful on‐site measurements a good prospect. Copyright © 2008 John Wiley & Sons, Ltd.     

Optimum spectral window for imaging of art with optical coherence tomography

Optical coherence tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS–NIR (400–2,400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use OCT for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 μm are highly desirable for OCT applications in art and potentially material science in general.     

Revealing the invisible: using surface‐enhanced Raman spectroscopy to identify minute remnants of color in Winslow Homer's colorless skies

The fading of pigments in items of importance to cultural heritage, such as paintings, works of art on paper, and textiles, is a ubiquitous problem. Tools currently available that can detect and identify organic colorants in severely degraded works of art are rare, given the heavy deterioration and restricted availability of the sample. Recently, however, surface‐enhanced Raman scattering (SERS) spectroscopy has shown great promise in detecting and identifying mass‐limited samples. The art conservation field has seized upon the opportunity opened up by this powerful analytical technique to enable the identification of microscopic amounts of organic molecules used as artists' colorants in complex matrices, such as biomaterials (i.e. dyed natural textiles, linseed oil biofilms present in oil paintings, etc.), a possibility that was previously precluded due to interfering fluorescence and small sample size. Here, we report SERS spectra recorded directly on single particles of red lake pigments from an important historical watercolor by the American master Winslow Homer (1836–1910) that suffered some degree of fading. The accurate colorant identification provided by SERS, enhanced by comparison with reference samples of historical watercolors, has thus enabled important discoveries regarding the materials and intended meanings behind artworks from one of the most influential American watercolor painters. Copyright © 2011 John Wiley & Sons, Ltd.     

Repetition rate multipliers for efficient implementation of multiphoton and pump-probe fluorescence microscopy

With the advances in pulsed laser systems, microscopic imaging techniques such as multiphoton and pump-probe fluorescence microscopy have developed into effective tools for investigating intensity and time-resolved phenomena inside biological systems. However, pulsed lasers used in these techniques usually are commercial systems with repetition frequencies of around 80 MHz. While these systems have proven to be adequate for multiphoton and pump-probe microscopic imaging applications, the temporal separation of the laser pulse train (around 12.5 ns) is long compared to the fluorescence lifetimes of many common fluorescence species. In this work, we present the designs of repetition rate multipliers based on passive optical components that can be used to increase the efficiency in multiphoton and pump-probe fluorescence microscopy. Depending on the lifetime of fluorescence molecules under investigation, the passive repetition rate multiplier can increase the duty cycle of multiphoton or pump-probe microscopy up to fourfold.     

Micro‐Raman and stratigraphic studies of the paintings on the ‘Cembalo’ model musical instrument (A.D. 1650) and laser‐induced degradation of the detected pigments

Micro‐fragments of the painted part of the ‘Cembalo’ model by Michele Todini (1625–1689) are investigated. The technique used for painting the terracotta base was studied via the stratigraphic analyses. No background layer of inorganic materials, e.g. gypsum, was found. To prevent absorption effects due to the terracotta porosity, a very thin layer of proteinaceous material was probably used. The micro‐Raman analyses have revealed the use of pigments currently used in the post‐Renaissance period (lead white, indigo, yellow of iron hydroxide, gypsum, hematite and carbon black) mixed with a pigment, the Prussian blue, discovered in A.D . 1704. This raises the authenticity problem of the work of art, a problem analysed and discussed in presenting the history of the work of art, and after the pigment study. The presence of degraded lead white is recognized via the laser‐induced degradation of the irradiated material. The possibility of a restoring action of the painted parts, as opposite to the non‐originality of the work, is considered and discussed. Since most part of the investigated pigments shows laser‐induced effects, a careful study of this phenomenon is performed by using the modern counterparts of the ancient pigments. For different laser powers, the temperatures of the investigated zones have been obtained via the detailed balance principle and connected to the laser‐induced degradation effects. Copyright © 2007 John Wiley & Sons, Ltd.     

A combined analytical approach applied to Medieval wall paintings from Puglia (Italy): The study of painting techniques and its conservation state

A combined analytical approach has been applied to the wall paintings, dated from 10th to 14th centuries, of the Santi Stefani crypt at Vaste (Lecce, Southern Italy). These paintings are a precious testimony of Medieval art in Southern Italy. However, the church shows problems of damp as well as clear evidences of flora, fungi and mold presence, and there is little knowledge of the pictorial methodologies used. Raman spectroscopy allowed to determine the palette and to reconstruct the worksite and the chronological sequence of the various paint layers. Kaolinite, calcite, carbon black, hematite, massicot, goethite, indigo and azurite were identified as pigments along with synthetic pigments, like phthalocyanine blue and chrome yellow. Attenuated total reflectance‐Fourier transform infrared spectroscopy suggested the presence of egg as a binder in some pictorial layers. The conservation state of the crypt is poor, and detachments of pigmented layers are frequent because of the presence of subflorescence and efflorescence: nitrate, sulfate and chloride salts have been identified spectroscopically and quantified by ion chromatography. The extensive use of kaolinite in Santi Stefani, actually not uncommon in Medieval art, is observed for the first time in a crypt of Puglia: its use to stabilize some pigments and to improve their adhesion on substrate is proposed. Copyright © 2015 John Wiley & Sons, Ltd.     

Raman spectroscopic study of medieval Indian art of 17th century

We report the first Raman spectroscopic investigations of medieval Indian art of 17th century. Three miniature paintings, belonging to Mogul and Rajput schools from the collections of the Madras Museum, were investigated by micro‐Raman spectroscopy using different excitation wavelengths. Many areas in the paintings exhibited rich spectra containing several intense Raman bands. The Raman bands were assigned on the basis of the reported reference spectra of the pigments. Evidences for the presence of massicot, red‐lead, lead‐white, vermilion, litharge, Indian yellow and anatase are found. In addition, tentative assignments of some of the Raman bands to atacamite and orpiment are also made. The present studies suggest that several mineral‐based unique pigments were popular among the Indian artists of this period. Copyright © 2010 John Wiley & Sons, Ltd.     

Klimt artwork: material investigation by backscattering Fe-57 Mössbauer and Raman spectroscopy

The long lost painting “Trumpeting Putto” was discovered and now is not only in the focus of art historian, but has also scientific interest too. We underwent this rare case of an inorganic layered artwork a non-destructive material investigation by employing Raman and MIMOSII Fe-57 Mössbauer spectroscopy. First results indicate several layers, where two layers of different pigments are on an inorganic background layer stabilised by a metallic wire within a wooden frame structure     

泵浦-探测实验影响因素的研究

结合泵浦-探测技术在材料非线性光学特性测量中的应用,介绍了影响泵浦-探测实验结果的几个因素,如样品厚度、样品距泵浦光会聚透镜焦点的距离、泵浦光强度等。通过40ps脉冲条件下的C60-甲苯溶液的实验结果证实了在满足薄样品近似条件下,使用厚一点的样品获得的泵浦-探测信号较大;样品放置距离泵浦光会聚透镜焦点较近时,泵浦-探测信号较大;在一定的泵浦光强范围内,泵浦光强度增大,泵浦-探测信号会随之增强。同时,对这几个因素影响实验结果的原因给与了简单解释。这些结论对于应用泵浦-探测技术探索材料非线性光学特性的物理本质具有实际的指导意义。