Raman spectroscopy of archaeological and ancient resins: problems with database construction for applications in conservation and historical provenancing

The adoption of Raman spectroscopy as a screening technique for the presence of organic resins on diverse substrates is now being advocated for the first pass non-destructive examination of potential sites for limited sampling using other analytical techniques. The characterisation of ancient resins in art work and specimens recovered from archaeological excavations is critically dependent upon the analytical capability of Raman spectroscopy using different wavelengths of excitation from the visible to the near infrared and the interpretation of the data illustrates the advantages and limitations of the technique. Resin specimens from art works and artefacts span a period of about 7000 years of recorded history and the influence of factors such as the environmental degradation, burial deposition, reaction with associated substrates and mineral pigments on the observed Raman spectra have been assessed. The key molecular Raman spectral features that are definitive for the discrimination between contemporary resins are considered in respect of these factors and thereby illustrative of the difficulties posed for the creation of a Raman spectral database of ancient resins, in contrast with the extensive and definitive literature equivalents that are available for their mineral pigment and organic dye analogues.     

Probing history with Raman spectroscopy

This Tutorial Review shows how Raman spectroscopic and microscopic techniques are utilised for non-destructive characterisation of archaeological artefacts and provide novel information for art historians and hints at the use of ancient technologies for the production and treatment of materials and skeletal remains.     

Investigation of fungal deterioration of synthetic paint binders using vibrational spectroscopic techniques

The deterioration of synthetic polymers caused by biological process is usually evaluated by visual inspection and measuring physical effects. In contrast to this approach, we have applied vibrational spectroscopies to study the biodegradation of the synthetic resins. 29 synthetic resins used as paint binding media, including acrylic, alkyd and poly(vinyl acetate) polymers, were examined for potential susceptibility to fungal degradation using the standard method ASTM G21-96(2002). In addition, the degraded resins were analysed by Raman spectroscopy, FT-IR and FT-IR photoacoustic spectroscopy. Almost all the acrylic resins studied proved to be resistant to microbial attack, while all alkyd resins and some poly(vinyl acetates) turned out to be biodegradable. Within a few days of inoculation Aspergillus niger was the most copious fungus on the biodegraded resins. A comparison of the IR and Raman spectra of control and biodegraded resins did not show any differences, but photoacoustic spectroscopy revealed additional bands for the fungal-degraded resins, consistent with the presence of fungal-derived substances. The additional bands in the photoacoustic spectra were due to the presence of Aspergillus niger and melanin, a fungal pigment. Since IR photoacoustic spectroscopy can be also a suitable technique for the chemical characterisation of binding media, the same spectroscopic analysis can be employed to both characterise the material and obtain evidence for fungal colonization. Microbial growth on Sobral 1241ML (alkyd resin) after 28 d (growth rating 4) compared with the non-inoculated resin.     

Vibrational spectroscopy: a 'vanishing' discipline?

The aim of this tutorial review is to convince a broad readership that vibrational spectroscopy, although according to some vibrational spectroscopists seemingly less in focus nowadays than in days past, is far from 'dead'. It may seem to some that infrared and Raman spectroscopy are less in focus than in times past, despite the unique analytical capabilities. Vibrational spectroscopy is particularly powerful for non-destructive characterisation of substances, including living material. But compared to the past, a shift in applications has taken place, bringing new opportunities. This is partly due to the introduction of new features, including imaging and 2D correlation spectroscopy. Another factor is the recognition that vibrational spectroscopy can play a role in new rather than only in the traditional fields of application, e.g. new applications in the life-science field (living cells, cancer research), the characterisation of soil. But also the traditional application in catalysis sees new development within the context of Operando spectroscopy.     

Non-destructive NIR-FT-Raman spectroscopy of plant and animal tissues, of food and works of art

Just after the discovery of Raman spectroscopy in 1928, it became evident that fluorescence with a quantum yield of several orders of magnitude higher than that of the Raman effect was a great and apparently unbeatable competitor. Raman spectroscopy could therefore, in spite of many exciting advantages during the last 60 years, not be applied as an analytical routine method: for nearly every sample, fluorescing impurities had to be removed by distillation or crystallisation. Purification, however, is not possible for cells and tissues, since the removal of the fluorescing enzymes and coenzymes would destroy the cells. There is fortunately one alternative solution. When excited with the radiation of the Nd:YAG laser at 1064 nm Raman spectra are practically free of fluorescence. Raman spectra can now be recorded with minimal sample preparation. In order to facilitate non-destructive Raman spectroscopy of any sample, cells and tissues, food, textiles and works of art, a new entrance optics for Raman spectrometers is used. Typical results from several fields are demonstrated.     

Analysis of post-Byzantine icons from the Church of the Assumption in Cephalonia, Ionian Islands, Greece: a multi-method approach

A multi-method approach has been developed for the characterisation of the proteinaceous binding media, drying oils and pigments present in samples from the panel paintings of the Church of the Assumption in Cephalonia (Ionian Islands, Greece). The analytical protocol involved the use of scanning electron microscopy/energy dispersive X-ray analysis (SEM/EDX), Raman spectroscopy and gas chromatography. The identification of the pigments was achieved by SEM/EDX and Raman spectroscopy. The latter technique was also used for the detection of the binding media, while their characterisation was achieved by gas chromatographic analysis of ethyl chloroformate derivatives. The aim of this multi-method protocol was to obtain as much information as possible from the panel paintings of the Church of the Assumption, through non-destructive methods, before proceeding to gas chromatography. Little scientific information is available for the understanding of the construction technique and the materials used by the post-Byzantine artists and whatever is available comes mainly from artists’ manuals. One of the aims of this paper is to provide a scientific background to the technology of the Ionian post-Byzantine icons.     

Nondestructive analysis of ancient Egyptian funerary relics by Raman spectroscopic techniques

The non-destructive Raman spectroscopic analysis of a range of ancient Egyptian funerary artefacts has been undertaken with a view to establish the identification of the pigment composition and nature of the interaction with the substrate. The specimens date from the New Kingdom to the Graeco-Roman period, ca. 3900-1800 years b.p. In this study a comparison has also been effected between the near-infrared and red excitation wavelengths for the characterisation of these materials. A particular problem for Raman analysis of these artefacts was found in the application of resin or organic compounds to the surface or substrata, as colourants or to aid adhesion of the pigments, and degradation of the resins with burial environment and exposure has resulted in large fluorescent backgrounds. Nevertheless, useful information has been obtained which assists in the interpretation of the construction of some of the artefacts.     

Potential application of Raman spectroscopy for determining burial duration of skeletal remains

Raman spectroscopy was used to study trends in chemical composition of bones in a burial environment. A turkey bone was sectioned and buried for short intervals between 12 and 62 days. Buried sections were analyzed using Raman microspectroscopy with 785 nm excitation. The results indicate that chemical changes in bone due to soil bacteria are time-dependent. Spectroscopic trends within buried bone segments were correlated to burial duration. A preliminary model was constructed using peak integration of Raman bands. Data collected within buried bone segments fit very well in this model. The model constructed is sensitive to changes in bone composition in a scale of days. This study illustrates the great potential of Raman spectroscopy as a non-destructive method for estimating the burial duration of bone for forensic purposes.     

Non-invasive analysis of turbid samples using deep Raman spectroscopy

Raman spectroscopy has recently seen major advances in the area of deep non-invasive characterisation of diffusely scattering samples; this progress is underpinned by the emergence of spatially offset Raman spectroscopy and associated renaissance of transmission Raman spectroscopy permitting the characterisation of diffusely scattering samples at depths not accessible by conventional Raman spectroscopy. Examples of emerging research activities include non-invasive diagnosis of bone disease and cancer, rapid quality control of pharmaceutical formulations and security screening of explosives and counterfeit drugs through unopened translucent bottles. This article reviews this field focusing on recent developments with high societal relevance.     

Applications of Raman spectroscopy in pharmaceutical analysis

As Raman spectroscopy enables rapid, non-destructive measurements, the technique appears a most promising tool for on-line process monitoring and analysis in the pharmaceutical industry. This article gives a short introduction to Raman spectroscopy and presents several applications in the pharmaceutical field.     

On-line FT-Raman and dispersive Raman spectra database of artists’ materials (e-VISART database)

Raman spectroscopy has been widely applied in the analysis of different types of artwork. This technique is sensitive, reliable, non-destructive and can be used in situ. However, there are few references in the literature regarding specific Raman spectra libraries for the field of artwork analysis. In this paper, the development of two on-line databases with Fourier transform Raman (FT-Raman; 1064 nm) and dispersive Raman (785 nm) spectra of materials used in fine art is presented; both are implemented in the e-vibrational spectroscopic databases of artists materials database (e-VISART). The database provides not only spectra, but also information about each pigment. It must be highlighted that for each pigment or material several spectra are available from different dealers. Some of the FT-Raman spectra available in the e-VISART database have not been published until now. Some examples in which the e-VISART database has been successfully used are presented.     

Examination of cellulose textile fibres in historical objects by micro-Raman spectroscopy

The investigation and characterisation of historical objects can be an exacting piece of work because of the small quantity of material that can be investigated and the degradation of the material and its value, which sometimes demands only non-destructive methods. In this study, as one such method, Raman spectroscopy was used to investigate the cellulose fibres of painting canvases and linings. Historical samples of fabrics were taken from different paintings and their linings from different locations in Slovenia. Raman spectra were recorded on the fibres of these historical samples. Additionally, a database of the Raman spectra of modern cellulose fibres was created and compared with the literature data. Differences in the Raman spectra of different cellulose fibres were observed, and on this basis fibres of different types were discriminated. The recorded Raman spectra of historical samples were compared with the database spectra of modern cellulose fibres. Strong luminescence effects because of the changes caused by ageing, degradation products and surface contamination caused difficulties in interpreting the Raman spectra of historical fibres. The luminescence effects were partly overcome by prolonged exposition times and previous "signal quenching" with the laser. The Raman spectra of historical cotton showed no luminescence effects, and only slight differences to the reference spectra of modern cotton fibres appeared, whereas the Raman spectra of historical flax fibres were overwhelmed with luminescence and showed changes in spectra through degradation. The research showed that by using Raman spectroscopy the identification and differentiation of different cellulose fibres and materials that accompany cellulose in the fibres are possible and that degraded and aged material can be differentiated.     

Micro-Raman analysis of coloured lithographs

Raman micro-spectroscopy was chosen for analysis and identification of the pigments present in four nineteenth-century hand-coloured lithographs, as this technique has several advantages over others for this purpose. The possibility of performing completely non-destructive analysis without any sampling is probably one of its most favourable qualities for art analysis. Raman spectroscopy can also be used to determine some pigments that cannot be detected using FTIR, such as vermilion, carbon blacks, cadmium pigments, etc. Among others, Prussian blue, ultramarine blue, carbon black, chrome yellow, yellow ochre, red lead, red iron oxide, burnt Sienna, indigo blue, chrome orange, phthalocyanine green, and some other organic pigments, were determined in the specimens. The results obtained have led to doubts about the age of the lithographs.     

Progress in the application of ATR-FTIR microscopy to the study of multi-layered cross-sections from works of art

As a non-invasive or micro-invasive technique attenuated total reflectance Fourier transform infrared spectroscopic (ATR-FTIR) microscopy is a valuable tool for the analysis of materials in works of art. An application for which it has received growing interest is in the analysis of paint cross-sections. However, FTIR microscope configurations, objectives' geometries and low spatial resolutions, and issues of sample preparation have often hampered the characterization of individual layers or features in cross-sections. With the use of case studies, it is demonstrated here that an ATR-FTIR microscope featuring a crystal of optimized geometry and a viewing capability feature allows characterization of individual layers, or areas within layers, of 10 microm thickness or less in single measurements. Of particular value is a remote aperturing feature which allows the analysis of selected areas within the contact footprint of the ATR crystal. Since the technique is non-destructive, the same area can be analyzed by complementary microscopic techniques such as Raman spectroscopy and scanning electron microscopy with energy-dispersive spectroscopy. Pyrolysis gas chromatography-mass spectrometry was also used in some cases to corroborate the spectroscopic data. The analyses presented provided data which were important in informing art historical interpretation and conservation of the artworks examined.     

Einfuehrung zur Raman Mikroanalyse

The Raman microanalysis techniques permit non-destructive molecular and structural determinations of micrometer sized samples. The origin and aspect of Raman spectra are mentioned and the apparatus Ramanor U 1000 is presented. We give the advantages on classical Raman spectroscopy and other methods.     

卡西酮类新精神活性物质的差分拉曼光谱分析研究

通过对14种卡西酮类新精神活性物质标准品的差分拉曼光谱分析研究,建立了一种简便快速、准确可靠、无损检材的卡西酮类新精神活性物质的分析方法。设置差分拉曼光谱仪激光光源785nm,激光功率200mW,积分时间1s,扫描范围为2400～200 cm^-1,对14种常见卡西酮类标准品样品进行了检验分析。可以通过对差分拉曼光谱的分析区分所有14种卡西酮类物质。利用该方法可以对卡西酮类物质进行快速无损的检验,该方法可以用于公安机关实际办案。     

Raman spectroscopy of C-, BN-, SiC-layers deposited on multifilament substrates

The analytic characterisation of various layers and layer systems on fibrous materials are presented. The layers, deposited by an isothermal CVD process, consisting mainly of pyrolytic carbon, hexagonal boron nitride and silicon carbide were characterised by different analytical methods, especially by Raman spectroscopy [1]. The surface enhanced Raman spectroscopy (SERS) was used first time for the investigation of boron nitride (BN) coatings on fibres.     

Preparation,Characterisation and Properties of Nanocomposites Based on Epoxy Resins – An Overview

An overview about the use of nanoparticles in epoxy resins is given. Deaggregated fumed silica, sol gel materials and other spheroidic nanoparticles improved the abrasion resistance and the mechanical properties of filled epoxides, and several properties can be improved by specific particles. Combustion properties, strength and permeation can be improved by organically modified layered silicates. The proper characterisation of the nanocomposites is still an art. TEM analysis of the cured materials and light scattering with 3D cross-correlation for the liquid samples were sufficient methods for the characterisation of filled epoxides.     

Nondestructive classification and identification of ballpoint pen inks by Raman spectroscopy for forensic document examinations

As a non-destructive analytical method, Raman spectroscopy often provides insufficient information to identify or differentiate the ink used for the preparation of a questioned document. In this study, blue and black ballpoint pen inks deposited on paper substrate were examined in situ by conventional Raman spectroscopy. Inks were successfully classified based on the total number of prominent bands in Raman spectra. It was found that more than 90% of the samples of the same type and color could be differentiated visually using only Raman spectra, i.e. 94 and 95% for blue and black inks, respectively. As a result of this study, a flow chart has been constructed for blue and black ballpoint pen inks allowing their systematic identification. Raman spectroscopy proved to be a fast and precise technique for forensic ink analysis.     

Development of tip-enhanced optical spectroscopy for biological applications: a review

Tip-enhanced optical spectroscopy is an approach that holds a good deal of promise for the nanoscale characterisation of matter. Tip-enhanced Raman spectroscopy (TERS) has been demonstrated on a variety of samples: inorganic, organic and biological. Imaging using TERS has been shown for carbon nanotubes due to their high scattering efficiency. There are a number of compelling motivations to consider alternative approaches for biological samples; most importantly, the potential for heat damage of biomolecules and long acquisition times. These issues may be addressed through the development of tip-enhanced coherent anti-Stokes Raman scattering microscopy.