Surface‐enhanced Raman spectroscopy (SERS) on silver colloids for the identification of ancient textile dyes. Part II: pomegranate and sumac

The effectiveness of surface‐enhanced Raman spectroscopy (SERS) spectrocsopy on Ag colloids has been successfully demonstrated for the identification of a yellow dye in two ancient wool threads found in the Royal Tumulus of In Aghelachem, Libyan Sahara, belonging to the Garamantian period (2nd–3rd century A.D.). High‐performance liquid chromatography (HPLC) highlighted the presence of ellagic acid in the extracts from the threads, excluding other chromophores. This result, together with the abundance of malic acid detected by gas chromatography‐mass spectrometry (GC‐MS), suggested the possible use of pomegranate rind or sumac berries as source of the yellow dye, both plants being documented in the Fezzan area during the Garamantian period. HPLC analyses and SERS spectra acquired on the extracts of the ancient threads were therefore compared with those obtained from pomegranate and sumac extracts of the corresponding fruits and reference dyed wool samples, allowing us to identify the yellow dye as deriving from pomegranate (Punica granatum L.). SERS spectra of ellagic acid and dyes extracted from pomegranate rind and sumac berries are reported here for the first time. A methodological improvement is also presented, based on the use of NaClO₄ as aggregating agent, that leads to a significant increase of the signal‐to‐noise ratio in the SERS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Evaluating the use of laser radiation in cleaning of copper embroidery threads on archaeological Egyptian textiles

Cleaning of copper embroidery threads on archaeological textiles is still a complicated conservation process, as most textile conservators believe that the advantages of using traditional cleaning techniques are less than their disadvantages. In this study, the uses of laser cleaning method and two modified recipes of wet cleaning methods were evaluated for cleaning of the corroded archaeological Egyptian copper embroidery threads on an archaeological Egyptian textile fabric. Some corroded copper thread samples were cleaned using modified recipes of wet cleaning method; other corroded copper thread samples were cleaned with Q-switched Nd:YAG laser radiation of wavelength 532 nm. All tested metal thread samples before and after cleaning were investigated using a light microscope and a scanning electron microscope with an energy dispersive X-ray analysis unit. Also the laser-induced breakdown spectroscopy (LIBS) technique was used for the elemental analysis of laser-cleaned samples to follow up the laser cleaning procedure. The results show that laser cleaning is the most effective method among all tested methods in the cleaning of corroded copper threads. It can be used safely in removing the corrosion products without any damage to both metal strips and fibrous core. The tested laser cleaning technique has solved the problems caused by other traditional cleaning techniques that are commonly used in the cleaning of metal threads on museum textiles.     

基于子结构技术的光机装置反射镜组件的稳定性分析

反射镜组件是光机装置的重要组成部分,反射镜片的转角稳定性对光路的传输有着直接影响。为了分析获得在地脉动载荷作用下反射镜片的转角响应,分别基于整体结构建模技术和子结构技术建立了某光机装置简化结构的有限元模型,并分析获得了装置中两个反射镜片的转角响应。两种方法得到的反射镜片的转角响应差别分别为3.99%,11.84%,说明基于子结构技术开展光机装置反射镜架组件的稳定性分析是可行的。     

基于子结构技术的光机装置反射镜组件的稳定性分析

反射镜组件是光机装置的重要组成部分,反射镜片的转角稳定性对光路的传输有着直接影响。为了分析获得在地脉动载荷作用下反射镜片的转角响应,分别基于整体结构建模技术和子结构技术建立了某光机装置简化结构的有限元模型,并分析获得了装置中两个反射镜片的转角响应。两种方法得到的反射镜片的转角响应差别分别为3.99%,11.84%,说明基于子结构技术开展光机装置反射镜架组件的稳定性分析是可行的。     

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.     

原子核内多个核子关联的一些子结构

对于轻原子核,我们把两个声子相干的结构做为四个粒子集团的子结构α⁺,用同样的办法可以给出四个空穴集团的子结构β⁺。在此基础上,我们以¹⁶O及¹⁸O为例,研究了粒子团与空穴团之间的结构。发现它们之间存在着很强的斥力,因而最低的态是粒子团与空穴团松散开的结构。这样就从微观结构上解释了这种态的变形,并且这种结构对E2跃迁是相干加强的。为了进一步研究中重核的粒子关联结构,我们把L-S耦合的相干结构推广到赝L-S耦合的相干结构,并在j-j耦合表象中给出了表达式。应用此结构对⁵⁶Ni附近的原子核,做了一点初步的分析。     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

In situ analysis of stratified glass eye beads from the tomb of Marquis Yi of the Zeng State in Hubei Province,China using XRF and micro‐Raman spectrometry

A total of 46 stratified glass eye beads in Hubei Provincial Museum, Wuhan, China were analyzed in situ by means of portable X‐ray fluorescence and Raman spectrometers. These beads were excavated from the famous tomb of Marquis Yi of the Zeng State, which was dated back to the early Warring States Period (433 bc or little late), in Hubei Province. It is determined that most of these elegant glass beads belong to the typical soda‐lime‐silicate glasses with low contents of MgO and K₂O. The colorants used within these beads are attributed to two types: antimony‐based compound opacifiers/colorants and the transition metals in their oxidized state such as Co, Cu, and Fe ions. According to their characteristics of typology, chemical composition, and micro‐crystals within samples, we classified them into three subtypes and evaluated the possible relations among them. In addition, through comparing with the similar contemporary samples unearthed from Xu Jialing Tomb (5th–4th century bc ) in Henan Province, we discussed the provenance of these stratified glass eye beads and relative issues briefly. Copyright © 2014 John Wiley & Sons, Ltd.     

X‐ray fluorescence analysis on a group of coins from the ancient roman city of Tridentum (Trento,Italy)

A group of 83 coins, found in the archeological excavations of the ancient Roman city of Tridentum (Trento, Italy), was studied for the determination of their composition, finalized to their classification and cataloging. The coins, mainly made of copper‐based alloys, were minted between the republican period (II century BC) and the last decades of the western empire (V century AD). The X‐Ray Fluorescence archaeometric analysis has allowed a revision of the typological classification of the coins through the identification of six broad groups, each one characterized by a peculiar composition of the coins in the group. A tentative assignation of all the unreadable coins to one of the groups identified was proposed, in a way that could suggest also a possible dating of these coins. Copyright © 2014 John Wiley & Sons, Ltd.     

Tribocharging studies on inhabited cleanroom garments

Studies are reported on the surface voltages created on inhabited cleanroom garments when these are subject to tribocharging actions. It is shown that the voltage created per unit of charge does not depend on whether the garment fabrics include core conductive threads, giving very high surface resistivity values, or surface conductive threads, which show resistivity values well within the requirements of formal electrostatic Standards. Lower surface voltages per unit of charge are observed for the closer spacing of the conductive threads. These results call into question whether measurement of resistivity is the most appropriate basis for assessing the suitability of materials.     

The influence of surface treatment of stitch threads and stitching on interlaminar properties of unidirectional laminates

An experimental investigation was carried out to study the influence of graft treatment for Kevlar stitch threads on the interlaminar properties of stitched unidirectional laminates. The surfaces of Kevlar stitch threads were immersed in a solution of Dimethyl sulfoxide mixed with NaH for some time, and then alkoxysilane was grafted onto the surface of modified Kevlar threads. The corresponding physical and chemical changes in the surface of Kevlar threads were carefully evaluated using XPS, SEM, water absorption, and tensile measurement. Results show that the treated Kevlar threads have much rougher surface morphologies, its tensile strength is slightly improved, and their wettability are greatly improved. The stitched carbon /epoxy composite using surface-treated Kevlar threads has excellent hydrothermal property. The resins can better wet the surface treatment of Kevlar stitch threads, and the sizes of rich resin can be reduced. The moisture uptake of stitched composites decreases by 53.3% and its residue ratio of interlaminar shear strength in a wet state improves by 13.1%.     

Tip streaming from a drop in the presence of surfactants

Drop breakup in a linear extensional flow is simulated numerically using a nonlinear model for the surface tension that accounts for maximum packing at the interface. Surface convection sweeps surfactant to the drop poles, where it accumulates and drives the surface tension to near zero. The drop assumes a transient shape with highly pointed tips. From these tips, thin liquid threads are pulled. Subsequently, small, surfactant-rich droplets are emitted from the termini of these threads. The scale of the shed drops depends on the initial surfactant coverage. Dilute initial coverage leads to tip streaming, while high initial coverage leads to the tip dropping breakup mode.     

Characterization of some ancient glass vessels fragments found in Xinjiang,China, using a portable energy dispersive XRF spectrometer

In this article, a portable energy dispersive X‐ray fluorescence spectrometer having determination capability for elements of Na and Mg is applied to characterization of the 58 ancient glass vessels fragments found in Xinjiang, China, successfully. These ancient glass samples were found in different historical sites dated from the Han Dynasty (202 B.C.–220 A.D.) to early Yuan Dynasty (1271–1368 A.D.). The chemical composition difference between the original weathered and inner fresh surfaces is distinguished. Using Mg, Ca, Al and K as the diagnostic elements, the glass samples analyzed are mainly classified into three types through cluster analysis. Each type of glass seems to be produced under different recipes. The techniques used to make these glasses and their possible provenances are discussed briefly. The obtained results provide new useful information for further understanding of the exchange and trade networks related to early glasses found in Xinjiang, China. Copyright © 2011 John Wiley & Sons, Ltd.     

Analysis of the internal structure of ancient copper coins by neutron tomography

The internal structure of copper coins—a Golden Horde pulo of the 14th century AD and an ancient coin found in Phanagoria at sites of the 5–4th centuries BC—are studied by neutron tomography method. From a set of angular projections of neutron absorption, three-dimensional models of the analyzed objects are reconstructed and the analysis of their physical state is performed. In the copper pulo, a region characterized by a greater neutron beam attenuation coefficient is found. It is assumed that this region was formed due to the gradual penetration of patina into the coin. The neutron tomography data also make it possible to analyze the remnants of an antique coin found in underwater archeological studies. Areas of surface damage and cracks in the antique coin are shown, visually separated from the corrosion layer.     

新疆两处遗址出土绿松石文物的成分分析和产源判别

绿松石是一种产地有限,却在世界范围内被广泛使用的珍稀宝石资源,研究绿松石文物的矿料来源可为了解古代不同地区间珍稀资源的获取与交流模式、文化传播途径、早期贸易网络等学术问题提供帮助。新疆绿松石文物的矿料来源是近年来科技考古关注的热点问题之一,目前存在中原说、波斯说、新疆说和多元说等观点。研究新疆绿松石文物的产源,其难点在于既要保证文物的安全,又要确保分析数据的准确性,同时要避免样品表面污染对数据结果带来的干扰。鉴于此,采用等离子体原子发射光谱LA-ICP-AES对新疆加依、西沟两处墓地出土的绿松石进行化学成分分析,并结合秦岭东部五处产地的绿松石成分数据,经主成分分析绘制散点图——建立产地区分模型。主成分分析结果显示加依墓地样品中有五枚是罕见的锌绿松石,其余同西沟墓地绿松石的成分相近,均含有相对较高比例的Fe和Sr。结合中原地区的绿松石成分数据对比分析,发现新疆两遗址绿松石的微量元素特征相近,以高B2O低BaO为特征区别于中原地区的绿松石样品。在产地区分模型中,代表加依墓地和西沟墓地出土绿松石的散点聚集成团,且明显区分于白河、郧县、洛南、竹山、淅川五地的散点分布区域。综上结果表明新疆东部两处遗址的绿松石制品与中原东秦岭五处绿松石矿区所产矿料的成分差异较大,鉴于近年来新疆哈密发现与两处遗址同时代的绿松石采矿遗址,推测加依墓地、西沟墓地的绿松石制品其矿料来自中原地区的可能性较小。     

Scanning transmission X-ray microscopic analysis of purified melanosomes of the mouse iris

Melanosomes are specialized intracellular membrane bound organelles that produce and store melanin pigment. The composition of melanin and distribution of melanosomes determine the color of many mammalian tissues, including the hair, skin, and iris. However, the presence of melanosomes within a tissue carries potentially detrimental risks related to the cytotoxic indole–quinone intermediates produced during melanin synthesis. In order to study melanosomal molecules, including melanin and melanin-related intermediates, we have refined methods allowing spectromicroscopic analysis of purified melanosomes using scanning transmission X-ray microscopy. Here, we present for the first time absorption data for melanosomes at the carbon absorption edge ranging from 284 to 290 eV. High-resolution images of melanosomes at discrete energies demonstrate that fully melanized mature melanosomes are internally non-homogeneous, suggesting the presence of an organized internal sub-structure. Spectra of purified melanosomes are complex, partially described by a predominating absorption band at 288.4 eV with additional contributions from several minor bands. Differences in these spectra were detectable between samples from two strains of inbred mice known to harbor genetically determined melanosomal differences, DBA/2J and C57BL/6J, and are likely to represent signatures arising from biologically relevant and tractable phenomena.     

The effect of thermal aging and color pigments on the Egyptian linen properties evaluated by physicochemical methods

Archaeologists in Egypt discovered ancient colored textiles in great quantities in comparison with the analogous uncolored ones. Furthermore, the latter are far more deteriorated. Most research investigations into archaeological linen have been concerned with manufacture, restoration, and conservation but little information is available about the properties of the fibers, and particularly their chemical and physical properties after dyeing with natural dyes or painted with pigments. The aim of this study is to evaluate the physicochemical properties of Egyptian linen textiles coloring with a variety of pigments used in painting in ancient times after thermally aged to get linen samples which are similar as possible to the ancient linen textiles. The evaluations were based on Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), X-ray diffraction and tensile strength, and elongation measurements. Results showed that beyond cosmetic reasons, colored textiles did indeed play a role as protecting agents affecting strength and reducing thermal deterioration. Specifically, in the molecular level, pigments under study seem to interact to cellulose and lignin compounds of the aged linen while in the macroscopic level tensile and elongation parameters are altered. Electron microscopy confirms that pigment particles are deposited on and between the fibers’ surfaces.     

Diagnostic analysis of stone materials from underwater excavations: the case study of the Roman archaeological site of Baia (Naples,Italy)

This work belongs to the framework of the national research project “COMAS” (Planned COnservation, “in situ”, of underwater archaeological artifacts), funded by the Italian Ministry of Education, Universities and Research (MIUR), concerning the submarine archaeological area of Baia (Naples, Italy). The site includes remains of the ancient cities of Baiae and Portus Iulius, which, since the 4th century AD, started to be submerged because of the bradyseism phenomenon. The work aims to the characterization of four different types of stone materials collected from the site, specifically marbles, limestones, ignimbrites, and bricks, in order to investigate their state of conservation. In particular, specimens were sampled from some masonry structures and pavement slabs (opus sectile) in a specific area of the submerged site, called “Villa a Protiro”. In order to characterize archaeological samples from a mineralogical-petrographic point of view, polarized optical microscopy and X-ray diffraction analyses were carried out, while to assess their conservation state, the surface colonization by biodeteriogen agents and their interaction with the substrate were studied through observations under a stereomicroscope, scanning electron microscopy and Fourier transform infrared spectroscopy. Marble and limestone samples revealed an intense bioerosion phenomena, attributable to epilithic and endolithic forms, particularly boring sponges. On the contrary, ignimbrites suffer a lower degree of biological colonization related to the activity of other species, such as serpulids and bryozoans. In bricks, biocolonisation is correlated to the type of temper used in the artifact, the quartz pastes having a greater susceptibility to biological attack than the volcanic ones.