Ion beam and infrared analysis of medieval stained glass

Ion beam analysis and Fourier Transform Infrared (FTIR) spectroscopy were used to characterize 15^th century stained glass fragments from Batalha Monastery. This information is being used to help establish their origins as well as the art schools and artistic trends involved in the manufacture of these panels.As the preservation of art objects and artefacts is a major issue, the combination of Rutherford Backscattering Spectrometry (RBS) and Particle Induced X-ray Emission (PIXE) with FTIR spectroscopy aims at determining non-destructively the elemental compositions of the bulk glass and painted layers as well as identifying corrosion products. Elemental spatial distributions were obtained with a nuclear microprobe, and compared with the results of micro-FTIR.Although the bulk composition determined is consistent with the glass manufacturing practices of the Middle Ages, the grisailles were found to have a significant Zn concentration, at variance with those same reported practices.The analysis also revealed a surface layer impoverished in Si and K and enriched in Ca. That may be due to the migration of Ca ions to the surface, a known glass corrosion process consistent with the presence of CaCO₃, as indicated by micro-FTIR. PACS 81.05.Kf; 33.20.Ea; 82.80     

Influence of environment on the corrosion of glass–metal connections

‘Glass sensors’ of the eighteenth century Backer glass and the sixteenth century enamel from Limoges have been chosen for a series of experiments. Combinations of these materials with different base materials such as copper and bronze has been investigated. To create surface changes on the ‘glass sensor’, a corrosion process was induced in a controlled environment. A variety of corrosive agents such as hydrochloric acid, sulfuric acid, water and formaldehyde were used. The sample immersed in the corrosive solution was exposed alternately to light and high temperature for a total of 38 weeks. During this period, macroscopic and microscopic observations were made and series of tests such as SEM/EDS and Raman spectroscopy were performed on the surface of the samples. ICP-MS methods were used to determine the change in the chemical composition of the solutions where the samples had corroded. The primary aim of this study was to identify the impact of a number of external corrosive variables such as temperature, humidity and local environment to identify the most damaging environments for glass–metal objects. The obtained results showed the chemical and physical phenomena acting on the surface of the glass, metal or in the place of their joints. Information obtained on this study was used to explain the influence of the environment on the surface of glass–metal materials. Results can be used in the design of conservation work as well as for sustainable conservation.     

新型多功能集成光学耐压保护窗口

针对特殊环境下光学系统的需求，设计了一种具有三层结构的新型光学耐压保护窗口，其外层为石英玻璃，内层为开有小孔的化学钢化K9玻璃，中间为夹有电阻丝的PVB（聚乙烯醇缩丁醛）胶层，电阻丝通过内层玻璃上的小孔引出。通过强度仿真优化得出了内层玻璃最佳开孔位置和孔直径，设计了这种三层结构的保护窗口的工艺流程，并对具有三层结构的保护窗口进行了性能测试和验证。结果表明，这种新型耐压窗口集成了透光、耐压、抗冲击、加热、表面快速脱水等功能。     

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.     

On‐site analysis of Limoges enamels from sixteenth to nineteenth centuries: an attempt to differentiate between genuine artefacts and copies

A selection of 15 painted enamels, most of which belong to Limoges productions, from 1500 to 1900 A.D. , has been studied on‐site in the storage rooms of musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those which were previously recorded on glazed pottery, enamelled and stained glasses as well as Chinese cloisonné enamels. Analysed enamels mostly belong to soda‐lime‐based glass. Three types of compositions such as soda‐lime (fifteenth to sixteenth century), soda‐rich (fifteenth, sixteenth/nineteenth centuries) and lead‐potash‐lime (sixteenth and nineteenth centuries) are identified on the basis of the Raman signature of the glaze according to the wavenumber maxima of the Si O stretching and bending multiplets. The pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the similarity of the technologies. Cassiterite as an opacifier and hematite red and Naples yellow pigment variations give characteristic Raman signatures. The presence of lead arsenate as a pigment opacifier in nineteenth‐century samples is confirmed. Attempts are made to establish tools for the differentiation between genuine artefacts and nineteenth‐century restoration or fakes. Copyright © 2010 John Wiley & Sons, Ltd.     

陕西临潼新丰墓地出土战国秦汉时期玻璃器分析研究

陕西临潼新丰墓地的年代分两个阶段,第一阶段是战国中期偏晚至秦代,第二个阶段是西汉中期至东汉时期。该墓地有700余墓葬,其中12座墓葬出土玻璃制品100余件,包括蜻蜓眼珠,玻璃珠、耳珰。选取5件样品,涵盖上述三种器形。采用光学显微镜和扫描电子显微镜观察玻璃的结构特征,能谱仪分析其成分。采用激光拉曼光谱分析玻璃相中的晶体。结果显示5件玻璃样品中有4件铅钡玻璃,蓝色玻璃主要为铜离子着色,红色玻璃为Fe2O3晶体着色,白色乳浊玻璃为析晶造成的乳浊效果。1件为钾钙钠釉层的费昂斯制品,着色元素为铜和铁。同时讨论了铅钡玻璃和钾钙釉费昂斯的技术问题。     

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.     

Medieval glass from the Cathedral in Paderborn: a comparative study using X-ray absorption spectroscopy, X-ray fluorescence, and inductively coupled laser ablation mass spectrometry

We have investigated four stained glass samples recovered from an archaeological excavation at the Cathedral in Paderborn (Germany) between 1978 and 1980. On two of the samples there are parts of paintings. Concentrations of major elements were determined using two independent techniques: LA–ICP–MS (a UV laser ablation microsampler combined with an inductively coupled plasma mass spectrometer) and synchrotron radiation X-ray excited X-ray fluorescence (SR-XRF). The SR-XRF data were quantified by using the program package PyMCA developed by the software group of the ESRF in Grenoble. Significant differences were found between the concentrations determined by the two techniques that can be explained by concentration gradients near the surface of the glasses caused, for example, by corrosion/leaching processes and the different surface sensitivities of the applied techniques. For several of the elements that were detected in the glass and in the colour pigments used for the paintings X-ray absorption near edge structure (XANES) spectra were recorded in order to determine the chemical speciation of the elements of interest. As was expected, most elements in the glass were found as oxides in their most stable form. Two notable exceptions were observed: titanium was not found as rutile—the most stable form of TiO₂—but in the form of anatase, and lead was not found in one defined chemical state but as a complex mixture of oxide, sulphate, and other compounds.     

On‐site analysis of Chinese Cloisonné enamels from fifteenth to nineteenth centuries

A selection of 22 rare Chinese cloisonné enamels, from fifteenth century to nineteenth century A.D ., has been studied on‐site in the storage rooms of the musée des Arts décoratifs in Paris. The Raman signatures of the transparent and/or opacified glass matrix are discussed and compared with those that were previously recorded on glazed pottery, enameled and stained glasses. Enamels mostly belong to lead‐based potash‐lime glasses. Three different compositions, lead‐potash‐lime (fifteenth, sixteenth, eighteenth and nineteenth century), soda‐rich (sixteenth–seventeenth century) and soda‐lime (seventeenth century) are identified according to the wavenumber maxima of the Si O stretching and bending multiplets. Most of the pigment signatures are similar to those recorded on ceramic glazes and glass enamels, which proves the link between the technologies but a specific opacifier is observed: fluorite (CaF₂). Naples Yellow pigment variations give characteristic signatures. Additionally, a comparison is made with Limoges enamels (sixteenth–nineteenth century A.D. ). Copyright © 2009 John Wiley & Sons, Ltd.     

新疆巴里坤石人子沟遗址群出土玻璃珠的成分分析

巴里坤县位于新疆东部哈密地区,是连接内地与北疆的重要通道,巴里坤县境内的石人子沟遗址群是新疆东天山地区的古代游牧民族大型聚落遗址,其中西沟遗址M1墓和石人子沟遗址M011墓分别出土了一批战国晚期至西汉早期的古代玻璃珠,为了解这批玻璃珠的来源,采用激光剥蚀电感耦合等离子体发射光谱(LA-ICP-AES)和激光拉曼光谱(LRS)方法对这两批玻璃珠样品进行化学成分分析。结果表明,西沟遗址M1墓出土玻璃珠均为钠钙玻璃体系,以植物灰作为助熔剂,同时其中七件绿色玻璃珠样品均以锑酸铅作为乳浊剂;石人子沟遗址M011墓出土玻璃珠均为铅钡玻璃体系,以含铅矿物作为助熔剂。与同时期其他已经发表的玻璃数据进行比较,显示西沟遗址出土玻璃珠在成分上与美索不达米亚及古埃及钠钙玻璃不同,推测西沟遗址出土玻璃珠在中亚或新疆地区制作而成;石人子沟遗址出土玻璃珠的化学组成相对集中,应在同一地点制作而成,可能为中原地区传入。本研究证实了新疆巴里坤地区是古代东西方物质文化交流的重要节点,而游牧民族在玻璃制品传播和交流过程中扮演着重要的角色。     

Polychrome glass from Etruscan sites: first non-destructive characterization with synchrotron μ-XRF, μ-XANES and XRPD

This work is devoted to the characterization of a suite of very rare, highly decorated and coloured glass vessels and beads from the VII to the IV century BC. The most serious difficulty in developing this study was that any sampling – even micro-sampling – was absolutely forbidden. As a consequence, the mineralogical and chemical nature of chromophores and opacifiers present in these Iron Age finds were identified by means of the following synchrotron-based, strictly non-destructive, techniques: micro X-ray fluorescence (μ-XRF), Fe K-edge micro X-ray absorption near edge spectroscopy (μ-XANES) and X-ray powder diffraction (XRPD). The μ-XRF mapping evidenced high levels of Pb and Sb in the yellow decorations and the presence of only Sb in the white and light-blue ones. Purple and black glass show high amounts of Mn and Fe, respectively. The XRPD analyses confirmed the presence of lead and calcium antimonates in yellow, turquoise and white decorations. Fe K-edge μ-XANES spectra were collected in different coloured parts of the finds, thus enabling the mapping of the oxidation state of these elements across the samples. In most of the samples iron is present in the reduced form Fe²⁺ in the bulk glass of the vessels, and in the oxidized form Fe³⁺ in the decorations, indicating that these glass artefacts were produced in at least two distinct processing steps under different furnace conditions. PACS  29.20.Lq; 81.80.Kf; 61.10.Ht     

Nondestructive on‐site identification of ancient glasses: genuine artefacts,embellished pieces or forgeries?

A selection of 23 rare glass objects, mostly enameled, of various provenance and age, from the 5th century BC to the 19th century AD including the Western and Islamic Middle Ages but with a focus on 16th–18th century Venetian and French ‘façon de Venise’ artefacts, have been studied on‐site at the Sèvres museum or at the laboratory. The Raman signatures of the transparent or opacified glass matrix and of enameled decorations are discussed and compared to those previously recorded on ceramics and stained glasses. The Raman parameters allow discrimination between 2 groups (with some variations) of glass bodies, belonging to mixed Ca–Na and Ca‐containing Na‐rich silicates, with some exceptions. Most enamels are instead lead‐based glasses, but we also found enamels having a composition close to that of the glass body. Most of the pigment signatures are similar to those recorded on ceramic glazes, which proves the link between the two technologies. A particular emphasis was given to the identification of white opacification techniques. Very specific signatures could question the authenticity of some artefacts, and at least in two cases, arguments have been found to identify a fake or embellished artefact. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of copper nanoparticle‐containing glass matrices: ancient red stained‐glass windows

A selection of red‐flashed and red‐coated medieval potash lime and 19th century soda lime stained glass pieces were studied in the laboratory using different instruments and laser wavelengths, both at lower and higher than the surface plasmon resonance (SPR) of copper. The Raman signatures of the transparent glass matrix and the red glass layers are discussed and compared with those recorded on model glasses containing a dispersion of Cu⁰ nanoparticles. Evidence is given that the conformation of the silica network in the vicinity of the metal nanoparticles differs from that of the glass matrix. Hematite and carbon traces are evidenced in the Cu⁰‐rich layers, which is consistent with the use of a combination of a reducing atmosphere and redox couples to control the growth of metallic copper particles. Copyright © 2009 John Wiley & Sons, Ltd.     

The origin of haze in CVD tin oxide thin films

The origin of haze was investigated in antimony-doped tin oxide thin films, and in double-stack thin films of fluorine-doped tin oxide/antimony-doped tin oxide, both deposited by chemical vapor deposition onto soda-lime–silica float glass substrates. These transparent conductive oxide thin films are of great importance in the production of solar control architectural glazing units. Therefore, understanding the origins of haze is necessary to the development of coated, IR-reflecting glass windows with low overall haze levels. Haze measurements of as-prepared and polished samples were correlated with surface roughness and concentration of internal hole defects. Surface roughnesses were evaluated by atomic force microscopy, and characterized by estimated RMS values. In thin tin oxide films (<2000 Å) internal hole defects caused haze, while in thick tin oxide films (>4000 Å) surface roughness was the primary source of haze.     

Microfracture surface structure versus network and swelling properties of segmented polyurethanes

Microfracture surface structure of segmented polyurethanes (PUs) with different chemical and physical structures was tested in manually broken samples far below their glass transition. To observe the microfracture surface, transmission electron microscopy (TEM) was utilized. Some correlations between swelling degree (thus physical structure) and the appearance of the microfracture surface pattern were found in chemically different PUs. A radial microfracture topology was observed for cross-linked PU networks.     

Effect of surface roughness on determination of bulk tissue optical parameters

Monte Carlo simulations have been conducted to investigate the effect of surface roughness on the inverse determination of bulk optical parameters. Results show that mus, mua, and g can be overestimated by an order of magnitude for thin slab tissue samples with a moderate index mismatch at the interfaces if typical surface roughness is neglected. Measurements of Intralipid samples between glass windows with smooth and rough surfaces have been carried out and agreement was found between the numerical and the experimental data. This study suggests that the surface roughness should be taken into account for both in vitro and in vivo determination of bulk tissue optical parameters.     

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.     

Investigation of the possible origins of sulfur in 19th century salted paper photographs by x‐ray fluorescence spectroscopy

An X‐ray fluorescence method to determine whether sulfur is present in 19th century photographs due to intentional toning or to environmental deterioration is proposed. In the 19th century salted paper print photographic process, AgCl formed on the surface of a sheet of paper was exposed to sunlight in contact with a negative, leading to the printing out of a Ag image that was fixed by immersing it in a sodium thiosulfate solution or hypo. The improper execution of the fixing in these photographs may result in the presence of sulfur, mostly manifested in image fading, irregular staining, and discoloration. Also, 19th century artists produced salted paper prints with a variety of image tonalities, for example, by using an artificially aged thiosulfate bath. The presence of sulfur in photographs may also be due to sulfur‐containing environmental pollutants. Therefore, knowledge about the location and amounts of sulfur is important to understand the artistic technique and/or the deterioration processes. In this study, the amounts of sulfur and the silver to sulfur signal ratios were determined for a salted paper print made in the laboratory following a 19th century procedure and for two artistic salted paper photographs using X‐ray fluorescence and standards prepared with different amounts of retained hypo and quantified by inductively coupled plasma atomic emission spectroscopy. The amounts of sulfur and the normalized silver to sulfur ratios for the artistic photographs were evaluated based on the results obtained in the samples prepared in the laboratory and in the context of the 19th century practices. Copyright © 2016 John Wiley & Sons, Ltd.     

湖北随州曾侯乙墓出土玉器材质分析与产源初探

曾侯乙墓位于湖北省随州市郊,是二十世纪重大考古发现之一,其中出土玉石器数量达五百余件,且种类齐全、工艺精湛。利用现代测试仪器对这批玉石器进行全面而科学的鉴定,对于东周时期曾国用玉水平的研究具有重要的学术意义。为了探知曾侯乙墓出土玉器的玉料类型及透闪石玉料可能来源地,以其中的319件玉器为研究对象,采用宝石学与光谱学的研究思路和方法对这些样品进行无损测试。通过十倍放大镜及天平等常规宝石学检测仪器对样品的表面特征、受沁程度及种类做出初步判断,利用傅里叶变换红外光谱仪（FTIR）和X射线荧光光谱仪（XRF）快速、无损的分析出土玉器样品的矿物相及化学成分。研究结果表明,常规仪器测试结合红外光谱及X射线荧光光谱可以很好的区分出土玉器的材质,在曾侯乙墓出土的319件玉器中,有264件透闪石质玉器,43件大理岩石璧、8件云母质玉器、1件石英岩、1件萤石以及2件水晶环。XRF测试结果显示,透闪石炙玉占全部检测样品的82.8%,其主要化学成分为MgO约占20.03%～27.00%（平均值为24.46%）, SiO₂约56.31%～61.17%（平均值为58.99%）, CaO约14.25%～19.91%（平均值为15.42%）, Fe_TO约0.19%～2.06%（平均值为0.551%）,计算可知m（Mg）/m（Mg+Fe）的值在0.91~0.99之间,其测试结果范围与标准透闪石含量很接近,该批样品中未检测出阳起石质的软玉。其中,大部分优质透闪石质玉器均出土自主墓室,反映出当时人们的用玉水平及用玉习惯。根据已有研究结果,结合化学成分分析及部分具有特征风化皮层及戈壁料特征的样品,推测曾侯乙墓部分出土玉器的玉料来源于甘肃古玉矿。该结论为进一步研究曾国用玉制度和战国时期玉石之路提供了更多的研究资料。     

一批金元时期古玻璃的EDXRF探针无损分析

利用EDXRF探针无损分析技术,分析了河南禹县阳翟遗址出土的一批金元时期的玻璃样品,以研究这批古玻璃的工艺技术特点.分析显示,所有蓝色玻璃样品的呈色剂均为CuO,而非CoO.从化学组成来看,这批古玻璃的种类较为复杂,主要包括钾钙玻璃、钠钙玻璃和铅钾钙玻璃等.