浙江古城墙传统灰浆材料的分析研究

灰浆材料一直是古代建筑类文化遗产研究的重要对象,文保工程中使用传统灰浆的诸多优点已广为人知,在认识传统灰浆的基础上开发新的石灰基粘结保护材料已然成为国际研究热点。随着中国的经济发展,很多古建筑的保护也开始提上日程,然而关于中国传统灰浆材料的研究颇为薄弱。实地调查浙江地区多座古代城墙遗址,采集灰浆样品,利用多功能密度仪、粉末X射线衍射仪(XRD)、傅里叶红外光谱仪(FTIR)、热重-差热分析仪(TG-DSC)和湿化学分析技术,对浙江地区7处古城墙灰浆样品进行了分析检测和研究。结果表明：这些古城墙使用的胶结材料是纯“白灰灰浆”,主要成分是碳酸钙,含量在75%～90%之间,其原料主要是钙质生石灰,个别来自镁质生石灰;其中有4座城墙灰浆添加有糯米成分,说明该地区在明代向灰浆里添加糯米等有机材料是建筑城墙十分普遍的工艺技术;检测发现这些建筑灰浆的密度较低,且数值相差较大,在1.2～1.9 g·cm-3之间,应是环境长期侵蚀的结果。同时,也分析了这些砌筑灰浆的其他物化特征,为下一步古城墙本体保护和保护材料的研发,以及传统灰浆全国范围内的比较研究提供了科学依据。     

Physico-chemical characterization of mortars as a tool in studying specific hydraulic components: application to the study of ancient Naxos aqueduct

Mortars and plasters from the ancient aqueduct on the island of Naxos, Greece, were studied with regard to mineralogical and chemical composition, grain size distribution, raw materials and hydraulic properties, in order to assess their characteristics and design compatible repair mortars. The authentic materials contained lime, crushed-brick, siliceous and calcitic aggregates, in different proportions according to mortar type. Crushed-bricks fired at low temperatures and lightweight volcanic aggregates contained amorphous phases, which upon reaction with lime yielded hydraulic components capable of protecting the construction from the continuous presence of water. Hydraulic calcium silicate/aluminate hydrates, the proportions and the perfect packing of the raw materials, along with the diligent application justify the longevity and durability of the studied samples. The hydraulic properties of samples were pointed out through (a) the well-established CO₂/H₂O ratio derived from the thermogravimetric analysis and (b) by introducing two powerful indices issued from the chemical analysis, namely CaO_hydr and soluble SiO_2 hydr. These indices improved the clustering of hydraulic mortars and provided better correlation between mortars, plasters and their binders. By comparing grain size distribution and hydraulicity indices it was possible to distinguish among the construction phases. Based on this study, repair mortars were formulated by hydraulic lime, siliceous sand, calcareous and crushed-brick aggregates, with the optimal water content, ensuring optimum workability and compatible appearance with the authentic ones.     

Applied geology in analytical characterization of stone materials from historical building

Investigations of the provenance and technology of ancient materials are an important part of archaeological research. Studies of the geology of a region combined with petrographic research and chemical analysis may allow one to establish a possible source of raw-materials used. They also enable selection of the materials from currently accessible sources in the process of renovation or reconstruction of buildings [1–3]. Until now, the authors have carried out the studies in order to determine provenance of the raw-materials, the detailed analysis of composition (for the stone materials from Romanesque buildings in South Wielkopolska – Poland, and from ancient ruins in northern Israel and northern Egypt. Petrographic analysis (macro- and microscopic observations), cathodoluminescence (CL), X-raydiffraction (XRD) and stable isotopes analysis have been applied. In the next step, the detailed composition analysis enables, in the case of mortars, selection of suitable samples for dating [4, 9] and to determine the age of a given object, either directly by absolute dating (e.g. ¹⁴C of lime mortars) or indirectly, by relative age estimation on the basis of finds and artifacts (their components and characteristic style for a specific period). PACS 07.60 Pb; 78.60 Hk; 91.65 Dt; 91.60.-x; 07.85.Nc     

Minero-petrographic, thermal and microchemical investigation of historical mortars used in Catania (Sicily) during the XVII century A.D.

The combination of X-Ray Diffraction (XRD), Scanning Electron Microscopy-Energy Dispersive Spectrometry (SEM-EDS), Differential Thermal Analysis-Thermogravimetry (DTA-TG) and Optical Microscopy (OM) has been used to study several different ancient mortars recovered in the S. Nicola Church (built after the devasting earthquake of the 1693) and other historic buildings located in the historical center of Catania (Eastern Sicily). Investigations have been focused on the identification of raw materials mixed in the different mortars and their provenance as well as on the study of the relevant technological aspects of manufacturing processes. Minero-petrographic data have often shown that local volcanic raw materials have been used as aggregate fractions and, in particular, a new volcanic material, the so-called ghiara, has been largely adopted for the construction of the walls of the monuments after the earthquake. It is worthy to note that ghiara is a by-product of erupted magma during the impressive Etna eruption of 1669, which almost completely covered the centre of Catania. The following reaction with the soil gave rise to the formation of a layer of this typical ochre-coloured material. Moreover, the precise provenance of the ghiara has been determined trough geological surveys of the most important historic quarries. Results have allowed the identification of exploited sources of ghiara.Furthermore, combination of SEM-EDS results and thermal information have indicated the hydraulic nature of the mortars due to the formation of hydraulic phases at the binder-aggregate interface. It, therefore, is due to the fact that the ghiara has slight pozzolanic properties.Present data have an important role for any satisfactory reproduction of the ancient manufacturing techniques to be used for the restoration of the S. Nicola Church. PACS 81.70.Pg; 82.80.d; 61.10.Nz; 61.66.Fn     

天然矿物合成“中国紫”过程中的变温XRD分析

以天然矿物为原料,结合中国紫的分子式及多数考古样品的分析结果进行配料(如或多或少都含有铅),对配制并加工好的试样进行热重-差热及变温XRD分析,以探讨古代烧制中国紫颜料时的原料选用及烧制条件等问题,为揭示诸如中国紫产生在中国的原因等问题提供依据。结果表明利用毒重石(BaCO3)配料,能够较容易地烧制出中国紫,这意味着中国紫的出现可能与这种独特的含钡矿物资源有关。     

一种新型的微束X射线荧光谱仪及其在考古学中的应用

介绍了一种新型的基于X光透镜的微束X射线荧光分析系统的结构、性能和特点及其在考古学中的应用.X光透镜将旋转阳极X射线发生器产生的X射线束聚成直径为几十微米的光束，实现了对考古样品的无损、原位、微区的分析.为了检验微束分析系统的可行性，分析了一片明代青花瓷残片中青花部位的元素分布，结果表明青花中Mn和Co元素的含量与青花颜色的深浅相一致；相关性分析表明Mn和Co呈现非常好的线性相关；Mn和Co的含量或比值对青花的产地和真伪的辨别有着重要的意义. 关键词： X光透镜 微束X射线荧光 青花     

The apparition of a new reaction at lower temperature in equiatomic CuAu alloy

Recently a lot of interest has been devoted to the study of order–disorder transitions in different materials. Although the equiatomic CuAu alloy represents a classical model of this type of transformation, it still receives considerable attention because many questions about phase transitions are still raised according to its equilibrium diagram. In this context, the present paper carries a new result observed in CuAu alloy consisting of a new anomaly observed on differential scanning calorimetry (DSC) curves at low temperature and new peaks in X-ray diffraction (XRD) spectra. For that, we will try to give an explanation of the origin of this new reaction, with the help of other techniques as electrical resistivity and microhardness measurements. The kinetic behaviour of this new reaction has been also studied by anisothermal analysis during DSC tests to estimate the kinetics parameters as activation energy E _act and Avrami exponent n.     

The longevity of old mortars

The study of old mortars has revealed a treasure of knowledge concerning the binders and their use in manufacturing mortars as well as the philosophy on which the building technology of the past was based. In this paper the characteristics of mortars taken from some important monuments with remarkable durability are presented and commented on so as to enable their resistance to weathering to be highlighted. Comparing them within the frame of modern durability issues, it could be said that the principles on which the design of long time resistant materials is based are diachronic. PACS 81.05.Rm; 81.40.-z; 81.70.-q; 81.70.Jb     

Development and trends in synchrotron studies of ancient and historical materials

Synchrotron photon-based methods are increasingly being used for the physico-chemical study of ancient and historical materials (archaeology, palaeontology, conservation sciences, palaeo-environments). In particular, parameters such as the high photon flux, the small source size and the low divergence attained at the synchrotron make it a very efficient source for a range of advanced spectroscopy and imaging techniques, adapted to the heterogeneity and great complexity of the materials under study. The continuous tunability of the source — its very extended energy distribution over wide energy domains (meV to keV) with a high intensity — is an essential parameter for techniques based on a very fine tuning of the probing energy to reach high chemical sensitivity such as XANES, EXAFS, STXM, UV/VIS spectrometry, etc. The small source size attained (a few micrometres) at least in the vertical plane leads to spatial coherence of the photon beams, giving rise in turn to a series of imaging methods already crucial to the field. This review of the existing literature shows that microfocused hard X-ray spectroscopy (absorption, fluorescence, diffraction), full-field X-ray tomography and infrared spectroscopy are the leading synchrotron techniques in the field, and presents illustrative examples of the study of ancient and historical materials for the various methods. Fast developing analytical modalities in scanning spectroscopy (STXM, macro-XRF scanning) and novel analytical strategies regarding optics, detectors and other instrumental developments are expected to provide major contributions in the years to come. Other energy domains are increasingly being used or considered such as far-infrared and ultraviolet/visible for spectroscopy and imaging. We discuss the main instrumental developments and perspectives, and their impact for the science being made on ancient materials using synchrotron techniques.     

Scientific analysis of some glazed pottery unearthed from Warring States Chu tombs in Jiangling,Hubei Province: Indication for the origin of the low-fired glazed pottery in China

A portable energy dispersive X-ray fluorescence spectrometer and a micro-Raman spectrometer are used for the nondestructive analysis of a batch of glazed pottery ornaments unearthed from Warring States Chu (楚) tombs (B.C.475–B.C.221) in Jiangling, Hubei Province, China. According to the chemical compositions obtained, all of the glazes belong to the lead–barium–silicate (PbO–BaO–SiO₂) system and contain certain levels of copper. The man-made barium copper silicate pigment crystals, such as Chinese blue (BaCuSi₄O₁₀) and Chinese purple (BaCuSi₂O₆), are identified from several samples by micro-Raman spectrometer. Besides, gypsum and hematite are found in the white and brown regions of two eye beads. Combined with other glazed pottery and the related silicate artifacts (e.g., lead–barium glass and faience, potash–lime glass and glazed pottery, high-lead glazed pottery, etc.), the origin, development, and affected factors of ancient Chinese low-fired glazed pottery have been discussed preliminarily. The present study provides principal evidences for the technological provenance, raw material recipes, and the relationship between low-fired glazed pottery and related vitreous materials of ancient China. It also provides some significant clues for the origin and the development of ancient Chinese lead–barium glass.     

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.     

Production of reference alloys for the conservation of archaeological silver-based artifacts

In the framework of the EC PROMET project, the chemical composition and metallurgical features of a large number of archaeological artifacts were investigated by different analytical surface and bulk techniques, such as Optical Microscopy (OM), Scanning Electron Microscopy coupled with energy dispersive X-ray micro-analysis (SEM-EDS), X-ray Diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS). The study of the corrosion products grown on the archaeological Ag-based artifacts revealed a quite ubiquitous and nearly constant presence of chlorine from the soil as the main corroding agent, mainly producing chlorargyrite (AgCl). Results of this extensive chemical, physical and metallurgical characterization were used to produce modern reference Ag-based alloys with a chemical composition and micro-chemical structure similar to that of ancient alloys. Furthermore, these reference Ag-based alloys were submitted to an accelerated degradation method in order to produce corroded samples to be used as sacrificial materials for testing corrosion inhibiting products. The production of artificial “patinas” and corrosion layers was made by a chemical and soil-induced degradation procedure. The comparison of the micro-chemical structures of natural and artificial corrosion layers shows that the selected degradation method produces “patinas” resembling those grown on archaeological artifacts from a chemical, structural and micro-morphological point of view.     

Archaeo-metallurgical studies of tuyeres and smelting slags found at Tharros (north-western Sardinia, Italy)

A large number of pyrometallurgical materials such as tuyeres, slags and refractory tools likely associated with metal extraction processes have been found at Tharros (north-western Sardinia, Italy) during archaeological excavations stratigraphically related to the Phoenician–Punic period (VI–III centuries BC). Micro-chemical, micro-structural and mineralogical studies have been carried out by means of the combined use of X-ray diffraction (XRD), selected-area X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) combined with energy-dispersive X-ray analysis (EDS) in order to identify pyrometallurgical processes and main relevant technological parameters. The results reveal that tuyeres, slags and refractory tools can be associated with an iron ore smelting process to extract the metal by slagging the unwanted by-products. Moreover, temperature and duration of the smelting process have been estimated through mineralogical studies and by a comparative analysis between the micro-chemical and structural features of thermally treated refractory materials and tuyeres. The results disclose the high level of technological competence of the ancient metallurgists able to carry out complex high-temperature processes to extract iron from ores by separating the metal from unwanted siliceous species.     

Degradation study of XVIII century graffiti on the walls of Chiaramonte Palace (Palermo, Italy)

A systematic investigation of the original materials and the degradation phenomena induced by soluble salts on the wall matrix and on the graffiti of the Inquisition jails of Chiaramonte Palace in Palermo (Italy) was carried out. Built in the XIV century, Chiaramonte Palace was used as Inquisition court during the XV–XVI centuries. The ancient graffiti, recently discovered, represent a unique historical witness of the prisoners that lived during that terrible period. In order to study the nature, the amount and the distribution of the salts in the masonry, stone materials sampled at different depth from the wall matrix and saline efflorescences were analysed. Different physical techniques were used, such as X-ray Photoelectron Spectroscopy, X-ray Fluorescence, Laser Induced Breakdown Spectroscopy, X-ray Diffraction and Ionic Chromatography. Results of the chemical and physical characterisation showed that the main cause of the degradation of graffiti and wall paintings was the presence of soluble salts, such as nitrates, chlorides and sulphates. Traces of oxalates, coming from a previous conservation treatment, were also found. The results obtained by the stratigraphical characterisation of soluble salts in the wall matrix can be used to recommend a procedure based on air humidification at high relative humidity values in order to avoid salt crystallisation and to prevent the crumbling process of the graffiti.     

EDXRF微量元素分析在文物断源断代中的研究

能量色散X荧光分析（EDXRF）是重要的元素成分析方法之一,现已成为一种强有力的定性和精确定量的无损分析测试技术。能量色散X荧光分析（EDXRF）技术具有不破坏分析样品,并能快速进行钠（Z11）至铀（Z92）的多元素的同时分析,以及分析的浓度范围宽广,精度高等特点,因此,特别适合于进行文物材料的成分分析研究,尤其适合测试极其珍贵的古陶瓷完整文物样品分析与鉴定。文章运用该方法对选自杭州南宋官窑窑址、龙泉古窑址出土的14个样品的南宋官窑青瓷、南宋龙泉窑青瓷和现代仿古青瓷等进行了元素分析的对比研究,分析测定古陶瓷样品中胎、釉的主、次量及微量元素组成,寻找组成中的“指纹”特征元素,试图为古陶瓷文物的断源、断代研究和真伪鉴定提供科学依据。研究结果表明能量色散X荧光分析（EDXRF）是一种较理想的文物研究和鉴定的科学分析手段。     

A deep view in cultural heritage—confocal micro X-ray spectroscopy for depth resolved elemental analysis

Quantitative X-ray fluorescence (XRF) and particle induced X-ray emission (PIXE) techniques have been developed mostly for the elemental analysis of homogeneous bulk or very simple layered materials. Further on, the microprobe version of both techniques is applied for 2D elemental mapping of surface heterogeneities. At typical XRF/PIXE fixed geometries and exciting energies (15–25 keV and 2–3 MeV, respectively), the analytical signal (characteristic X-ray radiation) emanates from a variable but rather extended depth within the analyzed material, according to the exciting probe energy, set-up geometry, specimen matrix composition and analyte. Consequently, the in-depth resolution offered by XRF and PIXE techniques is rather limited for the characterization of materials with micrometer-scale stratigraphy or 3D heterogeneous structures. This difficulty has been over-passed to some extent in the case of an X-ray or charged particle microprobe by creating the so-called confocal geometry. The field of view of the X-ray spectrometer is spatially restricted by a polycapillary X-ray lens within a sensitive microvolume formed by the two inter-sectioned focal regions. The precise scanning of the analyzed specimen through the confocal microvolume results in depth-sensitive measurements, whereas the additional 2D scanning microprobe possibilities render to element-specific 3D spatial resolution (3D micro-XRF and 3D micro-PIXE). These developments have contributed since 2003 to a variety of fields of applications in environmental, material and life sciences. In contrast to other elemental imaging methods, no size restriction of the objects investigated and the non-destructive character of analysis have been found indispensable for cultural heritage (CH) related applications. The review presents a summary of the experimental set-up developments at synchrotron radiation beamlines, particle accelerators and desktop spectrometers that have driven methodological developments and applications of confocal X-ray microscopy including depth profiling speciation studies by means of confocal X-ray absorption near edge structure (XANES) spectroscopy. The solid mathematical formulation developed for the quantitative in-depth elemental analysis of stratified materials is exemplified and depth profile reconstruction techniques are discussed. Selected CH applications related to the characterization of painted layers from paintings and decorated artifacts (enamels, glasses and ceramics), but also from the study of corrosion and patina layers in glass and metals, respectively, are presented. The analytical capabilities, limitations and future perspectives of the two variants of the confocal micro X-ray spectroscopy, 3D micro-XRF and 3D micro-PIXE, with respect to CH applications are critically assessed and discussed.     

New Raman Spectroscopic Data of the Almahata Sitta Meteorite

The archaeological site of Pintia (Padilla de Duero/Peñafiel, Valladolid), considered one of the first cities on the Iberian Peninsula, has yielded very interesting archaeological records regarding the different functional areas that involve the oppidum. Pottery, metal, and bone/skeletal remains are very well preserved, being optimal for analysis and study of the ancient food contained, such as milk-based products, animal fats, beer, and wine. The combination of Raman Microscopy (RM) with other analytical techniques such as Light Microscopy (LM) and Environmental Scanning Electron Microscopy equipped with Energy Dispersive X-ray Spectroscopy (ESEM-EDX) becomes a powerful tool to obtain information on the possible content in the ceramic receptacles from historical-archaeological heritage. It can lead to an interpretation of their specific use or functionality. In this work, a unique sample preparation was used for all techniques, which lead to a very simple procedure and documentation. The degradation and aging of natural fibers and the presence of organic matter with low crystallinity and calcium oxalate–related residuals can be studied by these combined techniques. The archaeological residuals can be separated from modern contamination coming from agriculture processes, surrounding land minerals, or fresh vegetal matter.     

Materials Research with X-ray Micro-beams at the Advanced Photon Source

X-ray scattering has had a rich and prominent place in the history of materials research. For samples that are large single crystals, X-ray diffraction provides very detailed, high-quality information about the atomic structure of almost every kind. However, most engineering materials are not a large single crystal, but mixtures of materials or a poly-crystalline material. Still, X-ray diffraction using X-ray beams significantly larger than the structures being investigated has produced much excellent information. Examples of this are powder diffraction, texture analysis, strain analysis, etc. While these types of analyses have been very useful in providing a microscopic understanding, they do not provide the microscopic information that we really want. What we really want to have is this useful X-ray diffraction information for every volume element in our sample; not just the diffraction information about small volume elements, but all of the volume elements, exactly where they are in our sample, and how each one diffracts. This detailed spatial and structural information is what is needed for a full understanding of the source of the properties that we find in engineering materials.     

便携式能量色散型X射线荧光光谱仪在中国古代玻璃化学成分分析中的应用

中国古玻璃研究的一个重要方面是古玻璃的化学成分分析,它为中国古玻璃的起源和技术发展提供了科学依据,因此,发展新的化学成分分析方法是非常有必要的.便携式能量色散型X射线荧光分析(portable energy-dispersive X-ray fluorescence annlysis,PXRE)技术的最大特点就是其便携性,可以对不可移动或难以移出博物馆的文物进行科技分析.文章详细介绍了中国科学院上海光学精密机械研究所科技考古中心与日本OURSTEX公司合作改进的便携式能量色散型X射线荧光分析仪的组成、工作原理及分析过程等,列举了将其应用于新疆出土古玻璃样品的测试结果,并与质子激发X射线荧光分析技术所获结果进行了比较.便携式能量色散型X射线荧光分析技术在现场分析方面具有极为广阔的应用前景.