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     

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。     

Sources of uncertainties in OSL dating of archaeological mortars: The case study of the Roman amphitheatre “Palais-Gallien” in Bordeaux

Archaeological mortars are more convenient and much more representative for the chronology of buildings than brick or wood constructions that can be re-used from older buildings. Before dating unknown samples of mortars, further investigation of OSL from mortars is required and the most efficient methodology needs to be established. In this study we compared the ages obtained by OSL dating of quartz extracted from mortars of the Roman amphitheatre Palais-Gallien in Bordeaux with independent age information.Resetting of the OSL signal occurred during the preparation of mortar when grains of sand (quartz) were extracted and mixed with lime and water. The mortar was subsequently hidden from light by embedding within the structure which is the event to be dated.Various factors contribute to uncertainties in the age determination. The frequency of measured equivalent doses reveals a large scattering. Optical bleaching of certain grains can be partial due to the short duration of the exposure to light. We worked with the single grain technique in order to find and select the grains that were sufficiently exposed to daylight. To determine the average equivalent dose, we tried three different approaches: a calculation of an arithmetic mean and one following either the central age model or the 3-parameter minimum age model, the latter turned out to be the only relevant way to evaluate the experimental data. The proportion of grains included in the calculation of the average equivalent dose represents 2.7–4.7 % of the overall analysed grains. The results obtained for the three out of four samples are approaching the expected age, however, the minimum doses and the corresponding ages are significantly over-estimated in case of two samples.The studied material is very coarse, which causes heterogeneity of irradiation at the single grain scale, and contributes to a dispersion of equivalent doses. Different analytical methods (scanning electron microscopy with energy dispersive X-ray spectroscopy cartography, Beta-radiography imaging, inductively coupled plasma mass spectrometry) were employed to demonstrate the presence of this phenomenon.Despite the extremely large proportion of high equivalent doses in equivalent dose distributions, there is an apparent presence of well-bleached grains at the beginning of equivalent dose distributions. The study shows the potential of dating mortars by single grain OSL.     

Studies of archaeological problems by Mössbauer spectroscopy

The recent developments and achievements of the application of Mössbauer spectroscopy to archaeological problems are reviewed. The relevances of Mössbauer spectroscopy in studies of provenance, manufacturing technology and age dating of ancient pottery, as well as the ancient bronzes are discussed.     

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.     

Study of ancient mortars from the Roman Villa of Pollio Felice in Sorrento (Naples)

The study of ancient mortars is an important aspect of building conservation: the choice of the materials has varied according to historical period, regional habits, and their specific function in the structure. Ancient mortars are composites, comprising hydraulic or aerial binding materials, and aggregates, passive or active, which may react with binding material. Moreover, they were modified during setting, hardening, and aging, according to processes not yet well known. In this paper, we present a study of ancient mortars from the Villa of Pollio Felice of Sorrento (Naples). The analysis has been performed by conventional techniques (grain-size distribution, lime-percentage analysis, optical and electron microscopy, and X-ray diffraction) and by means of a laboratory X-ray microdiffractometer equipped with an image plate detector. This system, applied for the first time to archaeological studies, can reach a spatial resolution of a few tenths of microns and it allows us to obtain separate phase identification of binder and filler particles. PACS 07.85.Nc; 61.10.Nz     

Degradation of stone materials in the archaeological context of the Greek–Roman Theatre in Taormina (Sicily, Italy)

In the present work results on the degradation phenomena of stone materials in the Ancient Theatre of Taormina, one of the most important Greek–Roman monuments of Sicily, are reported. Artificial stone materials in different conservation conditions were investigated. Samples of salt efflorescences from brick walls and degraded setting mortars were taken from the open gallery in “summa cavea”. The chemical, physical and structural characterization was performed by means of X-Ray Photoelectron Spectroscopy (XPS), X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF), both in situ and ex situ.     

Provenance identification of ancient pottery from Hachijojima Island,part of Izu Islands (Tokyo,Japan), using X-ray fluorescence spectrometry

A total of 47 pottery fragments were unearthed in Hachijojima Island, part of the Izu Islands (Tokyo, Japan). Among these samples, 36 found in the Kurawa site had designs resembling pottery dating back to the Jomon period (14,000–300 BC) distributed throughout Japan's main island, Honshu; five samples from the Jomon period found in the Yubama site were “undesigned”; the rest, found in the Yaene site, were undesigned Haji pottery samples dating back to the beginning of the late Kofun period (490–549 AD). X-ray fluorescence spectrometry (XRF) was used to determine the chemical composition (in terms of 10 major oxides and 12 minor elements) of the samples to identify their provenance, that is, local versus nonlocal. For this purpose, a portion of each pottery fragment was processed to obtain a glass bead specimen. The pottery samples were classified by multivariate statistical approaches, including principal component analysis and cluster analysis, on the basis of their chemical composition. Additionally, the XRF results were compared to geochemical data from Hachijojima Island using scatter diagrams. The data thus collected allowed the provenance of the pottery samples to be inferred. In particular, the 36 samples from the Kurawa site were concluded to have been brought to Hachijojima Island from Honshu in prehistoric times, whereas the other samples were concluded to have been manufactured locally.     

Provenance determination of prehistorical pottery from Oshima Island belonging to Izu islands (Tokyo,Japan) using X-ray fluorescence spectrometry

A total of 41 pottery shards originating in the Jomon period (14000–300 BC) and Yayoi period (300 BC–250 AD) were excavated from the Shimotakabora site on Oshima Island of the Izu islands (Tokyo, Japan). X-ray fluorescence spectrometry was used to determine the chemical composition (10 major oxides and 12 minor elements) of the potteries to identify the potteries' provenance, that is, local or nonlocal product. The calibration curves were drawn by synthetic standards prepared from a mixture of chemical reagents containing analytes, which presented good accuracy and reproducibility by analysis of the geochemical references. The pottery samples were classified by multivariate statistics such as principal component analysis and cluster analysis based on their chemical composition. Additionally, the X-ray fluorescence results were compared with geochemical data from Oshima Island using scatter diagrams. The pottery provenance was identified by their classification. This provenance estimation indicates that 37 of the 41 potteries were brought to Oshima island from Japan's main island, Honshu, in the prehistoric age.     

How the masters in Umbria,Italy, generated and used nanoparticles in art fabrication during the Renaissance period

Lustre was one of the most sophisticated techniques for the decoration of majolicas during the Renaissance period. Lustre consists of a thin metallic film containing silver, copper and other substances like iron oxide and cinnabar applied in a reducing atmosphere on a previously glazed ceramic. In this way, beautiful iridescent reflections of different colours (in particular gold and ruby-red) are obtained. The characterisation and the study of lustre-decorated majolicas is of great interest for archaeologists, but also offers possibilities for producing pottery with outstanding decoration today, following ancient examples, since nowadays Italian artisans are interested in the reproduction of the ancient recipes and procedures. Moreover, it can even suggest new procedures for obtaining uniform thin metallic films for technological applications. A study has been carried out on ancient lustre layers using numerous different analytical techniques such as XRD, SEM–EDX, TEM–EDX–SAED, ETAAS, ICP–OES, UV–vis reflectance spectroscopy and SAXS. Lustre films were shown to be formed by copper and silver clusters of nanometric dimension. The colour and the properties of the lustre films depend on the elemental composition of the impasto applied to the ceramic surface as well as on other factors like the metallic nanocluster dimension, the firing conditions, the underlying glaze composition and the procedure used. Received: 12 August 2002 / Accepted: 14 August 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +39-6/9067-2445, E-mail: pad@mlib.cnr.it     

Synthesis of mixed metallic nanoparticles by spark discharge

Short spark discharges (2 μs) were successfully applied to generate mixed particles a few nanometres in diameter by fast quenching. Alloyed Cr–Co electrodes were applied to demonstrate this. Further it was shown that if the anode and the cathode are different materials, the discharge process mixes the vapour of both materials, forming mixed nanoparticles. Electron microscopy (TEM, SEM), energy dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) analyses were performed on the collected particles to study their size, morphology, composition and structure. The average compositions of the particles were measured by inductively coupled plasma (ICP). In addition, online measurements of the particle size distribution by mobility analysis were carried out. In the case of alloyed electrodes (Cr–Co), the relative concentration of the elements in the nanoparticulate sample was consistent with the electrode composition. When using electrodes of different metals (Au–Pd and Ag–Pd) the individual nanoparticles showed a range of mixing ratios. No surface segregation was observed in these mixed noble metal particles. Crystalline nanoparticulate mixed phases were found in all cases.     

Toward superlensing with metal–dielectric composites and multilayers

We report on the fabrication of two types of adjustable, near-field superlens designs: metal–dielectric composites and metal–dielectric multilayer films. We fabricated a variety of films with different materials, thicknesses and compositions. These samples were characterized physically and optically to determine their film composition, quality, and optical responses. Our results on metal–dielectric composites indicate that although the real part of the effective permittivity generally follows effective medium theory predictions, the imaginary part does not and substantially higher losses are observed. Going forward, it appears that multilayer metal–dielectric designs are more suitable for sub-diffraction imaging applications because they could provide both tunability and low loss.     

Solution of the thermoelastoplastic problem for a thin disk of plastically compressible material subjected to thermal loading

Elastoplastic solutions for thin plates and disks are sensitive to loading and plasticity conditions [1–5]. The plasticity condition for a number of metal materials depends on the mean stress [6–8]. In this case, when using the associated flow rule, plastic deformations do not satisfy the incompressibility condition, which is commonly accepted in statements of boundary-value problems for thin elastoplastic plates and disks [9–13]. It is of interest to determine the effect of plastic compressibility on the behavior of solutions for such structures. In this paper, a hollow disk in a rigid container subjected to a uniform temperature field is considered. The plasticity condition proposed in [14] is accepted. A general study of the set of equations including this plasticity condition and the associated flow rule was performed in [15]. The solution under the Mises plasticity condition was obtained in [1].     

Spatially resolved synchrotron radiation induced X-ray fluorescence analyses of rare Rembrandt silverpoint drawings

New analyses of a series of very rare silverpoint drawings that were executed by Rembrandt Harmensz. van Rijn (1606–1669) which are kept today in the Kupferstichkabinett (Museum of Prints and Drawings) of the State Museums of Berlin are reported here. Analysis of these drawings requires particular attention because the study has to be fully non-destructive and extremely sensitive. The metal alloy on the paper does not exceed some hundreds of μg/cm². Therefore, synchrotron radiation induced X-ray fluorescence (SR-XRF) is – together with external micro-proton-induced X-ray emission – the only well-suited method for the analyses of metalpoint drawings. In some primary work, about 25 German and Flemish metalpoint drawings were investigated using spatially resolved SR-XRF analysis at the BAMline at BESSY. This study enlarges the existing French–German database of metalpoint drawings dating from the 15th and 16th centuries, as these Rembrandt drawings originate from the 17th century where this graphical technique was even rarer and already obsolete. It also illustrates how SR-XRF analysis can reinforce art historical assumptions on the dating of drawings and their connection. PACS 89.90.+n; 81.70.Jb; 81.05.Bx     

High-temperature thermoelectric behavior of lead telluride

Usefulness of a material in thermoelectric devices is temperature specific. The central problem in thermoelectric material research is the selection of materials with high figure-of-merit in the given temperature range of operation. It is of considerable interest to know the utility range of the material, which is decided by the degrading effect of minority carrier conduction. Lead telluride is among the best-known materials for use in the temperature range 400–900 K. This paper presents a detailed theoretical investigation of the role of minority carriers in degrading the thermoelectric properties of lead telluride and outlines the temperature range for optimal performance.     

XRF analysis without sampling of Etruscan depurata pottery for provenance classification

In order to settle the provenance of a set of ancient ceramic shards, the elemental composition data acquired are usually treated by multivariate analysis techniques. The quantitative X‐ray fluorescence (XRF) analysis is an appropriate tool if it is possible to grind ceramics and analyze a sample that is representative of the object. If we deal particularly with well‐preserved objects, we are often not allowed to sample them. Moreover, moving these objects from museum could be unfeasible as well. The aim of this work is to evaluate if spot XRF analysis on integral objects is adequate to classify row clay provenance even if ceramics is not an intrinsically homogeneous material. So, we performed measurements on a set of Etruscan fine ware already classified according to the archaeological, chemical and mineralogical examination. For each sample, several measurement points in polished areas were considered for XRF analyses, allowing a correct provenance classification. Copyright © 2010 John Wiley & Sons, Ltd.     

Laser induced micro-photoluminescence of marble and application to authenticity testing of ancient objects

For the last 70 years, the authenticity of disputable marble objects has been tested by using a black light lamp. According to empirical observations “fresh marbles are purple while ancient ones are blue under the lamp”. This discrimination lacks scientific basis but is very popular because sculptured stone dating is impossible. This work aims to test the reliability of the “UV method” by studying the laser excited photoluminescence (PL) of marble surfaces. An argon ion laser beam was focused through a microscope objective onto the sample, offering a PL spatial resolution of 3 μm. Newly-cut marbles show an intense emission at 610 nm ascribed to Mn²⁺ and a less intense one at 390 nm. Excavated surfaces show the 610 nm emission and a broadband (380–530 nm) one. Similar broadband emissions due to humic (HAs) and fulvic acids (FAs) are typical in soil PL spectra and were observed in the spectra of samples taken from the soil surrounding the excavated surfaces. Additionally, electron paramagnetic resonance (EPR) spectra of excavated surfaces show a peak at g=2.0045, typical in calcite doped with humic acids. We presume that the 380–550 nm emission originates from HA and FA salts existing in the infiltrated soil or the recrystallised calcite developed in marble patinas. Finally, the application of the “UV method” on twelve ancient and modern surfaces proved that the technique is only partly reliable and should be used together with other analytical techniques. PACS 78.55.-m; 78.55.Hx; 81.70.Fy; 87.64.Hd     

1999 chess users' meeting

Archeometry and conservation science are two emergent fields in materials science with an increasing demand of access to SR-based techniques such as X-ray fluorescence, X-ray diffraction, X-ray imaging and IR spectroscopy. These two fields deal with the investigation of the exact nature of art and archeological objects, the provenance of the materials, their dating, and also their alteration processes and preservation procedures. Materials concerned are as various as metals, minerals, pigments, glasses, ceramics, biomaterials, and organic materials. Characteristic features of the materials are often trace elements or minor phases. In addition, art and archeological objects are very complex and often composed of heterogeneous materials. Organic and inorganic materials can be intimately mixed from the macro- to the nanoscale. Surface layers formed by complex degradation processes show a different chemical composition and structure with respect to the bulk of the objects. Conservators and archeologists obviously prefer non-destructive or at least micro-destructive methods for the analysis of their materials and objects. Therefore, the analysis of art and archaeological objects represents a real challenge for materials science. Synchrotron radiation techniques, especially those with microbeams, provide powerful new tools to interrogate the records of our physical and cultural past.     

Large scale synthesis of silicon nanowires

Artificial nanostructures (Samuelson et al., Physica E 21:560–567, 2004; Xia et al., Adv Mater 15:353–389, 2003) show promise for the organization of functional materials (Huck and Samuelson, Nanotechnology 14:NIL_5–NIL_8, 2003) to create nanoelectronic (Mizuta and Oda, Science 279:208–211, 2008) or nano-optical devices (Mazur et al.; Tanemura et al., Synthesis, Optical Properties and Functional Applications of ZnO Nano-materials: A Review, 1–3:58–63, 2008). However, in most manufacturing recipes described so far, nanostructures are synthesized in solution and/or uncontrolled deposition results in random arrangements; this makes it difficult to measure the properties of attached nanodevices or to integrate them with conventionally fabricated microcircuitry. Here, we describe a fully CMOS compatible process technology for mass manufacture of polysilicon nanowires by the CVD (chemical vapor deposition) method. The large scale production of nanowires could successfully be synthesized on silicon (100) substrates. However, the method presented here can successfully be employed with all technologically useful substrates with good adhesion for silicon such as SiO₂, diamond-like carbon or III–V semiconductors. This opens up the possibility for the fabrication of strain-sensitive and defect-sensitive optoelectronic devices on the optimum III–V substrate (Fonstad et al.). Finally, scanning electron microscopy (SEM) was used to characterize the as-synthesized nanowires and energy-filtered transmission electron microscopy (EFTEM) and scanning transmission electron microscopy (STEM) analysis were used to determine the nanowire composition.