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.     

Advantages and limitations of OM, SEM, TEM and AFM in the study of ancient decorated pottery

This paper presents results from the study of two fragments of pre-Hispanic pottery, decorated with red pigment, using Optical Microscopy (OM), Scanning Electron Microscopy (SEM), High Resolution Transmission Electron Microscopy (HRTEM), Atomic Force Microscopy (AFM) and Magnetic Force Microscopy (MFM). Capabilities and limitations of these techniques in the analysis of archaeological material are highlighted with special emphasis on TEM, AFM and MFM due to their contribution in the study of the pigment layer at micro and nano scale. The analyzed samples come from the archaeological sites of El Tajin and Xochicalco, both in Mexico. Results of conventional TEM and HRTEM analysis of the red pigment showed nanometric Fe₂O₃ particles in both samples but different particle shape and size distributions: specimen from El Tajin presented irregular particles between 50–100 nm while that from Xochicalco exhibited semispherical shapes in the 3–25 nm range. AFM images showed the topography of the pigments, which are related to the texture of their surface and thus to the production process. Finally, MFM showed different contrast regions suggesting the presence of ferromagnetic elements forming clusters and domain orientations on the color layer.     

An integrated analytical characterization of corrosion products on ornamental objects from the necropolis of Colle Badetta-Tortoreto (Teramo, Italy)

Selected groups of copper-based artifacts found during archaeological excavations of the necropolis of Colle Badetta-Tortoreto (Teramo, Italy) were investigated in order to determine the chemical composition and metallurgical features of the alloys and the micro-chemical and micro-structural nature of the corrosion products grown during the long-term burial. The investigated Cu-based artifacts were ornamental objects, such as rivets, buckles and small rings that were applied to large belts to form complex patterns with the addition of small and large shaped pieces of amber. The analytical characterization was performed by using different 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).     

Analytical Instrumental Techniques to Study Archaeological Wood Degradation

Abstract

Historically, a very large variety of everyday artifacts were made of wood, which makes them representative of their historical period or social context and valuable for archaeologists and historians. In order to preserve degraded wood and to develop and apply suitable conservation treatments, chemical and physical characterization of archaeological wood is needed. This review provides the reader with a survey on state-of-the-art of instrumental analytical tools available to understand the morphology and the chemical composition of archaeological wood. The focus is on microscopic and spectroscopic techniques such as scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), Raman, nuclear magnetic resonance (NMR) and analytical techniques based on pyrolysis, such as direct exposure–mass spectrometry (DE-MS), pyrolysis–mass spectrometry (Py-MS), pyrolysis–gas chromtography–mass spectrometry (Py-GC/MS), with emphasis on their respective potentialities and limitations. The advantages of techniques based on synchrotron radiation are also discussed. In addition, the applicability of each examined technique is illustrated and discussed through specific examples from the literature.     

Cultural heritage and archaeology materials studied by synchrotron spectroscopy and imaging

The use of synchrotron radiation techniques to study cultural heritage and archaeological materials has undergone a steep increase over the past 10–15 years. The range of materials studied is very broad and encompasses painting materials, stone, glass, ceramics, metals, cellulosic and wooden materials, and a cluster of organic-based materials, in phase with the diversity observed at archaeological sites, museums, historical buildings, etc. Main areas of investigation are: (1) the study of the alteration and corrosion processes, for which the unique non-destructive speciation capabilities of X-ray absorption have proved very beneficial, (2) the understanding of the technologies and identification of the raw materials used to produce archaeological artefacts and art objects and, to a lesser extent, (3) the investigation of current or novel stabilisation, conservation and restoration practices. In terms of the synchrotron methods used, the main focus so far has been on X-ray techniques, primarily X-ray fluorescence, absorption and diffraction, and Fourier-transform infrared spectroscopy. We review here the use of these techniques from recent works published in the field demonstrating the breadth of applications and future potential offered by third generation synchrotron techniques. New developments in imaging and advanced spectroscopy, included in the UV/visible and IR ranges, could even broaden the variety of materials studied, in particular by fostering more studies on organic and complex organic–inorganic mixtures, while new support activities at synchrotron facilities might facilitate transfer of knowledge between synchrotron specialists and users from archaeology and cultural heritage sciences.     

二蕊荷莲豆环肽B的NMR应用研究

植物环肽的¹H 和¹³C NMR图谱, 由于各种氨基酸自旋系统质子和碳的化学位移非常接近，谱峰高度重叠，结构解析比较困难. 文中以二蕊荷莲豆环肽B为例讨论了
现代2D NMR新技术，在植物环肽结构解析中的应用. HMQC-TOCSY图谱在氢谱方向和碳谱方向分别提供每一个氨基酸自旋系统内的氢和除季碳外碳的全相关信息，从而将每个氨基酸残基的NMR信号相互区分开来；结合¹H-¹H COSY 和 HMQC或HSQC图谱，就可以准确归属每个氨基酸的氢和碳的化学位移. 氨基酸残基之间的连接顺序可用HMBC、NOESY或ROESY图谱获得.     

Non-Voigt line-shape effects on retrievals of atmospheric ozone: Collisionally isolated lines

This paper addresses the question of errors in retrievals of vertical profiles of ozone from atmospheric spectra caused by assuming that the absorption lines have pure Voigt line shapes. The case of collisionally isolated transitions (no line mixing) is treated by considering only the effects of the speed dependence (SD) of the pressure broadening. The case of O₃ retrievals from a sequence of limb transmission spectra is first treated theoretically. The results show that the influence of SD is very small, leading to changes in the residuals and in the retrieved O₃ mixing ratios smaller than 1%. These findings are then confirmed by treating a series of spectra recorded by the ACE-FTS instrument. Similar exercises are also made for other observation techniques by treating simulated or measured limb and nadir emission spectra as well as ground-based solar and in-situ laser transmission data. All lead to the general conclusion that SD (and Dicke narrowing) can be neglected in retrievals of ozone amounts from recorded atmospheric spectra. Indeed, the biases caused in the ozone profiles by the use of pure Voigt line shapes still remain significantly smaller than the total error/uncertainty from other sources such as improper line intensities and widths, uncertainty in the instrument function, errors in the pressure and temperature profiles and so forth.     

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.     

Analyses of HF/NH4F buffer-treated Si(111) surfaces using XPS,REM and SIMS

The effect of different cleaning procedures on Si(111) wafers has been studied. A three-step cleaning process was used. The first two steps (thermal oxidation followed by RCA cleaning) were common to all samples. The final step involved rinsing in one of a set of HF/NH4F buffer solutions with a wide range ofpH values. Three different surface techniques were used for characterizing the chemical condition and morphology of the treated surfaces: XPS (X-ray Photoemission Spectroscopy), REM (Reflection Electron Microscopy) and SIMS (Secondary-Ion Mass Spectroscopy). It has been found that thepH value of an HF solution does significantly affect the etching rate and morphology of the Si(111) surface: For the same type of solution, the smaller thepH value, the higher the etching rate. Basic solutions withpH values larger than eight have a much weaker etching effect on the surface, which is contradictory to some previous reports. The most effective solutions for the etching of the Si(111) surface are the solutions of HF buffered by NH₄F, with thepH in the range of 2–6. REM images indicate that the surface morphology after etching in the HF solution is strongly affected by the length of the etching time: Overetching will roughen the surface. The SIMS data show that water rinsing in air during the cleaning process does speed up oxidation, but it is necessary to use water to clean off the residuals from the HF solutions.     

Structural characterization of Rh/pumice SMAD catalysts

The structure of Rh/pumice catalysts prepared by the SMAD (Solvated Metal Atoms Dispersion) technique at different metal loadings has been investigated by EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy), XPS (X-ray Photoelectron Spectroscopy), SAXS (Small-Angle X-ray Scattering), WAXS (Wide-Angle X-ray Scattering) and TEM (Transmission Electron Microscopy). According to EXAFS and XPS, a fraction of the Rh atoms is oxidised, but a noticeable part is also present as Rh ⁰. The Rh oxidation is attributed to the interaction of the Rh atoms with the hydroxyls of the support; after the formation of the oxide, the nucleation of metallic rhodium becomes possible. The WAXS data do not show evidence of rhodium fcc crystallites; the metal-bearing particles are probably amorphous and/or very small, as results from the SAXS and TEM data analysis. The disagreement between the latter two techniques, resulting in a small-angle determination of the average size of the particles that is about half that of TEM in the catalyst with the higher Rh loading, is acknowledged and discussed. Preliminary catalytic tests are described, demonstrating the suitability of using a low surface area support for the preparation of SMAD catalysts. Received 2 February 1999     

Correlation between extrinsic defects and physical properties in incommensurate systems

A non-exhaustive survey of the influence of extrinsic defects (such as dislocation lines, substitutional or interstitial impurities and precipitates) on the physical properties of incommensurate systems is presented; special attention is paid to incommensurate insulators having a displacive modulation. Direct-imaging techniques such as X-ray Topography and Transmission Electron Microscopy are shown to be very fruitful tools in order to characterize the texture of the phase front at the lock-in transition, the mechanisms of the modulation wave-vector variation with temperature and the pinning action exerted by extrinsic defects of the crystal.     

The scientific investigation of artwork and archaeological artefacts: Raman microscopy as a structural,analytical and forensic tool

The impact of Raman microscopy on the study of artwork and archaeological artefacts is outlined. Important recent case studies are presented to illustrate the power of the technique to answer – either alone or in conjunction with other techniques – key questions of great art historical, conservational, cultural, archaeological and scientific interest. Raman microscopy also offers, via pigment identification, the possibility of testing the attribution of artwork, a matter which should be of great concern to galleries, auction houses and museums. PACS 82.80.Gk; 87.64.Je; 87.64.Ti     

Correlated Electron Materials and Field Effect Transistors for Logic: A Review

Correlated electron systems are among the centerpieces of modern condensed matter sciences, where many interesting physical phenomena, such as metal-insulator transition and high-T _c superconductivity appear. Recent efforts have been focused on electrostatic doping of such materials to probe the underlying physics without introducing disorder as well as to build field-effect transistors that may complement conventional semiconductor metal-oxide-semiconductor field effect transistor (MOSFET) technology. This review focuses on metal-insulator transition mechanisms in correlated electron materials and three-terminal field effect devices utilizing such correlated oxides as the channel layer. We first describe how electron-disorder interaction, electron-phonon interaction, and/or electron correlation in solids could modify the electronic properties of materials and lead to metal-insulator transitions. Then we analyze experimental efforts toward utilizing these transitions in field effect transistors and their underlying principles. It is pointed out that correlated electron systems show promise among these various materials displaying phase transitions for logic technologies. Furthermore, novel phenomena emerging from electronic correlation could enable new functionalities in field effect devices. We then briefly review unconventional electrostatic gating techniques, such as ionic liquid gating and ferroelectric gating, which enables ultra large carrier accumulation density in the correlated materials which could in turn lead to phase transitions. The review concludes with a brief discussion on the prospects and suggestions for future research directions in correlated oxide electronics for information processing.     

Laser studies of metallic artworks

Museum curators and archaeologists use analytical science to provide important information on artworks and objects. For example, scientific techniques provide information on artwork elemental composition, origin and authenticity, and corrosion products, while also finding use in the day-to-day conservation of many historical objects in museums and archaeological sites around the world. In this work two special cases are being discussed. In the first part of our work, physicochemical studies of an icon on a metal substrate were carried out using non-destructive, qualitative analysis of pigments and organic-based binding media, employing various microscopic and analytical techniques, such as Optical Fluorescence Microscopy, XRF, and Gas Chromatography. In the second part of our work, laser cleaning of late Roman coins has been performed using a Q-switched Nd:YAG laser (1064 nm, 6 ns) and a GaAlAs diode laser (780 nm, 90 ps). The corrosion products have been removed, while we observe increased concentrations in Ag, which is the main material of the silver plating found in late Roman coins.     

In-beam gamma-ray spectroscopy with exotic beams at the NSCL

Projectile fragmentation provides radioactive beams at intermediate velocities (v/c = 0.3-0.5) by physical means of fragment separation. With the development of position-sensitive photon detectors it has become possible to measure the energies and directions of photons emitted in-flight from such fast-moving exotic beams. This allows the reconstruction of the photons' energies emitted from an exotic projectile with high accuracy. It can be advantageous to employ photon detection in experiments with exotic beams since photons can traverse matter easily and their attenuation can be calculated. Experiments with standard luminosities can be carried out at intermediate beam energies with thick secondary targets (order of g/cm²) and very low incident beam rates (order of particle/s or less). Experimental success in this field is strongly correlated with the development of photon detectors such as position-sensitive scintillation detectors or segmented germanium detectors. In-beam gamma-ray spectroscopy of fast exotic beams has been successfully used at all projectile fragmentation facilities in intermediate-energy heavy-ion inelastic scattering experiments, knockout reactions and fragmentation reactions. Here, we focus on experimental results for neutron-rich exotic nuclei in the π(sd )-shell. Measurements and detector developments carried out at the NSCL at Michigan State University during the last four years are discussed. Received: 1 May 2001 / Accepted: 4 December 2001     

Correlations between Raman parameters and elemental composition in lead and lead alkali silicate glasses

This article examines the influence of the composition on the Raman spectra of lead silicate glass. Modern and historic lead alkali glasses and high‐lead glazed ceramics were analysed complementarily by Raman spectrometry and elemental techniques, either electron microprobe, proton induced X‐ray emission (PIXE) or scanning electron microscope with energy dispersive spectrometry (SEM‐EDS). The results showed that lead alkali silicate and high‐lead silicate glasses can be easily distinguished from their Raman spectra profile. In lead alkali silicate glasses, continuous variations were observed in the spectra with the compositional change. In particular, the position of the intense peak around 1070 cm⁻¹ was linearly correlated to the lead content in the glass. A unique decomposition model was developed for the spectra of lead alkali silicate glasses. From the combination of the Raman and elemental analyses, correlations were established between the spectral components and the composition. These correlations permitted to interpret the spectra and access additional compositional information, such as the lead content from area ratio A₉₉₀/A_900–1150, the total alkali + alkaline‐earth content from the area ratio A₁₁₀₀/A_900–1150 or the silica content from the area ratio A₁₁₅₀/A_900–1150. In lead silicate glass containing over 25 mol% PbO, the compositional variation induced no variation in the SiO₄ network region of the Raman spectra [150–1350 cm⁻¹], therefore no correlations and compositional information could be gained from the glass spectra in this range of composition. This new development of Raman spectroscopy for the analyses of glass will be very valuable for museums to not only access compositional information non‐destructively but also to understand the structural changes involved with their alteration. Copyright © 2008 John Wiley & Sons, Ltd.     

Analogue Models of and for Gravity

Condensed matter systems, such as acoustics in flowing fluids, light in moving dielectrics, or quasiparticles in a moving superfluid, can be used to mimic aspects of general relativity. More precisely these systems (and others) provide experimentally accessible models of curved-space quantum field theory. As such they mimic kinematic aspects of general relativity, though typically they do not mimic the dynamics. Although these analogue models are thereby limited in their ability to duplicate all the effects of Einstein gravity they nevertheless are extremely important—they provide black hole analogues (some of which have already been seen experimentally) and lead to tests of basic principles of curved-space quantum field theory. Currently these tests are still in the realm of gedanken-experiments, but there are plausible candidate models that should lead to laboratory experiments in the not too distant future.     

Dating study of two rock crystal carvings by surface microtopography and by ion beam analyses of hydrogen

Two artefacts made of rock crystal (quartz) from the collection of the Musée du quai Branly in Paris, France, a skull approximately half of the size of a real cranium and a smaller anthropomorphic head, purportedly attributed to pre-Columbian Mesoamerican cultures, were studied to assess their authenticity. The surface of the artefacts were examined by means of optical microscopy and scanning electron microscopy (SEM) and were analyzed nondestructively by ERDA (Elastic Recoil Detection Analysis), an ion beam analytical method that can measure hydrogen concentration profiles in depth. Optical and SEM imaging of tool marks indicates that the skull has been cut from a rock crystal block using machine lapidary techniques unavailable to pre-Columbian artisans, whereas the anthropomorphic head has more likely been carved and polished with manual techniques comparable to ancient ones. Hydrogen depth profiles in the first micron below the surface of the artefacts have been measured by ERDA with a 3-MeV He beam in a controlled helium atmosphere. Recently the progressive penetration of water at the surface of a quartz sample exposed to the natural environment has been proposed as a dating method (labeled quartz hydration dating or QHD) applicable to archaeological artefacts made of this material. The shallower penetration of H clearly indicates that the rock crystal skull was manufactured more recently than the reference quartz sample cut in 1740. As for the anthropomorphic head, the deep penetration profiles indicate an older artefact. Thus the converging micro-topographical examinations and hydrogen profiles of the samples surfaces indicate that the skull is probably not a pre-Columbian artefact but has been carved in the 18th or 19th century. The anthropomorphic head, on the other hand, could have been carved in the pre-Columbian period. In addition, the ERDA method carried out with an external beam presented here provides a new and simple approach for the nondestructive authentication of quartz-based archaeological artefacts by QHD.     

Tunneling into fuzzball states

String theory suggests that black hole microstates are quantum, horizon sized ‘fuzzballs’, rather than smooth geometries with horizon. Radiation from fuzzballs can carry information and does not lead to information loss. But if we let a shell of matter collapse then it creates a horizon, and it seems that subsequent radiation will lead to information loss. We argue that the resolution to this problem is that the shell can tunnel to the fuzzball configurations. The amplitude for tunneling is small because we are relating two macroscopically different configurations, but the number of states that we can tunnel to, given through the Bekenstein entropy, is very large. These small and large numbers can cancel each other, making it possible for the shell to tunnel into fuzzball states before a significant amount of radiation has been emitted. This offers a way to resolve the information paradox.