Spectroscopy, Diffraction and Tomography in Art and Heritage Science gives an overview of the main spectroscopy and diffraction techniques currently available for cultural heritage research. It starts with an introductory, general discussion of spectroscopy and diffraction and the kinds of information they can give. Further sections deal with, respectively, typical laboratory methods, mobile equipment, and large-scale instruments and infrastructural methods. The work concludes with comments on combining and comparing multiple techniques, sources of error, and limitations of the analytical methods.

In this introductory chapter we start with a brief summary of the implications of using radiation-in, radiation-out techniques for the analysis of historical artifacts and then move to the origins, and cultural/historical context of the principles underlying the analytical techniques described in the book. We touch on the use of vision in spectroscopy and discuss the interaction between wave and particle descriptions of radiation in ancient and modern thought. The 1635 discovery of diffraction by Francisco Grimaldi and its consequence, the 1807 "two slit" experiment of Thomas Young, and their ongoing implications for science in general and analytical techniques in particular, are discussed in detail. We then describe how different radiation beams are parameterized, and the implications of these parameters for destructive, nondestructive, and noninvasive analysis.

A new method using a high-sensitivity X-ray camera for a large-range diffraction pattern is presented; it confirms the effectiveness of over 35 years of conservation treatment for brass artefacts from the Mary Rose.

A dedicated, grower-friendly MBE computer control system is described, and its performance in demonstrated in growth of high resolution doped SiGe structures.

The alloy properties of depend on their chemical composition and microstructure. Regarding composition, antiquities are generally made of impure lead. Since the most frequently associated elements have a very limited room temperature solid solubility in the face-centered cubic lead structure (e.g. antimony < 0.01% [1], silver 0.02% and copper 0.005% [2]), a small concentration of these will exceed the solubility limit, and a new crystalline phase will be formed, changing the properties [3]. One of the exceptions is tin, which is soluble in lead up to 19.5% [4].

Copper-bearing intrauterine devices (CuIUDs) are frequently used for long-acting reversible contraception. The release of copper ions into the fluid medium of the uterus reduces the probability of ovum fertilisation and endometrial adhesion. It is widely believed that the primary source of these ions is cuprite (Cu2O) formed on the device surface through in-utero corrosion. However, cuprite has a very low solubility at the pH and temperature of the uterine fluid so this seems unlikely, especially when far more soluble compounds such as copper sulphate and chloride may also be formed.

The objective of this work is to study the initial corrosion of copper in the presence of gold when placed in simulated uterine fluid in order to better understand the evolution of active components of copper-IUDs. In order to carry out this study, a portable cell was designed to partially simulate the uterine environment and provide a way of tracking the chemical changes occurring in the samples in situ within a controlled environment over a long period of time using synchrotron spectroelectrochemistry. The dynamically forming crystalline corrosion products are determined in situ for a range of copper-gold surface ratios over the course of a 10-day experiment in the cell. It is concluded that the insoluble deposits forming over this time are not the origin of the anticonception mechanism.

Further to the previously published work in this journal "Towards a new coating for heritage lead", a coating has been trialled with samples replicating aged lead artefacts. Lead was corroded in an oak environment to simulate storage or display in a wooden case then coated with ethanolic solutions of tetradecanoic and octadecanoic acid. X-ray diffraction and electrochemical impedance data suggests an better-quality coating is formed leading to improved corrosion resistance.

The synthesis and characterization of a reference sample containing a distinct geometrical pattern of Cu2O (cuprite) are described. The sample is to be used as an assessment sample to evaluate a newly developed X-ray-excited optical luminescence (XEOL) microscope, built for non-destructive chemical imaging of metal and other surfaces. The sample was produced by heating in a reducing flame and subsequent air exposure. It was characterized both qualitatively and quantitatively using X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy in both fluorescence mode (XAS) and optical luminescence mode (XEOL-XAS) and X-ray diffraction (XRD). Results indicate the presence of a layered structure comprising a heterogeneous mixture of cuprite and tenorite (CuO) with mainly cuprite (91.4%) in the near-surface regions and larger amounts of tenorite in the top 1-3 nm. The cuprite produced via this protocol was found to provide intense optical luminescence upon X-ray bombardment, which is particularly useful during the evaluation of the microscope. (C) 2015 Elsevier B.V. All rights reserved.

Corrosion is the major problem in the degradation of heritage metal objects. The development of appropriate treatment methods to stabilize and protect artefacts is a undeniable scientific challenge. Here we propose a new coating method to protect lead heritage metal objects. This coating is environmentally safe, stable, reversible, easy to apply and to remove, and aesthetically justified. The coating consists of a compact and thick layer of lead ditetradecanoate, which is formed upon immersion of a lead substrate in a melted sample of tetradecanoic acid at 60°C. Coated lead samples were exposed either to an aqueous corrosive environment or to a closed chamber with high relative humidity and an oak corrosive atmosphere. The corrosion resistance of the coating was followed for 60 days by electrochemical impedance spectroscopy and X-ray diffraction. Results show an unprecedented corrosion inhibition of the new coatings.

An electrochemical cell for in situ grazing incidence x-ray diffraction is described, along with its implementation for characterization of corrosion in a model sweet oilfield environment. In order to mimic reservoir fluids, the cell has been designed to facilitate measurements from substrates immersed in solutions with low concentrations of dissolved oxygen. In addition, the temperature of the solution can be varied from room temperature up to ~ 80°C. Diffraction patterns acquired with synchrotron radiation from X65 pipeline steel immersed in CO2-saturated aqueous NaCl solution (pH = 6.8, T = 80°C) are presented. These data demonstrate the formation and temporal evolution of a multicomponent corrosion scale, which includes siderite (FeCO3) and chukanovite (Fe2(OH)2CO3).

This work presents the application of voltammetry of microparticles (VMP) to the characterization of metallic artefacts. The paper illustrates the principle of the technique and the methods for the identification of metals and copper minerals. VMP can be considered a non-invasive technique as it requires a minimum amount of material for performing the analyses. To emphasize the efficacy of this technique regarding characterization of cultural heritage materials, two bronze artefacts of different historical periods were investigated. By using a paraffin-impregnated graphite electrode, the composition of the alloy and the copper minerals present in their patinas were analysed and identified. The results obtained from the electrochemical characterization were confirmed by complementary analysis carried out with X-ray fluorescence and X-ray diffraction.

Several heritage systems have been studied using state-of-the-art synchrotron techniques. The cultural heritage value of silver is documented in museum collections across the globe. However, the silver surface is not as chemically stable as that of other precious metals, and is susceptible to corrosion by atmospheric gases. It is therefore of special interest to clarify these surface reactions by using in situ, time-lapse chemical and structural analysis in controlled ambients in order to develop strategies to reduce or even prevent the atmospheric attacks. In order to study the initial corrosion processes of silver in the presence of corrosive gases in situ time-lapse X-ray diffraction experiments were performed on the XMaS beamline at the European Synchrotron Radiation Facility, Grenoble. Highly pure silver samples were weathered with synthetic air containing 500 ppb of both H2S and ozone, at relative humidity (RH) levels, and XRD patterns were tracked every 10 min over a total weathering time of 24 h. The time-lapse Synchrotron Radiation (SR)-XRD data show that pure silver exposed to those atmospheres starts to form crystalline corrosion products after only 10 minutes. Silver sulfates, silver oxides, intermediates and mixed species are formed on the sample surface over the duration of the experiment. The data collected using a newly combined environmental cell/gas flow set up introduces a set of highly useful tools for scientists who wish to study time-lapse gaseous corrosion at ambient temperature and pressure.

The hydrolysis of nantokite to form cuprite could be a reaction step in the progression of bronze disease on cupreous objects d'art. In this paper, this transformation is visualized for the first time using a time-resolved synchrotron X-ray diffraction experiment. Complete conversion of nantokite to cuprite was observed on a nantokite patina over 5 h in water using time-resolved synchrotron X-ray diffraction. (C) 2014 Elsevier Ltd. All rights reserved.

This paper concerns a time lapse spectroelectrochemical study of the growth of lead dodecanoate layers on a lead substrate in an aqueous solution using cyclic voltammetry. In-situ synchrotron radiation X-ray diffraction measurements were carried out on station BM26A (DUBBLE) at the European Synchrotron Radiation Facility (ESRF) in France. The diffraction pattern images were taken using a two-dimensional Mar CCD camera. After deposition of the coating, a spectroelectrochemical study of a linear sweep voltammetry experiment using an acetic acid electrolyte, simulating ‘active’ lead corrosion, was carried out on both a bare and lead dodecanoate coated sample. The results show that the coating inhibits the formation of new lead corrosion products.

We describe a novel microscopy system which can obtain chemical maps from the surfaces of heritage metals in air or a controlled environment. The microscope, x-ray excited optical microscope Mk 1 (XEOM 1), forms images from x-ray excited optical luminescence (XEOL) induced by illuminating a few square millimetres of the sample with monochromated x-rays (broad beam or macroprobe illumination). XEOL is a spectroscopy tool in its own right and can, under the right circumstances, also be a vehicle for x-ray absorption spectroscopy. This (usually) synchrotron based technique provides information on the chemical state and short-range atomic order of the top few microns of a surface. It is thus well suited to heritage metal corrosion studies and is complementary to synchrotron x-ray diffraction.

OBJECTIVE:To assess the site-specific corrosive behavior of the frameless intrauterine device (IUD) following long-term exposure to the uterine environment.STUDY DESIGN:A qualitative and morphological study using X-ray diffraction (XRD) and scanning electron microscopy (SEM).RESULTS:Three GyneFix® IUDs that were in site up to 150 months were examined. In utero corroded copper sleeves were divided into 10 different groups based on their shape (U or O), orientation (inside or outside) and in utero residence time. XRD indicated the presence of solely cuprite (Cu2O) as corrosion product on both the inside and the outside of the copper sleeves, regardless of their shape. These results were confirmed by backscattered electron micrographs recorded on the inside, the outside and the cross-section of the IUD sleeve. SEM results suggest that shape and orientation slightly affect the corrosion rate.CONCLUSION:The apparent copper loss from both sides of GyneFix copper tubes proves that both sides are a potential copper source and therefore justifies the design of GyneFix IUD. This could be beneficial for women as the IUD could be reduced in size and therefore better tolerated. The impact on bleeding could also be minimized.IMPLICATION STATEMENT:Release of copper ions from both sides of the copper tubes of the frameless GyneFix® IUD allows the IUD to be reduced in size, contributing to better toleration. The impact on menstrual bleeding is also minimized by a smaller size of the foreign body.