B. Moignard

Development of an external beam nuclear microprobe on the Aglae facility of the Louvre museum

Abstract The external beam line of our facility has been recently equipped with the focusing system previously mounted on a classical nuclear microprobe. When using a 0.1 μm thick Si3N4 foil for the exit window and flowing helium on the sample under analysis, a beam spot as small as 10 μm is attainable at a distance of 3 mm from the window. Elemental micromapping is performed by mechanical scanning. An electronic device has been designed which allows XY scanning by moving the sample under the beam by steps down to 0.1 μm. Beam monitoring is carried out by means of the weak X-ray signal emitted by the exit foil and detected by a specially designed Si(Li) detector cooled by Peltier effect. The characteristics of external beams of protons and alpha particles are evaluated by means of resonance scanning and elemental mapping of a grid. An example of application is presented, dealing with elemental micro-mapping of inclusions in gemstones.

An external milli-beam for archaeometric applications on the AGLAE IBA facility of the Louvre museum

Abstract External beam lines have been built on numerous IBA facilities for the analysis of works of art to avoid sampling and vacuum potentially detrimental to the integrity of such precious objects. On the other hand, growing interest lies on microprobe systems which provide a high lateral resolution but which usually work under vacuum. Until recently, the AGLAE facility was equipped with separate external beam and microprobe lines. The need of a better spatial resolution in the external beam mode has led us to combine them into a single system which exhibits numerous advantages and allows the analysis of small heterogeneities like inclusions in gemstones or tiny components of composite samples. The triplet of quadrupole lenses bought from Oxford is used to focus the beam. By using a 0.75 μm thick Al foil as the exit window, blowing a helium flow around the beam spot and reducing the window-sample distance below 3 mm, a beam size of about 30 μm can be reached. The experimental setup includes two Si(Li), a HPGe and a Si surface barrier detectors for the simultaneous implementation of PIXE, NRA and RBS. The full description of this device is given as well as a few applications to highlight its capability.

Ion beam analysis with external beams: Recent set-up improvements

Accelerator-based analytical techniques using external beams are ideally fitted to the study of works of art because of their fully non-destructive character. However, accurate quantitative analysis is not straightforward, due in particular to difficult beam monitoring. Significant improvements have been progressively made on the external beam line of the IBA facility of the Louvre museum in order to increase the accuracy and to conduct combined analyses with different IBA techniques.

Micro-PIXE analysis of an ancient Egyptian papyrus: Identification of pigments used for the “Book of the Dead”

Abstract This paper reports a study of colours and inks of an ancient Egyptian papyrus using an external proton microprobe in PIXE mode. Representing the Book of the Dead, this papyrus is dated from the 19th dynasty, New Kingdom (c.1295–1186 BC). Elemental maps were obtained by moving the papyrus under a fixed focused external beam using a motorised support. The maps were compared to photographic pictures taken in visible light. Inks used in the hieroglyph text appeared to be based on carbon (black) and iron oxide (red). Coloured drawings illustrating the text showed a wider palette: hematite, ochre, orpiment, Egyptian blue, verdigris. Most intriguing was the observation in several parts of the drawing of a whitish pigment containing strontium. Deposits of strontium-rich minerals (e.g. strontianite, celestite) have been identified in Egypt. The exact nature and the archaeological implications of this pigment have still to be determined. Finally, fine powder and coarse grains of arsenic oxide were observed, probably remaining from an early preservation treatment against insect attacks after excavation.

First use of portable system coupling X-ray diffraction and X-ray fluorescence for in-situ analysis of prehistoric rock art.

Study of prehistoric art is playing a major role in the knowledge of human evolution. Many scientific methods are involved in this investigation including chemical analysis of pigments present on artefacts or applied to cave walls. In the past decades, the characterization of coloured materials was carried on by taking small samples. This procedure had two main disadvantages: slight but existing damage of the paintings and limitation of the number of samples. Thanks to the advanced development of portable systems, in-situ analysis of pigment in cave can be now undertaken without fear for this fragile Cultural Heritage. For the first time, a portable system combining XRD and XRF was used in an underground and archaeological environment for prehistoric rock art studies. In-situ non-destructive analysis of black prehistoric drawings and determination of their composition and crystalline structure were successfully carried out. Original results on pigments used 13,000 years ago in the cave of Rouffignac (France) were obtained showing the use of two main manganese oxides: pyrolusite and romanechite. The capabilities of the portable XRD-XRF system have been demonstrated for the characterization of pigments as well as for the analysis of rock in a cave environment. This first in-situ experiment combining X-ray diffraction and X-ray fluorescence open up new horizons and can fundamentally change our approach of rock art studies.

ERDA with an external helium ion micro-beam: Advantages and potential applications

Abstract Preliminary ERDA experiments at atmospheric pressure have been performed with our external microprobe set-up currently used for the analysis of museum objects by PIXE, RBS and NRA. The objective was to check the feasibility of hydrogen (and deuterium) profiling with an external beam of 3-MeV helium ions. The standard scattering geometry (incident beam at 15° with respect to sample surface and emerging protons or deuterons at 15° in the forward direction) was kept, but the thin foil absorber was replaced by helium gas filling the space between the beam spot and the detector over a distance of about 84 mm. Several standards prepared by ion implantation, with well known H or D depth profiles, were first analysed, which indicated that the analytical capability was as good as under vacuum. A striking feature is the much lower surface peak than under vacuum, a fact that enhances the sensitivity for H analysis near the surface. The same type of measurement was then performed on different materials to show the usefulness of the technique. As a first example, we have checked that the incorporation of H or D into sapphire crystals during mechanical polishing is below the detection limit. Another example is the measurement of the H content in emeralds which can be used as an additional compositional criterion for determining the provenance of emeralds set in museum jewels. The advantages and limitations of our set-up are discussed and several possible applications in the field of cultural heritage are described.

Portable apparatus for in situ x-ray diffraction and fluorescence analyses of artworks.

A portable X-ray fluorescence/X-ray diffraction (XRF/XRD) system for artwork studies has been designed constructed and tested. It is based on Debye Scherrer XRD in reflection that takes advantage of many recent improvements in the handling of X-rays (polycapillary optics; advanced two-dimensional detection). The apparatus is based on a copper anode air cooled X-ray source, and the XRD analysis is performed on a 5-20 μm thick layer from the object surface. Energy dispersive XRF elemental analysis can be performed at the same point as XRD, giving elemental compositions that support the interpretation of XRD diagrams. XRF and XRD analyses were tested to explore the quality and the limits of the analytical technique. The XRD diagrams are comparable in quality with diagrams obtained with conventional laboratory equipment. The mineral identification of materials in artwork is routinely performed with the portable XRF-XRD system. Examples are given for ceramic glazes containing crystals and for paintings where the determination of pigments is still a challenge for nondestructive analysis. For instance, lead compounds that provide a variety of color pigments can be easily identified as well as a pigment such as lapis lazuli that is difficult to identify by XRF alone. More than 70 works of art have been studied in situ in museums, monuments, etc. In addition to ceramics and paintings, these works include bronzes, manuscripts, etc., which permit improvement in the comprehension of ancient artistic techniques.

Study of Italian Renaissance sculptures using an external beam nuclear microprobe

Abstract The use of an extracted proton micro-beam for the PIXE analysis of glazes is discussed in the context of the growing interest in the creation of an analytical database on Italian Renaissance glazed terracotta sculptures. Some results concerning the frieze of an altarpiece of the Louvre museum, featuring white angels and cherubs heads, are presented.

In situ dynamic analysis of solids or aqueous solutions undergoing chemical reactions by RBS or PIXE with external beams

Abstract Non-conventional applications of IBA techniques are under development on an external micro-beam line dedicated to the study of materials relevant to cultural heritage. Special set-ups have been designed to investigate the kinetics of materials transformation by dynamic (real-time) analysis using either RBS or PIXE. The first technique is well fitted to the study of the thermal oxidation of solids in air, whereas the second one is suitable for measuring the rate of elemental release in the liquid phase during solid–solution interaction. Preliminary tests have been performed to demonstrate the usefulness of this approach. On one hand we have applied dynamic micro-RBS to study the oxidation kinetics at 360 °C of pure copper and a copper–gold alloy and on the other hand we have checked the ability of micro-PIXE to measure in real time the release of lead in solution during the aqueous dissolution of lead containing glass or glaze.

Non-invasive quantitative micro-PIXE–RBS/EBS/EBS imaging reveals the lost polychromy and gilding of the Neo-Assyrian ivories from the Louvre collection

Antique objects are known to have been brightly colored. However, the appearance of these objects has changed over time and paint traces are rarely preserved. The surface of ivory objects (8th century B.C., Syria) from the Louvre museum collection (Paris) have been non-invasively studied by simultaneous particle-induced X-ray emission (PIXE) and Rutherford and elastic backscattering spectrometry (RBS/EBS) micro-imaging at the AGLAE facility (C2RMF, Paris). Qualitative 2D chemical images of elements ranging from Na to Pb on the surface of the ancient ivory carvings provide evidence of lost polychromy and gilding. Quantitative PIXE data of specific areas allow discrimination between traces of sediments and former polychromy. Different shades of blue can be differentiated from particular Pb/Cu ratios. The characterization of gilding based on RBS data demonstrates the exceptional technological skills of the Phoenician craftsmen supposed to have carved the Arslan Tash ivories. More precise reconstructions of the original polychromy compared to previous studies and a criterion for the authentication of ancient gilded ivory object are proposed.