he present study discusses the best experimental conditions for the quantitative analysis of gold jewellery artefacts by ion beam techniques (PIXE, RBS, PIGE and NRA). Special attention is given to the detection of enhancement or depletion below the surface, down to 10 microns, without any sampling or destruction. PIXE is certainly the most interesting technique for this purpose and the optimal geometrical arrangement of the experiment is described: orientation of the incident beam relative to sample surface, selection of the characteristic signals, use of reference material, choice of the detector and incident particle energy and type, computation of absorption and secondary luorescence efects. Résumé : Nous discutons des conditions idéales d’utilisation des faisceaux de particules pour l’étude d’objets en or (PIXE, RBS, PIGE, et NRA). On attache une attention particulière au choix des paramètres expérimentaux pour détecter la présence éventuelle d’efets de surface sur une profondeur de l’ordre de 10 microns, sans prélèvement ni destruction. Le PIXE s’avère la technique idéale pour autant qu’on prenne en compte une série de paramètres comme l’orientation du faisceau incident relativement à la surface, choix des signaux pour la caratérisation, choix des échantillons de référence, choix du détecteur, choix de l’énergie et du type des particules incidentes, calcul des efets d’absorption et de luorescence secondaire.

The present study discusses the best experimental conditions for the quantitative analysis of gold jewellery artefacts by ion beam techniques (PIXE, RBS, PIGE and NRA). Special attention is given to the detection of enhancement or depletion below the surface, down to 10 microns, without any sampling or destruction. PIXE is certainly the most interesting technique for this purpose and the optimal geometrical arrangement of the experiment is described: orientation of the incident beam relative to sample surface, selection of the characteristic signals, use of reference material, choice of the detector and incident particle energy and type, computation of absorption and secondary fluorescence effects.

Little is known about goldsmithing during the period of the Great Kushans. In order to undertake a first approach to the technological choices and the gold alloys used in the fabrication of the different parts of Kushan objects, five gold jewellery items from the collections of the National Museum of Antiquities of Tajikistan containing wires and granulation were transported from Dushanbe to Paris to be studied within the European research project “AUTHENTICO” with non-destructive scientific-based techniques at the C2RMF. All the items were found in archaeological excavations carried out in the 1970s in several regions of Tajikistan and were examined by optical microscopy, scanning microscopy, and X-ray radiography. The compositions of the alloys were determined by ion beam analysis (PIXE) at the AGLAE accelerator.

The presence of fluoride in tooth enamel reduces the solubility of hydroxylapatite by acid attack. Fluoride presence (even at low concentration) in the oral cavity is efficient against caries process. We propose a new approach of the explanation of the increase of fluoride retention in the tooth enamel when low power laser irradiation is applied after the treatment with fluoride gel (fluoridation). External beam PIGE measurements of fluorine on extracted teeth have been made in order to determine the best sequence of the operations. The laser irradiation after fluoride application is more efficient than the reverse procedure. This observation is in agreement with previous observations that the fluorine penetration in the enamel takes place first in the soft organic material present between the polycrystalline (prismatic) structure before being integrated in the crystalline composition of hydroxylapatite in order to produce fluoro-apatite. As those in vitro measurements do not reflect the whole process in the saliva, in vivo PIGE measurements have been also performed. We have demonstrated, by repeating the PIGE measurements (at least five times at various time intervals) that a significant increase of the fluoride retention took place even 18 months after the unique laser treatment. The complete experimental procedure is described: fluoride application, laser irradiation, PIGE measurements with 2.7MeV protons (repeated measurements at the same place on the same tooth in order to follow the evolution) and safety tests before in vivo analyses.

Combination of the elemental nondestructive analysis of artifacts by ion beam analysis (IBA) multielemental techniques (but mostly PIXE) with the accelerator mass spectroscopy (AMS) measurement of the age of the organic material discovered in the close vicinity of these artifacts (mainly available for recent excavations) gives new tools to archaeologists to improve their diagnosis in the study of the composition of ancient objects and of their workmanship in ancient times by using the same experimental facility for IBA and AMS. For potteries and metallic samples, IBA and AMS are to be applied on different samples excavated in the same environment but for organic archaeological samples, IBA and AMS techniques could be sequentially used on the same material. Results of these combined techniques on artifacts of various origins recently studied at CEDAD (CEntro di Datatione e Diagnostica), University of Salento, Lecce, Italy, are presented. Copyright (C) 2008 John Wiley & Sons, Ltd.

More than four boron per unit cell has been introduced into the framework of silicalite-1, using fluorine containing media. The initial gels were of composition 9MF–xH3BO3–10SiO2–1.25TPABr–330H2O with M = NH4, Na, K and Cs and x = 0.1–10. The syntheses were carried out in hydrothermal conditions at 170°C. The amount of incorporated TPA+ ions remains quasi constant (3.5–3.8/u.c.) up to 4 B/u.c., while it decreases with increasing boron content. The amount of tetrahedral B/u.c. can be as high as 8 in presence of K+ or Cs+ ions in the as-synthesized samples. It is observed that the preferential countercations to framework negative charges related to the presence of tetrahedral boron, [SiOB]−, are TPA+, K+ and Cs+ ions. It is interpreted, that the −4.0 ppm versus BF3.OEt2 NMR line stems from tetrahedral framework boron, while the −2.9 ppm NMR line represents both extraframework and/or tetracoordinated deformed framework boron in the structure.

Proton-Induced X-ray Emission (PIXE) has been proved to be a very rapid and accurate method for the elemental analysis of ancient artefacts. Using protons whose energy is lower than 3 MeV, it is possible to obtain, in a few minutes, the actual composition of narrow parts of artefacts, without any sampling, even at microscopic level. Any element with an atomic weight higher than 20 may be analysed. Rutherford backscattering spectroscopy (RBS) and Nuclear Reaction Analysis (NRA) are complementary techniques mainly useful to control the homogeneity in depth and then to study superficial layers. RBS is mainly powerful for the profiling of heavy elements, but NRA is only used for light elements. Examples of applications will mainly concern, in this contribution, the study of metallic artefacts.

Quantitative analysis of major and minor elements in a heavy matrix with high relief requires a perfect knowledge of the geometry of irradiation and detection. We discuss in this paper, the contribution of these geometrical factors for the investigation of gold jewellery items which were studied with PIXE, RBS and NRA. The combination of all these techniques is often necessary to give us sufficient information on the workmanship of ancient goldsmiths. Examples of application to artefacts from Macedonia and Colombia are given.

The mystery of the construction of the great pyramids of Egypt could be elucidated by physico-chemical measurements on small pieces of the material. In this paper, we give several arguments against the present point of view of most Egyptologists who do not admit another method than hewn blocks. We give several pieces of evidence that the masonry was entirely built by a moulding procedure involving the use of ingredients that were all available in the region of Cairo.

In this paper we demonstrate the functionalization of single-walled carbon nanotubes prepared by chemical vapor deposition. The chosen functionalization agents were alkyl-halides such as trifluoromethane (TFM) and trichloromethane (TCM); or double bond containing alkyl-halides as tetrachloroethylene (TCE) and hexafluoropropene (HFP) that can easily form radicals. Functionalization of samples was carried out under mild conditions, by ball milling of nanotubes in an atmosphere of functionalization agent, at room temperature. For the sake of comparison, chlorination was also performed by chlorine gas. In this process the cleavage of nanotube C–C bonds results in active sites, which can activate molecules in gas phase or adsorbed on the surface of carbon nanotubes. Halogenated samples were characterized by means of particle induced γ-ray emission, transmission electron microscopy, thermogravimetry, and X-ray photoelectron spectroscopy. We concluded that this method gives functionalized single-walled carbon nanotubes in the range of 0.3–3.5wt.% of fluorine and 5.5–17.5wt.% of chlorine.

This paper gives an overview of the research activities within the European COST Actions G1 and G8. Both actions aim at achieving a better preservation and conservation of our cultural heritage by increasing the knowledge in art and archaeological objects through chemical and physical analyses.

This paper describes attempts made to improve diffusion bonding procedures based on antique processes as granulation and filigree. Two modern procedures implying diffusion of cadmium and silicon respectively are reported. The results obtained with PIXE and NRA using nuclear microprobe are discussed. This paper concludes with a comparison of these bonding techniques and some other modern methods with the antique procedures.

Photons, electrons and protons beams applied to the scientific investigation of archaeological materials provide complementary information for characterising the state of preservation and the provenance of the objects. Investigations were carried out on medieval silver coins of the “Friesacher Pfennig” and the “Tiroler Kreuzer” from the Kunsthistorisches Museum Vienna and the Oesterreichische Nationalbank. Techniques employed were EDXRF, SEM/EDX and PIXE. By determining the trace elements of the alloys it was possible to assign coins to their mint. The results outline advantages and disadvantages of EDXRF, SEM/EDX and PIXE when applied to corroded objects.

Chemical and structural modifications induced by protons at the surface of polyacrylonitrile and carbon nanotube/polyacrylonitrile composite films are analysed by TEM, profilometry, IR and XPS. Changes induced in the film are related to the energy of incident particle and implanted dose. The irradiation of the composite films induces the emergence of the nanotubes outside of the polymer but with no increase of the surface roughness. Spectroscopic modifications in both films are globally similar, the most significant feature being a lower relative concentration of nitrogen with respect to carbon close to the surface.

Matrix effects on the measurement of elements having close atomic masses using μ-PIXE are studied with emphasis to Ni and Co inclusions in iron matrices. Postulating that all the major components may be simultaneously detected through at least one well-isolated peak for each of them, and that a known reference material is available which contains all the elements of the unknown sample, we propose a direct method to extract the actual distribution of all elements during the scanning with a narrow microprobe.

El depósito de Lebrija (Sevilla) compuesto por seis objetos iguales se creía único en su género hasta la aparición en el mercado de antigüedades de un nuevo ejemplar que repite la morfología y técnica de fabricación de estos llamados candelabros. Hemos estudiado los siete ejemplares desde el punto de vista tecnológico, funcional y simbólico, además de realizar análisis de composición mediante el método PlXE. Creemos que se trata de una serie de piezas de fabricación indígena en los primeros momentos de contacto entre fenicios y tartésicos, hacia el siglo VIlI a.C. En cuanto a su funcionalidad, no se puede seguir aceptando su interpretación como incensarios, sino que fueron la representación anicónica de la divinidad según la mitología fenicia.

One hundred and fifty seven 'Tiroler Kreuzer', a medieval currency from the county of Tyrol/Austria, were analysed in order to determine their place of mintage. The silver coins were produced during the 15th century in the mints of Merano (South Tyrol) and Hall (North Tyrol) but they have no marks or punches which would allow a clear distinction. Energy-dispersive x-ray fluorescence analysis (EDXRF) was applied without sampling in order to determine the silver contents and also minor (Cu, Pb, Bi) and trace elements (Fe, Au, Hg, Ni). Owing to corrosion processes, which changed the chemical composition of the surfaces of the coins, investigations of cross-sections were necessary using energy-dispersive x-ray microanalysis in a scanning electron microscope (SEM/EDX) to determine the stage of corrosion and the Ag concentration of the core of the coins. The results showed differences of up to 50% between the composition of the core and the surface. Finally, proton-induced x-ray emission (PIXE) at an external proton beam was applied, in order to detect also Ni, an element which could not be measured by either EDXRF or SEM/EDX in the ppm range. The data show a clear difference in the Ni content between the coins from Merano (similar to0.1% Ni) and Hall (similar to0.01% Ni). Copyright (C) 2003 John Wiley Sons, Ltd.