Effects of the behaviour of the proton-induced isotopes production on the analysis of ancient alloys

The present work concerns non-destructive ion beam analysis carried out by means of proton-beam-induced nuclear reactions in the 10-30 MeV energy range. We focused our attention on the yield distribution of the isotopes produced in the internal region of a metal alloy. This distribution, which defines the analytical region, displays, at incident energy of about 20 MeV in a bronze based alloy, a bell-shaped curve centred at about 600 μm with an average width of about 400 μm. By changing the incident proton energy it is possible to displace the above region in the interior of the metal body. It should be pointed out that if we neglect to take into account the correct behaviour of the isotope yield distribution in samples with surface inhomogeneities we can obtain erroneous analytical results. We describe some experiments based on proton activation analysis (PAA) carried out at the INFN-Laboratori Nazionali del Sud (LNS) in Catania where we verified the bell-shape of the radioactive isotope distribution. The resulting formulas are given for quantitative analysis.It is straightforward that, by choosing the appropriate incident proton energy, it is possible to confine the whole analytical region to the interior of the body, thus eliminating any influence of surface effects. We have called this particular approach deep proton activation analysis (DPAA). Examples of its use on archaeological artefacts are given.     

PIXE as a complement to trace metal analysis of sediments by ICP-OES

The adverse effects of metal contamination in sediments require methods that can quickly and accurately assess the extent of environmental pollution. Particle induced X-ray emission spectrometry (PIXE) is demonstrated to be a viable alternative to an established method, which consists of acid digestion and Inductively coupled plasma-optical emission spectrometry (ICP-OES) to measure trace metals in sediment. The analysis of trace metal composition by both techniques on a NIST Standard Reference Material mud gives results that are consistent with the certified values for fourteen measured metals, seven of which are common to both methods. A comparison study conducted on a sediment core from a freshwater lake with a known chromium contamination in Muskegon County, MI also shows a good correlation between the methods for transition metals of environmental interest over a wide range of metal concentrations. Total sample preparation and analysis time for the PIXE measurements is roughly one third that of acid digestion and ICP-OES. Also, the acid digestion step does not elute all the metal, while the nondestructive PIXE approach is a total metals analysis method. However the PIXE method generally has higher limits of detection for many environmental metal contaminants. By combining the two techniques, the acid digestion elution factor can be quantified by running PIXE on an original sample and on the residue resulting from acid digestion.     

PIXE and RBS analysis of Tl-1223 superconducting phase substituted by scandium

Ion beam analysis techniques (IBA) were performed to determine the elemental stoichiometry of superconducting samples of type TlBa₂Ca_2−xSc_xCu₃O_9−δ, with 0 ? x ? 0.6, prepared via solid-state reaction technique. By combining particle induced X-ray emission (PIXE) with Rutherford backscattering spectrometry (RBS), the stoichiometry of the samples is determined. However, the oxygen content is obtained by using non-Rutherford backscattering cross-section at 3 MeV proton beam. Furthermore, the prepared samples were also characterized using X-ray powder diffraction (XRD) and electrical resistivity measurements. The X-ray data indicate that the partial substitution of Ca²⁺ by Sc³⁺ ions does not affect the tetragonal structure of Tl-1223 superconducting phase. The superconducting transition temperatures T_c, determined from electrical resistivity measurements, was found to be highly correlated to the Sc-content.     

Accelerator-based trace element analysis of foods and agriculture products

An accelerator-based analytical method for measuring trace elements in foods and agricultural products was developed, optimized, validated and compared using reference standards. The method’s initial phase is a new, rapid and effective digestion process of a small mass analyte in an aqueous media containing H₂O₂. Digestion is initiated by radicals formed in water with pulsed UV (PUV) induced (laser) photolysis, which rapidly react with organic matter. After digestion, trace metals are pre-concentrated as carbamates and deposited as thin targets onto Teflon filters. Conventional particle induced X-ray emission (PIXE) or X-ray fluorescence (XRF) methods are then used to analyze elements in the sample. When foods and other agricultural commodities (i.e., soils, feeds) are analyzed, the combined method named pulsed UV (PUV)/PIXE results in enhanced detection of trace elements such as Fe, Co, Ni, Cu, Zn and Pb at ∼1 mg/kg (1 ppm) levels, without lengthy, acid-based digestions. It provides improvements in digestion kinetics and processing time enhancing analytical sensitivity and element recovery. Precision and recovery yields were confirmed with food reference standards. The analysis of edible foods from contaminated agricultural areas is also reported.     

Differential and scanning-mode external PIXE for the analysis of the painting “Ritratto Trivulzio” by Antonello da Messina

Extensive PIXE investigations have been performed at the LABEC accelerator laboratory in Florence on the painting “Ritratto Trivulzio” by Antonello da Messina, one of the great Italian masters of XV Century and a pioneer in modern oil painting.It is well known that a complete and unambiguous characterisation of materials in paintings is often difficult, owing to their complex structure. For the “Ritratto Trivulzio”, the combination of advanced variants of PIXE, such as differential and scanning-mode analysis, provided a relevant contribution to the characterisation of paint layers, in terms of composition and structure, in a totally non-invasive and non-destructive way.Single-spot mode PIXE with external proton beams of about half millimetre diameter was first used for a general characterisation of different areas of the painting. Differential PIXE performed in many spots led to reconstruct the sequence of paints employed by the artist and to estimate in some cases the local paint layer thickness.A second run carried out with the external scanning microbeam facility, using a 3 MeV proton beam of about 80 μm size, was then crucial to clarify some issues raised by the first analysis. In particular, elemental maps from selected areas helped to understand the way some colour shades had been obtained on the red mantle of the portrayed gentleman, using different pigments irregularly distributed on the surface.     

Scanning-PIXE analysis of gold lace embroideries in a relic of St. Francis

In this work, we describe the compositional analysis performed by scanning-mode PIXE on the metal threads of a XIII century embroidery. The precious work analysed is the pillow-case used to cover the pillow, on which - according to tradition - St. Francis of Assisi was resting his head when he died. Measurements were performed in order to characterise the embroideries of the two sides and the passementerie in the lateral hems. Several areas, each of the order of two square millimetres, were scanned with a 3 MeV proton external beam of 20 μm size on target, using the external micro-beam facility of our laboratory, with list-mode acquisition. Analysis of elemental maps and spectra from selected homogeneous sub-areas allowed us to extract the quantitative composition of the gilded tape and estimates of its thickness.     

Micro-SR-XRF and micro-PIXE studies for archaeological gold identification - The case of Carpathian (Transylvanian) gold and of Dacian bracelets

Trace-elements are more significant for provenancing archaeological metallic artifacts than the main components. For gold, the most promising elements are platinum group elements (PGE), Sn, Te, Sb, Hg and Pb. Several small fragments of natural Transylvanian gold - placer and primary - were studied by using micro-PIXE technique at the Legnaro National Laboratory AN2000 microbeam facility, Italy and at the AGLAE accelerator, C2RMF, Paris, France and by using micro synchrotron radiation X-ray fluorescence (micro-SR-XRF) at BESSY synchrotron, Berlin, Germany. The goal of the study was to identify the trace-elements, especially Sn, Sb and Te. A spectacular application to five Dacian gold bracelets authentication is presented (Sn and Sb traces).     

Chemical shift measurements of chlorine K X-ray spectra using a high-resolution PIXE system

A high-efficiency high-resolution wavelength-dispersive spectrograph with a von-Hamos configuration was developed for chemical state identification of elements in environmental samples using PIXE analysis. To evaluate the performance of this system, chlorine K X-ray spectra for NaCl, NH₄Cl and polyvinylchloride (PVC) targets were measured and compared. Also, to study the applicability to environmental mixed samples, mixtures of NaCl and NH₄Cl with different mixing ratios were measured. Through observation of Cl Kα₁ X-ray from NaCl, the energy resolution of the system was determined to be 1.1 eV. For the NaCl sample, a Kβ_x line was observed at an energy, which is higher than that of the Kβ main peak by 2 eV, whereas no Kβ_x emission was observed for the NH₄Cl sample. The chemical shift of the Kβ main peak for PVC relative to that for NaCl was about 1.2 eV. For NaCl-NH₄Cl mixture targets, the relative intensity of Kβ_x satellite to the Kβ main line provided an indication of mixing ratio. Energies and relative intensity of Cl Kβ X-ray satellites for NaCl and NH₄Cl samples calculated by a simple molecular-orbital method agreed only qualitatively with the experimental results.     

Time-of-flight detection of monoatomic ions generated by femtosecond laser ablation from large molecules

Single-shot femtosecond laser ablation (fsLA) was applied to large molecules to analyze elemental composition through out wide range of mass-to-charge ratio. Molecular samples such as Eu-DNA and cosmetic powders were atomized and ionized simultaneously by the single-shot fsLA and positive atomic ions were detected using a reflectron time-of-flight (TOF) mass spectrometer. The ratios among the signal intensity of the detected stable isotopes including ^151,153Eu and ^182-184,186W were consistent with the respective natural abundances of the isotopes. The results demonstrate the feasibility of the fsLA-TOF method as a high-throughput analytical technique for elemental microanalysis of large molecular samples in small quantities.     

Biomonitoring study of seasonal anthropogenic influence at the Itamambuca beach (SP, Brazil)

The present work is focused on the study of a seasonal anthropogenic influence on the beach of Itamambuca (Ubatuba, SP, Brazil) carried out using Atherinella brasiliensis as biomonitor. In total 84 fish were caught between July 2004 and February 2005 in different locations at the beach and inside the Itamambuca river. The fish were pooled according to catch and their musculature was analyzed by Particle-Induced X-ray Emission (PIXE) and Rutherford Backscattering (RBS) techniques. While the concentration of light (matrix) elements like C and O were obtained using the RBS technique, major (Na, Mg, P, S, Cl, K and Ca) and trace (Si, Al, Ti, Cr, Mn, Fe, Ni, Cu, Zn, As, Se, Br and Sr) elements were measured by PIXE. The results show that differences were observed for several elemental concentrations of fish tissue between high season (spring-summer) and low season (winter-fall), indicating that increased human activity in the beach during high season may have some impact on the beach ecosystem. The role of the water salinity in the results is also discussed.     

Improved energy resolution of a cyclotron beam for RBS measurements

For RBS (Rutherford Back Scattering) analysis, the quality of the beam is of premium importance because the depth profile resolution of the method is strongly dependent on the energy resolution of the probing beam. A magnetic analyzer, consisting of two 90 left-right bending magnets forming an achromatic doublet has been adapted to the Liege 20 MeV (proton) AVF (Azimuthal Varying Field) cyclotron. The energy resolution of that system has been measured by recording the resonance width of a ³²S(p,p′γ)³²S (3.38 MeV. p⁺ lab. energy). We have obtained a value of ΔE = ± 2 keV, reducing by a factor of 20 the natural dispersion of our cyclotron.We describe our magnetic analyzer system and present the results of our RBS measurements at energies up to 14 MeV α.     

PIXE measurements of Renaissance silverpoint drawings at VERA

Silverpoint drawings from the Renaissance are among the most precious and rarest treasures of graphical art. Our research group is particularly interested in the analysis of silverpoint drawings by Albrecht Dürer (1471-1528). A very sensitive and non-destructive analytical method, either spatially resolved synchrotron-radiation induced X-ray fluorescence (SY-XRF) or proton-induced X-ray emission (PIXE), is needed to determine the chemical composition of the very faint silver marks on such drawings. Dürer drawings from the collection of the Albertina, Vienna, were analyzed to amend existing data on Dürer drawings. For this purpose an external-beam PIXE setup was installed at the Vienna Environmental Research Accelerator (VERA). It allows to analyze a spot of ∼0.15 mm on the object in air with 3 MeV protons, and to detect the emitted X-rays that are characteristic for the chemical composition with very good sensitivity and without harming the precious objects. After successful measurements on artificial test samples, four original silverpoint drawings were investigated: two portraits from Albrecht Dürer’s very early period (self-portrait and portrait of his father) and two drawings from Dürer’s sketch book of his travel to the Netherlands 1520/21.     

Silver surface enrichment controlled by simultaneous RBS for reliable PIXE analysis of ancient coins

Evidence of silver surface enrichment of ancient silver-copper coins has been pointed out in the past years. Surface enrichment can be fortuitous or intentional. In this paper, we have investigated the cleaning procedures usually performed after excavation or in museums. We have shown that chemicals or commercial products routinely used dissolve preferentially the copper phase and consequently contribute to the silver surface enrichment. As a result, surface analyses such as PIXE or XRF can be strongly affected by this effect. By using simultaneously RBS and PIXE, it is possible to check through the silver surface enrichment and then select the reliable measurements, characteristic of the bulk composition. Results on coins recently discovered and mechanically or chemically cleaned are presented.     

Development of a novel reaction chamber for ion beam analysis of large samples

A novel vacuum chamber for ion beam analysis of large-size industrial samples - whose analysis are not feasible in conventional ion beam analysis reaction chambers - has been designed, fabricated and successfully tested. Using the newly developed chamber, both PIXE and RBS analyses could be carried out at the same time and on the same point of the samples. Ion beam analysis using this novel chamber lacks the disadvantages of external beam analysis and benefits the advantages of in-vacuum analysis. This has been achieved by designing a tiny open port in the wall of the reaction chamber to be sealed with a small flat area of sample body where its analysis is of interest. As a case study, two samples of gas turbine blades, a corroded one at highly corrosive environment and a refurbished one after application of certain coatings are analysed using the novel chamber. Experimental results confirm the performance and capability of the reaction chamber.     

Post deposition annealing of Hf aluminate films on Si investigated by ion backscattering and nuclear reaction analyses

Layered Al₂O₃/HfO₂ structures were deposited on Si by atomic layer deposition and the atomic transport during rapid thermal annealing was investigated by low energy ion scattering, medium energy ion scattering and narrow nuclear resonant reaction profiling. The structures were dissociated during annealing by different mechanisms, such as interdiffusion of the layers and metal loss from the dielectric. The possible detrimental effects on device electrical properties of the observed decomposition are discussed.     

Evaluation of neutron cross sections for a complete set of Dy isotopes

Neutron cross sections for a complete set of Dy isotopes, ^{156,158,160,161,162,163,164}Dy, were evaluated in the incident energy range from 10⁻⁵ eV to 20 MeV. In the low energy region, including thermal and resolved resonances, our evaluations are based on the latest data published in the Atlas of Neutron Resonances. In the unresolved resonance region we performed additional evaluation by using the averages of the resolved resonances and adjusting them to the experimental data. In the fast neutron region, we used the nuclear reaction model code EMPIRE-2.19 with the model parameters adjusted to the experimental data. The results are compared with the available experimental data and with the existing nuclear data libraries, including ENDF/B-VI.8 and JEFF-3.1. The new evaluations are suitable for neutron transport calculations and they were adopted by the new US evaluated nuclear data library, ENDF/B-VII.0, released in December 2006.     

A comparison between a TESQ accelerator and a reactor as a neutron sources for BNCT

In this work, the performance of an accelerator-based neutron source design has been compared with that of a modern fluoride-filtered reactor-based epithermal beam having near-optimal quality for treatment of deep seated tumors in relation to its applicability for BNCT. The accelerator is a Tandem-Electrostatic-Quadrupole (TESQ) accelerator which is a design under development at the National Atomic Energy Commission (CNEA) in Buenos Aires, Argentina based on the ⁷Li(p,n)⁷Be reaction, relatively close to its energy threshold. The reactor is the Massachusetts Institute of Technology reactor upgraded with a Fission Converter Beam (MIT-FCB) and improved with an 8 mm thick ⁶Li filter. The comparison has been done by means of data reported on the MIT-FCB + ⁶Li filter performance and MCNP simulations on our TESQ design considering the neutron fluxes provided by the two sources and the doses delivered in a human phantom by both devices. The results show a deeper advantage depth (AD) for the TESQ which turns out to be a promising alternative to a reactor-based BNCT treatment.     

The effect of copper and manganese on magnetic minor hysteresis loops in neutron irradiated Fe model alloys

Changes of magnetic minor hysteresis loops in pure Fe, Fe-1 wt% Mn, Fe-0.9 wt% Cu, and Fe-0.9 wt% Cu-1 wt% Mn model alloys after neutron irradiation have been studied. Minor-loop coefficients which are obtained from scaling relations between minor-loop parameters and in proportion to internal stress, were found to decrease in all model alloys after the irradiation to a fluence of 3.32 × 10¹⁹ n cm⁻². The decrease of the coefficients is larger for alloys including Cu and is enhanced by 1 wt% Mn addition. Such decrease implying the reduction of internal stress during irradiation is in contrast with changes of yield strength after the irradiation that increase with Cu and Mn contents. A qualitative explanation was given on the basis of the preferential formation of Cu precipitates along pre-existing dislocations which reduces internal stress of the dislocations.     

Photoluminescence study of Ge nanocrystals irradiated by reactor neutron flux

Samples of Ge nanocrystals (Ge-ncs) embedded in amorphous SiO₂ film were prepared by Ge ion implantation and subsequent primary thermal annealing. These samples were irradiated by neutron flux in a nuclear reactor followed by the second annealing. Irradiation with thermal neutrons leads to doping of nanocrystals with Ga, As and Se impurities due to nuclear transmutation of isotope ⁷⁰Ge into ⁷¹Ga, isotope ⁷⁴Ge into ⁷⁵As, isotope ⁷⁶Ge into ⁷⁷Se, respectively (neutron transmutation doping, NTD). Irradiation with fast neutrons leads to appearance of radiation damages, which are expected to be removed after the second annealing. Photoluminescence (PL) measurements show that PL is quenched after neutron irradiation, and restored after annealing higher than 500 °C. The PL spectra of doped Ge-ncs samples show more intense exciton radiative luminescence than of undoped Ge-ncs sample, which is related to that the donor and acceptor impurities recombine the nonradiative centers in the interface of Ge-ncs and SiO₂ matrix, and enhance the probability of exciton recombination.     

Application of the thin layer activation technique to study surface erosion under high voltage electrical spark discharges

The thin layer activation technique using a heavy ion beam has been applied to measure the erosion loss of materials by electrical spark discharges with a discharge current in the mA range. Since the range of heavy ions such as ¹⁴N, ¹⁶O and ²⁰Ne, is about one order less than that of light ions such as p, d and α, the total activity can be generated within a narrow layer by activation with heavy ions. In the present work, a narrow layer of activity of ∼27 μm thickness was produced in copper-based materials by heavy ion induced nuclear reactions using 110 MeV ¹⁶O ions to measure the surface erosion in the range of hundreds of nanometers to few microns. The sensitivity can be enhanced to tens of nanometers using suitable heavy ions.