On the accuracy of element concentrations and masses of micron sized samples determined with the Heidelberg proton microprobe

We have already tested the reliability of element-normalized PIXE (Proton Induced X-ray Emission) data on small (10–100 μm) particles that we routinely obtain with the Heidelberg proton microprobe. Thus, we here discuss the accuracy of quantitative results, i.e., absolute concentrations inferred from PIXE analyses of such particles. We investigated and reduced the effects of mechanical vibrations and of the instability of the electronic devices on the achievable minimum beam spot. We implemented into our computer code a mapping software for qualitative element distributions (PIXE) and quantitative mass images using STIM (Scanning Transmission Ion Microscopy). The STIM images determine the area density required to calculate from PIXE spectra the absolute element concentrations in thin samples. The accuracy of absolute PIXE concentrations is tested by measurements on 15 μm soda lime glass microspheres. Finally, the complete results of PIXE and STIM analyses of an interplanetary dust particle (IDP) are described.     

Nuclear microprobe analysis of U-doped (Bi,Pb)2Sr2Ca2Cu3Oy/Ag superconducting tapes

Superconducting (Bi,Pb)₂Sr₂Ca₂Cu₃O_y/Ag tapes are doped with uranium compounds to introduce flux pinning defects from neutron-induced fission. The composition and distribution of elements in cross sections of the tapes were probed with a scanned 3 MeV proton microbeam using proton induced X-ray emission (PIXE). Distributions of the constituent elements were found to be heterogeneous on a scale of 10 μm. By combining the PIXE analysis with Rutherford backscattering spectrometry, the stoichiometry of the superconductor within the tape was measured, including oxygen from elastic scattering, revealing a departure from the desired 2223 composition. In one of the tapes, PIXE elemental maps of the Ag distribution showed diffusion of Ag into the superconductor from the enclosing jacket. Crystals of the same material, not fabricated into tapes, did not contain the contaminants and had a more ideal stoichiometry. Correlation maps between the constituent elements, deduced from the elemental maps, indicate the presence of secondary or unreacted phases.     

Use of the nuclear microprobe at the University of Arizona for the study of heavy metal deposition in rabbit renal tissue

Industrial wastes consigned to disposal sites frequently contain substantial amounts of heavy metals. We have successfully applied proton induced X-ray emission analysis (PIXE) in the conduct of heavy metal (Hg, Cd, Cr, As) toxicity studies using precision cut rabbit renal cortical slices. The large beam diameter (4000 μm) of the proton macroprobe at The University of Arizona Ion Beam Analysis facility allowed an overall concentration of the metal(s) of interest in the samples to be determined, but lacked the ability to resolve point concentrations in the tissue. The ability to locate these areas has now been made available to us with the addition of a rastering microprobe (μ-PIXE) to the facility. Studies now being conducted in our laboratory using this micro-technique include analysis of renal tissue taken from rabbits injected intraperitoneally with HgCl₂, K₂Cr₂O₇, and NaAsO₂. The small beam size (3 μm) and the ability to raster this beam over areas of up to 125 μm × 125 μm has allowed regional mapping of endogenous and non-endogenous metal concentrations and revealed trends in heavy metal deposition in in vivo treated renal tissue, significantly increasing the amount of information obtained from these animal studies using PIXE alone. The combination of small beam size, high resolution, and multi-element detection makes μ-PIXE a powerful tool for investigating the impact of non-endogenous metals on the kidney.     

Detailed mass size distributions of atmospheric aerosol species in the Negev desert, Israel, during ARACHNE-96

As part of the 1996 summer intensive of the Aerosol, RAdiation and CHemistry Experiment (ARACHNE-96), the mass size distribution of various airborne particulate elements was studied at a remote site in the Negev Desert, Israel. Aerosol collections were made with 8-stage PIXE International cascade impactors (PCIs) and 12-stage small deposit area low pressure impactors (SDIs) and the samples were analyzed by PIXE for about 20 elements. The mineral elements (Al, Si, Ca, Ti, Fe) exhibited a unimodal size distribution which peaked at about 6 μm, but the contribution of particles larger than 10 μm was clearly more pronounced during the day than during night. Sulphur and Br had a tendency to exhibit two modes in the submicrometer size range, with diameters at about 0.3 and 0.6 μm, respectively. The elements V and Ni, which are indicators of residual fuel burning, showed essentially one fine mode (at 0.3 μm) in addition to a coarse mode which represented the mineral dust contribution. Overall, good agreement was observed between the mass size distributions from the PCI and SDI devices. The PCI was superior to the SDI for studying the size distribution in the coarse size range, but the SDI was clearly superior for unravelling the various modes in the submicrometer size range.     

Study by PIXE method of trace elements transferred from prostheses to soft tissues and organs

Some metallic prostheses inserted in human hip undergo physico-chemical modification, a few years after their implantation. Tissues surrounding these prostheses are damaged by metallic element transfer. Surgeons in Clermont-Ferrand Hospital (France) recover tissues of abnormal coloration that were in contact with metallic implants. PIXE technique (particles induced X-ray emission) with a 400 μm proton beam and 3 MeV of energy is an efficient technique to analyze these tissues and to detect elements, which are transferred from prosthesis to tissues. PIXE analyses were carried at the CERI-CNRS Laboratory. We have applied this method to determine qualitatively and quantitatively trace elements migration from metallic implants to surrounding tissues and organs, like kidney, spleen, liver, lymphatic gland and lung.     

Study of particulate emissions near a steel plant in Genova by continuous sampling and PIXE hourly analysis

The particulate emissions near a large steel plant located in a densely inhabited suburb of the town of Genova (Italy) have been studied for a period of six months. We have used two-stage continuous streaker samplers and subsequent PIXE analysis with hourly resolution, to follow both seasonal and daily trends. The first streaker sampler remained installed very close to the plant cokery and furnaces, while another sampler was moved to different locations. Samples have been analysed by PIXE, deducing concentrations for elements from Na to Pb. During part of the campaign, the aerosol fractions with aerodynamic diameter (D_ae) < 2.5 μm (fine fraction) and with 2.5 < D_ae < 10 μm (coarse fraction) have been separately collected. We have measured and analysed about 8500 PIXE spectra: the steel plant emissions have been identified to some extent and resolved from other aerosol sources.     

The external beam microprobe facility in Florence: Set-up and performance

An external beam microprobe facility, based on a quadrupole doublet supplied by Oxford Microbeam Ltd, has been installed on a new beamline at the 3 MV single-ended Van de Graaff accelerator in Florence. The goal was to obtain a beam with a spot size on target of 10–20 μm and a current in the order of at least 1 nA, in order to allow PIXE, PIGE and RBS elemental analysis in air or in a helium atmosphere. The beam was extracted from the vacuum lines through a 0.1 μm thick Si₃N₄ window to minimise lateral straggling. The design goals have been successfully achieved; the measurements of the beam spot characteristics in vacuum as well as in air and in helium atmosphere, are here reported.     

Micro-PIXE analyses of trace elements in black shales from the Lower Zechstein copper deposits, Poland

Micro-PIXE analyses made, using the Heidelberg proton microprobe, of thucholite-like organic matter and noble metals bearing shale matrices from the Lower Zechstein copper deposits of the Fore-Sudetic Monocline (Poland) are reported. The experimental conditions included a proton microbeam with a beam spot of ˜ 3 × 3 μm, 3 MeV proton energy and a 195 μm thick external Al absorber. Quantitative results and the detection limits for various elements are reported.     

Application of the micro-PIXE technique for analyzing arsenic in biomat and lower plants of lichen and mosses around an arsenic mine site, at Gunma, Japan

Microhabitats of bacteria (biomat) and lower plants, such as lichen and mosses, are known to accumulate hazardous elements. Since the concentration of hazardous elements in the environment is quite low, we have applied the in-air μ-PIXE (particle induced X-ray emission) system developed in the TIARA facility of JAERI, which has low concentration detection limit of ppm, to measure As, one of the hazardous elements, distributions in biomat, lichen and mosses observed around an abandoned As mine site in Gunma, Japan to elucidate the applicability of these biomat and lower plants as bio-indicators of As. Spatial distributions of As, Fe, Si and S in all biomat, lichen and moss collected within 3 m from the mine entrance indicate that As is localized, and is associated with silicate and Fe-containing compounds. In addition, the intensity ratio of peak area for As to Fe in μ-PIXE spectrum of the moss collected from the concrete wall at 3 m downstream of the mine water discharge position is different from those of the lower plants on the rock near the closed entrance, but is the same as that of biomat formed at the mine water discharge position. This indicates that As trapped by the moss on the concrete wall probably has the same origin as the biomat. It is concluded that application of μ-PIXE analysis to the measurement of As in the lower plants and biomat gives not only the distribution of the hazardous element of As, but also the information of the origin.     

Size-fractionated aerosol composition during an intensive 1997 summer field campaign in northern Finland

A 12-stage small deposit area low pressure impactor (SDI) was used to collect size-fractionated aerosol samples during an intensive 1997 summer field campaign in northern Finland. The samples were analyzed for over 20 elements by PIXE, and some “difficult” elements such as As and Se could be quantified. The sea-salt and crustal elements had essentially a unimodal coarse size distribution with geometric mean aerodynamic diameter (GMAD) of about 4–5 μm. In one third of the samples, S showed only one mode in the fine size range, with GMAD of 0.4–0.5 μm. In the other samples, this fine S mode broke up into two modes, with GMADs of 0.3 and 0.6 μm, respectively. V, Zn, As, Se and Pb were mainly present in a single submicrometer mode, with GMAD of 0.4–0.5 μm for V and Se, and slightly larger (i.e., 0.6 μm) for the other three elements. The highest concentrations of S, V, Ni, Cu, Zn, As, Se and Pb were encountered in the SDI sample which had been collected in the period 14–16 July. During this sampling, the air masses came in from the west, but had recirculated over northern Scandinavia and passed over the Kola peninsula.     

Analysis of metallic pigments by ion microbeam

Metallic paints consist of metallic flakes dispersed in a resinous binder, i.e. a light-element polymer matrix. The spatial distribution and orientation of metallic flakes inside the matrix determines the covering efficiency of the paint, glossiness, and its angular-dependent properties such as lightness flop or color flop (two-tone). Such coatings are extensively used for a functional (i.e. security) as well as decorative purpose. The ion microbeam analysis of two types of silver paint with imbedded metallic flakes has been performed to determine the spatial distribution of the aluminum flakes in paint layer. The average sizes of the aluminum flakes were 23 μm (size distribution 10–37) and 49 μm (size distribution 34–75), respectively. The proton beam with the size of 2×2 μm² at Ljubljana ion microprobe has been used to scan the surface of the pigments. PIXE mapping of Al K map shows lateral distribution of the aluminum flakes, whereas the RBS slicing method reveals tomograms of the flakes in uppermost 7 μm of the pigment layer. The series of point analysis aligned over the single flake reveal the flake angle in respect to the polymer matrix surface. The angular sensitivity is well below 1 angular degree.     

Characterisation of ferromagnetic magnetic storage media surfaces by complementary particle induced X-ray analysis and time of flight-energy dispersive elastic recoil detection analysis

Thin (10 nm–1 μm) films of ferromagnetic material constitute an important class of materials that are difficult to analyse by conventional ion beam analytical (IBA) techniques because they are based on the ferromagnetic elements (Co, Fe, Mn, Ni, and Cr). The similar or overlapping isotope masses makes it difficult to separate the elemental signals using time of flight and energy dispersive elastic recoil detection (ToF-E ERD). In this exploratory study we have investigated the use of Particle Induced X-ray Emission (PIXE) measurements to refine the mass dispersive depth profile information from ToF-E ERD. The surfaces of two commercial magnetic media were investigated. One sample was a double density diskette with a coating of ferrite particles in an organic binder. The other sample was a complex C/Co/Cr/Ni–P/Al multilayer structure taken from a standard hard disc. The Lund nuclear microprobe with a 2.55 MeV proton beam was used for PIXE analysis. ToF-ERD measurements were carried out using a 55 MeV ¹²⁷I¹⁰⁺ ion beam incident at 67.5° to the surface normal. The time of flight and kinetic energy of recoils ejected at 45° to the ion beam direction was measured in a detector telescope. The findings demonstrate that by detailed analysis of the PIXE spectra it is possible to remove the ambiguities in mass assignment of the ToF-ERD data associated with the ferromagnetic elements.     

The performance of the Ljubljana ion microprobe

In August 2000 the setup of the Ljubljana ion microprobe, based on OM 150 triplet, has been completed. The beam line is installed at the 10° exit port of the 2 MeV Tandetron accelerator. It is equipped with motor driven slits, a precise five-axis goniometer and a spherically shaped measuring chamber with detectors for PIXE, PIGE, PESA, SE and RBS. In order to understand the beam optics along the complete system, consisting of the tandem accelerator and the beam line optical elements, an interactive computer code, based on a linear approximation, has been developed. The program is used both to determine the optimal parameters of the tandem focusing system in its daily use and to develop new beam line configurations. Test measurements performed on a copper grid yielded a spatial resolution of 1.0×1.5 μm² in the high current mode (30–100 pA) and 0.5×0.9 μm² in low current mode (10⁴ counts/s). First analytical results confirmed excellent performance of the new Ljubljana ion microprobe.     

Microbeam line with 1.5 MeV helium ions and protons at Osaka

A microprobe for Rutherford backscattering (RBS) and particle-induced X-ray emission (PIXE) measurements has been realized by focusing 1.5 MeV helium-ion or proton beams with a demagnification system consisting of piezo-driven objective slits and a magnetic quadrupole doublet. Minimum beam spot sizes of 1.3 × 2.2 μm² for helium ions and 2.2 × 4.0 μm² for protons have been achieved. The factors which may limit the minimum spot size are discussed using a Monte Carlo simulation procedure. Rutherford backscattering image mapping of 3-dimensional structures is demonstrated.     

M-shell X-ray production cross sections for PIXE applications

M-shell X-ray production cross sections by protons of energies 0.1–4.0 MeV are reported for the most intense M_β(M_4,5N_6,7), M_γ(M₃N_4,5) and M₃O_4,5 M-X ray transitions appearing in PIXE spectra. The cross sections have been measured systematically for selected heavy elements between Ta and Th (Z₂=73–90). Measured M-X-ray production cross sections were found to be universal with respect of M-shell scaled velocity ξ_M. The data are compared with available theoretical calculations of M-shell ionization by charged particles based on the plane-wave Born approximation (PWBA) and the semiclassical approximation (SCA), as well as the ECPSSR theory and relativistic RPWBA-BC which are going beyond the first order treatment. Simple parameterization of experimental proton induced M-X-ray cross sections is proposed for PIXE applications. This parameterization, being accurate within ±5%, can be used for precise determination of heavy metal concentrations by PIXE technique.     

A new mapping acquisition and processing system for simultaneous PIXE-RBS analysis with external beam

The combination of ion beam analysis techniques is particularly fruitful for the study of cultural heritage objects. For several years, the AGLAE facility of the Louvre laboratory has been implementing these techniques with an external beam. The recent set-up permits to carry out PIXE, PIGE and RBS simultaneously on the same analyzed spot with a particle beam of approximately 20 μm diameter.A new mapping system has been developed in order to provide elemental concentration maps from the PIXE and RBS spectra. This system combines the Genie2000 spectroscopy software with a homemade software that creates maps by handling acquisition with the object position. Each pixel of each PIXE and RBS maps contains the spectrum normalised by the dose. After analysing each pixel of the PIXE maps (low and high energy X-ray spectra) with the Gupixwin peak-fitting software, quantitative elemental concentrations are obtained for the major and trace elements. This paper presents the quantitative elemental maps extracted from the PIXE spectra and the development of RBS data processing for light element distribution and thin layer characterization. Examples on rock painting and lustrous ceramics will be presented.     

Microbeam RBS on flat panel displays

We have demonstrated the utility of microbeam-Rutherford BackScattering (μ-RBS) in spatially resolved studies of operational plasma effects on the interior surfaces of plasma flat panel displays manufactured by Photonics Imaging. The experiments were performed at the Sandia Nuclear microprobe using a 2.8 MeV He beam with an average beam spot size of less than 8 μm. The interior surface of the top panes of the flat panels is composed of approximately 800 nm of MgO on top of a 2000 nm thick PbO layer. μ-RBS of sample panels operated under varying conditions measured changes in the surface MgO film thickness due to plasma erosion and redeposition as accurately as ± 1.5 nm. The high accuracy in the MgO thickness measurement was achieved by inferring the MgO thickness from the shift of the Pb front edge in the RBS spectrum. An estimate for the thickness accuracy as a function of the acquired statistics is presented. The surface of the flat panels' bottom panes is also comprised of MgO on top of PbO. However, troughs 100 μm wide by 10 μm deep were partially filled with phosphor and cover the entire width of the surface. This leaves only 100 μm long sections of MgO within the trough exposed. Using μ-RBS, we were able to analyze the surface composition of these regions.     

Quadrupole-doublet with permanent magnets for proton beam focussing

For PIXE studies on inhomogeneous samples with medium spatial resolution of about 50 μm two quadrupole doublets with Co₅Sm pole pieces for focussing 2.0 and 2.5 MeV proton beams, respectively, have been designed and tested. Technical data and first results are presented.     

PESA as a complementary tool to PIXE at CTU Prague

Proton Elastic Scattering Analysis (PESA) is a simple convenient method for hydrogen analysis in thin samples. A Proton Induced X-ray Emission (PIXE) target chamber was equipped with a PIPS detector for detection of forward-scattered protons. One of the objectives was to perform PIXE and PESA analyses of air particulate targets simultaneously. Tests and calibrations were fulfilled mainly with Mylar foils 1.5–6.5 μm thick in the proton energy region between 1.35 and 2.3 MeV. The energy dependence of scattering cross section is different from the Rutherford formula. Comparison of PIXE/PESA analysis with the Guelph Scanning Proton Microprobe Laboratory at the University of Guelph, Canada on seven aerosol samples was carried out. The intercomparison results validated our PESA/PIXE quality assurance protocol. In addition, repeated measurements of Gelman Teflo^TM filters indicated a gradual increase of hydrogen content by 1 ng/cm² per 1 μC/cm² proton dose.     

The nuclear microprobe at the University of Arizona

A nuclear microprobe has been operational at the University of Arizona since early 1994. It utilizes a magnetic quadrupole doublet (model QL-300 from Microscope Associates, Inc.) with an 11 mm diameter aperture and lens lengths of 6 cm each. The magnetic pole tips are electrically insulated to enable electric rotational alignment and beam rastering by application of varying voltages to the pole tips. Ion beams are obtained from a 5.5 MV model CN, High Voltage Engineering Corp. Van de Graaff accelerator with a Penning type ion source. Present mininum beam spot size is about 2 μm obtained with a 4 MeV H₂⁺ beam with a current of about 40 pA. To date, the instrument has been successfully used to map concentrations of Hg, Cr, and As in rabbit renal slices using PIXE.