Grazing-exit X-ray spectrometry for surface and thin-film analyses.

Electron-probe x-ray micro analysis (EPMA) and particle-induced x-ray emission analysis (PIXE) were performed under grazing-exit conditions. To control the exit angle (take-off angle), a new sample holder having a stepping motor was developed for grazing-exit EPMA. A carefully polished surface of a stainless-steal sample was measured. The surface of stainless steel is normally covered with a thin native oxide layer. The intensity ratio of Cr K(alpha) to Fe K(alpha) increases significantly at the grazing angle, becoming about 5-times larger at 0.2 degrees than at 40 degrees. This result indicates that grazing-exit EPMA is useful for surface analysis. In addition, a new PIXE equipment was developed for grazing-exit x-ray measurements. The sample is fixed and the x-ray detector is moved by applying a linear stage. Preliminary experimental results of grazing-exit PIXE are also shown.     

Total reflection X-ray fluorescence analyses of samples from oil refining and chemical industries

The applicability and performance of the TXRF method for the analysis of sample materials from the oil refining and chemical industries were studied. One objective of the study was to develop rapid analytical procedures for the determination of elements present as traces in size fractionated diesel emission particles, in raw materials of resin production (ureas and phenols) and in trouble-shooting samples. Another goal was to determine the real, rather than the ideal, detection limits for the various applications. Absolute detection limits for most elements found in size fractionated diesel emission particles were below 1 ng. Relative detection limits determined for trace elements in ureas were between 5 and 30 μg kg⁻¹. Only the values for P, S and Ca exceeded this range. Additionally, remarkable differences in trace elements below 1 mg kg⁻¹ could be detected between five commercial ureas. © 1997 Elsevier Science B.V.     

A micro co-precipitation technique for use in X-ray fluorescence analysis

An apparatus and a procedure are described for the preconcentration of nanogram amounts of trace elements. Co-precipitation and pressure filtration confine the precipitate to a 1.27 mm diameter spot on a filter membrane. Trace elements in the 10-100 ng range are collected reproducibly and detected with high sensitivity by X-ray fluorescence, by use of a milliprobe instrument. Advantages of the technique for quantitative applications are discussed.     

Characterization of small particles by micro X-ray fluorescence

Micro X-ray fluorescence was used to study both homogeneous and heterogeneous particle systems. Specifically, homogeneous glass microspheres and heterogeneous soil particle samples were prepared by both bulk and single particle sample preparation methods for evaluation by micro X-ray fluorescence. Single particle sample preparation methods allow for single particles from a collected sample to be isolated and individually presented to the micro X-ray fluorescence instrument for analysis. Various particle dispersion methods, including immobilization onto Tacky Dot™ slides, mounting onto double-sided sticky tape affixed to polypropylene film, or attachment to polypropylene film using 3M Artist's Adhesive, were used to separate the sample particles for single particle analysis. These methods were then compared and evaluated for their ability to disperse the particles into an array of single separated particles for optimal micro X-ray fluorescence characterization with minimal background contribution from the particle mounting surface. Bulk methods of particle sample preparation, which included pellet preparation and aerosol impaction, used a large quantity of collected single particles to make a single homogeneous specimen for presentation to the instrument for analysis. It was found that single particle elemental analysis by micro X-ray fluorescence can be performed if the particles are well separated (minimum separation distance = excitation source beam diameter) down to a particle mass of ∼ 0.04 ng and a mean particle diameter of ∼ 0.06 μm. Homogeneous particulates can be adequately characterized by micro X-ray fluorescence using either bulk or single particle analysis methods, with no loss of analytical information. Heterogeneous samples are much harder to characterize, and both single particle as well as bulk analyses must be performed on the sample to insure full elemental characterization by micro X-ray fluorescence.     

Development of confocal micro X-ray fluorescence instrument using two X-ray beams

A new confocal micro X-ray fluorescence instrument was developed. This instrument has two independent micro X-ray tubes with Mo targets. A full polycapillary X-ray lens was attached to each X-ray tube. Another half polycapillary lens was attached to a silicon drift X-ray detector (SDD). The focal spots of the three lenses were adjusted to a common position. The effects of the excitation of two X-ray beams were investigated. The instrument enabled highly sensitive three-dimensional X-ray fluorescence analysis. We confirmed that the X-ray fluorescence intensity from the sample increased by applying the two independent X-ray tubes in confocal configuration. Elemental depth profiling of black wheat was demonstrated with the result that each element in the surface coat of a wheat grain showed unique distribution.     

A new fundamental parameter based calibration procedure for micro X-ray fluorescence spectrometers

Fundamental parameter based quantification of X-ray fluorescence (XRF) measurement data requires an accurate knowledge of the spectrometer parameters, including the spectral distribution of the excitation radiation. In case of micro-XRF where a polycapillary optic is utilized in the excitation channel this distribution is changed due to the transmission properties of the lens. A new calibration procedure, based on fluorescence data of thin standard samples, was developed to determine the excitation spectrum, i.e., the product of the X-ray tube spectrum and the transmission of the used X-ray optic of a micro-XRF setup. The calibration result was validated by the quantitative analyses of certified multi-element reference standards and shows uncertainties in the order of 2% for main components, 10% for minor elements and 25% for trace elements. The influence of secondary order effects like Coster-Kronig transitions and cascade effects is analyzed and the accuracy of fundamental parameters in common databases is discussed.     

X-ray diffraction and chemical analyses of magnesium aluminium fluoride

The preparation of magnesium aluminium fluoride by addition of hydrofluoric acid to a mixture of aluminium and magnesium nitrates is described. The x-ray diffraction pattern of the complex, identified by chemical and thermogravimetric analyses as MgAlF₅ · 2.2 H₂O, is reported.     

Grazing-exit electron probe X-ray microanalysis (GE-EPMA): Fundamental and applications

Electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) has been studied under grazing-exit conditions. That is, characteristic X-rays are detected at a very small take-off (exit) angle; the technique is known as grazing-exit electron probe microanalysis (GE-EPMA). Fundamental aspects, instrumentation, and characteristics of grazing-exit electron probe X-ray microanalysis method are described here. Since the observation depth decreases as the exit angle decreases, theoretically to a few nanometers, surface analysis is possible in grazing-exit electron probe X-ray microanalysis. Of course, the size of the electron beam is also small—less than 1 μm, enabling localized surface analysis. In the case of total reflection X-ray spectrometry that allows surface analysis, the whole sample surface must be flat. However, the requirement for flatness is not as strict in grazing-exit electron probe X-ray microanalysis. Grazing-exit electron probe X-ray microanalysis measurements can easily be applied using a commercially available electron probe microanalysis (or Scanning electron microscope-energy dispersive X-ray spectrometry) instrument. To change and control the exit angle in grazing-exit electron probe X-ray microanalysis, the inclination of the sample stage or movement of the X-ray detector is all that is required. Theoretically, this study shows that grazing-exit electron probe X-ray microanalysis would be useful in improving the lateral resolution of the sample surface. In addition, the study demonstrates that grazing-exit electron probe X-ray microanalysis can be applied successfully for surface, thin-film, and particle analyses. As an optional method of electron probe microanalysis, grazing-exit electron probe X-ray microanalysis will be useful in expanding the research fields of normal electron probe microanalysis.     

Possibilities of micro X-ray fluorescence spectrometry of solutions with preconcentration

Results of investigations in energy-dispersive X-ray fluorescence analysis aimed at the development of a high-sensitivity method of microanalysis of solutions are presented. A combined scheme of analysis of one drop of solution of the volume several microliters is proposed and tested. The scheme includes a new preconcentration method based on the drop evaporation in the presence of a micrograin of a hydrophilic adsorbent followed by the microanalysis of the solid phase on the portable device with a polycapillary lens with a focal spot of 10 μm designed at the Institute of Physical Optics. Analytically meaningful X-ray fluorescence spectra are obtained using DETATA (grain diameter about 100 μm) and SAC8 (50 μm) adsorbents and individual drops of model solutions containing Mn, Fe, Co, Ni, Cu, and Zn (0.2 mg/L and higher) and analytical characteristics of the proposed approach are demonstrated.     

Development of micro X-ray fluorescence spectrometer with multi excitation sources

X-ray fluorescence analysis (XRF) is a suitable technique for elemental analysis in nondestructive measurement. Recently, small area analysis by using the XRF technique has gained popularity. The synchrotron radiation source is responsible for the increase in the popularity of micro-XRF analysis. However, most people find it difficult to gain access to the synchrotron radiation facility. In this study, a micro-XRF system is developed for use in laboratories. To enable the use of this system, it is necessary to satisfy the following two conditions: (1) the excitation source must be optional for efficient excitation of the sample and (2) the X-rays must be focused. An X-ray tube with multi excitation sources has also been developed. In this tube, there are three targets, namely Cr, W, and Pd, on the anode, and each target can be excited sequentially. A doubly curved crystal (DCC) developed using a Si(111) crystal is used as the optics for focusing the X-rays into a beam with a diameter of less than 100 μm. A system composed of the X-ray tube and DCC optics is used to perform the small particle analysis of a Si wafer. The lower limit of detection (LLD) of the sample particle is estimated as 1.6 μm in diameter.     

Development and applications of grazing exit micro X-ray fluorescence instrument using a polycapillary X-ray lens

A polycapillary X-ray lens is an effective optics to obtain a μm-size X-ray beam for micro-X-ray fluorescence spectrometry (μ-XRF). We developed a μ-XRF instrument using a polycapillary X-ray lens, which also enabled us to perform Grazing Exit μ-XRF (GE-μ-XRF). The evaluated diameter of the primary X-ray beam was 48 μm at the focal distance of the X-ray lens. Use of this instrument enabled two-dimensional mapping of the elemental distributions during growth of the plant “Quinoa”. The results of the mapping revealed elemental transition during growth. In addition, a small region of thin film was analyzed by GE-μ-XRF. We expect that GE-μ-XRF will become an effective method of estimating the film thickness of a small region.     

Total reflection X-ray fluorescence analysis with chemical microchip

A chemical microchip, which has a flat region on the surface, was recently designed for total reflection X-ray fluorescence (TXRF) analysis. A sample solution was introduced from an inlet by a microsyringe and flowed into a microchannel. Finally it overflowed from the well-type microchannel on the flat region. The sample solution on this region was dried, and then measured by TXRF. The TXRF spectra could be measured with a low background level. This preliminary result indicated that the edge of the well-type channel would not cause a serious problem for TXRF analysis. In addition, a good linear relationship was obtained for Zn Kα in Zn standard solution. This suggests that quantitative analysis by TXRF is feasible in combination with a chemical microchip.     

Test method for the presence or absence of Pb in electrical components using energy-dispersive micro X-ray fluorescence.

The micro-EDXRF (energy dispersive X-ray fluorescence) method was applied to the screening of Pb in micrometer-area samples, such as a Cu contact in electrical components that had been coated by Pb-free Sn-Ag-Cu solder. The reliability of the screening method was evaluated by a comparison with a scanning electron microscope (SEM) observation and a precious chemical analysis method of inductively coupled plasma mass spectrometry (ICP-MS). Some factors that affect the testing reliability, such as the thickness of the solder, the segregation of Pb and Ag, etc. were found by SEM observations. By adjusting some calculation parameters, screening of the micrometer area (0.1 mm) was performed using the fundamental parameter (FP) method for a thin film in conjunction with micro-EDXRF. The measurement error ranged by 25% for the thin film-FP method. The resulted detection limit was 0.04 wt% for Pb, depending on the solder thickness. This method can be successively applied for quality control to check the purity of a Pb-free Sn-Ag-Cu solder coating in electrical components.     

ArtTAX - a new mobile spectrometer for energy-dispersive micro X-ray fluorescence spectrometry on art and archaeological objects

A newly developed spectrometer for energy-dispersive micro X-ray fluorescence spectrometry has been designed for the demands of archaeometry. ArtTAX combines the advantages of non-destructive and sensitive multi-elemental analysis at sub-mm resolution with the possibility of working outside the laboratory. The spectrometer consists of an air-cooled, low-power molybdenum tube, new generation polycapillary X-ray optics, a silicon drift detector without the need for liquid-nitrogen cooling, a CCD camera, and three light diodes for sample positioning. The motor-driven measurement head is fixed on a x,y,z-flexible tripod support which can be assembled and dismantled within minutes. The spot size of the primary X-ray beam was determined to be 94 microm for the Cu(Kalpha) energy, the detection limits are in a range of a few tens of microg g(-1) for the medium energy-range in glass. Additional open helium purging in the excitation and detection paths enables the determination of elements down to sodium, thus avoiding vacuum conditions or a size-limiting sample chamber. A selection of qualitative and quantitative results on pigment, metal, glass, and enamel analyses are presented to show the potential of ArtTAX in the field of art and archaeology.     

Characterization of a confocal three-dimensional micro X-ray fluorescence facility based on polycapillary X-ray optics and Kirkpatrick–Baez mirrors

A new confocal three-dimensional micro X-ray fluorescence (3D micro-XRF) facility based on polycapillary X-ray optics in the detection channel and Kirkpatrick–Baez (KB) mirrors in the excitation channel is designed. The lateral resolution (l_x, l_y) of this confocal three-dimensional micro-X-ray fluorescence facility is 76.3(l_x) and 53.4(l_y) µm respectively, and its depth resolution d_z is 77.1 μm at θ = 90°. A plant sample (twig of B. microphylla) and airborne particles are analyzed.     

Tube-excited energy-dispersive X-ray fluorescence analysis. II. Energy-dispersive X-ray fluorescence analysis of air particulate material.

The use of monoenergetic exciting radiation of molybdenum obtained with a secondary target set-up, a conventional water-cooled tungsten anode x-ray tube and a Si(Li) semiconductor detector permits many trace and minor constituents from chlorine to strontium to be determined in particulate material collected on cellulose filters. The method is rapid and economical compared to other multielement techniques. The use of one or more single-element thin-film standards to calibrate for the analysis of many elements appears to be possible, but some systematic errors must be prevented. Absorption of the fluorescent radiation is remedied by a simple correction method. The precision and the accuracy of the method were critically examined by independent analysis of a number of samples with instrumental neutron activation analysis and by interlaboratory comparisons on the same samples.