Development of a micro-X-ray fluorescence system based on polycapillary X-ray optics for non-destructive analysis of archaeological objects

A new micro-X-ray fluorescence (micro-XRF) system based on rotating anode X-ray generator and polycapillary X-ray optics has been set up in XOL Lab, BNU, China, in order to be used for analysis of archaeological objects. The polycapillary X-ray optics used here can focus the primary X-ray beam down to tens of micrometers in diameter that allows for non-destructive and local analysis of sub-mm samples with minor/trace level sensitivity. The analytical characteristics and potential of this micro-XRF system in archaeological research are discussed. Some described uses of this instrument include studying Chinese ancient porcelain.     

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.     

Hard X-ray micro-spectroscopy at Berliner Elektronenspeicherring für Synchrotronstrahlung II

The capabilities of the X-ray beamlines at Berliner Elektronenspeicherring für Synchrotronstrahlung II (BESSY II) for hard X-ray measurements with micro- and nanometer spatial resolution are reviewed. The micro-X-ray fluorescence analysis (micro-XRF), micro-extended X-ray absorption fine structure (micro-EXAFS), micro-X-ray absorption near-edge structure (micro-XANES) as well as X-ray standing wave technique (XSW), X-ray beam induced current (XBIC) in combination with micro-XRF and micro-diffraction as powerful methods for organic and inorganic sample characterization with synchrotron radiation are discussed. Mono and polycapillary optical systems were used for fine X-ray focusing down to 1 µm spot size with monochromatic and white synchrotron radiation. Polycapillary based confocal detection was applied for depth-resolved micro-XRF analysis with a volume resolution down to 3.4 · 10^− 6 mm³. Standing wave excitation in waveguides was also applied to nano-EXAFS measurements with depth resolution on the order of 1 nm. Several examples of the methods and its applications in material research, biological investigations and metal-semiconductor interfaces analysis are given.     

Application of confocal 3D micro-XRF for solid/liquid interface analysis.

Solid/liquid interfaces are important locations for various chemical reactions, such as electrode chemical reactions and metal corrosions. Conventional surface analytical methods, such as XPS and SEM-EDS, have been applied to solid materials after being removed from the liquid phase. These methods do not involve direct observation, although useful information is available. It is important to directly observe surface reactions on solid materials in the liquid phase in order to understand the details of these reactions. One feasible method of doing this is 3D micro-XRF analysis. The confocal 3D micro XRF method enables nondestructive x-ray elemental analysis of localized microspace. We have applied a confocal 3D micro-XRF instrument for solid/liquid interface analysis. This technique was applied for direct observation of the chemical deposition of Cu on an Fe plate and the dissolution of Fe in a CuSO4 solution.     

Three-dimensional micro-XRF investigations of paint layers with a tabletop setup

The non-destructive investigation of art and archaeological objects with depth sensitivity is now possible using 3D micro-XRF spectroscopy. More detailed answers for questions on painting techniques, on the pigment palette, on the production processes and indirectly on dating or provenancing of objects are accessible now. This was already illustrated by the investigation of Mughal miniatures with a confocal setup at the synchrotron source BESSY.In this paper we demonstrate the feasibility of 3D micro-XRF spectroscopy with a tabletop setup and discuss its sensitivity in comparison to the synchrotron-based setup. Investigated objects are glass standards and also prepared paint layers. Perspectives for other types of studies are proposed.     

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.     

微束X射线荧光光谱分析技术在一种黑色纸张物证检验中的应用研究

对7种真假纸币样本和2003年～2008年的32宗诈骗案件中共计225件被染黑的真假纸币物证,采用微束X射线荧光光谱仪(micro-XRF)分析其二维元素分布.结果表明:纸币元素分布特征都具有特定性,相同面额相同年版的纸币元素分布特征相同,相同面额不同年版的纸币元素分布特征有差异;真假纸币元素分布特征存在显著差异;被染黑的纸币元素分布特征与原纸币相同;因而可根据被染黑真假纸币的元素分布特征,鉴定其真伪并判断纸币种类.微束XRF分析在实际案件中黑色纸张物证的检验准确率为100%.因此,微束XRF技术能有效检验被染料染黑的真假纸币,具有灵敏度高,分析过程中不破坏样品,结果准确的特点,在该类物证的检验中具有较高的应用价值.     

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.     

Comparison of a portable micro-X-ray fluorescence spectrometry with inductively coupled plasma atomic emission spectrometry for the ancient ceramics analysis

Two multielement instrumental methods of analysis, micro X-ray fluorescence spectrometry (micro-XRF) and inductively coupled plasma atomic emission spectrometry (ICP-AES) were applied for the analysis of 7th and 5th century B.C. ancient ceramic sherds in order to evaluate the above two methods and to assess the potential to use the current compact and portable micro-XRF instrument for the in situ analysis of ancient ceramics. The distinguishing factor of interest is that micro-XRF spectrometry offers the possibility of a nondestructive analysis, an aspect of primary importance in the compositional analysis of cultural objects. Micro-XRF measurements were performed firstly directly on the ceramic sherds with no special pretreatment apart from surface cleaning (micro-XRF on sherds) and secondly on pressed pellet disks which were prepared for each ceramic sherd (micro-XRF on pellet). For the ICP-AES determination of elements, test solutions were prepared by the application of a microwave-assisted decomposition procedure in closed high-pressure PFA vessels. Also, the standard reference material SARM 69 was used for the efficiency calibration of the micro-XRF instrument and was analysed by both methods. In order to verify the calibration, the standard reference materials NCS DC 73332 and SRM620 as well as the reference materials AWI-1 and PRI-1 were analysed by micro-XRF. Elemental concentrations determined by the three analytical procedures (ICP-AES, micro-XRF on sherds and micro-XRF on pellets) were statistically treated by correlation analysis and Student's t-test (at the 95% confidence level).     

Three-dimensional micro-XRF under cryogenic conditions: a pilot experiment for spatially resolved trace analysis in biological specimens

Three-dimensional micro-XRF is a recently developed microprobe which facilitates three-dimensional resolved chemical analyses with a resolution of around 20 μm. Arbitrary sites or sections of samples can be investigated without the need to section specimens physically. In this paper we demonstrate the use of the microprobe in combination with a cold nitrogen gas stream for the cryogenic fixation of specimens. A 3D micro-XRF setup at the new microfocus beamline at BESSY II was equipped with a nitrogen cryogenic stream. The distribution of Ca, Fe, Zn and Cu across virtual cross sections of a water-rich sample, the root of common duckweed, could be investigated without further sample preparation. This paper demonstrates the capabilities of 3D micro-XRF under cryogenic conditions for investigations of biological specimens.     

Specific features of X-ray fluorescence analysis techniques using capillary lenses and synchrotron radiation

This paper discusses the features of an application of two versions of X-ray fluorescence analysis (XRF), commonly used at present, namely XRF using synchrotron radiation to excite the fluorescence in the sample investigated (SRXRF), and XRF using capillary X-ray optics. The operational characteristics of different models of micro-XRF spectrometers are considered. The general differences between conventional XRF and SRXRF and their influence on the choice of the analytical procedure are also presented. Examples of the typical errors resulting from the use of some classical analytical procedures in several applications are illustrated.     

Imaging modes for scanning confocal electron microscopy in a double aberration-corrected transmission electron microscope.

Aberration correction leads to reduced focal depth of field in the electron microscope. This reduced depth of field can be exploited to probe specific depths within a sample, a process known as optical sectioning. An electron microscope fitted with aberration correctors for both the pre- and postspecimen optics can be used in a confocal mode that provides improved depth resolution and selectivity over optical sectioning in the scanning transmission electron microscope (STEM). In this article we survey the coherent and incoherent imaging modes that are likely to be used in scanning confocal electron microscopy (SCEM) and provide simple expressions to describe the images that result. Calculations compare the depth response of SCEM to optical sectioning in the STEM. The depth resolution in a crystalline matrix is also explored by performing a Bloch wave calculation for the SCEM geometry in which the pre- and postspecimen optics are defocused away from their confocal conditions.     

Calibration of wavelength-dispersive X-ray spectrometer for standardless analysis

An experimental procedure for calibrating wavelength-dispersive X-ray spectrometer is presented. The detection efficiency was determined from the ratio of fluorescent radiation measured using the flow-proportional and the scintillation counter. The relative reflection efficiency of the analyzing crystal for various wavelengths was determined from the X-ray measurements of standard samples. The absorption correction for the atmosphere in the spectrometer chamber was also experimentally examined. All parameters (with the exception of reflection efficiency of the analyzing crystal) can be calculated from the X-ray measurements of unknown samples.     

A Micro-XRF Study of the Element Distribution on the Growth Front of Mussel Shell (Species of Unio Crassus Retzius)

 Micro-XRF spectrometry was used in a study of minor and trace metal content of the hard parts of historical and contemporary mussels from Tisza River at Szeged, Hungary. Synchrotron radiation measurements at LURE, Orsay, France and capillary-based laboratory (X-ray tube excitation) measurements were performed on the shell samples. The distribution of trace elements was determined along the growth line in the cross section of the shell. This application of micro-XRF for the analysis of mollusc shells in order to record historical trends demonstrates the power of this technique for extracting elemental information. The comparison of the X-ray spectra showed the distinct advantage of synchrotron measurement over capillary based laboratory measurement. Received June 15, 2000. Revision August 31, 2000.     

Three-dimensional conic beam X-ray microtomography in bone quality

In recent years, the 3D X-ray microcomputed tomography (3DμCT) has become a useful method to access the internal geometry based microarchitecture of bones. All measurements are based on the image quality. In this context, the aim of this work is to investigate bone quality in terms of strength parameters determined by 3DμCT. The system that was used to do the 3DμCT was a microfocus Fein Focus which has a microfocus X-ray tube, adjustment of the magnification factor of the captured image by mobile supports and an image intensifier with a diameter of 9 in. The results show that microtomography by microfocus X-ray tube is a powerful technique that can be used to analyze bone microstructures. A quantification procedure conducted with a locally developed program, produced images with 20 μm of resolution for different bone samples.     

Experimental optimization of p-polarized MAIR spectrometry performed on a fourier transform infrared spectrometer.

Optimized experimental conditions of infrared p-polarized multiple-angle incidence resolution spectrometry (p-MAIRS) for the analysis of ultrathin films on glass have been explored. When the original MAIRS technique is employed for thin-film analysis on a substrate of germanium or silicon, which exhibits a high refractive index, an established experimental condition without optimization can be adapted for the measurements. On the other hand, the p-MAIRS technique that has been developed for analysis on a low-refractive-index material requires, however, optimization of the experimental parameters for a 'quantitative' molecular orientation analysis. The optimization cannot be performed by considering only for optics in the spectrometer, but for optics concerning the substrate should also be considered. In the present study, an optimized condition for infrared p-MAIRS analysis on glass has been revealed, which can be used for quantitative molecular orientation analysis in ultrathin films on glass.     

A comparison of the performance of a fundamental parameter method for analysis of total reflection X-ray fluorescence spectra and determination of trace elements,versus an empirical quantification procedure

The performance has been compared of two different quantification methods — namely, the commonly used empirical quantification procedure and a fundamental parameter approach — for determination of the mass fractions of elements in particulate-like sample residues on a quartz reflector measured in the total reflection geometry. In the empirical quantification procedure, the spectrometer system needs to be calibrated with the use of samples containing known concentrations of the elements. On the basis of intensities of the X-ray peaks and the known concentration or mass fraction of an internal standard element, by using relative sensitivities of the spectrometer system the concentrations or mass fractions of the elements are calculated. The fundamental parameter approach does not require any calibration of the spectrometer system to be carried out. However, in order to account for an unknown mass per unit area of a sample and sample nonuniformity, an internal standard element is added. The concentrations/mass fractions of the elements to be determined are calculated during fitting a modelled X-ray spectrum to the measured one. The two quantification methods were applied to determine the mass fractions of elements in the cross-sections of a peat core, biological standard reference materials and to determine the concentrations of elements in samples prepared from an aqueous multi-element standard solution.     

X-ray fluorescence imaging with polycapillary X-ray optics

X-ray fluorescence spectrometry imaging is a powerful tool to provide information about the chemical composition and elemental distribution of a specimen. X-ray fluorescence spectrometry images were conventionally obtained by using a μ-X-ray fluorescence spectrometry spectrometer, which requires scanning a sample. Faster X-ray fluorescence spectrometry imaging would be achieved by eliminating the process of sample scanning. Thus, we developed an X-ray fluorescence spectrometry imaging instrument without sample scanning by using polycapillary X-ray optics, which had energy filter characteristics caused by the energy dependence of the total reflection phenomenon. In the present paper, we show that two independent straight polycapillary X-ray optics could be used as an energy filter of X-rays for X-ray fluorescence. Only low energy X-rays were detected when the angle between the two optical axes was increased slightly. Energy-selective X-ray fluorescence spectrometry images with projection mode were taken by using an X-ray CCD camera equipped with two polycapillary optics. It was shown that Fe Kα (6.40 keV) and Cu Kα (8.04 keV) could be discriminated for Fe and Cu foils.     

Construction and performance of a newly developed X-ray excited optical luminescence spectrometer

A newly developed XEOL spectrometer was constructed having the following features: (1) high energy X-ray tube and its well regulated power supply, (2) minimized leakage of scattered X-rays, (3) sample heating device suppressing host luminescence, and (4) improved resolving power of the optics.The direct determination of rare earth elements in La₂O₃ was explored using this instrument in a performance test. The results showed a great improvement in sensitivity and reproducibility using this method.