CN114740031A - X-ray fluorescence analysis system and analysis method thereof - Google Patents
X-ray fluorescence analysis system and analysis method thereof Download PDFInfo
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- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
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Abstract
The invention relates to an X-ray fluorescence analysis system and an analysis method thereof. The system comprises: an X-ray source; the monochromatic optical device is used for carrying out monochromatization on the X-ray emitted by the X-ray source to obtain monochromatic beams and exciting a sample to be detected by using the monochromatic beams; the detector is used for detecting an X-ray fluorescence signal generated after the sample to be detected is excited; the processor is used for receiving the X-ray fluorescence signals and carrying out elemental analysis on the sample to be detected according to the X-ray fluorescence signals. The invention monochromates the X-ray, can filter out the useless signals in the X-ray, effectively reduces the scattering background and improves the detection sensitivity; a part of energy section can be taken from useful signals of the X-ray, so that the subsequent focusing excitation of a sample to be detected is facilitated, and the detection sensitivity is further improved; can provide unprecedented low detection limit, can be used for element analysis of low detection limit of trace elements and the like in liquid samples, solid samples or other matrix samples, and widens the application range.
Description
Technical Field
The invention relates to the technical field of energy dispersion X-ray fluorescence, in particular to an X-ray fluorescence analysis system and an X-ray fluorescence analysis method.
Background
X-Ray Fluorescence analysis (XRF) is a mature elemental analysis technique, and is widely used in elemental analysis in many industrial and research fields because of its non-destructive, small sample preparation volume and large dynamic range.
The X-ray fluorescence analysis technique usually uses an X-ray source (X-ray light pipe + high voltage power supply) to generate X-rays, which contain characteristic spectral lines of target elements and continuous bremsstrahlung spectral lines. FIGS. 1-1 and 1-2 are the spectral lines emitted by the X-ray source of the molybdenum target, the hatched portion in FIG. 1-1 represents the characteristic spectral line of the target, and the hatched portion in FIG. 1-2 represents a part of the bremsstrahlung spectral line. When the generated X-rays are incident to a sample, three main effects can occur, namely photoelectric absorption, elastic scattering (also called metamorphic scattering or Rayleigh scattering) and inelastic scattering (also called metamorphic scattering or Compton scattering), wherein the photoelectric absorption effect means that the X-rays can excite elements in the sample to obtain characteristic X-ray fluorescence signals of the elements in the sample, and qualitative and quantitative analysis of the elements in the sample can be realized based on the characteristic X-ray fluorescence signals of the elements; elastic scattering means that incident X-ray photons collide with electrons which are combined more tightly in element atoms, the energy of the incident photons is not enough to enable the electrons to be free, and scattered rays are consistent with the energy of the incident rays; inelastic scattering refers to the collision of incident X-ray photons with weakly bound electrons in atoms, a part of energy is converted into kinetic energy of the electrons, and the energy of scattered rays is less than that of incident rays; the scattered incident X-rays are the main source of background in the final spectra, which is detrimental to the analysis of low content elements.
However, compared with ICP elemental analysis (Inductively coupled plasma), atomic absorption elemental analysis (ICP-atomic plasma), etc., the current X-ray fluorescence analysis has the disadvantage of low ratio of useful signal to background, resulting in low detection sensitivity, narrow application range, and strong limitation of the current X-ray fluorescence analysis, and according to the difference of instrument and element properties, the detection limit of the current X-ray fluorescence analysis system is only in the range of sub-ppm to ppm, and cannot be used for the elemental analysis of low detection limit of trace elements, etc.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is that the existing X-ray fluorescence analysis technology has low detection sensitivity, narrow application range and strong limitation, and cannot be used for element analysis with low detection limit such as trace elements.
In order to solve the above technical problem, the present invention provides an X-ray fluorescence analysis system, including:
an X-ray source;
the monochromatic optical device is arranged on an output light path of the X-ray source; the X-ray source is used for receiving X-rays emitted by the X-ray source, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting a sample to be tested by using the monochromatic light beams;
the detector is arranged near the sample to be detected; the X-ray fluorescence signal is used for detecting the X-ray fluorescence signal generated after the sample to be detected is excited by the monochromatic light beam;
and the processor is used for receiving the X-ray fluorescence signal and carrying out elemental analysis on the sample to be detected according to the X-ray fluorescence signal.
Preferably, the monochromating optic is comprised of at least one doubly curved crystal.
Preferably, the doubly curved crystal comprises a john-type point-to-point focusing crystal and a rotating logarithmic spiral doubly curved crystal.
Preferably, the monochromatic light beam is obtained by monochromatizing a characteristic spectral line of the X-ray, and the ratio of the energy of the monochromatic light beam to the energy bandwidth is greater than 100.
Preferably, the energy of the characteristic line is any one of 4.5keV, 5.4keV, 8.0keV, 8.4keV, 9.7keV, 17.5keV, 20keV and 22 keV.
Preferably, the monochromatic light beam is obtained by monochromating a bremsstrahlung spectral line of the X-ray, and the energy bandwidth of the monochromatic light beam is greater than 500 eV.
Preferably, the incident angle between the monochromatic light beam and the sample to be measured is less than 25 °.
Preferably, the distance between the surface of the probe and the surface of the sample to be measured is less than 5 mm.
Preferably, the surface of the sample to be detected is placed in the vertical direction, the detector is arranged on the side surface of the sample to be detected, and the surface of the detector is opposite to the surface of the sample to be detected.
Preferably, the processor is embodied as a digital pulse processor;
the digital pulse processor is specifically configured to:
receiving the X-ray fluorescence signal;
processing the X-ray fluorescence signal to obtain an energy dispersion X-ray fluorescence spectrogram;
and performing elemental analysis on the sample to be detected according to the energy dispersion X-ray fluorescence spectrogram.
In addition, the present invention further provides an X-ray fluorescence analysis method for performing elemental analysis by using the X-ray fluorescence analysis system, including:
acquiring X rays emitted by an X-ray source;
carrying out monochromatization on the X-ray to obtain a monochromatic beam;
exciting a sample to be detected by using the monochromatic light beam to generate an X-ray fluorescence signal;
detecting the X-ray fluorescence signal;
and performing elemental analysis on the sample to be detected according to the X-ray fluorescence signal obtained by detection.
The technical scheme provided by the invention has the following advantages:
according to the X-ray fluorescence analysis system and the analysis method thereof provided by the invention, the X-ray emitted by the X-ray source is subjected to monochromatization, on one hand, useless signals in the X-ray can be filtered out, the situation that the useless signals enter the detector to form a scattering background to influence the detection performance of the detector is avoided, the scattering background is effectively reduced, and the detection sensitivity is improved; on the other hand, a part of energy sections can be taken from useful signals of the X-ray, so that subsequent focusing excitation of a sample to be detected is facilitated, the focusing intensity is improved, and the detection sensitivity is further improved; the monochromatic light beam is used for exciting the sample to be detected, and the element analysis is carried out based on the X-ray fluorescence signal of the excited sample to be detected, so that the unprecedented low detection limit can be provided, and the method can be used for the element analysis of the low detection limit of trace elements and the like in liquid samples, solid samples or other matrix samples, and the application range is widened.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1-1 is a schematic diagram of characteristic spectral lines emitted by an X-ray source of a molybdenum target;
FIG. 1-2 is a schematic diagram of bremsstrahlung from an X-ray source of molybdenum target material;
FIG. 2 is a schematic structural diagram of an X-ray fluorescence analysis system according to an embodiment of the present invention;
FIG. 3 is a schematic diagram illustrating Bragg diffraction of a John-type point-to-point focusing crystal according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of an energy bandwidth of an X-ray characteristic spectral line after monochromatization by a germanium hyperbolic crystal according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of energy bandwidth of an X-ray bremsstrahlung line after monochromatization of LiF hyperbolic crystal according to an embodiment of the present invention;
FIG. 6 is a schematic diagram of a model for elemental analysis of a solid sample according to a first embodiment of the present invention;
FIG. 7 is a schematic diagram of a model for performing elemental analysis on a liquid sample according to an embodiment of the present invention;
FIG. 8 is an energy dispersive X-ray fluorescence spectrum obtained by irradiating a liquid sample with monochromatic light selected as the characteristic spectral line in the first embodiment of the present invention;
FIG. 9 is a graph of an energy dispersive X-ray fluorescence spectrum obtained by irradiating a liquid sample with a monochromatic beam selected from the bremsstrahlung spectrum in accordance with one embodiment of the present invention;
FIG. 10 is a flowchart illustrating a method for X-ray fluorescence analysis according to a second embodiment of the present invention.
Description of reference numerals:
1. the device comprises an X-ray source, 2, a monochromatic optical device, 3, a detector, 4, a processor, 5, a sample to be detected, 6, a transparent film, 501, a solid sample, 502 and a liquid sample.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. The invention will be described in detail hereinafter with reference to the accompanying drawings in conjunction with embodiments. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
In the present invention, unless specified to the contrary, use of the terms of orientation such as "upper, lower, top, bottom" or the like, generally refer to the orientation as shown in the drawings, or to the component itself in a vertical, perpendicular, or gravitational orientation; likewise, for ease of understanding and description, "inner and outer" refer to the inner and outer relative to the profile of the components themselves, but the above directional words are not intended to limit the invention.
Example one
As shown in fig. 2, the present embodiment provides an X-ray fluorescence analysis system including:
an X-ray source 1;
the monochromatic optical device 2 is arranged on an output light path of the X-ray source 1; the X-ray detector is used for receiving X-rays emitted by the X-ray source 1, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting a sample 5 to be detected by utilizing the monochromatic light beams;
the detector 3 is arranged near the sample 5 to be detected; the X-ray fluorescence detector is used for detecting an X-ray fluorescence signal generated after the sample 5 to be detected is excited by the monochromatic light beam;
and the processor 4 is used for receiving the X-ray fluorescence signal and carrying out elemental analysis on the sample 5 to be detected according to the X-ray fluorescence signal.
Trace elements refer to any element present in ppm levels. Elements other than ten elements of O, H, Si, Al, Fe, Ca, Mg, Na, K and Ti (the total abundance of the elements accounts for about 99 percent) in the crust are generally called trace elements or trace elements.
In a conventional X-ray fluorescence analysis system, due to the scattering effect, X-rays emitted from a sample to be measured not only contain fluorescent X-rays of elements contained in the sample, but also rayleigh scattering and compton scattering. The energy of the fluorescent X-rays is discrete and characteristic, whereas rayleigh scattering is the same as the incident X-ray energy and compton scattering is the incident X-ray energy minus the energy of the recoil electrons. If the incident X-ray contains a continuum, the emergent scattered X-ray is also a continuum. Because the characteristic spectral line of each element in the sample is interfered by a higher continuous scattering background, the peak-to-back ratio of the characteristic spectral line is very poor, and the quantitative and qualitative analysis of low-content or trace elements cannot be realized.
In the X-ray fluorescence system of the embodiment, the monochromatic optical device is used for carrying out monochromatization on the X-ray emitted by the X-ray source, so that on one hand, useless signals in the incident X-ray can be filtered, the situation that the useless signals enter the detector to form a scattering background to influence the detection performance of the detector is avoided, the scattering background is effectively reduced, and the detection sensitivity is improved; on the other hand, a part of energy sections can be taken from useful signals of the X-ray, so that subsequent focusing excitation of a sample to be detected is facilitated, the focusing intensity is improved, and the detection sensitivity is further improved; the monochromatic light beam is used for exciting the sample to be detected, and the element analysis is carried out based on the X-ray fluorescence signal of the sample to be detected after the sample to be detected is excited, so that the unprecedented low detection limit can be provided, the method can be used for the element analysis of the low detection limit of trace elements and the like in liquid samples, solid samples or other matrix samples, and the application range is widened.
Specifically, the X-ray source 1 of the present embodiment includes an electron bombardment type X-ray tube whose target includes, but is not limited to, titanium, chromium, copper, molybdenum, silver, and tungsten.
It should be noted that, in a general sense, a monochromatic light beam refers to a light beam with a narrow energy bandwidth. In the present invention, the monochromatic light beam may refer to a light beam with a narrow energy bandwidth; or a beam that has a relatively wide energy bandwidth but a relatively high energy-to-energy bandwidth ratio. When the energy bandwidth of a certain light beam is wide, but the ratio of the energy to the energy bandwidth reaches a higher value, the light beam can be considered to be similar to a quasi-monochromatic light beam and is also considered to be a monochromatic light beam.
Preferably, the monochromating optic 2 is composed of at least one doubly curved crystal.
A doubly curved crystal is a crystal that is curved in both the diffraction plane and the direction perpendicular to the diffraction plane.
In the traditional technology, the single-curved crystal is adopted, the single-curved crystal is only bent on a diffraction surface, the Bragg diffraction theorem is satisfied, the incident light in a focal circle plane can only be converged to a focal point, and the light in other directions is incident to other positions on the surface of the single-curved crystal, so that the light is diverged and cannot be converged to the focal point. The point light source can be considered to obtain a focusing line with certain energy after passing through the single-curved crystal, and the excitation and collection area of the sample to be detected is usually small, so that only a small part of light beams in the light beams emitted after passing through the single-curved crystal participate in excitation of the sample to be detected, namely only a small part of area on the surface of the single-curved crystal participate in Bragg diffraction effect, so that the effect is achieved, and the effective solid angle is small.
For a doubly curved crystal, for example, a john type point-to-point focusing crystal as shown in fig. 3, the device is curved in the plane of the focal circle, with a curvature in the plane of the focal circle (the horizontal plane in fig. 3) that is twice the radius R of the focal circle, and then curved in the diffraction plane (i.e., the plane of the focal circle) to satisfy the bragg diffraction theorem. While also being curved in a vertical plane (i.e., a plane perpendicular to the plane of the focal circle), the wafer is curved to 2Rsin about the axis connecting the source S and the focal point I2θBRadius (where θ)BThe angle of the X-ray incident on the surface of the hyperbolic crystal optical device), as long as the X-ray incident on the surface of the hyperbolic crystal and the monochromatic beam emergent after passing through the hyperbolic crystal converge to a point for exciting a sample, the whole surface of the hyperbolic crystal can be considered to participate in effective diffraction, and the collection solid angle of the monochromatic device on the X-ray is significantly increased (as shown in fig. 3)
)。
Therefore, the embodiment forms a monochromating optical device by at least one hyperbolic crystal, and the monochromating optical device is arranged on an optical path between the X-ray source and the detector, so that monochromating can be realized, the scattering background is reduced, and the detection sensitivity is improved; the effective solid angle of the incident X-ray can be increased, the focusing is realized while the monochromatic X-ray is monochromatized based on the Bragg diffraction theorem, the intensity of the monochromatized beam is further improved, a subsequent detector can better detect the fluorescent signal of the X-ray, and the detection sensitivity is further improved.
The monochromatic optical device can be composed of only one hyperbolic crystal, and the specific selection of the hyperbolic crystal can be determined according to the actual condition of the element to be measured; meanwhile, the combination of two or more hyperbolic crystals can be selected as a monochromatic optical device in a targeted manner according to the difference of excitation limits of characteristic spectral lines of elements to be detected, so that the high-sensitivity detection and analysis of all elements can be realized by only one set of analysis system, and the application range of the whole set of analysis system can be widened; when the combination is used as a monochromatic optical device, the placement positions of the devices in the combination can be determined and adjusted as the case may be.
In particular, doubly curved crystals include john-type point-to-point focusing crystals and rotational logarithmic spiral doubly curved crystals.
The John type point-to-point focusing crystal has the characteristics of good monochromaticity, extremely low continuous background, full focusing and high efficiency, can remarkably reduce the continuous scattering background of the emergent spectrum of a sample to be detected, and further effectively improves the detection sensitivity; the rotating logarithmic spiral hyperbolic crystal can provide pseudo focusing, when X rays are incident to the surface of the crystal device, the whole surface meets the advantages of Bragg diffraction conditions, the purpose of increasing a collection solid angle is achieved, and the detection sensitivity is improved.
In particular, the crystal material in the doubly curved crystal of the present embodiment may be LiF, Ge, Si, and any other single crystal. For example, LiF and Ge single crystals can be used to fabricate doubly curved crystals to provide monochromatic beams in the energy range of 4keV to 40 keV. The LiF single crystal is not a perfect single crystal and has a certain mosaic crystal structure, which can broaden the energy band pass of the hyperbolic crystal and is beneficial to excitation of quasi-monochromatic light beams.
Preferably, the monochromatic light beam is a light beam obtained by monochromating the characteristic line of the X-ray.
Since the output energy spectrum of the X-ray includes the characteristic spectral line from the electron bombardment target and the continuous bremsstrahlung spectral line, and the characteristic spectral line generally has the highest intensity, this embodiment selects the characteristic spectral line of the X-ray to perform monochromatization to obtain monochromatic light, and can deactivate the sample to be measured with the strongest monochromatic light of the X-ray, and at the same time, reduce the scattering background and improve the focusing intensity, thereby achieving the improvement of the detection sensitivity, and facilitating the elemental analysis of trace elements and other elements with low detection limits.
Preferably, the ratio of the energy of the monochromatic light beam to the energy bandwidth is greater than 100.
The monochromatic performance and the intensity performance of the strong monochromatic light beam provided for the sample to be detected can be ensured through the energy bandwidth and the energy within the range of the ratio of the characteristic spectral lines, so that the scattering background is reduced and the focusing intensity is improved;
specifically, the monochromatic light beam has an energy of any one of 4.5keV, 5.4keV, 8.0keV, 8.4keV, 9.7keV, 17.5keV, 20keV, and 22 keV.
In one embodiment, the X-ray source is a 50W chromium target X-ray tube, and the monochromating optic is a hyperbolic germanium crystal. The germanium hyperbolic crystal is designed to select photons of 5.4keV chromium target characteristic spectral line energy, providing a high intensity monochromatic beam of 5.4keV energy with a narrow energy bandwidth, as shown in figure 4, with a ratio of monochromatic beam energy to energy bandwidth greater than 500.
Preferably, the monochromatic light beam is obtained by monochromating a bremsstrahlung line of the X-ray, and the energy bandwidth of the monochromatic light beam is more than 500 eV.
Because the target material that the X-ray tube can choose is limited, so its characteristic spectral line that provides is limited too, when the monochromatic energy of goal is higher, there is not characteristic spectral line of the suitable target material element to choose; in this embodiment, a bremsstrahlung spectral line with an energy bandwidth greater than 500eV is selected as a monochromatic beam in an output spectrum of an X-ray, so that the ratio of the energy of the beam to the energy bandwidth is greater than 10 under the condition that the intensity of the bremsstrahlung spectral line is low, which is similar to a monochromatic beam (also called a quasi-monochromatic beam), thereby achieving the same purpose of selecting a characteristic spectral line of the X-ray to perform monochromatization, and achieving reduction of a scattering background and improvement of a focusing intensity.
In one embodiment, the X-ray source is a tungsten target X-ray tube and the monochromating optic is a LiF hyperbolic crystal designed to select photons of 30keV energy, providing a monochromatic beam of 30keV energy with a wider energy bandwidth from bremsstrahlung lines, as shown in FIG. 5. In another specific embodiment, highly oriented pyrolytic graphite can be used as a monochromatic optical device, and can also generate quasi monochromatic light beams, so that the purposes of reducing scattering background and improving focusing intensity are achieved, and the detection sensitivity is improved. Wherein, the highly oriented pyrolytic graphite is a novel graphite which is processed at high temperature and has the performance close to that of single crystal graphite.
By the two methods for selecting the monochromatic light beams (including selecting the characteristic spectral line of the X-ray and selecting the bremsstrahlung spectral line of the X-ray), the selection range of the X-ray source target and the monochromatic optical device is effectively widened, so that the X-ray fluorescence analysis system in the embodiment has a wider application range.
Preferably, the angle of incidence between the monochromatic light beam and the sample 5 to be measured is less than 25 °.
The incident angle between the monochromatic light beam and the sample to be detected is set to be less than 25 degrees, a tightly coupled geometric structure between the X-ray source, the detector and the sample to be detected can be realized, and the detector can be placed at a position which is very close to the surface of the sample to be detected, so that the collection solid angle of the detector is further optimized, and the detection sensitivity is further improved; on the other hand, higher signal acquisition efficiency can be obtained, and the counting rate of the detector is further improved.
Preferably, the spacing between the surface of the probe 3 and the surface of the sample 5 to be measured is less than 5 mm.
The distance between the surface of the detector and the surface of the sample to be detected is set to be less than 5mm, so that the tight coupling degree between the monochromatic optical device, the detector and the sample to be detected is further improved, and the detection sensitivity and the counting rate of the detector are further improved.
Specifically, the detector 3 in the present embodiment is a silicon drift detector. The silicon drift detector can respond to a large number of photons in a short time, improves the signal acquisition efficiency and simultaneously keeps excellent energy resolution.
In one embodiment, the angle of incidence between the monochromatic light beam and the sample to be measured is less than 15 °, and the distance between the surface of the detector and the sample to be measured is less than 4 mm. With this tightly coupled geometry, the detector can easily achieve high count rates of 50-100 ten thousand counts/second.
Preferably, the processor 4 is embodied as a digital pulse processor;
the digital pulse processor is specifically configured to:
receiving an X-ray fluorescence signal;
processing the X-ray fluorescence signal to obtain an energy dispersion X-ray fluorescence spectrogram;
and performing element analysis on the sample to be detected according to the energy dispersion X-ray fluorescence spectrogram.
After being irradiated by the monochromatic light beams, a sample to be detected is excited to generate X-ray fluorescence radiation, the X-ray fluorescence radiation is detected by a detector and converted into X-ray fluorescence signals, the signals are electric pulse signals, and the electric pulse signals are processed by the digital pulse processor, so that an energy dispersion X-ray fluorescence spectrogram with better quality can be obtained, and subsequent element analysis is facilitated; and after the energy dispersion X-ray fluorescence spectrogram is obtained, the content of each element in the sample to be detected is calculated by combining a quantitative spectrum solving algorithm, so that the element analysis of the sample to be detected is realized. The quantitative spectrum solving algorithm is the prior art, and the specific process is not described herein again. When the samples to be detected are different, the corresponding energy dispersion X-ray fluorescence spectrograms are obtained, and the corresponding content calculation can be realized only by adjusting parameters in the quantitative spectrum resolving algorithm.
Specifically, the processing performed on the X-ray fluorescence signal includes, but is not limited to, filtering processing, amplification processing, analog-to-digital conversion processing, statistical processing, and the like. In the above processes, some configurable parameters in the process can be optimized, and the effect of suppressing the back of the detector is realized.
Specifically, the sample 5 to be measured includes a solid sample 501 and a liquid sample 502.
The X-ray fluorescence analysis system can be applied to the fields of industry, agriculture, medical industry, food industry and the like, and remarkably promotes the development of trace element analysis in industrial discharge water, food, agricultural products, medical food and products.
Specifically, the substrate of the sample 5 to be measured is a substrate having a low atomic number.
The sample of the low atomic number matrix is mainly composed of elements such as C, N, O and H, and the content thereof can be detected with ultrahigh detection sensitivity and unprecedented low detection limit by the X-ray fluorescence analysis system of this example.
It should be noted that, in an actual situation, the surface of the sample to be detected may be placed in any direction, and it is only necessary to ensure that the light beam monochromatized by the monochromating optical device can be emitted to the surface of the sample to be detected at a low incident angle, and the surface of the detector is opposite to the surface of the sample to be detected, so that the signal of the sample to be detected after being excited can be detected.
In one embodiment, for a solid sample 501 consisting essentially of C, H, O and N elements, the solid sample 501 is subjected to elemental analysis according to the fluorescence analysis system shown in fig. 6.
In the fluorescence analysis system shown in fig. 6, the surface of the solid sample 501 is placed horizontally, the probe 3 is provided below the solid sample 501, and the surface of the probe 3 faces the surface of the solid sample 501. More specifically, the monochromatic light beam emitted from the monochromatic optical device is incident on the lower surface of the solid sample 501 at an incident angle of 15 ° (α in fig. 6), and the monochromatic light beam is a characteristic spectral line obtained by monochromatizing the X-ray; the detector 3 is arranged at a position 4mm away from the lower surface of the solid sample 501, is opposite to the lower surface of the solid sample 501, and detects the X-ray fluorescence radiation of the excited solid sample 501 to obtain an X-ray fluorescence signal; based on a mechanism that a digital pulse processor inhibits the back bottom of the detector, the corresponding energy dispersion X-ray fluorescence spectrogram is obtained. For convenience of subsequent description, in this embodiment, based on the relative position relationship between the solid sample and the detector, the sample injection manner is referred to as vertical direction injection.
Preferably, the surface of the sample 5 to be measured is placed in a vertical direction, the detector 3 is arranged on the side surface of the sample 5 to be measured, and the surface of the detector 3 faces the surface of the sample 5 to be measured.
When the sample to be tested is a liquid sample, if the surface of the liquid sample is placed in a non-vertical direction, for example, in a horizontal direction, that is, if the sample is injected in a vertical direction as shown in fig. 6, leakage of the liquid sample is easily caused during elemental analysis due to the characteristics of the liquid sample, and the leakage of the liquid sample may cause contamination and damage to the detector, the X-ray source, and the monochromatic optical device in the vicinity of the liquid sample. Therefore, by vertically placing the surface of the liquid sample and correspondingly arranging the detector on the side surface of the liquid sample, on one hand, the liquid sample can be effectively prevented from leaking to cause pollution and damage to the detector, the X-ray source and the monochromatic optical device nearby the liquid sample, and further, the smooth implementation of the element analysis of the liquid sample is ensured; on the other hand, the tight coupling degree among the X-ray source, the sample to be detected and the detector can be further increased, so that the portability of the instrument is convenient to realize, and the X-ray source, the sample to be detected and the detector can be widely applied to different use environments. For convenience of the following description, this manner is referred to as lateral sample introduction based on the relative position relationship between the sample and the detector.
It should be noted that, for the above-mentioned embodiment shown in fig. 6, the sample injection manner of the solid sample 501 may be set as vertical sample injection or lateral sample injection, and the operation is performed according to the placement manner of the liquid sample, that is, the surface of the solid sample 501 is placed in the vertical direction, the detector 3 is disposed on the side of the solid sample 501, and the surface of the detector 3 faces the surface of the solid sample 501; the monochromatic light beam emitted from the monochromatic optical device is incident on the side surface of the solid sample 501 at an incident angle of 15 °, and then the detector is disposed at a position 4mm away from the side surface of the solid sample 501 (this sample introduction manner is not shown). In actual operation, which sample introduction manner is selected for the solid sample 501 can be selected and adjusted according to actual conditions.
In another embodiment, the liquid sample 502 is subjected to elemental analysis according to a fluorescence analysis system as shown in FIG. 7 for the liquid sample 502. In the fluorescence analysis system shown in fig. 7, the liquid sample 502 is fed laterally, and the surface thereof is placed vertically, so that the surface thereof is always in a vertical state, and the detector 3 is disposed on the side surface of the liquid sample 502 and faces the surface of the liquid sample 502; more specifically, the monochromatic light beam emitted from the monochromating optical device 2 is incident on the surface of the liquid sample 502 in a vertical state at an incident angle of 15 °; the detector 3 is arranged at a position 4mm away from the surface of the liquid sample 502 in the vertical state and is opposite to the surface of the liquid sample 502 in the vertical state, and the detector 3 is used for detecting the X-ray fluorescence radiation of the liquid sample after being excited to obtain an X-ray fluorescence signal; based on the mechanism of suppressing the back of the detector by the digital pulse processor, the corresponding energy dispersive X-ray fluorescence spectrum is obtained, as shown in fig. 8 and 9.
In this embodiment, the liquid sample 502 is introduced laterally; by the lateral sample introduction mode, the liquid sample can be prevented from leaking to cause pollution and damage to a detector, an X-ray source and a monochromatic optical device nearby the liquid sample; in practice, a transparent film 6 is also provided between the probe 3 and the surface of the liquid sample 502 in a vertical state, as shown in fig. 7. Through the transparent film 6, the detector can be further protected from being polluted and damaged by the leakage of the liquid sample 502, and the detection of the X-ray radiation signal of the liquid sample 502 after being excited can not be blocked.
Fig. 8 is an energy dispersive X-ray fluorescence spectrum obtained by selecting a characteristic spectral line (with an energy of 17.5keV) of an X-ray to perform monochromatization as a monochromatic beam incident on the liquid sample 502, which can be obtained according to fig. 8: the energy dispersion X-ray fluorescence spectrum output by the digital pulse processor provides an unprecedented peak-to-back ratio, scattering peak intensity NSAnd the back bottom NBThe ratio of the scattering peak (including Compton scattering peak and Rayleigh scattering peak) can be as high as 25000SIs the integrated count over the full width of the scattering peak. Wherein, the full width refers to the energy window between two points at both sides of the peak reaching the peak Np value of 10%, and the background NBRefers to the integrated count centered at the minimum of the background level with an energy window of 100 eV. In the case of this high back ratio, trace element peaks (such as selenium and arsenic peaks) will be able to rise above the background and 10ppb levels can be detected.
Fig. 9 is an energy dispersive X-ray fluorescence spectrum obtained by monochromating a bremsstrahlung spectral line (with an energy of 38keV) of an X-ray as a monochromatic beam incident on a liquid sample 502, which can be obtained according to fig. 9: the energy dispersive X-ray fluorescence spectrum output by the digital pulse processor also reaches a peak-to-back ratio of about 25000 (where compton and rayleigh scattering peaks merge into one large scattering peak). Trace elements such as cadmium and antimony also rise above the background and 20ppb levels can be detected.
Based on the X-ray fluorescence analysis system composed of the X-ray source, the monochromatic optical device composed of at least one hyperbolic crystal, the tightly coupled geometric structure (that is, the incident angle between the monochromatic beam and the surface of the sample to be detected is less than 25 degrees, the distance between the surface of the detector and the surface of the sample to be detected is less than 5mm, and the relative position between the detector and the sample to be detected selects the lateral sample introduction mode), the silicon drift detector and the digital pulse processor of the embodiment, the following beneficial effects can be realized:
(1) the silicon drift detector will not see any scatter of X-ray photons from the X-ray source except for incident photons of energy E0. Compared with the traditional technology, the signal-to-noise ratio (or signal background ratio) of the energy dispersion X-ray fluorescence spectrum output by the digital pulse processor is obviously improved; the signal background ratio of the trace elements in the sample to be detected can reach 26:1, and reaches more than 10 times of the signal background ratio of a conventional X-ray fluorescence analysis system.
(2) Through the closely coupled geometric structure, even use low power system can also realize high count rate to can adopt light, do not have the X ray source of oil encapsulation, realize low-power consumption, small volume and the low weight of whole set of system, and then realize the portability of instrument, can extensively be applicable to different service environment. In order to reach the detection limit of target trace elements, a conventional X-ray fluorescence analysis system cannot use a light-weight and oil-free packaged X-ray source, and at least needs to be provided with a power supply of 3kW, the weight of the X-ray fluorescence analysis system exceeds 10kg, and the volume of the X-ray fluorescence analysis system is at least the size of a printer; the counting rate of the X-ray fluorescence analysis system can reach 50-100 ten thousand counts/second, the X-ray source only needs to be provided with a 50W power supply, the weight is only 2kg, and the volume is only the size of a common water cup.
(3) The high count rate significantly improves the count statistics, thereby further significantly improving detection sensitivity and providing an unprecedented low detection limit. The detection limit of a conventional X-ray fluorescence analysis system for Cd elements is 0.2ppm-2ppm, and the detection limit for Pb, As and Hg elements is more than 0.2 ppm; the detection limit of the X-ray fluorescence analysis system can reach below 0.1ppm, the detection limit of Cd elements can reach 0.02ppm-0.05ppm, and the detection limit of Pb, As and Hg elements can reach 0.01 ppm.
Example two
As shown in fig. 10, the present embodiment provides an X-ray fluorescence analysis method for performing elemental analysis by using the X-ray fluorescence analysis system in the first embodiment, including:
s1: acquiring X rays emitted by an X-ray source;
s2: carrying out monochromatization on the X-ray to obtain a monochromatic beam;
s3: exciting a sample to be detected by using the monochromatic light beam to generate an X-ray fluorescence signal;
s4: detecting an X-ray fluorescence signal;
s5: and performing element analysis on the sample to be detected according to the X-ray fluorescence signal obtained by detection.
According to the X-ray fluorescence analysis method, the X-ray emitted by the X-ray source is subjected to monochromatization, so that on one hand, useless signals in the X-ray can be filtered out, the situation that the useless signals enter the detector to form a scattering background to influence the detection performance of the detector is avoided, the scattering background is effectively reduced, and the detection sensitivity is improved; on the other hand, a part of energy sections can be taken from useful signals of the X-ray, so that subsequent focusing excitation of a sample to be detected is facilitated, the focusing intensity is improved, and the detection sensitivity is further improved; the monochromatic light beam is used for exciting the sample to be detected, and the element analysis is carried out based on the X-ray fluorescence signal of the sample to be detected after the sample to be detected is excited, so that the unprecedented low detection limit can be provided, the method can be used for the element analysis of the low detection limit of trace elements and the like in liquid samples, solid samples or other matrix samples, and the application range is widened.
Specifically, in S2, the X-ray is monochromatized using the monochromating optic in embodiment one; in S4, detecting the X-ray fluorescence signal of the sample to be detected after being excited by a detector; in S5, elemental analysis is performed by the processor based on the detected X-ray fluorescence signal.
The X-ray fluorescence analysis method described in this embodiment is completed by the X-ray fluorescence analysis system described in the first embodiment, details of which are not described in detail in the first embodiment and the specific descriptions of fig. 2 to 9 are omitted here for brevity.
It is to be understood that the above-described embodiments are only a few, and not all, embodiments of the present invention. Based on the embodiments of the present invention, those skilled in the art may make other variations or modifications without creative efforts, and shall fall within the protection scope of the present invention.
Claims (10)
1. An X-ray fluorescence analysis system, comprising:
an X-ray source;
the monochromatic optical device is arranged on an output optical path of the X-ray source; the X-ray source is used for receiving X-rays emitted by the X-ray source, carrying out monochromatization on the X-rays to obtain monochromatic light beams, and exciting a sample to be tested by using the monochromatic light beams;
the detector is arranged near the sample to be detected; the X-ray fluorescence signal is used for detecting the X-ray fluorescence signal generated after the sample to be detected is excited by the monochromatic light beam;
and the processor is used for receiving the X-ray fluorescence signal and carrying out elemental analysis on the sample to be detected according to the X-ray fluorescence signal.
2. The X-ray fluorescence analysis system of claim 1, wherein the monochromating optic is comprised of at least one doubly curved crystal.
3. The X-ray fluorescence analysis system of claim 1, wherein the monochromatic light beam is a monochromatic beam of the characteristic spectral line of the X-ray, and the ratio of the energy to the energy bandwidth of the monochromatic light beam is greater than 100.
4. The X-ray fluorescence analysis system of claim 3, wherein the monochromatic light beam has an energy of any one of 4.5keV, 5.4keV, 8.0keV, 8.4keV, 9.7keV, 17.5keV, 20keV, and 22 keV.
5. The X-ray fluorescence analysis system of claim 1, wherein the monochromatic beam is a monochromated bremsstrahlung line of the X-ray, and the energy bandwidth of the monochromatic beam is greater than 500 eV.
6. The X-ray fluorescence analysis system of claim 1, wherein an angle of incidence between the monochromatic light beam and the sample to be tested is less than 25 °.
7. The X-ray fluorescence analysis system of claim 6, wherein a spacing between a surface of the detector and a surface of the sample to be measured is less than 5 mm.
8. The X-ray fluorescence analysis system of claim 1, wherein the surface of the sample to be tested is vertically disposed, the detector is disposed on a side surface of the sample to be tested, and the surface of the detector faces the surface of the sample to be tested.
9. The X-ray fluorescence analysis system of any one of claims 1 to 8, wherein the processor is in particular a digital pulse processor;
the digital pulse processor is specifically configured to:
receiving the X-ray fluorescence signal;
processing the X-ray fluorescence signal to obtain an energy dispersion X-ray fluorescence spectrogram;
and performing elemental analysis on the sample to be detected according to the energy dispersion X-ray fluorescence spectrogram.
10. An X-ray fluorescence analysis method, comprising:
acquiring X rays emitted by an X-ray source;
carrying out monochromatization on the X-ray to obtain a monochromatic beam;
exciting a sample to be detected by using the monochromatic light beam to generate an X-ray fluorescence signal;
detecting the X-ray fluorescence signal;
and performing elemental analysis on the sample to be detected according to the X-ray fluorescence signal obtained by detection.
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