CN115038959A - Fluorescent X-ray analysis device, determination method, and determination program - Google Patents
Fluorescent X-ray analysis device, determination method, and determination program Download PDFInfo
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- CN115038959A CN115038959A CN202180007827.3A CN202180007827A CN115038959A CN 115038959 A CN115038959 A CN 115038959A CN 202180007827 A CN202180007827 A CN 202180007827A CN 115038959 A CN115038959 A CN 115038959A
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—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
- 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
- G01N23/2209—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 using wavelength dispersive spectroscopy [WDS]
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—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
- 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 provides a fluorescent X-ray analysis device, a method and a program for determining whether a mechanism for shielding part of fluorescent X-rays incident on a detector is normally installed or not. A fluorescent X-ray analyzer includes: an X-ray source (104), a Soxhlet slit (110), a spectroscopic element (112), and a detector (114), characterized by: a determination member (106) that contains an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays; a field-of-view limiting unit (108) which is configured to be detachable and limits fluorescent X-rays incident on the detector, among the fluorescent X-rays generated from the sample and the determination member; a storage unit (122) for storing in advance the intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and a determination unit (120) that determines whether the visual field limiting unit is normally attached, based on the intensity stored in the storage unit and the intensity measured by the detector.
Description
Technical Field
The present invention relates to a fluorescent X-ray analysis device, a determination method, and a determination program.
Background
Conventionally, a fluorescent X-ray detection device has been widely used which detects fluorescent X-rays generated from a sample irradiated with primary X-rays to qualitatively and quantitatively analyze elements contained in the sample. In a typical wavelength dispersive fluorescent X-ray analyzer, an X-ray source, Soller slits (Soller slips), a spectroscopic crystal, a detector, a sample, and the like are arranged in the analyzer.
When maintenance or correction is performed on each component disposed in the apparatus room, it is necessary to turn off the X-ray for safety. The X-ray must be turned on and off in stages with a long time, and after the X-ray is turned on, a highly accurate analysis can be performed until the temperature of the apparatus is stabilized. In addition, when evacuation is required, the operation becomes further complicated. In order to reduce this time and effort, for example, patent document 1 listed below discloses an invention for performing correction using detection data of X-rays obtained from a standard sample set on a shutter.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-48161
Disclosure of Invention
Problems to be solved by the invention
In order to limit the measurement range on the sample, a field limiting mechanism (e.g., an aperture) that blocks a part of the fluorescent X-rays incident on the detector may be disposed in the sample chamber. Although a sample mask is sometimes used to limit the measurement range on the sample, it is desirable to use a visual field limiting mechanism in combination to remove the fluorescent X-ray scattered rays caused by the sample mask. In order to change the measurement range on the sample, the visual field limiting mechanism may be configured to be detachable.
There are also fluorescent X-ray analyzers having a mechanism for mechanically removing or replacing the visual field limiting mechanism, but the mechanical removal or replacement mechanism is complicated and costly. On the other hand, if the visual field limiting mechanism is configured to be replaceable by a person, the visual field limiting device having a different measurement range may be erroneously mounted or may be incorrectly mounted, for example, the mounting position may be incorrect.
In this case, since it is impossible to check whether the device is correctly mounted from the outside, it is necessary to turn off the X-ray for confirmation, turn on the X-ray again after confirmation, and the operation is complicated. Further, even when there is a mechanism for mechanically removing or replacing the visual field limiting mechanism, it is impossible to see from the outside whether or not the visual field limiting mechanism is properly attached.
The present invention has been made in view of the above-described problems, and an object thereof is to provide a fluorescent X-ray analyzer, a determination method, and a determination program, which can easily confirm whether or not a visual field limiting device is normally attached.
Means for solving the problems
The fluorescent X-ray analyzer according to claim 1 of the present invention includes: an X-ray source for irradiating a sample with X-rays; a soller slit for allowing the fluorescent X-ray generated from the sample to pass therethrough as a parallel ray; a spectroscopic element for dispersing the fluorescent X-ray passed through the soller slits; and a detector for measuring the intensity of the fluorescent X-ray split by the splitting element, the detector being characterized by comprising: a determination member containing an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays; a field-of-view limiting unit configured to be detachable and limiting a fluorescent X-ray incident on the detector, among the fluorescent X-rays generated from the sample and the determination member; a storage unit that stores in advance the intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and a determination unit that determines whether or not the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
The fluorescent X-ray analyzer according to claim 2 of the present invention is the fluorescent X-ray analyzer according to claim 1, wherein the view restricting unit is capable of setting a plurality of openings having different sizes, the storage unit stores in advance the intensity of the fluorescent X-ray of the predetermined energy generated by the determination member for each size of the opening, and the determination unit determines the size of the opening of the view restricting unit based on the intensity stored in the storage unit and the intensity measured by the detector.
The fluorescent X-ray analyzer according to claim 3 of the present invention is characterized in that the determination unit performs the determination every time the X-ray source starts to irradiate X-rays once or before measurement of a sample to be analyzed is started in the fluorescent X-ray analyzer according to claim 1 or 2 of the present invention.
The fluorescent X-ray analysis apparatus according to claim 4 of the present invention is the fluorescent X-ray analysis apparatus according to any one of claims 1 to 3, wherein the element is fixed in a shape corresponding to the opening of the view restricting section on the surface on which the X-rays are irradiated in the determination member.
The fluorescent X-ray analyzer according to claim 5 of the present invention is the fluorescent X-ray analyzer according to any one of claims 1 to 4, wherein the determination member is a shutter for shielding a primary X-ray irradiated to a sample to be analyzed.
The determination method according to claim 6 of the present invention is characterized by comprising: a step of arranging a determination member including an element that generates a fluorescent X-ray of a predetermined energy when the primary X-ray is irradiated, in a region irradiated with the primary X-ray, before starting measurement of a sample to be analyzed; a step of attaching a field-of-view limiting unit that limits fluorescent X-rays incident on the detector, among fluorescent X-rays generated from the sample and the determination member; a step of storing in advance, in a storage unit, an intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and a step of determining whether or not the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
A determination program according to claim 7 of the present invention is a determination program executed by an information processing apparatus used in a fluorescent X-ray analysis apparatus, the fluorescent X-ray analysis apparatus including: a determination member containing an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays; and a field limiting member that limits fluorescent X-rays incident on the detector, among fluorescent X-rays generated from the sample and the determination member, wherein the determination program causes the information processing device to execute: a step of storing in advance, in a storage unit, an intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and a step of determining whether or not the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
Effects of the invention
According to the above aspects 1 to 7 of the present invention, whether or not the mechanism for shielding a part of the fluorescent X-ray incident on the detector is normally attached can be easily confirmed.
Drawings
FIG. 1 is a diagram schematically showing a fluorescent X-ray analyzer according to an embodiment of the present invention.
Fig. 2 is a diagram showing an example of the spectrum stored in the storage unit.
Fig. 3 is a diagram showing another example of the spectrum stored in the storage unit.
Fig. 4 is a flowchart showing a method of measuring the measurement intensity stored in the storage unit.
Fig. 5 is a flowchart showing a determination method.
Fig. 6 is a diagram showing a member for determination of a modification.
Detailed Description
Preferred embodiments (hereinafter, referred to as embodiments) for carrying out the present invention will be described below with reference to the drawings. In the present embodiment, a case where the fluorescent X-ray analyzer 100 is a wavelength-dispersive fluorescent X-ray analyzer will be described as a main example.
Fig. 1 is a diagram showing an overview of a fluorescent X-ray analyzer 100 according to an embodiment of the present invention. As shown in fig. 1, the fluorescent X-ray analyzer 100 is divided into a sample chamber 101, a bulb chamber 102, and a spectroscopic chamber 103. The fluorescent X-ray analyzer 100 includes an X-ray source 104, a determination member 106, a field limiting unit 108, a soller slit 110, a spectroscopic element 112, a detector 114, a counter 116, and a control unit 118. A sample 124 is disposed in the sample chamber 101. The X-ray source 104 and the field of view limiter 108 are disposed in the bulb chamber 102. In the spectroscopic chamber 103, a soller slit 110, a spectroscopic element 112, and a detector 114 are disposed. The sample 124 is disposed on a sample holder (not shown).
The X-ray source 104 generates a primary X-ray and irradiates the judgment part 106 or the sample 124 to be analyzed.
The determination member 106 contains an element (hereinafter referred to as an element for determination) that generates fluorescent X-rays of a predetermined energy (hereinafter referred to as fluorescent X-rays for determination) when X-rays are irradiated once. Specifically, the determination member 106 is a shutter that shields the sample 124 to be analyzed from the X-ray. The shutter is disposed between the sample 124 and the X-ray source 104 and can be opened and closed. When the sample 124 is analyzed, the shutter is opened and the sample 124 is irradiated with X-rays once. On the other hand, when the determination is made as described later, the shutter is closed and the shutter is irradiated with the X-ray once.
The element that generates fluorescent X-rays of a predetermined energy may be arbitrarily set as long as it is an element that can be used for determination described later. When the determination member 106 is a shutter, the element that generates fluorescent X-rays of a predetermined energy is preferably an element that does not transmit X-rays. Preferred elements are, for example, tungsten, lead, which are elements normally comprised by a shutter.
The light shield of the present embodiment also functions as a light shield for partitioning the sample chamber 101 and the bulb chamber 102. In the closed state of the shutter, gas does not move between the sample chamber 101 and the bulb chamber 102. Thus, when analyzing a certain sample 124 and then only the sample is replaced without replacing the visual field limiting unit 108, the analysis can be continued while maintaining the vacuum state of the bulb chamber 102 and the spectroscopic chamber 103. Further, a shutter for shielding the sample 124 from the primary X-ray and a shutter for partitioning the sample chamber 101 and the bulb chamber 102 may be provided separately.
The determination member 106 is not limited to a shutter, and may be disposed at a position where the fluorescent X-rays generated by the primary X-ray irradiation are emitted to the visual field limiting unit 108. The configuration of the fluorescent X-ray analyzer 100 can be simplified by using components arranged in the sample chamber 101 or the bulb chamber 102 in advance.
The field-of-view limiting unit 108 is configured to be detachable, and limits the generated fluorescent X-rays that enter the detector 114. Specifically, the field limiting unit 108 is, for example, an aperture having an opening through which the fluorescent X-rays pass.
Further, the visual field limiting section 108 can be provided with a plurality of openings having different sizes. For example, the visual field limiting section 108 may be 3 kinds of diaphragms having opening diameters of 30mm, 20mm, and 10 mm. In this case, a diaphragm having an opening diameter of 30mm is fixed inside the bulb chamber 102. The diaphragms having openings of 20mm and 10mm in diameter are detachable and attached so as to cover the openings of the diaphragms having openings of 30mm in diameter. Part of the fluorescent X-rays emitted from the determination member 106 and the sample 124 passes through the aperture of the aperture and reaches the detector 114 via the soller slits 110 and the like. On the other hand, the other part is shielded by the diaphragm and does not reach the detector 114. Therefore, the visual field limiting unit 108 has a function of limiting the visual field seen from the detector 114.
The soller slits 110 allow the fluorescent X-rays generated by the sample 124 to pass therethrough as parallel rays. Specifically, the soller slits 110 are configured by arranging flat plates in parallel, and only the fluorescent X-rays parallel to the flat plates are allowed to pass through the fluorescent X-rays that have passed through the opening of the control unit 118.
The spectroscopic element 112 disperses the fluorescent X-rays that have passed through the soller slits 110. Specifically, for example, among the fluorescent X-rays of a plurality of wavelengths generated by the sample 124 and the judgment member 106 and passed through the soller slits 110, the spectroscopic element 112 disperses the fluorescent X-rays of a specific wavelength satisfying the bragg conditional expression.
The detector 114 measures the intensity of the fluorescent X-ray split by the splitting element 112. The detector 114 and the spectroscopic element 112 are driven by a scanning mechanism not shown. For example, the scanning mechanism is a goniometer. The scanning mechanism changes the incident angle of the fluorescent X-ray incident on the spectroscopic element 112, and scans the detector 114 in the direction in which the dispersed fluorescent X-ray is emitted. The detector 114 measures the intensity of the fluorescent X-ray in an angle range including a peak angle, which is an angle at which the peak of the fluorescent X-ray used for judgment is observed. The detector 114 is, for example, a known proportional counter, a flicker counter, or the like.
The counter 116 counts the pulse signal output as the measurement intensity of the detector 114 based on the peak value, and outputs the pulse signal as the fluorescence X-ray intensity to the control unit 118.
The control unit 118 controls the operations of the respective components disposed in the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103, and determines whether or not the visual field limiting unit 108 is normally mounted. The control unit 118 is, for example, an information processing device used in the fluorescent X-ray analysis device 100, and is, for example, a personal computer. The control unit 118 functionally includes a storage unit 122 and a determination unit 120.
The storage unit 122 stores in advance the intensity of the fluorescent X-ray of a predetermined energy generated by the determination member 106 when the view limiting unit 108 is normally attached. Specifically, the storage unit 122 is an HDD or SSD included in a personal computer. The storage unit 122 stores in advance the intensity of the fluorescent X-ray for determination measured in a state where the view limiting unit 108 is normally attached. In the case of using 3 kinds of diaphragms having aperture diameters of 30mm, 20mm, and 10mm, the storage unit 122 stores in advance the intensity of the fluorescent X-ray of a predetermined energy generated by the determination member 106 for each aperture diameter. The storage unit 122 stores, for example, the ratio of the intensity of the fluorescent X-ray to the reference value shown in table 1.
[ TABLE 1 ]
Each of the measured intensities shown in table 1 is a peak intensity of W — L α rays measured for 4 seconds in the case where the element used for determination is tungsten contained in the shutter. In table 1, the measured strength in the case where the opening diameter was 30mm was taken as a reference value.
The theoretical standard deviation is calculated from each measured intensity and measurement time. Specifically, for example, the theoretical standard deviation is calculated using equation 1. In equation 1, I is the measured intensity (kcps) and t is the measurement time.
[ EQUATION 1 ]
The storage section 122 may store the spectrum shown in fig. 2 instead of table 1. Fig. 2 is a spectrum measured before and after 2 θ angle represented by W-L α ray. The storage section 122 may store not the peak angles shown in table 1 but the spectrum and the total intensity or the net intensity obtained from the spectrum. In addition, when the fluorescent X-ray used for the determination is a W — M α ray, the storage unit 122 may store the spectrum shown in fig. 3.
The method of measuring the measurement intensity stored in the storage unit 122 will be described with reference to the flow shown in fig. 4. First, the diameter of the opening used as a reference value is determined (S402). For example, it was determined that the intensity of fluorescent X-rays measured using an opening having a diameter of 30mm was used as a reference value.
Next, the visual field limiting section 108, which determines the diameter opening, is normally installed in the bulb chamber 102 (S404). Specifically, a diaphragm having an opening with a diameter of 30mm was installed in the bulb chamber 102. In step S404, the diaphragm is normally installed.
Subsequently, after the shutter is closed, the power of the X-ray source 104 is turned on (S406). In step S406, preparation is made for measurement by the fluorescent X-ray analysis apparatus 100. Specifically, the inside of the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103 is evacuated, and the X-ray source 104 is aged. In addition, when the analysis is performed in an atmospheric environment, evacuation is not performed. In the case of analysis in the He atmosphere, He is introduced into the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103 in a state where the insides of the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103 are vacuum. Further, He may be introduced into the bulb chamber 102 and the spectroscopic chamber 103 while evacuating the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103.
Next, the intensity of the fluorescent X-ray is measured (S408). Specifically, for example, X-rays are irradiated once onto a closed shutter, and tungsten contained in the shutter generates fluorescent X-rays. Part of the generated fluorescent X-rays passes through the 30mm opening of the visual field limiter 108, and the other part is shielded by the visual field limiter 108. The fluorescent X-ray passing through the opening passes through the Soxhlet slit 110, and the W-L α ray is split by the splitting element 112. The dispersed W-L α rays enter the detector 114, and the counter 116 and the controller 118 calculate the measured intensity based on the output of the detector 114. After the measurement, the power of the X-ray source 104 is turned off.
Next, the storage unit 122 stores the measured fluorescent X-ray intensity in association with the opening diameter (S410). Specifically, as in table 1 above, a strength of 119.21kcps was stored in association with a 30mm opening diameter. Since the opening diameter used as the reference value is 30mm, a ratio of 1.0 is stored in association with the intensity.
Next, when there is another diameter opening (yes in S412), the opening diameter is changed (S414), and the visual field limiting unit 108 having the diameter opening is attached to the inside of the bulb chamber 102. For example, a diaphragm having an opening with a diameter of 20mm is installed in the bulb chamber 102. When the bulb chamber 102 is evacuated, the bulb chamber 102 is opened to the atmosphere in steps S414 to S404. In this step, the diaphragm is normally installed.
The steps of S404 to S412 are repeatedly performed for all the opened diaphragms until the intensity measurement of the fluorescent X-ray is completed. Thus, the intensities and ratios of the fluorescent X-rays included in Table 1 in association with the opening diameters of 20mm and 10mm are stored in the storage section 122.
Next, when there is no other diameter opening (no in S412), the measurement flow of the measurement intensity stored in the storage unit 122 is ended. After S412, the standard theoretical deviation σ corresponding to each intensity ratio may be calculated and stored in the storage unit 122.
The determination unit 120 determines whether or not the visual field limiting unit 108 is normally mounted, based on the intensity stored in the storage unit 122 and the intensity measured by the detector 114. Specifically, the determination unit 120 performs the determination every time the X-ray source 104 starts to emit X-rays or before the measurement of the sample 124 to be analyzed is started. The determination by the determination unit 120 will be described with reference to the flowchart of fig. 5.
First, the shutter is closed, and the power of the X-ray source 104 is turned on (S502). Specifically, in a state where which of the view restricting units 108 is attached is unknown, preparation is made for measuring the fluorescent X-ray. This step is equivalent to S406. Further, it may not be known which field limiting device 108 is attached or whether it is normally attached by another user who has used the fluorescent X-ray analysis apparatus 100. Therefore, in this step, it is assumed that it is unknown which type of the visual field limiting section 108 is mounted and whether or not it is normally mounted.
Next, the intensity of the fluorescent X-ray is measured (S504). This step is the same as S408.
Next, the determination unit 120 refers to the intensity closest to the measured intensity from the intensity stored in the storage unit 122 (S506). Specifically, for example, when the intensity of the fluorescent X-ray measured in S504 is 119.35kcps, the intensity 119.21kcps is referred to as the intensity closest to the measured intensity in table 1.
Next, the determination unit 120 performs determination based on the intensity stored in the storage unit 122 and the intensity measured by the detector 114 (S508). Specifically, for example, the judgment unit 120 compares the 119.35kcps intensity measured in S504 with the reference 119.21kcps measured intensity. When the difference in the compared intensities is equal to or less than a predetermined threshold value, the determination unit 120 determines that the visual field limiting unit 108 having the opening diameter corresponding to the reference intensity is normally attached. For example, when the difference in the compared intensities is 3 times or less the theoretical standard deviation σ, the determination unit 120 determines that the mounting is normal. In the above example, the difference between 119.35kcps and 119.21kcps is less than 3 times the theoretical standard deviation σ of 0.17. Therefore, the determination unit 120 determines that the visual field limiting unit 108 having an opening with a diameter of 30mm is normally attached.
After the steps from S502 to S508 are completed and it is determined that the visual field limiting unit 108 is normally attached, the sample 124 to be analyzed is analyzed. This prevents the analysis of the sample 124 to be analyzed from being performed in a state where the visual field limiting unit 108 is not normally attached. Further, the steps of S504 to S508 may be performed every time the specimen 124 as an analysis object is replaced.
The determination unit 120 may perform the determination based on the ratio of the compared intensities. For example, the determination unit 120 may determine that the view limiting unit 108 having the opening diameter corresponding to the reference intensity is normally attached when the ratio of the compared intensities is equal to or less than a predetermined threshold (error 3%).
This is complicated by turning off the X-ray source 104 to confirm whether the view limiting unit 108 is normally mounted, and turning on the X-ray source 104 after confirmation, in order to confirm the diameter of the opening of the view limiting unit 108. Turning on and off the X-ray source 104 requires time to control the tube voltage and tube current in stages. Since the X-ray source 104 is also a heat source, it takes a long time to age after the X-ray source 104 is turned on in order to stabilize the temperature in the apparatus and to perform accurate measurement. The fluorescent X-ray analyzer 100 is often kept in a vacuum state in the bulb chamber 102 and the spectroscopic chamber 103. Therefore, when confirming whether or not the visual field limiting unit 108 is normally attached, it is necessary to open the bulb chamber 102 and the spectroscopic chamber 103 in the atmosphere and to put them in a vacuum state again, which is a complicated and time-consuming operation. According to the above method, it is possible to easily determine whether or not the visual field limiting unit 108 is normally mounted without taking time and complicated operations such as turning off, turning on, aging, and vacuuming of the X-ray source 104.
[ modified example ]
The following describes modifications. In the present modification, in the determination member 106, the predetermined element is fixed in a shape corresponding to the opening of the view limiting unit 108 on the surface to which the X-rays are irradiated. Specifically, for example, the determination member 106 in the modification is a light shield that is coated with a predetermined paint in a pattern shown in fig. 6.
The predetermined element may be arbitrarily selected as long as it is an element that can be used for determination, as in the above-described embodiment, but it is preferable to select the predetermined element while avoiding an element originally included in the determination unit 106 or an element having a high frequency as an analysis target.
In the example shown in fig. 6, a surface of the shutter to be irradiated with the primary X-ray is coated with a predetermined paint in a shape corresponding to the opening of the visual field limiting section 108. In the case where the visual field limiting unit 108 is normally mounted, the pattern is drawn along the outline of the region where the generated fluorescent X-ray is detected by the detector 114. That is, in the case where the diaphragms having opening diameters of 10mm, 20mm and 30mm are normally installed, the outlines of the ranges in which the fluorescence X-rays detected by the detector 114 are generated among the generated fluorescence X-rays are plotted in correspondence with the respective diameters.
In the graph shown in fig. 6, the smallest circle 602 corresponds to a diaphragm having an opening diameter of 10 mm. The middle size circle 604 corresponds to a diaphragm with an opening diameter of 20 mm. The largest circle 606 corresponds to a diaphragm with an opening diameter of 30 mm.
The pattern shown in fig. 6 is drawn by applying a paint containing a predetermined element. The predetermined element generates a unique fluorescent X-ray (fluorescent X-ray for judgment), and the fluorescent X-ray having an intensity corresponding to the aperture diameter is measured by the detector 114. Specifically, in the case where a diaphragm having an opening with a diameter of 10mm is installed, the detector 114 can detect only fluorescent X-rays generated from elements contained in the paint on which the smallest circle 602 shown in fig. 6 is plotted. In the case where a diaphragm having an opening with a diameter of 20mm is installed, the detector 114 detects fluorescent X-rays generated from elements contained in the paint on which the smallest circle 602 and the middle circle 604 shown in fig. 6 are drawn. Further, in the case where a diaphragm having an opening with a diameter of 30mm is installed, the detector 114 detects fluorescent X-rays generated from elements contained in the paint on which all circles shown in fig. 6 are drawn.
Therefore, when diaphragms having different opening diameters are installed, the intensities of different fluorescent X-rays are measured according to the diameters. This fluorescent X-ray is a fluorescent X-ray specific to a predetermined element contained in the paint, and is a fluorescent X-ray for determination as in the above-described embodiment. If the visual field limiting unit 108 is not properly attached, fluorescent X-rays are generated in a region centered at a position deviated from the center of the circle shown in fig. 6, and are detected by the detector. That is, the intensities of the fluorescent X-rays unique to the above-described elements contained in the paint are different between the case where the view restricting unit 108 is not attached correctly and the case where the view restricting unit 108 is attached correctly. Therefore, by performing the flow shown in fig. 5 by measuring and storing the intensity of the fluorescent X-ray as in the flow shown in fig. 4, it is possible to determine whether or not the visual field limiting unit 108 is normally attached, even in the modified example.
The present invention is not limited to the above-described embodiments, and various modifications can be made. The configuration of the fluorescent X-ray analysis apparatus 100 is not limited to this example. The present invention may be replaced with a configuration substantially similar to the configuration described in the above embodiment, a configuration exhibiting the same operational effects, or a configuration achieving the same object.
For example, the determination unit 106 may be a turntable (Turret). Specifically, the fluorescent X-ray analysis apparatus 100 may be a turntable having a plurality of holes in which sample racks are arranged in the sample chamber 101. The turntable is formed containing an element for judgment. In this case, in steps S408 and S504, the X-ray is irradiated once to the turntable in a state where the shutter is opened. Then, the same determination as described above can be performed by using the fluorescent X-ray generated by the turntable for determination.
Further, the determination member 106 may be a calibration sample. Specifically, for example, the determination member may be a sample arranged in one of a plurality of holes provided in the turntable, and may be a sample for calibration including an element used for determination. In the same manner as described above, in steps S408 and S504, the calibration sample is irradiated with X-rays once with the shutter open. Then, the same judgment as described above can be performed by using the fluorescent X-ray generated in the calibration sample for judgment. The calibration sample may be used in common with a sample for calibrating another configuration included in the fluorescent X-ray analyzer 100.
In the above-described embodiment, the case where the diaphragms having 3 kinds of aperture sizes are used has been described, but the present invention is not limited to this. The number of the opening sizes may be 1, 2 or 4 or more. When the types of the aperture sizes are 1, the determination unit 120 does not determine whether or not the aperture having a certain aperture size is attached, but determines whether or not the aperture is attached normally.
The case where the circular pattern shown in fig. 6 is drawn by applying a paint containing a predetermined element is described, but the invention is not limited thereto. For example, the shape of the figure may be an ellipse, a rectangle. The pattern shown in fig. 6 may be drawn by vapor deposition or sputtering, or may be drawn by embedding a material containing an element for judgment.
Description of the marks
100 fluorescent X-ray analyzer
101 sample chamber
102 bulb chamber
103 light splitting chamber
104X-ray source
106 judging member
108 visual field limiting part
110 soller slit
112 light splitting element
114 detector
116 counter
118 control section
120 judging part
122 storage section
124 test sample
60210 mm corresponding graph
60420 mm corresponding pattern
60630 mm corresponding graph
Claims (7)
1. A fluorescent X-ray analyzer comprising:
an X-ray source for irradiating a sample with X-rays;
a soller slit for allowing the fluorescent X-ray generated from the sample to pass therethrough as a parallel ray;
a spectroscopic element for dispersing the fluorescent X-ray passed through the soller slits; and
a detector that measures an intensity of the fluorescent X-ray split by the splitting element,
it is characterized by comprising:
a determination member containing an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays;
a field-of-view limiting unit which is configured to be detachable and limits fluorescent X-rays incident on the detector, among fluorescent X-rays generated from the sample and the determination member;
a storage unit that stores in advance the intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and
and a determination unit that determines whether or not the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
2. The fluorescent X-ray analysis apparatus according to claim 1,
the visual field limiting part can be provided with a plurality of openings with different sizes,
the storage unit stores in advance the intensity of the fluorescent X-ray of the predetermined energy generated by the determination member for each size of the opening,
the determination unit determines the size of the opening of the visual field limiting unit based on the intensity stored in the storage unit and the intensity measured by the detector.
3. The fluorescent X-ray analysis apparatus according to claim 1 or 2,
the determination unit performs the determination every time the X-ray source starts to irradiate X-rays once or before starting to measure a sample to be analyzed.
4. The fluorescent X-ray analysis apparatus according to any one of claims 1 to 3,
in the determination member, the element is fixed in a shape corresponding to the opening of the view restricting section on the surface to which the primary X-ray is irradiated.
5. The fluorescent X-ray analysis apparatus according to any one of claims 1 to 4,
the determination member is a shutter for shielding primary X-rays irradiated to a sample to be analyzed.
6. A judgment method is characterized by comprising the following steps:
a step of arranging a determination member including an element that generates a fluorescent X-ray of a predetermined energy when the primary X-ray is irradiated, in a region irradiated with the primary X-ray, before starting measurement of a sample to be analyzed;
a step of attaching a field-of-view limiting unit that limits fluorescent X-rays incident on the detector, among fluorescent X-rays generated from the sample and the determination member;
a step of storing in advance, in a storage unit, an intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view limiting unit is normally attached; and
and determining whether the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
7. A judgment program characterized by comprising, in a program,
the determination program is a determination program executed by an information processing apparatus used by a fluorescent X-ray analysis apparatus including: a determination member containing an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays; and a visual field limiting member that limits fluorescent X-rays incident on the detector from among fluorescent X-rays generated from the sample and the determination member,
the determination program causes the information processing apparatus to execute:
a step of storing in advance, in a storage unit, an intensity of the fluorescent X-ray of the predetermined energy generated by the determination member when the view restricting unit is normally attached; and
and determining whether the visual field limiting unit is normally attached based on the intensity stored in the storage unit and the intensity measured by the detector.
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| JP2020-105825 | 2020-06-19 | ||
| JP2020105825A JP6990460B2 (en) | 2020-06-19 | 2020-06-19 | X-ray fluorescence analyzer, judgment method and judgment program |
| PCT/JP2021/014468 WO2021256054A1 (en) | 2020-06-19 | 2021-04-05 | Fluorescent x-ray analysis device, determination method, and determination program |
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| CN115038959A true CN115038959A (en) | 2022-09-09 |
| CN115038959B CN115038959B (en) | 2023-09-26 |
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| JP (1) | JP6990460B2 (en) |
| CN (1) | CN115038959B (en) |
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Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS537394A (en) * | 1976-07-09 | 1978-01-23 | Nippon X Ray Kk | Xxray fluorescence analyzer |
| JPH08184573A (en) * | 1994-12-27 | 1996-07-16 | Rigaku Ind Co | Discrimination method for mask diameter in x-ray analysis |
| JPH08285798A (en) * | 1995-04-17 | 1996-11-01 | Rigaku Ind Co | X-ray analyzer |
| JPH1048161A (en) * | 1996-07-31 | 1998-02-20 | Shimadzu Corp | X-ray analyzer |
| JP2000121583A (en) * | 1998-10-15 | 2000-04-28 | Rigaku Industrial Co | Discrimination method for diameter of sample mask in x-ray fluorescence analysis and x-ray fluorescence analyzer |
| CN1739023A (en) * | 2003-03-27 | 2006-02-22 | 理学电机工业株式会社 | X-ray fluorescence analyzer |
| JP2008203245A (en) * | 2007-01-23 | 2008-09-04 | Sii Nanotechnology Inc | X-ray analysis apparatus and x-ray analysis method |
| CN103575757A (en) * | 2012-08-10 | 2014-02-12 | 日本株式会社日立高新技术科学 | Fluorescent x-ray analysis method and fluorescent x-ray analysis device |
| JP2015094643A (en) * | 2013-11-12 | 2015-05-18 | 株式会社島津製作所 | Fluorescent x-ray analyzer |
| CN105259196A (en) * | 2014-07-08 | 2016-01-20 | 日本株式会社日立高新技术科学 | Sample Plate for X-Ray Analysis and X-Ray Fluorescent Analyzer |
| CN110088603A (en) * | 2016-12-01 | 2019-08-02 | 株式会社理学 | Fluorescent x-ray analyzer |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3270829B2 (en) * | 1997-10-06 | 2002-04-02 | 理学電機工業株式会社 | X-ray fluorescence analyzer |
| JP2000346816A (en) | 1999-06-08 | 2000-12-15 | Shimadzu Corp | X-ray analysis device |
| JP5251330B2 (en) * | 2008-07-23 | 2013-07-31 | 株式会社島津製作所 | X-ray analyzer |
| WO2016187471A1 (en) | 2015-05-20 | 2016-11-24 | Tribogenics, Inc. | X-ray fluorescence device calibration |
-
2020
- 2020-06-19 JP JP2020105825A patent/JP6990460B2/en active Active
-
2021
- 2021-04-05 WO PCT/JP2021/014468 patent/WO2021256054A1/en active Application Filing
- 2021-04-05 CN CN202180007827.3A patent/CN115038959B/en active Active
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS537394A (en) * | 1976-07-09 | 1978-01-23 | Nippon X Ray Kk | Xxray fluorescence analyzer |
| JPH08184573A (en) * | 1994-12-27 | 1996-07-16 | Rigaku Ind Co | Discrimination method for mask diameter in x-ray analysis |
| JPH08285798A (en) * | 1995-04-17 | 1996-11-01 | Rigaku Ind Co | X-ray analyzer |
| JPH1048161A (en) * | 1996-07-31 | 1998-02-20 | Shimadzu Corp | X-ray analyzer |
| JP2000121583A (en) * | 1998-10-15 | 2000-04-28 | Rigaku Industrial Co | Discrimination method for diameter of sample mask in x-ray fluorescence analysis and x-ray fluorescence analyzer |
| CN101520423A (en) * | 2003-03-27 | 2009-09-02 | 株式会社理学 | X-ray fluorescence analyzer |
| CN1739023A (en) * | 2003-03-27 | 2006-02-22 | 理学电机工业株式会社 | X-ray fluorescence analyzer |
| CN101520422A (en) * | 2003-03-27 | 2009-09-02 | 株式会社理学 | X-ray fluorescence analyzer |
| JP2008203245A (en) * | 2007-01-23 | 2008-09-04 | Sii Nanotechnology Inc | X-ray analysis apparatus and x-ray analysis method |
| CN103575757A (en) * | 2012-08-10 | 2014-02-12 | 日本株式会社日立高新技术科学 | Fluorescent x-ray analysis method and fluorescent x-ray analysis device |
| JP2015094643A (en) * | 2013-11-12 | 2015-05-18 | 株式会社島津製作所 | Fluorescent x-ray analyzer |
| CN105259196A (en) * | 2014-07-08 | 2016-01-20 | 日本株式会社日立高新技术科学 | Sample Plate for X-Ray Analysis and X-Ray Fluorescent Analyzer |
| CN110088603A (en) * | 2016-12-01 | 2019-08-02 | 株式会社理学 | Fluorescent x-ray analyzer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6990460B2 (en) | 2022-01-12 |
| WO2021256054A1 (en) | 2021-12-23 |
| JP2022000616A (en) | 2022-01-04 |
| CN115038959B (en) | 2023-09-26 |
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