CN115038959B - 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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- CN115038959B CN115038959B CN202180007827.3A CN202180007827A CN115038959B CN 115038959 B CN115038959 B CN 115038959B CN 202180007827 A CN202180007827 A CN 202180007827A CN 115038959 B CN115038959 B CN 115038959B
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- G—PHYSICS
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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 judging method and a judging program, which can simply confirm whether a mechanism shielding part of fluorescent X-rays incident on a detector is normally installed. A fluorescent X-ray analysis device is provided with: an X-ray source (104), a soller slit (110), a spectroscopic element (112), and a detector (114), characterized by comprising: a judging member (106) that includes an element that generates fluorescent X-rays of a predetermined energy when X-rays are irradiated once; a visual field limiting unit (108) configured to be detachable, for limiting fluorescent X-rays that are incident on the detector, among fluorescent X-rays generated from the sample and the determination member; a storage unit (122) that stores in advance the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member when the visual field limiting unit is normally installed; and a judging unit (120) that judges whether or not the visual field limiting unit is normally mounted, 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 apparatus has been widely used that detects fluorescent X-rays generated from a sample irradiated with primary X-rays to perform qualitative and quantitative analysis of elements contained in the sample. In a typical wavelength-dispersive fluorescent X-ray analyzer, an X-ray source, a Soller slit (Soller slits), a spectroscopic crystal, a detector, a sample, and the like are disposed in the analyzer.
In the case of performing maintenance and correction of each component disposed in the apparatus chamber, it is necessary to shut off the X-rays for safety. The turning on and off of the X-ray must take a long time in stages, and after the turning on of the X-ray, it takes a long time until the device temperature is stabilized and the analysis can be performed with good accuracy. In addition, in the case where evacuation is required, the operation becomes further complicated. In order to reduce the time and effort, for example, patent document 1 below discloses an invention of performing correction using detection data of X-rays, which is obtained from a standard sample provided on a shutter.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open 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 (for example, a diaphragm) that shields a part of the fluorescent X-rays incident on the detector may be disposed in the sample chamber. In order to limit the measurement range on the sample, a sample mask is sometimes used, but in order to remove scattered fluorescent X-rays due to the sample mask, it is desirable to use a field limiting mechanism in combination. In order to change the measurement range on the sample, the visual field limiting mechanism may be detachably configured.
Although there are also fluorescent X-ray analyzers having a mechanism for mechanically removing or replacing the visual field limiting mechanism, the apparatus is complicated and costs are also incurred due to the provision of the mechanism for mechanically removing or replacing. On the other hand, when the visual field limiting mechanism is configured to be manually replaceable, incorrect mounting such as incorrect mounting or incorrect mounting position of the visual field limiting device having different measurement ranges may occur.
In this case, since it is impossible to check whether the device is properly 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 like, which is troublesome. In addition, even when a mechanism for mechanically removing or replacing the visual field limiting mechanism is provided, it is impossible to check from the outside whether or not the visual field limiting mechanism is properly mounted.
The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a fluorescent X-ray analysis device, a determination method, and a determination program that can easily confirm whether or not a visual field limiting device is normally mounted.
Solution for solving the problem
The fluorescent X-ray analysis apparatus according to claim 1 of the present invention includes: an X-ray source for irradiating the sample with X-rays once; a Soller slit for allowing fluorescent X-rays generated from the sample to pass therethrough as parallel rays; a spectroscopic element for spectroscopic of the fluorescent X-rays passing through the soller slit; and a detector for measuring the intensity of the fluorescent X-rays split by the beam splitter, wherein the detector comprises: a judging member including an element that generates fluorescent X-rays of a predetermined energy when irradiated with X-rays once; a visual field limiting unit configured to be detachable, for limiting fluorescent X-rays that are 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-rays of the predetermined energy generated by the determination member when the visual field limiting unit is normally installed; and a judging section that judges whether or not the visual field restriction section is normally mounted based on the intensity stored in the storage section and the intensity measured by the detector.
In the fluorescent X-ray analysis device according to claim 2 of the present invention, in the fluorescent X-ray analysis device according to claim 1, the field limiting unit may set a plurality of openings having different sizes, the storage unit may store in advance the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member according to the size of each of the openings, and the determination unit may determine the opening size of the field limiting unit based on the intensity stored in the storage unit and the intensity measured by the detector.
The fluorescent X-ray analysis apparatus according to claim 3 of the present invention is characterized in that, in the fluorescent X-ray analysis apparatus according to claim 1 or 2 of the present invention, the judgment unit makes the judgment every time the X-ray source starts to irradiate X-rays once or before starting to measure a sample to be analyzed.
A 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 to the surface on which the primary X-ray is irradiated in a shape corresponding to the opening of the visual field restriction portion in the determination member.
The fluorescent X-ray analysis device according to claim 5 of the present invention is the fluorescent X-ray analysis device according to any one of claims 1 to 4 of the present invention, wherein the determination member is a shutter that shields primary X-rays irradiated to a sample to be analyzed.
The judgment method according to claim 6 of the present invention is characterized by comprising: a step of disposing a determination member including an element that generates fluorescent X-rays of a predetermined energy when irradiated with primary X-rays in a region irradiated with the primary X-rays before starting measurement of a sample to be analyzed; a step of installing a field limiting unit that limits the incidence of fluorescent X-rays to the detector, out of fluorescent X-rays generated from the sample and the determination member; a step of storing in advance, in a storage unit, the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member when the visual field restriction unit is normally mounted; and a step of judging whether or not the visual field restriction portion is normally mounted based on the intensity stored in the storage portion and the intensity measured by the detector.
A judgment program according to claim 7 of the present invention is a judgment program executed by an information processing apparatus used in a fluorescent X-ray analysis apparatus including: a judging member including an element that generates fluorescent X-rays of a predetermined energy when irradiated with X-rays once; and a visual field limiting means for limiting fluorescent X-rays incident on the detector among fluorescent X-rays generated from the sample and the judging means, wherein the judging program causes the information processing apparatus to execute the steps of: a step of storing in advance, in a storage unit, the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member when the visual field restriction unit is normally mounted; and a step of judging whether or not the visual field restriction portion is normally mounted based on the intensity stored in the storage portion and the intensity measured by the detector.
Effects of the invention
According to the above-described aspects 1 to 7 of the present invention, it is possible to easily confirm whether or not the mechanism shielding a part of the fluorescent X-rays incident on the detector is normally mounted.
Drawings
Fig. 1 is a schematic diagram of a fluorescent X-ray analyzer according to an embodiment of the present invention.
Fig. 2 is a diagram showing an example of a 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 measurement method of the measurement intensity stored in the storage unit.
Fig. 5 is a flowchart showing a judgment method.
Fig. 6 is a diagram showing a member for determination according to a modification.
Detailed Description
Hereinafter, preferred embodiments (hereinafter referred to as embodiments) for carrying out the present invention will be described with reference to the drawings. In the present embodiment, a case where the fluorescent X-ray analysis apparatus 100 is a wavelength-dispersive fluorescent X-ray analysis apparatus will be described as a main example.
Fig. 1 is a diagram showing an outline of a fluorescent X-ray analysis apparatus 100 according to an embodiment of the present invention. As shown in fig. 1, the fluorescent X-ray analysis apparatus 100 is divided into a sample chamber 101, a bulb chamber 102, and a spectroscopic chamber 103. The fluorescent X-ray analysis apparatus 100 includes an X-ray source 104, a determination member 106, a field-of-view 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. An X-ray source 104 and a field limiting section 108 are disposed in the bulb chamber 102. A soller slit 110, a spectroscopic element 112, and a detector 114 are disposed in the spectroscopic chamber 103. The sample 124 is disposed on a sample holder (not shown).
The X-ray source 104 generates primary X-rays and irradiates the determination member 106 or the sample 124 to be analyzed.
The determination member 106 includes an element (hereinafter referred to as an element for determination) that generates fluorescent X-rays (hereinafter referred to as fluorescent X-rays for determination) of a predetermined energy when X-rays are irradiated once. Specifically, for example, the determination member 106 is a shutter that shields the sample 124 to be analyzed from being irradiated with the primary X-rays. The shutter is arranged between the sample 124 and the X-ray source 104 and can be opened and closed. When the analysis of the sample 124 is performed, the shutter is opened, and the sample 124 is irradiated with X-rays once. On the other hand, when the determination to be described later is made, the shutter is closed, and the shutter is irradiated with X-rays once.
The element that generates fluorescent X-rays of a predetermined energy can be arbitrarily set as long as it is an element that can be applied to the judgment 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 the elements normally comprised by shutters.
The shutter of the present embodiment also functions as a shutter that separates the sample chamber 101 and the bulb chamber 102. In the closed state of the shutter, the gas does not move between the sample chamber 101 and the bulb chamber 102. Accordingly, after analyzing a certain sample 124, when analyzing by replacing only the sample without replacing the visual field limiter 108, the vacuum state of the bulb chamber 102 and the spectroscopic chamber 103 can be maintained, and the analysis can be continued. A shutter for shielding the sample 124 from the primary X-ray irradiation 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 fluorescent X-rays generated by one X-ray irradiation are emitted to the visual field limiter 108. By using components that are arranged in advance in the sample chamber 101 or the bulb chamber 102, the structure of the fluorescent X-ray analysis apparatus 100 can be simplified.
The visual field limiter 108 is configured to be detachable, and limits fluorescent X-rays that enter the detector 114 from among the generated fluorescent X-rays. Specifically, the field limiting unit 108 is, for example, a diaphragm having an opening through which fluorescent X-rays pass.
The view restricting portion 108 may set a plurality of openings having different sizes. For example, the field-of-view restriction portion 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 opening diameters of 20mm and 10mm are detachable and mounted in such a manner as to cover the opening of the diaphragm having an opening diameter of 30 mm. A part of the fluorescent X-rays emitted from the determination member 106 and the sample 124 passes through the aperture of the diaphragm, passes through the soller slit 110, and the like, and reaches the detector 114. On the other hand, another part is shielded by the diaphragm, and does not reach the detector 114. Therefore, the visual field limiter 108 has a function of limiting the visual field seen from the detector 114.
The soller slits 110 pass fluorescent X-rays generated by the sample 124 as parallel rays. Specifically, the soller slits 110 are formed by arranging flat plates in parallel, and only fluorescent X-rays parallel to the flat plates pass through the fluorescent X-rays passing through the opening of the control unit 118.
The spectroscopic element 112 splits the fluorescent X-rays passing through the soller slit 110. Specifically, for example, among the fluorescent X-rays of a plurality of wavelengths generated in the sample 124 and the determination member 106 and passing through the soller slit 110, the spectroscopic element 112 separates fluorescent X-rays of a specific wavelength satisfying the bragg conditional expression.
The detector 114 measures the intensity of the fluorescent X-rays split by the spectroscopic 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 incidence angle of the fluorescent X-rays to the spectroscopic element 112, and scans the detector 114 in the direction in which the dispersed fluorescent X-rays are emitted. The detector 114 measures the intensity of the fluorescent X-rays in an angle range including the peak angle, which is the angle at which the peak of the fluorescent X-rays for judgment is observed. The detector 114 is, for example, a known proportional counter, a scintillation counter, or the like.
The counter 116 counts the pulse signal output as the measured intensity of the detector 114 based on the peak value, and outputs the pulse signal as the fluorescent X-ray intensity to the control unit 118.
The control unit 118 controls the operations of the respective components arranged in the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103, and determines whether or not the visual field restriction unit 108 is normally mounted. The control unit 118 is an information processing device, for example, a personal computer, for the fluorescent X-ray analysis device 100. The control unit 118 functionally includes a storage unit 122 and a determination unit 120.
The storage unit 122 stores the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member 106 in advance when the visual field limiting unit 108 is normally mounted. 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-rays for determination, which is measured in a state where the visual field limiting unit 108 is normally attached. In the case of using 3 types of diaphragms having opening diameters of 30mm, 20mm, and 10mm, the storage unit 122 stores in advance the intensity of fluorescent X-rays of predetermined energy generated by the judgment member 106 in accordance with the diameter of each opening. The storage unit 122 stores, for example, the ratio of the intensity of the fluorescent X-rays to the reference value shown in table 1.
[ Table 1 ]
In addition, each measured intensity shown in table 1 is the peak intensity of w—lα rays measured for 4 seconds when the element for judgment is tungsten included in the shutter. In table 1, the measured strength in the case where the opening diameter was 30mm was used 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 measured time.
Equation 1
The storage unit 122 may store the spectrum shown in fig. 2 instead of table 1. FIG. 2 is a spectrum measured before and after the angle 2 theta indicated by the W-Lalpha ray. The storage unit 122 may store not the peak angles shown in table 1 but the spectrum and the total intensity or net intensity obtained from the spectrum. In addition, in the case where the fluorescent X-ray used for the determination is set to the w—mα ray, the storage unit 122 may store the spectrum shown in fig. 3.
The measurement method of the measurement intensity stored in the storage unit 122 will be described with reference to the flow chart shown in fig. 4. First, the diameter of an opening used as a reference value is determined (S402). For example, it is determined that the intensity of fluorescent X-rays measured using an opening having a diameter of 30mm is used as a reference value.
Next, the view restricting portion 108 having the determined diameter opening is normally installed in the bulb chamber 102 (S404). Specifically, a diaphragm having an opening with a diameter of 30mm is mounted in the bulb chamber 102. In step S404, the diaphragm is normally installed.
Next, after the shutter is closed, the power supply 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 insides of the sample chamber 101, the bulb chamber 102, and the spectroscopic chamber 103 are evacuated, and the X-ray source 104 is aged. In addition, in the case of analysis under an atmospheric environment, no vacuum was applied. In the case of analysis under the He environment, he is introduced into the bulb chamber 102 and the spectroscopic chamber 103 in a state where the interiors of the sample chamber 101, the bulb chamber 102 and the spectroscopic chamber 103 are in a vacuum state. In addition, 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.
Subsequently, the intensity of the fluorescent X-rays is measured (S408). Specifically, for example, the shutter is closed and irradiated with X-rays once, and tungsten included in the shutter generates fluorescent X-rays. A part of the generated fluorescent X-rays passes through the 30mm opening of the view-restricting portion 108, and the other part is shielded by the view-restricting portion 108. The fluorescent X-rays passing through the opening pass through the soller slit 110, and the w-lα rays are split by the spectroscopic element 112. The split W-lα ray enters the detector 114, and the counter 116 and the control unit 118 calculate the measurement intensity based on the output of the detector 114. After measurement, the power to 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, the 119.21kcps intensity was stored in association with the 30mm opening diameter. Since the opening diameter used as the reference value was 30mm, the ratio of 1.0 was stored in association with the strength.
Next, if there is another diameter opening (yes in S412), the opening diameter is changed (S414), and the view restricting portion 108 having the diameter opening is mounted in the bulb chamber 102. For example, a diaphragm having an opening with a diameter of 20mm is installed in the bulb chamber 102. In addition, in the case where the bulb chamber 102 is evacuated, the bulb chamber 102 is opened to the atmosphere from the steps S414 to S404. In this step, the diaphragm is normally installed.
The steps of S404 to S412 are repeatedly performed for the diaphragms of all the openings until the intensity measurement of the fluorescent X-rays is completed. Thus, the intensities and ratios of fluorescent X-rays included in table 1, which are associated 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 ends. After S412, the standard 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 restriction 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 above determination every time the X-ray source 104 starts to irradiate X-rays or before starting to measure the sample 124 to be analyzed. The determination by the determining unit 120 will be described with reference to the flow chart 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 it is unclear which field limiting portion 108 is attached, preparation is made for measuring fluorescent X-rays. This step is equivalent to S406. In addition, it may not be known which view limiting device 108 was installed or whether it was installed normally by another user who previously used the fluorescent X-ray analysis device 100. Therefore, in this step, it is assumed that it is not known which view-restricting portion 108 is mounted and whether it is mounted normally.
Subsequently, the intensity of the fluorescent X-rays is measured (S504). This step is the same as S408.
Next, the determination unit 120 refers to the intensity closest to the measured intensity based on the intensity stored in the storage unit 122 (S506). Specifically, for example, in the case where the fluorescent X-ray intensity measured in S504 is 119.35kcps, the intensity of 119.21kcps is referred to as the intensity closest to the measured intensity in table 1.
Next, the judgment unit 120 makes a judgment based on the intensity stored in the storage unit 122 and the intensity measured by the detector 114 (S508). Specifically, for example, the judging section 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 the preset threshold value, the determination unit 120 determines that the visual field restriction 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 view restricting unit 108 having an opening with a diameter of 30mm is normally mounted.
After the steps S502 to S508 are completed, it is determined that the visual field restriction portion 108 is normally attached, and then analysis of the sample 124 to be analyzed is performed. This can prevent the analysis of the sample 124 to be analyzed from being performed in a state where the visual field restriction unit 108 is not normally attached. Further, the steps of S504 to S508 may be performed every time the sample 124 as the analysis target is replaced.
The determination unit 120 may perform the determination based on the ratio of the compared intensities. For example, when the ratio of the compared intensities is equal to or less than a preset threshold (error 3%), the determination unit 120 may determine that the visual field restriction unit 108 having the opening diameter corresponding to the reference intensity is normally installed.
To confirm the diameter of the opening of the view-field limiting portion 108, it is complicated to confirm whether the view-field limiting portion 108 is normally attached or not to turn off the X-ray source 104, and to turn on the X-ray source 104 after confirmation. The on/off of the X-ray source 104 requires a stepwise control of the tube voltage and tube current, and requires time. Further, since the X-ray source 104 is also a heat source, a long time of aging is required after the X-ray source 104 is turned on in order to stabilize the temperature in the apparatus and perform accurate measurement. The fluorescent X-ray analyzer 100 is often held in a vacuum state in the bulb chamber 102 and the spectroscopic chamber 103. Therefore, when confirming whether or not the view restricting section 108 is normally attached, it is necessary to open the bulb chamber 102 and the spectroscopic chamber 103 to the atmosphere and to put them in a vacuum state, which is a complicated operation and time-consuming operation. According to the above method, it is possible to easily determine whether or not the view-restricting portion 108 is normally attached without taking time and without taking a complicated operation such as turning off, turning on, aging, and vacuuming the X-ray source 104.
[ modification ]
The following describes modifications. In the present modification, in the determination member 106, a predetermined element is fixed to the surface on which the primary X-ray is irradiated in a shape corresponding to the opening of the view restricting portion 108. Specifically, for example, the determination member 106 in the modification is a shutter coated with a predetermined paint in the 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 embodiment, but it is preferable to select an element that is not originally included in the determination member 106 and that is a high-frequency element to be analyzed.
In the example shown in fig. 6, the surface of the shutter to be irradiated with the primary X-rays is coated with a predetermined paint in a shape corresponding to the opening of the view restricting portion 108. When the visual field limiting unit 108 is normally installed, a figure is drawn along the outline of the region where the generated fluorescent X-rays are detected by the detector 114. That is, in the case where diaphragms having opening diameters of 10mm, 20mm, and 30mm are normally attached, out of the generated fluorescent X-rays, the outline of the range in which the fluorescent X-rays detected by the detector 114 are generated is plotted corresponding to each diameter.
In the graph shown in fig. 6, the smallest circle 602 corresponds to a diaphragm with an opening diameter of 10 mm. The middle-sized 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 prescribed elements. The predetermined element generates a characteristic fluorescent X-ray (fluorescent X-ray for judgment), and the fluorescent X-ray of the intensity corresponding to the opening 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 by elements contained in the paint drawing the minimum circle 602 shown in fig. 6. In the case of a diaphragm having an opening with a diameter of 20mm, the detector 114 detects fluorescent X-rays generated by elements contained in the paint drawing the minimum circle 602 and the middle circle 604 shown in fig. 6. Further, in the case where a diaphragm having an opening with a diameter of 30mm is attached, the detector 114 detects fluorescent X-rays generated by elements contained in the paint drawing all circles shown in fig. 6.
Therefore, when diaphragms having different opening diameters are installed, the intensities of the different fluorescent X-rays are measured according to the diameters. The fluorescent X-ray is a fluorescent X-ray unique to a predetermined element contained in the paint, and is used for determination as in the above embodiment. When the visual field limiter 108 is not properly mounted, fluorescent X-rays are generated in a region centered at a position offset from the center of the circle shown in fig. 6, and detected by the detector. That is, when the visual field limiter 108 is not properly attached, the intensity of fluorescent X-rays inherent to the above elements contained in the paint is different from that when the visual field limiter 108 is properly attached. Therefore, by performing the flow shown in fig. 5 by measuring and storing the intensity of the fluorescent X-rays in the same manner as in the flow shown in fig. 4, it is possible to determine whether or not the visual field restriction portion 108 is normally attached even in the modification.
The present invention is not limited to the above-described embodiments, and various modifications can be made. The structure of the fluorescent X-ray analyzer 100 is an example, and is not limited thereto. The configuration may be replaced with a configuration substantially identical to that shown in the above embodiment, a configuration that exhibits the same operational effects, or a configuration that achieves the same purpose.
For example, the determination member 106 may be a turntable (turset). 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 by containing an element for judgment. In this case, in steps S408 and S504, the turntable is irradiated with X-rays once in a state where the shutter is open. Then, the same determination as described above can be performed by using fluorescent X-rays generated by the turntable for determination.
Further, the determination member 106 may be a calibration sample. Specifically, for example, the judgment member may be a sample placed in one of the plurality of holes provided in the turntable, and a sample for correction including an element for judgment. 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 determination as described above can be performed by using the fluorescent X-rays generated by the calibration sample for determination. The calibration sample may be used in common with a sample having another structure included in the fluorescent X-ray analysis apparatus 100.
In the above embodiment, the description has been made of the case where the aperture stop having 3 aperture sizes is used, but the present invention is not limited thereto. The kinds of opening sizes may be 1, 2 or 4 or more. When the type of opening size is 1, the determination unit 120 does not determine whether or not a diaphragm of a certain opening size is attached, but only determines whether or not the diaphragm is attached normally.
The description has been made of the case where the circular pattern shown in fig. 6 is drawn by applying a paint containing predetermined elements, but the present invention is not limited to this. For example, the shape of the graphic may be oval, rectangular. The graph 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 marking
100 fluorescent X-ray analysis device
101 sample chamber
102 ball tube chamber
103 beam splitting chamber
104X-ray source
106 determination member
108 visual field limiter
110 Soiler slit
112 spectroscopic element
114 detector
116 counter
118 control part
120 determination part
122 storage unit
124 sample
602 Pattern corresponding to 10mm
604 20mm corresponding graph
606 30mm corresponding graph
Claims (7)
1. A fluorescent X-ray analysis device is provided with:
an X-ray source for irradiating the sample with X-rays once;
a Soller slit for allowing fluorescent X-rays generated from the sample to pass therethrough as parallel rays;
a spectroscopic element for spectroscopic of the fluorescent X-rays passing through the soller slit; and
a detector for measuring the intensity of the fluorescent X-rays split by the beam splitter,
characterized by comprising:
a judging member which is disposed between the sample and the X-ray source so as to shield one X-ray irradiation of the sample, and which contains an element that generates fluorescent X-rays of a predetermined energy when the one X-ray is irradiated;
a visual field limiting unit configured to be detachable, for limiting fluorescent X-rays that are 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-rays of the predetermined energy generated by the determination member when the visual field limiting unit is normally installed; and
and a judging unit that judges whether or not the visual field restricting unit is normally mounted, based on the intensity stored in the storage unit and the intensity measured by the detector.
2. The apparatus according to claim 1, wherein the fluorescent X-ray analyzer comprises,
the view restricting portion can set a plurality of openings having different sizes,
the storage unit stores in advance the intensity of the fluorescent X-rays of the predetermined energy generated by the judging member according to the size of each opening,
the judgment unit judges the opening size of the visual field restriction 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, wherein,
the judgment unit makes the judgment 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 claim 1 or 2, wherein,
in the determination member, the element is fixed to a surface on which the primary X-ray is irradiated in a shape corresponding to an opening of the visual field restriction portion.
5. The fluorescent X-ray analysis apparatus according to claim 1 or 2, wherein,
the judging member is a shutter that can be opened and closed.
6. A method for determining whether or not a field-of-view limiting portion shielding fluorescent X-rays is normally attached, comprising the steps of:
a step of disposing a determination member including an element that generates fluorescent X-rays of a predetermined energy when irradiated with the primary X-rays between the sample and the X-ray source so as to shield the primary X-ray irradiation of the sample before starting measurement of the sample to be analyzed;
a step of installing a field limiting unit for limiting the incidence of fluorescent X-rays to the detector, among fluorescent X-rays generated from the sample and the judging member;
a step of storing in advance, in a storage unit, the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member when the visual field restriction unit is normally mounted; and
and judging whether the visual field limiting part is normally installed or not based on the intensity stored in the storage part and the intensity measured by the detector.
7. A recording medium which is a computer-readable recording medium storing a judgment program, characterized in that,
the determination program is a determination program executed by an information processing device used in a fluorescent X-ray analysis device including: a judging member which is disposed between the sample and the X-ray source so as to shield one X-ray irradiation of the sample, and which contains an element that generates fluorescent X-rays of a predetermined energy when the one X-ray is irradiated; and a field limiting member which limits fluorescent X-rays incident on the detector among fluorescent X-rays generated from the sample and the judging member,
the judgment program causes the information processing apparatus to execute the steps of:
a step of storing in advance, in a storage unit, the intensity of the fluorescent X-rays of the predetermined energy generated by the determination member when the visual field restriction unit is normally mounted; and
and judging whether the visual field limiting part is normally installed or not based on the intensity stored in the storage part and the intensity measured by the detector.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2020105825A JP6990460B2 (en) | 2020-06-19 | 2020-06-19 | X-ray fluorescence analyzer, judgment method and judgment program |
| JP2020-105825 | 2020-06-19 | ||
| 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 CN115038959A (en) | 2022-09-09 |
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| JP (1) | JP6990460B2 (en) |
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| JP2022000616A (en) | 2022-01-04 |
| CN115038959A (en) | 2022-09-09 |
| WO2021256054A1 (en) | 2021-12-23 |
| JP6990460B2 (en) | 2022-01-12 |
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