Management method, program, and x-ray analysis device

Abstract

A management method according to the present disclosure is a management method for a protective member that protects an interior section of an X-ray analysis device. The management method according to the present disclosure includes: a step for acquiring reference data; a step (S420) for acquiring target data that is obtained by irradiating the protective member with X-rays; a step (S430) for determining whether the protective member is contaminated on the basis of the reference data and the target data; and a step (S440) for issuing a warning when it has been determined that the protective member is contaminated.

Description

Management method, program, and X-ray analysis device

[0001] The present invention relates to a management method, a program, and an X-ray analysis apparatus, and more particularly to reducing the burden on a user in determining whether a protection member for preventing contamination in an X-ray analysis apparatus is dirty.

[0002] When a sample is irradiated with X-rays, each element that makes up the sample emits X-rays with a specific energy. An example of an X-ray analyzer is an X-ray fluorescence analyzer. X-ray fluorescence analyzers use X-ray fluorescence analysis (XRF) to analyze the energy and intensity of the fluorescent X-rays emitted from the sample. This allows the type and content of elements that make up the sample to be determined.

[0003] In XRF, if a leaked sample adheres to the tube or detector window inside the X-ray analysis device, the analysis accuracy may be reduced. Therefore, to prevent the sample from adhering to the tube or detector, a protective member for preventing contamination may be provided between the tube and the detector and the sample. Regarding a protective member for preventing contamination in an X-ray analysis device, International Publication No. 2022 / 003850 (Patent Document 1) discloses an X-ray analysis device including a protective member having an enclosing tube that surrounds a sample container and has an opening downward for irradiating the sample with X-rays, and a film that closes the opening of the enclosing tube.

[0004] International Publication No. 2022 / 003850

[0005] According to the X-ray analysis device disclosed in Patent Document 1, even if a sample leaks from a sample container, the sample is trapped inside a cylindrical protective member, preventing the sample from adhering to the tube or detector of the X-ray analysis device. However, Patent Document 1 does not consider what to do if the protective member becomes contaminated. For example, if a transparent sample leaks from a sample container and adheres to the protective member, the user may not notice that the sample is adhering to the protective member. If the sample is measured while the protective member is contaminated, the analytical accuracy may be reduced. Furthermore, the protective member may be installed in a location that is difficult for the user to easily remove, and the user may find it cumbersome to visually check the protective member and determine whether the protective member is contaminated.

[0006] The present disclosure has been made in consideration of the above circumstances, and its purpose is to reduce the burden on a user of determining whether a protective member for preventing contamination in an X-ray analysis apparatus is contaminated.

[0007] A first aspect of the present disclosure is a method for managing a protective member that protects the inside of an X-ray analysis apparatus, including: (a) a step of acquiring reference data; (b) a step of acquiring target data obtained by irradiating the protective member with X-rays; (c) a step of determining whether the protective member is contaminated based on the reference data and the target data; and (d) a step of issuing a warning when it is determined that the protective member is contaminated.

[0008] A second aspect of the present disclosure is a program that, when executed by a processor mounted on a computer, causes the computer to acquire reference data, acquire target data obtained by irradiating a protective member with X-rays, determine whether the protective member is contaminated based on the reference data and the target data, and issue a warning if it is determined that the protective member is contaminated.

[0009] A third aspect of the present disclosure is an X-ray analysis device that irradiates a sample with X-rays and analyzes the emitted X-rays, comprising a sample container, a mounting unit, an X-ray irradiation source, a detector, a protective member, a control device, and a display device. The sample container contains a sample. The mounting unit is capable of mounting the sample container. The X-ray irradiation source irradiates X-rays onto the sample in the sample container from below the mounting unit. The detector detects X-rays emitted from the sample below the mounting unit. The protective member is installed on the mounting unit and protects the interior of the X-ray analysis device. The control device receives a signal from the detector. The control device acquires reference data, irradiates X-rays from the X-ray irradiation source onto the protective member, acquires target data obtained by the detector, determines whether the protective member is contaminated based on the reference data and the target data, and displays a warning on the display device if it is determined that the protective member is contaminated.

[0010] According to the present disclosure, it is possible to reduce the burden on a user of an X-ray analysis apparatus in determining whether a protection member for preventing contamination is contaminated.

[0011] 5 is a schematic diagram showing the configuration of an analysis device. FIG. 6 is a schematic diagram showing the details of a protective member. FIG. 7 is an example of a spectrum obtained when measuring a protective member. FIG. 8 is a flowchart showing processing performed by a processor in the analysis device. FIG. 9 is a flowchart showing a subroutine of step S200 shown in FIG. 4. FIG. 10 is a flowchart showing a subroutine of step S400 shown in FIG. 4. FIG. 11 is a schematic diagram showing the configuration of an X-ray analysis device according to a modified example. FIG. 12 is a flowchart showing a subroutine of S200 according to a modified example. FIG. 13 is a flowchart showing a subroutine of S400 according to a modified example.

[0012] Hereinafter, embodiments of the present disclosure will be described in detail with reference to the drawings. In the drawings, the same or corresponding parts are designated by the same reference numerals, and description thereof will not be repeated.

[0013] [Overall Configuration of X-Ray Fluorescence Spectrometer] FIG. 1 is a schematic diagram showing the configuration of an analysis device 100 according to an embodiment of the present disclosure. The analysis device 100 irradiates a sample S to be analyzed with X-rays and measures the fluorescent X-rays emitted from the sample S to determine the types and amounts of elements contained in the sample. In one example, the analysis device 100 is an energy dispersive X-ray spectroscopy (EDX) device. However, instead of an EDX device, a wavelength dispersive X-ray spectroscopy (WDX) device, which uses a different method of detecting fluorescent X-rays than an EDX device, may be used. The analysis device 100 includes a control device 1, a main body 2, a holder 5, a display device 13, and an input device 14.

[0014] The main body 2 includes a housing 21, a housing 22, and a sample stage 23. The housing 21 is placed on a first surface 24 of the sample stage 23. The housing 21 and the sample stage 23 form a sample chamber 3. The housing 22 is placed on a second surface 25 of the sample stage 23. The housing 22 and the sample stage 23 form a measurement chamber 4. The sample chamber 3 and the measurement chamber 4 are enclosed by the housing 21 and the housing 22 in an airtight manner.

[0015] 1, the direction perpendicular to the sample stage 23 is defined as the Z axis, and the plane parallel to the surface of the sample stage 23 is defined as the XY plane. In one embodiment, the analysis device 100 is used in a state where it is installed so that the Z axis is approximately parallel to the direction of gravity. In this case, the first surface 24 of the sample stage 23 is the so-called "sample stage upper surface," and the second surface 25 of the sample stage 23 is the so-called "sample stage lower surface."

[0016] An opening 26 is formed in the sample stage 23. When analyzing the sample S, the sample S contained in the sample container 6 is placed on the sample stage 23 so as to cover the opening 26. As a result, the bottom surface of the sample S is exposed to the measurement chamber 4 through the opening 26.

[0017] An X-ray tube 41 and a detector 42 are disposed in the measurement chamber 4. The X-ray tube 41 generates X-rays and irradiates the sample S with the X-rays. The X-ray tube 41 includes a filament that emits thermoelectrons and a target that converts the thermoelectrons into predetermined primary X-rays and emits the primary X-rays. The X-ray tube 41 corresponds to one example of an "X-ray irradiation source."

[0018] The detector 42 detects X-rays emitted from the sample. The X-rays emitted from the sample include fluorescent X-rays and scattered X-rays. Fluorescent X-rays are X-rays emitted when the irradiated X-rays excite the inner shell electrons of atoms in the sample, resulting in the vacancies that are then filled by outer shell electrons. The emitted fluorescent X-rays correspond to the energy difference between the inner and outer shells, and the type of atom in the sample can be determined from the energy of the fluorescent X-rays. Scattered X-rays are X-rays that result from the scattering of the irradiated X-rays by each atom in the sample.

[0019] The detector 42 is configured by, for example, a semiconductor detector including a Si element. Note that the detector 42 may also be configured by a semiconductor detector including an element in which a Si element is doped with a Li element.

[0020] The X-ray tube 41 and the detector 42 are installed on the wall of the measurement chamber 4. Primary X-rays emitted from the X-ray tube 41 are irradiated onto the sample S through the opening 26. Fluorescent X-rays generated from the sample S and scattered X-rays scattered by the sample S are incident on the detector 42, which measures the energy and amount of the X-rays. More specifically, the energy of the X-rays is generally represented by their wavelength. The amount of X-rays is generally represented by the number of X-ray photons per unit time, and is also called the X-ray intensity. The detection result of the detector 42 is typically represented as an X-ray spectrum, which shows the relationship between the energy and amount of the detected X-rays.

[0021] The holder 5 holds a sample container 6 that contains a sample S. The sample S may be liquid or solid. The holder 5 prevents the sample S from adhering to the X-ray tube 41 or the detector 42 even if the sample S leaks out of the sample container 6, and corresponds to one example of a "protective member."

[0022] Fig. 2 is a schematic diagram showing the configuration of the holder 5 and the sample container 6. Referring to Fig. 2, the sample container 6 has a container body 61 and a film 62. The sample container 6 is a container for containing a sample S.

[0023] The container body 61 has a shape that surrounds the sample S and opens downward. The container body 61 is made of, for example, polypropylene (PP).

[0024] The film 62 closes the opening 61a of the container body 61 and supports the sample S. The film 62 is welded to the bottom end of the container body 61. The film 62 is made of a resin composed of carbon atoms and hydrogen atoms, or carbon atoms, hydrogen atoms, and oxygen atoms, such as polypropylene or polyethylene terephthalate. Because the fluorescent X-rays emitted from these elements are weak, the film has little effect on the fluorescent X-ray analysis in EDX.

[0025] The sample container 6 may have a hole for venting the liquid when it expands, and / or a liquid retainer.

[0026] The holder 5 is placed on the sample stage 23 and accommodates the sample container 6. The holder 5 is configured to be removable from the sample stage 23. The holder 5 has an enclosing cylinder 51 and a film 52.

[0027] The surrounding cylinder 51 has an outer shape larger than the opening 26. The surrounding cylinder 51 surrounds the sample container 6 and has a shape that opens downward. In this embodiment, the surrounding cylinder 51 is formed in a cylindrical shape. The surrounding cylinder 51 is made of, for example, polypropylene. The height of the surrounding cylinder 51 is greater than the height of the sample container 6. The position of the surrounding cylinder 51 relative to the opening 26 is determined by a positioning mechanism (not shown). The inner circumferential surface 51S of the surrounding cylinder 51 may gradually decrease in diameter as it approaches the sample stage 23. In this way, when the sample container 6 is placed inside the surrounding cylinder 51 from above the surrounding cylinder 51, the sample container 6 is guided to a predetermined position.

[0028] Film 52 closes opening 51a of enclosing tube 51. In other words, two films (film 62 and film 52) are stacked above opening 26. Film 52 is welded to the lower end of enclosing tube 51. The thickness of film 52 is approximately the same as that of film 62. For example, the thickness of film 52 is preferably set to be 0.5 to 2 times the thickness of film 62. Film 52 is made of a resin composed of carbon atoms and hydrogen atoms, or carbon atoms, hydrogen atoms, and oxygen atoms, such as polypropylene and polyethylene terephthalate.

[0029] Returning to FIG. 1 , the control device 1 has, as its main components, a processor 11, a memory 12, and an I / O (Input / Output) interface 15. The components are interconnected by a data bus. The control device 1 controls the main body 2. During measurement, the control device 1 performs analysis (qualitative analysis and quantitative analysis) of various elements contained in the sample S contained in the sample container 6 based on the spectrum of X-rays detected by the detector 42. Furthermore, the control device 1 determines whether the holder 5 is contaminated based on the received X-ray spectrum. The control device 1 can be, for example, a personal computer.

[0030] The processor 11 is an example of an electric circuit, and controls the operation of the control device 1 by executing a given program. The program executed by the processor 11 may be stored in the memory 12, or may be stored in a storage device external to the control device 1. The processor 11 is, for example, a CPU (Central Processing Unit) or an MPU (Micro Processing Unit).

[0031] The memory 12 non-temporarily stores programs executed by the processor 11, X-ray spectrum data obtained by measurement, and other programs. The X-ray spectrum data and programs stored in the memory 12 include reference data 121 and a contamination determination program 122. The memory 12 includes volatile memory (e.g., random access memory (RAM)) and non-volatile memory (e.g., read only memory (ROM), a hard disk drive, and a solid state drive). The database and / or program may be stored in an external storage device accessible by the processor 11.

[0032] The I / O interface 15 is an interface for exchanging various types of data between the processor 11 and external devices connected to the I / O interface 15. The external devices include the display device 13 and the input device 14. In this specification, the I / O interface 15 also includes devices that exchange data between the processor 11 and a storage terminal connected to the control device 1. The control device 1 controls the tube voltage, tube current, and exposure time of the X-ray tube 41, as well as the display on the display device 13, by sending control signals (commands) via the I / O interface 15.

[0033] The display device 13 is configured by, for example, a liquid crystal monitor, and displays the results of X-ray detection in accordance with commands from the processor 11.

[0034] The input device 14 is configured by, for example, a keyboard and a mouse. The input device 14 receives instructions from the user for the control device 1 and the main body 2, and outputs the instructions to the processor 11 via the I / O interface 15. Alternatively, a touch panel in which the display device 13 and the input device 14 are integrated may be used.

[0035] XRF is a useful analytical method for determining the elemental composition of a sample. Specifically, the type and amount of elements contained in the sample can be determined by irradiating the sample with primary X-rays and analyzing the fluorescent X-rays that are generated.

[0036] In XRF, if a leaked sample adheres to the tube or detector window inside the X-ray analysis device, the analytical accuracy may be reduced. Therefore, to prevent the sample from adhering to the tube or detector, a protective member may be provided between the tube and the detector and the sample. Regarding preventing the inside of the X-ray analysis device from being contaminated by the sample, Patent Document 1 discloses an X-ray analysis device equipped with a protective member including an enclosing cylinder that surrounds a sample container and has an opening downward for irradiating the sample with X-rays, and a film that closes the opening of the enclosing cylinder.

[0037] According to the X-ray analysis device disclosed in Patent Document 1, even if a sample leaks from a sample container, the sample remains inside the protective member, preventing the sample from adhering to the tube or detector of the X-ray analysis device. However, Patent Document 1 does not consider what to do if the protective member becomes contaminated. If a sample is measured with the X-ray analysis device using a contaminated protective member, the analysis accuracy may decrease.

[0038] Therefore, before measuring a sample, the user must visually check whether the protective member is dirty. However, if, for example, a transparent sample leaks from a sample container and adheres to the protective member, the user may not notice that the sample is adhered to the protective member.

[0039] Furthermore, the protective member may be installed in a position that is difficult for the user to remove, and the user may find it troublesome to check whether the protective member is contaminated.

[0040] [Analyzing Device According to the Embodiment] Therefore, in the analyzing device 100 according to the present embodiment, whether or not the holder 5 is contaminated is determined based on an X-ray spectrum obtained by irradiating X-rays onto the holder 5. This reduces the burden on the user of visually checking whether or not the holder 5 is contaminated.

[0041] Furthermore, in the analysis device 100 according to this embodiment, whether or not the holder 5 is contaminated is determined based on the X-ray spectrum. Therefore, even contamination that is difficult to confirm visually can be detected. According to the analysis device 100 according to this embodiment, contamination of the holder 5 can be reliably detected without being overlooked.

[0042] Furthermore, in the analysis device 100 according to this embodiment, there is no need to remove the holder 5 when determining whether the holder 5 is contaminated. Therefore, even if the holder 5 is installed in a position where the user cannot easily remove it, the user can have the analysis device 100 determine whether the holder 5 is contaminated. In other words, by having the analysis device 100 perform a contamination inspection, the user does not need to remove the protective member to determine whether the protective member is contaminated.

[0043] The following is a detailed description of the contamination inspection of the holder 5 performed by the analyzer 100. The contamination inspection is made up of two processes: receiving reference data and determining whether the holder 5 is contaminated.

[0044] <1. Receipt of Reference Data> The control device 1 acquires the reference data 121 to be compared with the X-ray spectrum data obtained by irradiating the holder 5 with X-rays.

[0045] Specifically, the reference data 121 is, for example, X-ray spectrum data obtained by irradiating an unused holder 5 on which a sample S has never been placed with X-rays.

[0046] The reference data 121 may be X-ray spectrum data obtained by placing an unused holder 5 on the sample stage 23 and irradiating it with X-rays, or a predetermined value may be input by the user. The predetermined value is, for example, X-ray spectrum data that is assumed to be obtained by irradiating an uncontaminated holder 5 with X-rays.

[0047] 2. Contamination Determination The control device 1 executes the contamination determination program 122 to determine whether the holder 5 is contaminated.

[0048] The control device 1 irradiates the holder 5 with X-rays from the X-ray tube 41 and detects the X-rays with the detector 42. The control device 1 generates an X-ray spectrum from the detected X-rays. The control device 1 determines whether the holder 5 is contaminated based on the generated X-ray spectrum and the reference data 121.

[0049] Whether the holder 5 is contaminated is determined, for example, by calculating the difference between the count number of X-rays contained in the generated X-ray spectrum that have an intensity above a predetermined range and the count number of X-rays contained in the reference data 121 that have an intensity above a predetermined range, and determining whether the holder 5 is contaminated based on the ratio of this difference to the count number of X-rays in the reference data 121. For example, if the count number of X-rays contained in the generated X-ray spectrum is 200 / second and the count number of X-rays in the reference data 121 is 160 / second, the difference is 40 / second, and the ratio of this difference to the count number of X-rays in the reference data 121, 160 / second, is 25%. If this ratio is greater than a predetermined value set as a threshold, the holder 5 is determined to be contaminated. The predetermined value may be determined in advance or by the user, and may be, for example, 1 to 10%.

[0050] Furthermore, the determination of whether the holder 5 is contaminated may be based on an intensity value at a predetermined energy. Specifically, the control device 1 extracts a first intensity value at a predetermined energy in the reference data and a second intensity value at the predetermined energy in the generated X-ray spectrum. The control device 1 then determines whether the holder 5 is contaminated based on the first intensity value and the second intensity value. Specifically, for example, the control device 1 calculates the difference between the first intensity value and the second intensity value, and determines that the holder 5 is contaminated if the difference is equal to or greater than a threshold. The intensity value at a predetermined energy may be an intensity value at an energy of 1 to 10 keV, an intensity value at an energy of 20 to 30 keV, or a specific energy.

[0051] If the above process determines that the holder 5 is contaminated, the control device 1 displays a warning on the display device 13. The warning displayed on the display device 13 is, for example, a message urging the user to replace the holder 5 with a new one, and a message informing the user that measurement accuracy will decrease if a sample is measured using the installed holder 5. The user who recognizes the warning replaces the holder 5 with a new one.

[0052] When the control device 1 determines whether the holder 5 is contaminated, the total count number of X-rays contained in the X-ray spectrum may be used.

[0053] The X-ray energy band used for contamination determination is selected by the user according to the type of contamination expected. For example, if it is expected that the holder 5 is contaminated with water or an organic compound composed of carbon, hydrogen, and oxygen, only the count number of X-rays with an energy of 1 to 10 keV, which is the so-called scattered X-ray energy band, is used. In this case, the background count number in the X-ray spectrum data tends to increase overall due to contamination.

[0054] In typical X-ray analysis, the type and / or amount of elements contained in a sample is measured by focusing on the fluorescent X-rays emitted when atoms are irradiated with X-rays. Therefore, X-rays with energies of 1 to 10 keV are often considered to be derived from the so-called background and are not used in the analysis. On the other hand, for example, if water, oil, or the base material of the sample container 6 adheres to the holder 5, peaks derived from the fluorescent X-rays are not detected and scattered X-rays increase. Therefore, if it is assumed that water, oil, or the base material of the sample container 6 adheres to the holder 5, contamination is determined using the count number of X-rays with energies of 1 to 10 keV.

[0055] Furthermore, for example, when it is predicted that contamination derived from a specific element is attached to the holder 5, only the count number of X-rays in the energy band of fluorescent X-rays derived from that element may be used. For example, when contamination derived from a light metal (e.g., aluminum and potassium) is expected to be attached, only the count number of X-rays with an energy of 1 to 7 keV may be used. When contamination derived from lead is expected to be attached, only the count number of X-rays with an energy of 5 to 15 keV may be used, and when contamination derived from cadmium is expected to be attached, only the count number of X-rays with an energy of 20 to 30 keV may be used.

[0056] By setting the range of X-ray energy used in the contamination determination process, it is possible to prevent X-rays detected due to causes other than contamination from affecting the determination of whether or not the holder 5 is contaminated.

[0057] 3 is a diagram showing the difference spectrum data between the X-ray spectrum data of a contaminated holder 5 and the X-ray spectrum data obtained when the holder 5 was unused. The holder 5 shown in FIG. 3 is assumed to be contaminated with an organic compound composed of carbon, hydrogen, and oxygen. As shown in FIG. 3, the contamination on the holder 5 is assumed to be derived from an organic compound, and therefore the intensity of scattered X-rays with energies of 1 to 10 keV is strong. Therefore, by focusing on X-rays in this energy band, the influence of X-rays derived from sources other than contamination can be suppressed, improving the accuracy of contamination determination.

[0058] Furthermore, a filter that passes only X-rays in a predetermined energy band may be installed between the holder 5 and the detector 42, and contamination inspection may be performed based on the obtained X-ray spectrum. In this way, the energy band of X-rays used in contamination inspection is limited to those that pass through the filter.

[0059] Alternatively, the X-ray spectrum data may be divided into multiple regions based on the energy of the X-rays, and for each region, the difference between the X-ray counts included in the X-ray spectrum obtained by measuring the holder 5 and the X-ray counts in the reference data 121 may be calculated, and the ratio of this difference to the X-ray counts in the reference data 121 may be calculated. In this case, for example, a different threshold may be set for each region, and the control device 1 may compare the calculated ratio with a threshold corresponding to that energy band to determine whether the holder 5 is contaminated. For example, the X-ray spectrum data may be divided into an energy region of 1 to 10 keV, an energy region of 10 to 20 keV, and an energy region of 20 to 30 keV. In this case, a threshold value lower than that for the 1 to 10 keV energy region corresponding to scattered X-rays is set than for the 20 to 30 keV energy region in which fluorescent X-rays are detected. This is because the count number of scattered X-rays generated when water, oil, and the base material of the sample container 6 are attached to the holder 5 is smaller than the count number of fluorescent X-rays generated when metal is attached to the holder 5. By setting different threshold values ​​for each region divided based on the energy of X-rays, the accuracy of detecting contamination of the holder 5 can be improved.

[0060] In the present embodiment, the difference between the number of X-ray counts contained in the X-ray spectrum obtained by measuring the holder 5 and the number of X-ray counts in the reference data 121 is calculated, and whether or not the holder 5 is contaminated is determined based on the ratio of this difference to the number of X-ray counts in the reference data 121. However, this is not limiting. For example, the control device 1 may determine that the holder 5 is contaminated if the difference is equal to or greater than a predetermined value.

[0061] Furthermore, the above-described contamination determination process may be performed when the user inputs a predetermined instruction to the input device 14, or may be performed before the timing of measuring the sample S.

[0062] [Processing Flow] The following describes the processing flow performed in the control device 1. Fig. 4 is a flowchart showing processing related to contamination inspection of the holder 5 performed by the processor 11 in the control device 1. In one implementation example, the processing in Fig. 4 is started by starting an application program for contamination inspection in the control device 1. The processing related to contamination inspection of the holder 5 performed by the processor 11 in the control device 1 includes a reference data reception process and a contamination determination process.

[0063] 4, in step S100, the control device 1 determines whether or not it has received an instruction to acquire reference data 121 that serves as a reference for determining whether the holder 5 is contaminated. In one implementation example, when an application program for contamination inspection is started, a start-up screen is displayed on the display device 13. The start-up screen includes one or more keys for selecting a menu. When a key for receiving reference data is operated on the start-up screen of the display device 13, an instruction to receive the reference data is input to the control device 1.

[0064] If control device 1 determines that an instruction to accept reference data 121 has been received (YES in step S100), control proceeds to step S200; otherwise (NO in step S100), control proceeds to step S300.

[0065] In step S200, the control device 1 executes a reference data reception process, and then advances the control to step S300.

[0066] 5 is a flowchart of the reference data reception process subroutine in step S200. The reference data reception process will be described with reference to FIG. 5. In step S200, when determining whether the holder 5 is contaminated, the control device 1 acquires reference data 121, which is data that serves as a reference for contamination, and stores the acquired data in the memory 12.

[0067] 5, in step S210, control device 1 erases stored reference data 121. If there is no stored reference data, step S210 does not need to be executed.

[0068] In step S220, the holder 5 is placed at the measurement position where X-rays are irradiated. In step S230, the control device 1 irradiates X-rays onto the holder 5 placed at the measurement position in step S220, and detects the X-rays with the detector 42.

[0069] In step S240, the control device 1 creates X-ray spectrum data from the X-rays detected in step S230, and stores the X-ray spectrum data in the memory 12 as reference data 121.

[0070] Returning to Fig. 4, in step S300, the control device 1 determines whether or not it has received an instruction to determine whether the device is dirty. In one implementation example, when a determination key for the holder to be determined is operated on the startup screen of the display device 13, an instruction to determine whether the device is dirty is input to the control device 1. If the control device 1 determines that it has received an instruction to determine whether the device is dirty (YES in step S300), it proceeds to step S400; otherwise (NO in step S300), it returns control to step S100. When returning control to step S100, the control device 1 causes the display device 13 to display the above-mentioned startup screen.

[0071] Fig. 6 is a flowchart of the contamination determination process subroutine of step S400 in Fig. 4. The contamination determination process for the holder 5 will be described with reference to Fig. 6. In step S400, the control device 1 determines whether the holder 5 is contaminated based on the reference data 121 set in step S200 and the X-ray spectrum data obtained by measuring the holder 5.

[0072] Referring to FIG. 6, in step S410, the holder 5 to be subjected to the contamination determination is placed at the measurement position.

[0073] In step S420, the control device 1 causes the X-ray tube 41 to irradiate the holder 5 with X-rays, and the detector 42 acquires an X-ray spectrum.

[0074] In step S430, the control device 1 determines whether the holder 5 is contaminated based on the reference data 121 stored in step S240 and the X-ray spectrum data acquired in step S420. If it is determined that the holder 5 is contaminated (YES in step S430), the control device 1 proceeds to step S440. If it is not determined that the holder 5 is contaminated (NO in step S430), the control device 1 ends the contamination determination process subroutine and returns the process to FIG. 4.

[0075] In step S440, the control device 1 displays a warning on the display device 13. Thereafter, the control device 1 ends the contamination determination process subroutine and returns the process to FIG.

[0076] According to the analyzing device 100 of this embodiment, whether or not the holder 5 is contaminated is determined based on the X-ray spectrum obtained by irradiating the holder 5 with X-rays. This reduces the burden on the user of visually checking whether or not the holder 5 is contaminated.

[0077] Furthermore, in the analysis device 100 according to this embodiment, whether or not the holder 5 is contaminated is determined based on the X-ray spectrum. Therefore, even contamination that is difficult to confirm visually can be detected. The analysis device 100 according to this embodiment can reliably detect contamination of the protective member without overlooking it.

[0078] Furthermore, in the analyzer 100 according to this embodiment, when determining whether the holder 5 is contaminated, there is no need to remove the holder 5 from the analyzer 100. Therefore, even if the protective member is installed in a position where it cannot be easily removed by the user, the user can determine whether the holder 5 is contaminated without removing the protective member.

[0079] [Modification] The analysis device may be provided with a filter that passes only X-rays in a predetermined energy band, and may determine whether the protective member is contaminated using X-ray spectrum data obtained using the filter. By using a filter that passes only X-rays in a predetermined energy band, it is possible to determine whether the holder 5 is contaminated using X-rays derived from dirt adhering to the holder 5.

[0080] FIG. 7 is a schematic diagram illustrating the overall configuration of an X-ray analysis apparatus according to a modified example. Referring to FIG. 11 , the analysis apparatus 101 differs from the analysis apparatus 100 (see FIG. 1 ) in that the measurement chamber 4 includes a drive mechanism 43, a first filter 44, and a second filter 45. The analysis apparatus 101 can install the first filter 44 and / or the second filter 45 between the X-ray tube 41 and the holder 5 using the drive mechanism 43, and only X-rays that pass through the installed filter are irradiated onto the sample S. Note that in the modified example, the same components as those of the analysis apparatus 100 described in the embodiment are designated by the same reference numerals, and detailed description thereof will not be repeated. Furthermore, the contents described in the embodiment can be combined with the modified example to the extent that they do not contradict each other.

[0081] The first filter 44 and the second filter 45 allow only X-rays of a specific energy to pass through. By absorbing X-rays in an energy range different from the X-rays of the specific energy, it is possible to irradiate the sample S with only X-rays of the specific energy. This prevents characteristic X-rays and continuous X-rays originating from the X-ray tube 41 from being detected by the detector 42. This reduces the number of detected X-rays and improves detection efficiency. The first filter 44 and the second filter 45 are formed, for example, from metal foil.

[0082] The range of energy magnitude of X-rays absorbed by the first filter 44 is different from the range of energy magnitude of X-rays absorbed by the second filter 45, and the energy magnitude of X-rays passed by the second filter 45 is configured to be lower than the energy magnitude of X-rays passed by the first filter 44.

[0083] The first filter 44 and the second filter 45 are configured to be slidable in the Y-axis direction in FIG.

[0084] The reference data 121 in the memory 12 includes a first reference signal 1211 and a second reference signal 1212. The first reference signal 1211 is X-ray spectrum data obtained by irradiating an unused holder 5 that has never had a sample S placed thereon with X-rays, with the first filter 44 in place. The second reference signal 1212 is X-ray spectrum data obtained by irradiating an unused holder 5 that has never had a sample S placed thereon with X-rays, with the second filter 45 in place.

[0085] [Analyzing Device According to Modification] The analyzing device 101 executes the contamination determining program 122 to determine whether the holder 5 is contaminated.

[0086] The control device 1 irradiates X-rays from the X-ray tube 41 onto the holder 5, which is the target of contamination determination, with the first filter 44 set, and detects the X-rays with the detector 42. The control device 1 generates an X-ray spectrum from the detected X-rays and uses the X-ray spectrum data as a first target signal. Furthermore, the control device 1 irradiates X-rays from the X-ray tube 41 onto the holder 5, which is the target of contamination determination, with the second filter 45 set, and detects the X-rays with the detector 42. The control device 1 generates an X-ray spectrum from the detected X-rays and uses the X-ray spectrum data as a second target signal.

[0087] When determining whether the holder 5 is contaminated, first, a first threshold value and a second threshold value are received. The first threshold value and the second threshold value may be set in advance or may be input by the user via the input device 14. The first threshold value is preferably larger than the second threshold value. The first threshold value and the second threshold value are, for example, 1 to 10%.

[0088] Next, the control device 1 retrieves the first reference signal 1211 and calculates a first difference, which is the difference between the first target signal and the first reference signal 1211 .

[0089] The control device 1 compares the ratio of the first difference to the first reference signal 1211 with a first threshold. If the ratio is greater than the first threshold, the control device 1 causes the display device 13 to display a warning. The warning displayed on the display device 13 is, for example, a message urging the user to replace the holder 5 with a new one, and a message informing the user that measuring a sample using the installed holder 5 will result in a decrease in measurement accuracy. Upon recognizing the warning, the user replaces the holder 5 with a new one.

[0090] The control device 1 compares the ratio of the first difference to the first reference signal 1211 with a first threshold, and if the ratio is less than or equal to the first threshold, the control device 1 calls the second reference signal 1212 and calculates a second difference, which is the difference between the second target signal and the second reference signal 1212.

[0091] The control device 1 compares the ratio of the second difference to the second reference signal 1212 with a second threshold value. If the ratio is greater than the second threshold value, the control device 1 causes the display device 13 to display a warning, as described above.

[0092] In this modified example, the control device 1 displays a warning on the display device 13 when the ratio of the first difference to the first reference signal 1211 is greater than the first threshold value or when the ratio of the second difference to the second reference signal 1212 is greater than the second threshold value in at least one of the cases.However, the control device 1 may also display a warning on the display device 13 when the ratio of the first difference to the first reference signal 1211 is greater than the first threshold value and the ratio of the second difference to the second reference signal 1212 is greater than the second threshold value.

[0093] Furthermore, in this modification, the analyzer 101 includes two filters, the first filter 44 and the second filter 45, but the number of filters is not limited to two, and may be three or more.

[0094] 8 and 9 are flowcharts showing the reference data reception process and the contamination determination process performed by the processor 11 in the analyzer 101. In Fig. 8 and Fig. 9, the same components as those in the flowcharts described in Fig. 5 and Fig. 6 are denoted by the same reference numerals, and detailed description thereof will not be repeated.

[0095] Referring to FIG. 8, in step S250, the control device 1 sets the first filter 44 between the X-ray tube 41 and the holder 5 by the driving mechanism 43, and acquires an X-ray spectrum.

[0096] In step S255, the control device 1 stores the X-ray spectrum data acquired in step S250 in the memory 12 as a first reference signal 1211.

[0097] In step S260, the control device 1 sets the second filter 45 between the X-ray tube 41 and the holder 5 using the drive mechanism 43, and acquires an X-ray spectrum.

[0098] In step S265, the control device 1 stores the X-ray spectrum data acquired in step S260 in the memory 12 as a second reference signal 1212.

[0099] Referring to FIG. 9, in step S450, the control device 1 accepts a first threshold value and a second threshold value.

[0100] In step S455, the control device 1 sets the first filter 44 between the X-ray tube 41 and the holder 5 using the drive mechanism 43, and acquires an X-ray spectrum.

[0101] In step S460, the control device 1 calculates a first difference, which is the difference between the X-ray spectrum data acquired in step S455 and the first reference signal.

[0102] In step S465, the control device 1 calculates the ratio of the first difference to the first reference signal, and determines whether the ratio is greater than the first threshold value received in step S450. If it is determined that the ratio is greater than the first threshold value (YES in step S450), the control device 1 proceeds to step S440; otherwise (NO in step S450), the control device 1 proceeds to step S470.

[0103] In step S470, the control device 1 sets the second filter 45 between the X-ray tube 41 and the holder 5 using the drive mechanism 43, and acquires an X-ray spectrum.

[0104] In step S475, the control device 1 calculates a second difference, which is the difference between the X-ray spectrum data acquired in step S470 and the second reference signal.

[0105] In step S480, the control device 1 calculates the ratio of the second difference to the second reference signal, and determines whether the ratio is greater than the second threshold value received in step S450. If it is determined that the ratio is greater than the second threshold value (YES in step S480), the control device 1 proceeds to step S440; otherwise (NO in step S480), the control device 1 ends the contamination determination process subroutine, and returns the process to FIG. 4.

[0106] According to this modification, a plurality of filters that pass X-rays in different energy bands are used to acquire a signal that serves as a reference for determining whether or not the holder 5 is contaminated. This makes it possible to prevent detection of X-rays with energies other than the energy band of the X-ray of interest, reduce the number of detected X-rays, and improve detection efficiency.

[0107] Furthermore, by using a plurality of filters and threshold values ​​corresponding to each filter, it is possible to set standards for the contamination determination process according to the type of contamination on the holder 5.

[0108] Aspects It will be understood by those skilled in the art that the exemplary embodiments described above are examples of the following aspects.

[0109] (Item 1) In one aspect, the management method is a method for managing a protective member that protects the inside of an X-ray analysis apparatus, and may include a step of acquiring reference data, a step of acquiring target data obtained by irradiating the protective member with X-rays, a step of determining whether the protective member is contaminated based on the reference data and the target data, and a step of issuing a warning if it is determined that the protective member is contaminated.

[0110] According to the management method described in the first aspect, it is possible to reduce the burden on the user of the task of determining whether or not the protection member for preventing contamination in the X-ray analysis apparatus is contaminated.

[0111] (Clause 2) In the management method described in Clause 1, the step of acquiring the reference data may include a step of acquiring an X-ray spectrum obtained by irradiating an unused protective member with X-rays.

[0112] According to the management method described in the second paragraph, it is possible to determine whether the target protective member is contaminated by comparing it with an unused protective member.

[0113] (Clause 3) In the management method according to clause 1 or 2, the warning may include a message urging the user to replace the protective member.

[0114] According to the management method described in the third aspect, the user is notified that the protective member needs to be replaced, and upon recognizing this, the user can replace the protective member.

[0115] (4) In the management method described in any one of paragraphs 1 to 3, the protective member comprises an enclosing tube and a film, the enclosing tube has an outer shape larger than an opening provided in the X-ray analysis device to allow X-rays irradiated from an X-ray irradiation source to pass through, surrounds a sample container that contains a sample, and has a shape that includes an opening on the opening side, and the film may close the opening.

[0116] According to the control method described in the fourth aspect, it is possible to determine whether the protective member including the enveloping tube and the film is contaminated.

[0117] (Clause 5) In the management method described in any one of clauses 1 to 4, the determining step may include a step of calculating a difference between the target data and the reference data, a step of calculating a ratio of the difference to the reference data, and a step of comparing the ratio with a predetermined value.

[0118] According to the management method described in the fifth aspect, it is possible to determine whether the protective member is contaminated or not based on the ratio of the difference between the target data and the reference data to the reference data.

[0119] (Item 6) In the management method according to any one of items 1 to 5, the predetermined value may be 1 to 10%.

[0120] According to the management method described in paragraph 6, when the ratio of the difference between the target data and the reference data is 1 to 10% with respect to the reference data, the protective member is determined to be contaminated.

[0121] (Clause 7) In the management method described in any one of clauses 1 to 6, the determining step may include a step of extracting a first count number, which is the count number of X-rays whose energy magnitude is within a predetermined range in the reference data, a step of extracting a second count number, which is the count number of X-rays whose energy magnitude is within the predetermined range in the target data, and a step of identifying the degree of contamination of the protective member based on the first count number and the second count number.

[0122] According to the management method described in paragraph 7, whether or not the protective member is contaminated is determined based on the count number of X-rays whose energy magnitude is within a predetermined range among the obtained X-ray spectrum data. By using only X-rays whose energy magnitude is within the predetermined range for contamination determination, it is possible to suppress the influence of X-rays whose energy magnitude is outside the predetermined range on the contamination determination.

[0123] (Item 8) In the management method described in any one of Items 1 to 7, the reference data and the target data may be acquired in a state where a filter that passes only X-rays whose energy magnitude is within a predetermined range is provided between the protective member and the X-ray irradiation source of the X-ray analysis device.

[0124] According to the management method described in paragraph 8, the sample is irradiated with X-rays having a predetermined range of energy. This makes it possible to suppress detection of characteristic X-rays and continuous X-rays originating from the X-ray irradiation source in the detector. This improves the detection efficiency of fluorescent X-rays originating from dirt adhering to the protective member.

[0125] (Item 9) In the management method according to any one of items 1 to 8, the predetermined range may be 1 to 7 keV.

[0126] According to the management method described in Section 9, it is possible to determine whether or not the protective member is contaminated based on the number of X-ray counts detected when the protective member is irradiated with X-rays having an energy magnitude of 1 to 7 keV.

[0127] (10) In the management method according to any one of the above items 1 to 8, the predetermined range may be 5 to 15 keV.

[0128] According to the management method described in paragraph 10, it is possible to determine whether or not the protective member is contaminated based on the number of X-ray counts detected when the protective member is irradiated with X-rays having an energy magnitude of 5 to 15 keV.

[0129] (Item 11) In the management method according to any one of items 1 to 8, the predetermined range may be 20 to 30 keV.

[0130] According to the management method described in paragraph 11, it is possible to determine whether or not the protective member is contaminated based on the number of X-ray counts detected when the protective member is irradiated with X-rays having an energy magnitude of 20 to 30 keV.

[0131] (Clause 12) In the management method described in any one of clauses 1 to 11, the determining step may include a step of extracting a first intensity value at a predetermined wavelength in the reference data, a step of extracting a second intensity value at a predetermined wavelength in the target data, and a step of identifying the degree of contamination of the protective member based on the first intensity value and the second intensity value.

[0132] According to the management method described in paragraph 12, it is determined whether the protective member is contaminated or not based on the intensity at a predetermined wavelength in the obtained X-ray spectrum data.

[0133] (Claim 13) The management method according to any one of paragraphs 1 to 12 may further include a step of accepting a first threshold value and a second threshold value that is smaller than the first threshold value, wherein the step of acquiring the reference data includes a step of installing a first filter between the protective member and a detector of the X-ray analysis device, the first filter allowing only X-rays having an energy magnitude within a predetermined range to pass, and acquiring a first reference signal, and a step of installing a second filter between the protective member and the detector, the second filter allowing a portion of X-rays having an energy magnitude lower than that passed by the first filter to pass, and acquiring a second reference signal, wherein the step of acquiring the object data includes a step of installing the first filter between the protective member and the detector and acquiring a first object signal, and a step of installing the second filter between the protective member and the detector and acquiring a second object signal, and wherein the step of determining may include a step of identifying a degree of contamination based on the first reference signal, the first object signal, and the first threshold value, and a step of identifying the degree of contamination based on the second reference signal, the second object signal, and the second threshold value.

[0134] According to the management method described in paragraph 13, a signal that serves as a reference for determining whether or not the protective member is contaminated is obtained using a plurality of filters that pass X-rays in different energy bands. This makes it possible to prevent detection of X-rays with energies other than the energy band of the X-ray of interest, reduce the number of detected X-rays, and improve detection efficiency.

[0135] Furthermore, by using a plurality of filters and threshold values ​​corresponding to each filter, it is possible to set criteria for determining whether or not the holder 5 is contaminated depending on the type of contamination on the holder 5 .

[0136] (Clause 14) In one aspect, the program may be executed by a processor mounted on a computer to cause the computer to acquire reference data, acquire target data obtained by irradiating a protective member with X-rays, determine whether the protective member is contaminated based on the reference data and the target data, and issue a warning if it is determined that the protective member is contaminated.

[0137] According to the program described in the fourteenth aspect, it is possible to reduce the burden on the user of the task of determining whether or not the protection member for preventing contamination in the X-ray analysis apparatus is contaminated.

[0138] (Item 15) An X-ray analysis apparatus in one aspect is an X-ray analysis apparatus that irradiates a sample with X-rays and analyzes the emitted X-rays, and includes: a sample container that stores the sample; a mounting section on which the sample container can be mounted; an X-ray irradiation source that irradiates X-rays onto the sample in the sample container from below the mounting section; a detector that detects X-rays emitted from the sample below the mounting section; a protective member that is installed on the mounting section and protects the inside of the X-ray analysis apparatus; a control device that receives a signal from the detector; and a display device, wherein the control device acquires reference data, irradiates X-rays from the X-ray irradiation source onto the protective member, acquires object data obtained by the detector, determines whether the protective member is contaminated based on the reference data and the object data, and displays a warning on the display device if it is determined that the protective member is contaminated.

[0139] According to the X-ray analysis apparatus described in the fifteenth aspect, it is possible to reduce the burden on the user of the task of determining whether or not the protection member for preventing contamination in the X-ray analysis apparatus is contaminated.

[0140] The embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present invention is defined by the claims, not by the above description, and is intended to include all modifications within the meaning and scope of the claims.

[0141] REFERENCE SIGNS LIST 1 Control device, 2 Main body, 3 Sample chamber, 4 Measurement chamber, 5 Holder, 6 Sample container, 11 Processor, 12 Memory, 13 Display device, 14 Input device, 15 I / O interface, 21, 22 Housing, 23 Sample stage, 24 First surface, 25 Second surface, 26, 51a, 61a Opening, 41 X-ray tube, 42 Detector, 43 Drive mechanism, 44 First filter, 45 Second filter, 51 Surrounding tube, 52, 62 Film, 61 Container body, 100, 101 Analytical device.

Claims

1. A method for managing a protective member that protects the inside of an X-ray analysis device, comprising: a step of acquiring reference data; a step of acquiring target data obtained by irradiating the protective member with X-rays; a step of determining whether the protective member is contaminated based on the reference data and the target data; and a step of issuing a warning if it is determined that the protective member is contaminated.

2. The management method according to claim 1, wherein the step of acquiring the reference data includes a step of acquiring an X-ray spectrum obtained by irradiating an unused protective member with X-rays.

3. The management method according to claim 1, wherein the warning includes a message urging the user to replace the protective member.

4. The management method according to claim 1, wherein the protective member comprises an enclosing tube and a film, the enclosing tube having an outer shape larger than an opening provided in the X-ray analysis device to allow X-rays irradiated from an X-ray irradiation source to pass therethrough, enclosing a sample container that contains a sample and having a shape that includes an opening on the opening side, and the film closing off the opening.

5. The management method described in claim 1, wherein the determining step includes the steps of: calculating the difference between the target data and the reference data; calculating the ratio of the difference to the reference data; and comparing the ratio with a predetermined value.

6. The management method according to claim 5, wherein the predetermined value is 1 to 10%.

7. The management method described in claim 1, wherein the determining step includes: a step of extracting a first count number, which is the count number of X-rays whose energy magnitude is within a predetermined range in the reference data; a step of extracting a second count number, which is the count number of X-rays whose energy magnitude is within the predetermined range in the target data; and a step of identifying the degree of contamination of the protective member based on the first count number and the second count number.

8. The management method according to claim 1, wherein the reference data and the target data are acquired in a state where a filter that allows only X-rays with energy levels within a predetermined range to pass is provided between the protective member and the X-ray irradiation source of the X-ray analysis device.

9. A management method according to claim 7 or claim 8, wherein the predetermined range is 1 to 7 keV.

10. A management method according to claim 7 or claim 8, wherein the predetermined range is 5 to 15 keV.

11. A management method according to claim 7 or claim 8, wherein the predetermined range is 20 to 30 keV.

12. The management method described in claim 1, wherein the determining step includes: a step of extracting a first intensity value at a predetermined energy in the reference data; a step of extracting a second intensity value at a predetermined energy in the target data; and a step of identifying the degree of contamination of the protective member based on the first intensity value and the second intensity value.

13. The management method according to claim 1, further comprising the step of accepting a first threshold value and a second threshold value smaller than the first threshold value, wherein the step of acquiring reference data comprises the steps of: installing a first filter between the protective member and an X-ray irradiation source of the X-ray analysis device, the first filter allowing only X-rays having an energy magnitude within a predetermined range to pass, and acquiring a first reference signal; installing a second filter between the protective member and the X-ray irradiation source, the second filter allowing a portion of X-rays having an energy magnitude lower than that passed by the first filter to pass, and acquiring a second reference signal; wherein the step of acquiring object data comprises the steps of installing the first filter between the protective member and the X-ray irradiation source and acquiring a first object signal; and installing the second filter between the protective member and the X-ray irradiation source and acquiring a second object signal; and wherein the step of determining comprises the steps of: identifying a degree of contamination based on the first reference signal, the first object signal, and the first threshold value; and identifying a degree of contamination based on the second reference signal, the second object signal, and the second threshold value.

14. A program that, when executed by a processor mounted on a computer, causes the computer to: acquire reference data; acquire target data obtained by irradiating a protective member with X-rays; determine whether the protective member is contaminated based on the reference data and the target data; and issue a warning if it is determined that the protective member is contaminated.

15. An X-ray analysis apparatus that irradiates a sample with X-rays and analyzes the emitted X-rays, comprising: a sample container that contains the sample; a mounting section on which the sample container can be mounted; an X-ray irradiation source that irradiates X-rays onto the sample in the sample container from below the mounting section; a detector that detects X-rays emitted from the sample below the mounting section; a protective member that is installed on the mounting section and protects the inside of the X-ray analysis apparatus; a control device that receives signals from the detector; and a display device, wherein the control device acquires reference data, irradiates X-rays from the X-ray irradiation source onto the protective member, and acquires object data obtained by the detector, determines whether the protective member is contaminated based on the reference data and the object data, and displays a warning on the display device if it is determined that the protective member is contaminated.

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