X-ray analysis device and X-ray analysis method

Abstract

The present invention provides an X-ray analysis device and an X-ray analysis method that can easily analyze the valence of a target element in a sample. A controller (22) of a signal processing device of the X-ray analysis device comprises: a storage unit (306) for storing Kα emitted from a metal monomer 1 The peak energy of the radiation and Kα 2 The peak energy of the radiation, the Kα radiation emitted from two or more compounds containing the metal monomer, 1 The peak energy of the radiation and Kα 2 The peak energy of the Kα ray and the valence of the metal of each of the two or more compounds are stored; the processing unit (302) obtains the Kα ray emitted from the metal contained in the unknown sample. 1 The peak energy of the ray and the Kα of the metal 2 The peak energy of the ray; the calculation unit (308) is obtained by 1 The peak energy of the radiation and Kα 2 The peak energy of the radiation is applied to the calibration curve and the average valence of the metal contained in the unknown sample is calculated.

Description

Technical Field

[0001] The present disclosure relates to an X-ray analysis device and an X-ray analysis method. Background Art

[0002] An X-ray analysis device is known that determines the valence of a sample by irradiating the sample with excitation radiation. The sample irradiated with the excitation radiation emits characteristic X-rays having a wavelength determined by the atoms contained in the sample. Therefore, the X-ray analysis device can determine the valence of the sample by detecting the intensity of each wavelength of the characteristic X-rays.

[0003] Atoms have multiple electron shells (K shell, L shell, M shell, etc.). When X-rays are irradiated on atoms contained in a sample, the electrons in the inner core are excited by the energy of the X-rays. Electrons are transferred from the outer shell of the shell (for example, the L shell) to the shell (for example, the K shell) that has become empty due to the excited electrons. The characteristic X-rays emitted when electrons are transferred from the L shell to the K shell are called Kα rays, and the characteristic X-rays emitted when electrons are transferred from the M shell to the K shell are called Kβ rays.

[0004] The following non-patent document 1 discloses an X-ray analyzer that detects the valence of a sample based on the peak energy of Kβ rays. In this X-ray analyzer, a calibration curve showing the relationship between the peak energy of Kβ rays and the valence is generated, and the average valence of the sample is detected based on the calibration curve.

[0005] Prior art literature

[0006] Non-patent literature

[0007] Non-patent document 1: Adachi et al., "Development of a Simultaneous Multi-Emission Wavelength Dispersive X-ray Fluorescence Analyzer (PS-WDXRF)", Shimadzu Review, Vol. 75, No. 3-4, 2018 Summary of the invention

[0008] Technical problem to be solved by the invention

[0009] However, sometimes you want to measure the average valence of a metal (Fe) in a sample that is a mixture of a metal monomer (e.g., Fe) and a compound containing the metal (e.g., Fe2O3). In addition, the valence of Fe as a metal monomer is "0", and the valence of Fe as a compound Fe2O3 is "3". In the sample, when the ratio of Fe to Fe2O3 is, for example, 1:2, the average valence is calculated by (0×1 / 3)+(3×2 / 3), and the average valence of the metal (Fe) is "2".

[0010] As described above, although the valence of a metal monomer (e.g., Fe) is 0, when a sample of the metal monomer is measured by the X-ray analyzer described in Non-Patent Document 1, an average valence different from 0 is detected. Therefore, when calculating the average valence of a sample containing a metal monomer by the X-ray analyzer described in Non-Patent Document 1, there is a problem that an average valence different from the actual average valence is sometimes calculated.

[0011] The present invention has been made to solve the above-mentioned technical problems, and an object of the present invention is to provide an X-ray analysis device and an X-ray analysis method capable of improving the calculation accuracy of the average valence of metals in a sample.

[0012] Solutions for solving the above technical problems

[0013] The X-ray analysis device of the present disclosure includes a device body and a signal processing device. The device body has a spectrometer that splits the characteristic X-rays emitted by the sample irradiated with the excitation ray to detect the intensity of each wavelength. The signal processing device processes the signal output from the device body. The signal processing device has a storage unit that stores a calibration curve generated based on the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metal monomer, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from two or more compounds containing metals and having different valences of the metals, and the valence of the metals of the two or more compounds. In addition, the signal processing device has a calculation unit that is configured to obtain the peak energy of Kα1 rays emitted from the metal contained in the unknown sample and the peak energy of Kα2 rays emitted from the metal based on the intensity of each wavelength detected by the device body, and apply the obtained peak energy of Kα1 rays and the peak energy of Kα2 rays to the calibration curve, thereby calculating the average valence of the metal contained in the unknown sample.

[0014] Effects of the Invention

[0015] According to the present disclosure, it is possible to provide an X-ray analysis device and an X-ray analysis method capable of improving the calculation accuracy of the average valence of metals in a sample. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a schematic diagram of the configuration of the analysis device 100 according to this embodiment.

[0017] Figure 2 It is a diagram schematically showing the internal structure of the device body.

[0018] Figure 3 It is a diagram schematically showing the internal structure of the device body.

[0019] Figure 4It is a diagram showing the relationship between the respective valences of Fe2O3, Fe3O4, and Fe and the peak energy of the Kα1 ray.

[0020] Figure 5 It is a diagram showing the relationship between the respective valences of Fe2O3, Fe3O4, and Fe and the peak energy of the Kα2 ray.

[0021] Figure 6 It is a diagram showing the relationship between the respective valences of Fe2O3, Fe3O4, and Fe and the signs of the peak energies of the Kα1 ray and the Kα2 ray.

[0022] Figure 7 It is a functional block diagram of the controller.

[0023] Figure 8 It is a diagram showing the specific values of the respective valences of Fe2O3, Fe3O4, and Fe and the peak energies of the Kα1 ray and the Kα2 ray.

[0024] Fig. 9 It is a diagram showing an example of a calibration curve for metallic Fe.

[0025] Fig.10 It is a diagram showing an example of a calibration curve for metallic Mn.

[0026] Fig.11 It is a diagram showing an example of a calibration curve for metallic CO.

[0027] Fig.12 It is a diagram showing an example of a calibration curve for metallic Ni.

[0028] Fig.13 It is an example of a flowchart showing the calculation method of the average valence.

[0029] Fig.14 It is a diagram showing the calibration curve generated by the least squares method.

[0030] Fig.15 It is a diagram showing all the composition ratios that the first substance and the second substance can take in tabular form.

[0031] Fig.16 It is a diagram showing the display mode of the determined composition ratio. Detailed implementation mode

[0032] Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, the same or corresponding parts in the drawings are given the same reference numerals, and their descriptions will not be repeated.

[0033] <Configuration of the X-ray analysis device>

[0034] The X-ray analyzer of this embodiment is an X-ray analyzer equipped with a wavelength dispersion type spectrometer. Hereinafter, a wavelength dispersion type fluorescence X-ray analyzer will be described as an example of the X-ray analyzer of this embodiment. The "wavelength dispersion type" is a method of measuring the intensity of characteristic X-rays for each target wavelength by using a spectroscopic element to split characteristic X-rays and detect characteristic X-ray spectra.

[0035] Figure 1 1 is a schematic diagram of the configuration of a wavelength dispersive X-ray fluorescence analyzer (hereinafter also referred to as “analyzer 100 ”) according to the present embodiment. Figure 1 The analysis device 100 includes a device body 10 and a signal processing device 20. The device body 10 is configured to irradiate an excitation ray to a sample and detect characteristic X-rays emitted by the sample. Typical excitation rays are X-rays. Characteristic X-rays and fluorescent X-rays are synonymous. Detection signals corresponding to the characteristic X-rays detected by the device body 10 are sent to the signal processing device 20. The signal processing device 20 includes a controller 22, a display 24, and an operation unit 26. The signal processing device 20 controls the operation of the device body 10. In addition, the signal processing device 20 is configured to process the detection signal sent from the device body 10 and display the results of the analysis on the display 24. The display 24 and the operation unit 26 are connected to the controller 22. The display 24 is composed of a liquid crystal panel that can display images. The operation unit 26 accepts user operation inputs to the analysis device 100. The typical operation unit 26 is composed of a touch panel, a keyboard, a mouse, etc.

[0036] The controller 22 includes a processor 30, a memory 32, a communication interface (I / F) 34, and an input / output I / F 36 as main components. These components are connected to each other via a bus so as to be communicable.

[0037] The processor 30 is typically a CPU (Central Processing Unit) or an MPU (MicroProcessing Unit) or other computing unit. The processor 30 controls the operation of each unit of the analysis device 100 by reading and executing a program stored in the memory 32. Specifically, the processor 30 detects characteristic X-rays emitted from the sample and analyzes the detected characteristic X-ray data by executing the program. Figure 1 In the example of FIG. 1 , although a single processor is illustrated, the controller 22 may be configured to include a plurality of processors.

[0038] The memory 32 is implemented by a non-volatile memory such as a RAM (Random Access Memory), a ROM (Read Only Memory), or a flash memory, and stores programs executed by the processor 30 or data used by the processor 30 .

[0039] The input / output I / F 36 is an interface for exchanging various data among the processor 30 , the display 24 , and the operation unit 26 .

[0040] The communication I / F 34 is a communication interface for exchanging various data with the device body 10, and is implemented through an adapter or a connector, etc. In addition, the communication method may be a wireless communication method based on a wireless LAN (Local Area Network) or the like, or a wired communication method using a USB (Universal Serial Bus) or the like.

[0041] Figure 2 as well as Figure 3 Schematically shows the internal structure of the device body 10. Figure 2 as well as Figure 3 The device body 10 includes a sample holder 110 for holding a sample S, an excitation source 120, a slit 130, a spectroscopic crystal 140, and a detector 150. Figure 2 In the embodiment, the surface of the sample holder 110 holding the sample S is set as the XY plane, and the irradiation direction of the excitation radiation from the excitation source 120 is set as the Z axis direction. The spectroscopic crystal 140 and the detector 150 constitute a "spectrometer". The sample S can be any of solid, liquid and gas, and the sample holder 110 corresponding to the state of the sample S is used.

[0042] The excitation source 120 is an X-ray source that irradiates the sample S with X-rays as excitation light (excitation rays). An electron beam source may be used instead of the X-ray source. The surface of the sample S is irradiated with the excitation light emitted by the excitation source 120. Figure 2 In the example, the excitation light may be irradiated perpendicularly to the surface of the sample S, or the excitation light may be irradiated at an inclined angle to the surface of the sample S.

[0043] In the spectroscopic crystal 140, a specific crystal plane is parallel to the surface of the crystal. It is possible to use only the specific crystal plane for detecting characteristic X-rays, and it is possible to prevent characteristic X-rays that are Bragg reflected on other crystal planes from being erroneously detected.

[0044] like Figure 3 The detector 150 shown has a plurality of detection elements 151. The plurality of detection elements 151 each extend in the Y-axis direction.

[0045] Next, the operation of the analysis device 100 of this embodiment will be described. Figure 2 As shown, when the sample S is held in the sample holder 110 and the excitation radiation is irradiated from the excitation source 120 to the surface of the sample S, characteristic X-rays are emitted from the sample S. The emitted characteristic X-rays have different wavelengths depending on the material constituting the sample S. Figure 2 In the example, the characteristic X-rays emitted by the excitation source 120 irradiate the region from position A1 to position A2 and pass through the slit 130 to reach the spectroscopic crystal 140. Figure 2 In FIG. 1 , characteristic X-rays emitted at positions A1 and A2 are exemplarily shown by dotted lines. Position A2 is located in the positive direction of position A1 in the X-axis direction. Position A1 and position A2 extend in the Y-axis direction (refer to Figure 3 ).

[0046] The characteristic X-ray emitted from the sample S passes through the slit 130 and irradiates the spectroscopic crystal 140. If the angle formed by the spectroscopic crystal 140 and the incident characteristic X-ray is set to θ, the incident angle of the characteristic X-ray is (90-θ) degrees. In order to fix the configuration angle between the surface of the sample S on the sample holder 110 and the surface of the spectroscopic crystal 140, the characteristic X-ray emitted at the position A1 is incident to the spectroscopic crystal 140 at an incident angle of (90-θ1) degrees, and the characteristic X-ray emitted at the position A2 is incident to the spectroscopic crystal 140 at an incident angle of (90-θ2) degrees. That is, depending on the emission position of the characteristic X-ray in the sample S, the incident angle of the characteristic X-ray to the spectroscopic crystal 140 is different.

[0047] Among the characteristic X-rays incident on the spectroscopic crystal 140 from the sample S at an incident angle of (90-θ) degrees, only the characteristic X-rays with a wavelength of λ=(2d / n)sinθ (λ is the wavelength of the characteristic X-rays, d is the crystal plane spacing of the spectroscopic crystal 140, and n is the order) that satisfy the condition of Bragg reflection will be diffracted by the spectroscopic crystal 140 and reach the detector 150.

[0048] Since the characteristic X-ray diffracted by the spectroscopic crystal 140 is emitted at the same angle as the incident angle, the characteristic X-ray reflected by Bragg is detected by the detection element 151 arranged at a position corresponding to the emission angle among the plurality of detection elements 151. Figure 2In the example, among the characteristic X-rays emitted from position A1, the characteristic X-rays satisfying the wavelength λ1=(2d / n)sinθ1 are detected by the detection element 1511. In addition, among the characteristic X-rays emitted from position A2, the characteristic X-rays satisfying the wavelength λ2=(2d / n)sinθ2 are detected by the detection element 1512. In this way, the plurality of detection elements each detect the characteristic X-rays having a wavelength that satisfies the Bragg conditions of a different diffraction angle. In other words, by knowing the detection element that detects the characteristic X-rays, the wavelength contained in the characteristic X-rays can be identified. On the other hand, the wavelength of the characteristic X-rays varies depending on the substance. Therefore, by determining the detection element that detects the characteristic X-rays in the detector 150, the substance contained in the sample of the analysis object can be determined.

[0049] In this way, the spectrometer of the device body 10 separates the characteristic X-rays emitted by the sample S irradiated with the excitation rays, thereby detecting the intensity of each wavelength. The device body 10 sends the intensity of each detection element (the intensity of each of the multiple detection elements) to the signal processing device 20. Thus, the signal processing device 20 can obtain multiple wavelengths and the intensity of the characteristic X-rays corresponding to each of the multiple wavelengths.

[0050] Next, the peak energy calculated by the signal processing device 20 is described. In the energy E and the wavelength λ, the formula E = hc / λ holds. Here, h is Planck's constant and c is the speed of light. According to this formula, the signal processing device 20 obtains the energy and the intensity of the characteristic X-ray corresponding to the energy. The signal processing device 20 measures the energy at which the intensity of the characteristic X-ray reaches a peak (hereinafter referred to as "peak energy").

[0051] In addition, the analysis device 100 of the present embodiment can adjust the average energy resolution by adjusting the size and arrangement of the spectroscopic crystal 140 and the size and arrangement of the detector 150. In addition, the average energy resolution is defined as the value obtained by dividing the difference between the maximum value and the minimum value of the energy of the characteristic X-ray incident on the detector 150 from the irradiation area of ​​the sample surface through the slit 130 and the spectroscopic crystal 140 by the number of detection elements of the detector 150. The maximum value and the minimum value of the energy of the characteristic X-ray are determined by the relative positional relationship between the sample S, the spectroscopic crystal 140 and the detector 150, and the size of the detector 150 in the direction perpendicular to the slit 130. The analysis device 100 of the present embodiment can distinguish between Kα rays and Kβ rays, or Lα rays and Lβ rays for any metal, and can calculate the peak energy of Kα1 rays and the peak energy of Kα2 rays by setting the average energy resolution to 20 eV or less, preferably 2 eV or less. The peak energy can be calculated by any method such as the technique described in Japanese Patent Application Laid-Open No. 2017-223638. 3 / 2 Kα2 rays are based on the transfer of electrons from the L2 energy level (2p orbital) to the K shell. 1 / 2 orbital) to transfer electrons to the K shell.

[0052] Hereinafter, a metal in its simple form is referred to as a “metal simple form”, and a compound containing the metal is referred to as a “metal compound”.

[0053] The unknown sample S sometimes contains a metal monomer and a metal compound of the metal and other elements. For example, when the metal monomer is Fe, the metal compounds are Fe3O4 and Fe2O3. Sometimes the user wants to calculate the average valence of the metal in the metal monomer contained in the unknown sample and two or more compounds containing the metal. The average valence is expressed as the sum of the multiplication values ​​obtained by multiplying the valence of each metal monomer and metal compound by the composition ratio of each substance in the unknown sample S. For example, when the composition ratio of Fe (metal monomer), Fe3O4, and Fe2O3 (metal compound) in the unknown sample S is P:Q:R, the valence of Fe is 0, the valence of Fe in Fe3O4 is 2.6667, and the valence of Fe in Fe2O3 is 3, so the average valence is (P×0+Q×2.6667+R×3) / (P+Q+R).

[0054] In addition, when the average valence is calculated by the analysis device, a calibration curve is generated in advance using a known sample, and the average valence of the unknown sample is calculated using the calibration curve. As such a calibration curve, for example, a calibration curve that associates the peak energy and valence of a known sample as disclosed in Non-Patent Document 1 is known. Here, when the calibration curve is a complex function, the amount of calculation used to generate the calibration curve sometimes increases. Therefore, the calibration curve is preferably a simple function such as a linear function.

[0055] Non-patent document 1 discloses a calibration curve of a linear function obtained from the relationship between the peak energy and the valence of two compounds (NiO and LiNiO2) containing a certain metal. However, in the method of non-patent document 1, as described later, since the relationship between the peak energy and the valence of a single metal with a valence of 0 obviously deviates from the calibration curve, the average valence of the metal cannot be correctly calculated when the sample contains a single metal.

[0056] The inventors conducted various verifications to solve this problem, and found that in metal monomers and metal compounds, the peak energy of Kα1 rays and the peak energy of Kα2 rays shift differently relative to the valence. Based on this understanding, the inventors used a parameter that used the peak energy of Kα1 rays and the peak energy of Kα2 rays, and found that the valence of the metal monomer and the valence of two or more compounds containing the metal can be expressed in a linear relationship (that is, the calibration curve is a linear function). As a result, even if a monomer metal with a valence of 0 is included in the sample, the decrease in the calculation accuracy of the average valence can be suppressed.

[0057] Figure 4 This is a diagram showing the relationship between the valence of Fe2O3, Fe3O4, and Fe and the peak energy of Kα1 radiation. Figure 5 It is a diagram showing the relationship between the valence of each of Fe2O3, Fe3O4, and Fe and the peak energy of Kα2 ray. Figure 4 as well as Figure 5 The horizontal axis shows the peak energy of Kα1 ray and the peak energy of Kα2 ray, and the vertical axis shows the valence. Figure 4 as well as Figure 5 It can be seen that the relationship between the peak energy and valence of the above three metals and metal compounds is not linear. Specifically, the valence value relative to the peak energy of the single metal Fe deviates greatly from the calibration curve calculated based on the case of Fe2O3 and the case of Fe3O4.

[0058] exist Figure 4In the curve, the dot plot of Fe2O3 and the dot plot of Fe3O4 have a linear relationship. However, there is no dot plot of Fe on the straight line connecting these dot plots. Therefore, the straight line connecting these dot plots is not preferred as a calibration curve. Figure 5 This is a graph showing the relationship between the valence of Fe2O3, Fe3O4, and Fe and the peak energy of Kα2 radiation. Figure 5 In order to generate a calibration curve of a linear function, even if the Fe2O3 plot and the Fe3O4 plot are connected, there is no Fe plot on the straight line connecting these plots. Therefore, the straight line connecting these plots is not preferred as a calibration curve. Figure 4 as well as Figure 5 In the present invention, it is also considered to set a curve connecting the dot plot of Fe2O3, the dot plot of Fe3O4 and the dot plot of Fe as a calibration curve, but such a calibration curve becomes a complex function. Therefore, the amount of calculation for generating the calibration curve increases.

[0059] Given that Figure 4 as well as Figure 5 As a result, the inventors found that the relationship between the parameter obtained by combining "the peak energy of Kα1 ray" and "the peak energy of Kα2 ray" and the valence is linear. Specifically, the inventors found that by using "the parameter obtained by subtracting the value obtained by multiplying the peak energy of Kα2 ray of the metal (Fe in this embodiment) by the coefficient n" (Kα1-n·Kα2) as a new index, the valence of metal Fe, Fe2O3 and Fe3O4 becomes linear (see below). Figures 9 to 12 In this embodiment, in order to simplify the calculation process of the average valence, the calibration curve is defined as a linear function y=px+q (hereinafter also referred to as equation (1)). Here, x is the above-mentioned parameter (Kα1-n·Kα2), and y is the average valence.

[0060] Hereinafter, the peak energy of the Kα1 ray of a metal monomer (e.g., Fe) is set to peak energy m1. The peak energy of the Kα2 ray of the metal monomer is set to peak energy m2. The valence of the first metal compound (e.g., Fe3O4) which is one of the two metal compounds is set to valence v. The peak energy of the Kα1 ray of the metal compound is set to a1. The peak energy of the Kα2 ray of the metal compound is set to a2. In addition, the valence of the second metal compound (e.g., Fe2O3) which is the other of the two metal compounds is set to valence w. The peak energy of the Kα1 ray of the metal compound is set to b1. The peak energy of the Kα2 ray of the metal compound is set to b2. Figure 6 These values ​​are summarized in a table. These two metal compounds are compounds containing a metal (Fe) with different valences of the metal.

[0061] In addition, the valence of the metal itself, the valence v contained in the first metal compound, and the valence w contained in the second metal compound are values ​​inherent to the substance. The valence of the metal itself is "0". When the first metal compound is Fe3O4, the valence v is 2.6667. In addition, when the second metal compound is Fe2O3, the valence w is 3.0000.

[0062] As described above, the analysis device 100 can calculate the peak energies m1, m2, a1, a2, b1, and b2. The analysis device 100 receives input of the valences of the first metal compound and the second metal compound from the user.

[0063] By Figure 6 Substitute the valence of the metal into y in the above formula (1), and substitute "m1-n·m2" of the metal into x to generate the following formula (2).

[0064] 0=p·(m1-n·m2)+q(2)

[0065] Similarly, by substituting the valence v of the first metal compound into y in the above formula (1), and substituting "a1-n·a2" of the first metal compound into x, the following formula (3) is generated.

[0066] v=p·(a1-n·a2)+q(3)

[0067] Similarly, by substituting the valence w of the second metal compound (eg, Fe2O3) into y in the above formula (1), and substituting "b1-n·b2" of the second metal compound into x, the following formula (4) is generated.

[0068] w=p·(b1-n·b2)+q(4)

[0069] As shown in equations (2) to (4), a three-dimensional linear equation of coefficient n, slope p, and intercept q is generated. If the three-dimensional linear equation is solved, the coefficient n, slope p, and intercept q are expressed by the following equations (5) to (7).

[0070] n={(vw)·m1-v·b1+w·a1} / {(vw)·m2-v·b2+w·a2} (5)

[0072] p=(vw) / {(a1-b1)-n·(a2-b2)}(6)

[0073] q={w·(a1-n·a2)-v·(b1-n·b2)} / {(a1-a2)-n·(a2-b2)} (7)

[0075] Using the slope p and intercept q calculated from equations (5) to (7), a calibration curve y=px+q is generated, and the coefficient n is determined.

[0076] Since the analysis device 100 makes the relationship between the metal alone and the compound linear by using the calibration curve generated as described above, the average valence can be calculated with high accuracy even when the metal alone is contained in the sample.

[0077] Next, the flow of generating the calibration curve by the controller 22 will be described. The calibration curve may be generated after the analysis device 100 is manufactured and before the analysis device 100 is shipped, or may be generated by a user operation after the analysis device 100 is shipped. Figure 7 3 is a functional block diagram of the controller 22 of the signal processing device 20. The controller 22 includes a processing unit 302, a generating unit 304, a storage unit 306, and a calculating unit 308.

[0078] The processing unit 302 acquires the valences v and w of the first metal compound and the second metal compound respectively input by the user through the operation unit 26. The valences of the first metal compound and the second metal compound respectively may be stored in the storage unit 306 or the like in advance.

[0079] The person who generates the calibration curve (for example, the manufacturer of the analysis device 100) places the metal monomer (known sample) on the sample holder 110, and irradiates the metal monomer with excitation radiation in the device body 10. As a result, the processing unit 302 obtains the peak energy m1 of the Kα1 radiation of the metal monomer and the peak energy m2 of the Kα2 radiation of the metal monomer. The manufacturer places the first metal compound (known sample) on the sample holder 110, and irradiates the first metal compound with excitation radiation in the device body 10. As a result, the processing unit 302 obtains the peak energy a1 of the Kα1 radiation of the first metal compound and the peak energy a2 of the Kα2 radiation of the first metal compound. The manufacturer places the second metal compound (known sample) on the sample holder 110, and irradiates the second metal compound with excitation radiation in the device body 10. As a result, the processing unit 302 obtains the peak energy m1 of the Kα1 radiation of the second metal compound and the peak energy m2 of the Kα2 radiation of the second metal compound. In addition, the metal element, the first metal compound, and the second metal compound are each pressed into powder form and arranged on the sample holder 110 .

[0080] The obtained valence numbers v, w and peak energies m1, m2, a1, a2, b1, b2 are output to the generator 304. The generator 304 calculates the parameters (slope p, intercept q) and coefficient n of the calibration curve. Specifically, the generator 304 substitutes the valence numbers v, w and peak energies m1, m2, a1, a2, b1, b2 into equations (5) to (7) to calculate the parameters and coefficient n of the calibration curve. The calculated parameters and coefficient n of the calibration curve are stored in the storage unit 306.

[0081] Figure 8 : is a diagram showing specific examples of the values ​​of Fe as metal, Fe2O3 as the first metal compound, and Fe3O4 as the second metal compound. Fig. 9 In the example of , the valence number v = 2.6667, the valence number w = 3.0000. In addition, the peak energy m1 = 6403.719, the peak energy a1 = 6403.793, and the peak energy b1 = 6403.780. In addition, the peak energy m2 = 6390.864, the peak energy a2 = 6390.731, and the peak energy b2 = 6390.687.

[0082] By substituting the valence numbers v, w and the peak energies m1, m2, a1, a2, b1, and b2 into equations (5) to (7), the generator 304 calculates n=0.806388, p=14.779, and q=-18477. Fig. 9 is a graph showing a calibration curve generated using the calculated slope p, intercept q, and coefficient n. Fig. 9 In the figure, the valence is shown on the vertical axis (Y axis), and Kα1-n·Kα2 is shown on the horizontal axis (X axis). The calibration curve is y=14.779x-18477, n=0.806388. Figure 4 as well as Figure 5 In the example, the valence of Fe2O3, Fe3O4 and metal Fe is not linearly related. Fig. 9 As shown, in the calibration curve generated by the generator 304 of this embodiment, the valences of Fe2O3, Fe3O4, and metal Fe are linearly related. Fig. 9 By using the calibration curve, even when the sample contains a single metal, the average valence of the metal Fe in the sample can be calculated with high accuracy.

[0083] Fig.10 This is an example of a calibration curve generated by the generator 304 for metal Mn, the first compound MnO, and the second compound MnO 2 . Fig.11 This is an example of a calibration curve generated by the generation unit 304 for metal Co, the first compound CoO, and the second compound Co 3 O 4 . Fig.12This is an example of a calibration curve generated by the generator 304 for metal Ni, the first compound NiO, and the second compound LiNiO2. The storage unit 306 can store, for example, Figures 9 to 12 At least one calibration curve among the calibration curves shown in .

[0084] Next, a method for calculating the average valence of the metal of an unknown sample (analysis target sample) will be described. Fig.13 The flowchart of the method for calculating the average valence is an example. The user identifies that the unknown sample contains at least one of a metal monomer, a first metal compound, and a second metal compound. However, the user cannot identify the average valence of the metal contained in the unknown sample, and the purpose of the analysis device 100 is to calculate the average valence. In addition, the storage unit 306 stores a plurality of calibration curves for each metal of which the average valence is to be measured. For example, the metal Fe is Fig. 9 The calibration curve relates metal Mn to Fig.10 The calibration curve relates metal Co to Fig.11 The calibration curve relates metal Ni to Fig.12 The user uses the operation unit 26 to input the metal to be calculated for the average valence into the signal processing device 20. The signal processing device 20 determines a calibration curve corresponding to the input metal. Here, the unknown sample contains at least one of Fe, Fe2O3, and Fe3O4, and the user inputs metal Fe as the metal to be calculated for the average valence. The signal processing device 20 determines a calibration curve corresponding to the metal Fe (i.e., Fig. 9 The calibration curve) is extracted from the storage unit 306.

[0085] In step S2, the processing unit 302 acquires the peak energy of the Kα1 ray of the metal Fe contained in the unknown sample and the peak energy of the Kα2 ray of the metal based on the detection signal from the device body 10. The peak energy of the Kα1 ray of the metal Fe and the peak energy of the Kα2 ray of the metal are acquired based on the intensity of each wavelength of the characteristic X-ray detected by the device body 10. The acquired peak energy Kα1 and peak energy Kα2 are output to the calculation unit 308.

[0086] Next, in step S4, the calculation unit 308 calculates the average valence of the metal Fe contained in the sample by applying the peak energy Kα1 and the peak energy Kα2 of the metal Fe to the extracted calibration curve. Specifically, the calculation unit 308 substitutes the peak energy Kα1 and the peak energy Kα2 of the metal Fe into “Kα1-n·Kα2” and substitutes the substituted values ​​into Fig. 9The average price is calculated by using the calibration curve of y=14.799x-18477. The calculation unit 308 displays the calculated average price on the display 24 and notifies the user. In addition, the output of the average price may be, for example, printing the average price on paper. The processing unit 302 and the calculation unit 308 correspond to the "calculation unit" of the present disclosure.

[0087] As described above, the analysis device 100 generates a calibration curve in which the valence of the metal monomer and the two metal compounds is linear based on the peak energy of the Kα1 ray and the peak energy of the Kα2 ray of the metal monomer, the peak energy of the Kα1 ray and the peak energy of the Kα2 ray of the two compounds of the metal, and the valence of the metal of the two metal compounds. Then, the analysis device 100 calculates the average valence of the target metal contained in the unknown sample by applying the peak energy of the Kα1 ray for the target metal detected for the unknown sample and the peak energy of the Kα2 ray of the metal to the calibration curve. As described above, in the calibration curve of the present embodiment, since the case of the metal monomer is also taken into account, the average valence of the target metal can be calculated with high accuracy even if the metal monomer is contained in the unknown sample.

[0088] In addition, in the present embodiment, the calibration curve is expressed by a linear function such as y=px+q. Therefore, compared with an analysis device that generates a calibration curve using a complicated function, the calibration curve can be generated with a smaller amount of calculation.

[0089] In addition, in the present embodiment, the coefficient n, the slope p, and the intercept q are obtained by the above-mentioned equations (5) to (7). Therefore, the analysis device 100 can generate a calibration curve by relatively simple calculation.

[0090] Furthermore, the analysis device 100 of the present embodiment displays the calibration curve on the display 24. Therefore, by displaying the calibration curve used for calculation of the average value, the user can understand the calibration curve used.

[0091] In the above description, the analysis of an unknown sample that can be composed of a metal monomer and two metal compounds, and the generation of a calibration curve for the analysis are described. Next, the analysis of an unknown sample that can be composed of a metal monomer and three or more metal compounds, and the generation of a calibration curve for the analysis are described. An example of an unknown sample in this embodiment is an electrode active material contained in a secondary battery. The electrode active material can be a positive electrode active material or a negative electrode active material.

[0092] As such, the charge and discharge action in a secondary battery is cited as an example in which the valence of the target metal contained in the unknown sample changes in four stages. Sometimes, the quality of the secondary battery is checked by repeating the charge and discharge of the secondary battery to produce a conversion reaction of the electrode active material contained in the secondary battery. For example, the conversion reaction of an iron fluoride secondary battery containing metal Fe and Fe fluoride (metal compound) is shown by the following formulas (a) to (c). The charge and discharge of the secondary battery is performed, for example, by the charge and discharge device 170.

[0093]

Number 1

[0094] (a) 1 electron reaction: Fe(III)F3+Li++e - →LiFe(II)F3

[0095] (b) 2-electron reaction: LiFe(II)F3+Li + +e - →LiFe(I)F2+LiF

[0096] (c) 3-electron reaction: LiFe(I)F2+Li + +e - →Fe(0)+2LiF

[0097] Generally, it is preferred that the average valence of a specific metal (here, Fe) changes significantly by charging and discharging the secondary battery. For example, the following secondary batteries are considered qualified: the change in the average valence of Fe caused by discharging a fully charged secondary battery for a specified period is greater than a specified value, and the change in the average valence of Fe caused by charging a fully discharged secondary battery for a specified period is greater than a specified value. On the other hand, a secondary battery in which the change in the average valence of Fe caused by a fully charged secondary battery for a specified period is less than a specified value is considered unqualified. In addition, a secondary battery in which the change in the average valence of Fe caused by charging a fully discharged secondary battery for a specified period is less than a specified value is also considered unqualified.

[0098] In the case of the conversion reaction shown in formula (a) to formula (c), the unknown sample (iron fluoride secondary battery) contains Fe, FeF3, LiFeF3 and LiFeF2. That is, the unknown sample contains a metal monomer (Fe) and three metal compounds (FeF3, LiFeF3, LiFeF2). Hereinafter, LiFeF2 is sometimes referred to as the first metal compound, LiFeF3 is referred to as the second metal compound, and FeF3 is referred to as the third metal compound.

[0099] Next, the generation of a calibration curve for analyzing an unknown sample that may be composed of three metal compounds is described. The analysis device 100 obtains the peak energy of Kα1 radiation and the peak energy of Kα2 radiation for a metal monomer as a known sample and three metal compounds, respectively. Specifically, the metal monomer is pressed into a powder state and is arranged on the sample holder 110. Then, by irradiating the metal monomer with X-rays, the processing unit 302 obtains the peak energy m1 of the Kα1 radiation of the metal and the peak energy m2 of the Kα2 radiation of the metal. In addition, the first metal compound is pressed into a powder state and is arranged on the sample holder 110. Then, the processing unit 302 obtains the peak energy a1 of the Kα1 radiation of the first metal compound and the peak energy a2 of the Kα2 radiation of the first metal compound. In addition, the second metal compound is pressed into a powder state and is arranged on the sample holder 110. Then, the processing unit 302 obtains the peak energy b1 of the Kα1 radiation of the second metal compound and the peak energy b2 of the Kα2 radiation of the second metal compound. The third metal compound is pressed into powder and placed on the sample holder 110. The processor 302 obtains the peak energy c1 of the Kα1 ray of the third metal compound and the peak energy c2 of the Kα2 ray of the third metal compound.

[0100] The valence v of the metal (Fe) for the first metal compound, the valence w of the metal (Fe) for the second metal compound, and the valence s of the metal (Fe) for the third metal compound are input by the user. The processing unit 302 obtains the valence v, the valence w, and the valence s. The valences of the metals (Fe) in the three or more metal compounds are different from each other.

[0101] The acquired valence numbers v, w, s and peak energies m1, m2, a1, a2, b1, b2, c1, c2 are outputted by the generator 304. The generator 304 calculates the coefficient n, the slope p and the intercept q by applying the least square method to the valence numbers v, w, s and the peak energies m1, m2, a1, a2, b1, b2, c1, c2 respectively.

[0102] Fig.14 : is a diagram showing an image of a calibration curve (slope p and intercept q) and coefficient n calculated by the least squares method. Fig.14 In the graph, the metal, the first metal compound, the second metal compound, and the third metal compound are each plotted. The generator 304 calculates the calibration curve (slope p, intercept q) and coefficient n so that the error from the plotting of the metal, the first metal compound, the second metal compound, and the third metal compound is minimized.

[0103] Next, an example of an iron oxide secondary battery different from an iron fluoride secondary battery is described. An iron oxide secondary battery contains metal Fe and Fe oxide (metal compound). The conversion reaction of an iron oxide secondary battery is shown by the following formulas (d) to (f). In this case, the valence of Fe also changes in four stages.

[0104]

Number 2

[0105] (d) 1 electron reaction: F(III)2O3+2Li + +2e - →Li2Fe(II)2O3

[0106] (e) 2-electron reaction: Li2Fe(II)2O3+2Li + +2e - →2LiFe(I)O+Li2O

[0107] (f) 3-electron reaction: 2LiFe(I)O+2Li + +2e - →2Fe(0)+2Li2O

[0108] When the conversion reactions shown in equations (d) to (f) are performed, the unknown sample (iron oxide secondary battery) contains Fe, Fe2O3, Li2Fe2O3, and LiFeO. That is, the unknown sample contains one metal monomer (Fe) and three metal compounds (Fe2O3, Li2Fe2O3, and LiFeO). The generator 304 can generate a calibration curve for the iron oxide secondary battery using the same method as that described for the iron fluoride secondary battery.

[0109] In addition, when the unknown sample contains a metal monomer and more than four metal compounds, the generation unit 304 calculates the coefficient n, slope p and intercept q by the least squares method so that the error between the dot plot of the one metal monomer and the dot plot of the four or more metal compounds is minimized.

[0110] As described above, the signal processing device 20 generates a calibration curve based on the peak energy of the Kα1 ray and the peak energy of the Kα2 ray of the metal alone, the peak energy of the Kα1 ray and the peak energy of the Kα2 ray of each metal of the three or more compounds, and the valence of the metal contained in each of the three or more compounds. Therefore, the signal processing device 20 can generate a calibration curve reflecting the parameters of the metal alone and the three or more compounds.

[0111] Next, an example of calculating the composition ratio of an unknown sample is described. Sometimes the user recognizes that the unknown sample is composed of a first substance and a second substance having different metal valences. The first substance and the second substance are each a metal monomer or a metal compound. The first substance and the second substance having different metal valences are, for example, Fe3O4 and Fe2O3, respectively.

[0112] In this case, the calculation unit 308 may also calculate the composition ratio of the unknown sample based on the calculated average valence ym and output the composition ratio. Hereinafter, the valence of the first substance is referred to as "valence i (i = 1, 2, ..., 7)", and the valence of the second substance is referred to as "valence j (i = 1, 2, ..., 7)". In this case, the ratio of the first substance to the second substance is expressed by the following formula (8).

[0113] First substance: Second substance = 1: (ym-i) / (j-ym) (8)

[0114] Among them, i<ym<j.

[0115] Fig.15 This is a diagram showing in a table all possible composition ratios of the first substance and the second substance when the average valence ym = 2.5. Fig.15 In the figure, the vertical direction of the paper is i, and the horizontal direction of the paper is j. Fig.15 In the example shown, 15 combinations are displayed.

[0116] exist Fig.15 For example, when the valence i of the first substance is 1 and the valence j of the second substance is 5, the corresponding value is "0.6". Therefore, first substance: second substance = 1:0.6 = 5:3.

[0117] The calculation unit 308 passes Fig.15 The table shown displays all possible composition ratios of the first substance and the second substance on the display 24 .

[0118] The analysis device 100 outputs all possible composition ratios of the first substance and the second substance, so that the user can recognize all the composition ratios. In addition, the analysis device 100 calculates the composition ratio of the first substance and the second substance based on the above-mentioned formula (8), so the composition ratio can be calculated.

[0119] The user can grasp the valence of the first substance and the valence of the second substance by other analysis methods such as X-ray diffraction, but may not grasp the composition ratio of the first substance and the second substance. In this case, the calculation unit 308 determines the composition ratio of the valence of the first substance and the valence of the second substance by comparing the valence of the first substance and the valence of the second substance input by the user with all possible composition ratios of the first substance and the second substance, and displays the determined composition ratio on the display 24.

[0120] Fig.16 It is a diagram showing a display form of a determined composition ratio. Fig.16 This is a diagram showing how the composition ratio is displayed when the user inputs, for example, "0" as the valence i of the first substance and "3" as the valence j of the second substance. Fig.16 In the example, the value at which the valence i of the first substance is "0" and the valence j of the second substance is "3" is "5". Therefore, the controller 22 displays the area indicated by "5" more prominently than the other areas on the display 24. By displaying in this way, the user can recognize that the composition ratio of the first substance to the second substance is 1:5. In addition, instead of displaying Fig.16 Table shown or except Fig.16 In addition to the table shown, the controller 22 may display an image of the composition ratio itself (for example, an image of "1:5").

[0121] Furthermore, when the user inputs "2" as the valence of the first substance and "4" as the valence of the second substance, the controller 22 sets Fig.16 The area indicated by "0.33" is displayed on the display 24 more prominently than other areas. By displaying in this way, the user can recognize that the composition ratio of the first substance and the second substance is 1:0.33=3:1. In summary, the user can recognize the composition ratio.

[0122] [Modifications]

[0123] (1) In the above embodiment, the generation unit 304 generates a calibration curve based on the peak energy of Kα1 radiation and the peak energy of Kα2 radiation of the metal alone, the peak energy of Kα1 radiation and the peak energy of Kα2 radiation of two or more compounds containing the metal, and the valence of the metal of the two or more compounds. However, the generation unit 304 may generate a calibration curve based on a plurality of peak energies (e.g., Kβ) based on the transfer of electrons of the metal contained in the sample irradiated with the excitation radiation. 1，3The peak energy of Kα rays and the peak energy of Kα2 rays), multiple peak energies of metal monomers, multiple peak energies of two or more compounds containing metals, and the valence of the metals in two or more compounds are used to generate a calibration curve. When this configuration is adopted, the analysis device obtains multiple peak energies of metals contained in the unknown sample (for example, Kβ 1，3 Then, the analysis device can also calculate the average valence of the metal contained in the unknown sample by applying the obtained multiple peak energies to the calibration curve.

[0124] (2) In the above embodiment, an example of a configuration in which the parameter Kα1-n·Kα2 is substituted into x of y=px+q as the calibration curve is described. However, the parameter may be another parameter as long as it is limited by two types of peak energies. For example, it may be n·Kα1-Kα2.

[0125] [plan]

[0126] Those skilled in the art will appreciate that the above-mentioned multiple exemplary embodiments are specific examples of the following schemes.

[0127] (Item 1) An X-ray analysis device of one embodiment comprises: a device body having a spectrometer for spectroscopically analyzing characteristic X-rays emitted by a sample irradiated with excitation rays to detect the intensity of each wavelength; and a signal processing device for processing a signal output from the device body. The signal processing device has a storage unit for storing a calibration curve generated based on the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from a single metal, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from two or more compounds containing metals and having different valences of the metals, and the valences of the metals of the two or more compounds. In addition, the signal processing device has a calculation unit configured to obtain the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metal contained in the unknown sample based on the intensity of each wavelength detected by the device body, and apply the obtained peak energy of Kα1 rays and the peak energy of Kα2 rays to the calibration curve, thereby calculating the average valence of the metal contained in the unknown sample.

[0128] According to the X-ray analysis apparatus of claim 1, it is possible to improve the calculation accuracy of the average valence of metals in a sample.

[0129] (Item 2) In the X-ray analysis device of Item 1, a calibration curve is represented by y=px+q, where y is a variable indicating an average valence, and x is a parameter obtained by subtracting a value obtained by multiplying a peak energy of Kα2 rays emitted from the metal by a coefficient n from a peak energy of Kα1 rays emitted from the metal, and a signal processing device calculates a slope p, an intercept q, and a coefficient n based on the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from a monomer of the metal, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metal contained in each of two or more compounds, and the valence of the metal contained in each of the two or more compounds, thereby generating a calibration curve.

[0130] According to the X-ray analysis device of claim 2, the amount of calculation for generating a calibration curve can be reduced compared to an analysis method for generating a complicated calibration curve.

[0131] (Item 3) In the X-ray analysis device described in Item 2, the signal processing device displays a calibration curve with the X-axis representing the parameter and the Y-axis representing the average value on the display unit.

[0132] According to the X-ray analysis apparatus of claim 3, by displaying the calibration curve used for calculation of the average valence number, the user can understand the calibration curve used.

[0133] (Item 4) In the X-ray analysis device of Item 2 or Item 3, the two or more compounds contain three or more compounds having metal valences different from each other, and the signal processing device generates a calibration curve by applying the least squares method to the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metal monomer, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metals of the three or more compounds, and the valences of the metals contained in each of the three or more compounds, to calculate the slope p, the intercept q, and the coefficient n.

[0134] According to the X-ray analysis device of item 4, a calibration curve can be generated that reflects the peak energy of Kα1 rays and the peak energy of Kα2 rays of a metal monomer, the peak energy of Kα1 rays and the peak energy of Kα2 rays of each metal of three or more compounds, and the valence of the metal contained in each of the three or more compounds.

[0135] (Item 5) In the X-ray analysis apparatus of Item 2 or Item 3, the two or more compounds include a first compound and a second compound having metal valences different from each other, and in the signal processing apparatus, the peak energy of Kα1 rays emitted from a single metal is set to m1, the peak energy of Kα2 rays emitted from a single metal is set to m2, the valence of the metal contained in the first compound is set to v, the valence of the metal contained in the second compound is set to w, the peak energy of Kα1 rays emitted from the first compound is set to a1, the peak energy of Kα2 rays emitted from the first compound is set to a2, and the peak energy of Kα1 rays emitted from the first compound is set to a3. When the peak energy of Kα1 radiation emitted from the second compound is set to b1 and the peak energy of Kα2 radiation emitted from the second compound is set to b2, the slope p, intercept q and coefficient n are calculated using the equation n={(vw)·m1-v·b1+w·a1} / {(vw)·m2-v·b2+w·a2}p=(vw) / {(a1-b1)-n·(a2-b2)}q={w·(a1-n·a2)-v·(b1-n·b2)} / {(a1-a2)-n·(a2-b2)}, thereby generating a calibration curve.

[0136] According to the X-ray analysis device of item 5, a calibration curve can be generated by relatively simple calculation.

[0137] (Item 6) According to the X-ray analysis device of any one of Items 1 to 5, the unknown sample is composed of a first substance and a second substance having different metal valences, and the signal processing device outputs all possible composition ratios of the first substance and the second substance based on the calculated average valence.

[0138] According to the X-ray analysis apparatus of claim 6, it is possible for the user to recognize all possible composition ratios of the first substance and the second substance.

[0139] (Item 7) In the X-ray analysis device of Item 6, the signal processing device accepts input of the valence of the metal contained in the first substance and the valence of the metal contained in the second substance, and outputs the composition ratio of the first substance and the second substance based on the valence of the metal contained in the first substance, the valence of the metal contained in the second substance and the average valence.

[0140] According to the X-ray analysis apparatus of claim 7, it is possible for a user to recognize the composition ratio between the first substance and the second substance.

[0141] (Item 8) In the X-ray analysis device of Item 7, when the signal processing device sets the valence of the metal contained in the first substance to i, the valence of the metal contained in the second substance to j, and the calculated average valence to ym, the composition ratio of the first substance and the second substance is calculated based on 1: (ym-i) / (j-ym), where i<ym<j.

[0142] According to the X-ray analyzer of claim 8, the composition ratio of the first substance and the second substance can be calculated by relatively simple calculation.

[0143] (Item 9) Another X-ray analysis device of the present invention comprises: a device body having a spectrometer for spectroscopically analyzing characteristic X-rays emitted by a sample irradiated with excitation rays to detect the intensity of each wavelength; and a signal processing device for processing a signal output from the device body. The signal processing device has a storage unit for storing a calibration curve generated based on a plurality of peak energies emitted from a single metal, a plurality of peak energies emitted from two or more compounds containing a metal and having different valences of the metal, and the valence of the metal in each of the two or more compounds. In addition, the signal processing device has a calculation unit configured to obtain a plurality of peak energies of the metal contained in an unknown sample based on the intensity of each wavelength detected by the device body, and to apply the obtained plurality of peak energies to the calibration curve, thereby calculating the average valence of the metal contained in the unknown sample.

[0144] According to the X-ray analysis apparatus of claim 9, it is possible to improve the calculation accuracy of the average valence of metals in a sample.

[0145] (Item 10) An analytical method of one scheme comprises: a step of obtaining the peak energy of Kα1 rays emitted from a metal contained in the unknown sample and the peak energy of Kα2 rays emitted from the metal by spectroscopically analyzing characteristic X-rays emitted from the unknown sample by irradiating the unknown sample with excitation rays; a step of calculating the average valence of the metal contained in the unknown sample by applying the obtained peak energy of Kα1 rays and peak energy of Kα2 rays to a calibration curve generated based on the peak energy of Kα1 rays and peak energy of Kα2 rays emitted from the metal, the peak energy of Kα1 rays and peak energy of Kα2 rays emitted from two or more compounds containing a metal and having different valences of the metals, and the valence of the metal in each of the two or more compounds.

[0146] According to the analysis method of item 10, it is possible to improve the calculation accuracy of the average valence of the metal in the sample.

[0147] The embodiments disclosed this time should be considered as illustrative in all aspects and not restrictive. The scope of the present invention is indicated by the claims rather than the above description, and is intended to include all modifications within the meaning and scope equivalent to the claims.

[0148] Description of Reference Numerals

[0149] 10 Device body

[0150] 20Signal processing device

[0151] 22 Controller

[0152] 24 monitors

[0153] 26 Operation Department

[0154] 30 processors

[0155] 32 Memory

[0156] 100 Analytical Devices

[0157] 110 sample holder

[0158] 120 Excitation source

[0159] 130 Slit

[0160] 140 Spectral Crystal

[0161] 150 detectors

[0162] 170 Charging and discharging device

[0163] 302 Processing Department

[0164] 304 Generation Department

[0165] 306 Storage Department

[0166] 308 Computing Department.

Claims

1. An X-ray analysis device, characterized in that: have: The device body has a spectrometer for splitting characteristic X-rays emitted by the sample irradiated with the excitation ray to detect the intensity of each wavelength; a signal processing device for processing a signal outputted by the device body, The signal processing device comprises: a storage unit storing a calibration curve generated based on the peak energy of Kα1 radiation and the peak energy of Kα2 radiation emitted from a single metal, the peak energy of Kα1 radiation and the peak energy of Kα2 radiation emitted from two or more compounds containing the metal and having different valences of the metal, and the valence of the metal in each of the two or more compounds, wherein the calibration curve is represented by y=px+q, where y is a variable indicating an average valence, and x is a parameter obtained by subtracting a value obtained by multiplying the peak energy of Kα2 radiation emitted from the metal by a coefficient n from the peak energy of Kα1 radiation emitted from the metal; a calculation unit that calculates a slope p, an intercept q, and a coefficient n based on the peak energy of Kα1 radiation and the peak energy of Kα2 radiation emitted from the metal alone, the peak energy of Kα1 radiation and the peak energy of Kα2 radiation emitted from the metal contained in each of the two or more compounds, and the valence of the metal contained in each of the two or more compounds, thereby generating a calibration curve; The calculation unit is configured to obtain the peak energy of Kα1 rays emitted from the metal contained in the unknown sample and the peak energy of Kα2 rays emitted from the metal based on the intensity of each wavelength detected by the device body, The acquired peak energy of Kα1 ray and the peak energy of Kα2 ray are applied to the calibration curve, thereby calculating the average valence of the metal contained in the unknown sample.

2. The X-ray analysis device according to claim 1, wherein: The signal processing device displays the calibration curve with the parameter on the X-axis and the average value on the Y-axis on the display unit.

3. The X-ray analysis device according to claim 1 or claim 2, characterized in that: The two or more compounds include three or more compounds of the metals having different valences from each other, The signal processing device generates the calibration curve by applying the least squares method to the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the monomer of the metal, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from each of the metals in the three or more compounds, and the valence of the metal contained in each of the three or more compounds, to calculate the slope p, the intercept q and the coefficient n.

4. The X-ray analysis device according to claim 1 or claim 2, characterized in that: The two or more compounds include a first compound and a second compound having different valences of the metal. The peak energy of the Kα1 ray emitted from the metal monomer is set to m1, The peak energy of the Kα2 ray emitted from the metal monomer is set to m2, The valence of the metal contained in the first compound is denoted by v, The valence of the metal contained in the second compound is w, The peak energy of the Kα1 ray emitted from the first compound is a1, The peak energy of the Kα2 ray emitted from the first compound is a2, The peak energy of the Kα1 ray emitted from the second compound is defined as b1, When the peak energy of Kα2 radiation emitted from the second compound is defined as b2, the signal processing device uses n={(vw)·m1-v·b1+w·a1} / {(vw)·m2-v·b2+w·a2} p=(vw) / {(a1-b1)-n・(a2-b2)} q=w・(a1-n・a2)-v・(b1-n・b2)} / {(a1-a2)-n・(a2-b2)} Such an equation calculates the slope p, intercept q and coefficient n, generating the calibration curve.

5. The X-ray analysis device according to claim 1 or claim 2, characterized in that: The unknown sample is composed of a first substance and a second substance having different valences of the metal. The signal processing device outputs all composition ratios of the first substance and the second substance based on the calculated average valence.

6. The X-ray analysis device according to claim 5, characterized in that The signal processing device receives input of the valence of the metal contained in the first substance and the valence of the metal contained in the second substance, The composition ratio of the first substance and the second substance is output based on the valence of the metal contained in the first substance, the valence of the metal contained in the second substance, and the average valence.

7. The X-ray analysis device according to claim 6, characterized in that When the valence of the metal contained in the first substance is i, The valence of the metal contained in the second substance is j, When the calculated average price is set to ym, The signal processing device calculates a composition ratio of the first substance to the second substance based on 1:(ym-i) / (j-ym), where i<ym<j.

8. An X-ray analysis method, characterized in that: have: A step of obtaining the peak energy of Kα1 rays emitted from a metal contained in the unknown sample and the peak energy of Kα2 rays emitted from the metal by spectroscopically detecting the intensity of each wavelength by irradiating the unknown sample with excitation rays; The step of calculating the average valence of the metal contained in the unknown sample by applying the obtained peak energy of Kα1 ray and the peak energy of Kα2 ray to a calibration curve generated based on the peak energy of Kα1 ray and the peak energy of Kα2 ray emitted from the metal, the peak energy of Kα1 ray and the peak energy of Kα2 ray emitted from two or more compounds containing the metal and having different valences of the metal, and the valence of the metal in each of the two or more compounds, The calibration curve is represented by y=px+q, y is a variable showing the average price, x is a parameter obtained by subtracting the peak energy of Kα1 rays emitted from the metal from the peak energy of Kα2 rays emitted from the metal multiplied by the coefficient n, Based on the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the monomer of the metal, the peak energy of Kα1 rays and the peak energy of Kα2 rays emitted from the metal contained in each of the two or more compounds, and the valence of the metal contained in each of the two or more compounds, the slope p, the intercept q and the coefficient n are calculated to generate a calibration curve.

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