Fluorescence X-ray analysis device

Abstract

The X-ray fluorescence analysis device of the present invention includes a quantitative mechanism (13) using the FP method, wherein the quantitative mechanism (13) performs: an intensity ratio device sensitivity curve preparation step, wherein the intensity ratio device sensitivity curve is prepared, and the intensity ratio device sensitivity curve is the correlation between the measured intensity ratio as the ratio of the measured intensity of the comparison main component to the measured intensity of the reference main component and the theoretical intensity ratio as the ratio of the theoretical intensity of the comparison main component to the theoretical intensity of the reference main component; an intensity ratio conversion step, wherein the measured intensity ratio is converted into a theoretical intensity scale as a converted measured intensity ratio based on the intensity ratio device sensitivity curve; a content ratio updating step, wherein the content ratio is updated based on the converted measured intensity ratio, and the content ratio is the ratio of the content of the comparison main component to the content of the reference main component; and a content updating step, wherein the content of each component is updated based on the latest content ratio.

Description

[0001] Related Applications

[0002] This application claims the benefit of Japanese Patent Application No. 2021-095721, filed on June 8, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present invention relates to a fluorescent X-ray analyzer which irradiates a sample with X-rays once and obtains the content of components in the sample by a quantitative mechanism using a fundamental parameter method or a calibration curve method based on the measured intensity of the generated fluorescent X-rays. Background Art

[0004] In the past, fluorescent X-ray analysis devices for quantitative analysis were roughly divided into devices based on the calibration curve method and devices based on the fundamental parameter method (also called the FP method). In quantitative analysis based on the calibration curve method, a set of standard samples whose content of components is known is used for the analysis of unknown samples, and a calibration curve is obtained as a correlation between the content of the components and the measured intensity of the fluorescent X-ray (measurement line) corresponding to the measured element of the components. In addition, a component refers to an element or a compound. In addition, in the case where the component is an element, the element itself is the measured element corresponding to the component, and in the case where the component is a compound, the element representing the compound becomes the measured element corresponding to the component (for example, refer to paragraph 0002 of Patent Document 1).

[0005] On the other hand, in the quantitative analysis based on the fundamental parameter method, a set of standard samples with known component contents are used for the analysis of unknown samples, and a device sensitivity curve is obtained as a correlation between the theoretical intensity calculated based on the known contents and the measured intensity (for example, see paragraphs 0009 of Patent Document 1, paragraphs 0003 of Patent Document 2, and Figure 4 ). In addition, the term "concentration ratio" in Patent Document 2 indicates the proportion of a certain component in the whole when the whole is set to 1, which is equivalent to the term "content rate" in the present application, and is not equivalent to the "content rate ratio" described later.

[0006] In addition, in both quantitative analysis based on the calibration curve method and quantitative analysis based on the fundamental parameter method, in order to perform a more accurate analysis depending on the morphology of the sample, a measurement intensity that is corrected in a manner that removes the influence of changes in the height of the analysis surface of the sample on the measurement intensity is used as the measurement intensity, and so-called height correction is performed (for example, refer to claims 2 and 12 of patent document 3).

[0007] In addition, in the quantitative analysis of samples of electronic materials, etc., when high precision is required for the ratio of the content rates of the main components, there is a fluorescent X-ray analysis device that prepares and uses a calibration curve as a correlation between the ratio of the measurement intensity and the ratio of the content rate for a sample of barium titanate composed of two main components (see "e. Calibration curve and measurement example" in non-patent document 1, Figure 13.45, etc.).

[0008] Prior art literature

[0009] Patent Literature

[0010] Patent Document 1: Japanese Patent Application Publication No. 2021-51053

[0011] Patent Document 2: WO2018 / 168939

[0012] Patent Document 3: Japanese Patent Application Publication No. 2002-82075

[0013] Non-patent literature

[0014] Edited by Izumi Nakai, "The Realm of X-Ray Analysis", first edition, 7th printing, Asakura Shoten, January 30, 2011, p.194-195. Summary of the invention

[0015] Problems to be solved by the invention

[0016] However, in non-patent document 1, there is no record of matrix correction (Matrich correction) for removing the effects of the sample's contained elements on the absorption and excitation of fluorescent X-rays. Therefore, when a more accurate analysis of the content ratio of each main component is required, even considering technical common sense, it is not clear how to perform matrix correction on the calibration curve that is the correlation between the ratio of measured intensities and the ratio of contents.

[0017] In addition, in the quantitative analysis based on the fundamental parameter method, in order to analyze the ratio of the content rates of the main components more accurately, it is also considered to prepare and use a device sensitivity curve as a correlation between the ratio of the measured intensity and the ratio of the theoretical intensity for a plurality of main components. However, in the fundamental parameter method, iterative calculations such as updating the content rate are performed based on the theoretical intensity calculated from the assumed content rate and the measured intensity converted to the theoretical intensity scale by the device sensitivity curve, and the content rate after convergence is used as the analysis result. Therefore, even if the device sensitivity curve as a correlation between the ratio of the measured intensity and the theoretical intensity is used, it is not clear how to perform the iterative calculations even if technical common sense is considered.

[0018] The present invention is proposed in view of the above-mentioned existing problems, and its purpose is to provide a fluorescent X-ray analysis device that can calculate the content rate of components in a sample by a quantitative mechanism using a fundamental parameter method or a calibration curve method, and the fluorescent X-ray analysis device can analyze the ratio of the content rates of main components with sufficient accuracy.

[0019] Technical solutions to solve problems

[0020] In order to achieve the above-mentioned purpose, the first scheme of the present invention relates to the following fluorescent X-ray analysis device, which first irradiates a sample with X-rays once, and based on the measured intensity of the generated fluorescent X-rays, calculates the content of the components in the above-mentioned sample by adopting a quantitative mechanism of the fundamental parameter method.

[0021] Next, the quantitative mechanism performs: a standard sample measurement step, wherein, for the standard sample, the intensity of the measurement line of the fluorescent X-ray corresponding to the component is measured, in which a single reference principal component as the principal component constituting the reference and a comparison principal component to be compared with the reference principal component are designated as components, and the content of each component is known; a standard sample theoretical intensity calculation step, wherein, for each measurement line, the theoretical intensity is calculated according to the known content; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio device sensitivity curve is prepared based on the measurement intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step, and the intensity ratio device sensitivity curve is a correlation between a measurement intensity ratio as the ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component and a theoretical intensity ratio as the ratio of the theoretical intensity of the comparison principal component to the theoretical intensity of the reference principal component.

[0022] Then, the quantitative mechanism performs: an unknown sample measurement step, wherein, for an unknown sample in which the reference principal component and the comparison principal component are designated as components and the content of each component is unknown, the intensity of the measurement line is measured; an intensity ratio conversion step, wherein, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, the measurement intensity ratio as the ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component is converted into a theoretical intensity scale as a converted measurement intensity ratio; and a content initial value setting step, wherein the initial value of the content of each component is set.

[0023] In addition, the quantitative mechanism performs: a theoretical intensity calculation step for an unknown sample, wherein the theoretical intensity is calculated for each measurement line based on the latest content; a content ratio updating step, wherein, for each comparison principal component, based on the converted measurement intensity ratio in the intensity ratio conversion step and the theoretical intensity ratio based on the theoretical intensity in the unknown sample theoretical intensity calculation step, the content ratio as the ratio of the content of the comparison principal component to the content of the reference principal component is updated; a content updating step, wherein the content of each component is updated based on the latest content ratio; a convergence judgment step, wherein a convergence judgment is performed based on a predetermined convergence condition; and a result output step, wherein the latest content is output as the content of the component in the unknown sample to be determined, and in the convergence judgment step, if it is judged that no convergence has been achieved, the process is returned to the unknown sample theoretical intensity calculation step, and if it is judged that convergence has been achieved, the process is performed to the result output step.

[0024] In the fluorescent X-ray analysis device of the first embodiment, the quantitative mechanism of the fundamental parameter method is used to perform: an intensity ratio device sensitivity curve preparation step of preparing an intensity ratio device sensitivity curve, the intensity ratio conversion step being a correlation between a measured intensity ratio of the measured intensity of the comparison principal component and the measured intensity of the reference principal component and a theoretical intensity ratio of the theoretical intensity of the comparison principal component and the theoretical intensity of the reference principal component, the intensity ratio conversion step being a step of converting the measured intensity ratio into a theoretical intensity scale based on the intensity ratio device sensitivity curve as a converted measured intensity ratio, the content ratio updating step being a step of updating the content ratio as a ratio of the content of the comparison principal component to the content of the reference principal component based on the converted measured intensity ratio, and the content ratio updating step being a step of updating the content ratio of each component based on the latest content ratio. By performing these steps which are not present in the algorithm of the fundamental parameter method of the prior art, sufficiently accurate analysis can be performed on the content ratio between the principal components.

[0025] A second aspect of the present invention relates to a fluorescent X-ray analyzer that first irradiates a sample with X-rays once and, based on the measured intensity of the generated fluorescent X-rays, determines the content of a component in the sample by a quantitative mechanism using a fundamental parameter method.

[0026] Next, the quantitative mechanism performs: a standard sample measuring step, in which the intensity of the measurement line of the fluorescent X-ray corresponding to the component is measured for the standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and a subcomponent are designated as components, and the content rate of each component is known; a standard sample theoretical intensity calculation step, in which the theoretical intensity is calculated for each measurement line based on the known content rate; and an apparatus sensitivity curve preparation step, in which the theoretical intensity is calculated for each measurement line corresponding to the subcomponent based on the measurement intensity in the standard sample measuring step and the content rate of the standard sample. The theoretical intensity in the theoretical intensity calculation step is used to prepare a device sensitivity curve that is a correlation between the measured intensity of the subcomponent and the theoretical intensity of the subcomponent; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison main component, based on the measured intensity in the above-mentioned standard sample measurement step and the theoretical intensity in the above-mentioned standard sample theoretical intensity calculation step, an intensity ratio device sensitivity curve is prepared, and the above-mentioned intensity ratio device sensitivity curve is a correlation between the measured intensity ratio that is the ratio of the measured intensity of the comparison main component to the measured intensity of the reference main component and the theoretical intensity ratio that is the ratio of the theoretical intensity of the comparison main component to the theoretical intensity of the reference main component.

[0027] In addition, the quantitative mechanism performs: an unknown sample measurement step, in which, for an unknown sample in which the reference principal component, the comparison principal component and the subcomponent are designated as components and the content of each component is unknown, the intensity of the measurement line is measured; an intensity conversion step, in which, for each measurement line corresponding to the subcomponent, based on the measurement intensity in the unknown sample measurement step and the device sensitivity curve in the device sensitivity curve preparation step, the measurement intensity of the subcomponent is converted into a theoretical intensity scale as a converted measurement intensity; an intensity ratio conversion step, in which, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, the measurement intensity ratio, which is the ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, is converted into a theoretical intensity scale as a converted measurement intensity ratio; and a content initial value setting step, in which the initial value of the content of each component is set.

[0028] Furthermore, the quantitative mechanism performs: a step of calculating the theoretical intensity of an unknown sample, wherein the theoretical intensity is calculated for each measurement line based on the latest content; a step of updating the content of a secondary component, wherein the content of each secondary component is updated based on the converted measurement intensity in the intensity conversion step and the theoretical intensity in the step of calculating the theoretical intensity of the unknown sample; and a step of updating the content ratio, wherein the content of the primary component for comparison is updated based on the converted measurement intensity ratio in the intensity ratio conversion step and the theoretical intensity ratio based on the theoretical intensity in the step of calculating the theoretical intensity of the unknown sample for each comparison main component. A content ratio of the ratio of the content ratio of the quasi-principal component; a main component content updating step, wherein the content of the comparison main component and the content of the reference main component are updated based on the latest content ratio and the latest content of the sub-component; a convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and a result output step, outputting the latest content as the content of the component in the unknown sample to be determined, in the above-mentioned convergence judgment step, when it is judged that there is no convergence, the process is returned to the above-mentioned unknown sample theoretical strength calculation step, and when it is judged that there is convergence, the process is proceeded to the above-mentioned result output step.

[0029] In the fluorescent X-ray analysis device of the second aspect, the quantitative mechanism of the fundamental parameter method is used to perform: an intensity ratio device sensitivity curve preparation step of preparing an intensity ratio device sensitivity curve, the intensity ratio conversion step being a correlation between a measured intensity ratio of the measured intensity of the comparison main component and the measured intensity of the reference main component and a theoretical intensity ratio of the theoretical intensity of the comparison main component and the theoretical intensity of the reference main component, the intensity ratio conversion step being a step of converting the measured intensity ratio into a theoretical intensity scale as a converted measured intensity ratio based on the intensity ratio device sensitivity curve, the content ratio updating step being a step of updating the content ratio of the comparison main component and the content ratio of the reference main component based on the converted measured intensity ratio, and the main component content updating step being a step of updating the content ratio of the comparison main component and the content ratio of the reference main component based on the latest content ratio. By performing these steps which are not present in the algorithm of the fundamental parameter method of the prior art, sufficiently accurate analysis can be performed on the content ratio between the main components.

[0030] A third aspect of the present invention relates to a fluorescent X-ray analyzer that first irradiates a sample with X-rays once and, based on the measured intensity of the generated fluorescent X-rays, determines the content of a component in the sample by a quantitative mechanism using a fundamental parameter method.

[0031] Next, the quantitative mechanism performs: a standard sample measuring step, in which the intensity of the measurement line of the fluorescent X-ray corresponding to the component is measured for the standard sample, in which a single reference main component constituting a reference main component, a comparison main component to be compared with the reference main component, and a subcomponent are designated as components, and the content rate of each component is known; a standard sample theoretical intensity calculation step, in which the theoretical intensity is calculated for each measurement line based on the known content rate; and an apparatus sensitivity curve preparation step, in which the theoretical intensity is calculated for each measurement line based on the measurement intensity in the standard sample measuring step and the standard sample. A device sensitivity curve is prepared as a correlation between the measured intensity and the theoretical intensity based on the theoretical intensity in the standard sample theoretical intensity calculation step; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio device sensitivity curve is prepared based on the measured intensity in the above-mentioned standard sample measurement step and the theoretical intensity in the above-mentioned standard sample theoretical intensity calculation step, and the above-mentioned intensity ratio device sensitivity curve is a correlation between the measured intensity ratio as the ratio of the measured intensity of the comparison principal component to the measured intensity of the reference principal component and the theoretical intensity ratio as the ratio of the theoretical intensity of the comparison principal component to the theoretical intensity of the reference principal component.

[0032] In addition, the quantitative mechanism performs: an unknown sample measurement step, wherein, for an unknown sample in which the reference principal component, the comparison principal component and the subcomponent are designated as components and the content of each component is unknown, the intensity of the measurement line is measured; an intensity conversion step, wherein, for each measurement line, based on the measurement intensity in the unknown sample measurement step and the device sensitivity curve in the device sensitivity curve preparation step, the measurement intensity is converted into a theoretical intensity scale as a converted measurement intensity; an intensity ratio conversion step, wherein, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, the measurement intensity ratio, which is the ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, is converted into a theoretical intensity scale as a converted measurement intensity ratio; and a content initial value setting step, wherein the initial value of the content of each component is set.

[0033] In addition, the quantitative mechanism performs: a step of calculating the theoretical intensity of an unknown sample, in which, for each measurement line, the theoretical intensity is calculated based on the latest content; a step of updating the content of a secondary component, in which, for each secondary component, the content is updated based on the converted measurement intensity in the intensity conversion step and the theoretical intensity in the step of calculating the theoretical intensity of the unknown sample; a step of calculating an estimated content, in which, for a comparison main component and a reference main component, the estimated content is calculated based on the converted measurement intensity in the intensity conversion step and the theoretical intensity in the step of calculating the theoretical intensity of the unknown sample; a step of updating the content ratio, in which, for each comparison main component, the estimated content is calculated based on the converted measurement intensity in the intensity ratio conversion step and the theoretical intensity in the step of calculating the theoretical intensity of the unknown sample. The theoretical intensity ratio of the degree is updated, and the content ratio as the ratio of the content of the comparison principal component to the content of the benchmark principal component is updated; a principal component content updating step, wherein the content of the comparison principal component and the content of the benchmark principal component are updated based on the sum of the estimated content of the comparison principal component and the estimated content of the benchmark principal component in the above-mentioned estimated content calculation step and the latest content ratio; a convergence judgment step, wherein a convergence judgment is performed based on a predetermined convergence condition; and a result output step, wherein the latest content as the content of the component in the unknown sample to be determined is output, and in the above-mentioned convergence judgment step, if it is judged that there is no convergence, the process is returned to the above-mentioned unknown sample theoretical strength calculation step, and if it is judged that there is convergence, the process is proceeded to the above-mentioned result output step.

[0034] In the fluorescent X-ray analysis device of the third embodiment, the quantitative mechanism using the basic parameter method performs: an intensity ratio device sensitivity curve preparation step of preparing an intensity ratio device sensitivity curve, an intensity ratio conversion step, an estimated content rate calculation step, a content rate ratio updating step, and a main component content rate updating step, wherein the intensity ratio device sensitivity curve is a correlation between a measured intensity ratio as a ratio of a measured intensity of a comparison main component to a measured intensity of a reference main component and a theoretical intensity ratio as a ratio of a theoretical intensity of the comparison main component to a theoretical intensity of the reference main component, and the intensity ratio conversion step is based on the intensity ratio device sensitivity curve. The sensitivity curve is a step of converting the measured intensity ratio into a theoretical intensity scale, the estimated content calculation step is a step of calculating the estimated content for the comparison principal component and the reference principal component, the content ratio updating step is a step of updating the content ratio as the ratio of the content of the comparison principal component to the content of the reference principal component based on the converted measured intensity ratio, and the main component content updating step is a step of updating the content of the comparison principal component and the content of the reference principal component based on the total of the estimated content of the comparison principal component and the estimated content of the reference principal component and the latest content ratio. By performing these steps that do not exist in the algorithm of the fundamental parameter method of the prior art, a sufficiently accurate analysis is performed on the content ratio between the principal components.

[0035] In the fluorescent X-ray analysis apparatus according to the third aspect, the quantification means skips the subcomponent content rate updating step when the subcomponent is not specified as a component for the standard sample and the unknown sample.

[0036] A fourth aspect of the present invention relates to a fluorescent X-ray analyzer that first irradiates a sample with X-rays once and determines the content of a component in the sample by a quantitative mechanism using a calibration curve method based on the measured intensity of the generated fluorescent X-rays.

[0037] Next, the quantitative mechanism performs: a standard sample measurement step, wherein, for the standard sample, the intensity of the measurement line of the fluorescent X-ray corresponding to the component is measured, in which a single reference principal component as the principal component constituting the reference and a comparison principal component to be compared with the reference principal component are designated as components, the content of each component is known, and an additional correction component for matrix correction is designated from all components; an intensity ratio calibration curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio calibration curve is prepared based on the known content and the measurement intensity in the standard sample measurement step, the intensity ratio calibration curve is a correlation between a measurement intensity ratio as the ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component and a content ratio as the ratio of the content of the comparison principal component to the content of the reference principal component, and includes a matrix correction term.

[0038] In addition, the quantitative mechanism performs: an unknown sample measurement step, wherein, for an unknown sample in which the reference principal component and the comparison principal component are designated as components, the content of each component is unknown and the additional correction component is designated, the intensity of the measurement line is measured; an uncorrected content ratio calculation step, wherein, for each comparison principal component, based on the measured intensity in the unknown sample measurement step and the intensity ratio calibration curve in the intensity ratio calibration curve preparation step, the uncorrected content ratio before matrix correction is calculated; and a content initial value setting step, wherein, for each component, based on the uncorrected content ratio in the uncorrected content ratio calculation step, the uncorrected content before matrix correction is calculated and set as the initial value of the content.

[0039] In addition, the quantitative mechanism performs: a content ratio updating step, in which, for each comparison main component, based on the content of the latest additional correction component, the uncorrected content ratio in the uncorrected content ratio calculation step is subjected to matrix correction to update the content ratio; a content updating step, in which the content of each component is updated based on the content ratio updated in the content ratio updating step; a convergence judgment step, in which a convergence judgment is performed based on a predetermined convergence condition; and a result output step, in which the latest content as the content of the component in the unknown sample to be determined is output, and in the convergence judgment step, if it is judged as non-convergence, the process is returned to the content ratio updating step, and if it is judged as convergence, the process is proceeded to the result output step.

[0040] In the fluorescent X-ray analysis apparatus of the fourth aspect, the quantitative mechanism using the calibration curve method performs: an intensity ratio calibration curve preparation step of preparing an intensity ratio calibration curve, wherein the intensity ratio calibration curve is a correlation between a measured intensity ratio, which is a ratio of a measured intensity of a comparison principal component to a measured intensity of a reference principal component, and a content ratio, which is a ratio of a content of the comparison principal component to a content of the reference principal component, and includes a matrix correction term; an uncorrected content ratio calculation step of calculating an uncorrected content ratio before matrix correction based on the intensity ratio calibration curve; a content ratio update step of updating the content ratio by performing matrix correction on the uncorrected content ratio based on the content of the latest additional correction component; and a content update step of updating the content ratio of each component based on the updated content ratio. By performing these steps which are not present in the algorithm of the calibration curve method of the prior art, sufficiently accurate analysis can be performed on the content ratio between the principal components.

[0041] A fifth aspect of the present invention relates to a fluorescent X-ray analyzer that first irradiates a sample with X-rays once and, based on the measured intensity of the generated fluorescent X-rays, determines the content of a component in the sample by a quantitative mechanism using a calibration curve method.

[0042] In addition, the quantitative mechanism performs: a standard sample measurement step, wherein the intensity of a measurement line of fluorescent X-rays corresponding to a component is measured for the standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and a subcomponent are designated as components, the content of each component is known, and an additional correction component for matrix correction is designated from all components; and a calibration curve preparation step, wherein, for each measurement line corresponding to the subcomponent, the intensity of the measurement line is determined based on the known content and the measurement intensity in the standard sample measurement step. , preparing a calibration curve, the calibration curve is the correlation between the measured intensity of the auxiliary component and the content of the auxiliary component, and includes a matrix correction term; an intensity ratio calibration curve preparing step, wherein, for each measurement line corresponding to the comparison main component, based on the known content and the measured intensity in the above-mentioned standard sample measurement step, an intensity ratio calibration curve is prepared, the intensity ratio calibration curve is the correlation between the measured intensity ratio as the ratio of the measured intensity of the comparison main component to the measured intensity of the reference main component and the content ratio as the ratio of the content of the comparison main component to the content of the reference main component, and includes a matrix correction term;

[0043] In addition, the quantitative mechanism performs: an unknown sample measurement step, in which the intensity of the measurement line is measured for an unknown sample in which the reference principal component, the comparison principal component and the subcomponent are designated as components, the content of each component is unknown and the additional correction component is designated; a subcomponent content initial value setting step, in which, for each subcomponent, based on the measurement intensity in the unknown sample measurement step and the calibration curve in the calibration curve preparation step, the uncorrected content before matrix correction is calculated and set as the initial value of the content; an uncorrected content ratio calculation step, in which, for each comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio calibration curve in the intensity ratio calibration curve preparation step, the uncorrected content ratio before matrix correction is calculated; and a main component content initial value setting step, in which, for the comparison principal component and the reference principal component, based on the uncorrected content ratio in the uncorrected content ratio calculation step and the uncorrected content of the subcomponent in the subcomponent content initial value setting step, the uncorrected content before matrix correction is calculated and set as the initial value of the content.

[0044] Furthermore, the quantitative mechanism performs: a subcomponent content updating step, wherein, for each subcomponent, based on the latest content of the additional correction component, the uncorrected content in the subcomponent content initial value setting step is subjected to matrix correction to update the content; a content ratio updating step, wherein, for each comparative main component, based on the latest content of the additional correction component used in the subcomponent content updating step, the uncorrected content ratio in the uncorrected content ratio calculation step is subjected to matrix correction to update the content ratio; a main component content updating step, wherein, based on the content ratio updated in the content ratio updating step and the content of the subcomponent updated in the subcomponent content updating step, the contents of the comparative main component and the reference main component are updated; a convergence judgment step, wherein a convergence judgment is performed based on a predetermined convergence condition; and a result outputting step, wherein the latest content is output as the content of the component in the unknown sample to be determined, wherein in the convergence judgment step, if it is judged that it has not converged, the process is returned to the subcomponent content updating step, and if it is judged that it has converged, the process is advanced to the result outputting step.

[0045] In the fluorescent X-ray analysis apparatus of the fifth aspect, the quantitative mechanism using the calibration curve method performs: an intensity ratio calibration curve preparation step of preparing an intensity ratio calibration curve, wherein the intensity ratio calibration curve is a correlation between a measured intensity ratio, which is a ratio of a measured intensity of a comparison main component to a measured intensity of a reference main component, and a content ratio, which is a ratio of a content of the comparison main component to a content of the reference main component, and includes a matrix correction term; an uncorrected content ratio calculation step of calculating an uncorrected content ratio before matrix correction based on the intensity ratio calibration curve; a content ratio update step of updating the content ratio by performing matrix correction on the uncorrected content ratio based on the content of the latest additional correction component; and a main component content update step of updating the contents of the comparison main component and the reference main component based on the updated content ratio. By performing these steps which are not present in the algorithm of the calibration curve method of the prior art, sufficiently accurate analysis can be performed on the content ratio between the main components.

[0046] A sixth aspect of the present invention relates to a fluorescent X-ray analyzer that first irradiates a sample with X-rays once and, based on the measured intensity of the generated fluorescent X-rays, determines the content of a component in the sample by a quantitative mechanism using a calibration curve method.

[0047] In addition, the quantitative mechanism performs: a standard sample measurement step, wherein the intensity of a measurement line of fluorescent X-rays corresponding to a component is measured for the standard sample, wherein a single reference principal component constituting a reference principal component, a comparison principal component to be compared with the reference principal component, and a subcomponent are designated as components in the standard sample, the content of each component is known, and an additional correction component for matrix correction is designated from all components; a calibration curve preparation step, wherein a calibration curve is prepared for each measurement line based on the known content and the measurement intensity in the standard sample measurement step, the calibration curve being a correlation between the measurement intensity and the content and including a matrix correction term; an intensity ratio calibration curve preparation step, wherein an intensity ratio calibration curve is prepared for each measurement line corresponding to the comparison principal component based on the known content and the measurement intensity in the standard sample measurement step, the intensity ratio calibration curve being a correlation between a measurement intensity ratio being a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component and a content ratio being a ratio of the content of the comparison principal component to the content of the reference principal component, and including a matrix correction term.

[0048] In addition, the quantitative mechanism performs: an unknown sample measurement step, wherein, for an unknown sample in which the reference principal component, the comparison principal component and the subcomponent are designated as components, the content of each component is unknown and the additional correction component is designated, the intensity of the measurement line is measured; an initial content value setting step, wherein, for each component, based on the measurement intensity in the unknown sample measurement step and the calibration curve in the calibration curve preparation step, the uncorrected content before matrix correction is calculated and set as the initial value of the content; an uncorrected content ratio calculation step, wherein, for each comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio calibration curve in the intensity ratio calibration curve preparation step, the uncorrected content ratio before matrix correction is calculated.

[0049] Furthermore, the quantitative mechanism performs: a subcomponent content updating step, wherein, for each subcomponent, based on the content of the latest additional correction component, the uncorrected content in the content initial value setting step is subjected to matrix correction to update the content; an estimated content calculation step, wherein, for the comparison main component and the reference main component, based on the content of the latest additional correction component used in the subcomponent content updating step, the uncorrected content in the content initial value setting step is subjected to matrix correction to calculate the estimated content; and a content ratio updating step, wherein, for each comparison main component, based on the content of the latest additional correction component used in the subcomponent content updating step, the uncorrected content in the content initial value setting step is subjected to matrix correction to calculate the estimated content. The uncorrected content ratio is subjected to matrix correction to update the content ratio; a main component content updating step, wherein the content of the comparison main component and the content of the baseline main component are updated based on the sum of the estimated content of the comparison main component and the estimated content of the baseline main component in the above-mentioned estimated content calculation step and the content ratio updated in the above-mentioned content ratio updating step; a convergence judgment step, wherein a convergence judgment is performed based on a predetermined convergence condition; and a result output step, outputting the latest content as the content of the component in the unknown sample to be determined, wherein in the above-mentioned convergence judgment step, if it is judged that there is no convergence, the process is returned to the above-mentioned sub-component content updating step, and if it is judged that there is convergence, the process is proceeded to the above-mentioned result output step.

[0050] In the fluorescent X-ray analysis apparatus of the sixth embodiment, a quantitative mechanism using a calibration curve method performs: an intensity ratio calibration curve preparation step of preparing an intensity ratio calibration curve, an uncorrected content ratio calculation step, an estimated content calculation step, a content ratio updating step, and a main component content updating step, wherein the intensity ratio calibration curve is a correlation between a measured intensity ratio constituting a ratio of a measured intensity of a comparison main component to a measured intensity of a reference main component and a content ratio constituting a ratio of a content of the comparison main component to a content of the reference main component, and includes a matrix correction term, and the uncorrected content ratio calculation step is a step of calculating the estimated content ratio based on the intensity ratio calibration curve. The step of calculating the uncorrected content ratio before matrix correction, the step of calculating the estimated content is a step of performing matrix correction on the uncorrected content of the comparison principal component and the reference principal component based on the content of the latest additional correction component and calculating the estimated content, the step of updating the content ratio is a step of performing matrix correction on the uncorrected content ratio and updating the content ratio based on the content of the latest additional correction component, and the step of updating the main component content is a step of updating the content of the comparison principal component and the reference principal component based on the total of the estimated content of the comparison principal component and the estimated content of the reference principal component and the latest content ratio. By performing these steps which do not exist in the algorithm of the calibration curve method of the prior art, sufficiently accurate analysis can be performed on the content ratio between the main components.

[0051] In the fluorescent X-ray analysis apparatus according to the sixth aspect, the quantitative means skips the subcomponent content rate updating step when the subcomponent is not specified as a component for the standard sample and the unknown sample.

[0052] In the fluorescent X-ray analysis device of the present invention, the quantitative mechanism may use, as the measurement intensity in the standard sample measurement step and the measurement intensity in the unknown sample measurement step, a measurement intensity that has been corrected in such a manner as to remove the influence of the change in the height of the analysis surface of the sample on the measurement intensity. By performing height correction in this way according to the form of the sample, a more accurate analysis can be performed on the ratio of the content rates of the main components.

[0053] Any combination of at least two structures disclosed in the claims and / or the specification and / or the drawings is also included in the present invention. In particular, any combination of more than two of the claims in the claims is also included in the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0054] The present invention can be more clearly understood by referring to the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and the accompanying drawings are for illustration and description only and should not be used to limit the scope of the present invention. The scope of the present invention is determined by the claims. In the accompanying drawings, the same reference numerals in multiple drawings represent the same parts.

[0055] Figure 1 This is a flowchart showing the operation of the quantitative mechanism of the fluorescent X-ray analyzer according to the first embodiment of the present invention;

[0056] Figure 2 This is a flowchart showing the operation of the quantitative determination mechanism included in the fluorescent X-ray analysis apparatus according to the second embodiment of the present invention.

[0057] Figure 3 This is a flowchart showing the operation of the quantitative mechanism of the fluorescent X-ray analyzer according to the third embodiment of the present invention;

[0058] Figure 4 This is a flowchart showing the operation of the quantitative mechanism of the fluorescent X-ray analyzer according to the fourth embodiment of the present invention;

[0059] Figure 5 This is a flowchart showing the operation of the quantitative mechanism of the fluorescent X-ray analyzer according to the fifth embodiment of the present invention;

[0060] Figure 6This is a flowchart showing the operation of the quantitative mechanism of the fluorescent X-ray analysis device according to the sixth embodiment of the present invention;

[0061] Figure 7 It is a schematic diagram showing the fluorescent X-ray analysis apparatus according to the first to sixth embodiments of the present invention. DETAILED DESCRIPTION

[0062] Hereinafter, a fluorescent X-ray analyzer according to a first embodiment of the present invention will be described. Figure 7 As shown in the figure, the fluorescent X-ray analyzer of the first embodiment is a scanning type fluorescent X-ray analyzer that measures the intensity of the secondary X-ray 5 generated by irradiating the sample 1, 14 (including both the unknown sample 1 and the standard sample 14) with the primary X-ray 3, and the fluorescent X-ray analyzer includes: a sample stand 2 on which the sample 1, 14 is placed; an X-ray source 4 such as an X-ray tube that irradiates the sample 1, 14 with the primary X-ray 3; a spectroscopic element 6 that spectrally separates the secondary X-ray 5 such as the fluorescent X-ray generated from the sample 1, 14; and a detector 8 that detects the intensity of the secondary X-ray 7 incident on the spectroscopic element 6. The output of the detector 8 is input to a control mechanism 11 such as a computer that controls the entire device via an amplifier, a wave height analyzer, a counting mechanism, etc. that are not shown in the figure.

[0063] The fluorescence X-ray analyzer of the first embodiment is a wavelength dispersive and scanning fluorescence X-ray analyzer, and includes a linkage mechanism 10, a so-called goniometer, which links the spectroscopic element 6 and the detector 8 in a manner that changes the wavelength of the secondary X-ray 7 incident on the detector 8. When the secondary X-ray 5 is incident on the spectroscopic element 6 at a certain incident angle θ, the extension line 9 of the secondary X-ray 5 and the secondary X-ray 7 split (diffracted) by the spectroscopic element 6 form a splitting angle 2θ that is twice the incident angle θ. However, the linkage mechanism 10 rotates the spectroscopic element 6 about an axis O that passes through the center of the surface of the spectroscopic element and is perpendicular to the paper surface, so that the detector 8 rotates about the axis O by twice the rotation angle, so that the detector 8 rotates along a circle 12 about the axis O. The value of the spectral angle 2θ (2θ angle) is input from the linkage mechanism 10 to the control mechanism 11 .

[0064] The fluorescent X-ray analyzer of the first embodiment includes a quantitative mechanism 13 as a program loaded in the control mechanism 11, and the quantitative mechanism 13 using the fundamental parameter method based on the measured intensity of the fluorescent X-ray 5 determines the content of the components in the samples 1 and 14. In addition, in the present invention, the fluorescent X-ray analyzer may be a wavelength dispersive and multi-element simultaneous analysis type fluorescent X-ray analyzer, or an energy dispersive fluorescent X-ray analyzer.

[0065] Next, follow Figure 1 The operation of the quantitative mechanism 13 of the fluorescent X-ray analyzer of the first embodiment is described with reference to the flowchart. The quantitative mechanism 13 first designates a single reference principal component b as a principal component constituting a reference and a single or multiple comparison principal components i1 to be compared with the reference principal component b as components i (including b and i1) in the standard sample measurement step, and the content rate W of each component i is calculated. i (including W b , W i1 ) is a known standard sample 14, and the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i is measured. The measured intensity I of the component i iM Including the measured intensity I of the reference principal component b bM and compare the measured intensity I of principal component i1 i1M .

[0066] Then, in the standard sample theoretical strength calculation step, for each measurement line, based on the known content W i , the theoretical strength I is calculated by the known theoretical strength formula iT (Including I bT ,I i1T ).

[0067] Then, in the intensity ratio device sensitivity curve preparation step, for each measurement line corresponding to the comparison main component i1, based on the measurement intensity I iM And the theoretical strength I in the above standard specimen theoretical strength calculation steps iT , making the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the theoretical intensity I i1T Theoretical intensity I with the benchmark principal component b bT The theoretical intensity ratio I i1bRT (i.e., I i1bRT =Ii1T / I bT ) is the intensity ratio device sensitivity curve of the correlation between . Specifically, the intensity ratio device sensitivity coefficient A of the following formula (1) representing the intensity ratio device sensitivity curve is obtained: i1R , B i1R , C i1R .

[0068] I i1bRT =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(1)

[0069] Next, in the unknown sample measurement step, the reference principal component b and the comparative principal component i1 are designated as components i, and the content ratio W of each component i is calculated. i Unknown unknown sample 1, measure the intensity I of the above measurement line iM .

[0070] Then, in the intensity ratio conversion step, based on each measurement line corresponding to the comparison principal component i1, the measured intensity I i1M ,I bM The intensity ratio device sensitivity curve (Formula (1)) in the intensity ratio device sensitivity curve preparation step is used as the measured intensity I of the main component i1 for comparison. i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM The intensity ratio I was converted to the theoretical intensity scale as shown in the following formula (2): i1bRTM .

[0071] I i1bRTM =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(2)

[0072] Next, in the content initial value setting step, the initial value W of the content of each component i1, b is set. i1 (0), W b (0) Specifically, first, for each comparison main component i1, the content ratio W of the comparison main component i1 is i1 The content ratio W of the reference principal component b b Ratio of content ratio R i1b The initial value R i1b (0) is set as shown in the following formula (3).

[0073] R i1b (0) = I i1bRTM / (I i1TPure / I bTPure )…(3)

[0074] I i1bRTM : the converted measured intensity ratio obtained in the intensity ratio conversion step;

[0075] I i1TPure : The theoretical intensity of the component i1 in the sample consisting only of the comparison main component i1;

[0076] I bTPure : Theoretical strength of component b in a sample consisting only of the reference main component b.

[0077] Then, based on the initial value R of the content ratio i1b (0), the initial value W of the content of each component i1 and b is calculated and set by the following formulas (4) and (5): i1 (0), W b (0).

[0078] W b (0) = 100 / (1 + ΣR i1b (0))…(4)

[0079] W i1 (0) = R i1b (0)×W b (0)…(5)

[0080] In addition, the initial value W of the content ratio of each component i (i1, b) in the fundamental parameter method is i (0)(W i1 (0), W b There are various known methods for setting the initial value W, so it is also possible to appropriately select from these methods and use them instead of using the above-mentioned formulas (3) to (5). For example, the average value of the known content of each component in a plurality of standard samples can be calculated and set as the initial value W i1 (0), W b (0), the value obtained by simply dividing 100 (mass %) by the amount of the component is set as the initial value W of the content of each component. i1 (0), W b (0). In this case, the ratio of the initial value of the content W i1 (0) / W b (0) As the initial value R of the content ratio i1b (0) It can also be set in the content ratio initial value setting step. In addition, in the content ratio initial value setting step, the initial value R of the content ratio is not set.i1b (0), in the first content ratio updating step described later, by changing the ratio of the initial content ratio to W i1 (0) / W b (0) is set as the content ratio R before updating i1b (n-1), you can also set the initial value R of the content ratio i1b (0).

[0081] Next, the calculation is repeated. In the unknown sample theoretical strength calculation step, for each measurement line, based on the latest content W i (n-1), the theoretical strength I is calculated by the known theoretical strength formula iT (n-1). Here, the content W i (n), the content ratio R as follows i1b The numerical value n in (n) represents the update content W i , content ratio R i1b The number of times of repeated calculation is repeated, and the first calculation is regarded as the first time (n=1) and the calculation of the initial value before the repeated calculation is regarded as the 0th time (n-1=0). The definition of the value n is the same in the devices of other embodiments.

[0082] Next, in the content ratio updating step, for each comparison main component i1, the intensity ratio I is measured based on the conversion in the intensity ratio conversion step. i1bRTM and the theoretical strength I in the above unknown sample theoretical strength calculation step i1T (n-1), I bT The theoretical intensity ratio of (n-1) is I i1bRT (n-1) (i.e., I i1bRT (n-1) = I i1T (n-1) / I bT (n-1)), the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1)(i.e., R i1b (n-1) = W i1 (n-1) / W b (n-1)) is updated as shown in the following formula (6) to R i1b Here, the content ratio R before updating is i1b (n-1), in the first repeated calculation, as described above, the ratio W of the initial value of the content is adopted i1 (0) / W b In the second recalculation, the content ratio W updated in the previous recalculation is used.i1 (n-1) / W b (n-1).

[0083] R i1b (n) = R i1b (n-1)×(I i1bRTM / I i1bRT (n-1))…(6)

[0084] Next, in the content updating step, based on the latest content ratio R i1b (n), the content ratio W of each component i1 and b i1 (n-1), W b (n-1) is updated to W obtained by the following equations (7) and (8): i1 (n), W b (n).

[0085] W b (n) = 100 / (1 + ΣR i1b (n))…(7)

[0086] W i1 (n) = R i1b (n)×W b (n)…(8)

[0087] Next, in the convergence judgment step, convergence judgment is performed based on a predetermined convergence condition. Here, as the predetermined convergence condition, based on a well-known method, for example, the ratio W of the content before and after the update in the content updating step is considered. i (n) / W i The absolute value of the difference between (n-1) and 1 is less than a predetermined value, and the number of repeated calculations n reaches a predetermined number. Then, the following process is repeated, that is, if the predetermined convergence condition is not met, it is judged as non-convergence (no), the process is returned to the unknown sample theoretical strength calculation step, and the content W updated in the content update step is replaced by i (n) is the latest content W i (n-1), until the convergence judgment step. On the other hand, when the predetermined convergence condition is satisfied, it is judged as convergence (yes), the iterative calculation is terminated, and the flow proceeds to the result output step.

[0088] In the result output step, the content W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0089] As described above, in the fluorescent X-ray analyzer of the first embodiment, the quantitative mechanism 13 using the fundamental parameter method performs the following steps: i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM , and the theoretical intensity I of the principal component i1 as a comparison i1T Theoretical intensity I with the benchmark principal component b bT The theoretical intensity ratio I i1bRT The intensity ratio device sensitivity curve preparation step of the intensity ratio device sensitivity curve of the correlation between the intensity ratio device sensitivity curve and the intensity ratio device sensitivity curve preparation step of measuring the intensity ratio I i1bRM The intensity ratio I was converted to the theoretical intensity scale and used as the conversion measurement i1bRTM Intensity ratio conversion steps; based on the conversion determination intensity ratio I i1bRTM , the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1) is updated to R i1b (n) content rate update step; based on the latest content rate ratio R i1b (n), the content ratio W of each component i1 and b i1 (n-1), W b (n-1) is updated to W i1 (n), W b By performing these steps which are not present in the algorithm of the fundamental parameter method of the prior art, the content ratio R between the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0090] In the quantitative analysis based on the fundamental parameter method in the fluorescent X-ray analyzer of the first embodiment, the intensity ratio device sensitivity curve as the correlation between the measured intensity ratio and the theoretical intensity ratio as shown in formula (1) is used for the main component, but the past device sensitivity curve as the correlation between the measured intensity and the theoretical intensity is not used. Such a quantitative method is called the first component quantitative method.

[0091] Next, the fluorescence X-ray analysis device of the second embodiment will be described. In the fluorescence X-ray analysis device of the second embodiment, the first component quantification method of the fundamental parameter method is used similarly to the fluorescence X-ray analysis device of the first embodiment, but the standard sample and the unknown sample used as the object include not only the main component but also the subcomponent. The subcomponent is, for example, a low-content component, which is a component for which the intensity ratio device sensitivity curve is not prepared for the corresponding measurement line. Since the scheme of the fluorescence X-ray analysis device of the second embodiment is different from that of the fluorescence X-ray analysis device of the first embodiment only in the operation of the quantification mechanism 13 it has, according to Figure 2 The different actions are described in detail with reference to the flowchart of FIG.

[0092] The quantitative mechanism 13 firstly designates a single reference principal component b as a principal component constituting a reference, a single or multiple comparison principal components i1 to be compared with the reference principal component b, and a single or multiple subcomponents i2 as components i (including b, i1, and i2) in the standard sample measurement step, and calculates the content rate W of each component i. i (including W b , W i1 , W i2 ) is a known standard sample 14, and the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i is measured. Here, the measured intensity I of the component i iM The measured intensity I including the reference principal component b bM , compare the measured intensity I of the principal component i1 i1M and the measured intensity I of the secondary component i2 i2M .

[0093] Next, in the standard sample theoretical strength calculation step, for each measurement line, based on the known content W i , the theoretical strength I is calculated by the known theoretical strength formula iT (Including I bT ,I i1T ,I i2T ).

[0094] Then, in the device sensitivity curve preparation step, for each measurement line corresponding to the subcomponent i2, based on the measurement intensity I in the above-mentioned standard sample measurement step, i2M And the theoretical strength I in the above standard specimen theoretical strength calculation steps i2T , making the measured intensity I as the secondary component i2 i2M , and the theoretical strength I of the secondary component i2 i2T Specifically, the device sensitivity coefficient A of the following equation (9) representing the device sensitivity curve is obtained: i2 , B i2, C i2 .

[0095] I i2T =A i2 I i2M 2 +B i2 I i2M +C i2 …(9)

[0096] Next, similarly to the fluorescent X-ray analyzer of the first embodiment, in the intensity ratio device sensitivity curve preparation step, for each measurement line corresponding to the comparison main component i1, based on the measurement intensity I in the above-mentioned standard sample measurement step, iM And the theoretical strength I in the above standard specimen theoretical strength calculation steps iT , make an intensity ratio device sensitivity curve, which is the measured intensity I of the comparison principal component i1 and the reference principal component b bM Determination intensity I i1M The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the theoretical intensity I i1T Theoretical intensity I with the benchmark principal component b bT The theoretical intensity ratio I i1bRT (i.e., I i1bRT =I i1T / I bT Specifically, the intensity ratio device sensitivity coefficient A of the following formula (1) representing the intensity ratio device sensitivity curve is obtained: i1R , B i1R , C i1R .

[0097] I i1bRT =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(1)

[0098] Then, in the unknown sample measurement step, the reference main component b, the comparative main component i1, and the subcomponent i2 are designated as components i, and the content ratio W of each component i is i Unknown unknown sample 1, measure the intensity I of the above measurement line iM .

[0099] Then, in the intensity conversion step, for each measurement line corresponding to the subcomponent i2, the intensity Ii2M The device sensitivity curve (Equation (9)) in the above-mentioned device sensitivity curve preparation step is converted into the measured intensity I of the secondary component i2. i2M The theoretical intensity scale is converted as shown in the following formula (10), and the converted measured intensity I i2TM .

[0100] I i2TM =A i2 I i2M 2 +B i2 I i2M +C i2 …(10)

[0101] Next, similarly to the fluorescent X-ray analyzer of the first embodiment, in the intensity ratio conversion step, for each measurement line corresponding to the comparison main component i1, based on the measurement intensity I in the above-mentioned unknown sample measurement step, i1M ,I bM The intensity ratio device sensitivity curve (Formula (1)) in the intensity ratio device sensitivity curve preparation step is used as the measured intensity I of the main component i1 for comparison. i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM The intensity ratio I was converted to the theoretical intensity scale as shown in the following formula (2): i1bRTM .

[0102] I i1bRTM =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(2)

[0103] Then, in the content initial value setting step, the initial value W of the content of each component i1, b, i2 is set. i1 (0), W b (0), W i2 (0) Specifically, first, for each comparison main component i1, the content ratio W of the comparison main component i1 is i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b The initial value R i1b (0) is set as shown in the following formula (3).

[0104] R i1b (0) = I i1bRTM / (I i1TPure / I bTPure )…(3)

[0105] I i1bRTM : the converted measured intensity ratio obtained in the intensity ratio conversion step;

[0106] I i1TPure : The theoretical intensity of the component i1 in the sample consisting only of the comparison main component i1;

[0107] I bTPure : Theoretical strength of component b in a sample consisting only of the reference main component b.

[0108] In addition, for each subcomponent i2, the initial value W of the content is i2 (0) is set as shown in the following formula (11).

[0109] W i2 (0)=(I i2TM / I i2TPure )×100…(11)

[0110] I i2TM : The converted measured strength obtained in the strength conversion step;

[0111] I i2TPure : Theoretical strength of component i2 in a sample consisting of only subcomponent i2.

[0112] Then, based on the initial value R of the content ratio i1b (0) Initial value W of the content of the secondary component i2 i2 (0), the initial value W of the content ratio of the main component i1 is compared i1 (0) W of the content ratio of the reference principal component b b (0) is calculated and set by the following equations (12) and (5).

[0113] W b (0) = (100-ΣW i2 (0)) / (1+ΣR i1b (0))…(12)

[0114] W i1 (0) = R i1b (0)×W b (0)…(5)

[0115] In addition, instead of the above method, similarly to the description of the fluorescent X-ray analyzer of the first embodiment, for example, the average value of the content of each component known in a plurality of standard samples may be obtained and used as the initial value W. i1 (0), W b (0), W i2(0), and the value obtained by simply dividing 100 (mass %) by the amount of the component is set as the initial value W of the content of each component. i1 (0), W b (0), W i2 (0). The initial value R of the content ratio in this case is i1b The setting of (0) is also the same as that described in relation to the fluorescent X-ray analysis apparatus according to the first embodiment.

[0116] Next, the calculation is repeated. As in the fluorescent X-ray analyzer of the first embodiment, in the unknown sample theoretical intensity calculation step, based on the latest content W for each measurement line, i (n-1), the theoretical strength is calculated by the known theoretical strength formula iT (n-1).

[0117] Then, in the subcomponent content updating step, the intensity I is measured based on the conversion in the above-mentioned intensity conversion step for each subcomponent i2. i2TM and the theoretical strength I in the above unknown sample theoretical strength calculation step i2T (n-1), as shown in the following formula (13), the content W i2 (n-1) is updated to W i2 (n).

[0118] W i2 (n) = W i2 (n-1)×(I i2TM / I i2T (n-1))…(13)

[0119] Then, similarly to the fluorescent X-ray analyzer of the first embodiment, in the content ratio updating step, the intensity ratio I1 is measured based on the conversion in the intensity ratio conversion step for each comparison main component i1. i1bRTM and the theoretical strength I in the above unknown sample theoretical strength calculation step i1T (n-1), I bT The theoretical intensity ratio of (n-1) is I i1bRT (n-1) (i.e., I i1bRT (n-1) = I i1T (n-1) / I bT (n-1)), the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1)(i.e., R i1b (n-1) = W i1 (n-1) / W b(n-1)) is updated as shown in the following formula (6) to R i1b (n).

[0120] R i1b (n) = R i1b (n-1)×(I i1bRTM / I i1bRT (n-1))…(6)

[0121] Then, in the main component content updating step, based on the latest content ratio R i1b (n) and the latest content W of the secondary component i2 i2 (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W obtained by the following equations (14) and (8): i1 (n) and W b (n).

[0122] W b (n)=(100-ΣW i2 (n)) / (1+ΣR i1b (n))…(14)

[0123] W i1 (n) = R i1b (n)×W b (n)…(8)

[0124] Next, similarly to the fluorescent X-ray analysis device of the first embodiment, in the convergence judgment step, convergence judgment is performed based on the predetermined convergence condition. When the predetermined convergence condition is not met, it is judged as non-convergence (No), and the process is returned to the unknown sample theoretical intensity calculation step. When the predetermined convergence condition is met, it is judged as convergence (Yes), and the process is performed to the result output step.

[0125] Then, similarly to the fluorescent X-ray analyzer of the first embodiment, in the result output step, the content rate W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0126] As described above, in the fluorescent X-ray analyzer of the second embodiment, the quantitative mechanism 13 using the fundamental parameter method performs the following operations: creating the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM , and the theoretical intensity I of the principal component i1 as a comparison i1T Theoretical intensity I with the benchmark principal component bbT The theoretical intensity ratio I i1bRT The intensity ratio device sensitivity curve preparation step of the intensity ratio device sensitivity curve of the correlation between the intensity ratio device sensitivity curve and the intensity ratio device sensitivity curve of the correlation between the intensity ratio device sensitivity curve and the intensity ratio device sensitivity curve i1bRM The intensity ratio I was converted to the theoretical intensity scale and used as the conversion measurement i1bRTM Intensity ratio conversion steps; based on the conversion determination intensity ratio I i1bRTM , the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1) is updated to R i1b (n) content ratio updating step; based on the latest content ratio R i1b (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W i1 (n), W b (n) Main component content updating step. By performing these steps which are not present in the algorithm of the fundamental parameter method of the prior art, the content ratio R of the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0127] Next, the third embodiment of the fluorescent X-ray analysis device is described. In the third embodiment of the fluorescent X-ray analysis device, unlike the first and second embodiments of the fluorescent X-ray analysis device, the second component quantitative method of the fundamental parameter method described later is used. The standard sample and the unknown sample as the object contain not only the main component but also the subcomponent. Since the structure of the fluorescent X-ray analysis device as the third embodiment is different from that of the fluorescent X-ray analysis device of the first and second embodiments only in the operation of the quantitative mechanism 13, Figure 3 The different actions are described in detail with reference to the flowchart of FIG.

[0128] The quantitative mechanism 13 firstly, similarly to the fluorescent X-ray analysis device of the second embodiment, specifies a single reference principal component b as a principal component constituting a reference, a single or multiple comparison principal components i1 to be compared with the reference principal component b, and a single or multiple subcomponents i2 as components i (including b, i1, and i2) in the standard sample measurement step, and calculates the content ratio W of each component i. i (including W b , W i1 , W i2 ) is a known standard sample 14, and the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i is measured. Here, the measured intensity I of the component iiM The measured intensity I including the reference principal component b bM , compare the measured intensity I of the principal component i1 i1M and the measured intensity I of the secondary component i2 i2M .

[0129] Next, similarly to the fluorescent X-ray analyzer of the second embodiment, in the standard sample theoretical intensity calculation step, based on the known content ratio W for each measurement line, i , the theoretical strength I is calculated by the known theoretical strength formula iT (Including I bT ,I i1T ,I i2T ).

[0130] Then, in the device sensitivity curve preparation step, for each measurement line, based on the measurement intensity I in the standard sample measurement step, iM And the theoretical strength I in the above standard specimen theoretical strength calculation steps iT , making it as the measured intensity I iM With theoretical strength II iT Specifically, the device sensitivity coefficient A of the following formula (15) representing the device sensitivity curve is obtained: i , B i , C i .

[0131] I iT =A i I iM 2 +B i I iM +C i …(15)

[0132] Then, similarly to the fluorescent X-ray analyzers of the first and second embodiments, in the intensity ratio device sensitivity curve preparation step, for each measurement line corresponding to the comparison main component i1, based on the measurement intensity I in the above-mentioned standard sample measurement step, iM And the theoretical strength I in the above standard specimen theoretical strength calculation steps iT , making the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the theoretical intensity I i1T Theoretical intensity I with the benchmark principal component b bT The theoretical intensity ratio Ii1bRT (i.e., I i1bRT =I i1T / I bT ) is the intensity ratio device sensitivity curve of the correlation between . Specifically, the intensity ratio device sensitivity coefficient A of the formula (1) representing the intensity ratio device sensitivity curve is obtained i1R , B i1R , C i1R .

[0133] I i1bRT =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(1)

[0134] Then, similarly to the fluorescent X-ray analyzer of the second embodiment, in the unknown sample measurement step, the reference main component b, the comparative main component i1, and the subcomponent i2 are designated as components i, and the content ratio W of each component i is calculated. i The unknown sample 1 is unknown, and the intensity I of the above measurement line is measured. iM .

[0135] Next, in the intensity conversion step, for each measurement line, the intensity I iM and the device sensitivity curve (formula (15)) in the above-mentioned device sensitivity curve preparation step, the measured intensity I iM As shown in the following formula (16), it is converted to the theoretical intensity scale and used as the converted measured intensity I iTM .

[0136] I iTM =A i I iM 2 +B i I iM +C i …(16)

[0137] Then, similarly to the fluorescent X-ray analyzers of the first and second embodiments, in the intensity ratio conversion step, for each measurement line corresponding to the comparison main component i1, based on the measurement intensity I in the above-mentioned unknown sample measurement step, i1M ,I bM The intensity ratio device sensitivity curve (Formula (1)) in the intensity ratio device sensitivity curve preparation step is used as the measured intensity I of the main component i1 for comparison. i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRMAs shown in the following formula (2), it is converted to the theoretical intensity scale and used as the converted measured intensity ratio I i1bRTM .

[0138] I i1bRTM =A i1R I i1bRM 2 +B i1R I i1bRM +C i1R …(2)

[0139] Then, in the content initial value setting step, the initial value W of the content of each component i1, b, i2 is set. i1 (0), W b (0), W i2 (0). Specifically, for each component i, the initial value W of the content is i (0) is set as shown in the following formula (17).

[0140] W i (0)=(I iTM / I iTPure )×100…(17)

[0141] I iTM : The converted measured strength obtained in the strength conversion step

[0142] I iTPure : Theoretical strength of component i in a sample consisting of component i alone

[0143] In addition, instead of the above method, similarly to the description of the fluorescent X-ray analyzer of the first embodiment, for example, the average value of the content of each component known in a plurality of standard samples is calculated to calculate the initial value W. i1 (0), W b (0), W i2 (0), the value obtained by simply dividing 100 (mass %) by the amount of the component is taken as the initial value W of the content of each component. i1 (0), W b (0), W i2 (0). The initial value R of the content ratio in this case is i1b The setting of (0) is also the same as that described in relation to the fluorescent X-ray analysis apparatus according to the first embodiment.

[0144] In addition, the calculation is repeated. As in the fluorescent X-ray analyzer of the first and second embodiments, in the unknown sample theoretical intensity calculation step, the latest content W is calculated for each measurement line. i (n-1) The theoretical strength I is calculated using the known theoretical strength formula iT (n-1).

[0145] Next, similarly to the fluorescent X-ray analyzer of the second embodiment, in the subcomponent content updating step, the intensity I 1 is measured based on the converted intensity in the intensity conversion step for each subcomponent i2. i2TM and the theoretical strength I in the above unknown sample theoretical strength calculation step i2T (n-1), as shown in the following formula (13), the content W i2 (n-1) is updated to W i2 (n).

[0146] W i2 (n) = W i2 (n-1)×(I i2TM / I i2T (n-1))…(13)

[0147] Then, in the estimated content calculation step, for the comparison principal component i1 and the reference principal component b, the intensity I i1TM ,I bTM and the theoretical strength I in the above unknown sample theoretical strength calculation step i1T (n-1), I bT (n-1), based on the latest content W i1 (n-1), W b (n-1), the estimated content W is calculated as shown in the following equations (18) and (19): i1 (S), W b (S).

[0148] W i1 (S)=W i1 (n-1)×(I i1TM / I i1T (n-1))…(18)

[0149] W b (S)=W b (n-1)×(I bTM / I bT (n-1))…(19)

[0150] Next, similarly to the fluorescent X-ray analyzers of the first and second embodiments, in the content ratio updating step, for each comparison main component i1, the intensity ratio i1 is measured based on the conversion in the intensity ratio conversion step. i1bRTM and the theoretical strength I in the above unknown sample theoretical strength calculation step i1T (n-1), I bT The theoretical intensity ratio of (n-1) is I i1bRT (n-1) (i.e., Ii1bRT (n-1) = I i1T (n-1) / I bT (n-1)), the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1)(i.e., R i1b (n-1) = W i1 (n-1) / W b (n-1)) is updated as shown in the following formula (6) to R i1b (n).

[0151] R i1b (n) = R i1b (n-1)×(I i1bRTM / I i1bRT (n-1))…(6)

[0152] Then, in the main component content updating step, the estimated content W of the comparison main component i1 in the above-mentioned estimated content calculation step is calculated. i1 (S) and the estimated content W of the reference principal component b b Total W of (S) Total (S)(i.e., W Total (S)=ΣW i1 (S)+W b (S)) and the latest content ratio R i1b (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W obtained by the following equations (20) and (8): i1 (n) and W b (n).

[0153] W b (n) = W Total (S) / (1+ΣR i1b (n))…(20)

[0154] W i1 (n) = R i1b (n)×W b (n)…(8)

[0155] Then, similarly to the fluorescent X-ray analysis apparatus of the first and second embodiments, in the convergence judgment step, convergence judgment is performed based on the predetermined convergence condition. When the predetermined convergence condition is not met, it is judged as non-convergence (No), and the process is returned to the unknown sample theoretical intensity calculation step. When the predetermined convergence condition is met, it is judged as convergence (Yes), and the process is performed to the result output step.

[0156] Then, similarly to the fluorescent X-ray analyzers of the first and second embodiments, in the result output step, the content rate W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0157] As described above, in the fluorescent X-ray analyzer of the third embodiment, the quantitative mechanism 13 using the fundamental parameter method performs the following operations: creating the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM , and compared with the theoretical intensity I of the principal component i1 i1T Theoretical intensity I with the benchmark principal component b bT The theoretical intensity ratio I i1bRT The intensity ratio device sensitivity curve preparation step of the intensity ratio device sensitivity curve of the correlation between the intensity ratio device sensitivity curve and ... i1bRM The intensity ratio I was converted to the theoretical intensity scale and used as the conversion measurement i1bRTM Intensity ratio conversion step; Calculate the estimated content W for the comparison principal component i1 and the reference principal component b i1 (S), W b (S) estimated content calculation steps; based on the conversion measurement intensity ratio I i1bRTM , the content ratio W of the main component i1 is used as the comparison i1 (n-1) and the content ratio W of the reference principal component b b (n-1) ratio R i1b (n-1) is updated to R i1b (n) content ratio updating step; estimated content ratio W based on comparison of main component i1 i1 (S) and the estimated content W of the reference principal component b b The total of (S) and the latest content ratio R i1b (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W i1 (n), W b(n) Main component content updating step. By performing these steps which are not present in the algorithm of the fundamental parameter method of the prior art, the content ratio R of the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0158] In the quantitative analysis based on the fundamental parameter method in the fluorescent X-ray analyzer of the third embodiment, for the main component, not only the intensity ratio device sensitivity curve as shown in formula (1) which is the correlation between the measured intensity ratio and the theoretical intensity ratio is used, but also the past device sensitivity curve as shown in formula (15) which is the correlation between the measured intensity and the theoretical intensity is used. Such a quantitative method is called a second component quantitative method.

[0159] In the fluorescent X-ray analyzer of the third embodiment, the quantification mechanism 13 also copes with the case where no subcomponent i2 is specified as the component i for the standard sample 14 and the unknown sample 1, and in this case, the subcomponent content rate updating step is skipped.

[0160] Next, the fluorescence X-ray analysis device of the fourth embodiment will be described. In the fluorescence X-ray analysis device of the fourth embodiment, unlike the fluorescence X-ray analysis devices of the first to third embodiments, the calibration curve method is adopted in the quantitative mechanism 13. The standard sample and the unknown sample as the object only contain the main component. Since the structure of the fluorescence X-ray analysis device of the fourth embodiment is different from that of the fluorescence X-ray analysis devices of the first to third embodiments only in the operation of the quantitative mechanism 13, Figure 4 The different actions are described in detail with reference to the flowchart of FIG.

[0161] The quantitative mechanism 13 first designates a single reference principal component b as a principal component constituting a reference and a single or multiple comparison principal components i1 to be compared with the reference principal component b as components i in the standard sample measurement step, and designates each component i (including b and i1) as a content ratio W of each component i. i (including W b , W i1 ) A standard sample 14 of which additional correction component j is known and specified from all components i for matrix correction is used to measure the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i.

[0162] Here, the measured intensity I of component i iM The measured intensity I including the reference principal component b bM and compare the measured intensity I of principal component i1 i1M, the reference principal component b and the comparative principal component i1 are both the component i whose content is to be quantified, that is, the analysis component i. Moreover, the component that absorbs or excites the intensity of the measurement line corresponding to the analysis component i and affects the measurement line is the additional correction component j, and in order to remove the influence, it is used for matrix correction of the analysis component i. The reference principal component b, the comparative principal component i1, and the analysis component i itself can all become the additional correction component j, but the additional correction component j is selected and specified from all the components i by a known method.

[0163] Next, in the intensity ratio calibration curve preparation step, for each measurement line corresponding to the comparative main component i1, based on the known content W i And the measured intensity I in the above standard sample measurement step iM , making the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b (i.e., R i1b =W i1 / W b ) and includes the matrix correction term ∑α jR W j Specifically, the intensity ratio calibration curve constant d of the following formula (21) representing the intensity ratio calibration curve is obtained: i1R 、e i1R 、f i1R , strength ratio matrix correction coefficient α jR In the semi-fundamental parameter method (SFP method) included in the calibration curve method, the matrix correction coefficient of the past calibration curve as the correlation between the measured intensity and the content is obtained by theoretical intensity calculation, but the intensity ratio matrix correction coefficient αjR can also be obtained by theoretical intensity calculation.

[0164] R i1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )(1+Σα jR W j )…(twenty one)

[0165] Then, in the unknown sample measurement step, the reference principal component b and the comparative principal component i1 are designated as components i, and the content ratio W of each component i is i is unknown, specify the unknown sample 1 with the additional correction component j, and measure the intensity I of the measurement line iM .

[0166] Next, in the uncorrected content ratio calculation step, for each comparison main component i1, based on the measured intensity I iM and the intensity ratio calibration curve (Equation (21)) in the above intensity ratio calibration curve preparation step, the uncorrected content X before matrix correction Ri1b The calculation is performed as shown in the following formula (22).

[0167] X Ri1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )…(twenty two)

[0168] Then, in the content ratio initial value setting step, as shown in the following equations (23) and (24), for each component i1, b, based on the uncorrected content ratio X in the uncorrected content ratio calculation step, Ri1b , calculate the uncorrected content X before matrix correction i1 , X b , set it as the initial value W of the content i1 (0), W b (0).

[0169] W b (0) = X b =100 / (1+ΣX Ri1b )…(twenty three)

[0170] W i1 (0) = X i1 =X Ri1b ×X b …(twenty four)

[0171] Next, the calculation is repeated. In the content ratio updating step, as shown in the following equation (25), for each comparison principal component i1, the uncorrected content ratio X in the uncorrected content ratio calculation step is calculated. Ri1b , based on the latest additional correction component j content W j (n-1) Perform matrix correction and update the content ratio to R i1b Here, the content ratio W of the latest additional correction component j is j(n-1), in the first iteration of the calculation, the initial value W in the content initial value setting step is used. i1 (0), W b (0) After the second recalculation, the content W updated in the previous recalculation is used. i1 (n-1), W b (n-1).

[0172] R i1b (n) = X Ri1b (1+Σα jR W j (n-1))…(25)

[0173] Then, in the content ratio updating step, based on the content ratio R updated in the content ratio updating step, i1b (n), the content ratio W of each component i1 and b i1 (n-1), W b (n-1) is updated to W obtained by the following equations (7) and (8): i1 (n), W b (n).

[0174] W b (n) = 100 / (1 + ΣR i1b (n))…(7)

[0175] W i1 (n) = R i1b (n)×W b (n)…(8)

[0176] Thereafter, similarly to the fluorescent X-ray analysis apparatus of the first to third embodiments, in the convergence judgment step, convergence judgment is performed based on the predetermined convergence condition. If the predetermined convergence condition is not satisfied, it is judged as non-convergence (No), and the process returns to the content ratio updating step. If the predetermined convergence condition is satisfied, it is judged as convergence (Yes), and the process proceeds to the result output step.

[0177] Then, similarly to the fluorescent X-ray analyzers of the first to third embodiments, in the result output step, the content rate W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0178] As described above, in the fluorescent X-ray analyzer of the fourth embodiment, the quantitative mechanism 13 using the calibration curve method performs the following operations: creating a measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM, and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b The correlation between them and includes the matrix correction term Σα jR W j The intensity ratio calibration curve preparation step of the intensity ratio calibration curve; Calculate the uncorrected content ratio X before matrix correction based on the intensity ratio calibration curve Ri1b The uncorrected content ratio calculation steps; relative to the uncorrected content ratio X Ri1b , based on the latest additional correction component j content W j (n-1) Perform matrix correction and update the content ratio to R i1b (n) content ratio updating step; based on the updated content ratio R i1b (n), the content ratio W of each component i1 and b i1 (n-1), W b (n-1) is updated to W i1 (n), W b By performing these steps which are not present in the algorithm of the conventional calibration curve method, the content ratio R of the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0179] In the quantitative analysis based on the calibration curve method in the fluorescent X-ray analyzer of the fourth embodiment, for the main component, an intensity ratio calibration curve as shown in formula (21) is used as the correlation between the measured intensity ratio and the content ratio, but a past calibration curve as the correlation between the measured intensity and the content ratio is not used. Such a quantitative method is also included in the first component quantitative method.

[0180] Next, the fluorescence X-ray analysis device of the fifth embodiment is described. In the fluorescence X-ray analysis device of the fifth embodiment, the first component quantification method of the calibration curve method is used in the same manner as the fluorescence X-ray analysis device of the fourth embodiment, but the standard sample and the unknown sample as the object include not only the main component but also the subcomponent. The subcomponent is, for example, a low-content component, which is a component for which an intensity ratio calibration curve is not prepared for the corresponding measurement line. Since the structure of the fluorescence X-ray analysis device of the fifth embodiment is different from that of the fluorescence X-ray analysis devices of the first to fourth embodiments only in the operation of the quantification mechanism 13 it has, Figure 5 The different actions are described in detail with reference to the flowchart of FIG.

[0181] The quantitative mechanism 13 firstly designates a single reference principal component b as a principal component constituting a reference, a single or multiple comparison principal components i1 to be compared with the reference principal component b, and a single or multiple subcomponents i2 as components i (including b, i1, and i2) in the standard sample measurement step, and calculates the content rate W of each component i. i (including W b , W i1 , W i2 ) A standard sample 14 of which additional correction component j is known and specified from all components i for matrix correction is used to measure the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i.

[0182] Here, the measured intensity I of component i iM Contains the measured intensity I of the reference principal component b bM , compared with the measured intensity I of principal component i1 i1M and the measured intensity I of the secondary component i2 i2M , the reference principal component b, the comparative principal component i1, and the subcomponent i2 are all the component i whose content is to be quantified, that is, the analysis component i. Moreover, the component that absorbs or excites the intensity of the measurement line corresponding to the analysis component i and affects the measurement line is the additional correction component j, and in order to remove the influence, it is used for matrix correction of the analysis component i. The reference principal component b, the comparative principal component i1, the subcomponent i2, and the analysis component i itself can all become the additional correction component j, but the additional correction component j is selected and specified from all the components i by a known method.

[0183] Then, in the calibration curve preparation step, for each measurement line corresponding to the subcomponent i2, based on the known content W i And the measured intensity I in the above standard sample measurement step iM , making the measured intensity I as the secondary component i2 i2M The content ratio W of the secondary component i2 i2 The correlation between them and includes the matrix correction term Σα j W j Specifically, the calibration curve constant d of the following formula (26) representing the calibration curve is obtained: i2 、e i2 、f i2 , matrix correction factor α j .

[0184] W i2 =(d i2 I i2M 2 +e i2 I i2M +f i2 )(1+Σα j Wj )…(26)

[0185] Next, similarly to the fluorescent X-ray analyzer of the fourth embodiment, in the intensity ratio calibration curve preparation step, for each measurement line corresponding to the comparative main component i1, based on the known content ratio W i And the measured intensity I in the above standard sample measurement step iM , making the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b (i.e., R i1b =W i1 / W b ) and includes the matrix correction term ∑α jR W j Specifically, the intensity ratio calibration curve constant d of the following formula (21) representing the intensity ratio calibration curve is obtained: i1R 、e i1R 、f i1R , strength ratio matrix correction coefficient α jR .

[0186] R i1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )(1+Σα jR W j )…(twenty one)

[0187] Then, in the unknown sample measurement step, the reference principal component b, the comparative principal component i1, and the subcomponent i2 are designated as components i, and the content ratio W of each component i is i is unknown, specify the unknown sample 1 with the additional correction component j, and measure the intensity I of the measurement line iM .

[0188] Then, in the subcomponent content initial value rate setting step, as shown in the following formula (27), for each subcomponent i2, based on the measured intensity I in the above-mentioned unknown sample measurement step, i2Mand the calibration curve (Equation (26)) in the calibration curve preparation step, calculate the uncorrected content X before matrix correction i2 , set it as the initial content value W i2 (0).

[0189] W i2 (0) = X i2 =d i2 I i2M 2 +e i2 I i2M +f i2 …(27)

[0190] Then, similarly to the fluorescent X-ray analyzer of the fourth embodiment, in the uncorrected content ratio calculation step, for each comparison main component i1, based on the measured intensity I in the above-mentioned unknown sample measurement step, iM The intensity ratio calibration curve (Equation (21)) in the intensity ratio calibration curve preparation step is used to calculate the uncorrected meaning ratio X before matrix correction as shown in the following equation (22): Ri1b .

[0191] X Ri1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )…(twenty two)

[0192] Then, in the main component content ratio initial value setting step, as shown in the following equations (28) and (24), for the comparison main component i1 and the reference main component b, based on the uncorrected content ratio X in the uncorrected content ratio calculation step, Ri1b and the uncorrected content rate X of the auxiliary component in the auxiliary component content rate initial value setting step i2 , calculate the uncorrected content X before matrix correction i1 , X b , set it as the initial value W of the content i1 (0), W b (0).

[0193] W b (0) = X b =(100-ΣX i2 ) / (1+ΣX Ri1b )…(28)

[0194] W i1 (0) = X i1 =X Ri1b ×X b …(twenty four)

[0195] Next, the calculation is repeated. In the subcomponent content rate updating step, as shown in the following equation (29), for each subcomponent i2, the uncorrected content rate x in the subcomponent content rate initial value setting step is calculated. i2 , based on the latest additional correction component j content W j (n-1), perform matrix correction and update the content to W i2 Here, the content ratio W of the latest additional correction component j is j (n-1), in the first repeated calculation, the initial value W in the initial value setting step of the auxiliary component content ratio is used. i2 (0), the initial value W in the step of setting the initial value of the main component content ratio i1 (0), W b (0) After the second recalculation, the content W updated in the previous recalculation is used. i2 (n-1), W i1 (n-1), W b (n-1).

[0196] W i2 (n) = X i2 (1+Σα j W j (n-1))…(29)

[0197] Then, in the content ratio updating step, as shown in the following equation (25), for each comparison principal component i1, the uncorrected content ratio X in the uncorrected content ratio calculation step is calculated. Ri1b , based on the latest content W of the additional correction component j used in the above-mentioned subcomponent content updating step j (n-1), perform matrix correction and update the content ratio to R i1b (n).

[0198] R i1b (n) = X Ri1b (1+Σα jR W j (n-1))…(25)

[0199] Next, in the main component content updating step, based on the content ratio R updated in the content ratio updating step, i1b (n) and the content ratio W of the auxiliary component updated in the auxiliary component content ratio updating step i2 (n), the content ratio W of the comparison principal component i1 and the reference principal component b i1 (n-1), W b(n-1) is updated to W obtained by the following equations (14) and (8): i1 (n), W b (n).

[0200] W b (n)=(100-ΣW i2 (n)) / (1+ΣR i1b (n))…(14)

[0201] W i1 (n) = R i1b (n)×W b (n)…(8)

[0202] Thereafter, similarly to the fluorescent X-ray analysis apparatus of the first to fourth embodiments, in the convergence judgment step, convergence judgment is performed based on the predetermined convergence condition. If the predetermined convergence condition is not satisfied, it is judged as non-convergence (No), and the process returns to the subcomponent content rate updating step. If the predetermined convergence condition is satisfied, it is judged as convergence (Yes), and the process proceeds to the result output step.

[0203] Then, similarly to the fluorescent X-ray analyzers of the first to fourth embodiments, in the result output step, the content rate W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0204] As described above, in the fluorescent X-ray analyzer of the fifth embodiment, the quantitative mechanism 13 using the calibration curve method performs the following operations: creating a measured intensity I as the main component i1 for comparison. i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM , and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b The correlation between them and includes the matrix correction term Σα jR W j The intensity ratio calibration curve preparation step of the intensity ratio calibration curve; Calculate the uncorrected content ratio X before matrix correction based on the intensity ratio calibration curve Ri1b The uncorrected content ratio calculation steps of Ri1b , based on the latest additional correction component j content W j (n-1) Perform matrix correction and update the content ratio to R i1b (n) content ratio updating step; based on the updated content ratio R i1b(n), the content ratio W of the comparison principal component i1 and the reference principal component b i1 (n-1), W b (n-1) is updated to W i1 (n), W b (n) Main component content updating step. By performing these steps which are not present in the algorithm of the conventional calibration curve method, the content ratio R of the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0205] Next, the fluorescence X-ray analysis device of the sixth embodiment is described. In the fluorescence X-ray analysis device of the sixth embodiment, unlike the fluorescence X-ray analysis devices of the first to fifth embodiments, the second component quantification method of the calibration curve method described later is used. The standard sample and the unknown sample as the object contain not only the main component but also the subcomponent. Since the structure of the fluorescence X-ray analysis device of the sixth embodiment is different from that of the fluorescence X-ray analysis devices of the first to fifth embodiments only in the operation of the quantification mechanism 13, Figure 6 The different actions are described in detail with reference to the flowchart of FIG.

[0206] The quantitative mechanism 13 is similar to the fluorescent X-ray analyzer of the fifth embodiment. In the standard sample measurement step, a single reference principal component b constituting a reference principal component, a single or multiple comparison principal components i1 to be compared with the reference principal component b, and a single or multiple subcomponents i2 are designated as components i (including b, i1, and i2). The content ratio W of each component i is calculated. i (including W b , W i1 , W i2 ) A standard sample 14 of which additional correction component j is known and specified from all components i for matrix correction is used to measure the intensity of the measurement line of the fluorescent X-ray 5 corresponding to the component i.

[0207] Next, in the calibration curve preparation step, for each measurement line, based on the known content W i And the measured intensity I in the above standard sample measurement step iM , making it as the measured intensity I iM and content W i The correlation between them and includes the matrix correction term Σα j W j Specifically, the calibration curve constant d of the following formula (30) representing the calibration curve is obtained: i 、e i 、f i , matrix correction factor α j .

[0208] Wi =(d i I iM 2 +e i I iM +f i )(1+Σα j W j )…(30)

[0209] Next, similarly to the fluorescent X-ray analyzers of the fourth and fifth embodiments, in the intensity ratio calibration curve preparation step, for each measurement line corresponding to the comparative main component i1, based on the known content ratio W i And the measurement intensity I in the standard sample measurement step iM , making the measured intensity I as the comparison main component i1 i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM (i.e., I i1bRM =I i1M / I bM ), and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1b (i.e., R i1b =W i1 / W b ) and includes the matrix correction term ∑α jR W j Specifically, the intensity ratio calibration curve constant d of the following formula (21) representing the intensity ratio calibration curve is obtained: i1R 、e i1R 、f i1R , strength ratio matrix correction coefficient α jR .

[0210] R i1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )(1+Σα jR W j )…(twenty one)

[0211] Next, similarly to the fluorescent X-ray analyzer of the fifth embodiment, in the unknown sample measurement step, the reference main component b, the comparative main component i1, and the subcomponent i2 are designated as components i, and the content ratio W of each component i is iis unknown, specify the unknown sample 1 with the additional correction component j, and measure the intensity I of the measurement line iM .

[0212] Then, in the content initial value setting step, as shown in the following formula (31), for each component i, based on the measured intensity I in the above-mentioned unknown sample measurement step, iM and the calibration curve (Equation (30)) in the calibration curve preparation step, calculate the uncorrected content X before matrix correction i , set it as the initial value W of the content i (0).

[0213] W i (0) = X i =d i I iM 2 +e i I iM +f i …(31)

[0214] Next, similarly to the fluorescent X-ray analyzers of the fourth and fifth embodiments, in the uncorrected content ratio calculation step, for each comparison main component i1, based on the measured intensity I in the above-mentioned unknown sample measurement step, iM and the intensity ratio calibration curve (Formula (21)) in the intensity ratio calibration curve preparation step, the uncorrected content X before matrix correction Ri1b The calculation is performed as shown in the following formula (22).

[0215] X Ri1b =(d i1R I i1bRM 2 +e i1R I i1bRM +f i1R )…(twenty two)

[0216] Then, the calculation is repeated. In the subcomponent content updating step, as shown in the following equation (29), for each subcomponent i2, the uncorrected content x in the content initial value setting step is calculated. i2 , based on the latest additional correction component j content W j (n-1) Perform matrix correction and update the content to W i2 Here, the content ratio W of the latest additional correction component j is j (n-1), in the first iteration of the calculation, the initial value W in the content initial value setting step is used. i2 (0), W i1 (0), W bAfter the second recalculation, the content W updated in the previous recalculation is used. i2 (n-1), W i1 (n-1), W b (n-1).

[0217] W i2 (n) = X i2 (1+Σα j W j (n-1))…(29)

[0218] Then, in the estimated content calculation step, as shown in the following equations (32) and (33), for the comparison principal component i1 and the reference principal component b, the uncorrected content x in the content initial value setting step is calculated. i1 , X b , based on the latest content W of the additional correction component j used in the above-mentioned subcomponent content updating step j (n-1) Perform matrix correction and calculate the estimated content W i1 (S), W b (S).

[0219] W i1 (S) = X i1 (1+Σα j W j (n-1))…(32)

[0220] W b (S) = X b (1+Σα j W j (n-1))…(33)

[0221] Then, similarly to the fluorescent X-ray analyzer of the fifth embodiment, in the content ratio updating step, as shown in the following equation (25), for each comparison principal component i1, the uncorrected content ratio X in the uncorrected content ratio calculation step is calculated. Ri1b , based on the latest content W of the additional correction component j used in the above-mentioned subcomponent content updating step j (n-1), perform matrix correction and update the content ratio to R i1b (n).

[0222] R i1b (n) = X Ri1b (1+Σα jR W j (n-1))…(25)

[0223] Next, in the main component content updating step, the estimated content W of the comparison main component i1 in the above-mentioned estimated content calculation step is calculated. i1 (S) and the estimated content W of the reference principal component b b Total W of (S) Total (S)(i.e., W Total (S)=ΣW i1 (S)+W b (S)), and the content ratio R updated in the above content ratio updating step i1b (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W obtained by the following equations (20) and (8): i1 (n) and W b (n).

[0224] W b (n) = W Total (S) / (1+ΣR i1b (n))…(20)

[0225] W i1 (n) = R i1b (n)×W b (n)…(8)

[0226] Next, similarly to the fluorescent X-ray analysis apparatus of the first to fifth embodiments, in the convergence judgment step, convergence judgment is performed based on the predetermined convergence condition. If the predetermined convergence condition is not satisfied, it is judged as non-convergence (No), and the process returns to the subcomponent content rate updating step. If the predetermined convergence condition is satisfied, it is judged as convergence (Yes), and the process proceeds to the result output step.

[0227] Then, similarly to the fluorescent X-ray analyzers of the first to fifth embodiments, in the result output step, the content rate W of the component i in the unknown sample 1 to be determined is output. i The latest content W i (n).

[0228] As described above, in the fluorescent X-ray analyzer of the sixth embodiment, the quantitative mechanism 13 using the calibration curve method performs the following operations: creating a measured intensity I as the main component i1 for comparison. i1M The measured intensity I with the reference principal component b bM The intensity ratio I i1bRM , and the content W of the main component i1 as a comparison i1 The content ratio W of the reference principal component b b The ratio of the content ratio R i1bThe correlation between them and includes the matrix correction term Σα jR W j The intensity ratio calibration curve preparation step of the intensity ratio calibration curve; based on the intensity ratio calibration curve, calculate the uncorrected content ratio X before matrix correction Ri1b The uncorrected content rate calculation steps of the relative comparison of the main component i1 and the reference main component b are as follows: i1 , X b , based on the latest additional correction component j content W j (n-1) Perform matrix correction and calculate the estimated content W i1 (S), W b (S) estimated content calculation steps; relative uncorrected content ratio X Ri1b , based on the latest additional correction component j content W j (n-1) Perform matrix correction and update the content ratio to R i1b (n) content ratio updating step; estimated content ratio W based on comparison of main component i1 i1 (S) and the estimated content W of the reference principal component b b (S) total and the latest content ratio R i1b (n), the content ratio W of the main component i1 is compared i1 (n-1) and the content ratio W of the reference principal component b b (n-1) is updated to W i1 (n), W b (n) Main component content updating step. By performing these steps which are not present in the algorithm of the conventional calibration curve method, the content ratio R of the main components is updated. i1b to conduct a sufficiently accurate analysis.

[0229] In the quantitative analysis based on the calibration curve method in the fluorescent X-ray analyzer of the sixth embodiment, for the main component, not only the intensity ratio calibration curve as shown in formula (21) which measures the correlation between the intensity ratio and the content ratio, but also the past calibration curve as shown in formula (30) which measures the correlation between the intensity and the content ratio is used. Such a quantitative method is also included in the second component quantitative method.

[0230] In addition, in the fluorescent X-ray analysis device of the sixth embodiment, the quantitative mechanism 13 also responds to the case where the subcomponent i2 is not specified as the component i for the standard sample 14 and the unknown sample 1. In this case, the subcomponent content rate updating step is skipped. In this case, the repetitive calculation starts from the estimated content rate calculation step, but the "latest additional correction component j content rate W used in the subcomponent content rate updating step" in the estimated content rate calculation step and the content rate ratio updating step is used. j(n-1)", as described in the description of the auxiliary component content updating step, in the first repeated calculation, the initial value W in the content initial value setting step is used. i2 (0), W i1 (0), W b (0) After the second recalculation, the content W updated in the previous recalculation is used. i2 (n-1), W i1 (n-1), W b (n-1).

[0231] In the fluorescent X-ray analysis apparatus of each of the above embodiments, the quantitative mechanism 13 uses the measured intensity I in the standard sample measurement step and the measured intensity I in the unknown sample measurement step as the measured intensity I in the standard sample measurement step. iM , it is also possible to use the measurement intensity that has been corrected in a manner that removes the influence of the change in the height of the analysis surface of the samples 1 and 14 on the measurement intensity based on the correlation between the height of the analysis surface of the samples 1 and 14. By performing height correction in this way according to the form of the samples 1 and 14, it is possible to calculate the content ratio R of the main components. i1b for a more precise analysis.

[0232] In the fluorescent X-ray analyzer of each of the above embodiments, as necessary, a known method is used, for example, before the convergence determination step, to determine the content W of all components i. i The standardization process was performed so that the total of (n) would be 100 (mass %).

[0233] As mentioned above, while referring to the attached Figure 1 While the preferred embodiments have been described, it is easy for a person skilled in the art to think of various changes and modifications within the obvious scope after reading this specification. Therefore, such changes and modifications should be interpreted as belonging to the scope of the present invention determined by the attached claims.

[0234] Description of the label:

[0235] Label 1 represents an unknown sample;

[0236] Reference numeral 3 indicates an X-ray;

[0237] Reference numeral 5 represents fluorescent X-rays;

[0238] Reference numeral 13 denotes a quantitative mechanism;

[0239] Reference numeral 14 denotes a standard sample.

Claims

1. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once, and obtains the content of a component in the sample by a quantitative mechanism using a fundamental parameter method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measuring step, wherein the intensity of a measurement line as fluorescent X-rays corresponding to components is measured for a standard sample, in which a single reference principal component as a principal component constituting a reference and a comparison principal component to be compared with the reference principal component are designated as components, and the content rate of each component is known; a step of calculating the theoretical strength of the standard sample, wherein the theoretical strength is calculated for each measurement line according to the known content ratio; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio device sensitivity curve is prepared based on the measurement intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step, wherein the intensity ratio device sensitivity curve is a correlation between a measured intensity ratio, which is a ratio of the measured intensity of the comparison principal component to the measured intensity of the reference principal component, and a theoretical intensity ratio, which is a ratio of the theoretical intensity of the comparison principal component to the theoretical intensity of the reference principal component; an unknown sample measuring step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference principal component and the comparative principal component are designated as components and the content rate of each component is unknown; an intensity ratio conversion step, wherein, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, is converted into a theoretical intensity scale as a converted measurement intensity ratio; a content ratio initial value setting step, wherein the initial value of the content ratio of each component is set; a step of calculating the theoretical strength of an unknown sample, wherein the theoretical strength is calculated based on the latest content rate for each measurement line; a content ratio updating step, wherein, for each comparison main component, based on the converted measured intensity ratio in the intensity ratio conversion step and the theoretical intensity ratio based on the theoretical intensity in the unknown sample theoretical intensity calculation step, the content ratio as the ratio of the content of the comparison main component to the content of the reference main component is updated; a content updating step of updating the content of each component based on the latest content ratio; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the above-mentioned convergence judgment step, if it is judged that there is no convergence, the process returns to the above-mentioned unknown sample theoretical strength calculation step, and if it is judged that there is convergence, the process proceeds to the above-mentioned result output step.

2. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once, and obtains the content of a component in the sample by a quantitative mechanism using a fundamental parameter method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measuring step, wherein the intensity of a measurement line as fluorescent X-rays corresponding to the components is measured for the standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and subcomponents are designated as components, and the content rate of each component is known; a step of calculating the theoretical strength of the standard sample, wherein the theoretical strength is calculated for each measurement line according to the known content ratio; a device sensitivity curve preparation step, wherein, for each measurement line corresponding to the subcomponent, a device sensitivity curve is prepared as a correlation between the measured intensity of the subcomponent and the theoretical intensity of the subcomponent based on the measured intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio device sensitivity curve is prepared based on the measurement intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step, wherein the intensity ratio device sensitivity curve is a correlation between a measured intensity ratio, which is a ratio of the measured intensity of the comparison principal component to the measured intensity of the reference principal component, and a theoretical intensity ratio, which is a ratio of the theoretical intensity of the comparison principal component to the theoretical intensity of the reference principal component; an unknown sample measuring step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference main component, the comparative main component, and the subcomponent are designated as components and the content rate of each component is unknown; an intensity conversion step, wherein, for each measurement line corresponding to the secondary component, based on the measurement intensity in the unknown sample measurement step and the device sensitivity curve in the device sensitivity curve preparation step, the measurement intensity of the secondary component is converted into a theoretical intensity scale as a converted measurement intensity; an intensity ratio conversion step, wherein, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, is converted into a theoretical intensity scale as a converted measurement intensity ratio; a content ratio initial value setting step, wherein the initial value of the content ratio of each component is set; a step of calculating the theoretical strength of an unknown sample, wherein the theoretical strength is calculated based on the latest content rate for each measurement line; a subcomponent content updating step of updating the content of each subcomponent based on the converted measured strength in the strength conversion step and the theoretical strength in the unknown sample theoretical strength calculation step; a content ratio updating step, wherein, for each comparison main component, based on the converted measured intensity ratio in the intensity ratio conversion step and the theoretical intensity ratio based on the theoretical intensity in the unknown sample theoretical intensity calculation step, the content ratio as the ratio of the content of the comparison main component to the content of the reference main component is updated; A main component content updating step, wherein the content of the comparison main component and the content of the reference main component are updated based on the latest content ratio and the latest content of the subcomponent; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the above-mentioned convergence judgment step, if it is judged that there is no convergence, the process returns to the above-mentioned unknown sample theoretical strength calculation step, and if it is judged that there is convergence, the process proceeds to the above-mentioned result output step.

3. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once, and obtains the content of a component in the sample by a quantitative mechanism using a fundamental parameter method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measuring step, wherein the intensity of a measurement line as fluorescent X-rays corresponding to the components is measured for the standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and subcomponents are designated as components, and the content rate of each component is known; a step of calculating the theoretical strength of the standard sample, wherein the theoretical strength is calculated for each measurement line according to the known content ratio; a device sensitivity curve preparation step, wherein, for each measurement line, a device sensitivity curve is prepared as a correlation between the measurement intensity and the theoretical intensity based on the measurement intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step; an intensity ratio device sensitivity curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio device sensitivity curve is prepared based on the measurement intensity in the standard sample measurement step and the theoretical intensity in the standard sample theoretical intensity calculation step, wherein the intensity ratio device sensitivity curve is a correlation between a measured intensity ratio, which is a ratio of the measured intensity of the comparison principal component to the measured intensity of the reference principal component, and a theoretical intensity ratio, which is a ratio of the theoretical intensity of the comparison principal component to the theoretical intensity of the reference principal component; an unknown sample measuring step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference main component, the comparative main component, and the subcomponent are designated as components and the content rate of each component is unknown; an intensity conversion step, wherein, for each measurement line, based on the measurement intensity in the unknown sample measurement step and the device sensitivity curve in the device sensitivity curve preparation step, the measurement intensity is converted into a theoretical intensity scale as a converted measurement intensity; an intensity ratio conversion step, wherein, for each measurement line corresponding to the comparison principal component, based on the measurement intensity in the unknown sample measurement step and the intensity ratio device sensitivity curve in the intensity ratio device sensitivity curve preparation step, a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, is converted into a theoretical intensity scale as a converted measurement intensity ratio; a content ratio initial value setting step, wherein the initial value of the content ratio of each component is set; a step of calculating the theoretical strength of an unknown sample, wherein the theoretical strength is calculated based on the latest content rate for each measurement line; a subcomponent content updating step, wherein the content is updated for each subcomponent based on the converted measured intensity in the intensity conversion step and the theoretical intensity in the unknown sample theoretical intensity calculation step; an estimated content calculation step, wherein, for the comparison principal component and the reference principal component, the estimated content is calculated based on the converted measured intensity in the intensity conversion step and the theoretical intensity in the unknown sample theoretical intensity calculation step; a content ratio updating step, wherein, for each comparison main component, based on the converted measured intensity ratio in the intensity ratio conversion step and the theoretical intensity ratio based on the theoretical intensity in the unknown sample theoretical intensity calculation step, the content ratio as the ratio of the content of the comparison main component to the content of the reference main component is updated; a principal component content updating step, wherein the content of the comparative principal component and the content of the reference principal component are updated based on the sum of the estimated content of the comparative principal component and the estimated content of the reference principal component in the estimated content calculating step and the latest content ratio; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the above-mentioned convergence judgment step, if it is judged that there is no convergence, the process returns to the above-mentioned unknown sample theoretical strength calculation step, and if it is judged that there is convergence, the process proceeds to the above-mentioned result output step.

4. The fluorescent X-ray analysis device according to claim 3, characterized in that: The quantitative determination unit skips the step of updating the subcomponent content rate when the subcomponent is not specified as a component for the standard sample and the unknown sample.

5. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once, and obtains the content of a component in the sample by a quantitative mechanism using a calibration curve method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measurement step, wherein the intensity of a measurement line as fluorescent X-rays corresponding to a component is measured for a standard sample, in which a single reference principal component as a principal component constituting a reference and a comparison principal component to be compared with the reference principal component are designated as components, the content of each component being known, and an additional correction component for matrix correction is designated from all the components; an intensity ratio calibration curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio calibration curve is prepared based on the known content and the measurement intensity in the above-mentioned standard sample measurement step, the intensity ratio calibration curve being a correlation between a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, and a content ratio, which is a ratio of the content of the comparison principal component to the content of the reference principal component, and including a matrix correction term; an unknown sample measuring step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference principal component and the comparative principal component are designated as components, the content rate of each component is unknown, and the additional correction component is designated; an uncorrected content ratio calculation step, wherein, for each comparison main component, the uncorrected content ratio before matrix correction is calculated based on the measured intensity in the above-mentioned unknown sample measurement step and the intensity ratio calibration curve in the above-mentioned intensity ratio calibration curve preparation step; a content ratio initial value setting step, wherein, for each component, based on the uncorrected content ratio in the uncorrected content ratio calculation step, an uncorrected content ratio before matrix correction is calculated and set as an initial value of the content ratio; a content ratio updating step, wherein, for each comparison main component, the uncorrected content ratio in the uncorrected content ratio calculation step is subjected to matrix correction based on the content of the latest additional correction component, thereby updating the content ratio; a content updating step of updating the content of each component based on the content ratio updated in the content ratio updating step; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the convergence determination step, if it is determined that the result has not converged, the flow returns to the content ratio updating step, and if it is determined that the result has converged, the flow proceeds to the result output step.

6. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once and obtains the content of a component in the sample by a quantitative mechanism using a calibration curve method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measuring step, wherein the intensity of a measuring line as fluorescent X-rays corresponding to a component is measured for a standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and a subcomponent are designated as components, the content of each component is known, and an additional correction component for matrix correction is designated from all components; a calibration curve preparation step, wherein, for each measurement line corresponding to the auxiliary component, a calibration curve is prepared based on the known content and the measurement intensity in the standard sample measurement step, wherein the calibration curve is a correlation between the measurement intensity of the auxiliary component and the content of the auxiliary component and includes a matrix correction term; an intensity ratio calibration curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio calibration curve is prepared based on the known content and the measurement intensity in the standard sample measurement step, the intensity ratio calibration curve being a correlation between a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, and a content ratio, which is a ratio of the content of the comparison principal component to the content of the reference principal component, and including a matrix correction term; an unknown sample measurement step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference main component, the comparison main component, and the subcomponent are specified as components, the content rate of each component is unknown, and the additional correction component is specified; a step of setting an initial value of the content of the secondary component, wherein, for each secondary component, based on the measured intensity in the unknown sample measuring step and the calibration curve in the calibration curve preparing step, an uncorrected content before matrix correction is calculated and set as an initial value of the content; an uncorrected content ratio calculation step, wherein, for each comparison main component, the uncorrected content ratio before matrix correction is calculated based on the measured intensity in the above-mentioned unknown sample measurement step and the intensity ratio calibration curve in the above-mentioned intensity ratio calibration curve preparation step; a main component content initial value setting step, wherein, for the comparison main component and the reference main component, based on the uncorrected content ratio in the uncorrected content ratio calculation step and the uncorrected content of the auxiliary component in the auxiliary component content initial value setting step, the uncorrected content before the matrix correction is calculated and set as the initial value of the content; a subcomponent content updating step, wherein, for each subcomponent, based on the latest content of the additional correction component, the uncorrected content in the subcomponent content initial value setting step is subjected to matrix correction to update the content; a content ratio updating step, wherein, for each of the compared main components, the uncorrected content ratio in the uncorrected content ratio calculation step is subjected to matrix correction based on the content of the latest additional correction component used in the subcomponent content ratio updating step, thereby updating the content ratio; a main component content updating step, wherein the content of the comparison main component and the reference main component are updated based on the content ratio updated in the content ratio updating step and the content of the auxiliary component updated in the auxiliary component content updating step; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the convergence determination step, if it is determined that the result has not converged, the flow returns to the subcomponent content rate updating step, and if it is determined that the result has converged, the flow proceeds to the result output step.

7. A fluorescent X-ray analyzer, which irradiates a sample with X-rays once, and obtains the content of a component in the sample by a quantitative mechanism using a calibration curve method based on the measured intensity of the generated fluorescent X-rays, characterized in that: The above quantitative institutions conduct: a standard sample measuring step, wherein the intensity of a measuring line as fluorescent X-rays corresponding to a component is measured for a standard sample, in which a single reference main component as a main component constituting a reference, a comparison main component to be compared with the reference main component, and a subcomponent are designated as components, the content of each component is known, and an additional correction component for matrix correction is designated from all components; a calibration curve preparation step, wherein, for each measurement line, a calibration curve is prepared based on the known content and the measurement intensity in the standard sample measurement step, wherein the calibration curve is a correlation between the measurement intensity and the content and includes a matrix correction term; an intensity ratio calibration curve preparation step, wherein, for each measurement line corresponding to the comparison principal component, an intensity ratio calibration curve is prepared based on the known content and the measurement intensity in the above-mentioned standard sample measurement step, the intensity ratio calibration curve being a correlation between a measurement intensity ratio, which is a ratio of the measurement intensity of the comparison principal component to the measurement intensity of the reference principal component, and a content ratio, which is a ratio of the content of the comparison principal component to the content of the reference principal component, and including a matrix correction term; an unknown sample measurement step, wherein the intensity of the measurement line is measured for an unknown sample in which the reference main component, the comparison main component, and the subcomponent are specified as components, the content rate of each component is unknown, and the additional correction component is specified; a content initial value setting step, wherein, for each component, based on the measured intensity in the unknown sample measuring step and the calibration curve in the calibration curve preparing step, an uncorrected content before matrix correction is calculated and set as an initial value of the content; an uncorrected content ratio calculation step, wherein, for each comparison main component, the uncorrected content ratio before matrix correction is calculated based on the measured intensity in the above-mentioned unknown sample measurement step and the intensity ratio calibration curve in the above-mentioned intensity ratio calibration curve preparation step; a subcomponent content updating step, wherein, for each subcomponent, based on the latest content of the additional correction component, the uncorrected content in the content initial value setting step is subjected to matrix correction to update the content; an estimated content calculation step, wherein, for the comparison main component and the reference main component, the uncorrected content in the content initial value setting step is subjected to matrix correction based on the content of the latest additional correction component used in the subcomponent content updating step to calculate the estimated content; a content ratio updating step, wherein, for each of the compared main components, the uncorrected content ratio in the uncorrected content ratio calculation step is subjected to matrix correction based on the content of the latest additional correction component used in the subcomponent content ratio updating step, thereby updating the content ratio; a main component content updating step, wherein the content of the comparison main component and the content of the reference main component are updated based on the sum of the estimated content of the comparison main component and the estimated content of the reference main component in the estimated content calculating step and the content ratio updated in the content ratio updating step; A convergence judgment step, wherein the convergence judgment is performed based on a predetermined convergence condition; and A result output step is performed, wherein the latest content rate is output as the content rate of the component in the unknown sample to be determined, In the convergence determination step, if it is determined that the result has not converged, the flow returns to the subcomponent content rate updating step, and if it is determined that the result has converged, the flow proceeds to the result output step.

8. The fluorescent X-ray analysis device according to claim 7, characterized in that: The quantitative determination unit skips the step of updating the subcomponent content rate when the subcomponent is not specified as a component for the standard sample and the unknown sample.

9. The fluorescent X-ray analysis device according to any one of claims 1 to 8, characterized in that: For the above-mentioned quantitative mechanism, as the measurement intensity in the above-mentioned standard sample measurement step and the measurement intensity in the above-mentioned unknown sample measurement step, a measurement intensity that is corrected in a manner that eliminates the influence of changes in the height of the analysis surface of the sample on the measurement intensity is used based on the correlation between the height of the analysis surface of the sample and the measurement intensity.

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