JP4417100B2 - X-ray analysis method, X-ray analysis apparatus and computer program - Google Patents

Description

  The present invention irradiates an object to be irradiated with a coating material with X-rays, measures fluorescent X-ray intensity and scattered X-ray intensity generated by irradiation, and uses the scattered X-ray intensity to fluoresce X-rays. The present invention relates to an X-ray analysis method, an X-ray analysis apparatus, and a computer program that correct intensity and perform quantitative analysis of the covering material using the corrected fluorescent X-ray intensity.

  As an apparatus for analyzing the composition of a sample, there is an X-ray analyzer that analyzes the composition by irradiating the sample with X-rays. The X-ray analyzer detects the fluorescent X-ray intensity generated when the sample is irradiated with X-rays with a detector, analyzes the elements in the sample from the wavelength of the detected fluorescent X-ray intensity spectral line, The concentration of each element is analyzed from the line intensity. For example, in a coated copper wire obtained by coating copper with a synthetic resin, the concentration of harmful elements such as lead or cadmium contained in the synthetic resin is analyzed.

However, there is a problem that measured values such as fluorescent X-ray intensity vary due to the influence of the thickness of the sample such as the diameter of the coated copper wire. As a method for solving this problem, a method of correcting a measured value of fluorescent X-ray intensity using a measured value of scattered X-ray intensity is used (for example, see Patent Document 1). FIG. 6A is a diagram illustrating an example of the measurement result of the X-ray spectrum of the coated copper wire, and FIG. 6B is a diagram illustrating an outline of correction using the scattered X-ray intensity. As shown in FIG. 6B, the thickness of the sample and the spectrum intensity of the harmful element corresponding to the thickness of the sample are obtained based on the scattered X-ray intensity.
Japanese Patent Laid-Open No. 7-197296

  Although the influence of the thickness of the sample can be corrected by using the measured value of the scattered X-ray intensity, in the case of a coated copper wire, the measured scattered X-ray contains a scattered X-ray component due to copper inside the sample. Therefore, there is an error in the measured scattered X-ray intensity, and there is a problem that accurate correction cannot be performed.

  The present invention has been made in view of such circumstances, and removes the influence of the scattered X-ray component of the object when performing quantitative analysis of the covering material of the irradiated object that is formed by covering the object with the covering material. An object of the present invention is to provide an X-ray analysis method, an X-ray analysis apparatus, and a computer program that can accurately perform quantitative analysis of the coating material by accurately correcting fluorescent X-rays.

  The present invention also provides an X-ray analysis method capable of performing an accurate quantitative analysis of harmful elements such as lead or cadmium contained in a synthetic resin of a coated copper wire (irradiated body) formed by coating copper with a synthetic resin. For other purposes.

  Another object of the present invention is to provide an X-ray analyzer capable of obtaining an accurate scattered X-ray intensity of the covering material without the influence of the scattered X-ray intensity of the object.

The X-ray analysis method according to the present invention irradiates an object to be irradiated, which is covered with a covering material, with X-rays, measures fluorescent X-ray intensity and scattered X-ray intensity generated by irradiation, and determines scattered X-ray intensity. In the X-ray analysis method in which the X-ray fluorescence intensity is corrected using the corrected X-ray fluorescence intensity and the coating material is quantitatively analyzed using the corrected X-ray fluorescence intensity, the correspondence between the fluorescent X-ray intensity of the object and the thickness of the irradiated object is measured. based on the engagement, based on the correspondence relationship determining a first irradiated object thickness corresponding to the measured value of the fluorescent X-ray intensity of the object, and the scattered X-ray intensity of the object and the irradiation object thickness Te based determining a scattered X-ray intensity of the object corresponding to the first object to be irradiated thickness determined, the correspondence relationship of the scattered X-ray intensity of the coating material and the irradiated body thickness, determined A temporary scattered X-ray intensity of the covering material corresponding to the thickness of the first irradiated object is determined. Calculating the ratio of the object in the X-ray irradiated portion of the irradiated object according to the step and the measured scattered X-ray intensity, the scattered X-ray intensity of the object, and the temporary scattered X-ray intensity of the covering material And the fluorescence X-ray intensity of the object and the thickness of the irradiated object, the fluorescent X-ray intensity of the object corresponding to the thickness of the irradiated object is multiplied by the calculated ratio according to the ratio. Obtaining a fluorescent X-ray intensity characteristic, determining a second irradiated object thickness corresponding to a measured value of the fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristic corresponding to the ratio, and Calculating the scattered X-ray intensity of the covering material corresponding to the determined second irradiated body thickness based on the correspondence between the scattered X-ray intensity of the covering material and the irradiated body thickness ; Calculated scattered X-ray intensity of the coating material There the measured value of the fluorescent X-ray intensity of the coating material is corrected, and performs a quantitative analysis of the coating material by using the measured values of the corrected X-ray fluorescence intensity.

X-ray analysis method according to the present invention irradiates X-rays to be irradiated body formed by coating a copper synthetic resin, and performing quantitative analysis of the synthetic resin.

The X-ray analysis apparatus according to the present invention irradiates an irradiated object that is an object covered with a coating material, measures the X-ray fluorescence intensity and the scattered X-ray intensity generated by the irradiation, and the scattered X-ray intensity. In the X-ray analyzer that corrects the fluorescent X-ray intensity using the X-ray and performs the quantitative analysis of the coating material using the corrected fluorescent X-ray intensity, the correspondence between the fluorescent X-ray intensity of the object and the thickness of the irradiated object , correspondence between the scattered X-ray intensity and irradiated body thickness before Symbol object, and the scattered X-ray intensity of the coating material and a storage unit for storing a correspondence between the irradiated object thickness, stored in the storage unit Means for determining a first irradiated body thickness corresponding to a measured value of the fluorescent X-ray intensity of the object based on a correspondence relationship between the fluorescent X-ray intensity of the object and the irradiated body thickness; based on the correspondence between the scattered X-ray intensity of said stored object and the irradiation object thickness section, determine Corresponding to the first and hand stage that determine the scattered X-ray intensity of the object corresponding to the irradiated body thickness is, the scattered X-ray intensity of the coating material stored in the storage unit and the irradiated body thickness A means for determining a provisional scattered X-ray intensity of the covering material corresponding to the determined first irradiated body thickness based on the relationship; a measured scattered X-ray intensity; a scattered X-ray intensity of the object; Means for calculating the proportion of the object in the X-ray irradiated part of the irradiated object according to the provisional scattered X-ray intensity of the covering material, and the fluorescent X-ray intensity of the object stored in the storage unit and the irradiated Means for obtaining a fluorescent X-ray intensity characteristic corresponding to the ratio by multiplying the calculated fluorescent X-ray intensity by the calculated ratio in the correspondence relationship with the body thickness; The fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristics according to the ratio Based on the correspondence between the means for determining the second irradiated object thickness corresponding to the measured value and the scattered X-ray intensity of the covering material stored in the storage unit and the irradiated object thickness Calculating means for calculating the scattered X-ray intensity of the covering material corresponding to the thickness of the irradiated body, and using the scattered X-ray intensity of the covering material calculated by the calculating means. The measurement value of the line intensity is corrected, and the covering material is quantitatively analyzed using the corrected measurement value of the fluorescent X-ray intensity.

An X-ray analysis apparatus according to the present invention obtains a difference between the first irradiated body thickness and the second irradiated body thickness, and compares the absolute value of the determined difference with a predetermined value; When the absolute value of the difference is larger than a predetermined value, the second irradiated body thickness is substituted for the first irradiated body thickness, and the scattered X-ray intensity of the object is determined. Means, means for determining a provisional scattered X-ray intensity of the covering material, means for calculating the ratio, means for determining fluorescent X-ray intensity characteristics according to the ratio, means for determining the second irradiated object thickness And a means for repeating the operation of the means for performing the comparison, wherein the calculating means corresponds to a second object thickness when the absolute value of the difference is equal to or less than a predetermined value. The scattered X-ray intensity of the covering material is calculated.

A computer program according to the present invention provides a computer that receives measurement data of fluorescent X-ray intensity and scattered X-ray intensity generated when X-rays are irradiated on an object to be irradiated that is covered with a coating material. In a computer program for executing a correction process of a fluorescent X-ray intensity using a line intensity and executing a quantitative analysis process of the coating material using the corrected fluorescent X-ray intensity, the computer causes the fluorescent X-ray intensity of the object to be based on the correspondence relationship between the irradiation object thickness, first the procedure Ru is determined irradiation object thickness corresponding to the measured value of the fluorescent X-ray intensity of the object, the computer, the scattered X-rays of the object strength and based on the correspondence between the irradiated object thickness, first and procedure for determining the scattered X-ray intensity of the object corresponding to the irradiated body thickness, the computer, the scattered X-rays of the coating material was determined Strength and A procedure for determining a temporary scattered X-ray intensity of the covering material corresponding to the determined first irradiated body thickness based on a correspondence relationship with the irradiated body thickness, and a computer to measure the scattered X-ray intensity measured, According to the scattered X-ray intensity of the object and the temporary scattered X-ray intensity of the covering material, a procedure for calculating the ratio of the object in the X-ray irradiated portion of the irradiated object, By multiplying the calculated ratio by the fluorescent X-ray intensity of the object corresponding to the irradiated body thickness in the correspondence relationship between the line intensity and the irradiated body thickness, the fluorescent X-ray intensity characteristic corresponding to the ratio is obtained. A procedure for determining, a procedure for causing a computer to determine a second irradiated object thickness corresponding to a measured value of the fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristics according to the ratio; and Scattering of coating material X Strength and based on the correspondence between the irradiated object thickness, corresponding to the second object to be irradiated thickness determined and a procedure for calculating the scattered X-ray intensity of the coating material, the computer calculated the coating A measurement value of the fluorescent X-ray intensity of the coating material is corrected using the scattered X-ray intensity of the material, and a quantitative analysis of the coating material is executed using the corrected measurement value of the fluorescent X-ray intensity. .

In the present invention, X-rays are irradiated to an irradiated object that is formed by coating an object with a coating material, the fluorescent X-ray intensity and scattered X-ray intensity generated by the irradiation are measured, and the fluorescence X of the object determined in advance is measured. The irradiated object corresponding to the measured value of the fluorescent X-ray intensity of the object based on the correspondence between the line intensity and the irradiated object thickness and the corresponding relationship between the scattered X-ray intensity of the object and the irradiated object thickness The thickness is determined, and the scattered X-ray intensity of the object corresponding to the determined thickness of the irradiated object is determined. Based on the determined scattered X-ray intensity of the object and the measured scattered X-ray intensity, the coating The scattered X-ray intensity of the material is calculated. Using the calculated scattered X-ray intensity of the covering material, the measured value of the fluorescent X-ray intensity of the covering material is corrected, and the covering material is quantitatively analyzed using the corrected measured value of the fluorescent X-ray intensity. In order to correct the fluorescent X-ray intensity of the covering material using the scattered X-ray intensity of the covering material calculated based on the measured scattered X-ray intensity and the scattered X-ray intensity of the object, the scattered X-ray intensity of the object is corrected. Thus, the accurate scattered X-ray intensity of the covering material can be obtained in consideration of the above, and the fluorescent X-ray intensity of the covering material can be accurately corrected.

In the present invention, a coated copper wire (irradiated body) obtained by coating copper with a synthetic resin is irradiated with X-rays, and quantitative analysis of the synthetic resin is performed. For example, it is possible to perform a quantitative analysis of harmful elements such as lead or cadmium contained in a synthetic resin.

In the present invention, based on the correspondence relationship between the scattered X-ray intensity of the covering material and the irradiated body thickness, the temporary scattered X-ray intensity of the covering material corresponding to the determined irradiated body thickness is determined. Based on the determined provisional scattered X-ray intensity of the covering material, the determined scattered X-ray intensity of the object, and the measured scattered X-ray intensity, the ratio of the object in the X-ray irradiated portion of the irradiated object is calculated. The scattered X-ray intensity of the covering material is calculated based on the calculated ratio, the determined scattered X-ray intensity of the object, and the measured scattered X-ray intensity. An accurate scattered X-ray intensity of the covering material can be calculated based on the proportion of the object in the X-ray irradiated portion of the irradiated body.

According to the present invention, when performing quantitative analysis of an element contained in the covering material of an irradiated object formed by coating an object with a covering material, the scattered X-ray intensity of the object is based on the fluorescent X-ray intensity of the object. And determining the scattered X-ray intensity of the coating material based on the calculated scattered X-ray intensity of the object and the measured scattered X-ray intensity, and based on the determined scattered X-ray intensity of the coating material By correcting the fluorescent X-ray intensity of the covering material, the accurate X-ray intensity of the covering material can be accurately determined by using the accurate scattered X-ray intensity of the covering material in which the error due to the scattered X-ray intensity of the object is corrected. It can correct | amend and can perform the quantitative analysis of the element contained in the said covering material correctly.

According to the present invention, a coated copper wire (irradiated body) formed by coating copper with a synthetic resin is irradiated with X-rays to accurately perform quantitative analysis of harmful elements such as lead or cadmium contained in the synthetic resin. Can do.

According to the present invention, the temporary scattered X-ray intensity of the covering material corresponding to the thickness of the irradiated object is further obtained, and the obtained temporary scattered X-ray intensity of the covering material and the scattered X-ray intensity of the object are determined. Based on the measured scattered X-ray intensity, the ratio of the object in the X-ray irradiated portion of the irradiated object is calculated, and the calculated ratio, the calculated scattered X-ray intensity of the object, and the measured scattered X-ray intensity are calculated. Based on this, by calculating the scattered X-ray intensity of the covering material, it is possible to obtain the accurate scattered X-ray intensity of the covering material excluding the influence of the scattered X-ray intensity of the object. Using the accurate scattered X-ray intensity of the covering material, the fluorescent X-ray intensity of the covering material can be accurately corrected.

  Hereinafter, the present invention will be specifically described with reference to the drawings showing embodiments thereof. The X-ray analyzer irradiates an irradiated object (sample) that covers an object with a coating material, measures the fluorescent X-ray intensity and scattered X-ray intensity generated by the irradiation, and calculates the scattered X-ray intensity. The fluorescent X-ray intensity is corrected by using, and the coating material is quantitatively analyzed using the corrected fluorescent X-ray intensity. In this description, a case where a coated copper wire formed by coating copper with a synthetic resin is used as an example will be described. Further, the case where the concentration of harmful elements such as lead or cadmium contained in the coating material of the coated copper wire as the sample is measured will be described as an example. It is also possible to measure the concentration of harmful elements such as mercury and chromium.

  FIG. 1 is a schematic diagram showing the configuration of an X-ray analyzer according to the present invention. The X-ray analyzer is provided with an X-ray source 2 for generating X-rays at the lower part of a box-shaped X-ray analyzer body 1, and a sample (irradiated body) at the upper part of the X-ray analyzer body 1. A mounting table 3 on which 10 is mounted is arranged. An X-ray transmission window 4 that transmits X-rays is formed on the mounting table 3. The X-ray transmission window 4 is closed by a diaphragm such as a synthetic resin that can transmit the X-ray, fluorescent X-ray, scattered X-ray and visible light described later. A side wall 18 is formed on the outer periphery of the mounting table 3, and an openable / closable lid 19 is attached to the top of the side wall 18.

  An X-ray conduit 5 for guiding X-rays generated from the X-ray source 2 to the X-ray transmission window 4 is suspended in the X-ray analyzer main body 1. An upper portion in the X-ray analyzer main body 1 is provided with a curved plate 1a that protrudes downward from the periphery of the X-ray transmission window 4 and into which the upper portion of the X-ray conduit 5 is inserted. A space between 1a and the X-ray transmission window 4 is a sealed X-ray irradiation space 6. The X-ray irradiation space 6 is preferably kept in vacuum in order to prevent attenuation of fluorescent X-rays and scattered X-rays. The X-ray conduit 5 is made of glass or the like. The X-ray generated by the X-ray source 2 is guided to a narrow beam diameter of, for example, 10 μm to 5 mm, preferably 10 μm to 100 μm. The X-ray transmission window 4 (sample 10) is irradiated. In this description, the primary X-ray is focused to a predetermined diameter using an X-ray conduit, but the X-ray conduit is replaced with another X-ray guide member such as a collimator. You can also squeeze it.

  Further, in the X-ray irradiation space 6, secondary X-rays such as fluorescent X-rays and scattered X-rays generated by irradiating the sample 10 with X-rays (primary X-rays) from the X-ray conduit 5 are detected. A detection means 7 such as a semiconductor detector, an illuminator (not shown) that illuminates the X-ray transmission window 4 (sample 10) with visible light, and an X-ray conduit 5 are arranged around the X-ray conduit 5 so that light from the sample 10 is transmitted. A reflector 8 that reflects in a direction orthogonal to the axis of the X-ray conduit 5 and a condenser lens 9 that collects the light reflected by the reflector 8 are housed.

  The detection means 7 is disposed on one side with respect to the X-ray conduit 5 while being accommodated in one end (insertion side) of the cylindrical housing 13 inserted into the curved plate 1a. By irradiating X-rays generated from the X-ray source 2 toward the sample 10 on the stage 3 from the upper end of the X-ray conduit 5, secondary X-rays such as fluorescent X-rays and scattered X-rays are generated. Secondary X-rays are detected by the detection means 7 in the X-ray irradiation space 6. In this description, the primary X-ray is irradiated perpendicularly to the sample placement position, and the detection means is arranged at an angle of about 45 degrees with the irradiation axis. However, the present invention is irradiated with the primary X-ray. The angle and the detection angle of the secondary X-ray are not limited to these angles.

  The condensing lens 9 is disposed on the opposite side to the detection means 7 with respect to the X-ray conduit 5 while being accommodated in one end (insertion side) of a cylindrical housing 14 inserted into the curved plate 1a. An imaging means 15 such as a CCD camera for imaging the sample 10 is provided at the other end of the housing 14. The condenser lens 9 is arranged so that its optical axis is approximately 45 degrees with a reflection surface of a reflector 8 described later. The light condensed by the condensing lens 9 enters the light receiving portion of a CCD camera as the image pickup means 15.

  The reflector 8 has an insertion portion that is cut into a long hole shape from one side to the center, and includes a mirror (reflection surface) through which the X-ray conduit 5 is inserted. It is supported by the housing 14 with the reflection surface facing upward so that the image of the sample 10 can be reflected around the axis. That is, the reflector 8 is disposed around the X-ray conduit 5 at an angle of approximately 45 degrees with respect to the axis of the X-ray conduit 5, and the light (visible light) from the sample 10 is transmitted to the X-ray conduit 5. It is arranged so as to be reflected at an angle of approximately 45 degrees with respect to the axial center. An image of the sample 10 reflected by the reflector 8 is picked up by the image pickup means 15. In this description, the X-ray irradiation position is shown as being configured to image the same axis as the primary X-ray irradiation direction, but the present invention is not limited to this. You may comprise the reflection angle in the reflector 8 in predetermined angles other than 45 degree | times.

  The detection value detected by the detection means 7 of the X-ray analyzer configured as described above is sent to the measurement means 16 that measures the intensity of fluorescent X-rays and scattered X-rays based on the detection values. Measurement data such as scattered X-ray intensity and fluorescent X-ray intensity measured by the measuring means 16 is sent to the computer 17. In addition, the image data captured by the imaging unit 15 is sent to the computer 17.

  FIG. 2 is a block diagram illustrating a configuration example of the computer 17. The computer 17 includes a CPU (Central Processing Unit) 21, a RAM 22 such as a DRAM (Dynamic Random Access Memory), a hard disk drive (hereinafter referred to as a hard disk) 23, and an external storage unit 24 such as a flexible disk drive or a CD-ROM drive. , An input unit 25 such as a keyboard or a mouse, an output unit 26 such as a display device or a printer, and a communication interface (hereinafter referred to as communication I / F) 27 that controls communication with the imaging unit 15 and the measurement unit 16.

  CPU21 controls each part 22-27 mentioned above. Further, the CPU 21 stores a program or data read from the hard disk 23 or the external storage unit 24 or data received from the input unit 25 or the communication I / F 27 in the RAM 22 and executes the program stored in the RAM 22 or calculates data. Various processing such as these are performed, and various processing results or temporary data used for various processing are stored in the RAM 22. Data such as calculation results stored in the RAM 22 is stored in the hard disk 23 or output from the output unit 26 by the CPU 21.

  Under the control of the CPU 21, the image data received by the communication I / F 27 from the imaging unit 15 is output to the output unit 26. Further, the CPU 21 stores the measurement data received by the communication I / F 27 from the measurement unit 16 in the RAM 22, creates display data based on the measurement data, and outputs the produced display data (measurement result) to the output unit 26. The In addition, the CPU 21 executes measurement data analysis processing, the analysis result is stored in the RAM 22 or the hard disk 23, and the analysis result is output to the output unit 26.

  The hard disk (storage unit) 23 includes a correspondence relationship between the copper fluorescent X-ray intensity and the sample thickness of the coated copper wire (sample 10) coated with synthetic resin, and the copper scattered X-ray intensity and the sample thickness. And correspondence data such as a table or a mathematical expression relating to the correspondence relationship between the scattered X-ray intensity of the synthetic resin and the sample thickness is stored. FIG. 3A is a diagram showing the correspondence between the thickness of the sample and the fluorescent X-ray intensity of copper, and FIG. 3B is a diagram showing the correspondence between the thickness of the sample and the scattered X-ray intensity of copper. FIG. 3C is a diagram showing the correspondence between the thickness of the sample and the scattered X-ray intensity of the synthetic resin.

  The CPU 21 determines the thickness of the sample corresponding to the measured value of the fluorescent X-ray intensity of copper based on the correspondence data read (obtained) from the hard disk 23, and the copper scattering corresponding to the determined thickness of the sample. It operates as means (decision means) for determining the X-ray intensity and determining the provisional scattered X-ray intensity of the synthetic resin corresponding to the determined thickness of the sample.

  Further, the CPU 21 operates as means (calculation means) for calculating the scattered X-ray intensity of the synthetic resin based on the determined scattered X-ray intensity of copper and the measured scattered X-ray intensity. For example, the CPU 21 calculates the ratio of copper in the X-ray irradiated portion of the sample 10 based on the measured scattered X-ray intensity, the determined copper scattered X-ray intensity, and the determined temporary scattered X-ray intensity of the synthetic resin. The scattered X-ray intensity of the synthetic resin is calculated based on the calculated ratio, the determined scattered X-ray intensity of copper, and the measured scattered X-ray intensity.

  The CPU 21 corrects the measured value of the fluorescent X-ray intensity of the synthetic resin using the calculated scattered X-ray intensity of the synthetic resin, and quantitatively analyzes the elements contained in the synthetic resin using the corrected measured value of the fluorescent X-ray intensity. I do. Correction of the fluorescent X-ray intensity using the scattered X-ray intensity and quantitative analysis using the corrected fluorescent X-ray intensity can be performed in the same manner as in the past.

  A computer program recorded on a recording medium 29 such as a CD-ROM is read by the external storage unit 24, stored in the hard disk 23 or RAM 22, and executed by the CPU 21, whereby the CPU 21 can be operated as each of the means described above. is there.

  Next, an X-ray analysis method using the X-ray analysis apparatus according to the present invention will be described. The user opens the lid 19 and places the sample 10 near the X-ray transmission part 4 of the mounting table 3. Light (visible light) generated by illumination from the illuminator is reflected on the lower surface of the sample 10, further reflected on the mirror surface of the reflector 8, and incident on the light receiving portion of the imaging means 15 from the condenser lens 9. Ten captured images are displayed on the display device (output unit 26) of the computer 17. The user adjusts the placement position of the sample 10 based on the captured image displayed on the output unit 26.

  After the adjustment of the placement position, the user closes the lid 19 and instructs the start of X-ray analysis. In response to an instruction to start X-ray analysis, X-rays are output from the X-ray source 2, and fluorescent X-rays and scattered X-rays generated by X-ray irradiation on the sample 10 are detected by the detection means 7, and based on the detection results. Measurement data is sent from the measuring means 16 to the computer 17. Since X-rays irradiated to the sample 10 are narrowed to a thin beam diameter by the X-ray conduit 5, X-rays are irradiated to a part of the sample 10. In this description, the picked-up image displayed on the output unit 26 is picked up from the direction coaxial with the X-ray conduit 5 by the reflector 8, for example, toward the center of the picked-up image of the sample 10. A line is irradiated.

  The coated copper wire as sample 10 has various thicknesses (cross-sections), and the fluorescent X-ray intensity varies depending on the thickness. Therefore, the computer 17 (CPU 21) that receives the measurement data is the same as the conventional technology. Similarly, the fluorescent X-ray intensity is corrected based on the scattered X-ray intensity. However, the scattered X-ray includes a scattered X-ray component of copper, and the conventional technique cannot obtain an accurate scattered X-ray intensity. In the present invention, the influence of the scattered X-ray component of copper is corrected to obtain an accurate scattered X-ray intensity.

  FIG. 4 is a flowchart illustrating an example of a procedure for correcting the scattered X-ray intensity. The CPU 21 reads (acquires) the correspondence relationship data (FIG. 3A) stored in the hard disk 23, and determines the thickness t1 of the sample 10 corresponding to the measured value of the fluorescent X-ray intensity of copper (S10). ) And stored in the RAM 22. Subsequently, the correspondence data (FIGS. 3B and 3C) stored in the hard disk 23 is read (obtained) by the CPU 21, and the scattered X-ray intensity of copper is determined from the determined thickness t1 of the sample 10. SC1, the scattered X-ray intensity SR1 of the synthetic resin is determined (S12) and stored in the RAM 22. Next, the CPU 21 calculates the copper ratio r from the measured value s (measurement data) of the scattered X-ray intensity (S14) and stores it in the RAM 22.

Here, the ratio r of copper is the ratio of copper in the X-ray irradiation area (irradiation part) of the sample 10, and r = 1 when the X-ray irradiation area is entirely copper. FIG. 5A shows an example of the X-ray irradiation area of the sample. The measured value s of scattered X-ray intensity, the scattered X-ray intensity SC1 of copper, the scattered X-ray intensity SR1 of synthetic resin, and the ratio r of copper are:
s = SR1 + (SC1 × r)
And
r = (s-SR1) / SC1
It is. The CPU 21 calculates r using s, SR1, and SC1 stored in the RAM 22.

  Next, the fluorescent X-ray intensity characteristic of copper is multiplied by r by the CPU 21 (S16). FIG. 5B is a diagram showing an example of r-folded copper fluorescent X-ray intensity characteristics. In the figure, the r-folded fluorescent X-ray intensity characteristics are indicated by a one-dot chain line. The X-ray fluorescence intensity indicated by the alternate long and short dash line is determined by r-folding the fluorescence X-ray intensity (indicated by the solid line) with 100% copper by the CPU 21. The obtained fluorescent X-ray intensity characteristics are stored in the RAM 22. Hereinafter, the curve indicated by the one-dot chain line is the fluorescent X-ray intensity characteristic of copper. The CPU 21 determines the thickness t2 of the sample 10 corresponding to the measured value of the fluorescent X-ray intensity of copper based on the fluorescent X-ray intensity characteristic (indicated by a one-dot chain line) stored in the RAM 22 (S18), and stores it in the RAM 22 Is done.

  Next, the CPU 21 obtains the difference between the thicknesses t1 and t2 of the sample 10, and compares the absolute value of the obtained difference with Δt stored in advance in the hard disk 23 (S20). When the absolute value | t1-t2 | is equal to or smaller than Δt (S20: YES), the CPU 21 obtains the scattered X-ray intensity corresponding to the thickness t2 of the sample 10 from the correspondence data (FIG. 3C). Using the scattered X-ray intensity of the synthetic resin, the measured value of the fluorescent X-ray intensity of the synthetic resin is corrected (S24). Thereafter, the CPU 21 creates display data based on the corrected measurement value of the fluorescent X-ray intensity of the synthetic resin (S24) and outputs the display data to the output unit 26. If the absolute value | t1-t2 | is greater than Δt (S20: NO), the CPU 21 assigns t2 to t1 (S22), returns to S12, and the same processing is performed.

  In the above-described embodiment, the sample 10 has been described by taking a coated copper wire formed by coating copper with a synthetic resin as an example. However, what is coated with a synthetic resin is not limited to copper, and penetrates the synthetic resin. Any substance that generates fluorescent X-rays can be coated with a synthetic resin. Further, the coating of a material such as copper is not limited to a synthetic resin, and the coating can be performed with an arbitrary coating material that allows fluorescent X-rays generated from a material such as copper to penetrate.

It is a schematic diagram which shows the structure of the X-ray analyzer which concerns on this invention. It is a block diagram which shows the structural example of a computer. (A) is a figure which shows the correspondence of the thickness of a sample, and the fluorescent X ray intensity of copper, (b) is a figure which shows the correspondence of the thickness of a sample and the scattered X-ray intensity of copper, (c ) Is a diagram showing the correspondence between the thickness of the sample and the scattered X-ray intensity of the synthetic resin. It is a flowchart which shows the example of the correction | amendment procedure of scattered X-ray intensity. (A) is a figure which shows the example of the X-ray irradiation area of a sample, (b) is a figure which shows the example of the fluorescent X-ray-intensity characteristic multiplied by r. (A) is a figure which shows the example of the measurement result of the X-ray spectrum of a covering copper wire, (b) is a figure explaining the outline of the correction | amendment using a scattered X-ray.

Explanation of symbols

2 X-ray source 3 Mount 5 X-ray conduit 7 Detection means 10 Sample 15 Imaging means 16 Measurement means 17 Computer 21 CPU
23 Hard disk 24 External storage

Claims (5)

X-rays are applied to the irradiated object that covers the object with the covering material, the fluorescent X-ray intensity and scattered X-ray intensity generated by the irradiation are measured, and the fluorescent X-ray intensity is corrected using the scattered X-ray intensity. In the X-ray analysis method for performing quantitative analysis of the coating material using the corrected fluorescent X-ray intensity,
Determining the fluorescent X-ray intensity and based on the corresponding relationship between the irradiation object thickness, the first object to be irradiated thickness corresponding to the measured value of the fluorescent X-ray intensity of the object of the object,
Determining the scattered X-ray intensity of the object corresponding to the determined first irradiated body thickness based on the correspondence between the scattered X-ray intensity of the object and the irradiated body thickness;
Determining a temporary scattered X-ray intensity of the covering material corresponding to the determined first irradiated body thickness based on the correspondence between the scattered X-ray intensity of the covering material and the irradiated body thickness;
Calculating the ratio of the object in the X-ray irradiated portion of the irradiated object according to the measured scattered X-ray intensity, the scattered X-ray intensity of the object, and the provisional scattered X-ray intensity of the covering material;
In the correspondence relationship between the fluorescent X-ray intensity of the object and the thickness of the irradiated object, the fluorescent X-ray intensity of the object corresponding to the irradiated body thickness is multiplied by the calculated ratio to obtain a fluorescence corresponding to the ratio. Obtaining X-ray intensity characteristics;
Determining a second irradiated object thickness corresponding to a measured value of the fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristic according to the ratio;
Calculating the scattered X-ray intensity of the covering material corresponding to the determined second irradiated object thickness based on the correspondence relationship between the scattered X-ray intensity of the covering material and the irradiated object thickness. Correcting the measurement value of the fluorescent X-ray intensity of the coating material using the calculated scattered X-ray intensity of the coating material, and performing the quantitative analysis of the coating material using the corrected measurement value of the fluorescent X-ray intensity X-ray analysis method characterized by the above.   2. The X-ray analysis method according to claim 1, wherein X-rays are irradiated to an irradiated object formed by coating copper with a synthetic resin, and quantitative analysis of the synthetic resin is performed. X-rays are applied to the irradiated object that covers the object with the covering material, the fluorescent X-ray intensity and scattered X-ray intensity generated by the irradiation are measured, and the fluorescent X-ray intensity is corrected using the scattered X-ray intensity. In the X-ray analyzer for quantitative analysis of the coating material using the corrected fluorescent X-ray intensity,
Correspondence between the fluorescent X-ray intensity and irradiated body thickness of the object, the corresponding relationship, and the scattered X-ray intensity of the coating material and the object to be irradiated thickness of the scattered X-ray intensity and irradiated body thickness before Symbol object A storage unit for storing the correspondence relationship of
Based on the correspondence between the fluorescent X-ray intensity of the object and the irradiated body thickness stored in the storage unit, the first irradiated body thickness corresponding to the measured value of the fluorescent X-ray intensity of the object is determined. Means to
Based on the correspondence relationship between the scattered X-ray intensity of the object and the irradiated object thickness stored in the storage unit, the scattered X-ray intensity of the object corresponding to the determined first irradiated object thickness is determined. and hand stage that,
Temporary scattered X-rays of the covering material corresponding to the first irradiated body thickness determined based on the correspondence relationship between the scattered X-ray intensity of the covering material and the irradiated body thickness stored in the storage unit Means for determining the strength;
Means for calculating the proportion of the object in the X-ray irradiated portion of the irradiated object according to the measured scattered X-ray intensity, the scattered X-ray intensity of the object, and the temporary scattered X-ray intensity of the covering;
In the correspondence relationship between the fluorescent X-ray intensity of the object stored in the storage unit and the irradiated body thickness, the fluorescent X-ray intensity of the object corresponding to the irradiated body thickness is multiplied by the calculated ratio. , Means for obtaining fluorescent X-ray intensity characteristics according to the ratio,
Means for determining a second irradiated object thickness corresponding to a measured value of the fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristic according to the ratio;
Based on the correspondence relationship between the scattered X-ray intensity of the covering material and the irradiated body thickness stored in the storage unit, the scattered X-ray intensity of the covering material corresponding to the determined second irradiated body thickness is determined. And calculating the fluorescent X-ray intensity of the covering material using the scattered X-ray intensity of the covering material calculated by the calculating means, and calculating the corrected measured value of the fluorescent X-ray intensity. An X-ray analyzer characterized in that it is configured to perform quantitative analysis of the covering material. Means for determining a difference between the first irradiated body thickness and the second irradiated body thickness, and comparing the absolute value of the determined difference with a predetermined value;
Means for substituting the second irradiated object thickness into the first irradiated object thickness and determining the scattered X-ray intensity of the object when the absolute value of the difference is larger than a predetermined value; , Means for determining the provisional scattered X-ray intensity of the covering material, means for calculating the ratio, means for obtaining fluorescent X-ray intensity characteristics according to the ratio, means for determining the second irradiated object thickness, And a means for repeating the operation of the means for performing the comparison,
The calculating means includes
When the absolute value of the difference is equal to or less than a predetermined value, the scattered X-ray intensity of the covering material corresponding to the second irradiated body thickness is calculated. The X-ray analyzer according to claim 3. Fluorescent X-rays using scattered X-ray intensity in a computer that has received measurement data of fluorescent X-ray intensity and scattered X-ray intensity generated when X-rays are irradiated to an irradiated object that covers an object with a covering material In a computer program that executes intensity correction processing and executes quantitative analysis processing of the coating material using the corrected fluorescent X-ray intensity,
The computer instructions based on the corresponding relationship between the fluorescent X-ray intensity and irradiated body thickness of the object, Ru is determined first irradiated object thickness corresponding to the measured value of the fluorescent X-ray intensity of the object When,
A step of causing a computer to determine the scattered X-ray intensity of the object corresponding to the determined first irradiated body thickness based on the correspondence between the scattered X-ray intensity of the object and the irradiated body thickness;
Based on the correspondence between the scattered X-ray intensity of the covering material and the irradiated body thickness, the computer determines the temporary scattered X-ray intensity of the covering material corresponding to the determined first irradiated body thickness. Procedure and
Procedure for causing a computer to calculate the ratio of the object in the X-ray irradiated portion of the irradiated object according to the measured scattered X-ray intensity, the scattered X-ray intensity of the object, and the temporary scattered X-ray intensity of the covering material When,
In the correspondence relationship between the fluorescent X-ray intensity of the object and the irradiated body thickness, the computer is multiplied by the calculated ratio by the calculated fluorescent X-ray intensity of the object corresponding to the irradiated body thickness. A procedure for obtaining the corresponding fluorescent X-ray intensity characteristics;
A procedure for causing a computer to determine a second irradiated object thickness corresponding to a measured value of the fluorescent X-ray intensity of the object in the fluorescent X-ray intensity characteristics according to the ratio;
A procedure for causing a computer to calculate the scattered X-ray intensity of the covering material corresponding to the determined second irradiated object thickness based on the correspondence between the scattered X-ray intensity of the covering material and the irradiated object thickness ; A computer is used to correct the measured value of the fluorescent X-ray intensity of the coating material using the calculated scattered X-ray intensity of the coating material, and the corrected measurement value of the fluorescent X-ray intensity of the coating material is used. A computer program for performing quantitative analysis.

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