JP5519569B2 - X-ray fluorescence analyzer and method - Google Patents

Description

  The present invention relates to a fluorescent X-ray analysis technique for analyzing components contained in an analysis target using fluorescent X-rays.

One of the methods for non-destructively analyzing the constituent elements constituting the analysis target or the adhering elements on the surface among the components included in the analysis target, which is the analysis target, is a fluorescent X-ray analysis method. An apparatus that executes this X-ray fluorescence analysis method is called an X-ray fluorescence analyzer.
Fluorescence X-ray analysis is an analysis method that can perform qualitative analysis, quantitative analysis, chemical state analysis, or any one of these simultaneously for many types of elements in an analysis target. However, the object of analysis is mainly solid material.

Among the above analysis methods, quantitative analysis is analysis relating to the concentration of the element such as composition analysis and trace analysis, and includes measurement of film thickness such as plating film thickness. In the present invention, these are called quantitative information.
In the quantitative analysis, quantitative information of the element is obtained through calculation from the measured fluorescent X-ray intensity of the element based on physical or chemical assumptions such as setting of physical or chemical constants. The quantitative information may indicate the density itself, but may be a relative value indicating the magnitude of the density. The fluorescent X-ray intensity of the measured element itself may be treated as quantitative information of the element without calculation, but this is not included in the present invention.

Large-scale devices placed in laboratories are the mainstream of X-ray fluorescence analyzers, but recently portable X-ray fluorescence analyzers have also been sold. For example, there is a portable fluorescent X-ray analyzer sold by HORIBA, Ltd. (see, for example, Non-Patent Document 1).
Examples of the application of quantitative information include non-destructive qualitative analysis and quantitative analysis on an analysis object such as a building structure on the site where the analysis object exists.

  On the other hand, in the field of electric power and telecommunications, which are social infrastructures, many structures that support transmission lines and communication lines are installed outdoors, so salt damage can cause corrosion due to the installation environment. Since it is an accelerating element, there is a need to measure chlorine contained in salinity on site (for example, see Non-patent Document 2).

http://www.horiba.com/jp/scientific/products-jp/x-ray-fluorescence-analysis/details/mesa-portable-8946/ http://www.ourstex.co.jp/application/data029.html

  In such a conventional fluorescent X-ray analysis method, when performing quantitative analysis, the uniformity of the analysis target is assumed as one of physical or chemical assumptions. The uniformity of the analysis target is, for example, when the analysis target itself is analyzed as it is, when the measurement surface for analysis is flat, or when sampling and measuring from the analysis target on the spot , Refers to uniformly distributing on a plane.

  However, when sampling and measuring in situ from an analysis object, even distribution on a plane means destroying the analysis object in sampling. For example, when measuring salinity in a concrete structure, sampling called “core removal” is performed from the concrete structure, and the sampled sample (core specimen) is pulverized to obtain a powder to be analyzed. The chlorine X-ray intensity of chlorine is measured by a fluorescent X-ray analyzer, and quantitative information on chlorine and salinity is obtained through calculation based on physical or chemical assumptions.

  At this time, if the concrete structure is, for example, a large-scale bridge or pier, there will be no problem with core removal by taking subsequent measures such as backfilling. Since there is a concern about the troubles associated with unplugging, sampling like this is usually not performed. In addition, when the analysis target is made of metal, it is difficult to obtain the analysis target powder as in the case of concrete.

  On the other hand, when analyzing the analysis object itself as it is, the fluorescent X-ray intensity of the element on the surface is measured by a fluorescent X-ray analyzer, and the element is assumed to have a flat measurement surface for analysis. Get quantitative information. In this case, for example, if the measurement surface to be analyzed is a flat surface of the pier, the premise can be considered to be sufficient, but for example, if the analysis target is a steel rod, the measurement surface has a certain curvature. Such a premise does not hold. If this assumption is not satisfied, it is impossible to accurately obtain information about the amount of the element to be analyzed included in the analysis target.

  As what uses a steel bar as an outdoor structure, there exists what is called a branch line which supports the concrete electric pole on which a power transmission line and a communication line are spanned, for example. There are various standards for the branch line, and depending on the standard, the diameter of the steel bar portion is different, that is, the curvature is different. If the curvature changes, the fluorescent X-ray intensity of the element to be analyzed changes even if the analysis target is a plurality of analysis objects having the same physical and chemical properties other than the curvature. That is, under conditions where the curvature is different, the fluorescent X-ray intensity itself of the element to be analyzed is not proportional to the amount of the element. That is, even if it is a relative value, it cannot be discussed with the amount of fluorescent X-ray intensity of the element to be analyzed.

  As described above, in the conventional X-ray fluorescence analysis method and X-ray fluorescence analyzer, when the measurement surface of the analysis target has a curvature, information about the amount of the element to be analyzed of the component included in the analysis target is accurate. There was a problem that could not be obtained.

  The present invention is for solving such problems, and even when the measurement surface of the analysis target has a curvature, information on the amount of the element to be analyzed of the component included in the analysis target can be accurately obtained. The object is to provide a fluorescent X-ray analysis technique.

In order to achieve such an object, an X-ray fluorescence analyzer according to the present invention generates an X-ray generated from an X-ray generation unit that irradiates an analysis target and the surface of the analysis target according to the X-ray. An X-ray detector that detects fluorescent X-rays and measures the intensity thereof, and a control unit that calculates quantitative information about elements present on the surface of the analysis target based on the fluorescent X-ray intensity measured by the X-ray detector And the control unit corrects the quantitative information calculated from the fluorescent X-ray intensity based on the curvature or radius of the analysis target surface. Specifically, the analysis target surface has the curvature 1 / R. The X-ray detection unit is arranged at a position facing the curved surface, has a detection surface for detecting fluorescent X-rays from the curved surface, and the control unit is a virtual plane parallel to the radial direction of the curved surface , The length of the intersecting line segment that intersects the virtual plane of the detection surface is D The position where the normal of the detection surface extending from the center point P of the intersecting line segment to the center point of the curved surface is orthogonal to the curved surface is point A, the distance from the center point P to point A is L, and the center point is the center. An arbitrary position where the radius of rotation is perpendicular to the curved surface is defined as point B, the angle formed by point A and point B with respect to the center point is defined as θ, and the length of the line segment connecting point B and point P is defined as d. When the angle formed by the line segment and the tangent to the point B is α, the quantitative information is corrected by a correction coefficient expressed by the equation (12) described later.

  At this time, a curvature measuring unit that measures the curvature of the surface to be analyzed is further provided, and the control unit corrects the quantitative information calculated from the fluorescent X-ray intensity based on the curvature obtained by the curvature measuring unit. May be.

Moreover, the fluorescent X-ray analysis method according to the present invention detects fluorescent X-rays generated from the surface of the analysis target according to the X-rays irradiated to the analysis target, measures the intensity, and based on the fluorescent X-ray intensity. Thus, when calculating quantitative information regarding an element present on the surface of the analysis target, the quantitative information is corrected based on the curvature or radius of the analysis target surface. Specifically, the analysis target surface has a curvature of 1 When detecting X-rays, a detection surface arranged at a position opposite to the curved surface detects fluorescent X-rays from the curved surface and corrects quantitative information. In the virtual plane parallel to the direction, the length of the crossing line segment that intersects the virtual plane in the detection surface is D, and the normal line of the detection surface extending from the center point P of the crossing line segment to the center point of the curved surface is orthogonal to the curved surface The position to be performed is point A, and the distance from the center point P to point A is L An arbitrary position where the radius of rotation that rotates around the center point is orthogonal to the curved surface is defined as point B, an angle formed by point A and point B with respect to the center point is defined as θ, and a line connecting point B and point P When the length of the minute is d and the angle between the line segment and the tangent of the point B is α, the quantitative information is corrected by the correction coefficient expressed by the equation (12) described later. is there.

  At this time, the curvature of the analysis target surface may be measured, and the quantitative information may be corrected based on the curvature.

  According to the present invention, even when the measurement surface to be analyzed has a curvature, it is possible to accurately obtain information on the amount of an element to be analyzed that is a component included in the analysis target.

It is explanatory drawing which shows the structure of the fluorescent-X-ray-analysis apparatus concerning one Embodiment. It is a flowchart which shows the fluorescent X ray analysis process concerning one Embodiment. It is explanatory drawing which shows the curvature measuring mechanism using a template. It is a perspective view which shows the positional relationship of an analysis object and an X-ray detector. It is a top view which shows the positional relationship (on a virtual plane) with an analysis object and an X-ray detector. It is a flowchart which shows the calculation procedure of the quantitative information in the conventional fluorescent X ray analysis method.

[Principle of the Invention]
In the X-ray fluorescence analysis method, X-rays are irradiated to an analysis object, and the X-ray fluorescence intensity is obtained for the X-ray fluorescence having a wavelength specific to the element type of the element included in the analysis object. At this time, the target element is directly the element to be analyzed, but in order to obtain quantitative information about the element to be analyzed, elements other than the element to be analyzed included in the analysis target are measured, and the fluorescent X-ray intensity of the element It may be necessary to get

FIG. 6 is a flowchart showing a procedure for calculating quantitative information in the conventional fluorescent X-ray analysis method.
In the conventional fluorescent X-ray analysis method, first, the intensity of fluorescent X-rays obtained by irradiating an analysis object with X-rays is measured (step 200), and the obtained fluorescent X-ray intensity is processed and analyzed. The quantitative information of the element is calculated (step 201), and the obtained quantitative information is output (step 202).

  In general, one of the simplest of the above arithmetic processes is that the fluorescent X-ray intensity of an element is proportional to the amount of the element, and the amount of the analyzed element in the standard sample whose amount of the analyzed element is known and this analyzed Division or multiplication by a proportional constant with the fluorescent X-ray intensity of the element is performed on the fluorescent X-ray intensity of the element to be analyzed whose amount contained in the analysis target is unknown.

  In such a conventional method, when the curvature of the analysis target changes, correction according to the curvature is not performed, so the correspondence between the amount of the analyzed element and the fluorescent X-ray intensity of the analyzed element is not 1: 1. In other words, it is difficult to obtain quantitative information on the element to be analyzed from the fluorescent X-ray intensity of the element to be analyzed unless the range of curvature values is limited.

  On the other hand, the present invention includes correction of quantitative information by curvature as a part of calculation processing, and after inputting a curvature that is a variable, performs calculation on the fluorescent X-ray intensity of the element to obtain quantitative information of the element. It ’s what you get. Therefore, according to the present invention, in order to obtain the quantitative information of the analyzed element in accordance with the curvature of the analysis target including the analyzed element, the fluorescent X-ray intensity of the analyzed element is used. Through correction according to the curvature, information on the amount of the element to be analyzed can be obtained accurately.

[X-ray fluorescence analyzer]
Next, a fluorescent X-ray analyzer according to an embodiment of the present invention will be described with reference to FIGS. FIG. 1 is an explanatory diagram illustrating a configuration of a fluorescent X-ray analyzer according to an embodiment. FIG. 2 is a flowchart showing a fluorescent X-ray analysis process according to an embodiment.

  The X-ray fluorescence analyzer 10 as a whole is a cancer type considering use in handheld, measures the intensity of X-ray fluorescence obtained by irradiating an analysis target with X-rays, and based on the measurement result. Thus, it is a device for calculating quantitative information such as concentration, for example, regarding elements constituting the analysis target.

The analysis target 20 is a target for performing fluorescent X-ray analysis. As a specific example, there is an outdoor facility having a curved surface, such as a steel pipe column, a suspension line, and a branch line, as a line facility related to communication.
The salinity adhering to this kind of equipment has a great influence on the corrosion of the equipment, so it is necessary to evaluate the amount of salt adhering. Since X-ray fluorescence analysis enables nondestructive measurement at a site where equipment is installed, a salinity measurement method using the X-ray fluorescence analyzer 10 is used.

  The X-ray fluorescence analyzer 10 mainly includes a main body 11, an X-ray entrance / exit 12, a curvature measurement unit 13, a display unit 14, a grip unit 15, and an X-ray emission button 16.

The main body 11 includes an X-ray generator 11A, an X-ray detector 11B, and a controller 11C.
The X-ray generation unit 11 </ b> A has a function of generating irradiation X-rays 21 in accordance with the operation of the X-ray generation button 16 and emitting the irradiation X-rays 21 from the X-ray entrance 12 to the analysis target 20.
The X-ray detector 11B measures the intensity of the fluorescent X-rays 22 generated from the analysis target 20 by the irradiation X-rays 21 irradiated by the irradiation X-rays 21 for each wavelength, that is, for each photon energy of the X-rays. It has a function to do. This fluorescent X-ray 22 has a wavelength peculiar to the element contained in the analysis target 20, that is, photon energy.

  The control unit 11C includes an arithmetic processing circuit such as a CPU, and based on the measurement result obtained by the X-ray detector 11B, calculates a quantitative information such as the concentration of an element constituting the analysis target 20, and an analysis A function for calculating a correction coefficient for correcting quantitative information based on the curvature of the object 20 or a device constant specific to the apparatus, a function for correcting quantitative information by this correction coefficient, and a measurement result or quantitative information The display unit 14 has a function of displaying various types of information.

  The X-ray entrance / exit part 12 includes an opening provided at the tip of the main body 11, and the irradiation X-ray 21 from the X-ray generation part 11 </ b> A and the fluorescent X-ray 22 from the analysis target 20 enter and exit.

  The curvature measuring unit 13 is provided at the distal end portion of the X-ray entrance / exit portion 12 and has a function of measuring the curvature of the analysis target 20. As a specific mechanism of the curvature measuring unit 13, for example, there is a mechanism that uses a template having a plurality of curvatures and closely contacts the analysis target 20 and adopts the curvature of the template having the best adhesion.

3A and 3B are explanatory views showing a curvature measuring mechanism using a template. FIG. 3A is an external view and FIG. 3B is a plan view.
A template 13A in which a concave portion 13B having a certain curvature is formed is attached to the tip of the curvature measuring unit 13, and as shown in FIG. 3, the concave portion 13B of the template 13A is brought into close contact with a cylindrical rod-shaped analysis target 20. Thereby, when the curvature of the analysis object 20 and the curvature of the recessed part 13B correspond, the curvature of the analysis object 20 can be grasped | ascertained.

  Therefore, in order to correspond to the analysis object 20 having an arbitrary curvature, a plurality of templates 13A having different curvatures are prepared, and these templates 13A are exchanged to be closely attached to the analysis object 20, so that the curvature of the template 13A having the best adhesion is obtained. Should be adopted. At this time, if an identification circuit for identifying the template 13A attached to the curvature measuring unit 13 and outputting an identification signal to the control unit 11C is provided, the identification result of the template 13A, that is, the curvature of the analysis target 20 is controlled by the control unit. It becomes possible to detect automatically by 11C.

If it is clear that the cross-sectional shape of the equipment is a circle, the outer circumference, that is, the circumference is measured without using a template, or the diameter is measured to obtain the radius R, and the curvature 1 / R is obtained. May be. Moreover, you may provide the mechanism which automates the above operation.
As a specific mechanism for measuring the curvature, in addition to the mechanism using the template described above, the shape of the analysis target 20 is measured using laser beam scanning, and a spherical surface or a cylindrical surface that can approximate this shape is obtained. A known technique such as a mechanism for obtaining a curvature and a mechanism for obtaining a curvature by obtaining the diameter of the analysis target 20 by an adjustment function such as that found in a mechanical aperture of a camera may be used.

  The display unit 14 is provided in the upper part of the main body 11 and is composed of a display device such as an LCD or LED, and has a function of displaying various information output from the control unit 11C. The display unit 14 may be provided with an operation input unit such as a touch panel or a cursor key, and various information such as a curvature measured with a template may be input to the control unit 11C. Various information such as the curvature measured by the curvature measuring unit 13 may be displayed on the display unit 14.

The grip portion 15 is provided at the lower portion of the main body 11 and has a function of being held by the user when performing fluorescent X-ray analysis and holding the fluorescent X-ray analyzer 10 at a position facing the analysis target 20. ing.
The X-ray generation button 16 includes an operation unit such as a push button or an operation lever, and has a function of detecting an X-ray generation operation of the user and notifying the X-ray irradiation unit 11A and the control unit 11C.

[X-ray fluorescence analysis]
Next, with reference to FIG. 2, the X-ray fluorescence analysis process in the X-ray fluorescence analyzer 10 according to the embodiment of the present invention will be described. Here, a case where quantitative information is corrected based on the curvature of the analysis target 20 measured by the curvature measuring unit 13 will be described as an example.

In response to pressing of the X-ray generation button 16, the X-ray generation unit 11 </ b> A included in the main body 11 irradiates the analysis target 20 with the irradiation X-ray 21 through the X-ray entrance 12. In FIG. 1, it seems that there is a distance from the X-ray entrance 12 for the convenience of explanation, but it is actually close.
Thereby, the fluorescent X-ray 22 having a wavelength peculiar to the element included in the analysis target 20, that is, photon energy, is detected by the X-ray detector 11B included in the main body 11 through the X-ray entrance 12. The intensity is measured for each photon energy of the X-ray (step 100).

Next, the curvature measuring unit 13 measures the curvature of the analysis target 20 (step 101).
In addition, the control unit 11C included in the main body 11 is used for correcting quantitative information such as the size of the detector of the X-ray detector 11B registered in advance in the storage unit of the control unit 11C. An apparatus constant specific to the analyzer 10 is acquired (step 102).
Subsequently, the control unit 11C calculates a correction coefficient for correcting the quantitative information based on the curvature of the analysis target 20 obtained by the curvature measurement unit 13 and the device constant obtained from the storage unit (step 103). ).

  Thereafter, the control unit 11C calculates quantitative information of the analysis target 20 based on the intensity for each photon energy of the X-rays obtained by the X-ray detector 11B (step 104), and corrects this with a correction coefficient. (Step 105) and displayed on the display unit 14 (Step 106).

[Correction of quantitative information]
Next, with reference to FIG. 4 and FIG. 5, correction of quantitative information in the fluorescent X-ray analysis apparatus 10 according to one embodiment of the present invention will be described. FIG. 4 is a perspective view showing the positional relationship between the analysis target and the X-ray detector. FIG. 5 is a plan view showing the positional relationship (on a virtual plane) between the analysis target and the X-ray detector.
Here, as shown in FIG. 4, an example in which the analysis target 20 has a columnar shape and the surface of the analysis target 20 is a curved surface C having a constant radius R (curvature 1 / R) will be described as an example.

Assuming a virtual plane Z parallel to the radial direction of the radius R of the curved surface C, the analysis target and the X-ray detector have the positional relationship shown in FIG.
The detection surface 11S of the X-ray detection unit 11B is disposed at a position facing the curved surface C, and has a rectangular shape extending along the longitudinal direction Y of the curved surface C. Therefore, the detection surface 11S intersects the virtual plane Z at the intersection line segment S, and the length of the intersection line segment S, that is, the length of the effective detection region of fluorescent X-rays in the virtual plane Z is defined as D. In other words, the width of the detection surface 11S that faces the bending direction Q of the curved surface C is D. In FIG. 4, the X-ray detection unit 11 </ b> B is drawn to have a thickness, but only the detection surface 11 </ b> S contributes to X-ray detection.

  In the detection surface 11S, the center point of the intersection line segment S is set as a point P, and the light source of the X-ray generation unit 11A is arranged as a point light source at the position of the center point P. At this time, the position of the point light source is actually on a line that passes through the central point P and is orthogonal to the virtual plane Z, and does not interfere with X-ray detection on the detection surface 11S. You may make it arrange | position to a position. Here, for ease of explanation, it is assumed that the longitudinal direction Y is not considered and absorption in space is not considered for both irradiation X-rays and fluorescent X-rays.

  In FIG. 5, the position where the normal line T of the detection surface 11S extending from the center point P of the intersecting line segment S to the center point O of the curved surface C is orthogonal to the curved surface C is defined as a point A, and the distance from the central point P to the point A is defined. Let L be. Therefore, the distance L is the shortest distance between the detection surface 11S and the curved surface C. This distance L is given as a device constant or from the device constant and the radius R. The lateral width D is given as a device constant.

Further, an area where the fluorescent X-rays generated at an arbitrary point on the curved surface C can be detected by the detection surface 11S is defined as an effective area W. Further, in this effective area W, an arbitrary position where a radius vector V rotating around the center point O is perpendicular to the curved surface C is defined as a point B, and an angle formed by the point A and the point B with respect to the center point O is defined as an angle. Let θ.
In addition, the length of the line segment D connecting the point B and the point P is d, and the angle formed by the line segment D and the tangent line H of the point B is α.
Further, of the points B, the points located at both end portions of the effective area W are defined as limit points. Among these, the limit point at which the radius V is rotated counterclockwise from the point A by a positive angle θMAX is defined as BMAX, and the radius V is rotated clockwise from the point A by a negative angle −θMAX. A certain limit point is defined as B-MAX.

In FIG. 5, the length d of the line segment D connecting the point B and the point P is obtained by the following equation (1).

If the angle formed between the normal line T and the line segment D is β, the shortest distance L and the radius of curvature R are calculated using the angle α formed between the tangent line H and the line segment D and the length d in Expression (1). The sum L + R is obtained by the following equation (2).

Here, when the irradiated X-ray 21 is irradiated onto the curved surface C of the analysis target 20, for the effective area W in which the fluorescent X-ray can be detected by the detection surface 11S in the curved surface C, θMAX indicating the angle region on the curved surface C is Is given by the following equation (3).

The length of a very short arc on the circumference with the point B is represented by Rdθ using a minute angle dθ. If the irradiation X-ray 21 is attenuated by the square of the distance, the following equation (4) is established for the irradiation X-ray intensity dI at Rdθ at the point B.

Further, when the element to be analyzed exists uniformly and thinly on the surface of the analysis target 20, the fluorescent X-ray intensity dI ′ of the element to be analyzed generated at Rdθ at the point B using the concentration c of the element to be analyzed per unit area. Similarly, the following equation (5) holds.

Here, if the fluorescent X-ray of the element to be analyzed generated at Rdθ at the point B isotropically spread, the fluorescent X-ray intensity dF of the analyzed element detected by the X-ray detector 11B is X-ray. The detection unit of the detector 11B is proportional to the solid angle stretched with respect to the point B. In the example of FIG. 5, since the analysis target 20 is assumed to be cylindrical, the angle γ is used instead of the solid angle. At this time, the following approximate expression (6) is obtained for the fluorescent X-ray intensity dF. K is a proportional constant between the concentration c and the fluorescent X-ray intensity F.

Therefore, the total fluorescent X-ray intensity F of the analysis element detected by the X-ray detector 11B is given by the following formula (7).

Here, referring to the expressions (1) and (2) described above, α and d in the expression (7) are functions of θ including R. Therefore, as shown in the following expression (8), The integrand is also expressed as a function of θ including R.

Therefore, if a function obtained by integrating Expression (8) with θ is G (R, θ), Expression (7) becomes the following Expression (9).

Further, according to Equation 3, θMAX is also a function of R, so Equation (9) is rewritten as the following Equation (10).

As a result, the concentration G of the element to be analyzed per unit area that has a proportional relationship with the fluorescent X-ray intensity F via the proportional constant K, that is, quantitative information, varies depending on the curvature R of the analysis target 20. Expression (11) indicating that correction is performed with the correction coefficient consisting of R) is obtained.

Therefore, it can be seen that the concentration c calculated by the fluorescent X-ray intensity F and the proportionality constant K is corrected by the function G (R) specified by the curvature R in the equation (11).
Thereby, using such a correction method, from the total fluorescent X-ray intensity F measured by the X-ray detector 11B, the concentration c of the element to be analyzed per unit area, that is, the quantity of the element to be analyzed is quantitative. Information can be obtained accurately.

As described above, generally, when the analysis target is a plane, the fluorescent X-ray intensity F and the concentration c can be expressed by a proportional relationship of F = cK using the proportional coefficient K. For this reason, the coefficient in the case of the curved surface C, that is, the correction coefficient G (R) is expressed by the following expression (12) using the integral term in the expression (7) and the expression (3). You can also.

[Effects of the present embodiment]
Thus, in the present embodiment, the control unit 11C corrects the quantitative information calculated from the fluorescent X-ray intensity based on the curvature 1 / R or the radius R of the surface of the analysis target 20. Even when the measurement target measurement surface has a curvature, information on the amount of the element to be analyzed of the component included in the analysis target can be obtained accurately.

  Moreover, in this Embodiment, the curvature measurement part 13 measures the curvature of the surface of the analysis target 20, and a control part is the quantity calculated from fluorescence X-ray intensity based on the curvature obtained in the curvature measurement part. Since the target information is corrected, it is not necessary to check the curvature of the surface in advance, and the work load required for the fluorescent X-ray analysis can be reduced.

  In the present embodiment, the surface of the analysis target 20 is a curved surface having a curvature 1 / R, and the X-ray detection unit 11B is arranged at a position facing the curved surface to detect fluorescent X-rays from the curved surface. In the virtual plane Z parallel to the radial direction of the curved surface C, the length of the intersecting line segment that intersects the virtual plane is D, and the length of the curved surface from the center point P of the intersecting line segment The position where the normal of the detection surface extending to the center point is orthogonal to the curved surface is point A, the distance from the center point P to point A is L, and the radius of rotation about the center point is an arbitrary position orthogonal to the curved surface Is the point B, the angle between the point A and the point B with respect to the center point is θ, the length of the line segment connecting the point B and the point P is d, and the line segment and the tangent line of the point B form When the angle is α, the correction coefficient is obtained by the above-described equation (12), so it is extremely accurate. It becomes possible to correct quantitative information.

  In the present embodiment, device constants necessary for correction of curvature may be input at the time of measurement, but since they are device-specific constants, it is better to store them in advance in a storage unit of a computer. The curvature may be input every time the curvature is different. In this case, when measuring different analysis objects having the same curvature, the curvature input in the previous measurement may be used as it is without inputting the curvature. Instead of the curvature, a method of inputting a radius of curvature that is the reciprocal of the curvature may be used. Further, the curvature may be obtained by using automatic measurement of the shape to be analyzed, manual measurement, or both. Further, the curvature may be displayed.

[Extended embodiment]
The present invention has been described above with reference to the embodiments, but the present invention is not limited to the above embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention within the scope of the present invention.

  DESCRIPTION OF SYMBOLS 10 ... X-ray fluorescence analyzer, 11 ... Main body, 12 ... X-ray entrance / exit part, 13 ... Curvature measuring part, 13A ... Template, 13B ... Recessed part, 14 ... Display part, 15 ... Gripping part, 16 ... X-ray generation button, 20 ... analytical object, 21 ... irradiated X-ray, 22 ... fluorescent X-ray.

Claims (4)

An X-ray generator that generates X-rays and irradiates the analysis target;
An X-ray detector that detects fluorescent X-rays generated from the surface of the analysis object according to the X-rays and measures the intensity thereof;
A controller that calculates quantitative information on the elements present on the surface of the analysis target based on the fluorescent X-ray intensity measured by the X-ray detector;
The analysis target surface is a curved surface having a curvature 1 / R,
The X-ray detection unit is disposed at a position facing the curved surface, and has a detection surface for detecting fluorescent X-rays from the curved surface,
The controller is
In a virtual plane parallel to the radial direction of the curved surface,
Let D be the length of the intersecting line segment that intersects the virtual plane of the detection surface,
A point where the normal of the detection surface extending from the center point P of the intersecting line segment to the center point of the curved surface is orthogonal to the curved surface is a point A,
The distance from the center point P to the point A is L,
An arbitrary position where a radius of rotation that rotates around the center point is orthogonal to the curved surface is a point B,
An angle formed by the point A and the point B with respect to the center point is θ,
The length of the line segment connecting the point B and the point P is d,
When the angle formed by the line segment and the tangent of the point B is α,
The following formula

The fluorescent X-ray analyzer is characterized in that the quantitative information calculated from the fluorescent X-ray intensity is corrected by a correction coefficient represented by: The X-ray fluorescence analyzer according to claim 1,
A curvature measuring unit for measuring the curvature of the surface to be analyzed;
The said control part correct | amends the said quantitative information calculated from the said fluorescence X-ray intensity based on the said curvature obtained in the said curvature measurement part. The fluorescent X-ray-analysis apparatus characterized by the above-mentioned. Fluorescence X-rays generated from the surface of the analysis object are detected according to the X-rays irradiated to the analysis object, the intensity thereof is measured, and the elements present on the surface of the analysis object are based on the fluorescence X-ray intensity. Calculate quantitative information ,
The analysis target surface is a curved surface having a curvature 1 / R,
When detecting the X-ray, a detection surface arranged at a position facing the curved surface detects fluorescent X-rays from the curved surface;
When correcting the quantitative information,
In a virtual plane parallel to the radial direction of the curved surface,
Let D be the length of the intersecting line segment that intersects the virtual plane of the detection surface,
A point where the normal of the detection surface extending from the center point P of the intersecting line segment to the center point of the curved surface is orthogonal to the curved surface is a point A,
The distance from the center point P to the point A is L,
An arbitrary position where a radius of rotation that rotates around the center point is orthogonal to the curved surface is a point B,
An angle formed by the point A and the point B with respect to the center point is θ,
The length of the line segment connecting the point B and the point P is d,
When the angle formed by the line segment and the tangent of the point B is α,
The following formula

The fluorescent X-ray analysis method , wherein the quantitative information is corrected by a correction coefficient represented by : The fluorescent X-ray analysis method according to claim 3 ,
A fluorescent X-ray analysis method characterized by measuring a curvature of the surface to be analyzed and correcting the quantitative information based on the curvature.

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