JP2013088216A - Calibration sample for fluorescent x-ray analysis, fluorescent x-ray analyzer with the same and fluorescent x-ray analysis method using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a calibration sample or the like for fluorescent X-ray analysis of a liquid sample, which can be used for a long time and in which accurate drift calibration can be performed.SOLUTION: A calibration sample 20 is a solid-state calibration sample for calibrating aging in measured X-ray intensity of an analysis target metal element in fluorescent X-ray analysis of a liquid sample S. In the calibration sample 20, a metal layer 21 containing the analysis target metal element is formed while overlapping a light element layer 22 in which at least one light element of hydrogen, boron, carbon, nitrogen, oxygen and fluorine has a maximum mol fraction and of which the thickness is 1 mm or more. In the metal layer 21, a surface at the side opposite to a surface confronted with the light element layer 22 is used as an analysis surface 23.

Description

  The present invention relates to a calibration sample for fluorescent X-ray analysis, an X-ray fluorescence analyzer equipped with the same, and a fluorescent X-ray analysis method using the same.

  Conventionally, in a fluorescent X-ray analyzer that measures the intensity of fluorescent X-rays generated by irradiating a sample with primary X-rays, the measured X-ray intensity of the same sample changes (drifts) over time due to various causes. A so-called drift calibration is performed periodically to calibrate. For this drift calibration, for example, if the X-ray intensity is measured again for each element for all the standard samples used to create a calibration curve, a great amount of labor and time are required for each calibration. Therefore, a calibration sample is set for drift calibration and the reference X-ray intensity is measured, and when calibrating, only the set calibration sample is measured and the measured X-ray intensity at that time is used as the reference. A drift calibration coefficient is obtained from the measured X-ray intensity, and the drift calibration coefficient is applied to the measured X-ray intensity of the sample to be analyzed for calibration.

  Therefore, various calibration samples are used in fluorescent X-ray analysis. For example, there is a calibration sample in which a metal film such as Au, Pt, or Co is formed on a silicon substrate, which is used when analyzing a sample in which a metal film is formed on a silicon substrate (Patent Document 1).

  In addition, there are calibration samples used for fluorescent X-ray analysis, such as a trace powder sample placed on a thin film, a trace solution sample held on a filter paper or a polymer film, and a thin film sample. This calibration sample is formed of a polyimide film and a polyimide film mixed with an element to be analyzed on the polyimide film (Patent Document 2). As a modified example of the calibration sample, a calibration sample in which a polyimide film in which an element to be analyzed is mixed is formed on a metal foil or a substrate is known.

  Furthermore, when measuring the concentration of sulfur in crude oil and petroleum products, the standard sample in which heavy oil with a known sulfur concentration is enclosed in a container changes over time due to changes in concentration due to liquid leakage or precipitation. Since it cannot be used, there is a method using a solid simulated sample as a standard sample. This simulated sample is formed of a disk-shaped molybdenum main body and an absorber made of polyethylene terephthalate or polyimide provided on the primary X-ray irradiation side of the molybdenum main body (Patent Document 3).

JP 2005-156213 A JP 2010-204087 A Japanese Patent Laid-Open No. 7-5127

  The calibration sample described in Patent Document 1 is used for analyzing a sample in which a metal film is formed on a silicon substrate, that is, a solid sample. The calibration sample described in Patent Document 2 is used for analyzing a solid sample such as a trace powder sample or a thin film sample, and for analyzing a trace solution sample held on a filter paper or a polymer film. Since this calibration sample is used for analysis of a trace sample such as a trace powder sample or a trace solution sample, the background generated from the calibration sample is configured to be as small as possible.

  The simulated sample described in Patent Document 3 is used only for measuring the concentration of sulfur contained in crude oil and petroleum products, and is not used for other elements or other liquid samples. This simulated sample is formed of a disk-shaped molybdenum main body and an absorber provided on the primary X-ray irradiation side of the main body. This absorber attenuates the fluorescent X-ray intensity generated from the molybdenum main body. The background generated from the sample is not considered at all. The liquid sample contains light elements such as hydrogen, carbon, and oxygen as the main components in the solvent water or organic solvent, so it generates a lot of scattered X-rays. In addition, a lot of scattered X-rays are contained, and a large background is generated by the scattered X-rays. However, there has been no solid calibration sample in consideration of the background generated from a liquid sample.

  Thus, conventionally, there has been no calibration sample that can accurately perform the calibration of the time-dependent change (drift) of the measured X-ray intensity including the background generated from the liquid sample and can be used for a long period of time.

  The present invention has been made in view of the above-described conventional problems. A calibration sample for fluorescent X-ray analysis of a liquid sample that can be used over a long period of time and can perform accurate drift calibration, and fluorescent X-rays including the calibration sample. An object is to provide an analyzer and a fluorescent X-ray analysis method using the same.

  To achieve the above object, the calibration sample of the present invention is a solid calibration sample for calibrating a change in measured X-ray intensity over time of a metal element to be analyzed in a fluorescent X-ray analysis of a liquid sample. Formed by overlapping a metal layer containing the target metal element and a light element layer having a thickness of 1 mm or more with at least one light element of hydrogen, boron, carbon, nitrogen, oxygen and fluorine as the maximum molar fraction. In the metal layer, the surface opposite to the surface facing the light element layer is an analysis surface.

  The calibration sample of the present invention includes a metal layer containing a metal element to be analyzed, and a light element having a thickness of 1 mm or more having a maximum molar fraction of at least one light element among hydrogen, boron, carbon, nitrogen, oxygen, and fluorine. Since it is a solid formed by overlapping layers, it does not change over time due to evaporation, precipitation, alteration, etc., and can be used over a long period of time. Further, the metal layer is an analysis surface irradiated with primary X-rays, and the primary X-rays transmitted through the metal layer are incident on the light element layer, so that the light elements in the light element layer are analyzed with the liquid sample to be analyzed. Since similar scattered X-rays (background) are generated, accurate drift calibration can be performed.

  In the fluorescent X-ray analysis method of the present invention, fluorescent X-ray analysis of a liquid sample is performed using the calibration sample of the present invention.

  According to the fluorescent X-ray analysis method of the present invention, since the calibration sample of the present invention is used, the same effects as the calibration sample of the present invention can be achieved.

  In the fluorescent X-ray analysis method of the present invention, it is further preferable to use a background calibration sample that is formed only by the light element layer of the calibration sample and calibrates a change with time of the background X-ray intensity of the liquid sample. . In this case, since a calibration sample formed by the metal layer and the light element layer and a background calibration sample formed only by the light element layer are used, more accurate calibration is used. It can be performed.

  The X-ray fluorescence analyzer of the present invention is a drift calibration means for calibrating a change in measured X-ray intensity of a liquid sample over time based on the calibration sample of the present invention and the measured X-ray intensity of a metal element to be analyzed of the calibration sample. And comprising.

  According to the fluorescent X-ray analysis apparatus of the present invention, the drift for calibrating the time-dependent change of the measured X-ray intensity of the liquid sample based on the calibration sample of the present invention and the measured X-ray intensity of the metal element to be analyzed of the calibration sample. Since the calibration means is provided, the same effect as the calibration sample of the present invention can be obtained.

  The fluorescent X-ray analysis apparatus of the present invention further includes a background calibration sample that is formed of only the light element layer and calibrates a change in the background X-ray intensity of the liquid sample with time, and the drift calibration unit includes: It is preferable to calibrate the time-dependent change of the measured X-ray intensity of the liquid sample based on the measured X-ray intensity of the metal element to be analyzed of the calibration sample and the measured X-ray intensity of the background calibration sample. In this case, since a calibration sample formed by the metal layer and the light element layer and a background calibration sample formed only by the light element layer are used, more accurate calibration is used. It can be performed.

1 is a schematic view of a fluorescent X-ray analyzer according to a first embodiment of the present invention. It is a side view of the calibration sample with which the fluorescent X-ray-analysis apparatus is provided. It is a figure which shows the procedure which calculates | requires the thickness of the metal layer and light element layer of the same calibration sample. It is side surface sectional drawing of the modification of the same calibration sample. It is a side view of another modification of the calibration sample. It is a perspective view of the background calibration sample with which the fluorescent X-ray-analysis apparatus of 2nd Embodiment of this invention is provided.

  Hereinafter, the X-ray fluorescence analyzer of the first embodiment of the present invention will be described. As shown in FIG. 1, the X-ray fluorescence analyzer irradiates the sample stage 3 on which the liquid sample S or the calibration sample 20 is placed and the primary X-ray 2 to the liquid sample S or the calibration sample 20, for example, An X-ray source 1 that is a rhodium X-ray tube, a spectroscopic element 5 that splits secondary X-rays 4 generated from the liquid sample S or the calibration sample 20, and secondary X-rays 6 that are split by the spectroscopic element 5 are detected. A detector 7 and drift calibration means 9 are provided. The spectroscopic element 5 and the detector 7 constitute detection means 8. The drift calibration means 9 calibrates the change over time in the measured X-ray intensity of the liquid sample S based on the measured X-ray intensity of the metal element to be analyzed in the calibration sample 20. Secondary X-rays 4 and 6 include fluorescent X-rays and scattered X-rays.

  The calibration sample 20 is preferably placed at a predetermined position of a sample changer (not shown) or built in the apparatus.

The operation of the X-ray fluorescence analyzer of the first embodiment, that is, the X-ray fluorescence analysis method according to one embodiment of the present invention will be described. When X-ray fluorescence spectrometer is operated, it is first calibrated specimen 20 is measured, drift calibration means 9 stores the measured X-ray intensities for the secondary X-ray 7 in the analyzed metal element as a reference intensity I _S . Then, when the liquid sample S is sequentially measured and the measured X-ray intensity of the analysis target metal element is calibrated, the calibration sample 20 is measured and the intensity I _M of the secondary X-ray 7 of the analysis target metal element is determined. Desired. When the intensity I _M is obtained, the drift calibration means 9 calculates the drift calibration coefficient α from the following equation (1) based on the obtained intensity I _M and the previously stored reference intensity I _S.

α = I _S / I _M (1)

The drift calibration means 9, by multiplying the drift calibration coefficient α to measure X-ray intensity I _n of the analyte metal elements of the liquid sample S to be measured and performs drift calibration.

In the above example, were subjected to drift calibration by multiplying the drift calibration coefficient α to measure X-ray intensity I _n, to calibrate a calibration curve by multiplying the drift calibration coefficient α to the gradient constant a linear expression calibration curve drift Calibration may be performed.

  The solid calibration sample 20 included in the X-ray fluorescence analyzer of the first embodiment will be described in detail below. As shown in FIG. 2, the calibration sample 20 has a thickness in which the metal layer 21 containing the metal element to be analyzed and at least one light element among hydrogen, boron, carbon, nitrogen, oxygen, and fluorine has a maximum molar fraction. A light element layer 22 having a thickness of 1 mm or more is overlaid, and the metal layer 21 is bonded to the light element layer 22 with an adhesive. In the metal layer 21, a surface opposite to the surface facing the light element layer 22 is an analysis surface 23.

  In the calibration sample 20 included in the fluorescent X-ray analyzer of the first embodiment, the metal layer 21 is within twice the thickness that generates the fluorescent X-ray intensity corresponding to the maximum content of the analysis target element of the liquid sample S. It is preferable that the light element layer 22 is formed with a thickness that generates a background X-ray intensity equivalent to that of the liquid sample S.

  A method of obtaining the thickness of the metal layer 21 and the thickness of the light element layer 22 that matches the liquid sample S as described above will be described based on the procedure shown in FIG.

  In the first stage S1, in order to obtain the thickness of the metal layer 21 and the thickness of the light element layer 22, the fluorescent X-ray intensity (net X-ray intensity) generated from the metal layer 21 and the background generated from the light element layer 22 are obtained. Each target value with X-ray intensity is determined. The fluorescent X-ray intensity (net X-ray intensity) of the standard sample that generates the maximum fluorescent X-ray intensity among the plurality of standard samples for creating the calibration curve of the liquid sample S is determined as the target value of the metal layer 21. . The background X-ray intensity, which is the X-ray intensity of the created section of the calibration curve, is determined as the target value of the light element layer 22.

  In the second stage S2, the fluorescent X-ray intensity of the metal layer 21 determined as the target value in the first stage S1 is used to calculate the fluorescent X-ray intensity within the allowable range of the target value (for example, The thickness of the metal layer 21 that achieves the X-ray intensity of the target value (within 100 to 200%) is calculated.

  In the third step S3, the metal layer 21 having the thickness calculated in the second step S2 is formed, and the metal layer 21 is overlaid on the light element layer 22 having an arbitrary thickness of 1 mm or more to calibrate the sample 20. Form. With respect to the formed calibration sample 20, the fluorescent X-ray intensity of the metal layer 21 and the background X-ray intensity of the light element layer 22 are measured with a fluorescent X-ray analyzer. A form in which the calibration sample 20 is formed by overlapping the metal layer 21 and the light element layer 22 will be described later.

  In the fourth step S4, it is determined whether or not the fluorescent X-ray intensity of the metal layer 21 is within the allowable range of the target value determined in the first step S1. If it is determined that the fluorescent X-ray intensity of the metal layer 21 is within the allowable range of the target value, the process proceeds to the fifth step S5. If it is determined in the fourth stage S4 that the fluorescent X-ray intensity of the metal layer 21 is not within the allowable range of the target value determined in the first stage S1, the process proceeds to a fourth A stage S4A.

  In the fourth A stage S4A, the thickness of the metal layer 21 is changed so that the fluorescent X-ray intensity of the metal layer 21 is within the allowable range of the target value determined in the first stage S1, and the third stage S3 Returning to Step 4, the fourth stage S4A to the fourth stage until it is determined in the fourth stage S4 that the fluorescent X-ray intensity of the metal layer 21 is within the allowable range of the target value determined in the first stage S1. The procedure up to S4 is repeated.

  In the fifth step S5, it is determined whether or not the background X-ray intensity of the light element layer 22 is within an allowable range of the target value determined in the first step S1. If it is determined that the background X-ray intensity of the light element layer 22 is within the allowable range of the target value, the process proceeds to a sixth step S6. If it is determined in the fifth step S5 that the background X-ray intensity of the light element layer 22 is not within the allowable range of the target value determined in the first step S1, the process proceeds to a fifth A step S5A.

  In the fifth A stage S5A, the thickness of the light element layer 22 is changed so that the background X-ray intensity of the light element layer 22 is within the allowable range of the target value determined in the first stage S1. Returning to the third step S3, the fifth A step S5A is performed until it is determined in the fifth step S5 that the fluorescent X-ray intensity of the light element layer 22 is within the allowable range of the target value determined in the first step S1. The procedure from step S5 to step S5 is repeated.

  In the sixth step S6, the thicknesses of the metal layer 21 and the light element layer 22 are determined.

  As a modified example of the calibration sample 20, the calibration sample 20 in the case of analyzing nickel in the liquid sample S which is a nickel plating solution will be described. In the case of this calibration sample 20, as shown in FIG. 4, for example, a metal layer 21 that is a nickel foil 21 having a thickness of 10 μm is a light element layer that is a rectangular parallelepiped acrylic resin 22 having a thickness (height) of 10 mm, for example. The outer surface of the metal layer 21 is an analysis surface 23. The rectangular parallelepiped acrylic resin 22 is composed of light elements such as carbon, hydrogen, and oxygen, with hydrogen being the maximum molar fraction. The dimensions of the rectangular parallelepiped acrylic resin 22 are, for example, 100 mm in width, 100 mm in length, and 10 mm in thickness (height). The thicknesses of the metal layer 21 and the light element layer 22 of the calibration sample 20 for the liquid sample S, which is the nickel plating solution, are values obtained by the procedure shown in FIG.

  The annular fixture 50 includes an annular plate 51 and a fixing screw 52, and the fixing screw 52 is screwed into a screw hole 25 formed in an upper portion of the light element layer 22 (a portion to which the annular fixture 50 is fixed). The metal layer 21 is sandwiched and fixed between the upper surface of the light element layer 22 and the lower surface of the annular fixture 50 (the surface facing the light element layer 22). The method for fixing the metal layer 21 is not limited to the annular fixture 50 as described above, and may be fixed by other fixtures.

  In the calibration sample 20 of FIG. 2, a single 100 μm nickel foil is used as the metal layer 21. For example, as shown in FIG. 5, a plurality of nickel foils 21 a, 21 b, and 21 c are bonded with an adhesive. Then, a plurality of metal foils may be fixed by an annular fixture 50 shown in FIG. Further, in the case of the calibration sample 20 used for a plurality of analysis target metal elements, even if the metal layer 21 is formed by overlapping metal foils of different analysis target metal elements, a single metal containing the plurality of analysis target metal elements is included. You may form with foil. Further, the metal layer 21 may not be a metal foil, and may be formed by laminating a thin film of a metal element to be analyzed on the light element layer 22 by vapor deposition (PVD, CVD, etc.), plating, or the like. The metal layer 21 is preferably formed to a thickness corresponding to the concentration of the metal element to be analyzed contained in the liquid sample S based on the procedure shown in FIG. If the concentration is high, it is thick and preferably 10 to 300 μm. If the concentration is low, the thickness is thin and 1 to 10 μm is preferable. If the concentration is extremely low, it is preferably greater than 0 μm and less than 10 μm.

  In the present embodiment, the calibration sample 20 is formed by adhering, adhering, and vapor-depositing the metal layer 21 to the light element layer 22. However, the calibration sample 20 is overlapped with a gap between the light element layer 22 and the metal layer 21. May be formed.

  An acrylic resin is used for the light element layer 22, but any material having a thickness of 1 mm or more with at least one light element of hydrogen, boron, carbon, nitrogen, oxygen, and fluorine having the maximum molar fraction may be used. , High molecular organic compounds (polypropylene, polyethylene, polyimide, fluororesin, etc.), graphite, boron nitride, metal boron, quartz, glass, and the like. In graphite, carbon is the largest mole fraction, and in boron nitride, nitrogen and boron are the largest mole fraction. The light element layer 22 of the calibration sample 20 shown in FIGS. 2, 4, and 5 may be formed to a thickness (height) H corresponding to the type of the liquid sample S based on the procedure shown in FIG. As a specific numerical value of H, for example, 1 to 100 mm is preferable. The shape of the light element layer 22 is not limited to a rectangular parallelepiped, but may be a cylinder, a prism, or the like, and may be accommodated in a liquid sample container into which the liquid sample S is injected.

  By forming the light element layer 22 in this way, a background equivalent to that of the liquid sample S can be generated, and the fluorescent X-ray intensity versus the scattered X-ray intensity equivalent to that of the liquid sample S to be measured. Therefore, accurate drift calibration can be performed. Each of the calibration samples 20 described above with reference to FIGS. 2, 4, and 5 is also an embodiment of the present invention.

  According to the fluorescent X-ray analysis apparatus of the first embodiment, the calibration sample 20 provided in the fluorescent X-ray apparatus has a metal layer 21 formed of a metal element to be analyzed and a light element layer 22 of hydrogen, boron, carbon, nitrogen. , A solid formed of a material having a thickness of 1 mm or more having at least one light element of oxygen and fluorine as a maximum molar fraction, and the light element of the light element layer 22 is approximately the same as the liquid sample S. Since scattered X-rays (background) are generated, it can be used for a long period of time, and the measured X-ray intensity drift of the metal element to be analyzed can be accurately calibrated.

  Hereinafter, a fluorescent X-ray analyzer according to the second embodiment of the present invention will be described. The X-ray fluorescence analyzer of the second embodiment is formed by only the calibration sample 20 included in the X-ray fluorescence analyzer of the first embodiment and the light element layer 22 of the calibration sample 20, and the background X of the liquid sample S Two types of calibration samples are provided with a background calibration sample 40 (FIG. 6) for calibrating the change in line intensity with time, and the drift calibration means 9 measures the measured X-ray intensity and sample of the metal element to be analyzed in the calibration sample 20 The point which calibrates the time-dependent change of the measured X-ray intensity of the liquid sample S based on the measured X-ray intensity of the background calibration sample 40 placed on the table 3 is different from the fluorescent X-ray analyzer according to the first embodiment. However, since other configurations are the same, different points will be described. In addition, it is preferable that the two types of calibration samples 20 and 40 are placed at predetermined positions of the sample exchanger or built in the apparatus, as in the fluorescent X-ray analysis apparatus of the first embodiment.

The operation of the X-ray fluorescence analyzer according to the second embodiment, that is, the X-ray fluorescence analysis method according to one embodiment of the present invention will be described. When X-ray fluorescence spectrometer is operated, it is first calibrated specimen 40 is measured, drift calibration means 9 stores the background X-ray intensity as a background reference intensity I _B. When the background X-ray intensity is calibrated, it is measured background calibration sample 40, the background X-ray intensity I _C is obtained. When the background X-ray intensity I _C is obtained, the drift calibration means 9 calculates the background calibration coefficient β from the following equation (2) based on the obtained intensity I _C and the previously stored reference intensity I _B. calculate.

β = I _B / I _C (2)

  Next, when the calibration sample 20 is measured similarly to the operation of the fluorescent X-ray apparatus of the first embodiment, the drift calibration means 9 calculates the drift calibration coefficient α. The drift calibration means 9 calibrates the calibration curve by calibrating the slope constant a and the intercept constant b of the linear equation calibration curve with the calculated drift calibration coefficients α and β. The liquid sample S measured after calibration of the calibration curve is quantified based on the calibrated calibration curve.

  The X-ray fluorescence analyzer of the second embodiment includes a calibration sample 20 that is the same as the calibration sample 20 included in the X-ray fluorescence analyzer of the first embodiment, and a background calibration sample 40 formed by only the light element layer 22. The calibration curve is calibrated by calibrating the slope constant a and the intercept constant b with two types of calibration samples, the calibration sample 20 for the high concentration region and the background calibration sample 40 for the low concentration region. The calibration curve can be accurately calibrated. In particular, when the time-dependent change in measured X-ray intensity of the metal element to be analyzed is different from the time-dependent change in background X-ray intensity, the effect is great.

  2, 4, and 5, which is provided in the fluorescent X-ray analysis apparatus described above, measures the scattered X-ray generated from the calibration sample 20 as an internal standard line (scattered ray monitoring method). Standard method) may be used. Scattered ray monitoring is often used for analysis of liquid samples and organic compounds that generate a lot of scattered X-rays. The measured X-ray intensity of the metal element to be analyzed and the X-ray intensity of the background (scattered X-rays) This is a fluorescent X-ray analysis method for correcting the influence of coexisting elements in the sample S by using the ratio of

For example, in a multi-element simultaneous X-ray fluorescence analyzer capable of monitoring scattered radiation, a measurement channel for measuring secondary X-rays of a metal element to be analyzed generated from a liquid sample S (a spectroscopic element suitable for the metal element to be analyzed) And an X-ray detector) and a background channel for measuring scattered X-rays generated from the liquid sample S (with a spectroscopic element suitable for background measurement and an X-ray detector) calibration curve the ratio I _{a /} I _d between the X-ray intensity I _a and background X-ray intensity measured by the channel I _d on the vertical axis, the concentration of the analyte metallic elements of the measurement to the liquid sample S and the horizontal axis And the liquid sample S is analyzed.

First, the calibration sample 20 is simultaneously measured in the measurement channel and the background channel, and the reference intensity I _p that is the X-ray intensity measured in the measurement channel and the reference intensity I that is the X-ray intensity measured in the background channel. the ratio _I p / _{I g} of _g is calculated. When the measured X-ray intensity is calibrated, the calibration sample 20 is measured simultaneously in the measurement channel and background channels, measured by the measuring channel X-ray intensity I _r and background channels measured X-ray intensity I _q The ratio I _r / I _q is calculated. Performing drift calibration to calibrate a calibration curve using the ratio of the calculated and the calculated ratio _I p / _{I g} ratio _{I r / I q (I p} / I g) / (I r / I q) .

  The calibration sample 20 can generate the same background as the liquid sample S to be analyzed, and the ratio of the fluorescent X-ray intensity to the scattered X-ray intensity is the same as that of the liquid sample S to be analyzed. Even in the line monitor method, accurate drift calibration can be performed.

  In the fluorescent X-ray analyzers of the first and second embodiments, the calibration sample 20 is used for calibration of the calibration curve. However, it may be used for a sensitivity stability test for evaluating the sensitivity stability of the fluorescent X-ray analyzer. The stability test sample used for the sensitivity stability test of the fluorescent X-ray analyzer generates fluorescent X-rays with the same intensity as the liquid sample S, and the fluorescent X-ray intensity versus the scattered X-ray intensity with the same level as the liquid sample S For example, the thickness of the metal layer 21 is preferably 5 μm, and the thickness of the light element layer 22 is preferably 5 mm.

  Although the fluorescent X-ray analyzer of the first and second embodiments has been described as a wavelength dispersive fluorescent X-ray analyzer, the apparatus of the present invention may be an energy dispersive fluorescent X-ray analyzer.

DESCRIPTION OF SYMBOLS 1 X-ray source 2 Primary X-ray 3 Sample stage 4, 6 Secondary X-ray 5 Spectroscopic element 7 Detector 8 Detection means 9 Drift calibration means 20 Calibration sample 21 Metal layer 22 Light element layer 23 Analytical surface 40 Background calibration sample S liquid sample

Claims (5)

In a fluorescent X-ray analysis of a liquid sample, a solid calibration sample for calibrating a time-dependent change in measured X-ray intensity of a metal element to be analyzed,
A metal layer containing the metal element to be analyzed;
A light element layer having a thickness of 1 mm or more having a maximum molar fraction of at least one light element of hydrogen, boron, carbon, nitrogen, oxygen and fluorine;
Is formed by overlapping,
The calibration sample which uses the surface on the opposite side of the surface facing the said light element layer in the said metal layer as an analysis surface.   A fluorescent X-ray analysis method for analyzing a liquid sample using the calibration sample according to claim 1. The fluorescent X-ray analysis method according to claim 2,
Furthermore, a fluorescent X-ray analysis method using a background calibration sample, which is formed of only the light element layer and calibrates a change with time of background X-ray intensity of a liquid sample. A calibration sample according to claim 1;
Drift calibration means for calibrating changes with time of the measured X-ray intensity of the liquid sample based on the measured X-ray intensity of the metal element to be analyzed of the calibration sample;
A fluorescent X-ray analyzer. The fluorescent X-ray analyzer according to claim 4,
Furthermore, a background calibration sample that is formed of only the light element layer and calibrates a change in background X-ray intensity of the liquid sample with time,
X-ray fluorescence in which the drift calibration means calibrates the change over time of the measured X-ray intensity of the liquid sample based on the measured X-ray intensity of the metal element to be analyzed of the calibration sample and the measured X-ray intensity of the background calibration sample Analysis equipment.

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