Scanning fluorescent x-ray analysis device, program used for same, and fluorescent x-ray analysis method using same

Abstract

In this scanning fluorescent X-ray analysis device, a quantification means (13) creates a peak profile by performing, on a preliminary measurement sample (14), measurement for a prescribed measurement time at a prescribed number of measurement points in a prescribed scanning angle range based on a theoretical 2θ peak angle, calculates a theoretical standard deviation for the intensity of the peak profile from the peak profile and the prescribed measurement time, and obtains an optimum measurement time on the basis of a reference value for the 2θ peak angle of the peak profile, a high-angle-side limit value and a low-angle-side limit value based on the theoretical standard deviation, and the allowable width of the 2θ peak angle.

Description

Scanning fluorescence X-ray analyzer, program used therefor, and fluorescence X-ray analysis method using the same Related applications

[0001] This application claims the priority of Japanese Patent Application No. 2024-228336 filed on December 25, 2024, and the entire contents thereof are incorporated herein by reference and made a part of this application.

[0002] The present invention relates to a scanning fluorescence X-ray analyzer that irradiates a sample with primary X-rays and determines the content ratio of elements in the sample based on the measured intensity of the generated fluorescence X-rays, and the like.

[0003] In a scanning fluorescence X-ray analyzer, for each analysis target element contained in a sample, scanning is stopped at a 2θ peak angle, which is a scanning angle corresponding to an analysis line, to measure the intensity of the analysis line, and quantitative analysis is performed based on the measured intensity. However, for accurate analysis, it is necessary to previously determine the 2θ peak angle that exactly corresponds to the analysis line.

[0004] [[ID=1�]] Therefore, for example, in the conventional first technique, as a preliminary measurement, a preliminary measurement sample having a composition similar to that of an unknown sample is used, the measurement time for each step of scanning is set, and continuous scan measurement is performed. The 2θ peak angle is determined from the resulting peak profile. In this case, the measurement time for each step in the continuous scan measurement is preferably long for accurately determining the 2θ peak angle, and preferably short from the viewpoint of work efficiency. However, an appropriate measurement time is set by trial and error, such as the operator performing multiple preliminary measurements with different measurement times and comparing and examining the shapes of the peak profiles.

[0005] Further, in the conventional second technique, two preliminary measurements are performed to determine the 2θ peak angle in advance. In the first preliminary measurement, continuous scan measurement is performed with a short measurement time to obtain a rough peak profile, and the wavelength range in which a true peak is presumed to exist is determined. In the second preliminary measurement, measurements are performed at both ends and the middle of the wavelength range with a long measurement time, and these three points are fitted with a quadratic equation to set the wavelength of the vertex as the peak wavelength (corresponding to the 2θ peak angle) (see Patent Document 1).

[0006] Patent No. 7367605

[0007] As described above, the 2θ peak angle is determined based on the measurement intensity in preliminary measurements. However, in conventional techniques, the measurement time is set without considering the composition of the sample. Therefore, for samples with low measurement intensity, the statistical fluctuations in measurement intensity are large, and the measurement time tends to be insufficient. Conversely, for samples with high measurement intensity, the measurement time tends to be unnecessarily long. Consequently, it is not possible to determine a sufficiently accurate 2θ peak angle in the shortest possible time.

[0008] The present invention has been made in view of the above-mentioned conventional problems, and aims to provide a scanning X-ray fluorescence analyzer, etc., which irradiates a sample with primary X-rays and determines the elemental content in the sample based on the measured intensity of the generated fluorescent X-rays, in order to determine a sufficiently accurate 2θ peak angle in the shortest possible time, by optimizing and setting the measurement time for each step of scanning in the preliminary measurement for determining the 2θ peak angle.

[0009] To achieve the above objective, the first configuration of the present invention is a scanning X-ray fluorescence analyzer that first irradiates a sample with primary X-rays and determines the elemental content in the sample based on the measured intensity of the generated fluorescent X-rays, and is equipped with a computer as a quantitative means that measures a preliminary sample of known composition to determine the 2θ peak angle, which is the scanning angle corresponding to the analysis line for each element to be analyzed, and performs quantitative analysis based on the measured intensity of an unknown sample at that 2θ peak angle.

[0010] Furthermore, when the quantitative means sets the measurement time for each step of scanning when measuring the preliminary measurement sample, an allowable range of the 2θ peak angle is set, and the preliminary measurement sample is measured at a predetermined number of measurement points within a predetermined scanning angle range based on the theoretical 2θ peak angle for a predetermined measurement time, a peak profile is created based on the measurement angle and measurement intensity of the predetermined number of measurement points, the intensity of the peak profile at the measurement angle of each measurement point is set as the virtual measurement intensity of each measurement point, and the 2θ peak angle of the peak profile is set as the reference 2θ peak angle.

[0011] The quantitative means further calculates a theoretical standard deviation for virtual measurement intensity based on the predetermined measurement time and the virtual measurement intensity of the measurement point with the maximum measurement intensity. Based on the theoretical standard deviation and the virtual measurement intensity of each measurement point, the high-angle limit value of the 2θ peak angles of the new peak profile is set as the high-angle deviation 2θ peak angle, and the low-angle limit value is set as the low-angle deviation 2θ peak angle. If the value obtained by subtracting the reference 2θ peak angle from the high-angle deviation 2θ peak angle is less than or equal to the allowable range, and the value obtained by subtracting the low-angle deviation 2θ peak angle from the reference 2θ peak angle is less than or equal to the allowable range, the most recently used measurement time is set as the optimal measurement time. If the judgment conditions are not met, a new predetermined measurement time longer than the most recently used measurement time is set, and the procedure from the step of calculating the theoretical standard deviation onward is repeated until the judgment conditions are met.

[0012] In the first configuration of the scanning X-ray fluorescence analyzer, the quantitative means estimates the fluctuation of the 2θ peak angle from the statistical variation of the measurement intensity of the sample used for preliminary measurement to determine the 2θ peak angle. The measurement time is optimized so that the fluctuation of the 2θ peak angle falls within the set tolerance range of the 2θ peak angle, allowing for the determination of a sufficiently accurate 2θ peak angle in the shortest possible time.

[0013] In the first configuration of the scanning X-ray fluorescence analyzer, when the quantitative means determines the high-angle displacement 2θ peak angle, it is preferable that, for the measurement points at a predetermined number of measurement points, the theoretical standard deviation is added to the virtual measurement intensity for measurement points at a higher angle than the measurement point with the maximum measurement intensity to obtain a new virtual measurement intensity, and the theoretical standard deviation is subtracted from the virtual measurement intensity for measurement points at a lower angle than the measurement point with the maximum measurement intensity to obtain a new virtual measurement intensity, and a new peak profile is created based on the measurement angle and virtual measurement intensity of the measurement point with the maximum measurement intensity and the measurement angle and new virtual measurement intensity of the measurement point with the new virtual measurement intensity, and the 2θ peak angle of the new peak profile is set as the high-angle displacement 2θ peak angle.

[0014] Furthermore, in determining the low-angle deviation 2θ peak angle, it is preferable that, at a predetermined number of measurement points, for measurement points on the higher angle side than the measurement point with the maximum measurement intensity, the theoretical standard deviation is subtracted from the virtual measurement intensity to obtain a new virtual measurement intensity, and for measurement points on the lower angle side than the measurement point with the maximum measurement intensity, the theoretical standard deviation is added to the virtual measurement intensity to obtain a new virtual measurement intensity, a new peak profile is created based on the measurement angle and virtual measurement intensity of the measurement point with the maximum measurement intensity and the measurement angle and new virtual measurement intensity of the measurement point with the new virtual measurement intensity, and the 2θ peak angle of this new peak profile is taken as the low-angle deviation 2θ peak angle.

[0015] Furthermore, in the first configuration of the scanning X-ray fluorescence analyzer, it is preferable that the peak profile and the new peak profile are created by fitting.

[0016] Furthermore, in the first configuration of the scanning X-ray fluorescence analyzer, it is preferable that a display is provided, and the quantitative means processes the measurement angle and measurement intensity of the measurement point in the specified measurement data in the same way as the measurement angle and measurement intensity of the measurement point for the preliminary measurement sample, and sets the value obtained by subtracting the reference 2θ peak angle from the high-angle deviation 2θ peak angle as the high-angle side angle fluctuation, and the value obtained by subtracting the low-angle deviation 2θ peak angle from the reference 2θ peak angle as the low-angle side angle fluctuation, and displays the high-angle side angle fluctuation and the low-angle side angle fluctuation, or the fluctuation of the 2θ peak angle based thereon, on the display.

[0017] The second configuration of the present invention is a program for causing the computer provided in the scanning X-ray fluorescence analyzer of the first configuration to function as the quantitative means.

[0018] The third configuration of the present invention is a fluorescent X-ray analysis method that performs quantitative analysis using the scanning fluorescent X-ray analyzer of the first configuration.

[0019] Any combination of at least two configurations disclosed in the claims and / or the specification and / or drawings is included in the present invention. In particular, any combination of two or more of each claim is included in the present invention.

[0020] This invention will be more clearly understood from the following description of preferred embodiments with reference to the accompanying drawings. However, the embodiments and drawings are for illustrative and explanatory purposes only and should not be used to define the scope of this invention. The scope of this invention is defined by the accompanying claims. In the accompanying drawings, the same part number in multiple drawings indicates the same part. This is a schematic diagram showing a scanning X-ray fluorescence analyzer of one embodiment of the present invention. This is a diagram showing an example of a peak profile prepared for a preliminary measurement sample using the apparatus. This is a diagram showing an example of the procedure for determining the high-angle displacement 2θ peak angle and the low-angle displacement 2θ peak angle using the apparatus. This is an example of the display of fluctuations in the θ peak angle on the display of the apparatus. This is a flowchart showing the operation of the apparatus.

[0021] The following describes an X-ray fluorescence analyzer according to one embodiment of the present invention. As shown in Figure 1, the X-ray fluorescence analyzer of this embodiment is a scanning type X-ray fluorescence analyzer that determines the elemental content in samples 1 and 14 (including both an unknown sample 1 and a preliminary measurement sample 14 having a composition similar to the unknown sample 1 but with a known composition) based on the measured intensity of fluorescent X-rays 5 generated by irradiating the samples 1 and 14 with primary X-rays 3. The analyzer comprises a sample stage 2 on which the samples 1 and 14 are placed, an X-ray source 4 such as an X-ray tube that irradiates the samples 1 and 14 with primary X-rays 3, a spectrometer 6 that spectrally analyzes the fluorescent X-rays 5 generated from the samples 1 and 14, and a detector 8 that receives the fluorescent X-rays 7 spectrally analyzed by the spectrometer 6 and detects their intensity. The output of the detector 8 is input to a control means 11, which is a computer that controls the entire apparatus, via an amplifier, pulse height analyzer, counting means, etc. (not shown).

[0022] The X-ray fluorescence analyzer of this embodiment is a wavelength-dispersive and scanning type X-ray fluorescence analyzer, and is equipped with an interlocking means 10, or so-called goniometer, that links the spectroscopic element 6 and the detector 8 so that the wavelength of the X-ray fluorescence 7 incident on the detector 8 changes. When X-ray fluorescence 5 is incident on the spectroscopic element 6 at a certain incident angle θ, the extension line 9 of the X-ray fluorescence 5 and the X-ray fluorescence 7 spectrally separated (diffracted) by the spectroscopic element 6 form a spectral angle 2θ which is twice the incident angle θ. The interlocking means 10 changes the wavelength of the spectrally separated X-ray fluorescence 7 by changing the spectral angle 2θ, and rotates the spectroscopic element 6 around an axis O perpendicular to the plane of paper passing through the center of its surface, so that the spectrally separated X-ray fluorescence 7 is incident on the detector 8, and rotates the detector 8 along a circle 12 around axis O by twice the angle of rotation. The value of the spectral angle 2θ (angle 2θ) is input from the interlocking means 10 to the control means 11.

[0023] The scanning X-ray fluorescence analyzer of this embodiment is equipped with a computer as a quantitative means 13 that measures a preliminary sample 14 of known composition, determines a 2θ peak angle, which is the scanning angle corresponding to the analysis line for each element to be analyzed, and performs quantitative analysis based on the measurement intensity of an unknown sample 1 at that 2θ peak angle. A program (a program as a type of product) that causes the control means 11, which is the computer in the scanning X-ray fluorescence analyzer of this embodiment, to function as the quantitative means 13 is also one embodiment of the present invention. This program is stored in a storage unit such as an SSD or RAM within the control means 11, which is the computer, and is read and executed by a control unit, which is, for example, a CPU. The control means 11 (computer) including the quantitative means 13 and / or the display unit described later may be connected separately from the X-ray fluorescence analyzer body by cable or wirelessly, or they may be incorporated into the X-ray fluorescence analyzer body or directly mounted on it. Furthermore, a program-readable storage medium (for example, a CD, DVD, Blu-ray disc, USB memory, etc.) for causing the control means 11, which is a computer in the scanning X-ray fluorescence analyzer of this embodiment, to function as a quantitative means 13 is also one embodiment of the present invention.

[0024] As explained in the first conventional technique, in order to determine the 2θ peak angle that accurately corresponds to the analysis line in advance, a preliminary measurement is performed using a preliminary measurement sample 14, setting the measurement time for each scanning step and performing a continuous scan measurement, from which the 2θ peak angle is determined. In this continuous scan measurement, the interlocking means 10, which is a goniometer, is moving at a constant velocity, for example, at a scan speed of 60 deg / min (= 0.04 deg / 0.04 sec), the measurement time for each scanning step (0.04 deg) is 0.02 sec, and the measurement interval (the angle between the measurement time of one step and the measurement time of the next step) is 0.02 deg (corresponding to 0.02 sec in time).

[0025] In the present invention, in order to obtain a sufficiently accurate 2θ peak angle in the preliminary measurement in the shortest possible time, the quantitative means 13 performs an additional measurement before the preliminary measurement, that is, a preliminary measurement of the preliminary measurement, and optimizes the measurement time for each step of scanning in the preliminary measurement.

[0026] First, when setting the measurement time for each scanning step when measuring the preliminary measurement sample 14 (measurement time in preliminary measurement), the allowable range of the 2θ peak angle is set to, for example, 0.04 deg, which corresponds to one scanning step (step S1 in Figure 5). Then, as shown in Figure 2, the preliminary measurement sample 14 is measured at a predetermined number of measurement points, for example, 9 measurement points, within a predetermined scanning angle range based on the theoretical 2θ peak angle, for example, the theoretical 2θ peak angle ±0.2 deg, for a predetermined measurement time, for example, 0.02 sec (preliminary measurement of the preliminary measurement) (step S2 in Figure 5). In Figure 2, the 9 measurement points within the predetermined scanning angle range are indicated by black squares within a vertically elongated rectangular frame. The predetermined scanning angle range may also be the full width at half maximum centered on the theoretical 2θ peak angle.

[0027] Next, based on the measurement angles and intensity of a predetermined number of measurement points, a peak profile is created by fitting using a quadratic equation, for example, as shown by the parabola in Figure 2. Then, among the three point groups arranged parabolaly in Figure 3, the intensity of the peak profile at the measurement angle of each measurement point is taken as the virtual measurement intensity of each measurement point, as represented by the central point group in the vertical direction. Furthermore, the 2θ peak angle of the peak profile, 46.940 degrees, shown as the 2θ angle at the vertex of the parabola in Figure 2, is taken as the reference 2θ peak angle (step S3 in Figure 5). Note that the 2θ peak angle of the peak profile can also be determined by smoothing, such as by moving average or Savizky-Golay, without using fitting.

[0028] Next, the virtual measurement intensity I of the measurement point P (Figure 3) with the predetermined measurement time t (0.02 sec) and the maximum measurement intensity is determined. P Based on (kcps), the theoretical standard deviation σI (kcps) for the virtual measured intensity I is calculated, for example, by the following equation (1) (step S4 in Figure 5).

[0029] σI = (I P (1000 tons) 1 / 2 (1)

[0030] Then, of the 2θ peak angles of the new peak profile based on the calculated theoretical standard deviation σI and the virtual measurement intensity of each measurement point, the high-angle limit value is set as the high-angle deviation 2θ peak angle, and the low-angle limit value is set as the low-angle deviation 2θ peak angle (step S5 in Figure 5). For example, when determining the high-angle deviation 2θ peak angle, at the predetermined number of nine measurement points in Figure 3, for the four measurement points on the higher angle side than the measurement point P with the maximum measurement intensity, the theoretical standard deviation σI is added to the virtual measurement intensity to create a new virtual measurement intensity (indicated by upward arrows), and for the four measurement points on the lower angle side than the measurement point P with the maximum measurement intensity, the theoretical standard deviation σI is subtracted from the virtual measurement intensity to create a new virtual measurement intensity (indicated by downward arrows). A new peak profile is created (not shown) by fitting based on the measurement angle and virtual measurement intensity of the measurement point P with the maximum measurement intensity, and the measurement angles and new virtual measurement intensities of the eight measurement points with new virtual measurement intensities, and the 2θ peak angle of 47.048 deg of this new peak profile is taken as the high-angle deviation 2θ peak angle.

[0031] On the other hand, in determining the low-angle deviation 2θ peak angle, at the predetermined number of nine measurement points in Figure 3, for the four measurement points on the higher angle side than the measurement point P with the maximum measurement intensity, the theoretical standard deviation σI is subtracted from the virtual measurement intensity to obtain a new virtual measurement intensity. For the four measurement points on the lower angle side than the measurement point P with the maximum measurement intensity, the theoretical standard deviation σI is added to the virtual measurement intensity to obtain a new virtual measurement intensity. A new peak profile is created (not shown) by fitting based on the measurement angle and virtual measurement intensity of the measurement point P with the maximum measurement intensity, and the measurement angles and new virtual measurement intensities of the eight measurement points with the new virtual measurement intensities. The 2θ peak angle of this new peak profile, 46.830 deg, is taken as the low-angle deviation 2θ peak angle. Note that the 2θ peak angle of the new peak profile can also be determined by smoothing, such as by moving average or Savizky-Golay, without using fitting.

[0032] Furthermore, in determining the high-angle displacement 2θ peak angle and the low-angle displacement 2θ peak angle, the above example used the theoretical standard deviation σI for the virtual measured intensity I. However, it is also possible to determine the high-angle displacement 2θ peak angle and the low-angle displacement 2θ peak angle by first calculating the theoretical standard deviation σI for the centroid position of the peak profile and then shifting the centroid position in the positive and negative directions of the 2θ angle by the calculated theoretical standard deviation value.

[0033] Following the above procedure, the quantitative means 13 determines that the value obtained by subtracting the reference 2θ peak angle of 46.940 deg from the high-angle deviation 2θ peak angle of 47.048 deg is less than or equal to the allowable range of 0.04 deg, and that the value obtained by subtracting the low-angle deviation 2θ peak angle of 46.830 deg from the reference 2θ peak angle of 46.940 deg is less than or equal to the allowable range of 0.04 deg (step S6 in Figure 5), and sets the most recently used measurement time of 0.02 sec as the optimal measurement time (step S7 in Figure 5). If the above determination conditions are not met, it sets a new predetermined measurement time of 0.04 sec, which is longer than the most recently used measurement time of 0.02 sec (step S8 in Figure 5), and repeats the procedure from step S4 in Figure 5 onward to calculate the theoretical standard deviation σI until the above determination conditions are met. In this example, the above procedure is repeated by setting new predetermined measurement times to 0.04 sec, 0.06 sec, 0.08 sec, 0.12 sec, and 0.15 sec, and 0.15 sec is determined to be the optimal measurement time.

[0034] Furthermore, in order to optimize the measurement time for each step of scanning in the preliminary measurement, the measurement before the preliminary measurement, i.e., the preliminary measurement of the preliminary measurement mentioned above, only needs to be performed once at the initial predetermined measurement time, which in the above example is 0.02 seconds. Based on the measurement angles and measurements of a predetermined number of measurement points, the peak profile, and the reference 2θ peak angle obtained at that time, the calculation procedure from the step of calculating the theoretical standard deviation σI, updating the predetermined measurement time to a longer duration, should be repeated until the aforementioned judgment condition is met.

[0035] As described above, in the scanning X-ray fluorescence analyzer of this embodiment, the quantitative means 13 estimates the measurement time for each step of scanning in the preliminary measurement to determine the 2θ peak angle from the statistical variation σI of the measurement intensity of the preliminary measurement sample 14 as fluctuations in the 2θ peak angle, namely (high-angle deviation 2θ peak angle - reference 2θ peak angle) and (reference 2θ peak angle - low-angle deviation 2θ peak angle). The quantitative means 13 then optimizes and sets the measurement time so that the fluctuations in the 2θ peak angle fall within the set tolerance range of the 2θ peak angle. A preliminary measurement to determine the measurement time for the preliminary measurement can be performed with a relatively high-speed single continuous scan measurement, and by using the optimal measurement time obtained therefrom, a preliminary measurement to determine the 2θ peak angle can also be performed with a single continuous scan measurement.

[0036] Therefore, unlike the conventional first technique, which involves repeating multiple preliminary measurements through trial and error, and the conventional second technique, which involves stopping scanning at three points during the second preliminary measurement and performing measurements for a long time without considering fluctuations in the 2θ peak angle, the scanning X-ray fluorescence analyzer of this embodiment can determine a sufficiently accurate 2θ peak angle in the shortest possible time.

[0037] Furthermore, the measurement intensity in the preliminary measurement of the preliminary measurement mentioned above does not need to be the net intensity with the background subtracted; it may be the gross intensity without the background subtracted. This is because the 2θ peak angle based on the gross intensity is affected by the background and therefore differs from the 2θ peak angle based on the net intensity, but the fluctuation of the 2θ peak angle obtained in the preliminary measurement of the preliminary measurement can be ignored even if it is based on the gross intensity.In addition, in this embodiment, as a preliminary measurement, a continuous scan measurement is exemplified in which measurements are taken at multiple measurement points by sequentially repeating measurements at each step of scanning while the interlocking means 10, which is a goniometer, is moving at a constant velocity.However, as a preliminary measurement, a step scan measurement may also be performed in which measurements are taken at one measurement point while the interlocking means 10 is stopped, then the interlocking means 10 is moved by one step of scanning, and the next measurement point is measured while the interlocking means 10 is stopped, and this is repeated to take measurements at multiple measurement points.In addition, the preliminary measurement of the preliminary measurement may also be performed by continuous scan measurement or by step scan measurement for multiple measurement points.

[0038] Although not an essential component of the present invention, the scanning X-ray fluorescence analyzer of this embodiment further includes a display 15 such as a liquid crystal display connected to the control means 11. The quantitative means 13 processes the measurement angle and measurement intensity of measurement points in data from previously performed continuous scan measurements, which are specified by the operator using an input means such as a mouse (not shown), in the same way as the measurement angle and measurement intensity of measurement points for the preliminary measurement sample 14. The value obtained by subtracting the reference 2θ peak angle from the high-angle deviation 2θ peak angle is defined as the high-angle side angle fluctuation, and the value obtained by subtracting the low-angle deviation 2θ peak angle from the reference 2θ peak angle is defined as the low-angle side angle fluctuation. The high-angle side angle fluctuation and the low-angle side angle fluctuation, or the fluctuation of the 2θ peak angle based thereon, can also be displayed on the display 15.

[0039] For example, as shown in Figure 4, the fluctuation of the 2θ peak angle is displayed on the display unit 15 as "2θ angle fluctuation tolerance range 0.040 deg" as part of the data from the specified continuous scan measurement. Here, the fluctuation of the 2θ peak angle based on the high-angle and low-angle fluctuations is, for example, the average value of the high-angle and low-angle fluctuations.

[0040] Furthermore, one embodiment of the present invention is a method of X-ray fluorescence analysis in which, using the scanning X-ray fluorescence analyzer of this embodiment, the optimal measurement time is determined in a preliminary measurement, the 2θ peak angle corresponding to the analysis line is determined by the preliminary measurement at the optimal measurement time, the scanning is stopped at the determined 2θ peak angle for an unknown sample, the intensity of the analysis line is measured, and quantitative analysis is performed based on the measured intensity.

[0041] As described above with reference to the drawings, preferred embodiments have been explained, but those skilled in the art will readily anticipate various changes and modifications within the obvious scope by reviewing this specification. Therefore, such changes and modifications will be interpreted as falling within the scope of this invention as defined by the attached claims.

[0042] 1, 14 Sample 3 Primary X-ray 5 Fluorescent X-ray 13 Quantitative means 15 Display

Claims

1. A scanning X-ray fluorescence analyzer that irradiates a sample with primary X-rays and determines the elemental content in the sample based on the measured intensity of the generated fluorescent X-rays, comprising a computer as a quantitative means that measures a preliminary sample of known composition to determine the 2θ peak angle, which is the scanning angle corresponding to the analytical line for each element to be analyzed, and performs quantitative analysis based on the measured intensity of an unknown sample at that 2θ peak angle, wherein the quantitative means sets the measurement time for each step of scanning when measuring the preliminary sample, and sets an allowable range for the 2θ peak angle, measures the preliminary sample at a predetermined number of measurement points within a predetermined scanning angle range based on the theoretical 2θ peak angle for a predetermined measurement time, creates a peak profile based on the measurement angle and measured intensity of the predetermined number of measurement points, sets the intensity of the peak profile at the measurement angle of each measurement point as the virtual measured intensity of each measurement point, and sets the 2θ peak angle of the peak profile as the reference 2θ peak angle, calculates the theoretical standard deviation of the virtual measured intensity based on the predetermined measurement time and the virtual measured intensity of the measurement point with the maximum measured intensity, A scanning X-ray fluorescence analyzer that, among the 2θ peak angles of a new peak profile based on the theoretical standard deviation and the virtual measurement intensity of each measurement point, sets the high-angle limit value as the high-angle deviation 2θ peak angle and the low-angle limit value as the low-angle deviation 2θ peak angle, and if the value obtained by subtracting the reference 2θ peak angle from the high-angle deviation 2θ peak angle is less than or equal to the allowable range, and the value obtained by subtracting the low-angle deviation 2θ peak angle from the reference 2θ peak angle is less than or equal to the allowable range, the most recently used measurement time is set as the optimal measurement time, and if the above conditions are not met, a new predetermined measurement time longer than the most recently used measurement time is set, and the procedure from the step of calculating the theoretical standard deviation onward is repeated until the above conditions are met.

2. In the scanning X-ray fluorescence analyzer according to claim 1, the quantitative means, in determining the high-angle deviation 2θ peak angle, adds the theoretical standard deviation to the virtual measurement intensity for measurement points on the higher angle side than the measurement point with the maximum measurement intensity to obtain a new virtual measurement intensity, subtracts the theoretical standard deviation from the virtual measurement intensity for measurement points on the lower angle side than the measurement point with the maximum measurement intensity to obtain a new virtual measurement intensity, creates a new peak profile based on the measurement angle and virtual measurement intensity of the measurement point with the maximum measurement intensity and the measurement angle and new virtual measurement intensity of the measurement point with the new virtual measurement intensity, sets the 2θ peak angle of the new peak profile as the high-angle deviation 2θ peak angle, and in determining the low-angle deviation 2θ peak angle, A scanning X-ray fluorescence analyzer, wherein, for a predetermined number of measurement points, for measurement points at a higher angle than the measurement point with the maximum measurement intensity, the theoretical standard deviation is subtracted from the virtual measurement intensity to obtain a new virtual measurement intensity, and for measurement points at a lower angle than the measurement point with the maximum measurement intensity, the theoretical standard deviation is added to the virtual measurement intensity to obtain a new virtual measurement intensity, a new peak profile is created based on the measurement angle and virtual measurement intensity of the measurement point with the maximum measurement intensity and the measurement angle and new virtual measurement intensity of the measurement point with the new virtual measurement intensity, and the 2θ peak angle of the new peak profile is defined as the low-angle displacement 2θ peak angle.

3. Scanning X-ray fluorescence analyzer according to claim 1 or 2, wherein the peak profile and the new peak profile are created by fitting.

4. Scanning X-ray fluorescence analyzer according to claim 1 or 2, comprising a display, wherein the quantitative means processes the measurement angle and measurement intensity of the measurement point in the specified measurement data in the same manner as the measurement angle and measurement intensity of the measurement point for the preliminary measurement sample, and sets the value obtained by subtracting the reference 2θ peak angle from the high-angle deviation 2θ peak angle as the high-angle side angle fluctuation, and the value obtained by subtracting the low-angle deviation 2θ peak angle from the reference 2θ peak angle as the low-angle side angle fluctuation, and displays the high-angle side angle fluctuation and the low-angle side angle fluctuation, or the fluctuation of the 2θ peak angle based thereon, on the display.

5. A program for causing the computer of the scanning X-ray fluorescence analyzer according to claim 1 or 2 to function as the quantitative means.

6. A method for quantitative analysis using a scanning X-ray fluorescence analyzer according to claim 1 or 2.

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