X-ray analysis device including a spectrometer to detect characteristic X-rays and related X-ray analysis method

Patent metadata

Field	Value
Publication number	US-11740190-B2
Application number	US-202117188619-A
Country	US
Kind code	B2
Filing date	Mar 1, 2021
Priority date	May 27, 2020
Publication date	Aug 29, 2023
Grant date	Aug 29, 2023

Abstract

Provided is an X-ray analysis device and an X-ray analysis method capable of easily analyzing a valence of a target element in a sample. A controller 22 of a signal processing device of the X-ray analysis device is provided with: a storage unit 360 for storing a calibration curve generated based on a peak energy of Kα 1 X-ray and a peak energy of Kα 2 X-ray emitted from a metal simple substance, a peak energy of Kα 1 X-ray and a peak energy of Kα 2 X-ray emitted from each of two or more types of compounds each containing the metal simple substance, and a valence of the metal in each of the two or more types of compounds; a processing unit 302 configured to acquire a peak energy of Kα 1 X-ray and a peak energy of Kα 2 X-ray of the metal emitted from the metal contained in an unknown sample; and a calculation unit 308 configured to calculate a mean valence of the metal contained in the unknown sample by applying the obtained peak energy of Kα 1 X-ray and peak energy of Kα 2 X-ray to the calibration curve.

First claim

The invention claimed is:

1. An X-ray analysis device comprising:
a device body including a spectrometer, the spectrometer being configured to detect an intensity of characteristic X-rays by dispersing the characteristic X-rays generated by a sample irradiated with an excitation ray; and
a signal processing device including a controller configured to process a signal output from the spectrometer,
wherein the controller includes a storage unit configured to store a calibration curve, the calibration curve being generated based on:
a peak energy of Kα 1 X-rays and a peak energy of Kα 2 X-rays emitted from a metal as formed as a metal simple substance,
each of a peak energy of Kα 1 X-rays and a peak energy of Kα 2 X-rays emitted from two or more types of compounds, each compound containing the metal in its composition, each of the two or more types of compounds being different in a valence of the metal, and
a valence of the metal as contained in each of the two or more types of compounds, and

wherein the controller is configured to acquire a peak energy of the Kα 1 X-rays and acquire a peak energy of the Kα 2 X-rays emitted from the metal as contained in an unknown sample based on an intensity for each wavelength detected by the spectrometer, and configured to calculate a mean valence of the metal as contained in the unknown sample by applying the acquired peak energy of the Kα 1 X-rays and the acquired peak energy of the Kα 2 X-rays to the calibration curve.

2. The X-ray analysis device as recited in claim 1 ,
wherein the calibration curve is represented by y=px+q,
where y is a variable showing the mean valence of the metal as contained in the unknown sample, and x is a parameter obtained by subtracting a value obtained by multiplying the peak energy of the Kα 2 X-rays emitted from the metal by a coefficient n from the peak energy of the Kα 1 X-rays emitted from the metal, and
wherein the controller generates the calibration curve by calculating a slope p, an intercept q, and a coefficient n, based on the peak energy of the Kα 1 X-rays and the peak energy of the Kα 2 X-rays emitted from the metal as formed as the metal simple substance, the peak energy of the Kα 1 X-rays and the peak energy of the Kα 2 X-rays emitted from the metal as contained in each of the two or more types of compounds, and the valence of the metal as contained in each of the two or more types of compounds.

3. The X-ray analysis device as recited in claim 2 ,
wherein the signal processing device comprises a display, and the signal processing device is configured to display the calibration curve in which an X-axis represents a parameter and a Y-axis represents the mean valence of the metal as contained in the unknown sample on the display.

4. The X-ray analysis device as recited in claim 2 ,
wherein the two or more types of compounds include three or more types of compounds different from each other in the valence of the metal, and
wherein the controller generates the calibration curve by calculating the slope p, the intercept q, and the coefficient n by applying a least-squares method to the peak energy of the Kα 1 X-rays and the peak energy of the Kα 2 X-rays emitted from the metal as formed as the simple substance, the peak energy of the Kα 1 X-rays and the peak energy of the Kα 2 X-rays emitted from the metal as contained in each of the three or more types of compounds, and the valence of the metal as contained in each of the three or more types of compounds.

5. The X-ray analysis device as recited in claim 2 ,
wherein the two or more types of compounds contains a first compound and a second compound different from each other in the valence of the metal, and
wherein the controller generates the calibration curve by calculating the slope p, the intercept q, and the coefficient n using the following formula:
n ={( v−w )· m 1− v·b 1+ w·a 1}/{( v−w )· m 2− v·b 2+ w·a 2}

p =( v−w )/{( a 1− b 1)− n ·( a 2− b 2)}

q={w ·( a 1− n·a 2)− v ·( b 1− n·b 2)/{( a 1− a 2)− n ·( a 2− b 2)}

where m1 is the peak energy of the Kα 1 X-rays emitted from the metal as formed as the metal simple substance,
m2 is the peak energy of the Kα 2 X-rays emitted from the metal as formed as the metal simple substance,
v is the valence of the metal as contained in the first compound,
w is the valence of the metal as contained in the second compound,
a1 is the peak energy of the Kα 1 X-rays emitted from the first compound,
a2 is the peak energy of the Kα 2 X-rays emitted from the first compound,
b1 is the peak energy of the Kα 1 X-rays emitted from the second compound, and
b2 is the peak energy of the Kα 2 X-rays emitted from the second compound.

6. The X-ray analysis device as recited in claim 1 ,
wherein the unknown sample is composed of a first substance and a second substance different from each other in the valence of the metal, and
wherein the signal processing device outputs several possible composition ratios of the first substance and the second substance based on the calculated mean valence of the metal as contained in the unknown sample.

7. The X-ray analysis device as recited in claim 6 ,
wherein the signal processing device:
is configured to accept inputs of the valence of the metal as contained in the first substance and the valence of the metal as contained in the second substance, and
is configured to output a composition ratio of the first substance to the second substance based on the valence of the metal as contained in the first substance, the valence of the metal as contained in the second substance, and the mean valence of the metal as contained in the unknown sample.

8. The X-ray analysis device as recited in claim 7 ,
wherein the controller is configured to calculate the composition ratio of the first substance to the second substance, based on 1:(ym−i)/(j−ym), wherein i<ym<j, where,
i is the valence of the metal as contained in the first substance,
j is the valence of the metal as contained in the second substance, and
ym is the calculated mean valence of the metal as contained in the unknown sample.

9. An X-ray analysis device comprising:
a device body including a spectrometer, the spectrometer being configured to detect an intensity of characteristic X-rays by dispersing the characteristic X-rays generated by a sample irradiated with an excitation ray; and
a signal processing device including a controller configured to process a signal output from the spectrometer,
wherein the controller includes a storage unit configured to store a calibration curve generated based on a plurality of types of peak energies emitted from a metal as formed as a metal simple substance, a plurality of types of peak energies emitted from two or more types of compounds, each of the two or more types of compounds containing the metal in its composition and having a valence of the metal that is different from the others, and the valence of the metal as contained in each of the two or more types of compounds, and
wherein the controller is configured to acquire a plurality of types of peak energies of the metal as contained in an unknown sample, based on an intensity for each wavelength detected by the spectrometer, and configured to calculate a mean valence of the metal as contained in the unknown sample by applying the acquired plurality of types of peak energies of the metal as contained in the unknown sample to the calibration curve.

10. An X-ray analysis method, comprising:
acquiring a peak energy of Kα 1 X-rays and acquiring a peak energy of Kα 2 X-rays emitted from a metal as contained in an unknown sample by dispersing characteristic X-rays generated from the unknown sample upon

Assignees

• Shimadzu Corp

Inventors

• Sato Kenji

Classifications

• G01N23/223 Primary

  by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence · CPC title

• G01N23/2076 Primary

  for spectrometry, i.e. using an analysing crystal, e.g. for measuring X-ray fluorescence spectrum of a sample with wavelength-dispersion, i.e. WDXFS · CPC title

• G01N23/22

  by measuring secondary emission from the material · CPC title

• G01N23/2209

  using wavelength dispersive spectroscopy [WDS] · CPC title

• G01N2223/0563

  measure of energy-dispersion spectrum of diffracted radiation · CPC title