WO2021059597A1 - Analyseur par fluorescence x - Google Patents

Analyseur par fluorescence x Download PDF

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Publication number
WO2021059597A1
WO2021059597A1 PCT/JP2020/022146 JP2020022146W WO2021059597A1 WO 2021059597 A1 WO2021059597 A1 WO 2021059597A1 JP 2020022146 W JP2020022146 W JP 2020022146W WO 2021059597 A1 WO2021059597 A1 WO 2021059597A1
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WIPO (PCT)
Prior art keywords
component
standard
value
quantitative
sample
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PCT/JP2020/022146
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English (en)
Japanese (ja)
Inventor
片岡　由行
直人 後藤
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株式会社リガク
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Priority to CN202080031348.0A priority Critical patent/CN113748333B/zh
Publication of WO2021059597A1 publication Critical patent/WO2021059597A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
    • G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence

Definitions

  • the present invention relates to a fluorescent X-ray analyzer based on the fundamental parameter method.
  • fluorescent X-ray analyzers that perform quantitative analysis are roughly classified into those based on the calibration curve method and those based on the fundamental parameter method (also called the FP method).
  • the quantitative analysis by the calibration curve method for the analysis of an unknown sample, a set of standard samples in which the content of the component is known as a standard value is used, and the content of the component and the fluorescence X of the measurement element corresponding to the component are used.
  • a calibration curve formula represented by the following formula (1) is obtained.
  • the component is an element or a compound, and the content of the component is generally represented by a mass percentage (mass%) including a standard value and a quantitative value of the content.
  • mass percentage mass percentage
  • Wi (AI i 2 + BI i + C) (1 + ⁇ j W j )... (1) Wi : Content of component i I i : Measurement intensity of fluorescent X-rays of the measurement element corresponding to component i A, B, C: Calibration curve constant W j : Content of correction component j ⁇ j : Correction component Matrix correction coefficient of j
  • a graph of the calibration curve represented by the following equation (2) is output as shown in FIG. 2 for, for example, the component Cr.
  • a graph of the calibration curve is displayed by a display or a printer.
  • the estimated reference value X i of the component i is assumed that the content W j of the correction component j is zero, that is, there is no matrix effect of absorption / excitation by the coexisting components on the component i. In this case, it is the content rate of the component i in the measured intensity I i.
  • the horizontal axis coordinates of the rectangular points are the estimated reference values of the standard sample
  • the horizontal axis coordinates of the white circle points are the standard values of the standard sample (chemistry). Analytical value) is shown.
  • the measurement intensity I i corresponding to the component i and the standard value of the component j as the content rate W j of the correction component j are substituted into the calibration curve equation (1) to obtain the component i.
  • obtains a quantitative value W ⁇ i of component i as a content W i further by the following equation (3), the standard value of the component i as a content W i of quantitative values W ⁇ i and the true component i of component i the standard deviation of the quantitative error (W ⁇ i -W i) which is a difference between the obtained accuracy S a for the entire quantitative value of the component i by a set of standard sample used.
  • I Ti aI Mi 2 + bI Mi + c ... (4)
  • I Ti The theoretical intensity of the fluorescent X-ray of the measurement element corresponding to the component i
  • I Mi The measurement intensity of the fluorescent X-ray of the measurement element corresponding to the component i a, b, c: Device sensitivity constant
  • the graph of the device sensitivity curve represented by the above equation (4) is displayed as shown in FIG. 3 for, for example, the component Cr.
  • the horizontal axis coordinates of the black circle points indicate the theoretical intensity for the standard sample.
  • the conversion measurement intensity I ⁇ Ti which is the measurement intensity converted to the theoretical intensity scale, is obtained, and further.
  • the present invention has been made in view of the above-mentioned conventional problems, and an object of the present invention is to facilitate evaluation of whether or not an apparatus sensitivity curve is appropriately created in a fluorescence X-ray analyzer by a fundamental parameter method.
  • the present invention first irradiates a sample with primary X-rays, and based on the measured intensity of the generated fluorescent X-rays, contains components in the sample by a quantitative means using a fundamental parameter method.
  • This is a fluorescent X-ray analyzer for obtaining a quantitative value of the rate.
  • the quantification means is used for a set of standard samples in which the content of the component is known as a standard value, and the mass fraction and the standard value of the measurement element corresponding to the standard value for each fluorescent X-ray of the measurement element corresponding to the component.
  • the device sensitivity constant is determined by obtaining the device sensitivity curve which is the correlation between the theoretical strength calculated by the theoretical strength formula and the measured strength using the mass fraction of the sample constituent elements obtained from.
  • the quantification means obtains the measurement intensity, the device sensitivity constant, and a proportional coefficient multiplied by the mass fraction of the measurement element in order to calculate the theoretical intensity in the theoretical intensity formula. It is used to calculate the quantitative value of the content of the component corresponding to the measurement element.
  • the quantification means is a graph showing the correlation between the standard value and the quantification value for each component, and / or the standard value, the quantification value, the quantification error for each standard sample and the entire quantification value by the set of standard samples. Outputs the accuracy of.
  • a graph showing the correlation between the standard value and the quantitative value and / or the standard value, the quantitative value, and the quantitative error for each standard sample were used for each component by the quantitative means.
  • the accuracy of the entire quantification value from a set of standard samples is output.
  • the calibration curve formula is used in the quantitative analysis by the calibration curve method. Just as it is easy to evaluate whether or not the device sensitivity curve is properly created, it is easy to evaluate whether or not the device sensitivity curve is properly created.
  • this apparatus measures the intensity of secondary X-rays 5 generated by irradiating samples 1 and 14 (including both unknown sample 1 and standard sample 14) with primary X-rays 3.
  • a scanning type fluorescent X-ray analyzer the sample table 2 on which the samples 1 and 14 are placed, the X-ray source 4 such as an X-ray tube that irradiates the samples 1 and 14 with the primary X-ray 3, and the X-ray source 4.
  • the output of the detector 8 is input to a control means 11 such as a computer that controls the entire apparatus via an amplifier (not shown), a pulse height analyzer, a counting means, and the like.
  • This device is a wavelength dispersive and scanning type fluorescent X-ray analyzer, and interlocks the spectroscopic element 6 and the detector 8 so that the wavelength of the secondary X-ray 7 incident on the detector 8 changes.
  • the means 10, that is, a so-called goniometer is provided.
  • the extension line 9 of the secondary X-ray 5 and the secondary X-ray 7 spectroscopically (diffused) by the spectroscopic element 6 are 2 at the incident angle ⁇ .
  • the interlocking means 10 changes the spectral angle 2 ⁇ to change the wavelength of the second-order X-ray 7 dispersed, and the dispersed second-order X-ray 7 is sent to the detector 8.
  • the spectroscopic element 6 is rotated about an axis O perpendicular to the paper surface passing through the center of the surface so as to be incident, and the detector 8 is rotated along the circle 12 about the axis O by twice the rotation angle. And rotate.
  • the value of the spectral angle 2 ⁇ (2 ⁇ angle) is input from the interlocking means 10 to the control means 11.
  • This device includes a quantification means 13 as a program mounted on the control means 11, and the quantification means 13 using the fundamental parameter method based on the measurement intensity of the fluorescent X-ray 5 is used to display the components in the samples 1 and 14. Obtain a quantitative value of the content rate.
  • the fluorescent X-ray analyzer may be a wavelength dispersive and multi-element simultaneous analysis type fluorescent X-ray analyzer, or an energy dispersive fluorescent X-ray analyzer.
  • step S1 for analysis of an unknown sample 1, in step S1, components i, the set content of the j W i, W j are known as the standard value using a standard sample 14, for each X-ray fluorescence 5 measurement element corresponding to component i, (1/100 of mass percentage) mass fraction w i of the measuring element corresponding to the standard values W i and standard values W i, the theoretical intensity I Ti calculated by theoretical strength equation using the mass fraction w k of the sample constituent element k obtained from W j, as a function of the measured intensity I Mi, tables as equation (4)
  • the device sensitivity curves to be obtained are obtained to determine the device sensitivity constants a, b, and c.
  • the sample constituent element k is all the elements constituting the samples 1 and 14, and includes the measurement element corresponding to the component i. Further, when the components i and j are compounds, the sample constituent element k has a one-to-one correspondence with the components i and j, so different symbols k are used.
  • ITpi K i w i / ⁇ k w k ... (6)
  • I Tpi Theoretical intensity of fluorescent X-rays of the measurement element corresponding to component i (primary excitation)
  • K i Constant
  • w i Mass fraction of the measurement element corresponding to the component i
  • ⁇ k Total absorption count of the sample constituent element k with respect to the fluorescent X-ray corresponding to the component i w k : Mass fraction of the sample constituent element k
  • K i / ⁇ k w k I Tpi ' , in theoretical strength formula (6), calculates the theoretical intensity I Tpi of the fluorescent X-ray measurement element corresponding to component i to have a proportional coefficient to be multiplied to the mass fraction w i of the measuring element corresponding to the component i.
  • This proportional coefficient I Tpi' is a theoretical intensity formula (6) for calculating the theoretical intensity I Tpi of the fluorescent X-ray of the measurement element corresponding to the component i, and the mass fraction wi of the measurement element corresponding to the component i. in it can be said that the numerical value which is calculated by dividing the formula K i / ⁇ k w k.
  • Theoretical strength I Tsi corresponding to component i of the secondary excitation is similarly proportional to the mass fraction w i of the measuring element corresponding to component i, when the proportionality coefficient I Tsi ', the primary excitation and a secondary even theoretical strength I Ti corresponding to component i of the combined following excitation is proportional to the mass fraction w i of the measuring element corresponding to the component i, the proportionality factor, I Ti by the following equation (7) ' It becomes.
  • the mass fraction of the measurement element is calculated from the standard value W i of component i as a mass fraction w i of the measuring element corresponding to the component i
  • the mass fraction of the sample constituent element k using mass fraction w k of each sample constituent element k to the rate w k is calculated from the standard values W i, W j, calculating the theoretical intensity I Ti.
  • the device sensitivity curve represented by the above equation (4) as the correlation between the theoretical intensity I Ti and the measurement intensity I Mi of the fluorescent X-ray 5 of the measurement element corresponding to the component i of the standard sample 14.
  • the content rate Wi of the component i (including the standard value and the quantitative value of the content rate, etc., is generally a mass fraction. conversion from represented) by (mass%), the mass fraction w i of the measuring element corresponding to component i is merely multiplied by 1/100. If component i is a compound, the content of W i of component i, is converted to the mass fraction w i of the measuring element corresponding to component i, representing the measurement element (the compound of molecular weight and the corresponding compounds It is done by a well-known technique based on the atomic weight of the element).
  • a sample such as an oxide is prepared as a glass bead and the glass bead is used as a sample for fluorescent X-ray analysis, or when a powder sample is mixed with a binder and the mixture is used as a sample for fluorescent X-ray analysis.
  • the mass fraction w i of the measuring element corresponding to the component in the sample i is dilution of the sample is vaporized by a glass bead prepared It is done by a well-known technique based on the content of the igros component and the like.
  • samples 1 and 14 are stainless steel, and five standard samples 14 having standard values as shown in Table 1 are used, and fluorescent X-rays of the measurement element Cr corresponding to the component Cr are used.
  • step S2 the quantification means 13 calculates the measured intensity I Mi , the device sensitivity constants a, b, and c, and the theoretical intensity I Ti in the theoretical intensity formula for each standard sample 14. It said measuring element by using the mass fraction w i to be multiplied proportionality factor I Ti 'of the calculated as follows quantitative value W ⁇ i of the content of components i corresponding to the measurement element.
  • Equation (4) and the formula derived from (7) (8) to calculate the quantitative value w ⁇ i mass fraction w i of the measuring element corresponding to the component i.
  • the proportional factor I Ti ' is the theoretical intensity formula used in step S1, for example, the formula Equation (6), divided by the mass fraction w i of the measuring element corresponding to the component i, for example, K i / ⁇ k w Calculate with k.
  • step S1 the inverse conversion to the conversion from the content W i of component i mentioned in step S1 to the mass fraction w i of the measuring element corresponding to the component i, the mass fraction w of the measuring element corresponding to component i by performing relative quantitative value w ⁇ i of i, to calculate the quantitative value W ⁇ i of the content of components i corresponding to the measurement element.
  • Quantitative value w ⁇ i (denoted as Cr mass fraction in Table 3) of the mass fraction w i of the measurement element Cr corresponding to the coefficient I Ti ', the component Cr, and the quantitative value of the content Cr of the component Cr corresponding to the measurement element Cr.
  • the value W ⁇ i (denoted as Cr quantitative value in Table 3) is calculated.
  • the quantification means 13 is a graph showing the correlation between the standard value Wi and the quantification value W ⁇ i for each component i, and / or the standard value Wi and the quantification value for each standard sample 14.
  • W ⁇ i and outputs the accuracy S C for the entire quantitative values by quantitative error (W ⁇ i -W i) a set of standard sample 14 used.
  • the graph and / or each numerical value is displayed on a display or a printer (not shown). It is also possible to display the accuracy S C superimposed on a graph showing the correlation between the standard value W i and quantitative values W ⁇ i.
  • accuracy S C is the following equation (9), determined as the standard deviation of quantitative error (W ⁇ i -W i).
  • the step of obtaining the quantitative value W ⁇ i of the content of the component i in the unknown sample 1 using the prepared device sensitivity curve is performed in the same manner as the quantitative analysis by the conventional fundamental parameter method.
  • the quantification means 13 is used to show the correlation between the standard value Wi and the quantification value W ⁇ i for each component i, and / or the standard sample.
  • standard values W i for each 14 quantitative values W ⁇ i, accuracy S C for the entire quantitative values by quantitative error (W ⁇ i -W i) a set of standard sample 14 used is output.
  • step S2 of the present embodiment the theoretical intensity type using in step S1 by the formula divided by the mass fraction w i of the measuring element corresponding to component i, and computes the proportionality factor I Ti ' .
  • the theoretical intensity I Ti of the fluorescent X-ray measurement element corresponding to component i also calculated in step S1
  • the mass fraction w i of the measuring element corresponding to component i It is also conceivable to simply divide by and obtain the proportionality coefficient I Ti'.
  • the mass fraction wi of the measurement element corresponding to the component i is 0, the divisor becomes 0 and it cannot be dealt with.
  • step S1 the composition mass fraction w i of the measuring element corresponding to component i is 0, the by replacing the mass fraction w i in trace amounts, for example, 10 -8 Then, it is conceivable to calculate the theoretical intensity of each component. That way, the mass fraction w i of the measuring element corresponding to component i is no longer zero.
  • the theoretical intensity I Ti of the fluorescent X-ray measurement element corresponding to components i then simply divided by the mass fraction w i of the measuring element corresponding to component i, can be determined proportionality factor I Ti ' ..

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Abstract

L'invention concerne un analyseur de fluorescence X qui comprend un moyen de quantification utilisant un procédé de paramètre fondamental. Pour chaque échantillon étalon, le moyen de quantification utilise une intensité de mesure, une constante de sensibilité de dispositif, et une constante de proportionnalité, qui est multipliée par la fraction massique d'un élément de mesure pour calculer une intensité théorique dans une équation d'intensité théorique, pour calculer une valeur quantitative pour la teneur d'un constituant correspondant à l'élément de mesure. Le moyen de quantification délivre en sortie la précision de la totalité de valeurs quantitatives à partir d'un ensemble d'échantillons étalons utilisés et une erreur de quantification, une valeur quantitative, et une valeur étalon pour chaque échantillon étalon et/ou un graphique indiquant la corrélation entre valeurs étalons et valeurs quantitatives, pour chaque constituant.
PCT/JP2020/022146 2019-09-26 2020-06-04 Analyseur par fluorescence x WO2021059597A1 (fr)

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Publication number Priority date Publication date Assignee Title
US20030118148A1 (en) * 2001-12-06 2003-06-26 Rigaku Industrial Corporation X-ray fluorescense spectrometer
WO2017038701A1 (fr) * 2015-08-28 2017-03-09 株式会社リガク Analyseur par fluorescence x
WO2018168939A1 (fr) * 2017-03-15 2018-09-20 株式会社リガク Procédé d'analyse par fluorescence des rayons x, programme d'analyse par fluorescence des rayons x et dispositif d'analyse par fluorescence des rayons x

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JP4908119B2 (ja) * 2005-10-19 2012-04-04 株式会社リガク 蛍光ｘ線分析装置
EP3336527B1 (fr) * 2015-08-10 2020-04-22 Rigaku Corporation Spectromètre de fluorescence des rayons x
CN106770407A (zh) * 2016-11-25 2017-05-31 成都中光电科技有限公司 一种玻璃配合料整体均匀度的熔片x荧光测定方法
CN108827993A (zh) * 2018-06-28 2018-11-16 北矿科技股份有限公司 实现快速测定高性能磁性材料bms-12中镧、钙、钴各元素含量的方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030118148A1 (en) * 2001-12-06 2003-06-26 Rigaku Industrial Corporation X-ray fluorescense spectrometer
WO2017038701A1 (fr) * 2015-08-28 2017-03-09 株式会社リガク Analyseur par fluorescence x
WO2018168939A1 (fr) * 2017-03-15 2018-09-20 株式会社リガク Procédé d'analyse par fluorescence des rayons x, programme d'analyse par fluorescence des rayons x et dispositif d'analyse par fluorescence des rayons x

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JP2021051053A (ja) 2021-04-01
CN113748333B (zh) 2022-07-12
JP6838754B1 (ja) 2021-03-03

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