A hybrid analysis method, device and system for ray transmission spectrum and fluorescence spectrum

Abstract

The present invention discloses a mixed analysis method, device and system of ray transmission spectrum and fluorescence spectrum, belonging to the field of instrumental analysis. The method comprises: obtaining the transmission spectrum and fluorescence spectrum corresponding to the target sample to be measured, a series of mixed standard samples and a blank standard sample; analyzing the transmission spectrum of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficient in the first linear fitting relationship; analyzing the transmission spectrum of the target sample to be measured and the blank standard sample, and calculating the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship; analyzing the fluorescence spectrum of the series of mixed standard samples and the target sample to be measured to obtain the concentration value of the M component in the target sample to be measured. Wherein, the cumulative transmittance is calculated in the transmission spectrum analysis. The measurement result of the target component concentration value obtained by the method is accurate, high in precision, and the calculation process is simple.

Description

Technical Field

[0001] The present invention belongs to the technical field of instrumental analysis, and in particular relates to a mixed analysis method, device and system of ray transmission spectrum and fluorescence spectrum. Background Art

[0002] At present, the principle of the hybrid analysis method based on transmission spectrum and fluorescence spectrum and the corresponding analytical instrument is: analyze the concentration of N component in the sample to be tested based on the transmission spectrum, and obtain the concentration ratio of N component and M component in the sample to be tested based on the fluorescence spectrum, and calculate the concentration of M component by combining the concentration of N component measured by the transmission spectrum. This hybrid analysis method is suitable for measuring mixed samples containing N and M components, in which the concentration of N component is recommended to be higher than 100g / L, and the concentration ratio of N component to M component is recommended to be 80-150. Small measurement error and good precision can be obtained in this concentration range. Such instruments include hybrid K boundary densitometers, hybrid L boundary densitometers, etc., and their advantage is that they can directly measure the sample without separating the N component and the M component and measuring them separately.

[0003] However, this mixed analysis method and instrument have application limitations. When the concentration of the N component is low, there is no obvious absorption mutation in the transmission spectrum. Affected by counting such as statistical fluctuations, the error of the measured concentration value is large.

[0004] In addition, the existing hybrid analysis method based on transmission spectrum and fluorescence spectrum has the following problems: the analysis process of transmission spectrum is relatively cumbersome and requires the absorption mutation edge energy E K or E L The inverse value of the transmission spectrum (T) is calculated channel by channel within a certain energy window on the left and right. Then, the fitting relationship curve between lnln(1 / T) and lnE is established within the range of the left and right energy windows respectively, and the boundary energy E of the left and right energy windows is calculated. - and E + The transmittance (E - Less than E K or E L About 5-6keV, E + Higher than E K or E L About 2.5keV), and then obtain the absorption mutation edge energy E K or E L The absorbance difference (ΔA) of the sample was used to calculate the concentration of component N using formula (1).

[0005]

[0006] This algorithm is not only complicated, but also requires the use of the logarithm of absorbance and the logarithm of energy to fit a linear relationship. The error will be exponentially expanded. At the same time, it is affected by the statistical fluctuations of the counts. The logarithm of the inverse of the transmittance corresponding to some energy channels may be ≤0, and a secondary logarithmic calculation cannot be performed again. In addition, the problem of atypical absorption of X-rays by the sample components themselves is also ignored (which directly affects the Δμ mass attenuation coefficient in equation (1)).

[0007] Therefore, the current mixed analysis method has the problems of large component measurement concentration errors, low precision, and complex transmission spectrum analysis process. Summary of the invention

[0008] The technical problem to be solved by the present invention is to provide a mixed analysis method, device and system of X-ray transmission spectrum and fluorescence spectrum in view of the above-mentioned deficiencies in the prior art, which has the advantages of accurate measurement results of component concentration values, high precision and simple calculation process.

[0009] In a first aspect, the present invention provides a mixed analysis method of radiation transmission spectrum and fluorescence spectrum, comprising: obtaining transmission spectra and fluorescence spectra corresponding to a target sample to be measured, a series of mixed standard samples, and a blank standard sample, wherein the series of mixed standard samples refers to a number of samples prepared according to the concentration ratio of N and M components in the target sample to be measured, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be measured; analyzing the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficient in a first linear fitting relationship, wherein the first linear fitting relationship includes a linear relationship between the concentration value of the N component and the absorbance difference; analyzing the transmission spectra of the target sample to be measured and the blank standard sample, and calculating the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship; analyzing the fluorescence spectra of the series of mixed standard samples and the target sample to be measured to obtain the concentration value of the M component in the target sample to be measured. Among them, the transmission spectra of the series of mixed standard samples / target samples to be tested and blank standard samples are analyzed, specifically including: calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and blank standard samples; calculating the absorbance difference according to the cumulative transmittance.

[0010] Preferably, the method of calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample specifically includes: determining the left and right window energy ranges of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample; respectively calculating the cumulative counts within the left and right window energy ranges of the series of mixed standard samples / target samples to be tested and the blank standard sample; and calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the cumulative counts.

[0011] Preferably, the cumulative transmittance satisfies:

[0012]

[0013]

[0014] Among them, T(E - ) is the cumulative transmittance corresponding to the left window boundary energy, T(E + ) is the cumulative transmittance corresponding to the right window boundary energy, is the cumulative counts within the left window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the right window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the accumulated counts in the left window energy range of the transmission spectrum of the blank standard sample, is the cumulative counts in the right window energy range of the transmission spectrum of the blank standard sample, n i is the count of the ith address, n 0i is the count of the ith channel of the transmission spectrum of the blank standard sample, ll is the left border of the left window, lr is the right border of the left window, rl is the left border of the right window, and rr is the right border of the right window.

[0015] Preferably, the calculating the absorbance difference according to the cumulative transmittance specifically comprises: calculating the absorbance of the left and right window boundary energies of the absorption mutation edge energy according to the cumulative transmittance:

[0016]

[0017]

[0018] Solve the absorbance difference according to the following formula:

[0019]

[0020] Among them, A - is the absorbance at the left window boundary energy of the absorption mutation edge energy, A + is the absorbance at the right window boundary energy of the absorption mutation edge energy, and ΔA is the absorbance difference.

[0021] Preferably, the first linear fitting relationship satisfies:

[0022] ρ(g / L)=a0+a1·ΔA (8)

[0023] Among them, ρ (g / L) is the concentration value of N component, and a0 and a1 are fitting coefficients.

[0024] Preferably, the step of analyzing the fluorescence spectra of the series of mixed standard samples and the target sample to be tested to obtain the concentration value of the M component in the target sample to be tested specifically includes: analyzing the fluorescence spectra of the series of mixed standard samples to obtain the fluorescence peak area ratio of the N and M components of the series of mixed standard samples. or According to the fluorescence peak area ratio of N and M components of a series of mixed standard samples or Formula (9) or formula (10) to calculate the R' of the series of mixed standard samples N / M :

[0025]

[0026]

[0027] According to the concentration value of N component in the series of mixed standard samples and R' of the series of mixed standard samples N / M , fitting to obtain the fitting coefficient in the second linear fitting relationship, wherein the second linear fitting relationship includes the linear relationship between the calibration factor and the concentration value of the N component, R′ N / M is the calibration factor; the fluorescence spectrum of the target sample to be measured is analyzed to obtain the fluorescence peak area ratio of the N and M components of the target sample to be measured or According to the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N and M components or The concentration value of the M component in the target sample to be tested is calculated using the second linear fitting relationship and formula (9) or formula (10).

[0028] Preferably, the fluorescence spectrum of the series of mixed standard samples / target samples to be tested is analyzed, specifically including: determining the total area of ​​the α1 and / or α2 fluorescence peak areas of the N component and the α1 and β fluorescence peak areas of the M component in the series of mixed standard samples / target samples to be tested; calculating the fluorescence peak area ratio of the N and M components of the series of mixed standard samples / target samples to be tested; or

[0029] Preferably, the second linear fitting relationship satisfies:

[0030] R′ N / M =b+k·ρ N (g / L) (11),

[0031] Among them, ρ N (g / L) is the concentration value of N component, b and k are fitting coefficients.

[0032] Preferably, according to the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N and M components is or The second linear fitting relationship and formula (9) or formula (10) are used to calculate the concentration value of the M component in the target sample to be tested, specifically including: substituting the concentration value of the N component in the target sample to be tested into the second linear fitting relationship to obtain the R′ of the target sample to be tested. N / M ; R' of the target sample to be tested N / M , the concentration of N component, and the fluorescence peak area ratio of N and M components or Substitute into formula (9) or formula (10) to calculate the concentration value of component M in the target sample to be tested.

[0033] In a second aspect, the present invention further provides a hybrid analysis device for ray transmission spectrum and fluorescence spectrum, comprising an acquisition module, a first analysis module, and a second analysis module.

[0034] The acquisition module is used to obtain the transmission spectra and fluorescence spectra corresponding to the target sample to be tested, the series of mixed standard samples, and the blank standard sample, wherein the series of mixed standard samples refers to a number of samples prepared according to the concentration ratio of N and M components in the target sample to be tested, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be tested.

[0035] The first analysis module is connected to the acquisition module and is used to analyze the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficients in the first linear fitting relationship, wherein the first linear fitting relationship includes the linear relationship between the concentration value of the N component and the absorbance difference.

[0036] It is also used to analyze the transmission spectra of the target sample to be measured and the blank standard sample, and calculate the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship.

[0037] The second analysis module is used to analyze the fluorescence spectra of the series of mixed standard samples and the target sample to be tested, and obtain the concentration value of the M component in the target sample to be tested. Among them, the first analysis module is specifically used to calculate the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample, and is also used to calculate the absorbance difference according to the cumulative transmittance.

[0038] In a third aspect, the present invention further provides a hybrid analysis system of ray transmission spectrum and fluorescence spectrum, comprising a hybrid K-boundary densitometer or a hybrid L-boundary densitometer, and the hybrid analysis device of ray transmission spectrum and fluorescence spectrum described in the second aspect. The hybrid analysis device of ray transmission spectrum and fluorescence spectrum is connected to the hybrid K-boundary densitometer or the hybrid L-boundary densitometer, and is used to obtain the transmission spectrum and fluorescence spectrum corresponding to the target sample to be measured, the series of mixed standard samples, and the blank standard sample measured by the hybrid K-boundary densitometer or the hybrid L-boundary densitometer.

[0039] In a fourth aspect, the present invention further provides a hybrid analysis system, comprising a memory and a processor, wherein the memory stores a computer program, and the processor is configured to run the computer program to implement the hybrid analysis method of the X-ray transmission spectrum and the fluorescence spectrum as described in the first aspect.

[0040] The present invention provides a mixed analysis method, device and system of ray transmission spectrum and fluorescence spectrum, which analyzes the transmission spectrum of a series of mixed standard samples and blank standard samples to determine the fitting coefficient in the first linear fitting relationship, and then analyzes the transmission spectrum of the target sample to be tested and the blank standard sample, and calculates the concentration value of the N component in the target sample to be tested based on the first linear fitting relationship, and then calculates the concentration value of the M component in the target sample to be tested based on the fluorescence spectrum analysis, thereby obtaining the concentration values ​​of the N component and the M component in the target sample to be tested. When performing the transmission spectrum analysis, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy is calculated, and the absorbance difference is directly obtained according to the cumulative transmittance. Therefore, there is no need to calculate the transmittance channel by channel within the left and right window energy ranges of the absorption mutation edge energy, and to fit lnln(1 / T) and lnE to obtain the absorbance difference of the absorption mutation edge energy. Instead, the total absorbance difference is directly obtained by using the cumulative transmittance of the transmission spectrum segment. This not only simplifies the calculation process, but also eliminates the influence of statistical fluctuations and takes into account the influence of atypical absorption, thereby greatly improving the accuracy and precision of the measured concentration value. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 This is a schematic flow chart of a hybrid analysis method of a ray transmission spectrum and a fluorescence spectrum according to Example 1 of the present invention;

[0042] Figure 2 This is a schematic diagram of the structure of a hybrid analysis device for ray transmission spectrum and fluorescence spectrum according to Example 3 of the present invention. DETAILED DESCRIPTION

[0043] In order to enable those skilled in the art to better understand the technical solution of the present invention, the embodiments of the present invention will be further described in detail below with reference to the accompanying drawings.

[0044] It should be understood that the specific embodiments and drawings described herein are only used to explain the present invention rather than to limit the present invention.

[0045] It can be understood that, in the absence of conflict, the various embodiments of the present invention and the various features in the embodiments can be combined with each other.

[0046] It can be understood that, for the convenience of description, the drawings of the present invention only show the parts related to the present invention, while the parts irrelevant to the present invention are not shown in the drawings.

[0047] It can be understood that each unit and module involved in the embodiments of the present invention may correspond to only one physical structure, or may be composed of multiple physical structures, or multiple units and modules may be integrated into one physical structure.

[0048] It can be understood that, without conflict, the functions and steps marked in the flowcharts and block diagrams of the present invention may occur in an order different from that marked in the drawings.

[0049] It is understood that the flowcharts and block diagrams of the present invention illustrate the possible architectures, functions, and operations of the systems, devices, equipment, and methods according to the various embodiments of the present invention. Each box in the flowchart or block diagram may represent a unit, module, program segment, or code, which contains executable instructions for implementing the specified functions. Moreover, each box or combination of boxes in the block diagram and flowchart may be implemented by a hardware-based system that implements the specified functions, or may be implemented by a combination of hardware and computer instructions.

[0050] It can be understood that the units and modules involved in the embodiments of the present invention can be implemented by software or hardware. For example, the units and modules can be located in a processor.

[0051] Embodiment 1:

[0052] like Figure 1 As shown, this embodiment provides a hybrid analysis method of ray transmission spectrum and fluorescence spectrum, wherein the ray includes X-ray, Y-ray, electron beam ray, ultraviolet light, visible light, and infrared light. This embodiment takes X-ray as an example and illustrates a hybrid analysis method of X-ray transmission spectrum and fluorescence spectrum, including:

[0053] Step 101, obtaining the transmission spectra and fluorescence spectra corresponding to the target sample to be tested, a series of mixed standard samples, and a blank standard sample, wherein the series of mixed standard samples refers to a number of samples prepared according to the concentration ratio of N and M components in the target sample to be tested, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be tested.

[0054] In the present embodiment, according to the concentration ratio of N and M components in the target sample to be measured, several mixed standard samples containing N and M components are prepared, and the concentration ratio of the mixed standard sample to the target sample to be measured is the same or close, but different from the actual concentration of the N and M components. According to the matrix of the target sample to be measured, a corresponding blank standard sample is prepared, for example, when the target sample to be measured is a nitric acid matrix, a corresponding blank nitric acid standard sample is prepared, and the blank nitric acid standard sample does not contain N and M components. Under the same measurement conditions, a mixed K boundary densitometer or a mixed L boundary densitometer is used to measure a series of mixed standard samples, blank standard samples, and the target sample to be measured, and the corresponding transmission spectra and fluorescence spectra are obtained respectively.

[0055] Specifically, this embodiment is explained by taking the analysis of a mixed sample containing thorium (Th) and uranium (U) as an example. The reference value of the target sample to be tested is: Th concentration 50g / L, U concentration 0.5g / L, and concentration ratio of 100:1. Therefore, a series (i.e., a group) of mixed standard samples are prepared according to the concentration ratio: Th concentration 40-380g / L, a total of 8 samples, Th / U concentration ratio of 100:1, 2mol / L nitric acid matrix. Preparation of blank standard sample: 2mol / L nitric acid solution, without Th and U. A mixed K boundary densitometer is used to measure the K absorption transmission spectrum of Th in the series of mixed standard samples, the target sample to be tested, and the blank standard sample, as well as the K-series fluorescence spectrum of Th and U, and the transmission spectrum and fluorescence spectrum data are obtained.

[0056] Step 102, analyzing the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficients in the first linear fitting relationship, wherein the first linear fitting relationship includes the linear relationship between the concentration value of the N component and the absorbance difference.

[0057] In this embodiment, for the K absorption transmission spectrum of Th, a series of mixed standard samples and blank standard samples are analyzed, specifically including: calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectrum of the series of mixed standard samples and the blank standard sample; calculating the absorbance difference according to the cumulative transmittance, and then determining the fitting coefficient in the first linear fitting relationship by a fitting method. In this embodiment, there is no need to calculate the transmittance channel by channel within the left and right window energy ranges of the absorption mutation edge energy, and to fit lnln(1 / T) with lnE to obtain the absorbance difference of the absorption mutation edge energy, but based on the cumulative transmittance of the spectrum segment, the total absorbance difference is directly obtained, which not only simplifies the calculation process, but also eliminates the influence of statistical fluctuations, thereby improving the accuracy and precision of the concentration calculation. The fitting method includes any one of the following: least squares method, regularization method, decision tree regression, random forest regression, neural network. Since the concentration values ​​of the N components in the series of mixed standard samples are all known, the fitting coefficient in the linear relationship between the concentration value of the N component and the absorbance difference can be determined. For example, the first linear fitting relationship is ρ(g / L)=p·ΔA, where p is the fitting coefficient and ΔA is the total absorbance difference.

[0058] Optionally, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy is calculated according to the transmission spectra of the series of mixed standard samples and the blank standard sample, specifically including: determining the left and right window energy ranges of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples and the blank standard sample; respectively calculating the cumulative counts within the left and right window energy ranges of the series of mixed standard samples and the blank standard sample; and calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the cumulative counts.

[0059] Optionally, the cumulative transmittance satisfies:

[0060]

[0061]

[0062] Among them, T(E - ) is the cumulative transmittance corresponding to the left window boundary energy, T(E + ) is the cumulative transmittance corresponding to the right window boundary energy, is the cumulative counts within the left window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the right window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the accumulated counts in the left window energy range of the transmission spectrum of the blank standard sample, is the cumulative counts in the right window energy range of the transmission spectrum of the blank standard sample, n i is the count of the ith address, n0i is the count of the ith channel of the transmission spectrum of the blank standard sample, ll is the left border of the left window, lr is the right border of the left window, rl is the left border of the right window, and rr is the right border of the right window.

[0063] In this embodiment, for the transmission spectrum analysis of the series of mixed standard samples and blank standard samples, the absorption mutation edge energy E K or E L (This embodiment is E K ) around a certain window energy range, and then calculate the cumulative counts in the left and right window energy ranges respectively, and then calculate the cumulative transmittance corresponding to the left and right energy window boundary energies of the absorption mutation edge, that is, the cumulative counts in the left window energy range of the mixed standard sample transmission spectrum absorption mutation edge energy are divided by the cumulative counts in the left window energy range of the blank standard sample transmission spectrum, and the T(E) in formula (3) is obtained. - ), similarly, the cumulative counts in the energy range of the right window of the absorption mutation edge energy of the mixed standard sample transmission spectrum are divided by the cumulative counts in the energy range of the right window of the blank standard sample to obtain T(E) in formula (4) + ).

[0064] Optionally, the absorbance difference is calculated according to the cumulative transmittance, specifically including: calculating the absorbance of the left and right window boundary energies of the absorption mutation edge energy according to the cumulative transmittance:

[0065]

[0066]

[0067] Solve the absorbance difference according to the following formula:

[0068]

[0069] Among them, A - is the absorbance at the left window boundary energy of the absorption mutation edge energy, A + is the absorbance at the right window boundary energy of the absorption mutation edge energy, and ΔA is the absorbance difference.

[0070] Optionally, the first linear fitting relationship of this embodiment satisfies:

[0071] ρ(g / L)=a0+a1·ΔA (8),

[0072] Wherein, ρ (g / L) is the concentration value of the N component, that is, the concentration value of the target component, and a0 and a1 are fitting coefficients. The first linear fitting relationship (8) established in this embodiment establishes a fitting relationship between the total absorbance difference at the left and right window boundary energies of the absorption mutation edge energy and the concentration of the target component. Compared with the prior art, the problem of atypical absorption of X-rays by the sample component itself is taken into account, thereby further improving the accuracy of the concentration calculation result.

[0073] In this embodiment, the transmission spectra of a series of mixed standard samples and blank standard samples are analyzed to obtain E K The energy range of the left window is 109.63keV, the energy range of the left window is 100.329-108.604keV, and the energy range of the right window is 111.656-120.021keV. The cumulative counts in the energy range of the left and right windows are calculated respectively, and then the cumulative transmittance corresponding to the energy at both ends of the absorption mutation edge is calculated. Finally, the absorbance difference between the left and right window boundary energies of the absorption mutation edge energy is calculated. The fitting relationship between the absorbance difference and the Th concentration in the mixed standard sample is determined by the least squares method: ρ(g / L)=7.534+0.2654·ΔA, R 2 =1, where R 2 =1 indicates an excellent fitting effect.

[0074] Step 103 , analyzing the transmission spectra of the target sample to be measured and the blank standard sample, and calculating the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship.

[0075] In this embodiment, the transmission spectra of the target sample to be tested and the blank standard sample are analyzed, specifically including: calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the target sample to be tested and the blank standard sample; calculating the absorbance difference according to the cumulative transmittance. Among them, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the target sample to be tested and the blank standard sample is calculated, specifically including: determining the left and right window energy range of the absorption mutation edge energy according to the transmission spectra of the target sample to be tested and the blank standard sample; respectively calculating the cumulative counts within the left and right window energy ranges of the target sample to be tested and the blank standard sample; calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the cumulative counts, and the cumulative transmittance satisfies formula (3) and formula (4). And the absorbance difference ΔA corresponding to the transmission spectrum of the N component in the target sample to be tested is calculated according to the cumulative transmittance and formula (7), and the concentration value of the N component in the target sample to be tested is calculated according to formula (8) in combination with the fitting coefficients (i.e., the values ​​of a0 and a1) in the first linear fitting relationship obtained in step 102. The calculated results showed that the average value of Th concentration of the target sample to be measured was 50.686 g / L, and the RSD (relative standard deviation) (n=6) was 0.77%.

[0076] Step 104, analyzing the fluorescence spectra of the series of mixed standard samples and the target sample to be tested to obtain the concentration value of the M component in the target sample to be tested.

[0077] In this embodiment, there are two ways to obtain the concentration value of the M component in the target sample to be tested by fluorescence spectrum analysis: one is to establish a corresponding relationship between the peak area and the concentration. For example, the analysis of the fluorescence spectrum adopts formula (2), and the concentration ratio of the N component and the M component and the measured net peak area ratio of the characteristic X-ray fluorescence peak are related as shown in formula 2.

[0078]

[0079] Among them, K is the K series fluorescence spectrum. If the L series fluorescence spectrum is used, it can be represented by L. A is the atomic weight, I is the fluorescence peak area, ORE is the overall relative detection efficiency of the fluorescence peak, and R is the calibration factor. In this method, the α1 fluorescence peak of the N component and the M component are used for calculation, but the α2 fluorescence peak of the M component may interfere with the α1 fluorescence peak of the N component; in addition, since the concentration of the M component is lower than that of the N component, the peak area count is smaller, and the statistical fluctuation has a greater impact, which in turn affects the accuracy and precision of the M component concentration analysis. Another method is to include the total area of ​​the α1 and β fluorescence peaks of the low-concentration component in the calculation, increase the count of the fluorescence peak area of ​​the low-concentration component, reduce the error caused by the low fluorescence peak count of the low-concentration component, and help improve the analysis accuracy of the low-concentration component; in addition, by mixing standard samples to establish R′ N / MWith the high concentration component concentration ρ N The second linear fitting relationship between the two is calculated, and the R′ of the target sample to be tested is calculated. N / M , which improves R′ N / M The accuracy of the component concentration measurement is ultimately improved.

[0080] Specifically, in the second method, the fluorescence spectra of the series of mixed standard samples and the target sample to be tested are analyzed to obtain the concentration value of the M component in the target sample to be tested, including steps 1041-1045:

[0081] Step 1041, analyzing the fluorescence spectra of the series of mixed standard samples to obtain the fluorescence peak area ratio of the N and M components of the series of mixed standard samples. or

[0082] In this embodiment, the fluorescence spectrum of the series of mixed standard samples is analyzed, including: determining the total area of ​​the α1 and / or α2 fluorescence peak areas of the N component and the α1 and β fluorescence peak areas of the M component in the series of mixed standard samples; calculating the fluorescence peak area ratio of the N and M components in the series of mixed standard samples. or In this example, because the Kα2 peak of U and the Kα1 peak of Th will interfere with each other, the total area of ​​the Kα2 fluorescence peak of Th and the Kα1+Kβ fluorescence peak of U is selected for calculation, that is,

[0083] Step 1042, based on the fluorescence peak area ratio of the N and M components of the series of mixed standard samples or Formula (9) or formula (10) to calculate the R' of the series of mixed standard samples N / M :

[0084]

[0085]

[0086] In this embodiment, since the concentrations of the N component and the M component in the series of mixed standard samples are known, the concentrations of the N component and the M component in the series of mixed standard samples are Bring in Calculate the R' of a series of mixed standard samples Th / U Value, that is, multiple R′ Th / U It should be noted that in formula (9) and formula (10) of this embodiment, ORE (the overall relative detection efficiency of the fluorescence peak) is included in R′ N / M (calibration factor), the existing formula (i.e., formula (2)) is simplified, thereby further simplifying the calculation process.

[0087] Step 1043, based on the concentration value of the N component in the series of mixed standard samples and the R′ of the series of mixed standard samples N / M , fitting coefficients in the second linear fitting relationship are obtained by fitting, wherein the second linear fitting relationship includes the linear relationship between the calibration factor and the concentration value of the N component, R′ N / M is the calibration factor.

[0088] In this embodiment, the second linear fitting relationship satisfies:

[0089] R′ N / M =b+k·ρ N (g / L) (11),

[0090] Among them, ρ N (g / L) is the concentration of N component, b and k are fitting coefficients. R' is established by mixing standard samples N / M With the high concentration component concentration ρ N The second linear fitting relationship (11) between the two is used to calculate the R′ of the target sample to be tested. N / M , which improves R′ N / M The accuracy of this embodiment is Th / U The mixed algorithm is used to calibrate the value with the Th concentration in the mixed standard sample, and the calibration result is R′ Th / U =0.5902+0.0002·ρ Th , R 2 =0.9236.

[0091] Step 1044, analyze the fluorescence spectrum of the target sample to be tested to obtain the fluorescence peak area ratio of the N and M components of the target sample to be tested. or

[0092] In this embodiment, the fluorescence spectrum analysis of the target sample to be tested includes: determining the total area of ​​the α1 and / or α2 fluorescence peak areas of the N component and the α1 and β fluorescence peak areas of the M component in the target sample to be tested; calculating the fluorescence peak area ratio of the N and M components of the target sample to be tested; or This embodiment calculates the target sample to be tested.

[0093] Step 1045, based on the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N component to the M component or The second linear fitting relationship and formula (9) or formula (10) are used to calculate the concentration value of the M component in the target sample to be tested.

[0094] Specifically, according to the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N and M components is or The second linear fitting relationship and formula (9) or formula (10) are used to calculate the concentration value of the M component in the target sample to be measured, including: bringing the concentration value of the N component in the target sample to be measured into the second linear fitting relationship to obtain R′ of the target sample to be measured N / M ; R' of the target sample to be tested N / M , the concentration of N component, and the fluorescence peak area ratio of N and M components or Substitute into formula (9) or formula (10) to calculate the concentration value of component M in the target sample to be tested.

[0095] In this embodiment, the Th concentration value of the target sample to be tested calculated in step 103 is substituted into the second linear fitting relationship determined in step 1043, that is, into formula (11), and the R′ of the target sample to be tested is calculated. Th / U Finally, the target sample to be tested and R′ Th / U Bring in In the results, the average value of the U concentration of the target sample to be tested was calculated to be 0.496 g / L, and the RSD (n=6) was 1.25%. According to the mixed analysis method of this embodiment, the average value of the Th concentration of the target sample to be tested was 50.686 g / L, and the average value of the U concentration was 0.496 g / L. Compared with the reference value of the target sample to be tested (Th concentration 50 g / L, U concentration 0.5 g / L), the component concentration measurement values ​​of this embodiment are very close to the reference value, indicating that the accuracy and precision of the concentration measurement values ​​obtained by the mixed analysis method in this embodiment are high. It should be noted that the mixed analysis method of this embodiment is also applicable to the analysis of at least three mixed samples. For example, the mixed sample includes N, M, and F components. The concentrations of the N and M components can be analyzed first, and then the concentration of the F component can be analyzed based on the N component or the M component.

[0096] The hybrid analysis method of the ray transmission spectrum and fluorescence spectrum of this embodiment analyzes the transmission spectra of the series of mixed standard samples and the blank standard sample to determine the fitting coefficient in the first linear fitting relationship, and then analyzes the transmission spectra of the target sample to be tested and the blank standard sample, and calculates the concentration value of the N component in the target sample to be tested based on the first linear fitting relationship, and then calculates the concentration value of the M component in the target sample to be tested based on the fluorescence spectrum analysis, thereby obtaining the concentration values ​​of the N component and the M component in the target sample to be tested. When performing the transmission spectrum analysis, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy is calculated, and the absorbance difference is directly obtained based on the cumulative transmittance. Therefore, it is not necessary to calculate the transmittance channel by channel within the energy range of the left and right windows of the absorption mutation edge energy, and to fit lnln(1 / T) with lnE to obtain the absorbance difference of the absorption mutation edge energy. Instead, the cumulative transmittance is calculated by the cumulative count of the transmission spectrum segment, and the total absorbance difference is directly obtained. This not only simplifies the calculation process, but also eliminates the influence of statistical fluctuations and takes into account the influence of atypical absorption, thereby greatly improving the accuracy and precision of the concentration measurement value. Furthermore, the first linear fitting relationship (8) established in this embodiment establishes a fitting relationship between the total absorbance difference at the left and right window boundary energies of the absorption mutation edge energy and the concentration of the target component. Compared with the prior art, the problem of atypical absorption of X-rays by the sample component itself is taken into account, thereby further improving the accuracy of the concentration measurement value. In addition, the total area of ​​the α1 and β fluorescence peaks of the low-concentration component is included in the calculation, the count of the fluorescence peak area of ​​the low-concentration component is increased, and the error caused by the low fluorescence peak count of the low-concentration component is reduced, which is conducive to improving the analysis accuracy of the low-concentration component; and R′ is established by mixing the standard sample. N / M With the high concentration component concentration ρ N The second linear fitting relationship between the two is calculated, and the R′ of the target sample to be tested is calculated. N / M , which improves R′ N / M The accuracy of the measured concentration value is further improved. According to the actual application, the fluorescence α1 and / or α2 peaks of the high-concentration component can be flexibly selected for calculation to avoid the interference of the low-concentration component on the high-concentration component. In summary, the hybrid analysis method of this embodiment can significantly improve the measurement accuracy and precision of the target component, and has the advantages of simple calculation process, accurate results, and wide application range.

[0097] Embodiment 2:

[0098] This embodiment provides a hybrid analysis method of X-ray transmission spectrum and fluorescence spectrum, based on a hybrid K-edge densitometer, to analyze a mixed sample containing thorium (Th) and uranium (U), and the hybrid analysis method includes the following steps:

[0099] (1) Preparation of mixed standard samples:

[0100] Group 1: Th concentration 100-380 g / L, 6 samples in total, Th / U concentration ratio 80:1, 2 mol / L nitric acid matrix;

[0101] Group 2: Th concentration 40-380 g / L, 8 samples in total, Th / U concentration ratio of 100:1, 2 mol / L nitric acid matrix.

[0102] (2) Preparation of blank standard sample: 2 mol / L nitric acid solution, without Th and U.

[0103] (3) Preparation value of the target sample to be tested (reference value):

[0104] Sample 1#: Th concentration 50g / L, U concentration 0.5g / L;

[0105] Sample 2#: Th concentration 230g / L, U concentration 2.3g / L;

[0106] Sample #3: Th concentration 320 g / L, U concentration 4 g / L.

[0107] (4) A hybrid K-edge densitometer was used to measure the K absorption and transmission spectra of Th and the K-series fluorescence spectra of Th and U, respectively.

[0108] (5) For the K absorption transmission spectrum of Th, the mixed standard sample and the blank standard sample were analyzed, with Ek of 109.63keV, the left window energy range of 100.329-108.604keV, and the right window energy range of 111.656-120.021keV. The cumulative counts in the energy range of the left and right windows were calculated respectively, and then the cumulative transmittance corresponding to the energy at both ends of the absorption mutation edge was calculated, and finally the absorbance difference of the left and right window boundary energies of the absorption mutation edge energy was calculated, and the fitting relationship between the absorbance difference and the Th concentration in the mixed standard sample was established:

[0109] Using the first group of mixed standard samples, the fitting relationship is ρ(g / L)=4.0111+0.2731·ΔA, R 2 =0.9995.

[0110] Using the second group of mixed standard samples, the fitting relationship is ρ(g / L)=7.534+0.2654·ΔA, R 2 =1.

[0111] (6) The target sample to be tested and the blank standard sample are used for transmission spectrum analysis, and the absorbance difference ΔA corresponding to the Th transmission spectrum in the target sample to be tested is calculated. Combined with the fitting result of the mixed standard sample in step (5), the concentration value of Th in the target sample to be tested can be obtained; for the 1# and 2# standard samples, the fitting relationship of the second group of mixed standard samples is selected, and for the 3# standard sample, the fitting relationship of the first group of mixed standard samples is selected. The calculated results are that the average value of the Th concentration of the 1# sample is 50.686 g / L, and the RSD (n=6) is 0.77%; the average value of the Th concentration of the 2# sample is 230.659 g / L, and the RSD (n=6) is 0.27%; the average value of the Th concentration of the 3# sample is 320.166 g / L, and the RSD (n=6) is 0.25%.

[0112] (7) Analyze the fluorescence spectrum and select the total area of ​​the Kα2 fluorescence peak of Th and the Kα1+Kβ fluorescence peak of U for calculation, because the Kα2 peak of U and the Kα1 peak of Th will interfere with each other.

[0113] (8) Mix the standard sample Bring in Calculate the series R' of the mixed standard sample Th / U Value. Th / U The mixed algorithm was used to calibrate the Th concentration in the mixed standard sample, and the results are as follows:

[0114] Using the first group of mixed standard samples, the calibration result is R' Th / U =0.6771+0.0004·ρ Th , R 2 =0.9464, using the second group of mixed standard samples, the calibration result is R' Th / U =0.5902+0.0002·ρ Th , R 2 =0.9236.

[0115] (9) Then perform fluorescence spectrum analysis on the target sample to obtain the At the same time, according to the Th concentration of the target sample to be tested, R′ is introduced Th / U Calculate the R′ of the target sample from the calibration curve Th / U Finally, the target sample to be tested and R′ Th / U Bring in , calculate the U concentration. The results are as follows: the average U concentration of sample 1# is 0.496 g / L, and the RSD (n=6) is 1.25%; the average Th concentration of sample 2# is 2.312 g / L, and the RSD (n=6) is 0.99%; the average Th concentration of sample 3# is 3.97 g / L, and the RSD (n=6) is 0.75%. Using a mixed analysis method of X-ray transmission spectrum and fluorescence spectrum of this embodiment, the measurement results of Th and U in the target sample to be measured are very accurate, and the precision of multiple measurements is also very good, indicating that the mixed analysis method can be applied to the analysis of such mixed samples, can expand the analysis concentration range of mixed samples, the analysis process is simpler than the prior art, and eliminates the influencing factors of statistical fluctuations and atypical absorption.

[0116] In the hybrid analysis method of X-ray transmission spectrum and fluorescence spectrum of this embodiment, the difference between the analysis method of transmission spectrum and the prior art lies in that: it is not necessary to calculate the transmittance one by one within the energy range of the left and right windows of the absorption mutation edge energy, and to fit lnln(1 / T) and lnE to obtain the absorbance difference of the absorption mutation edge energy, but to use the cumulative count of the spectrum segment to calculate the cumulative transmittance and directly obtain the total absorbance difference, which not only simplifies the calculation process, but also eliminates the influence of statistical fluctuations and takes into account the influence of atypical absorption. The difference between the analysis method of fluorescence spectrum and the prior art lies in that ORE (overall relative detection efficiency of fluorescence peak) is included in R' N / M (calibration factor), the existing calculation formula is simplified; at the same time, the total area of ​​α1 and β fluorescence peaks of low-concentration components is included in the calculation, which increases the count of fluorescence peak area of ​​low-concentration components and reduces the error caused by low fluorescence peak count of low-concentration components, which is conducive to improving the analysis accuracy of low-concentration components; in addition, R′ is established by mixing standard samples N / M With the high concentration component concentration ρ N The second linear fitting relationship between the two is calculated, and the R′ of the target sample to be tested is calculated. N / M , which improves R′ N / M Therefore, it can significantly improve the measurement accuracy and precision of the target component, and has the advantages of simple calculation process, accurate results and wide application range.

[0117] Embodiment 3:

[0118] like Figure 2 As shown, this embodiment provides a hybrid analysis device for ray transmission spectrum and fluorescence spectrum, including an acquisition module 21 , a first analysis module 22 , and a second analysis module 23 .

[0119] The acquisition module 21 is used to obtain the transmission spectra and fluorescence spectra corresponding to the target sample to be tested, the series of mixed standard samples, and the blank standard sample, wherein the series of mixed standard samples refers to a number of samples prepared according to the concentration ratio of N and M components in the target sample to be tested, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be tested.

[0120] The first analysis module 22 is connected to the acquisition module 21, and is used to analyze the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficient in the first linear fitting relationship, wherein the first linear fitting relationship includes the linear relationship between the concentration value of the N component and the absorbance difference. It is also used to analyze the transmission spectra of the target sample to be measured and the blank standard sample, and calculate the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship.

[0121] The second analysis module 23 is connected to the acquisition module 21 and the first analysis module 22, and is used to analyze the fluorescence spectra of the series of mixed standard samples and the target sample to be tested, and obtain the concentration value of the M component in the target sample to be tested. Among them, the first analysis module 22 is specifically used to calculate the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample, and is also used to calculate the absorbance difference according to the cumulative transmittance.

[0122] Optionally, the first analysis module is specifically used to determine the left and right window energy range of the absorption mutation edge energy based on the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample, and to respectively calculate the cumulative counts within the left and right window energy ranges of the series of mixed standard samples / target samples to be tested and the blank standard sample, and to calculate the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy based on the cumulative counts.

[0123] Optionally, the cumulative transmittance satisfies:

[0124]

[0125]

[0126] Among them, T(E - ) is the cumulative transmittance corresponding to the energy at the left window boundary, T(E + ) is the cumulative transmittance corresponding to the right window boundary energy, is the cumulative counts within the left window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the right window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the left window energy range of the transmission spectrum of the blank standard sample, is the cumulative counts in the right window energy range of the transmission spectrum of the blank standard sample, n i is the count of the ith address, n 0i is the count of the ith channel of the transmission spectrum of the blank standard sample, ll is the left border of the left window, lr is the right border of the left window, rl is the left border of the right window, and rr is the right border of the right window.

[0127] Optionally, the first analysis module is used to calculate the absorbance of the left and right window boundary energies of the absorption mutation edge energy according to the cumulative transmittance:

[0128]

[0129]

[0130] Solve the absorbance difference according to the following formula:

[0131]

[0132] Among them, A - is the absorbance at the left window boundary energy of the absorption mutation edge energy, A + is the absorbance at the right window boundary energy of the absorption mutation edge energy, and ΔA is the absorbance difference.

[0133] Optionally, the first linear fitting relationship satisfies:

[0134] ρ(g / L)=a0+a1·ΔA (8)

[0135] Among them, ρ (g / L) is the concentration value of N component, and a0 and a1 are fitting coefficients.

[0136] Optionally, the second analysis module is used to analyze the fluorescence spectrum of the series of mixed standard samples to obtain the fluorescence peak area ratio of the N and M components of the series of mixed standard samples. or It is also used to calculate the fluorescence peak area ratio of the N and M components of a series of mixed standard samples. or Formula (9) or formula (10) to calculate the R' of the series of mixed standard samples N / M :

[0137]

[0138]

[0139] Used to calculate the concentration of N component in the series of mixed standard samples and R' of the series of mixed standard samples N / M, fitting to obtain the fitting coefficient in the second linear fitting relationship, wherein the second linear fitting relationship includes the linear relationship between the calibration factor and the concentration value of the N component, R′ N / M It is a calibration factor and is also used to analyze the fluorescence spectrum of the target sample to be tested to obtain the fluorescence peak area ratio of the N and M components of the target sample to be tested. or And, for determining the fluorescence peak area ratio of N and M components according to the concentration value of N component of the target sample to be tested or The concentration value of the M component in the target sample to be tested is calculated using the second linear fitting relationship and formula (9) or formula (10).

[0140] Optionally, the second analysis module is specifically used to determine the total area of ​​the α1 and / or α2 fluorescence peak areas of the N component and the α1 and β fluorescence peak areas of the M component in the series of mixed standard samples / target samples to be tested, and calculate the fluorescence peak area ratio of the N and M components of the series of mixed standard samples / target samples to be tested. or

[0141] Optionally, the second linear fitting relationship satisfies:

[0142] R′ N / M =b+k·ρ N (g / L) (11),

[0143] Among them, ρ N (g / L) is the concentration value of N component, b and k are fitting coefficients.

[0144] Optionally, the second analysis module is further used to bring the concentration value of the N component in the target sample to be tested into the second linear fitting relationship to obtain the R′ of the target sample to be tested. N / M , and the R′ of the target sample to be tested N / M , the concentration of N component, and the fluorescence peak area ratio of N and M components or Substitute into formula (9) or formula (10) to calculate the concentration value of component M in the target sample to be tested.

[0145] The hybrid analysis device of this embodiment is used to eliminate the influence of statistical fluctuations by the cumulative counts of the transmission spectrum segment, and to establish a fitting relationship with the concentration of the target component by the total absorbance difference at the left and right window boundary energies of the absorption mutation edge energy, taking into account the problem of atypical absorption of X-rays by the sample component itself, and simultaneously simplifying the analysis process of the transmission spectrum. In the fluorescence spectrum analysis, the total area of ​​the α1 and β fluorescence peaks of the low-concentration component is included in the calculation, which solves the problem of relatively low counts of the low-concentration component and further reduces the influence of statistical fluctuations. And it is used to flexibly select the fluorescence α1 and / or α2 spectrum peaks of the high-concentration component for calculation according to actual applications to solve the problem of interference of the low-concentration component with the high-concentration component. Therefore, the hybrid analysis device based on the X-ray transmission spectrum and the fluorescence spectrum can significantly improve the measurement accuracy and precision of the target component, and has the advantages of simple calculation process, accurate results, and wide application range.

[0146] Embodiment 4:

[0147] This embodiment provides a hybrid analysis system of ray transmission spectrum and fluorescence spectrum, including a hybrid K-edge densitometer or a hybrid L-edge densitometer, and the hybrid analysis device of ray transmission spectrum and fluorescence spectrum of embodiment 3.

[0148] A hybrid analysis device for X-ray transmission spectrum and fluorescence spectrum is connected to a hybrid K-boundary densitometer or a hybrid L-boundary densitometer to obtain transmission spectra and fluorescence spectra corresponding to the target sample to be tested, a series of mixed standard samples, and a blank standard sample measured by the hybrid K-boundary densitometer or the hybrid L-boundary densitometer.

[0149] Embodiment 5:

[0150] This embodiment provides a hybrid analysis system, including a memory and a processor, wherein the memory stores a computer program, and the processor is configured to run the computer program to implement the hybrid analysis method of the radiation transmission spectrum and the fluorescence spectrum as described in Example 1.

[0151] It is to be understood that the above embodiments are merely exemplary embodiments used to illustrate the principles of the present invention, but the present invention is not limited thereto. For those of ordinary skill in the art, various modifications and improvements can be made without departing from the spirit and essence of the present invention, and these modifications and improvements are also considered to be within the scope of protection of the present invention.

Claims

1. A hybrid analysis method of X-ray transmission spectrum and fluorescence spectrum, characterized in that: include: Obtaining transmission spectra and fluorescence spectra corresponding to the target sample to be tested, a series of mixed standard samples, and a blank standard sample, wherein the series of mixed standard samples refers to a number of samples prepared according to the concentration ratio of N and M components in the target sample to be tested, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be tested; Analyzing the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficient in the first linear fitting relationship, wherein the first linear fitting relationship includes the linear relationship between the concentration value of the N component and the absorbance difference; Analyze the transmission spectra of the target sample to be measured and the blank standard sample, and calculate the concentration value of the N component in the target sample to be measured based on the first linear fitting relationship; Analyze the fluorescence spectra of the series of mixed standard samples and the target samples to be tested to obtain the concentration value of the M component in the target samples to be tested. The transmission spectra of a series of mixed standard samples / target samples to be tested and blank standard samples are analyzed, specifically including: According to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard samples, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy is calculated; The absorbance difference is calculated based on the cumulative transmittance, The method of calculating the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample specifically includes: Determine the left and right window energy range of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard samples; Calculate the cumulative counts within the left and right window energy ranges of the series of mixed standard samples / target samples to be tested and the blank standard sample respectively; According to the cumulative count, the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy is calculated, The cumulative transmittance satisfies: Among them, T(E - ) is the cumulative transmittance corresponding to the left window boundary energy, T(E + ) is the cumulative transmittance corresponding to the right window boundary energy, is the cumulative counts within the left window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the right window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the accumulated counts in the left window energy range of the transmission spectrum of the blank standard sample, is the cumulative counts in the right window energy range of the transmission spectrum of the blank standard sample, n i is the count of the ith address, n 0i is the count of the ith channel of the transmission spectrum of the blank standard sample, ll is the left border of the left window, lr is the right border of the left window, rl is the left border of the right window, rr is the right border of the right window, The first linear fitting relationship satisfies: ρ(g / L)=a0+a1·ΔA (8) Among them, ρ (g / L) is the concentration value of N component, and a0 and a1 are fitting coefficients.

2. The hybrid analysis method according to claim 1, characterized in that: The calculating the absorbance difference according to the cumulative transmittance specifically includes: The absorbance of the left and right window boundary energies of the absorption mutation edge energy is calculated based on the cumulative transmittance: Solve the absorbance difference according to the following formula: Among them, A - is the absorbance at the left window boundary energy of the absorption mutation edge energy, A + is the absorbance at the right window boundary energy of the absorption mutation edge energy, and ΔA is the absorbance difference.

3. The hybrid analysis method according to claim 1, characterized in that: The step of analyzing the fluorescence spectra of the series of mixed standard samples and the target sample to be tested to obtain the concentration value of the M component in the target sample to be tested specifically includes: The fluorescence spectra of the series of mixed standard samples were analyzed to obtain the fluorescence peak area ratio of the N and M components of the series of mixed standard samples. or According to the fluorescence peak area ratio of N and M components of a series of mixed standard samples or Formula (9) or formula (10) to calculate the R' of the series of mixed standard samples N / M : According to the concentration value of N component in the series of mixed standard samples and R' of the series of mixed standard samples N / M , fitting coefficients in the second linear fitting relationship are obtained by fitting, wherein the second linear fitting relationship includes the linear relationship between the calibration factor and the concentration value of the N component, R′ N / M is the calibration factor; Analyze the fluorescence spectrum of the target sample to be tested and obtain the fluorescence peak area ratio of the N and M components of the target sample to be tested. or According to the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N and M components or The second linear fitting relationship and formula (9) or formula (10) are used to calculate the concentration value of the M component in the target sample to be tested. Among them, A represents the atomic weight, and α1, α2, and β represent the fluorescence peaks formed by the X-ray photons emitted when electrons jump from a specific level to the K layer or the L layer, respectively.

4. The hybrid analysis method according to claim 3, characterized in that: The fluorescence spectra of the series of mixed standard samples / target samples to be tested are analyzed, specifically including: Determine the total area of ​​the α1 and / or α2 fluorescence peak areas of the N component and the α1 and β fluorescence peak areas of the M component in the series of mixed standard samples / target samples to be tested; Calculate the fluorescence peak area ratio of the N and M components of a series of mixed standard samples / target samples to be tested or 5. The hybrid analysis method according to claim 3, characterized in that: The second linear fitting relationship satisfies: R′ N / M =b+k·ρ N (g / L) (11), Among them, ρ N (g / L) is the concentration value of N component, b and k are fitting coefficients.

6. The hybrid analysis method according to claim 5, characterized in that: According to the concentration value of the N component of the target sample to be tested, the fluorescence peak area ratio of the N and M components or The second linear fitting relationship and formula (9) or formula (10) are used to calculate the concentration value of the M component in the target sample to be tested, specifically including: Substitute the concentration value of the N component in the target sample to be tested into the second linear fitting relationship to obtain the R' of the target sample to be tested. N / M ; The R' of the target sample to be tested N / M , the concentration of N component, and the fluorescence peak area ratio of N and M components or Substitute into formula (9) or formula (10) to calculate the concentration value of component M in the target sample to be tested.

7. A hybrid analysis device for X-ray transmission spectrum and fluorescence spectrum, characterized in that: It includes an acquisition module, a first analysis module, and a second analysis module. The acquisition module is used to obtain the transmission spectrum and fluorescence spectrum corresponding to the target sample to be tested, the series of mixed standard samples, and the blank standard sample, wherein the series of mixed standard samples refer to several samples prepared according to the concentration ratio of the N and M components in the target sample to be tested, and the blank standard sample refers to a sample prepared according to the matrix of the target sample to be tested. The first analysis module is connected to the acquisition module and is used to analyze the transmission spectra of the series of mixed standard samples and the blank standard sample to obtain the fitting coefficient in the first linear fitting relationship, wherein the first linear fitting relationship includes the linear relationship between the concentration value of the N component and the absorbance difference, It is also used to analyze the transmission spectra of the target sample to be tested and the blank standard sample, and calculate the concentration value of the N component in the target sample to be tested based on the first linear fitting relationship, The second analysis module is used to analyze the fluorescence spectra of the series of mixed standard samples and the target sample to be tested, and obtain the concentration value of the M component in the target sample to be tested. The first analysis module is specifically used to calculate the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample, and is also used to calculate the absorbance difference according to the cumulative transmittance. The first analysis module is specifically used to determine the energy range of the left and right windows of the absorption mutation edge energy according to the transmission spectra of the series of mixed standard samples / target samples to be tested and the blank standard sample, and respectively calculate the cumulative counts within the energy range of the left and right windows of the series of mixed standard samples / target samples to be tested and the blank standard sample, and to calculate the cumulative transmittance corresponding to the left and right window boundary energies of the absorption mutation edge energy according to the cumulative counts. The cumulative transmittance satisfies: Among them, T(E - ) is the cumulative transmittance corresponding to the left window boundary energy, T(E + ) is the cumulative transmittance corresponding to the right window boundary energy, is the cumulative counts within the left window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the cumulative counts within the right window energy range of the transmission spectrum of the mixed standard sample / target sample to be measured, is the accumulated counts in the left window energy range of the transmission spectrum of the blank standard sample, is the cumulative counts in the right window energy range of the transmission spectrum of the blank standard sample, n i is the count of the ith address, n 0i is the count of the ith channel of the transmission spectrum of the blank standard sample, ll is the left border of the left window, lr is the right border of the left window, rl is the left border of the right window, rr is the right border of the right window, The first linear fitting relationship satisfies: ρ(g / L)=a0+a1·ΔA (8) Among them, ρ (g / L) is the concentration value of N component, and a0 and a1 are fitting coefficients.

8. A hybrid analysis system of X-ray transmission spectrum and fluorescence spectrum, characterized in that: A hybrid K-edge densitometer or a hybrid L-edge densitometer, and a hybrid analysis device for the radiation transmission spectrum and the fluorescence spectrum as claimed in claim 7, A hybrid analysis device for X-ray transmission spectrum and fluorescence spectrum is connected to a hybrid K-boundary densitometer or a hybrid L-boundary densitometer to obtain transmission spectra and fluorescence spectra corresponding to the target sample to be tested, a series of mixed standard samples, and a blank standard sample measured by the hybrid K-boundary densitometer or the hybrid L-boundary densitometer.

9. A hybrid analysis system, characterized in that: It comprises a memory and a processor, wherein the memory stores a computer program, and the processor is configured to run the computer program to implement the hybrid analysis method of the radiation transmission spectrum and the fluorescence spectrum as claimed in any one of claims 1 to 6.

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