CN110530912B - X-ray fluorescence spectrum analysis method for precious metal component containing coating - Google Patents
X-ray fluorescence spectrum analysis method for precious metal component containing coating Download PDFInfo
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Abstract
The invention relates to an X-ray fluorescence spectrum analysis method of precious metal components containing a coating, wherein an analyzed object to be detected consists of a substrate and the coating coated outside the substrate, and the main component of the substrate is precious metal; the method comprises the following steps: s1, actually measuring the fluorescence measurement intensity I of the matrix composition elements of the object to be measured by utilizing X-ray fluorescence spectrum3Setting the initial content W of the constituent elements of the matrix according to the measured element informationn(ii) a S2, initial content W according to matrix component elementsnCalculating the theoretical intensity I of fluorescence of the constituent elements of the substrate based on the test conditions of the coated layer4The test condition of the plating layer is to introduce the density, thickness and quality of the plating layer to correct the absorption influence of the constituent elements of the plating layer on the constituent elements of the substrate; s3 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And calculating the actual content of the matrix composition elements by adopting a basic parameter method.
Description
Technical Field
The invention relates to the field of precious metal detection and analysis, in particular to an X-ray fluorescence spectrum analysis method for precious metal components containing a coating.
Background
The noble metal mainly refers to gold, silver and platinum group metals, the noble metal ornaments refer to ornaments and decorative parts made of noble metal materials, and in order to beautify the appearance effect of noble metal ornaments (gold, platinum), rhodium or ruthenium and other metal thin coatings are usually plated on the outer surfaces of the noble metal ornaments. The traditional gold, silver and platinum ornament analysis and detection methods (such as a fire test gold method, a titration method and the like) need to destroy a sample or polish and remove an outer metal plating layer of the sample, so that the components of the noble metal ornament are determined, and the method belongs to destructive analysis. However, precious metal jewelry is a valuable, inheritable consumer product for displaying beauty to most consumers. The noble metal ornaments are not easy to destroy, and if the precious metal ornaments are analyzed after the plating layer is polished, the significance of commodity circulation of the noble metal ornaments is lost.
In the prior art, the X-ray fluorescence spectrometry is used for measuring the components and the content of the noble metal ornaments, has the advantages of accuracy, rapidness, no damage to samples and the like, is established as a national standard detection method, and is an effective screening detection method for the current noble metal ornaments. The principle of the X-ray fluorescence spectrometry is that incident X-rays (primary X-rays) are generated by an X-ray tube to excite a sample to be detected, electrons in an internal electron layer of the excited sample can generate transition, generated vacancies are filled by electrons in an external layer, energy differences exist among different electron layers, the energy differences are emitted in the form of X-ray fluorescence radiation (secondary X-rays), the electron energy level structure of each element atom is characterized, and the X-ray fluorescence generated after the X-ray fluorescence is excited is also characterized; the existence of the corresponding element can be determined by measuring the energy or wavelength of the characteristic X-ray excited by each element, and the content of the element can be quantitatively determined according to the intensity of the X-ray.
However, the conventional X-ray fluorescence spectroscopy still has limitations, for example, when a noble metal sample with a coating is analyzed by X-ray fluorescence spectroscopy, the coating absorbs fluorescence of matrix constituent elements to different degrees, thereby causing interference to the fluorescence intensity of the matrix constituent elements to different degrees, namely, a matrix effect (which means that when X-fluorescence rays generated inside the sample reach the surface of the sample, surrounding coexisting elements absorb the X-fluorescence rays, and the X-fluorescence rays excite the coexisting elements secondarily, so that even if the content of the matrix elements is the same, the detected X-ray fluorescence intensities are different due to the difference of the coexisting elements), and finally causing deviation of the detection result of the noble metal matrix components.
Disclosure of Invention
Based on the above, the present invention aims to overcome the defects of the prior art, and provide an X-ray fluorescence spectrum analysis method for precious metal components containing a plating layer, which does not need to destroy the outer plating layer, and can correct the absorption interference of the outer plating layer metal to the fluorescence intensity of the substrate, so as to perform accurate quantitative analysis on the precious metal in the plating layer, and has high practicability.
The invention is realized based on the following inventive concept: an X-ray fluorescence spectrum analysis method for precious metal components containing a coating is characterized in that an object to be analyzed consists of a substrate and the coating coated outside the substrate, wherein the main component of the substrate is precious metal; the method comprises the following steps:
s1, actually measuring the fluorescence measurement intensity I of the matrix composition elements of the object to be measured by utilizing X-ray fluorescence spectrum3Setting the initial content W of the constituent elements of the matrix according to the measured element informationn；
S2, initial content W according to matrix component elementsnCalculating the theoretical intensity I of fluorescence of the constituent elements of the substrate based on the test conditions of the coated layer4The test condition of the plating layer is to introduce the density, thickness and quality of the plating layer to correct the absorption influence of the constituent elements of the plating layer on the constituent elements of the substrate;
s3 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And calculating the actual content of the matrix composition elements by adopting a basic parameter method.
Compared with the prior art, the X-ray fluorescence spectrum analysis method for precious metal components containing the coating, disclosed by the invention, has the advantages that when the content of a base body with the coating is analyzed, the absorption interference of the coating on the base body is fully considered, and the absorption influence of the coating on the base body is corrected by introducing correction factors such as coating density, coating thickness and coating quality; the analysis method provided by the invention can be used for analyzing without damaging the coating, and correcting the absorption interference of the coating on the fluorescence intensity of the matrix, so that the actual content of the noble metal matrix composition elements can be accurately analyzed, and the practicability is high.
In step S2, a group of substrates is calculated based on the plating test conditionsTheoretical intensity of fluorescence of element I4The formula of (1) is as follows:
in the formula (1), I4The theoretical intensity of fluorescence of the constituent elements of the matrix; rho is the density of the plating layer; t is the thickness of the plating layer; rho T is the quality of the plating layer; λ is the wavelength of the incident X-rays; i is0(λ) is the intensity of the incident X-rays; q (lambda) is the incidence of the fluorescent X-ray of the unit mass of the coating; ^ d λ is the integral of the shortest wavelength of the incident X-ray to the wavelength of the absorption edge of the fluorescent X-ray;
in the formula (2), μ (λ) is a mass absorption coefficient of the whole incident X-ray specimen; μ (ip) is the mass absorption coefficient of the entire specimen for fluorescent X-ray; phi is the incident angle of the incident X-ray; ψ is an extraction angle of fluorescent X-rays. The invention particularly provides a plating layer test condition, which comprises correction calculation items of plating layer density, plating layer thickness and plating layer weight, and different values can be input according to different plating layer parameters when analyzing precious metal components in a plating layer, so that the invention has better applicability and practicability.
Further, step S3 includes the steps of:
s31 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And a sensitivity coefficient f, calculating the fluorescence presumption intensity T of the matrix composition elements;
s32, initial content W according to matrix component elementsnThe estimated fluorescence intensity T of the base constituent element and the measured fluorescence intensity I of the base constituent element3Calculating New estimated content W 'of matrix constituent element'n+1Based on the new estimated content W 'of the matrix constituent element'n+1Is calculated by 100% normalizationn+1If the new quantitative value W of the constituent element of the substraten+1With the original initial content WnIs less than the set value, the new quantitative value W is determinedn+1Outputting as the actual content of the matrix constituent elements; otherwise, the new quantitative value W is usedn+1Replacing the original initial content WnAnd returns to step S2.
Further, in step S31, the sensitivity coefficient f is obtained by:
actually measuring fluorescence measurement intensity I of constituent elements of a series of standard samples by using X-ray fluorescence spectrum1The standard sample is a noble metal without a coating and with a known chemical composition;
calculating the fluorescence theoretical intensity I of the standard sample composition elements according to the standard sample composition elements and the content thereof2；
Determining the sensitivity coefficient f which is the fluorescence measurement intensity I of the component elements of the standard sample1And the theoretical intensity of fluorescence I2The ratio of (a) to (b).
Further, in step S31, the estimated fluorescence intensity T of the base constituent element is the theoretical fluorescence intensity I of the base constituent element4The product of the sensitivity coefficient f. In the X-ray fluorescence analysis method for the precious metal components in the coating, the sensitivity coefficient and the sensitivity coefficient curve are obtained by testing the fluorescence measurement intensity and the fluorescence theoretical intensity of a plurality of series of standard samples, and the sensitivity coefficient curve can be directly used in the subsequent calculation process because: because of the absorption influence of the coating, the fluorescence measurement intensity of the object to be measured directly by using an X-ray fluorescence spectrometer is reduced due to attenuation, if the fluorescence theoretical intensity of the object to be measured is obtained under the condition of no coating, the sensitivity coefficient is not equal to the ratio of the fluorescence measurement intensity to the fluorescence theoretical intensity because the fluorescence theoretical intensity of the object to be measured is not changed, and the calculation result has deviation. In order to correct the deviation of the calculation result, the invention provides a plating layer test condition, the fluorescence theoretical intensity of the object to be measured obtained based on the plating layer test condition is smaller than that obtained under the non-plating layer test condition, and the sensitivity coefficient is equal to the ratio of the fluorescence measurement intensity to the fluorescence theoretical intensity. Thus passing the standardThe sensitivity coefficient obtained by the sample can be applied to a non-standard sample for calculation.
Further, in step S32, the new estimated content W 'of the matrix constituent element'n+1Calculated as follows:
wherein n is a natural number; w'n+1Is a new estimated content of the base constituent element, WnIs the original initial content of the constituent elements of the matrix; i is3Measuring the fluorescence intensity of the composition elements of the substrate to be measured; t is the fluorescence intensity of the constituent elements of the matrix.
Further, in step S32, the set value is 0.005%.
Further, the constituent elements of the coating are single metal elements or alloy elements.
Further, the constituent element of the plating layer is rhodium or ruthenium.
Drawings
FIG. 1 is an analysis flowchart of the X-ray fluorescence spectrum analysis method of the precious metal component containing plating according to the present invention.
Detailed Description
The applicant found in the study of the analysis of precious metal components containing a coating based on an X-ray fluorescence spectrometer that: the coating has absorption effects of different degrees on the fluorescence intensity of the matrix composition elements, so that interference of different degrees on the fluorescence intensity of the matrix composition elements, namely a matrix effect, is generated; specifically, when the applicant utilizes X-ray fluorescence spectrometry to analyze and research a standard gold sample without a coating, the testing intensity of each element is in a functional relationship with the content of the element and is in a direct proportion relationship. However, when a gold sample containing a coating is analyzed by using an X-ray fluorescence spectrum, the coating has different degrees of absorption on the fluorescence of the constituent elements of the substrate, so that the fluorescence intensity measured by an X-ray fluorescence spectrometer is relatively low, and when the energy of a certain constituent element of the substrate is high, the fluorescence penetrability is strong, the absorption in the metal coating is relatively low, and the measured fluorescence intensity is relatively attenuated little; in contrast, when the energy of a certain constituent element of the substrate is low, the fluorescence transmittance is weak, the absorption in the coating layer is relatively large, and the measured fluorescence intensity attenuation is large. Finally, the content analysis and detection results of the constituent elements of the plating-containing precious metal matrix have obvious deviation.
Therefore, the applicant provides an X-ray fluorescence spectrum analysis method for precious metal components containing a coating, and particularly provides a coated test condition which can correct the absorption influence of the coating on the composition of a substrate, so that the interference of the coating on the fluorescence intensity of the substrate is avoided, and a more accurate analysis result is finally obtained.
The method for analyzing X-ray fluorescence spectrum containing precious metal components of the plating layer of the present invention is further described below by way of specific examples. Specifically, please refer to fig. 1, which includes the following steps:
s1, actually measuring the fluorescence measurement intensity I of the matrix composition elements of the object to be measured by utilizing X-ray fluorescence spectrum3Setting the initial content W of the constituent elements of the matrix according to the measured element informationn. It should be noted that the element information measured in step S1 is a matrix constituent element of the analyte, and the matrix constituent element contained in the analyte can be preliminarily analyzed through the characteristic spectral line of the analyte measured by the X-ray fluorescence spectrometer.
S2, initial content W according to matrix component elementsnCalculating the theoretical intensity I of fluorescence of the constituent elements of the substrate based on the test conditions of the coated layer4The test condition of the plating layer is to introduce the density, thickness and quality of the plating layer to correct the absorption influence of the constituent elements of the plating layer on the constituent elements of the substrate;
calculating the fluorescence theoretical intensity I of the matrix constituent elements based on the plating test conditions4The formula of (1) is as follows:
in the formula (1), I4The theoretical intensity of fluorescence of the constituent elements of the matrix; rho is the plating density (g/cm)3) (ii) a T is the plating thickness (cm); rho T is the coating mass (g/cm)2) (ii) a λ is the wavelength of the incident X-rays; i is0(λ) is the intensity of the incident X-rays; q (lambda) is the incidence (cm) of fluorescent X-rays per unit mass of the coating2(iv)/g); ^ d λ is the integral of the shortest wavelength of the incident X-ray to the wavelength of the absorption edge of the fluorescent X-ray;
in the formula (2), μ (λ) is the mass absorption coefficient (cm) of the whole incident X-ray specimen2(iv)/g); μ (ip) is the mass absorption coefficient (cm) of the entire specimen for fluorescent X-ray2(iv)/g); phi is the incident angle of the incident X-ray; ψ is an extraction angle of fluorescent X-rays.
S3 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And calculating the actual content of the matrix composition elements by adopting a basic parameter method. The basic parameter method (FP method) is a mathematical correction method which applies a fluorescent X-ray theoretical intensity formula and basic physical constants such as spectral distribution, mass attenuation coefficient, fluorescence yield, absorption gradient ratio, geometric factor and the like of primary X-rays and converts the measured intensity of the analysis influence spectral line into the operation content in a sample through mathematical operation. Specifically, the method comprises the following steps:
s31 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And a sensitivity coefficient f, calculating the fluorescence presumption intensity T of the matrix composition elements; wherein the sensitivity coefficient f is obtained by:
(i) actually measuring fluorescence measurement intensity I of constituent elements of a series of standard samples by using X-ray fluorescence spectrum1The standard sample is a noble metal without a coating and with a known chemical composition;
(ii) calculating the fluorescence theoretical intensity I of the standard sample composition elements according to the standard sample composition elements and the content thereof2(ii) a Because the standard sample has no plating layer, the calculation can be directly carried out by the existing method without introducing a plating layer correction factor (namely, the calculation is based on the plating layer-free test condition), and the reference formula is as follows:
in the formula (3), I1Is the theoretical intensity of fluorescence of the constituent elements of the standard sample; λ is the wavelength of the incident X-rays
I0(λ) is the intensity of the incident X-rays; q (. lamda.) is the efficiency (cm) of fluorescent X-ray generation per unit mass of the sample2(iv)/g); μ (λ) is the mass absorption coefficient (cm) of the whole incident X-ray sample2(iv)/g); μ (ip) is the mass absorption coefficient (cm) of the entire standard sample of fluorescent X-ray2(iv)/g); Φ is the angle of incidence (rad) of the X-rays; Ψ is the extraction angle (rad) of the fluorescent X-ray; d λ represents the integral from the shortest wavelength λ min of the incident X-ray to the absorption edge wavelength of the fluorescent X-ray ip.
(iii) Determining the sensitivity coefficient f which is the fluorescence measurement intensity I of the component elements of the standard sample1And the theoretical intensity of fluorescence I2The ratio of (a) to (b).
S32, initial content W according to matrix component elementsnThe estimated fluorescence intensity T of the base constituent element and the measured fluorescence intensity I of the base constituent element3Calculating New estimated content W 'of matrix constituent element'n+1Based on the new estimated content W 'of the matrix constituent element'n+1Is calculated by 100% normalizationn+1If the new quantitative value W of the constituent element of the substraten+1With the original initial content WnIs less than the set value, the new quantitative value W is determinedn+1Outputting as the actual content of the matrix constituent elements; otherwise, the new quantitative value W is usedn+1Replacing the original initial content WnAnd returns to step S2.
In step S32, the new estimated content W 'of the matrix constituent element'n+1Calculated as follows:
wherein n is a natural number; w'n+1Is a new estimated content of the base constituent element, WnIs the original initial content of the constituent elements of the matrix; i is3Measuring the fluorescence intensity of the composition elements of the substrate to be measured; t is the fluorescence intensity of the constituent elements of the matrix.
Wherein the 100% normalization process yields Wn+1The calculation method of (2) is as follows: respectively calculating to obtain the presumed contents of the matrix composition elements of W'Au n+1、W’Ag n+1、W’Cu n+1、W’Zn n+1W therein'Au n+1A quantitative value W of copper element recalculated by 100% normalization processing representing a new estimated content of copper elementAu n+1The calculation formula is as follows: wAu n+1＝W’Au n+1/(W’Au n+1+W’Ag n+1+W’Cu n+1+W’Zn n+1) 100%. Similarly, W can be calculated by 100% normalizationAg n+1、WCu n+1、WZn n+1。
The following further illustrates, by experimental data, that the X-ray fluorescence spectrum analysis method for precious metal components containing a plating layer of the present invention can correct the absorption influence of the plating layer on the substrate, and accurately analyze the content of the constituent elements of the substrate.
A. Instrument and sample preparation:
1) the instrument name: shimadzu EDX series X-ray fluorescence spectrometer
2) Analysis conditions were as follows: target material: rh; voltage: 50 kv; filter 5 #; current: auto; 3mm of collimator; the analysis time is 100 s;
3) standard samples: the standard sample is a rose gold standard sample without a coating, and the sample number is as follows: SZB 205.
4) The substance to be tested: the plating layer of the object to be detected is Rh, and the known matrix composition elements are Au, Ag, Cu and Zn. The sample number is: J9F27K17+ SZB205 (wherein J9F27K17 is a standard sample of a Calmetrics plating in the united states, and J9F27K17+ SZB205 constitutes the analyte of the embodiment).
B. Obtaining a sensitivity coefficient f:
1) fluorometric intensity I of Standard sample SZB205 measured by X-ray fluorescence Spectroscopy1Respectively obtaining the fluorescence measurement intensity of each matrix component element (Au, Ag, Cu and Zn), wherein the fluorescence measurement intensity is the area of a spectrum peak in a fluorescence spectrum obtained by an X-ray fluorescence spectrometer, the area is directly calculated by an instrument, and finally the fluorescence measurement intensity I of the matrix component element is obtainedAu、IAg、ICuAnd IZn。
2) The theoretical intensity I of fluorescence of the SZB205 standard sample was calculated using the plating-free test conditions in the examples, i.e., equations (1) and (2)2The theoretical intensity of fluorescence, i.e., I ', of the matrix constituent elements was calculated'Au、I’Ag、I’CuAnd l'Zn。
3) Fluorescence measurement of intensity I Using Standard sample SZB2051Divided by the theoretical intensity of fluorescence I2Separately obtaining the sensitivity coefficient f of each matrix component element, i.e. fAu、fAg、fCuAnd fZn。
C. Analyzing the substance to be detected:
1) fluorometric intensity I of test object J9F27K17+ SZB205 measured by X-ray fluorescence spectrometer3(IAu、IAg、ICuAnd IZn) Setting the initial content W of the constituent elements of the matrix according to the measured element informationn(WAu n、WAg n、WCu n、WZn n)；
2) According to the initial content W of the constituent elements of the matrixnThe theoretical intensity I of fluorescence of the constituent elements of the substrate was calculated based on the plating test conditions, i.e., equations (1) and (2) in the examples4(I’Au、I’Ag、I’CuAnd l'Zn)；
3) According to the theoretical intensity I of fluorescence of the constituent elements of the matrix4And sensitivityCoefficient f, calculating the estimated fluorescence intensity T (T) of the base constituent elementsAu、TAg、TCuAnd TZn) I.e. T ═ I4*f；
4) The new estimated content W 'of the constituent elements of the matrix was calculated by the formula (4) in the examples'n+1(W’Au n+1、W’Ag n+1、W’Cu n+1、W’Zn n+1) Calculating new quantitative value W of each element by 100% normalization methodn+1If the new quantitative value W of the constituent element of the substraten+1With the original initial content WnIs less than 0.005%, the new quantitative value W is determinedn+1Outputting as the actual content of the matrix constituent elements; otherwise, the quantitative value W is usedn+1(WAu n+1、WAg n+1、WCu n+1、WZn n+1) Replacing the original initial content Wn(WAu n、WAg n、WCu n、WZn n). And finally obtaining the actual content of the matrix composition elements of the object to be detected through multiple iterative calculations.
In addition, in order to prove the effectiveness of the plating test condition of the present invention, the fluorescence theoretical intensity of the object to be tested J9F27K17+ SZB205 was calculated as a control group under the non-plating test condition, and the actual content of the object to be tested J9F27K17+ SZB205 was finally obtained under the condition that other experimental conditions were not changed.
D. Discussion and analysis of results:
1) the actual contents of the constituent elements of the matrix of the SZB205, which were obtained as a standard sample on the basis of the test conditions without plating, are shown in Table 1: (in fact, the content of each matrix component element of the SZB205 as a standard sample is known, and the actual content measured by an X-ray fluorescence spectrometer can be compared with the actual content of the matrix component element of the object to be measured to reduce the deviation caused by the error of the instrument, so that the comparison is more objective.)
TABLE 1
| Constituent elements of matrix | Au | Ag | Cu | Zn |
| Actual content | 41.775％ | 2.332％ | 53.785％ | 2.094％ |
(2) The actual contents of the matrix constituent elements of the test object J9F27K17+ SZB205 obtained under the non-plating test condition are shown in Table 2:
TABLE 2
| Constituent elements of matrix | Au | Ag | Cu | Zn |
| Actual content | 42.540％ | 2.489％ | 52.896％ | 2.067％ |
3) The actual contents of the matrix constituent elements of the test object J9F27K17+ SZB205 obtained under the plating test conditions are shown in Table 3:
TABLE 3
| Constituent elements of matrix | Au | Ag | Cu | Zn |
| Actual content | 41.800％ | 2.345％ | 53.758％ | 2.086％ |
From the data of the above tables 1, 2 and 3, it can be seen that the actual contents of the matrix constituent elements of the specimen J9F27K17+ SZB205 obtained under the non-plating test condition largely deviate from the actual content of the SZB205, for example, 1.83% by comparing the contents of Au in tables 1 and 2, and that the actual contents of the matrix constituent elements of the specimen J9F27K17+ SZB205 obtained under the non-plating test condition largely deviate. On the other hand, the actual content of the matrix constituent elements of the specimen J9F27K17+ SZB205 obtained under the plating test condition was very close to the actual content of the SZB205, and the error was only 0.059% by comparing the Au contents in tables 1 and 3. Thus, it can be concluded that: the test condition of the plating layer can correct the influence of the plating layer on the fluorescence intensity of the matrix, thereby obtaining the accurate actual content of the constituent elements of the matrix.
Compared with the prior art, the invention provides the X-ray fluorescence spectrum analysis method for the precious metal component containing the coating, when the actual content of the constituent elements of the substrate provided with the coating is analyzed, the absorption interference of the coating on the substrate is fully considered, and the absorption influence of the coating on the substrate is corrected by introducing the correction factors such as coating density, coating thickness and coating quality; the analysis method provided by the invention can be used for analyzing without damaging the metal of the coating, and correcting the absorption interference of the coating on the fluorescence intensity of the matrix, so that the actual content of the constituent elements of the precious metal matrix is accurately analyzed, and the practicability is high.
The present invention is not limited to the above-described embodiments, and various modifications and variations of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (7)
1. An X-ray fluorescence spectrum analysis method for precious metal components containing a coating is characterized in that an object to be analyzed consists of a substrate and the coating coated outside the substrate, wherein the main component of the substrate is precious metal; the method is characterized in that: the method comprises the following steps:
s1, actually measuring the fluorescence measurement intensity I of the matrix composition elements of the object to be measured by utilizing X-ray fluorescence spectrum3Setting the initial content W of the constituent elements of the matrix according to the measured element informationn；
S2, initial content W according to matrix component elementsnCalculating the fluorescence of the constituent elements of the substrate based on the test conditions of the coated layerTheoretical intensity I4The test condition of the plating layer is to introduce the density, thickness and quality of the plating layer to correct the absorption influence of the constituent elements of the plating layer on the constituent elements of the substrate;
s3 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And a sensitivity coefficient f, calculating the actual content of the matrix constituent elements by adopting a basic parameter method;
in step S2, the theoretical intensity I of fluorescence of the constituent elements of the substrate is calculated based on the plating test conditions4The formula of (1) is as follows:
in the formula (1), I4The theoretical intensity of fluorescence of the constituent elements of the matrix; rho is the density of the plating layer; t is the thickness of the plating layer; rho T is the quality of the plating layer; λ is the wavelength of the incident X-rays; i is0(λ) is the intensity of the incident X-rays; q (lambda) is the incidence of the fluorescent X-ray of the unit mass of the coating; ^ d λ is the integral of the shortest wavelength of the incident X-ray to the wavelength of the absorption edge of the fluorescent X-ray;
in the formula (2), μ (λ) is a mass absorption coefficient of the whole incident X-ray specimen; μ (ip) is the mass absorption coefficient of the entire specimen for fluorescent X-ray; phi is the incident angle of the incident X-ray; psi is the extraction angle of the fluorescent X-ray;
in step S3, the sensitivity coefficient f is obtained by:
actually measuring fluorescence measurement intensity I of constituent elements of a series of standard samples by using X-ray fluorescence spectrum1The standard sample is a noble metal without a coating and with a known chemical composition;
calculating the fluorescence theoretical intensity I of the standard sample composition elements according to the standard sample composition elements and the content thereof2；
Determining the sensitivity coefficientf, the sensitivity coefficient f is the fluorescence measurement intensity I of the constituent elements of the standard sample1And the theoretical intensity of fluorescence I2The ratio of (a) to (b).
2. The X-ray fluorescence spectroscopic analysis method according to claim 1, characterized in that: step S3 includes the following steps:
s31 obtaining the theoretical intensity of fluorescence I of the base constituent elements4And a sensitivity coefficient f, calculating the fluorescence presumption intensity T of the matrix composition elements;
s32, initial content W according to matrix component elementsnThe estimated fluorescence intensity T of the base constituent element and the measured fluorescence intensity I of the base constituent element3Calculating New estimated content W 'of matrix constituent element'n+1Based on the new estimated content W 'of the matrix constituent element'n+1Is calculated by 100% normalizationn+1If the new quantitative value W of the constituent element of the substraten+1With the original initial content WnIs less than the set value, the new quantitative value W is determinedn+1Outputting as the actual content of the matrix constituent elements; otherwise, the new quantitative value W is usedn+1Replacing the original initial content WnAnd returns to step S2.
3. The X-ray fluorescence spectroscopic analysis method according to claim 2, characterized in that: in step S31, the estimated fluorescence intensity T of the base constituent element is the theoretical fluorescence intensity I of the base constituent element4The product of the sensitivity coefficient f.
4. The X-ray fluorescence spectroscopic analysis method according to claim 2, characterized in that: in step S32, the new estimated content W 'of the matrix constituent element'n+1Calculated as follows:
wherein n is a natural number; w'n+1Is a new estimated content of the base constituent element, WnIs the original initial content of the constituent elements of the matrix; i is3Measuring the fluorescence intensity of the composition elements of the substrate to be measured; t is the fluorescence intensity of the constituent elements of the matrix.
5. The X-ray fluorescence spectroscopic analysis method according to claim 2, characterized in that: in step S32, the set value is 0.005%.
6. The X-ray fluorescence spectroscopic analysis method according to claim 1, characterized in that: the constituent elements of the coating are one or more than one metal element.
7. The X-ray fluorescence spectroscopic analysis method according to claim 6, characterized in that: the component element of the plating layer is rhodium or ruthenium.
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| CN112630088A (en) * | 2020-12-28 | 2021-04-09 | 国家珠宝检测中心(广东)有限责任公司 | Low-purity gold quantitative detection method |
| CN114113184B (en) * | 2021-11-29 | 2023-11-03 | 南京航空航天大学 | Scattering correction method for X fluorescence thin layer analysis of tailing pulp |
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