CN109668920B - Detection method for liquid sample element analysis by upper liquid surface irradiation mode X fluorescence analysis technology - Google Patents
Detection method for liquid sample element analysis by upper liquid surface irradiation mode X fluorescence analysis technology Download PDFInfo
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- CN109668920B CN109668920B CN201910123487.5A CN201910123487A CN109668920B CN 109668920 B CN109668920 B CN 109668920B CN 201910123487 A CN201910123487 A CN 201910123487A CN 109668920 B CN109668920 B CN 109668920B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
Abstract
The invention relates to a detection method for analyzing elements of a liquid sample by an upper liquid surface irradiation mode X fluorescence analysis technology, which comprises the following steps: measuring the liquid surface irradiation mode on the sample; determining a reference element spectrum peak for liquid level height correction; establishing an algorithm of the liquid level height change coefficient; and (4) actually measuring the intensity of the liquid level height correction of the sample. The invention can eliminate the influence of the liquid level height change on the liquid sample element content result in the upper liquid level irradiation mode X fluorescence measurement, and the measured result has stronger repeatability and higher precision. And need not to install polyester film like during conventional liquid measurement, practice thrift the cost more.
Description
Technical Field
The invention relates to the field of sample analysis, and further relates to a detection method for liquid sample element analysis by an upper liquid surface irradiation mode X fluorescence analysis technology, in particular to a detection method for eliminating liquid surface height influence during liquid sample element analysis in the upper liquid surface irradiation mode X fluorescence analysis technology.
Background
Currently, in an X-ray fluorescence analyzer with an upper illumination mode (an excitation detector device is on the upper side, and a sample to be measured is on the lower side), the X-ray fluorescence analyzer is generally only used for measuring a solid powder sample tablet or a solid regular sample, and a liquid sample generally adopts a lower illumination type measurement mode (an excitation detector device is on the lower side, and a sample to be measured is on the upper side), so that the distance between a liquid surface and the excitation detector device is favorably controlled, and errors of the intensity of each element caused by the change of the air absorption coefficient due to the change of the distance between the sample and the excitation detector device are eliminated.
When the liquid is measured by the downward illumination type measuring mode, a 6-micron polyester film layer is arranged at the bottom of the sample cup, and the X-ray of light elements such as magnesium, aluminum, silicon and the like in the liquid sample cannot pass through the 6-micron polyester film due to low energy, so that the content of the heavy elements after phosphorus can be measured; however, in the lubricating oil sample test, light elements such as magnesium, aluminum, and silicon must be tested, and therefore, only the upper liquid level irradiation method is used for the measurement.
The liquid sample can be directly tested without installing a 6-micron polyester film in an upper liquid level irradiation mode, a quantitative adding mode of a liquid-transferring gun is generally adopted, but a large amount of viscous liquid in the liquid-transferring gun needs a long time to be completely discharged due to the fact that the viscosity of some liquid samples such as lubricating oil is large, and the liquid sample is only preliminarily and quickly injected into a sample cup due to the fact that the field test requires quick determination and the actual operation time is not allowed, so that the liquid level is not completely consistent, and a large measuring error is generated. Therefore, a calibration method capable of eliminating the influence of liquid level changes on the analysis result in the liquid sample test is urgently needed to detect the liquid sample more conveniently so as to improve the accuracy of the result and save the cost.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a detection method for analyzing elements in a liquid sample by an upper liquid surface irradiation type X fluorescence analysis technology.
The method can eliminate the influence of the height change of the liquid level on the element content result of the liquid sample when the upper liquid level irradiation mode X fluorescence measurement is carried out.
In order to realize the purpose of the invention, the adopted technical scheme is as follows:
a detection method for analyzing elements of a liquid sample by an upper liquid surface irradiation mode X fluorescence analysis technology comprises the following steps:
the method for measuring the upper liquid level of the sample in an irradiation mode comprises the following steps: the method comprises the following steps that an X-ray tube and a detector are arranged on the upper side, a liquid sample to be detected is arranged on the lower side, the liquid sample is injected into a sample cup, and the liquid surface on the sample cup is directly excited by irradiation and then is measured;
determining a reference element spectrum peak of liquid level height correction: determining a reference element spectrum peak for correcting the liquid level height, wherein the reference element spectrum peak for correcting the liquid level height is a Compton scattering peak of the target material Rh L alpha of the X-ray tube;
the algorithm establishment step of the liquid level height change coefficient comprises the following steps: the liquid level height variation coefficient algorithm adopts a quadratic curve fitting mode or a least square fitting mode between the relative intensity of the correction element and the relative intensity of the reference element;
and (3) calculating the correction intensity of the actually measured sample liquid level height: and calculating the corrected intensity of the liquid level height of the actually measured sample, namely calculating the corrected intensity of the original intensity of each element through the liquid level change coefficient and the intensity of the reference element.
In a preferred embodiment of the invention, the method comprises the steps of:
firstly, measuring X fluorescence spectrograms at different liquid level heights, then selecting a reference element spectral peak which can be used for correcting the liquid level height, namely a Compton scattering peak of an X-ray tube target material Rh L alpha, and then calculating the original intensity of each analysis element spectral peak; then calculating the relative strength of each element and the reference element to the reference liquid level under different liquid levels, performing quadratic curve fitting on the relative strength of each element and the relative strength of the reference element to obtain a coefficient between the strength of each element under different liquid level heights and the relative strength of the reference element, obtaining a variation coefficient, and storing for later use;
and performing spectrogram measurement on the actually measured sample to calculate the actually measured intensity of the spectral peak of each element, then calculating the corrected intensity of each element according to the change coefficient, and finally calculating the content value of each analysis element according to the corrected intensity of each element.
The invention has the beneficial effects that:
the invention can eliminate the influence of the liquid level height change on the liquid sample element content result in the upper liquid level irradiation mode X fluorescence measurement, and the measured result has stronger repeatability and higher precision. And need not to install polyester film like during conventional liquid measurement, practice thrift the cost more.
Drawings
FIG. 1 is a side view of a device for measuring an irradiation pattern of a liquid surface on a specimen according to the present invention.
FIG. 2 is a schematic diagram of the calculation process of the coefficient of variation of liquid level according to the present invention.
FIG. 3 is a schematic diagram of the process of calculating the content by using the coefficient of variation of the liquid level height according to the present invention.
FIG. 4 is a schematic diagram of an example of a liquid sample test X-ray spectrum used in the present invention.
FIG. 5 is a fitting curve and a coefficient chart for correcting the liquid level height of zinc element according to the present invention.
Detailed Description
The following provides embodiments of the present invention with reference to the accompanying drawings to explain technical solutions of the present invention in detail.
Referring to fig. 1-3, in the invention, the upper side is provided with an X-ray tube and a detector, and the lower side is provided with a liquid sample to be measured, the liquid sample is injected into the sample cup, the upper surface of the sample cup is not covered with any film, and the liquid surface of the sample cup is directly excited by irradiation, so that the contents of light elements such as Mg, Al, Si and the like and other heavy elements can be directly measured.
A measurement step:
the specific operation is as follows: and respectively sucking 5 lubricating oil samples with different volumes into the sample cups by using different scale marks of the pipette, wherein the volumes are respectively 6.2ml,6.4ml,6.6ml,6.8ml and 7.0ml, placing the lubricating oil sample cups with different volumes into an instrument for testing according to fixed test conditions, and an example of a test result is shown in figure 4.
Determining a change coefficient:
referring to the flow chart of fig. 2, the intensity of each element of each volume (height) sample is calculated. Wherein, table 1 shows the pre-calibration intensity calculation results of the respective elements of the lubricating oil samples of different volumes (heights).
TABLE 1
Next, the calculation process is described below by taking the element zinc (Zn) as an example (steps A to F):
A. firstly, the reference element spectrum peak of the liquid level height correction is selected as the compton scattering peak of the L alpha of the target material Rh of the X-ray tube, and Rh marked in the graph 4 is the compton scattering peak of the L alpha of Rh.
B. The strength values of Zn, Rh and Nb are calculated, and the results are shown in Table 2:
TABLE 2
C. Calculating the original intensity value of Zn:
since the strength of Zn is divided by the internal standard element Nb, the ratio (percentage) of the strength needs to be converted into the original strength value, and the method is as follows:
the initial Zn strength ═ strength of internal standard element Nb/100, the results obtained are shown in table 3:
TABLE 3
D. The relative intensities of Zn and Rh between the respective volumes (heights) and the reference volume (7.0ml) were calculated
The calculation method comprises the following steps: the relative strength R is a volume element strength/7.0 ml element strength, and the results are shown in table 4:
TABLE 4
E. A least squares curve fit is made to the relative Rh to Zn intensities, as shown in figure 5,
wherein the resulting equation is y-41.569X2+90.263 x-47.703, and wherein R is2The method has small error and high precision as 0.9961.
F. The coefficient of variation of the liquid level height of Zn element is shown in Table 5
TABLE 5
| Element(s) | A | B | C |
| Zn | -41.569 | 90.263 | -47.703 |
FIG. 5 is a fitting curve and a coefficient chart for correcting the liquid level height of zinc element according to the present invention.
The content determination step comprises:
the calculation procedure, using elemental zinc (Zn) as an example, is illustrated in Table 6(A-E) below:
TABLE 6
Original strength of Zn, Rh, Nb elements
B. The relative intensity R of Rh was calculated
The calculation method comprises the following steps: the relative Rh intensity, R, was obtained as Rh intensity in a certain volume/Rh intensity of 7.0ml, and the results are shown in table 7:
TABLE 7
C. Calculating the change coefficient of Zn according to the relative strength change of Rh at different liquid level heights
Calculating the formula:
coefficient of variation ═ a × RRh*RRh+B*RRh+ C, results are obtained in Table 8:
TABLE 8
D. Calculating the corrected intensity value of the liquid level
Calculating the formula:
corrected intensity is the original intensity/coefficient of variation, and the results are shown in table 9:
TABLE 9
E. Content calculation
The corrected element intensity is substituted into the working curve, and the final content result after liquid level height correction can be calculated.
Based on the above principle, the test results of other elements except the exemplified Zn element are as follows:
table 10 is a pre-calibration intensity calculation for each element of the lubricating oil samples of different volumes (heights).
Watch 10
Table 11 shows the liquid level change coefficients of the respective elements.
TABLE 11
Wherein the equation obtained is y ═ A × X2+B*x+C
Table 12 is the corrected strength calculations for each element for different volumes (heights) of lubricating oil samples.
TABLE 12
Table 13 shows the results of the content test before the liquid level height correction.
Watch 13
Table 14 shows the contents test results after correction of the liquid level height.
TABLE 14
From the analysis results of the graph, the accuracy of the analysis result of each element is greatly improved (particularly, the extreme difference between the strength test result and the content test result is smaller) by the liquid level height correction method, and the requirement of the industry standard is completely met. The method can help realize the aims of quick analysis, quick correction and accurate analysis.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are merely illustrative of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined by the appended claims and their equivalents.
Claims (1)
1. A detection method for analyzing elements of a liquid sample by an upper liquid surface irradiation mode X fluorescence analysis technology is characterized in that,
firstly, measuring X fluorescence spectrograms at different liquid level heights, then selecting a reference element spectral peak which can be used for correcting the liquid level height, namely a Compton scattering peak of an X-ray tube target material Rh L alpha, and then calculating the original intensity of each analysis element spectral peak; then calculating the relative intensity of each element and the reference element to the reference liquid level under different liquid level heights, performing quadratic curve fitting on the relative intensity of each element and the relative intensity of the reference element to obtain a liquid level height correction coefficient of each element, and calculating a change coefficient according to the relative intensity of the reference element and the liquid level height correction coefficient, wherein the change coefficient is A RRh*RRh+B*RRh+ C, where A, B, C is the liquid level correction factor, RRhThe relative intensity of the original intensity of the corresponding X-ray tube target Rh L alpha Compton scattering peak at one liquid level relative to the original intensity of the reference liquid level.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201373857Y (en) * | 2009-03-04 | 2009-12-30 | 上海精谱仪器有限公司 | X fluorescence analyser |
| CN201373856Y (en) * | 2009-03-04 | 2009-12-30 | 上海精谱仪器有限公司 | X fluorescence oil sulfur measuring instrument |
| CN103776859A (en) * | 2013-10-14 | 2014-05-07 | 无锡艾科瑞思产品设计与研究有限公司 | Fast detection method for content of heavy metal in liquid food |
| CN105937890A (en) * | 2015-03-03 | 2016-09-14 | 帕纳科公司 | Quantitative x-ray analysis-matrix thickness correction |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN201373857Y (en) * | 2009-03-04 | 2009-12-30 | 上海精谱仪器有限公司 | X fluorescence analyser |
| CN201373856Y (en) * | 2009-03-04 | 2009-12-30 | 上海精谱仪器有限公司 | X fluorescence oil sulfur measuring instrument |
| CN103776859A (en) * | 2013-10-14 | 2014-05-07 | 无锡艾科瑞思产品设计与研究有限公司 | Fast detection method for content of heavy metal in liquid food |
| CN105937890A (en) * | 2015-03-03 | 2016-09-14 | 帕纳科公司 | Quantitative x-ray analysis-matrix thickness correction |
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