CN112461877A - Method for quantitatively detecting cerium element by using x-ray fluorescence spectrometry - Google Patents
Method for quantitatively detecting cerium element by using x-ray fluorescence spectrometry Download PDFInfo
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- 238000004846 x-ray emission Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000004458 analytical method Methods 0.000 claims abstract description 25
- 230000003595 spectral effect Effects 0.000 claims abstract description 21
- 238000001228 spectrum Methods 0.000 claims abstract description 21
- 238000001514 detection method Methods 0.000 claims abstract description 16
- 238000004876 x-ray fluorescence Methods 0.000 claims abstract description 15
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 13
- 230000007547 defect Effects 0.000 claims abstract description 9
- 230000008030 elimination Effects 0.000 claims abstract description 4
- 238000003379 elimination reaction Methods 0.000 claims abstract description 4
- 238000012545 processing Methods 0.000 claims abstract description 4
- 230000000694 effects Effects 0.000 claims description 21
- 239000011159 matrix material Substances 0.000 claims description 18
- 239000012535 impurity Substances 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000005464 sample preparation method Methods 0.000 claims description 6
- 239000013558 reference substance Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 230000000052 comparative effect Effects 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000012216 screening Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 230000002159 abnormal effect Effects 0.000 claims description 3
- 238000004164 analytical calibration Methods 0.000 claims description 3
- 238000012863 analytical testing Methods 0.000 claims description 3
- 238000010835 comparative analysis Methods 0.000 claims description 3
- 238000012937 correction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000002784 hot electron Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 238000012067 mathematical method Methods 0.000 claims description 3
- 238000013178 mathematical model Methods 0.000 claims description 3
- 230000000704 physical effect Effects 0.000 claims description 3
- 238000012795 verification Methods 0.000 claims description 3
- 239000006185 dispersion Substances 0.000 abstract description 5
- 238000011156 evaluation Methods 0.000 abstract description 2
- 238000000275 quality assurance Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- JMBNQWNFNACVCB-UHFFFAOYSA-N arsenic tribromide Chemical compound Br[As](Br)Br JMBNQWNFNACVCB-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- -1 ferrous metals Chemical class 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
-
- 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
- G01N23/2202—Preparing specimens therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
- G01N2223/0763—Compton background correcting
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
A method for quantitatively detecting cerium element by using an X-ray fluorescence spectrometry method comprises the following steps: 1) purchasing a GBW magnesium alloy standard sample; 2) processing a GBW magnesium alloy standard sample; 3) electrifying an x-ray fluorescence spectrum instrument and aging a light pipe; 4) establishing working curve parameter setting and spectral line interference elimination by using a standard sample; 5) establishing a working curve by using a standard sample; 6) detecting a sample to be detected by using a working curve established by a standard sample; 7) obtaining a result from a computer or directly printing out a detection result; 8) and (6) arranging the detection report. The invention overcomes the technical defects of the existing wavelength dispersion X-ray fluorescence spectrometer, realizes the third party fair comparison detection, further perfects the product quality assurance evaluation system, ensures the requirements of uniformity and stability of the product quality, and ensures that the magnesium alloy spectrum standard sample obtains a satisfactory analysis result on the X-ray fluorescence instrument.
Description
Technical Field
The invention belongs to the analysis and detection technology of modern instruments, and particularly relates to a method for quantitatively detecting cerium element by using an X-ray fluorescence spectrometry.
Background
For a long time, GB/T13748.8-2005 gravimetric method, tribromoarsine spectrophotometry and GB/T13748 ICP-AES method are mostly adopted for detecting the total amount of rare earth in magnesium alloy, and no report is found for the condition of network query at present by adopting x-ray fluorescence spectrometry.
Disclosure of Invention
The invention aims to overcome two defects of the prior wavelength dispersion X-ray fluorescence spectrometer technology, break through the confidentiality and monopoly of the foreign technology, realize the third party fair comparison detection, further improve the product quality assurance evaluation system, ensure the requirements of the uniformity and the stability of the product quality, and ensure that the magnesium alloy spectrum standard sample obtains a satisfactory analysis result on an X-ray fluorescence instrument.
The invention relates to a method for quantitatively detecting cerium element by using an X-ray fluorescence spectrometry, which comprises the following steps:
1) purchasing a GBW magnesium alloy standard sample:
the purchased magnesium alloy spectrum standard sample is a GBW spectrum standard sample produced by verification of a 456 th regional measurement station in the weapon industry, the number of the GBW spectrum standard sample is 5 quick samples in total from GBW02249 to GBW02253, and the sample size is as follows: phi 440 x 350;
2) processing a GBW magnesium alloy standard sample, and paying attention to the control of the finish degree of the processed surface of the sample and the removal of oil stains on the surface of the sample; today's XRF can meet the requirements of general analytical testing, with errors mainly coming from the sample. Considerable attention is therefore paid to the preparation and handling of the samples. The sample to be analyzed is prepared using appropriate mechanical sample preparation methods. Taking a representative sample, testing the fluorescence intensity of X-rays by using X-ray irradiation, and quantitatively screening by adopting an analysis method based on reference substance comparison, namely a standard substance comparison method;
XRF, as a comparative analysis technique, requires that all standard and unknown samples that enter the instrument for testing have the same morphology and reproducibility. Any sample preparation method must ensure the repeatability of sample preparation and provide similar physical properties to the samples within a certain concentration range. A typical sample should be as follows: the surface is flat and smooth, and the sample is uniform; the sample thickness should be as infinite as required for XRF. The infinite thickness is the thickness when the incident X-ray is totally absorbed and can not be emitted;
3) electrifying an x-ray fluorescence spectrum instrument and aging a light pipe;
the aging treatment of the light tube is mainly used for reducing the influence of impurity lines of the X-ray tube and the influence of background, and simultaneously avoiding the danger of burning off due to abnormal heating of a filament caused by the large current under low voltage;
the aging of the light pipe is automatically performed by the instrument according to the set conditions,
4) establishing working curve parameter setting and spectral line interference elimination by using a standard sample;
since XRF spectroscopy is a comparative technique, its performance depends on the quality of the calibration, i.e., on the accuracy of the standards used to establish instrument calibration. XRF analysis is very sensitive to the substrate. This means that spectral and matrix interferences (e.g. absorption and enhancement phenomena) have to be taken into account at the time of analysis, especially for complex and variable samples;
some elements may have full or partial spectral line overlap, and the basic parametric equations require the use of net intensities that are not affected by spectral line overlap. Some empirical correction is included in these equations;
some inter-element interference or matrix effects may exist between elements. The empirical way to compensate for these effects is to prepare a series of calibration standards curves, with the concentration range covering the range to be analyzed; in this case, the reference substance needs to be carefully designed, and the content of all the elements that do not need to be analyzed is fixed, while the concentration of the elements to be analyzed is different. This is called matrix matching;
alternatively, mathematical methods can be used to compensate for the effects of inter-element or matrix effects;
interference may also come from the compton line or characteristic lines generated by the target in the X-ray tube, which can be removed by using filters, but may also lead to a reduction in the intensity of the analysis lines;
errors from metallographic structure, due to the density of the analysis target elements being affected by the mass absorption coefficient of the sample, and the mathematical model assuming a homogeneous mass, thus giving errors;
secondly, for XRF, the analytical bias is due to the nature of the solid sample injection being analysed, and the possible differences in the nature of the sample surface from the standard;
in summary, the greater the difference between the sample and the standard, the greater the error. The so-called dissimilarities include: the physicochemical properties of the matrix material, such as the density, structure, composition and concentration, surface condition, and even whether the content of the element to be tested in the sample is within the range of the standard sample, the position of each sample, etc., have an influence on the accuracy of the analysis result;
5) establishing a working curve by using a standard sample;
the invention adopts a new interference theory of the X-ray fluorescence spectrum-the Blimer line interference effect, wherein the Blimer line interference effect refers to the noise in the spectrum caused by the deceleration of electrons when accelerated cathode hot electrons bombard the anode of an X-ray tube; this is not mentioned in the previous literature; when a working curve is established by using a standard sample, the Blimer spectral line interference effect is properly and flexibly applied, the inherent defects of instrument hardware can be overcome, and a satisfactory working curve can be obtained;
6) detecting a sample to be detected by using a working curve established by a standard sample;
7) obtaining a result from a computer or directly printing out a detection result;
8) and (6) arranging the detection report.
Detailed Description
The present invention will be further described with reference to the following examples.
Examples
The embodiment relates to a method for quantitatively detecting cerium element by using an X-ray fluorescence spectrometry, in particular to a wavelength dispersion X-ray fluorescence spectrometry quantitative analysis method, which comprises the following steps:
1) purchasing a GBW magnesium alloy standard sample: the purchased magnesium alloy spectrum standard sample is a GBW spectrum standard sample produced by verification of a 456 th regional measurement station in the weapon industry, the number of the GBW spectrum standard sample is 5 quick samples in total from GBW02249 to GBW02253, and the sample size is as follows: phi 440 x 350;
2) processing a GBW magnesium alloy standard sample, and paying attention to the control of the finish degree of the processed surface of the sample and the removal of oil stains on the surface of the sample; today's XRF can meet the requirements of general analytical testing, with errors mainly coming from the sample. Considerable attention is therefore paid to the preparation and handling of the samples. Preparing a sample to be analyzed using an appropriate mechanical sample preparation method; a representative sample was taken and X-ray fluorescence intensity was measured using X-ray irradiation. Quantitative screening takes the form of reference-substance-contrast-based analytical methods. Namely a standard comparison method; XRF, as a comparative analysis technique, requires that all standard and unknown samples that enter the instrument for testing have the same morphology and reproducibility. Any sample preparation method must ensure the repeatability of sample preparation and provide similar physical properties to the samples within a certain concentration range. A typical sample should be as follows: the surface is flat and smooth, and the sample is uniform; the thickness of the sample is the infinite thickness required by XRF, i.e. the thickness when the incident X-ray is absorbed completely and cannot be emitted;
3) electrifying an x-ray fluorescence spectrum instrument and aging a light pipe; the aging treatment of the light tube is mainly used for reducing the influence of impurity lines of the X-ray tube and the influence of background, and simultaneously avoiding the danger of burning off due to abnormal heating of a filament caused by the large current under low voltage;
the aging work of the light pipe is automatically carried out by the instrument according to the set conditions, and the aging work comprises the following specific steps:
(1) opening S4 Tools, and reading instrument state information;
(2) in the tree structure on the left side, "X-Ray" is selected;
(3) in the menu, "uses", → "X-Ray uses" → "tube Conditioning ON/OFF" are selected;
(4) at this time, the high voltage applied to the light pipe is gradually increased from 20kV to 50kV (S4Explorer) or 60kV (S4 Pioneer), and the whole boosting process takes about 1 hour. After 1 hour, the voltage applied to the light pipe returned to 20kV 5mA, indicating that the light pipe aging was complete.
(5) Then, in the menu, "Utilities" is selected, → "X-Ray Utilities" → "tube conditioning ON/OFF", and the light pipe aging process is ended.
4) Establishing working curve parameter setting and spectral line interference elimination by using a standard sample; since XRF spectroscopy is a comparative technique, its performance depends on the quality of the calibration, i.e., on the accuracy of the standards used to establish instrument calibration. XRF analysis is very sensitive to the substrate. This means that spectral and matrix interferences (e.g. absorption and enhancement phenomena) have to be taken into account at the time of analysis, especially for complex and variable samples.
Some elements may have full or partial spectral line overlap. The basic parametric equation requires the use of net intensities that are not affected by spectral line overlap. Some empirical correction is included in these equations.
Some inter-element interference or matrix effects may exist between elements. The empirical way to compensate for these effects is to prepare a series of calibration standards, with concentration ranges covering the range to be analyzed. In this case, the reference substance needs to be carefully designed, and the content of all the elements that do not need to be analyzed is fixed, while the concentration of the elements to be analyzed is different. This is called matrix matching.
Alternatively, mathematical methods may be used to compensate for the effects of inter-element or matrix effects.
Interference may also come from the conpton line or characteristic lines generated by the target in the X-ray tube, which may be removed by using filters, but may also lead to a reduction in the intensity of the analysis lines.
Errors from metallographic structure are introduced because the density of the analysis target element is affected by the mass absorption coefficient of the sample and the mathematical model assumes a homogeneous mass.
Secondly, for XRF, the analytical bias is due to the nature of the solid sample injection being analysed, and the possible differences in the nature of the sample surface from the standard;
in short, the larger the difference between the sample and the standard sample is, the larger the error is; the so-called dissimilarities include: the physicochemical properties of the matrix material, such as the density, structure, composition and concentration, surface condition, and even whether the content of the element to be tested in the sample is within the range of the standard sample, the position of each sample, etc., have an influence on the accuracy of the analysis result;
5) establishing a working curve by using a standard sample; the invention adopts a new interference theory of X-ray fluorescence spectrum-the Blimem interference effect, which is the noise in the spectrum caused by the deceleration of electrons when accelerated cathode hot electrons bombard the anode of an X-ray tube. This is not mentioned in the previous literature. When a working curve is established by using a standard sample, the Blimer spectral line interference effect is properly and flexibly applied, the inherent defects of instrument hardware can be overcome, and a satisfactory working curve can be obtained;
6) detecting a sample to be detected by using a working curve established by a standard sample;
7) obtaining a result from a computer or directly printing out a detection result;
8) and (6) arranging the detection report.
When a sample is irradiated by x-rays, high-energy particle beams, ultraviolet light and the like, high-energy particles or photons collide with atoms of the sample, electrons in inner layers of the atoms are ejected to form holes, the atoms are in an excited state, the ion life of the excited state is short, when outer-layer electrons transit to inner-layer holes, redundant energy is released in the form of the x-rays, new holes are generated in the outer layers, new x-ray emission is generated, and therefore a series of characteristic x-rays are generated.
The detection principle of the wavelength dispersion spectrometer is as follows: the characteristic X-ray is collimated by the collimator and projected on the surface of the light splitting crystal, diffraction is generated according to the Bragg law, and fluorescent X-rays with different wavelengths are arranged into a spectrum according to the wavelength sequence. The spectral lines are detected by a detector at different diffraction angles, converted into pulse signals, amplified by a circuit and finally processed by a computer to output detection results.
The X fluorescence spectrometer (XPF) can rapidly perform multi-element analysis in a nondestructive way, can rapidly screen unknown components in various sample matrixes such as solid, slurry, powder, paste, film, air filter and other many matrix samples, and is a commonly adopted detection method for preliminary screening of harmful substances. An X-ray fluorescence spectrometer is a comparative measurement device, which has an indication of only one signal, not the measured quantity, and can convert the signal magnitude into the measured quantity only after calibration with a known quantity, such as the quantity of a standard substance, and a functional relationship between the known quantity and the indication signal is established. In actual work, due to the existence of matrix effect, the concentration of the analytical element and the indicating value signal are not strictly proportional, so that the sample to be measured is required to be consistent with the standard sample substrate for establishing the working curve.
When analyzing trace amounts of iron, nickel, copper, zinc, and other elements, the background tends to be increased by impurity lines generated by the X-ray tube. There are three methods for eliminating such impurities: one is to use a primary X-ray filter; the other is an X-ray tube with less impurity lines; yet another is to estimate the intensity of the impurity line. One of the methods for estimating the blank value of the impurity line is a method for correcting the blank value by mathematical calculation using a relationship that the ratio of the peak intensity to the background intensity of samples having similar compositions is not changed; continuous X-rays are radiated from the X-ray tube, and this continuous X-rays become background by sample scattering, which tends to lower precision and detection limit, and furthermore, characteristic X-ray coherent scattering (rayleigh scattering) and incoherent scattering (compton scattering) generated by the X-ray tube are severe in a sample of a light element matrix, and become a weak peak of an analysis line interfering with the appearance thereof in the vicinity. In public hazard analysis, when analyzing elements such as lead, arsenic, mercury, etc., a drill target or a rhodium target X-ray tube is generally used because characteristic X-rays such as MoK α, K β, RhK α, K β, etc. have high excitation efficiency, do not interfere with the spectral lines of elements such as lead, arsenic, etc., and have low background of continuous X-rays.
The establishment of quantitative working curves by using spectral standard samples is a conventional inspection method, however, due to technical reasons, some spectral standard samples cannot obtain satisfactory analysis results on an X-ray fluorescence instrument; the existing wavelength dispersion X-ray fluorescence spectrometer has two important defects in some quantitative detection: firstly, spectral line interference defects of the instrument cannot be automatically eliminated, and manual selection is needed; secondly, the stability of components and parts of an instrument hardware system such as a gas flow counter has certain defects and needs to be repaired periodically; the spectrum interference defect of the instrument is also shown in the places where the existing spectrum interference theory is disputed and imperfect, the interference is difficult to control and eliminate when the instrument is applied to instrument manufacturing, and on the other hand, the interference mechanism of colored and ferrous metals is still to be further explored.
Claims (1)
1. A method for quantitatively detecting cerium element by using an X-ray fluorescence spectrometry comprises the following steps:
1) purchasing a GBW magnesium alloy standard sample:
the purchased magnesium alloy spectrum standard sample is a GBW spectrum standard sample produced by verification of a 456 th regional measurement station in the weapon industry, the number of the GBW spectrum standard sample is 5 quick samples in total from GBW02249 to GBW02253, and the sample size is as follows: phi 440 x 350;
2) processing a GBW magnesium alloy standard sample, and paying attention to the control of the finish degree of the processed surface of the sample and the removal of oil stains on the surface of the sample; today's XRF can meet the requirements of general analytical testing, with errors mainly coming from the sample; considerable attention is therefore paid to the preparation and handling of the sample; preparing a sample to be analyzed using an appropriate mechanical sample preparation method; taking a representative sample, testing the fluorescence intensity of X-rays by using X-ray irradiation, and quantitatively screening by adopting an analysis method based on reference substance comparison, namely a standard substance comparison method;
XRF, as a comparative analysis technique, requires that all standard and unknown samples that enter the instrument for testing have the same morphology and reproducibility; any sample preparation method must ensure the repeatability of sample preparation and ensure that the samples have similar physical properties within a certain concentration range; a typical sample should be as follows: the surface is flat and smooth, and the sample is uniform; the thickness of the sample is infinite as required by XRF; the infinite thickness is the thickness when the incident X-ray is totally absorbed and can not be emitted;
3) electrifying an x-ray fluorescence spectrum instrument and aging a light pipe;
the aging treatment of the light tube is mainly used for reducing the influence of impurity lines of the X-ray tube and the influence of background, and simultaneously avoiding the danger of burning off due to abnormal heating of a filament caused by the large current under low voltage;
the aging of the light pipe is automatically performed by the instrument according to the set conditions,
4) establishing working curve parameter setting and spectral line interference elimination by using a standard sample;
since XRF spectroscopy is a comparative technique, its performance depends on the quality of the calibration, i.e., on the accuracy of the standard used to establish the instrument calibration; XRF analysis is very sensitive to the substrate; this means that spectral and matrix interferences, such as absorption and enhancement phenomena, have to be taken into account at the time of analysis, especially for complex and variable samples;
some elements may have full or partial spectral line overlap, and the basic parametric equation requires the use of net intensities that are not affected by spectral line overlap; some empirical correction is included in these equations;
some elements may have inter-element interference or matrix effect; the empirical way to compensate for these effects is to prepare a series of calibration standards curves, with the concentration range covering the range to be analyzed; at the moment, the reference substance needs to be carefully designed, the content of all elements which do not need to be analyzed is fixed, and the concentrations of the elements to be analyzed are different; this is called matrix matching;
alternatively, mathematical methods can be used to compensate for the effects of inter-element or matrix effects;
interference may also come from the compton line or characteristic lines generated by the target in the X-ray tube, which can be removed by using filters, but may also lead to a reduction in the intensity of the analysis lines;
errors from metallographic structure, due to the density of the analysis target elements being affected by the mass absorption coefficient of the sample, and the mathematical model assuming a homogeneous mass, thus giving errors;
secondly, for XRF, the analytical bias is due to the nature of the solid sample injection being analysed, and the possible differences in the nature of the sample surface from the standard;
in short, the larger the difference between the sample and the standard sample is, the larger the error is; the so-called dissimilarities include: the physicochemical properties of the matrix material, such as the density, structure, composition and concentration, surface condition, and even whether the content of the element to be tested in the sample is within the range of the standard sample, the position of each sample, etc., have an influence on the accuracy of the analysis result;
5) establishing a working curve by using a standard sample;
the invention adopts a new interference theory of the X-ray fluorescence spectrum-the Blimer line interference effect, wherein the Blimer line interference effect refers to the noise in the spectrum caused by the deceleration of electrons when accelerated cathode hot electrons bombard the anode of an X-ray tube; this is not mentioned in the previous literature; when a working curve is established by using a standard sample, the Blimer spectral line interference effect is properly and flexibly applied, the inherent defects of instrument hardware are overcome, and a satisfactory working curve is obtained;
6) detecting a sample to be detected by using a working curve established by a standard sample;
7) obtaining a result from a computer or directly printing out a detection result;
8) and (6) arranging the detection report.
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| WO2023077494A1 (en) * | 2021-11-08 | 2023-05-11 | Shenzhen Xpectvision Technology Co., Ltd. | Apparatus and method for x-ray fluorescence imaging |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104111263A (en) * | 2014-07-07 | 2014-10-22 | 大连理工大学 | X-ray fluorescent spectrum fundamental parameter method utilizing virtually synthesized standard sample |
| CN109030528A (en) * | 2018-09-26 | 2018-12-18 | 云南驰宏锌锗股份有限公司 | A kind of method that X-ray fluorescence spectra analyzes fluorine chlorine in smelting smoke dust |
| CN110865092A (en) * | 2019-12-10 | 2020-03-06 | 中国科学院金属研究所 | In-situ analysis method for representing component distribution of high-temperature alloy by utilizing X-ray fluorescence spectrum |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104111263A (en) * | 2014-07-07 | 2014-10-22 | 大连理工大学 | X-ray fluorescent spectrum fundamental parameter method utilizing virtually synthesized standard sample |
| CN109030528A (en) * | 2018-09-26 | 2018-12-18 | 云南驰宏锌锗股份有限公司 | A kind of method that X-ray fluorescence spectra analyzes fluorine chlorine in smelting smoke dust |
| CN110865092A (en) * | 2019-12-10 | 2020-03-06 | 中国科学院金属研究所 | In-situ analysis method for representing component distribution of high-temperature alloy by utilizing X-ray fluorescence spectrum |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023077494A1 (en) * | 2021-11-08 | 2023-05-11 | Shenzhen Xpectvision Technology Co., Ltd. | Apparatus and method for x-ray fluorescence imaging |
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