CN114295663A - Magnesium-based electron probe microbeam component analysis standard sample and preparation method thereof - Google Patents
Magnesium-based electron probe microbeam component analysis standard sample and preparation method thereof Download PDFInfo
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- 239000000523 sample Substances 0.000 title claims abstract description 127
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- 238000004458 analytical method Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
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- 238000000034 method Methods 0.000 claims abstract description 36
- 238000012360 testing method Methods 0.000 claims abstract description 36
- 229910052787 antimony Inorganic materials 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 14
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 12
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- 239000011135 tin Substances 0.000 description 19
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 18
- 238000001514 detection method Methods 0.000 description 11
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Abstract
The invention discloses a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof, belonging to the technical field of electron probe microbeam analysis. A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps: the preparation method mainly comprises the following steps: s1, melting treatment: uniformly mixing high-purity Mg and high-purity Sb elementary substance powder, sealing the mixture of Mg and Sb by using a tantalum tube, sealing the tantalum tube in a quartz glass tube, placing the quartz glass tube in a muffle furnace, and carrying out high-temperature melting treatment at 850 ℃; s2, annealing treatment: for Mg3Sb2Annealing at a rate of 2 deg.C/hr from 850 deg.C to 650 deg.C to obtain Mg3Sb2The single crystal grows slowly. Using Mg3Sb2The single crystal is used as a standard sample, and can effectively eliminate micro-area in-situ components of the magnesium-based thermoelectric material electron probe with the matrix effectThe influence of the analysis is mainly used for calibrating the test data of the magnesium-based thermoelectric material and can also be used for controlling the quality of the test process.
Description
Technical Field
The invention relates to the technical field of electron probe microbeam analysis, in particular to a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof.
Background
The thermoelectric material can realize the mutual conversion of heat energy and electric energy by utilizing the Seebeck effect or the Peltier effect of the thermoelectric material, and the thermoelectric power generation or refrigeration device developed based on the technology has the advantages of simple structure, durability, no noise, no pollution and the like, so the thermoelectric power generation or refrigeration device has huge commercial application potential.
The conventional room-temperature commercial bismuth-tellurium-based thermoelectric material has poor mechanical property and needs to use rare and expensive tellurium element, so that the large-scale application of the material is limited. Binary magnesium-based thermoelectric material Mg emerging in recent years2Si and Mg3XV 2(XVSb and Bi) and a multi-element magnesium-based thermoelectric material prepared by doping elements (such as Ni, Cu, Zn, Ge, Ag, Sn, Pb and the like) have thermoelectric properties equivalent to those of a bismuth telluride-based thermoelectric material and better mechanical toughness, and have the remarkable advantages of rich raw materials, low price, low density and the like, so that the multi-element magnesium-based thermoelectric material is expected to replace the traditional N-type room temperature thermoelectric material.
In order to further improve the thermoelectric performance of the magnesium-based thermoelectric material, higher requirements are put on the quality of the material and corresponding synthesis means, including good homogeneity, strict regulation and control of stoichiometric ratio, repeatability, capability of large-scale production and the like. The difficulties faced in achieving this result primarily from the high chemical activity of magnesium (which readily oxidizes in air) and the high vapor pressure of magnesium above 600 c, such that the normal stoichiometric proportions of the ingredients tend to form point defects of magnesium vacancies, while excess magnesium compensation tends to form point defects of magnesium interstitials.
The electron probe is a mature in-situ micro-area (micron-submicron) primary and secondary quantity element analysis technology, and the high accuracy of quantitative analysis is very suitable for the measurement of the stoichiometric ratio and the element surface distribution of the magnesium-based thermoelectric material. However, as limited by the principle of the test method, high quality test data relies on calibration and analytical quality control using matrix-matched standards.
The existing magnesium-containing microbeam analysis standard samples such as metal (such as high-purity simple substance Mg), oxide (such as MgO) and silicate mineral (such as forsterite, clinoptilolite and the like) are not suitable for analysis and test of magnesium-based thermoelectric materials due to easy oxidation, matrix mismatching and the like. Therefore, it is necessary to develop suitable standard samples for the analysis and further study of the micro-domain composition of such thermoelectric materials.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a magnesium-based electron probe microbeam component analysis standard sample and a preparation method thereof, and the standard sample can effectively eliminate the influence of a matrix effect on the in-situ component analysis of a magnesium-based thermoelectric material electron probe microcell in the in-situ component analysis process of the magnesium-based thermoelectric material electron probe, and can calibrate test data and control the quality of the test process.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, melting treatment:
uniformly mixing high-purity Mg and high-purity Sb elementary substance powder, sealing the mixture of Mg and Sb by using a tantalum tube, sealing the tantalum tube in a quartz glass tube, placing the quartz glass tube in a muffle furnace, and carrying out high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
for Mg3Sb2Annealing at a rate of 2 deg.C/hr from 850 deg.C to 650 deg.C to obtain Mg3Sb2Slowly growing up the single crystal;
s3, centrifugal separation:
putting the quartz glass tube into a centrifuge for high-speed centrifugation to ensure that Mg is contained3Sb2Separating single crystal from Sb fluxing agent to obtain layered Mg3Sb2Single crystal;
s4, preparing a light sheet:
mixing Mg3Sb2Preparing a single crystal into a polished section with a proper size, and evaporating a layer of carbon film on the surface of the polished section to obtain a standard sample suitable for micro-area in-situ component analysis by using an electronic probe method.
Preferably, the atomic molar ratio of the added Mg to the Sb elementary powder is 3: 7.
Preferably, the Mg and Sb elemental powders are uniformly mixed, the Mg and Sb mixture is sealed by using a tantalum tube, and then the tantalum tube is sealed in a quartz glass tube, and all the operations are carried out in an argon glove box.
Preferably, the purity of Mg is not lower than 99.8 percent, and the particle size of Mg is 100-200 meshes; the purity of Sb is not less than 99.999 percent, and the granularity of Sb is not less than 200 meshes.
Preferably, the layered Mg produced3Sb2The thickness of the single crystal is 0.2-1.5mm, and the length is 3-5 mm.
Preferably, Mg is added3Sb2The preparation process of single crystal to prepare light-forming sheet includes adding Mg3Sb2The single crystal is embedded in the epoxy resin, and then coarse grinding, fine grinding, polishing and ultrasonic cleaning are carried out on the single crystal, so that the surface of the finally obtained polished section is flat and smooth, and has no pollution or scratch.
Preferably, a carbon film with a thickness of 20nm is evaporated on the surface of the optical sheet.
Preferably, the polished section is placed in a vacuum drying oven for storage immediately after preparation.
Preferably, a Mg-based electron probe microbeam composition analysis standard sample, Mg prepared3Sb2The single crystal standard sample is applied to the technical field of electron probe microbeam analysis, is mainly used for calibrating the test data of the magnesium-based thermoelectric material, and can also be used for controlling the quality of the test process.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
the invention successfully prepares the lamellar Mg with high purity and compact structure by using a self-fluxing agent method with Sb as a flux3Sb2Compared with the existing magnesium-containing microbeam analysis standard samples such as elemental metal, oxide, silicate mineral and the like, the single crystal standard sample uses Mg3Sb2The single crystal serving as a magnesium standard sample can effectively eliminate the influence of the matrix effect on the in-situ composition analysis of the magnesium-based thermoelectric material electron probe in the micro-area, and can well perform the in-situ composition analysis on the magnesium-based thermoelectric material electron probe in the micro-areaIn the analysis process, the data are calibrated and the test quality is controlled.
Drawings
FIG. 1 is a layered Mg of the present invention3Sb2And (4) a single crystal sample diagram.
Detailed Description
Referring to fig. 1, a method for preparing a mg-based electron probe microbeam component analysis standard sample, includes: the preparation method comprises the following steps:
s1, melting treatment:
uniformly mixing high-purity Mg and high-purity Sb elementary substance powder, sealing the mixture of Mg and Sb by using a tantalum tube, sealing the tantalum tube in a quartz glass tube, placing the quartz glass tube in a muffle furnace, and carrying out high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
for Mg3Sb2Annealing at a rate of 2 deg.C/hr from 850 deg.C to 650 deg.C to obtain Mg3Sb2Slowly growing up the single crystal;
s3, centrifugal separation:
putting the quartz glass tube into a centrifuge for high-speed centrifugation to ensure that Mg is contained3Sb2Separating single crystal from Sb fluxing agent to obtain layered Mg3Sb2Single crystal;
s4, preparing a light sheet:
mixing Mg3Sb2Preparing a single crystal into a polished section with a proper size, and evaporating a layer of carbon film on the surface of the polished section to obtain a standard sample suitable for micro-area in-situ component analysis by using an electronic probe method.
The atomic molar ratio of Mg to Sb elementary powder is 3: 7.
Mg and Sb elementary substance powder are uniformly mixed, a tantalum tube is used for sealing the mixture of Mg and Sb, and then the tantalum tube is sealed in a quartz glass tube, and the operation processes are all finished in an argon glove box so as to prevent magnesium from being rapidly oxidized in the air.
The purity of Mg is not less than 99.8 percent, and the granularity of Mg is 100-200 meshes; the purity of Sb is not less than 99.999 percent, and the granularity of Sb is not less than 200 meshes.
Prepared layered Mg3Sb2The thickness of the single crystal is 0.2-1.5mm, and the length is 3-5 mm.
Mixing Mg3Sb2The process for preparing light-forming sheet from single crystal comprises adding Mg3Sb2The single crystal is embedded in the epoxy resin, the epoxy resin is subjected to coarse grinding, fine grinding, polishing and ultrasonic cleaning, and the surface of the finally obtained polished section is flat and smooth, pollution-free and scratch-free.
A carbon film with a thickness of 20nm is evaporated on the surface of the polished section.
And (5) immediately placing the polished section into a vacuum drying oven for storage after the polished section is prepared.
A magnesium-based electron probe microbeam component analysis standard sample, prepared Mg3Sb2The single crystal standard sample is applied to the technical field of electron probe microbeam analysis, is mainly used for calibrating the test data of the magnesium-based thermoelectric material, and can also be used for controlling the quality of the test process.
Electronic probe quantitative analysis generally uses the ZAF method, the PRZ method and the standard curve method to carry out correction processing on test data, but the high-quality test data depends on the standard sample matched with a matrix for calibration and analysis quality control by the principle of the method. For ease of discussion, the ZAF method was used in all examples.
The magnesium-based electron probe microbeam component analysis standard sample of the present invention is further described with reference to the following specific examples.
Example 1
Firstly, according to the requirement of an electronic probe on a sample, Mg is added2.983Ag0.017Sb2Preparing single crystal into optical sheet with proper size, evaporating a carbon film with thickness of 20nm on the surface, and adding Mg2.983Ag0.017Sb2In the process of preparing the polished section by the single crystal, the used liquid is absolute ethyl alcohol, so that Mg is avoided2.983Ag0.017Sb2Contacting the single crystal with water;
secondly, placing the prepared polished section on an electronic probe sample stage and pushing the polished section to an electronic probe vacuum sample bin;
setting a series of quantitative analysis conditions of acceleration voltage, electron beam current, spectroscopic single crystal, detector, standard sample and the like, wherein the acceleration voltage is set to be 20kV, and the electron beam current is set to be 2 multiplied by 10-8A, quantitative analytical testing was carried out on Mg using different combinations of standard samples (Nos. 1 to 4)2.983Ag0.017Sb2The results of the tests carried out on the single crystals calibrated by the ZAF method are shown in Table 1.
Table 1 different standard sample combinations versus Mg2.983Ag0.017Sb2Test results obtained by calibrating single crystals
And (3) analyzing a test result:
Mg2.983Ag0.017Sb2the standard values of the mass percent (wt.%) of Mg, Ag and Sb in the single crystal are 22.81%, 0.58% and 76.62%, respectively, and Mg2.983Ag0.017Sb2The standard value of the atomic mole ratio of magnesium, silver and antimony in the single crystal is 59.66: 0.34: 40.00.
selecting Mg simple substance or Mg2When Si single crystal is used as a standard sample of magnesium, since both are mixed with Mg2.983Ag0.017Sb2The single crystal has obvious difference of atomic number effect (Z) and absorption effect (A) (when Z, A, F is 1, representing complete matrix matching), and the test result shows that the average value of the mass percentage content of Mg and the average value of the atomic molar ratio of Mg at 11 collected detection points are obviously deviated from the standard value.
Selecting Mg2When Sn single crystal is used as a standard sample of magnesium, although the atomic number effect (Z) and the absorption effect (A) are obviously improved, the test result has non-negligible deviation from the standard value.
Selecting Mg3Sb2Using single crystals of magnesium and antimonyThe standard sample, the test result shows the mass percentage content of magnesium and antimony and Mg2.983Ag0.017Sb2The standard values of the mass percentage contents of magnesium and antimony in the single crystal are very consistent, and the average value of the atomic mole ratio of magnesium and antimony is equal to that of Mg2.983Ag0.017Sb2The atomic mole ratio standard values of magnesium and antimony in the single crystal are also very consistent, which shows that Mg3Sb2The single crystal can effectively inhibit the influence of the matrix effect on the in-situ composition analysis of the magnesium-based thermoelectric material electron probe micro-area.
Therefore, it is used in the case of Mg3Sb2When ternary or multicomponent solid solution prepared by taking single crystal as a substrate is used for electronic probe quantitative analysis, Mg is preferably selected3Sb2Single crystals were used as standard samples of magnesium and antimony.
Example 2
Firstly, according to the requirement of an electronic probe on a sample, preparing MgAgSb polycrystal into a light sheet with a proper size, and evaporating a carbon film with the thickness of 20nm on the surface of the light sheet, wherein in the process of preparing the MgAgSb polycrystal into the light sheet, the used liquid is absolute ethyl alcohol, so that the MgAgSb polycrystal is prevented from contacting water;
secondly, placing the prepared polished section on an electronic probe sample stage and pushing the polished section to an electronic probe vacuum sample bin;
setting a series of quantitative analysis conditions of acceleration voltage, electron beam current, spectroscopic single crystal, detector, standard sample and the like, wherein the acceleration voltage is set to be 20kV, and the electron beam current is set to be 2 multiplied by 10-8A, carrying out quantitative analysis test, and carrying out ZAF method calibration on MgAgSb polycrystal by using different standard sample combinations (serial numbers 1-4) to obtain test results shown in Table 2.
TABLE 2 test results obtained by calibrating MgAgSb polycrystals using different standard sample combinations
And (3) analyzing a test result:
the standard values of the mass percentage (wt.%) of magnesium, silver and antimony in the MgAgSb polycrystals were 9.57%, 42.48% and 47.95%, respectively, and the standard value of the atomic molar ratio of magnesium, silver and antimony in the MgAgSb polycrystals was 33.33: 33.33: 33.33 (i.e., 1: 1: 1).
Selecting Mg simple substance or Mg2When the Si single crystal is used as a standard sample of magnesium, because the two have obvious differences of atomic number effect (Z) and absorption effect (A) with MgAgSb polycrystal (when Z, A, F is 1, the sample represents complete matrix matching), the test result shows that the average value of the mass percentage content of Mg and the average value of the atomic molar ratio of Mg at 11 collected detection points obviously deviate from the standard value.
Selecting Mg2When Sn single crystal is used as a standard sample of magnesium, although the atomic number effect (Z) and the absorption effect (A) are obviously improved, the test result has non-negligible deviation from the standard value.
Selecting Mg3Sb2The single crystal is used as a standard sample of magnesium and antimony, and the test result shows that the mass percentage content average value of the magnesium and the antimony of 11 collected detection points is basically consistent with the mass percentage content standard value of the magnesium and the antimony in the MgAgSb polycrystal, and the atomic molar ratio average value of the magnesium and the antimony of the 11 detection points is also basically consistent with the atomic molar ratio standard value of the magnesium and the antimony in the MgAgSb polycrystal, which shows that the mass percentage content average value of the magnesium and the antimony of the 11 detection points is basically consistent with the atomic molar ratio standard value of the magnesium and the antimony in the MgAgSb polycrystal, and the results show that the mass percentage content average value of the magnesium and the antimony in the MgAgSb polycrystal is also consistent with the mass percentage content standard value of the magnesium and the antimony in the MgAgSb polycrystal3Sb2The single crystal can effectively inhibit the influence of the matrix effect on the in-situ composition analysis of the magnesium-based thermoelectric material electron probe micro-area.
Because a phase separation phenomenon often exists in a multi-single crystal system, the fine-grained Mg in the prepared MgAgSb polycrystalline sample: ag: the atomic ratio of Sb may deviate from 1: 1: 1.
therefore, in the case of quantitative electron probe analysis of MgAgSb polycrystal or multicomponent solid solution prepared with MgAgSb monocrystal as matrix in the absence of MgAgSb monocrystal standard sample, Mg is preferably used3Sb2Single crystals were used as standard samples of magnesium and antimony.
Example 3
Firstly, according to the requirement of an electronic probe on a sample, Mg is added2Si0.214Sn0.786Preparing single crystal into optical sheet with proper size, evaporating a carbon film with thickness of 20nm on the surface, and adding Mg2Si0.214Sn0.786Process for preparing polished sheet from single crystalIn the process, the used liquid is absolute ethyl alcohol, and Mg is avoided2Si0.214Sn0.786Contacting the single crystal with water;
secondly, placing the prepared polished section on an electronic probe sample stage and pushing the polished section to an electronic probe vacuum sample bin;
setting a series of quantitative analysis conditions of acceleration voltage, electron beam current, spectroscopic single crystal, detector, standard sample and the like, wherein the acceleration voltage is set to be 20kV, and the electron beam current is set to be 2 multiplied by 10-8A, quantitative analytical testing was carried out on Mg using different combinations of standard samples (Nos. 1 to 4)2Si0.214Sn0.786The results of the tests carried out on the single crystals calibrated by the ZAF method are shown in Table 3.
Table 3 different standard sample combinations versus Mg2Si0.214Sn0.786Test results obtained by calibrating single crystals
And (3) analyzing a test result:
Mg2Si0.214Sn0.786the standard values of the mass percent (wt.%) of Mg, Si and Sn in the single crystal were 32.87%, 4.06% and 63.07%, respectively, and Mg content in the single crystal was2Si0.214Sn0.786The standard value of the atomic mole ratio of magnesium, silicon and tin in the single crystal was 66.67: 7.13: 26.20.
selecting Mg simple substance or Mg2When Si single crystal is used as a standard sample of magnesium, since both are mixed with Mg2Si0.214Sn0.786The single crystal has obvious difference of atomic number effect (Z) and absorption effect (A) (when Z, A, F is 1, it represents complete matrix matching), the test result shows that the average value of Mg mass percentage content and the average value of Mg atomic molar ratio of 11 collected detection points are obviously deviated from the standard value.
Selecting Mg2Sn or Mg3Sb2When the single crystal is used as a magnesium standard sample, the atomic number effect (Z) and the absorption effect (A) are obviously improved, and the test result shows that the mass percentage content of the magnesium isAverage value and Mg2Si0.214Sn0.786The standard value of the mass percentage content of the single crystal magnesium is basically consistent, and the average value of the atomic mole ratio of the magnesium is equal to that of Mg2Si0.214Sn0.786The atomic mole ratio of magnesium in the single crystal is substantially the same as the standard value.
Although Mg is selected2The correction effect of Sn single crystal as the standard sample of magnesium is better than that of Mg3Sb2The single crystal has good effect because the former matrix and Mg2Si0.214Sn0.786Single crystals are more matched, but in the absence of Mg2For Mg in the case of Sn single crystal standards2Si1-xSnxWhen single crystal or multi-element solid solution prepared by taking the single crystal as a substrate is used for carrying out quantitative component analysis on an electronic probe, Mg is selected3Sb2Single crystals are also good candidates as standard samples of magnesium.
Wherein the content of the first and second substances,
ZAF correction formula introduction:
in the above formula, UNK and STD refer to unknown sample and standard sample, G, respectivelyZ、GAAnd GFThe atomic number correction coefficient (Z), the absorption correction coefficient (a), and the fluorescence correction coefficient (F), respectively, are abbreviated as ZAF correction methods.
The final objective of the calibration is to eliminate the matrix effect between the unknown sample and the standard sample, i.e. the difference in behavior of the incident electron beam in the sample, the absorption of characteristic X-rays in the sample, and the secondary fluorescent X-ray excitation.
In practical application, due to the complexity of material structure and components and various errors introduced by approximate calculation of various physical parameters (such as mass absorption coefficient, back scattering factor, permeability factor and the like) in the formula, the ZAF correction method cannot completely eliminate matrix effect difference between an unknown sample and a standard sample in many cases, and therefore, in order to obtain high-quality electronic probe test data, a matrix-matched standard sample should be preferably selected.
For layered Mg3Sb2The single crystals were analyzed for uniformity and stability as follows:
according to the specification of GB/T4930-3Sb2And randomly selecting 10 pieces of the single crystal particles to carry out the detection of the uniformity of the standard sample. Selecting the layered Mg according to the requirement of the electronic probe on the sample3Sb2The single crystal is placed with its exposed surface (ab surface) facing upwards, and Mg is added with epoxy resin3Sb2Coating a single crystal, performing coarse grinding, fine grinding, polishing and ultrasonic cleaning to prepare an epoxy resin polished section with the diameter of 25.4mm, evaporating a carbon film with the thickness of 20nm on the surface of the epoxy resin polished section, using absolute ethyl alcohol in the preparation process to avoid water contact, and setting a series of experimental analysis conditions such as acceleration voltage, electron beam current, spectroscopic single crystal, detector and the like, wherein the acceleration voltage is set to be 20kV, and the electron beam current is set to be 2 multiplied by 10-8The peak test times of A, Mg and Sb were set to 50s and 20s, respectively (total count not less than 1000000), and an analysis test was conducted using an electron beam focusing mode.
Before the heterogeneity detection, 5 Mg are randomly selected3Sb2The single crystal particles were randomly measured at 10 points for each edge and inside of the particles, and the results showed that there was no significant difference in the content of Mg and Sb at the edges and inside of the particles. For each particle, 7 points were randomly chosen, and 3X-ray counts were collected and recorded for each point. The particles were analyzed in a random order, twice for each particle and in a different order for each analysis. Therefore, the number of points for uniformity detection is 420 in total, and the statistical evaluation calculation result of the non-uniformity data shows that the relative uncertainty of the average content of Mg and Sb in the 95% confidence interval is 1.24% and 1.79% respectively, which indicates that the sample is uniform and meets the uniformity requirement as a standard sample. In addition, in order to detect the content trend of elements in the particles, 5 particles are randomly selectedTwo mutually perpendicular detection lines are used for carrying out line detection with the point distance of 5 mu m and the length of 200 mu m, and the result shows that the concentration change is within 99 percent confidence limit, which indicates that the content trend of Mg and Sb does not exist.
The slides were sampled 3 times over 3 months using an electronic probe and RSD% values for Mg and Sb were counted. The precision of the measured result is similar to that of the analysis method, so that the prepared layered Mg is considered to be3Sb2The single crystal is stable.
Claims (10)
1. A preparation method of a magnesium-based electron probe microbeam component analysis standard sample is characterized by comprising the following steps: the preparation method comprises the following steps:
s1, melting treatment:
uniformly mixing high-purity Mg and high-purity Sb elementary substance powder, sealing the mixture of Mg and Sb by using a tantalum tube, sealing the tantalum tube in a quartz glass tube, placing the quartz glass tube in a muffle furnace, and carrying out high-temperature melting treatment at 850 ℃;
s2, annealing treatment:
for Mg3Sb2Annealing at a rate of 2 deg.C/hr from 850 deg.C to 650 deg.C to obtain Mg3Sb2Slowly growing up the single crystal;
s3, centrifugal separation:
putting the quartz glass tube into a centrifuge for high-speed centrifugation to ensure that Mg is contained3Sb2Separating single crystal from Sb fluxing agent to obtain layered Mg3Sb2Single crystal;
s4, preparing a light sheet:
mixing Mg3Sb2Preparing a single crystal into a polished section with a proper size, and evaporating a layer of carbon film on the surface of the polished section to obtain a standard sample suitable for micro-area in-situ component analysis by using an electronic probe method.
2. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: the atomic molar ratio of Mg to Sb elementary powder is 3: 7.
3. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: mg and Sb elementary substance powder are uniformly mixed, a tantalum tube is used for sealing the mixture of Mg and Sb, and then the tantalum tube is sealed in a quartz glass tube, and all the operation processes are completed in an argon glove box.
4. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: the purity of Mg is not less than 99.8 percent, and the granularity of Mg is 100-200 meshes; the purity of Sb is not less than 99.999 percent, and the granularity of Sb is not less than 200 meshes.
5. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: prepared layered Mg3Sb2The thickness of the single crystal is 0.2-1.5mm, and the length is 3-5 mm.
6. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: mixing Mg3Sb2The process for preparing light-forming sheet from single crystal comprises adding Mg3Sb2The single crystal is embedded in the epoxy resin, and then coarse grinding, fine grinding, polishing and ultrasonic cleaning are carried out on the single crystal, so that the surface of the finally obtained polished section is flat and smooth, and has no pollution or scratch.
7. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: in the presence of Mg3Sb2In the process of preparing the polished section by the monocrystal, the used liquid is absolute ethyl alcohol.
8. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: the thickness of the deposited carbon film was 20 nm.
9. The method for preparing the magnesium-based electron probe microbeam composition analysis standard sample as claimed in claim 1, wherein: and (5) immediately placing the polished section into a vacuum drying oven for storage after the polished section is prepared.
10. A magnesium-based electron probe microbeam component analysis standard sample is characterized in that: mg produced by the production method according to any one of claims 1 to 93Sb2The single crystal standard sample is applied to the technical field of electron probe microbeam analysis, is mainly used for calibrating the test data of the magnesium-based thermoelectric material, and can also be used for controlling the quality of the test process.
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