CN115561052A - Preparation method and application of submicron calcite sample target - Google Patents
Preparation method and application of submicron calcite sample target Download PDFInfo
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- 229910021532 Calcite Inorganic materials 0.000 title claims abstract description 212
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 94
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 60
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims description 38
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000004321 preservation Methods 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 239000000919 ceramic Substances 0.000 claims description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000000608 laser ablation Methods 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000000918 plasma mass spectrometry Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 238000004458 analytical method Methods 0.000 abstract description 48
- 239000011230 binding agent Substances 0.000 abstract description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 description 6
- 239000011707 mineral Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 4
- 238000002307 isotope ratio mass spectrometry Methods 0.000 description 4
- 238000000095 laser ablation inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material 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
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
Abstract
The invention discloses a preparation method and application of a submicron calcite sample target, which comprises the following steps: tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample target; embedding the submicron calcite sample target into epoxy resin to obtain a submicron calcite sample target; wherein, the standard deviation of two times of the content percentage of CaCO3 in the submicron calcite powder is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand. The submicron calcite sample target prepared by the invention does not need to introduce a binder, has a compact structure, is not easy to oxidize, can be stored for a long time, has small isotope analysis error, and can meet the analysis requirements of high precision and high accuracy.
Description
Technical Field
The invention relates to the technical field of isotope standard products, in particular to a preparation method and application of a submicron calcite sample target.
Background
The wide application of carbon isotopes in the field of geology makes the determination method of carbon isotope composition very early paid attention. In recent decades, nowThe art is mostly based on the determination of carbon isotopes using conventional gas stable isotope mass spectrometry (GS-IRMS). When the carbon isotope of calcite is determined, the method needs to crush a sample, pick out pure calcite particles, grind the sample into powder with the particle size of less than 200 meshes, and finally digest the sample by acid to release CO 2 Introduction of CO 2 After purification, mass spectrometry was performed. The sample treatment process of the traditional determination method is complex and time-consuming, the sample consumption is large, and the measured result is the average carbon isotope ratio of the whole calcite in the obtained sample. With the development of carbon isotope application, it is found that the overall analysis method cannot meet the analysis of calcite carbon isotopes of different causes in the microscopic field, for example, the carbon isotope compositions in the range of calcite ring zones and micro-zones of different periods may have differences.
The laser multi-receiving inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) is one of important means for in-situ isotope analysis in mineral micro-areas, has the advantages of high spatial resolution, small sample consumption, low pollution risk, high speed, economy and the like, and can directly obtain carbon isotope information on the scale of the mineral micro-areas. However, LA-MC-ICP-MS analysis usually requires matrix-matched standard samples. And the isotope composition of the standard sample needs to be highly uniform, so that the high-precision carbon isotope analysis result of the sample can be obtained. The lack of calcite standard samples with highly uniform carbon isotope compositions at present limits the rapid development and wide application of the method.
The international standards commonly used for GS-IRMS analysis of calcite carbon isotopes are more, however these standards are powder samples, which are not suitable for direct laser analysis, and the powders that have been developed into standards are generally more expensive and partly not commercially available, which are not suitable for mass production of standards for micro-area analysis.
Generally, a LA-MC-ICP-MS isotope analysis test standard sample is prepared by selecting natural minerals from nature, crushing the natural minerals into small samples, embedding the small samples in resin, grinding and polishing the small samples, and then performing uniformity inspection and analysis fixed value to obtain a finished product. The above preparation method has the following disadvantages: calcite in nature is complex and diverse, and uniformity is difficult to meet high-precision analysis requirements. And the sample amount meeting the requirement is small, so that the method is not suitable for long-term and wide popularization and use.
Traditionally, the method for preparing a powder sample into a solid standard sample target is a powder tabletting method, which is the most convenient, efficient and rapid method and is the most commonly used sample pretreatment technology which is developed at the earliest. However, the powder tabletting method for preparing the standard sample directly compacts the powder sample into tablets, and the sample target is easy to loosen and oxidize and cannot be stored for a long time. In addition, in the laser ablation process, the beam spot, energy and frequency of the laser have great influence on the carbon isotope analysis, so that the carbon isotope analysis error is large, and the analysis requirements of high precision and high accuracy cannot be met.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a submicron calcite sample target, and aims to solve the problems that the sample target is easy to loosen, easy to oxidize and incapable of being stored for a long time in the prior art.
In order to achieve the purpose, the invention provides a preparation method of a submicron calcite sample target, which comprises the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample;
embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target;
wherein, in the submicron calcite powder, caCO 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand.
Optionally, the submicron calcite powder has a particle size ranging from 20 to 200nm.
Optionally, the step of tableting and sintering the sub-micron calcite powder to obtain a sub-micron calcite sample comprises:
loading submicron calcite powder into a press mold, pressurizing to a set pressure, and tabletting to obtain submicron calcite powder tablets;
and placing the submicron calcite powder sheet into a crucible, then placing the crucible into a muffle furnace, heating to a preset temperature, and carrying out heat preservation sintering to obtain a submicron calcite sample.
Optionally, in the step of loading the submicron calcite powder into a press die, pressurizing to a set pressure, and tabletting to obtain the submicron calcite powder tablet, the set pressure is 6-12 MPa.
Optionally, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace, heated to a preset temperature under normal pressure, and sintered under heat preservation to obtain a submicron calcite sample, wherein the crucible is made of ceramic, alumina or zirconia.
Optionally, the crucible is made of ceramic, and the mass fraction of the ceramic is not less than 99%; alternatively, the first and second electrodes may be,
the crucible is made of alumina, and the mass fraction of the alumina is not less than 99%; alternatively, the first and second electrodes may be,
the crucible is made of zirconia, and the mass fraction of the zirconia is not less than 99%.
Optionally, in the step of placing the submicron calcite powder sheet in a crucible, then placing the crucible in a muffle furnace, heating to a preset temperature, and performing heat preservation and sintering to obtain a submicron calcite sample, the heating rate is 1-3 ℃/min when the submicron calcite sample is heated to the preset temperature.
Optionally, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace to be heated to a preset temperature, and subjected to heat preservation and sintering to obtain a submicron calcite sample, wherein the preset temperature is 350-500 ℃.
Optionally, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace, heated to a preset temperature, and subjected to heat preservation and sintering, and in the step of obtaining the submicron calcite sample, the heat preservation and sintering time is 2-8 h.
The invention also provides a method for detecting the carbon isotope in the sample to be detected, which comprises the following steps:
providing a submicron calcite sample target, taking the submicron calcite sample target as a standard sample, and determining the content of carbon isotopes in the sample to be detected by using a laser ablation plasma mass spectrometry. The preparation method of the submicron calcite sample target comprises the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample;
embedding the submicron calcite sample target into epoxy resin to obtain a submicron calcite sample target;
wherein CaCO is present in the submicron calcite powder 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand.
The invention provides a preparation method of a submicron calcite sample target, which comprises the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample; embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target; wherein, in the submicron calcite powder, caCO 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand. The submicron calcite sample target prepared by the invention does not need to introduce a binder, has a compact structure, is not easy to oxidize, can be stored for a long time, has small isotope analysis error, and can meet the analysis requirements of high precision and high accuracy.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
Figure 1 is an X-ray diffraction pattern of a sub-micron calcite sample target prepared according to example 1 of the present invention;
figure 2 is an X-ray diffraction pattern of a sub-micron calcite sample target prepared according to comparative example 1 of the present invention;
figure 3 is a scanning electron micrograph of a submicron calcite sample target prepared according to example 1 of the present invention;
figure 4 is a graph of carbon isotope homogeneity analysis of a sub-micron calcite sample target prepared in example 1 of the present invention;
figure 5 is a graph of carbon isotope homogeneity analysis of sub-micron calcite sample targets prepared in example 2 of the present invention;
figure 6 is a graph of carbon isotope homogeneity analysis for sub-micron calcite sample targets prepared in example 3 of the present invention.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. In addition, the meaning of "and/or" appearing throughout includes three juxtapositions, exemplified by "A and/or B" including either A or B or both A and B. In addition, technical solutions between the various embodiments may be combined with each other, but must be based on the realization of the capability of a person skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination should not be considered to exist, and is not within the protection scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The laser multi-receiving inductively coupled plasma mass spectrometry (LA-MC-ICP-MS) is one of important means for in-situ isotope analysis in mineral micro-areas, has the advantages of high spatial resolution, small sample consumption, low pollution risk, high speed, economy and the like, and can directly obtain carbon isotope information on the scale of the mineral micro-areas. However, LA-MC-ICP-MS analysis usually requires matrix-matched standard samples. And the isotope composition of the standard sample needs to be highly uniform, so that a high-precision carbon isotope analysis result of the sample can be obtained. The lack of calcite standard samples with highly uniform carbon isotope compositions at present limits the rapid development and wide application of the method. There are more international standards for the GS-IRMS analysis of the carbon isotope of calcite, however these standards are powder samples, which are not suitable for direct use in laser analysis, and the powders that have developed into standards are generally more expensive and partly not commercially available, which are not suitable for mass production of micro-area analysis standards.
Traditionally, the method for preparing a powder sample into a solid standard sample target is a powder tabletting method, which is the most convenient, efficient and rapid method and is the most common sample pretreatment technology which is developed at the earliest. However, the powder tabletting method for preparing the standard sample directly compresses the powder sample into tablets, and the sample target is easy to loosen and oxidize and cannot be stored for a long time. In addition, in the laser ablation process, the beam spot, the energy and the frequency of the laser have great influence on the carbon isotope analysis, so that the carbon isotope analysis error is large, and the analysis requirements of high precision and high accuracy cannot be met. For powder samples with the particle size of micron order or above, the pressed powder tablets generally need to be granulated by introducing binders such as polyvinyl alcohol, and the like, otherwise, complete blanks cannot be obtained; the introduction of polyvinyl alcohol is easy to cause the pollution of carbon isotopes. The submicron calcite has the characteristics of fine granularity and strong interparticle cohesiveness, and can be directly used for pressing green bodies. In view of this, the invention provides a method for preparing a sub-micron calcite sample target. The submicron calcite sample target prepared by the invention does not need to introduce a binder, has a compact structure, is not easy to oxidize, can be stored for a long time, has small isotope analysis error, and can meet the analysis requirements of high precision and high accuracy.
The preparation method of the submicron calcite sample target provided by the invention comprises the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample;
embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target;
wherein, in the submicron calcite powder, caCO 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand.
The submicron calcite sample target prepared by the invention does not need to introduce a binder, has a compact structure, is not easy to oxidize, can be stored for a long time, has small isotope analysis error, and can meet the analysis requirements of high precision and high accuracy.
Specifically, submicron calcite powder was randomly divided into 3 parts, quantitatively weighed from each part, carbon isotope-valued the powder using conventional GS-IRMS, and the carbon isotope composition homogeneity of the powder was examined.
Specifically, the particle size of the submicron calcite powder is 20-200 nm. The submicron calcite with the particle size of 20-200 nm has better granularity and interparticle cohesiveness, can be directly used for pressing green bodies, and avoids using a binder.
Further, the step of tableting and sintering the submicron calcite powder to obtain a submicron calcite sample comprises:
loading the submicron calcite powder into a press mold, pressurizing to a set pressure, and tabletting to obtain a submicron calcite powder tablet;
and placing the submicron calcite powder sheet into a crucible, then placing the crucible into a muffle furnace, heating to a preset temperature, and carrying out heat preservation sintering to obtain a submicron calcite sample.
Further, in the step of loading the submicron calcite powder into a press die, pressurizing to a set pressure and tabletting to obtain submicron calcite powder tablets, the set pressure is 6-12 MPa. The set pressure of 6-12 MPa can ensure that the calcite powder tablet is not easy to loosen and has compact structure.
Further, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace, heated to a preset temperature under normal pressure, and subjected to heat preservation and sintering to obtain a submicron calcite sample, wherein the crucible is made of ceramics, aluminum oxide or zirconium oxide. The crucible is made of ceramic, alumina or zirconia, so that the sample can be prevented from being polluted in the sintering process.
Further, the crucible is made of ceramic, and the mass fraction of the ceramic is not less than 99%; or the crucible is made of alumina, and the mass fraction of the alumina is not less than 99%; or the crucible is made of zirconia, and the mass fraction of the zirconia is not less than 99%. The higher the mass fraction of the crucible material, the better the stability, and the less the pollution to the submicron calcite powder pieces.
Further, in the step of placing the submicron calcite powder sheet in a crucible, then placing the crucible in a muffle furnace, heating the crucible to a preset temperature, and performing heat preservation and sintering to obtain the submicron calcite sample target, the heating rate is 1-3 ℃/min when the sample target is heated to the preset temperature. The heating rate is 1-3 ℃/min, so that the heating time is long enough, the submicron calcite powder sheet is heated more uniformly inside and outside in the sintering process, and the final submicron calcite sample target is more uniform.
Further, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace, heated to a preset temperature, and subjected to heat preservation and sintering to obtain the submicron calcite sample target, wherein the preset temperature is 350-500 ℃. The preset temperature is 350-500 ℃, so that not only can a compact submicron calcite sample be obtained, but also the use influence caused by the phase change of the submicron calcite sample due to overhigh temperature can be avoided.
Further, the submicron calcite powder sheet is placed in a crucible, then placed in a muffle furnace, heated to a preset temperature, and subjected to heat preservation and sintering, so that a submicron calcite sample is obtained, wherein the heat preservation and sintering time is 2-8 hours. The sintering time is 2-8 h, so that a compact and uniform submicron calcite sample can be sintered, and the waste of energy for too long time and the influence on the use due to the phase change of the submicron calcite sample can be avoided.
In the invention, the normal pressure sintering method is adopted, the uniformity and stability of the sample are improved to the maximum extent under the condition of keeping the properties of the sample, the sample is easy to store, the analysis error of carbon isotopes caused by the loosening of the sample in the laser ablation process is reduced, the uniformity of the carbon isotopes is ensured, and the uniformity of the carbon isotopes is within 0.20 thousandth (2 SD).
The invention also provides a method for detecting the carbon isotope in the sample to be detected, which comprises the following steps:
providing a submicron calcite sample target, taking the submicron calcite sample target as a standard sample, and determining the content of carbon isotopes in the sample to be detected by using a laser ablation plasma mass spectrometry. The method for detecting the carbon isotope in the sample to be detected comprises all technical schemes of the submicron calcite sample target, so that all beneficial effects brought by the technical schemes are also achieved, and the detailed description is omitted.
The technical solutions of the present invention are further described in detail below with reference to specific examples and drawings, it should be understood that the following examples are merely illustrative of the present invention and are not intended to limit the present invention.
Example 1
A method for preparing a sub-micron calcite sample target, comprising the steps of:
the particle diameter is 50nm and CaCO 3 The submicron calcite powder with the standard deviation of 0.5 percent which is two times of the content percentage and the standard deviation of 0.16 per mill which is two times of the content percentage of the carbon isotope is filled into a press mold, and is pressed to 8MPa and then is tableted to obtain submicron calcite powder tablets;
placing the submicron calcite powder sheet into a ceramic crucible with the mass fraction of 99.5%, then placing the ceramic crucible into a muffle furnace, heating to 450 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation sintering for 4 hours to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Example 2
A preparation method of a submicron calcite sample target comprises the following steps:
2, 20nm of particle size, caCO 3 The submicron calcite powder with the standard deviation of 0.8 percent which is two times of the content percentage and the standard deviation of 0.15 per thousand which is two times of the content percentage of the carbon isotope is put into a press die and pressed into tablets after being pressurized to 6MPa, so that submicron calcite powder tablets are obtained;
placing the submicron calcite powder sheet into an alumina crucible with the mass fraction not less than 99.6%, then placing the alumina crucible into a muffle furnace, heating to 300 ℃ at the heating rate of 1 ℃/min, and carrying out heat preservation sintering for 8 hours to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Example 3
A method for preparing a sub-micron calcite sample target, comprising the steps of:
the particle diameter is 200nm 3 The submicron calcite powder with the standard deviation of 0.9 percent and the standard deviation of 0.19 per thousand which is two times of the content percentage of the carbon isotope is filled into a press mold, and is pressed to 12MPa and then is tabletted to obtain submicron calcite powder tablets;
placing the submicron calcite powder sheet into a zirconia crucible with the mass fraction of 99.5%, then placing the zirconia crucible into a muffle furnace, heating to 500 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 2h to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Example 4
A method for preparing a sub-micron calcite sample target, comprising the steps of:
the grain diameter is 130nm, caCO 3 The submicron calcite powder with the standard deviation of 0.8 percent which is two times of the content percentage and the standard deviation of 0.19 per thousand which is two times of the content percentage of the carbon isotope is put into a press mold, and is pressed to 10MPa and then is tableted to obtain submicron calcite powder tablets;
placing the submicron calcite powder sheet into a ceramic crucible with the mass fraction of 99%, then placing the ceramic crucible into a muffle furnace, heating to 400 ℃ at the heating rate of 1 ℃/min, and carrying out heat preservation sintering for 8 hours to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Example 5
A preparation method of a submicron calcite sample target comprises the following steps:
the grain diameter is 180nm 3 The standard deviation of two times of the content percentage is 0.9 percent, and the carbon isotope groupFilling the formed submicron calcite powder with the two-fold standard deviation of 0.16 per mill into a press mold, pressurizing to 9MPa, and tabletting to obtain submicron calcite powder tablets;
placing the submicron calcite powder sheet into an alumina crucible with the mass fraction of 99%, then placing the alumina crucible into a muffle furnace, heating to 370 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation sintering for 2h to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Example 6
A method for preparing a sub-micron calcite sample target, comprising the steps of:
the grain diameter is 120nm, caCO 3 The submicron calcite powder with the standard deviation of 0.7 percent which is two times of the content percentage and the standard deviation of 0.16 per thousand which is two times of the content percentage of the carbon isotope is put into a press die and pressed into tablets after being pressurized to 8MPa, so that submicron calcite powder tablets are obtained;
placing the submicron calcite powder sheet into a zirconia crucible with the mass fraction of 99%, then placing the zirconia crucible into a muffle furnace, heating to 480 ℃ at the heating rate of 2 ℃/min, and carrying out heat preservation sintering for 7 hours to obtain a submicron calcite sample;
and embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target.
Comparative example 1
Comparative example 1 is the same as example 1 except that the calcite particle size was 500nm as compared to example 1.
Comparative example 1 the particle size of calcite was too large, the caking was not tight during tabletting, and the sample was loose during sintering.
Comparative example 2
Comparative example 2 is the same as example 1 except that the temperature increase rate was 10 ℃/min, compared to example 1.
In comparative example 2, the sample was not uniform during sintering and had poor denseness due to too high temperature rise rate.
Comparative example 3
Comparative example 3 is the same as example 1 except that the sintering temperature is 800 c, compared with example 1.
In the comparative example 3, the phase of the sample is changed during sintering due to the over-high sintering temperature, which affects the use.
Comparative example 4
Comparative example 4 is the same as example 1 except that the sintering temperature and time was 15 hours, compared with example 1.
In the comparative example 4, the sample is subjected to phase change during sintering due to the overlong sintering time, so that the use is influenced.
Comparative example 5
Comparative example 5 is the same as example 1 except that it is not sintered, compared with example 1.
Comparative example 5 is not sintered, and thus the sample is not easy to store, is easy to loosen, is easy to oxidize, and affects the use.
Comparative example 6
Comparative example 6 comparison with example 1, with the exception of CaCO in submicron calcite powders 3 The same procedure as in example 1 was repeated except that the standard deviation of the content percentage was 2%.
Comparative example 6 due to CaCO in submicron Calcite powder 3 The two-fold standard deviation of the percentage content is greater than 1%, resulting in non-uniformity of the chemical composition of the micro-domains of the sintered sheet.
Comparative example 7
Comparative example 7 is the same as example 1 except that the standard deviation of two times of the carbon isotope composition in the submicron calcite powder is 0.5 ‰ compared to example 1.
Comparative example 7 resulted in poor homogeneity of carbon isotopes in the micro-regions of the sintered sheet due to non-uniformity (two times greater than 0.2% standard deviation) in the carbon isotope composition of the initial submicron calcite powder.
Test methods and results
X-ray diffraction pattern
X-ray diffraction was performed on the sub-micron calcite sample target prepared in example 1 of the present invention, and figure 1 is an X-ray diffraction pattern of the sub-micron calcite sample target prepared in example 1. Figure 2 is an X-ray diffraction pattern of the sub-micron calcite sample target prepared in comparative example 1.
As can be seen from fig. 1 and 2, the particle size of calcite affects the compactness of the sample. The smaller the particle size of calcite is, the more compact the structure of the prepared sintered tablet, and the better signal-to-noise ratio is obtained in the X-ray diffraction analysis, as shown in figure 1; the larger the particle size of calcite, the looser the structure of the sintered sheet prepared, so the signal-to-noise ratio of X-ray diffraction analysis is somewhat poor, as shown in fig. 2.
Scanning electron microscope
Electron microscopy scanning of the sub-micron calcite sample targets prepared in example 1 of the present invention is performed, and figure 3 is a scanning electron microscopy image of the sub-micron calcite sample targets prepared in example 1.
As can be seen from FIG. 3, the target density of the submicron sample prepared by the method is better.
Carbon isotope homogeneity analysis
Carbon isotope homogeneity analyses were performed on the sub-micron calcite sample targets prepared in examples 1 to 3 of the present invention, fig. 4 is a graph showing a carbon isotope homogeneity analysis of the sub-micron calcite sample target prepared in example 1 of the present invention, fig. 5 is a graph showing a carbon isotope homogeneity analysis of the sub-micron calcite sample target prepared in example 2 of the present invention, and fig. 6 is a graph showing a carbon isotope homogeneity analysis of the sub-micron calcite sample target prepared in example 3 of the present invention.
As can be seen from fig. 4-6, the standard deviation of two times of the carbon isotope composition of the sub-micron calcite sample targets prepared in examples 1-3 of the present invention is less than 0.2%, and the uniformity is good. The powder granularity is within 200nm, the prepared powder sintered sheet has good compactness, and the granularity is fine enough, so that the granularity effect is eliminated, and the carbon isotope of the sample is homogenized.
LA-ICP-MS analysis
The sub-micron calcite sample targets prepared in examples 1-6 and comparative examples 1-5 of the present invention were subjected to LA-ICP-MS analysis, and table 1 is a LA-ICP-MS analysis plot of the sub-micron calcite sample targets prepared in examples 1-6 and comparative examples 1-5 of the present invention.
TABLE 1 results of analysis of submicron calcite samples on target LA-ICP-MS
As can be seen from Table 1, caCO of submicron calcite sample targets prepared in accordance with examples 1-6 of the invention 3 The standard deviation of two times of the percentage of the content is less than 1 percent, while the comparative examples 1, 2 and 5 have poor compactness of the sample due to large powder granularity, over-high temperature rise speed, no sintering and the like, influence the laser ablation performance, and cause poor precision of in-situ micro-area chemical composition analysis, and the comparative examples 3 and 4 have obvious matrix effect in analysis due to over-high sintering temperature and over-long heat preservation time and phase change. While the initial powder of comparative examples 6 and 7 had non-uniform chemical composition and carbon isotope resulting in poor homogeneity of the micro-domains of the final sintered sheet.
In summary, the invention provides a preparation method of a submicron calcite sample target, which comprises the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample;
embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target;
wherein CaCO is present in the submicron calcite powder 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand.
The submicron calcite sample target prepared by the invention does not need to introduce a binder, has a compact structure, is not easy to oxidize, can be stored for a long time, has small isotope analysis error, and can meet the analysis requirements of high precision and high accuracy.
The above is only a preferred embodiment of the present invention, and it is not intended to limit the scope of the invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall be included in the scope of the present invention.
Claims (10)
1. The preparation method of the submicron calcite sample target is characterized by comprising the following steps:
tabletting and sintering the submicron calcite powder to obtain a submicron calcite sample;
embedding the submicron calcite sample into epoxy resin to obtain a submicron calcite sample target;
wherein, in the submicron calcite powder, caCO 3 The standard deviation of two times of the content percentage is less than 1 percent, and the standard deviation of two times of the carbon isotope composition is less than 0.20 per thousand.
2. The method of making a sub-micron calcite sample target of claim 1, wherein the sub-micron calcite powder has a particle size of 20 to 200nm.
3. The method of making a sub-micron calcite sample target of claim 1, wherein the step of tableting and sintering the sub-micron calcite powder to obtain a sub-micron calcite sample comprises:
loading the submicron calcite powder into a press mold, pressurizing to a set pressure, and tabletting to obtain a submicron calcite powder tablet;
and placing the submicron calcite powder sheet into a crucible, then placing the crucible into a muffle furnace, heating to a preset temperature, and carrying out heat preservation sintering to obtain a submicron calcite sample.
4. The method of preparing a sub-micron calcite sample target according to claim 3, wherein in the step of loading the sub-micron calcite powder into a press mold, pressing to a set pressure, and tabletting to obtain sub-micron calcite powder tablets,
the set pressure is 6-12 MPa.
5. The method for preparing the submicron calcite sample target according to claim 3, wherein the submicron calcite powder piece is placed in a crucible, then placed in a muffle furnace, heated to a predetermined temperature under normal pressure, and sintered under heat to obtain the submicron calcite sample,
the crucible is made of ceramics, aluminum oxide or zirconium oxide.
6. The method for preparing the submicron calcite sample target according to claim 5, wherein the crucible is made of ceramic, and the mass fraction of the ceramic is not less than 99%; alternatively, the first and second electrodes may be,
the crucible is made of alumina, and the mass fraction of the alumina is not less than 99%; alternatively, the first and second liquid crystal display panels may be,
the crucible is made of zirconia, and the mass fraction of the zirconia is not less than 99%.
7. The method of preparing a sub-micron calcite sample target according to claim 3, wherein in the step of placing the sub-micron calcite powder sheet in a crucible, then placing the crucible in a muffle furnace to heat to a predetermined temperature and sintering at a constant temperature to obtain the sub-micron calcite sample,
when the temperature is heated to the preset temperature, the heating rate is 1-3 ℃/min.
8. The method of preparing a sub-micron calcite sample target according to claim 3, wherein in the step of placing the sub-micron calcite powder tablet in a crucible, then placing the crucible in a muffle furnace to heat to a predetermined temperature and sintering at a constant temperature to obtain the sub-micron calcite sample target,
the preset temperature is 350-500 ℃.
9. The method of preparing a sub-micron calcite sample target of claim 3, wherein in the step of placing the sub-micron calcite powder tablet in a crucible, then in a muffle furnace to heat to a pre-determined temperature and sinter at an elevated temperature to obtain a sub-micron calcite sample,
the time of heat preservation and sintering is 2-8 h.
10. A method for detecting carbon isotopes in a sample to be detected is characterized by comprising the following steps:
providing a sub-micron calcite sample target produced by the method of making a sub-micron calcite sample target according to any of claims 1-9;
and determining the content of the carbon isotope in the sample to be detected by using the submicron calcite sample target as a standard sample through a laser ablation plasma mass spectrometry.
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| CN103471890A (en) * | 2013-09-16 | 2013-12-25 | 中国科学院上海硅酸盐研究所 | Pretreatment method for silicon carbide powder sample to be tested by using laser ablation inductively coupled plasma mass spectrometry |
| CN110806405A (en) * | 2019-10-16 | 2020-02-18 | 中国地质大学（武汉） | Method for determining hydrothermal activity age of carbonate reservoir |
| CN111007141A (en) * | 2019-12-04 | 2020-04-14 | 中国石油天然气股份有限公司 | Calcite mineral laser uranium-lead isotope dating process |
| CN111487097A (en) * | 2020-03-24 | 2020-08-04 | 上海材料研究所 | Method for preparing high-performance blocky standard sample blank by using powder as raw material |
| CN113624830A (en) * | 2021-08-04 | 2021-11-09 | 中国科学院地质与地球物理研究所 | In-situ micro-area calcite U-Pb dating method |
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| CN103471890A (en) * | 2013-09-16 | 2013-12-25 | 中国科学院上海硅酸盐研究所 | Pretreatment method for silicon carbide powder sample to be tested by using laser ablation inductively coupled plasma mass spectrometry |
| CN110806405A (en) * | 2019-10-16 | 2020-02-18 | 中国地质大学（武汉） | Method for determining hydrothermal activity age of carbonate reservoir |
| CN111007141A (en) * | 2019-12-04 | 2020-04-14 | 中国石油天然气股份有限公司 | Calcite mineral laser uranium-lead isotope dating process |
| CN111487097A (en) * | 2020-03-24 | 2020-08-04 | 上海材料研究所 | Method for preparing high-performance blocky standard sample blank by using powder as raw material |
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