CN115561053B - Preparation method of standard sample composed of massive hematite iron isotopes - Google Patents
Preparation method of standard sample composed of massive hematite iron isotopes Download PDFInfo
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- CN115561053B CN115561053B CN202211252341.9A CN202211252341A CN115561053B CN 115561053 B CN115561053 B CN 115561053B CN 202211252341 A CN202211252341 A CN 202211252341A CN 115561053 B CN115561053 B CN 115561053B
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 179
- 229910052595 hematite Inorganic materials 0.000 title claims abstract description 117
- 239000011019 hematite Substances 0.000 title claims abstract description 117
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000843 powder Substances 0.000 claims abstract description 53
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000000203 mixture Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000010439 graphite Substances 0.000 claims abstract description 29
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 29
- 238000004458 analytical method Methods 0.000 claims abstract description 27
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 34
- 238000002490 spark plasma sintering Methods 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 14
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 3
- 238000000608 laser ablation Methods 0.000 abstract description 19
- 238000001819 mass spectrum Methods 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 15
- 238000000918 plasma mass spectrometry Methods 0.000 description 13
- 239000002994 raw material Substances 0.000 description 10
- 229910052500 inorganic mineral Inorganic materials 0.000 description 9
- 239000011707 mineral Substances 0.000 description 9
- 235000010755 mineral Nutrition 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000011049 filling Methods 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001391944 Commicarpus scandens Species 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000006399 behavior Effects 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 230000001089 mineralizing effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052598 goethite Inorganic materials 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- AEIXRCIKZIZYPM-UHFFFAOYSA-M hydroxy(oxo)iron Chemical compound [O][Fe]O AEIXRCIKZIZYPM-UHFFFAOYSA-M 0.000 description 1
- 239000010423 industrial mineral Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000001948 isotopic labelling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002366 mineral element Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910021646 siderite Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
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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
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- 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
- G01N27/626—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 using heat to ionise a gas
- G01N27/628—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 using heat to ionise a gas and a beam of energy, e.g. laser enhanced ionisation
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- Biochemistry (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
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Abstract
The invention discloses a preparation method of a standard sample composed of massive hematite iron isotopes, which comprises the following preparation steps: weighing hematite powder in a graphite die of a discharge plasma sintering instrument, and then placing the hematite powder in the discharge plasma sintering instrument along with the die; and pressurizing and heating the plasma sintering instrument with the hematite powder to a preset temperature, and then preserving heat, so as to sinter the hematite powder and obtain a standard sample composed of massive hematite iron isotopes. The iron isotope composition of the prepared hematite standard sample is uniform, easy to store and block, and is suitable for the standard sample for laser ablation plasma mass spectrum micro-region in-situ iron isotope composition analysis.
Description
Technical Field
The invention relates to the technical field of stable isotope analysis of metal in a micro-region in-situ rock mine, in particular to a preparation method of a standard sample composed of massive hematite and iron isotopes.
Background
Iron is the most abundant valence-changing element on earth, is assigned to various rock, mineral, fluid and organism species in different valence states (0, +2, +3), and is widely involved in various geochemical and biochemical processes. The mineral is an important mineral element, and main industrial minerals comprise magnetite, hematite, limonite, goethite, siderite, iron-bearing green mud stone and the like, and are one of the elements which are important in the study of ore beds; it is an element closely related to vital activity, and distribution in nature has important influence on biological activity; therefore, the research of iron isotope composition has important potential in the aspects of trace mineral formation effect, biological evolution and the like.
Many significant advances in modern ore-bed technology have been associated with the use of stable isotope labeling techniques. However, in terms of metal deposit mineralization, the conventional H, C, O, S stable isotopes are indirect to the trace of the mineral sources and the concentration process, and the main research object is mineralizer elements instead of mineralizer elements, so that the research still has certain inferentiality and uncertainty. With the development of isotope testing technology and the remarkable improvement of testing accuracy in recent years, it is possible to directly trace the mineralization of iron using an iron isotope, and more research examples also show that the research results obtained using a mineralizing element (iron element) per se are more deterministic than those obtained by indirect mineralizing elements.
The laser ablation plasma mass spectrum is one of important means for in-situ isotope composition analysis of a mineral micro-region, has the advantages of high spatial resolution, less sample consumption, low pollution risk, rapidness, economy and the like, and can acquire isotope information on a mineral micro-scale. However, since the laser ablation plasma mass spectrometry analysis of isotopes is a relative method, i.e. analysis is performed by comparing the ratio of isotopes in the sample to be tested and the standard sample, the lack of a solid standard sample with uniform iron isotopes directly limits the wide application of the laser ablation plasma mass spectrometry micro-region in-situ iron isotope composition analysis method. Currently, there is still an international lack of iron oxide solid standard samples.
The standard sample for laser ablation plasma mass spectrum isotope composition analysis is prepared, natural minerals can be selected from the nature to be crushed into small samples, the small samples are embedded in resin, and the finished product is prepared through uniformity inspection and analysis of a customized value after polishing. However, in nature, mineral components are complex and various, uniformity and consistency are generally poor, the sample quantity which meets the requirement and has uniform components is extremely small, the sample quantity is often not found, and long-term and wide popularization and use cannot be realized.
Conventionally, a method for preparing a solid standard sample with relatively uniform components for micro-area analysis is a powder tabletting method, wherein a powder sample is directly pressed into tablets, and the method is simple, convenient, efficient and quick, but the sample has low hardness, loose internal structure and easy breakage, has a physical property far away from that of a natural sample, is easy to absorb moisture and cannot be stored for a long time, and when the method is used for laser ablation plasma mass spectrum micro-area in-situ iron isotope composition analysis, the standard sample and the natural sample show completely different laser ablation behaviors and iron isotope fractionation behaviors, so that iron isotope analysis errors are large, and the iron isotope composition analysis requirements of high precision and high accuracy cannot be realized.
The melting method is also a commonly used method for preparing a solid standard sample, but is mainly used for element content analysis, and because the melted raw material substances are difficult to ensure that the internal temperature and the external temperature are completely consistent in the cooling solidification process, the solidification time of each region is different, the iron isotopes are obviously fractionated, and therefore, the samples with uniform iron isotopes are difficult to obtain.
In summary, the preparation of the solid standard sample suitable for the micro-region in-situ iron isotope composition analysis in the prior art mainly faces the problems of non-uniform iron isotope composition, large deviation from a natural sample matrix, difficulty in long-term use and the like.
Disclosure of Invention
The invention mainly aims to provide a preparation method of a standard sample composed of massive hematite iron isotopes, and aims to prepare a standard sample which is uniform in iron isotopes, can be washed and polished, can be used for a long time, is in a massive shape and is suitable for laser ablation plasma mass spectrometry iron isotope composition analysis.
In order to achieve the above purpose, the preparation method of the standard sample composed of the massive hematite iron isotopes provided by the invention comprises the following preparation steps:
Obtaining hematite powder;
and sintering the hematite powder in a spark plasma sintering mode to obtain a hematite standard sample.
Optionally, the pressure of the spark plasma sintering is 20-40 MPa.
Optionally, the temperature of the spark plasma sintering is 600-800 ℃.
Optionally, the spark plasma sintering time is 4-6 min.
Optionally, sintering the hematite powder by means of spark plasma sintering to obtain a massive hematite iron isotope composition standard sample, which comprises the following steps: weighing the hematite powder, placing the hematite powder in a graphite mold, and placing the mold in a discharge plasma sintering instrument; and pressurizing the plasma sintering instrument in which the hematite powder is placed, heating to a spark plasma sintering temperature, and then preserving heat to sinter the hematite powder, so as to obtain a hematite standard sample.
Optionally, pressurizing the plasma sintering instrument with the hematite powder placed therein, heating to a preset temperature, and then preserving heat to sinter the hematite powder, thereby obtaining a hematite standard sample; the heating operation steps are as follows: heating to 200-400 ℃ at a heating rate of 90-110 ℃/min, then preserving heat, and heating to the temperature of spark plasma sintering at a heating rate of 100-300 ℃/min.
Optionally, in the heating operation step, the heat preservation time is 0.5-2 min .
Optionally, sintering the hematite powder by means of spark plasma sintering to obtain a standard sample composed of massive hematite iron isotopes, wherein the phase component of the standard sample composed of massive hematite iron isotopes is alpha-Fe 2O3.
Optionally sintering the hematite powder by means of spark plasma sintering, wherein in the step of obtaining the nanoscale hematite standard sample, the particle size of the hematite powder is 30 nm-1 mu m
In addition, the invention also provides an application of the standard sample composed of the massive hematite iron isotopes, which comprises the following steps:
obtaining the massive hematite iron isotope composition standard sample, wherein the massive hematite iron isotope composition standard sample is prepared by the preparation method of the massive hematite iron isotope composition standard sample according to any one of claims 1 to 9, and the prepared massive hematite iron isotope composition standard sample is applied to micro-area in-situ iron isotope composition analysis.
According to the technical scheme, nano-scale hematite powder is selected and subjected to spark plasma sintering by a spark plasma sintering method, and finally, a hematite standard sample which can be used for laser ablation plasma mass spectrometry iron isotope composition analysis is obtained, the hematite standard sample has good compactness, high mechanical strength, vickers hardness value of more than 600HV, hardness similar to that of stainless steel, good stability and easy preservation, uniform iron isotope composition, delta 56 Fe 2-fold standard deviation (2 SD) of less than 0.1 per mill, can be directly applied to high-precision analysis of iron isotope composition by a hematite laser ablation plasma mass spectrometry, and compared with a sample prepared by a powder press cake method, the standard sample obtained by the method has good compactness, high mechanical strength, can be washed and polished, is not easy to absorb moisture, is convenient to store, and meets the long-term use requirement of a laboratory.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to the structures shown in these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction pattern of the standard sample composed of the massive hematite iron isotopes prepared in examples 1 to 5 and the massive hematite iron isotopes prepared in comparative examples 1 to 3 provided by the present invention;
FIG. 2 is a scanning electron microscope image of the product of the standard sample composed of the bulk hematite iron isotopes prepared in example 4 provided by the present invention;
Fig. 3 shows the results of in-situ iron isotope analysis of the micro-regions of standard samples composed of the massive hematite iron isotopes prepared in examples 1 to 5 provided by the present invention.
The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention. In addition, the meaning of "and/or" as it appears throughout includes three parallel schemes, for example "A and/or B", including the A scheme, or the B scheme, or the scheme where A and B are satisfied simultaneously. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be regarded as not exist and not within the protection scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Conventionally, there are two methods for preparing a solid standard sample with relatively uniform components for micro-area analysis, namely, a powder tabletting method, wherein the powder sample is directly pressed into tablets, and the method is simple, convenient, efficient and quick, but the sample has low hardness, loose internal structure, easy breaking, physical properties far away from a natural sample, easy moisture absorption, no water washing and polishing and difficult long-term storage.
The other method is a melting method, and is also a commonly used method for preparing a solid standard sample, but is mainly used for element content analysis, and because the melted standard substance is difficult to ensure that the internal temperature and the external temperature are completely consistent in the cooling and solidifying process, the solidifying time of each region is further different, the iron isotope is obviously fractionated, and the sample with uniform iron isotope composition is difficult to obtain.
While the laser ablation plasma mass spectrometry is one of important means of in-situ isotope analysis of the mineral micro-regions, the laser ablation plasma mass spectrometry has the advantages of high spatial resolution, less sample consumption, low pollution risk, rapidness, economy and the like, and can acquire isotope information on the scale of the mineral micro-regions. However, since laser ablation plasma mass spectrometry is a relative method for analyzing isotopes by comparing the ratio of isotopes in a sample to be tested to that in a standard sample, the lack of a solid standard sample with uniform iron isotopes directly limits the wide application of laser ablation plasma mass spectrometry micro-region in-situ iron isotope analysis methods. Currently, there is still an international lack of iron oxide solid standard samples.
In view of the above, the invention provides a preparation method of a standard sample composed of massive hematite iron isotopes, and the iron isotopes in the standard sample prepared by the preparation method are uniformly distributed, have no phase change, can be directly applied to high-precision analysis of the iron isotope composition by a hematite laser ablation plasma mass spectrometry, and are simple in preparation process, easy to replicate and capable of being produced in a large scale and popularized and used. The preparation method of the hematite standard sample comprises the following steps:
s0, obtaining hematite powder. The finer the raw material particle size is, the more advantageous to improve the component uniformity of the finished product sample, and in the past, submicron or nanoscale powders may exhibit good component uniformity. In this example, the hematite powder selected was a commercially available α -Fe 2O3 powder with a particle size of 30nm and 1 μm.
S1, sintering the hematite powder in a spark plasma sintering mode to obtain a standard sample composed of massive hematite iron isotopes.
It should be noted that: spark Plasma Sintering (SPS) is a rapid novel material preparation method for directly introducing pulse current into a die and powder particle or block sample for sintering or connecting, and is also called plasma activated sintering or pulse current voltage sintering. SPS integrates plasma activation, hot pressing and resistance heating, has the advantages of uniform heating, high heating rate, low sintering temperature, short sintering time, high production efficiency and the like, can realize the surface purification effect, can inhibit the growth of crystal grains, and ensures that the product structure is uniform and controllable.
And S11, pressurizing the plasma sintering instrument with the hematite powder placed therein, heating to a temperature of spark plasma sintering, and then preserving heat to sinter the hematite powder, so as to obtain a standard sample composed of massive hematite iron isotopes.
In step S11, it should be noted that: firstly, a piece of graphite paper is filled on a graphite mold, nano-scale hematite powder is placed on the graphite paper, the graphite paper is used for separating the hematite powder from a graphite mold of a discharge plasma sintering instrument, the problem that a hematite sample is bonded with the graphite mold in the sintering experiment process can be avoided, the problem can corrode a graphite grinding tool, and the high temperature resistance of graphite materials can at least resist the high temperature of 3000 ℃ and the high pressure in an inert gas environment, so that the experiment process can be smoothly carried out.
The following should be further described: isotope fractionation refers to the effect of a system in which various isotope atoms or molecules of an element are distributed into various substances or phases in different ratios. Isotope fractionation occurs in various geochemical processes in nature due to differences in physicochemical properties (thermodynamic properties, differences in movement and reaction rates, etc.) between isotope atoms or compounds having the same number of protons and different numbers of neutrons.
Further, in the step S11, the following steps may be performed: pressurizing the plasma sintering instrument containing the hematite powder to 20-40 Mpa, heating to 200-400 ℃ at a heating rate of 90-110 ℃/min, preserving heat for 0.5-2 min, heating to the temperature of spark plasma sintering at a heating rate of 100-300 ℃/min, wherein the temperature of spark plasma sintering is 600-800 ℃ and the preserving heat time is 4-6 min, and obtaining a hematite standard sample, wherein special attention needs to be paid to: the sintering temperature range of the spark plasma is 600-800 ℃, and under the condition of the temperature range value, the prepared hematite standard sample can be directly agglomerated, but is not easy to loose, the particle surface is slightly molten, the particle surface is too low and loose and is easy to crush, the partial melting can occur when the temperature is too high, the iron isotope is easy to fractionate, the iron isotope composition is further uneven, and the standard sample can not be prepared finally.
Further, since the sample used in the spark plasma sintering process is small and has a thickness of about 1.5mm, the required holding time is not long.
Further, the heating rate of 90-110 ℃/min in the heating process is heated to 200-400 ℃, the temperature is kept for 0.5-2 min, the temperature is then increased to the temperature of the spark plasma sintering at the heating rate of 100-300 ℃/min, compared with the direct heating, the temperature of the sample to be prepared in the heating process is uniformly heated inside and outside, the compactness of the prepared standard sample is better, and the iron isotope is prevented from fractionating due to overlarge temperature difference inside and outside.
The method has the advantages that the phase of the standard sample consisting of the prepared massive hematite iron isotopes is not changed in the plasma sintering process of the hematite standard sample by adopting the spark plasma sintering method, the standard sample is still kept to be consistent with the original powder to be alpha-Fe 2O3 and is in a block shape, the Vickers hardness value is higher than 600HV and is similar to the hardness of stainless steel by a Vickers hardness detector, the stability is good, the storage is easy, the iron isotopes are uniform in composition, the 2-time standard deviation (2 SD) of delta 56 Fe is less than 0.1 per mill, the method can be directly applied to the high-precision analysis of the composition of the iron isotopes in the micro-area in situ by the hematite laser ablation plasma mass spectrometry, and the standard sample can be washed and polished and can meet the long-term use requirement of a laboratory.
The following technical solutions of the present invention will be described in further detail with reference to specific examples and drawings, and it should be understood that the following examples are only for explaining the present invention and are not intended to limit the present invention.
Example 1
(1) Hematite powder with a particle size of 30nm was purchased directly.
(2) Firstly, filling a layer of graphite paper in a graphite mould of a discharge plasma sintering instrument, weighing 0.7g of hematite powder, placing the graphite paper on the graphite paper, plugging a plug, placing the graphite paper into the discharge plasma sintering instrument, pressurizing to 20MPa, vacuumizing, firstly heating to 200 ℃ at a heating rate of 90 ℃/min, preserving heat for 0.5min, and then heating to 600 ℃ at a heating rate of 100 ℃/min, preserving heat for 4min to obtain a hematite standard sample.
Example 2
(1) Directly purchasing hematite sample raw materials with the particle size of 30 nm;
(2) Firstly, filling a layer of graphite paper in a graphite mould of a discharge plasma sintering instrument, weighing 0.7g of hematite sample raw material on the graphite paper, plugging a plug, loading into the discharge plasma sintering instrument, pressurizing to 30MPa, vacuumizing, firstly heating to 300 ℃ at a heating rate of 100 ℃/min, preserving heat for 1min, and then heating to 800 ℃ at a heating rate of 200 ℃/min, preserving heat for 5min to obtain a hematite standard sample.
Example 3
(1) Directly purchasing hematite sample raw material with the particle size of 1 mu m;
(2) Firstly, filling a layer of graphite paper in a graphite mould of a discharge plasma sintering instrument, weighing 0.7g of hematite sample raw material on the graphite paper, plugging a plug, loading into the discharge plasma sintering instrument, pressurizing to 20MPa, vacuumizing, heating to 400 ℃ at a heating rate of 110 ℃/min, preserving heat for 2min, heating to 800 ℃ at a heating rate of 300 ℃/min, and preserving heat for 5min to obtain a hematite standard sample.
Example 4
(1) Directly purchasing hematite sample raw materials with the particle size of 30 nm;
(2) Firstly, filling a layer of graphite paper in a graphite mould of a discharge plasma sintering instrument, weighing 0.7g of hematite sample raw material on the graphite paper, plugging a plug, loading into the discharge plasma sintering instrument, pressurizing to 30MPa, vacuumizing, firstly heating to 200 ℃ at a heating rate of 90 ℃/min, preserving heat for 0.5min, and then heating to 700 ℃ at a heating rate of 100 ℃/min, preserving heat for 5min to obtain a hematite standard sample.
Example 5
(1) Directly purchasing hematite sample raw materials with the particle size of 30 nm;
(2) Firstly, filling a layer of graphite paper in a graphite mould of a discharge plasma sintering instrument, weighing 0.7g of hematite sample raw material on the graphite paper, plugging a plug, placing the graphite paper into the discharge plasma sintering instrument, pressurizing to 40MPa, vacuumizing, firstly heating to 300 ℃ at a heating rate of 100 ℃/min, preserving heat for 1min, and then heating to 700 ℃ at a heating rate of 200 ℃/min, preserving heat for 6min to obtain a hematite standard sample.
Comparative example 1
And (3) heating the temperature of the final discharge plasma sintering device in the step (2) to 800 ℃, changing the temperature to 500 ℃, and keeping other conditions consistent with those of the embodiment 4.
Comparative example 2
And (3) heating the temperature of the final discharge plasma sintering device in the step (2) to 800 ℃, changing the temperature to 900 ℃, and keeping other conditions consistent with those of the embodiment 4.
Comparative example 3
The pressurizing to 30MPa in the step (2) was changed to pressurizing to 10MPa, and other conditions were kept in accordance with example 4.
Performance testing
(1) Phase test
The standard samples of the bulk hematite iron isotope composition prepared in examples 1 to 5 were subjected to phase test by X-ray diffraction (XRD), and the test results are shown in table 1 and fig. 1.
Table 1 test results
| Results of phase test | |
| Example 1 | Is consistent with the original powder and is alpha-Fe 2O3 |
| Example 2 | Is consistent with the original powder and is alpha-Fe 2O3 |
| Example 3 | Is consistent with the original powder and is alpha-Fe 2O3 |
| Example 4 | Is consistent with the original powder and is alpha-Fe 2O3 |
| Example 5 | Is consistent with the original powder and is alpha-Fe 2O3 |
From table 1 and fig. 1, it can be derived that: the standard sample composition of the bulk hematite iron isotopes prepared in examples 1 to 5 was unchanged compared to the original powder; when the sintering temperature of the comparative example 1 is too low, the overall density is low and loose, and when the sintering temperature of the comparative example 2 is too high, the particles are easy to break into small pieces, which shows that when the sintering temperature is insufficient, effective cementation cannot be formed among the particles, so that the whole is easy to break; comparative example 3 shows that the whole is easily broken into small pieces when the pressure is insufficient.
Fig. 2 shows that the standard sample is closely packed with fine round grains, showing that the sintered body is compact, and the grains are not completely fused, but fused and cemented among the grains, so that the isotope composition of the grains is not changed, and the whole sample has high mechanical strength.
(2) Hardness test
Hardness tests were performed on standard samples of the bulk hematite iron isotope composition prepared in examples 1 to 5 by a vickers hardness tester, and the test results are shown in table 2.
Table 2 test results
From table 2, it can be derived that: the standard hematite samples prepared in examples 1 to 5 have Vickers hardness values greater than 600HV, similar to stainless steel hardness and good stability.
(3) Uniformity of iron isotope composition
The iron isotope composition uniformity in the hematite standard samples prepared in examples 1 to 5 was examined by laser ablation plasma mass spectrometry at a uniform spot on the hematite standard samples, wherein uniformity was determined with a double standard deviation (2 SD), and the test results are shown in table 3:
Table 3 test results
| δ56Fe | |
| Example 1 | 0.00±0.08‰ |
| Example 2 | 0.00±0.08‰ |
| Example 3 | 0.02±0.09‰ |
| Example 4 | 0.01±0.06‰ |
| Example 5 | 0.00±0.08‰ |
As can be seen from fig. 3: the standard iron isotope composition samples of the massive hematite iron isotopes prepared in the examples 1 to 5 have uniform iron isotope composition, and the 2SD of delta 56 Fe is less than 0.1 per mill, so that the requirement of laser ablation plasma mass spectrum micro-region in-situ iron isotope quantitative analysis is met. The hematite isotopes prepared in comparative examples 1 to 3 had poor composition uniformity, and were not suitable for use as standard samples.
In conclusion, the standard sample is composed of the massive hematite iron isotopes prepared by the preparation method provided by the invention, the Vickers hardness value is more than 600HV, the standard sample is similar to the hardness of stainless steel, the stability is good, the storage is easy, the iron isotopes are uniform in composition, the standard deviation (2 SD) of delta 56 Fe which is 2 times less than 0.1 per mill, the standard sample can be directly applied to high-precision analysis of the iron isotopes by the hematite laser ablation plasma mass spectrometry, and the standard sample is suitable for being used as a sample for iron isotope test.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the scope of the present invention, but various modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the standard sample composed of the massive hematite iron isotopes is characterized by comprising the following preparation steps:
Obtaining hematite powder;
sintering the hematite powder in a spark plasma sintering mode to obtain a hematite standard sample;
wherein the temperature of the spark plasma sintering is 600-800 ℃;
sintering the hematite powder in a spark plasma sintering mode to obtain a hematite standard sample, wherein the step of sintering the hematite powder in a spark plasma sintering mode comprises the following steps of:
Weighing the hematite powder, placing the hematite powder in a graphite mold, and placing the graphite mold in a discharge plasma sintering instrument;
Pressurizing the plasma sintering instrument in which the hematite powder is placed, heating to the temperature of plasma sintering, and then preserving heat to sinter the hematite powder, so as to obtain a standard sample composed of massive hematite iron isotopes;
The step of heating includes: heating to 200-400 ℃ at a heating rate of 90-110 ℃/min, then preserving heat, and heating to the temperature of spark plasma sintering at a heating rate of 100-300 ℃/min.
2. The method for preparing a standard sample composed of massive hematite iron isotopes according to claim 1, characterized in that the pressure of spark plasma sintering is 20-40 MPa.
3. The method for preparing the standard sample composed of the massive hematite iron isotopes according to claim 1, characterized in that the spark plasma sintering time is 4-6 min.
4. The method for preparing a standard sample composed of massive hematite iron isotopes according to claim 1, characterized in that, in the heating operation, the time for heat preservation is 0.5-2 min.
5. The method for preparing the standard sample composed of the massive hematite iron isotopes according to claim 1, wherein in the step of obtaining the standard sample of hematite by sintering the hematite powder by means of spark plasma sintering, the phase component of the standard sample composed of the massive hematite iron isotopes is alpha-Fe 2O3.
6. The method for preparing a standard sample composed of massive hematite and iron isotopes according to claim 1, wherein in the step of obtaining the standard sample composed of massive hematite and iron isotopes by sintering the hematite powder by means of spark plasma sintering, the particle size of the hematite powder is 30 nm-1 μm.
7. The application of the standard sample composed of the massive hematite iron isotopes is characterized by comprising the following steps:
Obtaining the massive hematite iron isotope composition standard sample, wherein the massive hematite iron isotope composition standard sample is prepared by the preparation method of the massive hematite iron isotope composition standard sample according to any one of claims 1 to 6, and the prepared massive hematite iron isotope composition standard sample is applied to micro-area in-situ iron isotope composition analysis.
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