CN114964976A - Rare earth oxide standard sample and preparation method thereof - Google Patents
Rare earth oxide standard sample and preparation method thereof Download PDFInfo
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- CN114964976A CN114964976A CN202210913531.4A CN202210913531A CN114964976A CN 114964976 A CN114964976 A CN 114964976A CN 202210913531 A CN202210913531 A CN 202210913531A CN 114964976 A CN114964976 A CN 114964976A
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 219
- 238000002360 preparation method Methods 0.000 title abstract description 22
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 104
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 87
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000011780 sodium chloride Substances 0.000 claims abstract description 52
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 46
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 45
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims description 65
- 239000002994 raw material Substances 0.000 claims description 46
- 238000001514 detection method Methods 0.000 claims description 34
- KBLRIGLPGMRISA-UHFFFAOYSA-N neodymium(3+) oxygen(2-) praseodymium(3+) Chemical compound [O-2].[Pr+3].[Nd+3].[O-2].[O-2] KBLRIGLPGMRISA-UHFFFAOYSA-N 0.000 claims description 30
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical group [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 27
- 238000000227 grinding Methods 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 19
- 239000011573 trace mineral Substances 0.000 claims description 19
- 235000013619 trace mineral Nutrition 0.000 claims description 19
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008240 homogeneous mixture Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 37
- 150000002910 rare earth metals Chemical class 0.000 abstract description 27
- 239000003085 diluting agent Substances 0.000 abstract description 11
- -1 rare earth carbonate Chemical class 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 8
- 238000007689 inspection Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000002076 thermal analysis method Methods 0.000 description 7
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- 229910052777 Praseodymium Inorganic materials 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 3
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000003908 quality control method Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004677 hydrates Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000007619 statistical method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 239000004278 EU approved seasoning Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004164 analytical calibration Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000000192 social effect Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005303 weighing Methods 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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- 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
- G01N1/38—Diluting, dispersing or mixing samples
-
- 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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
- G01N2001/2866—Grinding or homogeneising
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention relates to the technical field of standard sample preparation, in particular to a rare earth oxide standard sample and a preparation method thereof. The rare earth oxide standard sample in the invention comprises a uniform mixture of rare earth oxide and sodium chloride; the mass percentage of the rare earth oxide in the rare earth oxide standard sample is 28% -42%, and the rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide; 0.1-15% of lanthanum oxide, 0.2-28% of cerium oxide, 0.1-8% of praseodymium oxide and 0.5-32% of neodymium oxide. By adopting sodium chloride as a diluent, the total concentration of the rare earth can be effectively reduced, the content range of a standard value is accurately controlled, the standard value of a standard sample is ensured to be consistent with the content of the total rare earth of an actual product (rare earth carbonate and rare earth chloride), and the quality of the product is further accurately controlled; and the standard sample has higher uniformity and stability.
Description
Technical Field
The invention relates to the technical field of standard sample preparation, in particular to a rare earth oxide standard sample and a preparation method thereof.
Background
Based on the standard analysis method of rare earth oxide and the social effect of the standard sample, the existing rare earth standard sample has the problem that the standard value and the proportion of the total rare earth are not greatly different from the actual products (rare earth carbonate and rare earth chloride). The standard value of the total amount of the rare earth in the rare earth oxide standard sample is prepared according to the deep development requirement of the rare earth standard in China, the calibration requirement of high-end detection equipment, the development of the rare earth industry and the analysis of international standardization requirement.
The constant value components of the existing rare earth oxide standard sample are almost all based on single rare earth oxide with higher purity, and mixed oxide products which have no binary or multi-element oxide and can control the total amount of rare earth are not available. In the process of popularizing and applying rare earth oxide standard samples, the problems of limited types, less constant value elements, incapability of covering actual products in the component content range and the like exist, and the rare earth industry urgently needs the standard samples to guide detection and production.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a rare earth oxide standard sample, which solves the technical problems that the constant-value components of the rare earth oxide standard sample in the prior art have no total rare earth value, the component content range cannot cover the actual product, and important rare earth products such as rare earth carbonate, rare earth chloride and the like cannot be used as candidates to prepare the standard sample due to unstable properties. According to the rare earth oxide standard sample, sodium chloride is used as a diluent, so that the total concentration of rare earth can be effectively reduced, the content range of a standard value is accurately controlled, and the requirements on uniformity and stability are met.
The invention also aims to provide a preparation method of the rare earth oxide standard sample, which is simple and feasible and can meet the requirement of the particle size range of the rare earth oxide by grinding and uniformly mixing the raw materials.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a rare earth oxide standard sample comprising a homogeneous mixture of rare earth oxide and sodium chloride; in the rare earth oxide standard sample, the content of the rare earth oxide is 28-42% by mass percent;
the rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide;
0.1-15% of lanthanum oxide, 0.2-28% of cerium oxide, 0.1-8% of praseodymium oxide and 0.5-32% of neodymium oxide.
In one embodiment, the particle size D10 of the rare earth oxide standard sample is 0.1-1 μm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 mu m;
the particle size D90 of the rare earth oxide standard sample is 1-8 mu m.
In one embodiment, the rare earth oxide is lanthanum cerium oxide or praseodymium neodymium oxide.
In one embodiment, the content of the lanthanum cerium oxide in the rare earth oxide standard sample is 38% -42% by mass;
the lanthanum-cerium oxide comprises the following components in percentage by mass of a rare earth oxide standard sample: 13-15% of lanthanum oxide, 24-28% of cerium oxide, 0.1-0.4% of praseodymium oxide and 0.5-1% of neodymium oxide.
In one embodiment, the mass ratio of cerium oxide to lanthanum oxide in the lanthanum-cerium oxide is 1.75-2.
In one embodiment, the mass ratio of neodymium oxide to praseodymium oxide in the lanthanum cerium oxide is 2.5-5.
In one embodiment, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28% -32% by mass;
the mass percentages of the components in the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively as follows: 0.1-0.3% of lanthanum oxide, 0.2-0.5% of cerium oxide, 6-8% of praseodymium oxide and 21-24% of neodymium oxide;
in one embodiment, in the praseodymium-neodymium oxide, a mass ratio of cerium oxide to lanthanum oxide is 1.65 to 2.
In one embodiment, in the praseodymium-neodymium oxide, the mass ratio of neodymium oxide to praseodymium oxide is 2.9-3.6.
In one embodiment, the rare earth oxide standard sample further comprises trace elements, and the content of the trace elements is 0.5-50 ppm;
the microelements comprise K, Ca, Fe, Cu and Zn.
The preparation method of the rare earth oxide standard sample comprises the following steps:
grinding a mixture of a rare earth oxide raw material and a sodium chloride raw material, and then uniformly mixing;
the rare earth oxide raw materials comprise a lanthanum oxide raw material, a cerium oxide raw material, a praseodymium oxide raw material and a neodymium oxide raw material.
In one embodiment, a method of preparing a mixture of a rare earth oxide feedstock and a sodium chloride feedstock includes: premixing the rare earth oxide raw material and a sodium chloride raw material;
and the premixing time is 2-3 h.
In one embodiment, the time of the grinding treatment is 170 to 200 seconds.
In one embodiment, the time of the blending treatment is 170-190 min.
In one embodiment, the sodium chloride feedstock is sodium chloride guaranteed to be sodium chloride.
In one embodiment, the method for preparing the rare earth oxide standard sample further comprises: and (4) carrying out uniformity detection and stability detection on the rare earth oxide standard sample.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the rare earth oxide standard sample, sodium chloride is used as a diluent, so that the total rare earth concentration can be effectively reduced, the content range of a standard value is accurately controlled, the standard value of the standard sample is consistent with the content of the total rare earth of an actual product, and the product quality is further accurately controlled; the rare earth oxide standard sample has excellent uniformity and stability.
(2) The rare earth oxide standard sample can effectively meet the quality control of production research and development, and gradually improves the standard sample series; the standard sample conforms to the strategic layout requirements of the rare earth industry, innovates the types of rare earth standard sample preparation, and plays an important role in building a new rare earth material test evaluation system, promoting the technical development of new rare earth materials, standardizing the quality of rare earth products, monitoring the detection of the rare earth products and the like.
(3) The preparation method of the rare earth oxide standard sample is simple and easy to implement, the requirements of the particle size range of the rare earth oxide are met by grinding and uniformly mixing the raw materials, and the uniformity and the stability are excellent.
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, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a flow chart of the preparation of a rare earth oxide standard sample according to one embodiment of the present invention;
FIG. 2 is a scanning electron microscope image of a standard sample of rare earth oxide in example 1 of the present invention under a condition of EHT of 3KV and magnification of 1000 times;
FIG. 3 is a scanning electron micrograph of a rare earth oxide standard sample of example 1 of the present invention at an EHT of 20KV magnified 500 times;
FIG. 4 is a scanning electron microscope image of a standard sample of rare earth oxide in example 4 of the present invention under the condition that EHT is 3KV and magnification is 1000 times;
FIG. 5 is a scanning electron micrograph of a standard sample of rare earth oxide according to example 4 of the present invention at an EHT of 20KV magnified 500 times;
FIG. 6 is a graph of the particle size distribution of mixed (lanthanum, cerium, praseodymium, neodymium) rare earth oxides;
FIG. 7 is a scanning electron micrograph of mixed (lanthanum, cerium, praseodymium, neodymium) rare earth oxides;
FIG. 8 is a graph showing a particle size distribution of a standard sample of the rare earth oxide in example 1;
FIG. 9 is a graph showing a particle size distribution of a standard sample of the rare earth oxide in example 4;
FIG. 10 is a comprehensive thermal analysis curve of mixed rare earth oxides, including thermogravimetric analysis (TG) curves and Differential Scanning Calorimetry (DSC) curves;
FIG. 11 is a thermal analysis curve, including thermogravimetric analysis (TG) curve and Differential Scanning Calorimetry (DSC) curve, of a standard sample of rare earth oxide in example 1;
FIG. 12 is a thermal analysis curve, including thermogravimetric analysis (TG) curve and Differential Scanning Calorimetry (DSC) curve, of a standard sample of rare earth oxide in example 4;
FIG. 13 is a schematic diagram of a lanthanum cerium oxide standard sample according to the present invention;
FIG. 14 is a drawing of a praseodymium-neodymium oxide standard sample according to the present invention;
FIG. 15 is a partial view of a lanthanum cerium oxide standard sample according to the present invention;
fig. 16 is a distribution diagram of a praseodymium-neodymium oxide standard sample of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. 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 commercially available.
According to one aspect of the invention, the invention relates to a rare earth oxide standard sample comprising a homogeneous mixture of a rare earth oxide and sodium chloride; in the rare earth oxide standard sample, the content of the rare earth oxide is 28-42% by mass percent;
the rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide;
in the rare earth oxide standard sample, by mass, the lanthanum oxide is 0.1-15%, the cerium oxide is 0.2-28%, the praseodymium oxide is 0.1-8%, and the neodymium oxide is 0.5-32%.
According to the rare earth oxide standard sample, sodium chloride is doped in the rare earth oxide, and the sodium chloride is used as a diluent, so that the total amount of the rare earth oxide in the rare earth oxide standard sample can be accurately controlled, and the rare earth oxide standard sample has wider applicability.
In one embodiment, the particle size D10 of the rare earth oxide standard sample is 0.1-1 μm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 mu m;
the particle size D90 of the rare earth oxide standard sample is 1-8 mu m.
In one embodiment, the particle size D10 of the rare earth oxide standard sample includes, but is not limited to, 0.2 μm, 0.35 μm, 0.47 μm, 0.5 μm, 0.63 μm, 0.75 μm, 0.88 μm, 0.96 μm, or 1 μm. In one embodiment, the particle size D50 of the rare earth oxide standard sample includes, but is not limited to, 0.5 μm, 0.86 μm, 0.9 μm, 1 μm, 1.24 μm, 1.57 μm, 1.81 μm, 2 μm, 2.24 μm, 2.55 μm, 2.73 μm, 2.9 μm, or 3 μm. In one embodiment, the particle size D90 of the rare earth oxide standard sample includes, but is not limited to, 1 μm, 1.56 μm, 1.8 μm, 2 μm, 2.54 μm, 3 μm, 3.05 μm, 3.58 μm, 4 μm, 4.25 μm, 4.8 μm, 5 μm, 5.54 μm, 6 μm, 7 μm, or 8 μm.
Further, by controlling the particle size ranges of the rare earth oxide and the sodium chloride, the rare earth oxide standard sample is ensured to have better uniformity and stability.
The diluent is based on sodium salt, respectively to Na 2 SO 4 、Na 2 CO 3 、NaHCO 3 And NaCl, and the suitability as a diluent is judged by combining the stability of the mixture of the NaCl and the rare earth oxide.
NaCl (sodium chloride), which is white crystal in appearance, has good stability, neutral melting point of 801 ℃, is industrially used for manufacturing soda ash, caustic soda and ore smelting, can be used for producing seasonings in life, and has no toxicity and high safety. Therefore, the invention selects NaCl as the diluent from the aspects of stable chemical property and no toxicity, and controls the total amount of rare earth.
Na 2 SO 4 (Sodium sulfate) is a monoclinic system, and the crystal of the monoclinic system is short columnar, colorless, transparent, neutral, easy to dissolve in water and low in toxicity. White crystals or powders in a normal state, having water absorption, easily form hydrates of 7 or 10 crystals, and have a melting point of 884 ℃. Na (Na) 2 SO 4 Although stable in nature, it is easily hydrated in humid air, and turns into powdered aqueous sodium sulfate to cover the surface, which, when mixed with rare earth oxides, reduces the stability of the standard sample.
Na 2 CO 3 (Sodium carbonate) is a white powder that is readily soluble in water, alkaline, and non-toxic. It is easily weathered in dry air, has water absorption, forms 10 crystal hydrates after absorbing water, has melting point of 851 ℃ and decomposition temperature of about 1200 ℃, and can be decomposed with CO 2 、H 2 O co-reaction to generate NaHCO 3 。Na 2 CO 3 Also due to its water absorption and CO 2 The characteristics of the reaction lead to poor stability as a rare earth oxide diluent.
NaHCO 3 (Sodium Bicarbonate) white powder or monoclinic crystalline powder, is easily soluble in water, alkaline, non-toxic, and slowly decomposes under heat or in humid air at a decomposition temperature of 270 ℃. The reaction starts at about 50 ℃ to form CO 2 All change to Na at 100 DEG C 2 CO 3 。NaHCO 3 Not only is easy to absorb water, but also has relatively low decomposition temperature, and reacts with Na 2 SO 4 And Na 2 CO 3 In contrast, it is less suitable for use as a diluent.
The particle size range and the chemical properties of the materials are key indexes for reflecting the uniformity of the standard sample, and loose and non-agglomerated powder is formed after the diluent and the rare earth oxide are mixed, so that the physical mixing of the standard sample is not influenced by the properties of the diluent and the rare earth oxide. The particle size range of each component has great influence on the uniformity of the rare earth oxide standard sample; if the particle size range of each component is wide, the standard sample has large particle difference, which easily causes the segregation of component elements; if the particle size range is small, the phenomena of agglomeration and inclusion between substances can occur, and the rare earth oxide is easily concentrated in a large area, so that the reasonable control of the particle size range of a standard sample is the key of uniformity.
In one embodiment, the rare earth oxide standard sample further comprises trace elements, and the content of the trace elements is 0.5-50 ppm; the microelements comprise K, Ca, Fe, Cu and Zn. Namely, the rare earth oxide standard sample of the invention comprises rare earth oxide, sodium chloride and trace elements.
In one embodiment, the rare earth oxide in the standard sample of rare earth oxide includes, but is not limited to, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, or 42% by mass.
In one embodiment, the content of sodium chloride in the rare earth oxide standard sample is 58-72% by mass. Sodium chloride includes, but is not limited to, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, or 71% by mass.
In one embodiment, the rare earth oxide is lanthanum cerium oxide or praseodymium neodymium oxide.
In one embodiment, the content of the lanthanum and cerium oxides in the rare earth oxide standard sample is 38-42% by mass percentage. In one embodiment, the mass percentages of the components in the lanthanum cerium oxide in the rare earth oxide standard sample are respectively as follows: 13-15% of lanthanum oxide, 24-28% of cerium oxide, 0.1-0.4% of praseodymium oxide and 0.5-1% of neodymium oxide.
In one embodiment, the content of the lanthanum cerium oxide in the rare earth oxide standard sample is 38%, 38.5%, 39%, 39.5%, 40%, 40.5%, 41%, 41.5% or 42% by mass. The mass percentage of each component in the lanthanum cerium oxide in the rare earth oxide standard sample is as follows: lanthanum oxide includes, but is not limited to, 13%, 13.2%, 13.5%, 14%, 14.5%, 14.7%, 14.8%, or 14.9%; cerium oxide includes, but is not limited to, 24%, 24.5%, 25%, 25.3%, 25.5%, 26%, 26.5%, 27%, 27.5%, or 28%; praseodymium oxide includes, but is not limited to, 0.1%, 0.12%, 0.15%, 0.17%, 0.2%, 0.22%, 0.25%, 0.27%, 0.3%, 0.32%, 0.34%, 0.35%, 0.36%, 0.39%, or 0.4%; neodymium oxide includes, but is not limited to, 0.5%, 0.52%, 0.55%, 0.57%, 0.6%, 0.62%, 0.65%, 0.67%, 0.69%, 0.7%, 0.75%, 0.78%, 0.8%, 0.82%, 0.85%, 0.9%, 0.95%, or 1%.
In one embodiment, the mass ratio of cerium oxide to lanthanum oxide in the lanthanum cerium oxide is 1.75-2, such as 1.76, 1.78, 1.8, 1.82, 1.84, 1.85, 1.86, 1.87, 1.9, 1.93, 1.95, or 1.97. In one embodiment, the mass ratio of the neodymium oxide to the praseodymium oxide in the lanthanum cerium oxide is 2.5 to 5, such as 2.5, 2.7, 3, 3.5, 3.8, 4, 4.2, 4.5, 4.7 or 5.
In one embodiment, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28% -32% by mass. In one embodiment, the mass percentages of the components in the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively: 0.1-0.3% of lanthanum oxide, 0.2-0.5% of cerium oxide, 6-8% of praseodymium oxide and 21-24% of neodymium oxide.
In one embodiment, the praseodymium neodymium oxide in the rare earth oxide standard sample includes, but is not limited to, 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5%, or 32% by mass. The mass percentage of each component in the praseodymium-neodymium oxide in a rare earth oxide standard sample is as follows: lanthanum oxide includes, but is not limited to, 0.1%, 0.12%, 0.15%, 0.17%, 0.2%, 0.22%, 0.25%, 0.27%, or 0.3%; cerium oxide includes, but is not limited to, 0.2%, 0.25%, 0.27%, 0.3%, 0.32%, 0.35%, 0.37%, 0.4%, 0.42%, 0.45%, 0.48%, or 0.5%, praseodymium oxide includes, but is not limited to, 6% to 8%, and neodymium oxide includes, but is not limited to, 21%, 21.5%, 22%, 22.5%, 23%, 23.5%, or 24%.
In one embodiment, the mass ratio of cerium oxide to lanthanum oxide in the praseodymium-neodymium oxide is 1.65-2, such as 1.65, 1.68, 1.7, 1.72, 1.75, 1.78, 1.8, 1.85, 1.9, 1.95, or 2. In one embodiment, the mass ratio of neodymium oxide to praseodymium oxide in the praseodymium-neodymium oxide is 2.9-3.6, such as 3, 3.1, 3.2, 3.3, 3.4, or 3.5.
In one embodiment, the ratio of lanthanum oxide to cerium oxide in the lanthanum cerium oxide standard sample is controlled to 35% and 65%, respectively, i.e., the mass ratio of cerium oxide to lanthanum oxide is about 1.86. In one embodiment, the praseodymium oxide and neodymium oxide in the praseodymium-neodymium oxide standard sample are respectively controlled at 25% and 75%, i.e. the mass ratio of neodymium oxide to praseodymium oxide is 3. As a standard product with characteristic quantity value, the product is closer to the components of the actual product, and the quality control effect is better.
According to another aspect of the invention, the invention also relates to a preparation method of the rare earth oxide standard sample, which comprises the following steps:
grinding a mixture of a rare earth oxide raw material and a sodium chloride raw material, and then uniformly mixing; the rare earth oxide raw materials comprise a lanthanum oxide raw material, a cerium oxide raw material, a praseodymium oxide raw material and a neodymium oxide raw material.
According to the invention, the rare earth oxide raw material and the sodium chloride raw material are ground and then uniformly mixed, the method is simple and easy to implement, and the obtained standard sample has excellent uniformity and stability. The preparation method of the standard sample can realize the quality control and instrument calibration in the detection process of rare earth products such as rare earth carbonate, rare earth chloride and the like, and is mainly used for evaluation and correction of a standard method for measuring the total amount of rare earth by a gravimetric method and an ICP-OES method. The method can solve the problem that the standard sample cannot be directly prepared due to unstable properties of products such as rare earth carbonate, rare earth chloride and the like.
In one embodiment, a method of preparing a mixture of a rare earth oxide feedstock and a sodium chloride feedstock comprises: premixing the rare earth oxide raw material and a sodium chloride raw material; the premixing time is 2-3 h.
In one embodiment, the time of the grinding treatment is 170 to 200 seconds. In one embodiment, the time of the grinding process includes, but is not limited to, 170s, 172s, 175s, 180s, 182s, 185s, 187s, 190s, 195s, 197s, or 200 s. The control of the particle size range depends on the time of grinding treatment, the time is short, the particle size range is wide, the standard sample has large particle difference, and the segregation of component elements is easily caused; the grinding treatment time is long, the particle size range is small, the phenomena of agglomeration and inclusion between substances can occur, and the rare earth oxide is easily concentrated in a large area; therefore, the grain size range of the standard sample can be reasonably controlled by adopting the proper grinding time.
In one embodiment, the time of the blending treatment is 170-190 min. In one embodiment, the time of the blending process includes, but is not limited to, 171min, 172min, 173min, 174min, 175min, 176min, 177min, 178min, 179min, 180min, 181min, 182min, 185min, 187min, or 190 min. The invention can ensure the full mixing of all the components by adopting proper mixing treatment time, so that the standard sample can obtain higher uniformity.
In one embodiment, the purity of each of the lanthanum oxide raw material, cerium oxide raw material, praseodymium oxide raw material, and neodymium oxide raw material is 4N grade or higher. In one embodiment, the sodium chloride feedstock is sodium chloride guaranteed to be sodium chloride.
In one embodiment, the method for preparing the rare earth oxide standard sample further comprises the following steps: carrying out uniformity detection and stability detection on the rare earth oxide standard sample; and after the uniformity and the stability of the rare earth oxide standard sample are qualified, carrying out constant value detection. In one embodiment, the constant value detection can be carried out by at least 6 detection mechanisms, at least 8 groups of constant value detection data are given, and the result statistics of the standard value are carried out.
In one embodiment, the uniformity detection is by glow discharge mass spectrometry (GD-MS). GD-MS is an analytical method for mass spectrometry by using glow discharge source as ion source and connecting with mass spectrometer. Inert gas (argon) is introduced into the glow discharge cell, an electric field is applied between the cathode and the anode, and the inert gas is broken down to ionize. The positive ions are accelerated to impact the surface of a sample serving as a cathode under the action of an electric field, surface atoms of the positive ions are sputtered to separate from the sample and enter glow discharge plasma, the sample is ionized in the plasma and then is guided into a mass spectrometer, and the separated ion beams are collected and detected by a detector. The computer automatically calculates the mass fraction of each element to be measured according to the standard relative sensitivity factor in the instrument software. And (3) according to the uniformity requirement of the standard sample, performing uniformity research on the standard sample by adopting a GD-MS method. The GD-MS and the ICP-MS have the same detection principle, but the GD-MS has the following advantages: 1) the ability to directly, rapidly and multi-element analyze solids; 2) a uniform response of most elements; 3) sub ppb detection limit; 4) simplicity of mass spectrometry; 5) the operation is convenient. These particular features make GD-MS technology feasible for samples that are present in complex solid matrices and are difficult to dissolve, and can be used to demonstrate the homogeneity of the sample to be tested.
In one embodiment, the uniformity detection specifically comprises: according to the requirements of GB/T15000 Standard sample work guide and YS/T409. 2012 Standard sample technical Specification for analyzing nonferrous metal products, when the total unit number N is less than 1000, 2-3% are extracted, and the number is not less than 15. And 15 bottles of samples were taken therefrom according to the random number table for homogeneity test. Selecting 15 groups of the rare earth oxide standard samples with the same quantity, measuring the content of each trace element in each group of standard samples, and calculating the relative standard deviation of the content of the same trace element in each group. In one embodiment, different persons of said at least 6 detection facilities perform said fixed value detection at different times. In one embodiment, the total amount of rare earth in the standard sample is determined by GB/T24635-; the rare earth distribution is measured by GB/T16484.3-2009. In one embodiment, the fixed value detection process adopts a qualified laboratory, and adopts a certified standard solution to accurately assign the total amount of the rare earth, the content of lanthanum, cerium, praseodymium and neodymium in the standard sample.
In a preferred embodiment, a method for preparing a rare earth oxide standard sample for controlling a standard value of total rare earth content, as shown in fig. 1, comprises the following steps:
firstly, designing components of a rare earth oxide standard sample:
raw materials: sodium chloride and rare earth oxides (lanthanum oxide, cerium oxide, praseodymium oxide, and neodymium oxide);
1. the component design of the lanthanum cerium oxide standard sample: in the rare earth oxide standard sample, the content of lanthanum and cerium oxide is 38-42% by mass percent; the mass percentage of each component in the lanthanum cerium oxide in the rare earth oxide standard sample is as follows: 13-15% of lanthanum oxide, 24-28% of cerium oxide, 0.1-0.4% of praseodymium oxide and 0.5-1% of neodymium oxide; in the lanthanum-cerium oxide, the mass ratio of cerium oxide to lanthanum oxide is 1.75-2, and the mass ratio of neodymium oxide to praseodymium oxide is 2.5-5;
2. component design of praseodymium-neodymium oxide standard sample: in the rare earth oxide standard sample, the praseodymium-neodymium oxide accounts for 28-32% by mass percent; the mass percentage of each component in the praseodymium-neodymium oxide in a rare earth oxide standard sample is as follows: 0.1-0.3% of lanthanum oxide, 0.2-0.5% of cerium oxide, 6-8% of praseodymium oxide and 21-24% of neodymium oxide; in the lanthanum-cerium oxide, the mass ratio of cerium oxide to lanthanum oxide is 1.65-2, and the mass ratio of neodymium oxide to praseodymium oxide is 2.9-3.6.
Preparation of rare earth oxide standard sample
Selecting high-grade pure sodium chloride with uniform particle size and rare earth oxide with more than 4N grade for premixing, grinding for 175-182 s, and mixing for 175-185 min to obtain a rare earth oxide standard sample.
Detection of rare earth oxide standard sample
The obtained rare earth oxide standard sample is researched on granularity and micro-morphology, the component design result and uniformity representation of the sample are determined, then the uniformity initial check is carried out, the judgment basis of the uniformity initial check is that the standard deviation of 7 tests is compared with the laboratory tolerance of the method, and when the standard deviation is smaller than the laboratory tolerance, the method can be used for judging the uniformity of the sample
When the uniformity is qualified in the initial inspection; when in use
And in time, the uniformity initial inspection is unqualified. And after the initial inspection is qualified, carrying out uniformity and stability inspection, and considering the combined verification of various statistical methods. After the uniformity test and the stability test both pass the technical specification requirements, 6 qualified furniture laboratories are selected, the fixed value detection is carried out at different times and different methods and by different personnel, at least 8 groups of data are given, and the result statistics and the fixed value are carried out. The valuing process requires that certified standard substances are adopted as standard curves in the detection process of each laboratory, detection equipment used needs to be verified or calibrated, detection personnel are certified and put on duty, and repeated tests are carried out, so that the value traceability of the valuing result is ensured. And carrying out uniformity inspection, value determination and data processing according to the technical specification YS/T409-2012 of the standard sample for analyzing the nonferrous metal product and the working guide rule GB/T15000.3-2008 of the standard sample.
The following is a further description with reference to specific embodiments and the accompanying drawings.
Example 1
A standard sample of rare earth oxide comprising a homogeneous mixture of lanthanum cerium oxide and sodium chloride; in the standard sample of lanthanum-cerium oxide, by mass percentage, the content of lanthanum-cerium oxide is 40%, wherein the content of lanthanum oxide is 13.8%, the content of cerium oxide is 25.4%, the content of praseodymium oxide is 0.2%, and the content of neodymium oxide is 0.6%; wherein the particle size D10 of the rare earth oxide standard sample is 0.251 μm; the particle size D50 of the rare earth oxide standard sample is 0.707 mu m; the particle size D90 of the rare earth oxide standard sample is 1.91 mu m.
The preparation method of the rare earth oxide standard sample in the embodiment includes the following steps:
mixing a high-grade pure sodium chloride raw material with a rare earth oxide raw material, grinding for 3min, and mixing for 3h to obtain a rare earth oxide standard sample.
Example 2
A standard sample of rare earth oxide comprising a homogeneous mixture of lanthanum cerium oxide and sodium chloride; in the rare earth oxide standard sample, by mass, the content of lanthanum and cerium oxide is 38%, wherein the content of lanthanum oxide is 13%, the content of cerium oxide is 24.4%, the content of praseodymium oxide is 0.1%, and the content of neodymium oxide is 0.5%; wherein the particle size D10 of the rare earth oxide standard sample is 0.292 mu m; the particle size D50 of the rare earth oxide standard sample is 0.855 μm; the particle size D90 of the rare earth oxide standard sample is 2.36 μm. The preparation method of the rare earth oxide standard sample in this example is the same as that of example 1.
Example 3
A standard sample of rare earth oxide comprising a homogeneous mixture of lanthanum cerium oxide and sodium chloride; in the rare earth oxide standard sample, by mass, the content of lanthanum and cerium oxide is 42%, wherein the content of lanthanum oxide is 14.1%, the content of cerium oxide is 26.6%, the content of praseodymium oxide is 0.3%, and the content of neodymium oxide is 1%; wherein the particle size D10 of the rare earth oxide standard sample is 0.311 μm; the particle size D50 of the rare earth oxide standard sample is 0.880 mu m; the particle size D90 of the rare earth oxide standard sample is 6.96 mu m. The preparation method of the rare earth oxide standard sample in this example is the same as that of example 1.
Example 4
A rare earth oxide standard sample comprising a homogeneous mixture of praseodymium neodymium oxide and sodium chloride; in the rare earth oxide standard sample, the praseodymium-neodymium oxide accounts for 30% by mass, wherein the lanthanum oxide accounts for 0.2%, the cerium oxide accounts for 0.4%, the praseodymium oxide accounts for 7.3%, and the neodymium oxide accounts for 22.1%; wherein the particle size D10 of the rare earth oxide standard sample is 0.269 mu m; the particle size D50 of the rare earth oxide standard sample is 0.910 mu m; the particle size D90 of the rare earth oxide standard sample is 5.51 mu m.
The preparation method of the praseodymium-neodymium oxide standard sample in the embodiment comprises the following steps:
mixing a sodium chloride raw material with a rare earth oxide raw material, grinding for 3min, and mixing for 3h to obtain a rare earth oxide standard sample.
Example 5
A rare earth oxide standard sample comprising a homogeneous mixture of praseodymium neodymium oxide and sodium chloride; in the rare earth oxide standard sample, the praseodymium-neodymium oxide accounts for 28% by mass, wherein the lanthanum oxide accounts for 0.3%, the cerium oxide accounts for 0.5%, the praseodymium oxide accounts for 6%, and the neodymium oxide accounts for 21.2%. The preparation method of the rare earth oxide standard sample in this example is the same as that of example 4.
Example 6
A rare earth oxide standard sample comprising a praseodymium neodymium oxide and sodium chloride uniform mixture; in the rare earth oxide standard sample, the praseodymium-neodymium oxide is 32% by mass, wherein the lanthanum oxide is 0.1%, the cerium oxide is 0.3%, the praseodymium oxide is 8%, and the neodymium oxide is 23.6%. The preparation method of the rare earth oxide standard sample in this example is the same as that of example 4.
Example 7
The preparation method of the rare earth oxide standard sample comprises the following steps: (1) preparing raw materials: 6000g of high-grade pure sodium chloride with uniform granularity is selected, 1380g of lanthanum oxide, 2540g of cerium oxide, 20g of praseodymium oxide and 60g of neodymium oxide are accurately weighed; (2) premixing the components in the step (1) for 2h, and grinding for 3min by using a grinding machine, wherein 150g of grinding is performed in each round; and (3) further uniformly mixing the ground materials by using a mixer for 3 hours to obtain a rare earth oxide standard sample, which can be seen in figure 13. The standard sample of rare earth oxide prepared in this example was aliquoted, as shown in FIG. 15.
Example 8
The preparation method of the rare earth oxide standard sample comprises the following steps: (1) preparing raw materials: selecting 7000g of high-grade pure sodium chloride with uniform particle size, and accurately weighing 20g of lanthanum oxide, 40g of cerium oxide, 730g of praseodymium oxide and 2210g of neodymium oxide; (2) premixing the raw materials in the step (1) for 2h, and grinding for 3min by a grinding machine, wherein 150g of grinding is carried out in each round; and (3) further uniformly mixing the ground materials by using a mixer for 3 hours to obtain a rare earth oxide standard sample, which can be seen in fig. 14. The standard sample of rare earth oxide prepared in this example was aliquoted as shown in FIG. 16.
The method comprises the following steps of (1) carrying out granularity and micro-morphology research on a rare earth oxide standard sample of each embodiment, determining a component design result and uniformity characterization of the sample, carrying out uniformity initial inspection, carrying out uniformity and stability inspection after the initial inspection is qualified, and considering the combined verification of various statistical methods; the uniformity detection adopts a glow discharge mass spectrometry method; the uniformity detection specifically comprises: randomly selecting 15 groups of standard samples with the same quantity at different parts in the rare earth oxide standard sample, measuring the content of each trace element in each group of standard samples, and calculating the average value, standard deviation and relative standard deviation of the same trace element in each group; in each group, the relative standard deviation of the contents of the same trace elements meets the allowable fluctuation range of the trace element determination.
Examples of the experiments
Scanning Electron Microscope (SEM) image of rare earth oxide standard sample
FIG. 2 is a scanning electron micrograph of a rare earth oxide standard sample of example 1 of the present invention at an EHT of 3KV magnified 1000 times; FIG. 3 is a scanning electron micrograph of a rare earth oxide standard sample of example 1 of the present invention at an EHT of 20KV magnified 500 times; FIG. 4 is a scanning electron microscope image of a standard sample of rare earth oxide in example 4 of the present invention under the condition that EHT is 3KV and magnification is 1000 times; FIG. 5 is a scanning electron micrograph of a rare earth oxide standard sample of example 4 of the present invention at an EHT of 20KV magnified 500 times. Referring to fig. 2, 3, 4 and 5, the EHT is 3KV, the SEM micro-morphology of the standard sample is observed in SE2 mode under 1000 times of magnification, and shows polygonal particles with uniform particle size, the EHT is 20KV, the SEM micro-morphology of the standard sample is observed in HDBSD mode under 500 times of magnification, and particles with light and dark differences are formed, which are sodium chloride particles and rare earth oxide particles, respectively, wherein the bright particles are rare earth oxide particles, and the dark particles are sodium chloride crystals. In the case of micro-domains, SEM images can demonstrate that both species are uniformly distributed.
Particle size distribution curve of rare earth oxide standard sample
The invention researches the particle size of the rare earth oxide and the particle size interval of the crystal sodium chloride, combines the particle size difference of the rare earth oxide and the crystal sodium chloride, analyzes that the uniformity requirement can be met when the particle size range accords with the particle size range interval of the mixed rare earth oxide, and researches and determines the particle size distribution (figure 6) and a scanning electron microscope (figure 7) of the mixed (lanthanum, cerium, praseodymium and neodymium) rare earth oxide, wherein in figure 6, the particle size D10 of the (lanthanum, cerium, praseodymium and neodymium) rare earth oxide is 1.53 mu m, the particle size D50 is 4.40 mu m, and the particle size D90 is 10.8 mu m. And (3) repeatedly testing the grinding time of the standard sample according to the particle size range of the mixed rare earth oxide, controlling the grinding effect, detecting the content of REO in the sample, and determining the grinding time for 3min according to stability analysis of the REO result to obtain the optimal particle size and the particle size distribution curve thereof, wherein the particle size distribution curve of the rare earth oxide standard sample in the embodiment 1 is shown in figure 8, and the particle size distribution curve of the rare earth oxide standard sample in the embodiment 4 is shown in figure 9.
Uniformity detection result of rare earth oxide standard sample
(1) Taking the 15 detection results of non-matrix elements in the rare earth oxide standard sample in example 1 as an example, the uniformity of the standard sample is determined, Average represents the mean value, Std Dev represents the standard deviation, and RSD represents the relative standard deviation. The results are shown in Table 1.
Table 1 results of uniformity measurement of non-matrix elements in rare earth oxide standard sample in example 1
| Number of measurements | K39 | Ca44 | | Cu65 | Zn66 | |
| 1 | 2.93 | 32.9 | 8.18 | 9.29 | 1.17 | |
| 2 | 3.42 | 42.3 | 6.32 | 6.33 | 0.55 | |
| 3 | 3.57 | 41.6 | 6.75 | 6.29 | 0.79 | |
| 4 | 3.69 | 43.5 | 6.96 | 6.82 | 0.93 | |
| 5 | 3.28 | 46.5 | 6.98 | 7.03 | 0.43 | |
| 6 | 3.59 | 44.3 | 6.77 | 6.66 | 0.46 | |
| 7 | 3.65 | 42.3 | 7.02 | 6.54 | 0.58 | |
| 8 | 3.88 | 42.9 | 6.59 | 6.82 | 0.67 | |
| 9 | 3.69 | 43.1 | 7.21 | 6.43 | 0.88 | |
| 10 | 3.58 | 45.5 | 7.36 | 6.58 | 0.67 | |
| 11 | 3.75 | 46.2 | 6.69 | 6.24 | 0.69 | |
| 12 | 3.83 | 44.8 | 6.83 | 6.78 | 0.71 | |
| 13 | 3.91 | 43.5 | 6.97 | 6.91 | 0.73 | |
| 14 | 3.56 | 41.6 | 7.11 | 6.71 | 0.59 | |
| 15 | 3.73 | 43.9 | 7.2 | 7.03 | 0.63 | |
| Average | 3.60 | 42.99 | 7.00 | 6.83 | 0.70 | |
| Std Dev | 0.25 | 3.18 | 0.42 | 0.73 | 0.19 | |
| RSD% | 6.92 | 7.41 | 6.03 | 10.63 | 27.09 |
As can be seen from the data in Table 1, the content range of trace elements of K, Ca, Fe, Cu and Zn is between 0.9 ppm and 30ppm, and the uniformity detection of the trace elements can better illustrate the uniformity of the substances. K. RSD of Ca, Fe, Cu and Zn is respectively 6.92%, 7.41%, 6.03%, 10.63% and 27.09%, and the standard sample can be proved to have good uniformity by meeting the measurement fluctuation of trace elements.
(2) Taking the 15 detection results of the non-matrix elements in the rare earth oxide standard sample in example 4 as an example, the uniformity of the standard sample is determined, and the results are shown in table 2.
Table 2 results of uniformity measurement of non-matrix elements in rare earth oxide standard sample in example 4
| Number of measurements | K39 | Ca44 | | Cu65 | Zn66 | |
| 1 | 2.72 | 31.02 | 7.96 | 8.89 | 0.78 | |
| 2 | 2.93 | 32.9 | 8.18 | 9.29 | 1.17 | |
| 3 | 2.7 | 34.6 | 8.52 | 9.47 | 1.04 | |
| 4 | 2.49 | 29.6 | 9.31 | 8.57 | 1.36 | |
| 5 | 2.63 | 27.8 | 8.85 | 8.79 | 0.87 | |
| 6 | 2.41 | 28.6 | 6.7 | 9.89 | 0.59 | |
| 7 | 2.84 | 26.3 | 6.99 | 10.3 | 0.51 | |
| 8 | 2.65 | 26.7 | 6.67 | 9.2 | 0.98 | |
| 9 | 2.97 | 28.7 | 7.97 | 11.3 | 0.82 | |
| 10 | 3.27 | 26.2 | 8.91 | 11.9 | 0.95 | |
| 11 | 3.4 | 27.9 | 8.42 | 11.8 | 0.97 | |
| 12 | 3.65 | 29.56 | 9.11 | 10.32 | 0.92 | |
| 13 | 2.96 | 31.12 | 8.35 | 9.96 | 0.87 | |
| 14 | 3.11 | 30.23 | 8.69 | 8.76 | 1.02 | |
| 15 | 2.86 | 28.73 | 7.22 | 9.7 | 0.59 | |
| Average | 2.91 | 29.33 | 8.12 | 9.88 | 0.90 | |
| Std Dev | 0.34 | 2.38 | 0.86 | 1.08 | 0.22 | |
| RSD% | 11.72 | 8.10 | 10.63 | 10.93 | 24.94 |
As can be seen from the data in Table 2, the content range of trace elements K, Ca, Fe, Cu and Zn is between 0.9 ppm and 30ppm, and the uniformity detection of the trace elements can better illustrate the uniformity of the substances. K. RSD of Ca, Fe, Cu and Zn is 11.72%, 8.10%, 10.63%, 10.93% and 24.94% respectively, and the standard sample can be proved to have good uniformity by meeting the measurement fluctuation of trace elements.
Stability detection result of rare earth oxide standard sample
And under the condition of eliminating the influence of factors such as sample quality, uniformity, heating rate, atmosphere pressure and the like, analyzing the TG curve and the DSC curve, judging whether the standard sample candidate changes according to the change of the quality corresponding to a certain thermal effect, and further judging the substance conversion process corresponding to the thermal effect. The current actual quality of the standard sample at the reaction temperature is known, so that the comprehensive thermal stability can be accurately judged conveniently. Wherein TG and DSC in the comprehensive thermal analysis are detected by adopting JB/T6856-1993 standard.
Wherein, fig. 10 is a comprehensive thermal analysis curve of the mixed rare earth oxide, wherein, in the DSC curve, the peak comprehensive analysis: the area is 27.36J/g, the peak value is 299.2 ℃, the starting point of the peak is 273.4 ℃, the end point of the peak is 326.3 ℃, the width of the peak is 41.8 ℃ and the height of the peak is 0.1264 mW/mg; in the TG curve corresponding to the peak of the DSC curve, the mass change of the mixed rare earth oxide was 1.89%, after 326.3 ℃ and until the heat treatment was completed, the mass change of the mixed rare earth oxide was 1.05%, and the final residual mass was 97.06% (1199 ℃).
Fig. 11 is a thermal analysis curve of a lanthanum cerium rare earth oxide standard sample in example 1, and a peak comprehensive analysis of a DSC curve: the peak area was 37.61J/g, the peak area was 322.1 deg.C, the peak origin was 289.6 deg.C, and the peak end-point was 346.8 deg.C. Fig. 12 is a thermal analysis curve of the praseodymium-neodymium rare earth oxide standard sample in example 4, wherein the peak comprehensive analysis of the DSC curve: the peak area is 180.71J/g, the peak value is 809.2 ℃, the peak starting point is 799.1 ℃, and the peak ending point is 816.3 ℃. As can be seen from TG curves and DSC curves of the lanthanum-cerium rare earth oxide standard sample and the praseodymium-neodymium rare earth oxide standard sample, the oxide standard sample has good thermal stability below 60 ℃. As can be seen from fig. 11 and 12, the lanthanum-cerium rare earth oxide standard sample and the praseodymium-neodymium rare earth oxide standard sample have no significant mass change and heat change in the temperature range of 30 ℃ to 300 ℃, and it is proved that the samples have no physical and chemical property change in this temperature range, and have storage and transportation conditions.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A rare earth oxide standard sample characterized by comprising a homogeneous mixture of a rare earth oxide and sodium chloride; in the rare earth oxide standard sample, the content of the rare earth oxide is 28-42% by mass percent;
the rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide;
0.1-15% of lanthanum oxide, 0.2-28% of cerium oxide, 0.1-8% of praseodymium oxide and 0.5-32% of neodymium oxide.
2. The rare earth oxide standard sample according to claim 1, wherein the particle size D10 of the rare earth oxide standard sample is 0.1 to 1 μm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 mu m;
the particle size D90 of the rare earth oxide standard sample is 1-8 mu m.
3. The rare earth oxide standard sample according to claim 1, wherein the rare earth oxide is lanthanum cerium oxide or praseodymium neodymium oxide.
4. The rare earth oxide standard sample according to claim 3, comprising at least one of the following features (1) - (3):
(1) in the rare earth oxide standard sample, the content of lanthanum and cerium oxide is 38-42% by mass percent;
the mass percentages of the components in the lanthanum cerium oxide in the rare earth oxide standard sample are respectively as follows: 13-15% of lanthanum oxide, 24-28% of cerium oxide, 0.1-0.4% of praseodymium oxide and 0.5-1% of neodymium oxide;
(2) in the lanthanum-cerium oxide, the mass ratio of cerium oxide to lanthanum oxide is 1.75-2;
(3) in the lanthanum-cerium oxide, the mass ratio of neodymium oxide to praseodymium oxide is 2.5-5.
5. The rare earth oxide standard sample according to claim 3, comprising at least one of the following features (1) - (3):
(1) in the rare earth oxide standard sample, the praseodymium-neodymium oxide accounts for 28-32% by mass percent;
the mass percentages of the components in the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively as follows: 0.1-0.3% of lanthanum oxide, 0.2-0.5% of cerium oxide, 6-8% of praseodymium oxide and 21-24% of neodymium oxide;
(2) in the praseodymium-neodymium oxide, the mass ratio of cerium oxide to lanthanum oxide is 1.65-2;
(3) in the praseodymium-neodymium oxide, the mass ratio of neodymium oxide to praseodymium oxide is 2.9-3.6.
6. The rare earth oxide standard sample as claimed in claim 1, further comprising trace elements, wherein the content of the trace elements is 0.5-50 ppm;
the microelements comprise K, Ca, Fe, Cu and Zn.
7. The method for preparing a rare earth oxide standard sample according to any one of claims 1 to 6, comprising the steps of:
grinding a mixture of a rare earth oxide raw material and a sodium chloride raw material, and then uniformly mixing;
the rare earth oxide raw materials comprise a lanthanum oxide raw material, a cerium oxide raw material, a praseodymium oxide raw material and a neodymium oxide raw material.
8. The method for preparing a rare earth oxide standard sample according to claim 7, wherein the method for preparing the mixture of the rare earth oxide raw material and the sodium chloride raw material comprises: premixing the rare earth oxide raw material and a sodium chloride raw material;
the premixing time is 2-3 h.
9. The method for preparing a rare earth oxide standard sample according to claim 7, wherein at least one of the following characteristics (1) to (3) is contained:
(1) the grinding time is 170-200 s;
(2) the time for the uniform mixing treatment is 170-190 min;
(3) the sodium chloride raw material is high-grade pure sodium chloride.
10. The method for preparing a rare earth oxide standard sample according to claim 7, further comprising: and (4) carrying out uniformity detection and stability detection on the rare earth oxide standard sample.
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| AU2023214242A AU2023214242A1 (en) | 2022-08-01 | 2023-06-05 | Rare earth oxide standard sample and preparation method thereof |
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