AU2023214242A1 - 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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- AU2023214242A1 AU2023214242A1 AU2023214242A AU2023214242A AU2023214242A1 AU 2023214242 A1 AU2023214242 A1 AU 2023214242A1 AU 2023214242 A AU2023214242 A AU 2023214242A AU 2023214242 A AU2023214242 A AU 2023214242A AU 2023214242 A1 AU2023214242 A1 AU 2023214242A1
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- oxide
- rare earth
- standard sample
- earth oxide
- praseodymium
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 218
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 96
- 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 82
- 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 80
- 239000011780 sodium chloride Substances 0.000 claims abstract description 48
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 41
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 41
- 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 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims description 71
- 239000002994 raw material Substances 0.000 claims description 52
- 238000001514 detection method Methods 0.000 claims description 36
- 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 32
- 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
- 239000011573 trace mineral Substances 0.000 claims description 22
- 235000013619 trace mineral Nutrition 0.000 claims description 22
- 238000000227 grinding Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 9
- 230000008859 change Effects 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 238000013461 design Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims description 6
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000011161 development Methods 0.000 claims description 5
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 claims description 4
- RKLPWYXSIBFAJB-UHFFFAOYSA-N [Nd].[Pr] Chemical compound [Nd].[Pr] RKLPWYXSIBFAJB-UHFFFAOYSA-N 0.000 claims description 4
- 238000011160 research Methods 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims 6
- 238000013329 compounding Methods 0.000 claims 1
- 230000000877 morphologic effect Effects 0.000 claims 1
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 38
- 150000002910 rare earth metals Chemical class 0.000 abstract description 28
- -1 rare earth carbonate Chemical class 0.000 abstract description 10
- 238000010586 diagram Methods 0.000 description 16
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000002411 thermogravimetry Methods 0.000 description 10
- 239000011734 sodium Substances 0.000 description 9
- 238000009826 distribution Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000002076 thermal analysis method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 6
- 229910052684 Cerium 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
- 229910052746 lanthanum Inorganic materials 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 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
- 239000000758 substrate Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012925 reference material Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007689 inspection Methods 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
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 238000012360 testing 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
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method 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
- 150000002500 ions Chemical class 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- 238000000581 reactive spray deposition Methods 0.000 description 2
- 238000005204 segregation Methods 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
- 238000005303 weighing Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 235000013409 condiments Nutrition 0.000 description 1
- 238000000200 discharge mass spectrometry Methods 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
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
PA22007140
Abstract
The present invention relates to the technical field of standard sample
preparation, and in particular to a rare earth oxide standard sample and a
preparation method thereof. The rare earth oxide standard sample in the present
invention comprises a uniform mixture of rare earth oxide and sodium chloride;
based on mass percentage, the rare earth oxide in the rare earth oxide standard
sample is 28%-42%; the rare earth oxide comprises lanthanum oxide, cerium
oxide, praseodymium oxide and neodymium oxide; 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%. Sodium chloride is used as a diluent,
which can effectively reduce the concentration of total rare earth content,
accurately control the content range of standard values, ensure that the standard
values of the standard sample are consistent with the total rare earth content of
actual products (rare earth carbonate and rare earth chloride) and further
accurately control product quality. Moreover, the standard sample has high
uniformity and stability.
1 PA22007140
Description
PA22007140
Description
Technical Field
The present invention relates to the technical field of standard sample preparation, and in particular to a rare earth oxide standard sample and a preparation method thereof.
1o Background
Based on the standard analysis method of rare earth oxide and the social function of standard samples, the current rare earth standard sample has the problems of no standard value of total rare earth content and large difference of partition proportion from actual products (rare earth carbonate and rare earth chloride). From the analysis of in-depth development requirements of rare earth standards in China, the calibration requirements of high-end detection equipment and the development and international standardization requirements of rare earth industry, it is of practical significance to prepare the standard value of total rare earth content of a rare earth oxide standard sample.
The setting components of the existing rare earth oxide standard samples are almost all single rare earth oxide with high purity, without binary or multicomponent oxide and mixed oxide that can control the total rare earth content. In the process of popularization and application of the rare earth oxide
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standard samples, there are problems of limited types, fewer setting elements, and incapability of covering the actual products by the content range of components, and the rare earth industry is in urgent need of such standard samples to guide detection and production.
In view of this, the present invention is proposed.
Summary
One purpose of the present invention is to provide a rare earth oxide standard sample, to solve the technical problems in the prior art that the setting component of the rare earth oxide standard sample has no total rare earth content, the content range of the component cannot cover an actual product, and important rare earth products such as rare earth carbonate and rare earth chloride cannot use the product as a candidate for preparing a standard sample due to unstable properties. Sodium chloride is used as a diluent in the rare earth oxide standard sample of the present invention, which can effectively reduce the concentration of the total rare earth content, accurately control the content range of standard values and satisfy the requirements of uniformity and stability.
Another purpose of the present invention is to provide a preparation method of the rare earth oxide standard sample. The method is simple and easy to implement. The raw material is ground and uniformly mixed to achieve the requirements of the particle size range of rare earth oxide.
To achieve the above purposes of the present invention, the present invention adopts the following technical solution:
The rare earth oxide standard sample comprises a uniform mixture of rare earth oxide and sodium chloride; based on mass percentage, the rare earth oxide 2 PA22007140
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in the rare earth oxide standard sample is 28%-42%;
The rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide;
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%.
In one embodiment, the particle size D10 of the rare earth oxide standard sample is 0.1-1 pm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 pm;
the particle size D90 of the rare earth oxide standard sample is 1-8 pm.
In one embodiment, the rare earth oxide is lanthanum-cerium oxide or praseodymium-neodymium oxide.
In one embodiment, based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 38%-42%;
The mass percentages of components of the lanthanum-cerium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 13%-15%, cerium oxide is 24%-28%, praseodymium oxide is 0.1%-0.4%, and neodymium oxide is 0.5%-1%.
In one embodiment, a mass ratio of cerium oxide and lanthanum oxide in the lanthanum-cerium oxide is 1.75-2.
In one embodiment, a mass ratio of neodymium oxide and praseodymium oxide in the lanthanum-cerium oxide is 2.5-5.
In one embodiment, based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28%-32%; 3 PA22007140
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The mass percentages of components of the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 0.1%-0.3%, cerium oxide is 0.2%-0.5%, praseodymium oxide is 6%-8% and neodymium oxide is 21%-24%.
In one embodiment, a mass ratio of cerium oxide and lanthanum oxide in the praseodymium-neodymium oxide is 1.65-2.
In one embodiment, a mass ratio of neodymium oxide and praseodymium oxide in the praseodymium-neodymium 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 trace elements comprise K, Ca, Fe, Cu and Zn.
A preparation method of the rare earth oxide standard sample comprises the following steps:
grinding and uniformly mixing a mixture of rare earth oxide raw material and sodium chloride raw material;
The rare earth oxide raw material comprises lanthanum oxide raw material, cerium oxide raw material, praseodymium oxide raw material and neodymium oxide raw material.
In one embodiment, a preparation method of the mixture of the rare earth oxide raw material and the sodium chloride raw material comprises: premixing the rare earth oxide raw material and the sodium chloride raw material;
The time of the premixing is 2-3 h.
In one embodiment, the time of the grinding is 170-200 s.
In one embodiment, the time of the uniform mixing is 170-190 min. 4 PA22007140
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In one embodiment, the sodium chloride raw material is guaranteed reagent sodium chloride.
In one embodiment, the preparation method of the rare earth oxide standard sample further comprises: detecting the uniformity and stability of the rare earth oxide standard sample.
Compared with the prior art, the present invention has the beneficial effects that:
(1) Sodium chloride is used as the diluent in the rare earth oxide standard sample of the present invention, which can effectively reduce the concentration of the total rare earth content, accurately control the content range of standard values, ensure that the standard values of the standard sample are consistent with the total rare earth content of actual products and further accurately control product quality. The rare earth oxide standard sample has excellent uniformity and stability.
(2) The rare earth oxide standard sample of the present invention can
effectively satisfy the quality control of production and development and
gradually improve the standard sample series; The standard sample conforms to
the strategic layout requirements of the rare earth industry, innovates the
preparation types of the rare earth standard sample and plays a important role in
building a test and evaluation system for rare earth new material, promoting the
technical development of the rare earth new material, standardizing the quality
of rare earth products and monitoring the detection of the rare earth products.
(3) The preparation method of the rare earth oxide standard sample in the present invention is simple and easy to implement. The raw material is ground 5 PA22007140
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and uniformly mixed to achieve the requirements of the particle size range of the rare earth oxide. The uniformity and the stability are excellent.
Description of Drawings
To more clearly describe the technical solutions in the specific
embodiments of the present invention or in prior art, the drawings required to be
used in the description of the specific embodiments or the prior art will be
simply presented below. Apparently, the drawings in the following description
are merely some embodiments of the present invention, and for those ordinary
skilled in the art, other drawings can also be obtained according to these
drawings without contributing creative labor.
Fig. 1 is a flow chart for preparation of a rare earth oxide standard sample
in an embodiment of the present invention;
Fig. 2 is a scanning electron microscope diagram of a rare earth oxide
standard sample under the condition that EHT is 3KV and magnification is at
1000 times in embodiment 1 of the present invention;
Fig. 3 is a scanning electron microscope diagram of a rare earth oxide
standard sample under the condition that EHT is 20KV and magnification is at
500 times in embodiment 1 of the present invention;
Fig. 4 is a scanning electron microscope diagram of a rare earth oxide
standard sample under the condition that EHT is 3KV and magnification is at
1000 times in embodiment 4 of the present invention;
Fig. 5 is a scanning electron microscope diagram of a rare earth oxide 6 PA22007140
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standard sample under the condition that EHT is 20KV and magnification is at
500 times in embodiment 4 of the present invention;
Fig. 6 is a curve chart of particle size distribution of mixed (lanthanum,
cerium, praseodymium and neodymium) rare earth oxide;
Fig. 7 is a scanning electron microscope diagram of mixed (lanthanum,
cerium, praseodymium and neodymium) rare earth oxide;
Fig. 8 is a curve chart of particle size distribution of a rare earth oxide
standard sample in embodiment 1;
Fig. 9 is a curve chart of particle size distribution of a rare earth oxide
standard sample in embodiment 4;
Fig. 10 is a comprehensive thermal analysis curve of mixed rare earth oxide,
comprising a thermogravimetric analysis (TG) curve and a differential scanning
calorimetry (DSC) curve;
Fig. 11 is a thermal analysis curve of a rare earth oxide standard sample in
embodiment 1, comprising a thermogravimetric analysis (TG) curve and a
differential scanning calorimetry (DSC) curve;
Fig. 12 is a thermal analysis curve of a rare earth oxide standard sample in
embodiment 4, comprising a thermogravimetric analysis (TG) curve and a
differential scanning calorimetry (DSC) curve;
Fig. 13 is a physical diagram of a lanthanum-cerium oxide standard sample
of the present invention;
Fig. 14 is a physical diagram of a praseodymium-neodymium oxide 7 PA22007140
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standard sample of the present invention;
Fig. 15 is a subpackage diagram of a lanthanum-cerium oxide standard
sample of the present invention;
Fig. 16 is a subpackage diagram of a praseodymium-neodymium oxide
standard sample of the present invention.
Detailed Description
The implementation solution of the present invention will be described below in detail in combination with the embodiments. However, those skilled in the art will understand that the following embodiments are only used for describing the present invention and should not be regarded as the limitation to the scope of the present invention. Experimental methods in which specific conditions are not specified in the embodiment are carried out under conventional conditions or as recommended by the manufacturer. The reagents or instruments used of which the manufacturers are not specified are all conventional products that can be purchased commercially.
According to one aspect of the present invention, the present invention relates to a rare earth oxide standard sample, comprising a uniform mixture of rare earth oxide and sodium chloride; and based on mass percentage, the rare earth oxide in the rare earth oxide standard sample is 28%-42%.
The rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide.
Based on mass percentage, in the rare earth oxide standard sample, the lanthanum oxide is 0.1%-15%, the cerium oxide is 0.2%-28%, the 8 PA22007140
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praseodymium oxide is 0.1%-8%, and the neodymium oxide is 0.5%-32%.
The rare earth oxide is doped with sodium chloride in the rare earth oxide standard sample of the present invention, and sodium chloride is used as the 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 standard sample has wide applicability.
In one embodiment, the particle size D10 of the rare earth oxide standard sample is 0.1-1 pm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 pm;
the particle size D90 of the rare earth oxide standard sample is 1-8 pm.
In one embodiment, the particle size D10 of the rare earth oxide standard sample includes but not limited to 0.2pm, 0.35pm, 0.47pm, 0.5pm, 0.63pm, 0.75pm, 0.88pm, 0.96pm or Ipm. In one embodiment, the particle size D50 of the rare earth oxide standard sample includes but not limited to 0.5pm, 0.86pm, 0.9pm, Ipm, 1.24pm, 1.57pm, 1.81pm, 2pm, 2.24pm, 2.55pm, 2.73pm, 2.9pm or 3pm. In one embodiment, the particle size D90 of the rare earth oxide standard sample includes but not limited to 1pm, 1.56pm, 1.8pm, 2pm, 2.54pm, 3pm, 3.05pm, 3.58pm, 4pm, 4.25pm, 4.8pm, 5pm, 5.54pm, 6pm, 7pm or 8pm.
The particle size ranges of the rare earth oxide and sodium chloride are further controlled to ensure that the rare earth oxide standard sample has better uniformity and stability.
The chemical properties of Na 2 SO 4 , Na 2 CO 3 , NaHCO3 and NaCl are
analyzed respectively by the diluent based on sodium salt, and the suitability as the diluent is judged in combination with the stability after mixing with the rare earth oxide.
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NaCl (sodium chloride) is white crystal in appearance, has good stability, is neutral, has a melting point of 801°C, is used for manufacture of soda and caustic soda and ore smelting in industry and used for condiments in life, and is non-toxic and high in safety. Therefore, the present invention selects NaCl as a diluent from the perspectives of chemical property stability and non-toxicity to control the total rare earth content.
Na 2 SO 4 (sodium sulfate) is a monoclinic crystal system, and the crystal is
short columnar, colorless, transparent, neutral, easy to dissolve in water and low in toxicity. The normal state is white crystal or powder, has water absorption, is easy to form 7 or 10 crystalline hydrates, and has a melting point of 884°C. Although Na 2 SO 4 is stable in properties, it is easily hydrated in humid air and changes into powdery aqueous sodium sulfate covering the surface. After mixing with the rare earth oxide, the stability of the standard sample may be reduced.
Na 2 CO 3 (sodium carbonate) is white powder easy to dissolve in water, and is alkaline and non-toxic. It is easy to weather in dry air and has water absorption. After water absorption, 10 crystalline hydrates are formed. It has a melting point of 851°C, is decomposed at about 1200°C, and may react with
CO2 and H 2 0 to produce NaHCO 3 . Na 2 CO3 has poor stability as a rare earth oxide diluent because of the characteristics of water absorption and reaction withCO 2 .
NaHCO3 (sodium bicarbonate) is white powder or monoclinic crystalline powder, is easy to dissolve in water, alkaline and non-toxic, is slowly decomposed under heat or in humid air, and has a decomposition temperature of 270°C. NaHCO3 starts to react at about 50°C to produceC0 2, and fully changes to Na 2 CO 3 at 100°C. NaHCO3 is not only easy to absorb water, but also relative
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low in decomposition temperature. Compared with Na 2 SO 4 and Na 2 CO 3
, NaHCO3 is not suitable for use as a diluent.
The chemical properties of the particle size range and the material are key indexes for reflecting the uniformity of the standard sample. After the diluent is mixed with the rare earth oxide, loose and non-agglomerating powder is formed of which the properties do not affect the physical mixing of the standard sample. 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 difference of the standard sample particles is large, which is easy to lead to the segregation of the component elements; and if the particle size range is small, there will be agglomeration and sandwiching phenomena between substances, which is easy to lead to massive concentration of the rare earth oxide, so reasonable control of the particle size range of the standard sample is the key to uniformity.
In one embodiment, the rare earth oxide standard sample further comprises trace elements; the content of the trace elements is 0.5-50 ppm; and the trace elements comprise K, Ca, Fe, Cu and Zn. That is, the rare earth oxide standard sample in the present invention comprises the rare earth oxide, sodium chloride and trace elements.
In one embodiment, based on mass percentage, the rare earth oxide in the rare earth oxide standard sample includes but not limited to 29%, 30%, 31%, 32%,33%,34%,35%,36%,37%,38%,39%,40%,41% or 42%.
In one embodiment, based on mass percentage, sodium chloride in the rare earth oxide standard sample is 58%-72%. Based on mass percentage, sodium chloride includes but not limited to 5 9 %, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70% or 71%. 11 PA22007140
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In one embodiment, the rare earth oxide is lanthanum-cerium oxide or praseodymium-neodymium oxide.
In one embodiment, based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 38%-42%. In one embodiment, the mass percentages of components of the lanthanum-cerium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 13%-15%, cerium oxide is 24%- 2 8 %, praseodymium oxide is 0.1-0.4%, and neodymium oxide is 0.5%-1%.
In one embodiment, based on mass percentage, 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%. The mass percentages of components of the lanthanum-cerium oxide in the rare earth oxide standard sample are specifically: lanthanum oxide includes but not limited to 13%, 13.2%, 13.5%, 14%, 14.5%, 14.7%, 14.8% or 14.9%; cerium oxide includes but not limited to 24%, 24.5%, 25%, 25.3%, 25.5%, 26%, 26.5%, 27%, 27.5% or 28%; praseodymium oxide includes but 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 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, a mass ratio of cerium oxide and 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, a mass ratio of neodymium oxide and praseodymium oxide in the lanthanum-cerium oxide is 2.5-5, such as 2.5, 2.7, 3, 3.5, 3.8, 4, 4.2, 4.5, 4.7 or 5.
In one embodiment, based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 12 PA22007140
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28%25-32%. In one embodiment, the mass percentages of components of the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 0.1%-0.3%, cerium oxide is 0.2%-0.5%, praseodymium oxide is 6%-8% and neodymium oxide is 21%-24%.
In one embodiment, based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample includes but not limited to 28%, 28.5%, 29%, 29.5%, 30%, 30.5%, 31%, 31.5% or 32%. The mass percentages of components of the praseodymium-neodymium oxide in the rare earth oxide standard sample are specifically: lanthanum oxide includes but 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 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 not limited to 6%-8%; and neodymium oxide includes but not limited to 21%, 21.5%, 22%, 22.5%, 23%, 23.5% or 24%.
In one embodiment, a mass ratio of cerium oxide and 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, a mass ratio of neodymium oxide and 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, in the lanthanum-cerium oxide standard sample, the proportions of lanthanum oxide and cerium oxide are controlled as 35% and 65% respectively, that is, the mass ratio of cerium oxide and lanthanum oxide is about 1.86. In one embodiment, in the praseodymium-neodymium oxide standard sample, the proportions of praseodymium oxide and neodymium oxide are controlled as 25% and 75% respectively, that is, the mass ratio of neodymium oxide and praseodymium oxide is 3. As a standard product with
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characteristic quantity, it is closer to the actual product component, and the quality control effect is better.
According to another aspect of the present invention, the present invention further relates to a preparation method of the rare earth oxide standard sample, comprising the following steps:
grinding and uniformly mixing a mixture of rare earth oxide raw material and sodium chloride raw material; and the rare earth oxide raw material comprises lanthanum oxide raw material, cerium oxide raw material, praseodymium oxide raw material and neodymium oxide raw material.
In the present invention, the rare earth oxide raw material and the sodium chloride raw material are ground and uniformly mixed. The method is simple and easy to implement. The obtained standard sample has excellent uniformity and stability. The preparation method of the standard sample can realize the control quality and calibration instrument of the detection process of rare earth products such as rare earth carbonate and rare earth chloride, and is mainly used for evaluation and calibration of a gravimetric method and an ICP-OES method, i.e., methods for determining the total rare earth content. The preparation method solves the problem that the rare earth carbonate and the rare earth chloride cannot directly prepare standard samples because of unstable properties.
In one embodiment, a preparation method of the mixture of the rare earth oxide raw material and the sodium chloride raw material comprises: premixing the rare earth oxide raw material and the sodium chloride raw material; and the time of the premixing is 2-3 h.
In one embodiment, the time of the grinding is 170-200 s. In one embodiment, the time of the grinding includes but not limited to 170s, 172s, 14 PA22007140
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175s, 180s, 182s, 185s, 187s, 190s, 195s, 197s or 200s. The control of the particle size range depends on the time of grinding. In case of short time, the particle size range is wide and the difference of the standard sample particles is large, which is easy to lead to the segregation of the component elements; if the time of grinding is long, then the particle size range is small and there will be agglomeration and sandwiching phenomena between substances, which is easy to lead to massive concentration of the rare earth oxide. Thus, the particle size range of the standard sample can be reasonably controlled by appropriate grinding time.
In one embodiment, the time of the uniform mixing is 170-190 min. In one embodiment, the time of the uniform mixing includes but not limited to 171min, 172min, 173min, 174min, 175min, 176min, 177min, 178min, 179min, 180min, 181min, 182min, 185min, 187min or 190min. The present invention adopts appropriate time of uniform mixing to ensure the full uniform mixing of the components, so that the standard sample obtains high uniformity.
In one embodiment, the purities of the lanthanum oxide raw material, the cerium oxide raw material, the praseodymium oxide raw material and the neodymium oxide raw material are above 4N grade. In one embodiment, the sodium chloride raw material is guaranteed reagent sodium chloride.
In one embodiment, the preparation method of the rare earth oxide standard sample further comprises the following steps: detecting the uniformity and stability of the rare earth oxide standard sample; and conducting setting detection after the uniformity and the stability of the rare earth oxide standard sample are qualified. In one embodiment, the setting detection can be conducted by at least 6 detection institutions, at least 8 groups of setting detection data are given and the results of standard values are counted.
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In one embodiment, the uniformity is detected by glow discharge mass spectrometry (GD-MS). GD-MS is an analytical method that uses a glow discharge source as an ion source to combine with a mass spectrometer for mass spectrometry determination. Inert gas (argon) is introduced into a glow discharge cell, an electric field is applied between a cathode and an anode, and the inert gas is punctured and ionized. Positive ions accelerate to impact the surface of the sample as the cathode under the action of the electric field, and the surface atoms are sputtered and separated from the sample to enter glow discharge plasma. After ionized in the plasma, the surface atoms are introduced into the mass spectrometer, and the separated ion beams are collected and detected by the detector. The computer automatically calculates the mass fraction of each element to be detected according to a "standard relative sensitivity factor" in instrument software. According to the uniformity requirement of the standard sample, the GD-MS method is used for researching the uniformity of the standard sample. GD-MS and ICP-MS have the same detection principle, but GD-MS has the following advantages: 1) direct, rapid and multi-element analysis of solid; 2) uniform response of most elements; 3) sub-ppb detection limit; 4) simplicity of mass spectrometry; 5) convenient operation. These special features make the GD-MS technique feasible for samples that exist in complex solid substrates and are difficult to dissolve, and can be used for proving the uniformity of the samples to be detected.
In one embodiment, the uniformity detection specifically comprises: according to the requirements of GB/T 15000 Directives for the Work of Reference Materials and YS/T 409-2012 Specification for Certified Reference Materials for Non-Ferrous Product Analysis, when the total number of units N < 1000, 2%-3% is extracted, not less than 15. 15 bottles of samples are extracted according to the random number table for uniformity detection. 15 groups of the 16 PA22007140
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same amount of rare earth oxide standard samples are selected, the content of each trace element in each group of standard samples is determined, and the relative standard deviation of the content of the same trace element in each group is calculated. In one embodiment, different personnel of the at least 6 detection institutions conduct the setting detection at different times. In one embodiment, the total rare earth content in the standard sample is determined by GB/T 24635-2020; and the partition of rare earth is determined by GB/T 16484.3-2009. In one embodiment, a qualified laboratory is used in the process of setting detection, and the contents of total rare earth, lanthanum, cerium, praseodymium and neodymium in the standard sample are accurately assigned with certified standard solutions.
In a preferred embodiment, a preparation method of the rare earth oxide standard sample for controlling the standard value of total rare earth content, as shown in Fig. 1, comprises the following steps:
I. Composition design of rare earth oxide standard sample:
Raw material: sodium chloride and rare earth oxide (lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide);
1. Composition design of lanthanum-cerium oxide standard sample: based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 38%-42%; the mass percentages of components of the lanthanum-cerium oxide in the rare earth oxide standard sample are: lanthanum oxide is 13%-15%, cerium oxide is 24%-28%, praseodymium oxide is 0.1%-0.4%, and neodymium oxide is 0.5%-1%; and in the lanthanum-cerium oxide, a mass ratio of cerium oxide and lanthanum oxide is 1.75-2 and a mass ratio of neodymium oxide and praseodymium oxide is 2.5-5.
2. Composition design of praseodymium-neodymium oxide standard 17 PA22007140
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sample: based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28%-32%; the mass percentages of components of the praseodymium-neodymium oxide in the rare earth oxide standard sample are: lanthanum oxide is 0.1%-0.3%, cerium oxide is 0.2%-0.5%, praseodymium oxide is 6%-8% and neodymium oxide is 21%-24%; and in the lanthanum-cerium oxide, a mass ratio of cerium oxide and lanthanum oxide is 1.65-2 and a mass ratio of neodymium oxide and praseodymium oxide is 2.9-3.6.
II. Preparation of rare earth oxide standard sample
Guaranteed reagent sodium chloride with uniform particle size and rare earth oxide above 4N grade are premixed, ground for 175-182s, and then mixed for 175-185 min to obtain the rare earth oxide standard sample.
III. Detection of rare earth oxide standard sample
The particle size and the micromorphology of the obtained rare earth oxide standard sample are researched, the composition design results and uniformity characterization of the sample are determined, and then the uniformity is initially detected. The judgment basis of the initial detection of the uniformity is comparison of the standard deviation of 7 tests with the admissible error 1 between laboratories of the method. When 2 , the initial detection of 1 the uniformity is considered to be qualified; and when 2 , the initial detection of the uniformity is unqualified. After the initial detection is qualified, the uniformity and the stability are inspected, and the combined verification of multiple statistical methods is considered. After the uniformity inspection and the stability inspection satisfy the requirements of the technical specifications, 6 qualified laboratories are selected, and at least 8 groups of data are given in setting detection at different times and by different methods and different 18 PA22007140
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personnel. The results are set statistically. The setting process requires that the detection process of each laboratory adopts the certified standard material as the standard curve, the detection equipment used must be verified or calibrated, and the detection personnel must be certified to work and repeat the test to ensure the value traceability of the setting result. According to Specification for Certified Reference Materials for Non-Ferrous Product Analysis YS/T409-2012 and Directives for the Work of Reference Materials GB/T15000.3-2008, the uniformity inspection, setting and data processing are conducted.
The present invention is further described below in combination with specific embodiments and drawings.
Embodiment 1
A rare earth oxide standard sample comprises a uniform mixture of lanthanum-cerium oxide and sodium chloride; based on mass percentage, the lanthanum-cerium oxide in the lanthanum-cerium oxide standard sample is 40%, wherein the lanthanum oxide is 13.8%, the cerium oxide is 25.4%, the praseodymium oxide is 0.2% and the neodymium oxide is 0.6%,wherein the particle size D10 of the rare earth oxide standard sample is 0.251 pm; the particle size D50 of the rare earth oxide standard sample is 0.707 pm; and the particle size D90 of the rare earth oxide standard sample is 1.91 pm.
A preparation method of the rare earth oxide standard sample in the present embodiment comprises the following steps:
mixing guaranteed reagent sodium chloride raw material with rare earth oxide raw material, grinding for 3 min, and then mixing for 3 h to obtain the rare earth oxide standard sample.
Embodiment 2 19 PA22007140
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A rare earth oxide standard sample comprises a uniform mixture of lanthanum-cerium oxide and sodium chloride; based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 38%, wherein the lanthanum oxide is 13%, the cerium oxide is 24.4%, the praseodymium oxide is 0.1% and the neodymium oxide is 0.5%,wherein the particle size D10 of the rare earth oxide standard sample is 0.292 pm; the particle size D50 of the rare earth oxide standard sample is 0.855 pm; and the particle size D90 of the rare earth oxide standard sample is 2.36 pm. A preparation method of the rare earth oxide standard sample in the present embodiment is the same as that of embodiment 1.
Embodiment 3
A rare earth oxide standard sample comprises a uniform mixture of lanthanum-cerium oxide and sodium chloride; based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 42%, wherein the lanthanum oxide is 15%, the cerium oxide is 26.6%, the praseodymium oxide is 0.3% and the neodymium oxide is 0.1%,wherein the particle size D10 of the rare earth oxide standard sample is 0.311 pm; the particle size D50 of the rare earth oxide standard sample is 0.880 pm; and the particle size D90 of the rare earth oxide standard sample is 6.96 pm. A preparation method of the rare earth oxide standard sample in the present embodiment is the same as that of embodiment 1.
Embodiment 4
A rare earth oxide standard sample comprises a uniform mixture of praseodymium-neodymium oxide and sodium chloride; based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 30%, wherein the lanthanum oxide is 0.2%, the cerium oxide 20 PA22007140
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is 0.4%, the praseodymium oxide is 7.3% and the neodymium oxide is 22.1%,wherein the particle size D10 of the rare earth oxide standard sample is 0.269 pm; the particle size D50 of the rare earth oxide standard sample is 0.910 pm; and the particle size D90 of the rare earth oxide standard sample is 5.51 pm.
A preparation method of the praseodymium-neodymium oxide standard sample in the present embodiment comprises the following steps:
mixing guaranteed reagent sodium chloride raw material with rare earth oxide raw material, grinding for 3 min, and then mixing for 3 h to obtain the rare earth oxide standard sample.
1o Embodiment 5
A rare earth oxide standard sample comprises a uniform mixture of praseodymium-neodymium oxide and sodium chloride; based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28%, wherein the lanthanum oxide is 0.3%, the cerium oxide is 0.5%, the praseodymium oxide is 6% and the neodymium oxide is 21.2%. A preparation method of the rare earth oxide standard sample in the present embodiment is the same as that of embodiment 4.
Embodiment 6
A rare earth oxide standard sample comprises a uniform mixture of praseodymium-neodymium oxide and sodium chloride; based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 32%, 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%. A preparation method of the rare earth oxide standard sample in the present embodiment is the same as that of embodiment 4.
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Embodiment 7
A preparation method of a rare earth oxide standard sample comprises: (1) raw material preparation: selecting 6000g of guaranteed reagent sodium chloride with uniform particle size, and accurately weighing 1380g of lanthanum oxide, 2540g of cerium oxide, 20g of praseodymium oxide and 60g of neodymium oxide; and (2) premixing the components in step (1) for 2 h, and then grinding by a grinding machine for 3 min, for 150g in each round; further uniformly mixing the ground material by a mixer for 3h to obtain the rare earth oxide standard sample, as shown in Fig. 13. The rare earth oxide standard sample prepared in the present embodiment is subpackaged, as shown in Fig. 15.
Embodiment 8
A preparation method of a rare earth oxide standard sample comprises: (1) raw material preparation: selecting 7000g of guaranteed reagent sodium chloride with uniform particle size, and accurately weighing 20g of lanthanum oxide, 40g of cerium oxide, 730g of praseodymium oxide and 221Og of neodymium oxide; and (2) premixing the raw material in step (1) for 2 h, and then grinding by a grinding machine for 3 min, for 150g in each round; further uniformly mixing the ground material by a mixer for 3h to obtain the rare earth oxide standard sample, as shown in Fig. 14. The rare earth oxide standard sample prepared in the present embodiment is subpackaged, as shown in Fig. 16.
The particle size and the micromorphology of the rare earth oxide standard samples in the embodiments are researched, the composition design results and uniformity characterization of the samples are determined, and then the uniformity is initially detected. After the initial detection is qualified, the uniformity and the stability are inspected, and the combined verification of multiple statistical methods is considered. The uniformity is detected by glow 22 PA22007140
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discharge mass spectrometry. The uniformity detection specifically comprises: randomly selecting 15 groups of the same amount of standard samples in different positions from the rare earth oxide standard samples, determining the content of each trace element in each group of standard samples and calculating the average value, the standard deviation and the relative standard deviation of the same trace element in each group. In each group, the relative standard deviation of the content of the same trace element satisfies the permissible fluctuation range of trace element determination.
Experiment Example
I. Scanning electron microscope (SEM) diagram of rare earth oxide
standard sample
Fig. 2 is a scanning electron microscope diagram of a rare earth oxide
standard sample under the condition that EHT is 3KV and magnification is at
1000 times in embodiment 1 of the present invention; Fig. 3 is a scanning
electron microscope diagram of a rare earth oxide standard sample under the
condition that EHT is 20KV and magnification is at 500 times in embodiment 1
of the present invention; Fig. 4 is a scanning electron microscope diagram of a
rare earth oxide standard sample under the condition that EHT is 3KV and
magnification is at 1000 times in embodiment 4 of the present invention; Fig. 5
is a scanning electron microscope diagram of a rare earth oxide standard sample
under the condition that EHT is 20KV and magnification is at 500 times in
embodiment 4 of the present invention. As shown in Fig.2, Fig.3, Fig.4 and
Fig.5, EHT is 3KV, and the SEM morphology of the standard sample is
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observed in SE2 mode under the condition of magnification at 1000 times,
which shows polygonal particles with uniform particle size; EHT is 20KV, and
the SEM morphology of the standard sample is observed in HDBSD mode under
the condition of magnification at 500 times, and particles with different
brightness are formed, i.e., sodium chloride particles and rare earth oxide
particles respectively, wherein the bright particles are rare earth oxide and the
dark particles are sodium chloride crystals. In the case of micro-region, the SEM
diagram can prove that the two kinds of substances are evenly distributed.
II. Particle size distribution curves of rare earth oxide standard sample
The present invention researches the particle size intervals of the rare earth oxide and crystal sodium chloride, analyzes that when the particle size range meets the particle size interval of the mixed rare earth oxide, the uniformity requirement can be met in combination with the particle size difference of the two, and researches and measures the particle size distribution (Fig. 6) and the scanning electron microscope diagram (Fig. 7) of mixed (lanthanum, cerium, praseodymium ad neodymium) rare earth oxide, wherein in Fig. 6, for the (lanthanum, cerium, praseodymium and neodymium) rare earth oxide, the particle size D10 is 1.53pm, the particle size D50 is 4.40pm and the particle size D90 is 10.8pm. According to the particle size range of the mixed rare earth oxide, the grinding time of the standard sample is repeatedly tested, the grinding effect is controlled, and the REO content in the sample is detected. According to the stability analysis of REO results, the grinding time of 3 min is determined to obtain the best particle size and the particle size distribution curve, wherein the particle size distribution curve of the rare earth oxide standard sample in embodiment 1 is shown in Fig. 8, and the particle size distribution curve of the 24 PA22007140
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rare earth oxide standard sample in embodiment 4 is shown in Fig. 9.
III. Uniformity detection results of rare earth oxide standard sample
(1) Taking 15 detection results of non-substrate elements in the rare earth oxide standard sample in embodiment 1 as an example, the uniformity of the standard sample is determined. Average represents the average value, Std Dev represents the standard deviation, and RSD represents the relative standard deviation. The results are shown in Table 1.
Table 1 Uniformity Detection Results of Non-Substrate Elements in Rare Earth Oxide
Standard Sample in Embodiment 1
Number of K39 Ca44 Fe56 Cu65 Zn66 determination 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
It can be seen from the data in Table 1 that the contents of K, Ca, Fe, Cu and Zn trace elements range from 0.9 to 30 ppm, and the uniformity detection of the trace elements can better explain the uniformity of substances. The RSDs of K, Ca, Fe, Cu and Zn are 6.92%, 7.41%, 6.03%, 10.63% and 27.09% 25 PA22007140
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respectively, which meet the determination fluctuation of the trace elements and can proved that the uniformity of the standard sample is good.
(2) Taking 15 detection results of non-substrate elements in the rare earth oxide standard sample in embodiment 4 as an example, the uniformity of the standard sample is determined. The results are shown in Table 2.
Table 2 Uniformity Detection Results of Non-Substrate Elements in Rare Earth Oxide
Standard Sample in Embodiment 4
Number of K39 Ca44 Fe56 Cu65 Zn66 determination 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
It can be seen from the data in Table 2 that the contents of K, Ca, Fe, Cu and Zn trace elements range from 0.9 to 30 ppm, and the uniformity detection of the trace elements can better explain the uniformity of substances. The RSDs of K, Ca, Fe, Cu and Zn are 11.72%, 8.10%, 10.63%, 10.93% and 24.94% respectively, which meet the determination fluctuation of the trace elements and can proved that the uniformity of the standard sample is good.
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IV. Stability detection results of rare earth oxide standard sample
Under the condition of eliminating the influence of sample mass,
uniformity, heating rate, atmosphere pressure and other factors, the TG curve
and the DSC curve are analyzed to judge whether a standard sample candidate is
based on the change of mass corresponding to a thermal effect, and further judge
the substance transformation process corresponding to the thermal effect. The
current actual mass of the standard sample at the reaction temperature is known,
which is convenient for accurate judgment of comprehensive thermal stability,
wherein TG and DSC are detected by JB/T6856-1993 standard in
comprehensive thermal analysis.
Fig. 10 is a comprehensive thermal analysis curve of mixed rare earth oxide,
wherein in the DSC curve, peak comprehensive analysis: the area is 27.36J/g,
the peak is 299.2°C, the peak starting point is 273.4°C, the peak end point is
326.3 0C, the peak width is 41.8 0C, and the peak height is 0.1264mW/mg; in the
TG curve corresponding to the peak of the DSC curve, the mass change of the
mixed rare earth oxide is 1.89%; after 326.3 0C up to the end of heat treatment,
the mass change of the mixed rare earth oxide is 1.05%, and the final residual
mass is 97.06% (1199 0 C).
Fig. 11 is a thermal analysis curve of a lanthanum-cerium rare earth oxide standard sample in embodiment 1. in the DSC curve, peak comprehensive analysis: the area is 37.61 J/g, the peak is 322.1 0 C, the peak starting point is 289.6 0C, and the peak end point is 346.8 0C. Fig. 12 is a thermal analysis curve
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of a praseodymium-neodymium rare earth oxide standard sample in embodiment 4, wherein in the DSC curve, peak comprehensive analysis: the area is 180.71 J/g, the peak is 809.2°C, the peak starting point is 799.1°C, and the peak end point is 816.3°C. It can be seen from the TG curve and the DSC curve of the lanthanum-cerium rare earth oxide standard sample and the praseodymium-neodymium rare earth oxide standard sample that the oxide standard samples have good thermal stability below 60°C. It can be seen from Fig. 11 and Fig. 12 that 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°C to 300 0C, which proves that the samples in the temperature range may change the physical and chemical properties and have storage and transportation conditions.
Finally, it should be noted that the above embodiments are only used for describing the technical solution of the present invention rather than limiting the present invention. Although the present invention is described in detail by referring to the above embodiments, those ordinary skilled in the art should understand that: the technical solution recorded in each of the above embodiments can be still amended, or part or all of technical features therein can be replaced equivalently; and the amendments or replacements do not enable the essence of the corresponding technical solution to depart from the scope of the technical solution of various embodiments of the present invention.
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Claims (12)
1. A rare earth oxide standard sample, comprising a uniform mixture of rare earth oxide and sodium chloride; based on mass percentage, the rare earth oxide in the rare earth oxide standard sample is 28%-42%;
the rare earth oxide comprises lanthanum oxide, cerium oxide, praseodymium oxide and neodymium oxide;
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%.
2. The rare earth oxide standard sample according to claim 1, wherein the particle size D10 of the rare earth oxide standard sample is 0.1-1 pm;
the particle size D50 of the rare earth oxide standard sample is 0.5-3 pm;
the particle size D90 of the rare earth oxide standard sample is 1-8 pm.
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) based on mass percentage, the lanthanum-cerium oxide in the rare earth oxide standard sample is 38%-42%;
the mass percentages of components of the lanthanum-cerium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 13%-15%, cerium oxide is 24%-28%, praseodymium oxide is 0.1%-0.4%, and neodymium oxide is 0.5%-1%;
(2) a mass ratio of cerium oxide and lanthanum oxide in the lanthanum cerium oxide is 1.75-2; 29 PA22007140
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(3) a mass ratio of neodymium oxide and praseodymium oxide in the lanthanum-cerium 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) based on mass percentage, the praseodymium-neodymium oxide in the rare earth oxide standard sample is 28%-32%;
the mass percentages of components of the praseodymium-neodymium oxide in the rare earth oxide standard sample are respectively: lanthanum oxide is 0.1%-0.3%, cerium oxide is 0.2%-0.5%, praseodymium oxide is 6%-8% and neodymium oxide is 21%-24%;
(2) a mass ratio of cerium oxide and lanthanum oxide in the praseodymium neodymium oxide is 1.65-2;
(3) a mass ratio of neodymium oxide and praseodymium oxide in the praseodymium-neodymium oxide is 2.9-3.6.
6. The rare earth oxide standard sample according to claim 1, wherein the rare earth oxide standard sample further comprises trace elements; the content of the trace elements is 0.5-50 ppm;
the trace elements comprise K, Ca, Fe, Cu and Zn.
7. A preparation method of the rare earth oxide standard sample according to any one of claims 1-6, comprising the following steps:
grinding and uniformly mixing a mixture of rare earth oxide raw material and sodium chloride raw material;
the rare earth oxide raw material comprises lanthanum oxide raw material, cerium oxide raw material, praseodymium oxide raw material and neodymium
30 PA22007140
PA22007140
oxide raw material.
8. The preparation method of the rare earth oxide standard sample according to claim 7, wherein a preparation method of the mixture of the rare earth oxide raw material and the sodium chloride raw material comprises: premixing the rare earth oxide raw material and the sodium chloride raw material;
the time of the premixing is 2-3 h.
9. The preparation method of the rare earth oxide standard sample according to claim 7, comprising at least one of the following features (1)-(3):
(1) the time of the grinding is 170-200 s;
(2) the time of the uniform mixing is 170-190 min;
(3) the sodium chloride raw material is guaranteed reagent sodium chloride.
10. The preparation method of the rare earth oxide standard sample according to claim 7, further comprising: detecting the uniformity and stability of the rare earth oxide standard sample.
31 PA22007140
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Drawings of Description
Stability Initial detection Preparation Solution Composition research of of total rare Qualified of standard design design diluent earth content sample
Qualified
Development Uniform Determination of Warehousing Compounding Mixing Grinding process of mixing standard value for storage standard sample
Particle size Morphological detection observation
Fig. 1
Fig. 2
1/9 PA22007140
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μm EHT=20.00kV SignalA=HDBSD WD=8.4mm Mag=500X
Fig. 3
Fig. 4
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10μm EHT=20.00kV SignalA=HDBSD WD=8.5mm Mag=500X
Fig. 5
Volume accumulation Bulk density Volume accumulation (%) Bulk density (%)
Particle size grading of mixed rare earth oxide (μm)
Fig. 6
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Fig. 7
Volume accumulation
Bulk density
Volume accumulation (%) Bulk density (%)
Lanthanum-cerium particle size grading (μm)
Fig. 8
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Volume accumulation
Bulk density
Volume accumulation (%) Bulk density (%)
Praseodymium-neodymium particle size grading (μm)
Fig. 9
(mW/mg)） TG curve
scanning calorimetrymW/mg 质量百分比（%） Mass percentage (%)
Mass change 1.89%
Mass change 1.05% 差示扫描量热法（ Residual mass 97.06% (1199℃) Differential
DSC curve
温度（℃） Temperature (℃)
Fig. 10
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Mass percentage (%) 质量百分比（%）
TG curve
6/9 DSC curve
Fig.
11 Temperature 温度（℃） (℃) Mass percentage (%) Temperature (℃)
PA22007140 PA22007140
Differential scanning calorimetry (mW/mg) 差示扫描量热法（mW/mg）
Mass percentage (%) 质量百分比（%） TG curve
DSC curve
7/9 Fig. 13 Fig.
12 Temperature (℃) Mass percentage (%) Temperature (℃)
Differential scanning calorimetry (mW/mg) 差示扫描量热法（mW/mg）
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Fig. 14
Fig. 15
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Fig. 16
9/9 PA22007140
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| PCT/CN2023/098356 WO2024027327A1 (en) | 2022-08-01 | 2023-06-05 | Rare earth oxide standard sample, and preparation process therefor |
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