CN113376194B - X-ray fluorescence melting sample preparation method of aluminum nitride - Google Patents
X-ray fluorescence melting sample preparation method of aluminum nitride Download PDFInfo
- Publication number
- CN113376194B CN113376194B CN202110574698.8A CN202110574698A CN113376194B CN 113376194 B CN113376194 B CN 113376194B CN 202110574698 A CN202110574698 A CN 202110574698A CN 113376194 B CN113376194 B CN 113376194B
- Authority
- CN
- China
- Prior art keywords
- melting
- aluminum nitride
- sample
- acidolysis
- crucible
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002844 melting Methods 0.000 title claims abstract description 161
- 230000008018 melting Effects 0.000 title claims abstract description 160
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 146
- 238000004876 x-ray fluorescence Methods 0.000 title claims abstract description 46
- 238000005464 sample preparation method Methods 0.000 title claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 57
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 34
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010304 firing Methods 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 112
- 239000000843 powder Substances 0.000 claims description 49
- 238000005266 casting Methods 0.000 claims description 39
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 30
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 20
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 9
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims description 4
- 229940107816 ammonium iodide Drugs 0.000 claims description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000004458 analytical method Methods 0.000 abstract description 7
- 238000001514 detection method Methods 0.000 abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 144
- 239000000523 sample Substances 0.000 description 104
- 229910052697 platinum Inorganic materials 0.000 description 72
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 35
- 239000011521 glass Substances 0.000 description 34
- 239000000243 solution Substances 0.000 description 31
- 238000001816 cooling Methods 0.000 description 29
- 239000000463 material Substances 0.000 description 27
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 19
- 238000007664 blowing Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 14
- 238000004846 x-ray emission Methods 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- 241000519995 Stachys sylvatica Species 0.000 description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000005259 measurement Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical class [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 description 4
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001338 liquidmetal Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- 238000009681 x-ray fluorescence measurement Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241001248531 Euchloe <genus> Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- -1 uses wet chemistry Chemical compound 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/2202—Preparing specimens therefor
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/07—Investigating materials by wave or particle radiation secondary emission
- G01N2223/076—X-ray fluorescence
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/10—Different kinds of radiation or particles
- G01N2223/101—Different kinds of radiation or particles electromagnetic radiation
- G01N2223/1016—X-ray
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2223/00—Investigating materials by wave or particle radiation
- G01N2223/60—Specific applications or type of materials
- G01N2223/652—Specific applications or type of materials impurities, foreign matter, trace amounts
Landscapes
- Physics & Mathematics (AREA)
- 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)
- Analysing Materials By The Use Of Radiation (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The application provides an X-ray fluorescence melting sample preparation method of aluminum nitride, which belongs to the technical field of analysis and detection of impurity components of aluminum nitride, and comprises the following steps: acid liquor is added into aluminum nitride for acidolysis, and acidolysis gel is obtained; firing the acidolysis gel to obtain alumina; and adding a melting reagent and a release agent into the alumina, and pouring a sample after melting to obtain the sample. The method can prepare transparent, smooth and uniform sample, solves the problem that the conventional aluminum nitride melting sample preparation is difficult to mold, and develops a novel method for preparing the aluminum nitride melting sample.
Description
Technical Field
The application belongs to the technical field of analysis and detection of aluminum nitride impurity components, and particularly relates to an X-ray fluorescence melting sample preparation method of aluminum nitride.
Background
The aluminum nitride powder is a powder material with excellent performance, is a basic key material for preparing high-performance aluminum nitride ceramics, has good heat conduction, electricity, machinery and chemical stability, is widely applied to industries such as integrated circuits, semiconductors, new energy sources and the like, and has extremely important application in the fields of electronic science and technology, high-speed rail, aerospace and military industry. Too high impurity elements in the aluminum nitride powder will seriously affect the heat conduction performance of the downstream aluminum nitride ceramics, so the analysis of the impurity elements in the aluminum nitride powder is an important task, but the research of the impurity element analysis method in the aluminum nitride powder is almost blank at present.
Since the high-end imported aluminum nitride powder relates to high-end technological projects such as electronics, aerospace, military and the like, and the imported powder is subject to international political relations and is frequently forbidden to be transported, the autonomous research and development of the high-end aluminum nitride powder are gradually paid attention to in recent years, the industrial layout and technological attack of the high-end aluminum nitride project are developed, and the aluminum nitride industry is very likely to develop newly, and under the background, the research on the impurity element method of aluminum nitride is very necessary to develop.
The aluminum nitride mainly comprises impurity elements such as silicon, iron, sodium, calcium, magnesium, potassium and the like, the content of the impurity elements is usually below 0.1%, the aluminum nitride impurity analysis methods reported in the current literature are very few, the wet chemistry is mainly used, the sample dissolution process is relatively complicated, only one element can be measured at a time, and the efficiency is low. The X-ray fluorescence spectrometry (XRF method) is an instrument analysis method for rapidly measuring multiple elements simultaneously, and has no great report on the detection of aluminum nitride impurity elements at present. In the conventional XRF melting sample preparation, a sample to be detected is directly added into a flux for high-temperature melting, and because aluminum nitride belongs to an atomic crystal, aluminum nitride is difficult to melt in the flux, the conventional melting sample can only obtain a slightly soluble glue-like melt, and a glass sheet is difficult to pour into a mold for casting, and even if the sample is forcibly cast into a sheet-like sheet, the sample sheet is opaque and has extremely poor uniformity and cannot be used for measurement.
Disclosure of Invention
In order to solve the technical problems that samples are difficult to melt, opaque and difficult to form in conventional aluminum nitride XRF melting sample preparation, the application provides an X-ray fluorescence melting sample preparation method of aluminum nitride, which can prepare transparent, smooth and uniform sample pieces, solves the problem that conventional aluminum nitride melting sample preparation is difficult to form, and develops a novel method for aluminum nitride melting sample preparation.
The application is realized by the following technical scheme:
the application provides an X-ray fluorescence melting sample preparation method of aluminum nitride, which comprises the following steps:
acid liquor is added into aluminum nitride for acidolysis, and acidolysis gel is obtained;
firing the acidolysis gel to obtain alumina;
and adding a melting reagent and a release agent into the alumina, and pouring a sample after melting to obtain the sample.
Optionally, the acid solution comprises a sulfuric acid solution and/or a perchloric acid solution.
Optionally, the step of adding acid liquor into aluminum nitride for acidolysis to obtain acidolysis gel specifically comprises the following steps:
adding acid liquor into aluminum nitride, preserving heat at 110-180 ℃ for 5-10 min, and preserving heat at 200 ℃ for 20-50 min to obtain acidolysis gel.
Optionally, the firing the acidolysis gel to obtain alumina specifically includes:
heating the acidolysis gel to volatilize residual acid to obtain acidolysis powder;
and firing the acidolysis powder to obtain alumina.
Optionally, heating the acidolysis gel to volatilize residual acid to obtain acidolysis powder, which specifically comprises the following steps:
and heating the acidolysis gel to 300-500 ℃, preserving heat for 15-30 min, and volatilizing residual acid to obtain acidolysis powder.
Optionally, the firing the acidolysis powder to obtain alumina specifically includes:
firing the acidolysis powder for 20-40 min at 950-1050 ℃ to obtain alumina.
Optionally, the firing the acidolysis gel to obtain alumina specifically includes:
firing the acidolysis gel at 950-1050 ℃ for 20-40 min to obtain alumina.
Optionally, the following relationship exists between the mass of the aluminum nitride and the volume of the acid solution:
3-12 mL of the acid liquor is added into each 0.5-1.2 g of aluminum nitride;
the acid liquor is prepared by mixing water and pure acid, and the volume ratio of the water to the pure acid is (1-6) to 2.
Optionally, adding a melting reagent and a release agent into the alumina, and pouring a sample after melting to obtain the sample, wherein the method specifically comprises the following steps of:
adding a melting reagent and a release agent into the alumina, melting at 1000-1100 ℃, and casting a transparent sample.
Optionally, the melting agent comprises at least one of lithium borate, lithium tetraborate, lithium metaborate, and lithium carbonate;
the release agent comprises lithium bromide and/or ammonium iodide.
One or more technical schemes of the application have at least the following technical effects or advantages:
according to the X-ray fluorescence melting sample preparation method of aluminum nitride, acid liquor is adopted to acidolyze the aluminum nitride, the acidolyzed gel is burned to obtain the aluminum oxide powder, the aluminum oxide powder is added with a melting reagent and a release agent to be melted, clear, clean and transparent sample pieces can be poured, the sample pieces are uniform in texture, the problem that melting, transparency and forming are difficult to achieve due to direct melting of aluminum nitride is effectively solved, and a novel method for melting sample preparation of aluminum nitride XRF is developed.
The foregoing description is only an overview of the present application, and is intended to be implemented in accordance with the teachings of the present application in order that the same may be more clearly understood and to make the same and other objects, features and advantages of the present application more readily apparent.
Drawings
In order to more clearly illustrate the technical solutions of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a flow chart of a method for preparing aluminum nitride by X-ray fluorescence melting;
FIG. 2 is a diagram of an acidolyzed gel of example 1 of the present application;
FIG. 3 is a photograph of a sample obtained after melting in example 2 of the present application;
FIG. 4 is a diagram of a sample obtained after the melt-casting in example 5 of the present application;
FIG. 5 is a sample sheet obtained after the melt-casting in example 9 of the present application;
FIG. 6 is a photograph of comparative example 1 in which aluminum nitride is directly melted;
FIG. 7 is a photograph of the mold after melting comparative example 4.
Detailed Description
The advantages and various effects of the present application will be more clearly apparent from the following detailed description and examples. It will be understood by those skilled in the art that these specific embodiments and examples are intended to illustrate the application, not to limit the application.
Throughout the specification, unless specifically indicated otherwise, the terms used herein should be understood as meaning as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. In case of conflict, the present specification will control.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present application are commercially available or may be prepared by existing methods.
It should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
It should be noted that in this document, relational terms such as "first" and "second" and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
The technical scheme provided by the application aims to solve the technical problems, and the general idea is as follows:
at present, the chemical analysis of aluminum nitride mainly uses wet chemistry, the operation is more complicated, and in the sample preparation for measuring the impurity components of aluminum nitride by an X-ray fluorescence spectrometry, the conventional melting sample preparation is difficult to melt the sample into a clear and transparent glass sheet. The method provided by the application is used for rapidly analyzing the steps of acidolysis, acidolysis gel decomposition, high-temperature melting and the like of the aluminum nitride, and brings great convenience to product quality control in the fields of production and application of the aluminum nitride and the like.
According to an exemplary embodiment of the present application, there is provided an X-ray fluorescence melting sample preparation method of aluminum nitride, as shown in fig. 1, the method comprising:
s1, adding acid liquor into aluminum nitride for acidolysis to obtain acidolysis gel;
s2, firing the acidolysis gel to obtain aluminum oxide;
s3, adding a melting reagent and a release agent into the alumina, and pouring a sample after melting to obtain the sample.
According to the application, the acid liquor is adopted to acidolyze the aluminum nitride, the obtained acidolyzed gel is burned to obtain the aluminum oxide powder, the aluminum oxide powder is added with the melting reagent and the release agent to be melted, so that a clear, clean and transparent sample piece can be poured, the texture of the sample piece is uniform, the problem that the aluminum nitride is difficult to melt, transparent and mold when directly melted is effectively solved, and a novel method for melting and preparing the aluminum nitride XRF sample is opened up.
As an alternative embodiment, the acid solution comprises a sulfuric acid solution and/or a perchloric acid solution.
In the application, the acid liquor can be obtained by diluting sulfuric acid solution, obtaining acidolysis gel containing aluminum sulfate after acidolysis, obtaining aluminum oxide after firing, or obtaining acidolysis gel containing perchlorate, aluminum hydroxide and other components after acidolysis by diluting perchloric acid solution, and obtaining aluminum oxide after firing, or obtaining a mixture of the two.
As an optional embodiment, the method for adding acid solution to aluminum nitride for acidolysis to obtain acidolysis gel specifically includes:
adding acid liquor into aluminum nitride, preserving heat at 110-180 ℃ for 5-10 min, and preserving heat at 200 ℃ for 20-50 min to obtain acidolysis gel.
In the application, aluminum nitride is kept at 110-180 ℃ for 5-10 min, then is kept at 200 ℃ for 20-50 min, and reacts at 110-180 ℃ first, mainly for the purpose of playing a buffering role, avoiding severe boiling of water and reducing the intensity of acidolysis, if acidolysis is directly carried out at a higher temperature of 200 ℃ and the like, the water boiling is faster, the acidolysis is more severe after the crucible is put in, and the splashing is easy to cause quality loss.
As an alternative embodiment, the firing of the acidolysis gel to obtain alumina specifically includes:
heating the acidolysis gel to volatilize residual acid to obtain acidolysis powder;
and firing the acidolysis powder to obtain alumina.
In the application, the acidolysis gel volatilizes residual acid by heating, and the obtained product is burnt, so that the boiling intensity of the high-temperature burning stage is reduced by the way of volatilizing the residual acid and water in advance, and the possible splash caused by directly burning the acidolysis gel is avoided.
As an optional implementation manner, the heating of the acidolysis gel to volatilize residual acid to obtain acidolysis powder specifically includes:
and heating the acidolysis gel to 300-500 ℃, preserving heat for 15-30 min, and volatilizing residual acid to obtain acidolysis powder.
In the application, if the temperature is too high, severe boiling of residual liquid is caused at the temperature of more than 500 ℃ to cause splashing, the residual acid removal rate is too low when the temperature is too low, the efficiency is affected, and most of residual acid can be removed at 300-500 ℃ for 15-30 min.
As an optional implementation manner, the firing of the acidolysis powder to obtain alumina specifically includes:
firing the acidolysis powder for 20-40 min at 950-1050 ℃ to obtain alumina.
In the application, acidolysis powder can be completely decomposed after being burned for 20-40 min at 950-1050 ℃ to obtain alumina.
As an alternative embodiment, the firing of the acidolysis gel to obtain alumina specifically includes:
firing the acidolysis gel at 950-1050 ℃ for 20-40 min to obtain alumina.
In the application, the acidolysis gel can be directly burned for 20-40 min at 950-1050 ℃, and residual acid, water, ammonia and other substances volatilize during the burning process to obtain the alumina.
As an alternative embodiment, the following relationship exists between the mass of the aluminum nitride and the volume ratio of the acid solution:
3-12 mL of the acid liquor is added into each 0.5-1.2 g of aluminum nitride;
the acid liquor is prepared by mixing water and pure acid, and the volume ratio of the water to the pure acid is (1-6) to 2.
In the application, the added acid liquor is obtained by diluting the pure acid in proportion, the concentration of the added acid liquor is water to pure acid= (1-6) to 2, if the concentration of the acid liquor is too large, the viscosity of the high-concentration acid liquor is strong although the added volume is small, the reaction of aluminum nitride at the bottom is not easy to complete, if the concentration of the acid liquor is too small, the added acid liquor is too large, the volume of a crucible for reaction is limited, boiling splashing of water in acidolysis is easy to be caused, meanwhile, the acidolysis effect is poor, and the influence efficiency of acidolysis time needs to be increased.
In the application, the mass concentration of the pure acid is more than or equal to 99 percent.
In the application, the water in the acid liquor can be pure water or deionized water or distilled water, and is suitable for not introducing impurities.
In the application, 3-12 mL of the acid liquor is added into every 0.5-1.2 g of aluminum nitride in the volume adding ratio of the aluminum nitride to the acid liquor, because the weighing mass of the aluminum nitride is lower than 0.5g, and the lower sample weighing amount is unfavorable for measuring microelements, so that enough X fluorescence intensity is excited in XRF measurement, and XRF measurement is difficult; the current general sample preparation device-crucible has the height of 3cm-5cm, the diameter of 3cm-5cm and the volume of 30mL-50mL, if the mass of aluminum nitride is higher than 1.2g, on one hand, aluminum oxide is too much after acidolysis and burning, the flux can not completely melt the aluminum oxide to obtain clear sample pieces, on the other hand, more aluminum nitride needs to be added with larger acid solution volume in acidolysis, the crucible has limited volume, and the excessive aluminum nitride easily causes splash in acidolysis, so that the material is scattered outside the platinum yellow crucible to cause loss, and the added acid solution has too small volume, so that acidolysis is incomplete. If the crucible is provided with a larger volume in the actual sample preparation process, the use amount of aluminum nitride and acid liquor can be moderately increased, so that splashing is not caused, and acidolysis is complete.
As an alternative embodiment, the adding a melting agent and a release agent to the alumina, and pouring a sample after melting to obtain a sample specifically includes:
adding a melting reagent and a release agent into the alumina, melting at 1000-1100 ℃, and casting a transparent sample.
The post-melting is carried out at 1000-1100 ℃, and specifically comprises the following steps:
then standing and melting for 5-8 min at 1000-1100 ℃ and swinging and melting for 6-10 min. The casting adopts an automatic casting mould or an artificial casting mould, and cooling and blowing are carried out for 1min-2min after casting.
In the application, the melting agent and the release agent can adopt the conventional components, and can melt the aluminum oxide at 1000-1100 ℃ to cast transparent sample.
As an alternative embodiment, the aluminum nitride has a particle size of 0.05 to 20 μm.
In the application, the grain diameter of aluminum nitride is 0.05-20 mu m, which belongs to the conventional grain diameter of aluminum nitride powder, and the powdery aluminum nitride can realize rapid acidolysis and improve the reaction efficiency.
As an alternative embodiment, the melting agent includes at least one of lithium borate, lithium tetraborate, lithium metaborate, and lithium carbonate;
the release agent comprises lithium bromide and/or ammonium iodide.
In the application, as the acidolysis product is alumina after being burnt, the melting reagent can well melt a sample, the release agent is one of lithium bromide or ammonium iodide, and 1-2 drops of the release agent are added by adopting a room-temperature saturated solution, because the release agent is added with excessive bromine and iodine on one hand and enters the sample, and on the other hand, a very small amount of impurities of the release agent can be introduced into the sample, although the release agent is a high-grade pure reagent.
An X-ray fluorescence melting sample preparation method of aluminum nitride according to the present application will be described in detail with reference to examples, comparative examples and experimental data.
In each example and comparative example of the application, the mass concentration of the pure sulfuric acid and the pure perchloric acid is equal to or more than 99 percent.
Example 1
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 0.5g of aluminum nitride powder sample is weighed into platinum Huang Ganguo, 3mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) is added, a platinum yellow crucible is placed into an oven, the temperature is kept at 110 ℃ for 10min, and then the temperature is kept at 200 ℃ for 20min, so that aluminum nitride is fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has no white spots, and the outside of the crucible has no material loss.
Wherein the platinum yellow crucible is made of platinum and gold=95:5 (mass ratio), has a height of 3cm-5cm, a diameter of 3cm-5cm and a volume of 30mL-50mL.
(2) Removing sulfuric acid: the platinum crucible is placed on an electric furnace, and the temperature is kept at 300 ℃ for 30min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 950 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate for 6.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 1 drop of saturated lithium bromide release agent, melting at 1000 ℃, standing and melting for 5min, swinging and melting for 6min, automatically casting by a machine, cooling and blowing for 1min, and casting into a clear and transparent glass sample.
Example 2
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 0.8g of aluminum nitride powder sample is weighed into platinum Huang Ganguo, 4.5mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) is added, a platinum yellow crucible is placed into an oven, the temperature is kept at 130 ℃ for 8min, and then the temperature is kept at 200 ℃ for 25min, so that aluminum nitride is fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has no white spots, and the outside of the crucible has no material loss.
(2) Removing sulfuric acid: the platinum crucible is placed on an electric furnace, and the temperature is kept at 400 ℃ for 25min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at the temperature of 1000 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding 7.0g of molten reagent lithium metaborate for X-ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated ammonium iodide release agent, melting at 1050 ℃, standing and melting for 5min, swinging and melting for 8min, automatically casting by a machine, cooling and blowing for 1.5min, and casting into clear and transparent glass sample.
Example 3
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.0g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 5.5mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 150 ℃ for 5min, then at 200 ℃ for 30min, so that aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has no white spots, and the outside of the crucible has no material loss.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 25min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding 7.0g X ray fluorescence melting reagent lithium tetraborate/lithium metaborate=12:22, stirring and mixing uniformly with a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 7min, and swinging during melting
Melting for 8min, manually casting, cooling, blowing for 1.5min, and casting into clear and transparent glass sample.
Example 4
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.0g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 7mL of sulfuric acid solution (pure water: pure sulfuric acid=1:1) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 120℃for 10min, and then at 200℃for 30min, so that the aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has extremely small white spots, and no material is lost outside the crucible.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate/lithium metaborate=67:33 for 7.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated ammonium iodide release agent, melting at 1075 ℃, standing and melting for 7min, swinging and melting for 8min, manually casting, cooling and blowing for 1.5min, and casting into a clear and transparent glass sample.
Example 5
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride ceramic is weighed, ground and then a powder sample is placed in platinum Huang Ganguo, 10mL of sulfuric acid solution (pure water: pure sulfuric acid=2:1) is added, a platinum yellow crucible is placed in an oven, the temperature is kept at 110 ℃ for 10min, and then the temperature is kept at 200 ℃ for 30min, so that aluminum nitride is fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has a little white spots, and no material is lost outside the crucible.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated ammonium iodide release agent, melting at 1075 ℃, standing and melting for 7min, swinging and melting for 8min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
Example 6
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 6mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 140℃for 10min, and then at 200℃for 30min, so that the aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has extremely small white spots, and no material is lost outside the crucible.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
Example 7
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 7.5mL of sulfuric acid solution (pure water: pure sulfuric acid=1:1) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 150℃for 10min, and then at 200℃for 30min, so that aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has extremely small white spots, and no material is lost outside the crucible.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
Example 8
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.0g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 5.0mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 150 ℃ for 5min, then at 200 ℃ for 30min, so that aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible has no white spots, and the outside of the crucible has no material loss.
(2) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (1) in a high-temperature furnace, and burning for 30min at 950 ℃ to directly decompose the acidolysis gel into aluminum oxide and sulfur trioxide (high-temperature escape).
(3) Melting and preparing a sample: cooling the crucible in the step (2) to room temperature, adding 7.0g X ray fluorescence melting reagent lithium tetraborate/lithium metaborate=12:22, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 7min, swinging and melting for 8min, manually casting, cooling and blowing for 1.5min, and casting into clear and transparent glass sample sheets.
Example 9
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 0.5g of aluminum nitride powder sample is weighed into platinum Huang Ganguo, 5mL of perchloric acid solution (pure water: pure perchloric acid=1:1) is added, a platinum yellow crucible is placed into an oven, the temperature is firstly kept at 150 ℃ for 10min, and then the temperature is kept at 200 ℃ for 40min, so that aluminum nitride is fully acidolyzed into perchlorate gel. After acidolysis, the upper half part of the crucible has no fine white spots, and the outside of the crucible has no material loss.
(2) Removing perchloric acid: the platinum yellow crucible is placed on a medium electric furnace and heated at 300 ℃ for 10min to volatilize and escape the perchloric acid.
(3) High-temperature decomposition of perchlorate materials: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at the temperature of 1000 ℃ to decompose the perchlorate material into aluminum oxide, chlorine (high-temperature escape) and oxygen (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
Example 10
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 7mL of perchloric acid solution (pure water: pure perchloric acid=1:2) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 180℃for 10min, and then at 200℃for 50min, so that the aluminum nitride was fully acidolyzed into a perchlorate gel. After acidolysis, the upper half part of the crucible has no fine white spots, and the outside of the crucible has no material loss.
(2) High-temperature decomposition of perchlorate materials: and (3) placing the platinum yellow crucible in the step (1) in a high-temperature furnace, and burning for 30min at 950 ℃ to decompose the perchlorate material into aluminum oxide, chlorine (high-temperature escape) and oxygen (high-temperature escape).
(3) Melting and preparing a sample: cooling the crucible in the step (2) to room temperature, adding 7.0g X ray fluorescence melting reagent lithium tetraborate/lithium metaborate=12:22, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into clear and transparent glass sample slices.
Example 11
The embodiment relates to an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.0g of aluminum nitride powder sample is weighed into platinum Huang Ganguo, 6mL of sulfuric acid and perchloric acid mixed solution (pure water: pure sulfuric acid: pure perchloric acid=1:1:1) is added, a platinum yellow crucible is placed into an oven, the temperature is firstly kept at 150 ℃ for 10min, and then the temperature is kept at 200 ℃ for 40min, so that aluminum nitride is fully acidolyzed into mixed gel of aluminum sulfate and perchlorate. After acidolysis, the upper half part of the crucible has no fine white spots, and the outside of the crucible has no material loss.
(2) Mixed gel of pyrolysis aluminium sulphate and perchlorate: the platinum yellow crucible in the step (1) is placed in a high-temperature furnace and burned for 30min at 950 ℃ to finally decompose materials such as aluminum sulfate, perchlorate, aluminum hydroxide and the like into aluminum oxide, sulfur trioxide (high-temperature escape), chlorine (high-temperature escape) and oxygen (high-temperature escape).
(3) Melting and preparing a sample: cooling the crucible in the step (2) to room temperature, adding 7.0g X ray fluorescence melting reagent lithium tetraborate/lithium metaborate=12:22, stirring and mixing uniformly by using a glass rod, adding 1 drop of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 1.5min, and casting into clear and transparent glass sample slices.
Comparative example 1:
the comparative example is an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) 7g of lithium tetraborate flux and 0.5g of aluminum nitride powder are weighed into a platinum yellow crucible, stirred and mixed uniformly by a glass rod, and then 2 drops of saturated lithium bromide release agent are added.
(2) Melting at 1075 ℃ for 8min, swinging for 8min, and pouring out the material in the crucible.
Comparative example 2:
the comparative example is an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) 7g of lithium tetraborate flux and 1.0g of aluminum nitride powder are weighed into a platinum yellow crucible, stirred and mixed uniformly by a glass rod, and then 2 drops of saturated ammonium iodide release agent are added.
(2) Melting at 1075 ℃ for 10min, swinging for 10min, melting in a crucible to form paste, and pouring the material into a manual mould.
Comparative example 3
The comparative example is an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 16mL of sulfuric acid solution (pure water: pure sulfuric acid=3:1) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 110℃for 10min, and then at 200℃for 30min, so that the aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, a large amount of white substances are accumulated on the upper half part of the crucible, and part of the materials are sprayed out of the crucible, so that loss is caused.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 2 drops of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
Comparative example 4
The comparative example is an X-ray fluorescence melting sample preparation method of aluminum nitride, which specifically comprises the following steps:
(1) Acidolysis in platinum Huang Ganguo: 1.2g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 2mL of sulfuric acid solution (pure water: pure sulfuric acid=3:1) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 110℃for 10min, and then at 200℃for 30min, so that the aluminum nitride was fully acidolyzed into aluminum sulfate. After acidolysis, the upper half part of the crucible is free of white substances, and part of the materials are sprayed out of the crucible, so that loss is caused.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding 8.0g of a melting reagent for X-ray fluorescence, namely lithium tetraborate, lithium metaborate=12:22, stirring and mixing uniformly by using a glass rod, adding 2 drops of a saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and ensuring that the glass sheet part is not clarified to be porcelain white. The addition amount of sulfuric acid in acidolysis process is too small, and acidolysis of aluminum nitride is incomplete.
The sample pieces obtained in examples 1 to 11 and comparative examples 1 to 4 were compared as shown in Table 1.
TABLE 1 Material sample data obtained for examples 1-11 and comparative examples 1-4
As can be seen from Table 1, examples 1-11, which used the X-ray fluorescence melting sample preparation method of aluminum nitride according to the present application, produced clear, clean and transparent glass sheets with uniform texture, which are useful for measuring impurity elements by XRF method.
In comparative examples 1 and 2, aluminum nitride powder was directly mixed with a melting agent and melted, and thus, aluminum nitride was difficult to directly melt as compared with aluminum oxide powder, and the obtained sample was opaque and difficult to mold, and thus, it was not possible to use the sample for measuring impurity elements by XRF method.
In comparative example 3, the addition amount of the sulfuric acid solution is excessive, and clear, clean and transparent glass sheets can be prepared, but the waste of materials is caused in the acidolysis process, and the sample preparation cost is increased.
In comparative example 4, the amount of sulfuric acid solution added was too small, the acidolysis reaction was difficult to proceed sufficiently, and the acidolysis of aluminum nitride was incomplete. The sample wafer is doped with opaque particles, which is unfavorable for the measurement of impurity elements by XRF method.
Correlation test:
in order to verify the effect of the application, a commercially available high-purity aluminum nitride reagent and a liquid metal ion solution are mixed, dried and uniformly ground to prepare aluminum nitride samples with different element gradients, and then ICP-OES chemical definite values are carried out to obtain 8 aluminum nitride reference standard samples.
Preparing a liquid metal ion suspension solution: preparing superior pure or analytically pure reagents such as sodium carbonate, zinc oxide, calcium phosphate, ferric oxide, nickel sesquioxide, potassium carbonate and the like, weighing substances with corresponding mass, putting the substances into a 500mL beaker, adding nitric acid (1+1 volume) into a fume hood, slightly stirring to prepare suspension, adding pure water into a 500mL volumetric flask to fix the volume, and vibrating each time because of precipitation at the bottom of the suspension. The theoretical concentration was 500. Mu.g/mL (Ca 1000. Mu.g/mL, P515. Mu.g/mL).
Preparation of aluminum nitride samples with different element gradients: preparing a high-purity aluminum nitride reagent, placing the reagent in a 500mL beaker, and adding liquid metal ion suspensions with different volumes; the beaker is placed in a baking oven at 130 ℃ for drying for 24 hours, and moisture and nitric acid are thoroughly removed; grinding each group of solid substances after drying by using a tungsten carbide vibration material pot for 120s, filling the solid substances into a white plastic barrel, adding zirconia balls, and vibrating and uniformly mixing the solid substances on a mixer for about 36 hours to obtain relatively uniform aluminum nitride samples with different element gradients.
ICP-OES stoichiometry of reference standard samples: the prepared relatively uniform aluminum nitride samples with different elemental gradients were subjected to ICP-OES set values.
ICP-OES constant value step: a sample of 0.2g of aluminum nitride reagent was selected, 15mL (pure water: pure sulfuric acid=1:1) of sulfuric acid was added, and after heating, dissolution and clarification by a hot plate, the sample was fixed in a 100mL volumetric flask, and then the measurement was performed. The measurement results are shown in Table 2.
TABLE 2ICP-OES constant value aluminum nitride reference sample data μg/g
The aluminum nitride reference samples in table 1 were prepared as per example 6 to prepare plaques: (1) acidolysis in platinum Huang Ganguo: 1.5g of aluminum nitride powder sample was weighed into platinum Huang Ganguo, 7.5mL of sulfuric acid solution (pure water: pure sulfuric acid=1:2) was added, the platinum yellow crucible was placed into an oven, and the temperature was kept at 140℃for 10min, and then at 200℃for 30min, so that the aluminum nitride was fully acidolyzed into aluminum sulfate.
(2) Removing sulfuric acid: the platinum yellow crucible is placed in a high temperature furnace, and the temperature is kept at 500 ℃ for 20min, so that sulfuric acid volatilizes and escapes.
(3) High temperature decomposition of aluminum sulfate: and (3) placing the platinum yellow crucible in the step (2) in a high-temperature furnace, and burning for 30min at 1050 ℃ to decompose aluminum sulfate into aluminum oxide and sulfur trioxide (high-temperature escape).
(4) Melting and preparing a sample: cooling the crucible in the step (3) to room temperature, adding a melting reagent lithium tetraborate and lithium metaborate=12:22 for 8.0g X ray fluorescence, stirring and mixing uniformly by using a glass rod, adding 1 drop of saturated lithium bromide release agent, melting at 1075 ℃, standing and melting for 8min, swinging and melting for 10min, automatically casting by a machine, cooling and blowing for 2.0min, and casting into a clear and transparent glass sample.
The prepared sample pieces were subjected to strength registration on Shimadzu XRF1800 equipment to prepare a working curve, the measurement conditions are shown in Table 3, aluminum nitride 3# and aluminum nitride 6# are used as unknown samples to be measured, the measurement results are shown in Table 4, and the ICP and XRF results are identical.
TABLE 3XRF1800 measurement conditions
TABLE 4XRF and ICP results control μg/g
Detailed description of figures 3-6:
FIG. 3 is a graph of the sample obtained after melting in example 2 of the present application, two sets of samples, sample A and sample B, were obtained, respectively, as can be seen from the graph, the two samples were clear, clean, transparent, and the appearance and texture of the samples were uniform;
FIG. 4 is a diagram of a sample obtained after the melt-casting in example 5 of the present application, and the sample is clear, clean, transparent and uniform in appearance and texture;
FIG. 5 is a graph of a sample obtained after the melt-casting in example 9 of the present application, and the sample was clarified, cleaned, and transparent by acidolysis with perchloric acid, and the appearance and texture of the sample were uniform.
FIG. 6 is a photograph of comparative example 1 aluminum nitride directly melted, the melt cloudy and difficult to pour;
the mold picture after melting in comparative example 4 is shown in FIG. 7, and the acidolysis process is incomplete due to the small addition amount of sulfuric acid, acidolysis materials in melting and incomplete melting, and the melt is white and opaque.
One or more of the technical schemes of the application has at least the following technical effects or advantages:
(1) According to the X-ray fluorescence melting sample preparation method of aluminum nitride, acid liquor is adopted to acidolyze the aluminum nitride, the acidolyzed gel is burned to obtain the aluminum oxide powder, the aluminum oxide powder is added with a melting reagent and a release agent to be melted, clear, clean and transparent sample pieces can be poured, the sample pieces are uniform in texture, the problem that melting, transparency and forming are difficult to achieve due to direct melting of aluminum nitride is effectively solved, and a novel method for melting sample preparation of aluminum nitride XRF is developed.
(2) The method for preparing the sample by melting aluminum nitride through X-ray fluorescence controls the dosage of aluminum nitride and sulfuric acid, controls the reaction temperature and time, and is characterized in that aluminum nitride powder is completely acidolyzed and converted into aluminum oxide after being burnt, compared with aluminum nitride, the aluminum oxide is easier to melt in the melting and sample preparation of lithium borate, and the obtained sample is clear, clean and transparent, and has uniform appearance texture.
Finally, it is also noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It is therefore intended that the following claims be interpreted as including the preferred embodiments and all such alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the spirit or scope of the application. Thus, it is intended that the present application also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (4)
1. An X-ray fluorescence melting sample preparation method for aluminum nitride, comprising:
adding acid liquor into aluminum nitride, preserving heat for 5-10 min at 110-180 ℃, and preserving heat for 20-50 min at 200 ℃ to obtain acidolysis gel;
heating the acidolysis gel to 300-500 ℃, preserving heat for 15-30 min, volatilizing residual acid to obtain acidolysis powder; firing the acidolysis powder for 20-40 min at 950-1050 ℃ to obtain alumina; or directly burning the acidolysis gel at 950-1050 ℃ for 20-40 min to obtain alumina;
adding a melting reagent and a release agent into the alumina, and pouring a sample after melting to obtain a sample;
the mass of the aluminum nitride and the volume of the acid liquor have the following relation:
3 mL-12 mL of the acid liquor is added into each 0.5g-1.2g of aluminum nitride;
the acid liquor is prepared by mixing water and pure acid, and the volume ratio of the water to the pure acid is (1-6): 2.
2. the method for preparing aluminum nitride X-ray fluorescence melting samples according to claim 1, wherein the acid solution comprises sulfuric acid solution and/or perchloric acid solution.
3. The method for preparing a sample by X-ray fluorescence melting of aluminum nitride according to claim 1, wherein the steps of adding a melting agent and a release agent to the aluminum oxide, and pouring a sample after melting to obtain the sample comprise:
adding a melting reagent and a release agent into the alumina, melting at 1000-1100 ℃, and casting a transparent sample.
4. An X-ray fluorescence melting sample method of aluminum nitride according to claim 3, wherein said melting reagent comprises at least one of lithium borate, lithium tetraborate, lithium metaborate and lithium carbonate;
the release agent comprises lithium bromide and/or ammonium iodide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574698.8A CN113376194B (en) | 2021-05-25 | 2021-05-25 | X-ray fluorescence melting sample preparation method of aluminum nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110574698.8A CN113376194B (en) | 2021-05-25 | 2021-05-25 | X-ray fluorescence melting sample preparation method of aluminum nitride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113376194A CN113376194A (en) | 2021-09-10 |
| CN113376194B true CN113376194B (en) | 2023-09-12 |
Family
ID=77571957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110574698.8A Active CN113376194B (en) | 2021-05-25 | 2021-05-25 | X-ray fluorescence melting sample preparation method of aluminum nitride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113376194B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114460117B (en) * | 2022-03-16 | 2023-06-06 | 清远南玻节能新材料有限公司 | Method for detecting component content of aluminum hydroxide product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102207475A (en) * | 2011-03-31 | 2011-10-05 | 厦门出入境检验检疫局检验检疫技术中心 | Metal alloy XRF spectrometry utilizing new sample preparation technology |
| CN104787790A (en) * | 2015-04-17 | 2015-07-22 | 北京矿冶研究总院 | Method for extracting aluminum oxide and silicon oxide from coal-based solid waste |
| CN107902683A (en) * | 2017-11-17 | 2018-04-13 | 北京矿冶研究总院 | Method for extracting silicon product and aluminum oxide step by mixing, reducing and roasting fly ash and sulfuric acid |
| CN110836810A (en) * | 2019-11-27 | 2020-02-25 | 中国电子科技集团公司第四十三研究所 | Sample dissolving method for testing trace elements of aluminum nitride powder |
-
2021
- 2021-05-25 CN CN202110574698.8A patent/CN113376194B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102207475A (en) * | 2011-03-31 | 2011-10-05 | 厦门出入境检验检疫局检验检疫技术中心 | Metal alloy XRF spectrometry utilizing new sample preparation technology |
| CN104787790A (en) * | 2015-04-17 | 2015-07-22 | 北京矿冶研究总院 | Method for extracting aluminum oxide and silicon oxide from coal-based solid waste |
| CN107902683A (en) * | 2017-11-17 | 2018-04-13 | 北京矿冶研究总院 | Method for extracting silicon product and aluminum oxide step by mixing, reducing and roasting fly ash and sulfuric acid |
| CN110836810A (en) * | 2019-11-27 | 2020-02-25 | 中国电子科技集团公司第四十三研究所 | Sample dissolving method for testing trace elements of aluminum nitride powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113376194A (en) | 2021-09-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Barry et al. | The structure of a glass-io nomer cement and its relationship to the setting process | |
| O'Hara et al. | Decomposition of diverse solid inorganic matrices with molten ammonium bifluoride salt for constituent elemental analysis | |
| CN113376194B (en) | X-ray fluorescence melting sample preparation method of aluminum nitride | |
| CN103822841A (en) | Method for detecting content of SiC in SiC | |
| Song et al. | Kinetic analysis on carbothermic reduction of GeO2 for germanium recovery from waste scraps | |
| CN111855722B (en) | MgO and SiO in light-burned magnesium and magnesium stone 2 X-ray fluorescence spectrum analysis method of content | |
| CN105271297A (en) | Method for preparing 4A molecular sieves by using tailings and application of 4A molecular sieves | |
| Tan et al. | Determination of silicon content in metallurgical-grade silicon refined slag using two-step dissolution chemical analysis method | |
| CN114592130B (en) | Recycling treatment method and system for lead-zinc smelting water-quenched slag | |
| CN113866143B (en) | Quick detection of SiO in resource samples 2 And/or CaO content | |
| Zhu et al. | Silica behavior in the alumina carbothermic reduction-chlorination process | |
| CN115753662A (en) | Method for detecting element content in transition metal boride | |
| CN116429551A (en) | Method for simultaneously digesting mercury, arsenic, antimony and thallium elements in mine solid waste | |
| CN108709882A (en) | Measure the method for element silicon and phosphorus element content in low-silicon nodulizer | |
| JP2019191012A (en) | Element analysis method of inorganic sample | |
| CN1117084A (en) | Stibium fire refining deleading agent, its preparation and application | |
| CN118270980B (en) | Ceramic frit with excellent thermal stability and no glaze defect and production and preparation method thereof | |
| CN115575432B (en) | Method for measuring main and secondary components in alunite ore by utilizing X-ray fluorescence spectrum | |
| Tertipis et al. | New fire assay for iridium | |
| CN113567481B (en) | Analysis method for raw slurry component content of sintering process by serial method | |
| CN117778749B (en) | Method for recycling lithium from waste lithium-containing glass | |
| CN118724007A (en) | A composite flux, a method for X-ray fluorescence detection of 11 elements in ferrosilicon alloy by direct oxidation melting sampling | |
| CN114486970B (en) | X-ray fluorescence determination method for metal element content in tempered salt | |
| CN111122373B (en) | Method for testing silicon content in nano silicon-based material | |
| Singh et al. | Quantitative estimation of constituents in fly ash by lithium tetraborate fusion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |