CN116858800A - Analysis method for trace carbon and sulfur elements in high-purity metal - Google Patents
Analysis method for trace carbon and sulfur elements in high-purity metal Download PDFInfo
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- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 133
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000011593 sulfur Substances 0.000 title claims abstract description 132
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 78
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 238000004458 analytical method Methods 0.000 title abstract description 15
- 239000000523 sample Substances 0.000 claims abstract description 153
- 238000012360 testing method Methods 0.000 claims abstract description 64
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000000126 substance Substances 0.000 claims abstract description 37
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002485 combustion reaction Methods 0.000 claims abstract description 10
- 239000012496 blank sample Substances 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 39
- 239000010949 copper Substances 0.000 claims description 38
- 229910052802 copper Inorganic materials 0.000 claims description 38
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007865 diluting Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical group [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 7
- 235000011151 potassium sulphates Nutrition 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 229930006000 Sucrose Natural products 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005720 sucrose Substances 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000002775 capsule Substances 0.000 claims description 4
- 238000005259 measurement Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000004907 flux Effects 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 3
- 238000010998 test method Methods 0.000 abstract description 2
- 239000012086 standard solution Substances 0.000 description 21
- 238000001514 detection method Methods 0.000 description 16
- 239000011550 stock solution Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 229910021642 ultra pure water Inorganic materials 0.000 description 11
- 239000012498 ultrapure water Substances 0.000 description 11
- 238000001816 cooling Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- AWXLLPFZAKTUCQ-UHFFFAOYSA-N [Sn].[W] Chemical compound [Sn].[W] AWXLLPFZAKTUCQ-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 229910001128 Sn alloy Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005477 sputtering target Methods 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- XWROUVVQGRRRMF-UHFFFAOYSA-N F.O[N+]([O-])=O Chemical compound F.O[N+]([O-])=O XWROUVVQGRRRMF-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000001036 glow-discharge mass spectrometry Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000000918 plasma mass spectrometry Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000000185 sucrose group Chemical group 0.000 description 1
- -1 targets Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/34—Purifying; Cleaning
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/44—Sample treatment involving radiation, e.g. heat
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/20—Metals
- G01N33/202—Constituents thereof
- G01N33/2022—Non-metallic constituents
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
- G01N2021/3572—Preparation of samples, e.g. salt matrices
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- Life Sciences & Earth Sciences (AREA)
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- Food Science & Technology (AREA)
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Abstract
The invention belongs to the technical field of high-purity metal chemical analysis, and particularly relates to a method for analyzing trace carbon and sulfur elements in high-purity metal. The method comprises the following steps: sample pretreatment, sulfur-carbon standard sample preparation, blank sample test, standard coefficient calculation, sample test and calculation of sulfur-carbon content in a sample; in the sample testing step, a sulfur carbon standard sample and a sample are mixed and tested, wherein the standard coefficient calculation is the same as or different from that of the sulfur carbon standard sample used in the sample test. The test method provided by the invention adopts a high-frequency combustion infrared absorption method, and is calibrated by a carbon-sulfur calibration sample, so that the operation is simple, the precision is good, and an accurate and reliable result can be obtained.
Description
Technical Field
The invention belongs to the technical field of high-purity metal chemical analysis, and particularly relates to a method for analyzing trace carbon and sulfur elements in high-purity metal.
Background
The high-purity metal is a novel material with high chemical purity, low impurity content and excellent physical and chemical properties, and is mainly applied to the industries of semiconductor materials, targets, aerospace materials, film plating layers and the like. With the rapid development of the electronic information industry, the market demand of high-purity copper is continuously increasing, and the purity requirement is also higher.
The content of gas impurity elements such as carbon and sulfur in the high-purity metal directly influences the purity and the performance of the high-purity metal material. The purity of the high-purity metal is generally calculated by an impurity element deduction method, and when the high-purity metal is used as a raw material to carry out purity fixed value in the standard substance development process, the total amount of all impurity elements is required to be deducted to obtain the purity value of the high-purity metal, and the deducted impurity must consider other gas elements such as C, S, O, N, H besides the metal element. Meanwhile, chemical purity is also a key factor influencing the performance of high-purity metal materials, and various product standards strictly limit gas impurity elements such as carbon, sulfur and the like. The detection limit of carbon, sulfur, oxygen, nitrogen and hydrogen in nonmetallic impurity elements is smaller than 10 mug/g specified in the industry standard YS/T935-2013 high-purity metal sputtering target material purity grade and impurity content analysis and report standard guideline. The national standard GB/T39159-2020 high-purity copper alloy target material for integrated circuits specifies that the content of carbon element is not more than 1 mug/g and the content of sulfur element is not more than 0.1 mug/g. Industry standard YS/T819-2012 high purity copper sputtering target for electronic thin film specifies that the content of carbon element in 5N high purity copper is lower than 10 mug/g and the content of sulfur element is lower than 1 mug/g.
At present, the trace gas element analysis capability in high-purity metal cannot meet the requirement of rapid development of high-purity metal industrialization, and further improvement is needed. The detection method of the carbon and sulfur element in the high-purity metal comprises a high-frequency combustion infrared method, an inductive coupling plasma mass spectrometry, a glow discharge mass spectrometry and the like. In the standard method 'GB/T5121.4-2008 copper and copper alloy chemical analysis method part 4 carbon and sulfur content determination', the high-frequency combustion infrared absorption method is adopted to determine carbon and sulfur in high-purity copper, the determination lower limit of the method is 10 mug/g, and the method cannot meet the detection requirement of trace carbon and sulfur elements in high-purity copper of 5N and above. Patent CN201410037569 proposes an analysis method for measuring carbon and sulfur elements in high-purity copper, which can measure the carbon and sulfur content of the high-purity copper, wherein the content of the carbon and sulfur is less than 1 mug/g, but the patent does not solve the problem of metering traceability. The carbon-sulfur analyzer is a relative analysis method, and the standard substances of the same matrix are required to be corrected, but the types of trace gas element standard substances in high-purity metal are limited, or the carbon-sulfur content range in the standard substances is greatly different from the level of the sample, so that an accurate and reliable test result cannot be obtained.
Disclosure of Invention
In order to solve the problem that the trace carbon-sulfur element determination result in high-purity metal cannot be accurately determined, the invention aims to provide a method for analyzing trace carbon-sulfur element in high-purity copper, which comprises the following steps of:
the analysis method of trace carbon and sulfur elements in high-purity metal comprises the following steps: sample pretreatment, sulfur-carbon standard sample preparation, blank sample test, standard coefficient calculation, sample test and calculation of sulfur-carbon content in a sample; in the sample testing step, the sulfur carbon standard sample and the sample are mixed and tested, wherein the standard coefficient calculation is the same as or different from the sulfur carbon standard sample used in the sample test, and preferably the standard coefficient calculation is different from the sulfur carbon standard sample used in the sample test.
Further, the sample pretreatment is to remove an oxide layer on the surface of the metal sample, preferably one or more of hydrochloric acid, nitric acid or hydrofluoric acid, and clean the surface of the metal sample. Among them, the purity of hydrochloric acid and nitric acid is preferably superior purity.
Further, after cleaning, cleaning by using a volatile organic solvent, and drying by using inert gas; preferably, the cleaning is followed by a methanol, ethanol or acetone rinse and a nitrogen blow-dry.
Further, the sulfur carbon standard sample preparation comprises the following steps: preparing a pure water solution of a carbon standard sample or a sulfur standard sample, and then diluting to obtain the sulfur carbon standard sample.
Preferably, the carbon standard is selected from sucrose purity standard, sodium oxalate reference, sodium carbonate purity standard, anhydrous sodium carbonate reference, or potassium hydrogen phthalate reference; and/or the sulfur standard sample is selected from sodium sulfate purity standard substance or potassium sulfate purity standard substance.
Further, the blank sample is tested by placing a fluxing agent and a tin bag into a crucible together, then placing the crucible into a high-frequency combustion infrared carbon-sulfur analyzer, carrying out repeated measurement for three times, and obtaining a sample blank M after taking an average value 0 。
Further, the standard coefficient is calculated as: standard sample B of carbon and sulfur 1 Placing the mixture and the fluxing agent into a crucible, then placing the crucible into a high-frequency combustion infrared carbon-sulfur analyzer for testing, manually inputting 1.0000g mass for testing to obtain the carbon-sulfur element content M 1 According to the calibration sample B 1 Theoretical value C of Medium carbon Sulfur 1 Calculating a calibration coefficient k as shown in formula (1)
Further, the sample test was: weighing 1.00g of metal sample, wherein the specific mass is a, the content of carbon and sulfur element is x, and the metal sample and the carbon and sulfur standard sample B are prepared 2 Put into a crucible together with a fluxing agent, wherein a carbon-sulfur calibration sample B 2 Theoretical value of C of medium carbon sulfur 2 Then placing the mixture in a high-frequency combustion infrared carbon-sulfur analyzer for testing to obtain the mixture with the carbon-sulfur content of M 2 M is then 2 Satisfies the relationship shown in the formula (2):
wherein, carbon sulfur standard sample B 1 With carbon sulfur standard sample B 2 The same or different. Preferably, the sample B is calibrated 1 Theoretical value C of Medium carbon Sulfur 1 Calibration sample B 2 Theoretical value C of Medium carbon Sulfur 2 。
Further, the blank sample test, standard coefficient calculation, and the flux equivalent used in the sample test.
Further, the high-purity metal comprises high-purity copper, high-purity aluminum, high-purity titanium, high-purity cobalt, high-purity nickel, high-purity tantalum, high-purity tungsten, high-purity molybdenum, high-purity vanadium, high-purity manganese, high-purity gold, high-purity silver, high-purity platinum, high-purity palladium, high-purity ruthenium, high-purity lanthanum and alloys, and the purity of the high-purity metal is more than 4N.
Further, the crucible disclosed by the invention is a burned crucible so as to reduce the carbon and sulfur content in the crucible as much as possible. The fluxing agent can be tungsten-tin fluxing agent, iron fluxing agent, tin fluxing agent, tungsten fluxing agent, copper fluxing agent and the like, and the fluxing agent with lower carbon-sulfur content is used as much as possible, so that the instrument blank can be further reduced.
The beneficial effects of the invention are as follows: the test method provided by the invention adopts a high-frequency combustion infrared absorption method, and is calibrated by a carbon-sulfur calibration sample, so that the operation is simple, the precision is good, and an accurate and reliable result can be obtained; the method has low cost and good applicability, and saves the cost of purchasing the gas element standard substance; because the carbon-sulfur standard sample is used for correction in the test process, the method has magnitude traceability and can ensure the accuracy and reliability of the result. The invention can improve the analysis and detection capability of the high-purity metal carbon sulfur element, perfect the high-purity metal quality evaluation system and promote the rapid development of the electronic information industry.
Detailed Description
The invention provides a method for analyzing trace carbon and sulfur elements in high-purity metal, and the invention is further described below with reference to examples.
For further clarity of explanation, the method for analyzing trace carbon and sulfur elements in high-purity metal provided by the invention specifically comprises the following steps:
step 1: pretreatment of high-purity metal: cleaning the metal surface by using high-purity hydrochloric acid and nitric acid mixed acid to remove an oxide layer, then cleaning by using methanol, and drying by using nitrogen for later use;
step 2: selecting a suitable standard substance or reference substance: for carbon element detection, sucrose purity standard substance, sodium oxalate standard substance, sodium carbonate purity standard substance or anhydrous sodium carbonate standard substance and potassium hydrogen phthalate standard substance can be selected; for sulfur element detection, sodium sulfate purity standard substance or potassium sulfate purity standard substance can be selected.
Step 3: preparing a carbon-sulfur standard solution: firstly, boiling ultrapure water to remove carbon dioxide therein; accurately weighing a proper amount of standard substance, adding boiled ultrapure water, and preparing standard stock solution A 1 Standard stock solution a was then 1 Diluting to obtain standard solution A 2 。
Step 4: carbon sulfur calibration sample B 1 Is prepared from the following steps: quantitative separation of Standard solution A 2 Placing in tin bag, heating at 100-110deg.C for 1-2 hr until the solution is evaporated to dryness, taking out, and cooling to room temperature in a dryer to obtain carbon-sulfur calibration sample B 1 Calibration sample B 1 Theoretical value of C of medium carbon sulfur 1 。
Step 5: carbon sulfur calibration sample B 2 Is prepared from the following steps: quantitative separation of Standard solution A 2 Placing in tin bag, heating at 100-110deg.C for 1-2 hr until the solution is evaporated to dryness, taking out, and cooling to room temperature in a dryer to obtain carbon-sulfur calibration sample B 2 Calibration sample B 2 Theoretical value of C of medium carbon sulfur 2 . Preferably, the sample B is calibrated 1 Theoretical value C of Medium carbon Sulfur 1 Calibration sample B 2 Theoretical value C of Medium carbon Sulfur 2 。
Step 6: blankAnd (3) testing: the fluxing agent and the tin capsule are put into a crucible together for parallel test, and a blank M of a sample is obtained 0 。
Step 7: calculating a calibration coefficient: carbon sulfur calibration sample B 1 Putting the fluxing agent equivalent to that in the step 6 into a crucible for testing, and manually inputting 1.0000g for measuring to obtain the content M of carbon and sulfur 1 According to the calibration sample B 1 Theoretical value C of Medium carbon Sulfur 1 Calculating a calibration coefficient k, wherein the calculation formula is shown in formula (1):
step 8: sample testing: weighing 1.00g (accurate to 0.1 mg) of high-purity copper sample, wherein the specific mass is a, the content of carbon and sulfur element is x, and calibrating the high-purity copper and carbon and sulfur sample B 2 And 6, putting the same amount of fluxing agent in the step into a crucible for testing to obtain the product with the carbon-sulfur content of M 2 。
Step 9: the calculation formula of the carbon and sulfur content in the high-purity copper is shown as formula (2):
example 1: the trace carbon content in high purity copper was tested according to the following procedure
Step 1: the high-purity copper is pretreated, firstly, acetone is used for cleaning for 60 seconds in ultrasonic waves to remove organic matters on the surface; washing with ultrapure water for 4-6 times, and then corroding with 1:1 hydrochloric acid and nitric acid mixed acid for 1min to remove an oxide layer on the surface; washing with ultrapure water for 4-6 times, and then washing with absolute ethyl alcohol in ultrasound for 60s; naturally drying the sample, weighing and immediately analyzing;
step 2: selecting a proper standard substance, and selecting a sucrose purity standard substance (GBW 10067, 99.7%) for carbon element detection;
step 3: preparing a carbon standard solution: firstly, boiling ultrapure water to remove carbon dioxide therein; preparing a carbon standard stock solution with the concentration of 1 g/L: sucrose purity standard substanceDrying at 100-105 deg.c for 2.5 hr, and cooling in drier. Weighing 0.2382g of sucrose purity standard substance, adding boiled deionized water, dissolving in a beaker, transferring to a volumetric flask with a constant volume of 100mL, and shaking to obtain carbon standard stock solution A 1 (1 g/L), accurately sucking 10.00mL of carbon standard stock solution A 1 Diluting with water to constant volume (1 g/L) in a 100mL volumetric flask, shaking to obtain 100 μg/mL carbon standard solution A 2 。
Step 4: carbon calibration sample B 1 Is prepared from the following steps: 200. Mu.L of carbon standard solution A was quantitatively removed using a pipette 2 (100 mug/mL) is placed in a tin bag, is placed in an oven to be heated for 1-2h at 100-110 ℃ until the solution is evaporated to dryness, is taken out and is placed in a dryer to be cooled to room temperature, thus obtaining a carbon calibration sample B 1， Calibration sample B 1 Theoretical value of medium carbon C 1 20. Mu.g.
Step 5: carbon calibration sample B 2 Is prepared from the following steps: quantitative fractionation of 100. Mu.L of carbon Standard solution A Using a pipette 2 (100 mug/mL) is placed in a tin bag, is placed in an oven to be heated for 1-2h at 100-110 ℃ until the solution is evaporated to dryness, is taken out and is placed in a dryer to be cooled to room temperature, thus obtaining a carbon calibration sample B 2 Carbon calibration sample B 2 Theoretical value of medium carbon C 2 10. Mu.g.
Detection was performed using a CS844 carbon sulfur analyzer from Leco corporation of america. The high-purity ceramic crucible is presintered for 4 hours at 1100 ℃, and high-purity tungsten-tin alloy particles are selected as fluxing agents, so that a lower blank value is obtained. The test conditions of the instrument are shown in table 1 below:
table 1 carbon sulfur instrument test conditions
Step 6: blank test: 1g of high-purity tungsten tin fluxing agent and tin bag are put into a crucible together, and are tested for three times in parallel to obtain a sample blank M 0 。
Step 7: calculating a calibration coefficient: carbon calibration sample B 1 Putting the fluxing agent equivalent to that in the step 6 into a crucible for testing, and manually inputting 1.0000g for measuring to obtain carbon elementsContent of element M 1 According to the calibration sample B 1 Theoretical value of medium carbon C 1 =20 μg, and the calibration coefficient k is calculated as shown in formula (1):
step 8: sample testing: weighing 1.00g (accurate to 0.1 mg) of high-purity copper sample, wherein the specific mass is a, the carbon element content is x, and the high-purity copper and carbon sulfur are calibrated to sample B 2 And 6, putting the same amount of fluxing agent in the step into a crucible for testing to obtain the alloy with the carbon content of M 2 。
Step 9: the carbon content x in the high-purity copper is calculated, and the calculation formula is shown as formula (2):
the test results of example 1 are shown in table 2.
Examples 2 to 4
The same high purity copper samples as in example 1 were weighed, the weight of each example sample was shown in table 3, the carbon content in the high purity copper was tested according to the same method as in example 1, the result was shown in table 2, and the precision of the test result according to the test result carbon was 6%, so that the test requirement could be satisfied.
TABLE 2 results of carbon detection in high purity copper samples of examples 1-4
To demonstrate the accuracy of the method, a labelling recovery experiment was performed, the results are shown in table 3. According to experimental data, the recovery rate of carbon is between 95% and 102%, which indicates that the release of carbon in a sample is better, and the method can be used for testing the carbon in the high-purity copper to obtain accurate and reliable analysis results.
TABLE 3 experiments on carbon-labeled recovery of high purity copper samples of examples 1-4
| Numbering device | Sample weighing mass/g | Background value/. Mu.g | Scalar/μg addition | Total amount/. Mu.g was measured | Recovery% |
| 1 | 1.0052 | 4.57 | 5 | 9.33 | 95.2 |
| 2 | 1.0045 | 4.36 | 5 | 9.25 | 97.8 |
| 3 | 1.0050 | 4.85 | 5 | 9.79 | 98.8 |
| 4 | 1.0042 | 4.84 | 5 | 9.92 | 101.6 |
Example 5: the sulfur content in the high purity copper was tested according to the following procedure
Step 1: pretreatment of high-purity copper: firstly, cleaning the surface of the glass for 60 seconds in ultrasonic waves by using acetone to remove organic matters on the surface; after 4-6 times of ultrapure water washing, ultrasonically washing for 10min by using 1:1 hydrochloric acid and nitric acid mixed acid, and removing an oxide layer on the surface; washing with ultrapure water for 4-6 times, and then washing with absolute ethyl alcohol in ultrasound for 60s; naturally drying the sample, weighing and immediately analyzing;
step 2: selecting a proper standard substance: and detecting sulfur element, wherein a sulfate radical component analysis standard substance (GBW 08665) in sodium sulfate is selected.
Step 3: preparing a sulfur standard solution: first, a sulfur standard stock solution of 1mg/mL is prepared: weighing 0.4430g of sulfate radical component analysis standard substance in sodium sulfate, adding deionized water, dissolving in a beaker, transferring to a volumetric flask with a constant volume of 100mL, and shaking uniformly to obtain sulfur standard stock solution A 1 (1 g/L); then accurately sucking 5.00mL of sulfur standard stock solution A 1 Diluting with water to constant volume (1 g/L) in a 100mL volumetric flask, shaking to obtain 50 μg/mL sulfur standard solution A 2 。
Step 4: sulfur calibration sample B 1 Is prepared from the following steps: quantitative pipetting of 100. Mu.L of Sulfur Standard solution A Using a pipette 2 (50 mug/mL) is placed in a tin bag, is placed in an oven to be heated for 1-2h at 100-110 ℃ until the solution is evaporated to dryness, is taken out and is placed in a dryer to be cooled to room temperature, thus obtaining a sulfur calibration sample B 1 Calibration sample B 1 Theoretical value C of Medium Sulfur 1 5. Mu.g.
Step 5: sulfur calibration sample B 2 Is prepared from the following steps: quantitative dispensing of 40. Mu.L Standard solution A Using a pipette 2 (50. Mu.g/mL), placing in tin bag, and placing in oven at 100-110deg.CHeating for 1-2h until the solution is evaporated to dryness, taking out, and cooling to room temperature in a dryer to obtain a sulfur calibration sample B 2 Sulfur calibration sample B 2 Theoretical value C of Medium Sulfur 2 2. Mu.g.
Detection was performed using a CS844 carbon sulfur analyzer from Leco corporation of america. The high-purity ceramic crucible is presintered for 4 hours at 1100 ℃, and high-purity tungsten-tin alloy particles are selected as fluxing agents, so that a lower blank value is obtained.
Step 6: blank test: 1g of high-purity tungsten tin fluxing agent and tin bag are put into a crucible together for parallel test, and a blank M of a sample is obtained 0 。
Step 7: calculating a calibration coefficient: calibration sample B with Sulfur 1 Putting the fluxing agent equivalent to that in the step 6 into a crucible for testing, and manually inputting 1.0000g for measuring to obtain the sulfur element content M 1 According to theoretical value C of sulfur in the calibration sample 1 =5 μg, the calibration coefficient k is calculated, the formula is shown in formula (1):
step 8: sample testing: weighing 1.00g (accurate to 0.1 mg) of high-purity copper sample, wherein the specific mass is a, the content of sulfur element is x, and the high-purity copper and sulfur are calibrated to sample B 2 And 6, putting the same amount of fluxing agent in the step into a crucible for testing to obtain the sulfur content M 2 。
Step 9: calculating the sulfur content x in the high-purity copper, wherein the calculation formula is shown in formula (2):
examples 6 to 8
The high-purity copper sample same as that of the example 5 is weighed, the sulfur content in the high-purity copper is tested according to the same method of the example 5, the result is shown in a table 4, the sulfur content in a cathode copper national standard sample GSB 04-2554-2010 2 is measured by the method, as shown in the table 4, the precision of sulfur in the measured standard sample is 3%, and the measurement result is in the uncertainty range of the standard value, so that the method has good precision and high accuracy, and can meet the test requirement of trace sulfur elements in the high-purity copper.
TABLE 4 detection results of Sulfur in high purity copper samples
Example 9: the sulfur content in the high purity aluminum was tested according to the following procedure
Step 1: pretreatment of high-purity aluminum: firstly, cleaning the surface of the glass for 60 seconds in ultrasonic waves by using acetone to remove organic matters on the surface; after 4-6 times of ultrapure water washing, ultrasonically washing for 10min by using 3:1 hydrochloric acid and nitric acid mixed acid, and removing an oxide layer on the surface; washing with ultrapure water for 4-6 times, and then washing with absolute ethyl alcohol in ultrasound for 60s; naturally drying the sample, weighing and immediately analyzing;
step 2: selecting a proper standard substance: and detecting sulfur element, wherein sulfate radical component analysis standard substances (GBW 08665) and potassium sulfate standard substances in sodium sulfate are selected.
Step 3: preparing a sulfur standard solution: first, a sulfur standard stock solution of 1mg/mL is prepared: weighing 0.4430g of sulfate radical component analysis standard substance in sodium sulfate, adding deionized water, dissolving in a beaker, transferring to a volumetric flask with a constant volume of 100mL, and shaking uniformly to obtain sulfur standard stock solution A 1 (1 g/L); then accurately sucking 10.00mL of sulfur standard stock solution A 1 Diluting with water to constant volume (1 g/L) in a 100mL volumetric flask, shaking to obtain 100 μg/mL sulfur standard solution A 2 。
Weighing 0.5434g of potassium sulfate standard substance, adding deionized water, dissolving in a beaker, transferring to a volumetric flask with a constant volume of 100mL, and shaking uniformly to obtain sulfur standard stock solution A 3 (1 g/L); then accurately sucking 10.00mL of sulfur standard stock solution A 3 Diluting with water to constant volume (1 g/L) in a 100mL volumetric flask, shaking to obtain 100 μg/mL sulfur standard solution A 4 。
Step 4: sulfur calibration sample B 1 Is prepared from the following steps: quantitative pipetting of 100. Mu.L of Sulfur Standard solution A Using a pipette 2 (100μg/mL) is placed in a tin bag, is placed in an oven for heating at 100-110 ℃ for 1-2h until the solution is evaporated to dryness, is taken out and is placed in a dryer for cooling to room temperature, and a sulfur calibration sample B is obtained 1 Calibration sample B 1 Theoretical value C of Medium Sulfur 1 10. Mu.g.
Step 5: sulfur calibration sample B 2 Is prepared from the following steps: quantitative separation of 20. Mu.L of Sulfur Standard solution A Using a pipette 4 (100 mug/mL) is placed in a tin bag, is placed in an oven for heating at 100-110 ℃ for 1-2h until the solution is evaporated to dryness, is taken out and is placed in a dryer for cooling to room temperature, and a sulfur calibration sample B is obtained 2 Sulfur calibration sample B 2 Theoretical value C of Medium Sulfur 2 2. Mu.g.
Detection was performed using a CS844 carbon sulfur analyzer from Leco corporation of america. The high-purity ceramic crucible is presintered for 4 hours at 1100 ℃, and high-purity tungsten-tin alloy particles and pure iron are selected as fluxing agents, so that a lower blank value is obtained.
Step 6: blank test: placing 0.5g of high-purity tungsten tin fluxing agent and 0.5g of pure iron fluxing agent together with tin capsule into a crucible for parallel test to obtain a sample blank M 0 。
Step 7: calculating a calibration coefficient: calibration sample B with Sulfur 1 Putting the fluxing agent equivalent to that in the step 6 into a crucible for testing, and manually inputting 1.0000g for measuring to obtain the sulfur element content M 1 According to theoretical value C of sulfur in the calibration sample 1 =10μg, calculate the calibration coefficient k, formula (1):
step 8: sample testing: weighing 1.00g (accurate to 0.1 mg) of high-purity aluminum sample, wherein the specific mass is a, the content of sulfur element is x, and the high-purity aluminum and sulfur are calibrated to sample B 2 And 6, putting the same amount of fluxing agent in the step into a crucible for testing to obtain the sulfur content M 2 。
Step 9: calculating the sulfur content x in the high-purity aluminum, wherein the calculation formula is shown in formula (2):
examples 10 to 12
The high-purity aluminum sample same as that of example 9 is weighed, the sulfur content in the high-purity aluminum is tested according to the same method of example 9, the result is shown in table 5, and the precision of sulfur in the measured sample is 2% according to the result shown in table 5, which indicates that the method of the invention has good precision and can meet the test requirement of trace sulfur element in the high-purity aluminum.
TABLE 5 detection results of Sulfur in high purity aluminum samples
Example 13: the sulfur content in the high purity titanium was tested according to the following procedure
Step 1: pretreatment of high-purity titanium: firstly, cleaning the surface of the glass for 60 seconds in ultrasonic waves by using acetone to remove organic matters on the surface; after 4-6 times of ultrapure water washing, ultrasonically cleaning for 10min by using 3:1 nitric acid hydrofluoric acid mixed acid, and removing an oxide layer on the surface; washing with ultrapure water for 4-6 times, and then washing with absolute ethyl alcohol in ultrasound for 60s; naturally drying the sample, weighing and immediately analyzing;
step 2: selecting a proper standard substance: and detecting sulfur element, and selecting a potassium sulfate standard substance with accurately determined purity.
Step 3: preparing a sulfur standard solution: first, a sulfur standard stock solution of 1mg/mL is prepared: weighing 0.5434g of potassium sulfate standard substance, adding deionized water, dissolving in a beaker, transferring to a volumetric flask with a constant volume of 100mL, and shaking uniformly to obtain sulfur standard stock solution A 1 (1 g/L); then accurately sucking 10.00mL of sulfur standard stock solution A 1 Diluting with water to constant volume (1 g/L) in a 100mL volumetric flask, shaking to obtain 100 μg/mL sulfur standard solution A 2 。
Step 4: sulfur calibration sample B 1 Is prepared from the following steps: 200. Mu.L of sulfur standard solution A was quantitatively removed using a pipette 2 (100. Mu.g/mL) is placed in tin bag, and is placed in a baking oven to be heated for 1-2h at 100-110 ℃ until the solution is evaporated to dryness, and is placed in a dryer for cooling after being taken outCooling to room temperature to obtain sulfur calibration sample B 1 Calibration sample B 1 Theoretical value C of Medium Sulfur 1 20. Mu.g.
Step 5: sulfur calibration sample B 2 Is prepared from the following steps: quantitative separation of 100. Mu.L of Sulfur Standard solution A Using a pipette 2 (100 mug/mL) is placed in a tin bag, is placed in an oven for heating at 100-110 ℃ for 1-2h until the solution is evaporated to dryness, is taken out and is placed in a dryer for cooling to room temperature, and a sulfur calibration sample B is obtained 2 Sulfur calibration sample B 2 Theoretical value C of Medium Sulfur 2 10. Mu.g.
Detection was performed using a CS844 carbon sulfur analyzer from Leco corporation of america. The high purity ceramic crucible is pre-burned for 4 hours at 1100 ℃, and pure copper is selected as a fluxing agent to obtain a lower blank value.
Step 6: blank test: 1.0g of high-purity copper fluxing agent and the tin capsule are put into a crucible together for parallel test, thus obtaining a sample blank M 0 。
Step 7: calculating a calibration coefficient: calibration sample B with Sulfur 1 Putting the fluxing agent equivalent to that in the step 6 into a crucible for testing, and manually inputting 1.0000g for measuring to obtain the sulfur element content M 1 According to theoretical value C of sulfur in the calibration sample 1 =10μg, calculate the calibration coefficient k, formula (1):
step 8: sample testing: weighing 1.00g (accurate to 0.1 mg) of high-purity titanium sample, wherein the specific mass is a, the content of sulfur element is x, and calibrating the high-purity titanium and sulfur to sample B 2 And 6, putting the same amount of fluxing agent in the step into a crucible for testing to obtain the sulfur content M 2 。
Step 9: calculating the sulfur content x in the high-purity titanium, wherein the calculation formula is shown in formula (2):
examples 14 to 16
The same high-purity titanium sample as in example 13 was weighed, and the sulfur content in the high-purity titanium was tested in the same manner as in example 13, and the results are shown in Table 6. As can be seen from Table 6, the precision of sulfur in the measurement sample of the present invention is 3%, which means that the method of the present invention has good precision and can meet the test requirements of trace sulfur elements in the high-purity titanium.
TABLE 6 detection results of Sulfur in high purity titanium samples
Comparative example 1
In this comparative example, the procedure was the same as in example 5 except that step 4 and step 7 were not performed, and the calibration coefficient k=1 was carried into the formula for calculation in step 9.
Comparative example 2
In this comparative example, no carbon calibration sample B was added in step 8, except that step 5 was not performed 2 The procedure of example 5 was repeated except that the apparatus for calculating the carbon content in step 9 automatically calculated the sulfur content in the high purity copper based on the calibration factor.
The test results of comparative examples 1 to 2 are shown in Table 7.
TABLE 7 detection results of Sulfur in high purity copper samples of comparative examples 1 and 2
| Comparative example | Test results/. Mu.g/g |
| Comparative example 1 | 5.12 |
| Comparative example 2 | 6.35 |
The calibration was performed using a single standard sample in comparative example 1 and comparative example 2, and the sample content was low, the instrument fluctuation was large, resulting in a higher result.
In conclusion, the invention adopts the pretreatment of the high-purity metal and selects the carbon-sulfur calibration sample B 1 And B 2 The trace carbon and sulfur element is measured, the operation is simple, and the test result with high precision, good accuracy and magnitude traceability can be obtained.
Claims (10)
1. The method for analyzing trace carbon and sulfur elements in high-purity metal is characterized by comprising the following steps of: sample pretreatment, sulfur-carbon standard sample preparation, blank sample test, standard coefficient calculation, sample test and calculation of sulfur-carbon content in a sample; in the sample testing step, a sulfur carbon standard sample and a sample are mixed and tested, wherein the standard coefficient calculation is the same as or different from that of the sulfur carbon standard sample used in the sample test.
2. The method for analyzing trace amounts of carbon and sulfur elements in high purity metal according to claim 1, wherein the sample pretreatment is to remove an oxide layer on the surface of the metal sample, preferably to clean the surface of the metal sample with one or more of hydrochloric acid, nitric acid, or hydrofluoric acid;
preferably, after cleaning, the cleaning is performed by using a volatile organic solvent, and the cleaning is performed by using inert gas for drying; preferably, the cleaning is followed by a methanol, ethanol or acetone rinse and a nitrogen blow-dry.
3. The method for analyzing trace carbon and sulfur elements in high purity metal according to claim 1, wherein the sulfur-carbon standard sample preparation comprises the steps of: preparing a pure water solution of a carbon standard sample or a sulfur standard sample, and then diluting to obtain the sulfur carbon standard sample.
4. The method for analyzing trace amounts of carbon and sulfur elements in high purity metal according to claim 3, wherein the carbon standard sample is selected from the group consisting of sucrose purity standard, sodium oxalate standard, sodium carbonate purity standard, anhydrous sodium carbonate standard, and potassium hydrogen phthalate standard;
and/or the sulfur standard sample is selected from sodium sulfate purity standard substance or potassium sulfate purity standard substance.
5. The method for analyzing trace carbon and sulfur elements in high-purity metal according to claim 1, wherein the blank sample is obtained by placing a fluxing agent and a tin capsule into a crucible together, then placing the crucible into a high-frequency combustion infrared carbon and sulfur analyzer, repeating the measurement for three times, and taking an average value 0 。
6. The method for analyzing trace carbon and sulfur elements in high purity metal according to claim 1, wherein the standard coefficient is calculated as: standard sample B of carbon and sulfur 1 Placing the mixture and the fluxing agent into a crucible, then placing the crucible into a high-frequency combustion infrared carbon-sulfur analyzer for testing, manually inputting 1.0000g mass for testing to obtain the carbon-sulfur element content M 1 Calibration sample B based on carbon sulfur 1 Theoretical value C of Medium carbon Sulfur 1 Calculating a calibration coefficient k as shown in formula (1)
7. The method for analyzing trace carbon and sulfur elements in high purity metal according to claim 1, wherein the sample test is: weighing 1.00g of metal sample, wherein the specific mass is a, the content of carbon and sulfur element is x, and the metal sample and the carbon and sulfur standard sample B are prepared 2 Put into a crucible together with a fluxing agent, wherein a carbon-sulfur calibration sample B 2 Theoretical value of C of medium carbon sulfur 2 Then placing the mixture in a high-frequency combustion infrared carbon-sulfur analyzer for testing to obtain the mixture with the carbon-sulfur content of M 2 M is then 2 Satisfies the relationship shown in the formula (2):
8. the method for analyzing trace carbon and sulfur elements in high purity metal according to claim 6 or 7 wherein sample B is calibrated 1 Theoretical value C of Medium carbon Sulfur 1 Calibration sample B 2 Theoretical value C of Medium carbon Sulfur 2 。
9. The method for analyzing trace amounts of carbon and sulfur elements in high purity metal according to any one of claims 5 to 7, wherein the blank sample test, standard coefficient calculation, and flux equivalent amount used in the sample test.
10. The method of claim 1, wherein the high purity metal comprises high purity copper, high purity aluminum, high purity titanium, high purity cobalt, high purity nickel, high purity tantalum, high purity tungsten, high purity molybdenum, high purity vanadium, high purity manganese, high purity gold, high purity silver, high purity platinum, high purity palladium, high purity ruthenium, high purity lanthanum, and alloys, and the high purity metal has a purity > 4N.
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