CN101046433B - Method of manufacturing analysis specimen - Google Patents
Method of manufacturing analysis specimen Download PDFInfo
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- CN101046433B CN101046433B CN2006101485772A CN200610148577A CN101046433B CN 101046433 B CN101046433 B CN 101046433B CN 2006101485772 A CN2006101485772 A CN 2006101485772A CN 200610148577 A CN200610148577 A CN 200610148577A CN 101046433 B CN101046433 B CN 101046433B
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- ruthenium
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Abstract
The present invention provides a method for analyzing generation of specimen of high purity quotient ruthenium powder by Glow-discharge mass spectrometry. The method is using mould for striking to mold with yttrium stable zirconia as material to molding the ruthenium powder in order to produce analyzing material of the ruthenium powder calcined in condition of using reductive gas in process of analyzing the quality of the ruthenium powder with the Glow-discharge mass spectrometry device.
Description
Technical field
The present invention relates to a kind of method for making of analyzing the test portion of ruthenium (ruthenium) powder with glow discharge spectrometry (GDMS).
Background technology
Highly purified ruthenium powder is used to the raw material that ruthenium that the target that uses or resistance uses is stuck with paste (ruthenium paste) in the manufacturing of semiconductor or hard disk.Therefore, just need to analyze the impurity of trace contained in the ruthenium.The analytical approach rough segmentation of high purity metal can be divided into the method for wet analysis and the method for dry analysis.
At first, as the method for analyzing by the former wet analysis, be with inductively coupled plasma Emission Spectrophotometer method (ICP-AES) or inductively coupled plasma mass analysis (ICP-MS), will decompose the method for the aqueous solution quantitative test of metal.But ruthenium has the character that is difficult to by all acid attacks on the degree that slowly is dissolved in acid with oxidisability or chloroazotic acid.Therefore, can not use the so-called general trace analysis that decomposes with high purity acid.
The method that ruthenium decomposes, for example shown in the document " new experimental science lecture " from 358 to 359 pages (non-patent literature 1), to ruthenium generally with oxygenant and use the alkali salt dissolution method.It is to add the such oxygenant of potassium nitrate to come the heating for dissolving ruthenium in NaOH, allows ruthenium be in method in the salt of solubility.But the ruthenium corrosion resistance is strong, lacks reactivity, and the ruthenium tetroxide (RuO as higher oxide is arranged when ruthenium-oxide
4) generate, still,, be difficult to stable problem of decomposing ruthenium so exist because ruthenium tetroxide has very high volatility.
In addition, analyze high purity metal, glow discharge spectrometry (GDMS) and spark source mass spectrometry (SSMS) are arranged by the latter's dry method.They are to come decomposable ions fractional analysis thing by discharge, carry out quantitative methods with quality analysis, can carry out the analysis of high sensitivity, wide dynamic range (dynamic range) to multielement.
But it is the method for the conductive material of analysis block (bulk) basically, and the problem of powder can not be directly analyzed in existence.Therefore, when the analysed for powder test portion, the method for imbedding the powder test portion and measure reguline metal etc. in the reguline metal (bulk metal) of soft high-purity indium (indium) etc. is arranged.In the method, because the reguline metal also decomposes simultaneously, so want the analysis sensitivity step-down of the powder test portion measured.In addition, if the particle of powder test portion is tiny, then the powder test portion disperses in mensuration, and has the problem of the analytical equipment that pollutes high sensitivity.
Become in the method for analyzable shape at powder that makes metal by glow discharge spectrometry or emboliform test portion, the method for fusing metal and casting is arranged.Be willing in 2005-088006 number (patent documentation 1) the spy, disclose the piece that the silver of ball shape fusion has been cast, be molded as certain shape by rolling and cutting, thereby as the test portion of glow discharge spectrometry.The silver that this method is lower to fusing point (961 ℃) is effective, still, because the fusing point of ruthenium is up to 2250 ℃, so the fusion difficulty.
In addition, the powder of metal with the temperature sintering lower than fusing point, can measure it in order to gain in strength with the glow discharge mass spectrometry device with the shape of metal pattern impact briquetting for analyzing.Metal pattern when the powder test portion is carried out moulding is the tool steel and the superhard alloy making of principal ingredient by iron, but, because ruthenium is very hard, so when powder for molding, metal pattern and ruthenium powder friction are because the wearing and tearing powder of metal pattern causes the contaminated problem of analytical sample.
Because the surface is stayed in the pollution that brings of wearing and tearing powder, thus can attempt removing by mechanical grinding, but because the formed body of powder and sintered body are porous matter, so the grinding powder remain in the test portion, so exist because the hard and crisp problem that is difficult to grinding of ruthenium.In addition, the wearing and tearing powder of metal pattern is principal ingredient with iron, but iron and ruthenium are all 8 family's elements in the periodic table of element, mutual compatibility height, if sintering is then because the iron on surface spreads easily and is deep into test portion inside, so the surface of removing test portion by discharge with the glow discharge mass spectrometry device is also very difficult.Therefore, being difficult to determine whether is the reason of the surface contamination that brings of the pollution from metal pattern.
Japanization association of [non-patent literature 1] civic organization compiles the kind Co., Ltd. of ball and issues new experimental science lecture 9 1976 years from 358 pages to 359 pages
[patent documentation 1] is special is willing to 2005-088006 number (March 25 2005 applying date)
Summary of the invention
The invention provides a kind of making and can not pollute the method for the test portion of analyzing with glow discharge spectrometry of ruthenium powder.
Metal pattern wear problems during with metal pattern moulding ruthenium powder, distinguish to be following reason: with the metal pattern moulding time, the gap of metal pattern has ruthenium powder to enter, and when pressurizeing with stamping machine, makes the metal pattern wearing and tearing at the hard ruthenium powder of sliding part.This is that (moh ' s hardness) is 6.5 because the Mohs value of ruthenium, and than 4.5 of iron, 5～6 of general tool steel is all wanted firmly, so cause the wear extent of metal pattern many.Therefore, come ruthenium powder is carried out impact briquetting by the mould that uses impact briquetting to use with the yttrium harder (yttrium) stabilizing zirconia than ruthenium, thus pollution abatement when moulding.
Stamping forming ruthenium test portion is because crisp and can not directly measure with the glow discharge mass spectrometry device.Therefore, sintering is to gain in strength in the electric furnace of high temperature with stamping forming ruthenium test portion, still, if comprise oxygen, then test portion can oxidation in atmosphere gas, or quantitatively property with variation.And find by with stamping forming ruthenium test portion adopted hydrogen or contain the hydrogen of the hydrogen more than the 1vol% and the atmosphere gas of the mixed gas of argon (argon) in calcine, can carry out not can ruthenium-oxide sintering, can stably analyze.
That is, the present invention,
(1) provides a kind of method of making the analysis specimen of ruthenium powder, in operation with the quality of glow discharge mass spectrometry device analysis ruthenium powder, the mould that uses material to use as the impact briquetting of yttrium stable zirconium oxide comes ruthenium powder is carried out moulding, used hydrogen or comprise the hydrogen of the hydrogen more than the 1vol% and the atmosphere of the mixed gas of argon in calcine.
Use method of the present invention,
(1) can not pollute the mensuration test portion that highly purified ruthenium powder just can moulding glow discharge mass spectrometry device be used.
(2) when the sintering test portion, oxidation can be suppressed, the quality of highly purified ruthenium powder can be correctly measured.
Description of drawings
Fig. 1 is the process flow diagram of embodiments of the invention.
Embodiment
Set forth detailed content of the present invention.The objective of the invention is to, in order to measure the quality of high-purity ruthenium by glow discharge spectrometry, can not pollute ruthenium powder and have the intensity that to measure, and can correctly measure the test portion of quality and obtain an impact briquetting.
The material of the mould of impact briquetting ruthenium powder need be that 6.5 ruthenium is hard than Mohs value.But, if material hardens, then can be crisp and easy cracking also will be difficult to process.The test material shape that glow discharge mass spectrometry is used, manufacturing plant is different with measuring anchor clamps (holder) according to device, but, as the test material shape of the standard of the makers' F.I.Elemental Analysis of glow discharge mass spectrometry device company the biggest in the world, be the following pin shape of 2mm * 2mm * 20mm.In addition, the particle size of ruthenium powder is below 80 screen sizes (mesh) (about 180 microns), if the gap is big on the mould, then powder is run away when impact briquetting.Therefore, the material of mould needs obdurability, can critically carry out Mould Machining, and the inhomogenous stress that is applied when being difficult to the impact briquetting because of the processing of mould and test portion ftractures.
General than the hard material that obtains easily of ruthenium, quartz (Mohs value 7), zirconia (Mohs value 8.5), aluminium oxide (Mohs value 9) etc. are arranged, but they have all and character easy cracking crisp.In the present invention, thus selected by in zirconia, adding the yttrium stable zirconium oxide of mechanical property excellences such as yttrium intensity and toughness.Yttrium stable zirconium oxide can machining, can also carry out the processing of accurate mould.In addition, can be when impact briquetting because of ruthenium powder does not wear and tear, can the contamination analysis test portion.
With the stamping forming test portion of ruthenium powder, so, have powder and peel off because just powder is compressed very weakly.Carry out the mensuration of high sensitivity because after the glow discharge mass spectrometry device is in high vacuum, noble gas discharge can be allowed, so the pollution that must avoid powder to cause.For this reason with stamping forming ruthenium test portion in the electric furnace of high temperature sintering to gain in strength.Sintering temperature does not have special provision, still, owing to the fusing point of ruthenium is difficult to sintering up to 2250 ℃, if sintering temperature uprises, the pollution from furnace lining is then arranged easily, so preferably carry out 1～2 hour calcining with 900 ℃～1200 ℃ temperature.
In addition since in atmosphere gas if contain oxygen, then ruthenium oxidation and become volatile ruthenium tetroxide, thereby quantitative property variation generate the low ruthenic oxide (RuO of electric conductivity on the test portion surface
2), so preferred sintering under reducing atmosphere.By used hydrogen or contain the hydrogen of the hydrogen more than the 1vol% and the atmosphere gas of the mixed gas of argon in the stamping forming ruthenium test portion of calcining, not ruthenium-oxide and carry out sintering.Concentration at hydrogen is lower than in the argon gas or pure nitrogen gas of 1vol%, because of the test portion that influences of the contained oxygen of trace can variable color.
In the present invention, because be in the atmosphere gas of the reductibility that contains hydrogen, to calcine, the analysis of the composition (for example oxygen, chlorine) that gasifies so can't be easy to react.They will be measured by the method beyond the powder (for example based on the oxygen analysis of thermal decomposition method, based on the chlorine analysis of the chromatography of ions of steam distillation).
[embodiment]
(embodiment 1)
Embodiments of the invention below are described.With flowchart text embodiment 1 shown in Figure 1.
The ruthenium powder is made by the following method.
In the aqueous solution of platinum group metal metal that with the cupric electrolysis sediment is raw material, add sodium bromate, allow ruthenium become volatile ruthenium tetroxide and distill, in the hydrochloric acid solution of 6mol/L, reclaim as ruthenic chloride.
In 7 liters of hydrochloric acid solutions that contains this ruthenic chloride, add ammonium chloride, with 90 ℃ of heating put in 2 hours be chilled to room temperature after, the sour ammonium of chlordene ruthenium (hexachloro ruthenium) with the filter paper filtering crystallization, put into the container of high-purity mangesium oxide aluminum, kept 2 hours with 600 ℃ in nitrogen atmosphere with tube furnace, carry out the calcining of phase one, obtain the thick ruthenium of spongy (sponge).It is pulverized with mortar, obtain to pass through the ruthenium powder of the sieve of mesh 180 μ m, and it is put into the container of high-purity mangesium oxide aluminum once again, and kept 2 hours with 900 ℃ in 5vol% hydrogen-argon mixture gas atmosphere gas with tube furnace, carry out the calcining of subordinate phase.Obtain to pass through the ruthenium powder 345g of the sieve of mesh 180 μ m.
This ruthenium powder is made into the test portion of glow discharge mass spectrometry analysis usefulness by process flow diagram shown in Figure 1.Table 1 shows the manufacturing conditions of test portion.Mould with yttrium stable zirconium oxide system carries out impact briquetting with load 9.8kN to ruthenium powder, calcines 1 hour with 1000 ℃ in 5% hydrogen-argon gas body.Analyzing the size with test portion, is 2mm * 2mm * 20mm during moulding, and the oversintering post shrinkage does not become 1.9mm * 1.9mm * 19mm, but decrement not.The appearance that the silver color oxide generates is can't see on the surface.It is clean that it has been mixed the pickling of hydrofluorite and nitric acid with 1 to 1, washing, dry intactly with the glow discharge mass spectrometry device 70 element is analyzed.Table 2 display analysis result.Zirconium (atomic number 40) and yttrium (atomic number 39) as the principal ingredient that is used for forming mould are lower than 1mass ppm.Few from the pollution that is used for forming mould.
The analysis specimen manufacturing conditions of table 1 embodiment and comparative example
YZT: yttrium stable zirconium oxide
The composition of the ruthenium powder that table 2 is analyzed in embodiment and comparative example (unit: mass ppm)
(embodiment 2)
Embodiment 2 is that the mould with yttrium stable zirconium oxide system carries out moulding to ruthenium powder, uses in the atmosphere to its sintering the time the pure hydrogen, all according to the same method making test portion of embodiment 1.Analysis specimen surface behind the sintering does not have variable color.With glow discharge spectrometry it is measured, zirconium (atomic number 40) and yttrium (atomic number 39) are lower than 1mass ppm, thereby obtain the assay value identical substantially with embodiment 1.(with reference to table 2)
(comparative example 1)
Comparative example below is described.Comparative example 1 is to be that the mould of the instrument steel of major component carries out moulding to ruthenium powder with iron, carbon, manganese, in addition all according to making analysis specimen with the identical method of embodiment.Analysis specimen surface behind the sintering does not have variable color.Result to its mensuration shows at table 2 with glow discharge spectrometry.Iron (atomic number 26) is detected a lot, is 56mass ppm.This is from the pollution that is used for forming mould.Manganese (atomic number 25) is lower than 1mass ppm, does not see variation.This be because be contained in the mould manganese seldom, be 2.5mass%.
(comparative example 2)
Comparative example 2 is that the mould with pure nickel system comes ruthenium powder is carried out moulding, in addition all according to making analysis specimen with the identical method of embodiment.Result to its mensuration shows at table 2 with glow discharge spectrometry.Nickel (atomic number 28) is detected a lot, is 400mass ppm.This is from the pollution that is used for forming mould.Because nickel is very soft, Mohs value is 5, so wear extent is many.
(comparative example 3)
Comparative example 3 is that the mould with yttrium stable zirconium oxide system carries out moulding to ruthenium powder, uses purity nitrogen in the atmosphere gas to its sintering the time, in addition all according to making analysis specimen with the identical method of embodiment.Analysis specimen surface behind the sintering has variable color slightly, cleans through acid and can not remove variable color portion.When it being measured, produce paradoxical discharge in the glow discharge and can't analyze with glow discharge spectrometry.
Claims (1)
1. method of making the analysis specimen of ruthenium powder, it is characterized in that, in the operation of the quality of using glow discharge mass spectrometry device analysis ruthenium powder, the mould that uses material to use as the impact briquetting of yttrium stable zirconium oxide comes ruthenium powder is carried out moulding, use hydrogen or contain the hydrogen of the hydrogen more than the 1vol% and the atmosphere of the mixed gas of argon in calcine.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006096630A JP4351224B2 (en) | 2006-03-31 | 2006-03-31 | Analytical sample preparation method |
| JP2006-096630 | 2006-03-31 | ||
| JP2006096630 | 2006-03-31 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101046433A CN101046433A (en) | 2007-10-03 |
| CN101046433B true CN101046433B (en) | 2010-05-19 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2006101485772A Expired - Fee Related CN101046433B (en) | 2006-03-31 | 2006-11-16 | Method of manufacturing analysis specimen |
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| JP (1) | JP4351224B2 (en) |
| CN (1) | CN101046433B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102175754B (en) * | 2010-12-27 | 2013-07-17 | 中国科学院上海硅酸盐研究所 | New method for analyzing non-conductor material by utilizing glow discharge mass spectrum |
| CN104267021A (en) * | 2014-09-20 | 2015-01-07 | 河北钢铁股份有限公司 | Glow spectrometer alloy sample and preparation method thereof |
| CN104458370A (en) * | 2014-11-23 | 2015-03-25 | 昆明贵金属研究所 | Method for preparing glow discharge mass spectrometer analysis test sample |
| CN109030130A (en) * | 2017-06-08 | 2018-12-18 | 宁波江丰电子材料股份有限公司 | Titanium crystalline substance sample preparation methods and titanium crystalline substance sample for GDMS detection |
| CN108680411A (en) * | 2018-05-31 | 2018-10-19 | 宁波江丰电子材料股份有限公司 | High purity tungsten sample and preparation method thereof for GDMS detections |
| CN109239179A (en) * | 2018-08-27 | 2019-01-18 | 新疆众和股份有限公司 | The measuring method of trace impurity in a kind of high purity aluminium oxide polycrystal material |
| CN109298065A (en) * | 2018-11-07 | 2019-02-01 | 新疆众和股份有限公司 | The detection method of impurity content in a kind of Al alloy powder |
| CN111551422A (en) * | 2020-05-22 | 2020-08-18 | 宁波江丰电子材料股份有限公司 | Metal powder sample preparation method for glow discharge mass spectrometry |
| CN111964997A (en) * | 2020-08-14 | 2020-11-20 | 宁波江丰电子材料股份有限公司 | Sample preparation method for glow discharge mass spectrometry detection of high-purity silver sample |
| CN113092228A (en) * | 2021-03-23 | 2021-07-09 | 宁波创润新材料有限公司 | Titanium crystal sample for GDMS detection and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587062A (en) * | 2004-09-03 | 2005-03-02 | 湖北葛店开发区地大纳米材料制造有限公司 | Nano structure yttrium stabilized zirconium oxide aggregated powder and its producing method |
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2006
- 2006-03-31 JP JP2006096630A patent/JP4351224B2/en not_active Expired - Fee Related
- 2006-11-16 CN CN2006101485772A patent/CN101046433B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1587062A (en) * | 2004-09-03 | 2005-03-02 | 湖北葛店开发区地大纳米材料制造有限公司 | Nano structure yttrium stabilized zirconium oxide aggregated powder and its producing method |
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| Publication number | Publication date |
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| CN101046433A (en) | 2007-10-03 |
| JP4351224B2 (en) | 2009-10-28 |
| JP2007271419A (en) | 2007-10-18 |
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