CN1041653C - Direct measuring method of steel single-rare-earth solid solution capacity - Google Patents
Direct measuring method of steel single-rare-earth solid solution capacity Download PDFInfo
- Publication number
- CN1041653C CN1041653C CN94115528A CN94115528A CN1041653C CN 1041653 C CN1041653 C CN 1041653C CN 94115528 A CN94115528 A CN 94115528A CN 94115528 A CN94115528 A CN 94115528A CN 1041653 C CN1041653 C CN 1041653C
- Authority
- CN
- China
- Prior art keywords
- weight
- solution
- rare earth
- rare
- solid solution
- 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.)
- Expired - Fee Related
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The present invention belongs to the rationalized detection technique, which has the main advantages that the rationalized detection technique carries out direct measurement, and error superposition and interactive influence caused by the indirect measurement of the existing subtraction method can be avoided and decreased; the present invention has higher precision and sensitivity and has important significance for scientific experiments and industrial production. The direct measurement has the key point that pure solid-solution rare earth is obtained. The inventor of the present invention filters rare-earth inclusion by low-temperature electrolysis and rapid separation, removes organic substances in an electrolyte in a volatilization mode, and obtains the pure solid-solution rare earth for a plasma spectrograph to analyze by means of strong acid cationic exchange resin, etc.
Description
The invention belongs to metal solid solution quantitative measurement technology.
It is known by people already to the beneficial effect that its tissue and performance are produced to add a small amount of rare earth in metal and alloy.But people are not fully aware of to the form and the mechanism of action that rare earth exists in for a long time.(iron と steel 1974.60.1935) was once used electrolysis, separation, measurement re inclusion, thereby was estimated as the solid solution capacity of rare earth in steel with the difference that the steel middle rare earth is mingled with content and total amount for Japanese Chuan Cun in 1974 and youth.This kind method subtracts error stack and reciprocal effect that mode is measured indirectly because of it is subjected to difference, and sensitivity is lower.This article thinks, not having the conclusion of solid solution rare earth (Ce of the present invention Ding And be far from it) when steel middle rare earth total amount≤0.1% (weight) is exactly the low excessively proof of this method sensitivity.Li Wenbin had been studied form and distribution that rare earth exists with the in-fighting method in steel in 1981, but failed to make quantitative test (seeing first the academic meeting of national in-fighting instrument paper).Han Qiyong and Fang Ke bright (seeing iron and steel 1982,17 (2) and the 5th materialization nd Annual Meeting, 1984) also measured the solid solution capacity of rare earth in steel with the radio-label method once, high nearly 1 order of magnitude of its remolding sensitivity minusing.Therefore but method is by the sample remelting, artificially adds a certain amount of radioisotope tracer and measures, and institute surveys and tries that sample And is non-to be taken from the material of commercial production and Experiment Preparation and can't be used for actual measurement.
The objective of the invention is to seek a kind of highly sensitive, simple and easy to do, directly measure single rare earth solid solution capacity method in the steel.The inventor by 0～-10 ℃ of low-temperature electrolytic, equal, less than separate fast in 15 minutes leach re inclusion, to nonaqueous electrolytic solution with the volatilization mode remove organism methyl alcohol or ethanol, the employing strongly acidic cation-exchange is got rid of interference element Fe, Ca, Mg, Al, obtain pure solid solution rare earth for the plasma spectrometer analysis to realize above-mentioned purpose of the present invention.
Specific embodiments is:
(1) when low-temperature electrolytic,, selects suitable electrolytic solution system and component according to many steel grades and composition, prediction re inclusion kind and rule.The inventor adjusts existing two kinds of each set of dispense ratios of electrolytic solution, has reached good electrolysis effectiveness, and a kind of proportioning is:
～4.0% 1.5 (weight) tetramethyl ammonium chloride+1%＜three ethanol≤4.0% (weight)+glycerine＜0.5% or 0.5%＜glycerine≤4.0% (weight)+methyl alcohol, another kind of proportioning is:
1%＜tetramethyl ammonium chloride≤4.0% (weight)+1%＜triethanolamine≤4.0% (weight)+2～4.0% (weight) ethylene glycol+absolute ethyl alcohol.When sulfur-bearing in the steel is lower than 0.008% (weight), also can adopt 7～10% (weight) KCl+0.5～1.0% (weight) lemon acid amide+0.5～1.0% (weight) oxammonium hydrochloride+water to carry out electrolysis.
(2) be by quantitative filter paper and one deck aperture, top are that the thickness that adds one deck compacting between the 0.15 μ m filter membrane is that the filtering bodies made of 0.5～0.8cm paper pulp is to leach all re inclusion residues that are not dissolved in electrolytic solution at a slow speed in bottom two layers when separating fast.
(3) subsequently to non-aqueous electrolyte (wherein have is the rare earth ion of solid solution originally) in the water-bath crucible under 80～85 ℃, carry out volatilization, remove organism methyl alcohol or ethanol (certainly aqueous electrolyte then not being had this necessity).
(4) be to get rid of interference element Fe, Ca, Mg, Al at last.Specific embodiments is that the non-water system electrolyte through the removal of impurities volatilization is dissolved in the water of a certain amount of (such as being dissolved in the 250ml volumetric flask), with its furnishing acidity is 5～6% (then can directly regulate acidity for water system), get a certain amount of (such as getting 100ml) and cross post (promptly crossing the strongly acidic cation-exchange post), make that all ions all are attracted on the exchange resin in the solution, then earlier with energy wash-out Fe, Ca, Mg, low concentration 1.75～2.0 N hydrochloric acid flushing of Al, to get rid of Fe, Ca, Mg, Al, subsequently again with can wash-out high concentration 4～5 N hydrochloric acid flushing of solid solution rare earth ion, to obtain pure solid solution rare-earth ion solution.Through concentrating (such as simmer down to 10ml), the acid adjustment degree is that 5～6% backs implement to measure for plasma spectrometer.Rare earth solid solution capacity computing formula is:
X-is the rare earth solid solution capacity
A=μ g/ml is that plasma spectrometry is to the rare earth detection limit
B-is the last machine sample size (such as can be 10ml) of going up
C-is the electrolytic weight loss amount
D-was the ratio (crossing post as taking out 100ml among the 250ml) of solution amount and total solution amount of exchange column, then specifically was calculated as
Embodiment sees the following form: (videing infra)
Claims (1)
1, a kind of steel middle rare earth solid solution capacity inductively coupled plasma spectrometry analytical approach, it comprises that solution with non-water system tetramethyl ammonium chloride+triethanolamine+glycerine+methyl alcohol or tetramethyl ammonium chloride+triethanolamine+ethylene glycol+absolute ethyl alcohol or water system Kcl+ lemon acid amide+oxammonium hydrochloride+water is as electrolytic solution, carry out low-temperature electrolytic down at 0～10 ℃, equaling, separating fast and plasma spectroscopy in less than 15 minutes, it is characterized in that:
(1) said electrolyte component proportioning is:
A tetramethyl ammonium chloride is 1.5～4.0% (weight)+1%＜triethanolamine≤4.0% (weight)+glycerine＜0.5% (weight)+methyl alcohol; Wherein also can select 0.5%＜glycerine≤4.0% (weight);
B 1%＜tetramethyl ammonium chloride≤4.0% (weight)+1%＜triethanolamine≤4.0% (weight)+2～4.0% (weight) ethylene glycol+absolute ethyl alcohol; (above for non-be electrolytic solution)
When c is lower than 0.008% (weight) when sulfur-bearing in the steel, can adopt aqueous electrolyte, its set of dispense ratio is: 7～10% (weight) Kcl+0.5～1.0% (weight) lemon acid amide+0.5～1.0% (weight) oxammonium hydrochloride+water;
(2) described quick separation is meant when the rare-earth separating snotter it is by quantitative filter paper and one deck aperture, top are to add filtering bodies that the thick 0.5～0.8cm of the being paper pulp of one deck compacting constituted between the 0.15 μ m filter membrane to leach the re inclusion residue that is not dissolved in electrolytic solution at a slow speed in bottom two layers;
(3) the non-aqueous solution electrolysis filtrate to filtering and impurity removing needs to carry out volatilization down at 80～85 ℃ in the water-bath crucible, removes organism methyl alcohol or ethanol;
(4) get rid of interference element Fe, Ca, Mg, Al by strongly acidic cation-exchange at last, scheme is soluble in water to the non-aqueous solution electrolysis thing through removal of impurities, volatilization, acidity is transferred to 5～6% cross the strongly acidic cation-exchange post, be that the hydrochloric acid flushing of 1.75～2.0N is to get rid of Fe, Ca, Mg, Al earlier subsequently with concentration, be that 4～5N hydrochloric acid wash-out is to obtain pure solid solution rare-earth ion solution with concentration again, through concentrating, after the acid adjustment degree is 5～6%, measure for plasma spectrometer, its computing formula is:
X-is the rare earth solid solution capacity,
A=μ g/ml is the detection limit of plasma spectrometry to rare earth,
B-is the last machine sample size of going up,
C-is the electrolytic weight loss amount,
D-was the exchange column solution amount and the ratio of total solution amount.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115528A CN1041653C (en) | 1994-09-12 | 1994-09-12 | Direct measuring method of steel single-rare-earth solid solution capacity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94115528A CN1041653C (en) | 1994-09-12 | 1994-09-12 | Direct measuring method of steel single-rare-earth solid solution capacity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1120167A CN1120167A (en) | 1996-04-10 |
| CN1041653C true CN1041653C (en) | 1999-01-13 |
Family
ID=5037561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94115528A Expired - Fee Related CN1041653C (en) | 1994-09-12 | 1994-09-12 | Direct measuring method of steel single-rare-earth solid solution capacity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1041653C (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5098843B2 (en) * | 2007-06-29 | 2012-12-12 | Ｊｆｅスチール株式会社 | Method for determining the solid solution content of the element of interest in a metal sample |
| CN102538703B (en) * | 2011-12-21 | 2014-05-28 | 北京科技大学 | Method for extracting and observing three-dimensional appearance of non-metallic inclusion in steel in full-scale mode |
| CN103063589B (en) * | 2012-12-25 | 2015-02-18 | 内蒙古科技大学 | Method for measuring misch metal solid solubility in steel and iron materials |
| CN104764792A (en) * | 2014-12-29 | 2015-07-08 | 内蒙古包钢钢联股份有限公司 | Determination method for solid-solution niobium content of steel |
| CN104569126B (en) * | 2014-12-29 | 2018-02-27 | 内蒙古包钢钢联股份有限公司 | Single rare earth is mingled with the assay method of sulfur oxides level in steel |
| CN104569128A (en) * | 2014-12-29 | 2015-04-29 | 内蒙古包钢钢联股份有限公司 | Method for determining content of solid-solution rear earth in steel |
| CN105954139A (en) * | 2016-05-04 | 2016-09-21 | 内蒙古工业大学 | Method for directly measuring solid solubility of rare earth in rare earth magnesium alloy |
| CN109001128A (en) * | 2018-06-29 | 2018-12-14 | 国网河南省电力公司电力科学研究院 | A kind of method of analysis of metallic materials matrix and precipitated phase Elemental partition |
| CN111855644A (en) * | 2020-07-07 | 2020-10-30 | 中国科学院金属研究所 | Method for enriching and quantifying rare earth elements in solubility product driven electrolyte |
| CN113109321A (en) * | 2021-04-07 | 2021-07-13 | 北京首钢吉泰安新材料有限公司 | Method for measuring content of solid solution yttrium in iron-chromium-aluminum alloy |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53114492A (en) * | 1977-03-16 | 1978-10-05 | Mitsubishi Heavy Ind Ltd | Micro-segregation analysis of sulfup containing in minute amount in steel |
| SU899474A1 (en) * | 1980-03-07 | 1982-01-23 | Предприятие П/Я Р-6409 | Process for spectro photometrically detecting rare-earth elements and scandium |
-
1994
- 1994-09-12 CN CN94115528A patent/CN1041653C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53114492A (en) * | 1977-03-16 | 1978-10-05 | Mitsubishi Heavy Ind Ltd | Micro-segregation analysis of sulfup containing in minute amount in steel |
| SU899474A1 (en) * | 1980-03-07 | 1982-01-23 | Предприятие П/Я Р-6409 | Process for spectro photometrically detecting rare-earth elements and scandium |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1120167A (en) | 1996-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8222038B2 (en) | Method for analyzing metal specimen | |
| CN1041653C (en) | Direct measuring method of steel single-rare-earth solid solution capacity | |
| KR20100137539A (en) | Method of determining particle size distribution of fine particles contained in metallic material | |
| CN105445208B (en) | The measuring method of Determination of Trace Thallium in a kind of high-salt wastewater | |
| Knudsen et al. | Detection of metallothionein isoforms from three different species using on-line Capillary electrophoresis–Mass spectrometry | |
| Lo et al. | Dithiocarbamate extraction and Au (III) back extraction for determination of mercury in water and biological samples by anodic stripping voltammetry | |
| Weiss et al. | Microwave digestion of ancient peat and determination of Pb by voltammetry | |
| Panday et al. | Trace analysis of rare earth elements and other impurities in high purity scandium by inductively coupled plasma mass spectrometry after liquid-liquid extraction of the matrix | |
| CN103063589B (en) | Method for measuring misch metal solid solubility in steel and iron materials | |
| Pointurier et al. | Combined use of medium mass resolution and desolvation introduction system for accurate plutonium determination in the femtogram range by inductively coupled plasma-sector-field mass spectrometry | |
| ŞENDİL et al. | Simultaneous determination of Cr (III) and Cr (VI) using differential pulse polarography and application to Gerede River | |
| SOMER et al. | A new and simple procedure for the trace determination of mercury using differential pulse polarography and application to a salt lake sample | |
| Soriano et al. | Multielemental determination of trace mineral elements in seawater by dynamic reaction cell inductively coupled plasma-mass spectrometry after Al (OH) 3 coprecipitation | |
| Chen et al. | Determination of microamounts of palladium (II) by extraction method without usual organic solvents | |
| Kagaya et al. | Rapid coprecipitation technique using yttrium hydroxide for the preconcentration and separation of trace elements in saline water prior to their ICP-AES determination | |
| Agrawal et al. | Selective extraction and separation of thorium from monazite using N-phenylbenzo-18-crown-6-hydroxamic acid | |
| Biju et al. | Spectrofluorometric determination of erbium in seawater with 5, 7-diiodoquinoline-8-ol and rhodamine 6G | |
| CN102830074A (en) | Quantitative analysis method of scandium in titanium slag chlorinated waste | |
| CN111855644A (en) | Method for enriching and quantifying rare earth elements in solubility product driven electrolyte | |
| Mohammed et al. | Extraction and Spectrophotometric Assay of Yttrium (III) with TOPO, Application to Water Samples and Alloys | |
| Shabani et al. | Determination of bismuth at ultra-trace levels in sea-water by inductively coupled plasma mass spectrometry after preconcentration with solvent extraction and back-extraction | |
| Guo et al. | Capillary electrophoretic determination of apoptosis of rat cerebellar granule cells induced by 1‐methyl‐4‐phenyl pyridium ion | |
| Rajec et al. | Micellar enhanced microfiltration of strontium | |
| Jin et al. | On the adsorption voltammetry of the boron‐Beryllon III system: Part I. Determination of boron in plants and soils | |
| JP2965102B2 (en) | Electrolyte for analysis of precipitates and inclusions in steel materials |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |