CN102253098A - Manufacturing method of sulfur determining probe - Google Patents
Manufacturing method of sulfur determining probe Download PDFInfo
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- CN102253098A CN102253098A CN2011100893934A CN201110089393A CN102253098A CN 102253098 A CN102253098 A CN 102253098A CN 2011100893934 A CN2011100893934 A CN 2011100893934A CN 201110089393 A CN201110089393 A CN 201110089393A CN 102253098 A CN102253098 A CN 102253098A
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- solid electrolyte
- sulfur
- cao
- mgo
- mgs
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Abstract
The invention belongs to the field of high-temperature electrochemistry and relates to a direct measurement technology for the sulfur content in molten metal. The direct measurement technology is characterized in that a ZrO2+MgO(CaO,Y2O3) solid electrolyte tube is taken as the main body of a sulfur determining probe, a layer of ZrS2+MgS(CaS,Y2S3) auxiliary electrode is prepared on the outer surface of the tube through using a plasma spraying method, and Cr+Cr2O3 is taken as a reference electrode. ZrS2+MgS(CaS,Y2S3) powder is uniformly sprayed on the outer surface of a ZrO2-MgO(CaO,Y2O3) solid electrolyte tube under the vacuum or inert gas protection condition when the plasma spraying method is adopted to prepare the auxiliary electrodes. According to the method in the invention, the sulfur determining probe can be manufactured inexpensively in a large quantity and has the characteristics of stable performance and high precision.
Description
Technical field
The present invention relates to a kind of in the motlten metal sulfur content direct measuring and decide the sulphur solid electrolyte, in particular for the sulfur determination probe of measuring sulfur content in the motlten metal and the method for making of auxiliary electrode thereof.
Background technology
Sulfur content in the motlten metal has material impact for smelting process and product quality, express-analysis and the correct sulfur content of smelting process of automatization level grasp to(for) raising motlten metal smelting process realize that accurate forecast of smelting endpoint and steel products quality have crucial meaning.
At present, carrying out the direct method of measuring of motlten metal sulfur content mainly is to utilize the method for solid electrolyte concentration cell.That is, utilize the solid electrolyte sulfur determination probe to form the sulphur concentration cell, measure the sulfur content in the motlten metal.The sulfur determination probe that uses mainly contains two kinds, and a kind of is the solid electrolyte tube that directly is prepared from sulfide, and another is with ZrO
2(MgO, CaO or Y
2O
3) as solid electrolyte tube, and be prepared from as auxiliary electrode at its outside surface coating one deck sulfocompound.For first kind of sulfur determination probe, owing to the following characteristic of sulfide is not applied it as yet in actual production process.
(1) is difficult in a large number synthetic in order to the sulfide of preparation solid electrolyte, is easy to generate blast because the evaporation of sulphur pressure is higher in the building-up process.
(2) sulfide easy-sintering not is difficult to obtain the good solid electrolyte of compactness.
The above-mentioned properties influence of sulfide the stability and the reappearance of solid electrolyte measured signal in its use.Therefore, second kind of sulfur determination probe, that is, what have an auxiliary electrode compoundly decides the effective way that sulfur solid electrolyte is considered to the development of new sulfur determination probe.
At present, the main method for preparing the sulfide auxiliary electrode at oxide based solid electrolyte tube outer surface has:
(1) cladding process: utilize paraffin or glycerine sulfide to be coated in the electrolytic tube surface, by high temperature sintering it is combined with the solid electrolyte tube body then with the method for physics.
(2) in-situ reducing synthetic method: the outside surface at oxide based solid electrolyte tube has prepared one deck sulfide auxiliary electrode by reaction in-situ.
In the said method, method (1) is owing to be not easy sintering between the sulfide of cladding process and oxide, and therefore, the auxiliary electrode adhesion that forms at the solid electrolyte body surface is low, and measuring accuracy and reappearance are bad.And method (2) though in combine between sulfide auxiliary electrode and solid electrolyte body well, measuring-signal is stable, measurement result also has good reappearance, also has some problems, mainly is:
(1) utilizes H
2When S gas prepares the sulfide auxiliary electrode at the solid electrolyte tube outer surface by reaction in-situ, because H
2S gas at high temperature decomposes easily, and its product sulphur condenses and makes course of reaction wayward at low-temperature space, and the performance of auxiliary electrode is difficult to obtain assurance.
(2) owing to be subjected to the restriction of the building-up process and the equipment of use, the synthetic negligible amounts of deciding sulfur solid electrolyte of original position can not satisfy industrial needs.
(3) owing to be used for the H of in-situ reducing
2The S gas price is higher, and the utilization factor of this gas is low and can not recycling in the course of reaction in addition, therefore, makes the price of deciding sulfur solid electrolyte of preparation higher, has limited its promoting the use of in field of metallurgy.
Summary of the invention
At the problems referred to above that exist in the sulfur determination probe preparation process, the invention provides a kind of can be in enormous quantities and prepare the motlten metal sulphur content determination at an easy rate with the preparation method of sulfur determination probe.
The technical solution used in the present invention is: adopt the method for plasma spraying, with synthetic ZrS
2+ MgS (CaS, Y
2S
3) powder is sprayed on ZrO
2-MgO (CaO, Y
2O
3) solid electrolyte surface preparation ZrS
2-MgS (CaS, Y
2S
3) auxiliary electrode, and with Cr+Cr
2O
3For the reference utmost point is formed sulfur determination probe.
Method for making as auxiliary electrode is: with weak acid with ZrO
2-MgO (CaO, Y
2O
3) the solid electrolyte surface carries out cleaning treatment, to remove the dirt and the impurity on surface.After the drying, electrolytic tube is poured on the corundum matter pallet that has about 3mm hole depth.The corundum pallet is positioned on the Work turning table in the plasma winding-up equipment, under vacuum or with argon gas, the electrolytic tube on the worktable is sprayed as blanket gas.Utilize the ZrS that obtains after the spraying
2-MgS (CaS, Y
2S
3)/ZrO
2-MgO (CaO, Y
2O
3) decide the following sulphur concentration cell of sulfur solid electrolyte assembling:
Mo|Cr+Cr
2O
3(or Mo+MoO
2) | ZrO
2-MgO (CaO, Y
2O
3) | ZrS
2-MgS (CaS, Y
2S
3) | [S]
Fe| Mo (+)
The another kind of method for making of auxiliary electrode is: at first to ZrO
2-MgO (CaO, Y
2O
3) in the solid electrolyte tube | Cr+Cr
2O
3(or Mo+MoO
2) the reference utmost point and insert Mo lead-in wire, use the high-temperature cement shutoff then.With weak acid with ZrO
2-MgO (CaO, Y
2O
3) the solid electrolyte surface carries out cleaning treatment.After the drying, electrolytic tube is put on the corundum matter pallet.The corundum pallet is positioned on the Work turning table in the plasma winding-up equipment, under vacuum or with argon gas, the electrolytic tube on the worktable is sprayed and obtain ZrS as blanket gas
2-MgS (CaS, Y
2S
3)/ZrO
2-MgO (CaO, Y
2O
3) decide sulfur solid electrolyte.
Utilize the inventive method can prepare sulfur determination probe in enormous quantities, at an easy rate, and the sulfur determination probe stable performance, the precision height.
Embodiment
Embodiment 1
To ZrO
2Cr+Cr in the-MgO solid electrolyte tube
2O
3The reference utmost point and insert Mo lead-in wire after, use the high-temperature cement shutoff.Utilize weak acid that electrolytic tube is cleaned, after super-dry, electrolytic tube is poured on the corundum matter pallet that has about 3mm hole depth.Then the corundum pallet is positioned on the Work turning table in the plasma winding-up equipment, under vacuum or with argon gas as blanket gas with ZrS
2-MgS sprays on the electrolytic tube.Utilize the ZrS that obtains after the spraying
2-MgS/ZrO
2-MgO decides the following sulphur concentration cell of sulfur solid electrolyte assembling:
Mo|Cr+Cr
2O
3|ZrO
2-MgO|ZrS
2-MgS|[S]
Fe|Mo(+)
Embodiment 2
To ZrO
2Mo+MoO in the-CaO solid electrolyte tube
2The reference utmost point and insert Mo lead-in wire after, use the high-temperature cement shutoff.Utilize weak acid that electrolytic tube is cleaned, after super-dry, electrolytic tube is poured on the corundum matter pallet that has about 3mm hole depth.Then the corundum pallet is positioned on the Work turning table in the plasma winding-up equipment, under vacuum or with argon gas as blanket gas with ZrS
2-CaS sprays on the electrolytic tube.Utilize the ZrS that obtains after the spraying
2-CaS/ZrO
2-CaO decides the following sulphur concentration cell of sulfur solid electrolyte assembling:
Mo|Mo+MoO
2|ZrO
2-CaO|ZrS
2-CaS|[S]
FeMo(+)
Embodiment 3
To ZrO
2-Y
2O
3Cr+Cr in the solid electrolyte tube
2O
3The reference utmost point and insert Mo lead-in wire after, use the high-temperature cement shutoff.Utilize weak acid that electrolytic tube is cleaned, after super-dry, electrolytic tube is poured on the corundum matter pallet that has about 3mm hole depth.Then the corundum pallet is positioned on the Work turning table in the plasma winding-up equipment, under vacuum or with argon gas as blanket gas with ZrS
2-Y
2S
3Spray on the electrolytic tube.Utilize the ZrS that obtains after the spraying
2-Y
2S
3/ ZrO
2-Y
2O
3Decide the following sulphur concentration cell of sulfur solid electrolyte assembling:
Mo|Cr+Cr
2O
3|ZrO
2-Y
2O
3|ZrS
2-Y
2S
3|[S]
Fe|Mo(+)
Claims (2)
1. a probe of directly measuring the motlten metal sulfur content is characterized in that adopting the partially stabilized or completely stable Zirconia electrolytic pipe of magnesium oxide, calcium oxide or yttria (ZrO
2-MgO (CaO, Y
2O
3)) be matrix, the ZrS in the pipe outside
2+ MgS (CaS, Y
2S
3) auxiliary electrode layer, and the Cr+Cr in the pipe
2O
3The reference utmost point and Mo silk lead-in wire.
The described sulfide auxiliary electrode layer of claim 1 be method by plasma spraying under vacuum or inert gas shielding condition with ZrS
2And MgS (CaS, Y
2S
3) powder is coated in ZrO
2-MgO (CaO, Y
2O
3) the outside surface preparation of matter solid electrolyte tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100893934A CN102253098A (en) | 2011-04-11 | 2011-04-11 | Manufacturing method of sulfur determining probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011100893934A CN102253098A (en) | 2011-04-11 | 2011-04-11 | Manufacturing method of sulfur determining probe |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102253098A true CN102253098A (en) | 2011-11-23 |
Family
ID=44980480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011100893934A Pending CN102253098A (en) | 2011-04-11 | 2011-04-11 | Manufacturing method of sulfur determining probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102253098A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196974A (en) * | 2012-01-10 | 2013-07-10 | 东北大学 | Manufacturing method of sensor for phosphorus determination |
| CN103207228A (en) * | 2012-01-12 | 2013-07-17 | 东北大学 | Molten steel phosphorus sensor auxiliary electrode manufacturing method |
| CN103207229A (en) * | 2012-01-16 | 2013-07-17 | 东北大学 | A production method for a sulfur-content determining sensor |
| CN112179966A (en) * | 2020-11-05 | 2021-01-05 | 中民驰远实业有限公司 | Sulfur determination sensor for online determination of sulfur content in molten metal and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616956A (en) * | 2004-12-08 | 2005-05-18 | 东北大学 | Method for making sulphur determining probe and auxiliary electrode |
| CN101196488A (en) * | 2006-12-04 | 2008-06-11 | 于景坤 | Sulfur determination probe for molten metal |
-
2011
- 2011-04-11 CN CN2011100893934A patent/CN102253098A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1616956A (en) * | 2004-12-08 | 2005-05-18 | 东北大学 | Method for making sulphur determining probe and auxiliary electrode |
| CN101196488A (en) * | 2006-12-04 | 2008-06-11 | 于景坤 | Sulfur determination probe for molten metal |
Non-Patent Citations (1)
| Title |
|---|
| 刘涛 等: "MgS+TiS2固体电解质定硫探头的研制", 《东北大学学报（自然科学版）》, vol. 26, no. 4, 30 April 2005 (2005-04-30), pages 370 - 372 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103196974A (en) * | 2012-01-10 | 2013-07-10 | 东北大学 | Manufacturing method of sensor for phosphorus determination |
| CN103207228A (en) * | 2012-01-12 | 2013-07-17 | 东北大学 | Molten steel phosphorus sensor auxiliary electrode manufacturing method |
| CN103207229A (en) * | 2012-01-16 | 2013-07-17 | 东北大学 | A production method for a sulfur-content determining sensor |
| CN112179966A (en) * | 2020-11-05 | 2021-01-05 | 中民驰远实业有限公司 | Sulfur determination sensor for online determination of sulfur content in molten metal and preparation method thereof |
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Application publication date: 20111123 |