CN100514051C - Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method - Google Patents
Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method Download PDFInfo
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- CN100514051C CN100514051C CNB2006100729089A CN200610072908A CN100514051C CN 100514051 C CN100514051 C CN 100514051C CN B2006100729089 A CNB2006100729089 A CN B2006100729089A CN 200610072908 A CN200610072908 A CN 200610072908A CN 100514051 C CN100514051 C CN 100514051C
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- reference electrode
- oxygen sensor
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Abstract
This invention discloses a solid reference electrode of a zirconia smelt metal definite oxygen sensor mixed by Cr and Fe powder, in which, one end of said reference electrode is a closed cavity of CrO material and electrode core in the cavity, the inside core includes Cr powder and Fe< 2 >0< 3 > to be mixed evenly with Al< 2 >0< 3 >powder in the proportion of (5-95%): (95-5%): (0-90%) then to be injected into the cavity and sealed, the lead of the electrode is set in a sleeve, which is led out via the electrode cavity and a central hole of the cap on the top of the cavity to constitute CrO smelt definite oxygen sensor solid reference electrode of said Cr/Fe< 2 >0< 3 > system.
Description
Technical field:
The present invention relates to a kind of metallurgical analysis technology, be specifically related to a kind of technology of preparing of metallurgical melt fixed lambda sensor.
Background technology:
Steelmaking process is a complex physicochemical process, its important step be accurately measure and control molten steel temperature and oxygen position (oxygen content), the sixties in 20th century, the solid electrolyte Oxygen Probing Technology begins to be applied to Iron and Steel Production, promoted molten steel to decide the development and the development of lambda sensor, make it at various types of converters, ladle, tundish, continuous casting, detect in the production runes such as degasser, and in measured parameter oxygen activity chemical reaction dynamic changing process, carry out at random, simpler than traditional molten steel sampling back in the method for laboratory assay evaluation, quicker, more accurate.
The core component of metallurgic oxygen sensor is solid electrolyte oxidation zirconium half-cell, adds MO/MO in the tubular zirconium-oxide that its structure is at one end sealed
2Or Cr/Cr
2O
3Mixed-powder adopts Cr/Cr as solid reference electrode in actual applications
2O
3The solid reference electrode system.Research is found, because the Cr of Metal Cr surface stages of labor
2O
3Very fine and close, cause to produce polarization phenomena in the test process, make test result produce corresponding illusion, cause actual value and measured value that relatively large deviation is arranged.And the reappearance of test result is relatively poor.Simultaneously, because Cr/Cr
2O
3Melting phenomenon takes place in reference electrode system easily in test process, cause the solid reference electrode sintering, and polarization phenomena are further aggravated.Also have a kind of for overcoming Cr/Cr in the prior art
2O
3Reference electrode oozes the scheme that phenomenon that reference electrode that oxygen causes lost efficacy has proposed to arrange reverse reparation current system because of solid electrolyte in long-life lambda sensor use procedure, but this technology more complicated, and only be only applicable to the long-life sensor, in addition, because the requirement of environmental protection reduces and uses Cr/Cr as far as possible
2O
3Solid reference electrode also is the developing direction of novel environment friendly sensor.
Summary of the invention:
Technical matters to be solved by this invention has provided a kind of novel environment friendly metallurgic oxygen sensor solid reference electrode, this contrast electrode had both reduced the consumption of Cr compound, can avoid fusing, the sintering phenomenon of solid reference electrode in the use again, test result is stable, and repeatability is very good.
For solving the problems of the technologies described above, the invention provides a kind of zirconia metallurgic oxygen sensor solid reference electrode, its main component is Cr powder and Fe
2O
3The powder system is called for short Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode.Constituting of this reference electrode: the electrode chamber of the zirconia material of end sealing and place electrode inner core in the zirconia electrode chamber, this inner core comprises that two parts consist of, and are Cr powder and Fe
2O
3Injecting electrode Cr powder and Fe in the mixture of powders, cavity
2O
3Seal behind the mixture of powders inner core, the lead-out wire of electrode is drawn, and consists of this Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode;
This Cr/Fe
2O
3The preparation method of system zirconia metallurgic oxygen sensor solid reference electrode is:
(1), with Metal Cr powder and Fe
2O
3Powder and AL
2O
3Powder is (5%-95%) by weight percentage: (95%-5%): (0%-90%) ratio fully mixes;
(2), will an end inject the powder that should (1) step mixes in the zirconia electrode chamber of sealing, the contact conductor of packing into, sealing namely is prepared into this Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode.
Adopt the Cr/Fe of this case method preparation
2O
3System zirconia metallurgic oxygen sensor solid reference electrode Fe
2O
3Powder has substituted traditional Cr
2O
3Powder is because Fe
2O
3And Cr
2O
3Powder has identical crystal structure, can form the system solid solution that dissolves each other fully, and in test process, the reference electrode system is along with the rising of temperature, and the Metal Cr powder rapidly and Fe
2O
3Powder generation displacement reaction, its course of reaction is:
2Cr+Fe
2O
3＝Cr
2O
3+2Fe
The Cr that generates
2O
3Be coated on Fe
2O
3The outside of powder forms fine and close oxide-film compacted zone, makes the equilibrium oxygen partial pres-sure of system and traditional Cr
2O
3System is consistent, and test result can not change because of the above-mentioned change of solid reference electrode composition.Because reaction is from traditional Cr/Cr
2O
3New reference electrode Cr/Fe is transferred on the metal dust Cr surface of reference electrode system
2O
3Fe in the system
2O
3The surface of powder so just makes Cr and Cr
2O
3Between balance realize easily, avoided producing polarization because of the growth of metal dust surface passivated membrane.Even there is Cr/Cr in metal dust Cr surface
2O
3Passivating film is because Fe
2O
3And Cr
2O
3Lattice mechanism is identical and dissolve each other fully, so Fe
3+Solid solution enters passivating film is destroyed rapidly, and equilibrium oxygen partial pres-sure can be set up within a short period of time.
Simultaneously, Fe
2O
3And Cr
2O
3The foundation of system solid solution can suppress Cr powder and Cr
2O
3Molten sintering phenomenon between the powder, AL
2O
3The adding of powder can make the molten sintering phenomenon between each powder further reduce.
Description of drawings:
Fig. 1 is a structural representation of the present invention;
Embodiment:
As shown in Figure 1: a kind of zirconia metallurgic oxygen sensor solid reference electrode, this reference electrode comprise the electrode chamber 1 of the zirconia material of end sealing, are provided with by Cr powder and Fe in its cavity
2O
3The electrode inner core 2 that mixture of powders consists of is provided with electrode outlet line 3, and this electrode outlet line places in the sleeve pipe 4, consists of this Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode;
This Cr/Fe
2O
3The preparation method of system zirconia metallurgic oxygen sensor solid reference electrode is:
(1), with Metal Cr powder and Fe
2O
3Powder and AL
2O
3Powder is (5%-95%) by weight percentage: (95%-5%): (0%-90%) ratio fully mixes;
(2), will an end inject the powder that should (1) step mixes in the zirconia electrode chamber of sealing, the contact conductor of packing into, sealing namely is prepared into this Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode.
Its theoretical foundation has been stated in this case, confirms simultaneously above-mentioned Metal Cr powder and Fe through test
2O
3Powder and AL
2O
3Powder, gross data and test result all do not have to change because of the variation of this solid reference electrode composition that this case provides.So this case no longer provides the concrete numerical value of corresponding component ratio, embody concrete test result.Just determine its consumption to get final product with reference to its market price of above-mentioned raw materials.
The above, it only is preferred embodiment of the present invention, be not that the present invention is done any pro forma restriction, though the present invention discloses as above with preferred embodiment, yet be not in order to limit the present invention, any those skilled in the art, when the technology contents that can utilize above-mentioned announcement is made a little change, in every case be not break away from technical solution of the present invention,, all still belong in the scope of technical solution of the present invention any simple modification, equivalent variations and the modification that above embodiment did.
Claims (3)
1, a kind of metallurgical melt fixed oxygen sensor reference electrode is characterized in that: described metallurgical melt fixed oxygen sensor reference electrode comprises zirconia electrode chamber, electrode inner core, electrode outlet line and the sleeve pipe of end sealing;
Described electrode inner core comprises Cr powder and Fe
2O
3Mixture of powders;
Described electrode inner core places in the zirconia electrode chamber;
Described bobbin seal zirconia electrode chamber;
Described contact conductor passes sleeve pipe and places the electrode inner core.
2, metallurgical melt fixed oxygen sensor reference electrode as claimed in claim 1 is characterized in that: the main component of described electrode also comprises Al
2O
3Powder.
3, metallurgical melt fixed oxygen sensor reference electrode as claimed in claim 2 is characterized in that: the preparation method of this electrode is:
(1), with Metal Cr powder and Fe
2O
3Powder and Al
2O
3Powder is (5%-95%) by weight percentage: (95%-5%): (0%-90%) ratio fully mixes;
(2), will an end inject the powder that should (1) step mixes in the zirconia electrode chamber of sealing, the contact conductor of packing into, sealing namely is prepared into this Cr/Fe
2O
3System zirconia metallurgic oxygen sensor solid reference electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100729089A CN100514051C (en) | 2006-04-03 | 2006-04-03 | Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100729089A CN100514051C (en) | 2006-04-03 | 2006-04-03 | Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1821769A CN1821769A (en) | 2006-08-23 |
| CN100514051C true CN100514051C (en) | 2009-07-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100729089A Expired - Fee Related CN100514051C (en) | 2006-04-03 | 2006-04-03 | Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012093727A1 (en) * | 2011-01-07 | 2012-07-12 | 国立大学法人三重大学 | Reference electrode |
| CN103586455B (en) * | 2013-10-15 | 2015-07-08 | 钟祥市中原电子有限责任公司 | Reference electrode powder for molten metal oxygen-measuring batteries and production process |
| CN104297311B (en) * | 2014-09-24 | 2017-06-13 | 中国科学院上海应用物理研究所 | A kind of silver/silver chloride reference electrode and preparation method thereof |
| CN113504282A (en) * | 2021-06-23 | 2021-10-15 | 北京浩德楚业新材料科技有限公司 | Preparation method of oxygen reference electrode material and oxygen determination probe |
-
2006
- 2006-04-03 CN CNB2006100729089A patent/CN100514051C/en not_active Expired - Fee Related
Non-Patent Citations (6)
| Title |
|---|
| 定氧技术的现状及质量评价. 邓茂焕，黄正.工业计量，第14卷第4期. 2004 |
| 定氧技术的现状及质量评价. 邓茂焕，黄正.工业计量，第14卷第4期. 2004 * |
| 氧传感器用ZrO2-Y2O3固体电解质电导性能的研究. 陈家林，万吉高，王开军，陈亮维，马骏.贵金属，第22卷第1期. 2001 |
| 氧传感器用ZrO2-Y2O3固体电解质电导性能的研究. 陈家林，万吉高，王开军，陈亮维，马骏.贵金属，第22卷第1期. 2001 * |
| 钢铁冶金中的氧传感器及其应用. 安胜利，赵文广，安立国.华东冶金学院学报，第14卷第4期. 1997 |
| 钢铁冶金中的氧传感器及其应用. 安胜利，赵文广，安立国.华东冶金学院学报，第14卷第4期. 1997 * |
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|---|---|
| CN1821769A (en) | 2006-08-23 |
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Denomination of invention: Novel metallurgical melt fixed oxygen sensor reference electrode and its preparing method Effective date of registration: 20130711 Granted publication date: 20090715 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: Kehai Longhua Industry Automation Instrument Co., Ltd., Beijing Registration number: 2013990000448 |
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