CN1063761A - Obtain the new method of long-life continuous oxygen measuring probe - Google Patents
Obtain the new method of long-life continuous oxygen measuring probe Download PDFInfo
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- CN1063761A CN1063761A CN 91100437 CN91100437A CN1063761A CN 1063761 A CN1063761 A CN 1063761A CN 91100437 CN91100437 CN 91100437 CN 91100437 A CN91100437 A CN 91100437A CN 1063761 A CN1063761 A CN 1063761A
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- oxygen
- contrast electrode
- solid electrolyte
- gauge head
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- Measuring Oxygen Concentration In Cells (AREA)
Abstract
The invention belongs to physico-chemical examination technique.It comprises and gives the reverse reparation electric current opposite with working current at interval and according to the gauge head working temperature to the oxygen measuring probe battery at each oxygen determination, should with reference to binary or ternary phase, choose suitable alloy system and composition and mix and make contrast electrode, make it in the oxygen determination temperature range, become the mixing fritting body of oxygen-saturated solid-liquid two-phase coexistent with metal oxide.The former can make the consume of gauge head contrast electrode oxygen be replenished, and the latter can prevent that contrast electrode from producing significant oxygen concentration polarization in working order down.Two kinds of methods all make gauge head than existing gauge head durable and simple and easy to do.
Description
The invention belongs to physico-chemical examination technique.
Solid electrolyte battery oxygen measuring probe (abbreviation gauge head) is significant to the development of current metallurgical technology, because can all genus oxidation-reduction smelting processes, in time measure oxygen in the liquation as steel-making to the equal tool decisive influences of problems such as consumption, steel quality and lumber recovery of the carrying out of smelting reaction, speed, alloy material.So the research and development oxygen measuring probe has become the important topic that domestic and international physics and chemistry detects.
Fig. 1 is the synoptic diagram of solid electrolyte gauge head structure.It is (as Mo+MoO or Cr+Cr by interior dress metal and oxide powder thereof
2O
3) preparation contrast electrode (1), Al
2O
3Filler (2), metal lead wire (3) and port are coated with the end solid electrolyte tube (5) that has of envelope with cement (4), and (material is generally got ZrO
2+ Y
2O
3Or ZrO
2+ MgO) with by metallic ceramics (Mo+ZrO
2) loop electrode (6) fired constitutes.7 is the common metal lead among the figure, and 8 is tested metal bath.
Fig. 2 is the principle of work synoptic diagram of probe.Among the figure, 9-contrast electrode system,
Be the equilibrium oxygen partial pres-sure of contrast electrode system, 10-solid electrolyte system, the tested melt system of 11-,
Equilibrium oxygen partial pres-sure for tested melt system.
E is a cell emf in Fig. 1～2.
Gauge head battery expression formula is:
（+）Mo，
，
Cathode reaction is: O
2(
)+4e → 2O
=
Cathode reaction is: α O
=→ O
2(
)+4e
That is to say, when gauge head is worked, the MoO of contrast electrode (1)
2At high temperature be decomposed into Mo+O
2, or Cr
2O
3Be decomposed into Cr+O
2, O
2Obtain electronics by metal lead wire anode (3) and become 20
=, 20
=Enter tested metal bath (8) by solid electrolyte (5) self excess electron is transferred to loop electrode (6), thereby produce certain cell emf E.At thermodynamic equilibrium and transference number of ions t
iUnder=1 the ideal conditions, there is following relation:
R-ideal gas constant in the formula
The F-Faraday constant
T-oxygen determination temperature
When
Known, measure E and T, can calculate
, and calculate the activity and the content of oxygen in the tested melt thus.
When
The time, principle is identical, the gauge head function is constant, just oxonium ion transmission direction, direction of current and battery polar and
The time situation opposite.
The gauge head that adopts both at home and abroad mostly is disposable or claims instantaneous gauge head at present.Because this gauge head is short-lived, measure inconvenience, cost is too high, and inconvenience is satisfied the further requirement of programmed control aspect and is improved by many scholars.Improved approach mostly is and changes the drawing materials as with ZrO of solid electrolyte
2+ Y
2O
3Replace ZrO
2+ MgO(sees USPatent No 4627892 (Dec.91986) and WLWorrell and QLiu, Solid State Ionic 40/41 (1990) 761-764North-Holland) and increase solid electrolyte thickness and (see DJanke, Solid State Ionics 40/41 (1990) 764-769, the scholar of the Tang Yu Asus paper that North-Holland and Liu Qingguo, Li Fu Rui instruct, University of Science ﹠ Technology, Beijing's Physical Chemistry of Metallurgy specialty 88 years), reducing the electronic conductivity and the microporosity of solid electrolyte, the seepage of anti-block and prolong gauge head serviceable life.These methods can make gauge head use about 3 hours continuously under laboratory condition.
The objective of the invention is to seek a kind of alternative method of prior art, to obtain the oxygen measuring probe more stable, that serviceable life is more lasting.
For achieving the above object, the inventor has mainly adopted two kinds of technical schemes:
The first on the cell circuit of once popping one's head in by adjustable constant current supply of reversing switch series connection, in time impose the reverse reparation electric current opposite in each oxygen determination gap by reversing switch, so that contrast electrode (1) is replenished because of the electronic conduction of solid electrolyte (5), micropore and the rapid loss that forms the oxygen that working current caused when closed circuit because of the battery external circuit with its working current direction to oxygen measurement battery.This point can be illustrated by gauge head principle of work synoptic diagram 2: 1. have electronic conduction because of solid electrolyte, electronics issues the motion of being conigenous a dextrad left side in the electric field force effect, cell emf is descended and destroy original balance, thereby accelerate oxygen from left to right migration under the oxygen potential difference promotes; 2. because of there is the microporosity in solid electrolyte, make oxygen carry out physical diffusion or seepage to the right-hand member of low oxygen partial pressure from the left end of high keto sectional pressure; 3. form at the battery external circuit and have a working current when closed circuit, for keeping original balance, oxygen can further move from left to right.All of these factors taken together causes the migration in the same way of oxygen, and making the rapid loss of oxygen in the contrast electrode (1) is to cause the oxygen concentration polarization to occur, makes battery failure.The employing reverse current is repaired, can make because of above-mentioned reason taken place from left end to the oxygen of right-hand member migration again migration from right to left side go back, oxygen in the contrast electrode is in time replenished, the oxygen concentration polarization that rapid consume because of oxygen is caused is eased or eliminates, thereby an original gauge head can be used continuously lastingly.The key of this method is the correct electric current of selecting to repair.Electric current is too little, and the oxygen of loss can not get replenishing; Electric current is excessive, causes opposite oxygen concentration polarization also of no avail.The theoretical formula that suitable reparation electric current can be derived according to three factors of the loss that causes oxygen seepage that is electronic conduction, oxygen and working current with reference to the inventor (
):
Calculated.In the formula:
The R-ideal gas constant
The F-Faraday constant
T-oxygen determination temperature (battery operated temperature)
(
)
P
eThe electronic conductive characteristics of partial pressure of oxygen of '-solid electrolyte
L-solid electrolyte thickness
σ
iThe ionic conductivity of-solid electrolyte
The coefficient of diffusion of D-oxygen in solid electrolyte material
R
lThe input impedance of-electro-motive force measurement instrument
The working area of A-battery
When
The time, in the 1st, 2 of the above-mentioned formula
Fig. 3～5th, the result that the inventor measures with the reverse current repairing method.Among the figure
-be a gauge head measurement result; ■-for not adding the measurement result of repairing electric current; The measurement result that ●-be repaired through reverse current.E-is the cell emf of gauge head, and t-is the time.
Test condition:
Fig. 3, T(oxygen determination temperature)=1836k, I(repairs electric current)=500 μ A.
Fig. 4, T=1828k, I=60 μ A.
Fig. 5, T=1830k, I=440 μ A.
It two is at the preparation contrast electrode when (1), make it in the oxygen determination temperature range, be in the mixing fritting state of oxygen-saturated solid-liquid two-phase coexistent just, that is to say to be foundation with the oxygen determination temperature range, with reference to binary or ternary solid solution phasor, at first choose alloy system and composition, and then sneak into and to make contrast electrode (1) guarantee that in the oxygen determination temperature range oxide that reaches a certain metal in the oxygen-saturated alloy makes contrast electrode (1).Such as when the T=1873k, according to the optional Fe-Cr 55～73%(of binary phase diagraml weight) as alloy system, contrast electrode is then got Fe-Cr 55～73%(weight)+Cr
2O
3Or+Fe
2O
3; When T=1473K, optional Cu-Ni 22～40%(weight) as alloy system, contrast electrode is then got Cu-Ni 22～40%(weight)+NiO or+CuO.Why this method can make gauge head stable, durable in use, be because oxygen in melt diffusion ratio in solid fast 10
4, can effectively prevent the appearance of block concentration polarization.
Fig. 6 is contrast electrode oxygen saturation solid-liquid two-phase coexistent half melt method gauge head test result (black line is the continuous coverage point that computing machine is got among the figure).
Test condition: T=1873K, the contrast electrode system is: Fe-Cr 55%(weight)+Cr
2O
330%(weight).
In addition, the inventor also replaces the existing first burning process that gives with loop electrode (6) preparation method who uses time nature sintering to form after the first compression moulding again by gauge head, makes that operation is simplified, cost reduces.This method and reverse current repairing method (test result is seen Fig. 7～9) and contrast electrode oxygen saturation solid-liquid two-phase coexistent half melt method (test result is seen Figure 10) logotype all have good result.
Test condition:
Fig. 7, T=1834K, I=80 μ A.
Fig. 8, T=1829K, I=100 μ A.
Fig. 9, T=1829K, I=750 μ A.
Figure 10, T=1873K, the contrast electrode system is: Fe-Cr 70%(weight)+Fe
2O
330%(weight).The same Fig. 3 of symbol implication～5 in Fig. 6～10.
Description of test, compared with prior art, that the present invention has is durable in use, measure advantages such as stable, simple and easy to do, especially wherein reverse current repairing method both can extensively utilize existing disposable gauge head in addition, make it become the long-life gauge head, also can be used for other forms of long-life gauge head, make it have characteristics such as more durable, stable more.
Claims (2)
1, a kind of contrast electrode [1], Al by interior dress metal and oxide powder preparation thereof
2O
3Filler [2], metal lead wire [3] and port are coated with solid electrolyte battery oxygen measuring probe that the loop electrode [6] that end solid electrolyte tube [5] is arranged and fired by metallic ceramics of envelope constituted is implemented continuous oxygen measuring to metal bath [8] new method with cement [4], it is characterized in that in time imposing the reverse reparation electric current opposite by reversing switch by constant current supply with its working current direction to oxygen measurement battery in each oxygen determination gap, when
The time this electric current size by formula
Determined, in the formula:
The R-ideal gas constant,
The F-Faraday constant,
T-oxygen determination temperature,
To opposite reverse reparation electric current, when '
The equilibrium oxygen partial pres-sure of-contrast electrode system and tested melt system,
P
' eThe electronic conductive characteristics of partial pressure of oxygen of-solid electrolyte,
L-solid electrolyte thickness,
The ionic conductivity of δ j-solid electrolyte,
The coefficient of diffusion of D-oxygen in solid electrolyte,
The input impedance of Rl-electro-motive force measurement instrument,
The working area of A-battery:
When to opposite reverse reparation electric current, when
The time, in the 1st, 2 of the formula
Or when preparation contrast electrode [1], make it in the oxygen determination temperature range, be in the mixing fritting figure of oxygen-saturated solid-liquid two-phase coexistent just, be foundation promptly with the oxygen determination temperature range, with reference to binary or ternary solid solution phasor, at first choose alloy system and composition, and then sneak into and to make contrast electrode [1] guarantee that in the oxygen determination temperature range oxide that reaches a certain metal in the oxygen-saturated alloy makes contrast electrode [1].
2, the method for claim 1 is characterized in that said loop electrode (6) is that natural sintering forms when using by gauge head after the compression moulding formerly again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100437 CN1024479C (en) | 1991-01-28 | 1991-01-28 | Method for long-life continuous oxygen measuring probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91100437 CN1024479C (en) | 1991-01-28 | 1991-01-28 | Method for long-life continuous oxygen measuring probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1063761A true CN1063761A (en) | 1992-08-19 |
| CN1024479C CN1024479C (en) | 1994-05-11 |
Family
ID=4904631
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91100437 Expired - Fee Related CN1024479C (en) | 1991-01-28 | 1991-01-28 | Method for long-life continuous oxygen measuring probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1024479C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586455A (en) * | 2013-10-15 | 2014-02-19 | 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 |
| CN109521077A (en) * | 2018-11-13 | 2019-03-26 | 国电南瑞科技股份有限公司 | A kind of two-wave interpretation formula online Analysis Apparatus of Permanganate Index titration end-point instruction device |
-
1991
- 1991-01-28 CN CN 91100437 patent/CN1024479C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103586455A (en) * | 2013-10-15 | 2014-02-19 | 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 |
| CN109521077A (en) * | 2018-11-13 | 2019-03-26 | 国电南瑞科技股份有限公司 | A kind of two-wave interpretation formula online Analysis Apparatus of Permanganate Index titration end-point instruction device |
| WO2020098361A1 (en) * | 2018-11-13 | 2020-05-22 | 国电南瑞科技股份有限公司 | Titration end point indicating device for permanganate index on-line analyzer of double platinum electrode type |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1024479C (en) | 1994-05-11 |
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