CN1097508A - A kind of reference electrode of hydrogen sensor and preparation method thereof - Google Patents
A kind of reference electrode of hydrogen sensor and preparation method thereof Download PDFInfo
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- CN1097508A CN1097508A CN 93112063 CN93112063A CN1097508A CN 1097508 A CN1097508 A CN 1097508A CN 93112063 CN93112063 CN 93112063 CN 93112063 A CN93112063 A CN 93112063A CN 1097508 A CN1097508 A CN 1097508A
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- yttrium
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Abstract
The invention discloses a kind of employing yttrium-hydrogen is that alloy is made reference electrode of hydrogen sensor and preparation method thereof.Be to consider or approach the metallic yttrium of purity 〉=99.9% to be worth doing bits to place molybdenum boat to be put in the quartz ampoule, find time and argon filling, at a certain temperature, constant temperature.Be cooled to room temperature, taking-up places the protection of argon filling container stand-by, or considers or approach metallic yttrium to be worth doing bits elder generation through being hydrogenated to YH
3, the dehydrogenation of finding time is to the yttrium powder, feeds that pure hydrogen or hydrogen---argon mixture gas is made again, and has making, use, easy to carry, characteristics such as cost is low, accuracy rate of measuring height.Be used to detect metal bath or gas phase hydrogen concentration or hydrogen partial pressure value.
Description
The invention belongs to the metallurgical material field, be particularly useful for material of reference electrode of hydrogen sensor and preparation method thereof.
Former great some perofskite type oxide of discovery such as professor of educating of Japan Nagoya university rock is as BaCeO
3, CaZrO
3Base or SrCeO
3Base oxide presents proton conductive about 500～1000 ℃, this characteristic can be used for making the solid electrolyte of hydrogen sensor, to detect hydrogen activity or hydrogen partial pressure value in metal bath or the gas phase.They once adopted Ce under study for action
2(SO
4)
38H
2O is mixed with fused salt or AlPO
4XH
2O is as the contrast electrode of hydrogen sensor, but seldom arrives stability number; Adopt 1% hydrogen calibrating gas as contrast electrode again., carry and use equal inconvenience as contrast electrode equipment complexity not only with calibrating gas, and price is higher.
Deficiency in view of above-mentioned prior art exists the invention provides a kind of solid phase material as reference electrode of hydrogen sensor and preparation method thereof.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
Mixed-powder with yttrium-hydrogen two-phase coexistent is made the contrast electrode of hydrogen sensor.
The present invention learns in this system the result of study of yttrium-hydrogen system phasor according to document to exist the two-phase coexistent district, and the two-phase coexistent district has the principle of stablizing constant hydrogen partial pressure value to make in certain temperature range.Learn that from yttrium-hydrogen system phasor temperature range is at 601.4 ℃ to 949.4 ℃, gram-atom hydrogen/gram-atom yttrium is 0.7～1.3 o'clock, and corresponding hydrogen partial pressure value is 1 * 10
-3～8mmHg.
The material of contrast electrode of the present invention can be by following three kinds of methods preparation.
1, elder generation places molybdenum boat to be put in quartz ampoule or other boiler tube in the metallic yttrium fines or the thin bits of purity 〉=99.9%; find time and fill to purify argon 3～4 times; after finding time again; again with in the slow access tube of purified hydrogen; at 300～400 ℃, constant temperature 70～90 minutes is cooled to room temperature then rapidly; take out sample, place the protection of argon filling container stand-by.
2, considering or approach the metallic yttrium of purity 〉=99.9% to be worth doing bits earlier places molybdenum boat to be put in quartz ampoule or other boiler tube, find time to fill purify argon, find time, behind the argon filling 3～4 times, at 600～650 ℃, after finding time again, charge into the hydrogen-argon mixture gas that certain hydrogen partial pressure value is arranged (hydrogen gives first purification) that calculates by yttrium-argon system phase diagram or slowly feed purified hydrogen, detect hydrogen partial pressure value in the metallic yttrium bisque with the solid electrolyte hydrogen sensor, when constant, be desired two-phase mixture to the hydrogen partial pressure value.Then molybdenum boat is cooled to room temperature rapidly, takes out sample, place the protection of argon filling container stand-by.Hydrogen sensor with High Purity Hydrogen or hydrogen-argon standard mixture as contrast electrode.
3, consider or approach the metallic yttrium of purity 〉=99.9% to be worth doing bits earlier and be hydrogenated to YH 200～300 ℃ of processes
3, the dehydrogenation of finding time feeds pure hydrogen or hydrogen-argon mixture gas again and is prepared into desired yttrium-hydrogen two-phase mixture to the yttrium powder.The advantage of this method is to be prepared into the hydrogenation again of yttrium powder earlier, and the time of homogenising is short.
The present invention compared with prior art has the following advantages:
Japan has and decide hydrogen sensor production in aluminium liquid, and the calibrating gas with hydrogeneous 1% is as contrast electrode.The equipment complexity, the cost height.The present invention can make hydrogen sensor make, use, carry, change conveniently.And easy to utilize, and cost is low; Because there is the thermal diffusion phenomenon in hydrogeneous 1% mixed gas, be not quite similar with the room temperature air composition in the stove again, easily produce error.And the present invention has improved accuracy rate.
Below in conjunction with accompanying drawing contrast electrode is further specified.
Accompanying drawing 1 is that contrast electrode provided by the invention is used for the structural representation on the hydrogen sensor.
With reference to Fig. 1, can find out that hydrogen sensor is popped one's head in by the Al after solid electrolyte tube [1], reference electrode [2], contact conductor [3], encapsulant [5], the calcination2O
3Powder [4] consists of. When the mixed-powder of yttrium-hydrogen two-phase coexistent is packed solid electrolyte tube into, be under argon atmospher, to carry out. With metal nickel wire or molybdenum filament as contact conductor. The height of powder filler and the encapsulating method of sensor probe are similar to the method for general oxygen sensor probe.
Below provide contrast electrode preparation method's of the present invention embodiment.
Embodiment 1
Metallic yttrium fines with purity 〉=99.9% places molybdenum boat to be put in the quartz ampoule earlier, finds time to fill to purify argon 3 times, after finding time again; again with in the slow access tube of purified hydrogen, at 400 ℃, constant temperature 70 minutes; be cooled to room temperature then rapidly, take out sample, place the protection of argon filling container stand-by.
Metal fines with purity 〉=99.9% places molybdenum boat to be put in the quartz ampoule earlier, finds time to fill to purify argon 4 times, after finding time again; again with in the slow access tube of purified hydrogen, at 350 ℃, constant temperature 80 minutes; be cooled to room temperature then rapidly, take out sample, place the protection of argon filling container stand-by.
Metal fines with purity 〉=99.9% places molybdenum boat to be put in the quartz ampoule earlier; find time to fill purify argon, find time, behind the argon filling 3 times; at 600 ℃, after finding time again, charge into by behind the good hydrogen-argon mixture gas that certain hydrogen partial pressure value is arranged of yttrium-hydrogen system PHASE DIAGRAM CALCULATION; with the hydrogen partial pressure value in the solid electrolyte hydrogen sensor detection metallic yttrium bisque; when constant, be desired two-phase mixture to the hydrogen partial pressure value, then molybdenum boat be cooled to room temperature rapidly; take out sample, place the protection of argon filling container stand-by.Hydrogen sensor uses the High Purity Hydrogen calibrating gas as contrast electrode.
The thin bits of metallic yttrium with purity 〉=99.9% place molybdenum boat to be put in the quartz ampoule earlier, find time to fill purify argon, find time, behind the argon filling 4 times, at 650 ℃, after finding time again, slowly charge into purified hydrogen, detect hydrogen partial pressure value in the metallic yttrium bisque with the solid electrolyte hydrogen sensor, when constant, be desired two-phase mixture to the hydrogen partial pressure value.Then molybdenum boat is cooled to room temperature rapidly, takes out sample, place the protection of argon filling container stand-by.Hydrogen sensor uses hydrogen-argon standard mixture as contrast electrode.
The thin bits of metallic yttrium with purity 〉=99.9% are hydrogenated to YH 200 ℃ of elder generation's processes earlier
3, the dehydrogenation of finding time is to the yttrium powder, feeds the yttrium-hydrogen two-phase mixture of the expectation that pure hydrogen is prepared into again.
Embodiment 6
Metallic yttrium bits with purity 〉=99.9% are hydrogenated to YH 300 ℃ of elder generation's processes earlier
3, the dehydrogenation of finding time feeds hydrogen-argon mixture gas again and is prepared into desired yttrium-argon two-phase mixture to the yttrium powder.
Claims (4)
1, a kind of reference electrode of hydrogen sensor is characterized in that constituting with the mixed-powder of yttrium-hydrogen two-phase coexistent.
2, a kind of preparation method according to the described reference electrode of hydrogen sensor of claim 1; it is characterized in that: metal fillings or the thin bits with purity 〉=99.9% place molybdenum boat to be put in quartz ampoule or other boiler tube earlier; find time and fill purified hydrogen 3～4 times; after finding time again, again with in the slow access tube of purified hydrogen, at 300～400 ℃; constant temperature 70～90 minutes; be cooled to room temperature then rapidly, take out sample, place the protection of argon filling container stand-by.
3; a kind of preparation method according to the described reference electrode of hydrogen sensor of claim 1; it is characterized in that: metallic yttrium bits or the thin quiet molybdenum boat that places with purity 〉=99.9% is put in quartz ampoule or other pipe earlier; find time to fill purified hydrogen; find time; behind the argon filling 3～4 times; at 600～650 ℃; after finding time again; charge into the hydrogen-argon mixture gas that certain hydrogen partial pressure value is arranged that calculates by yttrium-argon system phase diagram or slowly feed purified hydrogen; with the hydrogen partial pressure value in the solid electrolyte hydrogen sensor detection metallic yttrium bisque; to the hydrogen partial pressure value when constant; then molybdenum boat is cooled to room temperature rapidly; take out sample, place that to fill the hydrogen tank protection stand-by.Hydrogen sensor with High Purity Hydrogen or hydrogen-argon standard mixture as contrast electrode.
4, a kind ofly pass the preparation method of device contrast electrode, it is characterized in that: earlier with the metallic yttrium bits of purity 〉=99.9% or thin quietly be hydrogenated to YH 200～300 ℃ of processes according to the described hydrogen of claim 1
3, the dehydrogenation of finding time feeds pure hydrogen or hydrogen-argon mixture gas again and is prepared into desired yttrium-argon two-phase mixture to the yttrium powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112063 CN1097508A (en) | 1993-07-12 | 1993-07-12 | A kind of reference electrode of hydrogen sensor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93112063 CN1097508A (en) | 1993-07-12 | 1993-07-12 | A kind of reference electrode of hydrogen sensor and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1097508A true CN1097508A (en) | 1995-01-18 |
Family
ID=4989805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93112063 Pending CN1097508A (en) | 1993-07-12 | 1993-07-12 | A kind of reference electrode of hydrogen sensor and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045480A (en) * | 2016-05-27 | 2016-10-26 | 内蒙古科技大学 | Method for preparing proton conductive electrolyte of molten metal hydrogen-determining sensor |
| CN106568672A (en) * | 2015-10-12 | 2017-04-19 | 哈尔滨理工大学 | Continuous hydrogen measurement technology based on hydrogen sensor inert gas cycle method |
-
1993
- 1993-07-12 CN CN 93112063 patent/CN1097508A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106568672A (en) * | 2015-10-12 | 2017-04-19 | 哈尔滨理工大学 | Continuous hydrogen measurement technology based on hydrogen sensor inert gas cycle method |
| CN106045480A (en) * | 2016-05-27 | 2016-10-26 | 内蒙古科技大学 | Method for preparing proton conductive electrolyte of molten metal hydrogen-determining sensor |
| CN106045480B (en) * | 2016-05-27 | 2021-03-16 | 内蒙古科技大学 | Preparation method of proton conductive electrolyte of molten metal hydrogen determination sensor |
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