CN1033103C - Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe - Google Patents
Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe Download PDFInfo
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- CN1033103C CN1033103C CN92111197A CN92111197A CN1033103C CN 1033103 C CN1033103 C CN 1033103C CN 92111197 A CN92111197 A CN 92111197A CN 92111197 A CN92111197 A CN 92111197A CN 1033103 C CN1033103 C CN 1033103C
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- solid electrolyte
- pipe
- hydrogen
- reference electrode
- alundum tube
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- Measuring Oxygen Concentration In Cells (AREA)
Abstract
The present invention relates to a proton electric conducting solid electrolyte solid phase reference electrode electrochemical fixed hydrogen measuring head. A solid electrolyte ceramic tube with one end sealed is filled with a Ca/CaH2 mixture to keep hydrogen partial pressure constant to be used as a reference electrode, an alundum tube into which an electrode conducting wire penetrates is inserted into the open end of the solid electrolyte tube, and then, the open end of the solid electrolyte tube is sealed. The outer side of the solid electrolyte tube of the gas phase fixed hydrogen measuring head is coated with a thin sintered Ag/Pd layer, and a conducting wire is wound around the solid electrolyte tube. The measuring head has the advantages of simple structure, simple manufacturing technology, high measuring precision and long service life and can be widely used for refining metal, and controlling and monitoring the process automation of industrial furnaces.
Description
The present invention relates to the hydrogen richness in quick or METHOD FOR CONTINUOUS DETERMINATION gas phase or molten metal and the alloy.
Hydrogen solubleness reduces greatly when liquid metal or alloy graining, separates out hydrogen quality of materials is descended.Should do dehydrogenation before the particularly high-quality metal material casting handles.The industry sintering furnace, hydrogen content or vapour content also are the important technology indexs in the cylinder-drying kiln atmosphere.The detection of hydrogen richness and vapour content is very important in these production runes.
Usually the sample analysis that adopts is difficult to accomplish because of the hydrogen diffusivity is extremely strong accurately, and must the long period.
The zirconia solid electrolyte gauge head can only be measured the oxygen content of finite concentration scope, can not measure the content of hydrogen.
Reported with SrCeO recent years
3(+Yb
2O
3) the proton conductive sintered body is solid electrolyte, with the known hydrogen dividing potential drop gas hydrogen concentration cell type hydrogen sensor (referring to openly speciallyying permit flat 1-265152 backgrounds narration part day) that is the contrast electrode material.This class gauge head
Contrast electrode needs the certain hydrogen dividing potential drop of air supply system supply gas, and device is complicated, and reference gas may leak to tested systems.Therefore be difficult to practical application.
Fa Ming polarization current type hydrogen sensor is to apply potential difference (PD) between proton conducting solid electrolyte two lateral electrodes after a while, and the mensuration polarization current is obtained tested systems hydrogen richness (a day special permission openly puts down 1-265152), and this sensor will be at SrCeO
3(+Yb
2O
3) potsherd is coated with electrode, fixing cord, bonding with alumina tube then, also to keep two interpolar potential difference (PD) by potentiostat, measure electric current with reometer.
The objective of the invention is to solve the above-mentioned problem that hydrogen test probe exists of deciding, Ca and CaH at one end pack in Feng Bi the proton conductive ceramic pipe
2Potpourri makes this gauge head not need air supply system as keeping the constant contrast electrode of hydrogen dividing potential drop, and manufacture craft is simple in structure, and easy to use and reliable, improves measuring accuracy, life-saving.
Principle of the present invention is that the hydrogen concentration cell can be remembered work:
H
2(I) | S5rCeO
3(+Yb
2O
3) | H
2(II) pass of cell emf and electrode hydrogen dividing potential drop is:
-2FE=RTIn (PH
2(II)/PH
2(I)) (1) R-gas law constant, T-absolute temperature, F-faraday constant, E-balance electric gesture.The low hydrogen voltage grading electrode is anodal relatively.
Ca and CaH
2The potpourri two-phase coexistent is kept the constant hydrogen dividing potential drop.In 873-1053K temperature range, β Ca and α CaH
2The equilibrium hydrogen dividing potential drop is:
logPH
2(Torr)＝-9610/T+10.227 (2)
The hydrogen richness that dissolves in the metal is corresponding one by one with metal ambient hydrogen content.For example the pass of hydrogen concentration and equilibrium hydrogen dividing potential drop is in the aluminium liquid:
Log (S/PH
2 1/2Hydrogen concentration in the 276O/T+1.356 of)=-(3) S-aluminium, cm
3/ 100gAl; PH
2-equilibrium hydrogen dividing potential drop, Torr, T-absolute temperature.
Therefore the equilibrium hydrogen dividing potential drop of measuring aluminium liquid can be tried to achieve aluminium liquid hydrogen content.
With (2), (3) formula substitution (1) formula can get the relational expression between the electromotive force E of aluminium liquid hydrogen concentration and gauge head of the present invention:
LogS=-2FE/ (4.60 6RT)-7565/T+6.47 (4) symbolic significance, unit is with (3) formula.Measure electromotive force E and temperature T by gauge head of the present invention, can directly try to achieve hydrogen concentration in the tested aluminium liquid by (4) formula.
The present invention is by proton conductive ceramic pipe (1), Ca/CaH
2Potpourri (2), plain conductor (3), alundum tube (4) becomes.Ca and CaH are equipped with in the sealing of proton conductive ceramic pipe one end in the pipe
2Potpourri and plain conductor, that end plate that plain conductor inserts porcelain tube becomes spring-like closely to contact with the inwall of pipe, and the ceramic pipe other end has sealant that contrast electrode is isolated from the outside.It is outer and insert in the ceramic pipe that alundum tube is through plain conductor.The outer coating sintering Ag/Pd thin layer of gas phase hydrogen richness gauge head, and be wound with another electrode cable.
Adopting density is that the above Ca-Ti ore type high temperature proton conductive sintered ceramic pipe of 94% theoretical value is a solid electrolyte, and composition is MC
E1-xR
xO
3-α(M=Sr, Ba, R=Yb, Nd, X=0.01～0.1), the end sealing of pipe.
Get the certain-length plain conductor, an end plate becomes spring-like, and it is pushed in the ceramic pipe.
Being assembled in the Ar gas glove box of gauge head of the present invention carried out.From the sealing iron flask, take out Ca, CaH
2Piece, the Ca piece is rasped to fine powder and CaH
2Mix and also insert compacting in the proton conductive ceramic pipe rapidly.With the fire-resistant quick hardening cement sealing of phosphate base.Be through on the plain conductor and insert with the external diameter alundum tube close and install in Ca/CaH and the proton conductive ceramic pipe by fire-resistant quick hardening cement sealing with proton conductive ceramic pipe internal diameter.
Prior coating sintering Ag/Pd in the proton conductive ceramic pipe outside or Pd thin layer that gas phase is decided hydrogen test probe are the mensuration electrode.All the other operations are identical with the former.After quick hardening cement solidifies, the gauge head outside around on tinsel be lead.
Plain conductor can adopt Mo among the present invention, FeCrAl, and the Pt silk is decided on tested systems character.Two electrode cable materials are not tackled electromotive force value correction metal fever electromotive force simultaneously.
When gauge head uses, gauge head and another lead and thermopair are together inserted molten metal form the hydrogen concentration cell, the balance electric gesture under the mensuration uniform temperature can be tried to achieve the hydrogen richness of tested systems.Adopt the gauge head outside that thin layer electrode is arranged when measuring gas phase hydrogen dividing potential drop and be wound with the gauge head of electrode.
To Ar+H
2Mixed gas and melting Al have made to decide hydrogen respectively and have measured.Experimental determination device such as Fig. 2.
Gas phase hydrogen dividing potential drop mensuration process and result are as follows:
Pack in the crystal reaction tube (8) gas phase hydrogen test probe and thermopair.Programmed temperature control instrument control tube type resistance furnace keeps furnace temperature constant.Behind the logical Ar gas displacement reaction air in tube, feed the Ar+H of known hydrogen dividing potential drop
2Mixed gas changes hydrogen dividing potential drop and temperature and has carried out a series of mensuration.The balance electric gesture is 10 by input impedance
9The Ω digital voltmeter is measured.Contrast electrode hydrogen dividing potential drop by (2) so formula determines tested gas phase hydrogen dividing potential drop known to the theoretical as can be known electromotive force of (1) formula.At Fig. 3 measured value and theoretical electromotive force are contrasted.Both are well consistent, prove gauge head of the present invention accurately and reliably, can be used for measuring the gas of unknown hydrogen dividing potential drop.Then try to achieve steam partial pressure the gas phase as partial pressure of oxygen in the gas phase is known from the hydrogen-oxygen equilibrium relation.
Aluminium liquid hydrogen assay process and result are as follows:
The aluminium block crucible of packing into, proving installation such as Fig. 2.After there was air in Ar gas displacement reaction pipe Central Plains, it was constant to be warming up to 1023K, and temperature is measured by thermopair (7).Electrode cable (3) and gauge head (5) are inserted in the aluminium liquid (6).Digital voltmeter shows that immediately numerical value and very fast (about 10 seconds) reach balance, has only by a small margin slowly fluctuation later on for a long time.When adding hydrogen in Ar gas, electromotive force just has acute variation.Fig. 4 is the measured value of several different gauge heads.Hydrogen richness from the relation of electromotive force and time and atmosphere gauge head energy of the present invention as can be known fast measuring aluminium liquid also can be monitored hydrogen concentration for a long time.
With electromotive force value substitution (4) formula that records, can try to achieve under this experiment condition hydrogen richness in the aluminium liquid.Among Fig. 4 zero; The measured value of the different gauge heads of △ point expression, corresponding hydrogen richness is 0.068cm
3/ 100gAl.This value is higher than hydrogen solubleness 0.03cm in the solid aluminium that it is generally acknowledged
3/ 100gA this be since the water vapour absorption portion hydrogen institute that aluminium liquid contains from the Ar gas that feeds extremely.The electromotive force value of Fig. 4 mid point gauge head when feeding dry Ar gas.Hydrogen richness is lower in the slightly high expression aluminium of the electromotive force value liquid, and obtaining hydrogen richness by (4) formula is 0.052cm
3/ 100gAl.Said determination presentation of results gauge head of the present invention can accurately reflect the variation of hydrogen richness in the aluminium liquid.
The relational expression of the dissolving of the hydrogen in the concrete metal or alloy and equilibrium hydrogen dividing potential drop can be replaced (3) formula when measuring beyond the aluminium hydrogen richness in the metal or alloy, equally can obtain hydrogen richness from the emf measurement value.
Can be when the production scene is measured with electrode cable, thermopair is fixed on the gauge head limit, together inserts liquid metal and gets final product.
Preparation technology of the present invention is simple, manipulates very conveniently, can measure micro-hydrogen richness.Can be widely used in refining of metal, aspects such as industrial furnace gas phase monitoring.
Fig. 1 decides the hydrogen test probe structure
Fig. 2 decides the hydrogen determinator
The comparison of Fig. 3 gas phase hydrogen test probe electromotive force and theoretical value (---,---: theoretical value; Zero; ●; △; ▲; Measured value).
Fig. 4 aluminium liquid is decided hydrogen measurement result (: initial atmosphere dry Ar)
Claims (3)
1. a probe that is used for measuring the hydrogen richness of gaseous sample comprises solid electrolyte ceramic pipe (1), solid reference electrode (2), plain conductor (3) and alundum tube (4), therein
The sealing of described solid electrolyte ceramic Guan Weiyi end, the other end has the fire cement sealant, and the contrast electrode material is housed in the pipe, and remaining space is with an alundum tube in the pipe, the solid electrolyte ceramic pipe outside is coated with sintering Ag/Pd or Pd electrically conductive layer, and is wound with electrode cable;
Described solid state reference electrode is contained in the ceramic pipe, by ca and caH
2Potpourri form;
Described plain conductor inserts an end plate or the spring-like of electrode material at the alundum tube center, closely contacts with the solid electrolyte ceramic inside pipe wall,
Described alundum tube matches with the ceramic pipe internal diameter.
2, a kind of probe that is used for measuring the hydrogen richness of motlten metal sample comprises solid electrolyte ceramic pipe (1), solid reference electrode (2), plain conductor (3) and alundum tube (4), therein,
The sealing of described solid electrolyte ceramic Guan Weiyi end, the other end has the fire clay sealant, and the contrast electrode material is housed in the pipe, and remaining space is with an alundum tube in the pipe, and the solid electrolyte ceramic pipe outside is provided with electrically conductive layer and electrode cable;
Described solid state reference electrode is contained in the ceramic pipe, by Ca and CaH
2Potpourri form;
Described plain conductor inserts an end plate or the spring-like of electrode material at the alundum tube center, closely contacts with the solid electrolyte ceramic inside pipe wall;
Described alundum tube matches with the ceramic pipe internal diameter.
3, probe according to claim 1 and 2 is characterized in that described solid electrolyte ceramic is high temperature proton conductive Ca-Ti ore type sintered body MC
El-xR
xO
3-α(M=Sr, Ba, R=Yb, Nd, X=0.01～0.1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111197A CN1033103C (en) | 1992-09-30 | 1992-09-30 | Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92111197A CN1033103C (en) | 1992-09-30 | 1992-09-30 | Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1085317A CN1085317A (en) | 1994-04-13 |
| CN1033103C true CN1033103C (en) | 1996-10-23 |
Family
ID=4945218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92111197A Expired - Fee Related CN1033103C (en) | 1992-09-30 | 1992-09-30 | Proton conducting solid electrolyte solid-phase reference electrode hydrogen test probe |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1033103C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101661016B (en) * | 2009-09-18 | 2012-11-21 | 东北大学 | Method for measuring hydrogen pressure in solid steel and device |
| JP6382162B2 (en) * | 2015-07-08 | 2018-08-29 | 株式会社Ｓｏｋｅｎ | Gas sensor pump electrode and reference electrode |
| CN106045482B (en) * | 2016-05-27 | 2019-05-10 | 内蒙古科技大学 | Rare earth oxide doped aluminium base high-performance metal bath determines the preparation method of HydroNit sensor material |
| CN106248760B (en) * | 2016-09-09 | 2018-12-14 | 中广核研究院有限公司 | Measure the solid-phase reference electrode lambda sensor that oxygen activity is dissolved in liquid metal |
| CN112129824B (en) * | 2020-09-24 | 2021-11-30 | 东北大学 | Device and method for nondestructively measuring hydrogen content in solid steel |
-
1992
- 1992-09-30 CN CN92111197A patent/CN1033103C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1085317A (en) | 1994-04-13 |
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