JP2000088794A - Sensor for dissolved hydrogen in molten metal - Google Patents
Sensor for dissolved hydrogen in molten metalInfo
- Publication number
- JP2000088794A JP2000088794A JP10253860A JP25386098A JP2000088794A JP 2000088794 A JP2000088794 A JP 2000088794A JP 10253860 A JP10253860 A JP 10253860A JP 25386098 A JP25386098 A JP 25386098A JP 2000088794 A JP2000088794 A JP 2000088794A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- metal
- oxide
- electromotive force
- molten metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- Measuring Oxygen Concentration In Cells (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明はプロトン導電性をもつ固
体電解質を用いた溶融金属中の溶存水素センサに関す
る。The present invention relates to a sensor for dissolved hydrogen in molten metal using a solid electrolyte having proton conductivity.
【０００２】[0002]
【従来の技術】溶融金属中特に溶鋼中には酸素、水素、
等のガス成分が含まれている。このまま凝固させると割
れや内部欠陥の原因となるため、真空あるいは不活性ガ
ス中で脱ガス処理を行いこれらを除去している。脱ガス
処理でこれらガスがどれだけ除去されたかを検出する必
要がある。溶鋼中の溶存酸素は従来から固体電解質型酸
素センサで検出されているが、溶存水素については高温
であるため検出するセンサがなく、無管理状態で脱ガス
処理をせざるを得なかった。2. Description of the Related Art In a molten metal, particularly in a molten steel, oxygen, hydrogen,
And other gas components. Solidification as it is may cause cracks and internal defects. Therefore, these are removed by degassing in a vacuum or inert gas. It is necessary to detect how much these gases have been removed in the degassing process. Dissolved oxygen in molten steel has been conventionally detected by a solid electrolyte type oxygen sensor, but since dissolved hydrogen is at a high temperature, there is no sensor to detect it, and degassing treatment has to be performed without management.
【０００３】[0003]
【本発明が解決しようとする課題】本発明はこれまでに
ない高温の溶融金属中の溶存水素を検出するセンサを提
供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a sensor for detecting dissolved hydrogen in a molten metal at a high temperature, which has never been seen before.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決した本発
明に係る溶存水素センサは、測定すべき水素が溶存して
いる溶融金属と接触するプロトン導電性固体電解質から
なる第１電極と、該第１電極の該溶融金属と接触する面
と背向する面に形成された金属と金属酸化物とからなる
第２電極と、該溶融金属と接触する酸化物イオン導電性
固体電解質からなる第３電極と、該第３電極の該溶融金
属と接触する面と背向する面に形成された該金属と該金
属酸化物とからなる第４電極と、該第１電極と該第２電
極間の起電力Ｅ12を測定する第１起電力測定手段と、該
第３電極と該第４電極間の起電力Ｅ34を測定する第２起
電力測定手段と、からなることを特徴とするAccording to the present invention, there is provided a dissolved hydrogen sensor comprising: a first electrode made of a proton conductive solid electrolyte which comes into contact with a molten metal in which hydrogen to be measured is dissolved; A second electrode formed of a metal and a metal oxide formed on a surface of the first electrode opposite to a surface in contact with the molten metal; and a third electrode formed of an oxide ion conductive solid electrolyte in contact with the molten metal. An electrode; a fourth electrode formed of the metal and the metal oxide formed on a surface of the third electrode opposite to a surface in contact with the molten metal; and a fourth electrode formed between the first electrode and the second electrode. A first electromotive force measuring means for measuring the electromotive force E12; and a second electromotive force measuring means for measuring an electromotive force E34 between the third electrode and the fourth electrode.
【０００５】[0005]
【発明の実施の形態】水素が溶存している溶融金属と接
触するプロトン導電性固体電解質からなる第１電極とし
ては、例えば、酸化物イオン導電性電解質であるホタル
石型酸化物の表面にプロトン−酸化物イオン混合導電性
電解質であるＡＢＯ3型のペロブスカイト酸化物が膜状
に積層したものが使用できる。第１電極の形状は第１電
極をベースにする場合と後述の第２電極をベースにする
場合で異なる。第１電極をベースにする場合は、第１電
極を円筒状や試験管状等所定の形状にプレス成形後焼成
する。第２電極をベースにする場合は、例えば円柱状の
第２電極をベースにして、その外周面に固体電解質を膜
状に形成して第２電極とすることになる。BEST MODE FOR CARRYING OUT THE INVENTION As a first electrode made of a proton-conductive solid electrolyte which comes into contact with a molten metal in which hydrogen is dissolved, for example, a proton-type solid electrolyte which is an oxide ion-conductive electrolyte has A film in which an ABO 3 type perovskite oxide which is a mixed oxide ion conductive electrolyte is laminated in a film shape can be used. The shape of the first electrode is different between a case where the first electrode is used as a base and a case where the second electrode described below is used as a base. When the first electrode is used as a base, the first electrode is press-formed into a predetermined shape such as a cylindrical shape or a test tube, and then fired. When the second electrode is used as a base, for example, the second electrode is formed by forming a solid electrolyte in a film shape on the outer peripheral surface of the second electrode in the form of a column.
【０００６】ＡＢＯ3型のＡ元素は、アルカリ土類金属
（Ｓｒ，Ｃａ，Ｂａ）からなる群から選択された一種以
上の元素である。Ｂ元素は前記ホタル石型酸化物の金属
元素またはその一部をアルカリ土類金属（Ｍｇ，Ｃａ，
Ｓｒ，Ｂａ）、および、希土類元素（Ｓｃ，Ｙ，Ｌａ，
Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，Ｈｏ，Ｙｂ）からなる
群から選択された一種以上の元素で１〜３０モル％置換
固溶されて生じるホタル石型酸化物の金属元素である。The ABO 3 type A element is one or more elements selected from the group consisting of alkaline earth metals (Sr, Ca, Ba). The B element is a metal element of the fluorite-type oxide or a part thereof is an alkaline earth metal (Mg, Ca,
Sr, Ba) and rare earth elements (Sc, Y, La,
Nd, Sm, Eu, Gd, Dy, Ho, Yb) is a metal element of a fluorite-type oxide formed by being substituted with 1 to 30 mol% of one or more elements selected from the group consisting of:
【０００７】このようなＡＢＯ3型のペロブスカイト酸
化物としては、ＳｒＺｒＯ3，ＢａＣｅＯ3，ＳｒＣｅＯ
3，ＢａＺｒＯ3，あるいはＣａＺｒＯ3がある。ホタル
石型酸化物表面へのペロブスカイト酸化物膜の形成は、
プラズマ溶射、スパッタ等でもできるが、次の方法が簡
便でコスト的にも優れている。すなわち、ホタル石型酸
化物の表面にたとえば、アルカリ土類金属の無機酸塩、
有機酸塩、および有機金属化合物の一種以上を塗布し、
大気中等の酸化性雰囲気中で８００℃以上の温度で加熱
焼成することにより、ペロブスカイト酸化物膜を形成す
ることができる。このペロブスカイト酸化物の膜厚は１
０μｍ以上が望ましい。膜厚が１０μｍ未満では水素が
ホタル石型酸化物層に侵入し、これを還元するためであ
る。Such ABO 3 type perovskite oxides include SrZrO 3 , BaCeO 3 , and SrCeO.
3 , BaZrO 3 or CaZrO 3 . The formation of a perovskite oxide film on the surface of fluorite oxide
Plasma spraying, sputtering, etc. can be used, but the following method is simple and excellent in cost. That is, for example, on the surface of the fluorite type oxide, an inorganic acid salt of an alkaline earth metal,
Apply one or more organic acid salts and organometallic compounds,
The perovskite oxide film can be formed by heating and baking at a temperature of 800 ° C. or more in an oxidizing atmosphere such as the air. The thickness of this perovskite oxide is 1
0 μm or more is desirable. If the thickness is less than 10 μm, hydrogen penetrates into the fluorite-type oxide layer and reduces it.
【０００８】ホタル石型酸化物としては、ジルコニア
（ＺｒＯ2）あるいはセリア（ＣｅＯ2）の一部をアルカ
リ土類金属（Ｍｇ，Ｃａ，Ｓｒ，Ｂａ）および希土類元
素（Ｓｃ，Ｙ，Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，
Ｈｏ，Ｂａ）からなる群から選択した一種以上の元素の
酸化物で１〜３０モル％置換固溶させた安定化ジルコニ
アまたは安定化セリアが望ましい。上記ホタル石型酸化
物は酸化物イオン導電性に優れており、かつ熱膨張によ
る亀裂発生の問題もない。As the fluorite-type oxide, part of zirconia (ZrO 2 ) or ceria (CeO 2 ) is converted to an alkaline earth metal (Mg, Ca, Sr, Ba) and a rare earth element (Sc, Y, La, Nd). , Sm, Eu, Gd, Dy,
Stabilized zirconia or stabilized ceria in which 1 to 30 mol% of an oxide of one or more elements selected from the group consisting of Ho and Ba) is solid-displaced and dissolved is desirable. The fluorite-type oxide is excellent in oxide ion conductivity and has no problem of crack generation due to thermal expansion.
【０００９】このようなホタル石型酸化物には、たとえ
ば（ＺｒＯ2）0.89（ＣａＯ）0.11、（ＺｒＯ2）
0.92（Ｙ2Ｏ3）0.08、（ＣｅＯ2）0.9（Ｙ2Ｏ3）0.1、
（ＣｅＯ2）0.9（ＳｍＯ1.5）0.1、（ＣｅＯ2）0.8（Ｃ
ａＯ）0.2、（ＣｅＯ2）0.8（ＳｒＯ）0.2等がある。前
記金属と金属酸化物とからなる第２電極は、発明者らの
実験によれば、Ｐｔ、Ａｕ、Ｆｅ、Ｎｉ、Ｃｕ、Ｚｎ、
Ｃｒ、Ｍｏ等の電気伝導性に優れた金属と、Ｆｅ2Ｏ3、
Ｎｉ2Ｏ3、Ｃｕ2Ｏ、ＺｎＯ、Ｃｒ2Ｏ3、Ｍｏ2Ｏ3等の
金属酸化物との混合物のとき、水素検出感度が高くなる
ことが示された。さらに、前記金属がＣｕで前記金属酸
化物がＣｕ2Ｏのとき、あるいは、前記金属がＣｒで前
記金属酸化物がＣｒ2Ｏ3のとき、より一層検出感度が高
くなることが示された。Such fluorite-type oxides include, for example, (ZrO 2 ) 0.89 (CaO) 0.11 and (ZrO 2 )
0.92 (Y 2 O 3 ) 0.08 , (CeO 2 ) 0.9 (Y 2 O 3 ) 0.1 ,
(CeO 2 ) 0.9 (SmO 1.5 ) 0.1 , (CeO 2 ) 0.8 (C
aO) 0.2 and (CeO 2 ) 0.8 (SrO) 0.2 . According to experiments performed by the inventors, the second electrode composed of the metal and the metal oxide is formed of Pt, Au, Fe, Ni, Cu, Zn,
Metals having excellent electrical conductivity such as Cr and Mo, Fe 2 O 3 ,
It was shown that the hydrogen detection sensitivity was increased when a mixture with a metal oxide such as Ni 2 O 3 , Cu 2 O, ZnO, Cr 2 O 3 , and Mo 2 O 3 was used. Furthermore, it was shown that the detection sensitivity was further improved when the metal was Cu and the metal oxide was Cu 2 O, or when the metal was Cr and the metal oxide was Cr 2 O 3 .
【００１０】前記金属と金属酸化物との混合物である第
２電極は、該第２電極をベースにする場合と、前記プロ
トン導電性固体電解質からなる第１電極をベースにする
場合で作り方が異なる。第２電極をベースにする場合
は、例えば次のようにして形成される。すなわち、金属
と金属酸化物の粉末を適当な割合で混合し、円柱、平板
等所用の形状にプレス成形した後、８００℃以上で焼成
する。The second electrode, which is a mixture of the metal and the metal oxide, is formed differently depending on whether the second electrode is a base or the first electrode made of the proton conductive solid electrolyte. . When the second electrode is used as a base, it is formed, for example, as follows. That is, powders of a metal and a metal oxide are mixed at an appropriate ratio, pressed into a shape for a column, a flat plate or the like, and then fired at 800 ° C. or more.
【００１１】ＣｕとＣｕ2Ｏ、ＣｒとＣｒ2Ｏ3のように
金属が金属酸化物の金属と同じ場合は、金属あるいは金
属酸化物の粉末だけを用いて、第２電極を作ることがで
きる。例えば、Ｃｕ2Ｏ粉末をプレス成形した後還元性
雰囲気中で焼成することにより、Ｃｕ2Ｏの一部が還元
され、ＣｕとＣｕ2Ｏの混合物となる。あるいはＣｒ粉
末をプレス成形した後酸化性雰囲気中で焼成することに
より、Ｃｒの一部が酸化され、ＣｒとＣｒ2Ｏ3の混合物
となる。第１電極をベースにする場合は、例えば試験管
状の第１電極の中に前記金属と金属酸化物の粉末を圧入
して第２電極とすることができる。When the metal is the same as the metal oxide such as Cu and Cu 2 O or Cr and Cr 2 O 3 , the second electrode can be formed using only the metal or metal oxide powder. . For example, by pressing a Cu 2 O powder and then firing in a reducing atmosphere, a part of the Cu 2 O is reduced to form a mixture of Cu and Cu 2 O. Alternatively, Cr powder is press-molded and then fired in an oxidizing atmosphere to partially oxidize Cr to form a mixture of Cr and Cr 2 O 3 . When the first electrode is used as a base, for example, the powder of the metal and the metal oxide is press-fitted into the first electrode of a test tube to form a second electrode.
【００１２】溶融金属と接触する酸化物イオン導電性固
体電解質からなる第３電極は、前記第１電極を形成する
酸化物イオン導電性電解質と同じである。すなわち、た
とえば、第１電極の酸化物イオン導電性電解質がホタル
石型酸化物である（ＺｒＯ2）0.89（ＣａＯ）0.11であ
る場合は、第３電極の酸化物イオン導電性電解質も（Ｚ
ｒＯ2）0.89（ＣａＯ）0.11である。The third electrode made of an oxide ion conductive solid electrolyte in contact with the molten metal is the same as the oxide ion conductive electrolyte forming the first electrode. That is, for example, when the oxide ion conductive electrolyte of the first electrode is a fluorite-type oxide (ZrO 2 ) 0.89 (CaO) 0.11 , the oxide ion conductive electrolyte of the third electrode is also (ZrO 2 ).
rO 2 ) 0.89 (CaO) 0.11 .
【００１３】第４電極は、前記第２電極と同じ金属と金
属酸化物とからなり、製法も同じである。すなわち、第
２電極がＣｒとＣｒ2Ｏ3の混合物である場合は、第４電
極もＣｒとＣｒ2Ｏ3の混合物である。第１起電力測定手
段は前記第１電極と前記第２電極とリード線で接続さ
れ、両電極間の起電力Ｅ12を測定するもので、通常の電
圧計、電流計、ガルバノメータ等が使われる。The fourth electrode is made of the same metal and metal oxide as the second electrode, and has the same manufacturing method. That is, when the second electrode is a mixture of Cr and Cr 2 O 3 , the fourth electrode is also a mixture of Cr and Cr 2 O 3 . The first electromotive force measuring means is connected to the first electrode and the second electrode by a lead wire, and measures the electromotive force E12 between the two electrodes. A normal voltmeter, ammeter, galvanometer or the like is used.
【００１４】第２起電力測定手段は前記第３電極と前記
第４電極とリード線で接続され、両電極間の起電力Ｅ34
を測定するもので、通常の電圧計、電流計、ガルバノメ
ータ等が使われる。第１起電力測定手段と第１電極の接
続および第２起電力測定手段と第３電極の接続は、それ
ぞれ溶融金属を介して行われる。具体的には溶融金属中
に電気伝導性および耐熱性に優れたＮｉ、Ｍｏ、Ｗ等の
金属円柱等を浸漬し、それに第１起電力測定手段と第２
起電力測定手段に一端が接続されたリード線を接続する
ことで、達成される。なお、発明者等の実験によると、
前記第２電極と第４電極がＣｒとＣｒ2Ｏ3の混合物であ
る場合は、前記溶融金属中に浸漬する金属円柱をＣｒと
同族のＭｏ製にし、前記リード線もＭｏ線にした方が水
素の検出感度が高いことが示された。The second electromotive force measuring means is connected to the third electrode and the fourth electrode by a lead wire, and generates an electromotive force E34 between the two electrodes.
And a normal voltmeter, ammeter, galvanometer or the like is used. The connection between the first electromotive force measuring means and the first electrode and the connection between the second electromotive force measuring means and the third electrode are respectively performed via a molten metal. Specifically, a metal column or the like made of Ni, Mo, W or the like having excellent electrical conductivity and heat resistance is immersed in a molten metal, and the first electromotive force measuring means and the second
This is achieved by connecting a lead wire having one end connected to the electromotive force measuring means. According to experiments by the inventors,
When the second electrode and the fourth electrode are a mixture of Cr and Cr 2 O 3 , it is preferable that the metal column immersed in the molten metal is made of Mo, which is the same as Cr, and the lead wire is also made of Mo. It was shown that the detection sensitivity of hydrogen was high.
【００１５】[0015]
【作用】一般に溶融金属中には水素の他に酸素や窒素等
が溶存している。溶融金属に接触するプロトン導電性固
体電解質からなる第１電極近傍では水素がプロトンにな
り、電子を発生する。生成されたプロトンは第１電極中
を移動して第２電極に達する。発生した電子は第１電極
と第２電極をつなぐリード線の中を通り第１起電力測定
手段を経て第２電極に達する。そうすると、第２電極を
構成する金属酸化物が酸化剤として働き、金属酸化物と
プロトンおよび電子が反応して金属酸化物が還元され
る。この一連の反応で第１電極から第２電極に電子が移
動する。In general, oxygen, nitrogen and the like are dissolved in a molten metal in addition to hydrogen. In the vicinity of the first electrode made of a proton-conductive solid electrolyte that comes into contact with the molten metal, hydrogen becomes a proton and generates an electron. The generated protons move through the first electrode and reach the second electrode. The generated electrons pass through a lead wire connecting the first electrode and the second electrode, and reach the second electrode via the first electromotive force measuring means. Then, the metal oxide constituting the second electrode functions as an oxidizing agent, and the metal oxide reacts with protons and electrons to reduce the metal oxide. In this series of reactions, electrons move from the first electrode to the second electrode.
【００１６】一方、溶融金属と接触する酸化物イオン導
電性固体電解質からなる第３電極近傍では酸素が電子と
反応してマイナスの酸素イオンを発生する。発生した酸
素イオンは第１電極の中を移動して第２電極に達すると
共に、第３電極の中を移動して第４電極に達する。そう
すると、第２電極と第４電極を構成する金属が還元剤と
して働き、金属と酸素イオンが反応して金属が酸化され
電子を発生する。第２電極で発生した電子は、リード線
の中を通り第１起電力測定手段を経て第１電極に達す
る。第４電極で発生した電子は、第４電極と第３電極を
つなぐリード線の中を通り第２起電力測定手段を経て第
３電極に達する。On the other hand, in the vicinity of the third electrode made of an oxide ion conductive solid electrolyte in contact with the molten metal, oxygen reacts with electrons to generate negative oxygen ions. The generated oxygen ions move in the first electrode to reach the second electrode, and also move in the third electrode to reach the fourth electrode. Then, the metal forming the second electrode and the fourth electrode functions as a reducing agent, and the metal reacts with oxygen ions to oxidize the metal and generate electrons. The electrons generated at the second electrode pass through the lead wire and reach the first electrode via the first electromotive force measuring means. The electrons generated at the fourth electrode pass through a lead wire connecting the fourth electrode and the third electrode, and reach the third electrode via the second electromotive force measuring means.
【００１７】したがって、第１起電力測定手段で測定さ
れる起電力Ｅ12には水素と酸素の両方の反応による電子
が寄与しているが、第２起電力測定手段で測定される起
電力Ｅ34には酸素だけの反応による電子が寄与している
ので、両起電力の差分すなわちＥ12−Ｅ34から水素量を
知ることができる。Therefore, although the electron by the reaction of both hydrogen and oxygen contributes to the electromotive force E12 measured by the first electromotive force measuring means, the electromotive force E34 measured by the second electromotive force measuring means is increased. Since electrons due to the reaction of oxygen alone contribute, the amount of hydrogen can be known from the difference between the two electromotive forces, that is, E12-E34.
【００１８】[0018]
【実施例】本発明の実施例を示し、本発明をさらに具体
的に説明する。本実施例の溶存水素センサを測定すべき
溶融金属中に取り付けた主要部断面図を図１に示す。本
溶存水素センサ１は、溶融金属４と接触する下端部が閉
じた円筒状のプロトン導電性固体電解質からなる第１電
極１１と、その円筒状第１電極１１の中に圧入された金
属と金属酸化物とからなる第２電極１２と、溶融金属４
と接触する下端部が閉じた円筒状の酸化物イオン導電性
固体電解質からなる第３電極１３と、その円筒状第３電
極１４の中に圧入された金属と金属酸化物とからなる第
４電極１４と、一端が溶融金属４に浸積している金属円
柱１８に、他端が第２電極１２にリード線１７で接続さ
れた第１起電力測定手段１５と、一端が金属円柱１８
に、他端が第４電極１４にリード線１８で接続された第
２起電力測定手段１６と、からなる。The present invention will be described in more detail with reference to Examples of the present invention. FIG. 1 is a sectional view of a main part in which the dissolved hydrogen sensor of this embodiment is mounted in a molten metal to be measured. The present dissolved hydrogen sensor 1 includes a first electrode 11 made of a cylindrical proton-conductive solid electrolyte having a closed lower end in contact with the molten metal 4, and a metal and a metal pressed into the first cylindrical electrode 11. A second electrode 12 made of an oxide;
A third electrode 13 made of a cylindrical oxide ion conductive solid electrolyte having a closed lower end and a fourth electrode made of a metal and a metal oxide pressed into the cylindrical third electrode 14. A first electromotive force measuring means 15 having one end connected to a metal column 18 immersed in the molten metal 4, the other end connected to the second electrode 12 by a lead wire 17, and one end connected to the metal column 18.
And a second electromotive force measuring means 16 whose other end is connected to the fourth electrode 14 by a lead wire 18.
【００１９】溶存水素センサ１は、金属円柱１８を真ん
中にして第１電極１１と第３電極１３が左右に対称にな
るように上端部が取付治具２に固定され、下端部が容器
３に入った溶融金属４に浸積されている。本実施例では
リード線１７のとり回しをしやすくするために左右対称
にしたが、水素センサの性能と機能面では左右対称でな
くてもよい。The dissolved hydrogen sensor 1 has an upper end fixed to the mounting jig 2 so that the first electrode 11 and the third electrode 13 are symmetrical left and right with the metal column 18 in the middle, and a lower end connected to the container 3. It is immersed in the molten metal 4 that has entered. In the present embodiment, the lead wires 17 are symmetrical in order to facilitate the routing, but the hydrogen sensor may not be symmetrical in terms of performance and function.
【００２０】円筒状のプロトン導電性固体電解質からな
る第１電極１１は、内径２０ｍｍ、外径２５ｍｍ、内空
深さ５０ｍｍの円筒状のホタル石型酸化物１１１と、そ
の外周面に形成された膜状のペロブスカイト酸化物１１
２とからなる。円筒状のホタル石型酸化物１１１は、安
定化ジルコニア、（ＣａＯ）0.11（ＺｒＯ3）0.89で、
市販の（ＣａＯ）0.11（ＺｒＯ3）0.89粉末を金型に入
れ１ｔｏｎ／ｃｍ2の圧力で円筒状に成型した後、焼成
炉で空気中、１５００℃、保持５時間の条件で焼成した
ものである。The first electrode 11 made of a cylindrical proton-conductive solid electrolyte was formed on a cylindrical fluorite oxide 111 having an inner diameter of 20 mm, an outer diameter of 25 mm, and a depth of 50 mm in the inner space, and was formed on the outer peripheral surface thereof. Perovskite oxide film 11
Consists of two. The cylindrical fluorite oxide 111 is stabilized zirconia, (CaO) 0.11 (ZrO 3 ) 0.89 ,
A commercially available (CaO) 0.11 (ZrO 3 ) 0.89 powder was placed in a mold, molded into a cylindrical shape at a pressure of 1 ton / cm 2 , and fired in a firing furnace at 1500 ° C. for 5 hours in air. is there.
【００２１】膜状のペロブスカイト酸化物１１２は、Ｓ
ｒＺｒＯ3で、円筒状のホタル石型酸化物１１１の外周
面にアルカリ土類金属の中のＳｒの硝酸塩の飽和水溶液
（ペースト）を塗布し、室温で乾燥後、空気中、１２０
０℃、保持１０時間の条件で焼成したもので、膜厚は１
０μｍである。第２電極１１は、ＣｒとＣｒ2Ｏ3の混合
物で、前記円筒状ホタル石型酸化物１１１の円筒の中央
に太さ１ｍｍのＭｏ線であるリード線１７を挿入した
後、ＣｒとＣｒ2Ｏ3を１対１の割合で混合した粉末を圧
入して作られた。第２電極の長さは４０ｍｍである。The film-like perovskite oxide 112 is
A saturated aqueous solution (paste) of nitrate of Sr in alkaline earth metal is applied to the outer peripheral surface of the cylindrical fluorite-type oxide 111 with rZrO 3 , and dried at room temperature.
It was baked under the conditions of 0 ° C. and holding for 10 hours.
0 μm. The second electrode 11 is a mixture of Cr and Cr 2 O 3 , and after inserting a lead wire 17 which is a Mo wire having a thickness of 1 mm into the center of the cylindrical fluorite oxide 111, the second electrode 11 is made of Cr and Cr 2. It was made by injecting powder mixed with O 3 in a ratio of 1: 1. The length of the second electrode is 40 mm.
【００２２】円筒状の酸化物イオン導電性固体電解質か
らなる第３電極１３は、前記円筒状ホタル石型酸化物１
１１と組成、製法、寸法、形状が全く同じである。すな
わち、固体電解質１５は（ＣａＯ）0.11（ＺｒＯ3）
0.89製で、内径２０ｍｍ、外径２５ｍｍ、内空深さ５０
ｍｍの円筒である。第４電極１４は前記第２電極と組
成、製法、寸法が全く同じである。すなわち、第４電極
１４はＣｒとＣｒ2Ｏ3を１対１の割合で混合した粉末を
円筒状の第３電極１３の中に圧入したものである。The third electrode 13 made of a cylindrical oxide ion conductive solid electrolyte is used for the cylindrical fluorite oxide 1
11 has exactly the same composition, manufacturing method, dimensions, and shape. That is, the solid electrolyte 15 is (CaO) 0.11 (ZrO 3 )
Made of 0.89 , inner diameter 20mm, outer diameter 25mm, inner depth 50
mm cylinder. The fourth electrode 14 has exactly the same composition, manufacturing method, and dimensions as the second electrode. That is, the fourth electrode 14 is obtained by pressing a powder obtained by mixing Cr and Cr 2 O 3 at a ratio of 1: 1 into the cylindrical third electrode 13.
【００２３】溶融金属４の中に下端部が浸積される金属
円柱１８は直径６ｍｍ，長さ４０ｍｍのＭｏ製である。
上端部には太さ１ｍｍのＭｏ線であるリード線１７が固
着されてある。第１電極１１と第２電極１２の間の起電
力Ｅ12を測定する第１起電力測定手段１５は電圧計であ
る。同様に、第３電極１３と第４電極１４の間の起電力
Ｅ34を測定する第２起電力測定手段１６は同じタイプの
電圧計である。The metal column 18 whose lower end is immersed in the molten metal 4 is made of Mo having a diameter of 6 mm and a length of 40 mm.
A lead wire 17, which is a Mo wire having a thickness of 1 mm, is fixed to the upper end. The first electromotive force measuring means 15 for measuring the electromotive force E12 between the first electrode 11 and the second electrode 12 is a voltmeter. Similarly, the second electromotive force measuring means 16 for measuring the electromotive force E34 between the third electrode 13 and the fourth electrode 14 is a voltmeter of the same type.
【００２４】溶融金属４を温度１６００〜１６５０℃の
溶鋼とし、溶存水素分圧を変化させたときの、本溶存水
素センサの起電力差Ｅ12−Ｅ34と溶存水素分圧の関係を
図２に示す。水素分圧が０．０００１〜０．１ａｔｍ範
囲で直線性よく水素を検出できることがわかる。FIG. 2 shows the relationship between the electromotive force difference E12-E34 of the present dissolved hydrogen sensor and the dissolved hydrogen partial pressure when the molten metal 4 is molten steel at a temperature of 1600-1650 ° C. and the dissolved hydrogen partial pressure is changed. . It can be seen that hydrogen can be detected with good linearity when the hydrogen partial pressure is in the range of 0.0001 to 0.1 atm.
【００２５】[0025]
【発明の効果】本発明の溶存水素センサは、コモン電極
としての第２電極および第４電極と、プロトン導電性固
体電解質からなる第１電極と、酸化物イオン導電性固体
電解質からなる第３電極とからなり、第１電極と第２電
極間の起電力Ｅ12と第３電極と第４電極間の起電力Ｅ34
の差分をとることにより、酸素による起電力をキャンセ
ルして高温の溶融金属中の水素を検出することができ
る。The dissolved hydrogen sensor of the present invention has a second electrode and a fourth electrode as common electrodes, a first electrode made of a proton conductive solid electrolyte, and a third electrode made of an oxide ion conductive solid electrolyte. And an electromotive force E12 between the first electrode and the second electrode and an electromotive force E34 between the third electrode and the fourth electrode.
By taking the difference, the electromotive force due to oxygen can be canceled and hydrogen in the high-temperature molten metal can be detected.
【図１】実施例の溶存水素センサを溶融金属中に取り付
けた断面図。FIG. 1 is a cross-sectional view in which a dissolved hydrogen sensor of an embodiment is mounted in a molten metal.
【図２】実施例の溶存水素センサの起電力と水素分圧の
関係を示すグラフ。FIG. 2 is a graph showing a relationship between an electromotive force and a hydrogen partial pressure of the dissolved hydrogen sensor of the embodiment.
１・・溶存水素センサ、２・・取付治具、３・・容器、
４・・溶融金属、１１・・プロトン導電性固体電解質か
らなる第１電極、１２・・金属と金属酸化物からなる第
２電極、１３・・酸化物イオン導電性固体電解質からな
る第３電極、１４・・金属と金属酸化物からなる第４電
極、１５・・第１起電力測定手段、１６・・第２起電力
測定手段、１７・・リード線、１８・・金属円柱、１１
１・・ホタル石型酸化物、１１２・・ペロブスカイト酸
化物。1. Dissolved hydrogen sensor 2. Mounting jig 3. Container
4. a molten metal, a first electrode composed of a proton-conductive solid electrolyte, a second electrode composed of a metal and a metal oxide, a third electrode composed of an oxide ion-conductive solid electrolyte, ... A fourth electrode composed of a metal and a metal oxide, 15... A first electromotive force measuring means, 16... A second electromotive force measuring means, 17.
1. fluorite-type oxide, 112 perovskite oxide.
Claims (6)
接触するプロトン導電性固体電解質からなる第１電極
と、該第１電極の該溶融金属と接触する面と背向する面
に形成された金属と金属酸化物とからなる第２電極と、
該溶融金属と接触する酸化物イオン導電性固体電解質か
らなる第３電極と、該第３電極の該溶融金属と接触する
面と背向する面に形成された該金属と該金属酸化物とか
らなる第４電極と、該第１電極と該第２電極間の起電力
Ｅ12を測定する第１起電力測定手段と、該第３電極と該
第４電極間の起電力Ｅ34を測定する第２起電力測定手段
と、からなることを特徴とする溶融金属中の溶存水素セ
ンサ。1. A first electrode comprising a proton-conductive solid electrolyte in contact with a molten metal in which hydrogen to be measured is dissolved, and a first electrode formed on a surface of the first electrode opposite to a surface in contact with the molten metal. A second electrode made of a metal and a metal oxide,
A third electrode made of an oxide ion conductive solid electrolyte in contact with the molten metal, and the metal and the metal oxide formed on the surface of the third electrode opposite to the surface in contact with the molten metal. A fourth electrode, a first electromotive force measuring means for measuring an electromotive force E12 between the first electrode and the second electrode, and a second electromotive force E34 for measuring an electromotive force E34 between the third electrode and the fourth electrode. A sensor for dissolved hydrogen in molten metal, comprising: an electromotive force measuring means.
2Ｏである請求項１記載の溶存水素センサ。2. The method according to claim 1, wherein the metal is Cu, and the metal oxide is Cu.
Dissolved hydrogen sensor of claim 1 wherein the 2 O.
Ｏ3である請求項１記載の溶存水素センサ。3. The method according to claim 1, wherein the metal is Cr and the metal oxide is Cr 2.
O 3 is dissolved hydrogen sensor according to claim 1, wherein.
オン導電性電解質であるホタル石型酸化物の表面にプロ
トン−酸化物イオン混合導電性電解質であるＡＢＯ3型
のペロブスカイト酸化物が膜状に積層しており、該Ａ元
素がアルカリ土類金属（Ｓｒ，Ｃａ，Ｂａ）からなる群
から選択された一種以上の元素であり、該Ｂ元素は該ホ
タル石型酸化物の金属元素またはその一部をアルカリ土
類金属（Ｍｇ，Ｃａ，Ｓｒ，Ｂａ）、および、希土類元
素（Ｓｃ，Ｙ，Ｌａ，Ｎｄ，Ｓｍ，Ｅｕ，Ｇｄ，Ｄｙ，
Ｈｏ，Ｙｂ）からなる群から選択された一種以上の元素
で置換されて生じる該ホタル石型酸化物の金属元素であ
る請求項１記載の溶存水素センサ。4. The proton-conductive solid electrolyte comprises a fluorite-type oxide which is an oxide ion-conductive electrolyte, and an ABO 3 type perovskite oxide which is a proton-oxide ion mixed conductive electrolyte formed on the surface of the oxide-ion conductive electrolyte. The element A is at least one element selected from the group consisting of alkaline earth metals (Sr, Ca, Ba), and the element B is a metal element of the fluorite-type oxide or one of the elements. Parts are alkaline earth metals (Mg, Ca, Sr, Ba) and rare earth elements (Sc, Y, La, Nd, Sm, Eu, Gd, Dy,
The dissolved hydrogen sensor according to claim 1, wherein the dissolved hydrogen sensor is a metal element of the fluorite-type oxide generated by being replaced with one or more elements selected from the group consisting of Ho, Yb).
ル石型酸化物である請求項１記載の溶存水素センサ。5. The dissolved hydrogen sensor according to claim 1, wherein the oxide ion conductive solid electrolyte is a fluorite-type oxide.
または安定化セリアであり、前記ＡＢＯ3型のペロブス
カイト酸化物はＳｒＺｒＯ3，ＢａＣｅＯ3，ＳｒＣｅＯ
3，ＢａＺｒＯ3，あるいはＣａＺｒＯ3である請求項４
あるいは請求項５記載の溶存水素センサ。6. The fluorite-type oxide is stabilized zirconia or stabilized ceria, and the ABO 3 type perovskite oxide is SrZrO 3 , BaCeO 3 , SrCeO.
3, BaZrO 3 claim 4 or a CaZrO 3,
Alternatively, the dissolved hydrogen sensor according to claim 5.
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|---|---|---|---|
| JP25386098A JP4155632B2 (en) | 1998-09-08 | 1998-09-08 | Dissolved hydrogen sensor in molten metal |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25386098A JP4155632B2 (en) | 1998-09-08 | 1998-09-08 | Dissolved hydrogen sensor in molten metal |
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| Publication Number | Publication Date |
|---|---|
| JP2000088794A true JP2000088794A (en) | 2000-03-31 |
| JP4155632B2 JP4155632B2 (en) | 2008-09-24 |
Family
ID=17257145
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25386098A Expired - Fee Related JP4155632B2 (en) | 1998-09-08 | 1998-09-08 | Dissolved hydrogen sensor in molten metal |
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Cited By (4)
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| JP2006513403A (en) * | 2002-09-14 | 2006-04-20 | ケンブリッジ ユニバーシティ テクニカル サービシズ リミティド | Hydrogen detection apparatus and method |
| EP2827137A4 (en) * | 2012-03-14 | 2015-11-18 | Korea Advanced Inst Sci & Tech | Hydrogen measurement sensor having junction structure of solid oxygen ion conductor and solid hydrogen ion conductor in molten metal |
| JP2016011936A (en) * | 2014-06-30 | 2016-01-21 | 東京窯業株式会社 | Hydrogen sensor |
| EP3045900A4 (en) * | 2013-09-12 | 2017-08-30 | Korea Advanced Institute Of Science And Technology | Hydrogen sensor element for measuring concentration of hydrogen gas dissolved in liquid and method for measuring concentration of hydrogen gas using same |
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| JPH0829375A (en) * | 1994-07-12 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| JP2000019152A (en) * | 1998-07-01 | 2000-01-21 | Tokyo Yogyo Co Ltd | Hydrogen gas sensor |
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| JPH02264856A (en) * | 1989-04-06 | 1990-10-29 | Nkk Corp | Method and probe for measuring activity of solute element in molten metal |
| JPH0829375A (en) * | 1994-07-12 | 1996-02-02 | Tokyo Yogyo Co Ltd | Sensor for measuring quantity of hydrogen dissolved in molten metal |
| JP2000019152A (en) * | 1998-07-01 | 2000-01-21 | Tokyo Yogyo Co Ltd | Hydrogen gas sensor |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006513403A (en) * | 2002-09-14 | 2006-04-20 | ケンブリッジ ユニバーシティ テクニカル サービシズ リミティド | Hydrogen detection apparatus and method |
| JP4773094B2 (en) * | 2002-09-14 | 2011-09-14 | ケンブリッジ エンタープライズ リミティド | Hydrogen detection apparatus and method |
| EP2827137A4 (en) * | 2012-03-14 | 2015-11-18 | Korea Advanced Inst Sci & Tech | Hydrogen measurement sensor having junction structure of solid oxygen ion conductor and solid hydrogen ion conductor in molten metal |
| US9366646B2 (en) * | 2012-03-14 | 2016-06-14 | Korea Advanced Institute Of Science And Technology | Hydrogen measurement sensor having junction structure of solid oxygen ion conductor and solid hydrogen ion conductor in molten metal |
| EP3045900A4 (en) * | 2013-09-12 | 2017-08-30 | Korea Advanced Institute Of Science And Technology | Hydrogen sensor element for measuring concentration of hydrogen gas dissolved in liquid and method for measuring concentration of hydrogen gas using same |
| US9977006B2 (en) | 2013-09-12 | 2018-05-22 | Korea Advanced Institute Of Science And Technology | Hydrogen sensor element for measuring concentration of hydrogen gas dissolved in liquid and method for measuring concentration of hydrogen gas using same |
| JP2016011936A (en) * | 2014-06-30 | 2016-01-21 | 東京窯業株式会社 | Hydrogen sensor |
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| Publication number | Publication date |
|---|---|
| JP4155632B2 (en) | 2008-09-24 |
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