JPH0465665A - Reference electrode for testing corrosion of fused salt - Google Patents
Reference electrode for testing corrosion of fused saltInfo
- Publication number
- JPH0465665A JPH0465665A JP2177492A JP17749290A JPH0465665A JP H0465665 A JPH0465665 A JP H0465665A JP 2177492 A JP2177492 A JP 2177492A JP 17749290 A JP17749290 A JP 17749290A JP H0465665 A JPH0465665 A JP H0465665A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- protective tube
- fused salt
- reference electrode
- salt
- 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.)
- Pending
Links
- 150000003839 salts Chemical class 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 title claims description 13
- 238000005260 corrosion Methods 0.000 title claims description 13
- 238000012360 testing method Methods 0.000 title claims description 6
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000010416 ion conductor Substances 0.000 claims abstract description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 12
- 238000002848 electrochemical method Methods 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000004056 waste incineration Methods 0.000 description 1
Landscapes
- Testing Resistance To Weather, Investigating Materials By Mechanical Methods (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は溶融塩環境下における金属材料の腐食速度を電
気化学的に測定するための参照電極に関するものである
。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a reference electrode for electrochemically measuring the corrosion rate of metal materials in a molten salt environment.
従来の技術
金属材料が高温ガス環境中で、たとえばに（Ｑ−ＮａＣ
Ｉ２やＫＣｔ−ＬｉＣｉｌからなる溶融塩の皮膜に覆わ
れた場合に高温腐食と呼ばれる著しい損傷をうけること
がある。この現象は火力発電用ボイラチューブ、ガスタ
ービン動翼部、ごみ焼却用ボイラチューブ等の高温燃焼
部で観測されている。Conventional technology metal materials are used in high-temperature gas environments, for example (Q-NaC).
When covered with a film of molten salt made of I2 or KCt-LiCil, it may suffer significant damage called high-temperature corrosion. This phenomenon has been observed in high-temperature combustion parts such as boiler tubes for thermal power generation, gas turbine rotor blades, and boiler tubes for waste incineration.
特に、ごみ焼却用ボイラーでは燃焼効率アップのために
燃焼温度を従来の４００℃から５００℃〜７００℃に上
昇させており従来使用されていた材料では高温腐食が発
生する。また最近の石油供給事情の悪化から石炭専焼ボ
イラーが見直され９００℃近傍での運転が行われている
。これらの高温腐食問題は現象を再現することが困難で
研究も材料を溶融塩環境に長時間浸漬することにより重
量変化を測定するにとどまっている。In particular, in garbage incineration boilers, the combustion temperature is raised from the conventional 400°C to 500°C to 700°C to improve combustion efficiency, and the materials used in the past suffer from high-temperature corrosion. Additionally, due to the recent deterioration in the oil supply situation, coal-fired boilers have been reconsidered and are now being operated at temperatures around 900°C. It is difficult to reproduce these high-temperature corrosion problems, and research has been limited to measuring weight changes by immersing materials in a molten salt environment for a long time.
しかし、新材料の開発に
おいては、高温腐食がいかなる機構に従って発生してい
るのかを明らかにしなければ新材料の開発は困難である
。腐食の機構を解明する手段としては電気化学的測定が
あり、水溶液中の腐食においてはたとえば特開昭８１−
３１９５３号公報に開示されているような安定した電位
の得られる参照電極が確立されているが、溶融地中の腐
食には安定な参照電極が存在しないために測定方法はい
まだに確立されていない、溶融塩中の電気化学測定用の
参照電極としては１８８６年発行のＣｏＲＲＯＳＩＯＮ
紙、第４２巻、第５７８ベニジに簡単な構造が開示され
ているが限られた環境範囲にのみ適用可能で一般性がな
い・。However, in the development of new materials, it is difficult to develop new materials unless the mechanism by which high-temperature corrosion occurs is clarified. Electrochemical measurements are available as a means of elucidating the mechanism of corrosion, and for corrosion in aqueous solutions, for example,
Although a reference electrode capable of obtaining a stable potential as disclosed in Publication No. 31953 has been established, a measurement method for corrosion in molten soil has not yet been established as there is no stable reference electrode. CoRROSION, published in 1886, is a reference electrode for electrochemical measurements in molten salts.
Paper, Vol. 42, No. 578 Beniji discloses a simple structure, but it is applicable only to a limited range of environments and is not general.
発明が解決しようとする課題
本発明は上記のような高−の溶融塩環境中での電気化学
的測定に耐えられる安定な参照電極を提供することを目
的とするものである。Problems to be Solved by the Invention It is an object of the present invention to provide a stable reference electrode that can withstand electrochemical measurements in the above-mentioned high-temperature molten salt environment.
課題を解決するための手段
本発明の要旨とするところは、
Ｍ２ＳｊＯｎ製の、保護管内にＡｇ／ムｇＣＱ電極とイ
オン伝導体の塩とを収容し、モル％でＹ２Ｏ３が２０超
〜２５％、Ｌａ２Ｏ３が３３超〜３９％の一種また゛は
二種を残部のＺｒＯ２に含有する液絡棒によって保護管
の外部の溶融塩と内部のＡｇ／ＡｇＣｌ電極とを電気的
に接続されることを特徴とする溶融塩腐食試験用参照電
極である。Means for Solving the Problems The gist of the present invention is to house an Ag/mugCQ electrode and an ion conductor salt in a protection tube made of M2SjOn, and to contain Y2O3 in mole % of more than 20 to 25%; The molten salt on the outside of the protection tube and the Ag/AgCl electrode inside are electrically connected by a liquid junction rod containing one or two types of La2O3 of more than 33 to 39% with the remaining ZrO2. This is a reference electrode for molten salt corrosion tests.
作用 以下、本発明の詳細な説明する。action The present invention will be explained in detail below.
まず本発明にかかる参照電極の構造の概要を第１図に基
づき説明する０本発明にかかる保護管２の先端に本発明
にがかる液絡棒１を埋め込み、該保護管内に充填したイ
オン伝導体の塩、たとえばＫＣＱ−ＬｉＣＱ粉４中にＡ
ｇ／ＡｇＣ１１電極３を埋め込む。First, the outline of the structure of the reference electrode according to the present invention will be explained based on FIG. salt, for example A in KCQ-LiCQ powder 4
g/AgC11 electrode 3 is embedded.
該Ａｇ／ＡｇＣｌ電極は保護管内でその位置が変動しな
いようにピストン１０および０リング１１によって固定
され、さらにシールプラグ１２を貫通して電極ホルダー
７の外部へ導かれ電気的接触を与えられる。該シールプ
ラグ１２はナツト１３およびリング１４によって固定さ
れ該保護管本体もその位置の変動が抑えられる。該電極
ホルダー７は高温の溶融塩を収容する容器の蓋６を介し
て設置されており、該電極ホルダーの本体が高温になる
のを避けるため水冷室８を有している。紘水冷室は止め
金９によって固定されている０以上のように構成された
参照電極の該保護管を高温の溶融塩中に浸漬することに
よって試験用電極の電位が得られる。The Ag/AgCl electrode is fixed by a piston 10 and an O-ring 11 so that its position does not change within the protective tube, and is further guided to the outside of the electrode holder 7 through a sealing plug 12 to provide electrical contact. The seal plug 12 is fixed by a nut 13 and a ring 14, and the position of the protection tube body is also suppressed from changing. The electrode holder 7 is installed through a lid 6 of a container containing high-temperature molten salt, and has a water cooling chamber 8 to prevent the main body of the electrode holder from becoming hot. The electrical potential of the test electrode is obtained by immersing the protective tube of the reference electrode, which is fixed by a stopper 9 in the cold water cooling chamber, into a high-temperature molten salt.
本発明の発明者ら、溶融塩中で安定性かつ信頼性の高い
参照電極に関して多くの実験結果に基づいて溶融塩環境
中での電気化学測定を可能ならしめる参照電極を得た０
本発明において電極の構成材質を限定したのは次の理由
による。The inventors of the present invention have obtained a reference electrode that enables electrochemical measurements in a molten salt environment based on many experimental results regarding a reference electrode that is stable and reliable in a molten salt environment.
The reason why the constituent materials of the electrodes are limited in the present invention is as follows.
Ａｉ、 ２Ｓ ’ ！ ０４は高い温度領域まで化学的
に安定でかつ入手しやすく取扱も比較的容易であるため
保護管として採用した。 ＺｒＯ２は溶融塩中で化学的
に安定でかつＮａ” 、 Ｌｉ”等のイオン伝導体であ
るため溶融集中に存在するイオンを保護管内部のＡｇ／
ＡｇＣ１２電極にまで到達せしめ、溶融塩中に設置され
た試験極の電位の測定を可能ならしめる。Ai, 2S'! 04 was used as the protective tube because it is chemically stable up to high temperature ranges and is easily available and relatively easy to handle. Since ZrO2 is chemically stable in molten salt and is an ion conductor of Na'', Li'', etc., it transfers ions present in the molten salt to Ag/Li'' inside the protection tube.
It reaches the AgC12 electrode, making it possible to measure the potential of the test electrode placed in the molten salt.
Ｙ２Ｏ３は溶融塩中で化学的に安定でかつＺｒＯ２を安
定化させる効果がある。７００℃以上の溶融塩中ではモ
ル％で２０％を超えて添加しないとその効果が現れず、
２５モル％を超えて添加してもその効果は変わらない。Y2O3 is chemically stable in the molten salt and has the effect of stabilizing ZrO2. In a molten salt at a temperature of 700°C or higher, the effect will not appear unless it is added in a mol% exceeding 20%.
Even if it is added in an amount exceeding 25 mol%, the effect remains the same.
Ｌａ２Ｏ３は溶融塩中で化学的に安定でかつＺｒＯ２を
安定化させる効果がある。７００℃以上の溶融塩中では
、：、モル％で３３％を超えて添加しないとその効果が
現れず、３９モル％を超えて添加してもその効果は変わ
らない、 Ｌａ２Ｏ３はＺｒＯ２の安定化に対してＹ２
Ｏ３と組み合わせればその効果はきわめて大である。La2O3 is chemically stable in molten salt and has the effect of stabilizing ZrO2. In a molten salt at 700°C or higher, the effect does not appear unless it is added in an amount exceeding 33% by mole, and the effect remains unchanged even if it is added in an amount exceeding 39% by mole.La2O3 stabilizes ZrO2. against Y2
When combined with O3, the effect is extremely large.
実施例
第１表に示す組成を有する液絡棒を用いて参照電極を製
作し、第２図に示す測定回路を構成し、重量％で１６％
Ｃｒ−１１３％ＮＯからなるＸｉ基合金ＩＢと上記参照
電極１８を、７５０℃のＫＣＩＩ−ＬｉＣＩｌ溶融墳中
に浸漬し、３３６時間にわたって電位差計１７によって
電位測定を実施した。第３図はその電位測定結果を示す
図の一例で、測定開始３分後から定常値を示し長時間に
わたって安定な電位を示した。第１表に示す組成の液綿
棒を備えた参照電極による測定結果はすべて第３図に示
す電位変化と同様の安定な電位を示した。Example A reference electrode was manufactured using a liquid junction rod having the composition shown in Table 1, and the measuring circuit shown in Fig. 2 was constructed, and the composition was 16% by weight.
The Xi-based alloy IB made of Cr-113% NO and the reference electrode 18 were immersed in a KCII-LiCII molten mound at 750° C., and the potential was measured using a potentiometer 17 over a period of 336 hours. FIG. 3 is an example of a diagram showing the results of the potential measurement, and the potential showed a steady value from 3 minutes after the start of the measurement and remained stable for a long period of time. All measurement results using a reference electrode equipped with a liquid cotton swab having the composition shown in Table 1 showed stable potentials similar to the potential changes shown in FIG.
（以下余白）
発明の効果
本発明は溶融塩環境中での電気化学測定用の参照電極を
提供し、試験極の電位が長期間にわたって測定可能とな
り溶融塩環境中での腐食機構を解明し、新材料の開発に
寄与するところ大である。(Left below) Effects of the Invention The present invention provides a reference electrode for electrochemical measurements in a molten salt environment, enables the potential of the test electrode to be measured over a long period of time, and elucidates the corrosion mechanism in the molten salt environment. This will greatly contribute to the development of new materials.
第１図は参照電極の構造を示す断面図、第２図は電位測
定の回路図、第３図は測定された電位の時間変化を示す
図である。
１・・Φ液絡棒、２拳・・Ｍ２５ｊＱ４製保護管、３・
・・Ａｇ／ＡｇＣｌ電極、４・・・ にＣＱ／ＬｉＣｌ
２粉、５・・・Ａｇ線、６番・・容器蓋板、７・・・電
極ホルダー、８・・０水冷室、９・・・止め金、ｌＯ・
・・ピストン、 １１・・・０リング、１２・・φシー
ルプラグ、１３１１・・す７ド、１４・・・リング、１
５・・・被覆材、１６・嗜・Ｎｉ基合金、１７・・・電
位差計、１８・・・参照電極。FIG. 1 is a cross-sectional view showing the structure of a reference electrode, FIG. 2 is a circuit diagram for potential measurement, and FIG. 3 is a diagram showing changes in measured potential over time. 1..Φ liquid junction rod, 2..M25jQ4 protection tube, 3.
・・Ag/AgCl electrode, 4... CQ/LiCl
2 Powder, 5... Ag wire, No. 6... Container lid plate, 7... Electrode holder, 8... 0 Water cooling chamber, 9... Stopper, lO.
...Piston, 11...0 ring, 12...φ seal plug, 1311...S7 de, 14...Ring, 1
5... Covering material, 16... Ni-based alloy, 17... Potentiometer, 18... Reference electrode.
Claims (1)
とイオン伝導体の塩とを収容し、モル％でＹ＿２Ｏ＿３
が２０超〜２５％、Ｌａ＿２Ｏ＿３が３３超〜３９％の
一種または二種を残部のＺｒＯ＿２に含有する液絡棒に
よって保護管の外部の溶融塩と内部のＡｇ／ＡｇＣｌ電
極とを電気的に接続されたことを特徴とする溶融塩腐食
試験用参照電極。An Ag/AgCl electrode and an ion conductor salt are housed in a protection tube made of Al_2SiO_4, and Y_2O_3 is
The molten salt outside the protective tube and the Ag/AgCl electrode inside are electrically connected by a liquid junction rod containing one or two of more than 20 to 25% of La_2O_3 and more than 33 to 39% of La_2O_3 in the remaining ZrO_2. A reference electrode for molten salt corrosion testing, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177492A JPH0465665A (en) | 1990-07-06 | 1990-07-06 | Reference electrode for testing corrosion of fused salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2177492A JPH0465665A (en) | 1990-07-06 | 1990-07-06 | Reference electrode for testing corrosion of fused salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0465665A true JPH0465665A (en) | 1992-03-02 |
Family
ID=16031851
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2177492A Pending JPH0465665A (en) | 1990-07-06 | 1990-07-06 | Reference electrode for testing corrosion of fused salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0465665A (en) |
-
1990
- 1990-07-06 JP JP2177492A patent/JPH0465665A/en active Pending
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