JPH0452552A - Reference electrode for corrosion test of molten salt - Google Patents
Reference electrode for corrosion test of molten saltInfo
- Publication number
- JPH0452552A JPH0452552A JP2161221A JP16122190A JPH0452552A JP H0452552 A JPH0452552 A JP H0452552A JP 2161221 A JP2161221 A JP 2161221A JP 16122190 A JP16122190 A JP 16122190A JP H0452552 A JPH0452552 A JP H0452552A
- Authority
- JP
- Japan
- Prior art keywords
- molten salt
- electrode
- reference electrode
- protecting tube
- tube
- 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 35
- 238000012360 testing method Methods 0.000 title claims abstract description 7
- 230000007797 corrosion Effects 0.000 title claims description 12
- 238000005260 corrosion Methods 0.000 title claims description 12
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 9
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000010416 ion conductor Substances 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 14
- 238000002848 electrochemical method Methods 0.000 abstract description 6
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 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
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 abstract 2
- 230000000694 effects Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 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
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004056 waste incineration Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009528 severe injury Effects 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ＫＣＩ−ＮａＣ
ＱやＫＣ９−ＬｉＣｉ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。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。こ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
。しかし、新材料を開発するという人類の使命において
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８１−３１９
５３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、溶融塩中の腐食には
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的測定の参照電
極としては１８８６年発行のＧＯＲＲＯ９ＩＯＮ誌、第
４２巻、第５７８ペー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。Conventional technology metal materials are used in high-temperature gas environments, such as KCI-NaC.
When covered with a film of molten salt made of Q or KC9-LiCi, it may suffer severe 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. In particular, for waste incineration boilers, the combustion temperature has been increased from the conventional 400°C to 500°C to improve combustion efficiency.
℃ to 700℃, and high-temperature corrosion occurs in conventionally used materials. It is difficult to reproduce the phenomenon of this high-temperature corrosion problem, and research has been limited to measuring weight changes by immersing materials in a molten salt environment for a long time. However, in humanity's mission to develop new materials, it is difficult to develop new materials unless we clarify the mechanism by which high-temperature corrosion occurs. Electrochemical measurements are a means of elucidating the mechanism of corrosion.
Regarding corrosion in aqueous solution, for example, JP-A No. 81-319
Although a reference electrode that provides a stable potential as disclosed in Publication No. 53 has been established, a measurement method for corrosion in molten salts has not yet been established because there is no stable reference electrode. As a reference electrode for electrochemical measurements in molten salt, a simple structure is disclosed in GORRO 9ION magazine published in 1886, volume 42, page 578, but it is applicable only to a limited environmental range and is not general. do not have.
発明が解決しようとする課題
本発明は上記のような高温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 The object of the present invention is to provide a stable reference electrode that can withstand electrochemical measurements in a high-temperature molten salt environment as described above.
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。Means to solve problems What is the gist of the present invention?
ＡＲ２Ｓｉ０４製の保護管内にＡｇ／ＡｇＣｌ電極とイ
オン伝導体の塩とを収容し、モル％でＹ２Ｏ３が１５超
〜２０％、Ｌａ２Ｏ３が１６〜３３％の一種または二種
を残部のＺｒＯ２に含有する液絡線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。An Ag/AgCl electrode and an ion conductor salt are housed in a protection tube made of AR2Si04, and the remaining ZrO2 contains one or two of Y2O3 in mole% of more than 15 to 20% and La2O3 in 16 to 33%. This is a reference electrode for molten salt corrosion testing, characterized in that the molten salt outside the protection tube and the Ag/AgCl electrode inside are electrically connected by a liquid junction wire.
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
にかかる液絡線ｌ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−ＬｉＣＧｊＲ目中に
Ａｇ／ＡｇＣｌ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. The Ag/AgCl electrode 3 is embedded in a salt of, for example, KCQ-LiCGjR.
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。該水冷室は止め
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 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 water cooling chamber, into a high-temperature molten salt.
本発明の発明者等は、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 stable and reliable reference electrode in a molten salt environment. The reason why the constituent materials of the electrodes were limited is as follows.
ＡＱ２ＳｉＯ，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ｅ ＺｒＯ２は溶融塩中で化学的に安定でかつ
Ｈａ＋、 Ｌｉ＋等のイオン伝導体であるため溶融塩中
に存在するイオンを保護管内部のＡｇ／ＡｇＣｌ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。AQ2SiO was used as a protective tube because it is chemically stable up to high temperatures, easily available, and relatively easy to handle.ZrO2 is chemically stable in molten salt and is an ion conductor such as Ha+ and Li+. Therefore, the ions present in the molten salt are allowed to reach the Ag/AgCl electrode inside the protection tube, making it possible to measure the potential of the test electrode installed 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５せる効果がある。５００℃以上の溶融塩中ではモ
ル％で１５％超添加しないとその効果が現れず２０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 500° C. or higher, the effect will not appear unless it is added in an amount exceeding 15 mol %, and the effect will not change even if it is added in an amount exceeding 20 mol %.
Ｌａ２Ｏ３は溶融塩中で化学的に安定でかっＺｒＯ２を
安定化させる効果がある。５００℃以上の溶融塩中では
モル％で１６％超添加しないとその効果が現れず３３モ
ル％を越えて添加してもその効果は代わらない、 Ｌａ
２Ｏ３はＺｒＯ２の安定化に対してＹ２Ｏ３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 a temperature of 500°C or higher, the effect does not appear unless more than 16% by mole is added, and the effect does not change even if more than 33% by mole is added.
2O3 has an extremely large effect on stabilizing ZrO2 when combined with Y2O3.
実施例
第１表に示す組成を有する液絡線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。Example A reference electrode was manufactured using a liquid junction wire having the composition shown in Table 1, and a measurement circuit shown in FIG. 2 was constructed.
重量％で１６％Ｃｒ−１θ％ＭＯからなるＮｉ基合金１
６と上記参照電極１８を、６００℃のＫＣｔ−Ｌｉｃｔ
溶融塩中に浸漬し、３３６時間にわたっての電位差計１
７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
組成の液絡線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。Ni-based alloy 1 consisting of 16% Cr-1θ% MO by weight%
6 and the reference electrode 18 at 600°C.
Potentiometer 1 immersed in molten salt for 336 hours
Potential measurements were carried out by 7. 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 junction 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、試験極の電位が長時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。
ｌ・・・液絡線、２・・・ Ａｌ２ＳｉＯ４製保護管、
３・・争Ａｇ／ＡｇＣｕ電極、４−・・ Ｋ ＣＱ ／
Ｌ ｉ ＣＱ粉、５・・・Ａｇ線、６・・・容器蓋板
、７−・・電極ホルダー、８・―−水冷室、９・・・止
め金、１０−・・ピストン、１１−・・０リング、１２
・・・シールプラグ、１３・・・ナツト、１４＠・・リ
ング、１５・・・被覆材、１６・・・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. l...liquid junction wire, 2...Al2SiO4 protection tube,
3. Ag/AgCu electrode, 4-... K CQ /
L i CQ powder, 5...Ag wire, 6--container lid plate, 7--electrode holder, 8--water cooling chamber, 9--stop, 10--piston, 11--・0 ring, 12
... Seal plug, 13 ... Nut, 14 @ ring, 15 ... 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１５超〜２０％、Ｌａ＿２Ｏ＿３が１６超〜３３％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 15 to 20% of La_2O_3 and more than 16 to 33% 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 |
|---|---|---|---|
| JP2161221A JPH0452552A (en) | 1990-06-21 | 1990-06-21 | Reference electrode for corrosion test of molten salt |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2161221A JPH0452552A (en) | 1990-06-21 | 1990-06-21 | Reference electrode for corrosion test of molten salt |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0452552A true JPH0452552A (en) | 1992-02-20 |
Family
ID=15730927
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2161221A Pending JPH0452552A (en) | 1990-06-21 | 1990-06-21 | Reference electrode for corrosion test of molten salt |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0452552A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10908119B2 (en) * | 2015-11-23 | 2021-02-02 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Reference electrode for electrochemical measurements at high temperatures |
-
1990
- 1990-06-21 JP JP2161221A patent/JPH0452552A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10908119B2 (en) * | 2015-11-23 | 2021-02-02 | Arizona Board Of Regents On Behalf Of The University Of Arizona | Reference electrode for electrochemical measurements at high temperatures |
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