JP5754566B2 - Device for measuring the amount of hydrogen penetrating into metal - Google Patents
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- 229910052739 hydrogen Inorganic materials 0.000 title claims description 180
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- 229910052751 metal Inorganic materials 0.000 title claims description 30
- 239000002184 metal Substances 0.000 title claims description 30
- 230000000149 penetrating effect Effects 0.000 title claims description 24
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- 238000005260 corrosion Methods 0.000 claims description 35
- 230000007797 corrosion Effects 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 28
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000007769 metal material Substances 0.000 claims description 19
- 239000008151 electrolyte solution Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
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- 150000002894 organic compounds Chemical class 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 7
- 230000000903 blocking effect Effects 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 235000011187 glycerol Nutrition 0.000 claims description 3
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- 239000000463 material Substances 0.000 description 16
- 230000003111 delayed effect Effects 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000007747 plating Methods 0.000 description 11
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000012937 correction Methods 0.000 description 7
- 229910001252 Pd alloy Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- 238000009792 diffusion process Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
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- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
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- -1 hydrogen ions Chemical class 0.000 description 3
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- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- 238000012935 Averaging Methods 0.000 description 1
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- 229910021069 Pd—Co Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Description
本発明は、金属の腐食に伴い金属内部へ侵入する水素量を正確に検出することができる、金属内部への侵入水素量の測定装置に関するものである。 The present invention relates to an apparatus for measuring the amount of hydrogen penetrating into a metal, which can accurately detect the amount of hydrogen penetrating into the metal due to corrosion of the metal.
近年、地球温暖化防止の観点から、移動体である自動車、船舶、鉄道車両などの重量を低減させることによって、エネルギー効率の向上、例えば自動車であれば、ガソリンの燃費向上が求められている。そこで、構成材料、特に鉄鋼材料においては板厚を減少させた場合でも同等の安全性を確保するために、高強度化した鋼材の使用量が拡大している。 In recent years, from the viewpoint of preventing global warming, by reducing the weight of moving vehicles such as automobiles, ships, railway vehicles, etc., there has been a demand for improved energy efficiency, for example, improved fuel efficiency of gasoline for automobiles. Therefore, in the case of constituent materials, particularly steel materials, the amount of steel materials with increased strength is increasing in order to ensure the same safety even when the plate thickness is reduced.
しかしながら、鋼材の強度を高めていくと、「遅れ破壊」という現象が生じやすくなることが知られている。この「遅れ破壊」は鋼材強度の増大と共に著しく激しくなり、特に引張り強度が1180MPa以上の高強度鋼で顕著となる（非特許文献１）。なお、「遅れ破壊」とは、高強度鋼材が静的な負荷応力（引張り強さ以下の負荷応力）を受けた状態で、ある時間が経過したとき、外見上はほとんど塑性変形を伴うことなく、突然脆性的な破壊が生じる現象であり、ここでは水素が鋼材に入ることによって引き起こされる水素脆化型の遅れ破壊を意味する。
鋼材に侵入する水素は、鋼板の腐食に伴って発生し、その一部が鋼材に侵入することによって引き起こされると考えられている。このような観点から、鋼材への水素侵入に着目した遅れ破壊の評価方法が種々提案されている。
However, it is known that the phenomenon of “delayed fracture” is likely to occur when the strength of the steel material is increased. This “delayed fracture” becomes remarkably severe as the steel strength increases, and becomes particularly noticeable in high-strength steel having a tensile strength of 1180 MPa or more (Non-patent Document 1). “Delayed fracture” means that high strength steel is subjected to static load stress (load stress less than tensile strength) and, when a certain amount of time has passed, there is almost no plastic deformation. This is a phenomenon in which sudden brittle fracture occurs, and here it means hydrogen embrittlement type delayed fracture caused by hydrogen entering the steel material.
It is considered that hydrogen that intrudes into a steel material is generated along with corrosion of the steel plate, and a part thereof is caused by intrusion into the steel material. From such a viewpoint, various methods for evaluating delayed fracture focusing on hydrogen intrusion into steel materials have been proposed.
例えば、特許文献１には、鋼材に陰極チャージによって拡散性水素を含有させ、限界拡散性水素量を測定することによって、鋼材の遅れ破壊特性を評価する遅れ破壊特性の評価方法において、限界拡散性水素量の測定中に鋼材から水素が放出されることを防止するために、鋼材に亜鉛めっきを施す方法が提案されている。
しかしながら、特許文献１に記載された技術は、鋼中への水素侵入は陰極チャージにより強制的に水素を侵入させる加速試験であることから、実際の使用環境とは異なる条件の下で、供試材の種類による遅れ破壊発現の優劣をつけることはできるものの、実際の使用環境での腐食に伴う水素侵入量で遅れ破壊が起こるか否かを推定するための判断材料にはならない。
For example, Patent Document 1 discloses that in a delayed fracture property evaluation method for evaluating delayed fracture characteristics of a steel material by making the steel material contain diffusible hydrogen by cathodic charging and measuring the critical diffusible hydrogen content, In order to prevent hydrogen from being released from the steel during measurement of the amount of hydrogen, a method of galvanizing the steel has been proposed.
However, since the technique described in Patent Document 1 is an accelerated test in which hydrogen intrusion into steel is forced to enter hydrogen by cathodic charging, the test was performed under conditions different from the actual usage environment. Although it is possible to give the superiority or inferiority to the occurrence of delayed fracture depending on the type of material, it is not a judgment material for estimating whether or not delayed fracture occurs due to the amount of hydrogen intrusion due to corrosion in the actual use environment.
また、近年、水素侵入に着目した研究が多く報告されているが、例えば非特許文献２には、チオシアン酸アンモニウムを用いた水素侵入挙動について報告がなされている。この非特許文献２には、チオシアン酸アンモニウムによる水素侵入と、陰極チャージ法による水素侵入の比較がなされている。
しかしながら、非特許文献２に開示のチオシアン酸アンモニウムを用いた水素侵入量の評価方法においては、表面の腐食による水素侵入を得られるものではなく、例えば近年自動車の防錆用途として用いられる亜鉛めっき等が水素侵入に及ぼす影響を測定できるものではない。
In recent years, many studies focusing on hydrogen intrusion have been reported. For example, Non-Patent Document 2 reports on hydrogen intrusion behavior using ammonium thiocyanate. In this Non-Patent Document 2, a comparison between hydrogen penetration by ammonium thiocyanate and hydrogen penetration by the cathodic charging method is made.
However, in the method for evaluating the amount of hydrogen intrusion using ammonium thiocyanate disclosed in Non-Patent Document 2, hydrogen intrusion due to surface corrosion cannot be obtained. For example, zinc plating used for rust prevention of automobiles in recent years, etc. The effect of hydrogen on hydrogen intrusion cannot be measured.
さらに、非特許文献３には、大気暴露環境下で一定期間腐食させた高強度ボルトを回収して、ボルトに吸蔵された水素濃度を測定した例が報告されている。また、この非特許文献３には、鋼板の片面を外部環境に暴露する試験装置を用いた電気化学的水素透過法によって、反対面側から検出されるアノード電流値の変化から、大気暴露環境下での腐食による水素侵入挙動を調査した結果が報告されている。
じかしながら、非特許文献３に開示の大気暴露試験によって得られるデータは、いずれも地勢的な特定環境と結びついた環境因子の下での試験結果にすぎず、構造体の移動に伴い変化する種々の環境下における腐食を継続的に把握することについては、考慮が払われていない。
また、非特許文献３に示された鋼板の片面を外部環境に暴露する試験装置を用いた大気暴露における水素透過試験では、環境の温度変化に伴うアノード側の残余電流の変化が考慮されていないことから、測定値の定量性にも問題があった。
Furthermore, Non-Patent Document 3 reports an example in which a high-strength bolt that has been corroded for a certain period of time in an atmospheric exposure environment is collected and the hydrogen concentration occluded in the bolt is measured. Further, in this Non-Patent Document 3, from the change of the anode current value detected from the opposite surface side by an electrochemical hydrogen permeation method using a test apparatus that exposes one side of a steel sheet to the external environment, The results of investigating the hydrogen intrusion behavior due to corrosion in the sea are reported.
However, all the data obtained by the atmospheric exposure test disclosed in Non-Patent Document 3 are only the test results under environmental factors linked to the terrain specific environment, and change with the movement of the structure. No consideration has been given to continuously grasping corrosion in various environments.
Further, in the hydrogen permeation test in the atmospheric exposure using the test apparatus that exposes one side of the steel sheet shown in Non-Patent Document 3 to the external environment, the change in the residual current on the anode side due to the temperature change in the environment is not taken into consideration. For this reason, there was a problem in the quantitativeness of the measured value.
なお、上述したように、現時点で最も遅れ破壊の問題が懸念される金属材料は、実用材料として広範に使用されている鋼材であるが、その他の金属材料においても今後は遅れ破壊の問題が生じる可能性が指摘されている（例えば非特許文献４）。 As described above, the metal material that is most concerned about the problem of delayed fracture is a steel material that is widely used as a practical material. However, the problem of delayed fracture will also occur in other metal materials in the future. The possibility is pointed out (for example, non-patent document 4).
上記したように、自動車のような移動体では、移動することによって地勢的な環境が変化し、さらに物理的要因（例えば振動、塵埃堆積−脱落、水・泥跳ね付着−乾燥など）が加わると、腐食環境が極端に変化する場合がある。
しかしながら、上記した振動などの物理的要因や地勢的な環境変化が避けられない移動体について、腐食に伴う水素侵入量を継続的かつ定量的に計測した例は、これまで皆無であった。
As described above, in a moving body such as an automobile, when the terrain environment is changed by moving, and physical factors (for example, vibration, dust accumulation-dropping, water / mud splash adhesion-drying, etc.) are added. The corrosive environment may change drastically.
However, there have been no examples of continuously and quantitatively measuring the amount of hydrogen intrusion due to corrosion of a moving body in which physical factors such as vibrations and terrain environmental changes cannot be avoided.
上記の状況に鑑み、発明者らは、先に、
「 金属材料の腐食に伴って発生し金属内部に侵入する水素の量を、電気化学的水素透過法を用いて測定する方法であって、被検体の片面を腐食環境に暴露し腐食反応により発生する水素の侵入面とする一方、該被検体の他面を水素検出面とし、該水素検出面側の電位を−0.1〜＋0.3V vs SCEに保持した状態で該検出面に拡散してくる水素の流束をアノード電流として測定するに際し、
該被検体の水素検出面側に、少なくとも２つに分割された複数のセル群で構成された電気化学セルを配置し、該セル群の個々のセルの内部にはpHが９〜13の電解質水溶液を充填すると共に、それぞれ独立した参照電極と対極を設置し、
該セル群のうち少なくとも一つのセルを残余電流を補正するための基準セルとし、該基準セルの水素侵入面側に対応する箇所には腐食環境との接触を遮断する保護膜を設け、
該基準セル以外のセルで検出したアノード電流値を、該基準セルで検出した残余電流値により補正し、この補正したアノード電流値に基づいて腐食面側からの侵入水素量を算出することを特徴とする金属内部への侵入水素量の測定方法。」
を開発し、特許文献２において開示した。
In view of the above situation, the inventors first
`` A method for measuring the amount of hydrogen generated by corrosion of metal materials and penetrating into the metal using an electrochemical hydrogen permeation method, which occurs due to a corrosion reaction by exposing one side of the specimen to a corrosive environment The other surface of the subject is a hydrogen detection surface, and the potential on the hydrogen detection surface side is diffused to the detection surface while being kept at −0.1 to +0.3 V vs. SCE. In measuring the hydrogen flux as the anode current,
An electrochemical cell composed of a plurality of cell groups divided into at least two cells is disposed on the hydrogen detection surface side of the analyte, and an electrolyte having a pH of 9 to 13 is placed inside each cell of the cell group. Fill with aqueous solution and install independent reference electrode and counter electrode,
At least one cell in the cell group is used as a reference cell for correcting the residual current, and a protective film that blocks contact with the corrosive environment is provided at a location corresponding to the hydrogen entry surface side of the reference cell,
An anode current value detected in a cell other than the reference cell is corrected by a residual current value detected in the reference cell, and an intrusion hydrogen amount from the corroded surface side is calculated based on the corrected anode current value. A method for measuring the amount of hydrogen penetrating into a metal. "
Was developed and disclosed in US Pat.
上記特許文献２の開発により、環境の温度変化に伴うアノード側の残余電流の変化を考慮した上で、腐食に伴って金属内部へ侵入する水素量を正確に計測することができるようになった。
本発明は、上掲した特許文献２に記載の「金属内部への侵入水素量の測定方法」の実施に供して好適な金属内部への侵入水素量の測定装置を提案することを目的とする。
With the development of the above-mentioned Patent Document 2, it is possible to accurately measure the amount of hydrogen that penetrates into the metal due to corrosion in consideration of the change in the residual current on the anode side accompanying the temperature change in the environment. .
An object of the present invention is to propose a device for measuring the amount of hydrogen penetrating into a metal suitable for implementation of the “method for measuring the amount of hydrogen penetrating into the metal” described in Patent Document 2 listed above. .
すなわち、本発明の要旨構成は次のとおりである。
１．金属材料からなる被検体の腐食に伴って発生し金属内部に侵入する水素の量を、電気化学的水素透過法を用いて測定する装置であって、
該被検体の一方の面を腐食環境に暴露し腐食反応により発生する水素の侵入面、他方の面を水素検出面とするとき、
該水素検出面側に、複数のセル群で構成された電気化学セルを設け、該セル群の個々のセルの内部にpHが９〜13の電解質水溶液を充填すると共に、それぞれ独立した参照電極と対極を設置し、
前記電解質水溶液中に、凍結防止のために有機化合物を添加し、
該セル群のうち少なくとも一つのセルを残余電流を補正するための基準セルとし、該基準セルの水素検出領域に対応する水素侵入面側の領域に、腐食環境との接触を遮断するための保護膜を設け、
該被検体の水素侵入面のうち、該基準セル以外のセルに対応する箇所には、該金属材料が直接腐食環境に暴露するよう保護膜を設けず、
該基準セル以外のセルで検出したアノード電流値を、該基準セルで検出した残余電流値により補正し、この補正したアノード電流値に基づいて腐食面側からの侵入水素量を算出することを特徴とする金属内部への侵入水素量の測定装置。
That is, the gist configuration of the present invention is as follows.
1. An apparatus for measuring the amount of hydrogen generated by corrosion of an object made of a metal material and entering the metal using an electrochemical hydrogen permeation method,
When one surface of the specimen is exposed to a corrosive environment and a hydrogen intrusion surface generated by a corrosion reaction, and the other surface is a hydrogen detection surface,
An electrochemical cell composed of a plurality of cell groups is provided on the hydrogen detection surface side, and each cell of the cell group is filled with an electrolyte aqueous solution having a pH of 9 to 13, and an independent reference electrode and Install a counter electrode,
In the electrolyte aqueous solution, an organic compound is added to prevent freezing,
Protection for blocking contact with the corrosive environment in a region on the hydrogen intrusion surface side corresponding to the hydrogen detection region of the reference cell, with at least one cell of the cell group serving as a reference cell for correcting the residual current Providing a membrane,
Of the hydrogen intrusion surface of the specimen, a portion corresponding to a cell other than the reference cell is not provided with a protective film so that the metal material is directly exposed to a corrosive environment,
An anode current value detected in a cell other than the reference cell is corrected by a residual current value detected in the reference cell, and an intrusion hydrogen amount from the corroded surface side is calculated based on the corrected anode current value. A device for measuring the amount of hydrogen penetrating into a metal.
２．前記参照電極としてIr/Ir酸化物電極を用いることを特徴とする前記１に記載の金属内部への侵入水素量の測定装置。 2. 2. The apparatus for measuring the amount of hydrogen penetrating into a metal according to 1 above, wherein an Ir / Ir oxide electrode is used as the reference electrode.
３．前記電解質水溶液中に添加する有機化合物が、イソプロピルアルコール、グリセリンまたはエチレングリコールあるいはジメチルスルフォキシドまたはジメチルフォルモアミドであることを特徴とする前記１または２に記載の金属内部への侵入水素量の測定装置。 3. 3. Measurement of the amount of hydrogen penetrating into the metal according to 1 or 2 above, wherein the organic compound added to the electrolyte aqueous solution is isopropyl alcohol, glycerin, ethylene glycol, dimethyl sulfoxide or dimethylformamide apparatus.
４．金属材料からなる被検体の腐食に伴って発生し金属内部に侵入する水素の量を、電気化学的水素透過法を用いて測定する装置であって、
該被検体の一方の面を腐食環境に暴露し腐食反応により発生する水素の侵入面、他方の面を水素検出面とするとき、
該水素検出面側に、複数のセル群で構成された電気化学セルを設け、該セル群の個々のセルの内部にpHが９〜13の電解質水溶液を充填すると共に、それぞれ独立した参照電極と対極を設置し、
前記電解質水溶液を充填した電気化学セルの内部に、水素検出面との接触を避けて、気泡を配置し、
該セル群のうち少なくとも一つのセルを残余電流を補正するための基準セルとし、該基準セルの水素検出領域に対応する水素侵入面側の領域に、腐食環境との接触を遮断するための保護膜を設け、
該被検体の水素侵入面のうち、該基準セル以外のセルに対応する箇所には、該金属材料が直接腐食環境に暴露するよう保護膜を設けず、
該基準セル以外のセルで検出したアノード電流値を、該基準セルで検出した残余電流値により補正し、この補正したアノード電流値に基づいて腐食面側からの侵入水素量を算出することを特徴とする金属内部への侵入水素量の測定装置。
4). An apparatus for measuring the amount of hydrogen generated by corrosion of an object made of a metal material and entering the metal using an electrochemical hydrogen permeation method,
When one surface of the specimen is exposed to a corrosive environment and a hydrogen intrusion surface generated by a corrosion reaction, and the other surface is a hydrogen detection surface,
An electrochemical cell composed of a plurality of cell groups is provided on the hydrogen detection surface side, and each cell of the cell group is filled with an electrolyte aqueous solution having a pH of 9 to 13, and an independent reference electrode and Install a counter electrode,
Inside the electrochemical cell filled with the aqueous electrolyte solution, avoiding contact with the hydrogen detection surface, placing bubbles,
Protection for blocking contact with the corrosive environment in a region on the hydrogen intrusion surface side corresponding to the hydrogen detection region of the reference cell, with at least one cell of the cell group serving as a reference cell for correcting the residual current Providing a membrane,
Of the hydrogen intrusion surface of the specimen, a portion corresponding to a cell other than the reference cell is not provided with a protective film so that the metal material is directly exposed to a corrosive environment,
An anode current value detected in a cell other than the reference cell is corrected by a residual current value detected in the reference cell, and an intrusion hydrogen amount from the corroded surface side is calculated based on the corrected anode current value. A device for measuring the amount of hydrogen penetrating into a metal.
５．前記電解質水溶液を充填した電気化学セルの内部に、水素検出面との接触を避けて、気泡を配置したことを特徴とする前記１〜３のいずれかに記載の金属内部への侵入水素量の測定装置。 5. The amount of hydrogen penetrating into the metal according to any one of 1 to 3 above, wherein bubbles are arranged inside the electrochemical cell filled with the electrolyte aqueous solution so as to avoid contact with the hydrogen detection surface. measuring device.
本発明装置によれば、腐食に伴って金属の内部へ侵入する水素量を正確に検出することができる。
また、本発明装置を用いれば、自動車、船舶、鉄道車両などの移動体を構成する金属材料の各部位が、その使用状態で曝される腐食環境下で腐食することに伴い発生し、金属材料中に侵入する水素の量を連続的にモニタリングすることが可能となり、実際の使用環境での腐食に伴う水素侵入量で遅れ破壊が生じるか否かを判断するために必要な情報を得ることができる。
According to the apparatus of the present invention, it is possible to accurately detect the amount of hydrogen that penetrates into the metal due to corrosion.
Further, if the apparatus of the present invention is used, each part of the metal material constituting the moving body such as an automobile, a ship, and a railway vehicle is generated as it corrodes in a corrosive environment exposed in the use state, and the metal material It is possible to continuously monitor the amount of hydrogen penetrating into it, and to obtain information necessary to determine whether or not delayed fracture occurs due to the amount of hydrogen penetrating due to corrosion in the actual use environment. it can.
本発明は、自動車、自動二輪車、鉄道などの各種車両や船舶、航空機など自力で移動可能な移動体のすべてに適用可能な技術であるが、以下、自動車を代表例として実施の形態について詳細に説明する。また、評価対象とする金属材料としては必ずしも鋼板に限定されるわけではないが、ここでは代表例として鋼板に適用した場合について説明する。 The present invention is a technique that can be applied to various vehicles such as automobiles, motorcycles, railways, and mobile bodies that can be moved on their own, such as ships and airplanes. Hereinafter, embodiments will be described in detail with reference to automobiles as representative examples. explain. The metal material to be evaluated is not necessarily limited to a steel plate, but here, a case where it is applied to a steel plate will be described as a representative example.
本発明は、金属材料の腐食に伴い発生し内部に侵入する水素の量を、電気化学的水素透過法の測定原理を適用して測定するもので、水素侵入面側の鋼板表面を腐食環境に曝すことにより、腐食時に発生した水素が鋼中に侵入するので、反対面側から水素を取り出すことによって侵入水素量を測定する。 The present invention measures the amount of hydrogen generated by metal material corrosion and penetrating into the interior by applying the measurement principle of the electrochemical hydrogen permeation method. By exposing, the hydrogen generated during the corrosion penetrates into the steel, and the amount of penetrating hydrogen is measured by taking out hydrogen from the opposite side.
電気化学的水素透過法は、1962年にDevanathanとStachurskiによって開発された手法（非特許文献５）で、図１に模式的に示すように、２つの電解槽１ａ，１ｂが１枚の試料２を挟んで向かい合わせに配置されている。同図の場合、左側の電解槽１ａの試料面を定電位または定電流でカソード分極して、水素発生・水素チャージを行い、右側の電解槽１ｂでは試料２を定電位アノード分極することによって試料２を透過してきた水素を水素イオンに酸化し、その電流値から透過した水素の量を求めるものである。
図中、符号３ａ，３ｂは参照電極、４ａ，４ｂは電極であり、特に４ｂは対電極または係数電極という。そして、電極４ａは、定電位を付与するポテンショスタットまたは定電流を付与するガルバノスタットと接続され、一方と電極４ｂは、定電位を付与するポテンショスタットと接続されている。なお、５ａ，５ｂは、対電極４ａ，４ｂで発生するガス等の影響を除去するための焼結ガラスフリットである。
The electrochemical hydrogen permeation method is a technique developed by Devanathan and Stachurski in 1962 (Non-Patent Document 5). As schematically shown in FIG. 1, two electrolytic cells 1a and 1b are formed of one sample 2 It is arranged facing each other across. In the case of the figure, the sample surface of the left electrolytic cell 1a is cathode-polarized at a constant potential or a constant current to generate hydrogen and charge, and the right electrolytic cell 1b is subjected to constant-potential anodic polarization. The hydrogen permeated through 2 is oxidized into hydrogen ions, and the amount of permeated hydrogen is determined from the current value.
In the figure, reference numerals 3a and 3b are reference electrodes, 4a and 4b are electrodes, and 4b is particularly referred to as a counter electrode or a coefficient electrode. The electrode 4a is connected to a potentiostat for applying a constant potential or a galvanostat for applying a constant current, and one of the electrodes 4b is connected to a potentiostat for applying a constant potential. Reference numerals 5a and 5b denote sintered glass frits for removing the influence of gas and the like generated at the counter electrodes 4a and 4b.
上記した電気化学的水素透過法そのものは、「鋼板中の水素拡散係数の測定手法」として従来から良く知られた手法である。
本来の電気化学的水素透過法は、図１に示したように、試料の片面側を陰極にして水素を電解チャージし、反対面側を陽極にして引き抜く手法であるが、これを応用して、水素チャージ面側に相当する面を腐食環境に曝すという研究が報告されている（前掲非特許文献３）。
しかしながら、非特許文献３に開示された測定方法では、温度の変化による測定電流値の変化が考慮されていないという問題があったことは、前述したとおりである。また、電気化学的水素透過法によって水素検出面側で測定されるアノード電流には、水素の酸化電流の他に、供試材の不動態保持電流が重畳されている。この不動態保持電流は、残余電流の主体をなすもので、様々な因子に影響されるが、特に温度による変化が大きい。
The above-described electrochemical hydrogen permeation method itself is a method that has been well known as “a method for measuring a hydrogen diffusion coefficient in a steel sheet”.
As shown in FIG. 1, the original electrochemical hydrogen permeation method is a method in which hydrogen is electrolytically charged with one side of the sample as a cathode and extracted with the opposite side as an anode. A study has been reported in which the surface corresponding to the hydrogen charge surface is exposed to a corrosive environment (Non-Patent Document 3).
However, as described above, the measurement method disclosed in Non-Patent Document 3 has a problem that a change in the measurement current value due to a change in temperature is not taken into consideration. In addition to the hydrogen oxidation current, the anode holding current measured on the hydrogen detection surface side by the electrochemical hydrogen permeation method is superimposed with the passive holding current of the test material. This passive holding current is the main component of the residual current, and is influenced by various factors, but it varies greatly with temperature.
電気化学的水素透過法によって水素検出面側で測定されるアノード電流は微弱な電流であることから、残余電流の温度依存性を補正しないと正確なアノード電流を測定することはできない。 Since the anode current measured on the hydrogen detection surface side by the electrochemical hydrogen permeation method is weak, accurate anode current cannot be measured unless the temperature dependence of the residual current is corrected.
上記の問題を解決するために、本発明者等は、種々検討を重ねた結果、水素検出面側に設ける電気化学セルを、同一の被検体の上に少なくとも２つ以上に分割された複数のセル群で構成し、その内の少なくとも一つのセルについては残余電流を補正するための基準セルとし、かつこの基準セルの水素検出領域に対応する水素侵入面側の領域に、腐食環境を遮断するための保護膜を設けることによって、残余電流の温度依存性の補正を可能としたのである。 In order to solve the above problem, the present inventors have made various studies, and as a result, the electrochemical cell provided on the hydrogen detection surface side is divided into at least two or more divided on the same subject. Consists of cells, and at least one of the cells is used as a reference cell for correcting the residual current, and the corrosive environment is shut off in a region on the hydrogen entry surface side corresponding to the hydrogen detection region of this reference cell. By providing a protective film for this purpose, the temperature dependence of the residual current can be corrected.
図２に、本発明の測定装置の一例を模式的に示す。図２の例は、被検体としての鋼板６の水素検出面側に４つのセル７ａ，７ｂ，７ｃ，７ｄを設け、一番左側のセル７ａを残余電流を補正するための基準セルとした場合である。図中、符号８が対極（Pt線）、９が参照電極（Ir線）である。なお、本発明においてセルの個数は少なくとも２個あれば良く、またあまりにセル数が多いと取り扱いが煩雑になるので、最大4個程度とするのが好ましい。
同図において、各セルにおける鋼板の表面温度、セル内の電解質溶液の温度等はすべて同じ温度とする。また、基準セル７ａの水素侵入面側には保護膜10が設けられている。このような保護膜10で被覆された部分は腐食せず、従って水素侵入も起こらないことから、基準セルの水素検出面側で測定される電流は残余電流そのものと考えられる。
FIG. 2 schematically shows an example of the measuring apparatus of the present invention. In the example of FIG. 2, four cells 7a, 7b, 7c, 7d are provided on the hydrogen detection surface side of a steel plate 6 as an object, and the leftmost cell 7a is used as a reference cell for correcting the residual current. It is. In the figure, reference numeral 8 is a counter electrode (Pt line), and 9 is a reference electrode (Ir line). In the present invention, it is sufficient that the number of cells is at least two, and if the number of cells is too large, handling becomes complicated.
In the figure, the surface temperature of the steel plate in each cell, the temperature of the electrolyte solution in the cell, etc. are all the same temperature. A protective film 10 is provided on the hydrogen entry surface side of the reference cell 7a. Since the portion covered with such a protective film 10 does not corrode and therefore does not enter hydrogen, the current measured on the hydrogen detection surface side of the reference cell is considered as the residual current itself.
図３に、保護膜の無いセル（チャンネルともいう）の腐食面（水素侵入面）側および水素検出面側での反応を模式的に示す。
水素検出面側の表面電位を水素のイオン化反応に十分な電位に保持することで、拡散によって検出面側に到達した水素はすべて水素イオンとして取り出される。なお、本発明において、水素検出面側の鋼板の表面は不動態化されている。これにより、水素検出側で検出されるアノード電流が実質的に水素透過電流に相当すると考えることができる。
従って、かくして得られた電流値を、基準セルて求めた残余電流値で補正することにより、温度変化に伴う残余電流の変化にかかわらず、正確なアノード電流値を計測することができ、その結果、このアノード電流値に基づいて正確な侵入水素量を算出することが可能になるのである。
FIG. 3 schematically shows reactions on the corroded surface (hydrogen intrusion surface) side and the hydrogen detection surface side of a cell (also referred to as a channel) without a protective film.
By maintaining the surface potential on the hydrogen detection surface side at a potential sufficient for the ionization reaction of hydrogen, all the hydrogen that has reached the detection surface side by diffusion is taken out as hydrogen ions. In the present invention, the surface of the steel plate on the hydrogen detection surface side is passivated. Thereby, it can be considered that the anode current detected on the hydrogen detection side substantially corresponds to the hydrogen permeation current.
Therefore, by correcting the current value thus obtained with the residual current value obtained from the reference cell, an accurate anode current value can be measured regardless of the change in the residual current due to the temperature change. Thus, it is possible to calculate an accurate intrusion hydrogen amount based on the anode current value.
本発明において、水素検出面側の鋼板を不動態の状態に保持するためには、アノード極室内の溶液はpH：９〜13の電解質溶液とすることが必要である。というのは、ｐHが９未 満では所定の電位において鋼板の表面の不動態を保持することが困難であり、一方、pHが13を超えると、不慮の事故により漏洩した場合に、環境へのダメージが大きいからである。適正なpHの電解質溶液としては、0.1〜0.2M（モル／リットル）程度のNaOH水溶液が好適である。なお、本発明では、適正なpHの電解質溶液として、必ずしも0.1〜0.2MのNaOH 水溶液に限定されるわけではなく、水素検出面の鋼板表面を水素のイオン化反応に十分な電位に保持する際に、鋼板の表面の不動態化状態を確保できる電解質溶液であればいずれでも良い。さらに、電解質溶液に代えて、ゲル状の電解質を用いることは、液漏れの防止だけでなく、取り扱いの容易さからも有利である。 In the present invention, in order to keep the steel plate on the hydrogen detection surface side in a passive state, the solution in the anode electrode chamber needs to be an electrolyte solution having a pH of 9 to 13. This is because if the pH is less than 9, it is difficult to maintain the passivation of the surface of the steel sheet at a predetermined potential. On the other hand, if the pH exceeds 13, if it is accidentally leaked, This is because the damage is great. As an electrolyte solution having an appropriate pH, an aqueous NaOH solution of about 0.1 to 0.2 M (mol / liter) is suitable. In the present invention, the electrolyte solution having an appropriate pH is not necessarily limited to a 0.1 to 0.2M NaOH aqueous solution, but when the steel plate surface of the hydrogen detection surface is maintained at a potential sufficient for the ionization reaction of hydrogen. Any electrolyte solution can be used as long as it can ensure a passivated state of the surface of the steel sheet. Furthermore, using a gel electrolyte instead of the electrolyte solution is advantageous not only for preventing liquid leakage but also for ease of handling.
また、本発明において、水素検出面の電位は、常時、−0.1〜＋0.3V vs SCEに保持しておく必要がある。というのは、水素検出面の電位がこの範囲を外れると、安定した水素のイオン化電流を得ることができなくなるからである。
ここで、SCEは、飽和カロメル電極のことであり、このSCEの標準水素電極（SHE）に対 する電位は＋0.244 V（vs SHE，25℃）で示される。
In the present invention, the potential of the hydrogen detection surface must be kept at −0.1 to +0.3 V vs. SCE at all times. This is because if the potential of the hydrogen detection surface is out of this range, a stable hydrogen ionization current cannot be obtained.
Here, SCE is a saturated calomel electrode, and the potential with respect to the standard hydrogen electrode (SHE) of this SCE is indicated as +0.244 V (vs SHE, 25 ° C.).
なお、電位を制御するための参照電極としては、現在実用化されている各種電極が使用可能である。
ただし、Ag/AgCl電極のような塩化物を含む電極を用いる場合、アノード極室溶液中へ の塩化物イオンによる汚染によって、サンプル表面の不動態が破壊されて残余電流が大きくなり、測定値が不正確になるおそれがある。
In addition, as the reference electrode for controlling the potential, various electrodes that are currently in practical use can be used.
However, when using an electrode containing chloride such as an Ag / AgCl electrode, contamination of the anode electrode chamber solution with chloride ions destroys the passivation of the sample surface, increasing the residual current, resulting in a measured value. May be inaccurate.
そこで、上記のような問題を回避できる参照電極について種々検討した結果、アノード極室溶液中にIr線を浸漬することでIr/Ir酸化物電極となり、長期間安定な電位が得られ ることが解明された。すなわち、参照電極として最も好適な電極はIr/Ir酸化物電極であ り、−0.04 vs SSE程度の電位を安定して得ることができる。
ここで、SSEは、銀−塩化銀電極のことであり、このSSEの標準水素電極（SHE）に対する電位は＋0.199 V（vs SHE，25℃）で示される。
Therefore, as a result of various studies on a reference electrode that can avoid the above problems, it is possible to obtain an Ir / Ir oxide electrode by immersing Ir wire in an anode electrode chamber solution, and a stable potential can be obtained for a long time. It was elucidated. That is, the most suitable electrode as a reference electrode is an Ir / Ir oxide electrode, and a potential of about −0.04 vs SSE can be stably obtained.
Here, SSE is a silver-silver chloride electrode, and the potential of this SSE with respect to a standard hydrogen electrode (SHE) is represented by +0.199 V (vs SHE, 25 ° C.).
また、本発明において、水素検出面の表面は、水素拡散定数が大きく、かつ水素の酸化反応を促進させるような金属で被覆することが好ましく、かような金属としては、PdやPd合金、Niなどが挙げられる。これらの金属または合金を被覆することによって、水素検出面の残余電流を低い値に保持することが可能となるだけでなく、水素検出面側での侵入水素の酸化反応が促進されるので、水素のイオン化によるアノード電流の感度を高めることができる。なお、Pdは、Niに比べると、水素拡散定数が大きく、また残余電流を低減できるという利点がある。 In the present invention, the surface of the hydrogen detection surface is preferably coated with a metal having a large hydrogen diffusion constant and promoting the oxidation reaction of hydrogen. Examples of such a metal include Pd, Pd alloy, Ni Etc. By coating these metals or alloys, it is possible not only to keep the residual current of the hydrogen detection surface at a low value, but also to promote the oxidation reaction of the intruding hydrogen on the hydrogen detection surface side. The sensitivity of the anode current due to ionization of can be increased. Note that Pd has an advantage that the hydrogen diffusion constant is large and the residual current can be reduced compared to Ni.
PdやPd合金で被覆する場合は、[Pd(NH3)4]Cl2・H2O等のパラジウムイオンを含有する水溶液中で陰極電解することで、めっきを行えばよい。Pd合金としては、Pd−NiやPd−Co合金などが使用可能である。ここに、PdめっきまたはPd合金めっきの膜厚は10〜100nmとす ることが好ましい。
また、Niで被覆する場合は、ワット浴等の既う知のめっき浴中で陰極電解することで、Niめっきを行えばよい。Niめっきの膜厚も10〜100nmにすることが好ましい。
さらに、Niめっきの上に、PdやPd合金をめっきすることもできる。
When coating with Pd or a Pd alloy, plating may be performed by cathodic electrolysis in an aqueous solution containing palladium ions such as [Pd (NH 3 ) 4 ] Cl 2 .H 2 O. As the Pd alloy, Pd—Ni, Pd—Co alloy or the like can be used. Here, the film thickness of Pd plating or Pd alloy plating is preferably 10 to 100 nm.
In the case of covering with Ni, Ni plating may be performed by cathodic electrolysis in a known plating bath such as a Watt bath. The thickness of the Ni plating is preferably 10 to 100 nm.
Further, Pd or a Pd alloy can be plated on the Ni plating.
水素侵入面に設ける保護膜については、特に制限はなく、腐食環境を遮断できるものであればいずれでもよい。具体的手段としては、有機物系の接着剤等を介したステンレス箔の貼着が挙げられる。 The protective film provided on the hydrogen entry surface is not particularly limited, and any protective film can be used as long as it can block the corrosive environment. Specific examples include attaching stainless steel foil via an organic adhesive or the like.
上記したように、本発明では、温度変化などの環境の変化の如何にかかわらず、腐食に伴って金属の内部へ侵入する水素量を正確に検出することができる。
従って、本発明の測定装置を、自動車、船舶、鉄道車両などの移動体に取り付ければ、移動体を構成する金属材料の各部位が、その使用状態で曝される環境の変化に左右されることなく、金属材料中に侵入する水素量を連続的かつ正確にモニタリングすることができる。
その結果、各種移動体にについて、それらの実際の使用環境での腐食に伴う水素侵入量で遅れ破壊が生じるか否かを的確に判断することが可能となる。
As described above, according to the present invention, it is possible to accurately detect the amount of hydrogen that enters the interior of the metal due to corrosion regardless of environmental changes such as temperature changes.
Therefore, if the measuring device of the present invention is attached to a moving body such as an automobile, a ship, and a railway vehicle, each part of the metal material constituting the moving body is affected by changes in the environment exposed in the usage state. In addition, the amount of hydrogen penetrating into the metal material can be continuously and accurately monitored.
As a result, it is possible to accurately determine whether or not various types of moving bodies are delayed and destroyed by the amount of hydrogen intrusion due to corrosion in their actual use environment.
ところが、本発明装置を用いて種々の検討を繰り返している中、冬季腐食環境をシミュレートした条件下において、セル内部から溶液が漏出する場合があることが判明した。
そこで、上記した溶液漏出の原因について調査した結果、低温時に内部溶液が凍結し、溶液が膨張することによって、セルが破損するためであることが明らかとなった。
本発明の特徴である移動体の金属部位内部へ侵入する水素量を正確にモニタリングするためには、冬季走行においても安定した正確な侵入水素量の測定が必要である。
However, while various studies were repeated using the apparatus of the present invention, it was found that the solution might leak from the inside of the cell under the conditions simulating the winter corrosive environment.
Therefore, as a result of investigating the cause of the above-described solution leakage, it has been clarified that the cell is damaged when the internal solution is frozen and the solution expands at a low temperature.
In order to accurately monitor the amount of hydrogen penetrating into the metal part of the moving body, which is a feature of the present invention, it is necessary to measure the amount of penetrating hydrogen stably and accurately even during winter driving.
そこで、発明者らは、冬季においても内部溶液の凍結に起因したセルの破損なしに、金属内部に腐食を伴って侵入する水素量を安定して測定可能な装置について検討した。
一般的な市街地における走行環境下においては、移動体の発熱を考慮するとセル内部の電解液が−５℃以下になることは少ないと考えられるため、電解液の凝固点温度を−５℃以下にすれば良いと考えられる。
In view of this, the inventors examined an apparatus that can stably measure the amount of hydrogen that penetrates into a metal with corrosion without damaging the cell due to freezing of the internal solution even in winter.
In the driving environment in a general urban area, it is considered that the electrolyte solution inside the cell is less than −5 ° C. considering the heat generated by the moving body. I think it would be good.
そこで、電解液の凝固点温度を−５℃以下にする手法について検討した結果、電解質水溶液中に、凝固点降下に有効な有機化合物を添加すればよいことが究明された。
そして，かかる有機化合物としては、特に制限はされないものの、イソプロピルアルコールやグリセリン、エチレングリコールなどが特に好適であることが判明した。さらに、電気化学的活性の低い極性溶媒であるジメチルスルフォキシド（DMSO）やジメチルフォルモアミド（DMFA）なども有利に適合することが判明した。
ここに、かような有機化合物の好適な添加割合は、５〜３０体積％程度である。また、添加量を増加するに従って凝固点はより降下する。
これらの有機化合物は、ウィンドウォッシャー液等にも充填されている有機化合物類であり、万が一漏出した場合においても環境への悪影響はほとんどない。
Therefore, as a result of studying a technique for setting the freezing point temperature of the electrolytic solution to −5 ° C. or lower, it has been found that an organic compound effective for lowering the freezing point may be added to the aqueous electrolyte solution.
And as such an organic compound, although it does not restrict | limit in particular, it turned out that isopropyl alcohol, glycerol, ethylene glycol, etc. are especially suitable. Furthermore, dimethyl sulfoxide (DMSO) and dimethylformamide (DMFA), which are polar solvents with low electrochemical activity, have been found to be advantageously compatible.
Here, the suitable addition rate of such an organic compound is about 5-30 volume%. Moreover, the freezing point is further lowered as the addition amount is increased.
These organic compounds are organic compounds filled in a window washer liquid or the like, and even if they leak, there is almost no adverse effect on the environment.
さらに、セル内部に気泡を配することで、想定を超える低温環境にセルが曝されて電解液が凝固し、電解液の体積膨張が起こった場合においても、気泡が収縮することでセル本体へのダメージを軽減できることが判明した。しかしながら、このような場合において、気泡が水素検出面に接すると、侵入水素量の検出感度が下がり、本発明の本質的な意義が損なわれるため、気泡は水素検出面に接しない位置に配置することが重要である。
気泡を水素検出面に接しないように配する方法については、特に限定はされないが、例えばセル内部に気泡を入れた袋状の物を配しても良いし、図４及び図５のようなセルの内部構造とすればよい。図４，５中、符号11が気泡、12が電解液であり、13でＯリングを示す。
なお、気泡の量は特に規定されないが、水の凝固における体積膨張を考慮すると、体積率で溶液の５〜15％程度とすることが好ましい。気泡に酸素が存在する場合、水素検出面のアノード反応に影響を与える為、気泡の種類は不活性ガスが好ましい。
Furthermore, by arranging bubbles inside the cell, the cell is exposed to a low-temperature environment that exceeds expectations and the electrolyte is solidified, and even when volume expansion of the electrolyte occurs, the bubble shrinks to the cell body. It was found that the damage of can be reduced. However, in such a case, if the bubble comes into contact with the hydrogen detection surface, the detection sensitivity of the amount of invading hydrogen decreases, and the essential significance of the present invention is impaired. Therefore, the bubble is arranged at a position where it does not contact the hydrogen detection surface. This is very important.
The method of arranging the bubbles so as not to contact the hydrogen detection surface is not particularly limited. For example, a bag-like object containing bubbles may be arranged inside the cell, as shown in FIGS. 4 and 5. The internal structure of the cell may be used. 4 and 5, reference numeral 11 denotes bubbles, 12 denotes an electrolytic solution, and 13 denotes an O-ring.
The amount of bubbles is not particularly defined, but considering volume expansion in coagulation of water, it is preferable that the volume ratio be about 5 to 15% of the solution. In the case where oxygen is present in the bubbles, the anodic reaction on the hydrogen detection surface is affected.
実施例１
実験は、図２に示した構造になるセル数４個（CH１〜４）の測定装置を用いて行った。被検体としては、水素検出面側にPdを厚み：100nmでめっきした板厚：1.0mmの軟鋼板を用いた。基準セルはチャンネル３（CH３）であり、このCH３の腐食面側に対応する箇所には保護膜としてステンレス箔を貼着した。各セルの腐食面側の表面に0.5M NaClを300mL 滴 下、ついで25℃,35%RH（相対湿度）で４時間以上乾燥したのち、25℃,85％RH（相対湿度 ）に24時間以上保持し、その後、段階的に温度を上昇させた。水素検出面の電位は０V vs SCEに保持した。この時の温度変化および湿度変化を図６に示す。
Example 1
The experiment was performed using a measuring device having four cells (CH1 to CH4) having the structure shown in FIG. As a test object, a mild steel plate having a thickness of 1.0 mm plated with Pd at a thickness of 100 nm on the hydrogen detection surface side was used. The reference cell was channel 3 (CH3), and a stainless steel foil was attached as a protective film to the portion corresponding to the corroded surface side of CH3. Drop 300 mL of 0.5M NaCl on the corrosive surface of each cell, then dry it at 25 ° C and 35% RH (relative humidity) for 4 hours or more, then at 25 ° C and 85% RH (relative humidity) for 24 hours or more The temperature was maintained, and then the temperature was increased stepwise. The potential of the hydrogen detection surface was kept at 0 V vs SCE. The temperature change and humidity change at this time are shown in FIG.
図６に示した温度変化に対応して、各チャンネルで検出されたアノード電流密度の変化を図７に示す。
本来、鋼板表面で腐食の起こっていない基準電極（CH３）のアノード電流密度値も、温度の上昇に伴って上昇していることが分かる。これは、水素検出面側のPdの酸化電流による残余電流が温度の上昇により増加したためと考えられる。このように、残余電流の温度依存性は、無視できないレベルである。
FIG. 7 shows changes in the anode current density detected in each channel corresponding to the temperature changes shown in FIG.
It can be seen that the anode current density value of the reference electrode (CH3), which does not inherently corrode on the steel plate surface, also increases as the temperature increases. This is presumably because the residual current due to the oxidation current of Pd on the hydrogen detection surface side increased due to the temperature rise. Thus, the temperature dependence of the residual current is a level that cannot be ignored.
実験後のサンプルの腐食面側の外観写真を図８に示す。
４Chのアノード電流密度値が他のChに比べて小さかったのは、最初に滴下した0.2M NaClの位置がずれていたために、検出面に対応する水素侵入面側の腐食面積が小さかったた めである。
An appearance photograph of the corroded surface side of the sample after the experiment is shown in FIG.
The reason why the anode current density value of 4Ch was smaller than that of other Ch was that the corrosion area on the hydrogen entry surface side corresponding to the detection surface was small because the position of 0.2M NaCl dropped first was shifted. is there.
従って、CH１およびCH２で得られたアノード電流密度値から、基準電極（CH３）のアノード電流密度値をそれぞれ差し引けば、各セル（CH１，CH２）における正確な透過水素電流密度値を得ることができ、さらにこれらの値を平均することにより、被検体鋼板の透過水素電流密度値を求めることができる。
そして、上記のようにして求めた透過水素電流密度値から、次式により、透過水素量（侵入水素量）を算出する。
かくして、温度変化の如何にかかわらず、正確な透過水素電流値ひいては透過水素量（侵入水素量）を検出することができる。
Therefore, by subtracting the anode current density value of the reference electrode (CH3) from the anode current density values obtained for CH1 and CH2, it is possible to obtain an accurate permeated hydrogen current density value in each cell (CH1, CH2). Further, by averaging these values, the permeated hydrogen current density value of the specimen steel plate can be obtained.
Then, the permeated hydrogen amount (intrusion hydrogen amount) is calculated from the permeated hydrogen current density value obtained as described above by the following equation.
Thus, it is possible to detect an accurate permeated hydrogen current value and thus a permeated hydrogen amount (intruded hydrogen amount) regardless of the temperature change.
透過水素量の換算は以下の式に従う。
透過水素電流密度 ｉH （mA/cm2＝10-6A/cm2）
単位面積当たりの透過水素量 ＭH（mol／scm2），ｍH（個／scm2）
ＭH ＝ ｉH × 1.036×10-11 （mol／scm2），
ｍH ＝ ｉH × 6.24×1012 （個／scm2）
The permeated hydrogen amount is converted according to the following formula.
Permeated hydrogen current density i H (mA / cm 2 = 10 -6 A / cm 2 )
Permeated hydrogen per unit area MH (mol / scm 2 ), m H (pieces / scm 2 )
M H = i H × 1.036 × 10 -11 (mol / scm 2 ),
m H = i H x 6.24 x 10 12 (pieces / scm 2 )
実施例２
実施例１で用いた測定装置を、実際に自動車に搭載し、図９に模式的に示す計測システムを構築した。４チャンネルセルの設置箇所は、ａ）フェンダー、ｂ）室内、ｃ）床下（フロア下面）の３箇所とした。バッテリー駆動のマルチチャンネルポテンショスタットを作成し、専用バッテリーと一緒にトランク内に収納した。供試材は、実施例１と同じ板厚：1.0mmの軟鋼板とし、月曜日から金曜日までの５日間、毎日、9：00〜15：00の６時間にわたって製鉄所の構内を平均時速：40km/hで走行する。なお、15：00から翌日の9：00 までは駐車場に停車する。
Example 2
The measurement apparatus used in Example 1 was actually mounted on an automobile, and a measurement system schematically shown in FIG. 9 was constructed. Four channel cells were installed at three locations: a) a fender, b) a room, and c) under the floor (floor lower surface). A battery-powered multichannel potentiostat was created and housed in the trunk along with a dedicated battery. The test material is the same steel plate thickness of 1.0 mm as in Example 1, and the average speed of 40 km in the premises of the steel works for 6 hours from 9:00 to 15:00 every day for 5 days from Monday to Friday. Drive at / h. In addition, it will stop at the parking lot from 15:00 to 9:00 the next day.
この間に検出されたアノード電流密度の最大値について、基準電極による補正を行ったものを発明例とし、補正を行わなかったものを比較例として、図10に比較して示す。
試験片をセットしてから初期の５日間で、各部位での腐食はまだほとんど起きておらず、図10に示したとおり、発明例のアノード電流密度は設置部位による違いは見られなかった。これに対し、比較例では、設置部位によるアノード電流密度の違いが見られた。この違いは、設置部位により、昼間の日照で温度が上昇した部位（フェンダー）と、あまり温度が上昇しなかった（床下）部位の違いと考えられる。
実測されたアノード電流密度値について、本発明に従い、基準電極による補正を行うことにより、温度変化の影響を受けることなしに正確なアノード電流密度値（透過水素電流密度値）が得られることが分かる。
The maximum value of the anode current density detected during this period is shown as an invention example in which correction by the reference electrode is performed, and as a comparative example in which correction is not performed, it is shown in comparison with FIG.
In the first 5 days after setting the test piece, corrosion at each site has hardly occurred, and as shown in FIG. 10, the anode current density of the invention example did not differ depending on the installation site. On the other hand, in the comparative example, a difference in anode current density depending on the installation site was observed. This difference is considered to be the difference between the site where the temperature rose due to daylight (fender) and the site where the temperature did not rise much (under the floor) depending on the installation site.
It can be seen that an accurate anode current density value (permeated hydrogen current density value) can be obtained without being affected by a temperature change by correcting the measured anode current density value by the reference electrode according to the present invention. .
実施例３
使用した鋼板は商用の軟鋼板（厚さ：0.8mm）を用い、40×50mmにせん断加工を行い、両面を♯2000まで研磨した。ついで、研磨時に形成される加工層を除去するために両面を弗酸と過酸化水素水の混合液からなる水溶液により約60μm 化学研磨を行った。
（水素検出面へのめっき）
水素検出面に商用のＫ−ピュアパラジウムめっき液（小島化学社製）を用いて約100mmのPdめっきを行った。
（セル内の電解質水溶液）
電解質水溶液として、0.1Ｎの水酸化ナトリウム水溶液にジメチルスルフォキシド（DMSO）を種々の比率で添加したものを用い、各場合における凝固点を測定した。
（検出面側のセルの構成）
図11に示す２個のセルを有する構造のものを用い、７ａ，７ｂにあたる部位の構造を以下のように変更した。
構造Ａ：図５に示す構造で、気泡を含まず、電解液を充填した。
構造Ｂ：図５に示す構造とし、気泡量は電解水溶液体積の15vol％とし、気泡は窒素を封入した。
Example 3
The steel plate used was a commercial mild steel plate (thickness: 0.8 mm), sheared to 40 x 50 mm, and polished on both sides to # 2000. Next, in order to remove the processed layer formed at the time of polishing, about 60 μm of chemical polishing was performed on both sides with an aqueous solution composed of a mixture of hydrofluoric acid and hydrogen peroxide.
(Plating on the hydrogen detection surface)
About 100 mm of Pd plating was performed on the hydrogen detection surface using a commercial K-pure palladium plating solution (manufactured by Kojima Chemical Co., Ltd.).
(Aqueous electrolyte solution in the cell)
As the electrolyte aqueous solution, 0.1N sodium hydroxide aqueous solution added with dimethyl sulfoxide (DMSO) at various ratios was used, and the freezing point in each case was measured.
(Configuration of cells on the detection surface side)
A structure having two cells shown in FIG. 11 was used, and the structure of the portion corresponding to 7a and 7b was changed as follows.
Structure A: The structure shown in FIG. 5 was filled with electrolyte without containing bubbles.
Structure B: The structure shown in FIG. 5 was used, the amount of bubbles was 15 vol% of the electrolytic aqueous solution volume, and the bubbles were sealed with nitrogen.
以上の構造になるセルに、図11に示すように鋼板を設置した。参照電極はIr/IrOX電極、対極にはPt線を配して電位を０Ｖに設定してセルを腐食環境に配置した。
セルの１つのチャンネル上にはエポキシ系樹脂及びステンレス箔を配することで温度変化を補正するために腐食をしないセルを設置した。
以上のセルを、商用の乗用車に搭載し、製鉄所内を2011年１月18日から２月２日まで15日間走行した。気象庁ＨＰより期間中の最低気温変化を図12に示す。なお、凍結による内容液漏出を防ぐため、腐食される鋼板面以外を袋で覆った上で走行を行った。
In the cell having the above structure, a steel plate was installed as shown in FIG. The reference electrode was an Ir / IrO X electrode, the Pt line was placed on the counter electrode, the potential was set to 0 V, and the cell was placed in a corrosive environment.
A cell that does not corrode was installed on one channel of the cell in order to correct the temperature change by arranging an epoxy resin and a stainless steel foil.
The above cells were installed in a commercial passenger car and ran for 15 days from January 18 to February 2 in the steelworks. Figure 12 shows the minimum temperature change during the period from the Japan Meteorological Agency HP. In addition, in order to prevent the leakage of the content liquid due to freezing, the vehicle was run after covering with a bag other than the corroded steel plate surface.
期間中にセル破損又は電解溶液の漏出が認められた日付を表１に示す。また期間毎に得られた電流密度の最大値、及び本発明に従って補正した後の電流密度の最大値を表１に併せて示す。
さらに、期間終了後、No.２及びNo.４のセルを実験室に設置している−20℃の冷凍試験機内に放置し、セルの破損状態について調べた結果も、表１に併記する。
Table 1 shows the date when cell breakage or leakage of electrolyte solution was observed during the period. Table 1 also shows the maximum value of current density obtained for each period and the maximum value of current density after correction according to the present invention.
In addition, Table 1 also shows the results of examining the damaged state of the cells by leaving the No. 2 and No. 4 cells in the -20 ° C. refrigeration tester installed in the laboratory after the period.
表１の結果から以下のことが明らかとなった。
No.１は、電解液に水酸化ナトリウム水溶液のみの比較例であるが、１月27日にセルの破損による電解液の漏出が認められたものの、発明例であるNo.２〜No.４にはセルの破損は認められなかった。
また、期間１においては、鋼板表面にほとんど腐食した形跡は認められなかったため、腐食による鋼板への水素侵入はなく、電流値は検出されないはずであるが、温度補正を行わない場合、比較的大きな電流値が検出されていることが分かる。これは上述したとおり、気温変化による残余電流変化と考えられ、発明例による温度補正を行うことで、温度変化を除去できていることが分かる。
さらに、ジメチルスルフォキシド（DMSO）を添加したNo.２〜No.４と、添加していないNo.１を比較すると、その電流値に差異は認められないことから、ジメチルスルフォキシド（DMSO）を添加することによる精度への影響はないことが分かる。
次に、期間２及び期間３においては、路面水上を走行したため、鋼板の腐食が認められ、それに対応する電流密度の増加が認められたが、腐食に伴い発生し鋼板中に侵入する水素量をモニタリングできていることが分かる。
さらに、−20℃の低温環境に保持した場合、セルNo.２には破損が認められた。一方、内部に気泡を配したセルNo.４の場合には凍結は認められたもののセルの破損は認められなかった。このことから、想定を超える気温変化に対してもセル内部に気泡を配することによって、破損を抑制できることが確認された。
From the results in Table 1, the following became clear.
No. 1 is a comparative example in which only an aqueous sodium hydroxide solution is used as the electrolyte solution, but leakage of the electrolyte solution due to cell breakage was observed on January 27, but No. 2 to No. 4 which are invention examples. The cell was not damaged.
Moreover, in period 1, since there was almost no evidence of corrosion on the steel sheet surface, there was no hydrogen intrusion into the steel sheet due to corrosion and no current value should be detected, but when temperature correction is not performed, it is relatively large. It can be seen that the current value is detected. As described above, this is considered to be a change in residual current due to a change in temperature, and it can be seen that the temperature change can be removed by performing the temperature correction according to the invention example.
Furthermore, when No. 2 to No. 4 to which dimethyl sulfoxide (DMSO) was added and No. 1 to which dimethyl sulfoxide (DMSO) was not added were compared, there was no difference in the current value. Therefore, dimethyl sulfoxide (DMSO) It can be seen that there is no influence on the accuracy by adding).
Next, in period 2 and period 3, since the steel sheet ran on the road surface, corrosion of the steel sheet was observed, and a corresponding increase in current density was observed. However, the amount of hydrogen generated by corrosion and penetrating into the steel sheet was reduced. It can be seen that monitoring is possible.
Furthermore, the cell No. 2 was found to be damaged when kept in a low temperature environment of −20 ° C. On the other hand, in the case of cell No. 4 in which bubbles were arranged inside, the cell was not damaged although freezing was observed. From this, it was confirmed that damage can be suppressed by disposing air bubbles inside the cell even when the temperature changes beyond expectations.
本発明により、環境が絶え間なく変化する移動体について、それを構成する金属材料の各部位が使用状態で曝される腐食環境下での腐食に伴い発生し、金属材料中に侵入する水素の量を、連続的かつ正確にモニタリングすることが可能となる。 According to the present invention, the amount of hydrogen generated by corrosion in a corrosive environment in which each part of the metal material constituting the moving body whose environment changes continuously is exposed in use and enters the metal material. Can be continuously and accurately monitored.
１ 電解槽
２ 試料
３ 参照電極
４ 電極
４ｂ 対電極
５ 焼結ガラスフリット
６ 被検体（鋼板）
７ セル
７ａ 基準セル
８ 対極
９ 参照電極
10 保護膜
11 気泡
12 電解液
13 Ｏリング
DESCRIPTION OF SYMBOLS 1 Electrolysis tank 2 Sample 3 Reference electrode 4 Electrode 4b Counter electrode 5 Sintered glass frit 6 Test object (steel plate)
7 cell 7a reference cell 8 counter electrode 9 reference electrode
10 Protective film
11 bubbles
12 Electrolyte
13 O-ring
Claims (5)
該被検体の一方の面を腐食環境に暴露し腐食反応により発生する水素の侵入面、他方の面を水素検出面とするとき、
該水素検出面側に、複数のセル群で構成された電気化学セルを設け、該セル群の個々のセルの内部にpHが９〜13の電解質水溶液を充填すると共に、それぞれ独立した参照電極と対極を設置し、
前記電解質水溶液中に、凍結防止のために有機化合物を添加し、
該セル群のうち少なくとも一つのセルを残余電流を補正するための基準セルとし、該基準セルの水素検出領域に対応する水素侵入面側の領域に、腐食環境との接触を遮断するための保護膜を設け、
該被検体の水素侵入面のうち、該基準セル以外のセルに対応する箇所には、該金属材料が直接腐食環境に暴露するよう保護膜を設けず、
該基準セル以外のセルで検出したアノード電流値を、該基準セルで検出した残余電流値により補正し、この補正したアノード電流値に基づいて腐食面側からの侵入水素量を算出することを特徴とする金属内部への侵入水素量の測定装置。 An apparatus for measuring the amount of hydrogen generated by corrosion of an object made of a metal material and entering the metal using an electrochemical hydrogen permeation method,
When one surface of the specimen is exposed to a corrosive environment and a hydrogen intrusion surface generated by a corrosion reaction, and the other surface is a hydrogen detection surface,
An electrochemical cell composed of a plurality of cell groups is provided on the hydrogen detection surface side, and each cell of the cell group is filled with an electrolyte aqueous solution having a pH of 9 to 13, and an independent reference electrode and Install a counter electrode,
In the electrolyte aqueous solution, an organic compound is added to prevent freezing,
Protection for blocking contact with the corrosive environment in a region on the hydrogen intrusion surface side corresponding to the hydrogen detection region of the reference cell, with at least one cell of the cell group serving as a reference cell for correcting the residual current Providing a membrane,
Of the hydrogen intrusion surface of the specimen, a portion corresponding to a cell other than the reference cell is not provided with a protective film so that the metal material is directly exposed to a corrosive environment,
An anode current value detected in a cell other than the reference cell is corrected by a residual current value detected in the reference cell, and an intrusion hydrogen amount from the corroded surface side is calculated based on the corrected anode current value. A device for measuring the amount of hydrogen penetrating into a metal.
該被検体の一方の面を腐食環境に暴露し腐食反応により発生する水素の侵入面、他方の面を水素検出面とするとき、 When one surface of the specimen is exposed to a corrosive environment and a hydrogen intrusion surface generated by a corrosion reaction, and the other surface is a hydrogen detection surface,
該水素検出面側に、複数のセル群で構成された電気化学セルを設け、該セル群の個々のセルの内部にpHが９〜13の電解質水溶液を充填すると共に、それぞれ独立した参照電極と対極を設置し、 An electrochemical cell composed of a plurality of cell groups is provided on the hydrogen detection surface side, and each cell of the cell group is filled with an electrolyte aqueous solution having a pH of 9 to 13, and an independent reference electrode and Install a counter electrode,
前記電解質水溶液を充填した電気化学セルの内部に、水素検出面との接触を避けて、気泡を配置し、 Inside the electrochemical cell filled with the aqueous electrolyte solution, avoiding contact with the hydrogen detection surface, placing bubbles,
該セル群のうち少なくとも一つのセルを残余電流を補正するための基準セルとし、該基準セルの水素検出領域に対応する水素侵入面側の領域に、腐食環境との接触を遮断するための保護膜を設け、 Protection for blocking contact with the corrosive environment in a region on the hydrogen intrusion surface side corresponding to the hydrogen detection region of the reference cell, with at least one cell of the cell group serving as a reference cell for correcting the residual current Providing a membrane,
該被検体の水素侵入面のうち、該基準セル以外のセルに対応する箇所には、該金属材料が直接腐食環境に暴露するよう保護膜を設けず、 Of the hydrogen intrusion surface of the specimen, a portion corresponding to a cell other than the reference cell is not provided with a protective film so that the metal material is directly exposed to a corrosive environment,
該基準セル以外のセルで検出したアノード電流値を、該基準セルで検出した残余電流値により補正し、この補正したアノード電流値に基づいて腐食面側からの侵入水素量を算出することを特徴とする金属内部への侵入水素量の測定装置。 An anode current value detected in a cell other than the reference cell is corrected by a residual current value detected in the reference cell, and an intrusion hydrogen amount from the corroded surface side is calculated based on the corrected anode current value. A device for measuring the amount of hydrogen penetrating into a metal.
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| CN112630273A (en) * | 2020-12-30 | 2021-04-09 | 核工业西南物理研究院 | Electrochemical hydrogen permeation electrolytic cell in multi-atmosphere environment and application method thereof |
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