JP3577517B2 - Method and apparatus for simultaneous measurement of pH and potential on material surface - Google Patents
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Description
【０００１】
【発明の属する技術分野】
この出願の発明は、材料表面のｐＨおよび電位の同時測定方法とそのための装置に関するものである。さらに詳しくは、この出願の発明は、材料表面の１００μｍ平方以下の微小領域内におけるｐＨおよび電位の同時測定方法とそのための装置に関するものである。
【０００２】
【従来の技術と発明の課題】
金属材料の腐食メカニズムの解明や耐腐食性を決定する要因の特定は、新たな耐腐食性金属の開発に貢献するものと考えられている。腐食の進行と金属材料表面のｐＨや電位分布の間には、関係があることが示唆されており、金属材料表面のｐＨや電位分布を詳細に測定するための装置の開発が、金属材料の腐食メカニズムの解明や耐腐食性を決定する要因の特定には、必須であると考えられている。
【０００３】
従来技術においては、溶液のｐＨを測定するための各種の測定手法が公知であるが、これらの手法は溶液全体のｐＨを測定する技術であり、局所的なｐＨ分布測定を実現するものではない。すなわち、金属材料の腐食メカニズムの解明や耐腐食性を決定する要因の特定を実現するために必要とされるような、材料表面の１００μｍ平方以下の微小領域内におけるｐＨ分布を測定する技術は、これまで開発されてこなかった。また、ｐＨ分布と電位分布とを同時に測定することを可能とする新たな測定手段も、これまで提案されていない。
【０００４】
そこで、この出願の発明は、以上の通りの事情に鑑みてなされたものであり、材料表面の１００μｍ平方以下の微小領域内におけるｐＨ分布および電位分布を同時測定するための新たな測定方法とそのための装置を提供することを課題としている。
【０００５】
【課題を解決するための手段】
この出願の発明は、上記の課題を解決するものとして、第１には、溶液中に設置された試料の表面近傍領域におけるｐＨおよび電位を同時に測定する材料表面のｐＨおよび電位の同時測定方法であって、試料の表面近傍領域に設置される微小電極と試料との間の電圧差Ｖ1と微小電極と溶液中に設置される基準電極との間の電位差Ｖ2とを同時に測定し、測定された電圧差Ｖ2から微小電極と試料との間の領域におけるｐＨを算出し、電圧差Ｖ2−Ｖ1から微小電極近傍領域の局所的な電位を算出することを特徴とする材料表面のｐＨ分布および電位分布の同時測定方法を提供する。
【０００６】
この材料表面のｐＨ分布および電位分布の同時測定方法においては、第２の発明として、微小電極または試料を３軸方向に走査するための走査手段により試料の表面近傍領域において微小電極を相対的に走査させ、微小電極と試料との間の電圧差Ｖ１の分布と微小電極と基準電極との間の電圧差Ｖ２の分布とを測定し、電圧差Ｖ２の分布から表面近傍領域におけるｐＨの分布を算出し、電圧差Ｖ２−Ｖ１の分布から表面近傍領域における電位の分布を算出することを、第３の発明として、微小電極をＳＴＭ探針として用い、微小電極と試料との間に発生するトンネル電流を測定し、走査手段に対してフィードバックをかけることでトンネル電流が一定となるように微小電極と試料との間隔を制御し、このときの走査手段の制御量から、表面近傍領域における試料表面の形状を、表面近傍領域におけるｐＨの分布および電位の分布と同時に取得することを、第４の発明として、微小電極をＡＦＭ探針として用い、微小電極と試料との間に発生する原子間力を測定し、走査手段に対してフィードバックをかけることで原子間力が一定となるように微小電極と試料との間隔を制御し、このときの走査手段の制御量から、表面近傍領域における試料表面の形状を、表面近傍領域におけるｐＨの分布および電位の分布と同時に取得することを特徴とする材料表面のｐＨ分布および電位分布の同時測定方法を提供する。
そして、この出願の発明は、上記方法のための装置として、第５には、溶液中に設置された試料の表面近傍領域におけるｐＨおよび電位を同時に測定する材料表面のｐＨおよび電位の同時測定装置であって、試料の表面近傍領域に設置される微小電極と溶液中に設置される基準電極を有し、微小電極と試料との間の電圧差Ｖ１を測定する手段と微小電極と溶液中に設置される基準電極との間の電圧差Ｖ２を測定する手段を備えて、Ｖ１とＶ２とを同時に測定し、測定された電圧差Ｖ２から微小電極と試料との間の領域におけるｐＨを算出し、電圧差Ｖ２−Ｖ１から微小電極近傍領域の局所的な電位を算出するｐＨ算出手段と局所電位算出手段とを備えていることを特徴とする材料表面のｐＨ分布および電位分布の同時測定装置を提供し、第６には、微小電極または試料を３軸方向に走査するための走査手段を備え、これにより試料の表面近傍領域において微小電極を相対的に走査させ、微小電極と試料との間の電圧差Ｖ１の分布と微小電極と基準電極との間の電圧差Ｖ２の分布とを測定し、電圧差Ｖ２の分布から表面近傍領域におけるｐＨの分布を算出し、電圧差Ｖ２−Ｖ１の分布から表面近傍領域における電位の分布を算出することを特徴とする材料表面のｐＨおよび電位の同時測定装置を提供し、第７には、算出された表面近傍領域におけるｐＨの分布または電位の分布を、画像化して表示する手段を備えることを特徴とする材料表面のｐＨおよび電位の同時測定装置を提供する。
【０００７】
さらにまた、この出願の発明は、第８には、微小電極がＳＴＭ探針であって、微小電極と試料との間に発生するトンネル電流を測定し、走査手段に対してフィードバックをかけることでトンネル電流が一定となるように微小電極と試料との間隔を制御し、このときの走査手段の制御量から、表面近傍領域における試料表面の形状を、表面近傍領域におけるｐＨの分布および電位の分布と同時に取得することを特徴とする前記の材料表面のｐＨおよび電位の同時測定装置を提供し、第９には、微小電極がＡＦＭ探針であって、微小電極と試料表面に設置されたＡＦＭ用カンチレバーとの間に発生する原子間力を測定し、走査手段に対してフィードバックをかけることで原子間力が一定となるように微小電極と試料との間隔を制御し、このときの走査手段の制御量から、表面近傍領域における試料表面の形状を、表面近傍領域におけるｐＨの分布および電位の分布と同時に取得することを特徴とする前記の材料表面のｐＨおよび電位の同時測定装置を提供する。
【０００８】
また、第１０には、算出された微小領域におけるｐＨの分布／電位の分布／表面の形状を、画像化して表示する手段を備えることを特徴とする前記いずれかの装置を提供する。
【０００９】
【発明の実施の形態】
この出願の発明は、上記のとおりの特徴をもつものであるが、以下に、その実施の形態について説明する。
【００１０】
この出願の発明である材料表面のｐＨおよび電位の同時測定方法の概略とその装置の構成を図１に例示する。
【００１１】
図１に例示したとおり、この出願の発明である材料表面のｐＨおよび電位の同時測定装置では、たとえば、ピット（１）中の溶液（２）内に、試料（３）が設置されている。この試料（３）の表面近傍領域には、微小電極（４）が設置されており、また、溶液（２）中には基準電極（５）が設置されている。
【００１２】
ここで、試料（２）と微小電極（４）との間の電圧差Ｖ１および微小電極（４）と基準電極（５）との間の電圧差Ｖ２を、マルチタイプのエレクトロメータ（６）等の測定手段により同時に測定する。同時に測定された電圧差Ｖ１および電圧差Ｖ２から、それぞれ、試料（３）と微小電極（４）との間の微小領域におけるｐＨ、および、微小電極（４）の近傍の微小領域における局所的な電位を算出することができる。
【００１３】
ここで、微小電極は、試料（３）と微小電極（４）との間の微小領域におけるｐＨと微小電極（４）と基準電極（５）との間の電圧差Ｖ２との間に比例関係が成立する材料が用いられる。これにより、例えば、酸化タングステン電極を用いた場合には、ｐＨは、
ｐＨ＝（１３０−Ｖ２）／５０
と、求まる。また、微小電極（４）の近傍の微小領域における試料の局所的な電位は、Ｖ２−Ｖ１と、算出される。
【００１４】
この出願の発明である材料表面のｐＨおよび電位の同時測定装置では、試料（３）を３軸方向に走査するための走査手段（７）を備えることができる。この走査手段（７）によって、試料（３）の表面近傍領域において微小電極（４）を相対的に走査させることで、試料（３）と微小電極（４）との間の電圧差Ｖ１の分布と微小電極（４）と基準電極（５）との間の電圧差Ｖ２の分布とを、同時に測定することができる。測定される電圧差Ｖ２の分布から、表面近傍領域におけるｐＨの分布を、また、電圧差Ｖ２−Ｖ１の分布から、表面近傍領域における電位の分布を算出することができる。走査手段（７）は、微小電極（４）に接続されてもよく、この場合は、試料（３）の表面近傍領域において微小電極（４）を走査させることで、試料（３）と微小電極（４）との間の電圧差Ｖ１の分布と微小電極（４）と基準電極（５）との間の電圧差Ｖ２の分布とを、同時に測定し、電圧差Ｖ１の分布と電圧差Ｖ２の分布とから、表面近傍領域におけるｐＨの分布と表面近傍領域における電位の分布とを、算出処理手段（８）により、それぞれ算出する。
【００１５】
この出願の発明である材料表面のｐＨおよび電位の同時測定装置においては、ＣＲＴディスプレイ装置や液晶ディスプレイ装置などの画像出力手段（９）を備えることができ、算出された微小領域におけるｐＨの分布または局所的な電位の分布を、画像化して表示することも可能である。
【００１６】
また、この出願の発明である材料表面のｐＨおよび電位の同時測定装置においては、走査型トンネル顕微鏡の原理を適用することで、ｐＨの分布および局所的な電位の分布だけでなく、試料表面の形状に関する情報をも同時に測定することが可能である。
【００１７】
具体的には、図２に例示したとおり、微小電極（２４）を、ＳＴＭ探針として適用する。つまり、トンネル電流測定手段（２０）により試料（２３）と微小電極（２４）との間に発生するトンネル電流を測定し、走査手段（２７）に対してフィードバックをかけることで、トンネル電流が一定となるように、試料（２３）と微小電極（２４）との間隔を制御し、この走査手段（２７）に対するフィードバックから、表面近傍領域における試料表面の形状を、ｐＨの分布および電位の分布と同時に取得する。
さらに、この出願の発明である材料表面のｐＨおよび電位の同時測定装置においては、原子間力顕微鏡の原理を適用することで、ｐＨの分布および局所的な電位の分布だけでなく、試料（２３）表面の形状に関する情報をも同時に測定することも可能である。以上により取得された試料表面の形状は、画像出力手段（２９）により、画像として出力されてもよい。
【００１８】
具体的には、図３に例示したとおり、ＡＦＭ用カンチレバー型の微小電極（３４）を用いる。この電極は、一般的には、走査電気化学顕微鏡に利用されており、例えば、非常に細いタングステン電極をガラスコーティングすることで形成されている。
【００１９】
つまり、試料（３３）とＡＦＭ用カンチレバー型の微小電極（３４）との間に発生する原子間力を測定し、走査手段（３７）に対してフィードバックをかけることで、原子間力が一定となるように、試料（３３）と微小電極（３４）との間隔を制御し、この走査手段（３７）に対するフィードバックから、表面近傍領域における試料（３３）表面の形状を、ｐＨの分布および電位の分布と同時に取得する。以上により取得された試料表面の形状は、画像出力手段（３９）により、画像として出力されてもよい。
【００２０】
以上は、この出願の発明である材料表面のｐＨおよび電位の同時測定装置における態様の一例であり、この出願の発明が以上で示した形態に限定されることはなく、その細部について、様々な形態をとりうることが考慮されるべきであることは言うまでもない。
この出願の発明は、以上の特徴を持つものであるが、以下に実施例を示し、さらに具体的に説明する。
【００２１】
【実施例】
この出願の発明である材料表面のｐＨおよび電位の同時測定装置の測定原理に基づき、５％塩化マグネシウム水溶液中を純鉄に付着させ、腐食が進行していく際の、純鉄の表面近傍領域におけるｐＨおよび電位の変化について調べた。微小電極として、微小酸化タングステンｐＨ電極を用いた。
【００２２】
図４は、純鉄の表面近傍領域におけるｐＨと電位の経時変化を示したグラフである。時間の経過とともに、純鉄表面の腐食が進行し、腐食の進行に伴い、ｐＨおよび電位が同時に低下していくことがわかる。
【００２３】
以上の通り、この出願の発明である材料表面のｐＨおよび電位の同時測定装置の測定原理により、材料の表面近傍領域におけるｐＨおよび電位を同時に測定できることが明らかとなった。微小電極を相対的に走査することで、ｐＨおよび電位の平面分布が得られ、これを画像化することも容易に実現できる。
【００２４】
【発明の効果】
この出願の発明によって、以上詳しく説明したとおり、材料表面の１００μｍ平方以下の微小領域内におけるｐＨ分布および電位分布を同時測定するための新たな測定方法が提供される。
【００２５】
この出願の発明は、従来技術では不可能であった、局部腐食内部のｐＨ分布および電位分布の測定を実現し、種々の電気化学測定に応用可能であり、耐腐食性材料などの新規機能性材料の開発を行う上で、その指針を得るための重要な技術であると考えられることから、その実用化が強く期待される。
【図面の簡単な説明】
【図１】この出願の発明である材料表面のｐＨおよび電位の同時測定装置の構成について示した概要図である。
【図２】この出願の発明である材料表面のｐＨおよび電位の同時測定装置の構成について示した概要図である。
【図３】この出願の発明である材料表面のｐＨおよび電位の同時測定装置の構成について示した概要図である。
【図４】この出願の発明である材料表面のｐＨおよび電位の同時測定装置の実施例において、純鉄の表面近傍領域におけるｐＨと電位の経時変化を示したグラフである
【符号の説明】
１ ピット
２ 溶液
３ 試料
４ 微小電極
５ 基準電極
６ エレクトロメータ
７ 走査手段
８ 算出処理手段
９ 画像出力手段
２０ トンネル電流測定手段
２１ ピット
２２ 溶液
２３ 試料
２４ 微小電極
２５ 基準電極
２６ エレクトロメータ
２７ 走査手段
２８ 算出処理手段
２９ 画像出力手段
３０ トンネル電流測定手段
３１ ピット
３２ 溶液
３３ 試料
３４ 微小電極
３５ 基準電極
３６ エレクトロメータ
３７ 走査手段
３８ 算出処理手段
３９ 画像出力手段[0001]
TECHNICAL FIELD OF THE INVENTION
The invention of this application relates to a method and apparatus for simultaneously measuring the pH and potential of a material surface. More specifically, the invention of this application relates to a method and apparatus for simultaneously measuring pH and potential in a minute area of 100 μm square or less on the surface of a material.
[0002]
[Prior Art and Problems of the Invention]
Elucidation of the corrosion mechanism of metallic materials and identification of factors that determine corrosion resistance are thought to contribute to the development of new corrosion resistant metals. It has been suggested that there is a relationship between the progress of corrosion and the pH and potential distribution on the metal material surface. It is considered indispensable to elucidate the corrosion mechanism and identify the factors that determine corrosion resistance.
[0003]
In the prior art, various measurement techniques for measuring the pH of a solution are known, but these techniques are techniques for measuring the pH of the entire solution and do not realize local pH distribution measurement. . In other words, a technique for measuring the pH distribution in a small area of 100 μm square or less on the material surface, as required to elucidate the corrosion mechanism of a metal material and to specify factors that determine corrosion resistance, It has not been developed so far. Further, no new measuring means capable of simultaneously measuring the pH distribution and the potential distribution has been proposed.
[0004]
Therefore, the invention of this application has been made in view of the above circumstances, and a new measurement method and a new measurement method for simultaneously measuring the pH distribution and the electric potential distribution in a minute area of 100 μm square or less on the material surface. It is an object of the present invention to provide an apparatus.
[0005]
[Means for Solving the Problems]
The invention of this application solves the above-mentioned problems. First, a method for simultaneously measuring the pH and the potential of a material surface by simultaneously measuring the pH and the potential in a region near the surface of a sample placed in a solution. there are, at the same time measuring the potential difference V 2 between the voltage difference V 1 and microelectrode and the solution reference electrode is placed in between the microelectrode and the sample to be placed in the region near the surface of the sample, the measurement has been pH was calculated from the voltage difference V 2 in the region between the microelectrode and the sample, the voltage difference V 2 -V 1 material surface and calculates the local potential of the micro-electrode neighborhood Provided is a method for simultaneously measuring pH distribution and potential distribution.
[0006]
In the method for simultaneously measuring the pH distribution and the potential distribution on the material surface, as a second invention, the microelectrode or the scanning means for scanning the sample in three axial directions relatively moves the microelectrode in a region near the surface of the sample. is scanned, pH near the surface region and the distribution of the voltage difference V 2 is measured, from the distribution of the voltage difference V 2 between the distribution and the microelectrodes and the reference electrode of the voltage difference V 1 of the between the microelectrode and the sample Calculating the distribution of the potential and the distribution of the potential in the vicinity of the surface from the distribution of the voltage difference V 2 −V 1 as a third invention. The distance between the microelectrode and the sample is controlled so that the tunnel current is constant by measuring the tunnel current generated between them and applying feedback to the scanning means. As a fourth invention, obtaining the shape of the sample surface in the vicinity region at the same time as the distribution of the pH and the distribution of the potential in the region near the surface is described as follows. The distance between the microelectrode and the sample is controlled so that the atomic force is constant by measuring the generated atomic force and applying feedback to the scanning means. Provided is a method for simultaneously measuring the pH distribution and the potential distribution on a material surface, wherein a shape of a sample surface in a vicinity region is obtained simultaneously with a distribution of a pH and a distribution of a potential in a region near the surface.
Fifthly, the invention of this application is a device for the above method, which is a device for simultaneous measurement of pH and potential on a material surface for simultaneously measuring pH and potential in a region near the surface of a sample placed in a solution. Means for measuring a voltage difference V 1 between the microelectrode and the sample, the microelectrode being provided in a region near the surface of the sample and a reference electrode being installed in the solution; area between comprises means for measuring the voltage difference V 2 between the reference electrode is placed, to measure the V 1 and V 2 at the same time, the micro-electrode and the sample from the voltage difference V 2 which is measured pH was calculated in, pH distribution of the material surface, characterized in that it comprises a pH calculating means and local potential calculating means for calculating the local potential of the micro-electrode neighborhood from the voltage difference V 2 -V 1 and Provides a simultaneous measurement device for potential distribution Sixth, scanning means for scanning the microelectrode or the sample in three axial directions is provided, whereby the microelectrode is relatively scanned in a region near the surface of the sample, and a voltage difference between the microelectrode and the sample is provided. and measuring the distribution of the voltage difference V 2 between the distribution and the microelectrodes and the reference electrodes V 1, to calculate the pH of the distribution in the region near the surface from the distribution of the voltage difference V 2, the voltage difference V 2 -V 1 A device for simultaneously measuring the pH and the potential of the material surface, wherein the device calculates the distribution of the potential in the region near the surface from the distribution of the pH. Provided is a device for simultaneously measuring the pH and the potential of a material surface, comprising a means for imaging and displaying a distribution.
[0007]
Eighth, the invention of this application is based on the fact that the microelectrode is an STM probe, and the tunnel current generated between the microelectrode and the sample is measured and fed back to the scanning means. The distance between the microelectrode and the sample is controlled so that the tunnel current is constant, and the shape of the sample surface in the region near the surface is determined based on the control amount of the scanning means at this time. A ninth aspect of the present invention provides a device for simultaneously measuring the pH and potential of the material surface, wherein the microelectrode is an AFM probe, and the AFM probe is provided on the microelectrode and the sample surface. The interatomic force generated between the sample and the cantilever is measured, and the distance between the microelectrode and the sample is controlled by applying feedback to the scanning means so that the atomic force is constant. A simultaneous measurement device for measuring the pH and potential of the material surface, wherein the shape of the surface of the sample in the region near the surface is obtained simultaneously with the distribution of the pH and the potential in the region near the surface from the control amount of the inspection means. provide.
[0008]
In a tenth aspect, there is provided any one of the above devices, further comprising means for imaging and displaying the calculated distribution of pH / potential distribution / surface shape in the minute region.
[0009]
BEST MODE FOR CARRYING OUT THE INVENTION
The invention of this application has the features as described above, and embodiments thereof will be described below.
[0010]
FIG. 1 illustrates an outline of a method for simultaneous measurement of pH and potential on a material surface and a configuration of an apparatus according to the invention of this application.
[0011]
As illustrated in FIG. 1, in the apparatus for simultaneously measuring the pH and the potential on the material surface according to the invention of this application, for example, a sample (3) is placed in a solution (2) in a pit (1). A microelectrode (4) is provided in a region near the surface of the sample (3), and a reference electrode (5) is provided in the solution (2).
[0012]
Here, a voltage difference V 2 between the sample (2) and the voltage difference V 1 and microelectrode (4) and the reference electrode between the microelectrode (4) (5), multi-type electrometer (6 ) Are measured at the same time. The voltage difference V 1 and the voltage difference V 2 measured at the same time, respectively, pH in the small area between the sample (3) and microelectrode (4), and the local in a minute region near the microelectrode (4) Potential can be calculated.
[0013]
Here, microelectrodes, proportional between the voltage difference V 2 between a sample (3) pH and microelectrode (4) and the reference electrode in the small region between microelectrodes (4) (5) Materials that have a relationship are used. Thereby, for example, when a tungsten oxide electrode is used, the pH becomes
pH = (130−V 2 ) / 50
I get it. Further, the local potential of the sample in the minute region near the minute electrode (4) is calculated as V 2 −V 1 .
[0014]
The apparatus for simultaneously measuring the pH and the potential on the material surface according to the invention of the present application can include a scanning unit (7) for scanning the sample (3) in three axial directions. This scanning means (7), the sample (3) by causing relative scan the microelectrode (4) in the region near the surface of the sample (3) and of the voltage difference V 1 of the between the microelectrode (4) distribution and microelectrode and (4) the distribution of the voltage difference V 2 between the reference electrode (5) can be measured simultaneously. From the measured distribution of the voltage difference V 2, the pH of the distribution near the surface region, the distribution of the voltage difference V 2 -V 1, it is possible to calculate the distribution of potential in the vicinity of the surface region. The scanning means (7) may be connected to the microelectrode (4). In this case, the sample (3) and the microelectrode (4) are scanned by scanning the microelectrode (4) in a region near the surface of the sample (3). voltage difference and distribution of the voltage difference V 2 between V 1 of the distribution and microelectrode and (4) and the reference electrode (5), measured at the same time, distribution and voltage of the voltage difference V 1 of the between (4) and a distribution of the difference V 2, and a distribution of the potential in the distribution and the surface region near the pH near the surface region, the calculation processing means (8), is calculated.
[0015]
The apparatus for simultaneously measuring the pH and the electric potential of the material surface according to the invention of the present application can include an image output means (9) such as a CRT display device or a liquid crystal display device, and can calculate the distribution of pH or the calculated pH distribution in a minute area. It is also possible to image and display the local potential distribution.
[0016]
In the apparatus for simultaneously measuring the pH and the potential of the material surface according to the invention of the present application, the principle of the scanning tunneling microscope is applied to not only the distribution of the pH and the distribution of the local potential but also the distribution of the sample surface. Information on the shape can be measured at the same time.
[0017]
Specifically, as illustrated in FIG. 2, the microelectrode (24) is applied as an STM probe. That is, the tunnel current generated between the sample (23) and the microelectrode (24) is measured by the tunnel current measuring means (20), and the tunnel current is made constant by applying feedback to the scanning means (27). The distance between the sample (23) and the microelectrode (24) is controlled so that the shape of the sample surface in the region near the surface can be determined from the feedback to the scanning means (27) with the distribution of pH and the distribution of potential. Acquire at the same time.
Further, in the apparatus for simultaneously measuring the pH and the potential on the material surface according to the invention of the present application, by applying the principle of the atomic force microscope, not only the distribution of the pH and the distribution of the local potential but also the sample (23) ) It is also possible to simultaneously measure information about the surface shape. The shape of the sample surface obtained as described above may be output as an image by the image output means (29).
[0018]
Specifically, as shown in FIG. 3, a cantilever-type microelectrode (34) for AFM is used. This electrode is generally used for a scanning electrochemical microscope, and is formed, for example, by coating a very thin tungsten electrode with glass.
[0019]
That is, by measuring the atomic force generated between the sample (33) and the microelectrode (34) of the cantilever type for AFM, and applying feedback to the scanning means (37), the atomic force is made constant. The distance between the sample (33) and the microelectrode (34) is controlled so that the shape of the surface of the sample (33) in the vicinity of the surface can be determined by feedback to the scanning means (37). Acquire at the same time as the distribution. The shape of the sample surface acquired as described above may be output as an image by the image output means (39).
[0020]
The above is an example of the embodiment of the simultaneous measurement device for the pH and the potential of the material surface according to the invention of the present application, and the invention of the present application is not limited to the above-described embodiment, and the details thereof are various. It goes without saying that it is possible to take the form.
The invention of this application has the above-mentioned features, and will be described in more detail with reference to examples below.
[0021]
【Example】
Based on the measurement principle of the simultaneous measurement device for pH and potential on the material surface according to the invention of this application, a 5% magnesium chloride aqueous solution is adhered to pure iron, and a region near the surface of pure iron when corrosion proceeds. The changes in pH and electric potential were examined. A micro tungsten oxide pH electrode was used as the micro electrode.
[0022]
FIG. 4 is a graph showing changes over time in pH and potential in a region near the surface of pure iron. It can be seen that the corrosion of the pure iron surface progresses with the passage of time, and the pH and the potential decrease simultaneously as the corrosion progresses.
[0023]
As described above, it has been clarified that the pH and the electric potential in the region near the surface of the material can be simultaneously measured by the measurement principle of the simultaneous measurement device for the pH and the electric potential of the material surface according to the invention of this application. By relatively scanning the microelectrodes, a planar distribution of pH and potential can be obtained, and it can be easily realized as an image.
[0024]
【The invention's effect】
According to the invention of this application, as described in detail above, a new measurement method for simultaneously measuring the pH distribution and the potential distribution in a minute region of 100 μm square or less on the material surface is provided.
[0025]
The invention of this application realizes the measurement of pH distribution and electric potential distribution inside local corrosion, which was impossible with the prior art, and can be applied to various electrochemical measurements. Since it is considered to be an important technology for obtaining the guideline in the development of materials, its practical application is strongly expected.
[Brief description of the drawings]
FIG. 1 is a schematic diagram showing a configuration of a device for simultaneously measuring pH and potential of a material surface according to the invention of the present application.
FIG. 2 is a schematic diagram showing the configuration of a device for simultaneously measuring pH and potential on a material surface according to the invention of the present application.
FIG. 3 is a schematic diagram showing a configuration of a device for simultaneously measuring pH and potential of a material surface according to the invention of the present application.
FIG. 4 is a graph showing time-dependent changes in pH and potential in a region near the surface of pure iron in an embodiment of the apparatus for simultaneous measurement of pH and potential of a material surface according to the invention of the present application.
Claims (10)
測定する材料表面のｐＨおよび電位の同時測定方法あって、試料の表面近傍領域に設置される微小電極と試料との間の電圧差Ｖ1と微小電極と溶液中に設置される基準電極との間
の電位差Ｖ2とを同時に測定し、測定された電圧差Ｖ2から微小電極と試料との間の領域におけるｐＨを算出し、電圧差Ｖ2−Ｖ1から微小電極近傍領域の局所的な電位を算出することを特徴とする材料表面のｐＨ分布および電位分布の同時測定方法。There simultaneous measuring method of the pH and the potential of the material surface to simultaneously measure the pH and the potential in the region near the surface of the sample placed in the solution, the voltage between the microelectrode and the sample to be placed in the region near the surface of the sample simultaneously measuring the potential difference V 2 between the difference V 1 and microelectrode and the solution reference electrode is placed in, pH calculates the region between the measured voltage difference V 2 between microelectrodes and sample , simultaneous measuring method of pH distribution and the potential distribution of the material surface and calculates the local potential of the micro-electrode neighborhood from the voltage difference V 2 -V 1.
ネル電流を測定し、走査手段に対してフィードバックをかけることでトンネル電流が一定となるように微小電極と試料との間隔を制御し、このときの走査手段の制御量から、表面近傍領域における試料表面の形状を、表面近傍領域におけるｐＨの分布および電位の分布と同時に取得することを特徴とする請求項２の材料表面のｐＨおよび電位の同時測定方法。Using the microelectrode as an STM probe, measure the tunnel current generated between the microelectrode and the sample, and apply feedback to the scanning means so that the gap between the microelectrode and the sample becomes constant so that the tunnel current becomes constant. 3. The material surface according to claim 2, wherein the shape of the sample surface in the near-surface region is acquired simultaneously with the distribution of the pH and the potential in the near-surface region from the control amount of the scanning means at this time. Method for simultaneous measurement of pH and potential.
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