JP6015368B2 - Electrode for measuring minute potential in liquid - Google Patents
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- JP6015368B2 JP6015368B2 JP2012248004A JP2012248004A JP6015368B2 JP 6015368 B2 JP6015368 B2 JP 6015368B2 JP 2012248004 A JP2012248004 A JP 2012248004A JP 2012248004 A JP2012248004 A JP 2012248004A JP 6015368 B2 JP6015368 B2 JP 6015368B2
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Description
この発明は、特に海水中に設置されて海水中の微小電位差を測定するのに使用される液中微小電位測定用電極に関する。 The present invention particularly relates to an in-liquid micropotential measurement electrode that is installed in seawater and used to measure a micropotential difference in seawater.
そのような液中微小電位測定用電極としては、例えば図４に示すようなものがある。この電極では、一端部が開口した円筒状のケース８０内に電極としての円柱状の導体（例えば、銀／塩化銀電極）８１が配置され、ケース８０の一端部の開口に多孔質のフィルタ８２が取り付けられ、ケース８０内に電解液（塩水）９０が充填されている。（例えば、特許文献１参照）。 An example of such an electrode for measuring a minute potential in liquid is shown in FIG. In this electrode, a columnar conductor (for example, a silver / silver chloride electrode) 81 as an electrode is disposed in a cylindrical case 80 whose one end is open, and a porous filter 82 is opened in one end of the case 80. The case 80 is filled with an electrolytic solution (salt water) 90. (For example, refer to Patent Document 1).
このセンサは、例えば海水中に投入されると、ケース８０外部の海水がフィルタ８２を通じてケース８０内部の塩水９０と物理的・電気的に接触することにより得られる電位が導体８１で検出されるようになっている。 When this sensor is put into, for example, seawater, the conductor 81 detects the potential obtained when the seawater outside the case 80 comes into physical and electrical contact with the saltwater 90 inside the case 80 through the filter 82. It has become.
しかしながら、上記のような電極では、次のような問題点がある。
ａ）ケース８０内部に塩水９０を入れておく必要がある上に、保管には外フタを要し、保管に手間が掛かる。
ｂ）使用時に泡がフィルタ８２に付着しないように、また内部の塩水９０が流出しないように注意を払わなければならず、海水中への設置作業が楽でない。
However, the electrodes as described above have the following problems.
a) It is necessary to put salt water 90 in the case 80, and an outer lid is required for storage, which takes time and effort.
b) Care must be taken to prevent bubbles from adhering to the filter 82 and to prevent the salt water 90 inside from flowing out during use, and installation work in seawater is not easy.
また、図４の電極では、導体が電解液（塩水）に浸漬されているので保管時から平衡状態となっている。しかし、仮に、導体を電解液（塩水）に浸漬させずに保管する場合には、海水中での電位測定時に電極を海水に浸漬した後、平衡状態となって電位が安定し、電位測定使用可能となるまでに時間が掛かる。例えば、導体として銀／塩化銀電極を使用した場合、難溶の塩化銀が海水に溶けて、ＡｇＣｌ⇔Ａｇ＋＋Ｃｌ−となるまでに時間を要する。従って、従来の技術では、導体を電解液（塩水）に浸漬させずに保管することは現実的ではない。 Moreover, in the electrode of FIG. 4, since the conductor is immersed in electrolyte solution (salt water), it has been in the equilibrium state from the time of storage. However, if the conductor is stored without being immersed in the electrolyte solution (salt water), the potential becomes stable after the electrode is immersed in seawater when measuring the potential in seawater. It takes time to become possible. For example, when a silver / silver chloride electrode is used as a conductor, it takes time until the hardly soluble silver chloride dissolves in seawater and becomes AgCl⇔Ag + + Cl − . Therefore, in the conventional technique, it is not realistic to store the conductor without immersing the conductor in the electrolytic solution (salt water).
本発明は、上記従来の課題を解決するためになされたものであり、その目的は、保管を容易にすることができる液中微小電位測定用電極を提供することである。 The present invention has been made to solve the above-described conventional problems, and an object thereof is to provide an electrode for measuring a micropotential in liquid that can be easily stored.
前記課題を解決するために、本発明の液中微小電位測定用電極は、外部と内部とを連通する一対の通水口が形成されたケースと、前記ケースの一対の通水口にそれぞれ設けられた通水用のフィルタと、前記ケース内部に一対のフィルタ間の通水路を塞ぐように配置されるとともに、少なくとも１つの通水・空気抜き用の孔を有する平板状の銀導体と、海中で前記導体にめっきするためのめっき用電極とを備える。前記めっき用電極は海中で前記銀導体に塩化銀をめっきする。 In order to solve the above-mentioned problems, the electrode for measuring a micropotential in liquid of the present invention is provided in a case in which a pair of water passages for communicating the outside and the inside are formed, and a pair of water passages in the case, respectively. A water-passing filter, a flat silver conductor disposed in the case so as to close a water passage between a pair of filters, and having at least one water / air vent hole, and the conductor in the sea And an electrode for plating for plating. The electrode for plating plating silver chloride on the silver conductor in the sea.
この液中微小電位測定用電極によると、海水に浸漬したときに、海水がフィルタを通じてケース内部に浸入する。この浸漬時に、ケース内部の空気は、フィルタのみを、或いは導体の通水・空気抜き用の孔とフィルタを経て、ケース外部に出る。海水浸漬後、すなわちケース内部の空気がケース外部に出て、ケース内部が海水で満たされた後は、ケースの通水口に設けられたフィルタにより、ケース内部の海水が動かなくなる。電極を海水（電解液）に浸漬した後、導体とめっき用電極との間で通電を行うと、導体がめっきされる。 According to the electrode for measuring a micropotential in liquid, when immersed in seawater, the seawater enters the case through the filter. At the time of this immersion, the air inside the case comes out of the case only through the filter, or through the hole for water passage and air vent of the conductor and the filter. After immersion in seawater, that is, after the air inside the case has come out of the case and the inside of the case is filled with seawater, the seawater inside the case does not move due to the filter provided at the water passage opening of the case. When the electrode is immersed in seawater (electrolytic solution) and then energized between the conductor and the plating electrode, the conductor is plated.
従って、本発明の電極では、保管時にはケース内部に電解液（塩水）を入れておく必要がなく、つまり、導体を電解液（塩水）に浸漬させおく必要がないので、保管が容易となる。電極を海水（電解液）に浸漬した後、導体とめっき用電極との間で通電を行うと、導体が銀からなるため、海中の塩化物イオンにより導体表面の銀が塩化銀になり、銀／塩化銀電極が形成されることになる。この作用は迅速であるため、当初から導体として電解液なしの銀／塩化銀電極を使用した場合に比べて、電位が安定して電位測定使用可能となるまでの時間（平衡状態となるまでの時間）が短縮される。 Therefore, in the electrode of the present invention, it is not necessary to put an electrolytic solution (salt water) in the case at the time of storage, that is, it is not necessary to immerse the conductor in the electrolytic solution (salt water). When the electrode is immersed in seawater (electrolyte) and then energized between the conductor and the electrode for plating, the conductor is made of silver. Therefore, the silver on the conductor surface becomes silver chloride due to chloride ions in the sea. / A silver chloride electrode will be formed. Since this action is rapid, compared to the case where a silver / silver chloride electrode without electrolyte is used as a conductor from the beginning, the time until the potential becomes stable and the potential measurement can be used (until the equilibrium state is reached). Time).
なお、本発明において、めっき用電極の材料としては、銀が例示される。 In the present invention, silver is exemplified as a material for the electrode for plating.
本発明によれば、次の効果が得られる。保管時にはケース内部に電解液（塩水）を入れておく必要がないので保管が容易となる。海水中に浸漬後、速やかに導体が銀／塩化銀電極となるため、電解液なしで保管した銀／塩化銀電極と比較して、電位が安定して電位測定使用可能となるまでの時間が短縮される。 According to the present invention, the following effects can be obtained. Since it is not necessary to put an electrolytic solution (salt water) in the case during storage, storage becomes easy. Since the conductor quickly becomes a silver / silver chloride electrode after being immersed in sea water, the time until the potential is stable and the potential measurement can be used compared to the silver / silver chloride electrode stored without the electrolyte. Shortened.
以下、実施の形態により、この発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to embodiments.
その一実施形態に係る液中微小電位測定用電極を図１、図２に示す。この液中微小電位測定用電極では、ケース１は円筒状を呈し、両端の開口が一対の通水口１１，１２となる。この通水口１１，１２には、円板状の通水用のフィルタ２１，２２が取り付けられている。フィルタ２１，２２は、例えばケース１の通水口１１，１２寄りの内周面に周溝を形成し、この周溝にフィルタ２１，２２の外周部分を嵌合することでケース１に取り付けられる。フィルタ２１，２２が取り付けられたケース１内部において、一対のフィルタ２１，２２間が通水路１５となる。 An electrode for measuring a micropotential in liquid according to one embodiment is shown in FIGS. In this electrode for measuring a minute potential in liquid, the case 1 has a cylindrical shape, and the openings at both ends become a pair of water inlets 11 and 12. Disk-shaped water filters 21 and 22 are attached to the water inlets 11 and 12, respectively. The filters 21 and 22 are attached to the case 1 by, for example, forming a circumferential groove on the inner peripheral surface of the case 1 near the water inlets 11 and 12 and fitting the outer peripheral portions of the filters 21 and 22 into the circumferential groove. Inside the case 1 to which the filters 21 and 22 are attached, a water passage 15 is formed between the pair of filters 21 and 22.
ケース１内部において、その縦断方向のほぼ中央部分には、平板状（ここでは円板状）の導体３０がフィルタ２１，２２間の通水路１５を塞ぐように配置されている。導体３０は、例えばケース１の縦断方向のほぼ中央部分の内周面に周溝を形成し、この周溝に導体３０の外周部分を嵌合することでケース１に取り付けられる。また、導体３０は、ここでは海水浸漬後に導体表面に塩化銀を形成するために銀（Ａｇ）からなる。つまり、保管中には、導体である銀はめっきされていない。更に、導体３０は、少なくとも１つ（ここでは４つ）の通水・空気抜き用の円形状の孔３１を有する。なお、孔３１は通水・空気抜き機能を果たすのであれば、その個数、形状、大きさに特定はない。 Inside the case 1, a flat plate-like (disc-like here) conductor 30 is arranged at a substantially central portion in the longitudinal direction so as to block the water passage 15 between the filters 21 and 22. The conductor 30 is attached to the case 1 by, for example, forming a circumferential groove on the inner circumferential surface of the substantially central portion in the longitudinal direction of the case 1 and fitting the outer circumferential portion of the conductor 30 in the circumferential groove. The conductor 30 is made of silver (Ag) in order to form silver chloride on the conductor surface after immersion in seawater. That is, during storage, the conductor silver is not plated. Furthermore, the conductor 30 has at least one (here, four) circular holes 31 for water passage and air venting. Note that the number, shape, and size of the holes 31 are not particularly limited as long as the holes 31 fulfill a water flow / air venting function.
一方、ケース１の外周面において、その縦断方向のほぼ中央部分には、海中で導体３０に塩化銀をめっきするためのめっき用電極４０が例えば貼着により設けられている。すなわち、ケース１のほぼ中央部分の外周面は環状のめっき用電極４０で覆われている。また、導体３０には通電用のリード線３５が、めっき用電極４０には通電用のリード線４５が接続されている。 On the other hand, on the outer peripheral surface of the case 1, a plating electrode 40 for plating silver chloride on the conductor 30 in the sea is provided, for example, by sticking at a substantially central portion in the longitudinal direction. That is, the outer peripheral surface of the substantially central portion of the case 1 is covered with the annular plating electrode 40. In addition, a lead wire 35 for energization is connected to the conductor 30, and a lead wire 45 for energization is connected to the plating electrode 40.
なお、めっき用電極４０は、ケース１外周面の全周にわたって設ける必要はなく、一部分（例えば半周分）のみであってもよいだけでなく、その位置もケース１外周面のほぼ中央部分である必要はなく、その形状も帯状である必要はなく、導体３０に塩化銀をめっきできるのであれば特に制限はない。 Note that the plating electrode 40 does not have to be provided over the entire circumference of the outer peripheral surface of the case 1, and may be only a part (for example, a half circumference), and the position thereof is also a substantially central portion of the outer peripheral surface of the case 1. There is no need, and the shape does not need to be a band, and there is no particular limitation as long as the conductor 30 can be plated with silver chloride.
この液中微小電位測定用電極を使用して微小電位測定を行う場合は、まず電極を海中に浸漬する。すると、海水がフィルタ２１，２２を通じてケース１内部に浸入する。このとき、ケース１内部の空気は、フィルタ２１，２２だけを、或いは導体３０の孔３１及びフィルタ２１，２２を通ってケース１外部に出る。海水浸漬後、すなわちケース１内部の空気がケース１外部に出て、ケース１内部が海水で満たされた後は、ケース１の通水口１１，１２に設けられたフィルタ２１，２２により、ケース１内部の海水が動かなくなる。 When performing micropotential measurement using the electrode for measuring micropotential in liquid, the electrode is first immersed in the sea. Then, seawater enters the case 1 through the filters 21 and 22. At this time, the air inside the case 1 goes out of the case 1 only through the filters 21 and 22 or through the hole 31 of the conductor 30 and the filters 21 and 22. After immersion in seawater, that is, after the air inside the case 1 comes out of the case 1 and the inside of the case 1 is filled with seawater, the filters 21 and 22 provided in the water inlets 11 and 12 of the case 1 The seawater inside does not move.
次いで、図３に示すように、導体３０とめっき用電極４０との間で通電を行う。導体３０は銀からなるため、海中の塩化物イオンにより導体３０の表面の銀が塩化銀になり（めっきされ）、導体３０は銀／塩化銀電極となる。この作用は迅速であるため、当初から導体として電解液を用いずに銀／塩化銀電極を使用した場合に比べて、電位が安定して電位測定使用可能となるまでの時間（平衡状態となるまでの時間）が短縮される。 Next, as shown in FIG. 3, energization is performed between the conductor 30 and the plating electrode 40. Since the conductor 30 is made of silver, silver on the surface of the conductor 30 becomes silver chloride (plated) by chloride ions in the sea, and the conductor 30 becomes a silver / silver chloride electrode. Since this action is rapid, compared with the case of using a silver / silver chloride electrode without using an electrolyte as a conductor from the beginning, the time until the potential becomes stable and potential measurement can be used (becomes in an equilibrium state). Time).
導体３０が銀／塩化銀電極となった後、当該液中微小電位測定用電極を用いて海中の微小電位測定を行う。 After the conductor 30 becomes a silver / silver chloride electrode, the micropotential measurement in the sea is performed using the in-liquid micropotential measurement electrode.
１ ケース
１１，１２ 通水口
１５ 通水路
２１，２２ フィルタ
３０ 導体
３１ 通水・空気抜き用の孔
４０ めっき用電極
DESCRIPTION OF SYMBOLS 1 Case 11,12 Water flow hole 15 Water flow path 21,22 Filter 30 Conductor 31 Hole for water flow and air vent 40 Plating electrode
Claims (2)
前記ケースの一対の通水口にそれぞれ設けられた通水用のフィルタと、
前記ケース内部に一対のフィルタ間の通水路を塞ぐように配置されるとともに、少なくとも１つの通水・空気抜き用の孔が形成された平板状の銀導体と、
海中で前記導体にめっきするためのめっき用電極とを備えることを特徴とする、液中微小電位測定用電極。 A case in which a pair of water passages communicating the outside and the inside are formed;
A water filter provided at each of the pair of water inlets of the case;
A flat silver conductor in which the water passage between the pair of filters is arranged inside the case and at least one hole for water passage / air venting is formed,
And wherein the obtaining Bei a plating electrode for plating to the conductor in the sea in a liquid micro-potential measuring electrode.
前記液中微小電位測定用電極を海中に浸漬する工程と、Immersing the electrode for measuring a micropotential in liquid in the sea;
前記ケースの内部を海水で満たす工程と、Filling the inside of the case with seawater;
前記ケースの内部を海水で満たした後、前記銀導体と前記めっき用電極との間で通電を行い、海中の塩化物イオンにより前記銀導体の表面の銀が塩化銀になることで、前記銀導体に前記塩化銀をめっきする工程と、After filling the inside of the case with seawater, energization is performed between the silver conductor and the plating electrode, and the silver on the surface of the silver conductor becomes silver chloride by chloride ions in the sea, whereby the silver Plating the silver chloride on the conductor;
前記銀導体に前記塩化銀をめっきした後、前記液中微小電位測定用電極を用いて海中の微小電位測定を行う工程とを含む、微小電位測定方法。And a step of measuring the micropotential in the sea using the electrode for measuring micropotential in liquid after plating the silver chloride on the silver conductor.
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