JPH02285249A - Electrolytic cell for polarization measurement - Google Patents

Abstract

PURPOSE:To carry a cell in the assembled state thereby making it unnecessary to fill an electrolyte every time said cell is used by providing a cell cylinder, a fixing ring, a valve, a plurality of legs fixed to said valve and an electrolyte injection pipe. CONSTITUTION:A cell cylinder 3 is opened at the side of an object 12 to be measured. A reference electrode 6 and a counter electrode 11 are accommodated in the cell cylinder 3. An electrolyte injection pipe 9 injects an electrolyte into a communicating vacancy defined by the inside of a fixing ring 14 and the inside of the cell cylinder 3. Then the ring 14 is brought into tight contact with the object 12, a plurality of legs 28 of a valve 27 are brought to touch with the object 12, so that the valve 27 are raised upward. Therefore, the electrolyte 8 comes in touch with the object 12 through an opening 19, enabling polarization measurement. When an electrolytic cell 29 is separated from the object 12 after the measurement, a plurality of springs 26 press the valve 27 at the bottom of the ring 14, thereby closing the opening 19, and accordingly, the electrolyte never leaks. Since the cell 29 can be carried out in the assembled state, it becomes unnecessary to inject or discharge the electrolyte 8 into or out of the cell cylinder 3 for every measurement, and the polarization measurement at a high place etc. can be easily carried out.

Description

[Detailed description of the invention] [Industrial application field]

The present invention relates to an electrolytic cell for polarization measurement used to non-destructively inspect the deterioration of a metal material by measuring the polarization characteristics of the material without cutting a sample from the material.

[Prior Art] As a means of inspecting the deterioration of metal materials that have been used at high temperatures for long periods of time, there is a polarization measurement method that measures the polarization characteristics of these materials. In this polarization measurement method, the shape of the polarization curve obtained when an electrolytic reaction is caused in an electrolytic solution using the material to be tested as a working electrode is the result of precipitation of carbides and phosphorus compounds caused by creep or age hardening in the material to be tested. This method utilizes the phenomenon that polarization changes depending on the polarization, etc., and attempts to detect metal deterioration by observing the polarization curve as described above. As a method for inspecting the deterioration of metal materials by polarization measurement, a so-called non-destructive method has recently become popular, in which the test is performed at a site where a structure made of the material to be inspected exists, without cutting out a sample from the structure. Various electrolytic cells for polarization measurement have already been devised for use in such testing methods. Figure 6 is the application filed by the present applicant (Utility Application No. 1988-191)
282) is a configuration diagram of a known electrolysis cell for polarization measurement. In Fig. 6, 1°2 indicates an upper tank and a lower tank formed by dividing one cylindrical cell cylinder 3 into upper and lower parts with a partition wall 4, and the upper tank 1 has a lid 5 provided at the top of the tank.
A reference electrode 6, which is a saturated calomel electrode, is placed perpendicularly to the liquid through the tank 1, and a saturated potassium chloride solution 7, which is the same as the internal liquid of the electrode 6, is sealed as a potential transfer liquid in the tank 1. . Reference numeral 9 denotes an electrolyte injection pipe 1 which is provided in the upper tank 1 and is configured to inject the electrolyte 8 into the lower tank 2 from outside the tank.
0 is a deaeration pipe provided in the upper tank 1 similarly to the electrolyte injection pipe 9, and this deaeration pipe is used to degas the gas in the lower tank 2 when injecting the electrolytic WL 8 from the injection pipe 9 into the lower tank 2. It is set in. The injection pipe 9 and the deaeration pipe 10 constitute a double pipe with the deaeration pipe 10 serving as an outer pipe. Reference numeral 11 denotes a plate-shaped counter electrode that is placed in the lower tank 2 and constitutes an electrolytic reaction system, which will be described later, together with the electrolyte 8. The counter electrode 11 is usually made of platinum or carbon, and its surface area is large enough to be used as a working electrode, which will be described later. Measurement object 120
The size is set to be at least twice the area and up to about 100 times the area. The counter electrode 11 is connected to one end of a conductive wire 13 provided in the upper tank 1 in an electrically insulating manner. Reference numeral 14 denotes a cylindrical fixing ring with both ends open, one end of which is fixed to the liquid honey on the surface of the object to be measured 12 using an adhesive 15.
6 is inserted into the fixing ring 14, and screwed together by screws provided on the inner surface of the fixing ring 14 and the outer surface of the lower end 16. Reference numeral 17 denotes a disc-shaped rubber sheet that is adhered to the surface of the object to be measured 12 using an adhesive 18 within the fixing ring 14, and a through hole 19 is provided in this sheet approximately in the center. Reference numeral 20 denotes an O-ring, and the vicinity of the threaded portion between the cell tube 3 and the fixing ring 14 is configured as described above, so that in this state, the inside of the lower tank 2 is almost a hollow space for liquid honey. Now, when the electrolytic solution 8 is injected into this liquid cavity through the injection pipe 9 so that the pair 8i11 is immersed in the electrolytic solution 8, the electrolytic solution 8 passes through the through hole 19 and enters the measured object 12. Because of this, an electrolytic reaction system can be formed by the part of the object to be measured 12 exposed to the through hole 19, the electrolytic solution 8, and the counter electrode 11.
is connected to a potentiostat 22 via a conducting wire 13, and the object to be measured 12 is connected to a potentiostat 22 via a conducting wire 21 whose one end is connected to the object to be measured. The reference electrode 6 is also connected to the potentiostat 22 and is used to determine the reference potential in the electrolytic reaction system. Reference numeral 23 denotes a Luggin tube disposed in the partition wall 4 so as to electrically connect the electrolytic solution 8 in the lower tank 2 and the saturated potassium chloride solution 7 near the reference electrode 6 as described above. 24 is a recorder connected to the potentiostat 22. In FIG. 6, the electrolyte 8 is injected into the lower tank 2 and the object to be measured 1 is
2 and the counter electrode 11 are brought into contact with the electrolytic solution 8, and when an appropriate voltage is applied between the object to be measured 12 and the counter electrode 11 by the potentiostat 22, the object to be measured 12 in the through hole 19 is actuated. A polar electrolytic reaction occurs, and a polarization curve based on this reaction is automatically recorded on the recorder 24. Therefore, by observing this polarization curve, the state of deterioration of the object to be measured 12 can be inspected. In FIG. 6, the deterioration test is performed as described above. In this case, when the counter electrode 11 is brought close to the through hole 19, the electric path distance of the electrolyte 8 portion in the electrolytic reaction system is shortened, and the electrical resistance of this portion is reduced. is small, so the voltage required to cause electrolysis may be low, which has the advantage of simplifying the electrolysis power supply. However, on the other hand, if the counter electrode 11 is too close to the through hole 19, the voltage required to cause electrolysis may be low. Hydrogen bubbles generated in the object to be measured 12 adhere to the counter electrode 11, resulting in a decrease in the surface area of the counter electrode 11. As a result, the shape of the polarization curve may change, causing an error in the deterioration test. Therefore, in FIG. 6, the counter electrode 11 must be placed a considerable distance above the lower end 16 of the cell tube 3 as the open end on the side of the object to be measured 12. Reference numeral 25 denotes an electrolytic cell for polarization measurement, which is composed of the parts shown in the figure except for the object to be measured 12, the potentiostat 22, and the recorder 24. Since the electrolytic cell 25 is constructed as described above, first the rubber sheet 17, the O-ring 20, and the fixing ring 14 are attached to the object to be measured 12, and then the counter electrode 11, reference electrode 6, etc. are attached, and the measurement is started. After the measurement is completed, the cell tube 3, fixing ring 14, ring 20, and rubber sheet 17 are discarded or reused. (Problems to be Solved by the Invention) The conventional electrolytic cell 25 is used as described above, and after fixing the fixing ring 14 to the object to be measured 12, the cell tube 3 is connected, and the electrolytic solution 8 is injected. There is a problem in that it is difficult to inject the electrolyte and install the cell tube 3 in a place with poor footing, and that the discharge of the electrolyte 8 at the end of measurement cannot be completely removed. The purpose of the present invention is to provide an electrolytic cell for polarization measurement that can be carried while assembled and does not require injection of electrolyte each time the electrolytic cell is used. A cell cylinder having an opening on the side to be measured and housing a reference electrode and a counter electrode, an opening on the side to be measured and fixed to the object to be measured in liquid honey, and the opposite side being detachable from the cell cylinder. A fixed ring connected to the fixed ring, a valve that is attached to the bottom of the fixed ring so as to be freely movable up and down and pressed toward the opening by a plurality of springs, and has a diameter larger than the opening, and fixed to the side of the valve. an electrolytic solution injection tube for injecting an electrolytic solution into a communicating space formed by a plurality of legs that penetrate the bottom of the fixing ring, and an inside of the fixing ring fixed to the object to be measured and an inside of the cell cylinder; This is achieved by an electrolytic cell for polarization measurement equipped with the following functions: If the fixing ring of the electrolytic cell for polarization measurement is brought into close contact with the object to be measured, the multiple legs of the valve will hit the object to be measured and push up the valve. , the electrolyte in the electrolytic cell comes into contact with the object to be measured through the opening, and polarization measurement becomes possible.After polarization measurement is completed, when the electrolytic cell is lifted away from the object to be measured, multiple valves attached to the bottom of the fixing ring are opened. Since the opening of the fixing ring is closed by pressing with a spring, the electrolyte will not leak from the opening.

【Example】

FIG. 1 is a configuration diagram of an electrolytic cell for polarization measurement according to an embodiment of the present invention, FIG. 2 is a detailed sectional view of section A in FIG. 1, and FIG. 3 is a view taken in the direction of arrow B in FIG. In FIGS. 1, 2, and 3, the same parts as in FIG. 6 are designated by the same numbers. In Fig. 1, reference numeral 1.2 denotes an upper tank and a lower tank formed by dividing a single cylindrical cell cylinder 3 into upper and lower parts with a partition wall 4. A reference electrode 6, which is a saturated calomel electrode, is provided perpendicularly to the fluid, and a saturated potassium chloride solution 7, which is the same as the internal liquid of the reference electrode 6, is sealed in the upper tank 1 as a potential transfer liquid. The reference electrode 6 is immersed in the solution. Reference numeral 9 denotes an electrolyte injection pipe that penetrates the upper tank 1 and injects the electrolyte 8 into the lower tank 2 from outside the tank, and 10, similar to the electrolyte injection pipe 9, connects the upper tank 1.
This degassing pipe is provided to degas the gas in the lower tank 2 when the electrolyte 8 is injected into the lower tank 2 from the injection pipe 9. The injection pipe 9 and the deaeration pipe 10 constitute a double pipe with the deaeration pipe 10 serving as an outer pipe. Reference numeral 11 denotes a plate-shaped counter electrode that is placed in the lower tank 2 and constitutes an electrolytic reaction system, which will be described later, together with the electrolyte 8. The counter electrode 11 is usually made of platinum or carbon, and its surface area is the same as that of a working electrode, which will be described later. The size is set to be at least twice the area of the object to be measured 12 and up to about 100 times the area. The counter electrode 11 is connected to one end of a conductive wire 13 that passes through the upper tank 1 in an electrically insulating manner. Reference numeral 14 denotes a cylindrical fixing ring whose bottom part is fixed to the surface of the object to be measured 12 in a liquid state using an adhesive 18. Both are screwed together by screws provided on the inner surface of the lower end 16 and the outer surface of the lower end 16. A through hole 19 is provided approximately in the center of the bottom of the fixing ring 14 . 20 is cell tube 3
and the fixing ring 14 as described above.
This is an O-ring placed between the upper end surface of the cell cylinder and the surface of the cell cylinder. In FIG. 2, a spring 26 attached to the bottom of the fixing ring 14 via an arm presses the valve 27 downward. The valve 27 has a leg 28 which passes through the bottom of the fixing ring 14. As shown in FIGS. 2 and 3, in this embodiment, two springs 26 and two legs 28 are each attached to the valve 27. FIG. 4 shows an electrolytic cell 2 for polarization measurement according to an embodiment of the present invention.
FIG. 5 is a sectional view showing a state in which the electrolytic cell 29 for polarization measurement according to an embodiment of the present invention is adhered to the object to be measured 12. FIG. Fourth
In the figure, when the electrolytic cell 29 is separated from the object to be measured, the plurality of springs 26 press against the valve 27, the legs 28 pass through the bottom of the fixing ring 14, and the valve 27 closes the opening 19. In this state, the electrolytic solution 8 will not leak from the opening 19. When the electrolytic cell is attached to the object to be measured 12 as shown in FIG. 5, the plurality of legs 28 hit the object to be measured 12 and push up the valve 27, so the valve 27 moves upward and the electrolyte 8 flows through the opening 19 to the object to be measured. Contact the surface of object 12. When the electrolyte 8 comes into contact with the surface of the object to be measured 120, an electrolytic reaction system is formed by the part of the object to be measured exposed to the through hole 19, the electrolyte 8, and the counter electrode 11. In order to configure the counter electrode 11, the counter electrode 11 is connected to the object to be measured 12 via the conductor 13.
are connected to a potentiostat 22 via a conductive wire 21 whose one end is connected to the object to be measured 12. The reference electrode 6 is also connected to the potentiostat 22 and is used to determine the reference potential in the electrode reaction system. In the electrolytic reaction system formed by injecting the electrolytic solution 8 into the lower tank 2 as described above, 23 indicates the electrolytic solution 8 near the through hole 19 and the saturated potassium chloride solution 7 near the reference electrode 6. This is a Luggin tube installed in the partition wall 4 to electrically connect the two. 24 is a recorder connected to the potentiostat 22. In FIG. 1, the electrolyte 8 is injected into the lower tank 2 and the object to be measured 1 is
2 and the counter electrode 11 are brought into contact with the electrolytic solution 8, and when an appropriate voltage is applied between the object to be measured 12 and the counter electrode 11 by the potentiostat 22, the object to be measured 12 in the through hole 19 is actuated. A polar electrolytic reaction occurs, and a polarization curve based on this reaction is automatically recorded on the recorder 24. Therefore, by observing this polarization curve, the state of deterioration of the object to be measured 12 can be inspected. Reference numeral 29 denotes an electrolytic cell for polarization measurement, which is composed of the parts shown in the figure except for the object to be measured 12, the potentiostat 22, and the recorder 24. Since the electrolytic cell 29 is constructed as described above, first the bottom of the fixing ring 14 is attached to the object to be measured 1 using the adhesive 18.
After the electrolytic solution 8 is attached to the surface of the object 12 to form liquid honey, the electrolytic solution 8 is brought into contact with the surface of the object 12 through the opening 19 to perform measurement.After the measurement is completed, when the electrolytic cell 29 is separated from the object 12, Since the valve 27 closes the opening 19, the electrolytic solution 8 can be carried while being stored in the cell tube 3. Thereafter, similar operations are repeated to measure the polarization of the object to be measured.

【Effect of the invention】

This invention includes a fixing ring detachably connected to a cell cylinder, a valve attached to the bottom of the fixing ring so as to be freely movable up and down and pressed toward the opening by a plurality of springs, and When the electrolytic cell is moved away from the object to be measured, the valve closes the opening, preventing the electrolyte in the cell cylinder from leaking from the opening. do not have. Therefore, since the electrolytic cell can be carried while assembled, there is no need to inject and drain electrolyte into the cell cylinder each time polarization measurement is performed, making it easy to perform polarization measurement work at high places or in places with poor footing. . Therefore, work efficiency is improved. In addition, there is no need to clean up electrolyte leaked onto the surface of the object to be measured after work.

[Brief explanation of drawings]

Fig. 1 is a configuration diagram of an electrolytic cell for polarization measurement according to an embodiment of the present invention, Fig. 2 is a detailed sectional view of section A in Fig. 1, Fig. 3 is a view taken in the direction of arrow B in Fig. 2, and Fig. 4. 5 is a sectional view showing the electrolytic cell according to the embodiment of the present invention in a state separated from the object to be measured;
The figure is a sectional view showing a state in which an electrolytic cell according to an embodiment of the present invention is adhered to an object to be measured, and FIG. 6 is a configuration diagram of an electrolytic cell for polarization measurement according to a conventional example. 3: Cell cylinder, 6: Reference electrode, 8: Electrolyte, 9: Electrolyte injection tube, 11: Counter electrode, 12: Measured object, 14: Fixing ring, 19: Opening, 25, 29: Electrolytic cell, 26 : Spring, 27: Valve, 28: Leg.

Claims (1)

[Claims] 1) A cell cylinder having an opening on the side to be measured and housing a reference electrode and a counter electrode, a cell cylinder having an opening on the side to be measured and fixed to the object to be measured in liquid honey, and a cell cylinder on the opposite side. a fixing ring that is detachably connected; a valve that is attached to the bottom of the fixing ring so as to be freely movable up and down, is pressed toward the opening by a plurality of springs, and has a diameter larger than the opening;
An electrolytic solution is introduced into a communication space consisting of a plurality of legs fixed to the side of the valve and penetrating the bottom of the fixing ring, the inside of the fixing ring fixed to the object to be measured, and the inside of the cell cylinder. An electrolysis cell for polarization measurement, characterized by comprising an electrolyte injection tube for injecting an electrolyte.