CN110887765A - Electrochemical hydrogen permeation test electrolytic cell for simulating deep sea environment and application method - Google Patents
Electrochemical hydrogen permeation test electrolytic cell for simulating deep sea environment and application method Download PDFInfo
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Abstract
The invention provides an electrochemical hydrogen permeation test electrolytic cell for simulating a deep sea environment and an application method thereof, and belongs to the field of electrochemical hydrogen permeation tests in a deep sea hydrostatic pressure environment. The invention designs a double electrolytic cell for simulating the deep sea environment hydrogen permeation test, which has a light structure and can perform the hydrogen permeation test of metal materials in a high-pressure and low-temperature sea water environment. The double electrolytic tanks and the auxiliary testing electrodes are of non-pressure-bearing structures, so that the strength requirement of the electrolytic tanks is reduced to the greatest extent. When the double electrolytic cells are placed in the simulated deep sea environment test chamber for use, the test medium in the electrolytic cells and the seawater medium in the simulated deep sea environment test chamber can be isolated by utilizing the flexible diaphragm structure of the double electrolytic cells, and meanwhile, the pressure and temperature conditions in the simulated deep sea environment test chamber are conducted into the double electrolytic cells, so that the simulated deep sea environment conditions are established in the double electrolytic cells, and the hydrogen permeation test under the simulated deep sea environment is realized.
Description
Technical Field
The invention relates to the field of electrochemical hydrogen permeation testing under a deep sea hydrostatic pressure environment, in particular to a double electrolytic cell for simulating hydrogen diffusion testing in metal under a deep sea environment and an application method. The electrolytic cell can effectively solve the problems of metal hydrogen diffusion coefficient test and the like in deep sea high-pressure low-temperature environment.
Background
The hydrogen has influence on the mechanical property of the metal material, excessive hydrogen can cause embrittlement of the material after diffusing into the metal material, and the material is easy to induce hydrogen induced cracking under the action of load, thereby threatening the safety of an engineering structure. Research shows that the higher the strength grade of the metal material, the stronger the hydrogen brittleness sensitivity is, and the more easily hydrogen-induced failure occurs. With the continuous deepening of deep sea development in China, deep sea equipment is rapidly developed, and high-strength structural materials such as high-strength steel, high-strength stainless steel, high-strength titanium alloy and the like are generally adopted by the deep sea equipment for safety and economic consideration. In a deep sea environment, due to the effects of cathode polarization, environmental hydrogen evolution, marine microorganisms and the like, a metal structure can be caused to generate surface hydrogen evolution, and the hydrogen evolution behavior is also related to environmental conditions such as seawater pressure, temperature, dissolved oxygen concentration, pH value and the like; under the action of deep sea high static pressure, hydrogen generated on the surface of the metal is easier to diffuse into the metal, so that the embrittlement of the material is aggravated; in addition, according to the diffusion theory, the temperature change of the deep sea water can also have a significant influence on the diffusion of hydrogen in the metal. Therefore, the research on the hydrogen permeation and diffusion behaviors of the metal material in the deep sea environment is of great significance.
At present, a Devanthan-Stachyrski double-electrolytic-cell electrochemical hydrogen permeation test method is commonly adopted for performing metal hydrogen diffusion tests at home and abroad, and the method is characterized in that two electrolytic cells are respectively arranged on two sides of a sheet-shaped metal sample, wherein one electrolytic cell is a hydrogen charging electrolytic cell (or called as a cathode cell), and a hydrogen charging medium (seawater or other solution) is added into the electrolytic cell to charge hydrogen on a cathode working surface of the metal sample; the other is a hydrogen measuring electrolytic cell (or called an anode cell), wherein the medium is usually sodium hydroxide solution, the flux of hydrogen diffused from the cathode working surface to the anode working surface of the sample is monitored in the anode cell, and the diffusion coefficient of the hydrogen in the material is calculated according to parameters such as diffusion time, sample thickness and the like. The method relates to two independent testing environments and two different testing media, and is limited to be carried out under the conditions of normal temperature and normal pressure at present.
The invention patent 201810287092.4 discloses a test device for simulating deep sea hydrogen permeation, which improves double electrolytic cells to ensure that the electrolytic cells have certain pressure bearing capacity, and realizes the simulation of deep sea high-pressure environment by pressurizing the electrolytic cells, but the device has extremely high requirements on cell bodies, auxiliary electrodes for testing, reference electrodes and other accessories, needs to have sufficient pressure resistance and insulating sealing performance, and also needs to solve the insulating and sealing problems between samples and cell bodies, and the patent adopts an O-shaped ring and an insulating gasket for insulating sealing, so that the pressure resistance is relatively limited, and the simulation of high static pressure environment is difficult to realize; in addition, in the use process, the pressure balance of the left electrolytic cell and the right electrolytic cell is difficult to master, and because the test sample is very thin (generally less than 1 mm), the sample can be deformed or damaged due to a small pressure difference, so that the test result is influenced.
The invention patent CN103293093B designs a deep sea stress corrosion and hydrogen permeation experiment simulation device, the device is arranged in a high-pressure kettle by arranging double electrolytic tanks, and then high-pressure nitrogen is introduced into the high-pressure kettle to simulate deep sea pressure, the method can effectively solve the problems of pressure bearing and insulation sealing of the electrolytic tanks, test samples and electrodes, and is easy to operate, but the device only realizes the simulation of deep sea pressure conditions, does not consider the influence of other deep sea environment parameters such as sea water temperature, dissolved oxygen concentration and the like, can not truly simulate the deep sea environment, and the introduction of the high-pressure nitrogen can change the medium atmosphere in the electrolytic tanks, thereby influencing the hydrogen evolution behavior of the test samples; in addition, the pressure grade which can be realized by using the high-pressure gas cylinder is limited, generally not more than 15MPa, the simulation of higher pressure cannot be realized, and the operation of the high-pressure gas also has the problem of safety.
Disclosure of Invention
The invention aims at the requirement of a metal hydrogen permeation test under the existing simulated deep sea environment, designs a double electrolytic cell for an electrochemical hydrogen permeation test in the simulated deep sea environment and an application method thereof. The prepared simulated deep sea water and hydrogen measuring medium are added into the double electrolytic cells, the flexible membrane is adopted to isolate the test medium in the electrolytic cells from the external sea water medium, and the balance of the internal pressure and the external pressure and the temperature of the double electrolytic cells is realized by utilizing the characteristics of the low compression ratio of the liquid medium, the toughness, the local deformation and the like of the flexible membrane, so that the pressure bearing requirements of the double electrolytic cells and the test electrode are reduced to the maximum extent, the simulated deep sea environment condition is established in the electrolytic cells, and the hydrogen permeation test is carried out.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides an electrochemical hydrogen permeation test electrolytic cell for simulating a deep sea environment, which consists of a cathode cell and an anode cell double electrolytic cell, wherein the cathode cell and the anode cell have the same structure and are arranged symmetrically left and right, the electrolytic cell is assembled by fastening bolts, the cathode cell and the anode cell are respectively filled with corresponding hydrogen charging solution and hydrogen measuring solution,
the cathode tank and the anode tank respectively comprise a tank body, an end plate, an end cover, a flexible membrane and a porous plate, wherein the tank body is a horizontal hollow cylinder with two open ends, the upper edge of the tank body is provided with two threaded holes, the test device is used for placing a reference electrode and an auxiliary electrode for experiments and injecting test solution, an end plate is fixed at one end of the cell body, a working round hole is reserved in the middle of the end plate to be used as a medium channel, a test sample is arranged at the position, right opposite to the working round hole of the end plate, between a cathode tank and an anode tank, of the working round hole, a round hole is reserved at each of four corners of the end plate to be used for installing a fastening bolt, a thread and groove structure is processed at the other end of the cell body, a flexible film is adopted to seal the other end of the cell body, the flexible film, the end cover is screwed on the other end of the groove body through threads and simultaneously compresses the flexible membrane and the porous plate.
Preferably, the tank body is fixed on the end plate by gluing or welding.
Preferably, the end plate is square, and the working round hole is arranged in the middle of the end plate.
Preferably, a sealing ring is arranged between the test sample and the end plate.
2. The invention also provides an application method of the electrochemical hydrogen permeation test electrolytic tank for simulating the deep sea environment, which comprises the following steps:
a. the double electrolytic tanks are composed of cathode tanks and anode tanks with symmetrical structures, wherein the cathode tanks and the anode tanks respectively comprise tank bodies, end plates, end covers, flexible membranes and porous plates, the tank bodies, the end plates and the end cover porous plates are made of corrosion-resistant non-metallic materials or metal materials, and the flexible membranes are made of corrosion-resistant tough materials;
b. connecting one end of the groove body of the cathode groove and the anode groove with an end plate, sealing the other end by using a flexible diaphragm, protecting and supporting the flexible film by using a porous plate, and tightly pressing and fixing the flexible film and the porous plate by using an end cover;
c. clamping a test sample between a cathode tank and an anode tank, performing insulation sealing on two sides of the sample by using sealing rings, and tightly pressing and fixing the sample by using bolts at four corners of an end plate;
d. filling simulated deep sea water in the cathode tank, and filling hydrogen into the cathode working surface of the test sample by adopting a cathode polarization method; filling the anode tank with sodium hydroxide solution for testing the hydrogen flux diffused to the anode working surface of the test sample;
e. the double electrolytic tanks are placed in a deep sea environment simulation test cabin for use, and test cables are led out from the deep sea environment simulation test cabin, connected with an electrochemical workstation for testing and used for test testing;
f. and adjusting the test pressure and temperature by using a simulated deep sea environment test device, and starting the hydrogen permeation test after the set conditions are reached.
Preferably, in the step a, the bath body, the end plates and the end covers of the double electrolytic baths may be made of non-metallic materials resistant to corrosion of seawater and acid and alkali media, such as organic glass, polyvinyl chloride, polytetrafluoroethylene, glass fiber reinforced plastic, and the like, or corrosion-resistant metallic materials, such as stainless steel, nickel-based alloy, titanium alloy, and the like, the porous plate may be made of non-metallic materials, such as polyvinyl chloride, polyethylene, plastics, and the like, and the flexible film may be made of materials, such as polyethylene, rubber, and the like, which have good toughness and are corrosion-resistant. The double electrolytic tanks can meet the watertight requirement without pressure bearing design.
Preferably, in the step b, the cell bodies of the cathode cell and the anode cell are horizontal hollow cylinders, two threaded holes are formed in the upper edge of each cell body and used for placing a reference electrode and an auxiliary electrode for tests and injecting test solution, one end of each cell body is horizontally bonded or welded on an end plate, the end plate is square, a working round hole with the diameter of 10-20 mm is reserved in the middle of the center of each cell body and used as a medium channel of a test sample, and round holes are reserved in four corners of each cell body and used for installing fastening bolts. The other end processing at the cell body has external screw thread and groove structure, adopts the flexible membrane to seal the cell body, and the flexible membrane is tied up on the recess of cell body through the bundle rope, and the perforated plate is hugged closely in the flexible membrane outside, and the thick 2~5mm of board, the perforated plate middle part processing several diameter is not more than 5 mm's aperture, compresses tightly flexible membrane and perforated plate with the interior threaded cavity end cover.
Preferably, in the step c, the test sample is a sheet sample, the thickness of the test sample is usually not more than 1mm, the thickness of the test sample is uniform, the working surfaces on two sides are polished, a copper wire is welded or connected at the edge of the test sample for testing, and the joint of the copper wire is coated with resin or waterproof cement. The anode working surface of the test sample is subjected to nickel plating treatment in advance and is passivated; the test sample is arranged between the end plates of the cathode tank and the anode tank, the working surface is opposite to the round hole in the center of the end plate, and the end plate is insulated and sealed by using an insulating sealing gasket, wherein the sealing gasket can be made of rubber, polyethylene and the like; and fastening bolts on the end plates of the cathode tank and the anode tank are adopted to tightly press the test sample, and the fastening bolts are made of corrosion-resistant metal materials such as stainless steel or titanium alloy.
Preferably, in the step d, the seawater for the test in the cathode tank can be natural seawater or can be prepared by referring to the water quality standard of seawater, and the parameters such as seawater salinity, dissolved oxygen concentration and pH value need to be adjusted by combining hydrological parameters of the deep seawater no matter the seawater is natural seawater or prepared seawater so as to meet the environmental conditions of the deep seawater, and the seawater in the cathode tank should be filled as full as possible to avoid gaps; the hydrogen charging test can adopt a constant current or constant potential cathode polarization method, the auxiliary electrode for hydrogen charging adopts a platinum electrode, a graphite electrode or a metal oxide electrode, the reference electrode for hydrogen charging adopts an all-solid Ag/AgX/seawater electrode or a high-purity zinc electrode, and the auxiliary electrode and the reference electrode are packaged by resin and then are installed on the body of the cathode tank in a threaded connection mode. Monitoring the hydrogen flux diffused to the anode working surface of the test sample in an anode tank by adopting a constant potential polarization method, wherein a test medium is usually a sodium hydroxide solution, and the anode tank is filled with the test medium as much as possible to avoid generating gaps; the auxiliary electrode for hydrogen measurement of the anode tank adopts a platinum electrode, the reference electrode for hydrogen measurement adopts a Hg/HgO electrode or an Ag/AgX electrode, and the auxiliary electrode and the reference electrode are packaged by resin and then are installed on the body of the anode tank in a threaded connection mode.
Preferably, in the step e, the assembled double electrolytic tanks are horizontally or vertically placed in a test cabin simulating deep sea environment, the test cable is a watertight cable, no metal wire is exposed outside, the cable joint is coated by a watertight connector or resin, the electrochemical workstation for testing adopts a multi-channel electrochemical workstation, or two electrochemical workstations, wherein one channel or one workstation is used for hydrogen charging, and the other channel or the other workstation is used for hydrogen testing.
Preferably, in the step f, the simulated deep sea environment test chamber utilizes a high-pressure circulating water pump to control the pressure of the seawater in the chamber, a condensation temperature control system is utilized to control the temperature of the seawater in the chamber, after the pressure and the temperature reach set values, the electrochemical workstation can be started to perform hydrogen permeation test, after the test is finished, the electrochemical workstation is stopped, the pressure in the simulated deep sea environment test chamber is unloaded, the double electrolytic tanks are taken out, the conditions of the sample and the electrolytic tanks are checked, the conditions that the installation parts of the sample, the electrodes and the flexible membrane are not damaged or leaked are confirmed, and finally test data analysis is performed.
Compared with the prior art, the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment and the application method thereof have the beneficial effects that:
the invention designs a double electrolytic cell for simulating the deep sea environment hydrogen permeation test, which has a light structure and can perform the hydrogen permeation test of metal materials in a high-pressure and low-temperature sea water environment. The double electrolytic tanks and the auxiliary testing electrodes are of non-pressure-bearing structures, so that the strength requirement of the electrolytic tanks is reduced to the greatest extent. When the double electrolytic cells are placed in the simulated deep sea environment test chamber for use, the test medium in the electrolytic cells and the seawater medium in the simulated deep sea environment test chamber can be isolated by utilizing the flexible diaphragm structure of the double electrolytic cells, and meanwhile, the pressure and temperature conditions in the simulated deep sea environment test chamber are conducted into the double electrolytic cells, so that the simulated deep sea environment conditions are established in the double electrolytic cells, and the hydrogen permeation test under the simulated deep sea environment is realized.
Drawings
FIG. 1 is a schematic diagram of the structure of the apparatus of the present invention;
FIG. 2 is an enlarged structural view of portion A of FIG. 1;
FIG. 3 is an enlarged structural view of portion B of FIG. 1;
figure 4 is a schematic diagram of the use of the apparatus of the present invention.
The reference numerals in the figures denote:
1-cathode channel; 2-anode groove; 3-a groove body; 4-end cover; 5-end plate; 6-bolt; 7-a reference electrode; 8-an auxiliary electrode; 9-testing the sample; 10-a sealing ring; 11-a flexible membrane; 12-a perforated plate; 13-a tying rope; 14-a groove; 15-screw thread; 16-a working circular hole; 17-a threaded hole; 18-simulating a deep sea environment test chamber; 19-test cable; 20-a cross-cabin watertight joint; 21-high pressure water pump; 22-seawater; 23-condensation temperature control system; 24-electrochemical work station.
Detailed Description
The electrochemical hydrogen permeation test electrolytic cell for simulating deep sea environment and the application method thereof according to the present invention will be described in detail below with reference to the accompanying drawings 1-4.
As shown in attached figures 1-3, the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment comprises a cathode cell 1 and an anode cell 2, wherein the cathode cell 1 and the anode cell 2 are consistent in structure and are arranged in a bilateral symmetry mode, and the electrochemical hydrogen permeation test electrolytic cell is assembled by fastening bolts 6.
The cathode tank 1 and the anode tank 2 both comprise a tank body 3, an end plate 5, an end cover 4, a flexible membrane 11 and a porous plate 12, wherein the tank body 3 is a cylinder with two open ends and a horizontal hollow, two threaded holes 17 are formed in the upper edge of the tank body 3 and used for accommodating a reference electrode 7 and an auxiliary electrode 8 for experiments and injecting test solution, one end of the tank body 3 is fixed on the end plate 5 in a gluing or welding mode, the end plate 5 is square, a working round hole with the diameter of 10-20 mm is reserved in the middle of the end plate 5 as a medium channel, a round hole is reserved at each of four corners of the end plate 5 and used for installing a fastening bolt 6, the other end of the tank body 3 is processed with a thread 15 and a groove 14 structure, the other end of the tank body 3 is sealed by the flexible membrane 11, the flexible membrane 11 is tied up on the groove 14 of the tank body 3 by a tying rope 13, the hollow end cap 4 is screwed on the other end of the groove body 3 through the screw thread 15, and meanwhile, the flexible membrane 11 and the porous plate 12 are pressed tightly.
During the test, the test sample 9 is arranged at the position of a working round hole which is just opposite to the end plate 5 between the cathode tank 1 and the anode tank 2, sealing rings 10 are added on two sides of the test sample 9, and the test sample 9 is tightly pressed by the fastening bolt 6 to be sealed and fixed. The cathode tank 1 and the anode tank 2 are filled with a hydrogen-charging solution and a hydrogen-measuring solution, respectively, and a reference electrode 7 and an auxiliary electrode 8 for a test are inserted and screwed. The whole double electrolytic tanks are placed in a simulated deep sea environment test cabin 18, a test cable 19 is connected with a cabin penetrating watertight connector 20, an electrochemical workstation 24 is connected to carry out testing after cabin penetrating, a high-pressure circulating water pump 21 is used for filling seawater 22 into the simulated deep sea environment test cabin 18, the pressure of the seawater 22 is adjusted, a condensation temperature control system 23 is used for controlling the test temperature, and a hydrogen permeation test is carried out after the test condition is reached, as shown in figure 4.
The invention relates to an application method of an electrochemical hydrogen permeation test electrolytic tank for simulating a deep sea environment, which comprises the following steps:
a. the double electrolytic tank is composed of a cathode tank 1 and an anode tank 2 which are symmetrical in structure, the cathode tank 1 and the anode tank 2 both comprise a tank body 3, an end plate 5, an end cover 4, a flexible membrane 11 and a porous plate 12, the tank body 3, the end plate 5 and the end cover 4 of the double electrolytic tank can adopt organic glass, polyvinyl chloride, polytetrafluoroethylene, glass fiber reinforced plastic and other seawater 22 and acid-base medium corrosion resistant non-metallic materials, and can also adopt stainless steel, nickel-based alloy, titanium alloy and other corrosion resistant metallic materials, the porous plate 12 can adopt polyvinyl chloride, polyethylene, plastics and other non-metallic materials, and the flexible membrane 11 can adopt good toughness, corrosion resistant polyethylene, rubber and other materials. The double electrolytic tanks can meet the watertight requirement without pressure bearing design.
b. One end of a tank body 3 of a cathode tank 1 and an anode tank 2 is connected with an end plate 5, the other end of the tank body is sealed by a flexible diaphragm, a porous plate 12 is used for protecting and supporting a flexible film 11, and an end cover 4 is used for compressing and fixing the flexible film 11 and the porous plate 12; the cell bodies 3 of the cathode cell 1 and the anode cell 2 are horizontal hollow cylinders, the upper edges of the cell bodies are provided with two threaded holes 17 for placing a reference electrode 7 and an auxiliary electrode 8 for tests and injecting test solution, one end of each cell body 3 is horizontally bonded or welded on the end plate 5, the end plate 5 is square, a working round hole with the diameter of 10-20 mm is reserved in the middle of the center of the cell body and serves as a medium channel of a test sample 9, and round holes for mounting fastening bolts 6 are reserved on the four corners of the cell body. The other end of the groove body 3 is provided with an external thread 15 and a groove 14, the groove body 3 is sealed by a flexible film 11, the flexible film 11 is tied up on the groove 14 of the groove body 3 through a binding rope 13, the outer side of the flexible film 11 is tightly attached to a porous plate 12, the thickness of the plate is 2-5 mm, the middle part of the porous plate 12 is provided with a plurality of small holes with the diameter not larger than 5mm, and the hollow end cover 4 with the internal thread 15 is used for tightly pressing the flexible film 11 and the porous plate 12.
c. Clamping a test sample 9 between a cathode tank 1 and an anode tank 2, insulating and sealing two sides of the sample by using a sealing ring 10, and tightly pressing and fixing the sample by using bolts 6 at four corners of an end plate 5; the test sample 9 is a sheet sample, the thickness is usually not more than 1mm, the thickness is uniform, working surfaces on two sides are polished, a copper wire is welded or connected at the edge of the sample for testing, and the joint of the copper wire is coated with resin or waterproof cement. The anode working surface of the test sample 9 is subjected to nickel plating treatment in advance and is passivated; the test sample 9 is arranged between the end plates 5 of the cathode tank 1 and the anode tank 2, the working surface is opposite to the round hole in the center of the end plate 5, and the end plate 5 is insulated and sealed by using an insulating sealing gasket, wherein the sealing gasket can be made of rubber, polyethylene and other materials; the test sample 9 is pressed tightly by the fastening bolts 6 on the end plates 5 of the cathode tank 1 and the anode tank 2, and the fastening bolts 6 are made of corrosion-resistant metal materials such as stainless steel or titanium alloy.
d. Filling simulated deep sea water 22 in the cathode tank 1, and filling hydrogen into the cathode working face of the test sample 9 by adopting a cathode polarization method; the anode tank 2 is filled with sodium hydroxide solution for testing the hydrogen flux diffused to the anode working surface of the test sample 9; the seawater 22 for the test in the cathode tank 1 can adopt natural seawater 22, and can also be prepared by referring to the water quality standard of the seawater 22, and the natural seawater 22 or the prepared seawater 22 needs to be combined with hydrological parameters of the deep seawater 22 to adjust the parameters such as the salinity, the dissolved oxygen concentration, the pH value and the like of the seawater 22 so as to meet the environmental conditions of the deep seawater 22, and the seawater 22 in the cathode tank 1 is filled as much as possible to avoid gaps; the hydrogen charging test can adopt a constant current or constant potential cathode polarization method, the auxiliary electrode 8 for hydrogen charging adopts a platinum electrode, a graphite electrode or a metal oxide electrode, the reference electrode 7 for hydrogen charging adopts an all-solid Ag/AgX/seawater 22 electrode or a high-purity zinc electrode, and the auxiliary electrode 8 and the reference electrode 7 are packaged by resin and then are installed on the body 3 of the cathode slot 1 in a threaded connection mode. Monitoring the hydrogen flux diffused to the anode working surface of the test sample 9 in the anode tank 2 by adopting a constant potential polarization method, wherein a test medium is usually a sodium hydroxide solution, and the anode tank 2 is filled with the test medium as much as possible to avoid gaps; the auxiliary electrode 8 for hydrogen measurement of the anode tank 2 adopts a platinum electrode, the reference electrode 7 for hydrogen measurement adopts an Hg/HgO electrode or an Ag/AgX electrode, and the auxiliary electrode 8 and the reference electrode 7 are installed on the tank body 3 of the anode tank 2 in a threaded connection mode after being packaged by resin.
e. The double electrolytic cells are placed in a deep sea environment simulation test chamber 18 for use, a test cable 19 is led out from the deep sea environment simulation test chamber 18 and is connected with a test electrochemical workstation 24, and the test is carried out by the electrochemical workstation 24; the assembled double electrolytic tanks are horizontally or vertically placed in a test cabin 18 for simulating the deep sea environment, the test cable 19 adopts a watertight cable, metal leads cannot be exposed outside, the cable joint adopts a watertight connector or is coated by resin and the like, the test electrochemical workstation 24 adopts a multi-channel electrochemical workstation 24, or two electrochemical workstations 24 can be adopted, wherein one channel or one workstation is used for hydrogen charging, and the other channel or the other workstation is used for hydrogen measurement.
f. Utilize simulation deep sea environment test device to adjust test pressure and temperature, begin to ooze the hydrogen test after reaching the settlement condition, simulation deep sea environment test cabin 18 utilizes high-pressure circulating water pump 21 to control cabin interior sea water 22 pressure, utilize condensation temperature control system 23 control cabin interior sea water 22 temperature, after pressure and temperature all reach the setting value, just can start electrochemical workstation 24 and carry out the infiltration hydrogen test, after the test, shut down electrochemical workstation 24, unload the pressure in simulation deep sea environment test cabin 18, take out two electrolysis tanks, the inspection sample and electrolysis trough condition, confirm the sample, electrode and flexible membrane 11 installation site do not have the damage, the condition such as seepage, carry out experimental data analysis at last.
Practical application
A double electrolytic cell is adopted to test the hydrogen diffusion coefficient of a certain high-strength steel under the simulated 3000m deep sea environment. The environmental parameters of 3000m deep sea water 22 are as follows:
| pressure of | Temperature of | Concentration of dissolved oxygen | pH | Salinity |
| 30MPa | ||||
| 4℃ | 3ppm | 7.5 | 3.4 |
Preparing a hydrogen-filled test medium by adopting natural seawater 22, controlling the concentration of dissolved oxygen in the seawater 22 by filling nitrogen or oxygen, adjusting the pH value of the seawater 22 by adding dilute hydrochloric acid or sodium hydroxide solution, adjusting the salinity of the seawater 22 by adding distilled water or saturated sodium chloride solution, and sealing and storing for later use after the test medium is prepared.
The processing size of a test sample 9 is phi 20 multiplied by 1mm, two sides are polished and polished, a micrometer is adopted to accurately measure the thickness of the sample, a copper wire is welded on the edge of the sample, and an epoxy putty is used for coating and sealing a welding joint. The anode working face of the test specimen 9 was nickel plated and then passivated until the background current density was less than 10-7A/cm2。
The double electrolytic tanks for the test are made of organic glass materials, the wall thickness is 10mm, the internal sizes of the cathode tank 1 and the anode tank 2 are phi 60 multiplied by 80mm, and the size of the working area of the reserved sample is 1cm2. The sample is arranged in a double electrolytic tank, the cathode working face faces to a cathode tank 1, the anode working face is plated with nickel and faces to an anode tank 2, an O-shaped sealing ring 10 is placed between the sample and the electrolytic tank, and the sample and the sealing ring 10 are tightly pressed by a bolt 6 on the electrolytic tank. The other sides of the cathode tank 1 and the anode tank 2 are covered with a rubber flexible film 11 with the thickness of about 1mm, the rubber flexible film is tied on the tank body 3 by a rubber rope, and after a porous plate 12 is buckled, the end cover 4 is screwed down. Injecting the prepared seawater 22 into the cathode slot 1 until the cathode slot is full, respectively inserting a platinum electrode and an Ag/AgX/seawater 22 electrode as an auxiliary electrode 8 and a reference electrode 7, and screwing the electrodes to avoid the leakage of the seawater 22; 1mol/L sodium hydroxide solution is injected into the anode tank 2 until the anode tank is full, and a platinum electrode and an Hg/HgO electrode are respectively inserted as an auxiliary electrode 8 and a reference electrode 7, and the electrodes are screwed down.
The double electrolytic tanks are placed in a test cabin 18 for simulating the deep sea environment, cables of a test sample 9 and electrodes are connected with a cabin penetrating watertight joint 20 of the test sample cabin, a wiring part is wound and sealed by adopting a pressure-resistant waterproof adhesive tape, and the test cable 19 is connected with a multi-channel electrochemical workstation 24 outside the test cabin. Filling seawater 22 into the test chamber 18 for simulating the deep sea environment, starting the high-pressure circulating water pump 21 and the temperature control system, controlling the pressure of the seawater 22 in the test chamber to be 30MPa and the temperature to be 4 ℃, starting the electrochemical workstation 24 for testing after the pressure and the temperature of the seawater 22 are stable, and carrying out the test by utilizing the electrochemical methodThe chemical workstation 24 carries out constant current hydrogen charging on the cathode working surface of the sample, and the hydrogen charging current density is 5mA/cm2Meanwhile, a constant potential of 0.15V vs. Hg/HgO is applied to the working surface of the sample anode to measure hydrogen, and the change of the hydrogen permeation current is continuously monitored.
After the test is finished, the following are calculated according to the penetration time: the diffusion coefficient of hydrogen in the high-strength steel for test is 2.1 multiplied by 10 under the simulated 3000m deep sea environment-6mm/s。
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
Claims (10)
1. An electrochemical hydrogen permeation test electrolytic tank for simulating a deep sea environment is characterized by consisting of a cathode tank (1) and an anode tank (2) which are double electrolytic tanks, wherein the cathode tank (1) and the anode tank (2) have the same structure and are symmetrically arranged in the left and right directions, and are assembled by fastening bolts (6), and corresponding hydrogen charging solution and hydrogen measuring solution are respectively filled in the cathode tank (1) and the anode tank (2),
the cathode tank (1) and the anode tank (2) both comprise a tank body (3), an end plate (5), an end cover (4), a flexible membrane (11) and a porous plate (12), wherein the tank body (3) is a cylinder with two open ends and a hollow horizontal surface, two threaded holes (17) are formed in the upper edge of the tank body (3) and used for accommodating a reference electrode (7) and an auxiliary electrode (8) for experiments and injecting a test solution, the end plate (5) is fixed at one end of the tank body (3), a working round hole is reserved in the middle of the end plate (5) and used as a medium channel, a test sample (9) is arranged between the cathode tank (1) and the anode tank (2) and is just at the working round hole of the end plate (5), a round hole is reserved at each of four corners of the end plate (5) and used for installing a fastening bolt (6), a thread (15) and a groove (14) structure is processed at the other end of the tank, the flexible film (11) is tied up on recess (14) of cell body (3) through binding rope (13), and a porous plate (12) is filled up outward to flexible film (11) for support and protection flexible film (11), and end cover (4) are screwed up at the other end of cell body (3) through screw thread (15), compress tightly flexible film (11) and porous plate (12) simultaneously.
2. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment as claimed in claim 1, comprising the steps of:
a. the double-electrolytic cell consists of a cathode cell (1) and an anode cell (2) which are symmetrical in structure, wherein the cathode cell (1) and the anode cell (2) respectively comprise a cell body (3), an end plate (5), an end cover (4), a flexible membrane (11) and a porous plate (12);
b. one end of a groove body (3) of a cathode groove (1) and an anode groove (2) is connected with an end plate (5), the other end of the groove body is sealed by a flexible diaphragm, a porous plate (12) is used for protecting and supporting a flexible film (11), and an end cover (4) is used for compressing and fixing the flexible film (11) and the porous plate (12);
c. clamping a test sample (9) between a cathode tank (1) and an anode tank (2), insulating and sealing two sides of the test sample (9) by using sealing rings (10), and tightly pressing and fixing the test sample (9) by using fastening bolts (6) at four corners of an end plate (5);
d. filling simulated deep sea water (22) in the cathode tank (1), and filling hydrogen into the cathode working surface of the test sample (9) by adopting a cathode polarization method; the anode tank (2) is filled with sodium hydroxide solution and used for testing the hydrogen flux diffused to the anode working surface of the test sample (9);
e. the double electrolytic tanks are placed in a simulated deep sea environment test cabin (18) for use, a test cable (19) is led out from the simulated deep sea environment test cabin (18) and is connected with a test electrochemical workstation (24), and the test is carried out by the electrochemical workstation (24);
f. and adjusting the test pressure and temperature by using a simulated deep sea environment test device, and starting the hydrogen permeation test after the set conditions are reached.
3. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment is characterized in that in the step a, the cell body (3), the end plate (5), the end cover (4) and the porous plate (12) of the double electrolytic cell are made of corrosion-resistant non-metallic materials or metal materials, and the flexible membrane (11) is made of corrosion-resistant flexible materials.
4. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment is characterized in that in the step b, the cell bodies (3) of the cathode cell (1) and the anode cell (2) are horizontal hollow cylinders, two threaded holes (17) are formed in the upper edges of the cell bodies for placing the reference electrode (7) and the auxiliary electrode (8) for the test and for injecting the test solution, one end of each cell body (3) is horizontally bonded or welded on the end plate (5), the end plate (5) is square, a working round hole with the diameter of 10-20 mm is reserved in the middle of the cell body as a medium channel of the test sample (9), and a round hole is reserved in each of the four corners of the cell body for installing the fastening bolt (6); the other end of the tank body (3) is processed to form a structure with an external thread (15) and a groove (14), the tank body (3) is sealed by a flexible film (11), the flexible film (11) is tied up on the groove (14) of the tank body (3) through a tying rope (13), a porous plate (12) is tightly attached to the outer side of the flexible film (11), the thickness of the plate is 2-5 mm, a plurality of small holes with the diameter not larger than 5mm are processed in the middle of the porous plate (12), and the flexible film (11) and the porous plate (12) are tightly pressed by a hollow end cover (4) with the internal thread (15).
5. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment is characterized in that in the step c, the test sample (9) is a sheet sample, the thickness of the sheet sample is not more than 1mm, the thickness of the sheet sample is uniform, working surfaces on two sides of the sheet sample are polished, a copper wire is welded or connected to the edge of the sheet sample for testing, and the joint of the copper wire is coated with resin or waterproof daub; the anode working surface of the test sample (9) is subjected to nickel plating treatment in advance and is passivated; the test sample (9) is arranged between the end plates (5) of the cathode tank (1) and the anode tank (2), the working face is opposite to the round hole in the center of the end plate (5), the insulating sealing gasket is used for insulating and sealing the end plate (5), and the test sample (9) is tightly pressed by the fastening bolts (6) on the end plates (5) of the cathode tank (1) and the anode tank (2).
6. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment according to the claim 5 is characterized in that the sealing gasket is made of rubber or polyethylene, and the fastening bolt (6) is made of stainless steel or titanium alloy corrosion-resistant metal material.
7. The method for applying the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment according to the claim 2 or 6, wherein in the step d, the seawater (22) for the test in the cathode cell (1) is prepared by using the natural seawater (22) or the water quality standard of the reference seawater (22), and the salinity, the dissolved oxygen concentration and the pH value of the seawater (22) need to be adjusted by combining the hydrological parameters of the deep sea seawater (22) no matter the natural seawater (22) or the prepared seawater (22) so as to meet the environmental conditions of the deep sea seawater (22), and the seawater (22) in the cathode cell (1) should be filled as full as possible to avoid gaps.
8. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment is characterized in that a constant current or constant potential cathode polarization method is adopted in a hydrogen charging test, a platinum electrode, a graphite electrode or a metal oxide electrode is adopted as an auxiliary electrode (8) for hydrogen charging, an all-solid Ag/AgX/seawater (22) electrode or a high-purity zinc electrode is adopted as a reference electrode (7) for hydrogen charging, and the auxiliary electrode (8) and the reference electrode (7) are installed on a cell body (3) of a cathode cell (1) in a threaded connection mode after being packaged by resin; monitoring the hydrogen flux diffused to the anode working surface of the test sample (9) in the anode tank (2) by adopting a constant potential polarization method, wherein a test medium is usually a sodium hydroxide solution, and the anode tank (2) is filled with the test medium to the greatest extent so as to avoid the occurrence of gaps; the auxiliary electrode (8) for hydrogen measurement of the anode tank (2) adopts a platinum electrode, the reference electrode (7) for hydrogen measurement adopts a Hg/HgO electrode or an Ag/AgX electrode, and the auxiliary electrode (8) and the reference electrode (7) are installed on the tank body (3) of the anode tank (2) in a threaded connection mode after being packaged by resin.
9. The method for applying the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment according to the claim 2, 6 or 8, characterized in that in the step e, the assembled double electrolytic cells are horizontally or vertically placed in the test chamber (18) for simulating the deep sea environment, the test cable (19) adopts a watertight cable, no metal wire is exposed outside, the cable joint adopts a watertight connector or is coated by resin and the like, the test electrochemical workstation (24) adopts a multi-channel electrochemical workstation (24), or adopts two electrochemical workstations (24), wherein one channel or one workstation is charged with hydrogen, and the other channel or the other workstation is used for measuring hydrogen.
10. The application method of the electrochemical hydrogen permeation test electrolytic cell for simulating the deep sea environment according to the claim 2, 6 or 8 is characterized in that in the step f, the pressure of seawater (22) in the test chamber (18) for simulating the deep sea environment is controlled by a high-pressure circulating water pump (21), the temperature of the seawater (22) in the test chamber is controlled by a condensation temperature control system (23), after the pressure and the temperature reach set values, the electrochemical workstation (24) can be started to perform the hydrogen permeation test, after the test is finished, the electrochemical workstation (24) is closed, the pressure in the test chamber (18) for simulating the deep sea environment is unloaded, the double electrolytic cells are taken out, the conditions of the sample and the electrolytic cells are checked, the conditions of the sample, the electrodes and the installation part of the flexible membrane (11) are confirmed to be free from damage and leakage, and finally test data analysis is performed.
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