CN114252491A - Marine steel corrosion hydrogen permeation monitoring sensor and monitoring method in ocean tidal range area - Google Patents

Marine steel corrosion hydrogen permeation monitoring sensor and monitoring method in ocean tidal range area Download PDF

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Publication number
CN114252491A
CN114252491A CN202111483544.4A CN202111483544A CN114252491A CN 114252491 A CN114252491 A CN 114252491A CN 202111483544 A CN202111483544 A CN 202111483544A CN 114252491 A CN114252491 A CN 114252491A
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steel
insulating
insulated
steel sample
hydrogen permeation
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许勇
黄彦良
蔡凡帆
王正泉
路东柱
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Institute of Oceanology of CAS
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Institute of Oceanology of CAS
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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Abstract

The invention belongs to the field of monitoring of corrosion hydrogen permeation current in a marine corrosion environment, in particular to a marine steel corrosion hydrogen permeation monitoring sensor and a monitoring method in a marine tidal range area, wherein the monitoring sensor comprises a monitoring unit, a sealing unit and a fixing unit, the monitoring sensor is fixed on an insulated steel cable through a clamp, a cylindrical steel sample with one side plated with palladium inside is hermetically connected with an insulated threaded cap, an insulated sealing cock and an insulated shell to form a closed space, a metal oxide electrode and a steel bolt are fixed on the insulated sealing cock in the closed space, and electrolyte is filled in the closed space; the cylindrical steel sample, the metal oxide electrode and the steel bolt are respectively connected with a signal lead, the monitoring sensor is led out through a waterproof joint, and the other end of the signal lead is connected with a constant potential rectifier. The monitoring sensor provided by the invention has the advantages of good tightness, high stability and convenience in operation, and is suitable for real-time monitoring of hydrogen permeation behavior of marine steel in an ocean tidal range area.

Description

Marine steel corrosion hydrogen permeation monitoring sensor and monitoring method in ocean tidal range area
Technical Field
The invention belongs to the field of monitoring of corrosion hydrogen permeation current in a marine corrosion environment, and particularly relates to a sensor and a method for monitoring corrosion hydrogen permeation of marine steel in a marine tidal range area.
Background
The sea tidal range zone is one of the most complex zones of the corrosion behavior of metal materials in the sea corrosion environment, and steel materials applied to the sea engineering are inevitably corroded to different degrees. Research has shown that hydrogen penetrates into the steel matrix along with the corrosion process. The infiltration of hydrogen can cause the reduction of the mechanical properties of steel materials, particularly sensitive materials such as high-strength steel and the like, shorten the service life of the materials and cause great potential safety hazards. At present, the research on the corrosion behavior characteristics and the law of metal materials in ocean tidal range areas is relatively deep; however, the study on the hydrogen permeation behavior of hydrogen into the interior of the material, which occurs simultaneously with the material corrosion in the tidal range, is rather weak. Due to the complex test environment of the tidal range and the lack of applicable hydrogen permeation monitoring sensors, the research on the hydrogen permeation behavior of the steel material in the tidal range is far more difficult than the research on the corresponding metal corrosion behavior.
In order to study the hydrogen permeation behavior of the metallic material in the tidal range region, a hydrogen permeation sensor which is easy to operate and convenient to install is needed. For studying the hydrogen permeation behavior into metal materials caused by corrosion, the Devanathan-Stachurski double electrolytic cell principle is generally adopted, which requires good sealing of the sensor. In addition, the tidal effect of the seawater in the tidal range tends to cause violent oscillation of the sensor, thereby causing large current noise; therefore, there is a higher demand for stability of the tidal range hydrogen permeation sensor.
In summary, no hydrogen permeation sensor and monitoring method suitable for monitoring corrosion hydrogen permeation in ocean tidal range zone exists at present.
Disclosure of Invention
In order to break through the technical bottleneck of monitoring the hydrogen permeation behavior of the steel material in the ocean tidal range, the invention aims to provide a sensor and a method for monitoring the hydrogen permeation of the corrosion of the marine steel in the ocean tidal range, which are used for monitoring the hydrogen permeation of the permeation behavior of hydrogen to the steel material caused by corrosion in the dynamic change process of seawater in the ocean tidal range.
The purpose of the invention is realized by the following technical scheme:
the monitoring sensor comprises a monitoring unit, a sealing unit and a fixing unit, wherein the monitoring sensor is fixed on an insulated steel cable through the fixing unit, the monitoring unit comprises a steel sample, a metal oxide electrode, a steel bolt and a signal lead, the sealing unit comprises an insulated sealing cock, an upper insulated threaded cap, a bottom insulated threaded cap, an insulated shell and a waterproof joint, the steel sample is of an internal hollow structure, the upper end and the lower end of the steel sample are respectively in sealed threaded connection with the upper insulated threaded cap and the bottom insulated threaded cap, the insulated sealing cock is in sealed threaded connection with the inside of the upper end of the steel sample and is positioned below the upper insulated threaded cap, the outer parts of the upper insulated threaded cap and the bottom insulated threaded cap are respectively in sealed connection with the insulated shell, and the upper insulated threaded cap is in sealed connection with the waterproof joint; the inner side surface of the steel sample is plated with palladium, electrolyte is filled in the steel sample, the insulating sealing cock is respectively provided with a metal oxide electrode and a steel bolt, the metal oxide electrode and the steel bolt are soaked in the electrolyte, the steel sample, the metal oxide electrode and the steel bolt are respectively connected with signal leads, and the signal leads are led out through the waterproof joints and are respectively connected with a potentiostat.
Wherein: the steel sample is of a cylindrical structure with openings at two ends, internal threads are formed on the inner surfaces of the upper end and the lower end of the steel sample, the outer surfaces of the upper end and the lower end of the steel sample respectively extend outwards along the radial direction to form protruding parts, and the insulating shell in sealing connection with the upper insulating thread cap and the bottom insulating thread cap is axially limited through the protruding parts at the upper end and the lower end.
The upper insulating threaded cap is of a stepped shaft-shaped structure, the position with the largest diameter is positioned outside the upper end of the steel sample and is in sealed threaded connection with the insulating shell, and the rest parts except the part with the largest diameter are inserted into the upper end of the steel sample and are in sealed connection with the steel sample; and a threaded hole for being in sealing threaded connection with the waterproof connector is formed in the center of the upper insulating threaded cap along the axial direction.
The bottom insulation threaded cap is of a stepped shaft-shaped structure, the position with the largest diameter is located outside the lower end of the steel sample and is in sealed threaded connection with the insulation shell, and the rest parts except the part with the largest diameter are inserted inside the lower end of the steel sample and are in sealed connection with the steel sample.
The insulating shell is of a hollow cylindrical structure with two open ends, the inner wall of the insulating shell is provided with an internal thread which is used for being in sealing threaded connection with the upper insulating threaded cap or the bottom insulating threaded cap, and the outer surface of the insulating shell is provided with an annular groove used for installing a fixing unit.
The insulating sealing cock is disc-shaped, the outer surface of the insulating sealing cock is provided with external threads used for being in sealing threaded connection with the steel sample, and the insulating sealing cock is provided with lead holes with the same number as the signal leads along the axial direction.
The insulating sealing cock is screwed into the threaded bottom of the upper-end internal thread from the upper-end internal thread of the steel sample, and sealing epoxy resin is filled and sealed between the insulating shell and the upper insulating threaded cap and between the insulating threaded caps at the bottom of the insulating shell to form a closed space.
The electrolyte is a mixed solution containing 30 vol% DMSO (dimethyl sulfoxide) and 70 vol% 0.2mol/L NaOH, and the electrolyte is further subjected to N2And (4) carrying out aeration and oxygen removal treatment for 2 hours.
Plating a palladium layer on the steel sample in an electroplating mode; wherein the palladium plating solution consists of 35g/L [ Pd (NH3)2Cl2], 23g/L [ NH4 Cl.6H 2O ] and 50g/L [ NH4OH ], the palladium plating current is 3-3.5 mA/cm2, and the plating time is less than or equal to 8 min.
The monitoring method comprises the following steps:
the monitoring sensor as claimed in any one of claims 1 to 9, wherein an electrolyte is injected into the monitoring sensor, a potentiostat is adjusted to make the potential of the cylindrical steel sample with palladium plated on one side of the inner side at 0mV (relative to Hg/HgO electrode), the current at the potential is monitored and recorded by the potentiostat as background current, after the background current is stabilized, the monitoring sensor is placed in a tidal range area, the current signal is continuously detected and recorded by the potentiostat, and the current after the background current is subtracted is the hydrogen permeation current.
The invention has the advantages and positive effects that:
1. the monitoring sensor disclosed by the invention is small in size, convenient to fix, simple to operate and suitable for monitoring the hydrogen permeation behavior in the corrosion process of the steel material in the ocean tidal range area.
2. The monitoring sensor of the invention adopts the potentiostat to control and monitor the hydrogen permeation current, and can reflect the real-time change of the hydrogen permeation behavior in the corrosion process of the steel material in the tidal range area.
3. The monitoring sensor has good sealing performance and high stability, and solves the problem of background current noise caused by seawater fluctuation in the hydrogen permeation monitoring process of the tidal range region.
4. The addition of the DMSO solvent in the electrolyte of the monitoring sensor reduces the integral freezing point of the electrolyte, and solves the problem that the sensor is applied under extreme meteorological conditions.
Drawings
FIG. 1 is a schematic diagram of a monitoring sensor according to the present invention;
FIG. 2A is a front view of the structure of a steel coupon in the monitoring sensor of the present invention;
FIG. 2B is a top view of FIG. 2A;
FIG. 3A is a front view of the upper insulating threaded cap of the monitoring sensor of the present invention;
FIG. 3B is a top view of FIG. 3A;
FIG. 4A is a front view of the structure of the bottom insulating threaded cap in the monitoring sensor of the present invention;
FIG. 4B is a top view of FIG. 4A;
FIG. 5A is a front view of the structure of the insulating housing of the present invention;
FIG. 5B is a top view of FIG. 5A;
FIG. 6A is a front view of the structure of the insulating sealing faucet of the present invention;
FIG. 6B is a top view of FIG. 6A;
FIG. 7 is a background current test result of a hydrogen permeation sensor provided in an embodiment of the present invention;
FIG. 8 is a hydrogen permeation current test result of a hydrogen permeation sensor provided in an embodiment of the present invention in a corrosive environment in a sea tidal range region;
wherein: 1 is the steel sample, 2 is the metal oxide electrode, 3 is the insulating seal cock, 4 is insulating casing, 5 is water joint, 6 is first signal lead, 7 is the second signal lead, 8 is the third signal lead, 9 is the insulating screw cap in upper portion, 10 is the steel bolt, 11 is electrolyte, 12 is the clamp, 13 is the insulating screw cap in bottom, 14 is the bulge, 15 is the screw hole, 16 is the ring channel, 17 is the pin hole.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1, the monitoring sensor of the present invention comprises a monitoring unit, a sealing unit and a fixing unit, wherein the monitoring sensor is fixed on an insulated steel cable by the fixing unit; the fixing unit of the embodiment is a hoop 12; the monitoring unit comprises a steel sample 1, a metal oxide electrode 2, a steel bolt 10 and a signal lead, the sealing unit comprises an insulating sealing cock 3, an upper insulating thread cap 9, a bottom insulating thread cap 13, an insulating shell 4 and a waterproof joint 5, the steel sample 1 is of an internal hollow structure, the upper end and the lower end of the steel sample are respectively in sealing thread connection with the upper insulating thread cap 9 and the bottom insulating thread cap 13, the insulating sealing cock 3 is in sealing thread connection with the inside of the upper end of the steel sample 1 and is positioned below the upper insulating thread cap 9, the insulating shell 4 is respectively in sealing connection with the outside of the upper insulating thread cap 9 and the bottom insulating thread cap 13, and the waterproof joint 5 is in sealing connection with the upper insulating thread cap 9; the inner side surface of a steel sample 1 is plated with palladium (the thickness of a working surface is 0.5mm), electrolyte 11 is filled in the steel sample 1, a metal oxide electrode 2 and a steel bolt 10 are respectively arranged on an insulating seal cock 3, the metal oxide electrode 2 and the steel bolt 10 are soaked in the electrolyte 11, the steel sample 1, the metal oxide electrode 2 and the steel bolt 10 are respectively connected with signal leads, and all the signal leads are led out through a waterproof connector 5 and are respectively connected with a potentiostat; the signal leads of this embodiment are three in number, and include a first signal lead 6 connected to the steel sample 1, a second signal lead 7 connected to the metal oxide electrode 2, and a third signal lead 8 connected to a steel bolt 10.
As shown in fig. 1, 2A and 2B, the steel sample 1 of the present embodiment is a cylindrical structure with two open ends, the inner surfaces of the upper and lower ends are provided with internal threads, the outer surfaces of the upper and lower ends of the steel sample 1 extend outward in the radial direction to form protruding portions 14, and the insulating housing 4 hermetically connected to the upper insulating screw cap 9 and the bottom insulating screw cap 13 is axially limited by the protruding portions 14 of the upper and lower ends.
As shown in fig. 1, 3A and 3B, the upper insulating screw cap 9 of the present embodiment has a stepped shaft-like structure, the maximum diameter portion is located outside the upper end of the steel sample 1 and is in sealed screw connection with the insulating housing 4, and the rest portions except the maximum diameter portion are inserted into the upper end of the steel sample 1 and are in sealed connection with the steel sample 1; the center of the upper insulating threaded cap 9 is provided with a threaded hole 15 along the axial direction for being in sealed threaded connection with the waterproof connector 5.
As shown in fig. 1, 4A and 4B, the bottom insulating screw cap 13 of the present embodiment has a stepped shaft-like structure, the maximum diameter portion is located outside the lower end of the steel sample 1 and is connected to the insulating housing 4 in a sealing and screw manner, and the remaining portion except the maximum diameter portion is inserted into the lower end of the steel sample 1 and is connected to the steel sample 1 in a sealing manner.
As shown in fig. 1, 5A and 5B, the insulating housing 4 of the present embodiment has a hollow cylindrical structure with two open ends, the inner wall of the insulating housing is provided with an internal thread for sealing and threaded connection with the maximum diameter portion of the upper insulating screw cap 9 or the maximum diameter portion of the bottom insulating screw cap 13, and the outer surface of the insulating housing 4 is provided with an annular groove 16 for mounting the clip 12.
As shown in fig. 1, 6A and 6B, the insulating seal cock 3 of the present embodiment is disc-shaped, the outer surface of the insulating seal cock is provided with external threads for sealing and threaded connection with the steel sample 1, and the insulating seal cock 3 is provided with lead holes 17 in the same number as the number of the signal leads along the axial direction; the number of the lead holes 17 is three, and the first signal lead 6, the second signal lead 7 and the third signal lead 8 respectively pass through one lead hole 17 and are led out through the waterproof connector 5 to be connected to the potentiostat. The insulating sealing cock 3 of the present embodiment is screwed from the upper end internal thread of the steel sample 1 to the thread bottom of the upper end internal thread, and the space between the insulating housing 4 and the upper insulating thread cap 9 and the space between the insulating housing 4 and the bottom insulating thread cap 13 are filled with the sealing epoxy resin and sealed to form a closed space.
The electrolyte 11 of this example was a mixed solution containing 30 vol% DMSO (dimethyl sulfoxide) and 70 vol% 0.2mol/L NaOH, and the electrolyte 11 was further subjected to N2And (4) carrying out aeration and oxygen removal treatment for 2 hours.
The steel sample 1 of the present example was plated with a palladium layer by electroplating; wherein the palladium plating solution consists of 35g/L [ Pd (NH3)2Cl2], 23g/L [ NH4 Cl.6H 2O ] and 50g/L [ NH4OH ], the palladium plating current is 3-3.5 mA/cm2, and the plating time is less than or equal to 8 min.
The metal oxide electrode 2 of this example is an Hg/HgO electrode and the steel bolt 10 is M3 standard.
The monitoring method comprises the following steps:
will N2Injecting the electrolyte 11 after aeration and deoxygenation into the monitoring sensor to make the electrolyte 11 fill the whole sealed space of the monitoring sensor 11, forming a three-electrode system in the monitoring sensor by taking a cylindrical steel sample 1 with one side plated with palladium as a working electrode, taking an Hg/HgO metal oxide electrode 2 as a reference electrode and taking a steel bolt 10 as an auxiliary electrode, wherein the working electrode, the reference electrode and the auxiliary electrode are respectively connected with a first signal lead 6, a second signal lead 7 and a third signal lead 8 and are connected to a potentiostat through a waterproof joint 5, then adjusting the potentiostat to make the potential of the cylindrical steel sample 1 with one side plated with palladium at 0mV (relative to the Hg/HgO electrode), monitoring and recording current data under the potential through the potentiostat, after the background current is stabilized (24h), fixing the cylindrical steel sample on an insulated steel cable through a clamp 12 and vertically placing the cylindrical steel sample in an ocean tidal range, the current signal is continuously detected and recorded by a potentiostat. The recorded current data is the hydrogen permeation current after the background current is subtracted.
See the above sea-working steel corrosion hydrogen permeation monitoring sensor in sea area of Qingdao sea-tidal range area, it can be seen from fig. 7 that the background current change situation of the hydrogen permeation sensor in indoor environment after the preparation is completed, the ordinate in fig. 7 represents the hydrogen permeation background current density, and fig. 7 shows that the hydrogen permeation current is gradually stabilized after the continuous polarization is about 24 hours. Fig. 8 shows the hydrogen permeation current change condition of the hydrogen permeation sensor after the background current is stabilized in the corrosion environment of the sea tidal range area, the ordinate in fig. 8 represents the hydrogen permeation current density, and fig. 8 shows that the permeation behavior of hydrogen to the metal matrix of the sensor caused by the natural corrosion of the hydrogen permeation sensor within the monitoring time lasting 84 hours fluctuates greatly along with the tidal change.
The invention is used for researching the hydrogen permeation condition of steel materials caused by corrosion in an ocean tidal range area in a mode of being fixed on a steel cable through a hoop 12, so as to reflect the hydrogen absorption condition of the materials in the tidal range area in the corrosion process in real time and evaluate the possibility of delayed fracture caused by hydrogen absorption of the materials caused by corrosion in the ocean tidal range area. The monitoring sensor is small in size, convenient to fix and simple to operate, is suitable for monitoring the hydrogen permeation behavior in the corrosion process of the steel material in the ocean tidal range, is good in sealing performance and high in stability, and solves the problem of background current noise caused by seawater fluctuation in the hydrogen permeation monitoring process in the tidal range.

Claims (10)

1. The utility model provides a marine steel corrodes hydrogen infiltration monitoring sensor in ocean tidal range district which characterized in that: the device comprises a monitoring unit, a sealing unit and a fixing unit, wherein the monitoring sensor is fixed on an insulated steel cable through the fixing unit, the monitoring unit comprises a steel sample (1), a metal oxide electrode (2), a steel bolt (10) and a signal lead, the sealing unit comprises an insulated sealing cock (3), an upper insulated threaded cap (9), a bottom insulated threaded cap (13), an insulated shell (4) and a waterproof joint (5), the steel sample (1) is of an internal hollow structure, the upper end and the lower end of the steel sample are respectively in sealed threaded connection with the upper insulated threaded cap (9) and the bottom insulated threaded cap (13), the insulated sealing cock (3) is in sealed threaded connection with the inner part of the upper end of the steel sample (1) and is positioned below the upper insulated threaded cap (9), and the outer parts of the upper insulated threaded cap (9) and the bottom insulated threaded cap (13) are respectively in sealed connection with the insulated shell (4), a waterproof joint (5) is hermetically connected to the upper insulating threaded cap (9); the inner side surface of the steel sample (1) is plated with palladium, electrolyte (11) is filled in the steel sample, the insulating sealing cock (3) is respectively provided with a metal oxide electrode (2) and a steel bolt (10), the metal oxide electrode (2) and the steel bolt (10) are soaked in the electrolyte (11), the steel sample (1), the metal oxide electrode (2) and the steel bolt (10) are respectively connected with signal leads, and the signal leads are led out through the waterproof joint (5) and are respectively connected with a potentiostat.
2. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the steel sample (1) is of a cylindrical structure with openings at two ends, internal threads are formed on the inner surfaces of the upper end and the lower end of the steel sample, the outer surfaces of the upper end and the lower end of the steel sample (1) extend outwards along the radial direction to form a protruding part (14), and an insulating shell (4) which is hermetically connected with the upper insulating thread cap (9) and the bottom insulating thread cap (13) is axially limited through the protruding parts (14) at the upper end and the lower end.
3. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the upper insulating threaded cap (9) is of a stepped shaft-shaped structure, the position with the largest diameter is positioned outside the upper end of the steel sample (1) and is in sealed threaded connection with the insulating shell (4), and the rest parts except the part with the largest diameter are inserted into the upper end of the steel sample (1) and are in sealed connection with the steel sample (1); and a threaded hole (15) for being in sealed threaded connection with the waterproof connector (5) is formed in the center of the upper insulating threaded cap (9) along the axial direction.
4. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the bottom insulation threaded cap (13) is of a stepped shaft-shaped structure, the position with the largest diameter is located outside the lower end of the steel sample (1) and is in sealed threaded connection with the insulation shell (4), and the rest parts except the part with the largest diameter are inserted into the lower end of the steel sample (1) and are in sealed connection with the steel sample (1).
5. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the insulating shell (4) is of a hollow cylindrical structure with two open ends, the inner wall of the insulating shell is provided with an internal thread which is used for being in sealing threaded connection with the upper insulating threaded cap (9) or the bottom insulating threaded cap (13), and the outer surface of the insulating shell (4) is provided with an annular groove (16) which is used for installing and fixing the unit.
6. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the insulating seal cock (3) is disc-shaped, and the surface system has and is used for with the external screw thread of steel sample (1) sealed threaded connection, lead wire hole (17) that quantity is the same with the signal lead wire are seted up along the axial on the insulating seal cock (3).
7. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the insulating sealing cock (3) is screwed into the threaded bottom of the upper-end internal thread from the upper-end internal thread of the steel sample (1), and sealing epoxy resin is filled and sealed between the insulating shell (4) and the upper insulating threaded cap (9) and between the insulating threaded caps (13) at the bottom of the insulating shell (4) to form a closed space.
8. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: the electrolyte (11) is a mixed solution containing 30 vol% DMSO and 70 vol% 0.2mol/L NaOH.
9. The marine steel corrosion hydrogen permeation monitoring sensor of claim 1, wherein: plating a palladium layer on the steel sample (1) in an electroplating mode; wherein the palladium plating solution consists of 35g/L [ Pd (NH3)2Cl2], 23g/L [ NH4 Cl.6H 2O ] and 50g/L [ NH4OH ], the palladium plating current is 3-3.5 mA/cm2, and the plating time is less than or equal to 8 min.
10. A method for monitoring corrosion hydrogen permeation of marine steel in an ocean tidal range area is characterized by comprising the following steps: use of a sensor as claimed in any one of claims 1 to 9, the electrolyte (11) being injected into the sensor, the potentiostat being calibrated, the current at this potential being monitored and recorded by the potentiostat as background current, the sensor being placed in the tidal range after the background current has stabilized, the current signal being continuously detected and recorded by the potentiostat, the current after subtraction of the background current being the hydrogen permeation current.
CN202111483544.4A 2021-12-07 2021-12-07 Marine steel corrosion hydrogen permeation monitoring sensor and monitoring method in ocean tidal range area Pending CN114252491A (en)

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