Reference electrode device suitable for different seawater flow rate environments

Abstract

The application provides a reference electrode device suitable for different seawater flow rate environments, which comprises a reference electrode assembly, a shell, a mounting piece and a signal cable, the shell comprises a porous ceramic shell, a semi-permeable membrane and a natural sponge, the natural sponge is arranged in the porous ceramic shell, the semi-permeable membrane is arranged on the inner wall of the porous ceramic shell, and the semi-permeable membrane is located between the inner wall of the porous ceramic shell and the natural sponge; the reference electrode assembly comprises a high-purity zinc reference electrode, the high-purity zinc reference electrode is at least partially located in the natural sponge, and the signal cable is electrically connected with the high-purity zinc reference electrode; the porous ceramic shell is fixedly connected with the mounting piece, and the mounting piece is used for being fixedly connected with a protected body. The reference electrode device suitable for different seawater flow rate environments can reduce or avoid the influence of seawater flow, has good potential stability in different seawater flow rate environments, can reduce or avoid the adhesion of marine microorganisms, and has a long service life.

Description

Technical Field

[0001] This invention relates to the field of cathodic protection and corrosion prevention technology, and in particular to a reference electrode device suitable for different seawater flow rate environments. Background Technology

[0002] Currently, the marine economy and marine technology have been elevated to an unprecedented strategic level. Strategic emerging marine industries such as coastal engineering, marine exploration, and offshore energy are rapidly developing, and numerous marine engineering projects, including offshore wind power and offshore platforms, are also developing rapidly. Offshore wind power and offshore oil platforms, among other marine engineering structures, are located in harsh marine environments, experiencing severe corrosion, and are also subjected to the impact of waves, tides, and currents. Currently, the commonly used corrosion prevention technologies for offshore wind power are impressed current cathodic protection and sacrificial anode cathodic protection, and the reference electrode is a crucial testing component for monitoring the proper functioning of cathodic protection technologies.

[0003] High-purity zinc reference electrodes are one of the most commonly used reference electrodes in marine engineering due to their advantages such as simple fabrication, convenient installation, and long service life. However, they suffer from poor potential stability. TSLee, in his study on the effect of seawater flow velocity on metallic materials, found that the higher the seawater flow velocity, the worse the stability of the high-purity zinc reference electrode. Wang Zengdi of Harbin Engineering University and Kong Xiangchao of Ocean University of China studied the performance of zinc reference electrodes under different seawater flow velocities. When the seawater flow velocity reached 4 m / s, the potential fluctuation of the high-purity zinc reference electrode reached 73 mV; when the seawater flow velocity reached 6 m / s, the potential fluctuation reached 67 mV. Because wind, waves, and ocean currents significantly affect seawater flow velocity, conventional high-purity zinc reference electrodes cannot meet the requirements for stable use under different seawater flow velocities. Furthermore, Claude E et al. believe that marine microorganisms easily adhere to the surface of conventional high-purity zinc reference electrodes, causing a continuous positive shift in the reference electrode potential, and even after stabilization, the potential fluctuation is still large, thus affecting the accuracy of potential detection.

[0004] In view of this, it is necessary to design a reference electrode device that can be applied to different seawater flow environments and reduce the attachment of marine microorganisms. Summary of the Invention

[0005] The purpose of this invention is to provide a reference electrode device suitable for different seawater flow velocity environments. It can reduce or avoid the influence of seawater flow, has good potential stability in different seawater flow velocity environments, and can reduce or avoid the attachment of marine microorganisms, and has a long service life.

[0006] This invention provides a reference electrode device suitable for different seawater flow velocity environments, comprising a reference electrode assembly, a housing, a mounting component, and a signal cable. The housing includes a porous ceramic shell, a semi-permeable membrane, and a natural sponge. The natural sponge is disposed within the porous ceramic shell, and the semi-permeable membrane is disposed on the inner wall of the porous ceramic shell, with the semi-permeable membrane located between the inner wall of the porous ceramic shell and the natural sponge. The reference electrode assembly includes a high-purity zinc reference electrode, at least partially located within the natural sponge. The signal cable is electrically connected to the high-purity zinc reference electrode. The porous ceramic shell is fixedly connected to the mounting component, which is used for fixed connection to the protected object.

[0007] Furthermore, the outer shell is located below the mounting component, and the top end of the porous ceramic shell is fixedly connected to the mounting component; the bottom of the high-purity zinc reference electrode is located inside the natural sponge, the top end of the high-purity zinc reference electrode is located inside the mounting component, the signal cable is electrically connected to the top end of the high-purity zinc reference electrode, and the electrical connection portion of the signal cable and the high-purity zinc reference electrode is located inside the mounting component; the mounting component is provided with sealing filler, and the sealing filler seals the electrical connection portion of the signal cable and the high-purity zinc reference electrode.

[0008] Furthermore, the mounting component includes a flange and a steel pipe, the steel pipe being located below the flange, the top end of the steel pipe being fixedly connected to the flange, and the flange being used for fixed connection to the protected body; the outer shell is located below the steel pipe, the top end of the porous ceramic shell having an opening, the open end of the porous ceramic shell being fixedly connected to the bottom end of the steel pipe; the reference electrode assembly also includes an insulating base, the insulating base being located inside the steel pipe, the top of the high-purity zinc reference electrode extending from the open end of the porous ceramic shell to the outside of the natural sponge and being fixedly connected to the insulating base, an mounting plate being provided inside the steel pipe, and the insulating base being fixedly connected to the mounting plate.

[0009] Furthermore, the outer wall of the open end of the porous ceramic shell is provided with a first external thread, the inner wall of the steel pipe is provided with a first internal thread, the open end of the porous ceramic shell is located inside the steel pipe, and the open end of the porous ceramic shell and the steel pipe are connected by threads.

[0010] Furthermore, the insulating base is provided with a through hole that extends vertically through the insulating base. The inner wall of the through hole is provided with a second internal thread, and the outer wall of the top of the high-purity zinc reference electrode is provided with a second external thread. The top of the high-purity zinc reference electrode is located inside the through hole, and the top of the high-purity zinc reference electrode is connected to the insulating base by a thread.

[0011] Furthermore, the reference electrode assembly also includes a conductive rod located inside the steel pipe. The conductive rod is electrically connected to the high-purity zinc reference electrode, and one end of the signal cable is electrically connected to the conductive rod. A wiring hole is provided on the flange corresponding to the position of the steel pipe. The wiring hole communicates with the inner cavity of the steel pipe. The signal cable passes through the wiring hole from inside the steel pipe and extends to the side of the flange away from the steel pipe.

[0012] Furthermore, the mounting plate divides the inner cavity of the steel pipe into a first cavity and a second cavity arranged vertically adjacent to each other. The electrical connection between the signal cable and the high-purity zinc reference electrode is located in the first cavity, and the open end of the porous ceramic shell is located in the second cavity. The sealing filler includes a first sealing filler and a second sealing filler. The first sealing filler is located in the first cavity and seals the electrical connection between the signal cable and the high-purity zinc reference electrode. The second sealing filler is located in the second cavity, and the second sealing filler is located between the open end of the porous ceramic shell and the mounting plate.

[0013] Furthermore, the porosity of the porous ceramic shell is 60% to 80%, and the pore diameter of the porous ceramic shell is 8 to 14 micrometers.

[0014] Furthermore, a ceramic glaze layer is provided on the outer surface of the porous ceramic shell.

[0015] Furthermore, the ceramic glaze layer is an antibacterial ceramic glaze layer containing rare earth composite phosphate inorganic antibacterial materials.

[0016] Furthermore, the semipermeable membrane is an anion exchange membrane, and the pore size of the semipermeable membrane is 0.2 to 0.45 micrometers.

[0017] Furthermore, the outer surface of the mounting component is provided with an anti-corrosion paint coating.

[0018] The present invention provides a reference electrode device suitable for different seawater flow velocity environments. This device consists of a shell surrounding a high-purity zinc reference electrode. The shell comprises a porous ceramic shell, a semi-permeable membrane, and a natural sponge. The porous ceramic shell possesses advantages such as high pressure resistance, resistance to acid, alkali, and organic media corrosion, low surface energy, good bioinertness, long service life, and low cost. It can effectively resist the impact of seawater at different flow velocities and filter pollutants and most microorganisms. The semi-permeable membrane effectively prevents impurity ions (such as magnesium ions and iron ions) and microorganisms from adhering to the surface of the high-purity zinc reference electrode without affecting the diffusion of Cl- and dissolved oxygen, thereby reducing or avoiding the impact on the potential of the high-purity zinc reference electrode. The natural sponge has excellent water absorption and antibacterial properties, and its soft and elastic texture allows it to buffer and store seawater, ensuring the potential stability of the high-purity zinc reference electrode. Therefore, this outer shell not only reduces or avoids the impact of excessively fast seawater flow on the surface of the high-purity zinc reference electrode, thus reducing or avoiding fluctuations in the measured potential of the high-purity zinc reference electrode, but also does not hinder the exchange of seawater and dissolved oxygen, making the reference electrode device suitable for environments with different seawater flow rates. Simultaneously, the shell surface is unfavorable for the attachment of marine organisms and can filter impurity ions, microorganisms, and pollutants in the seawater, thereby avoiding the problem of a continuous positive shift in the measured potential of the high-purity zinc reference electrode due to the attachment of microorganisms in the seawater. Furthermore, by incorporating mounting components, the porous ceramic shell is fixedly connected to the mounting components, allowing the reference electrode device to be quickly and easily installed on the protected object. Attached Figure Description

[0019] Figure 1 This is a cross-sectional schematic diagram of a reference electrode device suitable for different seawater flow velocity environments in an embodiment of the present invention.

[0020] Figure 2 for Figure 1 A cross-sectional schematic diagram of the mounting component.

[0021] Figure 3 for Figure 1 A cross-sectional schematic diagram of the reference electrode assembly.

[0022] Figure 4 for Figure 1 A cross-sectional schematic diagram of the inner shell.

[0023] Figure 5 for Figure 4 A partial cross-sectional schematic diagram of a porous ceramic shell.

[0024] Figure 6 This is a schematic diagram comparing the potential change over time of the reference electrode device in this embodiment of the invention with that of a conventional high-purity zinc reference electrode in a seawater environment with a flow rate of 4 m / s.

[0025] Figure 7This is a schematic diagram comparing the potential change over time of the reference electrode device in this embodiment of the invention with that of a conventional high-purity zinc reference electrode in a seawater environment with a flow rate of 6 m / s. Detailed Implementation

[0026] The specific embodiments of the present invention will be described in further detail below with reference to the accompanying drawings and examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

[0027] The terms “first,” “second,” “third,” “fourth,” etc. (if present) in the specification and claims of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence.

[0028] The directional terms such as "up," "down," "left," "right," "front," "back," "top," and "bottom" (if present) used in the specification and claims of this invention are defined by the position of the structures in the drawings and the relative positions of the structures, and are only for the clarity and convenience of expressing the technical solution. It should be understood that the use of directional terms should not limit the scope of protection claimed in this application.

[0029] like Figures 1 to 4 As shown in the embodiment of the present invention, a reference electrode device suitable for different seawater flow rates is applied in a seawater environment. This reference electrode device includes a reference electrode assembly 1, a housing 2, a mounting component 3, and a signal cable 4. The housing 2 includes a porous ceramic shell 21, a semi-permeable membrane 22, and a natural sponge 23. The natural sponge 23 is disposed within the porous ceramic shell 21, and the semi-permeable membrane 22 is disposed on the inner wall of the porous ceramic shell 21, located between the inner wall of the porous ceramic shell 21 and the natural sponge 23. The reference electrode assembly 1 includes a high-purity zinc reference electrode 11, which is at least partially located within the natural sponge 23. That is, external seawater must pass sequentially through the porous ceramic shell 21, the semi-permeable membrane 22, and the natural sponge 23 to reach the surface of the high-purity zinc reference electrode 11. The signal cable 4 is electrically connected to the high-purity zinc reference electrode 11 and is used to electrically connect to an external detection device, thereby transmitting the potential signal to the external detection device. The porous ceramic shell 21 is fixedly connected to the mounting component 3, which is used to fix the protected body (the protected body can be marine engineering equipment such as offshore wind power and offshore platforms).

[0030] Specifically, in this embodiment, a shell 2 is provided outside the high-purity zinc reference electrode 11. The shell 2 includes a porous ceramic shell 21, a semi-permeable membrane 22, and a natural sponge 23. The porous ceramic shell 21 has advantages such as high pressure resistance, resistance to acid, alkali, and organic media corrosion, low surface energy, good biological inertness, long service life, and low cost. It can effectively resist the impact of seawater with different flow rates and can filter pollutants and most microorganisms. The semi-permeable membrane 22 can effectively block impurity ions (such as magnesium ions, iron ions, etc.). These cations adhere to the surface of the high-purity zinc reference electrode 11 and... The impurity ions and microorganisms enter and adhere to the surface of the high-purity zinc reference electrode 11, causing potential changes, and do not affect the diffusion of Cl- and dissolved oxygen, thereby reducing or avoiding the influence of impurity ions and microorganisms on the potential of the high-purity zinc reference electrode 11; the natural sponge 23 is a natural marine organism with good water absorption and antibacterial properties, and its soft and elastic texture can play a role in buffering and storing seawater (because the natural sponge 23 has good water absorption properties, the external seawater can more easily enter the shell 2 for exchange under its suction), ensuring the potential stability of the high-purity zinc reference electrode 11. Therefore, the outer shell 2 not only reduces or avoids the impact of excessively fast seawater flow on the surface of the high-purity zinc reference electrode 11, but also does not hinder the exchange of seawater and dissolved oxygen (i.e., ensures the stability of seawater and dissolved oxygen on the surface of the high-purity zinc reference electrode 11), thereby reducing or avoiding fluctuations in the measured potential of the high-purity zinc reference electrode 11. This allows the reference electrode device to be suitable for environments with different seawater flow rates. Simultaneously, the surface of the outer shell 2 is not conducive to the attachment of marine organisms and can filter impurity ions, microorganisms, and pollutants in the seawater, thus avoiding the problem of a continuous positive shift in the measured potential of the high-purity zinc reference electrode 11 due to the attachment of microorganisms in the seawater. Furthermore, by providing the mounting component 3, the porous ceramic shell 21 is fixedly connected to the mounting component 3, allowing the reference electrode device to be quickly and easily installed on the protected object.

[0031] The reference electrode device exhibits an electrode potential of -1.044V to -1.014V (relative to a saturated calomel electrode), demonstrating excellent potential stability in seawater environments with varying flow velocities. The maximum potential fluctuation is 10mV in a seawater environment with a flow velocity of 4m / s and 15mV in a seawater environment with a flow velocity of 6m / s. Compared to traditional high-purity zinc reference electrodes, this invention's reference electrode device achieves a maximum potential fluctuation of only 15mV under different seawater flow velocities, solving the problem of unstable reference electrode potential caused by excessively fast seawater flow and microbial adhesion. It can be used in complex operating conditions such as typhoon weather or ocean currents where seawater flow velocities are excessively high, as well as in environments with abundant microorganisms. Furthermore, this reference electrode device possesses good mechanical strength and a long service life of 30 years, and offers advantages such as simple installation, convenient processing, and mass production capability.

[0032] Furthermore, in this embodiment, the porosity of the porous ceramic shell 21 is 60% to 80%, and the pore diameter of the porous ceramic shell 21 is 8 to 14 micrometers.

[0033] Furthermore, in this embodiment, the porous ceramic shell 21 is a metal oxide ceramic such as alumina ceramic or zirconium oxide ceramic.

[0034] Furthermore, such as Figure 4 and Figure 5 As shown, in this embodiment, a ceramic glaze layer 211 is provided on the outer surface of the porous ceramic shell 21. It should be noted that this ceramic glaze layer 211 is oleophobic but not hydrophobic, allowing water to pass through it smoothly (water cannot pass through a hydrophobic glaze layer). Specifically, glaze is a thin, glassy layer adhering to the surface of a ceramic body. It is generally made by mixing mineral raw materials (such as feldspar, quartz, kaolin, and chemical raw materials in a certain proportion and grinding them into a slurry-like liquid), applying it to the surface of the body, and then firing it at high temperature. It not only increases the mechanical strength, thermal stability, and dielectric strength of the ceramic, but also increases the smoothness of the ceramic surface, making it less prone to contamination. Therefore, by providing a ceramic glaze layer 211 on the outer surface of the porous ceramic shell 21, the adhesion of marine organisms to the outer surface of the porous ceramic shell 21 can be further reduced.

[0035] Furthermore, in this embodiment, the ceramic glaze layer 211 is an antibacterial ceramic glaze layer containing rare earth composite phosphate inorganic antibacterial material (i.e., the material used to make the ceramic glaze layer 211 contains rare earth composite phosphate inorganic antibacterial material). The rare earth composite phosphate inorganic antibacterial material has good antibacterial properties, which can further reduce the adhesion of marine organisms to the outer surface of the porous ceramic shell 21.

[0036] As another implementation, instead of providing a ceramic glaze layer 211 on the outer surface of the porous ceramic shell 21, a rare earth composite phosphate inorganic antibacterial material can be directly added to the material used to make the porous ceramic shell 21. That is, the porous ceramic shell 21 is an antibacterial porous ceramic shell containing a rare earth composite phosphate inorganic antibacterial material.

[0037] Furthermore, in this embodiment, the semi-permeable membrane 22 is an anion exchange membrane, which selectively allows anions (e.g., chloride ions) to pass through while blocking the passage of cations (e.g., magnesium ions, iron ions). Specifically, the semi-permeable membrane 22 can be a mixed cellulose ester filter membrane, or a semi-permeable membrane made of other materials such as cellulose acetate membrane or polypropylene membrane. The semi-permeable membrane 22 functions as a filter, effectively preventing impurity ions and microorganisms from entering and adhering to the surface of the high-purity zinc reference electrode 11, without affecting the diffusion of Cl- and dissolved oxygen.

[0038] Furthermore, in this embodiment, the pore size of the semipermeable membrane 22 is 0.2 to 0.45 micrometers.

[0039] Furthermore, such as Figure 1 As shown, in this embodiment, the outer shell 2 is located below the mounting component 3, and the top of the porous ceramic shell 21 is fixedly connected to the mounting component 3. The bottom of the high-purity zinc reference electrode 11 is located inside the natural sponge 23, and the top of the high-purity zinc reference electrode 11 is located inside the mounting component 3. The signal cable 4 is electrically connected to the top of the high-purity zinc reference electrode 11, and the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11 is located inside the mounting component 3. The mounting component 3 is provided with a sealing filler 5, which seals the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11. The sealing filler 5 can play an insulating and sealing role. The sealing filler 5 can prevent seawater from penetrating into the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11, thereby preventing corrosion of the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11. The sealing filler 5 can also insulate the high-purity zinc reference electrode 11 from the mounting component 3.

[0040] Furthermore, in this embodiment, the sealing filler 5 is an epoxy resin sealing filler.

[0041] Furthermore, such as Figures 1 to 3 As shown, in this embodiment, the mounting component 3 includes a flange 31 and a steel pipe 32. The steel pipe 32 is located below the flange 31, and its top end is fixedly connected to the flange 31. The flange 31 is used for fixed connection with the protected body. The outer shell 2 is located below the steel pipe 32. The top end of the porous ceramic shell 21 has an opening, and the opening end of the porous ceramic shell 21 is fixedly connected to the bottom end of the steel pipe 32. The porous ceramic shell 21 is at least partially located outside the steel pipe 32. The reference electrode assembly 1 also includes an insulating base 12, which is located inside the steel pipe 32. The top of the high-purity zinc reference electrode 11 extends from the opening end of the porous ceramic shell 21 to the outside of the natural sponge 23 and is fixedly connected to the insulating base 12. An mounting plate 33 is provided inside the steel pipe 32, and the insulating base 12 is fixedly connected to the mounting plate 33.

[0042] Furthermore, such as Figure 1 and Figure 4 As shown, in this embodiment, the natural sponge 23 is provided with an installation groove 231, and the bottom of the high-purity zinc reference electrode 11 is located in the installation groove 231.

[0043] Furthermore, in this embodiment, the flange 31, the steel pipe 32, and the mounting plate 33 are all made of steel. The flange 31 and the steel pipe 32 are fixed by welding, and the mounting plate 33 is fixed to the steel pipe 32 by welding.

[0044] Furthermore, in this embodiment, the steel pipe 32, the outer shell 2, and the high-purity zinc reference electrode 11 are all cylindrical structures.

[0045] Furthermore, in this embodiment, the insulating base 12 is made of nylon, which not only has good insulation properties but also good corrosion resistance.

[0046] Furthermore, such as Figure 1 As shown, in this embodiment, the insulating base 12 and the mounting plate 33 are fixedly connected by bolts 14.

[0047] Furthermore, in this embodiment, the outer wall of the open end of the porous ceramic shell 21 is provided with a first external thread (not shown in the figure), the inner wall of the steel pipe 32 is provided with a first internal thread (not shown in the figure), the open end of the porous ceramic shell 21 is located inside the steel pipe 32, and the open end of the porous ceramic shell 21 and the bottom end of the steel pipe 32 are connected by threads.

[0048] Furthermore, such as Figure 1 and Figure 3 As shown, in this embodiment, the insulating base 12 is provided with a through hole 120, which extends through the insulating base 12 from top to bottom. The inner wall of the through hole 120 is provided with a second internal thread (not shown). The outer wall of the top of the high-purity zinc reference electrode 11 is provided with a second external thread (not shown). The top of the high-purity zinc reference electrode 11 is located inside the through hole 120, and the top of the high-purity zinc reference electrode 11 is connected to the insulating base 12 by a thread.

[0049] Furthermore, such as Figure 1 and Figure 3 As shown, in this embodiment, the high-purity zinc reference electrode 11 includes a main body 111 and an extension 112 connected to each other. The extension 112 is located above the main body 111, and the outer diameter of the extension 112 is smaller than the outer diameter of the main body 111. The extension 112 is located inside the through hole 120, and a second external thread is provided on the outer wall of the extension 112. The extension 112 is threadedly connected to the insulating base 12. The signal cable 4 is electrically connected to the extension 112. The top of the main body 111 abuts against the lower surface of the insulating base 12.

[0050] Furthermore, such as Figures 1 to 3 As shown, in this embodiment, the insulating base 12 is located below the mounting plate 33, and the top wall of the insulating base 12 abuts against the lower surface of the mounting plate 33 (of course, in other embodiments, the insulating base 12 can also be disposed above the mounting plate 33). The mounting plate 33 is provided with a mounting hole 331, and the insulating base 12 is provided with a protrusion 121, which is inserted into the mounting hole 331, so that the insulating base 12 and the mounting plate 33 are more stably connected.

[0051] Furthermore, such as Figures 1 to 3As shown, in this embodiment, the reference electrode assembly 1 further includes a conductive rod 13, which is located inside the steel pipe 32 and electrically connected to the high-purity zinc reference electrode 11. One end of the signal cable 4 is electrically connected to the conductive rod 13. A wiring hole 311 is provided on the flange 31 at a position corresponding to the steel pipe 32. The wiring hole 311 communicates with the inner cavity of the steel pipe 32. The signal cable 4 passes through the wiring hole 311 from inside the steel pipe 32 and extends to the side of the flange 31 away from the steel pipe 32, thereby facilitating the electrical connection of the signal cable 4 with an external detection device.

[0052] Furthermore, such as Figures 1 to 3 As shown, in this embodiment, the conductive rod 13 is connected to the high-purity zinc reference electrode 11 by a thread. A nut 15 is provided on the conductive rod 13, and the end of the signal cable 4 is connected to the conductive rod 13 and secured by the nut 15.

[0053] Furthermore, such as Figure 1 and Figure 2 As shown, in this embodiment, the mounting plate 33 is arranged horizontally. The mounting plate 33 divides the inner cavity of the steel pipe 32 into a first cavity 32A and a second cavity 32B arranged vertically adjacent to each other. The first cavity 32A is located above the second cavity 32B. The electrical connection part of the signal cable 4 and the high-purity zinc reference electrode 11 is located in the first cavity 32A, and the opening end of the porous ceramic shell 21 is located in the second cavity 32B. The sealing filler 5 includes a first sealing filler 51 and a second sealing filler 52. The first sealing filler 51 is located in the first cavity 32A and seals the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11. The second sealing filler 52 is located in the second cavity 32B and is located between the opening end of the porous ceramic housing 21 and the mounting plate 33. The second sealing filler 52 fills the space between the outer wall of the high-purity zinc reference electrode 11 and the inner wall of the steel pipe 32. The second sealing filler 52 can prevent seawater from seeping into the electrical connection between the signal cable 4 and the high-purity zinc reference electrode 11 from the opening end of the porous ceramic housing 21.

[0054] Furthermore, in this embodiment, the outer surface of the mounting component 3 (including flange 31 and steel pipe 32) is provided with an anti-corrosion paint coating (not shown in the figure), thereby protecting the mounting component 3 in conjunction with cathodic protection.

[0055] Furthermore, such as Figure 1 and Figure 2 As shown, in this embodiment, the flange 31 is provided with bolt holes 312, which are used for the flange 31 and the protected body to be fixedly connected by bolts.

[0056] The reference electrode device for different seawater flow velocities provided in this invention embodiment consists of an outer shell 2 surrounding a high-purity zinc reference electrode 11. The outer shell 2 comprises a porous ceramic shell 21, a semi-permeable membrane 22, and a natural sponge 23. The porous ceramic shell 21 possesses advantages such as high pressure resistance, resistance to acid, alkali, and organic media corrosion, low surface energy, good bioinertness, long service life, and low cost. It can effectively resist the impact of seawater at different flow velocities and filter pollutants and most microorganisms. The semi-permeable membrane 22 effectively prevents impurity ions and microorganisms from entering and adhering to the surface of the high-purity zinc reference electrode 11 without affecting the Cl- content. - The diffusion of dissolved oxygen reduces or avoids the influence of impurity ions and microorganisms on the potential of the high-purity zinc reference electrode 11. The natural sponge 23, a natural marine organism, has excellent water absorption and antibacterial properties, and its soft and elastic texture can buffer and store seawater, ensuring the potential stability of the high-purity zinc reference electrode 11. Therefore, the outer shell 2 not only reduces or avoids the impact of excessively fast seawater flow on the surface of the high-purity zinc reference electrode 11, but also does not hinder the exchange of seawater and dissolved oxygen, thereby reducing or avoiding fluctuations in the measured potential of the high-purity zinc reference electrode 11, making the reference electrode device suitable for environments with different seawater flow rates. Simultaneously, the surface of the outer shell 2 is not conducive to the attachment of marine organisms and can filter impurity ions, microorganisms, and pollutants in seawater, thus avoiding the problem of a continuous positive shift in the measured potential of the high-purity zinc reference electrode 11 due to the attachment of microorganisms in seawater. Furthermore, by setting the mounting component 3, the porous ceramic shell 21 is fixedly connected to the mounting component 3, allowing the reference electrode device to be quickly and easily installed on the protected object.

[0057] The reference electrode device exhibits an electrode potential of -1.044V to -1.014V (relative to a saturated calomel electrode), demonstrating excellent potential stability in seawater environments with varying flow velocities. The maximum potential fluctuation is 10mV in a seawater environment with a flow velocity of 4m / s and 15mV in a seawater environment with a flow velocity of 6m / s. Compared to traditional high-purity zinc reference electrodes, this invention's reference electrode device achieves a maximum potential fluctuation of only 15mV under different seawater flow velocities, solving the problem of unstable reference electrode potential caused by excessively fast seawater flow and microbial adhesion. It can be used in complex operating conditions such as typhoon weather or ocean currents where seawater flow velocities are excessively high, as well as in environments with abundant microorganisms. Furthermore, this reference electrode device possesses good mechanical strength and a long service life of 30 years, and offers advantages such as simple installation, convenient processing, and mass production capability.

[0058] Example 1

[0059] This embodiment provides a reference electrode device suitable for different seawater flow velocity environments, including a reference electrode assembly 1, a housing 2, a mounting component 3, and a signal cable 4. The housing 2 includes a porous ceramic shell 21, a semi-permeable membrane 22, and a natural sponge 23. The porous ceramic shell 21 is made of porous alumina ceramic, and the semi-permeable membrane 22 is a cellulose acetate membrane with a pore size of 0.2 micrometers. The reference electrode assembly 1 includes a high-purity zinc reference electrode 11, an insulating base 12, and a conductive rod 13. The mounting component 3 includes a flange 31 and a steel pipe 32, with a mounting plate 33 inside the steel pipe 32. The specific connection structure is described above.

[0060] The reference electrode device of this invention was used to test the cathodic protection technology of an offshore wind power plant in the Jiangsu and Zhejiang region. Due to the frequent typhoons in the Jiangsu and Zhejiang coastal areas during the summer, and the fact that the area is mostly tidal flats with abundant nutrients and numerous pollutants and microorganisms.

[0061] Specifically, in use, the reference electrode device is installed below sea level (installation depends on specific requirements) and connected to the wind turbine pile via flange 31. During operation, seawater enters the surface of the high-purity zinc reference electrode 11 through the outer casing 2. The high-purity zinc reference electrode 11 is used for potential measurement. During typhoon weather, with wind speeds reaching 50 m / s and seawater flow speeds of approximately 4 m / s, the potential of the reference electrode device in this embodiment is -1.025 to -1.035 V (relative to a saturated calomel electrode), with a potential fluctuation of 10 mV. This is mainly due to the outer casing 2's ability to impede the impact of excessively fast seawater flow on the high-purity zinc reference electrode 11, while not hindering the exchange of seawater and oxygen molecules between the inside and outside of the outer casing 2. The natural sponge 23 can store seawater and dissolved oxygen, maintaining the stability of seawater and dissolved oxygen on the reference electrode surface, thus achieving potential stability in high-velocity seawater environments.

[0062] Furthermore, during long-term service in this sea area, the reference electrode device of this embodiment exhibits no biofouling on its surface and maintains a stable potential without any sustained positive potential shift. This is because the porous ceramic shell 21 is made of inorganic material with good biological inertness, the rare earth composite phosphate inorganic antibacterial material has extremely strong antibacterial properties, preventing biofouling, and the cellulose acetate membrane has high hydrophilicity, low adsorption, and low non-specific binding capacity, which can prevent impurities and microorganisms from entering the reference electrode surface, thus achieving effective antifouling.

[0063] Example 2

[0064] This embodiment provides a reference electrode device suitable for different seawater flow velocity environments, including a reference electrode assembly 1, a housing 2, a mounting component 3, and a signal cable 4. The housing 2 includes a porous ceramic shell 21, a semi-permeable membrane 22, and a natural sponge 23. The porous ceramic shell 21 is made of zirconium oxide porous ceramic, and the semi-permeable membrane 22 is a mixed cellulose ester filter membrane with a pore size of 0.45 micrometers. The reference electrode assembly 1 includes a high-purity zinc reference electrode 11, an insulating base 12, and a conductive rod 13. The mounting component 3 includes a flange 31 and a steel pipe 32, with a mounting plate 33 inside the steel pipe 32. The specific connection structure is described above.

[0065] The cathodic protection technology of a certain offshore oil production platform was tested using the reference electrode device of this embodiment. The offshore oil production platform is located in the deep sea, where typhoons are frequent in summer, and the ocean currents in summer and winter have a significant impact on the seawater flow velocity.

[0066] Specifically, in use, the reference electrode device is installed below sea level (installation depends on specific requirements) and connected to the offshore platform's jacket via flange 31. During operation, seawater enters the surface of the high-purity zinc reference electrode 11 through the outer shell 2. The high-purity zinc reference electrode 11 is used for potential measurement. During summer typhoon weather, wind speeds reach 50 m / s, and seawater flow speeds are approximately 3.8 m / s, resulting in a combined seawater flow speed of approximately 6 m / s. In this embodiment, the potential of the reference electrode device is -1.025 to -1.035 V (relative to a saturated calomel electrode), with a potential fluctuation of 15 mV. This is mainly due to the outer shell 2's ability to prevent the impact of excessively fast seawater flow on the high-purity zinc reference electrode 11. The zirconia ceramic has four times the toughness of alumina ceramic, exhibiting strong impact resistance, while also not hindering the exchange of seawater and oxygen molecules between the inside and outside of the outer shell 2. The 0.45-micron mixed cellulose ester filter membrane effectively prevents impurities and microorganisms from entering the reference electrode surface, achieving effective antifouling. Natural sponge 23 can store seawater and dissolved oxygen, maintain the stability of seawater and dissolved oxygen on the reference electrode surface, and achieve potential stability in high-velocity seawater environments.

[0067] To verify the potential stability of the reference electrode device of this invention and the conventional high-purity zinc reference electrode in seawater environments with different flow rates, the potential stability test methods of GB / T 7387-1999 "Technical Conditions for Marine Reference Electrodes" were used to conduct potential stability tests on the reference electrode device of this invention and the conventional high-purity zinc reference electrode in seawater environments with flow rates of 4 m / s and 6 m / s, respectively. The test methods are as follows:

[0068] Test medium: 3.5% sodium chloride solution (analytical grade);

[0069] Medium temperature: 25℃±0.5℃;

[0070] Potential stability test duration: 30 days;

[0071] Test frequency: The reference electrode is immersed in the above medium solution and soaked for 240 hours. Its potential value is measured with a saturated calomel electrode. The measurement is performed once every 24 hours, and the test cycle is 30 days.

[0072] Potential stability tests were conducted according to the above experimental methods, and the potential variation curves of the reference electrode device of this invention and the conventional high-purity zinc reference electrode over time in seawater environments with speeds of 4 m / s and 6 m / s were obtained. The test results are as follows: Figure 6 and Figure 7 As shown.

[0073] like Figure 6 As shown, in an environment with a seawater flow velocity of 4 m / s, the reference electrode device (i.e., ...) of this embodiment of the invention... Figure 6 The potential of the new reference electrode (in the context of the reference electrode) is -1.025 to -1.035 V (relative to the saturated calomel electrode), with a potential fluctuation of 10 mV; while the conventional high-purity zinc reference electrode (i.e., Figure 6 The potential of the conventional reference electrode (in the example) is -0.917 to -0.986 (relative to the saturated calomel electrode), with a potential fluctuation of 69 mV. Figure 7 As shown, in an environment with a seawater flow velocity of 6 m / s, the potential of the reference electrode device in this embodiment of the invention is -1.025 to -1.040 V (relative to a saturated calomel electrode), with a potential fluctuation of 10 mV; while the potential of a conventional high-purity zinc reference electrode is -0.917 to -0.993 (relative to a saturated calomel electrode), with a potential fluctuation of 76 mV.

[0074] Therefore, in environments with seawater flow velocities of 4 m / s and 6 m / s, the reference electrode device of this invention exhibits better potential stability and is more suitable for potential monitoring of marine structures in seawater environments with different flow velocities.

[0075] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A reference electrode device suitable for environments with different seawater flow velocities, characterized in that, The device includes a reference electrode assembly (1), a housing (2), a mounting component (3), and a signal cable (4). The housing (2) includes a porous ceramic shell (21), a semi-permeable membrane (22), and a natural sponge (23). The natural sponge (23) is disposed inside the porous ceramic shell (21), and the semi-permeable membrane (22) is disposed on the inner wall of the porous ceramic shell (21) and is located between the inner wall of the porous ceramic shell (21) and the natural sponge (23). The semi-permeable membrane (22) is an anion exchange membrane. The reference electrode assembly (1) includes a high-purity zinc reference electrode (11), which is at least partially located inside the natural sponge (23). The signal cable (4) is electrically connected to the high-purity zinc reference electrode (11). The porous ceramic shell (21) is fixedly connected to the mounting component (3), which is used to fix the device to be protected.

2. The reference electrode device suitable for different seawater flow velocity environments as described in claim 1, characterized in that, The outer shell (2) is located below the mounting component (3), and the top of the porous ceramic shell (21) is fixedly connected to the mounting component (3); the bottom of the high-purity zinc reference electrode (11) is located inside the natural sponge (23), the top of the high-purity zinc reference electrode (11) is located inside the mounting component (3), the signal cable (4) is electrically connected to the top of the high-purity zinc reference electrode (11), and the electrical connection part of the signal cable (4) and the high-purity zinc reference electrode (11) is located inside the mounting component (3); the mounting component (3) is provided with a sealing filler (5), and the sealing filler (5) seals the electrical connection part of the signal cable (4) and the high-purity zinc reference electrode (11).

3. The reference electrode device suitable for different seawater flow velocity environments as described in claim 2, characterized in that, The mounting component (3) includes a flange (31) and a steel pipe (32). The steel pipe (32) is located below the flange (31). The top end of the steel pipe (32) is fixedly connected to the flange (31). The flange (31) is used to fix the connection with the protected body. The outer shell (2) is located below the steel pipe (32). The top end of the porous ceramic shell (21) has an opening. The opening end of the porous ceramic shell (21) is fixedly connected to the bottom end of the steel pipe (32). The reference electrode assembly (1) also includes an insulating base (12). The insulating base (12) is located inside the steel pipe (32). The top of the high-purity zinc reference electrode (11) extends from the opening end of the porous ceramic shell (21) to the outside of the natural sponge (23) and is fixedly connected to the insulating base (12). An mounting plate (33) is provided inside the steel pipe (32). The insulating base (12) is fixedly connected to the mounting plate (33).

4. The reference electrode device suitable for different seawater flow velocity environments as described in claim 3, characterized in that, The porous ceramic shell (21) has a first external thread on the outer wall of the opening end, and the steel pipe (32) has a first internal thread on the inner wall. The opening end of the porous ceramic shell (21) is located inside the steel pipe (32), and the opening end of the porous ceramic shell (21) is connected to the steel pipe (32) by a thread.

5. The reference electrode device suitable for different seawater flow velocity environments as described in claim 3, characterized in that, The insulating base (12) is provided with a through hole (120) that extends through the insulating base (12) from top to bottom. The inner wall of the through hole (120) is provided with a second internal thread. The outer wall of the top of the high-purity zinc reference electrode (11) is provided with a second external thread. The top of the high-purity zinc reference electrode (11) is located inside the through hole (120), and the top of the high-purity zinc reference electrode (11) is connected to the insulating base (12) by a thread.

6. The reference electrode device suitable for different seawater flow velocity environments as described in claim 3, characterized in that, The reference electrode assembly (1) further includes a conductive rod (13), which is located inside the steel pipe (32). The conductive rod (13) is electrically connected to the high-purity zinc reference electrode (11), and one end of the signal cable (4) is electrically connected to the conductive rod (13). A wiring hole (311) is provided on the flange (31) at a position corresponding to the steel pipe (32). The wiring hole (311) is connected to the inner cavity of the steel pipe (32). The signal cable (4) passes through the wiring hole (311) from inside the steel pipe (32) and extends to the side of the flange (31) away from the steel pipe (32).

7. The reference electrode device suitable for different seawater flow velocity environments as described in claim 3, characterized in that, The mounting plate (33) divides the inner cavity of the steel pipe (32) into a first cavity (32A) and a second cavity (32B) arranged adjacent to each other. The electrical connection between the signal cable (4) and the high-purity zinc reference electrode (11) is located in the first cavity (32A), and the opening end of the porous ceramic shell (21) is located in the second cavity (32B). The sealing filler (5) includes a first sealing filler (51) and a second sealing filler (52). The first sealing filler (51) is located in the first cavity (32A) and seals the electrical connection between the signal cable (4) and the high-purity zinc reference electrode (11). The second sealing filler (52) is located in the second cavity (32B) and is located between the opening end of the porous ceramic shell (21) and the mounting plate (33).

8. The reference electrode device suitable for different seawater flow velocity environments as described in claim 1, characterized in that, The porous ceramic shell (21) has a porosity of 60% to 80% and a pore diameter of 8 to 14 micrometers.

9. The reference electrode device suitable for different seawater flow velocity environments as described in claim 1, characterized in that, The outer surface of the porous ceramic shell (21) is provided with a ceramic glaze layer (211).

10. The reference electrode device suitable for different seawater flow velocity environments as described in claim 9, characterized in that, The ceramic glaze layer (211) is an antibacterial ceramic glaze layer containing rare earth composite phosphate inorganic antibacterial materials.

11. The reference electrode device suitable for different seawater flow velocity environments as described in claim 1, characterized in that, The pore size of the semipermeable membrane (22) is 0.2 to 0.45 micrometers.

12. The reference electrode device suitable for different seawater flow velocity environments as described in claim 1, characterized in that, The outer surface of the mounting component (3) is provided with an anti-corrosion paint coating.

Images