CN215678035U - Electrochemical device for monitoring corrosion behavior of metal surface - Google Patents
Electrochemical device for monitoring corrosion behavior of metal surface Download PDFInfo
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- CN215678035U CN215678035U CN202122160296.1U CN202122160296U CN215678035U CN 215678035 U CN215678035 U CN 215678035U CN 202122160296 U CN202122160296 U CN 202122160296U CN 215678035 U CN215678035 U CN 215678035U
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Abstract
The utility model discloses an electrochemical device for monitoring corrosion behavior of a metal surface, which comprises: the tow electrode is used as a working electrode and comprises a working end face and a non-working end face, wherein the working end face is used for simulating the corrosion condition of the whole metal surface, an insulated wire is welded on the non-working end face, the saturated calomel electrode is used as a reference electrode, a microporous filter membrane, a metal base body and a data processing unit are used for scanning the potential/current of the working end face of the tow electrode and processing the potential/current data, the microporous filter membrane is used for being laid on the metal base body and is matched with a corrosion solution to form a corrosion environment, and the tow electrode and the reference electrode are respectively and independently placed on the microporous filter membrane. The electrochemical device can accurately evaluate the difference of corrosion resistance among all parts of the surface of the metal material, and can more sensitively analyze the difference of metal crevice corrosion and galvanic corrosion behaviors compared with the traditional electrochemical scheme.
Description
Technical Field
The utility model belongs to the field of electrochemical microscopic tests, and particularly relates to an electrochemical device for monitoring corrosion behavior of a metal surface.
Background
Electrochemical tests are the most widely applied methods for evaluating the corrosion resistance of materials, and mainly comprise open circuit potential-time (OCP), electrochemical impedance method (alternating current impedance EIS), electrode potential method (EP), potentiodynamic polarization curve (Tafel), Electrochemical Noise (EN) and the like. However, conventional electrochemical tests collect more global, average electrochemical information from the surface of the sample, which inevitably reduces the sensitivity and accuracy of local electrochemical information collection from the surface of the sample. In fact, corrosion of metallic materials tends not to be achieved at once, but rather begins locally from a point, degrading the process of failure over time and thus overall.
The array electrode, also called Wire Beam Electrode (WBE), is formed by arranging hundreds of metal wires in a 10 × 10, 11 × 11 or more array form, wherein each metal wire is not connected and insulated with each other, thus ensuring that the surface potential and current of each metal wire relative to the saturated calomel electrode can be measured, and therefore, the potential current distribution information of the whole surface of the array electrode can be obtained macroscopically. Meanwhile, by combining the micro-integration idea, the surface area of a single wire only accounts for one percent of the total working end area of the whole array electrode, and the geometric dimension of the single wire is very small (usually the diameter is 1.5mm), so that the electrochemical process generated on the surface of the single wire is considered to be uniform, namely uniform corrosion is generated, the traditional single large electrode can be simulated by utilizing a plurality of metal microelectrodes, the traditional single large electrode is different from the traditional electrode which can only obtain average electrochemical information of a unit area, and the electrochemical parameter variation of each position of the electrode surface can be provided. Therefore, the array electrode has extremely important significance for detecting local corrosion of metal and is also a very effective detection means. Compared with the traditional electrode, the electrochemical sensor can provide overall electrochemical parameters and measure information such as potential at different positions, current density distribution and difference, and the application range of the electrochemical sensor is expanded by combining with methods such as a potentiodynamic polarization curve, alternating current impedance, electrochemical noise and the like.
In recent years, researchers have developed tow electrode technology into the detection of pesticides and coating as probes. The organic molecular film is uniformly coated on the surfaces of the tow electrodes, and the same electric signal is applied to each electrode, so that the electrochemical parameters of different parts are obtained, and the rapid and qualitative evaluation of the pesticide residue is realized. The Huang Fuchuan is also applied to the characteristic that the filament bundle electrode can measure the interval potential distribution nonuniformity in the study of the influence of the addition of the antirust agent on the instability of the antirust oil film.
Chinese patent publication No. CN107860707A discloses a method for characterizing the heterogeneity of galvanic corrosion of micro-regions on the surface of aluminum alloy by using a tow electrode. The technical scheme of the patent application is that the test is carried out in the solution, but the gap corrosion and galvanic corrosion behaviors between two metal materials (the two metal materials are made of the same material or different materials) cannot be simulated well in the solution, and substances in the solution are too complex, so that certain interference can be generated on electrochemical signals, and then deviation is caused, and the measured data are not accurate enough.
Therefore, it is desirable to provide an electrochemical device that can simulate the corrosion behavior of a metal surface between two metallic materials.
SUMMERY OF THE UTILITY MODEL
The utility model aims to provide an electrochemical device for monitoring the corrosion behavior of a metal surface, which can effectively simulate the crevice corrosion and galvanic corrosion behaviors of a metal material and has the advantages of equivalence, rapidness and high efficiency.
The utility model adopts the following technical scheme to realize the purpose:
an electrochemical device for monitoring the corrosion behavior of a metal surface, the electrochemical device comprising:
the tow electrode is used as a working electrode and comprises a working end face and a non-working end face, the working end face is used for simulating the corrosion condition of the whole metal surface, the non-working end face is welded with an insulated wire,
a saturated calomel electrode, which serves as a reference electrode,
a microporous filter membrane is arranged on the inner wall of the filter,
a metal matrix, and
a data acquisition and processing unit for potential/current scanning of the working end face of the tow electrode and processing the potential/current data,
the microporous filter membrane is laid on a metal substrate and matched with a corrosive solution to form a corrosive environment, and the tow electrode and the reference electrode are respectively and independently placed on the microporous filter membrane.
Preferably, the electrochemical device further comprises a container for containing the etching solution.
Preferably, the wire bundle electrode comprises 50-200 metal wires.
Preferably, each wire has a diameter of 1 to 2 mm.
Preferably, each wire is covered with an insulating layer except for two ends, and cured and arranged in an array.
Preferably, the array is frontal in cross-section and the cross-section of the array, when cured, to form the tow electrode is circular.
Preferably, the microporous filter membrane has a pore radius of 0.1-0.4 μm and a thickness of 0.5-0.8 mm.
Preferably, the metal base is in the shape of a cylinder.
Preferably, the shape and area of the microporous filter membrane are the same as those of the bottom surface of the metal substrate.
Preferably, the data acquisition and processing unit comprises an array tow electrode potential current scanner and a controller. The array tow electrode potential current scanner is used for scanning the surface potential/current of the working end face of the tow electrode, and the controller is used for controlling the operation of the array tow electrode potential current scanner and processing potential/current data.
The electrochemical device for monitoring the corrosion behavior of the metal surface can accurately capture the distribution information of the potential current of the metal surface by constructing a thin liquid film test system, accurately evaluate the corrosion resistance difference between all parts of the metal material surface, and can more sensitively analyze the difference of the metal crevice corrosion and the galvanic corrosion behavior compared with the traditional electrochemical device.
The electrochemical device of the utility model can be used for simulating and detecting the corrosion phenomenon between the automobile internal bridging pieces, such as parts such as bolts and nuts. This is because the parts are made of different metal materials or the same metal material, and the galvanic corrosion phenomenon is frequent, but is not easy to detect. The electrochemical device can well simulate and research the corrosion from the mechanism and provide a theoretical basis.
Drawings
FIG. 1 is one embodiment of an electrochemical device for monitoring the corrosion behavior of a metal surface of the present invention. Wherein, 1 represents a metal matrix, 2 represents a microporous filter membrane (which forms a thin liquid membrane after being wetted by a corrosive solution), 3 represents a tow electrode (used as a working electrode), 4 represents a saturated calomel electrode (used as a reference electrode), 5 represents a controller, 6 represents an array tow electrode potential current scanner, and 7 represents a container.
Fig. 2 is a schematic structural view of a tow electrode of the electrochemical device of fig. 1, wherein 3' denotes a working end face, 3 "denotes a non-working end face, and 31 denotes an insulated wire drawn from the non-working end face.
FIG. 3 is a cross-sectional view of the contact of the tow electrode, reference electrode, and microfiltration membrane of the electrochemical device of FIG. 1. Wherein 2 represents a microporous filter membrane, 3 'represents a working end face (the middle square of the working end face is the section of a metal wire array), and 4' represents the working end of a saturated calomel electrode.
Detailed Description
Tow electrodes are commercially available and may be prepared according to conventional methods known in the art for the purpose of describing the present invention. In one embodiment of the present utility model, the method for manufacturing the tow electrode comprises: (1) taking 100 metal wires with the diameter of 1.5mm, sequentially polishing the metal wires with 200#, 600#, 800#, 1000#, 2000# sand paper, cleaning with acetone and ethanol, and performing acetone ultrasonic: after visual inspection, the sample meets the requirements (the surface is flat and smooth, no residual magazine is observed by naked eyes, and metallic luster exists), is washed by clear water, is dried by cold air, and is immediately put into acetone for ultrasonic cleaning, wherein the ultrasonic cleaning time is not more than 30 s; the metal wire is impregnated with insulating paint, so that the effects of good insulation and preventing crevice corrosion (no hole and crack are observed by amplifying 800 times), and two end surfaces of the metal wire are non-insulating surfaces and are respectively used as a non-working end surface and a working end surface; (2) arranging the metal wires into a dense array, curing the dense array by using epoxy resin, respectively welding insulating copper wires on the non-working end surface of each metal wire in the cured array, leading out the metal wires, sequentially polishing the working end surfaces of the metal wires by 200#, 600#, 800#, 1000# and 2000# abrasive paper step by step, cleaning the metal wires by using absolute ethyl alcohol and distilled water, and putting the metal wires into a dryer for standby application.
In the description of the utility model, the materials of the tow electrode and the metal matrix are respectively selected from copper, copper alloy, aluminum alloy, iron alloy, titanium alloy, nickel alloy and high-entropy alloy. The materials of the tow electrode and the metal matrix can be the same or different.
In the description of the present invention, the etching solution is dropped on the microfiltration membrane and then permeates into the microfiltration membrane to form a thin liquid film with the microfiltration membrane, which is used as an etching medium. The corrosion solution includes but is not limited to NaCl water solution with mass concentration of 0.5-5.0%,
in the description of the utility model, the microporous filter membrane is made of nylon, the pore radius is 0.1-0.4 μm, and the thickness is 0.5-0.8 mm. In one embodiment of the present invention, the thickness of the microfiltration membrane is δ 0.5 mm. The addition amount of the corrosive solution on the microporous filter membrane is usually 1-2 ml/cm2. After the corrosion solution is dripped on the microporous filter membrane, the corrosion solution can slowly permeate the whole microporous filter membrane, so that the tow electrode, the reference electrode and the metal matrix which are placed on the microporous filter membrane are connected to form a current conduction loop, and the actual conditions of crevice corrosion and galvanic corrosion among different metals are simulated and constructed.
In the description of the present invention, the data acquisition and processing may also use potential and current data acquisition and processing devices commonly used in the art.
The utility model will be further illustrated with reference to the following specific examples. The specific embodiment is implemented on the premise of the technical scheme of the utility model, and a detailed implementation mode and an operation process are given. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
As shown in fig. 1, in the present embodiment, the electrochemical device for monitoring the corrosion behavior of the metal surface comprises a metal substrate 1 in a cylindrical shape, a microporous filter membrane 2, a tow electrode 3, a saturated calomel electrode 4, a controller 5, an array tow electrode potential current scanner 6 and a container 7.
The tow electrode 3 is used as a working electrode and comprises a working end face 3 'and a non-working end face 3', the working end face 3 'is a non-insulated exposed metal wire section and is used for simulating the corrosion condition of the whole metal surface, and a plurality of insulated wires 31 are welded on the non-working end face 3', wherein each metal wire is connected with one insulated wire (see figure 2).
The tow electrode 3 is made of a plurality of metal wires, each of which is covered with an insulating layer except for both end faces thereof, and then cured into an array. The overall cross-section of the tow electrode 3 is circular, with the array of wires in the cross-section being square (i.e. square with origin) (see figure 3).
The array tow electrode potential current scanner 6 is used for scanning the surface potential/current of the working end face 3' of the tow electrode 3.
The controller 5 is respectively connected with the saturated calomel electrode 4 and the array tow electrode potential current scanner 6 through wires and is used for controlling the operation of the array tow electrode potential current scanner 6 and processing the surface potential/current data of the working end face of the tow electrode 3, which is obtained by the array tow electrode potential current scanner 6.
In this embodiment, the container 6 is a bottle containing the formulated etching solution.
When the wire bundle electrode is in work, the array wire bundle electrode potential current scanner 6 is used for scanning the surface potential/current of the working end face 3' of the wire bundle electrode 3, and the controller controls and circularly measures the open-circuit potential and the coupling current of each metal wire forming the wire bundle electrode. For example, the controller controls the surface potential and the current to be scanned for 10-20 min; the surface potential scanning measures the open circuit potential of the relative saturated calomel electrode of the single metal wire electrode in the tow electrode one by one, the surface current scanning measures the coupling current between the integral electrode WR formed by any single metal wire electrode Wj and the other 99 metal wire electrodes which are mutually short-circuited through a zero resistance current meter, wherein j is 1-100, and j is the ordinal number of the single metal wire electrode in the tow electrode; and controlling the amplitude of the excitation sine wave to be 5-20 mV by adopting an electrochemical impedance spectrum, and carrying out frequency sweep under an open-circuit potential within a range of 100kHz-0.01 Hz. And obtaining surface potential/current information of the working end face of the tow electrode, wherein the surface potential/current information comprises charge transfer resistance, average corrosion current density, average corrosion potential and the number of corroded electrodes, and further judging the corrosion condition of the working end face according to the surface potential/current information.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. All simple and equivalent changes and modifications made according to the claims and the content of the specification of the present application fall within the scope of the claims of the present patent application. The utility model has not been described in detail in order to avoid obscuring the utility model.
Claims (10)
1. An electrochemical device for monitoring the corrosion behavior of a metal surface, said electrochemical device comprising:
the tow electrode is used as a working electrode and comprises a working end face and a non-working end face, the working end face is used for simulating the corrosion condition of the whole metal surface, the non-working end face is welded with an insulated wire,
a saturated calomel electrode, which serves as a reference electrode,
a microporous filter membrane is arranged on the inner wall of the filter,
a metal matrix, and
a data acquisition and processing unit for scanning the potential/current of the working end face of the tow electrode and processing the potential/current data,
the millipore filter membrane is used for being laid on the metal matrix and forming a corrosion environment by matching with a corrosion solution, and the tow electrode and the reference electrode are respectively and independently placed on the millipore filter membrane.
2. The electrochemical device for monitoring the corrosion behavior of a metal surface of claim 1, further comprising a container for holding the corrosion solution.
3. The electrochemical device for monitoring the corrosion behavior of a metal surface according to claim 1, wherein the wire bundle electrode comprises 50-200 metal wires.
4. An electrochemical device for monitoring the corrosion behavior of a metal surface as defined in claim 3, wherein each wire has a diameter of 1-2 mm.
5. An electrochemical device for monitoring the corrosion behavior of a metal surface as claimed in claim 3, wherein each wire is covered with an insulating layer except at both ends and cured in an array.
6. The electrochemical device according to claim 5, wherein the array is frontal in cross-section and the cross-section that is cured to form the tow electrode is circular.
7. The electrochemical device for monitoring corrosion behavior of a metal surface as claimed in claim 1, wherein the material of the microporous filter membrane has a pore radius of 0.1-0.4 μm and a thickness of 0.5-0.8 mm.
8. The electrochemical device for monitoring the corrosion behavior of a metal surface of claim 1, wherein said metal substrate is in the shape of a cylinder.
9. The electrochemical device for monitoring the corrosion behavior of a metal surface as recited in claim 8, wherein said microporous filter membrane has the same shape and area as the bottom surface of said metal substrate.
10. The electrochemical apparatus for monitoring the corrosion behavior of a metal surface of claim 1, wherein said data acquisition and processing unit comprises an array tow electrode potential current scanner and a controller.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202122160296.1U CN215678035U (en) | 2021-09-08 | 2021-09-08 | Electrochemical device for monitoring corrosion behavior of metal surface |
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| CN202122160296.1U CN215678035U (en) | 2021-09-08 | 2021-09-08 | Electrochemical device for monitoring corrosion behavior of metal surface |
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