CN112461745B - Electrochemical probe and measuring method for on-site monitoring corrosion of weathering steel rust layer - Google Patents
Electrochemical probe and measuring method for on-site monitoring corrosion of weathering steel rust layer Download PDFInfo
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- G01N17/02—Electrochemical measuring systems for weathering, corrosion or corrosion-protection measurement
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Abstract
The invention discloses an electrochemical probe and a test method for on-site monitoring corrosion of a weathering steel rust layer, and belongs to the technical field of on-site monitoring of material corrosion. The outer edge of the electrochemical probe is composed of inert metal electrodes, the center of the probe is provided with a metal electrode to be measured, 4 reference electrodes in special positions are arranged between the metal electrode and the reference electrode, the electrodes are isolated by filling and curing insulating glue for electric signal isolation, and lead-out wires are arranged for all the electrodes. When the electrode is in work, the surface of the electrode is horizontally placed, and a large flat working surface is provided. The electrochemical monitoring probe has the characteristics of simple structure and easy processing, has strong applicability to materials, particularly considers the factor of a thin liquid layer under atmospheric corrosion, reasonably designs the structure and the connection mode of the probe, and furthest ensures the transmission of electric signals.
Description
Technical Field
The invention relates to the technical field of on-site monitoring of material corrosion, in particular to an electrochemical probe and a measuring method for on-site monitoring of corrosion of a weather-resistant steel rust layer.
Background
In order to know the corrosiveness and sustainability of the weathering steel rust layer in the natural environment in real time, particularly to carry out real-time on-site monitoring on the weathering steel in service, it is important to research and develop an electrochemical probe for on-site monitoring of the corrosion of the weathering steel rust layer.
Weather-resistant steel has better atmospheric corrosion resistance compared with common carbon steel, and the reason is that a compact oxide layer is formed on the surface, so that the corrosion medium is prevented from entering, and a steel matrix is protected [ Kaesche H.Metalli c corros, National Association of corrosion enterprises, 1985: 8; yamashita M, Miyuki H, Matsuda Y et al Br Corros J,1994,2:283 ].
Because the corrosion resistance of the steel matrix is relatively weak, whether a weathering steel rust layer with good corrosion resistance is formed on the surface of the weathering steel is a key for evaluating the corrosion resistance of the weathering steel. In the field service condition, if the compact protective rust layer is damaged, for example, the surface rust layer becomes loose or microcracks exist, the protective effect of the compact protective rust layer on a steel matrix is seriously influenced [ beam colorful phoenix, Houwini. The corrosion resistance of the weathering steel is closely related to the structure, components and electrochemical behavior of the rust layer, so that the research on the rust layer is always the focus of the research on the weathering steel, and the used instruments and devices comprise testing means such as X-ray diffraction analysis (XRD), an electron probe microanalyzer, Mossbauer spectrum analysis and various electrochemical analyses.
The invention relates to a measuring electrode combination for rapidly measuring the corrosion rate of a weathering steel rust layer on site by an electrochemical method, which is different from a method for collecting a sample on site of the rust layer and carrying out instrument analysis (such as XRD and the like) for a longer time. The electrochemical probe for on-site monitoring corrosion of the weathering steel rust layer is suitable for all electrochemical measuring instruments capable of measuring polarization potential and polarization current.
Disclosure of Invention
The invention provides an electrochemical probe and a measuring method for on-site monitoring of corrosion of a weathering steel rust layer, designs a measuring electrode combination for corrosion of the weathering steel rust layer, and carries out on-site measurement on corrosion of the rust layer by using an electrochemical method, and is particularly suitable for being applied in a scene with the requirement of timely acquiring corrosion data of the weathering steel rust layer.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
an electrochemical probe for on-site monitoring corrosion of a weathering steel rust layer, comprising an inert metal electrode, a metal electrode to be measured, a reference electrode and cured insulating glue, wherein: the inert metal electrode is arranged on the outer edge of the probe, the metal electrode to be measured is arranged in the center of the probe, a plurality of reference electrodes are arranged in the space between the inert metal electrode and the metal electrode to be measured, and gaps among the inert metal electrode, the metal electrode to be measured and the reference electrodes are filled with cured insulating glue for electric signal isolation.
The inert metal electrode is of an annular plate-shaped structure, the cross section of the inert metal electrode is in a square ring shape, and the side length of the inner frame is d; the metal electrode to be measured is positioned in the middle of the inert metal electrode, the metal electrode to be measured is of a circular structure, and the radius of the radial section of the metal electrode to be measured is R; the number of the reference electrodes is 4, the reference electrodes are respectively positioned between four corners of the inner side of the inert metal and the outer edge of the metal electrode to be measured, the reference electrodes are cylindrical, and the radius of the radial section is r; the shortest distance between the edges of any two of the three electrodes is the same.
The size design of each electrode in the electrochemical probe needs to satisfy the following formula (1):
when each electrode in the probe is assembled, the shortest distances from the outer edge of the reference electrode to two right-angle sides of a right angle of the inert electrode inner frame are both x, the shortest distance from the outer edge of the metal electrode to be measured to the inert electrode inner frame is x, the shortest distance from the outer edge of the reference electrode to the outer edge of the metal electrode to be measured is x, and the following formula (2) is required to be satisfied:
x＝d/2-R (2)。
the inert metal electrode, the metal electrode to be measured and the reference electrode are all connected with electrode leads and are led out from the lower part of the cured insulating glue (connected with lead leading-out ends); the electrochemical probe is also provided with a square cylindrical shell which is sleeved on the outer side surface of the inert metal electrode, and the inner gap of the electrochemical probe is filled by curing insulating glue.
The measuring method for monitoring the corrosion of the weathering steel rust layer on site by utilizing the electrochemical probe comprises the following steps: connecting a corrosion electrochemical monitoring instrument with each electrode of an electrochemical probe, applying an electrochemical polarization excitation signal between a metal electrode to be measured and an inert metal electrode, measuring the polarization potential of the metal electrode relative to a reference electrode, measuring the electrochemical polarization current between the metal electrode and the inert metal electrode, and finally calculating according to a Butler-Volmer formula to obtain the metal corrosion rate to be measured.
In the measuring process, for short-term (generally less than 3 months) field monitoring application, the value of the shortest distance x between the electrodes is between 0.2mm and 1.0 mm; for long-term on-site monitoring applications on an annual basis, the value of x should be between 0.5mm and 5.0 mm.
In the measuring process, the electrochemical probe for monitoring the corrosion of the weathering steel rust layer on site is horizontally arranged, has a larger horizontal working surface, and is convenient for a thin liquid layer which can cause corrosion to appear on the surface of an electrode.
The invention has the following advantages and beneficial effects:
1. the invention ensures that the shortest distance x between the outer edge of the reference electrode and the inner frame of the inert electrode, the shortest distance x between the outer edge of the reference electrode and the metal electrode to be measured and the shortest distance x between the electrode to be measured and the inner frame of the inert electrode are equal through the precise design of the size of the electrode; the design considers the factor of the thin liquid layer under atmospheric corrosion, reasonably designs the structure and the connection mode of the probe, and furthest ensures the effective transmission of the electric signal.
2. The electrochemical monitoring probe has the characteristics of simple structure and easy processing, has strong applicability to materials, particularly considers the factor of a thin liquid layer under atmospheric corrosion, reasonably designs the structure and the connection mode of the probe, and furthest ensures the transmission of electric signals.
Drawings
FIG. 1 is a schematic top view of an electrochemical probe for in situ corrosion monitoring of a weathering steel rust layer according to the present invention.
FIG. 2 is a schematic diagram of a method of designing dimensional parameters of electrodes in an electrochemical probe according to example 1 of the present invention.
Fig. 3 is a schematic diagram of a cross-sectional structure of a square in a diagonal direction of an electrochemical probe according to example 2 of the present invention.
In the figure: 1-inert metal electrode, 2-metal electrode to be measured, 3-reference electrode, 4-cured insulating glue, 5-electrode lead, 6-probe shell, 7-thin liquid layer and 8-metal rust layer (7 and 8 are formed in the service and use process of probe)
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more clear, the present invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and should not be construed as limiting the scope of the invention.
The invention provides an electrochemical probe for monitoring corrosion of a weathering steel rust layer on site, which comprises an inert metal electrode 1, a metal electrode to be measured 2, a reference electrode 3 and a cured insulating glue 4, as shown in figure 1, wherein: the inert metal electrode is arranged on the outer edge of the probe, the metal electrode to be measured is arranged in the center of the probe, a plurality of reference electrodes are arranged in the space between the inert metal electrode and the metal electrode to be measured, and gaps among the inert metal electrode, the metal electrode to be measured and the reference electrodes are filled with cured insulating glue for electric signal isolation.
The inert metal electrode is of an annular plate-shaped structure, the cross section of the inert metal electrode is in a square annular shape, and the side length of the inner frame is d; the metal electrode to be measured is positioned in the middle of the inert metal electrode, the metal electrode to be measured is of a circular structure, and the radius of the radial section of the metal electrode to be measured is R; the number of the reference electrodes is 4, the reference electrodes are respectively positioned between four inner corners of the inert metal and the outer edge of the metal electrode to be measured, the reference electrodes are cylindrical, and the radius of the radial cross section is r. The shortest distance between the edges of any two of the three electrodes is the same.
The inert metal electrode, the metal electrode to be measured and the reference electrode are all connected with an electrode lead 5 and are led out from the lower part of the cured insulating glue 4 (connected with a lead leading-out end); the electrochemical probe is also provided with a square cylindrical probe shell 6 which is sleeved on the outer side surface of the inert metal electrode, and the inner gap of the electrochemical probe is filled by curing insulating glue.
The probe is a combination of the electrodes, the surface of the electrode is generally horizontally placed, and the probe has a larger flat working surface.
Example 1:
in this embodiment, the size of each electrode is precisely designed, and as shown in fig. 2, the principle and calculation steps of the electrode size according to the formula (1) are described as follows:
in fig. 2, the line segment length OP ═ OQ ═ d/2, OA ═ OQ + QA ═ d/2+ R, OM ═ ON-MN ═ R,
equation (1) is demonstrated considering that OMA is an isosceles right triangle.
Thus, equation (1) can be followed:
and (5) carrying out electrode size design.
In this example, R is 20mm and R is 3mm, and d is 42.08 mm.
When the electrode is assembled, the shortest distances from the outer edge of the reference electrode to the two right-angle sides of the right angle of the inner frame of the inert electrode are both x, the shortest distance from the outer edge of the metal electrode to be measured to the inner frame of the inert electrode is x, and the shortest distance from the outer edge of the reference electrode to the outer edge of the metal electrode to be measured is x, so that the following formula (2) needs to be satisfied:
x＝d/2-R (2)。
example 2:
when designing the electrode, the inert electrode 1 is made of metal Ti, the reference electrode 3 is made of graphite, and the metal electrode 2 to be measured is made of high-strength weathering steel Q370.
As shown in fig. 3, fig. 3 is a schematic cross-sectional structure of the electrochemical probe in fig. 2 along a diagonal direction of a square thereof. The electrochemical probe is also provided with a probe shell 6 which can protect all electrodes and electrode leads 5 and is made of PVC material; the inert electrode 1, the metal electrode 2 to be measured and the reference electrode 3 all penetrate through the probe shell 6 through the electrode lead 5, and epoxy resin is filled in the probe shell 6 to serve as filled cured insulating glue 4.
The electrochemical probe for monitoring the corrosion of the weathering steel rust layer on site generally needs to be horizontally placed on site in a test environment, and a thin liquid layer 7 ranging from nanometer to micrometer and even up to millimeter is formed on the surface of the probe under the combined action of natural atmosphere and natural meteorological conditions; on prolonged exposure to corrosion, the surface of the metal electrode 2 to be measured also has a newly formed corrosion rust layer 8.
For long-term monitoring, the amplitude of electrochemical polarization cannot be too large, and a weak polarization technology or a linear polarization technology can be selected; the electrochemical probe for monitoring the corrosion of the weathering steel rust layer on site is suitable for all electrochemical measuring instruments capable of measuring polarization potential and polarization current.
The specific measurement process is as follows: connecting a corrosion electrochemical monitoring instrument with each electrode of an electrochemical probe, applying an electrochemical polarization excitation signal between a metal electrode 2 (high-strength weathering steel Q370) to be measured and an inert metal electrode 1 (metal Ti), measuring the polarization potential of the metal electrode 2 (high-strength weathering steel Q370) relative to a reference electrode 3 (graphite), measuring the electrochemical polarization current between the metal electrode 2 (high-strength weathering steel Q370) and the inert electrode 1 (metal Ti), and finally calculating according to a Butler-Volmer formula to obtain the metal corrosion rate to be measured.
Example 3:
this example is an extension of and further illustrates example 1.
Designed according to the size of the electrodeFormula (1):
designing the size of the electrode;
assembling formula (2) according to electrode position: and assembling the electrode by x-d/2-R.
By accurately designing the size of the electrode, the shortest distance x between the outer edge of the reference electrode and the inner frame of the inert electrode and the shortest distance x between the outer edge of the reference electrode and the metal electrode to be measured can be ensured to be equal.
As shown in table 1, some common design dimensions of the inner frame section side length d of the inert metal electrode, the section radius R of the measured electrode, the section radius R of the reference electrode, and the minimum distance x between the electrodes are recommended.
Electrochemical probes for in-situ monitoring, particularly for in-situ monitoring of weathering steel rust, are not all reasonably spaced. For short-term on-site monitoring application, the value of x is between 0.2mm and 1.0 mm; for long-term field monitoring applications on an annual basis, the value of x should be between 0.5mm and 5.0 mm. The electrode spacing is designed to take into account the potential development of the metal rust layer and to prevent it from adversely affecting other electrodes over the service life.
Table 1 partial exemplary list of optional dimensional parameters for electrochemical probe devices of the invention
Claims (5)
1. The utility model provides an electrochemistry probe that is used for on-spot monitoring resistant steel rust layer to corrode which characterized in that: the electrochemical probe comprises an inert metal electrode, a metal electrode to be measured, a reference electrode and cured insulating glue, wherein: the inert metal electrode is arranged at the outer edge of the probe, the metal electrode to be measured is arranged in the center of the probe, a plurality of reference electrodes are arranged in the space between the inert metal electrode and the metal electrode to be measured, and gaps among the inert metal electrode, the metal electrode to be measured and the reference electrodes are filled with cured insulating cement for electric signal isolation;
the inert metal electrode is of an annular plate-shaped structure, the cross section of the inert metal electrode is in a square ring shape, and the side length of the inner frame is d; the metal electrode to be measured is positioned in the middle of the inert metal electrode, the metal electrode to be measured is of a circular structure, and the radius of the radial section of the metal electrode to be measured is R; the number of the reference electrodes is 4, the reference electrodes are respectively positioned between four corners of the inner side of the inert metal and the outer edge of the metal electrode to be measured, the reference electrodes are cylindrical, and the radius of the radial section is r; the shortest distances between the edges of any two electrodes in the three electrodes are the same;
the size design of each electrode in the electrochemical probe needs to satisfy the following formula (1):
when each electrode in the probe is assembled, the shortest distances from the outer edge of the reference electrode to two right-angle sides of a right angle of the inert electrode inner frame are both x, the shortest distance from the outer edge of the metal electrode to be measured to the inert electrode inner frame is x, the shortest distance from the outer edge of the reference electrode to the outer edge of the metal electrode to be measured is x, and the following formula (2) is required to be satisfied:
2. the electrochemical probe for in situ monitoring of corrosion of a weathering steel rust layer of claim 1, characterized in that: the inert metal electrode, the metal electrode to be measured and the reference electrode are all connected with electrode leads and are led out from the lower part of the cured insulating glue; the electrochemical probe is also provided with a square cylindrical shell which is sleeved on the outer side surface of the inert metal electrode, and the inner gap of the electrochemical probe is filled by sealing with a cured insulating glue.
3. A measurement method for in-situ monitoring of corrosion of a weathering steel rust layer using an electrochemical probe according to claim 1 or 2, characterized in that: the measuring method comprises the following steps: connecting a corrosion electrochemical monitoring instrument with each electrode of an electrochemical probe, applying an electrochemical polarization excitation signal between a metal electrode to be measured and an inert metal electrode, measuring the polarization potential of the metal electrode relative to a reference electrode, measuring the electrochemical polarization current between the metal electrode and the inert metal electrode, and finally calculating according to a Butler-Volmer formula to obtain the metal corrosion rate to be measured.
4. A measurement method for in-situ monitoring of corrosion of a weathering steel rust layer by an electrochemical probe according to claim 3, characterized in that: in the measuring process, for short-term field monitoring application, the value of the shortest distance x between the electrodes is between 0.2mm and 1.0 mm; for long-term on-site monitoring applications on an annual basis, the value of x is between 0.5mm and 5.0 mm.
5. A measurement method for in-situ monitoring of corrosion of a weathering steel rust layer by an electrochemical probe according to claim 3, characterized in that: in the measuring process, the electrochemical probe for monitoring the corrosion of the weathering steel rust layer on site is horizontally arranged, has a larger horizontal working surface, and is convenient for a thin liquid layer which can cause corrosion to appear on the surface of the electrode.
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