CN113740405B - Device and method for measuring ion concentration on surface of electrode under action of direct current electric field - Google Patents
Device and method for measuring ion concentration on surface of electrode under action of direct current electric field Download PDFInfo
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Abstract
The invention discloses a device and a method for measuring the ion concentration on the surface of an electrode under the action of a direct current electric field, wherein the device comprises: a boost circuit and a measurement circuit; the boosting loop is formed by sequentially connecting a power supply, a transformer, a rectifying device and a current-limiting resistor in series from left to right; the measurement loop is poured into a glass vessel through a sample solution, an iron rod electrode is inserted into the sample solution, one end of the iron rod electrode is connected with a high-voltage end in the boosting loop, and the other end of the iron rod electrode is connected with the anode of an oscilloscope; one end of the iron plate electrode is connected with the low-voltage end in the boosting loop and is grounded, and the other end of the iron plate electrode is connected with the negative electrode of the oscilloscope. According to the principle of capacitance partial pressure, the magnitude of the voltage distribution of the sample solution is not greatly different from the external electric field, and the detection voltage can generate a large amplification effect relative to the detection current. According to the invention, after the external electric field is removed and short-circuit discharge is carried out, the two ends of the rod plate electrode are short-circuited again twice, and the change of residual charges on the surface of the electrode is observed more clearly according to the change recovery process of the electric potential.
Description
Technical Field
The invention relates to the technical field of corrosion of water attached to the surface of a hardware fitting, in particular to a device and a method for measuring ion concentration on the surface of an electrode under the action of a direct current electric field.
Background
The insulator hardware corrosion phenomenon widely exists in the ultra-high voltage direct current transmission line, and the safe operation of the transmission line is seriously influenced. Relevant scholars at home and abroad carry out research work on the problem of corrosion of the hardware of the direct-current transmission line, the electrolytic corrosion caused by leakage current is considered to be the main cause of the corrosion of the hardware, but with the operation age of the direct-current transmission line and the rise of operation voltage, a direct-current electric field becomes an important factor of the corrosion of the insulator hardware, the electrochemical corrosion caused by the water drops adsorbed on the surface of the insulator hardware is an important cause of the corrosion of the insulator hardware, and the principle that the direct-current electric field accelerates the corrosion of the hardware is not clear.
In fact, the ion migration inside the solution is difficult to measure directly, and random brownian motion can exist inside the solution without the influence of external force. Under the action of an external electric field, anions and cations move towards opposite potential directions, the ion accumulation effect on an electrode electrolyte interface is more obvious, the accumulation of space charges is accompanied with repeated trap and trap of free charges, and energy loss caused by the process can cause voltage drop in macroscopical scale.
At present, the corrosion of water adsorbed on the surface of an insulator hardware is mainly concentrated on electrolytic corrosion, the research on the corrosion of the hardware under the influence of a direct current electric field is less, the research is mainly carried out from the angle of the microstructure of an iron-zinc corrosion product under the action of the direct current electric field, the explanation on the process mechanism of ion migration under the action of the electric field is lacking, instruments such as a scanning electron microscope and an X-ray spectrometer are required to be used for post-treatment, the cost is overhigh, and the time period is long.
In the prior art, a polarization depolarization current method is mainly suitable for diagnosing the aging state of equipment such as transformers and cables, when an external electric field is removed, a polarized pole changes from ordered to disordered and is balanced from instantaneous polarization to new polarization, which is a depolarization process, and the time for a dielectric medium to reach the new polarization balance is called relaxation time. The change of the charge quantity is obtained through the change of polarization and depolarization current, and then the aging state of the insulating material is diagnosed. There are two problems with the polarization depolarization current detected using this method. First, since the power of the power supply and the magnitude of the current that can flow through the current measuring module are limited, the charging and discharging processes of the insulator capacitor cannot be instantaneously completed, so that a large error exists in the measurement result. Secondly, because the sample to be measured is an electrolyte but the solution is not a dielectric medium, the migration mechanism of ions in the solution under the action of an electric field is different from that of a solid dielectric medium, and the small current to be measured is easily influenced by external interference.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a device and a method for measuring the ion concentration on the surface of an electrode under the action of a direct current electric field.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a measuring device for ion concentration on the surface of an electrode under the action of a direct current electric field comprises: a boost circuit and a measurement circuit;
the boost circuit includes: the power supply, the transformer, the rectifying device, the current-limiting resistor and the voltage-stabilizing capacitor;
the power supply, the transformer, the rectifying device and the current-limiting resistor are sequentially connected in series from left to right;
the power supply is 220V, the rectifying device adopts a half-wave rectifying circuit, and the voltage stabilizing capacitor is connected to two ends of the output port in parallel to provide stable direct-current voltage for the measuring circuit.
The measurement circuit includes: glassware, sample solution, iron rod electrode, iron plate electrode and oscilloscope. In the glassware was poured into to sample solution, glassware thickness was 3mm, glassware's lower bottom surface and iron plate electrode direct contact, and in the iron bar electrode inserted sample solution, the high-voltage terminal in the return circuit that steps up was connected to iron bar electrode one end, and oscilloscope's 1 is connected to the other end: 1000 attenuation probe positive;
one end of the iron plate electrode is connected with the low-voltage end in the boosting loop and is grounded, and the other end of the iron plate electrode is connected with 1: 1000 negative pole of attenuating probe. The 220V mains supply is rectified into a direct-current power supply through a half-wave rectification loop, and the voltage output range is 0-10 kV.
Preferably, the iron rod has a diameter of 12mm and a length of 12cm, and is placed in the glass ware with a distance of 20mm between the iron rod and the iron plate.
Preferably, the sample solution type is a NaCl or KCl solution.
The invention also discloses a method for measuring the ion concentration on the surface of the electrode under the action of the direct current electric field, which comprises the following steps:
step one, 220V mains supply is used as an excitation source, 220V alternating current is converted into direct current through a transformer and a rectifying device, the maximum output direct current potential amplitude is 10kV, and the output direct current voltage is controlled to be adjusted within 0-10 kV according to needs.
And step two, applying positive voltage to the iron rod electrode, grounding the iron plate electrode, so as to achieve the effect of applying direct current voltage to two ends of the sample without forming electrolytic reaction, maintaining the direct current voltage for a period of time, and then reducing the voltage by using the discharge rod, wherein the voltage reduction time is kept consistent.
Step three, after the step down, get rid of the electric connecting wire at steady voltage electric capacity and iron bar, iron plate electrode both ends, make sample solution no longer bear the residual voltage of steady voltage electric capacity, reduce the interference, and with 1: 1 the attenuation probe is connected with the sample solution and the oscilloscope, and then the potential change on the oscilloscope is recorded. And (4) carrying out short circuit twice on the iron rod electrode and the iron plate electrode, and measuring the attenuation process of the voltages at the two ends of the iron rod electrode and the iron plate electrode.
And step four, deducing the attenuation process of the charge quantity according to the voltage change curve and the formulas (1) and (2), and obtaining the influence of the external voltage on the internal polarization time of the sample solution according to different pressurizing intensities and pressurizing times to define the polarization characteristic.
Q＝nzF＝Nze (2)
Wherein U is the voltage across the rod, Q is the charge adsorbed on the electrode, C is the capacitance across the rod, N is the number of particles, z is the charge valence, F is the Faraday constant, and e is the elementary charge.
And fifthly, changing the positive and negative polarities of the two ends of the iron bar electrode, retesting, and analyzing the difference of the depolarization potential curves.
And step six, changing the amplitude and time of the applied direct current voltage, measuring the time curve distribution of the potential in the solution, and researching the distribution of the ions accumulated on the surface of the electrode under different potential gradients and pressurizing time.
Compared with the prior art, the invention has the advantages that:
the ion concentration effect of the electrode surface under the external direct current field can be more clearly explained, the change rule of the charge quantity is deduced by measuring the residual potential of the electrode surface, and the measurement error is very small and is only zero drift inside the oscilloscope. The method can compare and analyze the change rule of different ions adsorbed on the surface of the electrode by measuring the recovery time of the depolarization potential of the electrode.
Drawings
FIG. 1 is a circuit diagram of a measurement device according to an embodiment of the present invention;
FIG. 2 is a graph of depolarization potentials in 0.01mol/L KCl solution of example of the present invention;
FIG. 3 is a diagram illustrating an initial state of ions after removing an applied electric field according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be further described in detail below with reference to the accompanying drawings by way of examples.
As shown in fig. 1, a device for measuring the ion concentration on the surface of an electrode under the action of a dc electric field comprises: a boost circuit and a measurement circuit;
the booster circuit includes: the power supply, the transformer 1, the rectifying device 2, the current-limiting resistor 3 and the voltage-stabilizing capacitor 4;
the power supply, the transformer 1, the rectifying device 2 and the current-limiting resistor 3 are sequentially connected in series from left to right;
the power supply is 220V, the rectifying device 2 adopts a half-wave rectifying circuit, and the voltage stabilizing capacitor 4 is connected in parallel at two ends of the output port to provide stable direct-current voltage for the measuring circuit.
The measurement circuit includes: a glass vessel 9, a sample solution 6, an iron rod electrode 5, an iron plate electrode 7 and an oscilloscope 8. In glassware 9 was poured into to sample solution 6, glassware 9 thickness was 3mm, glassware's lower bottom surface and iron plate electrode direct contact, and iron plate and solution direct contact not, iron bar electrode 5 inserts in sample solution 6, and the high-voltage end in the return circuit that steps up is connected to iron bar electrode 5 one end, and oscilloscope 8's 1 is connected to the other end: 1000 attenuation probe positive;
one end of the iron plate electrode 7 is connected with the low-voltage end in the boosting loop and grounded, and the other end is connected with the voltage of 1: 1000 negative pole of an attenuating probe. 220V commercial power is rectified into a direct-current power supply through a half-wave rectification loop, and the voltage output range is 0-10 kV. The sample of this embodiment adopts the mode of bar board pressurization, and iron bar electrode 5 connects the high voltage end of DC power supply, and bottom iron plate electrode 7 connects the negative pole of DC power supply and ground connection. The diameter of the iron rod is 12mm, the length is 12cm, the iron rod is placed in the glass ware 9, and the distance between the iron rod and the iron plate is kept constant at 20 mm. The solution type adopts NaCl solution and Kcl solution in sequence, the solution volume is kept consistent before the beginning of each experiment, the solution volume is measured after the experiment, the error is not more than 5 percent, and the loss of water caused by air evaporation is ignored.
In the embodiment, a depolarization potential detection method is adopted to measure the change of residual voltage at two ends of an electrode, and the change rule of ion migration of a solid-liquid contact surface along with a direct current electric field in a water attaching state on the surface of a hardware fitting is researched. Depolarization potential detection methods approximate polarization depolarization current detection methods.
Wherein: 1 is a transformer; 2 is a rectifying device; 3 is a current limiting resistor; 4 is a voltage-stabilizing capacitor; 5 is an iron rod electrode; 6 is a sample solution; 7 is an iron plate electrode; 8 is oscilloscope, 9 is glass ware.
A method for measuring the ion concentration on the surface of an electrode under the action of a direct current electric field comprises the following steps:
firstly, 220V mains supply is used as an excitation source, 220V alternating current is converted into direct current through a transformer 1 and a rectifying device 2, the maximum output direct current potential amplitude is 10kV, and the output direct current voltage is controlled to be adjusted within 0-10 kV according to requirements.
Secondly, by applying positive polarity voltage to the iron rod electrode 5 and grounding the iron plate electrode 7, the effect of applying direct current voltage to the two ends of the sample without forming electrolytic reaction is achieved, and after maintaining the direct current voltage for a period of time, the voltage is reduced by using the discharge rod, and the voltage reduction time is kept consistent.
Thirdly, after the step-down, get rid of the electrical connection line at voltage-stabilizing capacitor 4 and iron bar, iron plate electrode both ends, make sample solution no longer bear voltage-stabilizing capacitor's residual voltage, reduce the interference to with 1: the 1 attenuation probe was connected to sample solution 6 and oscilloscope 8, and then the potential change on oscilloscope 8 was recorded. And (3) short-circuiting the iron rod electrode 5 and the iron plate electrode 7 twice, and measuring the attenuation process of the voltage at two ends of the iron rod electrode 5 and the iron plate electrode 7.
Fourthly, deducing the attenuation process of the charge quantity according to the voltage change curve and the formulas (1) and (2), and obtaining the influence of the applied voltage on the internal polarization time of the sample solution 6 according to different pressurizing intensities and pressurizing times to define the polarization characteristic.
Q＝nzF＝Nze (2)
Wherein U is the voltage across the rod, Q is the charge adsorbed on the electrode, C is the capacitance across the rod, N is the number of particles, z is the charge valence, F is the Faraday constant, and e is the elementary charge.
Fifthly, changing the positive and negative polarities of the two ends of the iron rod electrode 5, re-testing, and analyzing the difference of depolarization potential curves.
And sixthly, changing the amplitude and time of the applied direct current voltage, measuring the time curve distribution of the potential in the solution, and researching the distribution of the ions accumulated on the surface of the electrode under different potential gradients and pressurizing time.
In this example, a voltage was applied to a 0.01mol/L Kcl solution, an auxiliary electrode was further added to the sample, and a time profile of the potential in the solution was measured as shown in FIG. 2:
after the external direct current electric field is removed, due to the action of relaxation polarization, charges are still adsorbed at the two ends of the rod plate electrode, and the direction of the charges is opposite to that of the original electric field, as shown in fig. 3. In the figure 2, the rod-plate electrode is short-circuited twice within 0-20 s, and the ion self-recovery process in the solution is carried out within 20-600 s.
Aiming at the defects of the prior art, the invention adopts a detection method for measuring the depolarization potential, and according to the principle of capacitance voltage division, the magnitude of the voltage distribution of the solution in the sample is not greatly different from the magnitude of the applied electric field, and the detection voltage can generate a larger amplification effect relative to the detection current due to the existence of the internal resistance of the solution. According to the invention, after the external electric field is removed and short-circuit discharge is carried out, the two ends of the rod plate electrode are short-circuited again twice, and the change of residual charges on the surface of the electrode is observed more clearly according to the change recovery process of the electric potential.
It will be appreciated by those of ordinary skill in the art that the examples described herein are intended to assist the reader in understanding the practice of the invention, and it is to be understood that the scope of the invention is not limited to such specific statements and examples. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (3)
1. A method for measuring the ion concentration on the surface of an electrode under the action of a direct current electric field is characterized by comprising the following steps:
the measuring method is realized under a specific measuring device;
the measuring device includes: a boost circuit and a measurement circuit;
the boost circuit includes: the power supply, the transformer, the rectifying device, the current-limiting resistor and the voltage-stabilizing capacitor;
the power supply, the transformer, the rectifying device and the current-limiting resistor are sequentially connected in series from left to right;
the power supply is 220V, the rectifying device adopts a half-wave rectifying circuit, and the voltage stabilizing capacitor is connected to two ends of the output port in parallel and provides stable direct-current voltage for the measuring circuit;
the measurement circuit includes: a glass ware, a sample solution, an iron rod electrode, an iron plate electrode and an oscilloscope; in the glassware was poured into to sample solution, glassware thickness was 3mm, glassware's lower bottom surface and iron plate electrode direct contact, and in the iron bar electrode inserted sample solution, the high-voltage terminal in the return circuit that steps up was connected to iron bar electrode one end, and oscilloscope's 1 is connected to the other end: 1000 attenuation probe positive;
one end of the iron plate electrode is connected with the low-voltage end in the boosting loop and is grounded, and the other end of the iron plate electrode is connected with 1: 1000 of attenuation probe negative; rectifying 220V mains supply into a direct-current power supply through a half-wave rectification loop, wherein the voltage output range is 0-10 kV;
the measuring method comprises the following steps:
step one, 220V mains supply is used as an excitation source, 220V alternating current is converted into direct current through a transformer and a rectifying device, the maximum output direct current potential amplitude is 10kV, and the output direct current voltage is controlled to be adjusted within 0-10 kV as required;
applying positive voltage to the iron rod electrode, and grounding the iron plate electrode to achieve the effect of applying direct current voltage to two ends of the sample without forming electrolytic reaction, maintaining the direct current voltage for a period of time, and then reducing the voltage by using a discharge rod, wherein the voltage reduction time is kept consistent;
step three, after the step down, get rid of the electric connecting wire at steady voltage electric capacity and iron bar, iron plate electrode both ends, make sample solution no longer bear the residual voltage of steady voltage electric capacity, reduce the interference, and with 1: 1, after the attenuation probe is connected with a sample solution and an oscilloscope, starting to record potential change on the oscilloscope; the iron rod electrode and the iron plate electrode are in short circuit twice, and the attenuation process of the voltage at the two ends of the iron rod electrode and the voltage at the two ends of the iron plate electrode are measured;
deducing the attenuation process of the charge quantity according to the voltage change curve and the formulas (1) and (2), and obtaining the influence of the external voltage on the internal polarization time of the sample solution according to different pressurizing strengths and pressurizing times to define the polarization characteristic;
Q＝Nze (2)
wherein U is the voltage at two ends of the bar plate, Q is the electric charge absorbed on the electrode, C is the capacitance value at two ends of the bar plate, N is the number of particles, z is the valence number of the electric charge, and e is the elementary charge;
changing the positive and negative polarities of two ends of the iron bar electrode, retesting, and analyzing the difference of depolarization potential curves;
and step six, changing the amplitude and time of the applied direct current voltage, measuring the time curve distribution of the potential in the solution, and researching the distribution of the ions accumulated on the surface of the electrode under different potential gradients and pressurizing time.
2. The measurement method according to claim 1, characterized in that: the diameter of the iron rod is 12mm, the length of the iron rod is 12cm, the iron rod is placed in a glass ware, and the distance between the iron rod and the iron plate is kept 20 mm.
3. The measurement method according to claim 1, characterized in that: the sample solution type is NaCl or KCl solution.
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| CN100514075C (en) * | 2006-07-14 | 2009-07-15 | 华北电力大学 | DC electric filed detection method of insulator for high-voltage DC transmission line |
| JP5145525B2 (en) * | 2008-01-22 | 2013-02-20 | 国立大学法人九州工業大学 | High frequency electromagnetic wave signal generation method and apparatus |
| CN107525731A (en) * | 2017-09-04 | 2017-12-29 | 成都本华清博科技有限公司 | Device and method for measuring water absorption of silicone rubber material under action of electric field |
| CN107797036B (en) * | 2017-10-19 | 2020-11-17 | 广东电网有限责任公司电力科学研究院 | Method for evaluating composite insulator interface performance based on high voltage and salt solution |
| CN109142463A (en) * | 2018-10-09 | 2019-01-04 | 李晨天 | Transient DC method for measuring conductance and device |
| CN111537430A (en) * | 2020-05-08 | 2020-08-14 | 浙江华电器材检测研究所有限公司 | Testing device and testing method for simulating atmospheric corrosion of power grid metal |
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