CN114894873A - Chloride ion sensing electrode and preparation method and application thereof - Google Patents
Chloride ion sensing electrode and preparation method and application thereof Download PDFInfo
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- CN114894873A CN114894873A CN202210382643.1A CN202210382643A CN114894873A CN 114894873 A CN114894873 A CN 114894873A CN 202210382643 A CN202210382643 A CN 202210382643A CN 114894873 A CN114894873 A CN 114894873A
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title abstract description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052709 silver Inorganic materials 0.000 claims abstract description 57
- 239000004332 silver Substances 0.000 claims abstract description 57
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 36
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 36
- 230000008021 deposition Effects 0.000 claims abstract description 34
- 239000003822 epoxy resin Substances 0.000 claims abstract description 15
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 15
- 238000000151 deposition Methods 0.000 claims description 38
- 238000005498 polishing Methods 0.000 claims description 30
- 238000004140 cleaning Methods 0.000 claims description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000012153 distilled water Substances 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 229910000831 Steel Inorganic materials 0.000 description 13
- 239000010959 steel Substances 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 239000004568 cement Substances 0.000 description 9
- 239000004567 concrete Substances 0.000 description 7
- 239000011150 reinforced concrete Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000002386 leaching Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004506 ultrasonic cleaning Methods 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- 230000002787 reinforcement Effects 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
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- C25D5/56—Electroplating of non-metallic surfaces of plastics
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/307—Disposable laminated or multilayered electrodes
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Abstract
The invention discloses a chloride ion sensing electrode and a preparation method and application thereof. The chloride ion sensing electrode comprises a PVC pipe, an epoxy resin condensate filled in the PVC pipe and a filamentous silver electrode packaged in the epoxy resin condensate, wherein one end of the filamentous silver electrode extends out of the bottom surface of the PVC pipe, a first AgCl deposition layer and a second AgCl deposition layer are sequentially arranged on the end surface of the end of the filamentous silver electrode, the compactness of the first AgCl deposition layer is lower than that of the second AgCl deposition layer, and the other end of the filamentous silver electrode extends out of a hole reserved in the side wall of the PVC pipe. The chloride ion sensing electrode has the advantages of high sensitivity, good stability, good durability, simple structure and simple preparation process, and is suitable for large-scale industrial application.
Description
Technical Field
The invention relates to the technical field of concrete detection, in particular to a chloride ion sensing electrode and a preparation method and application thereof.
Background
Reinforced concrete is a composite material formed by adding reinforcing mesh, steel plates or steel fibers to concrete, and the reinforcing mesh, steel plates and steel fibers can improve the mechanical properties of the concrete. Stress expansion due to corrosion of the steel reinforcement is one of the important factors that cause the decrease in the durability of the reinforced concrete. The pH value of the pore solution after cement hydration is generally between 12.6 and 13.5, and under the high-alkalinity environment, a relatively stable passive film can be formed on the surface of the steel bar, so that the steel bar can be protected from directly contacting corrosive factors. However, once the aggressive ions penetrate into the interior of the concrete and reach the surface of the steel reinforcement, the passive film on the surface of the steel reinforcement is damaged, causing corrosive damage to the steel reinforcement. Among the factors inducing the corrosion of the steel bars, chloride ions are the most recognized factors for damaging the passivation film of the steel bars and causing the rapid corrosion of the steel bars. Chloride ions can damage a passivation film and complex ferrous ions, promote the dissolution of iron, accelerate the electrochemical corrosion process, and the accumulation of corrosion products can cause volume expansion, further damage the structure of concrete and influence the durability of a reinforced concrete structure. Therefore, for the reinforced concrete structure, especially the reinforced concrete structure in the marine environment serving high chlorine salt, the detection of the chloride ion concentration in the used cement raw material leachate or the in-situ monitoring of the chloride ion concentration in the concrete is very important.
At present, indicator titration or potentiometric titration is mostly adopted for detecting the concentration of chloride ions in a cement leaching solution, and the problems of long time consumption, low efficiency, high cost and the like exist. In recent years, ion selective electrode testing methods have been developed, but common ion selective electrodes are easily interfered by other ions in the testing process, and generally need to be tested in a neutral environment, and the application is greatly limited. In addition, the current commonly used ion sensing electrode for detecting chloride ions has slow test response and poor durability, the service life in slurry is less than 2 months, and the practical application requirements are difficult to completely meet.
Therefore, the development of the chloride ion sensing electrode with high sensitivity, good stability and good durability is of great significance.
Disclosure of Invention
The invention aims to provide a chloride ion sensing electrode and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a chloride ion sensing electrode comprises a PVC pipe, an epoxy resin condensate filled in the PVC pipe and a filiform silver electrode encapsulated in the epoxy resin condensate; one end of the filiform silver electrode extends out of the bottom surface of the PVC pipe, and the end surface of the end is also sequentially provided with a first AgCl deposition layer and a second AgCl deposition layer; the compactness of the first AgCl deposition layer is lower than that of the second AgCl deposition layer; and the other end of the filiform silver electrode extends out of a hole reserved on the side wall of the PVC pipe.
Preferably, one end of the filiform silver electrode extends out of the center of the bottom surface of the PVC pipe.
Preferably, the inner diameter of the PVC pipe is 8 mm-16 mm.
Preferably, the filiform silver electrode has a diameter of 0.1 mm-2 mm, a length of 10 mm-30 mm and a purity of > 99.5%.
The preparation method of the chloride ion sensing electrode comprises the following steps:
1) fixing the PVC pipe and the filamentous silver electrode, wherein one end of the filamentous silver electrode extends out of the bottom surface of the PVC pipe, the other end of the filamentous silver electrode extends out of a hole reserved in the side wall of the PVC pipe, and then injecting epoxy resin and a curing agent into the PVC pipe for defoaming and curing;
2) polishing and cleaning the end face of the end of the filamentous silver electrode extending out of the bottom surface of the PVC pipe, immersing the end face into an HCl solution, taking the filamentous silver electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode, performing cyclic voltammetry treatment, immersing the end face into a KCl solution for first electrochemical deposition, reducing current density and performing second electrochemical deposition to obtain the chloride ion sensing electrode.
Preferably, the defoaming mode in the step 1) is to exhaust bubbles by negative pressure, and the defoaming time is 5-20 min.
Preferably, the polishing in step 2) is specifically performed by: polishing with #500 abrasive paper in distilled water environment for 0.5-1 min, polishing with #1000 abrasive paper in distilled water environment for 1-2 min, polishing with #2000 abrasive paper in distilled water environment for 5-10 min, and polishing with #4000 abrasive paper in distilled water environment for 20-30 min.
Preferably, the specific operation of the cleaning in the step 2) is as follows: and (4) carrying out ultrasonic cleaning by using ethanol and acetone in sequence, wherein the cleaning is carried out for 5-10 min each time.
Preferably, the concentration of the HCl solution in the step 2) is 0.05 mol/L-2.0 mol/L.
Preferably, the upper potential scan limit of the cyclic voltammetry treatment in the step 2) is 0.5V-1.0V, the lower potential scan limit is-0.6V-1.2V, and the scan rate is 1 mV/s-20 mV/s.
Preferably, the concentration of the KCl solution in the step 2) is 0.1-3.0 mol/L.
Preferably, the first electrochemical deposition in step 2) is carried out at a current density of 4.0mA/cm 2 ～10.0mA/cm 2 Is carried out under the condition of (1), and the deposition time is 200-500 s.
Preferably, the second electrochemical deposition in step 2) is carried out at a current density of 0.5mA/cm 2 ～2.0mA/cm 2 The deposition time is 1000-4000 s.
The thickness calculation formula of the AgCl deposition layer in the chloride ion sensing electrode is as follows:
The detection principle of the chloride ion sensing electrode of the invention is as follows: during the test, electrochemical reaction
May occur at the interface of the chloride ion sensing electrode, when the concentration of chloride ions near the surface of the electrode changes, in order to maintain the K of AgCl sp The precipitation or dissolution of AgCl alters the Ag in the vicinity of the electrode + Concentration, in turn, causes a change in the potential of the sensing electrode.
The beneficial effects of the invention are: the chloride ion sensing electrode has the advantages of high sensitivity, good stability, good durability, simple structure and simple preparation process, and is suitable for large-scale industrial application.
Specifically, the method comprises the following steps:
1) compared with the chloride ion sensing electrode which is sold in the market and made of the same basic material, the durability of the chloride ion sensing electrode for measuring the cement leaching liquid is greatly improved (by more than 6 times);
2) the binding force of the silver substrate and the AgCl film layer in the chloride ion sensing electrode is strong, the sensitivity is ensured, and meanwhile, the long-term detection can be carried out on the chloride ion content in a concrete pore solution before the corrosion of reinforced concrete is induced (a reference electrode is connected with the chloride ion sensing electrode through a high-resistance potential meter to form a loop, the long-term monitoring of open-circuit potential is carried out on a cement leaching solution, and after the potential is stabilized, the potential is shifted abnormally), so that important parameters can be provided for the induction of the corrosion of the reinforced concrete.
Drawings
Fig. 1 is a schematic structural diagram of a chloride ion sensing electrode according to the present invention.
The attached drawings indicate the following: 10. PVC pipes; 20. a cured epoxy resin; 30. a filiform silver electrode.
FIG. 2 is an SEM photograph showing a cross-section of one end of the chloride ion-sensing electrode of example 1.
FIG. 3 is an SEM photograph showing a cross section of one end of the chloride ion-sensing electrode of example 2.
Fig. 4 is an SEM image of a cross section of one end of the chloride ion sensing electrode of comparative example 1.
Fig. 5 is a graph showing the response potential of the chloride ion sensing electrodes of example 1, comparative example 1 and comparative example 2 in a cement leaching solution as a function of time.
Fig. 6 is a graph of response potential versus time for the chloride ion sensing electrodes of example 2, comparative example 1, and comparative example 3 in a cement leach solution.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a chloride ion sensing electrode (the schematic structural diagram is shown in figure 1) comprises a PVC pipe 10, an epoxy resin cured product 20 filled in the PVC pipe 10 and a filamentous silver electrode 30 encapsulated in the epoxy resin cured product 20; one end of the filiform silver electrode 30 extends out of the bottom surface of the PVC pipe 10, and the end surface of the end is also sequentially provided with a first AgCl deposition layer and a second AgCl deposition layer; the compactness of the first AgCl deposit layer is lower than that of the second AgCl deposit layer; the other end of the filiform silver electrode 30 extends out of a hole reserved on the side wall of the PVC pipe 10.
The preparation method of the chloride ion sensing electrode comprises the following steps:
1) fixing a PVC pipe with the inner diameter of 10mm, the outer diameter of 14mm and the height of 10mm and a filamentous silver electrode with the diameter of 0.5mm, the length of 30mm and the purity of more than 99.5%, folding the filamentous silver electrode into an L shape, extending one end of the filamentous silver electrode out of the bottom surface of the PVC pipe, extending the other end of the filamentous silver electrode out of a hole reserved on the side wall of the PVC pipe, filling a gap between the filamentous silver electrode and the hole with paraffin, mixing epoxy resin glue and a curing agent according to the mass ratio of 3:1, vacuumizing to 0.08MPa for 10min for defoaming, injecting into the PVC pipe, vacuumizing to 0.08MPa for 25min for defoaming, and standing at room temperature for 24h for curing;
2) polishing the end surface of one end of the filamentous silver electrode, which extends out of the bottom surface of the PVC pipe, wherein the polishing operation comprises the following steps: polishing with #500 sandpaper in a distilled water environment for 1min, then polishing with #1000 sandpaper in a distilled water environment for 2min, then polishing with #2000 sandpaper in a distilled water environment for 10min, then polishing with #4000 sandpaper in a distilled water environment for 30min, and then cleaning, wherein the specific cleaning operation is as follows: sequentially ultrasonic cleaning with ethanol and acetone for 10min, soaking in 0.1mol/L HCl solution, using filiform silver electrode as working electrode, platinum electrode as counter electrode, and saturated calomel electrode (saturated Ca (OH)) 2 SCE, standard reduction electrode potential at 25 ℃ of about +0.2415V) as a reference electrode, performing cyclic voltammetry treatment, wherein the upper potential scanning limit of the cyclic voltammetry treatment is 1.0V, the lower potential scanning limit is-1.0V, the scanning rate is 10mV/s, and immersing the solution into KCl solution with the concentration of 0.1mol/L at the current density of 8.0mA/cm 2 Depositing for 200s under the condition of (1) to form an AgCl deposition layer with low compactness, and then, depositing at a current density of 2.0mA/cm 2 Depositing for 1000s under the condition of (1) to form an AgCl deposition layer with high compactness, and obtaining the chloride ion sensing electrode.
Example 2:
a chloride ion sensing electrode (the structure is the same as that of the embodiment 1) is prepared by the following steps:
1) fixing a PVC pipe with the inner diameter of 10mm, the outer diameter of 14mm and the height of 10mm and a filamentous silver electrode with the diameter of 0.5mm, the length of 30mm and the purity of more than 99.5%, folding the filamentous silver electrode into an L shape, extending one end of the filamentous silver electrode out of the bottom surface of the PVC pipe, extending the other end of the filamentous silver electrode out of a hole reserved on the side wall of the PVC pipe, filling a gap between the filamentous silver electrode and the hole with paraffin, mixing epoxy resin glue and a curing agent according to the mass ratio of 3:1, vacuumizing to 0.08MPa for 10min for defoaming, injecting into the PVC pipe, vacuumizing to 0.08MPa for 25min for defoaming, and standing at room temperature for 24h for curing;
2) polishing the end surface of one end of the filamentous silver electrode, which extends out of the bottom surface of the PVC pipe, wherein the polishing operation comprises the following steps: first using #500 sandpaper in distilled water environmentPolishing for 1min, then polishing for 2min in a distilled water environment by using #1000 abrasive paper, polishing for 10min in a distilled water environment by using #2000 abrasive paper, polishing for 30min in a distilled water environment by using #4000 abrasive paper, and then cleaning, wherein the specific operation of cleaning is as follows: sequentially carrying out ultrasonic cleaning by using ethanol and acetone for 10min each time, then immersing the electrode into HCl solution with the concentration of 0.1mol/L, taking a filamentous silver electrode as a working electrode, taking a platinum electrode as a counter electrode and taking a saturated calomel electrode as a reference electrode to carry out cyclic voltammetry treatment, wherein the potential scanning upper limit of the cyclic voltammetry treatment is 0.8V, the potential scanning lower limit is-0.8V, the scanning rate is 5mV/s, and then immersing the electrode into KCl solution with the concentration of 0.1mol/L, and the current density is 5.0mA/cm 2 Depositing for 500s under the condition of (1) to form an AgCl deposition layer with low compactness, and then, depositing at a current density of 1.0mA/cm 2 And (3) depositing for 2200s under the condition to form an AgCl deposition layer with high compactness, namely obtaining the chloride ion sensing electrode.
Comparative example 1:
a commercially available chloride ion sensing electrode (Ag/AgCl-3.8 from Shanghai Toshima electronics Co., Ltd.).
Comparative example 2:
a chloride ion sensing electrode is prepared by the following steps:
1) fixing a PVC pipe with the inner diameter of 10mm, the outer diameter of 14mm and the height of 10mm and a filamentous silver electrode with the diameter of 0.5mm, the length of 30mm and the purity of more than 99.5%, folding the filamentous silver electrode into an L shape, extending one end of the filamentous silver electrode out of the bottom surface of the PVC pipe, extending the other end of the filamentous silver electrode out of a hole reserved on the side wall of the PVC pipe, filling a gap between the filamentous silver electrode and the hole with paraffin, mixing epoxy resin glue and a curing agent according to the mass ratio of 3:1, vacuumizing to 0.08MPa for 10min for defoaming, injecting into the PVC pipe, vacuumizing to 0.08MPa for 25min for defoaming, and standing at room temperature for 24h for curing;
2) polishing the end surface of one end of the filamentous silver electrode, which extends out of the bottom surface of the PVC pipe, wherein the polishing operation comprises the following steps: polishing with #500 sandpaper in distilled water environment for 1min, then polishing with #1000 sandpaper in distilled water environment for 2min, then polishing with #2000 sandpaper in distilled water environment for 10min, then polishing with #4000 sandpaper in distilled water environmentPolishing for 30min, and cleaning, wherein the specific cleaning operation is as follows: sequentially ultrasonic cleaning with ethanol and acetone for 10min each time, soaking in 0.1mol/L KCl solution at current density of 8.0mA/cm 2 Depositing for 250s under the condition of (1) to form an AgCl deposition layer, namely obtaining the chloride ion sensing electrode.
Comparative example 3:
a chloride ion sensing electrode is prepared by the following steps:
1) fixing a PVC pipe with the inner diameter of 10mm, the outer diameter of 14mm and the height of 10mm and a filamentous silver electrode with the diameter of 0.5mm, the length of 30mm and the purity of more than 99.5%, folding the filamentous silver electrode into an L shape, extending one end of the filamentous silver electrode out of the bottom surface of the PVC pipe, extending the other end of the filamentous silver electrode out of a hole reserved on the side wall of the PVC pipe, filling a gap between the filamentous silver electrode and the hole with paraffin, mixing epoxy resin glue and a curing agent according to the mass ratio of 3:1, vacuumizing to 0.08MPa for 10min for defoaming, injecting into the PVC pipe, vacuumizing to 0.08MPa for 25min for defoaming, and standing at room temperature for 24h for curing;
2) polishing the end surface of one end of the filamentous silver electrode, which extends out of the bottom surface of the PVC pipe, wherein the polishing operation comprises the following steps: polishing with #500 sandpaper in a distilled water environment for 1min, then polishing with #1000 sandpaper in a distilled water environment for 2min, then polishing with #2000 sandpaper in a distilled water environment for 10min, then polishing with #4000 sandpaper in a distilled water environment for 30min, and then cleaning, wherein the specific cleaning operation is as follows: sequentially carrying out ultrasonic cleaning by using ethanol and acetone for 10min each time, then immersing the electrode into HCl solution with the concentration of 0.1mol/L, taking a filamentous silver electrode as a working electrode, taking a platinum electrode as a counter electrode and taking a saturated calomel electrode as a reference electrode to carry out cyclic voltammetry treatment, wherein the potential scanning upper limit of the cyclic voltammetry treatment is 0.8V, the potential scanning lower limit is-0.8V, the scanning rate is 5mV/s, and then immersing the electrode into KCl solution with the concentration of 0.1mol/L, and the current density is 4.0mA/cm 2 Depositing for 500s under the condition of (1) to form an AgCl deposition layer, namely obtaining the chloride ion sensing electrode.
And (3) performance testing:
1) scanning Electron Microscope (SEM) images of the cross-sections of one end (the end containing the AgCl deposition layer) of the chloride ion sensing electrodes of example 1, example 2 and comparative example 1 are shown in fig. 2 to 4, respectively.
As can be seen from FIGS. 2 to 4: the silver substrate in the chloride ion sensing electrodes of examples 1 and 2 was closely bonded to the AgCl deposition layer, and two AgCl deposition layers having different densities were observed, whereas the AgCl deposition layer in the chloride ion sensing electrode of comparative example 1 did not have such a structure.
2) The response potential versus time of the chloride ion sensing electrodes of example 1, comparative example 1 and comparative example 2 in the cement leaching solution is shown in fig. 5.
As can be seen from fig. 5: the durability of the chloride ion sensing electrode in the embodiment 1 is obviously better than that of the chloride ion sensing electrodes in the comparative examples 1 and 2, which shows that the two AgCl deposition layers with different densities in the chloride ion sensing electrode in the embodiment 1 are beneficial to mutual occlusion of AgCl crystal grains, the electrode potential is more stable, the durability of the electrode is obviously enhanced, and the service life is greatly prolonged.
3) The response potential versus time of the chloride ion sensing electrodes of example 2, comparative example 1 and comparative example 3 in the cement leaching solution is shown in fig. 6.
As can be seen from fig. 6: the durability of the chloride ion sensing electrode in the embodiment 2 is obviously superior to that of the chloride ion sensing electrodes in the comparative examples 1 and 3, which shows that two AgCl deposition layers with different compactness in the chloride ion sensing electrode in the embodiment 2 are beneficial to mutual occlusion of AgCl crystal grains, the electrode potential is more stable, the durability of the electrode is obviously enhanced, and the service life is greatly prolonged.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The chloride ion sensing electrode is characterized by comprising a PVC pipe, an epoxy resin condensate filled in the PVC pipe and a filiform silver electrode encapsulated in the epoxy resin condensate; one end of the filamentous silver electrode extends out of the bottom surface of the PVC pipe, and the end surface of the end is also sequentially provided with a first AgCl deposition layer and a second AgCl deposition layer; the compactness of the first AgCl deposition layer is lower than that of the second AgCl deposition layer; and the other end of the filiform silver electrode extends out of a hole reserved on the side wall of the PVC pipe.
2. The chloride ion sensing electrode of claim 1, wherein: one end of the filiform silver electrode extends out from the center of the bottom surface of the PVC pipe.
3. The chloride ion sensing electrode according to claim 1 or 2, wherein: the inner diameter of the PVC pipe is 8-16 mm.
4. The chloride ion sensing electrode according to claim 1 or 2, wherein: the diameter of the filiform silver electrode is 0.1 mm-2 mm, the length is 10 mm-30 mm, and the purity is more than 99.5%.
5. The method for preparing the chloride ion sensing electrode according to any one of claims 1 to 4, comprising the steps of:
1) fixing the PVC pipe and the filamentous silver electrode, wherein one end of the filamentous silver electrode extends out of the bottom surface of the PVC pipe, the other end of the filamentous silver electrode extends out of a hole reserved in the side wall of the PVC pipe, and then injecting epoxy resin and a curing agent into the PVC pipe for defoaming and curing;
2) polishing and cleaning the end surface of one end of the filiform silver electrode extending out of the bottom surface of the PVC pipe, immersing the end surface into HCl solution, taking the filiform silver electrode as a working electrode, a platinum electrode as a counter electrode and a saturated calomel electrode as a reference electrode,
and carrying out cyclic voltammetry treatment, immersing the electrode into a KCl solution for carrying out first electrochemical deposition, reducing the current density, and carrying out second electrochemical deposition to obtain the chloride ion sensing electrode.
6. The method for preparing a chloride ion sensing electrode according to claim 5, wherein: the defoaming mode in the step 1) is to exhaust bubbles by negative pressure, and the defoaming time is 5-20 min.
7. The method for producing a chloride ion sensing electrode according to claim 5 or 6, characterized in that: the concentration of the HCl solution in the step 2) is 0.05 mol/L-2.0 mol/L; the concentration of the KCl solution in the step 2) is 0.1-3.0 mol/L.
8. The method for producing a chloride ion sensing electrode according to claim 5 or 6, characterized in that: and 2) the potential scanning upper limit of the cyclic voltammetry treatment is 0.5V-1.0V, the potential scanning lower limit is-0.6V-1.2V, and the scanning rate is 1 mV/s-20 mV/s.
9. The method for producing a chloride ion sensing electrode according to claim 5 or 6, characterized in that: step 2) the first electrochemical deposition is carried out at a current density of 4.0mA/cm 2 ～10.0mA/cm 2 The deposition time is 200-500 s; step 2) the second electrochemical deposition is carried out at a current density of 0.5mA/cm 2 ～2.0mA/cm 2 The deposition time is 1000-4000 s.
10. Use of the chloride ion sensing electrode of any one of claims 1 to 4 for chloride ion concentration detection.
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