CN112179839A - Sealing structure and sealing method of electrochemical sample used in high-temperature and high-pressure aqueous solution environment - Google Patents
Sealing structure and sealing method of electrochemical sample used in high-temperature and high-pressure aqueous solution environment Download PDFInfo
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- 238000007789 sealing Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 title claims description 17
- 238000012360 testing method Methods 0.000 claims abstract description 68
- 239000004696 Poly ether ether ketone Substances 0.000 claims abstract description 35
- 229920002530 polyetherether ketone Polymers 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 17
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000003292 glue Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- 230000007704 transition Effects 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000005520 cutting process Methods 0.000 claims description 3
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006068 polycondensation reaction Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 238000012512 characterization method Methods 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- 238000003466 welding Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910001039 duplex stainless steel Inorganic materials 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 239000008358 core component Substances 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000003566 sealing material Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000010431 corundum Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000011398 Portland cement Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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
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Abstract
The invention belongs to the technical field of corrosion electrochemical measurement and material characterization, and relates to a sealing structure and a sealing method of an electrochemical sample used in a high-temperature and high-pressure water solution environment, wherein the sealing structure comprises a heat-shrinkable sleeve which is sleeved outside a lead and wraps the lead, a support rod which is used for the lead to be arranged and provides a support function, a heat-shrinkable tube which wraps the sample and the support rod and is internally sleeved with the heat-shrinkable sleeve, the lead is electrically connected to the sample, the bottom of the support rod is in sealed contact with the sample, the heat-shrinkable sleeve and the heat-shrinkable tube are made of polytetrafluoroethylene materials, and the support rod is made of polyether-ether-. The electrochemical working electrode capable of being used in the high-temperature and high-pressure water solution environment is prepared by adopting a simple process, the operation is simple and easy to implement, and the problem of working electrode packaging in the high-temperature and high-pressure water solution environment is solved. Wherein, the metal wire wrapped by the thermal polycondensation tetrafluoroethylene and the polyether-ether-ketone rod can be recycled, so that the test cost is saved.
Description
Technical Field
The invention belongs to the technical field of corrosion electrochemical measurement and material characterization, and relates to a sealing structure and a sealing method of an electrochemical sample used in a high-temperature and high-pressure water solution environment. In particular to: the method comprises the steps of packaging a sample by using a thermal polycondensation tetrafluoroethylene tube, connecting the sample by using a lead wrapped by polytetrafluoroethylene, supporting the sample by using a polyether-ether-ketone rod, solving the problem of sealing failure caused by great difference of radiuses between the sample and the lead, and connecting the test sample and the polyether-ether-ketone rod by using high-temperature insulating glue, thereby preparing a working electrode which can be used in a high-temperature and high-pressure water solution environment.
Background
Electrochemical testing is an important means for characterizing the corrosion sensitivity, corrosion rate and surface state of materials, and is commonly used in laboratories, and the electrochemical testing is generally carried out by adopting a three-electrode system, including a reference electrode, a counter electrode and a working electrode. The reference electrode is a non-consumable product and can be reused under the condition of proper operation and maintenance, and the current electrochemical test under the high-temperature and high-pressure environment has mature commercial electrodes of brands such as Dongsheng, Corrtest and the like; the counter electrode is usually a platinum sheet and can also be reused; the working electrode is prepared from a test material, the surface state of the material is changed after the test is finished, and the consumable product cannot be reused, so that the development of the working electrode with simple structure, easy preparation and low cost is very important and has high practical value.
Typically, the working electrode is encapsulated with an epoxy resin, limited by the high temperature stability of the epoxy resin, and the use temperature of such electrodes is typically below 150 ℃. In a high-temperature and high-pressure water solution environment, the conventional working electrode preparation mainly comprises two modes of pouring a sealed sample through a high-temperature resistant insulating material such as portland cement and exposing a working surface and connecting the working sample through spot welding and a wire made of the same material to avoid galvanic corrosion caused by connection of dissimilar materials. The method of pouring and sealing by using high temperature resistant materials usually faces that the high temperature resistant materials such as silicate and the like are slightly dissolved in water environment to influence the test environment and the test surface and further influence the test result. The electrode manufacturing method of connecting the sample and the lead made of the same material as the sample through the spot welding mode avoids test errors caused by high-temperature failure of the sealing material in a complex electrode structure and avoids galvanic corrosion caused by connection of dissimilar materials, but the structure of the welded part solidified again after the materials are melted is different from the structure of the original material, so that the galvanic corrosion is caused to occur near the welding point in the test to influence the test result.
CN101470093A discloses a working electrode for realizing electrochemical test of high-temperature high-pressure aqueous solution system and its preparation, the working electrode is composed of a core component and a sealing assembly, wherein the insulation unit of the core component is composed of two parts of high-temperature and low-temperature: the high-temperature part is made of a corundum tube, a working electrode wire penetrates through the high-temperature part, and a port is sealed with the working electrode wire; the low-temperature part is made of a Polytetrafluoroethylene (PTFE) pipe, a working electrode wire penetrates through the low-temperature part, a port is sealed with the working electrode wire, the high-temperature part is sealed with the low-temperature part, and the high-temperature and high-pressure sealing is realized between the electrode and the high-pressure kettle through a sealing assembly. The insulating unit consists of a high-temperature part and a low-temperature part, and has the advantages that the corundum tube forming the high-temperature unit has the characteristic of high temperature resistance, the high-temperature test environment of the working electrode can be ensured, and the Polytetrafluoroethylene (PTFE) tube of the low-temperature unit has elasticity, so that the core component and the sealing component of the working electrode can be effectively sealed. The sealing assembly is composed of a fastening nut, a pressing device, a cylindrical sealing element, a conical sealing element and a sealing nut, and the structure has the advantages of being convenient to install and capable of achieving effective sealing. The adopted electrode material is a metal wire with a certain length, which provides higher requirements for the size (length) of an original test material, and because an electrochemical test result is closely related to the surface state of the material, the surface roughness control of a test surface is usually required before the electrochemical test, a plane sample is usually required to be polished step by using abrasive paper with different meshes, and finally 1200# or 2000# abrasive paper is adopted for final polishing treatment, and the metal wire has a plurality of inconveniences and difficult judgment of the polishing effect in the polishing process, so that the surface roughness control in the test process is unstable. And the processing of the metal wire requires that the original material has a larger size in at least one direction of length, width and height so as to ensure that a metal wire with enough length can be obtained, and the size requirement on the material is higher.
CN110095405A discloses a sealing device for a high-temperature high-pressure corrosion electrochemical working electrode and a use method thereof, which have no obvious defects in design, but have complex structure and higher requirements on processing precision, and the processing precision of a test sample and the matching between the test sample and an electrode sealing sleeve directly influence the sealing effect of the electrode.
Disclosure of Invention
The invention aims to provide a sealing structure of an electrochemical sample used in a high-temperature and high-pressure aqueous solution environment, so that the preparation of a working electrode which has simple structure, low cost and simple operation, resists high temperature and high pressure and can work in the aqueous solution environment for a long time is realized. The electrochemical electrode sample sealing method can realize the sealing of the sample and the exposure of a specific test surface, the sealing material is stable in a high-temperature and high-pressure water environment, the high-temperature failure cannot occur to influence the test result, and a galvanic couple exposed in the test environment cannot be generated in the sealing process.
The technical scheme adopted by the invention is as follows:
the sealing structure of the electrochemical sample used in the high-temperature and high-pressure water solution environment comprises a heat-shrinkable sleeve, a support rod and a heat-shrinkable tube, wherein the heat-shrinkable sleeve is sleeved outside a lead and wraps the lead, the support rod is used for the lead to be arranged and provides a support function, the heat-shrinkable tube wraps the sample, the support rod and the heat-shrinkable sleeve, the lead is electrically connected to the sample, and the bottom of the support rod is in sealing contact with the sample.
The heat-shrinkable sleeve and the heat-shrinkable tube are made of polytetrafluoroethylene materials, and the support rod is made of polyether-ether-ketone materials.
In the technical scheme of the invention, the heat-shrinkable sleeve is adopted to seal and wrap the lead to realize the sealing of the lead; by arranging the supporting rod, the problem that sealing fails due to the fact that the shrinkage rates of the heat shrinkable tube in the sample section and the lead section are inconsistent because of great radius difference between the sample and the lead during heat shrinkage is solved; and finally, the purpose of exposing a test surface is achieved by using the lead, the sample and the support rod which are wrapped by the polytetrafluoroethylene heat-shrinkable tube.
Preferably, the sample is cylindrical, the cylindrical sample is adopted because the edge of the cylindrical sample is smooth, and a gap is not easy to generate after the thermal shrinkage is finished, and the side surface of the sample such as a square sample, a triangle sample and the like is easy to generate a gap after the thermal shrinkage is finished, so that the sealing quality is influenced.
Preferably, the diameter of the support rod is the same as the diameter of the sample, and the support rod is disposed coaxially with the sample. The supporting rod is arranged to solve the problem that sealing failure is caused by inconsistent shrinkage rates of the heat shrinkable tube at the sample section and the lead section due to large radius difference between the sample and the lead when the heat shrinkable tube is subjected to heat shrinkage, the diameter is the same and the same, shrinkage synchronism is better ensured, and sealing effect is ensured.
Preferably, the support rod and the sample are hermetically connected by adopting high-temperature-resistant insulating glue. And the transition part between the sample and the support rod is filled with high-temperature insulating glue to form smooth transition, so that the heat-shrinkable tube can be tightly attached to the sample/the high-temperature insulating glue/the support rod at the transition part in the subsequent heat-shrinkable sealing process, the gap is eliminated, and the sealing quality can still be ensured. However, the coating operation requirement of the high-temperature insulating glue is high, and improper operation easily causes gaps at transition positions in the subsequent thermal shrinkage sealing process, so that the sealing quality is affected. Therefore, a polyetheretherketone rod with the same diameter as the sample is used as a support rod to be combined with the high-temperature-resistant insulating glue.
Preferably, one side of the support rod is provided with a vertical mounting groove, and the lead sheathed with the heat-shrinkable sleeve is mounted in the mounting groove. The arrangement of the wires is carried out through the mounting groove, the stability is good, and the sealing effect of the heat-shrinkable tube is favorably improved.
Preferably, in the installation groove, a high-temperature-resistant insulating glue is filled between the lead and the gap of the installation groove.
According to the technical scheme, the defects in the prior art are overcome, the test sample can be sealed, the specific test surface is exposed, the sealing material is stable in a high-temperature and high-pressure water environment, the test result cannot be influenced by high-temperature failure, and galvanic couples exposed in the test environment cannot be generated in the sealing process.
Another object of the present invention is to provide a method for sealing an electrochemical sample used in a high-temperature and high-pressure aqueous environment, based on the above-mentioned sealing structure, comprising the steps of:
s-1, wrapping the wire by using a heat-shrinkable sleeve, and heating the heat-shrinkable sleeve to uniformly shrink the wire.
S-2, connecting a lead to the upper plane edge of the sample.
And S-3, connecting the sample and the support rod through high-temperature insulating glue, ensuring that the support rod is coaxial with the sample, placing the lead in a mounting groove on the side surface of the support rod, and filling the residual gap in the mounting groove through the high-temperature insulating glue to ensure that the surface of the support rod is in smooth transition, so that the next step of closely attaching the thermal polycondensation tetrafluoroethylene and the polyether-ether-ketone rod can be ensured without generating a gap to influence the sealing quality.
And S-4, after the high-temperature insulating glue is completely solidified and shaped, wrapping the sample and the support rod by using a heat-shrinkable tube, and uniformly heating and polycondensing tetrafluoroethylene at 330-400 ℃ by using a hot air gun to realize uniform shrinkage of the heat-shrinkable tube.
And S-5, cutting off redundant heat shrink tubes at two ends of the electrode and polishing a test surface of the sample to obtain the electrochemical working electrode which can be used in a high-temperature and high-pressure water solution environment.
The invention has the advantages that: the electrochemical working electrode capable of being used in the high-temperature and high-pressure water solution environment is prepared by adopting a simple process, the operation is simple and easy to implement, and the problem of working electrode packaging in the high-temperature and high-pressure water solution environment is solved. Wherein, the metal wire wrapped by the thermal polycondensation tetrafluoroethylene and the polyether-ether-ketone rod can be recycled, so that the test cost is saved.
Drawings
FIG. 1 is a schematic diagram of the connection of a test sample and a heat-shrinkable sleeve by a wire;
FIG. 2 is a schematic view showing the connection between a sample with a lead and a PEEK rod through a high temperature resistant insulating adhesive;
FIG. 3 is a schematic view of a working electrode obtained according to the present invention;
FIG. 4a is a Nyquist plot of EIS test results of S32750 duplex stainless steel in an aqueous environment of high temperature and high pressure at 200 ℃;
FIG. 4b is a Bode diagram of the EIS test result of the S32750 duplex stainless steel in the environment of 200 ℃ high-temperature high-pressure aqueous solution;
FIG. 5 shows the results of the potentiodynamic polarization curve test of N08028 austenitic stainless steel in the environment of 240 ℃ high-temperature and high-pressure aqueous solution.
FIG. 6 is a schematic view of a working electrode obtained in comparative example 1;
FIG. 7 is an enlarged view of transition between (a) a test material for a whole test sample and (b) a support rod of the working electrode obtained in comparative example 3;
FIG. 8 is an enlarged view of transition between (a) a test material for a whole test sample and (b) a support rod of the working electrode obtained in comparative example 4;
FIG. 9 is a schematic representation of the working electrode obtained in comparative example 5 (a) before and (b) after the test;
FIG. 10 is a schematic representation of the working electrode obtained in example 1 (a) before and (b) after the test.
In the figure: 1 sample, 2 leads, 3 heat-shrinkable tubes, 4 high-temperature insulating glue, 5 support rods and 6 heat-shrinkable sleeves.
Detailed Description
The technical solution of the present invention is further described in detail below by specific embodiments with reference to the accompanying drawings.
It is to be understood that the embodiments of the present invention are merely for illustrating the present invention and not for limiting the present invention, and that various substitutions and alterations made according to the common knowledge and conventional means in the art without departing from the technical idea of the present invention are included in the scope of the present invention.
The technical schemes described in the embodiments of the present invention are all conventional technical schemes, unless otherwise specified.
Example 1:
s32750 duplex stainless steel with phi of 10mm multiplied by 8mm is selected to be connected with a single-stranded copper conductor with phi of 1mm wrapped by thermal-condensation tetrafluoroethylene by means of spot welding. The polyether-ether-ketone with the diameter of 10mm multiplied by 80mm is used as a supporting rod, and a groove with the depth of about 1.5mm and the width of 1.5mm is formed on the side surface of the supporting rod. And (3) coating high-temperature silica gel in the groove and one end of the support rod, attaching the sample to one end of the support rod coated with the high-temperature silica gel, enabling the polyether-ether-ketone rod to be coaxial with the sample, and placing the copper wire wrapped by the thermal-polycondensation tetrafluoroethylene in the groove. Fixing the sample and the PEEK rod, filling a gap between the sample and the PEEK rod and a groove on the side surface of the PEEK rod with high-temperature silica gel, and scraping off redundant high-temperature silica gel to enable smooth transition from the sample to the PEEK rod and the groove on the side surface of the PEEK rod. The assembled system was placed in an oven and cured at 50 ℃ for 24 hours according to the instructions for the high temperature silica gel. After curing, the system was placed in a thermal polycondensation tetrafluoroethylene tube (diameter before thermal shrinkage was 10.90mm, thermal shrinkage was 2:1, wall thickness after thermal shrinkage was 0.38), the thermal polycondensation tetrafluoroethylene tube was heated at 380 ℃ with a hot air gun, and during heating, the tube was rotated at a constant speedThe polycondensation tetrafluoroethylene pipe ensures that the polytetrafluoroethylene pipe is heated uniformly so as to realize uniform shrinkage. After the thermal shrinkage step is finished, the thermal polycondensation tetrafluoroethylene tube is confirmed to be tightly attached to the surface of the polyether-ether-ketone rod and the surface of the sample, and no gap exists so as to ensure the sealing quality. Excess thermal-condensation tetrafluoroethylene tube at both ends of the electrode was cut off and the exposed surface of the sample was mechanically polished using a 1200# sandpaper, thereby obtaining an S32750 duplex stainless steel working electrode capable of being used in an environment of high temperature and high pressure aqueous solution. In the using process, the lower end of the electrode is ensured to be in the solution, and the upper end of the polyether-ether-ketone rod is above the liquid level of the solution, so that the solution can not contact the high-temperature silica gel, and the high-temperature silica gel is prevented from losing efficacy under the water environment to influence the test solution and the test surface and further influence the test result. Introducing 32 bar CO into a to-be-tested system after the sample is installed2And raising the temperature, stabilizing the test system for 0.5 hour after the temperature is raised to 200 ℃, and performing Electrochemical Impedance Spectroscopy (EIS) test on the sample to obtain a result as shown in the following graph (1). The test result shows that the electrode works well at the temperature of 200 ℃, the test result is in line with expectation, and no obvious noise exists.
Example 2:
n08028 austenitic alloy with the diameter of 10mm multiplied by 8mm is selected to be connected with a single-stranded copper conductor with the diameter of 1mm and wrapped by thermal-condensation tetrafluoroethylene by spot welding. Polyether-ether-ketone with the diameter of 10mm multiplied by 80mm is selected as a supporting rod, and a groove with the depth of 1.5mm and the width of 1.5mm is formed in the side surface of the supporting rod. And (3) coating high-temperature silica gel in the groove and one end of the support rod, attaching the sample to one end of the support rod coated with the high-temperature silica gel, enabling the polyether-ether-ketone rod to be coaxial with the sample, and placing the copper wire wrapped by the thermal-polycondensation tetrafluoroethylene in the groove. Fixing the sample and the PEEK rod, filling a gap between the sample and the PEEK rod and a groove on the side surface of the PEEK rod with high-temperature silica gel, and scraping off redundant high-temperature silica gel to enable smooth transition from the sample to the PEEK rod and the groove on the side surface of the PEEK rod. Placing the assembled system in an ovenThe mixture was cured at 50 ℃ for 24 hours according to the instructions for the use of high-temperature silica gel. After curing, the system is placed in a thermal polycondensation tetrafluoroethylene tube (the diameter is 10.90mm before thermal shrinkage, the thermal shrinkage rate is 2:1, and the wall thickness is 0.38mm after thermal shrinkage), the thermal polycondensation tetrafluoroethylene tube is heated by using a hot air gun at 380 ℃, and the thermal polycondensation tetrafluoroethylene tube is rotated at a constant speed in the heating process to ensure that the thermal polycondensation tetrafluoroethylene tube is heated uniformly so as to realize uniform shrinkage. After the thermal shrinkage step is finished, the thermal polycondensation tetrafluoroethylene tube is confirmed to be tightly attached to the surface of the polyether-ether-ketone rod and the surface of the sample, and no gap exists so as to ensure the sealing quality. Excess hot-polycondensed tetrafluoroethylene tubes at both ends of the electrode were cut off and the exposed surface of the sample was mechanically polished to obtain a N08028 austenitic alloy working electrode capable of being used in an atmosphere of high-temperature and high-pressure aqueous solution. In the using process, the lower end of the electrode is ensured to be in the solution, and the upper end of the polyether-ether-ketone rod is above the liquid level of the solution, so that the solution can not contact the high-temperature silica gel, and the high-temperature silica gel is prevented from losing efficacy under the water environment to influence the test solution and the test surface and further influence the test result. Introducing 32 bar CO into a to-be-tested system after the sample is installed2And raising the temperature, stabilizing the test system for 1 hour after the temperature is raised to 240 ℃ and carrying out potentiodynamic cyclic polarization curve test on the sample to obtain a result as shown in the following figure (5), wherein the test result can obviously show information such as open circuit potential, pitting potential, repassivation potential and the like of the N08028 austenitic stainless steel in the high-temperature high-pressure test environment. Also shows that the working electrode can be normally used in an environment of 240 ℃ high-temperature and high-pressure aqueous solution.
Comparative example 1:
different from example 1, there is no supporting rod of polyetheretherketone, because the teflon heat-shrinkable tube has a certain proportion of heat shrinkage, when the supporting rod is not provided, the wire portion can not be tightly wrapped (as shown in fig. 6), and the upper metal surface of the sample is exposed and can not be completely sealed.
Comparative example 2:
the difference from example 1 is that the diameter of the supporting rod of polyetheretherketone is 2 times of the diameter of the sample, and when the diameter of the unsupported rod has a large difference (generally more than 2 times) from the diameter of the sample, the completely opposite result to comparative example 1 occurs because the heat shrinkage rate of the teflon heat shrinkable tube is limited, the sample part cannot be tightly wrapped, the side metal surface of the sample is exposed, and the sample cannot be completely sealed.
Comparative example 3:
the difference from example 1 is that the diameter of the peek support rod is 1.1 times of the diameter of the sample, and when the diameter of the peek support rod is smaller than the diameter of the sample (generally within 2 times), the sample and the support rod can be tightly wrapped in the shrinkage range of the heat shrink tube, but a groove with an approximately triangular cross section is formed at the transition between the test material and the support rod due to the diameter difference, and the sealing quality is affected by a gap (as shown in fig. 7).
Comparative example 4:
the difference from example 1 is that the polyetheretherketone support rod and the sample were not coaxially arranged, and the resulting sealing electrode was shown in fig. 8, in which a groove was formed at the transition between the test material and the support rod (shown in fig. 8 (b)), and the thermally condensed tetrafluoroethylene tube was not in close contact with the test material and the support rod at the transition, thereby generating a gap at the transition, and affecting the sealing quality. Under the condition that slight deviation exists, the groove formed at the transition position of the test material and the support rod caused by different shafts is filled with high-temperature insulating glue, and the subsequent thermal shrinkage sealing cannot be influenced. However, if the deviation degree of the different axes is large, the sealing effect is as shown in the following figure, the groove is obvious, and a gap is generated after thermal shrinkage, so that the sealing quality is seriously influenced.
Comparative example 5:
the difference from example 1 is that polytetrafluoroethylene is used as the material of the support rod. The comparison of the physical and chemical properties and the high-temperature stability of various materials shows that the materials which can be stably used at the temperature higher than 200 ℃ can be stably used in water environment, can not be decomposed and aged and are not easy to corrode by the environment mainly comprise Polytetrafluoroethylene (PEEK) and polyether ether ketone (PTFE). The sample was sealed by using teflon and polyetheretherketone, and the sample was taken out after the test in the high-temperature high-pressure aqueous solution environment as shown in fig. 9 below. It was found that the side surface of the sample using polytetrafluoroethylene as the support rod was partially exposed after the test, and it is considered that the side surface of the sample was gradually exposed during the shrinkage process of the thermal polycondensation tetrafluoroethylene tube, mainly because the thermal polycondensation tetrafluoroethylene tube had a tendency to further creep and shrink in a high temperature environment, and when the support rod was made of polytetrafluoroethylene, the friction coefficient between the thermal polycondensation tetrafluoroethylene tube and the polytetrafluoroethylene support rod was small, and the creep and shrink of the thermal polycondensation tetrafluoroethylene tube was not hindered. And the electrode adopting the polyether-ether-ketone as the support rod inhibits the creep shrinkage of the thermal polycondensation tetrafluoroethylene tube in a test environment due to the fact that the friction force between the polyether-ether-ketone and the thermal polycondensation tetrafluoroethylene tube is large enough, and the sealing performance of the electrode is guaranteed.
The stability of the test area is very important for electrochemical testing, some test parameters need to be calculated and adjusted according to the exposed test area, the post-processing of test data is closely related to the test area, and the change of the exposed area in the test process can not influence the test, but has great influence on the post-processing of the test data, so that the test result is not credible. Polytetrafluoroethylene is therefore not suitable for making support rods.
Claims (10)
1. A sealing structure of an electrochemical sample used in a high-temperature and high-pressure water solution environment comprises a heat-shrinkable sleeve which is sleeved outside a lead and wraps the lead, and is characterized by further comprising a support rod for arranging the lead and providing a support function, and a heat-shrinkable tube which wraps the sample, the support rod and the heat-shrinkable sleeve, wherein the lead is electrically connected to the sample, and the bottom of the support rod is in sealed contact with the sample; the heat-shrinkable sleeve and the heat-shrinkable tube are made of polytetrafluoroethylene materials, and the support rod is made of polyether-ether-ketone materials.
2. A sealing structure for an electrochemical sample used in an atmosphere of high temperature and high pressure aqueous solution according to claim 1, wherein said support rod is provided coaxially with said sample.
3. A sealing structure of an electrochemical sample used under an environment of high temperature and high pressure aqueous solution according to claim 2, wherein the diameter of the support rod is the same as the diameter of the sample.
4. A sealing structure of an electrochemical sample used in an environment of high temperature and high pressure aqueous solution according to claim 1, wherein said sample has a cylindrical shape.
5. A sealing structure of an electrochemical sample used in high temperature and high pressure water solution environment according to claim 1, characterized in that the supporting rod and the sample are hermetically connected by high temperature resistant insulating glue.
6. A sealing structure for an electrochemical sample used under an environment of high temperature and high pressure aqueous solution according to claim 1, wherein a vertical seating groove is formed at one side of the support rod, and a lead sheathed with a heat-shrinkable sheath is seated in the seating groove.
7. A sealing structure of an electrochemical sample used under high temperature and high pressure aqueous solution environment according to claim 6, wherein a high temperature resistant insulating glue is filled in the mounting groove between the lead and the mounting groove.
8. A working electrode for use in an environment of high temperature and high pressure aqueous solution, comprising a sealing structure according to any one of claims 1 to 7.
9. A method for sealing an electrochemical sample used in a high-temperature and high-pressure aqueous environment, comprising the steps of:
s-1, wrapping the wire by using a heat-shrinkable sleeve, and heating the heat-shrinkable sleeve to uniformly shrink the wire;
s-2, connecting a lead to the upper plane edge of the sample;
s-3, connecting the sample and the support rod through high-temperature insulating glue, ensuring that the support rod is coaxial with the sample, placing a lead in a mounting groove on the side surface of the support rod, and filling the residual gap in the mounting groove through the high-temperature insulating glue to ensure that the surface of the support rod is in smooth transition;
s-4, after the high-temperature insulating glue is completely solidified and shaped, wrapping the sample and the supporting rod by using a heat-shrinkable tube, and realizing uniform shrinkage of the heat-shrinkable tube at the temperature of 330-400 ℃;
and S-5, cutting off redundant heat shrink tubes at two ends of the electrode to obtain the electrochemical working electrode which can be used in a high-temperature and high-pressure water solution environment.
10. The method of claim 9, wherein the sample test surface is polished while or after cutting off excess heat shrinkable tubing at both ends of the electrode.
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| CN202011128551.8A CN112179839B (en) | 2020-10-21 | 2020-10-21 | Sealing structure and sealing method of electrochemical sample used in high-temperature high-pressure aqueous solution environment |
| PCT/CN2020/123940 WO2022082824A1 (en) | 2020-10-21 | 2020-10-27 | Sealing structure and sealing method for electrochemical sample used in high-temperature high-pressure aqueous solution environment |
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| CN112179839B (en) | 2024-06-28 |
| WO2022082824A1 (en) | 2022-04-28 |
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