WO2023040239A1 - Zinc-magnesium alloy intelligent sacrificial anode material and use thereof - Google Patents
Zinc-magnesium alloy intelligent sacrificial anode material and use thereof Download PDFInfo
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- WO2023040239A1 WO2023040239A1 PCT/CN2022/085020 CN2022085020W WO2023040239A1 WO 2023040239 A1 WO2023040239 A1 WO 2023040239A1 CN 2022085020 W CN2022085020 W CN 2022085020W WO 2023040239 A1 WO2023040239 A1 WO 2023040239A1
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- zinc
- magnesium alloy
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- reinforced concrete
- steel
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 45
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000010405 anode material Substances 0.000 title claims abstract description 22
- 239000011701 zinc Substances 0.000 claims abstract description 59
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 57
- 239000010959 steel Substances 0.000 claims abstract description 57
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000011777 magnesium Substances 0.000 claims abstract description 34
- 239000004567 concrete Substances 0.000 claims abstract description 25
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005260 corrosion Methods 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 20
- 230000007797 corrosion Effects 0.000 claims abstract description 18
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000011150 reinforced concrete Substances 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 15
- 229910017706 MgZn Inorganic materials 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- 230000006698 induction Effects 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 230000010287 polarization Effects 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000001514 detection method Methods 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- -1 0.1-0.3% of Al Substances 0.000 abstract 1
- 229910019805 Mg2Zn11 Inorganic materials 0.000 abstract 1
- 229910017708 MgZn2 Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000000956 alloy Substances 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 239000012085 test solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F2201/00—Type of materials to be protected by cathodic protection
- C23F2201/02—Concrete, e.g. reinforced
Definitions
- the invention belongs to the technical field of alloy materials, and in particular relates to a zinc-magnesium alloy intelligent sacrificial anode material and its application.
- reinforced concrete As a structural material, reinforced concrete is widely used in various architectural and civil engineering structures such as bridges, buildings, viaducts, dams, submarine tunnels and large ocean platforms. In today's increasingly prolific development of marine resources, the use of reinforced concrete is undoubtedly will become more widespread. However, corrosion damage abounds due to durability problems of reinforced concrete. The destruction of reinforced concrete not only causes great economic losses, but also brings great hidden dangers to the safety of people's lives and properties.
- Concrete is a material that is mixed with sand, cement and water and solidified after a certain period of time. Its interior is not a dense structure, and there are usually voids.
- the silicate water product of concrete exists in the pore space, and the water product is mainly saturated calcium hydroxide solution, and its pH can reach about 13.
- a passivation film can be formed on the surface of the steel bar. As time goes on, chloride ions gradually diffuse into the concrete. Once the chloride ions reach the surface of the steel bar, the passivation film of the steel bar is easily destroyed by the chloride ions, which induces localized corrosion of the steel bar.
- Corrosion products of steel bars will accumulate between steel bars and concrete, and the volume of corrosion products of steel bars will expand, further reducing the bonding force between steel bars and concrete, easily cracking concrete, and causing accelerated damage to reinforced concrete. Therefore, the protection of steel bars in reinforced concrete is particularly important.
- chloride ions are an important cause of steel bar corrosion, the monitoring of chloride ion intrusion in concrete is also extremely important.
- Sacrificial anode cathodic protection method is a relatively convenient and widely used method to protect steel bars.
- Zinc is currently the most widely used sacrificial anode material, but zinc dissolves very quickly in the strongly alkaline environment of concrete pore fluid. The excessive dissolution rate makes it insensitive to chloride ions, and cannot detect the intrusion of chloride ions into concrete.
- Magnesium is very sensitive to chloride ions and can be used as a material to detect whether chloride ions have invaded concrete. When chloride ions invade concrete, it can spontaneously corrode and provide cathodic current for steel bars to protect steel bars from corrosion. It is an intelligent sacrificial anode material in reinforced concrete.
- the purpose of the present invention is to overcome the defects of the prior art and provide the application of zinc-magnesium alloy parts in the detection of chloride ion intrusion in reinforced concrete.
- Another object of the present invention is to provide the application of zinc-magnesium alloy parts in preventing galvanic corrosion of steel bars in reinforced concrete.
- Another object of the present invention is to provide a zinc-magnesium alloy intelligent sacrificial anode material and a preparation method thereof.
- the chemical composition mass percentage of said zinc-magnesium alloy parts is: Mg: 10-11%, Al: 0.1-0.3%, impurity ⁇ 0.02%, balance It is Zn and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- it includes: embedding the zinc-magnesium alloy piece as a chloride ion response piece in reinforced concrete, and then performing a polarization curve test on the zinc-magnesium alloy piece.
- the second technical scheme of the present invention is as follows:
- a method for detecting chloride ion intrusion in reinforced concrete comprising: burying a zinc-magnesium alloy piece as a chloride ion response piece in reinforced concrete, and then performing a polarization curve test on the zinc-magnesium alloy piece, the chemical properties of the zinc-magnesium alloy piece
- the composition mass percent is: Mg: 10-11%, Al: 0.1-0.3%, impurity ⁇ 0.02%, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- the third of the technical scheme of the present invention is as follows:
- the chemical composition mass percentages of the zinc-magnesium alloy parts are: Mg: 10-11%, Al: 0.1-0.3%, impurities ⁇ 0.02% , the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- the present invention includes embedding the zinc-magnesium alloy piece as a sacrificial anode in reinforced concrete, and contacting the steel bar therein, and the zinc-magnesium alloy piece provides the reinforcement for the steel bar when chloride ions invade into the concrete. cathodic current.
- a method for preventing galvanic corrosion of steel bars in reinforced concrete comprising embedding a zinc-magnesium alloy piece as a sacrificial anode in reinforced concrete and contacting the steel bars therein, the zinc-magnesium alloy piece being exposed when chloride ions invade the concrete Provide cathodic current for the steel bar; wherein, the chemical composition mass percentage of the zinc-magnesium alloy is: Mg: 10-11%, Al: 0.1-0.3%, impurity ⁇ 0.02%, the balance is Zn, and it is composed of Zn phase, MgZn 2 phases and Mg 2 Zn 11 phases.
- the fifth of the technical scheme of the present invention is as follows:
- a zinc-magnesium alloy intelligent sacrificial anode material its chemical composition mass percentage is: Mg: 10-11%, Al: 0.1-0.3%, impurity ⁇ 0.02%, the balance is Zn, and it is composed of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase composition.
- the preparation method of the above-mentioned zinc-magnesium alloy intelligent sacrificial anode material comprises the following steps:
- the step (2) is: feeding high-purity argon into the vacuum induction melting furnace and heating to 700-900°C.
- the zinc-magnesium alloy intelligent sacrificial anode material in the present invention is sensitive to chloride ions, and can effectively detect whether chloride ions have invaded concrete.
- the galvanic potential of the zinc-magnesium alloy intelligent sacrificial anode material and steel in the present invention is higher than the hydrogen evolution potential of steel, which can protect steel from corrosion in concrete, and does not form under-protection and over-protection to steel bars at the same time, improving the role of zinc as Response of traditional sacrificial anode materials to chloride ions and galvanic corrosion with steel.
- the zinc-magnesium alloy intelligent sacrificial anode material in the present invention has low self-corrosion current density and long service life.
- FIG. 1 is an XRD crystal diffraction pattern of Zn-11Mg prepared in Example 1 of the present invention.
- Fig. 2 is a micrograph of the crystal phase of Zn-11Mg prepared in Example 1 of the present invention.
- Example 3 is a diagram showing the test results of polarization curves of zinc and Zn-11Mg in saturated calcium hydroxide solutions containing different concentrations of chloride ions in Example 2 of the present invention.
- Fig. 4 is a galvanic test result graph of zinc and Zn-11Mg in Example 3 of the present invention and steel in saturated calcium hydroxide solutions containing different concentrations of chloride ions.
- the zinc-magnesium alloy intelligent sacrificial anode material (Zn-11Mg) in the present embodiment is as shown in Figure 1 and 2, and its chemical composition mass percent is: Mg: 10-11%, Al: 0.1-0.3%, other concrete impurity Content: ⁇ 0.02%, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- the Zn-11Mg prepared in Example 1 is tested for sensitivity to chloride ions in a strong alkaline solution, and the sensitivity test is evaluated using a polarization curve.
- the specific test method is: soak the material in the test solution for 10 minutes from - 1.5 Scan in the positive direction to 0.8V Ag/AgCl/Sat.KCl , if the anode curve current reaches 200 ⁇ A/ cm2 during the scanning process, stop the test, and use the pure zinc material with a purity of 99.99% and a zinc phase as a comparison sacrificial anode material.
- the Zn-11Mg prepared in Example 1 is coupled with steel to test their galvanic potential and galvanic current, so as to characterize their protective properties.
- the process of testing is: steel and Zn-11Mg are connected with an outer wire, and the outer wire Outside the test solution, steel and Zn-11Mg were immersed in the solution with a distance of 3 cm, and the galvanic current and galvanic potential were tested with an electrochemical workstation. A pure zinc material with a purity of 99.99% and a zinc phase is used as a comparison.
- Test solution saturated calcium hydroxide solution containing 0-0.60mol/L chloride ions
- the solid line in Figure 3 is the cathodic curve of steel, which can be divided into three areas: underprotected area, suitable protected area and overprotected area. If the galvanic couple potential is located in the underprotected area, the steel in the concrete pore solution containing chloride ions Corrosion can still occur, and there is a risk of hydrogen embrittlement in the steel in the over-protected area. Only in a suitable protected area is effective protection. It can be found that the galvanic potentials of pure zinc (Zn) (Fig. 4(a)) and Zn-11Mg (Fig.
- the invention discloses a zinc-magnesium alloy intelligent sacrificial anode material and its application.
- the mass percentage of its chemical composition is: Mg: 10-11%, Al: 0.1-0.3%, impurity ⁇ 0.02%, and the balance is Zn.
- Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase composition is a zinc-magnesium alloy intelligent sacrificial anode material and its application.
- the zinc-magnesium alloy intelligent sacrificial anode material in the present invention is sensitive to chloride ions, and can effectively detect whether chloride ions have invaded concrete; the galvanic potential with steel is higher than the hydrogen evolution potential of steel, which can protect steel from corrosion in concrete, At the same time, it does not form under-protection and over-protection to steel bars, and improves the response of zinc as a traditional sacrificial anode material to chloride ions and the galvanic corrosion with steel, which has industrial applicability.
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Abstract
Disclosed in the present invention are a zinc-magnesium alloy intelligent sacrificial anode material and the use thereof. The chemical components of the material comprise, in percentages by mass: 10-11% of Mg, 0.1-0.3% of Al, and impurities <0.02%, with the balance being Zn. In addition, the material is composed of a Zn phase, an MgZn2 phase and an Mg2Zn11 phase. The zinc-magnesium alloy intelligent sacrificial anode material in the present invention is sensitive to chloride ions, and can effectively detect whether chloride ions invade concrete. The galvanic potential of the material with respect to steel is higher than the hydrogen evolution potential of the steel, such that the steel can be protected from being corroded in concrete, and the under-protection and over-protection of steel bars also do not occur, thereby improving the response of zinc, which serves as a traditional sacrificial anode material, to chloride ions, and alleviating galvanic corrosion with respect to the steel.
Description
本发明属于合金材料技术领域，具体涉及一种锌镁合金智能牺牲阳极材料及其应用。The invention belongs to the technical field of alloy materials, and in particular relates to a zinc-magnesium alloy intelligent sacrificial anode material and its application.
钢筋混凝土作为一种结构材料,广泛应用于桥梁、建筑物、高架桥、堤坝、海底隧道和大型海洋平台等各种建筑与土木工程结构物，在海洋资源开发日渐兴盛的今天，钢筋混凝土的使用无疑会越来越广泛。然而，因钢筋混凝土耐久性问题而产生的腐蚀破坏比比皆是。钢筋混凝土的破坏不仅造成重大经济损失,也给人民生命财产安全带来重大隐患。As a structural material, reinforced concrete is widely used in various architectural and civil engineering structures such as bridges, buildings, viaducts, dams, submarine tunnels and large ocean platforms. In today's increasingly prosperous development of marine resources, the use of reinforced concrete is undoubtedly will become more widespread. However, corrosion damage abounds due to durability problems of reinforced concrete. The destruction of reinforced concrete not only causes great economic losses, but also brings great hidden dangers to the safety of people's lives and properties.
混凝土是一种由沙石、水泥和水混合后经一定时间凝固后的材料，其内部并不是致密的结构，通常有空隙的存在。在海洋环境中，孔间隙存在混凝土的硅酸盐水产物，该水产物主要为饱和氢氧化钙溶液，其pH能达到13左右。在完好的混凝土即没有氯离子入侵到混凝土内部时，钢筋表面能够生成一种钝化膜。随着时间的延长，氯离子逐渐扩散到混凝土内部，一旦氯离子到达钢筋表面，钢筋的钝化膜便很容易被氯离子破坏，诱发钢筋发生局部腐蚀。钢筋的腐蚀产物会堆积在钢筋与混凝土之间，且钢筋的腐蚀产物体积膨胀，进一步降低了钢筋与混凝土的结合力，容易使混凝土开裂，造成钢筋混凝土的加速破坏。因此对于钢筋混凝土中钢筋的保护显得格外重要，此外，氯离子作为造成钢筋锈蚀的重要原因，对混凝土中氯离子入侵的监测也显得及其重要。Concrete is a material that is mixed with sand, cement and water and solidified after a certain period of time. Its interior is not a dense structure, and there are usually voids. In the marine environment, the silicate water product of concrete exists in the pore space, and the water product is mainly saturated calcium hydroxide solution, and its pH can reach about 13. When the concrete is intact, that is, there is no chloride ion intrusion into the interior of the concrete, a passivation film can be formed on the surface of the steel bar. As time goes on, chloride ions gradually diffuse into the concrete. Once the chloride ions reach the surface of the steel bar, the passivation film of the steel bar is easily destroyed by the chloride ions, which induces localized corrosion of the steel bar. Corrosion products of steel bars will accumulate between steel bars and concrete, and the volume of corrosion products of steel bars will expand, further reducing the bonding force between steel bars and concrete, easily cracking concrete, and causing accelerated damage to reinforced concrete. Therefore, the protection of steel bars in reinforced concrete is particularly important. In addition, as chloride ions are an important cause of steel bar corrosion, the monitoring of chloride ion intrusion in concrete is also extremely important.
牺牲阳极的阴极保护法是一种比较方便且广泛使用的保护钢筋的方法。锌是目前使用最广泛的牺牲阳极材料，但是锌在混凝土孔隙液这种强碱性环境中溶解很快，过快的溶解速度导致其对氯离子不敏感，不能检测氯离子入侵到混凝土中。而镁对氯离子很敏感，可作为一种检测氯离子是否入侵到混凝土中的材料，当氯离子入侵到混凝土中，其可自发地进行腐蚀，为钢筋提供阴极电流保护钢筋不受腐蚀，因此是一种钢筋混凝土中的智能牺牲阳极材料。但镁作为钢筋混凝土中牺牲阳极材料的智能程度仍有待提高，因为镁的电位较低，在高氯离子的混凝土孔溶液中与钢的电偶电位会低于钢的析氢电位，使得钢有发生氢脆的风险。Sacrificial anode cathodic protection method is a relatively convenient and widely used method to protect steel bars. Zinc is currently the most widely used sacrificial anode material, but zinc dissolves very quickly in the strongly alkaline environment of concrete pore fluid. The excessive dissolution rate makes it insensitive to chloride ions, and cannot detect the intrusion of chloride ions into concrete. Magnesium is very sensitive to chloride ions and can be used as a material to detect whether chloride ions have invaded concrete. When chloride ions invade concrete, it can spontaneously corrode and provide cathodic current for steel bars to protect steel bars from corrosion. It is an intelligent sacrificial anode material in reinforced concrete. However, the intelligence of magnesium as a sacrificial anode material in reinforced concrete still needs to be improved, because the potential of magnesium is low, and the galvanic potential with steel in the concrete pore solution with high chloride ions will be lower than the hydrogen evolution potential of steel, so that steel has Risk of hydrogen embrittlement.
发明内容Contents of the invention
本发明的目的在于克服现有技术缺陷，提供锌镁合金件在检测钢筋混凝土中氯离子入侵中的应用。The purpose of the present invention is to overcome the defects of the prior art and provide the application of zinc-magnesium alloy parts in the detection of chloride ion intrusion in reinforced concrete.
本发明的另一目的在于提供锌镁合金件在防止钢筋混凝土中的钢筋的电偶腐蚀中的应用。Another object of the present invention is to provide the application of zinc-magnesium alloy parts in preventing galvanic corrosion of steel bars in reinforced concrete.
本发明的再一目的在于提供一种锌镁合金智能牺牲阳极材料及其制备方法。Another object of the present invention is to provide a zinc-magnesium alloy intelligent sacrificial anode material and a preparation method thereof.
本发明技术方案之一如下：One of the technical solutions of the present invention is as follows:
锌镁合金件在检测钢筋混凝土中氯离子入侵中的应用，所述锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
Application of zinc-magnesium alloy parts in detecting chloride ion intrusion in reinforced concrete, the chemical composition mass percentage of said zinc-magnesium alloy parts is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, balance It is Zn and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
在本发明的一个优选实施方案中，包括：将所述锌镁合金件作为氯离子响应件埋于钢筋混凝土中，然后对该锌镁合金件进行极化曲线测试。In a preferred embodiment of the present invention, it includes: embedding the zinc-magnesium alloy piece as a chloride ion response piece in reinforced concrete, and then performing a polarization curve test on the zinc-magnesium alloy piece.
本发明技术方案之二如下：The second technical scheme of the present invention is as follows:
一种检测钢筋混凝土中氯离子入侵的方法，包括：将锌镁合金件作为氯离子响应件埋于钢筋混凝土中，然后对该锌镁合金件进行极化曲线测试，该锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
A method for detecting chloride ion intrusion in reinforced concrete, comprising: burying a zinc-magnesium alloy piece as a chloride ion response piece in reinforced concrete, and then performing a polarization curve test on the zinc-magnesium alloy piece, the chemical properties of the zinc-magnesium alloy piece The composition mass percent is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
本发明技术方案之三如下：The third of the technical scheme of the present invention is as follows:
锌镁合金件在防止钢筋混凝土中的钢筋的电偶腐蚀中的应用，所述锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
Application of zinc-magnesium alloy parts in preventing galvanic corrosion of steel bars in reinforced concrete, the chemical composition mass percentages of the zinc-magnesium alloy parts are: Mg: 10-11%, Al: 0.1-0.3%, impurities <0.02% , the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
在本发明的一个优选实施方案中，包括将所述锌镁合金件作为牺牲阳极埋于钢筋混凝土中，并与其中的钢筋接触，该锌镁合金件在氯离子入侵到混凝土中时为钢筋提供阴极电流。In a preferred embodiment of the present invention, it includes embedding the zinc-magnesium alloy piece as a sacrificial anode in reinforced concrete, and contacting the steel bar therein, and the zinc-magnesium alloy piece provides the reinforcement for the steel bar when chloride ions invade into the concrete. cathodic current.
本发明技术方案之四如下：Four of technical solutions of the present invention are as follows:
一种防止钢筋混凝土中的钢筋的电偶腐蚀的方法，包括将锌镁合金件作为牺牲阳极埋于钢筋混凝土中，并与其中的钢筋接触，该锌镁合金件在氯离子入侵到混凝土中时为钢筋提供阴极电流；其中，该锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
A method for preventing galvanic corrosion of steel bars in reinforced concrete, comprising embedding a zinc-magnesium alloy piece as a sacrificial anode in reinforced concrete and contacting the steel bars therein, the zinc-magnesium alloy piece being exposed when chloride ions invade the concrete Provide cathodic current for the steel bar; wherein, the chemical composition mass percentage of the zinc-magnesium alloy is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, the balance is Zn, and it is composed of Zn phase, MgZn 2 phases and Mg 2 Zn 11 phases.
本发明技术方案之五如下：The fifth of the technical scheme of the present invention is as follows:
一种锌镁合金智能牺牲阳极材料，其化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
A zinc-magnesium alloy intelligent sacrificial anode material, its chemical composition mass percentage is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, the balance is Zn, and it is composed of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase composition.
上述锌镁合金智能牺牲阳极材料的制备方法，包括如下步骤：The preparation method of the above-mentioned zinc-magnesium alloy intelligent sacrificial anode material comprises the following steps:
(1)将打磨好的纯镁和纯锌置于坩埚中，将坩埚置于真空感应熔炼炉中并抽真空；(1) Place the polished pure magnesium and pure zinc in the crucible, place the crucible in a vacuum induction melting furnace and evacuate it;
(2)在上述真空感应熔炼炉中通入高纯氩气并进行加热；(2) Feed high-purity argon into the above-mentioned vacuum induction melting furnace and heat it;
(3)待纯镁和纯锌完全融化后继续保温10-20min后，随炉冷却后即得。(3) After the pure magnesium and pure zinc are completely melted, continue to keep warm for 10-20 minutes, and then cool down in the furnace.
在本发明的一个优选实施方案中，所述步骤(2)为：在所述真空感应熔炼炉中通入高纯氩气并加热至700-900℃。In a preferred embodiment of the present invention, the step (2) is: feeding high-purity argon into the vacuum induction melting furnace and heating to 700-900°C.
本发明的有益效果是：The beneficial effects of the present invention are:
1、本发明中的锌镁合金智能牺牲阳极材料对氯离子敏感，能够有效检测氯离子是否入侵到混凝土中。1. The zinc-magnesium alloy intelligent sacrificial anode material in the present invention is sensitive to chloride ions, and can effectively detect whether chloride ions have invaded concrete.
2、本发明中的锌镁合金智能牺牲阳极材料与钢的电偶电位高于钢的析氢电位，能够保护钢在混凝土中不受腐蚀，同时不对钢筋形成欠保护和过保护，改善了锌作为传统牺牲阳极材料对氯离子的响应和与钢的电偶腐蚀。2. The galvanic potential of the zinc-magnesium alloy intelligent sacrificial anode material and steel in the present invention is higher than the hydrogen evolution potential of steel, which can protect steel from corrosion in concrete, and does not form under-protection and over-protection to steel bars at the same time, improving the role of zinc as Response of traditional sacrificial anode materials to chloride ions and galvanic corrosion with steel.
3、本发明中的锌镁合金智能牺牲阳极材料的自腐蚀电流密度小，服役寿命长。3. The zinc-magnesium alloy intelligent sacrificial anode material in the present invention has low self-corrosion current density and long service life.
图1为本发明实施例1中制得的Zn-11Mg的XRD晶体衍射图。FIG. 1 is an XRD crystal diffraction pattern of Zn-11Mg prepared in Example 1 of the present invention.
图2为本发明实施例1制得的Zn-11Mg的晶相显微照片。Fig. 2 is a micrograph of the crystal phase of Zn-11Mg prepared in Example 1 of the present invention.
图3为本发明实施例2中锌和Zn-11Mg在含不同氯离子浓度的饱和氢氧化钙溶液中的极化曲线测试结果图。3 is a diagram showing the test results of polarization curves of zinc and Zn-11Mg in saturated calcium hydroxide solutions containing different concentrations of chloride ions in Example 2 of the present invention.
图4为本发明实施例3中锌和Zn-11Mg在含不同氯离子浓度的饱和氢氧化钙溶液中与钢的电偶测试结果图。Fig. 4 is a galvanic test result graph of zinc and Zn-11Mg in Example 3 of the present invention and steel in saturated calcium hydroxide solutions containing different concentrations of chloride ions.
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。The technical solutions of the present invention will be further illustrated and described below through specific embodiments in conjunction with the accompanying drawings.
实施例1Example 1
本实施例中的锌镁合金智能牺牲阳极材料(Zn-11Mg)如图1和2所示，其化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，其他的具体杂质含量：<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。
The zinc-magnesium alloy intelligent sacrificial anode material (Zn-11Mg) in the present embodiment is as shown in Figure 1 and 2, and its chemical composition mass percent is: Mg: 10-11%, Al: 0.1-0.3%, other concrete impurity Content: <0.02%, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
其制备为根据合金配方，称取相应的合金元素，采用真空熔炼炉熔炼铸造制成。具体包括如下步骤：It is prepared by weighing the corresponding alloy elements according to the alloy formula, and melting and casting in a vacuum melting furnace. Specifically include the following steps:
(1)将打磨好的纯镁和纯锌置于坩埚中，将坩埚置于真空感应熔炼炉中并抽真空；(1) Place the polished pure magnesium and pure zinc in the crucible, place the crucible in a vacuum induction melting furnace and evacuate it;
(2)在真空感应熔炼炉中通入高纯氩气并打开感应炉进行加热到700-900℃，保温40min；(2) Introduce high-purity argon into the vacuum induction melting furnace and turn on the induction furnace to heat to 700-900°C and keep it warm for 40 minutes;
(3)待纯镁和纯锌完全融化后继续加热15min后停止加热，合金液随炉自然冷却后即得。(3) After the pure magnesium and pure zinc are completely melted, continue heating for 15 minutes, then stop heating, and the alloy liquid will be ready after natural cooling in the furnace.
实施例2Example 2
将实施例1制备的Zn-11Mg在强碱性溶液中对氯离子进行敏感程度测试，敏感度测试采用极化曲线进行评价，具体测试方法为：将材料在测试溶液中浸泡10分钟后从-1.5向正方向扫描至0.8V
Ag/AgCl/Sat.KCl，若扫描过程中发现阳极曲线电流达到200μA/cm
2即停止测试，并以纯度为99.99％且有锌相构成的纯锌材料作为对比的牺牲阳极材料。
The Zn-11Mg prepared in Example 1 is tested for sensitivity to chloride ions in a strong alkaline solution, and the sensitivity test is evaluated using a polarization curve. The specific test method is: soak the material in the test solution for 10 minutes from - 1.5 Scan in the positive direction to 0.8V Ag/AgCl/Sat.KCl , if the anode curve current reaches 200μA/ cm2 during the scanning process, stop the test, and use the pure zinc material with a purity of 99.99% and a zinc phase as a comparison sacrificial anode material.
强碱性溶液pH范围为12-12.8。从图3中阳极曲线上可以发现，随氯离子浓度提高，Zn-11Mg(图3(b))钝化膜破裂电位下降比纯锌(Zn)(图3(a))更明显，因此Zn-11Mg比纯锌对氯离子更敏感。此外这两种材料中，Zn-11Mg的自腐蚀电流密度较小，意味着其服役寿命比锌更长。Strongly alkaline solutions have a pH range of 12-12.8. From the anode curve in Figure 3, it can be found that as the concentration of chloride ions increases, the breakdown potential of the passive film of Zn-11Mg (Figure 3(b)) decreases more significantly than that of pure zinc (Zn) (Figure 3(a)), so Zn -11Mg is more sensitive to chloride ions than pure zinc. In addition, among the two materials, Zn-11Mg has a lower self-corrosion current density, which means that its service life is longer than that of zinc.
实施例3Example 3
将实施例1制备的Zn-11Mg与钢偶合以测试它们的电偶电位和电偶电流，从而表征它们的保护性能，测试的过程为：将钢与Zn-11Mg用外导线连接起来，外导线 在测试溶液之外，将钢和Zn-11Mg浸入溶液中，两者之间的距离是3cm，用电化学工作站测试电偶电流和电偶电位。并以纯度为99.99％且有锌相构成的纯锌材料作为对比。The Zn-11Mg prepared in Example 1 is coupled with steel to test their galvanic potential and galvanic current, so as to characterize their protective properties. The process of testing is: steel and Zn-11Mg are connected with an outer wire, and the outer wire Outside the test solution, steel and Zn-11Mg were immersed in the solution with a distance of 3 cm, and the galvanic current and galvanic potential were tested with an electrochemical workstation. A pure zinc material with a purity of 99.99% and a zinc phase is used as a comparison.
测试溶液：含0-0.60mol/L氯离子的饱和氢氧化钙溶液，测试结果如图3所示。图3中实线为钢的阴极曲线，其可以分为欠保护区、合适保护区和过保护区三个区域，若电偶电位位于欠保护区内，钢在含有氯离子的混凝土孔溶液中依然可以发生腐蚀，在过保护区内钢有发生氢脆的风险，只有在合适保护区内是有效保护。可以发现，纯锌(Zn)(图4(a))和Zn-11Mg(图4(b))在不含有氯离子(0mo/L Cl
-)的强碱性溶液中与钢的电偶电位位于欠保护区内，但这种情况是可以接受的，因为在不含有氯离子的溶液中钢不会发生腐蚀；锌与钢的电偶电位在含有氯离子的溶液中大部分情况下位于欠保护区，这种情况下钢会面临保护性不足的风险，而Zn-11Mg与钢的电偶电位在含有氯离子的溶液中全部位于合适保护区，因此可保护钢不受腐蚀。
Test solution: saturated calcium hydroxide solution containing 0-0.60mol/L chloride ions, the test results are shown in Figure 3. The solid line in Figure 3 is the cathodic curve of steel, which can be divided into three areas: underprotected area, suitable protected area and overprotected area. If the galvanic couple potential is located in the underprotected area, the steel in the concrete pore solution containing chloride ions Corrosion can still occur, and there is a risk of hydrogen embrittlement in the steel in the over-protected area. Only in a suitable protected area is effective protection. It can be found that the galvanic potentials of pure zinc (Zn) (Fig. 4(a)) and Zn-11Mg (Fig. 4(b)) with steel in a strong alkaline solution without chloride ions (0mo/L Cl - ) Located in the underprotected area, but this situation is acceptable because steel does not corrode in solutions that do not contain chloride ions; the galvanic couple potential of zinc and steel is in the underprotected area in most cases in solutions containing chloride ions. Protected area, in which case the steel will face the risk of insufficient protection, while the galvanic potentials of Zn-11Mg and steel are all in the appropriate protected area in the solution containing chloride ions, thus protecting the steel from corrosion.
以上所述，仅为本发明的较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。The above is only a preferred embodiment of the present invention, so the scope of the present invention cannot be limited accordingly, that is, equivalent changes and modifications made according to the patent scope of the present invention and the content of the specification should still be covered by the present invention In the range.
本发明公开了一种锌镁合金智能牺牲阳极材料及其应用，其化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn
2相和Mg
2Zn
11相组成。本发明中的锌镁合金智能牺牲阳极材料对氯离子敏感，能够有效检测氯离子是否入侵到混凝土中；与钢的电偶电位高于钢的析氢电位，能够保护钢在混凝土中不受腐蚀，同时不对钢筋形成欠保护和过保护，改善了锌作为传统牺牲阳极材料对氯离子的响应和与钢的电偶腐蚀,具有工业实用性。
The invention discloses a zinc-magnesium alloy intelligent sacrificial anode material and its application. The mass percentage of its chemical composition is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, and the balance is Zn. Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase composition. The zinc-magnesium alloy intelligent sacrificial anode material in the present invention is sensitive to chloride ions, and can effectively detect whether chloride ions have invaded concrete; the galvanic potential with steel is higher than the hydrogen evolution potential of steel, which can protect steel from corrosion in concrete, At the same time, it does not form under-protection and over-protection to steel bars, and improves the response of zinc as a traditional sacrificial anode material to chloride ions and the galvanic corrosion with steel, which has industrial applicability.
Claims (9)
- 锌镁合金件在检测钢筋混凝土中氯离子入侵中的应用，其特征在于：所述锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn 2相和Mg 2Zn 11相组成。 The application of zinc-magnesium alloy parts in the detection of chloride ion intrusion in reinforced concrete is characterized in that: the chemical composition mass percentage of the zinc-magnesium alloy parts is: Mg: 10-11%, Al: 0.1-0.3%, impurities <0.02 %, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- 如权利要求1所述的应用，其特征在于：包括：将所述锌镁合金件作为氯离子响应件埋于钢筋混凝土中，对该锌镁合金件进行极化曲线测试。The application according to claim 1, characterized in that it comprises: embedding the zinc-magnesium alloy part as a chloride ion response part in reinforced concrete, and performing a polarization curve test on the zinc-magnesium alloy part.
- 一种检测钢筋混凝土中氯离子入侵的方法，其特征在于：包括：将锌镁合金件作为氯离子响应件埋于钢筋混凝土中，对该锌镁合金件进行极化曲线测试，该锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn 2相和Mg 2Zn 11相组成。 A method for detecting chloride ion intrusion in reinforced concrete, characterized in that it comprises: embedding a zinc-magnesium alloy piece in reinforced concrete as a chloride ion response piece, and performing a polarization curve test on the zinc-magnesium alloy piece, the zinc-magnesium alloy piece The mass percent of the chemical composition of the piece is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- 锌镁合金件在防止钢筋混凝土中的钢筋腐蚀中的应用，其特征在于：所述锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn 2相和Mg 2Zn 11相组成。 The application of zinc-magnesium alloy parts in preventing corrosion of steel bars in reinforced concrete is characterized in that: the chemical composition mass percentage of the zinc-magnesium alloy parts is: Mg: 10-11%, Al: 0.1-0.3%, and impurities <0.02 %, the balance is Zn, and consists of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- 如权利要求5所述的应用，其特征在于：包括将所述锌镁合金件作为牺牲阳极埋于钢筋混凝土中，并与其中的钢筋接触，该锌镁合金件在氯离子入侵到混凝土中时为钢筋提供阴极电流。The application according to claim 5, characterized in that: it includes embedding the zinc-magnesium alloy part as a sacrificial anode in reinforced concrete and contacting the steel bars therein, when the zinc-magnesium alloy part invades the concrete when chloride ions Provides cathodic current to the reinforcement.
- 一种防止钢筋混凝土中的钢筋腐蚀的方法，其特征在于：包括将锌镁合金件作为牺牲阳极埋于钢筋混凝土中，并与其中的钢筋接触，该锌镁合金件在氯离子入侵到混凝土中时为钢筋提供阴极电流；其中，该锌镁合金件的化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且由Zn相、MgZn 2相和Mg 2Zn 11相组成。 A method for preventing corrosion of steel bars in reinforced concrete, characterized in that: the zinc-magnesium alloy parts are buried in the reinforced concrete as sacrificial anodes and contacted with the steel bars therein. Provide cathodic current for steel bars; wherein, the chemical composition mass percentage of the zinc-magnesium alloy parts is: Mg: 10-11%, Al: 0.1-0.3%, impurity <0.02%, the balance is Zn, and is composed of Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase composition.
- 一种锌镁合金智能牺牲阳极材料，将锌镁合金件作为牺牲阳极埋于钢筋混凝土中，并与其中的钢筋接触，其特征在于：其化学成分质量百分比为：Mg：10-11％，Al：0.1-0.3％，杂质<0.02％，余量为Zn，且包括Zn相、MgZn 2相和Mg 2Zn 11相。 A zinc-magnesium alloy intelligent sacrificial anode material, the zinc-magnesium alloy parts are buried in reinforced concrete as sacrificial anodes, and are in contact with the steel bars therein, and are characterized in that: the mass percentage of its chemical composition is: Mg: 10-11%, Al : 0.1-0.3%, impurity <0.02%, the balance is Zn, and includes Zn phase, MgZn 2 phase and Mg 2 Zn 11 phase.
- 权利要求8所述的一种锌镁合金智能牺牲阳极材料的制备方法，其特征在于：包括如下步骤：The preparation method of a zinc-magnesium alloy intelligent sacrificial anode material according to claim 8, characterized in that it comprises the following steps:(1)将打磨好的纯镁和纯锌置于坩埚中，将坩埚置于真空感应熔炼炉中并抽真空；(1) Place the polished pure magnesium and pure zinc in the crucible, place the crucible in a vacuum induction melting furnace and evacuate it;(2)在上述真空感应熔炼炉中通入高纯氩气并进行加热；(2) Feed high-purity argon into the above-mentioned vacuum induction melting furnace and heat it;(3)待纯镁和纯锌完全融化后继续保温10-20min后，随炉冷却后即得。(3) After the pure magnesium and pure zinc are completely melted, continue to keep warm for 10-20 minutes, and then cool down in the furnace.
- 如权利要求9所述的制备方法，其特征在于：所述步骤(2)为：在所述真空感应熔炼炉中通入高纯氩气并加热至700-900℃。The preparation method according to claim 9, characterized in that: said step (2) is: passing high-purity argon gas into said vacuum induction melting furnace and heating to 700-900°C.
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| CN113817934A (en) * | 2021-09-15 | 2021-12-21 | 厦门大学 | Zinc-magnesium alloy intelligent sacrificial anode material and application thereof |
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| JP4264167B2 (en) * | 1999-09-10 | 2009-05-13 | 新日本製鐵株式会社 | Hot-dip steel sheet with excellent corrosion resistance |
| CN106835149B (en) * | 2017-01-09 | 2019-03-05 | 青岛双瑞海洋环境工程股份有限公司 | A kind of heat exchanger tube outer wall galvanic anode protection protecting system |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008111150A (en) * | 2006-10-30 | 2008-05-15 | Nippon Steel Corp | Highly corrosion-resistant hot dip galvanized steel sheet |
| CN104862710A (en) * | 2015-06-09 | 2015-08-26 | 青岛双瑞海洋环境工程股份有限公司 | Environment-friendly sacrificial zinc alloy anode |
| CN105624689A (en) * | 2016-04-08 | 2016-06-01 | 厦门大学 | Corrosion automatic detection and intelligent protection system |
| CN107663636A (en) * | 2016-07-27 | 2018-02-06 | 上海法赫桥梁隧道养护工程技术有限公司 | Sacrificial anode and preparation method thereof built in a kind of reinforcement in concrete anticorrosion use |
| CN110964947A (en) * | 2019-12-02 | 2020-04-07 | 兰州理工大学 | Zinc alloy sacrificial anode material for reinforced concrete structure in chloride corrosion environment |
| CN113817934A (en) * | 2021-09-15 | 2021-12-21 | 厦门大学 | Zinc-magnesium alloy intelligent sacrificial anode material and application thereof |
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| CN113817934B (en) | 2022-11-01 |
| CN113817934A (en) | 2021-12-21 |
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