CN115198277B - Zn-Li alloy sacrificial anode for deep sea and preparation method thereof - Google Patents
Zn-Li alloy sacrificial anode for deep sea and preparation method thereof Download PDFInfo
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- 229910000733 Li alloy Inorganic materials 0.000 title claims abstract description 32
- 239000001989 lithium alloy Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000005275 alloying Methods 0.000 claims abstract description 25
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 238000010791 quenching Methods 0.000 claims description 12
- 230000000171 quenching effect Effects 0.000 claims description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 11
- 239000000956 alloy Substances 0.000 claims description 11
- 229910013391 LizN Inorganic materials 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000032683 aging Effects 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000000265 homogenisation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 230000033228 biological regulation Effects 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000011701 zinc Substances 0.000 abstract description 25
- 238000005260 corrosion Methods 0.000 abstract description 22
- 230000007797 corrosion Effects 0.000 abstract description 21
- 230000000694 effects Effects 0.000 abstract description 14
- 229910052725 zinc Inorganic materials 0.000 abstract description 11
- 238000004090 dissolution Methods 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 abstract description 10
- 239000001301 oxygen Substances 0.000 abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001297 Zn alloy Inorganic materials 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 231100000701 toxic element Toxicity 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 229910000846 In alloy Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910002056 binary alloy Inorganic materials 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910002058 ternary alloy Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000004210 cathodic protection Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002706 hydrostatic effect Effects 0.000 description 3
- 229910002059 quaternary alloy Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910018087 Al-Cd Inorganic materials 0.000 description 2
- 229910018188 Al—Cd Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000009931 pascalization Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018137 Al-Zn Inorganic materials 0.000 description 1
- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000746 Structural steel Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
Abstract
The invention belongs to the technical field of corrosion protection of metal materials, and particularly relates to a Zn-Li alloy sacrificial anode for deep sea and a preparation method thereof, wherein the Zn-Li alloy sacrificial anode comprises Li, alloying elements and Zn, has a lower open circuit potential of-1.18 to-1.02V in a low-temperature, low-dissolved oxygen and high-pressure environment in deep sea, has a working potential of-1.12 to-0.94V, has current efficiency of more than 90 percent, has good activating capability, is easy to fall off corrosion products, has uniform dissolution morphology and no obvious local corrosion, and meets the cathode protection requirement of deep sea metal marine equipment; the preparation method of the Zn-Li alloy sacrificial anode comprises two steps of vacuum melting and heat treatment, namely, the metal element Li with highest activity is added into the Zn alloy sacrificial anode for the first time, li is easy to ionize in a liquid environment, the activity of the zinc anode in deep sea low-temperature, low-dissolved oxygen and high-pressure environments can be obviously improved, and the zinc anode does not contain toxic elements such as Cd and the like, is beneficial to environmental protection, and is an ideal metal sacrificial anode for deep sea.
Description
Technical field:
the invention belongs to the technical field of corrosion protection of metal materials, and particularly relates to a Zn-Li alloy sacrificial anode for deep sea and a preparation method thereof, which can keep high activity and high current efficiency in a deep sea environment and provide good cathodic protection for metal equipment.
The background technology is as follows:
structural steel is the primary material of deep sea equipment structural facilities, which faces severe corrosion damage problems in severe deep sea environments. The sacrificial anode protection technology is one of the most effective means in the metal material corrosion prevention technology, and has the advantages of easy installation and maintenance and no need of an external power supply. However, the low temperature (2-5 ℃) and high hydrostatic pressure (10-100 MPa) and low dissolved oxygen content (0.5-3 mg/L) of the deep sea environment with the water depth of more than 1000m can lead to the phenomena of reduced dissolution capacity, reduced current efficiency, even self passivation and the like of the traditional sacrificial anode applied to shallow sea, and lead to the failure of cathodic protection.
The results of analysis and research on the electrical performance of the Al-Zn-In alloy anode under the simulated deep sea condition show that: the high hydrostatic pressure can cause the Al-Zn-In alloy anode to generate grain boundary corrosion, and the dissolution capacity of the matrix is reduced; the low dissolved oxygen content and low temperature can reduce the In atom diffusion capacity of the surface of the Al-Zn-In alloy anode; dense Al 2 O 3 The oxide layer is easier to passivate and difficult to fall off, so that the overall current efficiency of the Al-Zn-In alloy anode is reduced by more than 10 percent. For example, chinese patent 201811288181.7 discloses a high-performance Al-Zn-In sacrificial anode material which comprises the following components In percentage by mass: 3.0 to 7.0 percent of zinc, 0.02 to 0.05 percent of indium, 1.0 to 1.5 percent of magnesium, 0.03 to 0.07 percent of titanium, 0.02 to 0.05 percent of silver, less than or equal to 0.15 percent of impurity total amount and the balance of aluminum; wherein, the iron content in the impurity is less than or equal to 0.10 percent; the preparation method comprises the following steps: heating a high-frequency induction smelting furnace, and controlling the temperature to be 720-760 ℃ to melt an aluminum ingot; calculating and measuring the mass percentages of Al-Zn alloy, al-In alloy, al-Mg alloy, pure titanium and pure silver, and adding the alloy and the pure silver into molten aluminum liquid; and uniformly stirring by using a graphite rod, deslagging, pouring the deslagged mixed solution by using a cast steel mold, and cooling to obtain the Al-Zn-In sacrificial anode material. Therefore, there is a need for further improving the activity and electrochemical performance of Al-Zn-In alloy anodes In deep sea environments.
The zinc anode is widely applied to the cathode protection of metal materials in shallow sea environment, and has the advantages of high current efficiency, loose surface oxide layer, low smelting energy consumption and the like compared with an aluminum alloy anode. The zinc anode commonly used in the prior art mainly comprises a high-purity zinc anode and a Zn-Al-Cd anode: the high-purity zinc anode has coarse grains, is easy to generate local corrosion during dissolution, and has poor stability; the Cd element in the Zn-Al-Cd anode is a high-harm toxic substance, which is not beneficial to environmental protection. Therefore, a need exists for preparing a novel high-activity and uniformly corroded sacrificial zinc alloy anode for deep sea by selecting a proper high-activity alloying element.
The key to improving the activity and electrochemical performance of zinc alloy is to add high-activity alloying elements and regulate the microstructure thereof. Li element has the lowest standard electrode potential (-3.405V/SHE) in metal, and alloy potential can be reduced after alloying; meanwhile, li element has the smallest first ionization energy, the value of which is only 520kJ/mol, and is lower than metal elements such as Al (577.5 kJ/mol), fe (762 kJ/mol), mg (737 kJ/mol) and the like, and is the metal element with the easiest electron loss. Under the low-temperature condition of the deep sea environment, lithium element in the sacrificial anode is easy to ionize, the activity and the current efficiency of the sacrificial anode can be ensured, and effective protection is provided for deep sea engineering equipment. In addition, the theoretical capacitance of Li element is as high as 3860 A.h/Kg, and the density is only 0.53g/cm 3 The theoretical capacitance of the zinc alloy can be improved. Alloying elements such as Al, mg, ca, sr, ga, sn, mn, ti, si and the like can eliminate the influence of impurity elements such as Fe and the like, and the alloying elements are dissolved in a matrix or separated out to form a dispersed nanoscale second phase through a heat treatment process, so that the effects of refining a grain structure and stabilizing working potential and current are achieved, and the performance of the zinc alloy sacrificial anode is greatly improved.
The invention comprises the following steps:
the invention aims to overcome the defects of the prior art, and develops and designs a Zn-Li alloy sacrificial anode and a preparation method thereof, and the Zn-Li alloy sacrificial anode has the advantages of enough negative and stable working potential, easy falling of surface corrosion products, uniform dissolution morphology and the like in deep sea low-temperature, low-oxygen and high-pressure environments.
In order to achieve the aim, the Zn-Li alloy sacrificial anode comprises the components of Li, alloying elements and Zn, wherein the content of the Li is 0.01-2.50wt%, the content of the alloying elements is less than or equal to 3%, and the balance is Zn; wherein, the alloying element is one or more of Al, mg, ca, sr, ga, sn, mn, ti and Si, the content of Al is 0.01-1.20wt%, the content of Mg, ca, sr, mn, ti and Si is 0.01-0.50wt%, the content of Ga is 0.01-0.03wt%, the content of Sn is 0.01-0.25wt%, and the content of impurities is less than or equal to 0.30wt%.
The process of the Zn-Li alloy sacrificial anode preparation method comprises two steps of vacuum smelting and heat treatment:
(1) Vacuum melting
Firstly, mixing Li, alloying element simple substance or intermediate alloy and Zn to form a mixture;
then, in CO 2 And SF (sulfur hexafluoride) 6 Or smelting, stirring and standing the mixture under the protection of argon;
finally, cooling after casting to obtain a Zn-Li alloy cast ingot;
wherein the smelting temperature is 500-850 ℃, the standing time is 3-5min, and the casting temperature is 450-750 ℃;
the vacuum melting step may be replaced with metallurgical means including powder metallurgy;
(2) Heat treatment of
Performing microstructure regulation and control on the Zn-Li alloy cast ingot according to the high-temperature homogenization treatment, quenching, aging treatment and quenching processes to obtain a Zn-Li alloy sacrificial anode;
the high-temperature homogenization treatment process comprises the following steps: heating to 300-350deg.C at a rate of 1-20deg.C/min
Keeping the temperature for 2-4 hours, accelerating the diffusion of alloying elements, reducing the segregation of the alloying elements and improving the solubility of the alloying elements in the matrix so as to obtain a uniform matrix;
the aging treatment process comprises the following steps: heating to 150-250deg.C at a speed of 1-5deg.C/min, and maintaining for 1-6 hr to obtain fine Zn+LiZn 4 The phase micron-level multilayer structure has a lamellar phase spacing of 5-20 mu m, and the aging treatment temperature is higher than the phase precipitation temperature of alloying elements so as to ensure the solid solubility of the alloying elements in Zn, prevent precipitation of coarse second phases and reduce self-corrosion;
the quenching adopts water or oil with the temperature of 0-100 ℃ and finally the quenching obtains Zn+LiZn 4 The phase micron-level multilayer structure and the dispersed nano-level/micron-level precipitated phase, wherein Zn phase is supersaturated solid solution at normal temperature, and can improve the dissolution uniformity.
The invention is thatCompared with the prior art, the low open-circuit potential in deep sea low temperature (2-5 ℃), low dissolved oxygen (0.5-3 mg/L) and high pressure environment (10-100 MPa) is-1.18 to-1.02V (vs. Ag/AgCl reference electrode, the same applies below), the working potential is-1.12 to-0.94V, the current efficiency is more than 90%, the high-activity corrosion-resistant metal-sea equipment has good activation capability, corrosion products are easy to fall off, the dissolution morphology is uniform and no obvious local corrosion exists, the cathodic protection requirement of deep sea metal-sea equipment is met, and the high-activity corrosion-resistant metal-sea equipment mainly comprises micron-sized Zn+LiZn 4 The phase multilayer structure and the dispersed nano-scale/micron-scale precipitated phase are formed, alloying elements are completely dissolved in Zn or precipitated in nano-scale/micron-scale precipitated phase, so that the uniformity of macroscopic scale is ensured, the dissolution in a deep sea environment is uniform, the exfoliation of corrosion products is facilitated, meanwhile, the metal element Li with the highest activity is firstly added into a Zn alloy sacrificial anode, li is extremely easy to ionize in a liquid environment, the activity of the zinc anode in the deep sea low-temperature, low-dissolved oxygen and high-pressure environment can be remarkably improved, and the metal sacrificial anode does not contain toxic elements such as Cd, is favorable for environmental protection and is an ideal deep sea metal sacrificial anode.
Description of the drawings:
FIG. 1 is a microstructure metallographic photograph of a Zn-Li alloy sacrificial anode prepared in example 1 of the present invention.
FIG. 2 is an X-ray diffraction pattern of a Zn-Li alloy sacrificial anode prepared in example 1 of the present invention.
FIG. 3 is a surface dissolution profile after removal of corrosion products of the Zn-Li alloy sacrificial anode prepared in example 1 of the present invention.
The specific embodiment is as follows:
the invention will be further described with reference to the accompanying drawings and specific embodiments.
Example 1:
the technical process of the Zn-Li alloy sacrificial anode comprises two steps of vacuum smelting and heat treatment:
(1) Vacuum melting
Mixing Zn and Li, and placing in CO 2 And SF (sulfur hexafluoride) 6 Or vacuum smelting furnace under argon protection, smelting and stirring at 500-550deg.C, standing for 3-5min, and cooling at 450-500deg.CCasting downwards, and cooling to obtain a Zn-Li alloy anode cast ingot, wherein the Li content is 0.01-2.50wt%;
(2) Heat treatment of
Placing the Zn-Li alloy anode cast ingot into a box type heating sintering furnace, heating to 300 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and then carrying out water quenching at room temperature;
casting the Zn-Li alloy anode in a box type heating sintering furnace, heating to 150 ℃ at the speed of 1 ℃/min, preserving heat for 2 hours, and then quenching with water at room temperature;
obtaining the Zn-Li binary alloy sacrificial anode.
The microstructure metallographic photograph of the Zn-Li binary alloy sacrificial anode prepared in the embodiment is shown in figure 1, the cast structure is a multi-layer structure, and the adjacent phase spacing is 5-10 mu m;
as shown in FIG. 2, the X-ray diffraction pattern is that only Zn and LiZn are present 4 The multi-layer structure of the two-phase, namely Zn-Li binary alloy sacrificial anode consists of Zn and LiZn 4 Two phases are formed;
the accelerated test of the electrochemical performance of the sacrificial anode is carried out according to national standard GB/T17848-1999, and the test result of the Zn-Li binary alloy sacrificial anode in seawater with the temperature of 2-3 ℃, the hydrostatic pressure of 10-30MPa and the dissolved oxygen of 0.51mg/L is as follows: the open-circuit potential is-1.18 to-1.12V, the working potential is-1.12 to-1.06V, the current efficiency is 90.4 to 92.1 percent, and corrosion products have no obvious adhesion;
the surface dissolution morphology of the corrosion product is shown in figure 3, and the Zn-Li binary alloy sacrificial anode is uniformly dissolved without obvious local corrosion.
Example 2:
the technical process of the Zn-Li alloy sacrificial anode comprises two steps of vacuum smelting and heat treatment:
(1) Vacuum melting
Mixing Zn, li and alloying element simple substance or intermediate alloy according to the content shown in Table 1, and placing in CO 2 And SF (sulfur hexafluoride) 6 Or vacuum smelting furnace under argon protection, smelting and stirring at 500-850deg.C, standing for 3-5min, and cooling at 500-800 deg.CCasting at the temperature of between 1 and 9 ℃ and cooling to obtain a Zn-Li alloy anode cast ingot with the number of between 1 and 9,
(2) Heat treatment of
Respectively placing the Zn-Li alloy anode ingots with the numbers of 1-9 into a box type heating sintering furnace, heating to 350 ℃ at the speed of 10 ℃/min, preserving heat for 2 hours, and then carrying out water quenching at the temperature of 50 ℃;
casting Zn-Li alloy anodes with the numbers of 1-9 into a box type heating sintering furnace, heating to 250 ℃ at the speed of 1 ℃/min, preserving heat for 2 hours, and then quenching with water at room temperature;
the Zn-Li ternary alloy sacrificial anode with the number of 1-9 is obtained.
Table 1:
the microstructure of the Zn-Li ternary alloy sacrificial anode prepared in the embodiment consists of 5-30 mu m-sized crystal grains, and Zn+LiZn is arranged in the crystal grains 4 Lamellar structure, wherein the spacing between lamellar layers is 10-15 μm, and nanometer/micrometer precipitated phases of dispersed distribution composed of alloying elements are precipitated in crystal;
the accelerated test of the electrochemical performance of the sacrificial anode is carried out according to national standard GB/T17848-1999, and the test result of the Zn-Li ternary alloy sacrificial anode alloy in seawater with the temperature of 3-4 ℃, the hydrostatic pressure of 30-60MPa and the dissolved oxygen of 1-2mg/L is as follows: the open-circuit potential is-1.12 to-1.07V, the working potential is-1.06 to-1.00V, the current efficiency is 92.1 to 95.0 percent, no obvious adhesion exists on corrosion products, and the Zn-Li ternary alloy sacrificial anode is uniformly dissolved and has no obvious local corrosion.
Example 3:
the procedure of the Zn-Li alloy sacrificial anode of this example was the same as that of example 2, except that Zn and Li were used in the amounts shown in Table 2, to prepare Zn-Li alloy sacrificial anodes having numbers 10 to 18.
Table 2:
the microstructure of the Zn-Li quaternary alloy sacrificial anode prepared in the embodiment is composed of Zn+LiZn 4 Lamellar structure, wherein the spacing between lamellar layers is 15-20 μm, and nanometer/micrometer precipitated phases which are formed by alloying elements and are dispersed and distributed are precipitated in crystals;
the accelerated test of the electrochemical performance of the sacrificial anode is carried out according to national standard GB/T17848-1999, and the test result of the Zn-Li quaternary alloy sacrificial anode alloy in seawater with the temperature of 4-5 ℃, the hydrostatic pressure of 60-100MPa and the dissolved oxygen of 2-3mg/L is as follows: the open-circuit potential is-1.07 to-1.02V, the working potential is-1.00 to-0.94V, the current efficiency is more than 95 percent, corrosion products are not obviously attached, and the Zn-Li quaternary alloy sacrificial anode is uniformly dissolved and has no obvious local corrosion.
Claims (6)
1. A Zn-Li alloy sacrificial anode for deep sea is prepared from micron-class Zn+LiZn 4 The phase multi-layer structure and the dispersed nano-scale/micro-scale precipitated phase are formed, and alloying elements are precipitated in the nano-scale/micro-scale precipitated phase, and the phase multi-layer structure is characterized by comprising Li, alloying elements and Zn; the spacing between layers is 5-20 μm; the content of Li is 0.01-2.50wt%, the content of alloying element is less than or equal to 3wt%, and the balance is Zn; the alloying element is one or two of Al and Ga, the content of Al is 0.01-1.20wt%, the content of Ga is 0.01-0.03wt%, and the content of impurities is less than or equal to 0.30wt%.
2. The method for preparing a Zn-Li alloy sacrificial anode for deep sea according to claim 1, wherein the process comprises two steps of vacuum melting and heat treatment:
(1) Vacuum melting
Firstly, mixing Li, alloying element simple substance or intermediate alloy and Zn to form a mixture;
then, in CO 2 And SF (sulfur hexafluoride) 6 Or CO 2 Smelting, stirring and standing the mixture under the protection of argon;
finally, cooling after casting to obtain a Zn-Li alloy cast ingot;
(2) Heat treatment of
Performing microstructure regulation and control on the Zn-Li alloy cast ingot according to the flow of high-temperature homogenization treatment, quenching, aging treatment and quenching to obtain a Zn-Li alloy sacrificial anode for deep sea;
wherein smelting can be replaced with metallurgical means including powder metallurgy.
3. The method for producing a sacrificial anode of a Zn-Li-based alloy for deep sea according to claim 2, wherein the smelting temperature in step (1) is 500 to 850 ℃, the standing time is 3 to 5 minutes, and the casting temperature is 450 to 750 ℃.
4. The method for preparing a sacrificial anode of a Zn-Li-based alloy for deep sea according to claim 2, wherein the high-temperature homogenization treatment process of step (2) is as follows: heating to 300-350deg.C at a speed of 1-20deg.C/min, and maintaining for 2-4 hr.
5. The method for preparing a sacrificial anode of a Zn-Li-based alloy for deep sea according to claim 2, wherein the aging treatment process of step (2) is as follows: heating to 150-250deg.C at a speed of 1-5deg.C/min, and maintaining for 1-6 hr to obtain micrometer Zn+LiZn 4 The temperature of aging treatment is higher than the phase precipitation temperature of alloying elements.
6. The method for producing a sacrificial anode of a Zn-Li alloy for deep sea according to claim 2, wherein the quenching in the step (2) is performed with water or oil at a temperature of 0 to 100℃and the final quenching is performed to obtain micro-sized Zn+LiZn 4 Phase multilayer structure and dispersed nano-scale/micro-scale precipitated phase。
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