CN115637434A - Aluminum sacrificial anode alloy and preparation method thereof - Google Patents
Aluminum sacrificial anode alloy and preparation method thereof Download PDFInfo
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 147
- 239000000956 alloy Substances 0.000 title claims abstract description 147
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 35
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 69
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- 238000002844 melting Methods 0.000 claims abstract description 12
- 230000008018 melting Effects 0.000 claims abstract description 12
- 238000007670 refining Methods 0.000 claims abstract description 12
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 12
- 229910018117 Al-In Inorganic materials 0.000 claims abstract description 6
- 229910018137 Al-Zn Inorganic materials 0.000 claims abstract description 6
- 229910018456 Al—In Inorganic materials 0.000 claims abstract description 6
- 229910018573 Al—Zn Inorganic materials 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000005520 cutting process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 5
- 229910018125 Al-Si Inorganic materials 0.000 claims description 4
- 229910018140 Al-Sn Inorganic materials 0.000 claims description 4
- 229910018520 Al—Si Inorganic materials 0.000 claims description 4
- 229910018564 Al—Sn Inorganic materials 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims 1
- 239000000047 product Substances 0.000 claims 1
- 238000007872 degassing Methods 0.000 abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 4
- 239000011701 zinc Substances 0.000 description 25
- 229910052725 zinc Inorganic materials 0.000 description 24
- 229910052718 tin Inorganic materials 0.000 description 19
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- 239000010405 anode material Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 229910052738 indium Inorganic materials 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
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- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the field of aluminum anode sacrificial alloy, and particularly discloses an aluminum sacrificial anode alloy and a preparation method thereof. The aluminum sacrificial anode alloy comprises the following alloy elements in percentage by mass: 0.5-5%, si:2-10%, sn:0.1-3%, in:0.01-0.2%, and the balance of Al and inevitable impurities (Fe element reaches a saturated state). The preparation method comprises the following steps: firstly melting an aluminum ingot, then adding Al-Zn intermediate alloy, al-Si intermediate alloy, al-Sn intermediate alloy and Al-In intermediate alloy, casting the mixture into a casting blank after refining, degassing and deslagging, and then annealing the anode alloy for a long timeThen, al is obtained 9 Fe 2 And the occurrence of the Si phase can reduce the electrode potential of the aluminum sacrificial anode alloy, improve the current efficiency of the aluminum alloy and the performance of the sacrificial anode simultaneously, and the corrosion product is easier to fall off.
Description
Technical Field
The invention relates to the field of aluminum anode sacrificial alloy, and particularly discloses an aluminum sacrificial anode alloy and a preparation method thereof.
Background
The zinc base alloy has good sacrificial performance and is the best choice for sacrificial anode alloy. However, the average content of zinc in the crust is only 0.004%, and the reserve amount of zinc is only enough to be used for 22 years. Therefore, it is important to develop an alloy with high current efficiency and good sacrificial performance, and aluminum is the most promising sacrificial material to replace zinc. Compared with magnesium-based and zinc-based alloys, the aluminum alloy has the advantages of small density, high current efficiency, centered driving potential and large actual capacitance, and is the most applicable anode material in the periodic table. However, pure aluminum forms hydrous oxides on its surface in aqueous solution to cause passivation of aluminum, and thus pure aluminum cannot be used as a sacrificial anode material. In order to remove the passivation film on the surface of aluminum, alloying, in which an alloying element such as zinc or indium is added to aluminum, is generally performed. The basic idea for developing the aluminum alloy sacrificial anode is to change the surface state of aluminum through alloying, limit or prevent the surface from forming a continuous compact oxide layer and promote surface activation, so that the alloy has a relatively negative electrode potential and a relatively high current efficiency to meet the basic requirements of serving as the sacrificial anode.
In order to improve the performance of the aluminum alloy anode, researchers at home and abroad develop aluminum alloy anode materials with various component systems. Domestic researchers have also developed ternary, quaternary and higher aluminum alloy anode materials. However, the current efficiency of the existing ternary and quaternary sacrificial anode alloy is low; five-element and even multi-element sacrificial anode alloy in the presence of Cl - A passive film is generated quickly in the environment, the performance of the sacrificial anode alloy is reduced due to the passive film, and a multi-element sacrificial anode alloy corrosion product is easy to adhere to the surface of the alloy and is difficult to fall off.
Disclosure of Invention
The invention aims to provide a sacrificial anode alloy, which comprises the following components in percentage by mass: zn:0.5-5%, si:2-10%, sn:0.1-3%, in:0.01-0.2%, the rest is Al and inevitable impurities, and Fe element reaches a saturated state.
The anode alloy preferably comprises the following components in percentage by mass: zn:0.5-5%, si:2-10%, sn:1.5-3%, in:0.05-0.2%, the rest is Al and inevitable impurities, and Fe element reaches a saturated state.
The invention also aims to provide a preparation method of the anode alloy after long-time annealing, the preparation method is simple, and the obtained aluminum sacrificial anode alloy has high anode utilization rate. Al can be obtained by annealing for a long time 9 Fe 2 The Si phase and the Al9Fe2Si phase are cathode phases compared with alpha-Al, and can form more micro primary cells with the alpha-Al, the existence of the primary cells can reduce the potential of aluminum alloy electrodes, and meanwhile, the current efficiency of aluminum alloy is improved and the performance of sacrificial anodes is improved.
The preparation method of the aluminum sacrificial anode alloy comprises the following steps:
(1) Firstly melting an aluminum ingot, then adding Al-Zn intermediate alloy, al-Si intermediate alloy, al-Sn intermediate alloy and Al-In intermediate alloy, refining, degassing, deslagging, and then pouring to prepare a casting blank.
In an optional embodiment, after melting, the aluminum ingot is heated to 680-800 ℃, the temperature is kept for 1 hour, and then the Al-Zn intermediate alloy, the Al-Si intermediate alloy, the Al-Sn intermediate alloy and the Al-In intermediate alloy are sequentially added.
After the intermediate alloy is added, the temperature is continuously raised to 710-750 ℃, the temperature is kept for 1-2 hours, and then casting is carried out at 710 ℃.
(2) And carrying out long-time annealing treatment on the casting blank.
The annealing treatment comprises the following steps: carrying out homogenization annealing firstly, and then carrying out long-time finished product annealing;
preferably, the homogenizing annealing comprises the steps of putting the casting blank into a furnace at room temperature, and annealing for 1-10h at the temperature rising speed of 18-20 ℃/min to 400-550 ℃; after annealing, air cooling to room temperature;
preferably, the finished product is annealed for a long time, which comprises the steps of putting the casting blank into a furnace at room temperature, raising the temperature to 400-550 ℃ at the temperature raising speed of 18-20 ℃/min, annealing for 50-200h, and cooling in air to room temperature after annealing.
In an alternative embodiment, after the homogenizing annealing is carried out and before the finished product is annealed for a long time, the method further comprises the step of removing an oxide layer on the surface of the slab. After annealing, the alloy was air-cooled to room temperature and then cut into 10X 10mm alloy pieces at room temperature.
The invention has the following beneficial effects: in the invention, al is promoted by limiting the components of the anode alloy and carrying out long-time annealing treatment 9 Fe 2 Occurrence of Si phase. The alloy phase and alpha-Al form a large number of tiny primary batteries, and the appearance of the primary batteries can reduce the potential of an aluminum alloy electrode, improve the current efficiency and sacrifice the performance of an anode.
According to the invention, si can improve the fluidity of the alloy liquid, reduce the content of oxide impurities in the alloy liquid, and obviously reduce the casting defects of the alloy when the Si is used in a sacrificial anode aluminum process; the Sn can reduce the resistance of the passive film on the surface of the aluminum anode, so that the passive film on the surface of the anode generates pores, the falling of the passive film is facilitated, and the Sn also has higher hydrogen evolution overpotential and can effectively inhibit the hydrogen evolution reaction; zn is the most basic active element in the aluminum alloy anode, and the addition of Zn can ensure that the aluminum anode is easy to alloy and has the potential negative shift of 0.1-0.3V; the trace In element is also an important activating element of the aluminum-based anode, exists In the aluminum-plated layer In the form of an In-rich segregation phase, reduces electronegativity, improves the current efficiency of the aluminum-based anode, and effectively improves the anode sacrificial protection capability of the alloy.
Description of the drawings:
FIG. 1 the overall morphology of the Al-1Zn-7Si-3Sn-0.20In alloy In example 1;
FIG. 2 is the overall morphology of the Al-1Zn-7Si-3Sn-0.10In alloy In example 2;
FIG. 3 is the overall morphology of the Al-1Zn-7Si-3Sn-0.05In alloy In example 3;
FIG. 4 is the overall morphology of the Al-1Zn-7Si-3Sn-0.05In alloy In example 4;
FIG. 5 is the overall morphology of the Al-4Zn-7Si-1Sn-0.15In alloy In example 5;
FIG. 6 the overall morphology of the Al-1Zn-7Si-0.5Sn-0.20In alloy In example 6;
FIG. 7 is the overall morphology of the Al-1Zn-7Si-3Sn-0.20In alloy In comparative example 1;
FIG. 8 is a graph showing the overall morphology of an Al-1Zn-7Si-3Sn-0.05In alloy In comparative example 2;
FIG. 9 is a graph showing the overall morphology of an Al-4Zn-3Sn-0.20In alloy In comparative example 3;
figure 10 XRD pattern of the alloy of example 4;
FIG. 11 is a plot of polarization for comparative examples 1-2 and example 4;
FIG. 12 is a graph showing the results of corrosion weight loss for comparative examples 1-2 and example 4.
Detailed Description
In order to make the objects, advantages and technical solutions of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention are fully and clearly described below. The mass percent of pure aluminum in the embodiment is more than 99.99 percent; the mass percent of Zn in the Al-Zn intermediate alloy is 10 percent; the mass percent of Si in the Al-Si intermediate alloy is 20 percent; the mass percent of Sn in the Al-Sn intermediate alloy is 10 percent; the mass percent of In the Al-In intermediate alloy is 1 percent. Al-10% by weight of a commercially available Al10Zn master alloy; al-20% by weight of the Si master alloy is a commercially available Al20Si master alloy; al-10% of Sn master alloy is commercial Al10Sn master alloy; al-1 percent of In intermediate alloy, adopting pure Al and pure In with the mass percent of more than 99.99, preparing the materials according to the mass percent, and smelting the materials In a vacuum arc furnace.
The features and properties of the present invention are further described in detail in the following examples.
Example 1
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.20% in, the remainder being Al and inevitable impurities (Fe element saturation).
(2) Melting 250g of pure Al and raising the temperature to 680 ℃, holding the temperature for 60min, adding 500g of Al-10% Zn intermediate alloy, 1750g of Al-20% Si intermediate alloy, 1500g of Al-10% Sn intermediate alloy, 1000g of Al-1% in intermediate alloy, putting one piece of 40X 3mm Q235 steel sheet, continuing raising the temperature to 710 ℃ and holding the temperature for 1 hour so as to enable the Fe element to reach a saturated state, and casting the saturated state by refining, degassing and deslagging to prepare a casting blank, wherein the casting temperature is 710 ℃.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) cutting the plate blank into alloy blocks with the thickness of 10 multiplied by 20mm after an oxide layer on the surface of the cast ingot is removed, then annealing the finished product for a long time, and raising the temperature to the annealing temperature of 550 ℃ at the temperature raising speed of 20 ℃/min for annealing for 50 hours. Then, the cast slab was cut into 10X 10mm alloy pieces.
Example 2
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.10% in, the remainder being Al and inevitable impurities (Fe element saturation).
(2) Melting 750g of pure Al and raising the temperature to 680 ℃, holding the temperature for 60min, adding 500g of Al-10% Zn intermediate alloy, adding 1750g of Al-20% Si intermediate alloy, 1500g of Al-10% Sn intermediate alloy, 500g of Al-1% in intermediate alloy, putting one piece of 40X 3mm Q235 steel sheet, continuing raising the temperature to 710 ℃ and holding the temperature for 1 hour so as to enable the Fe element to reach a saturated state, and casting the saturated Fe element into a casting blank after refining, degassing and deslagging, wherein the casting temperature is 710 ℃.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) cutting the plate blank into alloy blocks of 10 multiplied by 20mm after the oxide layer on the surface of the cast ingot is removed, then annealing the finished product for a long time, and raising the temperature to the annealing temperature of 550 ℃ at the temperature raising speed of 20 ℃/min for annealing for 100h. Then, the cast slab was cut into 10X 10mm alloy pieces.
Example 3
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.05% in, the remainder being Al and inevitable impurities (Fe element saturation).
(2) Melting 1000g pure Al and heating to 680 deg.C, keeping the temperature for 60min, adding 500g Al-10% Zn intermediate alloy, 1750g Al-20% Si intermediate alloy, 1500g Al-10% Sn intermediate alloy, 250g Al-1% in intermediate alloy, putting a piece of 40X 3mm Q235 steel sheet, heating to 710 deg.C and keeping the temperature for 1 h to make the Fe element reach saturation state, refining, degassing and deslagging, and casting to obtain a casting blank, wherein the casting temperature is 710 deg.C.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) cutting the plate blank into alloy blocks of 10 multiplied by 20mm after the oxide layer on the surface of the cast ingot is removed, then annealing the finished product for a long time, and raising the temperature to the annealing temperature of 550 ℃ at the temperature raising speed of 20 ℃/min for annealing for 150h. Then, the cast slab was cut into 10X 10mm alloy pieces.
Example 4
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.05% in, the remainder Al and unavoidable impurities (Fe element saturation).
(2) Melting 1000g pure Al and heating to 680 deg.C, keeping the temperature for 60min, adding 500g Al-10% Zn intermediate alloy, 1750g Al-20% Si intermediate alloy, 1500g Al-10% Sn intermediate alloy, 250g Al-1% in intermediate alloy, putting a piece of 40X 3mm Q235 steel sheet, heating to 710 deg.C and keeping the temperature for 1 h to make the Fe element reach saturation state, refining, degassing and deslagging, and casting to obtain a casting blank, wherein the casting temperature is 710 deg.C.
(3) Carrying out homogenization annealing on the casting blank, heating to the uniform annealing temperature of 400 ℃ at the heating rate of 20 ℃/min, and preserving heat for 5 hours; and (3) cutting the plate blank into 10 × 10 × 20mm alloy blocks after removing the oxide layer on the surface of the cast ingot, then annealing the finished product for a long time, and heating to the annealing temperature of 550 ℃ at the heating rate of 20 ℃/min for annealing for 200h. Then, the cast slab was cut into 10X 10mm alloy pieces.
Example 5
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 4% Zn,7% Si,1% Sn,0.15% in, the remainder being Al and inevitable impurities (Fe element saturation).
(2) Firstly, al-10% Zn2000g is melted and heated to 680 ℃, the temperature is kept for 60min, al-20% Si intermediate alloy 1750g, al-10% Sn intermediate alloy 500g, al-1% in intermediate alloy 750g are added, a piece of Q235 steel sheet with the thickness of 40 multiplied by 3mm is put into the mixture, the temperature is continuously heated to 710 ℃ and kept for 1 h, the Fe element is saturated, and casting is carried out after refining, degassing and deslagging to prepare a casting blank, wherein the casting temperature is 710 ℃.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) cutting the plate blank into 10 × 10 × 20mm alloy blocks after removing the oxide layer on the surface of the cast ingot, then annealing the finished product for a long time, and heating to the annealing temperature of 550 ℃ at the heating rate of 20 ℃/min for annealing for 200h. Then, the cast slab was cut into 10X 10mm alloy pieces.
Example 6
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,0.5% Sn,0.20% in, the remainder being Al and inevitable impurities (Fe element saturation).
(2) Melting 1500g of pure Al and raising the temperature to 680 ℃, holding the temperature for 60min, adding 500g of Al-10% Zn intermediate alloy, 1750g of Al-20% Si intermediate alloy, 250g of Al-10% Sn intermediate alloy, 1000g of Al-1% in intermediate alloy, putting one piece of 40X 3mm Q235 steel sheet, continuing raising the temperature to 710 ℃, holding the temperature for 1 hour so as to enable the Fe element to reach a saturated state, and casting the mixture after refining and degassing to prepare a casting blank, wherein the casting temperature is 710 ℃.
(3) Carrying out homogenization annealing on the casting blank, heating to the uniform annealing temperature of 400 ℃ at the heating rate of 20 ℃/min, and preserving heat for 5 hours; and (3) cutting the plate blank into alloy blocks with the thickness of 10 multiplied by 20mm after an oxide layer on the surface of the cast ingot is removed, then annealing the finished product for a long time, and raising the temperature to the annealing temperature of 550 ℃ at the temperature raising speed of 20 ℃/min for annealing for 200 hours. Then, the cast slab was cut into 10X 10mm alloy pieces.
Comparative example 1
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.20% in, the remainder being Al and unavoidable impurities (Fe element saturation).
(2) Melting 250g pure Al and heating to 680 deg.C, keeping the temperature for 60min, adding 500g Al-10% Zn intermediate alloy, 1750g Al-20% Si intermediate alloy, 1500g Al-10% Sn intermediate alloy, 1000g Al-1% in intermediate alloy, putting a piece of 40X 3mm Q235 steel sheet, heating to 710 deg.C and keeping the temperature for 1 h to make the Fe element reach saturation state, refining, degassing and deslagging, and casting to obtain a casting blank, wherein the casting temperature is 710 deg.C.
(3) And (3) carrying out homogenizing annealing on the casting blank, heating to the homogenizing annealing temperature at the heating rate of 20 ℃/min, keeping the temperature for 5h at 400 ℃, removing an oxide layer on the surface of the cast ingot, and then cutting the casting blank into alloy blocks of 10 x 10 mm.
Comparative example 2
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 1% Zn,7% Si,3% Sn,0.05% in, the remainder Al and unavoidable impurities (Fe element saturation).
(2) Melting 1000g pure Al and heating to 680 deg.C, keeping the temperature for 60min, adding 500g Al-10% Zn intermediate alloy, 1750g Al-20% Si intermediate alloy, 1500g Al-10% Sn intermediate alloy, 250g Al-1% in intermediate alloy, putting a piece of 40X 3mm Q235 steel sheet, heating to 710 deg.C and keeping the temperature for 1 h to make the Fe element reach saturation state, refining, degassing and deslagging, and casting to obtain a casting blank, wherein the casting temperature is 710 deg.C.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) removing the oxide layer on the surface of the cast ingot, cutting the plate blank into alloy blocks with the size of 10 multiplied by 20mm, annealing the finished product, and heating to the annealing temperature of 550 ℃ at the heating speed of 20 ℃/min for annealing for 10 hours. Then, the cast slab was cut into 10X 10mm alloy pieces.
Comparative example 3
(1) The invention provides an anode alloy which comprises the following components in percentage by mass: 4% Zn,3% Sn,0.05% in, the remainder Al and unavoidable impurities (Fe element saturation).
(2) Melting pure Al500g, heating to 680 deg.C, holding for 60min, adding Al-10% Zn intermediate alloy 2000g, al-10% Sn intermediate alloy 1500g, al-1% in intermediate alloy 1000g, adding a piece of Q235 steel sheet with thickness of 40X 3mm, heating to 710 deg.C, holding for 1 hr to make Fe element be saturated, refining, degassing and removing slag, pouring to obtain casting blank, and pouring at 710 deg.C.
(3) Carrying out homogenization annealing on the casting blank, raising the temperature to the uniform annealing temperature at the temperature raising speed of 20 ℃/min, and keeping the temperature for 5h at the temperature of 400 ℃; and (3) removing the oxide layer on the surface of the cast ingot, cutting the plate blank into alloy blocks with the size of 10 multiplied by 20mm, annealing the finished product, and heating to the annealing temperature of 550 ℃ at the heating speed of 20 ℃/min for annealing for 10 hours. Then, the cast slab was cut into 10X 10mm alloy pieces.
FIG. 11 is a polarization curve of the sacrificial anode alloys of example 4 and comparative examples 1-2, from which it can be seen that the self-corrosion potential of the sacrificial anode alloy is reduced, the corrosion current density is reduced, and the sacrificial anode performance is improved by the long-time annealing treatment.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing embodiments, or that certain features may be substituted or modified. Any modification, equivalent replacement, or modification made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The aluminum sacrificial anode alloy is characterized by comprising the following components in percentage by mass: 0.5-5%, si:2-10%, sn:0.1-3%, in:0.01-0.2%, the rest is Al and inevitable impurities, and Fe element reaches a saturated state.
2. The aluminum sacrificial anode alloy as recited in claim 1, wherein the anode alloy comprises, in elemental mass percent: zn:0.5-5%, si:2-10%, sn:1.5-3%, in:0.05-0.2%, the rest is Al and inevitable impurities, and Fe element reaches a saturated state.
3. The method for preparing the aluminum sacrificial anode alloy as recited in claim 1, comprising the steps of:
(1) Melting an aluminum ingot, sequentially adding an Al-Zn intermediate alloy, an Al-Si intermediate alloy, an Al-Sn intermediate alloy and an Al-In intermediate alloy, refining and standing the mixture, and then pouring the mixture to prepare a casting blank;
(2) And (3) annealing the casting blank in the step (1).
4. The method for preparing the aluminum sacrificial anode alloy according to claim 3, wherein the aluminum ingot In the step (1) is melted, heated to 680-800 ℃, kept warm for 1 hour, and then added with the Al-Zn intermediate alloy, the Al-Si intermediate alloy, the Al-Sn intermediate alloy and the Al-In intermediate alloy In sequence.
5. The method for preparing aluminum sacrificial anode alloy as claimed in claim 3, wherein the temperature is increased to 710-750 ℃ and kept for 1-2 hours after adding the intermediate alloy in step (1), and then casting is carried out at 710 ℃.
6. The method for preparing an aluminum sacrificial anode alloy according to claim 3, wherein the annealing the cast slab in the step (2) comprises: first, uniform annealing is carried out, and then, finished product annealing is carried out.
7. The method for preparing an aluminum sacrificial anode alloy as recited in claim 6, wherein the homogenizing annealing is: putting the casting blank into a furnace at room temperature, heating to 400-550 ℃ at a heating rate of 18-20 ℃/min, and annealing for 1-10h; and after annealing, air cooling to room temperature.
8. The method for preparing an aluminum sacrificial anode alloy as recited in claim 6, wherein the final annealing is: and (3) putting the casting blank into a furnace at room temperature, heating to 400-550 ℃ at the heating rate of 18-20 ℃/min, annealing for 50-200h, and cooling to room temperature in air after annealing.
9. The method of claim 3, further comprising removing an oxide layer on the surface of the slab before the final product is annealed for a long time, cooling the slab to room temperature after annealing, and cutting the slab into 10 x 10mm alloy pieces.
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Citations (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1810635A1 (en) * | 1967-11-24 | 1969-07-10 | British Aluminium Co Ltd | Aluminum-based alloy for use as a material for a self-consuming anode |
| US4885045A (en) * | 1987-06-16 | 1989-12-05 | Comalco Aluminum Limited | Aluminium alloys suitable for sacrificial anodes |
| GB9608964D0 (en) * | 1995-04-28 | 1996-07-03 | British Aluminium Holdings Lim | Aluminium alloy |
| CN1129258A (en) * | 1994-11-11 | 1996-08-21 | 古河电气工业株式会社 | Aluminum alloy brazing sheet, method of producing said brazing sheet, heat-exchanger used said brazing sheet and method of producing said heat-exchanger |
| JP2001105173A (en) * | 1999-09-30 | 2001-04-17 | Mitsubishi Alum Co Ltd | Aluminum alloy compound material for heat exchanger and its manufacturing method |
| CN101693999A (en) * | 2009-09-07 | 2010-04-14 | 河南科技大学 | Aluminum-zinc-tin system sacrificial anode material and preparation method thereof |
| CN102002715A (en) * | 2010-10-12 | 2011-04-06 | 青岛双瑞防腐防污工程有限公司 | High-performance aluminium alloy sacrificial anode |
| CN102471836A (en) * | 2009-09-21 | 2012-05-23 | 古河Sky株式会社 | Highly corrosion-resistant aluminum alloy brazing sheet, process for production of the brazing sheet, and highly corrosion-resistant heat exchanger equipped with the brazing sheet |
| WO2015015767A1 (en) * | 2013-07-29 | 2015-02-05 | 株式会社Uacj | Aluminum-alloy clad member, method for producing same, and heat exchanger using aluminum-alloy clad member |
| CN104532089A (en) * | 2014-12-26 | 2015-04-22 | 中国石油天然气股份有限公司 | Anticorrosive alloy composition and device, preparation and application thereof |
| CN105734588A (en) * | 2016-04-06 | 2016-07-06 | 北京科技大学 | High-performance aluminum alloy sacrificial anode for deep sea environment and preparation method for high-performance aluminum alloy sacrificial anode |
| CN106784772A (en) * | 2017-03-22 | 2017-05-31 | 长沙迅洋新材料科技有限公司 | A kind of battery aluminium alloy negative material and preparation method thereof |
| CN107901536A (en) * | 2017-10-20 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Lithium ion battery flexible package aluminum plastic film aluminium foil and preparation method thereof |
| CN108193110A (en) * | 2018-01-24 | 2018-06-22 | 合肥国轩高科动力能源有限公司 | Preparation method of magnesium alloy anode material |
| CN109576619A (en) * | 2018-12-17 | 2019-04-05 | 新疆众和股份有限公司 | A kind of mirror surface aoxidizes the heat treatment process of 5505 aluminium alloys |
| CN111057914A (en) * | 2019-12-30 | 2020-04-24 | 广东省材料与加工研究所 | Anode alloy material, preparation method thereof, anode for aluminum-air battery and aluminum-air battery |
| CN111485189A (en) * | 2020-05-26 | 2020-08-04 | 常州大学 | Hot-dip Al-Mg-Si-Er-In anode alloy coating and preparation method thereof |
| CN114231994A (en) * | 2021-12-30 | 2022-03-25 | 浙江钰烯腐蚀控制股份有限公司 | Aluminum alloy sacrificial anode and preparation method and application thereof |
| US20220098704A1 (en) * | 2019-03-18 | 2022-03-31 | Vdm Metals International Gmbh | Nickel alloy having good resistance to corrosion and high tensile strength, and method for producing semi-finished products |
| CN114574733A (en) * | 2020-11-30 | 2022-06-03 | 华为技术有限公司 | Aluminum alloy section bar and terminal equipment |
| CN115889708A (en) * | 2022-10-25 | 2023-04-04 | 南通海门鑫瑞船舶配件有限公司 | Casting method of aluminum alloy sacrificial anode |
| CN116334457A (en) * | 2023-03-30 | 2023-06-27 | 常州大学 | Continuous hot dip Al-Si-Mn-In sacrificial anode alloy for inhibiting Fe harmful effect and preparation method thereof |
-
2022
- 2022-10-20 CN CN202211285092.3A patent/CN115637434B/en active Active
Patent Citations (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1810635A1 (en) * | 1967-11-24 | 1969-07-10 | British Aluminium Co Ltd | Aluminum-based alloy for use as a material for a self-consuming anode |
| US4885045A (en) * | 1987-06-16 | 1989-12-05 | Comalco Aluminum Limited | Aluminium alloys suitable for sacrificial anodes |
| CN1129258A (en) * | 1994-11-11 | 1996-08-21 | 古河电气工业株式会社 | Aluminum alloy brazing sheet, method of producing said brazing sheet, heat-exchanger used said brazing sheet and method of producing said heat-exchanger |
| GB9608964D0 (en) * | 1995-04-28 | 1996-07-03 | British Aluminium Holdings Lim | Aluminium alloy |
| JP2001105173A (en) * | 1999-09-30 | 2001-04-17 | Mitsubishi Alum Co Ltd | Aluminum alloy compound material for heat exchanger and its manufacturing method |
| CN101693999A (en) * | 2009-09-07 | 2010-04-14 | 河南科技大学 | Aluminum-zinc-tin system sacrificial anode material and preparation method thereof |
| CN102471836A (en) * | 2009-09-21 | 2012-05-23 | 古河Sky株式会社 | Highly corrosion-resistant aluminum alloy brazing sheet, process for production of the brazing sheet, and highly corrosion-resistant heat exchanger equipped with the brazing sheet |
| CN102002715A (en) * | 2010-10-12 | 2011-04-06 | 青岛双瑞防腐防污工程有限公司 | High-performance aluminium alloy sacrificial anode |
| WO2015015767A1 (en) * | 2013-07-29 | 2015-02-05 | 株式会社Uacj | Aluminum-alloy clad member, method for producing same, and heat exchanger using aluminum-alloy clad member |
| CN105378126A (en) * | 2013-07-29 | 2016-03-02 | 株式会社Uacj | Aluminum-alloy clad member, method for producing same, and heat exchanger using aluminum-alloy clad member |
| CN104532089A (en) * | 2014-12-26 | 2015-04-22 | 中国石油天然气股份有限公司 | Anticorrosive alloy composition and device, preparation and application thereof |
| CN105734588A (en) * | 2016-04-06 | 2016-07-06 | 北京科技大学 | High-performance aluminum alloy sacrificial anode for deep sea environment and preparation method for high-performance aluminum alloy sacrificial anode |
| CN106784772A (en) * | 2017-03-22 | 2017-05-31 | 长沙迅洋新材料科技有限公司 | A kind of battery aluminium alloy negative material and preparation method thereof |
| CN107901536A (en) * | 2017-10-20 | 2018-04-13 | 上海华峰新材料研发科技有限公司 | Lithium ion battery flexible package aluminum plastic film aluminium foil and preparation method thereof |
| CN109703128A (en) * | 2017-10-20 | 2019-05-03 | 上海华峰铝业股份有限公司 | Lithium ion battery flexible package aluminum plastic film aluminium foil and preparation method thereof |
| CN108193110A (en) * | 2018-01-24 | 2018-06-22 | 合肥国轩高科动力能源有限公司 | Preparation method of magnesium alloy anode material |
| CN109576619A (en) * | 2018-12-17 | 2019-04-05 | 新疆众和股份有限公司 | A kind of mirror surface aoxidizes the heat treatment process of 5505 aluminium alloys |
| US20220098704A1 (en) * | 2019-03-18 | 2022-03-31 | Vdm Metals International Gmbh | Nickel alloy having good resistance to corrosion and high tensile strength, and method for producing semi-finished products |
| CN111057914A (en) * | 2019-12-30 | 2020-04-24 | 广东省材料与加工研究所 | Anode alloy material, preparation method thereof, anode for aluminum-air battery and aluminum-air battery |
| CN111485189A (en) * | 2020-05-26 | 2020-08-04 | 常州大学 | Hot-dip Al-Mg-Si-Er-In anode alloy coating and preparation method thereof |
| CN114574733A (en) * | 2020-11-30 | 2022-06-03 | 华为技术有限公司 | Aluminum alloy section bar and terminal equipment |
| CN114231994A (en) * | 2021-12-30 | 2022-03-25 | 浙江钰烯腐蚀控制股份有限公司 | Aluminum alloy sacrificial anode and preparation method and application thereof |
| CN115889708A (en) * | 2022-10-25 | 2023-04-04 | 南通海门鑫瑞船舶配件有限公司 | Casting method of aluminum alloy sacrificial anode |
| CN116334457A (en) * | 2023-03-30 | 2023-06-27 | 常州大学 | Continuous hot dip Al-Si-Mn-In sacrificial anode alloy for inhibiting Fe harmful effect and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| "铝合金牺牲阳极在船舶保护上的应用", 腐蚀与防护, no. 04, 15 November 1980 (1980-11-15) * |
| XIA ZIJIE等: "Influence of Sn, Cd, and Si addition on the electrochemical performance of Al-Zn-In sacrificial anodes", MATERIALS AND CORROSION-WERKSTOFFE UND KORROSION, vol. 71, no. 4, 30 April 2020 (2020-04-30) * |
| 池国明;胡展奎;李继林;许光明;: "硅含量对3104铝合金组织及性能的影响", 轻合金加工技术, no. 02, 20 February 2016 (2016-02-20) * |
| 邓和平;: "铝基牺牲阳极的组成及熔铸", 腐蚀与防护, no. 03, 15 June 1983 (1983-06-15) * |
| 马正青;李晓翔;: "Al-Mg-Pb-Sn-Ga铝合金阳极材料组织对电化学性能的影响", 湖南科技大学学报(自然科学版), no. 04, 25 December 2011 (2011-12-25) * |
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