CN112609186A - Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting steel structure at sea entrance and preparation process thereof - Google Patents
Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting steel structure at sea entrance and preparation process thereof Download PDFInfo
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- CN112609186A CN112609186A CN202011309327.9A CN202011309327A CN112609186A CN 112609186 A CN112609186 A CN 112609186A CN 202011309327 A CN202011309327 A CN 202011309327A CN 112609186 A CN112609186 A CN 112609186A
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- aluminum alloy
- sacrificial anode
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 43
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 23
- 239000010959 steel Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 9
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000007670 refining Methods 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 229910052749 magnesium Inorganic materials 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 10
- 239000000155 melt Substances 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 5
- -1 aluminum-manganese Chemical compound 0.000 claims description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910000914 Mn alloy Inorganic materials 0.000 claims description 3
- 229910004883 Na2SiF6 Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000000034 method Methods 0.000 claims 4
- 239000000463 material Substances 0.000 claims 1
- 239000013505 freshwater Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000004210 cathodic protection Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 238000003860 storage Methods 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
- C22C1/026—Alloys based on aluminium
-
- 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
- C22C1/00—Making non-ferrous alloys
- C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/06—Alloys based on aluminium with magnesium as the next major constituent
- C22C21/08—Alloys based on aluminium with magnesium as the next major constituent with silicon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
The invention belongs to the technical field of sacrificial anodes, and particularly relates to an Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting a steel structure at sea entrance and a preparation process thereof. The aluminum alloy sacrificial anode is made of the following elements in percentage by weight: mg: 7-10%, Ga: 0.02 to 0.04%, Mn: 0.8-1.4%, Bi: 0.25 to 0.35 percent of Fe, less than or equal to 0.09 percent of Si, less than or equal to 0.01 percent of Cu, and the balance of Al. The open-circuit potential of the aluminum alloy sacrificial anode prepared by the invention is-1.35 to-1.25V, the working potential is-1.27 to-1.15V, the current efficiency is more than or equal to 85 percent, the actual capacitance is more than or equal to 2400 A.h/Kg, the grain size is less than 100 mu m, and the aluminum alloy sacrificial anode can continuously and stably protect the steel structure at the sea entrance.
Description
Technical Field
The invention belongs to the technical field of sacrificial anodes, and particularly relates to an Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting a steel structure at sea entrance and a preparation process thereof.
Background
The salinity of the estuary region is diluted by the fresh water flowing in from the river to form a state of higher than the fresh water concentration and lower than the seawater concentration. The different concentrations result in a lower resistivity water at the mouth than fresh water and a higher resistivity water than normal seawater. The sacrificial anode commonly used for the cathodic protection of the steel structure at the sea entrance at present is Al-Zn-In alloy, the working potential of the aluminum-zinc-indium alloy sacrificial anode is about-1.12 to-1.05V according to the standard GB4948, and the sacrificial anode is suitable for the cathodic protection of ships, harbor work and ocean engineering facilities, seawater cooling water systems, storage tank deposition water parts and other industrial fields In seawater media, while the sacrificial anode commonly used In fresh water is a magnesium alloy sacrificial anode, the working potential of the magnesium alloy sacrificial anode is usually-1.50 to-1.7V, and the aluminum anode required for the cathodic protection at the sea entrance is-1.27 to-1.15V. Therefore, it is necessary to develop an aluminum alloy sacrificial anode with a protective potential suitable for steel structures at sea entrances, and to make up for the shortage of the current sacrificial anode protective area.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the defects of the prior art are overcome, the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting the steel structure at the sea entrance is provided, the steel structure at the sea entrance can be continuously and stably protected, and meanwhile, the invention also provides a preparation process of the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode.
The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting the steel structure of the sea entrance comprises the following elements in percentage by weight: mg: 7-10%, Ga: 0.02 to 0.04%, Mn: 0.8-1.4%, Bi: 0.25 to 0.35 percent of Fe, less than or equal to 0.09 percent of Si, less than or equal to 0.01 percent of Cu, and the balance of Al.
The open-circuit potential of the aluminum alloy sacrificial anode is-1.35 to-1.25V, the working potential is-1.27 to-1.15V, the current efficiency is more than or equal to 85 percent, and the actual capacitance is more than or equal to 2400 A.h/Kg.
The grain size of the aluminum alloy sacrificial anode is less than 100 mu m.
The invention relates to a preparation process of an Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting a steel structure at sea entrance, which comprises the following steps:
(1) putting an aluminum ingot and an aluminum-manganese alloy into a crucible in advance, setting the temperature of a temperature control instrument (hearth) at 850 ℃, heating until the aluminum ingot is completely melted, adjusting the temperature of aluminum liquid to 700-720 ℃, then adding magnesium blocks into the crucible in batches, pressing the magnesium ingot into the melt by using a tool, and keeping the magnesium ingot for later use when the magnesium ingot is completely melted;
(2) pouring the molten liquid in the crucible in the step (1) into another 30# crucible, adding gallium ingots and bismuth ingots, fully stirring by using a carbon rod, and slowly pouring the molten liquid into the crucible in the step (1) after the molten liquid is completely melted;
(3) adjusting the temperature of the aluminum liquid to 740-740 ℃ and preferably 750 ℃, adding an aluminum alloy environment-friendly refining agent, pressing the aluminum alloy environment-friendly refining agent into a melt by using a stirring tool, refining, breaking surface reaction products after the reaction is finished, floating for a moment, skimming surface oxidation scum, standing for 10-15 minutes, adjusting the temperature to 720-740 ℃, and pouring.
3-5kg of molten liquid in the crucible in the step (1) is poured in the step (2).
In the step (3), the addition amount of the aluminum alloy environment-friendly refining agent is 0.05-0.15% of the weight of the aluminum ingot, preferably 0.1%, and the aluminum alloy environment-friendly refining agent comprises the following chemical components in percentage by weight: KCl: 30-40%, NaCl: 20-30%, NaF: 10-15% of CaF2：10-15％、Na3A1F6：5-10％、Na2SiF6：5-10％。
Compared with the prior art, the invention has the following beneficial effects:
the open-circuit potential of the aluminum alloy sacrificial anode prepared by the invention is-1.35 to-1.25V, the working potential is-1.27 to-1.15V, the current efficiency is more than or equal to 85 percent, the actual capacitance is more than or equal to 2400 A.h/Kg, the grain size is less than 100 mu m, and the aluminum alloy sacrificial anode can continuously and stably protect the steel structure at the sea entrance.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting the steel structure of the sea entrance comprises the following elements in percentage by weight: mg: 7.33%, Ga: 0.025%, Mn: 1.12%, Bi: 0.30%, Fe: 0.055%, Si: 0.032%, Cu: 0.005% and the balance Al.
The preparation process of the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for the protection of the steel structure at the sea entrance comprises the following steps:
(1) putting an aluminum ingot and an aluminum-manganese alloy into a crucible in advance, setting the temperature of a temperature control instrument (hearth) at 850 ℃, heating until the aluminum ingot is completely melted, adjusting the temperature of aluminum liquid to 700-720 ℃, then adding magnesium blocks into the crucible in batches, pressing the magnesium ingot into the melt by using a tool, and keeping the magnesium ingot for later use when the magnesium ingot is completely melted;
(2) pouring 4kg of the melt in the crucible in the step (1) into another 30# crucible, adding gallium ingots and bismuth ingots, fully stirring by using a carbon rod, and slowly pouring the melt into the crucible in the step (1) after the melt is completely melted;
(3) adjusting the temperature of the aluminum liquid to 750 ℃, adding an aluminum alloy environment-friendly refining agent, pressing the aluminum alloy environment-friendly refining agent into a melt by using a stirring tool, refining, crushing a surface reaction product after the reaction is finished, floating for a moment, then slagging off, removing surface oxidation scum through slagging off, standing for 15 minutes, adjusting the temperature to 720 + 740 ℃, casting, and cooling to obtain the aluminum alloy sacrificial anode.
In the step (3), the addition amount of the aluminum alloy environment-friendly refining agent is 0.1 percent of the weight of the aluminum ingot, and the aluminum alloy environment-friendly refining agent comprises the following chemical components in percentage by weight: KCl: 35%, NaCl: 25%, NaF: 10% CaF2：15％、Na3A1F6：5％、Na2SiF6：10％。
Example 2
The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting the steel structure of the sea entrance comprises the following elements in percentage by weight: mg: 8.56%, Ga: 0.03%, Mn: 1.35%, Bi: 0.28%, Fe: 0.036%, Si: 0.048%, Cu: 0.005% and the balance Al.
The preparation process is the same as in example 1.
Example 3
The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting the steel structure of the sea entrance comprises the following elements in percentage by weight: mg: 9.68%, Ga: 0.025%, Mn: 0.88%, Bi: 0.26%, Fe: 0.073%, Si: 0.063%, Cu: 0.006% and the balance of Al.
The preparation process is the same as in example 1.
The sacrificial anodes of aluminum alloys prepared in examples 1-3 were tested according to the standard test method specified in GB/T17848-1999, and the test results are shown in Table 1.
Table 1 examples 1-3 electrochemical performance of aluminum alloy sacrificial anodes
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit and scope of the present invention should be construed as being included in the scope of the present invention.
Claims (7)
1. An Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting a steel structure at sea entrance is characterized in that: the material comprises the following elements in percentage by weight: mg: 7-10%, Ga: 0.02 to 0.04%, Mn: 0.8-1.4%, Bi: 0.25 to 0.35 percent of Fe, less than or equal to 0.09 percent of Si, less than or equal to 0.01 percent of Cu, and the balance of Al.
2. The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protection of steel structures at sea entrances of claim 1, wherein: the open-circuit potential of the aluminum alloy sacrificial anode is-1.35 to-1.25V, the working potential is-1.27 to-1.15V, the current efficiency is more than or equal to 85 percent, and the actual capacitance is more than or equal to 2400 A.h/Kg.
3. The Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protection of steel structures at sea entrances of claim 1, wherein: the grain size of the aluminum alloy sacrificial anode is less than 100 mu m.
4. A process for preparing the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for the protection of steel structures at sea entrances as claimed in claims 1 to 3, wherein: the method comprises the following steps:
(1) putting an aluminum ingot and an aluminum-manganese alloy into a crucible in advance for heating, after the aluminum ingot is completely melted, adjusting the temperature of aluminum liquid to 700-720 ℃, then adding magnesium blocks into the crucible in batches, and after the aluminum ingot is completely melted, keeping the magnesium blocks for later use;
(2) pouring the melt in the crucible in the step (1) into another crucible, adding gallium ingots and bismuth ingots, and slowly pouring the melt into the crucible in the step (1) after the melt is completely melted;
(3) adjusting the temperature of the aluminum liquid to 740-760 ℃, adding an aluminum alloy environment-friendly refining agent for refining, removing surface oxidation scum through slagging off after the reaction is finished, standing for 10-15 minutes, adjusting the temperature to 720-740 ℃, and pouring.
5. The process for preparing the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for the protection of steel structures at sea entrances according to claim 4, wherein the process comprises the following steps: 3-5kg of molten liquid in the crucible in the step (1) is poured in the step (2).
6. The process for preparing the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for the protection of steel structures at sea entrances according to claim 4, wherein the process comprises the following steps: the aluminum alloy environment-friendly refining agent in the step (3) comprises the following chemical components in percentage by weight: KCl: 30-40%, NaCl: 20-30%, NaF: 10-15% of CaF2：10-15％、Na3A1F6：5-10％、Na2SiF6：5-10％。
7. The process for preparing the Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for the protection of steel structures at sea entrances according to claim 4 or 6, wherein the process comprises the following steps: in the step (3), the addition amount of the aluminum alloy environment-friendly refining agent is 0.05-0.15% of the weight of the aluminum ingot.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011309327.9A CN112609186A (en) | 2020-11-20 | 2020-11-20 | Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting steel structure at sea entrance and preparation process thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011309327.9A CN112609186A (en) | 2020-11-20 | 2020-11-20 | Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting steel structure at sea entrance and preparation process thereof |
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| CN112609186A true CN112609186A (en) | 2021-04-06 |
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| CN202011309327.9A Pending CN112609186A (en) | 2020-11-20 | 2020-11-20 | Al-Mg-Ga-Mn-Bi aluminum alloy sacrificial anode suitable for protecting steel structure at sea entrance and preparation process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025022469A1 (en) * | 2023-07-24 | 2025-01-30 | Tecnoseal Foundry S.r.l. | Alloy containing bismuth used for a sacrificial anode, and preparation process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2042589A (en) * | 1979-02-05 | 1980-09-24 | Inst Organic Kataliza I Electr | Aluminium-base alloy for cathodic protection |
| US4238233A (en) * | 1979-04-19 | 1980-12-09 | Mitsubishi Aluminum Kabushiki Kaisha | Aluminum alloy for cladding excellent in sacrificial anode property and erosion-corrosion resistance |
| CN101153398A (en) * | 2006-09-28 | 2008-04-02 | 赵全玺 | Corrosion-resistant break-resistant steel rail or steel wheel of train |
| CN110241322A (en) * | 2019-06-27 | 2019-09-17 | 广东顺博铝合金有限公司 | A kind of secondary aluminium alloy refining agent |
-
2020
- 2020-11-20 CN CN202011309327.9A patent/CN112609186A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2042589A (en) * | 1979-02-05 | 1980-09-24 | Inst Organic Kataliza I Electr | Aluminium-base alloy for cathodic protection |
| US4238233A (en) * | 1979-04-19 | 1980-12-09 | Mitsubishi Aluminum Kabushiki Kaisha | Aluminum alloy for cladding excellent in sacrificial anode property and erosion-corrosion resistance |
| CN101153398A (en) * | 2006-09-28 | 2008-04-02 | 赵全玺 | Corrosion-resistant break-resistant steel rail or steel wheel of train |
| CN110241322A (en) * | 2019-06-27 | 2019-09-17 | 广东顺博铝合金有限公司 | A kind of secondary aluminium alloy refining agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2025022469A1 (en) * | 2023-07-24 | 2025-01-30 | Tecnoseal Foundry S.r.l. | Alloy containing bismuth used for a sacrificial anode, and preparation process |
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Application publication date: 20210406 |