Aluminum alloy sacrificial anode for deep sea environment and manufacturing method thereof

Abstract

The invention discloses an aluminum alloy sacrificial anode for a deep sea environment and a manufacturing method of the aluminum alloy sacrificial anode. The sacrificial anode comprises the following components: 0.84 to 1.46 percent of Zn, 0.75 to 1.13 percent of Ga, 0.36 to 0.47 percent of In, 0.04 to 0.12 percent of Mn, 045 to 0.62 percent of Sn, 0.34 to 0.57 percent of Mg, 0.29 to 0.46 percent of Si, 0.02 to 0.35 percent of Ti, less than or equal to 0.25 percent of impurities and the balance of Al. The manufacturing method comprises the following steps: heating and melting an Al ingot in advance, subsequently adding other excess materials to form an alloy solution, degassing the alloy solution, pulling out slag, and preparing for casting; and maintaining the mold at a certain temperature condition for casting to finally obtain a finished product. According to the aluminum alloy sacrificial anode provided by the invention, aluminum is used as a substrate, and other various components are added to form an alloy, so that the electrochemical performance of the sacrificial anode is obviously improved, and the sacrificial anode can play a role in protecting a protected metal structure in severe corrosive environments such as deep sea and the like; and corrosion products generated during working are non-toxic and harmless, so that no extra pollution is caused to the environment.

Description

Technical Field

[0001] The present invention relates to the field related to sacrificial anodes, and specifically to an aluminum alloy sacrificial anode for deep - sea environment and a manufacturing method thereof. Background Art

[0002] The ocean accounts for about 70% of the total area of the earth, with vast space and rich resources. Therefore, the development and utilization of ocean resources are of great significance to a country. Seawater is the most abundant natural medium in nature and has corrosiveness; seawater corrosion has a serious impact on the service performance and service life of ocean engineering equipment and structures.

[0003] Due to reasons such as the low temperature of seawater in the deep - sea environment and the change of dissolved oxygen concentration in seawater with water depth, sacrificial anodes suitable for conventional seawater environments are often difficult to be applied to the deep - sea environment, mainly having technical problems such as ineffective activation of the anode, insufficient working potential, uneven corrosion morphology, and low capacitance. These problems lead to the premature failure of the cathodic protection system and the corrosion of metal structures in actual engineering. Summary of the Invention

[0004] The purpose of the present invention is to provide an aluminum alloy sacrificial anode for deep - sea environment and a manufacturing method thereof to solve the problems raised in the above - mentioned background art.

[0005] To achieve the above - mentioned purpose, the present invention provides the following technical solutions: An aluminum alloy sacrificial anode for deep - sea environment, comprising the following components: Zn: 0.84 - 1.46%, Ga: 0.75 - 1.13%, In: 0.36 - 0.47%, Mn: 0.04 - 0.12%, Sn: 0.45 - 0.62%, Mg: 0.34 - 0.57%, Si: 0.29 - 0.46%, Ti: 0.02 - 0.35%, the content of impurities ≤ 0.25%, and the balance is Al.

[0006] As a preferred technical solution of the present invention, the mass percentages of each component are specifically: Zn: 1.24%, Ga: 0.95%, In: 0.42%, Mn: 0.07%, Sn: 0.55%, Mg: 0.47%, Si: 0.34%, Ti: 0.18%, the content of impurities ≤ 0.25%, and the balance is Al.

[0007] As a preferred technical solution of the present invention, the impurities are Cu and Fe elements, and the content ratio of Cu element does not exceed 0.18%, and the content ratio of Fe element does not exceed 0.15%.

[0008] As a preferred technical solution of the present invention, the Ga and In components are in the form of a Ga-In master alloy ingot, the Zn component is in the form of a Zn ingot, the Sn component is in the form of a Sn ingot, the Al component is in the form of an Al ingot, the Mn component is in the form of Mn powder, the Mg component is in the form of Mg powder, the Ti component is in the form of Ti powder, and the Si component is in the form of crystalline silicon.

[0009] As a preferred technical solution of the present invention, the present invention also provides a manufacturing method for an aluminum alloy sacrificial anode for deep-sea environments, comprising the following steps: S1. Weigh each component raw material according to the weight ratio; S2. Add the Al ingot into a vacuum induction furnace, heat to melt the Al ingot to obtain an aluminum solution, and perform injection, refining, degassing, and slag removal on the aluminum solution; S3. Sequentially add the Zn ingot, Sn ingot, and Ga-In master alloy ingot, raise the temperature, and continue melting to obtain a first mixed solution; S4. Add the Mn powder, Mg powder, Ti powder, and crystalline silicon into the first mixed solution, continue melting, and perform degassing after standing to remove the floating slag to obtain a second mixed solution; S5. Maintain the heating of the second mixed solution and perform stirring, and at the same time preheat the mold; S6. After preheating for a period of time, perform casting; S7. Leave the alloy in the mold for a period of time and then remove it, place it in the air, and air-cool it to room temperature.

[0010] As a preferred technical solution of the present invention, in step S2, the heating temperature is 670°C to 720°C. After the temperature reaches the set temperature, continue heating for 60 min to 80 min, and then perform injection, refining, degassing, and slag removal in sequence.

[0011] As a preferred technical solution of the present invention, in step S3, the temperature is raised to 820°C to 860°C, and after the temperature reaches the set temperature, continue heating for 50 min to 70 min to obtain a first mixed solution; in step S4, after adding the Mn powder, Mg powder, Ti powder, and crystalline silicon, maintain the temperature for 20 min to 30 min to obtain a second mixed solution.

[0012] As a preferred technical solution of the present invention, in step S5, the stirring time of the second mixed solution is 10 min to 15 min, and the preheating temperature of the mold is 380°C to 460°C.

[0013] As a preferred technical solution of the present invention, in step S6, the mold performs the casting operation after reaching the preheating temperature for no less than 20 min.

[0014] As a preferred technical solution of the present invention, in step S7, after the alloy casting is completed, it is placed in a mold for 6 h to 8 h and then taken out, and cooled to room temperature in the air.

[0015] Compared with the prior art, the beneficial effects of the present invention are as follows: The aluminum alloy sacrificial anode provided by the present invention uses aluminum as the substrate and adds a variety of other components to form an alloy, so that the electrochemical performance of the sacrificial anode is significantly improved, and it can protect the metal structure to be protected in harsh corrosion environments such as the deep sea; and the corrosion products generated during operation are non-toxic and harmless, and will not cause additional pollution to the environment. Specific embodiments

[0016] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0017] Embodiment 1: An aluminum alloy sacrificial anode for deep-sea environment, the mass percentage of each component is specifically: Zn: 1.24%, Ga: 0.95%, In: 0.42%, Mn: 0.07%, Sn: 0.55%, Mg: 0.47%, Si: 0.34%, Ti: 0.18%, the content of impurities ≤ 0.25%, and the balance is Al.

[0018] The impurities are Cu and Fe elements, and the content ratio of the Cu element does not exceed 0.18%, and the content ratio of the Fe element does not exceed 0.15%. The Ga and In components use Ga-In master alloy ingots, the Zn component uses Zn ingots, the Sn component uses Sn ingots, the Al component uses Al ingots, the Mn component uses Mn powder, the Mg component uses Mg powder, the Ti component uses Ti powder, and the Si component uses crystalline silicon.

[0019] A manufacturing method of an aluminum alloy sacrificial anode for deep-sea environment includes the following steps: S1. Weigh each component raw material according to the weight ratio; S2. Add the Al ingot into a vacuum induction furnace, heat to melt the Al ingot to obtain an aluminum solution; the heating temperature is 700 °C, and after the temperature reaches the set temperature, continue to heat for 70 min, and then perform blowing, refining, degassing and slag removal in sequence; S3. Add the Zn ingot, Sn ingot and Ga-In master alloy ingot in sequence, and raise the temperature to 840 °C, and continue to heat for 60 min after the temperature reaches the set temperature to obtain a mixed solution I; S4. Add Mn powder, Mg powder, Ti powder and crystalline silicon to the first mixed solution. After adding, maintain the temperature for 25 min, and after standing, degas, remove the dross, and obtain the second mixed solution. S5. Keep heating the second mixed solution and stir for 13 min. At the same time, preheat the mold, and the preheating temperature is 420 °C. S6. Carry out the casting work 35 min after the mold reaches the preheating temperature. S7. After the alloy casting is completed, place it in the mold for 7 h and then take it out, and cool it to room temperature in the air.

[0020] Example 2: An aluminum alloy sacrificial anode for deep-sea environment, the mass percentages of each component are specifically: Zn: 0.86, Ga: 0.76%, In: 0.37%, Mn: 0.05%, Sn: 0.46%, Mg: 0.34%, Si: 0.31%, Ti: 0.05%, the content of impurities ≤ 0.25%, and the balance is Al.

[0021] The impurities are Cu and Fe elements, and the content ratio of Cu element does not exceed 0.18%, and the content ratio of Fe element does not exceed 0.15%. The Ga and In components use Ga-In master alloy ingots, the Zn component uses Zn ingots, the Sn component uses Sn ingots, the Al component uses Al ingots, the Mn component uses Mn powder, the Mg component uses Mg powder, the Ti component uses Ti powder, and the Si component uses crystalline silicon.

[0022] A manufacturing method of an aluminum alloy sacrificial anode for deep-sea environment, comprising the following steps: S1. Weigh each component raw material according to the weight ratio. S2. Add the Al ingot into a vacuum induction furnace, heat to melt the Al ingot to obtain an aluminum solution; the heating temperature is 670 °C. After the temperature reaches the set temperature, continue heating for 60 min, and then carry out spraying, refining, degassing and slag removal in sequence. S3. Add Zn ingots, Sn ingots and Ga-In master alloy ingots in sequence, and raise the temperature to 830 °C. After the temperature reaches the set temperature, continue heating for 50 min to obtain the first mixed solution. S4. Add Mn powder, Mg powder, Ti powder and crystalline silicon to the first mixed solution. After adding, maintain the temperature for 20 min, and after standing, degas, remove the dross, and obtain the second mixed solution. S5. Keep heating the second mixed solution and stir for 10 min. At the same time, preheat the mold, and the preheating temperature is 380 °C. S6. Carry out the casting work 25 min after the mold reaches the preheating temperature. S7. After the alloy casting is completed, place it in the mold for 6 h and then take it out, and cool it to room temperature in the air.

[0023] Example 3: An aluminum alloy sacrificial anode for deep - sea environment, the specific mass percentages of each component are as follows: Zn: 1.46%, Ga: 1.12%, In: 0.45%, Mn: 0.12%, Sn: 0.60%, Mg: 0.55%, Si: 0.45%, Ti: 0.32%, the content of impurities ≤ 0.25%, and the balance is Al.

[0024] The impurities are Cu and Fe elements, and the content ratio of Cu element does not exceed 0.18%, and the content ratio of Fe element does not exceed 0.15%. The Ga and In components use Ga - In master alloy ingots, the Zn component uses Zn ingots, the Sn component uses Sn ingots, the Al component uses Al ingots, the Mn component uses Mn powder, the Mg component uses Mg powder, the Ti component uses Ti powder, and the Si component uses crystalline silicon.

[0025] A manufacturing method of an aluminum alloy sacrificial anode for deep - sea environment, comprising the following steps: S1. Weigh each component raw material according to the weight ratio. S2. Add the Al ingot into a vacuum induction furnace, heat to melt the Al ingot to obtain an aluminum solution; the heating temperature is 720°C, after the temperature reaches the set temperature, continue heating for 80 min, and then carry out spraying, refining, degassing and slag removal in sequence. S3. Add the Zn ingot, Sn ingot and Ga - In master alloy ingot in sequence, and raise the temperature to 840°C, and continue heating for 70 min after the temperature reaches the set temperature to obtain a first mixed solution. S4. Add the Mn powder, Mg powder, Ti powder and crystalline silicon into the first mixed solution, maintain the temperature for 20 min - 30 min after adding, and carry out degassing after standing to remove the floating slag to obtain a second mixed solution. S5. Maintain the heating of the second mixed solution and stir, the stirring time is 15 min, and at the same time preheat the mold, the preheating temperature is 440°C. S6. Carry out casting work 45 min after the mold reaches the preheating temperature. S7. After the alloy casting is completed, place it in the mold for 8 h and then take it out, and cool it to room temperature in the air.

[0026] Select the sacrificial anodes prepared in Example 1, Example 2 and Example 3 for simulation tests, and select the commonly used aluminum - zinc - indium - cadmium sacrificial anode in existing ocean engineering as the control group; the test environment is: simulate the ocean environment at a water depth of 700 - 1200 meters, and the experimental results are as follows:

[0027] As can be seen from the above table, the embodiments of the present invention have higher current efficiency compared with the control group, and the dissolution on the anode surface is uniform, the corrosion products are easy to fall off, and the performance is superior to that of the control group.

[0028] Although the embodiments of the present invention have been shown and described, those of ordinary skill in the art can understand that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principle and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An aluminum alloy sacrificial anode for deep - sea environment, characterized in that: It includes the following components: Zn: 0.84 - 1.46%, Ga: 0.75 - 1.13%, In: 0.36 - 0.47%, Mn: 0.04 - 0.12%, Sn: 0.45 - 0.62%, Mg: 0.34 - 0.57%, Si: 0.29 - 0.46%, Ti: 0.02 - 0.35%. The content of impurities ≤ 0.25%, and the balance is Al.

2. The sacrificial aluminum alloy anode for deep-sea environment according to claim 1, wherein: The specific mass percentages of each component are: Zn: 1.24%, Ga: 0.95%, In: 0.42%, Mn: 0.07%, Sn: 0.55%, Mg: 0.47%, Si: 0.34%, Ti: 0.18%. The content of impurities ≤ 0.25%, and the balance is Al.

3. The sacrificial aluminum alloy anode for deep - sea environment according to claim 1, wherein: The said impurities are Cu and Fe elements, and the content percentage of Cu element does not exceed 0.18%, and the content percentage of Fe element does not exceed 0.15%.

4. The sacrificial aluminum alloy anode for deep - sea environment according to claim 1, characterized in that: For the Ga and In components, Ga-In master alloy ingots are used; for the Zn component, Zn ingots are used; for the Sn component, Sn ingots are used; for the Al component, Al ingots are used; for the Mn component, Mn powder is used; for the Mg component, Mg powder is used; for the Ti component, Ti powder is used; for the Si component, crystalline silicon is used.

5. The manufacturing method of an aluminum alloy sacrificial anode for deep - sea environment according to any one of claims 1 - 4, characterized in that, It includes the following steps: S1. Weigh each component raw material according to the weight ratio. S2. Add the Al ingot into a vacuum induction furnace, heat to melt the Al ingot to obtain an aluminum solution, and conduct spraying, refining, degassing and slag removal on the aluminum solution. S3. Add the Zn ingot, Sn ingot and Ga-In master alloy ingot in sequence, raise the temperature, and continue to melt to obtain a first mixed solution. S4. Add the Mn powder, Mg powder, Ti powder and crystalline silicon into the first mixed solution, continue to melt, and conduct degassing after standing, and remove the floating slag to obtain a second mixed solution. S5. Keep heating the second mixed solution and conduct stirring, and preheat the mold at the same time. S6. After preheating for a period of time, conduct casting. S7. Leave the alloy in the mold for a period of time and then remove it, place it in the air, and air-cool it to room temperature.

6. The preparation method of an aluminum alloy sacrificial anode for deep - sea environment and its manufacturing method according to claim 5, characterized in that: In the said step S2, the heating temperature is 670°C - 720°C. After the temperature reaches the set temperature, continue to heat for 60 min - 80 min, and then conduct spraying, refining, degassing and slag removal in sequence.

7. The preparation method of an aluminum alloy sacrificial anode for deep-sea environment and its manufacturing method according to claim 5, characterized in that: In the said step S3, the temperature is raised to 820°C - 860°C, and after the temperature reaches the set temperature, continue to heat for 50 min - 70 min to obtain a first mixed solution; in the said step S4, after adding the Mn powder, Mg powder, Ti powder and crystalline silicon, maintain the temperature for 20 min - 30 min to obtain a second mixed solution.

8. The preparation method of an aluminum alloy sacrificial anode for deep - sea environment and its manufacturing method according to claim 5, characterized in that: In the said step S5, the stirring time of the second mixed solution is 10 min - 15 min, and the preheating temperature of the mold is 380°C - 460°C.

9. The preparation method of an aluminum alloy sacrificial anode for deep - sea environment and its manufacturing method according to claim 5, characterized in that: In the said step S6, the casting work is carried out after the mold reaches the preheating temperature and not less than 20 min.

10. The preparation method of an aluminum alloy sacrificial anode for deep - sea environment and its manufacturing method according to claim 5, characterized in that: In the said step S7, after the alloy casting is completed, it is left in the mold for 6 h - 8 h and then taken out, and cooled to room temperature in the air.

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