CN114059072A - Zinc-free aluminum alloy sacrificial anode - Google Patents
Zinc-free aluminum alloy sacrificial anode Download PDFInfo
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- CN114059072A CN114059072A CN202111335697.4A CN202111335697A CN114059072A CN 114059072 A CN114059072 A CN 114059072A CN 202111335697 A CN202111335697 A CN 202111335697A CN 114059072 A CN114059072 A CN 114059072A
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- 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
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- 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
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- 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
Abstract
The invention provides a zinc-free aluminum alloy sacrificial anode, which comprises the following components of aluminum, tin and indium, wherein the mass fraction of the tin is 0.01-0.04%, the mass fraction of the indium is 0.005-0.03%, and the balance is aluminum; the mass fraction of iron impurity in the zinc-free aluminum alloy sacrificial anode is less than or equal to 0.06%, the mass fraction of silicon impurity is less than or equal to 0.07%, and the mass fraction of copper impurity is less than or equal to 0.005%. The zinc-free aluminum alloy sacrificial anode does not contain zinc, so that the influence of the dissolution of zinc element in the sacrificial anode on marine ecology is avoided, the open circuit potential of the zinc-free aluminum alloy sacrificial anode is-1.23V to-1.1V, the working potential is-1.11V to-1.04V, and the capacitance is more than or equal to 2500 A.h/Kg, so that the zinc-free aluminum alloy sacrificial anode not only meets the standard requirement on the working potential, but also has high capacitance. Meanwhile, the zinc-free aluminum alloy sacrificial anode has uniform surface dissolution, is easy to shed corrosion products, and can be widely applied to cathodic protection engineering of marine structures, submarine pipeline engineering, marine equipment and the like.
Description
Technical Field
The invention relates to the technical field of corrosion prevention, in particular to a zinc-free aluminum alloy sacrificial anode.
Background
The sacrificial anode cathodic protection method is a common corrosion protection method for marine structures, has the advantages of simplicity, reliability, low cost, maintenance-free property and the like, and the protection effect of the sacrificial anode cathodic protection method is closely related to that of a sacrificial anode material. The aluminum alloy sacrificial anode has the advantages of light weight, high capacitance, low price and the like, is widely applied to corrosion protection of various steel structures, and is the Al-Zn-In (aluminum-zinc-indium) alloy anode which is most widely applied to the current marine environment.
Along with the great service of offshore platforms, harbor work docks, offshore wind power, submarine pipelines and other ocean engineering, the use amount of aluminum alloy sacrificial anodes is increased sharply, and taking the cathode protection of steel piles of east-sea bridges as an example, the number of the used aluminum alloy anodes reaches more than 2000, and the quality reaches thousands of tons. The sacrificial anode reduces the corrosion risk of the marine steel structure, and simultaneously, the heavy metal ions generated after the sacrificial anode is dissolved also have certain influence and harm on the marine ecological environment. In recent years, with the increasing demand of clean energy, a large amount of offshore wind power facilities are started and constructed and are close to a mariculture area, and environmental monitoring finds that the zinc content in the surrounding sea exceeds 0.05mg/L (the upper limit of zinc element in the second class water quality of the aquaculture area) specified by national standard GB3097-1997 seawater quality standard. Although zinc is an essential element, the content of zinc in organisms exceeds a certain threshold value, so that respiratory movement of the organisms is hindered, growth and maturation of the organisms are hindered, and if the content of zinc in fishes and mollusks is too high, blue spots appear on the body surfaces of the fishes and the mollusks, so that the production of the mariculture industry is reduced and the quality of aquatic products is reduced. The reason that the zinc content exceeds the standard is that besides the discharge of the land-source zinc-containing wastewater, the dissolution of the zinc element In the sacrificial anode is also an important reason, and according to the requirements of the national standard GB/T4948-2002 aluminum-zinc-indium series alloy sacrificial anode, the Zn content In the Al-Zn-In series sacrificial anode is 2.2-7.0 percent, and the Zn content of most supplied anodes is about 5 percent. Therefore, in order to reduce the increase of the release amount of zinc element caused by the mass application of the aluminum alloy sacrificial anode and reduce the influence of the zinc element on the metabolism of marine organisms, an environment-friendly zinc-free aluminum alloy sacrificial anode material needs to be developed, so that the influence on the marine ecological environment is reduced while effective cathodic protection is provided for marine engineering equipment.
Disclosure of Invention
The invention aims to provide a zinc-free aluminum alloy sacrificial anode, aiming at solving the defects existing in the prior art, the zinc-free aluminum alloy sacrificial anode does not contain zinc, the influence of the dissolution of zinc element in the sacrificial anode on the marine ecology is avoided, the open circuit potential of the zinc-free aluminum alloy sacrificial anode is-1.23V-1.1V (relative to a saturated calomel electrode), the working potential is-1.11V-1.04V (relative to the saturated calomel electrode), and the capacitance is more than or equal to 2500 A.h/Kg, so the zinc-free aluminum alloy sacrificial anode not only meets the standard requirement on the working potential, but also has high capacitance. Meanwhile, the zinc-free aluminum alloy sacrificial anode has uniform surface dissolution, is easy to shed corrosion products, and can be widely applied to cathodic protection engineering of marine structures, submarine pipeline engineering, marine equipment and the like. And the zinc-free aluminum alloy sacrificial anode has the advantages of simple smelting process and low energy consumption.
The invention provides a zinc-free aluminum alloy sacrificial anode, which comprises the following components of aluminum, tin and indium, wherein the mass fraction of the tin is 0.01-0.04%, the mass fraction of the indium is 0.005-0.03%, and the balance is aluminum; the mass fraction of iron impurity in the zinc-free aluminum alloy sacrificial anode is less than or equal to 0.06%, the mass fraction of silicon impurity is less than or equal to 0.07%, and the mass fraction of copper impurity is less than or equal to 0.005%.
Furthermore, the open circuit potential of the zinc-free aluminum alloy sacrificial anode is-1.23V to-1.1V, and the working potential of the zinc-free aluminum alloy sacrificial anode is-1.11V to-1.04V.
Furthermore, the capacitance of the zinc-free aluminum alloy sacrificial anode is more than or equal to 2500 A.h/Kg.
Further, the mass fraction of indium is 0.005% to 0.009%.
Furthermore, the manufacturing materials of the zinc-free aluminum alloy sacrificial anode comprise an aluminum ingot, a tin block and an indium block.
Further, the preparation process of the zinc-free aluminum alloy sacrificial anode adopts a fusion casting method, and the preparation method of the zinc-free aluminum alloy sacrificial anode comprises the following steps:
weighing an aluminum ingot, a tin block and an indium block according to a formula ratio before smelting, and preheating the aluminum ingot, the tin block and the indium block to a first temperature so as to remove moisture in the aluminum ingot, the tin block and the indium block;
putting the aluminum ingot into a heating device, heating the aluminum ingot to a second temperature, and completely melting the aluminum ingot to obtain aluminum liquid;
scooping the aluminum liquid, wrapping the tin block and the indium block with aluminum foil, adding the wrapped tin block and indium block into the aluminum liquid, stirring to dissolve the wrapped tin block and indium block, and pouring the wrapped tin block and indium block into the heating device to obtain an aluminum-tin-indium mixed solution;
continuing to heat the aluminum-tin-indium mixed solution, and stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution; and stopping heating after the aluminum-tin-indium mixed solution is fully melted, casting the aluminum-tin-indium mixed solution into a mold when the temperature of the aluminum-tin-indium mixed solution is reduced to a third temperature, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
Further, the first temperature is more than or equal to 100 ℃.
Further, the second temperature is 720 ℃ to 750 ℃.
Further, the third temperature is 680-700 ℃.
The zinc-free aluminum alloy sacrificial anode provided by the invention contains no zinc in the composition materials, so that the influence of the dissolution of zinc element in the sacrificial anode on marine ecology is avoided; in addition, the zinc-free aluminum alloy sacrificial anode has low added alloy elements (tin and indium), so the cost is low, the specific weight of the anode is smaller than that of a conventional Al-Zn-In alloy anode, and the weight load of a cathode protection object is reduced. The open circuit potential of the zinc-free aluminum alloy sacrificial anode is-1.23V to-1.1V (relative to a saturated calomel electrode), the working potential is-1.11V to-1.04V (relative to the saturated calomel electrode), and the capacitance is more than or equal to 2500 A.h/Kg, so that the zinc-free aluminum alloy sacrificial anode not only meets the standard requirement on the working potential, but also has high capacitance (the capacitance is equivalent to the national standard Al-Zn-In sacrificial anode).
The zinc-free aluminum alloy sacrificial anode takes aluminum as a raw material, and the influence of impurity elements on the electrochemical performance of the sacrificial anode is eliminated by adding tin elements and indium elements in proportion. Tin element is dissolved in aluminum to form a solid solution, and ion defects are formed in the aluminum passive film to destroy the passivity of aluminum, so that the anode potential of the aluminum alloy is shifted negatively, and meanwhile, the tin element can catalyze the hydrogen evolution reaction on the surface of the anode, so that the alkalinity of the solution on the surface of the anode is increased, the dissolution of the aluminum passive film is promoted, and the anode activity is improved; however, the increase of the tin content can accelerate the hydrogen reduction reaction on the surface of the anode, cause anode short circuit and reduce the current efficiency of the aluminum alloy anode, and meanwhile, excessive tin can be segregated at grain boundaries, so that the corrosion tendency of the grain boundaries is enhanced, and the current efficiency of the anode is reduced. Indium element destroys the passivation film of aluminum through the process of dissolution-redeposition, promotes the activation of the aluminum alloy anode, makes the anode electrode potential shift negative, and simultaneously indium can partially inhibit the adverse effect of impurities such as iron, silicon and the like on the aluminum anode; the indium can also inhibit the hydrogen evolution process on the surface of the anode, improve the current efficiency of the anode and reduce the adverse effect of the tin element. Indium and tin elements enriched at the grain boundary form a new couple pair to accelerate the oxidation of indium, and formed indium ions are reduced on the surface of the aluminum anode to destroy a passivation film, so that the aluminum alloy anode has higher current efficiency and uniform surface solubility by adding the tin and indium elements.
Meanwhile, the zinc-free aluminum alloy sacrificial anode has uniform surface dissolution, is easy to shed corrosion products, and can be widely applied to cathodic protection engineering of marine structures, submarine pipeline engineering, marine equipment and the like. The zinc-free aluminum alloy sacrificial anode has the advantages of simple material components, low cost, simple and mature smelting process and low energy consumption.
Drawings
FIG. 1 is a schematic diagram of the electrochemical performance of a sacrificial anode without a zinc-type aluminum alloy according to various embodiments of the present invention.
Detailed Description
The following detailed description of embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The terms "first," "second," "third," "fourth," and the like in the description and in the claims, if any, are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order.
The terms of orientation, up, down, left, right, front, back, top, bottom, and the like (if any) referred to in the specification and claims of the present invention are defined by the positions of structures in the drawings and the positions of the structures relative to each other, only for the sake of clarity and convenience in describing the technical solutions. It is to be understood that the use of the directional terms should not be taken to limit the scope of the claims.
The zinc-free aluminum alloy sacrificial anode (Al-Sn-In sacrificial anode) provided by the embodiment of the invention takes aluminum as a raw material, and the influence of impurity elements on the electrochemical performance of the sacrificial anode is eliminated by adding tin elements and indium elements In proportion. The composition materials of the zinc-free aluminum alloy sacrificial anode comprise aluminum (Al), tin (Sn) and indium (In). Wherein the mass fraction of tin is 0.01-0.04%, the mass fraction of indium is 0.005-0.03%, and the balance is aluminum. The mass fraction of impurity iron (Fe) in the zinc-free aluminum alloy sacrificial anode is less than or equal to 0.06%, the mass fraction of impurity silicon (Si) is less than or equal to 0.07%, and the mass fraction of impurity copper (Cu) is less than or equal to 0.005%.
Specifically, the solubility of tin element in aluminum is 0.07% (700 ℃) and 0.017% (156 ℃) within the solubility, the tin element is dissolved in aluminum to form a solid solution, ion defects are formed in an aluminum passive film, the passivity of aluminum is damaged, the anode potential of the aluminum alloy is shifted negatively, and meanwhile, the tin element can catalyze the hydrogen evolution reaction on the surface of an anode, so that the alkalinity of the solution on the surface of the anode is increased, the dissolution of the aluminum passive film is promoted, and the anode activity is improved; however, the increase of the tin content can accelerate the hydrogen reduction reaction on the surface of the anode, cause anode short circuit and reduce the current efficiency of the aluminum alloy anode, and meanwhile, excessive tin can segregate at grain boundaries, so that the grain boundary corrosion tendency is enhanced, and the current efficiency of the anode is reduced. Indium element destroys the passivation film of aluminum through the process of dissolution-redeposition, promotes the activation of the aluminum alloy anode, makes the anode electrode potential shift negative, and simultaneously indium can partially inhibit the adverse effect of impurities such as iron, silicon and the like on the aluminum anode; the indium can also inhibit the hydrogen evolution process on the surface of the anode, improve the current efficiency of the anode and reduce the adverse effect of the tin element. Indium and tin elements enriched at the grain boundary form a new couple pair to accelerate the oxidation of indium, and formed indium ions are reduced on the surface of the aluminum anode to destroy a passivation film, so that the aluminum alloy anode has higher current efficiency and uniform surface solubility by adding the tin and indium elements.
Further, in the present embodiment, in normal temperature seawater, the open circuit potential of the sacrificial anode is-1.23V to-1.1V (relative to saturated calomel electrode SCE), the working potential of the sacrificial anode is stabilized at-1.11V to-1.04V (relative to saturated calomel electrode SCE), and the capacitance of the sacrificial anode is not less than 2500A · h/Kg. Therefore, the performance of the zinc-free aluminum alloy sacrificial anode meets the design requirement of the aluminum alloy sacrificial anode recommended by DNV GL RP-B401 standard: the working potential is minus 1.05V, and the capacitance is more than or equal to 2000 A.h/Kg.
Preferably, the mass fraction of indium in the zinc-free aluminum alloy sacrificial anode is 0.005% -0.009%.
Further, in this embodiment, the material for making the zinc-free aluminum alloy sacrificial anode includes an aluminum ingot, a tin block and an indium block. The preparation process of the zinc-free aluminum alloy sacrificial anode adopts a fusion casting method, and the preparation method of the zinc-free aluminum alloy sacrificial anode comprises the following steps:
before smelting, weighing an aluminum ingot, a tin block and an indium block which meet the proportioning requirement according to the formula proportion, and preheating the aluminum ingot, the tin block and the indium block to a first temperature so as to remove moisture in the aluminum ingot, the tin block and the indium block;
then, putting the aluminum ingot into a heating device (a smelting furnace, a crucible or a heating furnace, etc.) and heating the aluminum ingot to a second temperature to completely melt the aluminum ingot to obtain aluminum liquid (no solid aluminum ingot is seen);
then scooping aluminum liquid by using a small crucible, wrapping tin blocks and indium blocks by using aluminum foil, adding the wrapped tin blocks and indium blocks into the aluminum liquid in the small crucible, stirring the aluminum liquid and the wrapped indium blocks by using a graphite rod to dissolve the aluminum liquid, and pouring the aluminum liquid and the wrapped indium blocks into a high-temperature heating device to obtain aluminum-tin-indium mixed liquid;
continuously heating the aluminum-tin-indium mixed solution, stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution, and removing dregs in the aluminum-tin-indium mixed solution; and stopping heating after the aluminum-tin-indium mixed solution is fully melted, taking the aluminum-tin-indium mixed solution out of the heating device, casting the aluminum-tin-indium mixed solution into a preheated cast iron mold for molding when the temperature of the aluminum-tin-indium mixed solution is reduced to a third temperature, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
Further, in this embodiment, the first temperature is equal to or higher than 100 ℃ (preferably 100 ℃), the second temperature is 720 ℃ to 750 ℃, and the third temperature is 680 ℃ to 700 ℃.
The zinc-free aluminum alloy sacrificial anode provided by the embodiment has the advantages that:
1. the zinc-free aluminum alloy sacrificial anode contains no zinc in the composition materials, so that the influence of the dissolution of zinc element in the sacrificial anode on the marine ecology is avoided; in addition, the zinc-free aluminum alloy sacrificial anode has low added alloy elements (tin and indium), so the cost is low, the specific weight of the anode is smaller than that of a conventional Al-Zn-In alloy anode, and the weight load of a cathode protection object is reduced. The open circuit potential of the zinc-free aluminum alloy sacrificial anode is-1.23V to-1.1V (relative to a saturated calomel electrode), the working potential is-1.11V to-1.04V (relative to the saturated calomel electrode), and the capacitance is more than or equal to 2500 A.h/Kg, so that the zinc-free aluminum alloy sacrificial anode not only meets the standard requirement on the working potential, but also has high capacitance;
2. the zinc-free aluminum alloy sacrificial anode takes aluminum as a raw material, and the influence of impurity elements on the electrochemical performance of the sacrificial anode is eliminated by adding tin elements and indium elements in proportion. Tin element is dissolved in aluminum to form a solid solution, and ion defects are formed in the aluminum passive film to destroy the passivity of aluminum, so that the anode potential of the aluminum alloy is shifted negatively, and meanwhile, the tin element can catalyze the hydrogen evolution reaction on the surface of the anode, so that the alkalinity of the solution on the surface of the anode is increased, the dissolution of the aluminum passive film is promoted, and the anode activity is improved; however, the increase of the tin content can accelerate the hydrogen reduction reaction on the surface of the anode, cause anode short circuit and reduce the current efficiency of the aluminum alloy anode, and meanwhile, excessive tin can be segregated at grain boundaries, so that the corrosion tendency of the grain boundaries is enhanced, and the current efficiency of the anode is reduced. Indium element destroys the passivation film of aluminum through the process of dissolution-redeposition, promotes the activation of the aluminum alloy anode, makes the anode electrode potential shift negative, and simultaneously indium can partially inhibit the adverse effect of impurities such as iron, silicon and the like on the aluminum anode; the indium can also inhibit the hydrogen evolution process on the surface of the anode, improve the current efficiency of the anode and reduce the adverse effect of the tin element. Indium and tin elements enriched at the crystal boundary form a new galvanic couple to accelerate the oxidation of indium, and formed indium ions are reduced on the surface of the aluminum anode to destroy a passivation film, so that the aluminum alloy anode has higher current efficiency and uniform surface solubility by adding the tin and indium elements;
3. the zinc-free aluminum alloy sacrificial anode has the advantages that the surface of the zinc-free aluminum alloy sacrificial anode is uniformly dissolved, corrosion products are easy to fall off, and the zinc-free aluminum alloy sacrificial anode can be widely used for cathode protection engineering of marine structures, submarine pipeline engineering, marine equipment and the like;
4. the zinc-free aluminum alloy sacrificial anode has the advantages of simple material components (the main components only comprise aluminum, tin and indium) and low cost; meanwhile, the preparation process of the zinc-free aluminum alloy sacrificial anode adopts a fusion casting method, the smelting process is simple and mature, and the energy consumption is low.
On the premise of meeting the design specification of cathode protection of ocean engineering equipment, the zinc-free aluminum alloy sacrificial anode provided by the embodiment has high capacitance (the capacitance is equivalent to that of a national standard Al-Zn-In sacrificial anode), does not add zinc, and is a novel efficient and environment-friendly electrochemical cathode protection material.
Example one:
the formula of the zinc-free aluminum alloy sacrificial anode comprises the following components in percentage by mass: 0.01 percent of Sn, 0.005 percent of In, 0.058 percent of impurity element Fe, 0.056 percent of Si, 0.004 percent of Cu and the balance of Al.
Putting the aluminum ingot into a heating device (a smelting furnace, a crucible or a heating furnace, etc.), heating the aluminum ingot to 720-750 ℃, and completely melting the aluminum ingot to obtain aluminum liquid (no solid aluminum ingot is seen); then scooping aluminum liquid by using a small crucible, wrapping tin blocks and indium blocks by using aluminum foil, adding the wrapped tin blocks and indium blocks into the aluminum liquid in the small crucible, stirring the aluminum liquid and the wrapped indium blocks by using a graphite rod to dissolve the aluminum liquid, and pouring the aluminum liquid and the wrapped indium blocks into a high-temperature heating device to obtain aluminum-tin-indium mixed liquid; continuously heating the aluminum-tin-indium mixed solution, stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution, and removing dregs in the aluminum-tin-indium mixed solution; stopping heating after the aluminum-tin-indium mixed solution is fully melted, taking the aluminum-tin-indium mixed solution out of the heating device, casting the aluminum-tin-indium mixed solution into a preheated cast iron mold for molding when the temperature of the aluminum-tin-indium mixed solution is reduced to 680-700 ℃, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
As shown in FIG. 1, the sacrificial anode of zinc-free aluminum alloy obtained in the first example was tested for electrochemical performance according to the standard test method specified in GB/T17848-1999, and the sacrificial anode of zinc-free aluminum alloy had an open circuit potential of-1.18V (relative to saturated calomel electrode), an operating potential of-1.11V (relative to saturated calomel electrode), a capacitance of 2685 A.h/Kg, and the surface of the sacrificial anode of zinc-free aluminum alloy was uniformly dissolved, and corrosion products were easily detached.
Example two:
the formula of the zinc-free aluminum alloy sacrificial anode comprises the following components in percentage by mass: 0.01 percent of Sn, 0.03 percent of In, 0.058 percent of impurity element Fe, 0.062 percent of Si, 0.004 percent of Cu and the balance of Al.
Putting the aluminum ingot into a heating device (a smelting furnace, a crucible or a heating furnace, etc.), heating the aluminum ingot to 720-750 ℃, and completely melting the aluminum ingot to obtain aluminum liquid (no solid aluminum ingot is seen); then scooping aluminum liquid by using a small crucible, wrapping tin blocks and indium blocks by using aluminum foil, adding the wrapped tin blocks and indium blocks into the aluminum liquid in the small crucible, stirring the aluminum liquid and the wrapped indium blocks by using a graphite rod to dissolve the aluminum liquid, and pouring the aluminum liquid and the wrapped indium blocks into a high-temperature heating device to obtain aluminum-tin-indium mixed liquid; continuously heating the aluminum-tin-indium mixed solution, stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution, and removing dregs in the aluminum-tin-indium mixed solution; stopping heating after the aluminum-tin-indium mixed solution is fully melted, taking the aluminum-tin-indium mixed solution out of the heating device, casting the aluminum-tin-indium mixed solution into a preheated cast iron mold for molding when the temperature of the aluminum-tin-indium mixed solution is reduced to 680-700 ℃, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
As shown in FIG. 1, the sacrificial anode of zinc-free aluminum alloy obtained in example two was tested for electrochemical performance according to the standard test method specified in GB/T17848-1999, and the sacrificial anode of zinc-free aluminum alloy had an open circuit potential of-1.15V (relative to saturated calomel electrode), an operating potential of-1.09V (relative to saturated calomel electrode), a capacitance of 2738 A.h/Kg, and the surface of the sacrificial anode of zinc-free aluminum alloy was dissolved uniformly, and corrosion products were easily detached.
Example three:
the formula of the zinc-free aluminum alloy sacrificial anode comprises the following components in percentage by mass: 0.04% of Sn, 0.005% of In, 0.058% of impurity element Fe, 0.062% of Si, 0.004% of Cu and the balance of Al.
Putting the aluminum ingot into a heating device (a smelting furnace, a crucible or a heating furnace, etc.), heating the aluminum ingot to 720-750 ℃, and completely melting the aluminum ingot to obtain aluminum liquid (no solid aluminum ingot is seen); then scooping aluminum liquid by using a small crucible, wrapping tin blocks and indium blocks by using aluminum foil, adding the wrapped tin blocks and indium blocks into the aluminum liquid in the small crucible, stirring the aluminum liquid and the wrapped indium blocks by using a graphite rod to dissolve the aluminum liquid, and pouring the aluminum liquid and the wrapped indium blocks into a high-temperature heating device to obtain aluminum-tin-indium mixed liquid; continuously heating the aluminum-tin-indium mixed solution, stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution, and removing dregs in the aluminum-tin-indium mixed solution; stopping heating after the aluminum-tin-indium mixed solution is fully melted, taking the aluminum-tin-indium mixed solution out of the heating device, casting the aluminum-tin-indium mixed solution into a preheated cast iron mold for molding when the temperature of the aluminum-tin-indium mixed solution is reduced to 680-700 ℃, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
As shown in FIG. 1, the sacrificial anode of zinc-free aluminum alloy obtained in example III was tested for electrochemical performance according to the standard test method specified in GB/T17848-1999, and the sacrificial anode of zinc-free aluminum alloy had an open circuit potential of-1.23V (relative to saturated calomel electrode), an operating potential of-1.15V (relative to saturated calomel electrode), a capacitance of 2543 A.h/Kg, and the surface of the sacrificial anode of zinc-free aluminum alloy was uniformly dissolved, and corrosion products were easily detached.
Example four:
the formula of the zinc-free aluminum alloy sacrificial anode comprises the following components in percentage by mass: 0.04% of Sn, 0.03% of In, 0.058% of impurity element Fe, 0.062% of Si, 0.004% of Cu and the balance of Al.
Putting the aluminum ingot into a heating device (a smelting furnace, a crucible or a heating furnace, etc.), heating the aluminum ingot to 720-750 ℃, and completely melting the aluminum ingot to obtain aluminum liquid (no solid aluminum ingot is seen); then scooping aluminum liquid by using a small crucible, wrapping tin blocks and indium blocks by using aluminum foil, adding the wrapped tin blocks and indium blocks into the aluminum liquid in the small crucible, stirring the aluminum liquid and the wrapped indium blocks by using a graphite rod to dissolve the aluminum liquid, and pouring the aluminum liquid and the wrapped indium blocks into a high-temperature heating device to obtain aluminum-tin-indium mixed liquid; continuously heating the aluminum-tin-indium mixed solution, stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution, and removing dregs in the aluminum-tin-indium mixed solution; stopping heating after the aluminum-tin-indium mixed solution is fully melted, taking the aluminum-tin-indium mixed solution out of the heating device, casting the aluminum-tin-indium mixed solution into a preheated cast iron mold for molding when the temperature of the aluminum-tin-indium mixed solution is reduced to 680-700 ℃, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
As shown in FIG. 1, the sacrificial anode of zinc-free aluminum alloy obtained in example four was tested for electrochemical performance according to the standard test method specified in GB/T17848-1999, and the sacrificial anode of zinc-free aluminum alloy had an open circuit potential of-1.19V (relative to saturated calomel electrode), an operating potential of-1.13V (relative to saturated calomel electrode), a capacitance of 2590 A.h/Kg, and the surface of the sacrificial anode of zinc-free aluminum alloy was uniformly dissolved, and corrosion products were easily detached.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (9)
1. The zinc-free aluminum alloy sacrificial anode is characterized in that the zinc-free aluminum alloy sacrificial anode comprises aluminum, tin and indium, wherein the mass fraction of the tin is 0.01-0.04%, the mass fraction of the indium is 0.005-0.03%, and the balance is aluminum; the mass fraction of iron impurity in the zinc-free aluminum alloy sacrificial anode is less than or equal to 0.06%, the mass fraction of silicon impurity is less than or equal to 0.07%, and the mass fraction of copper impurity is less than or equal to 0.005%.
2. The sacrificial anode of claim 1, wherein the open circuit potential of the sacrificial anode is-1.23V-1.1V, and the working potential of the sacrificial anode is-1.11V-1.04V.
3. The sacrificial anode of claim 1, wherein the capacity of the sacrificial anode is not less than 2500 A.h/Kg.
4. The sacrificial anode of claim 1, wherein the indium comprises 0.005% to 0.009% by weight.
5. The sacrificial anode of claim 1, wherein the sacrificial anode is made of materials comprising aluminum ingot, tin block and indium block.
6. The sacrificial anode of zinc-free aluminum alloy as claimed in any one of claims 1 to 5, wherein the sacrificial anode of zinc-free aluminum alloy is prepared by a fusion casting method, and the method for preparing the sacrificial anode of zinc-free aluminum alloy comprises:
weighing an aluminum ingot, a tin block and an indium block according to a formula ratio before smelting, and preheating the aluminum ingot, the tin block and the indium block to a first temperature so as to remove moisture in the aluminum ingot, the tin block and the indium block;
putting the aluminum ingot into a heating device, heating the aluminum ingot to a second temperature, and completely melting the aluminum ingot to obtain aluminum liquid;
scooping the aluminum liquid, wrapping the tin block and the indium block with aluminum foil, adding the wrapped tin block and indium block into the aluminum liquid, stirring to dissolve the wrapped tin block and indium block, and pouring the wrapped tin block and indium block into the heating device to obtain an aluminum-tin-indium mixed solution;
continuing to heat the aluminum-tin-indium mixed solution, and stirring the aluminum-tin-indium mixed solution to fully melt the aluminum-tin-indium mixed solution; and stopping heating after the aluminum-tin-indium mixed solution is fully melted, casting the aluminum-tin-indium mixed solution into a mold when the temperature of the aluminum-tin-indium mixed solution is reduced to a third temperature, and cooling to obtain the zinc-free aluminum alloy sacrificial anode.
7. The sacrificial anode of claim 6, wherein the first temperature is at least 100 ℃.
8. The sacrificial anode of claim 6, wherein the second temperature is 720 ℃ to 750 ℃.
9. The sacrificial anode of claim 6, wherein the third temperature is between 680 ℃ and 700 ℃.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830720A (en) * | 1970-05-30 | 1974-08-20 | Nippon Yakin Kogyo Co Ltd | Material for preventing crevice corrosion |
| JPH0433769A (en) * | 1990-05-25 | 1992-02-05 | Mitsubishi Alum Co Ltd | Manufacture of al alloy-made high strength sacrificial anode fin material in heat exchanger manufactured with brazing |
| CN1260408A (en) * | 2000-01-26 | 2000-07-19 | 冶金工业部钢铁研究总院 | Aluminium alloy sacrificial anode material to be used in fresh water |
| CN105219993A (en) * | 2015-10-21 | 2016-01-06 | 中国海洋石油总公司 | T-shaped sacrificial aluminium alloy anode founding |
| CN109252170A (en) * | 2018-11-08 | 2019-01-22 | 青岛钢研纳克检测防护技术有限公司 | The sacrificial aluminium alloy anode of high temperature resistant smeary sea water |
| CN109609959A (en) * | 2018-12-28 | 2019-04-12 | 青岛双瑞海洋环境工程股份有限公司 | High-performance low potential aluminium sacrificial anode material applied to ocean engineering cathodic protection |
| CN111201133A (en) * | 2017-09-14 | 2020-05-26 | 由海军部长代表的美利坚合众国 | Aluminum anode alloy |
| CN113293384A (en) * | 2021-06-02 | 2021-08-24 | 青岛双瑞海洋环境工程股份有限公司 | Zinc-free aluminum alloy sacrificial anode |
| CN113322467A (en) * | 2021-06-02 | 2021-08-31 | 青岛双瑞海洋环境工程股份有限公司 | Micro-zinc type aluminum alloy sacrificial anode |
-
2021
- 2021-11-11 CN CN202111335697.4A patent/CN114059072A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3830720A (en) * | 1970-05-30 | 1974-08-20 | Nippon Yakin Kogyo Co Ltd | Material for preventing crevice corrosion |
| JPH0433769A (en) * | 1990-05-25 | 1992-02-05 | Mitsubishi Alum Co Ltd | Manufacture of al alloy-made high strength sacrificial anode fin material in heat exchanger manufactured with brazing |
| CN1260408A (en) * | 2000-01-26 | 2000-07-19 | 冶金工业部钢铁研究总院 | Aluminium alloy sacrificial anode material to be used in fresh water |
| CN105219993A (en) * | 2015-10-21 | 2016-01-06 | 中国海洋石油总公司 | T-shaped sacrificial aluminium alloy anode founding |
| CN111201133A (en) * | 2017-09-14 | 2020-05-26 | 由海军部长代表的美利坚合众国 | Aluminum anode alloy |
| CN109252170A (en) * | 2018-11-08 | 2019-01-22 | 青岛钢研纳克检测防护技术有限公司 | The sacrificial aluminium alloy anode of high temperature resistant smeary sea water |
| CN109609959A (en) * | 2018-12-28 | 2019-04-12 | 青岛双瑞海洋环境工程股份有限公司 | High-performance low potential aluminium sacrificial anode material applied to ocean engineering cathodic protection |
| CN113293384A (en) * | 2021-06-02 | 2021-08-24 | 青岛双瑞海洋环境工程股份有限公司 | Zinc-free aluminum alloy sacrificial anode |
| CN113322467A (en) * | 2021-06-02 | 2021-08-31 | 青岛双瑞海洋环境工程股份有限公司 | Micro-zinc type aluminum alloy sacrificial anode |
Non-Patent Citations (1)
| Title |
|---|
| 齐卫东: "《压铸工艺与模具设计》", 北京理工大学出版社, pages: 38 - 39 * |
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