CN110983224B - Hot-dip galvanized aluminum-magnesium coated steel and preparation method thereof - Google Patents
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- 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
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
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- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
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Abstract
The invention discloses hot-dip galvanized aluminum-magnesium coating steel and a preparation method thereof, wherein the hot-dip galvanized aluminum-magnesium coating steel comprises a zinc-aluminum-magnesium coating, and the chemical components and the mass fraction of the zinc-aluminum-magnesium coating are as follows: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities. The hot-dip galvanized aluminum-magnesium coated steel prepared by the method has good blackening resistance, is simple to operate, has low manufacturing cost and is easy to popularize and use.
Description
Technical Field
The invention belongs to the technical field of coating and plating, and particularly relates to hot-dip galvanized aluminum-magnesium coated steel and a preparation method thereof.
Background
Hot dip galvanizing combines both a steel substrate and a coating by reacting molten metal with the steel substrate to produce an alloy layer. Hot-dip galvanized steel has the advantages of uniform coating, strong adhesion, long service life, simple manufacturing process, low product price and the like, and the demand in various industries, such as automobile industry, electrical appliance industry and building industry, is increasing day by day.
In order to improve the corrosion resistance of hot-dip galvanized steel, zinc alloy coated steel, including zinc-aluminum-magnesium coated steel, is manufactured by adding elements such as magnesium, aluminum, etc. to pure zinc coated steel. However, aluminum and magnesium elements in the coating are easily oxidized in the air to form an oxide film, the oxide film easily causes the surface of the coating to be dark, if the thickness of the oxide film is uneven, the degree of the dark surface of the coating is different, so that the color of the surface of the coating cannot meet the use requirement, and the coating has a blackening defect, as shown in fig. 1.
The invention CN 200810041723 provides a blackening-resistant electrogalvanized steel sheet and a manufacturing method thereof, the invention puts the electrogalvanized steel sheet into a steel sheet containing Ni2+Soaking in the acidic solution for more than 1 second, and then coating the surface with oil. The method can not provide a preparation method and a product of a blackening-resistant zinc-aluminum-magnesium coating, and Ni2+Has environmental toxicity.
The invention CN 201380081069 provides a galvanized steel sheet with excellent blackening resistance and corrosion resistance, and a manufacturing method thereof, wherein the surface of the galvanized steel sheet is provided with a Zn-Al-Mg-Si alloy plating layer, a coating containing Al is formed on the plating layer, and the coating containing Al is composed of an insulating substance containing scaly Al particles. The surface of the product of the invention is coated with an insulating substance, so that the product is difficult to be used in the field of automobiles which need surface electrophoresis treatment.
The invention CN 201610737502 provides a high corrosion resistance hot dip zinc aluminum magnesium nickel rare earth alloy plating layer steel plate and a production method thereof, trace Ni element is added in a hot dip zinc aluminum magnesium plating layer and is matched with a proper amount of coexisting Mg element, and magnesium nickel element enrichment is formed on the surface of the plating layer, thereby effectively improving the oxidation resistance of the surface of the steel plate plating layer and improving the blackening resistance and the corrosion resistance of the steel plate plating layer. Therefore, the invention is similar to the technology of the invention CN 200810041723, and the addition of Ni can cause the formation of Ni-Al and Ni-Mg phases in the plating layer and deteriorate the corrosion resistance of the plating layer.
The invention CN 201610166546 provides a hot-dip plated steel and a manufacturing method thereof, and the aim of avoiding the blackening defect of a plating layer is achieved by adding Ca and/or Ba and Li elements in the plating layer. However, the method requires that the alloy elements are added into the alloy plating bath of the hot-dip galvanizing, and the alloy elements have the characteristics of easy burning loss and easy combustion at high temperature, and have larger production safety risk and larger difficulty in stable control.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides hot-dip galvanized aluminum-magnesium coated steel and a preparation method thereof, and aims to solve the problems that the surface of the hot-dip galvanized aluminum-magnesium coated steel in the prior art has a blackening defect, the appearance is influenced, and the use requirements of users cannot be met.
The invention realizes the purpose through the following technical scheme:
on one hand, the invention provides hot-dip galvanized aluminum-magnesium coated steel, which comprises a zinc-aluminum-magnesium coating, wherein the zinc-aluminum-magnesium coating comprises the following chemical components in percentage by mass: al: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities.
Further, in the chemical composition, the mass fraction relation of Al and Mg is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, the content of Al-Mg is more than or equal to 1.5 percent.
Further, the zinc-aluminum-magnesium coating contains an eutectic structure, and the volume fraction of the eutectic structure is less than 15%.
Further, the volume fraction of the eutectic structure is less than 13%.
Further, the volume fraction of the eutectic structure is less than 10%.
Further, the hot-dip galvanized aluminum-magnesium coated steel further comprises an oxide film, the thickness of the oxide film is 10-100 nanometers, and the porosity of the oxide film is not more than 0.1%.
In another aspect, the invention provides a method for preparing hot-dip galvanized aluminum-magnesium coated steel, which comprises the following steps,
smelting molten steel to obtain a plate blank; sequentially heating, hot rolling, pickling and cold rolling the plate blank to obtain a cold-rolled plate;
sequentially carrying out primary surface treatment and heat treatment on the cold-rolled sheet to obtain a heat-treated sheet;
sequentially carrying out hot dip coating, post-treatment, secondary surface treatment and coiling on the heat-treated plate to obtain hot-dip galvanized aluminum-magnesium coated steel; in the hot dip plating, the chemical components and the mass fraction of the plating solution are as follows: al: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities.
Further, in the chemical composition, the mass fraction relation of Al and Mg is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, the content of Al-Mg is more than or equal to 1.5 percent.
Further, the post-treatment comprises cooling treatment, wherein the cooling speed of the cooling treatment is 50-100 ℃/S.
Further, the secondary surface treatment includes a surface oxidation treatment including one of: anodic oxidation treatment, chemical oxidation treatment and high-temperature oxidation treatment.
The beneficial effects of the invention at least comprise:
the invention discloses hot-dip galvanized aluminum-magnesium coated steel and a preparation method thereof, wherein the hot-dip galvanized aluminum-magnesium coated steel comprises a zinc-aluminum-magnesium coating, and the zinc-aluminum-magnesium coating comprises the following components in percentage by mass: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities. The content of Mg element in the hot dip coating aluminum magnesium coating is controlled by controlling the content of alloy elements in the hot dip coating plating solution, so that the Mg entering the thin liquid film from the zinc aluminum magnesium coating is reduced, oxidized oxides of Mg in the thin liquid film are reduced, oxygen atom vacancies of the oxides are reduced, the absorption of visible light is reduced, the color difference is almost disappeared, and the occurrence of blackening defects is avoided. Therefore, the hot-dip galvanized aluminum-magnesium coated steel prepared by the method has good anti-blackening performance.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a defect diagram of blackening of a hot-dip galvanized aluminum-magnesium coated steel according to an embodiment of the invention;
FIG. 2 is a process step diagram of a method for preparing a hot-dip galvanized aluminum-magnesium coated steel according to an embodiment of the present invention;
FIG. 3 is a normal view of the surface of a hot-dip galvanized aluminum-magnesium coated steel according to an embodiment of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the technical scheme in the embodiment of the invention has the following general idea:
on one hand, the embodiment of the invention provides hot-dip galvanized aluminum-magnesium coated steel, which comprises a zinc-aluminum-magnesium coating, wherein the zinc-aluminum-magnesium coating comprises the following chemical components in percentage by mass: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities;
the zinc-aluminum-magnesium plating layer generally contains a zinc-rich solid solution phase, a zinc-aluminum solid solution phase, and magnesium-rich phases, depending on the content of alloy elements. A thin liquid film can be formed on the surface of the zinc-aluminum-magnesium coating in the atmosphere, an electrochemical reaction is carried out between a magnesium-rich phase in the coating and a zinc-rich solid solution, and the magnesium-rich phase is preferentially dissolved to release magnesium ions. Magnesium ions are oxidized in the thin liquid film to magnesium oxide. Due to the insufficient dissolved oxygen in the thin liquid film, vacancies exist at the oxygen atom positions in the oxide, so that this oxide has an absorption effect on visible light, and appears as a gray black color, see fig. 1. Therefore, the control requirement of the magnesium element in the coating is provided in the invention, and the content of the magnesium element in the coating is required to be not more than 2%. However, if the magnesium content in the coating is less than 0.4%, the corrosion resistance of the zinc-aluminum-magnesium coating is impaired. Therefore, the invention requires that the content of magnesium element in the coating is in the range of 0.4-2%, preferably in the range of 0.4-1.5%, and more preferably in the range of 0.4-1.2%.
Aluminum in the zinc-aluminum-magnesium coating mainly affects the corrosion resistance and the processability of the coating, the corrosion resistance is seriously deteriorated if the aluminum content is too low, and the processability is deteriorated if the aluminum content exceeds 4 percent, and a brittle aluminum-zinc compound intermediate phase appears in the coating. In the present invention, it is specified that the aluminum content is in the range of 0.7% to 4%, preferably in the range of 1.0% to 4%, more preferably in the range of 1.0% to 3.5%.
Further, in the chemical composition, the mass fraction relation of Al and Mg is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, the content of Al-Mg is more than or equal to 1.5 percent.
When the content of aluminum element in the zinc-aluminum-magnesium coating exceeds the content of magnesium element, the solid solubility of magnesium in a zinc-rich solid solution phase and a zinc-aluminum solid solution is increased, and meanwhile, the proportion of Mg in a magnesium-rich phase is reduced, so that the Mg entering a thin liquid film is also reduced. Therefore, the invention simultaneously puts requirements on the interrelation of the aluminum element and the magnesium element, and the content of the aluminum element is required to be higher than that of the magnesium element. Further, as the content of magnesium element in the plating layer increases, the amount of increase of aluminum element should exceed the amount of increase of magnesium element. Specifically, when the content of the magnesium element is between 0.4% and 0.7%, the aluminum element is at least 0.3% more than the magnesium element; when the content of the magnesium element is between 0.7 and 1.0 percent, the aluminum element needs to be at least 1.0 percent more than the magnesium element; when the content of the magnesium element is between 1.0 percent and 2.0 percent, the aluminum element is at least 1.5 percent more than the magnesium element.
Further, the zinc-aluminum-magnesium coating contains an eutectic structure, and the volume fraction of the eutectic structure is less than 15%.
Further, the volume fraction of the eutectic structure is less than 13%.
Further, the volume fraction of the eutectic structure is less than 10%.
The microstructure of the surface layer of the zinc-aluminum-magnesium coating also has direct influence on the blackening reaction. The surface structure of the zinc-aluminum-magnesium plating layer is generally composed of a large zinc-rich solid solution structure and a small amount of fine eutectic structures, wherein the eutectic structures contain a zinc-aluminum solid solution, a zinc-rich solid solution, and a magnesium-rich phase. Electrochemical reaction occurs between the magnesium-rich phase in the eutectic structure and the zinc-rich solid solution, the magnesium-rich phase is preferentially dissolved to release magnesium ions, and the magnesium ions are oxidized into magnesium oxide in the thin liquid film. Because the thin liquid film is insufficient in dissolved oxygen, vacancies exist at oxygen atom positions in the oxide, so that the oxide has an absorption effect on visible light and is represented as gray black. Therefore, the invention simultaneously puts control requirements on the content of the eutectic structure in the surface layer, and requires that the proportion of the eutectic structure is less than 15%, preferably less than 13%, and more preferably less than 10%.
Further, the hot-dip galvanized aluminum-magnesium coated steel further comprises an oxide film, the thickness of the oxide film is 10-100 nanometers, and the porosity of the oxide film is not more than 0.1%.
In order to further eliminate the adverse effect caused by the magnesium-rich phase in the zinc-aluminum-magnesium coating, the invention provides that the surface of the zinc-aluminum-magnesium coating steel plate is covered with a layer of oxide film, the oxide film can block the electrochemical reaction connection between the eutectic structure and the atmosphere, and weaken the diffusion speed of electrons and oxygen atoms, so that the magnesium in the magnesium-rich phase does not form oxide with the oxygen. In order to achieve a barrier against the diffusion of oxygen atoms, the oxide film must have a certain thickness. It is specified in the present invention that the thickness of the oxide film must exceed 10 nm. However, if the thickness of the oxide film is too thick, the oxide film itself absorbs light to darken the surface of the plating layer, so that the thickness of the oxide film is defined not to exceed 100 nm in the present invention.
The porosity of the oxide film is also an important factor affecting the diffusion rate of oxygen atoms in the oxide film. The diffusion rate of oxygen atoms in the pores is 10 ten thousand times higher than that in the crystal lattice of the oxide film, and therefore the present invention requires that the porosity of the oxide film be reduced to 0.1% or less, preferably the porosity should not exceed 0.02%, more preferably the porosity should not exceed 0.005%.
On the other hand, the embodiment of the method also provides the above method for preparing the hot-dip galvanized aluminum-magnesium coated steel, fig. 2 is a process step diagram of the method for preparing the hot-dip galvanized aluminum-magnesium coated steel according to the embodiment of the invention, and with reference to fig. 2, the method includes,
s1, smelting the molten steel to obtain a plate blank; sequentially heating, hot rolling, pickling and cold rolling the plate blank to obtain a cold-rolled plate;
s2, sequentially carrying out primary surface treatment and heat treatment on the cold-rolled sheet to obtain a heat-treated sheet;
s3, sequentially carrying out hot dip coating, post-treatment, secondary surface treatment and coiling on the heat-treated plate to obtain hot-dip galvanized aluminum-magnesium coated steel; the hot dip plating solution comprises the following components in percentage by mass: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities.
Depending on the content of the alloy elements, the alloy generally contains a zinc-rich solid solution phase, a zinc-aluminum solid solution phase, and a magnesium-rich phase. A thin liquid film can be formed on the surface of the zinc-aluminum-magnesium coating in the atmosphere, an electrochemical reaction is carried out between a magnesium-rich phase in the coating and a zinc-rich solid solution, and the magnesium-rich phase is preferentially dissolved to release magnesium ions. Magnesium ions are oxidized in the thin liquid film to magnesium oxide. Because the thin liquid film is insufficient in dissolved oxygen, vacancies exist at oxygen atom positions in the oxide, so that the oxide has an absorption effect on visible light and is represented as gray black. Therefore, the zinc-aluminum-magnesium coating with specific Mg content is formed on the surface of the heat treatment plate through the steps and the control of the alloy element content of the hot dip coating solution, so that Mg entering a thin liquid film is reduced, oxidized oxides of Mg in the thin liquid film are reduced, oxygen atom vacancies of the oxides are reduced, the absorption of visible light is reduced, color difference is almost eliminated, and the occurrence of black defect is avoided. .
Aluminum in the zinc-aluminum-magnesium coating mainly affects the corrosion resistance and the processability of the coating, the corrosion resistance is seriously deteriorated if the aluminum content is too low, and the processability is deteriorated if the aluminum content exceeds 4 percent, and a brittle aluminum-zinc compound intermediate phase appears in the coating. Therefore, the aluminum content in the hot dip plating bath specified in the present invention is in the range of 0.7% to 4%, preferably in the range of 1.0% to 4%, more preferably in the range of 1.0% to 3.5%.
Further, in the chemical composition, the mass fraction relation of Al and Mg is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, the content of Al-Mg is more than or equal to 1.5 percent.
The alloy component content of the hot dip plating solution determines the alloy component content of the zinc-aluminum-magnesium coating, when the aluminum element content in the zinc-aluminum-magnesium coating exceeds the magnesium element content, the solid solubility of magnesium in a zinc-rich solid solution phase and a zinc-aluminum solid solution phase is increased, and the proportion of Mg in a magnesium-rich phase is reduced, so that the Mg entering a thin liquid film is also reduced. Therefore, the invention simultaneously puts requirements on the interrelation of the aluminum element and the magnesium element, and the content of the aluminum element is required to be higher than that of the magnesium element. Further, as the content of magnesium element in the plating layer increases, the amount of increase of aluminum element should exceed the amount of increase of magnesium element. In the hot dip plating solution, when the content of the magnesium element is between 0.4 and 0.7 percent, the aluminum element is at least 0.3 percent more than the magnesium element; when the content of the magnesium element is between 0.7 and 1.0 percent, the aluminum element needs to be at least 1.0 percent more than the magnesium element; when the content of the magnesium element is between 1.0 percent and 2.0 percent, the aluminum element is at least 1.5 percent more than the magnesium element.
Further, the post-treatment comprises cooling treatment, wherein the cooling speed of the cooling treatment is 50-100 ℃/S.
The rapid cooling in the solidification process can obviously improve the solid solubility of the magnesium element in the initially solidified zinc-rich solid solution, thereby reducing the precipitation amount of eutectic structures. In practical production, the cooling speed of rapid solidification must reach more than 50 ℃/s to obviously inhibit the segregation of magnesium element from the zinc-rich solid solution into eutectic structures. However, if the cooling rate is too high, thermal stress in the plating layer becomes too large, and cracking of the plating layer tends to occur in subsequent use.
Further, the secondary surface treatment includes a surface oxidation treatment including one of: anodic oxidation treatment, chemical oxidation treatment and high-temperature oxidation treatment. And an oxide film uniformly covered on the surface of the zinc-aluminum magnesium layer can be obtained through surface oxidation treatment.
The invention discloses hot-dip galvanized aluminum-magnesium coated steel and a preparation method thereof, wherein the content of Mg in a hot-dip galvanized aluminum-magnesium coating is controlled by controlling the content of alloy elements in a hot-dip galvanizing plating solution, so that Mg entering a thin liquid film from the hot-dip galvanized aluminum-magnesium coating is reduced, the oxidized oxide of Mg in the thin liquid film is reduced, the oxygen atom vacancy of the oxide is reduced, the absorption of visible light is reduced, the color difference is almost disappeared, and the occurrence of blackening defect is avoided. Meanwhile, the invention also provides a method for controlling the volume ratio of the eutectic structure, the thickness of an oxide film and the porosity so as to further improve the blackening resistance of the hot-dip galvanized aluminum-magnesium coated steel. The hot-dip galvanized aluminum-magnesium plated steel prepared by the method has excellent blackening resistance, good corrosion resistance, convenient production and suitability for large-scale popularization.
The technical scheme of the invention is further explained by combining specific examples, wherein the technical scheme of the invention comprises 19 examples and 10 comparative examples, and the specific preparation method comprises the following steps,
s1, smelting the molten steel to obtain a plate blank; sequentially heating, hot rolling, pickling and cold rolling the plate blank to obtain a cold-rolled plate; the thickness of the cold-rolled plate is 1.50mm, the width of the cold-rolled plate is 1200mm, and the cold-rolled plate is made of CQ grades;
s2, sequentially carrying out primary surface treatment and heat treatment on the cold-rolled sheet to obtain a heat-treated sheet;
s3, sequentially carrying out hot dip coating, post-treatment, secondary surface treatment and coiling on the heat-treated plate to obtain hot-dip galvanized aluminum-magnesium coated steel, which is shown in figure 3; the thickness of the zinc-aluminum-magnesium coating of the hot-dip galvanized aluminum-magnesium coating steel is 10 microns.
The specific process parameter control of examples 1 to 19 and comparative examples 1 to 10 is detailed in tables 1 and 2, and the characteristics of the hot-dip galvanized aluminum-magnesium coated steel prepared in examples 1 to 19 and comparative examples 1 to 10 are detailed in table 3.
TABLE 1
TABLE 2
| Item | Al content/% of plating bath | Mg content/% of plating solution | Cooling Rate/. degree. C.s-1 | Secondary surface treatment |
| Example 1 | 0.7 | 0.4 | 60 | Anodic oxidation treatment |
| Example 2 | 0.8 | 0.4 | 50 | Chemical oxidation treatment |
| Example 3 | 0.9 | 0.5 | 70 | High temperature oxidation treatment |
| Example 4 | 1 | 0.6 | 50 | Anodic oxidation treatment |
| Example 5 | 1.2 | 0.6 | 50 | Chemical oxidation treatment |
| Example 6 | 1.4 | 0.6 | 70 | High temperature oxidation treatment |
| Example 7 | 1.8 | 0.7 | 70 | Anodic oxidation treatment |
| Example 8 | 2 | 0.7 | 80 | Chemical oxidation treatment |
| Example 9 | 2.3 | 0.8 | 100 | High temperature oxidation treatment |
| Example 10 | 2.8 | 1 | 50 | Anodic oxidation treatment |
| Example 11 | 3 | 1.3 | 50 | Chemical oxidation treatment |
| Example 12 | 3.1 | 1.2 | 90 | High temperature oxidation treatment |
| Example 13 | 3.5 | 1.5 | 50 | Anodic oxidation treatment |
| Example 14 | 3.8 | 1.8 | 70 | Chemical oxidation treatment |
| Example 15 | 4 | 2 | 50 | Anodic oxidation treatment |
| Example 16 | 3.8 | 2 | 50 | Chemical oxidation treatment |
| Example 17 | 3.1 | 1.5 | 60 | High temperature oxidation treatment |
| Example 18 | 2.5 | 1 | 50 | Anodic oxidation treatment |
| Example 19 | 1.7 | 0.7 | 60 | Chemical oxidation treatment |
| Comparative example 1 | 0.2 | 0.4 | 20 | High temperature oxidation treatment |
| Comparative example 2 | 0.3 | 0.7 | 30 | Anodic oxidation treatment |
| Comparative example 3 | 1.2 | 0.8 | 60 | Chemical oxidation treatment |
| Comparative example 4 | 1.5 | 0.8 | 60 | High temperature oxidation treatment |
| Comparative example 5 | 2.4 | 1.7 | 10 | Anodic oxidation treatment |
| Comparative example 6 | 3.2 | 1 | 5 | Chemical oxidation treatment |
| Comparative example 7 | 5.1 | 2.4 | 10 | Anodic oxidation treatment |
| Comparative example 8 | 4 | 2 | 5 | Chemical oxidation treatment |
| Comparative example 9 | 4.5 | 3.1 | 50 | High temperature oxidation treatment |
| Comparative example 10 | 3.5 | 2.4 | 50 | Anodic oxidation treatment |
TABLE 3
| Item | Proportion of surface eutectic structure/%) | Oxide film thickness/nm | Oxide film porosity/%) |
| Example 1 | 10 | 10 | 0.1 |
| Example 2 | 10 | 20 | 0.02 |
| Example 3 | 8 | 20 | 0.08 |
| Example 4 | 12 | 30 | 0.09 |
| Example 5 | 13 | 35 | 0.002 |
| Example 6 | 13 | 50 | 0.003 |
| Example 7 | 15 | 40 | 0.008 |
| Example 8 | 8 | 100 | 0.03 |
| Example 9 | 8 | 80 | 0.08 |
| Example 10 | 12 | 90 | 0.02 |
| Example 11 | 13 | 70 | 0.07 |
| Example 12 | 7 | 40 | 0.009 |
| Example 13 | 12 | 50 | 0.006 |
| Example 14 | 11 | 15 | 0.002 |
| Example 15 | 14 | 30 | 0.004 |
| Example 16 | 13 | 40 | 0.003 |
| Example 17 | 12 | 20 | 0.07 |
| Example 18 | 10 | 70 | 0.03 |
| Example 19 | 8 | 60 | 0.04 |
| Comparative example 1 | 16 | 5 | 0.12 |
| Comparative example 2 | 14 | 4 | 0.12 |
| Comparative example 3 | 12 | 15 | 0.7 |
| Comparative example 4 | 15 | 20 | 0.32 |
| Comparative example 5 | 19 | 20 | 0.54 |
| Comparative example 6 | 20 | 40 | 0.78 |
| Comparative example 7 | 17 | 50 | 0.08 |
| Comparative example 8 | 19 | 200 | 0.14 |
| Comparative example 9 | 16 | 300 | 0.34 |
| Comparative example 10 | 14 | 7 | 0.34 |
The thickness of the oxide film layer was measured by X-ray photoelectron spectroscopy, and the depth from the surface to the position where the oxygen atom percentage concentration was reduced to 1% was defined as the thickness of the oxide film layer.
The hot dip galvanized aluminum magnesium plated steels of examples 1 to 19, comparative examples 1 to 10, which were prepared using the process parameters in table 2, were subjected to evaluation of blackening resistance, evaluation of appearance brightness, evaluation of brittleness of the zinc aluminum magnesium plating, and evaluation of corrosion resistance.
The blackening resistance evaluation was carried out by subjecting the hot-dip galvanized aluminum-magnesium plated steel specimens prepared in examples and comparative examples to NaHCO3The treatment (soaking in 0.2mol/L NaHCO3 solution for 10mins followed by rinsing and drying) was carried out, and the mixture was left under moist heat (RH 95%, T50 ℃) for one week to observe the blackening reaction. The color difference L of the sample before and after treatment is measured by a color difference meter, and the blackening resistance of the hot-dip galvanized aluminum-magnesium coating steel is evaluated by the color difference delta L before and after treatment, namely L before the test and L after the test, the invention adopts excellent, good, qualified, poor and unaligned color difference corresponding to the difference, and the detail is shown in Table 4.
TABLE 4
| Is excellent in | △L*≤10 |
| Good effect | 10＜△L*≤12 |
| Qualified | 12＜△L*≤15 |
| Is poor | 15＜△L*≤17 |
| Difference (D) | △L*＞17 |
The evaluation of the apparent brightness was carried out by measuring hot-dip galvanized aluminum-magnesium plated steel samples prepared in examples and comparative examples using a color difference meter and evaluating the apparent brightness based on the measured chromaticity L, and the comparison of the apparent brightness and the chromaticity in the present invention is shown in Table 5.
TABLE 5
| Darker color | L＜60 |
| In general | 60≤L＜70 |
| Is brighter | L≥70 |
The brittleness evaluation of the zinc-aluminum-magnesium coating is to perform a bending test on hot-dip zinc-aluminum-magnesium coating steel samples prepared in examples and comparative examples, wherein the execution standard of the bending test is GB/T232, the bending radius is 1.5mm, and the bending angle is 180 degrees. And (3) observing the surface appearance of the outer edge of the sample after bending, wherein the corresponding relation between the surface appearance of the outer edge of the sample and the evaluation result is shown in a table 6.
TABLE 6
| Good effect | No occurrence of cracks |
| Qualified | Cracks exist within the range of 3mm from the edge part, and no cracks exist at other positions |
| Fail to be qualified | Cracks appeared outside the range of 3mm from the edge |
The corrosion resistance was evaluated by treating the hot-dip galvanized aluminum-magnesium plated steel specimens prepared in examples and comparative examples with a neutral salt spray test method specified in GB/T10125, and evaluating the corrosion resistance based on the time at which red rust occurred in the test, and the comparison between the time at which red rust occurred and the corrosion resistance evaluation standard in the present invention is shown in Table 7.
TABLE 7
| ○ | The red rust generation time exceeds 700 hours, and the corrosion resistance is excellent |
| □ | The time for red rust to appear exceeds 600 hours and is less than 700 hours, and the corrosion resistance is good |
| ■ | The time of red rust occurrence exceeds 500 hours and is less than 600 hours, and the corrosion resistance is general |
| ● | The time for red rust occurrence is less than 500 hours, and the corrosion resistance is poor |
The hot dip galvanized aluminum-magnesium plated steels prepared in examples and comparative examples were treated by the above-described methods of evaluation of blackening resistance, evaluation of brightness of appearance, evaluation of brittleness of zinc-aluminum-magnesium plating, and evaluation of corrosion resistance, and the results are shown in table 8.
TABLE 8
| Item | Anti-melanogenesis | Brightness of appearance | Brittleness of zinc-aluminum-magnesium coating | Corrosion resistance |
| Example 1 | Qualified | Is brighter | Good effect | □ |
| Example 2 | Good effect | Is brighter | Good effect | □ |
| Example 3 | Good effect | Is brighter | Good effect | □ |
| Practice ofExample 4 | Is excellent in | Is brighter | Good effect | □ |
| Example 5 | Good effect | Is brighter | Good effect | □ |
| Example 6 | Qualified | Is brighter | Good effect | □ |
| Example 7 | Good effect | Is brighter | Good effect | □ |
| Example 8 | Is excellent in | In general | Good effect | □ |
| Example 9 | Is excellent in | In general | Good effect | ○ |
| Example 10 | Qualified | In general | Good effect | ○ |
| Example 11 | Good effect | In general | Good effect | ○ |
| Example 12 | Is excellent in | Is brighter | Good effect | ○ |
| Example 13 | Qualified | Is brighter | Good effect | ○ |
| Example 14 | Qualified | Is brighter | Qualified | ○ |
| Example 15 | Qualified | Is brighter | Qualified | ○ |
| Example 16 | Qualified | Is brighter | Qualified | ○ |
| Example 17 | Qualified | Is brighter | Good effect | ○ |
| Example 18 | Good effect | In general | Good effect | ○ |
| Example 19 | Is excellent in | Is brighter | Good effect | ○ |
| Comparative example 1 | Difference (D) | Is brighter | Good effect | ● |
| Comparative example 2 | Difference (D) | Is brighter | Good effect | ■ |
| Comparative example 3 | Is poor | Is brighter | Good effect | □ |
| Comparative example 4 | Difference (D) | Is brighter | Good effect | □ |
| Comparative example 5 | Difference (D) | Is brighter | Good effect | ○ |
| Comparative example 6 | Difference (D) | Is brighter | Good effect | ○ |
| Comparative example 7 | Difference (D) | Is brighter | Fail to be qualified | ○ |
| Comparative example 8 | Difference (D) | Darker color | Fail to be qualified | ○ |
| Comparative example 9 | Is poor | Darker color | Fail to be qualified | ○ |
| Comparative example 10 | Difference (D) | Is brighter | Qualified | ○ |
As can be seen from the data in table 8, the blackening resistance of 100% of the hot dip galvanized al-mg coated steel prepared in the examples reached the acceptable level, and 21.05% thereof was at the excellent level; the appearance brightness is normal or brighter; the brittleness of the zinc-aluminum-magnesium coating reaches the qualified level by 100 percent, and 68.4 percent is in a good level; the corrosion resistance was 57.89% at an excellent level and 42.11 at a good level. The blackening resistance of the hot-dip galvanized aluminum-magnesium coated steel prepared by the comparative example is in a poor or poorer level, and most of the blackening resistance is poor; the appearance brightness is 20% darker, 80% brighter; the brittleness of the zinc-aluminum-magnesium coating is not qualified for 30 percent, and the rest is good or qualified; the corrosion resistance was at a poor level of 10%, at a normal level of 10%, at a good level of 20% and at a good level of 60%. Compared with the prior art, the hot-dip galvanized aluminum-magnesium coated steel prepared by the invention has good black deformation resistance, and also has excellent comprehensive properties of high appearance brightness, low brittleness of a zinc-aluminum-magnesium coating, corrosion resistance and the like.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. The hot-dip galvanized aluminum-magnesium coated steel is characterized by comprising a zinc-aluminum-magnesium coating, wherein the zinc-aluminum-magnesium coating comprises the following chemical components in percentage by mass: al: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities;
in the chemical components, the mass fraction relation of Al and Mg is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, Al-Mg is more than or equal to 1.5 percent;
the zinc-aluminum-magnesium coating contains an eutectic structure, the volume fraction of the eutectic structure is less than 15%, and the eutectic structure comprises a zinc-aluminum solid solution, a zinc-rich solid solution and a magnesium-rich phase.
2. A hot-dip galvanized aluminum-magnesium coated steel according to claim 1, characterized in that the volume fraction of the eutectic structure is less than 13%.
3. A hot-dip galvanized aluminum-magnesium coated steel according to claim 1, characterized in that the volume fraction of the eutectic structure is less than 10%.
4. The hot-dip galvanized aluminum-magnesium coated steel according to claim 1, further comprising an oxide film, wherein the thickness of the oxide film is 10 to 100 nm, and the porosity of the oxide film is not more than 0.1%.
5. The method for preparing hot-dip galvanized aluminum-magnesium coated steel according to any one of claims 1 to 4, characterized by comprising,
smelting molten steel to obtain a plate blank; sequentially heating, hot rolling, pickling and cold rolling the plate blank to obtain a cold-rolled plate;
sequentially carrying out primary surface treatment and heat treatment on the cold-rolled sheet to obtain a heat-treated sheet;
sequentially carrying out hot dip coating, post-treatment, secondary surface treatment and coiling on the heat-treated plate to obtain hot-dip galvanized aluminum-magnesium coated steel; in the hot dip plating, the chemical components and the mass fraction of the plating solution are as follows: al: 0.7-4%, Mg: 0.4-2%, and the balance of Zn and inevitable impurities.
6. The method for preparing hot-dip galvanized aluminum-magnesium coated steel according to claim 5, characterized in that the mass fraction relationship of Al and Mg in the chemical components is as follows:
if the content of Mg is more than or equal to 0.4 percent and less than 0.7 percent, the content of Al-Mg is more than or equal to 0.3 percent;
if the content of Mg is more than or equal to 0.7 percent and less than 1.0 percent, Al-Mg is more than or equal to 1.0 percent;
if the content of Mg is more than or equal to 1.0 percent and less than or equal to 2.0 percent, the content of Al-Mg is more than or equal to 1.5 percent.
7. The method for preparing hot-dip galvanized aluminum-magnesium coated steel according to claim 5, characterized in that the post-treatment comprises cooling treatment, and the cooling rate of the cooling treatment is 50-100 ℃/S.
8. A method for preparing a hot-dip galvanized aluminum-magnesium coated steel according to claim 5, characterized in that said secondary surface treatment comprises a surface oxidation treatment, and said surface oxidation treatment comprises one of the following: anodic oxidation treatment, chemical oxidation treatment and high-temperature oxidation treatment.
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| CN111575626A (en) * | 2020-06-08 | 2020-08-25 | 首钢集团有限公司 | Hot-dip galvanized hot-rolled steel and preparation method thereof |
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| EP4296399A1 (en) | 2022-06-23 | 2023-12-27 | ThyssenKrupp Steel Europe AG | Method for producing hot-dip coated steel sheet, and hot-dip coated steel sheet |
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