CN113025937A - Hot-dip galvanized steel plate and preparation method thereof - Google Patents
Hot-dip galvanized steel plate and preparation method thereof Download PDFInfo
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- CN113025937A CN113025937A CN202110168555.7A CN202110168555A CN113025937A CN 113025937 A CN113025937 A CN 113025937A CN 202110168555 A CN202110168555 A CN 202110168555A CN 113025937 A CN113025937 A CN 113025937A
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- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 83
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title description 8
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 125
- 239000010959 steel Substances 0.000 claims abstract description 125
- 238000007747 plating Methods 0.000 claims abstract description 118
- 239000011248 coating agent Substances 0.000 claims abstract description 102
- 238000000576 coating method Methods 0.000 claims abstract description 102
- 239000011701 zinc Substances 0.000 claims abstract description 95
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 84
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 31
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 14
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000010410 layer Substances 0.000 claims description 141
- 238000010438 heat treatment Methods 0.000 claims description 61
- 239000011777 magnesium Substances 0.000 claims description 28
- 238000004519 manufacturing process Methods 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 239000011247 coating layer Substances 0.000 claims description 18
- 239000000395 magnesium oxide Substances 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 12
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000011787 zinc oxide Substances 0.000 claims description 10
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005253 cladding Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 230000007797 corrosion Effects 0.000 abstract description 55
- 238000005260 corrosion Methods 0.000 abstract description 55
- 239000012466 permeate Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 41
- 238000000034 method Methods 0.000 description 28
- 229910052782 aluminium Inorganic materials 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 229910052749 magnesium Inorganic materials 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007774 longterm Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
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- 230000007935 neutral effect Effects 0.000 description 5
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- 238000009792 diffusion process Methods 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical compound [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
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- 230000004580 weight loss Effects 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021328 Fe2Al5 Inorganic materials 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- 229910015392 FeAl3 Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004210 cathodic protection Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
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- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
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- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/26—After-treatment
- C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention discloses a hot-dip galvanized steel sheet, which comprises a steel sheet base body, an interface layer and a plating layer, wherein the plating layer comprises: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities; the plating layer comprises a zinc plating layer and an oxidation layer; the interface layer is positioned between the steel plate substrate and the zinc coating; the oxidation layer is positioned on the surface of the zinc coating; the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni. The hot-dip galvanized steel sheet provided by the invention has good high-temperature service performance, corrosion resistance and mechanical property, the zinc volatilization phenomenon is not easy to occur, and the zinc in the coating is difficult to permeate into the steel sheet.
Description
Technical Field
The invention belongs to the technical field of steel preparation, and particularly relates to a hot-dip galvanized steel plate and a preparation method thereof.
Background
Galvanized steel sheet is a steel sheet in which molten zinc or alloy reacts with a steel sheet base to form a strong metallurgically bonded plated steel sheet. The galvanized steel sheet has the advantages of strong coating binding force, good corrosion resistance, long service life, simple manufacturing process, low product price and the like. There is an increasing demand in different industries, such as the automotive industry, the electrical industry and the construction industry. Among them, in the automobile industry, high strength steel sheets are used in a wider range in order to reduce the weight of a vehicle body. Hot formed steel is widely used because of its low forming difficulty. However, hot formed steels are press formed at high temperatures, forming temperatures in excess of 800 ℃, and forming times typically not exceeding 5 minutes. The forming temperature far exceeds the melting point temperature of a common zinc coating and also exceeds the melting point temperature of a zinc-iron alloy. Therefore, when hot forming is performed using a galvanized steel sheet, problems such as melting and volatilization of the plating layer tend to occur, and in particular, zinc in the plating layer tends to infiltrate into the steel sheet. Thus, on the one hand, the corrosion resistance of the coating is reduced, and on the other hand, the liquid zinc existing between the coating and the steel plate substrate causes the galvanized steel plate to be corroded and eroded by the zinc, so that the mechanical property is obviously reduced, namely the problem commonly called LME.
In addition, aluminum-silicon plating may also be used for the hot-formed steel sheet. However, the al-si plating layer has poor corrosion resistance, and particularly lacks cathodic protection capability, and once the steel sheet has cracks, it is more difficult to control deterioration of the corrosion phenomenon.
In the electrical industry, it is often necessary to subject galvanized steel sheets to high temperature treatment. For example, a galvanized steel sheet and a copper pipe are connected by flame welding. In this case, the surface of the galvanized steel sheet will be subjected to high temperatures exceeding 800 ℃, and the high temperature time will not generally exceed 1 minute. The temperature is far higher than the melting point temperature of the coating of the common galvanized steel sheet and also higher than the melting point temperature of the zinc-iron alloy, so that the problems of melting, volatilization and the like of the coating are easy to occur, and the corrosion resistance of the coating is reduced.
Therefore, there is a need for a hot-dip galvanized steel sheet and a method for manufacturing the same, which overcome the defects that the galvanized steel sheet has poor high-temperature service performance, the zinc volatilization phenomenon is easy to occur on the surface of the coating layer, and the zinc in the coating layer is easy to permeate into the steel sheet.
Disclosure of Invention
In view of the above problems, the present invention provides a hot-dip galvanized steel sheet and a method for manufacturing the same. The hot-dip galvanized steel plate provided by the invention has good high-temperature service performance, corrosion resistance and mechanical property, the phenomenon of zinc volatilization is not easy to occur, and zinc in the coating is difficult to permeate into the steel plate.
The technical scheme for realizing the purpose is as follows:
in one aspect of the present invention, there is provided a hot-dip galvanized steel sheet including a steel sheet base, an interface layer, and a plating layer, wherein:
the coating comprises the following components in percentage by mass: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
wherein the plating layer comprises a zinc plating layer and an oxidation layer;
the interface layer is positioned between the steel plate substrate and the zinc coating;
the oxidation layer is positioned on the surface of the zinc coating;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
In some embodiments of the present invention, the hot-dip galvanized steel sheet according to the present invention includes one or more of Ti 0.01 to 0.1%, B0.005 to 0.02%, Ca 0.002 to 0.02%, Si 0.01 to 0.5%, and Ni 0.02 to 0.2% by mass.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the interface layer includes, in mass percent: 40-65% of Al, 0-10% of Zn and the balance of iron;
the thickness of the interface layer is 1-2 microns.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the zinc coating layer includes, in mass percent: 0.4-1% of Al, 0.2-2% of Mg, less than or equal to 1% of trace alloy elements and the balance of zinc;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the oxidized layer is composed of, in mass percent: 0-10% of aluminum oxide, 30-50% of zinc oxide and the balance of magnesium oxide;
the thickness of the oxide layer is 0.01-0.5 microns.
In another aspect of the present invention, there is also provided a method of manufacturing a hot-dip galvanized steel sheet according to the present invention, including the steps of:
preparing a plating solution;
heating the plating solution to obtain a preheated plating solution;
preparing a steel plate;
heating the steel plate, and then immersing the steel plate into the preheating plating solution to obtain the steel plate with the plating layer;
carrying out heat treatment on the steel plate with the coating in the air, and then cooling to 18-31 ℃ to obtain a hot-dip galvanized steel plate;
wherein, the plating solution comprises the following components by mass percent: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the bath includes one or more of 0.01 to 0.1% by mass of Ti, 0.005 to 0.02% by mass of B, 0.002 to 0.02% by mass of Ca, 0.01 to 0.5% by mass of Si, and 0.02 to 0.2% by mass of Ni (i.e., the minor alloying element).
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the method for manufacturing a steel sheet is not limited, and methods including cold rolling, hot rolling, and the like may be used.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the temperature of the preheated plating bath is 500 ℃ or less;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheating plating solution, and the temperature of the T-the preheating plating solution is less than or equal to 10 ℃.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the temperature of the preheated plating solution is 400 to 500 ℃;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheated plating solution, and T-the temperature of the preheated plating solution is (0-5) DEG C.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 400-600 ℃ in air at a heating speed of more than or equal to 5 ℃/s, and keeping the temperature for 5-60 seconds.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 450-480 ℃ in air at a heating speed of 5-80 ℃/s, and keeping the temperature for 10-45 seconds.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 450-480 ℃ in air at a heating speed of 8-10 ℃/s, and keeping the temperature for 10-45 seconds.
One or more technical embodiments of the present invention have at least the following technical effects or advantages:
(1) the hot-dip galvanized steel plate provided by the invention has good high-temperature service performance, corrosion resistance and mechanical property, the phenomenon of zinc volatilization is not easy to occur, and zinc in the coating is difficult to permeate into the steel plate.
(2) The preparation method of the hot-dip galvanized steel sheet provided by the invention is simple and convenient to operate, low in cost and easy to implement, and the coating of the hot-dip galvanized steel sheet prepared by the method has obviously improved long-term corrosion resistance in an accelerated corrosion environment.
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 are briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
Fig. 1 shows a schematic cross-sectional microstructure of a hot-dip galvanized steel sheet 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 embodiment of the invention provides the following general ideas:
in some embodiments of the present invention, there is provided a hot-dip galvanized steel sheet including a steel sheet base, an interface layer, and a plating layer, wherein:
the coating comprises the following components in percentage by mass: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
wherein, referring to fig. 1, the plating layer comprises a zinc plating layer and an oxide layer;
the interface layer is positioned between the steel plate substrate and the zinc coating;
the oxidation layer is positioned on the surface of the zinc coating;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
The inventors of the present invention have conducted extensive studies to recognize that the addition of an appropriate amount of Al and Mg to a plating layer can significantly improve the corrosion resistance of the plating layer itself. The mechanism is mainly as follows: al and Mg will be preferentially dissolved in the atmospheric environment and form dense corrosion products on the surface of the coating. The corrosion product can stably exist in neutral and alkalescent environments, and meanwhile, the electrolyte solution on the surface of the coating can be promoted to be changed into alkalescent solution, so that the corrosion resistance of the coating of the hot-dip galvanized steel plate is improved. Meanwhile, an Fe-Al compound layer can be formed between Al in the coating and the steel plate substrate, so that the stability of the coating at high temperature can be improved, liquid zinc can be prevented from appearing between the coating and the steel plate substrate at high temperature, and the corrosion and corrosion effects of the liquid zinc on the steel plate can be reduced. Therefore, the technical scheme provided by one or more embodiments of the invention can well overcome the problem that the coating of the traditional galvanized steel sheet has LME at high temperature. Further, if the Mg content in the plating layer is too high, a large Mg — Zn phase is easily formed, which causes brittleness of the plating layer, and is easily oxidized and volatilized at high temperature to form plating layer pores, thereby deteriorating high-temperature performance. If the Al content in the coating is too high, a large amount of massive aluminum-rich phase is precipitated in the coating. And electrochemical corrosion reaction is easy to occur between the massive aluminum-rich phase and the zinc, so that the corrosion resistance is weakened. In addition, if the Al content in the coating is too high, it tends to form a discontinuous Al-rich oxide film at high temperatures, which can undermine the protective role of the coating at high temperatures. In one or more embodiments of the present invention, the coating layer is defined to include 0.5-4% Mg and 1-4% Al.
Meanwhile, a small amount of trace alloy elements can be added into the coating, and the trace alloy elements can be selected from one or more of Ti, B, Ca, Si and Ni. Wherein, a small amount of Ti element can refine Al crystal grains in the coating, thereby improving the corrosion resistance of the coating. However, excessive addition of Ti causes formation of large precipitates in the plating layer, resulting in brittleness of the plating layer and deterioration of corrosion resistance at high temperatures. The small amount of Ca element can promote the oxide film on the surface of the plating layer to be more compact, thereby improving the stability and corrosion resistance of the plating layer at high temperature. However, excessive addition of Ca element causes cracks to form on the surface of the plating layer, and deteriorates the corrosion resistance of the plating layer at high temperatures. This is caused by volume shrinkage due to a violent reaction between the oxide of the Ca element and the oxide of the Al element. The small amount of B element can also refine Al crystal grains in the plating layer, thereby improving the corrosion resistance of the plating layer. However, excessive B forms hard and coarse precipitates, which cause cracks in the coating and deteriorate the corrosion resistance of the coating at high temperatures. The Si element can prevent the formation of an excessively thick Fe-Al compound phase, which has a loose interior and cannot prevent liquid zinc from penetrating into the steel sheet at high temperatures, during hot dip coating. However, excessive addition of Si will cause deterioration of the corrosion resistance of the plating layer. This is because the Si element forms a large amount of Al — Si compound in the plating layer, causing an electrochemical corrosion phenomenon. The Ni element is a strengthening and toughening element and mainly plays a role in enhancing the high-temperature resistance of the Fe-Al compound. However, excessive addition of Ni leads to the formation of Ni-Al compounds in the coating, which in turn impairs the action of Fe-Al compounds and reduces the corrosion resistance of the coating at high temperatures. In view of this, in one or more embodiments of the present invention, it is defined that the minor alloy element is 1% or less and is selected from one or more of Ti, B, Ca, Si, and Ni.
In some embodiments of the present invention, the hot-dip galvanized steel sheet according to the present invention includes one or more of Ti 0.01 to 0.1%, B0.005 to 0.02%, Ca 0.002 to 0.02%, Si 0.01 to 0.5%, and Ni 0.02 to 0.2% by mass.
In order to further improve the high-temperature service performance, the corrosion resistance and the mechanical property of the hot-dip galvanized steel sheet, the invention further limits that the coating contains one or more than two of 0.01-0.1% of Ti, 0.005-0.02% of B, 0.002-0.02% of Ca, 0.01-0.5% of Si and 0.02-0.2% of Ni.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the interface layer includes, in mass percent: 40-65% of Al, 0-10% of Zn and the balance of iron;
the thickness of the interface layer is 1-2 microns.
In order to further improve the stability between the plating layer and the steel sheet substrate at high temperature and to prevent liquid zinc between the plating layer and the steel sheet substrate, the present inventors defined that the interface layer includes: 40-65% of Al, 0-up to10% and the balance of iron. Specifically, the interface layer is mainly made of Fe-Al compound and contains Fe2Al5、FeAl、FeAl3And the like. The compounds have higher melting point temperature and higher internal density, and are continuously distributed between the coating and the steel plate matrix, so that the penetration of liquid zinc can be obviously hindered. Wherein, if the content of zinc in the interface layer exceeds 10%, the denseness of the Fe-Al compound is deteriorated. Whereas if the Al content in the interface layer is less than 40%, an excessive amount of Fe-Zn compounds, which cannot prevent liquid zinc from corroding the steel sheet, may occur. However, if the Al content in the interface layer exceeds 65%, Fe-Al is again unstable and tends to rapidly collapse at high temperatures. Furthermore, the inventor also limits the thickness of the interface layer to 1-2 microns. This is mainly because: if the interfacial layer is too thin, dissolution and corrosion of the interfacial layer in the liquid zinc inevitably occur, and the liquid zinc infiltrates into the steel sheet along the weak grain boundary positions of the interfacial layer. If the interface layer is too thick, the brittleness of the interface layer itself may cause cracks in the interface layer, which may not prevent the penetration of liquid zinc, but may cause cracks in the plated layer of the galvanized steel sheet during hot forming.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the zinc coating layer includes, in mass percent: 0.4-1% of Al, 0.2-2% of Mg, less than or equal to 1% of trace alloy elements and the balance of zinc;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
Referring to fig. 1, it can be seen that in one or more embodiments of the present invention, a zinc coating is provided on the interface layer. The galvanized layer is a main part for enhancing the corrosion resistance of the plated layer of the hot-dip galvanized steel sheet. And a proper amount of Al and Mg are added into the zinc coating, so that the corrosion resistance of the coating can be obviously improved. The mechanism is mainly as follows: al and Mg dissolve preferentially in the atmospheric environment and form dense corrosion products on the surface of the coating. The corrosion product can stably exist in neutral and alkalescent environments, and meanwhile, the electrolyte solution on the surface of the coating can be promoted to be changed into alkalescent solution, so that the corrosion resistance of the coating of the hot-dip galvanized steel plate can be improved. According to a great deal of research by the inventor, when the Mg content in the zinc coating reaches 0.2 percent or more, the corrosion resistance of the coating in an accelerated corrosion environment can be obviously improved. Compared with a pure zinc coating, the corrosion resistance of the zinc coating provided by the invention can be improved by more than 30%. In addition, when the Al content in the galvanized layer reaches 0.4% or more, the long-term corrosion resistance of the plating layer can be further improved, and the corrosion resistance in the atmospheric environment is improved by 30% or more compared with that of a pure zinc plating layer. However, the contents of Mg and Al in the galvanized layer are not necessarily too high. If the content is too high, the melting point temperature of the zinc coating layer is too low, and liquid metal is more easily formed at high temperature. Meanwhile, the corrosion of liquid metal is obviously improved due to the excessively high contents of Mg and Al in the zinc coating, the steel plate matrix is seriously corroded, and the steel plate matrix has obvious cracks at high temperature. In view of this, in one or more embodiments of the present invention, it is defined that the zinc coating layer includes 0.4 to 1% of Al, 0.2 to 2% of Mg, 1% or less of trace alloy elements, and the balance of zinc.
In some embodiments of the present invention, in the hot-dip galvanized steel sheet according to the present invention, the oxidized layer is composed of, in mass percent: 0-10% of aluminum oxide, 30-50% of zinc oxide and the balance of magnesium oxide;
the thickness of the oxide layer is 0.01-0.5 microns.
Referring to fig. 1, in one or more embodiments of the present invention, it can be seen that an oxide layer is further coated on the surface of the zinc coating layer. The oxide layer has the function of providing stability of the surface of the coating at high temperature and preventing the coating from cracking and volatilizing at high temperature. Of course, it is difficult for the oxide layer to completely avoid deterioration of the plating layer at high temperatures, but such deterioration of the plating layer can be inhibited in a short time. The oxide layer has a high melting point temperature, and the oxide layer can be continuously distributed on the surface of the coating. In the prior art, loose and porous zinc oxide and easily broken aluminum oxide are easy to appear on the surface of a pure zinc coating at high temperature. In one or more embodiments of the present invention, the oxide layer is based on magnesium oxide and zinc oxide, plus a small amount of aluminum oxide. Among them, magnesium oxide is a dense oxide which is stable at high temperature, can maintain good ductility at high temperature, and is not easy to crack, so that the defect that zinc oxide is loose and porous and the defect that aluminum oxide is easy to break can be well compensated. If the magnesium oxide is completely used as the oxide layer, the magnesium oxide is not compatible with zinc which accounts for a large proportion of the content of the zinc coating, and obvious lattice mismatch exists between the magnesium oxide and the zinc coating, so that the oxide layer is easy to strip from the zinc coating at high temperature, and the high-temperature corrosion resistance of the coating is reduced. Therefore, a certain amount of zinc oxide is also required in the oxide layer. In addition, the oxide layer contains aluminum oxide, which is difficult to avoid because aluminum and zinc have certain solid solubility, and aluminum is an active metal and tends to diffuse outward at room temperature to form an oxide film. In view of this, the present invention provides an oxide layer comprising 0-10% of alumina, 30-50% of zinc oxide, and the balance of magnesium oxide.
In addition, if the thickness of the oxide layer is too large, cracking is likely to occur, which may adversely decrease the corrosion resistance of the plating layer. This is because: the toughness of the oxide layer is poor as a whole, and the difference of the high temperature expansion coefficient with the zinc coating is large. However, the oxide layer is too thin to meet the protection requirement of the coating, and the oxidizing gas permeates through the oxide layer to generate oxidation reaction with the zinc coating at high temperature, so that the overall performance of the coating is not favorable. Accordingly, the thickness of the oxide layer provided by the invention is 0.01-0.5 micrometer.
In another aspect of the present invention, there is also provided a method of manufacturing a hot-dip galvanized steel sheet according to the present invention, including the steps of:
preparing a plating solution;
heating the plating solution to obtain a preheated plating solution;
preparing a steel plate;
heating the steel plate, and then immersing the steel plate into the preheating plating solution to obtain the steel plate with the plating layer;
carrying out heat treatment on the steel plate with the coating in the air, and then cooling to 18-31 ℃ to obtain a hot-dip galvanized steel plate;
wherein, the plating solution comprises the following components by mass percent: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
In some embodiments of the present invention, in the method of manufacturing a hot-dip galvanized steel sheet according to the present invention, the temperature of the preheated bath is 500 ℃ or less;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheating plating solution, and the temperature of the T-the preheating plating solution is less than or equal to 10 ℃.
The inventors have found through long-term studies that preheating of the bath is necessary in the production of hot-dip galvanized steel sheets. This is because: if the temperature of the preheated plating solution is too low, solidification occurs. However, if the temperature of the preheated bath is too high, iron in the bath at a higher temperature of the steel sheet reacts rapidly with zinc in the preheated bath. Wherein the reaction rate of iron and zinc will exceed the reaction rate of iron and aluminum, thereby forming dendrite-like grown Fe-Zn grains between the steel sheet substrate and the coating. Such Fe-Zn grains have a sparse spatial structure, which hardly hinders the diffusion of liquid zinc at high temperature, and thus are not conducive to improving the high temperature performance of the coating. At the same time, the temperature at which the steel sheet is heated cannot be too high, otherwise the reaction rate of iron and zinc exceeds that of iron and aluminum. However, the temperature at which the steel sheet is heated cannot be lower than the temperature at which the bath is preheated, otherwise it is difficult to form a stable plating layer on the steel sheet during hot dip plating, which causes a problem of peeling off the surface of the plating layer. In view of this, in one or more embodiments of the present invention, it is defined that T (heating the steel sheet to the temperature T) is not less than the temperature of the preheated plating bath, and (T-the temperature of the preheated plating bath) is not more than 10 ℃.
In some embodiments of the present invention, in the method for manufacturing a hot-dip galvanized steel sheet, the temperature of the preheated plating solution is 400 to 500 ℃;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheated plating solution, and T-the temperature of the preheated plating solution is (0-5) DEG C.
In order to further improve the overall performance of the hot-dip galvanized steel sheet provided by the present invention, the inventors prefer the temperature of the preheating bath to 400 to 500 ℃ and T through a large amount of screening time.
In some embodiments of the present invention, the method of manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 400-600 ℃ in air at a heating speed of more than or equal to 5 ℃/s, and keeping the temperature for 5-60 seconds.
The inventors found through long-term studies that when a steel sheet is subjected to hot dip coating to obtain a steel sheet with the coating layer, the steel sheet with the coating layer is subjected to heat treatment in air. When this heat treatment is performed, since aluminum in the plated layer reacts more easily with iron, aluminum tends to diffuse to the interface position between the plated layer and the steel sheet substrate to form an Fe — Al compound layer. This Fe — Al compound layer is located at the interface between the plating layer and the steel sheet substrate, thereby forming a characteristic interface layer. At the same time, a part of magnesium in the plating layer diffuses to the surface of the plating layer, and reacts with oxygen in the air and an oxidizing gas such as carbon dioxide to form magnesium oxide. Meanwhile, the magnesium in the coating can reduce the original aluminum oxide on the surface of the coating into aluminum, so that an oxide film taking magnesium oxide and zinc oxide as main components is formed on the surface of the coating. For the purpose of the invention, the temperature and time for heat treatment of the steel sheet with the coating in air cannot be too low, otherwise it is difficult to achieve diffusion of the respective elements and reaction of the compounds. However, if the heating temperature is too high and the holding time is too long, dendritic Fe-Zn crystals appear at the interface between the coating and the steel sheet matrix, and the Fe-Zn crystals cannot prevent the liquid zinc from penetrating into the steel sheet matrix. Meanwhile, too much Zn element is infiltrated into the Fe-Al crystal, so that Fe-Al crystal grains are decomposed. In addition, if the heating temperature is too high and the holding time is too long, too much magnesium element is diffused to the surface of the plating layer and too much aluminum element is diffused to the interface between the plating layer and the steel sheet substrate, resulting in too little contents of magnesium element and aluminum element in the zinc plating layer, thereby lowering the corrosion resistance of the plating layer. In addition, the oxide layer on the surface of the zinc coating can also permeate excessive oxygen atoms at a high temperature for a long time, so that the oxide layer can expand, the compactness of the oxide layer is reduced, and the original protection effect is lost. In addition, the heating rate during the heat treatment also has a great influence on the structure of the coating. When the heating rate is too low, the oxide film formed on the surface of the plating layer is broken. This is due to: during the heat treatment with too slow heating speed, the diffusion speed of magnesium at the surface of the coating is lower than the inward diffusion speed of oxygen atoms, which causes the oxygen atoms to form oxide particles below the coating, and the aluminum in the oxide layer is not fully reduced. In this case, the alumina content is too high, so that the plating layer maintains the crushed state of alumina. In view of this, in one or more embodiments provided by the present invention, it is defined that the steel sheet with the coating layer is heated to 400 to 600 ℃ in air at a heating rate of 5 ℃/s or more and is maintained for 5 to 60 seconds.
In some embodiments of the present invention, the method of manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 450-480 ℃ in air at a heating speed of 5-80 ℃/s, and keeping the temperature for 10-45 seconds.
In order to further improve the comprehensive performance of the hot-dip galvanized steel sheet provided by the invention, the inventor preferably heats the steel sheet with the coating to 450-480 ℃ in air at a heating speed of 5-80 ℃/s and keeps the temperature for 10-45 seconds through a large amount of screening time.
In some embodiments of the present invention, the method of manufacturing a hot-dip galvanized steel sheet according to the present invention, the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 450-480 ℃ in air at a heating speed of 8-10 ℃/s, and keeping the temperature for 10-45 seconds.
In order to further improve the comprehensive performance of the hot-dip galvanized steel sheet, the inventor preferably heats the steel sheet with the coating to 450-480 ℃ in air at a heating rate of 8-10 ℃/s and keeps the temperature for 10-45 seconds through a large amount of screening time.
Hereinafter, the hot-dip galvanized steel sheet and the method for manufacturing the same according to the present application will be described in detail with reference to examples, comparative examples, and experimental data.
Examples
Examples 1 to 15 below hot-dip galvanized steel sheets were produced by the method for producing a hot-dip galvanized steel sheet according to the present invention, and the method included:
firstly, preparing a plating solution; wherein, the plating solution comprises the following components by mass percent: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
wherein, the plating solution comprises one or more than two of 0.01 to 0.1 percent of Ti, 0.005 to 0.02 percent of B, 0.002 to 0.02 percent of Ca, 0.01 to 0.5 percent of Si and 0.02 to 0.2 percent of Ni (namely the trace alloy elements) by mass percentage.
Secondly, heating the plating solution to obtain a preheated plating solution; wherein the temperature of the preheated plating solution is less than or equal to 500 ℃.
Thirdly, preparing a steel plate; the method for manufacturing the steel sheet is not limited, and common methods may include cold rolling, hot rolling, and the like. In examples 1 to 8 of the present invention, a cold-rolled steel sheet was used as a substrate, and in examples 9 to 15, a hot-rolled steel sheet was used as a substrate.
Fourthly, heating the steel plate, and then immersing the steel plate into the preheating plating solution to obtain the steel plate with the plating layer; wherein the steel sheet is heated to a temperature T; t is more than or equal to the temperature of the preheated plating solution, and the temperature (T-the temperature of the preheated plating solution) is less than or equal to 10 ℃.
Fifthly, carrying out heat treatment on the steel plate with the coating in the air, and then cooling to 18-31 ℃ to obtain the hot-dip galvanized steel plate; and heating the steel plate with the coating to 400-600 ℃ in air at a heating speed of more than or equal to 5 ℃/s, and keeping the temperature for 5-60 seconds.
The specific process parameters are shown in tables 1 and 2.
Table 1: the plating solutions of examples 1 to 15 of the present invention contained chemical components (%)
Table 2: preparation process parameters in embodiments 1-15 of the invention
The hot-dip galvanized steel sheet prepared in the above embodiments 1 to 15 of the present invention includes, as shown in fig. 1, a steel sheet base, an interface layer, and a plating layer; the plating layer comprises a zinc plating layer and an oxidation layer; the interface layer is positioned between the steel plate substrate and the zinc coating; the oxide layer is positioned on the surface of the zinc coating. Wherein, the coating layer comprises: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities; the coating comprises one or more of Ti 0.01-0.1%, B0.005-0.02%, Ca 0.002-0.02%, Si 0.01-0.5%, and Ni 0.02-0.2% (i.e. the trace alloy elements). The interface layer includes: 40-65% of Al, 0-10% of Zn and the balance of iron; the thickness of the interface layer is 1-2 microns. The zinc coating layer comprises: 0.4-1% of Al, 0.2-2% of Mg, less than or equal to 1% of trace alloy elements and the balance of zinc; the trace alloy element is one or more of Ti, B, Ca, Si and Ni. The oxide layer consists of the following components: 0-10% of aluminum oxide, 30-50% of zinc oxide and the balance of magnesium oxide; the thickness of the oxide layer is 0.01 to 0.5 μm.
Comparative example
The following comparative examples 1 to 15 adopt a method of producing a galvanized steel sheet, comprising:
firstly, preparing a plating solution;
and secondly, heating the plating solution to obtain a preheated plating solution.
And thirdly, preparing a steel plate.
And fourthly, heating the steel plate, and then immersing the steel plate into the preheating plating solution to obtain the steel plate with the plating layer.
And fifthly, carrying out heat treatment on the steel plate with the coating in air.
The specific process parameters in the above comparative examples are shown in tables 3 and 4.
Table 3: the plating solutions of comparative examples 1 to 15 contain chemical components (%)
Table 4: preparation Process parameters in comparative examples 1 to 15
The plated steel sheets prepared in examples 1 to 15 and comparative examples 1 to 15 were subjected to evaluation of plating corrosion resistance and high temperature resistance.
The corrosion resistance evaluation of the coating adopts a neutral salt spray corrosion test, and the coating corrosion weight loss rate of the coated steel plate under the neutral salt spray corrosion test environment is measured.
The high temperature resistance evaluation method comprises the following steps: the coated steel sheets prepared in examples 1 to 15 and comparative examples 1 to 15 were placed in a high temperature furnace at 800 ℃, baked for 2 minutes, and then taken out. Then, each steel sheet after baking was evaluated for corrosion resistance and steel sheet cracking.
And evaluating the corrosion weight loss rate of each baked steel plate by adopting a neutral salt spray corrosion test.
And observing the cracks of the steel plate at the interface between the coating and the steel plate matrix by adopting a metallographic method, and measuring the maximum length of the cracks. The results of the experimental evaluation are shown in Table 5.
Table 5: results of evaluating the corrosion resistance and high temperature resistance of the plating layer of the plated steel sheets prepared in examples 1 to 15 and comparative examples 1 to 15
Referring to fig. 1, it can be seen from the above examples and comparative examples that the hot-dip galvanized steel sheet and the method for manufacturing the same according to the present invention have at least the following advantageous effects:
(1) according to the hot-dip galvanized steel sheet provided by the invention, the chemical components in the coating layer, the interface layer, the zinc coating layer and the oxide layer in the coating layer are limited, and the thickness of each layer is limited, so that the prepared galvanized steel sheet has good high-temperature service performance, corrosion resistance and mechanical property, the zinc volatilization phenomenon is not easy to occur, and the zinc in the coating layer is difficult to permeate into the steel sheet.
(2) According to the preparation method of the hot-dip galvanized steel plate, the temperature of the preheating plating solution, the heating temperature of the steel plate and the heat treatment parameters of the steel plate with the coating are limited, and the plating solution containing specific chemical components is matched, so that the obtained hot-dip galvanized steel plate can well overcome the LME problem of the coating of the galvanized steel plate at high temperature in the prior art, and can well overcome the defect that the coating has cracks in the hot-dip galvanized steel plate in the hot forming process. The hot-dip galvanized steel sheet provided by the invention has excellent corrosion resistance after high temperature and remarkably improved long-term corrosion resistance in an accelerated corrosion environment. Compared with pure zinc-plated steel plates in the prior art, the corrosion resistance of the coating of the hot-dip galvanized steel plate provided by the invention can be improved by more than 30%.
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 (10)
1. A hot-dip galvanized steel sheet, includes steel sheet base member, boundary layer and cladding material, its characterized in that:
the coating comprises the following components in percentage by mass: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
wherein the plating layer comprises a zinc plating layer and an oxidation layer;
the interface layer is positioned between the steel plate substrate and the zinc coating;
the oxidation layer is positioned on the surface of the zinc coating;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
2. The hot-dip galvanized steel sheet according to claim 1, wherein the coating layer contains one or more of 0.01 to 0.1% by mass of Ti, 0.005 to 0.02% by mass of B, 0.002 to 0.02% by mass of Ca, 0.01 to 0.5% by mass of Si, and 0.02 to 0.2% by mass of Ni.
3. The hot-dip galvanized steel sheet according to claim 1, wherein the interface layer includes, in mass percent: 40-65% of Al, 0-10% of Zn and the balance of iron;
the thickness of the interface layer is 1-2 microns.
4. The hot-dip galvanized steel sheet according to claim 1, wherein the galvanized layer comprises, in mass percent: 0.4-1% of Al, 0.2-2% of Mg, less than or equal to 1% of trace alloy elements and the balance of zinc;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
5. Hot-dip galvanized steel sheet according to claim 1, characterized in that the oxide layer consists, in mass percentage, of: 0-10% of aluminum oxide, 30-50% of zinc oxide and the balance of magnesium oxide;
the thickness of the oxide layer is 0.01-0.5 microns.
6. Method of manufacturing a hot-dip galvanized steel sheet according to any one of claims 1 to 5, comprising the steps of:
preparing a plating solution;
heating the plating solution to obtain a preheated plating solution;
preparing a steel plate;
heating the steel plate, and then immersing the steel plate into the preheating plating solution to obtain the steel plate with the plating layer;
carrying out heat treatment on the steel plate with the coating in the air, and then cooling to 18-31 ℃ to obtain a hot-dip galvanized steel plate;
wherein, the plating solution comprises the following components by mass percent: 0.5-4% of Mg, 1-4% of Al, less than or equal to 1% of trace alloy elements, and the balance of zinc and inevitable impurities;
the micro-alloy elements are selected from one or more of Ti, B, Ca, Si and Ni.
7. The method of manufacturing a hot-dip galvanized steel sheet according to claim 6, characterized in that the temperature of the preheated bath is 500 ℃ or less;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheating plating solution, and the temperature of the T-the preheating plating solution is less than or equal to 10 ℃.
8. The method of manufacturing a hot-dip galvanized steel sheet according to claim 7, wherein the temperature of the preheated bath is 400 to 500 ℃;
the heating the steel sheet includes:
heating the steel sheet to a temperature T;
wherein T is more than or equal to the temperature of the preheated plating solution, and T-the temperature of the preheated plating solution is (0-5) DEG C.
9. The method of manufacturing a hot-dip galvanized steel sheet according to claim 6 or 7, wherein the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 400-600 ℃ in air at a heating speed of more than or equal to 5 ℃/s, and keeping the temperature for 5-60 seconds.
10. The method of manufacturing a hot-dip galvanized steel sheet according to claim 9, wherein the heat-treating the steel sheet with the plating layer in air includes:
and heating the steel plate with the coating to 450-480 ℃ in air at a heating speed of 5-80 ℃/s, and keeping the temperature for 10-45 seconds.
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| CN114214540A (en) * | 2021-11-26 | 2022-03-22 | 首钢集团有限公司 | Galvanized steel sheet with excellent coating quality and coating and preparation method thereof |
| CN114182188A (en) * | 2021-12-02 | 2022-03-15 | 首钢集团有限公司 | Hot-dip zinc-aluminum-magnesium-coated steel plate and preparation method thereof |
| CN114182188B (en) * | 2021-12-02 | 2023-07-11 | 首钢集团有限公司 | Hot-dip galvanized aluminum magnesium coated steel plate and preparation method thereof |
| WO2023241515A1 (en) * | 2022-06-13 | 2023-12-21 | 宝山钢铁股份有限公司 | Steel sheet plated with zinc-aluminum-magnesium-calcium alloy by means of hot dipping and manufacturing method therefor |
| CN115287565A (en) * | 2022-07-13 | 2022-11-04 | 首钢集团有限公司 | Coated steel plate and preparation method thereof |
| CN115287565B (en) * | 2022-07-13 | 2023-10-13 | 首钢集团有限公司 | Coated steel plate and preparation method thereof |
| CN116590640A (en) * | 2023-05-17 | 2023-08-15 | 宝山钢铁股份有限公司 | Zinc-based coated steel plate, zinc-based hot stamping part and manufacturing method thereof |
| CN116641009A (en) * | 2023-05-17 | 2023-08-25 | 宝山钢铁股份有限公司 | Zinc-based plated steel sheet having excellent corrosion resistance, hot stamped member, and method for manufacturing same |
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