CN115491544A - Zinc-aluminum-magnesium coating and zinc-aluminum-magnesium coating steel plate - Google Patents
Zinc-aluminum-magnesium coating and zinc-aluminum-magnesium coating steel plate Download PDFInfo
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- CN115491544A CN115491544A CN202211122186.9A CN202211122186A CN115491544A CN 115491544 A CN115491544 A CN 115491544A CN 202211122186 A CN202211122186 A CN 202211122186A CN 115491544 A CN115491544 A CN 115491544A
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- -1 Zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 97
- 238000000576 coating method Methods 0.000 title claims abstract description 79
- 239000011248 coating agent Substances 0.000 title claims abstract description 78
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 50
- 239000010959 steel Substances 0.000 title claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 6
- 229910052718 tin Inorganic materials 0.000 claims abstract description 6
- 238000007747 plating Methods 0.000 claims description 55
- 239000011701 zinc Substances 0.000 claims description 54
- 239000000463 material Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910000611 Zinc aluminium Inorganic materials 0.000 claims 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical compound [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000007888 film coating Substances 0.000 abstract description 2
- 238000009501 film coating Methods 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 41
- 230000007797 corrosion Effects 0.000 description 26
- 238000005260 corrosion Methods 0.000 description 26
- 239000011777 magnesium Substances 0.000 description 17
- 238000000034 method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000005496 eutectics Effects 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011575 calcium Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 229910007981 Si-Mg Inorganic materials 0.000 description 3
- 229910008316 Si—Mg Inorganic materials 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910017706 MgZn Inorganic materials 0.000 description 1
- 229910003310 Ni-Al Inorganic materials 0.000 description 1
- 229910004349 Ti-Al Inorganic materials 0.000 description 1
- 229910004692 Ti—Al Inorganic materials 0.000 description 1
- 229910007570 Zn-Al Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000010960 cold rolled steel Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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
- 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
Abstract
The invention provides a zinc-aluminum-magnesium coating and a zinc-aluminum-magnesium coating steel plate, belonging to the technical field of coating, wherein the zinc-aluminum-magnesium coating comprises the following components: al, mg, a third metal element, zn and inevitable impurity elements; the third metal element includes at least one of Sn and Pb; the zinc-aluminum-magnesium coating contains Mg-Zn compound; the average size of the Mg-Zn compound is less than 5um. The zinc-aluminum-magnesium coating is applied to zinc-aluminum-magnesium coated steel, so that the problem that the surface color is dark easily when the conventional zinc-aluminum-magnesium coated steel is used in the atmosphere can be effectively solved. Meanwhile, the operation of film coating treatment on the surface of the zinc-aluminum-magnesium coated steel plate is avoided, and the production cost is saved.
Description
Technical Field
The application relates to the technical field of coating, in particular to a zinc-aluminum-magnesium coating and a zinc-aluminum-magnesium coating steel plate.
Background
The zinc-aluminum-magnesium coated steel plate is a novel high corrosion-resistant alloy coated steel plate. The plating layer is developed on the basis of the traditional pure zinc plating layer, and magnesium element and aluminum element are added into the plating layer, so that the plane corrosion resistance and the notch corrosion resistance of the plating layer are obviously improved, and the plating layer can be widely used for manufacturing external wall surfaces of automobiles, household appliances, buildings and the like.
However, when the conventional zinc-aluminum-magnesium plated steel sheet is used in the atmosphere, the surface color tends to be dark.
Disclosure of Invention
The embodiment of the application provides a zinc-aluminum-magnesium coating, zinc-aluminum-magnesium coating steel sheet to when solving current zinc-aluminum-magnesium coating steel sheet and using in the atmosphere, appear the technical problem that the surface color darkens easily.
In a first aspect, an embodiment of the present application provides a zinc aluminum magnesium plating layer, where the zinc aluminum magnesium plating layer includes the following components:
al, mg, a third metal element, zn and inevitable impurity elements;
the third metal element includes at least one of Sn and Pb;
the zinc-aluminum-magnesium coating contains Mg-Zn compound;
the average size of the Mg-Zn compound is less than 5um.
Further, the zinc-aluminum-magnesium coating comprises the following components in percentage by mass:
al:4 to 25 percent; mg:2 to 8 percent; a third metal element: 0.0005 to 0.5 percent; the balance of Zn and inevitable impurity elements.
Further, the zinc-aluminum-magnesium plating layer also comprises: at least one of Ni, fe, mn, ca, ti and Si.
Further, the Ni is less than or equal to 0.01 percent by mass fraction.
Further, the Fe is less than or equal to 0.1 percent in mass fraction.
Further, the Mn is less than or equal to 0.5 percent in mass fraction.
Further, the Ca is less than or equal to 0.01 percent in mass fraction.
Further, the Ti is less than or equal to 0.05 percent by mass fraction.
Further, the Si is less than or equal to 2 percent in mass fraction.
In a second aspect, embodiments of the present application provide a zinc-aluminum-magnesium coated steel sheet, which includes a steel sheet substrate and a coating layer attached to a surface of the steel sheet substrate;
the plating layer is the zinc-aluminum-magnesium plating layer of the first aspect.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
the embodiment of the application provides a zinc-aluminum-magnesium coating, on one hand, the zinc-aluminum-magnesium coating contains an Mg-Zn compound with the average size less than 5um, and the Mg-Zn compound is kept stable in the air due to the small size of the Mg-Zn compound, so that Mg is not dissolved and separated out easily, and does not react with oxygen in the air, thereby obviously inhibiting the defect that the surface of the zinc-aluminum-magnesium coating becomes dark in the air; on the other hand, sn and/or Pb elements are added into the zinc-aluminum-magnesium coating, so that the surface energy of the Zn-rich phase can be obviously reduced, the Zn-rich phase can grow fast and thick, the Mg-Zn phase occupies the growth position of the Mg-Zn phase, the Mg-Zn phase forms particles with small volume, and the phenomenon that the surface color of the existing zinc-aluminum-magnesium coating steel is dark is further avoided. Therefore, the zinc-aluminum-magnesium coating is applied to the zinc-aluminum-magnesium coated steel, so that the problem that the surface color is easy to darken when the conventional zinc-aluminum-magnesium coated steel is used in the atmosphere can be effectively solved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive labor.
Fig. 1 is a microstructure diagram of a zinc-aluminum-magnesium plating layer in a zinc-aluminum-magnesium plated steel sheet according to an embodiment of the present application.
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.
The zinc-aluminum-magnesium coated steel plate is a novel high corrosion-resistant alloy coated steel plate. The plating layer is developed on the basis of the traditional pure zinc plating layer, and magnesium element and aluminum element are added into the plating layer, so that the plane corrosion resistance and the notch corrosion resistance of the plating layer are obviously improved, and the plating layer can be widely used for manufacturing external wall surfaces of automobiles, household appliances, buildings and the like.
However, when the conventional zinc-aluminum-magnesium plated steel sheet is used in the atmosphere, the surface color tends to be dark. Therefore, a special film is coated on the surface of the plating layer by adopting a surface treatment technology so as to avoid the phenomenon of darkening of the surface color. However, this method still has its drawbacks. Because the surface treatment causes a significant increase in production costs while the surface-coated film is easily damaged during the processing, transportation, storage, etc. of the steel sheet, thereby losing its effect.
In order to solve the technical problems, the embodiment of the invention provides the following general ideas:
in a first aspect, an embodiment of the present application provides a zinc-aluminum-magnesium coating, which includes the following components:
al, mg, a third metal element, zn and unavoidable impurity elements;
the third metal element includes at least one of Sn and Pb;
the zinc-aluminum-magnesium coating contains Mg-Zn compound;
the average size of the Mg-Zn compound is less than 5um.
The embodiment of the application provides a zinc-aluminum-magnesium coating, on one hand, the zinc-aluminum-magnesium coating contains an Mg-Zn compound with the average size less than 5um, and the Mg-Zn compound is kept stable in the air due to the small size of the Mg-Zn compound, so that Mg is not dissolved and separated out easily, and does not react with oxygen in the air, thereby obviously inhibiting the defect that the surface of the zinc-aluminum-magnesium coating becomes dark in the air; on the other hand, sn and/or Pb elements are added into the zinc-aluminum-magnesium coating, so that the surface energy of the Zn-rich phase can be obviously reduced, the Zn-rich phase can grow fast and thick, the Mg-Zn phase occupies the growth position of the Mg-Zn phase, the Mg-Zn phase forms particles with small volume, and the phenomenon that the surface color of the existing zinc-aluminum-magnesium coating steel is dark is further avoided. Therefore, the zinc-aluminum-magnesium coating is applied to the zinc-aluminum-magnesium coating steel, and the problem that the surface color is darkened easily when the conventional zinc-aluminum-magnesium coating steel is used in the atmosphere can be effectively solved. Meanwhile, the operation of film coating treatment on the surface of the zinc-aluminum-magnesium coated steel plate is avoided, and the production cost is saved.
In the present application, the term "Mg-Zn compound" means specifically MgZn 2 And Mg 2 Zn 11 。
As an implementation manner of the embodiment of the present invention, the zinc-aluminum-magnesium plating layer comprises the following components by mass:
al:4 to 25 percent; mg:2 to 8 percent; a third metal element: 0.0005 to 0.5 percent; the balance of Zn and inevitable impurity elements.
The design principle of each element and dosage of the zinc-aluminum-magnesium coating in the application is as follows:
the Al element in the zinc-aluminum-magnesium coating can provide high-quality corrosion resistance for the coating, because the Al element can form compact oxides and compact hydroxides on the surface during corrosion. In order to obtain high corrosion resistance, the mass fraction of Al element in the plating layer should not be less than 4%. However, if the content of the aluminum element exceeds 25%, the problem of cracking of the plating layer occurs, which in turn leads to a decrease in the corrosion resistance of the plating layer.
The corrosion resistance of the coating can be obviously improved by adding 2% of Mg element into the coating, and the mechanism is that Mg in the coating can be preferentially dissolved into a water film on the surface of the coating in the atmospheric environment and reacts with dissolved carbon dioxide in the water film to precipitate a compact protective film, the protective film can stably exist in neutral and alkalescent environments, and meanwhile, electrolyte solution on the surface of the coating can be promoted to be alkalescent solution, so that the corrosion resistance of the coating is improved. However, if the content of Mg element is too high, a large amount of relatively coarse Mg-Zn compounds appear in the coating, and the compounds cause cracking of the coating and reduce the corrosion resistance and appearance quality of the coating. Therefore, the Mg content in the plating layer does not exceed 8%.
The aluminum-magnesium coating contains Mg-Zn compounds with the average size less than 5um, and the Mg-Zn compounds are stable in the air and are not easy to dissolve out due to the small size of the Mg-Zn compounds, so that the Mg does not react with oxygen in the air, and the defect that the surface of the zinc-aluminum-magnesium coating becomes dark in the air can be obviously inhibited; on the other hand, the Mg — Zn compound is present in both the binary eutectic structure and the ternary eutectic structure in the zinc-aluminum-magnesium plating layer. The so-called binary eutectic structure is a eutectic structure formed by the Mg-Zn compound and the Zn-rich phase. The ternary eutectic structure is a eutectic structure formed by a Mg-Zn compound, a Zn-rich phase and an Al-rich phase. Sn and/or Pb elements are added into the zinc-aluminum-magnesium coating, so that the surface energy of the Zn-rich phase can be obviously reduced, the Zn-rich phase can grow fast and thick, the Mg-Zn phase occupies the growth position of the Mg-Zn phase, the Mg-Zn phase forms particles with small volume, and the phenomenon that the surface color of the existing zinc-aluminum-magnesium coating steel is dark is further avoided. Therefore, the zinc-aluminum-magnesium coating is applied to the zinc-aluminum-magnesium coated steel, so that the problem that the surface color is easy to darken when the conventional zinc-aluminum-magnesium coated steel is used in the atmosphere can be effectively solved.
The addition of Sn and/or Pb elements as the third metal element to the zinc-aluminum-magnesium plating layer significantly reduces the surface energy of the Zn-rich phase. This is because both Sn and Pb elements tend to aggregate on the surface of the Zn-rich phase, lowering the surface energy. To achieve this object, the sum of the mass fractions of the Sn element and the Pb element (i.e., the total amount of the third metal element) is not less than 0.0005%. However, if the amount is too large, a significant Sn or Pb-containing precipitate is formed in the Zn-Al magnesium plating layer. Such precipitates become cathodes during the corrosion process, accelerate the corrosion reaction of the surface, and reduce the corrosion resistance of the plating layer. Therefore, the third metal element does not exceed 0.5%.
As an implementation manner of the embodiment of the present invention, the zinc-aluminum-magnesium plating layer further includes: at least one of Ni, fe, mn, ca, ti and Si.
As an implementation mode of the embodiment of the invention, the Ni is less than or equal to 0.01 percent by mass fraction.
The Ni element is easy to combine with Al in the zinc-aluminum-magnesium coating to form needle-shaped Ni-Al compound, thereby occupying the space formed by the Mg-Zn compound and reducing the size of the Mg-Zn compound. However, too much addition results in brittleness of the plating layer and also lowers the corrosion resistance of the plating layer. Therefore, the amount of addition is in the range of 0 to 0.01%.
As an implementation mode of the embodiment of the invention, the Fe is less than or equal to 0.1 percent in mass fraction.
Fe element is easy to combine with Al in the zinc-aluminum-magnesium coating to form granular Fe-Al compound, thereby occupying the space formed by Mg-Zn compound and reducing the size of the Mg-Zn compound. However, too much addition results in brittleness of the plating layer and also lowers the corrosion resistance of the plating layer. Therefore, the amount of addition is in the range of 0 to 0.1%.
As an implementation mode of the embodiment of the invention, the Mn is less than or equal to 0.5 percent in mass fraction.
Mn element is easy to combine with Zn in the zinc-aluminum-magnesium coating to form MnZn 13 Thereby having the effect of refining grains. However, too much addition results in a decrease in the corrosion resistance of the plating. Therefore, the amount of addition is in the range of 0 to 0.5%.
As an implementation mode of the embodiment of the invention, the Ca is less than or equal to 0.01 percent in mass fraction.
The Ca element is easy to combine with oxygen in the air in the zinc-aluminum-magnesium coating to form calcium oxide, so that the reaction of the oxygen in the air and Mg in the zinc-aluminum-magnesium coating is inhibited to form Mg oxide, and the color change of the coating surface is inhibited. However, addition of too much Ca results in the occurrence of quality defects of irregularities on the surface of the plating layer, and therefore the range of addition is 0 to 0.01%.
As an implementation mode of the embodiment of the invention, the Ti is less than or equal to 0.05 percent in mass fraction.
Ti element is easy to combine with Al in the zinc-aluminum-magnesium coating to form granular Ti-Al compound, which has the effect of refining grains. However, too much addition results in brittleness of the plating layer and also lowers the corrosion resistance of the plating layer. Therefore, the amount of addition is in the range of 0 to 0.05%.
As an implementation mode of the embodiment of the invention, the Si is less than or equal to 2 percent in mass fraction.
Si element can be combined with Mg in the zinc-aluminum-magnesium coating to form a Si-Mg compound, and the reaction of oxygen in the air and the Mg in the zinc-aluminum-magnesium coating is inhibited to form Mg oxide, so that the surface color change of the coating is inhibited. However, if Si is added too much, the Si-Mg compound itself becomes too large in size, and the Si-Mg compound becomes unstable, deteriorating the darkening of the plating surface. Therefore, the amount of addition is in the range of 0 to 2%.
In a second aspect, embodiments of the present application provide a zinc-aluminum-magnesium coated steel sheet, which includes a steel sheet substrate and a coating layer attached to a surface of the steel sheet substrate;
the plating layer is the zinc-aluminum-magnesium plating layer of the first aspect.
The application provides a zinc-aluminum-magnesium coated steel sheet, owing to adopt the first aspect zinc-aluminum-magnesium coating as the cladding material, this zinc-aluminum-magnesium coated steel sheet can effectively avoid current zinc-aluminum-magnesium coated steel when using in the atmosphere, appears the problem that the surface colour darkened easily, has performance such as excellent corrosion resisting property simultaneously.
In the present application, the zinc-aluminum-magnesium plated steel sheet can be prepared by batch hot dip plating and continuous hot dip plating, and the zinc-aluminum-magnesium plated layer of the first aspect is obtained by controlling alloy element components in the plating solution (i.e., controlling the plating solution to be the same as the elements and the amounts in the zinc-aluminum-magnesium plated layer of the first aspect). In addition, the zinc-aluminum-magnesium plated steel sheet can also be obtained by chemical vapor deposition, physical vapor deposition, chemical plating and other techniques. In the preparation process of the zinc-aluminum-magnesium plating steel plate provided by the application, except for the need of controlling the alloy element components in the plating solution, other preparation steps and parameters can be performed according to the conventional process, and repeated description is not repeated in the application document.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental methods of the following examples, which are not specified under specific conditions, are generally determined according to national standards. If there is no corresponding national standard, it is carried out according to the universal international standard, the conventional conditions, or the conditions recommended by the manufacturer.
Examples 1 to 7 and comparative examples 1 to 5 provide zinc-aluminum-magnesium coated steel sheets, the characteristics of the coatings in each example are shown in table 1, the specific preparation process is continuous hot dip coating, and the specific process comprises the following steps: cleaning the surface of a hot-rolled or cold-rolled steel plate, then sending the cleaned surface into an annealing furnace, heating the cleaned surface to a high-temperature state in a slight oxidation or reduction atmosphere, cooling the cleaned surface to the temperature close to the temperature of a plating solution after heat preservation, then directly immersing the cleaned surface into a molten zinc-aluminum-magnesium alloy plating solution, wherein the component range of the alloy plating solution is the same as that of a plating layer, leaving the plating solution for completing hot dip plating of the plated steel plate, and cooling the plated steel plate to the room temperature to obtain the zinc-aluminum-magnesium plated steel plate.
TABLE 1 parameters of Zn-Al-Mg plating in each example
Test example
This example provides zinc-aluminum-magnesium-plated steel sheets of examples 1 to 7 and comparative examples 1 to 5, and the results of the tests are shown in Table 2.
The corrosion evaluation method comprises the steps of putting the galvanized steel sheet into a cyclic corrosion test box, carrying out a one-week cyclic corrosion test, measuring the mass loss of the plating layer before and after the test, and evaluating the corrosion resistance of the plating layer by using the mass loss amount in unit area. The less mass loss, the better the corrosion resistance. The zinc-aluminum-magnesium coated steel plate is placed in an acid solution with the pH value of 5 to be soaked for 60 seconds, then is rinsed by deionized water, and is dried by drying air flow, the surface brightness of the zinc-aluminum-magnesium coated steel plate is measured to be L0, then a sample is placed in a damp and hot environment, the damp and hot temperature is 50 ℃, the relative humidity is 60%, the sample is placed for 120 hours, then is taken out to be measured to be L1, L1 is subtracted from L0 to obtain the brightness change delta L, and the larger delta L is, the more serious the coating darkening tendency is indicated.
Table 2 results of performance test of each example
The microstructure of the Al-Mg-Zn coating in the Al-Mg-Zn coated steel sheet obtained in example 1 is shown in FIG. 1, and the size of Mg-Zn compound in the Al-Mg-Zn coating is not more than 5um.
It is understood that the endpoints of the ranges and any values disclosed herein are not limited to the precise range or value and that such ranges or values are to be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, 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. In addition, the term "and/or" appearing herein is only one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B, may represent: a exists alone, A and B exist simultaneously, and B exists alone.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The zinc-aluminum-magnesium coating is characterized by comprising the following components:
al, mg, a third metal element, zn and inevitable impurity elements;
the third metal element includes at least one of Sn and Pb;
the zinc-aluminum-magnesium coating contains Mg-Zn compound;
the average size of the Mg-Zn compound is less than 5um.
2. The zinc aluminum magnesium coating of claim 1, wherein the zinc aluminum magnesium coating comprises the following composition in mass fraction:
al:4 to 25 percent; mg:2 to 8 percent; a third metal element: 0.0005 to 0.5 percent; the balance of Zn and inevitable impurity elements.
3. The zinc aluminum magnesium coating of claim 1 or 2, further comprising: at least one of Ni, fe, mn, ca, ti and Si.
4. The zinc-aluminum magnesium coating according to claim 3, characterized in that Ni is 0.01% or less in mass fraction.
5. The zinc-aluminum magnesium coating of claim 3, wherein Fe is 0.1% or less in mass fraction.
6. The zinc-aluminum-magnesium coating of claim 3, wherein Mn is 0.5% or less by mass.
7. The zinc-aluminum magnesium plating layer of claim 3, wherein the Ca content is 0.01% by mass or less.
8. The zinc-aluminum magnesium coating of claim 3, wherein the Ti is 0.05% or less by mass.
9. The zinc-aluminum magnesium coating according to claim 3, characterized in that Si is not more than 2% by mass.
10. A zinc-aluminum-magnesium coated steel sheet is characterized by comprising a steel sheet base material and a coating attached to the surface of the steel sheet base material;
the coating is a zinc aluminium magnesium coating as claimed in any one of claims 1 to 9.
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| WO2021199953A1 (en) * | 2020-03-30 | 2021-10-07 | 日本製鉄株式会社 | Hot dip plated steel sheet |
| US20220145425A1 (en) * | 2019-04-19 | 2022-05-12 | Nippon Steel Corporation | Plated steel sheet |
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