CN114107860B - Zinc-aluminum alloy coating material for inhibiting liquid metal embrittlement and improving wear resistance in high-strength steel hot forming process and preparation method thereof - Google Patents
Zinc-aluminum alloy coating material for inhibiting liquid metal embrittlement and improving wear resistance in high-strength steel hot forming process and preparation method thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 242
- 239000010959 steel Substances 0.000 title claims abstract description 242
- 239000000956 alloy Substances 0.000 title claims abstract description 172
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 151
- 239000011248 coating agent Substances 0.000 title claims abstract description 134
- 238000000576 coating method Methods 0.000 title claims abstract description 134
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 57
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 30
- 230000002401 inhibitory effect Effects 0.000 title claims abstract description 24
- 229910000611 Zinc aluminium Inorganic materials 0.000 title description 2
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 title description 2
- 239000011701 zinc Substances 0.000 claims abstract description 167
- 238000007747 plating Methods 0.000 claims abstract description 143
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 116
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 112
- -1 zinc-aluminum-magnesium Chemical compound 0.000 claims abstract description 55
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 239000011777 magnesium Substances 0.000 claims abstract description 46
- 229910052718 tin Inorganic materials 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000003618 dip coating Methods 0.000 claims abstract description 23
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000002474 experimental method Methods 0.000 claims abstract description 18
- 229910020830 Sn-Bi Inorganic materials 0.000 claims abstract description 13
- 229910018728 Sn—Bi Inorganic materials 0.000 claims abstract description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 66
- 239000003795 chemical substances by application Substances 0.000 claims description 66
- 239000007864 aqueous solution Substances 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 238000001816 cooling Methods 0.000 claims description 45
- 229910018134 Al-Mg Inorganic materials 0.000 claims description 43
- 229910018467 Al—Mg Inorganic materials 0.000 claims description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 34
- 229910019074 Mg-Sn Inorganic materials 0.000 claims description 34
- 229910019382 Mg—Sn Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 34
- 239000011780 sodium chloride Substances 0.000 claims description 33
- 239000000843 powder Substances 0.000 claims description 25
- 239000007787 solid Substances 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 230000002378 acidificating effect Effects 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 24
- 238000005303 weighing Methods 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 21
- 238000005498 polishing Methods 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 230000005764 inhibitory process Effects 0.000 claims description 9
- 229910019021 Mg 2 Sn Inorganic materials 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000003929 acidic solution Substances 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 238000000861 blow drying Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 8
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000005554 pickling Methods 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 6
- 229910017706 MgZn Inorganic materials 0.000 claims description 5
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- 238000001764 infiltration Methods 0.000 claims description 5
- 239000000155 melt Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 abstract description 19
- 238000001514 detection method Methods 0.000 abstract description 8
- 230000035515 penetration Effects 0.000 abstract description 8
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- 238000003856 thermoforming Methods 0.000 abstract description 3
- 230000000452 restraining effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 36
- 239000002585 base Substances 0.000 description 22
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 10
- 229910052749 magnesium Inorganic materials 0.000 description 10
- 229910000838 Al alloy Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 238000005261 decarburization Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
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- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
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- 230000003595 spectral effect Effects 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 229910000734 martensite Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
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- 238000012360 testing method Methods 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 1
- 229910017708 MgZn2 Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
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- 238000011946 reduction process Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
- 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
- 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
- C23C2/30—Fluxes or coverings on molten baths
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention discloses a zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from embrittling in a high-strength steel hot forming process and a preparation method thereof, and provides a Zn-Al-Mg-Sn-Bi alloy coating material with excellent wear resistance. The invention adds Sn and Bi, the alloy plating layer comprises 0.2-5.0% of Al, 2.6-4.0% of Mg, 0-4.0% of Sn, 0-4.0% of Bi and the balance of Zn and unavoidable impurities according to mass percentage. In the hot forming process of advanced high-strength steel, the invention provides a restraining effect for embrittling a steel plate matrix caused by liquid zinc penetration; on the other hand, the coating also provides excellent wear resistance coating and reduces the wear amount in the thermoforming process. The invention provides an alloy coating material which can inhibit the embrittlement of liquid metal and provide excellent wear resistance for advanced high-strength steel through hot dip coating experiments, heat treatment experiments, cross section structure observation of the coating, mechanical tensile property detection, hardness detection and friction experiment detection of the coating respectively.
Description
Technical Field
The invention relates to a coating material and a preparation method thereof, in particular to a coating material for inhibiting liquid metal embrittlement in the hot stamping forming process of an advanced high-strength steel plate, a preparation method thereof and an immersion plating method for improving the wear resistance of the coating in the hot stamping forming process, wherein the immersion plating method effectively increases the fluidity of the coating liquid in the hot immersion plating process, reduces the surface tension of the coating liquid, improves the wettability and improves the surface quality and the mechanical property of the coating.
Background
The problems of energy consumption and environmental pollution in the travel fields of automobiles and the like are reduced, and the problems of energy consumption and environmental pollution in various countries and automobile industries in the world are faced with serious challenges.
Automobile weight reduction is one of effective ways for realizing energy conservation and emission reduction of automobiles, and along with the promotion of automobile weight reduction process, the application of advanced high-strength steel to the automobile industry is becoming more and more popular.
The advanced high-strength steel not only can lighten the automobile and achieve the aim of energy conservation and emission reduction of the automobile, but also can improve the collision safety performance of the automobile, so that more and more high-strength steel plates are applied to the manufacture of parts and structural members of the automobile by enterprises at present.
At present, the parts in the automobile body fully utilize the hot forming stamping parts for advanced high-strength steel, so that the weight of the automobile body is reduced, and the collision safety performance of the automobile body is improved.
In order to solve the problems of decarburization and oxidation scaling of the surface of a steel plate, corrosion resistance of a hot formed part and the like in the process of directly hot stamping an advanced high-strength steel bare plate, a high-strength steel plating technology is introduced.
The high-strength steel zinc-based coating can solve the decarburization and oxidation problems occurring during the hot forming of the bare plate, and can also provide excellent corrosion resistance and wear resistance. However, the zinc-based coating is melted in the hot forming process and penetrates into the steel plate matrix, brittle failure of the steel plate is caused after stress is applied, and cracks are generated between the hot forming piece and the die due to friction in the hot forming process of the traditional high-strength steel zinc-based coating, and the cracks propagate to the steel plate matrix. Patent document CN 105648273a discloses that 0.3 to 0.5wt.% of W, 0.5 to 0.8wt.% of Ti and patent document CN110512118a disclose that 0.1 to 0.6wt.% of Cr, 0.2 to 1.0wt.% of Ti and 0.5 to 2.5wt.% of Cu are added to the basis of zinc-aluminum-magnesium plating to improve the surface quality, hardness and the like of the plating, but the surface quality of the material and the prevention of embrittlement of liquid metal generated in the hot forming process of high-strength steel cannot be considered, and the performance and quality of the plating cannot meet the requirements of the automobile industry. At present, how to solve or inhibit the problem of metal embrittlement caused by reducing the liquid zinc of a high-strength steel zinc-based coating, and the problem of friction cracking caused between a hot formed part and a die have become important points of research, and development of a coating applied to hot forming is highly demanded, so that the surface quality of the coating is improved, and the problems of embrittlement and friction cracking caused by liquid metal are prevented.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a zinc-aluminum-magnesium-based alloy coating material for inhibiting the brittleness caused by liquid metal in the hot forming process of high-strength steel and a preparation method thereof, wherein the fluidity and wettability of a plating solution are improved by adding low-content aluminum, magnesium, tin and bismuth elements into a traditional zinc-based coating so as to improve the surface quality of the coating; the liquid zinc embrittlement of the advanced high-strength steel zinc-based plating layer in hot forming is suppressed, and the abrasion resistance and corrosion resistance are improved. The tin element is added, and the Fe-Al alloy layer in the coating is thicker on the basis of the zinc-aluminum-magnesium coating, so that molten liquid zinc can be delayed to enter the steel plate matrix, and brittle failure of the steel plate matrix can be avoided during hot forming; tin and magnesium elements are added to form fine Mg-Zn phases and Mg-Sn phases, so that the hardness and wear resistance of the surface of a plating layer can be improved, and the loss caused by friction between a formed part and a die in the thermoforming process can be reduced; the magnesium element is added, and the magnesium element and the zinc element form an Mg-Zn compound, so that the corrosion resistance of the plating layer is further improved, the bismuth element is added, the fluidity of the plating solution in the hot dip plating process is effectively increased, the surface tension of the plating solution is reduced, the wettability is improved, and the surface quality and the mechanical property of the plating layer are improved.
In order to achieve the above purpose, the invention adopts the following technical scheme:
A zinc aluminum magnesium base alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel is Zn-Al-Mg alloy, zn-Al-Mg-Sn alloy or Zn-Al-Mg-Sn-Bi alloy, and has the following composition and weight percentage: al:0.2 to 5.0 percent; mg:2.6 to 4 percent; sn:0 to 4.0 percent, bi:0 to 4.0 percent, and the balance of Zn and unavoidable impurities.
Preferably, the zinc aluminum magnesium base alloy coating material comprises the following components in percentage by weight: zn:83.0 to 96.9 percent; al:0.2 to 5.0 percent; mg:2.6 to 4.0 percent; sn:0 to 4.0 percent; bi:0 to 4.0 percent and the balance of unavoidable impurities.
Preferably, the zinc aluminum magnesium base alloy coating material comprises the following components in percentage by weight: zn:83.0 to 93.7 percent; al:0.2 to 3.5 percent; mg:2.8 to 4.0 percent; sn:0 to 0.8 percent; bi:0 to 4.0 percent and the balance of unavoidable impurities.
Preferably, the zinc aluminum magnesium base alloy coating material comprises the following components in percentage by weight: al:0.2 to 3.5 percent; mg:2.8 to 4 percent; sn:0 to 4.0 percent; bi:0 to 4.0 percent, and the balance of Zn and unavoidable impurities.
Preferably, in forming the zinc-aluminum magnesium base alloy plating layer on the surface of the high-strength steel, an Fe-Al suppression layer having a thickness of not less than 0.5 μm is formed, the Fe-Al suppression layer including Fe 2Al5 phase. In the invention, a thicker Fe-Al inhibition layer is formed in a tin-rich zinc-based coating formed on the surface of steel. In the invention, in the formation of a tin-rich zinc-based coating on the surface of steel, mg element, zn and Sn element form fine Mg 2Zn11、MgZn2 or Mg 2 Sn phases respectively.
Preferably, the zinc aluminum magnesium base alloy plating layer is formed on the surface of the high-strength steel and comprises at least one of Mg 2 Sn phase, mg 2Zn11 phase and MgZn 2 phase.
Preferably, in the method, in forming the tin-rich zinc-based coating on the surface of the steel, the surface quality of the coating is more smooth.
Preferably, the hardness Hv of the zinc-aluminum-magnesium base alloy coating material is not lower than 150. Further preferably, the hardness Hv of the zinc-aluminum-magnesium-based alloy plating material is not lower than 170.
A preparation method of zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel comprises the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: al:0.2 to 5.0 percent; mg:2.6 to 4 percent; the balance of Zn and unavoidable impurities, and Al blocks, mg blocks and Zn blocks are used as raw materials;
a-1, preparation of a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
a-2, smelting and preparing alloy according to raw materials with a set formula in a resistance furnace under the protection of a covering agent;
Preparation of Al-Mg master alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
a-4, preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for at least 2 hours after the Zn blocks are completely melted, then starting adding the Al-Mg intermediate alloy prepared in the step a-3), keeping the temperature for at least 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; pouring the zinc-rich zinc-based coating alloy material into a mould for cooling and forming to prepare a tin-rich zinc-based coating alloy material;
b. And (3) hot dip plating:
Step 1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the concentration of NaOH in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, the concentration of NaCO 3 mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath kettle, heated to not lower than 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is not lower than 5 wt%, the urotropine mass percentage concentration of the acidic aqueous solution is not lower than 0.5 wt%, washing the surface of the steel subjected to alkali washing with deionized water and absolute ethyl alcohol in sequence, drying, and then putting the steel into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to be not lower than 630 ℃, the reduction atmosphere is the atmosphere of mixed gas of N 2 and H 2, wherein the volume percentage of H 2 in the mixed gas is not lower than 10vol.%, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment of the step 6 is completed, immersing the steel into the molten Zn-Al-Mg hot-dip coating solution prepared in the step 1, and carrying out hot dip coating for 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
A preparation method of zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel comprises the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: al:0.2 to 5.0 percent; mg:2.6 to 4 percent; sn is less than or equal to 4.0 percent, and the balance is Zn and unavoidable impurities, wherein Al blocks, mg blocks, sn blocks and Zn blocks are used as raw materials;
1) Preparing a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for at least 2 hours after the Zn blocks are completely melted, then starting to add the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for at least 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for at least 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; pouring the zinc-rich zinc-based coating alloy material into a mould for cooling and forming to prepare a tin-rich zinc-based coating alloy material;
b. And (3) hot dip plating:
step 1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the concentration of NaOH in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, the concentration of NaCO 3 mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath kettle, heated to not lower than 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is not lower than 5 wt%, the urotropine mass percentage concentration of the acidic aqueous solution is not lower than 0.5 wt%, washing the surface of the steel subjected to alkali washing with deionized water and absolute ethyl alcohol in sequence, drying, and then putting the steel into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to be not lower than 630 ℃, the reduction atmosphere is the atmosphere of mixed gas of N 2 and H 2, wherein the volume percentage of H 2 in the mixed gas is not lower than 10vol.%, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment in the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
A preparation method of zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel comprises the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: al:0.2 to 5.0 percent; mg:2.6 to 4 percent; sn is less than or equal to 4.0 percent, bi is less than or equal to 4.0 percent, and the balance is Zn and unavoidable impurities, and Al blocks, mg blocks, sn blocks, bi blocks and Zn blocks are taken as raw materials;
1) Preparing a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparation of Al-Bi intermediate alloy:
step 1: taking the rest Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: heating to 600-700 ℃, preserving heat until the Al blocks are completely melted, then gradually adding Bi blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Bi intermediate alloy;
6) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for at least 2 hours after the Zn blocks are completely melted, then starting to add the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for at least 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for at least 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; then adding the Al-Bi intermediate alloy prepared in the step 5), preserving heat for at least 1h, stirring to obtain Zn-Al-Mg-Sn-Bi alloy melt, pouring the melt into a mould, and cooling and forming to prepare a tin-rich zinc-based plating alloy material;
b. And (3) hot dip plating:
step1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn-Bi hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the concentration of NaOH in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, the concentration of NaCO 3 mass percent of the mixed alkaline aqueous solution is not lower than 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath kettle, heated to not lower than 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is not lower than 5 wt%, the urotropine mass percentage concentration of the acidic aqueous solution is not lower than 0.5 wt%, washing the surface of the steel subjected to alkali washing with deionized water and absolute ethyl alcohol in sequence, drying, and then putting the steel into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to be not lower than 630 ℃, the reduction atmosphere is the atmosphere of mixed gas of N 2 and H 2, wherein the volume percentage of H 2 in the mixed gas is not lower than 10vol.%, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment of the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn-Bi hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
Preferably, the following elements are weighed and prepared according to the composition and weight percentage of the elements required for preparing the target zinc-aluminum-magnesium-based alloy coating material: al:0.2 to 5.0 percent; mg:2.6 to 4 percent; sn:0.8 to 4.0 percent, bi is less than or equal to 4.0 percent, and the balance is Zn and unavoidable impurities.
The zinc-aluminum-magnesium-tin-bismuth alloy coating material provided by the invention can inhibit the brittleness of liquid metal and has excellent wear resistance in the advanced high-strength steel hot forming process.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. The invention provides the method for inhibiting the embrittlement of the liquid metal in the hot forming process of the high-strength steel, which has excellent surface quality, hardness and the like, and has great research significance; the invention can inhibit the metal embrittlement caused by the liquid zinc of the high-strength steel zinc-based coating, prevent the occurrence of friction cracks generated between a hot forming part and a die, is suitable for the coating in hot forming, improves the surface quality of the coating, and prevents the problems of the embrittlement and the friction cracks of the liquid metal.
2. The tin-rich zinc-based coating has the main core effects that: firstly, the fluidity of the plating solution in the hot dip plating process is improved, the tension of the surface of the plating solution is reduced, the wettability is improved, and the surface quality of a plating layer is improved; secondly, the liquid zinc generated in the hot forming process of the advanced high-strength steel zinc-based coating is inhibited from being brittle; thirdly, a coating material with excellent wear resistance is improved during hot stamping forming; fourthly, providing a coating material with excellent corrosion resistance for advanced high-strength steel;
3. According to the invention, low-content Al and Mg elements are added into the traditional zinc-based plating solution, so that an Fe-Al inhibition layer is formed to inhibit brittle failure caused by penetration of liquid zinc into a steel plate in a hot forming process;
4. According to the invention, the Sn element is added, so that a thicker Fe-Al inhibition layer is formed between the interface of the steel plate and the plating layer in the hot dip plating process, and the brittle failure phenomenon caused by penetration of liquid zinc into the steel plate in the hot forming process is inhibited;
5. The addition of Sn element can generate a tiny Mg 2 Sn phase with Mg element, and the tiny Mg 2 Sn phase can improve the hardness and the wear resistance of the surface of the plating layer;
6. The Mg element and the Zn element can form Mg 2Zn11 and MgZn 2 phases with good corrosion resistance, so that the corrosion resistance of the coating is further improved.
7. The Bi element is added in the invention, so that the fluidity of the plating solution in the hot dip plating process can be effectively increased, the surface tension of the plating solution is reduced, the wettability is improved, and the surface quality and the mechanical property of the plating layer are improved.
Drawings
FIG. 1 is a graph of microscopic morphology and spectral scan of a Zn-3.5wt.% Al-2.8wt.% Mg plating in accordance with an embodiment of the present invention.
FIG. 2 is a graph of the micro-topography of an example Zn-3.5wt.% Al-2.8wt.% Mg-0.8wt.% Sn plating of the invention.
FIG. 3 is a graph of hardness testing of example one Zn-3.5wt.% Al-2.8wt.% Mg and example two Zn-3.5wt.% Al-2.8wt.% Mg-0.8wt.% Sn plating of the invention.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
Embodiment one:
In this embodiment, a zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel is a zn—al—mg alloy, having the following composition and weight percentage: 93.7% of Zn; al:3.5%; mg:2.8%; the balance being unavoidable impurities.
In this embodiment, a method for preparing a zinc aluminum magnesium base alloy coating material for inhibiting liquid metal embrittlement in a hot forming process of high-strength steel includes the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: 3.5wt.% of Al, 2.8wt.% of Mg, and the balance Zn and unavoidable impurities, wherein Al blocks, mg blocks and Zn blocks are used as raw materials;
a-1, preparation of a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
a-2, smelting and preparing alloy according to raw materials with a set formula in a resistance furnace under the protection of a covering agent;
Preparation of Al-Mg master alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
a-4, preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for 2 hours after the Zn blocks are completely melted, then starting adding the Al-Mg intermediate alloy prepared in the step a-3), keeping the temperature for 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; pouring the zinc-rich zinc-based coating alloy material into a mould for cooling and forming to prepare a tin-rich zinc-based coating alloy material;
b. And (3) hot dip plating:
Step 1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the mass percent concentration of NaOH of the mixed alkaline aqueous solution is 5 wt%, the mass percent concentration of NaCO 3 of the mixed alkaline aqueous solution is 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath, heated to 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is 5wt.%, the urotropine mass percentage concentration of the acidic aqueous solution is 0.5wt.%, the surface of the steel subjected to alkali washing treatment is washed by deionized water and absolute ethyl alcohol in sequence and then dried, and then the steel is put into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to 630 ℃, the reduction atmosphere is the mixed gas atmosphere of N 2 and H 2, wherein the mixed gas contains 10vol.% of H 2, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment of the step 6 is completed, immersing the steel into the molten Zn-Al-Mg hot-dip coating solution prepared in the step 1, and carrying out hot dip coating for 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
Experimental detection analysis:
The coated base material piece was taken out of the cooling water to obtain the intended Zn-3.5wt.% Al-2.8wt.% Mg alloy coating material. The embodiment solves the problems that the brittle failure of the steel plate is caused by the penetration of liquid zinc into the steel plate matrix in the hot forming process of the advanced high-strength steel zinc-based coating and the excellent corrosion resistance is provided. Al and Mg elements are added into the plating solution, so that an Fe-Al inhibition layer is formed to inhibit brittle failure of the steel plate caused by penetration of liquid zinc into the steel plate in the hot forming process; and by adding Mg element, the Mg element reacts with Zn element in the plating solution in the hot dip plating process to form Mg 2Zn11 and MgZn 2 phases, so that the corrosion resistance of the plating layer is further improved. The micro morphology and spectral scanning of Zn-3.5wt.% Al-2.8wt.% Mg-based zinc-based coating are shown in FIG. 1.
The heat treatment method of the aluminum-rich zinc-based coating material comprises the following steps:
in order to obtain the liquid zinc infiltration condition of a coating of the steel plate after hot dip plating under the heat treatment process, the steel plate is put into a vertical resistance furnace for heat treatment experiments, and the heat treatment temperature is 400-930 ℃. The specific experimental steps are as follows:
Step 1: cutting a steel plate sample into 15mm multiplied by 15mm, and processing a round hole with the diameter of 3mm at the position 3mm away from the edge for taking an experimental sample;
Step 2: heating the vertical furnace to 930 ℃, measuring the position corresponding to the temperature in the hearth, and placing a graphite crucible filled with water below the vertical furnace;
step 3: placing the sample with the high-temperature alloy wire at a position corresponding to the temperature in the furnace body from the top of the vertical resistance furnace, and reaching the corresponding temperature according to the corresponding time in the measured temperature curve;
Step 4: and after the heat treatment time is up, opening a furnace door below the vertical furnace, cutting off alloy wires above the furnace door, and feeding the sample into a crucible for water cooling to finish water quenching.
The method for detecting the infiltration condition of the liquid zinc after the heat treatment of the aluminum-rich zinc-based coating material comprises the following steps:
step 1: taking each group of samples after heat treatment, and cutting the samples into a size suitable for a scanning electron microscope sample holder by using a linear cutting instrument;
Step 2: bonding each group of cut samples on a scanning electron microscope sample base by using conductive adhesive, and observing the section of a coating of the heat-treated samples by adopting a scanning electron microscope (SEM+EDS) provided with an X-ray spectrometer;
step 3: determining the phase composition of the plating layer and the cut section of the sample by adopting an X-ray diffractometer (XRD), wherein the scanning speed is 4 degrees/min;
Step 4: observing the element distribution of the cut section of the sample in the plating layer by adopting Electron Probe Microscopic Analysis (EPMA);
step 5: carrying out layer-by-layer analysis of surface chemical components on the cut sections of the plating layer and the sample by adopting a glow discharge emission atomic spectrometer (GDMS);
Step 6: a Transmission Electron Microscope (TEM) was used to observe more subtle tissue structures in the coating and in the cut section of the sample.
The method for detecting the mechanical properties of the steel plate after the heat treatment of the aluminum-rich zinc-based coating material comprises the following steps:
In order to obtain the cracking behavior of the base plate in the hot forming process of the steel plate after hot dip plating, a Gleeble 3500 thermal simulation tester is adopted to carry out a uniaxial hot stretching experiment on the steel plate, and the specific experimental steps are as follows:
Step 1: heating the heat-treated steel plate to a target temperature of 930 ℃ in a Gleeble 3500 thermal simulation testing machine at a heating speed of 10 ℃/s, preserving heat for 30s, and then carrying out 40% strain at a strain rate of 0.5s -1;
step 2: after the strain is finished, quenching the steel plate by using compressed air at a cooling speed exceeding 60 ℃/s to obtain a martensitic structure with ultra-high strength;
step 3: carrying out hot stretching on the steel plate along the rolling direction, breaking the steel plate after the hot stretching is finished, analyzing the fracture morphology of the steel plate, obtaining a crack sample of the steel plate, and identifying and analyzing the crack morphology and microstructure in the crack sample;
Step 4: preparing a crack sample from a hot-dip plated steel plate hot-tensile sample by adopting a metallographic sample preparation means, and carrying out analysis on crack morphology and microstructure after grinding and polishing the sample;
step 5: observing the morphology and the structure of the crack by adopting a scanning electron microscope (SEM+EDS) provided with an X-ray energy spectrometer;
Step 6: observing element distribution of the plating layer and the substrate at the crack by adopting Electron Probe Microscopic Analysis (EPMA);
Step 7: cutting and analyzing the microstructure of the interface between the coating at the crack and the substrate by adopting a dual-beam Focused Ion Beam (FIB) and a field emission transmission electron microscope (FE-TEM);
step 8: and analyzing the elongation and tensile strength of the steel plate coated with the aluminum-rich zinc-based coating after hot dip coating by combining a stress-strain curve provided on the Gleeble 3500 thermal simulation tester.
Referring to fig. 3, the hardness Hv of the zinc-aluminum-magnesium base alloy coating material of this embodiment is not lower than 150. The aluminum-rich zinc-based coating is coated on the hot stamping steel plate, so that the problems of decarburization and oxide peeling of the surface of the steel plate in the hot stamping processing process can be solved, and the corrosion resistance of the steel plate can be improved. In the embodiment, aiming at the situation that liquid zinc generated in the hot forming process permeates into the steel plate to cause brittle fracture of the matrix, the Al element is added to form the Fe-Al alloy layer, and the Fe-Al alloy layer can inhibit contact between the liquid zinc melted by high temperature influence and the steel plate matrix in the hot forming process, so that the brittle fracture of the steel plate matrix can be avoided in the hot forming process.
Embodiment two:
this embodiment is substantially the same as the first embodiment, and is characterized in that:
In the embodiment, a zinc aluminum magnesium base alloy coating material for inhibiting liquid metal embrittlement in the hot forming process of high-strength steel is a Zn-Al-Mg-Sn alloy, and has the following composition and weight percentage: 92.9wt.% Zn, al:3.5%; mg:2.8%; sn:0.8% and the balance of unavoidable impurities.
In this embodiment, a method for preparing a zinc aluminum magnesium base alloy coating material for inhibiting liquid metal embrittlement in a hot forming process of high-strength steel includes the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
the preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: 92.9wt.% Zn; 3.5wt.% Al; 2.8wt.% of Mg, 0.8wt.% of Sn, and the balance of unavoidable impurities, wherein Al blocks, mg blocks, sn blocks and Zn blocks are used as raw materials;
1) Preparing a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for 2 hours after the Zn blocks are completely melted, then starting adding the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; pouring the zinc-rich zinc-based coating alloy material into a mould for cooling and forming to prepare a tin-rich zinc-based coating alloy material;
b. And (3) hot dip plating:
step 1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the mass percent concentration of NaOH of the mixed alkaline aqueous solution is 5 wt%, the mass percent concentration of NaCO 3 of the mixed alkaline aqueous solution is 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath, heated to 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is 5wt.%, the urotropine mass percentage concentration of the acidic aqueous solution is 0.5wt.%, the surface of the steel subjected to alkali washing treatment is washed with deionized water and absolute ethyl alcohol in sequence and then dried, and then the steel is put into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to 630 ℃, the reduction atmosphere is the mixed gas atmosphere of N 2 and H 2, wherein the mixed gas contains 10vol.% of H 2, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment in the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
Experimental detection analysis:
the coated base material piece was taken out of the cooling water to obtain the intended Zn-3.5wt.% Al-2.8wt.% Mg-0.8wt.% Sn aluminum-rich zinc-based coating material. The embodiment solves the problems that the brittle failure of the steel plate is caused by the penetration of liquid zinc into the steel plate matrix in the hot forming process of the advanced high-strength steel zinc-based coating and the excellent corrosion resistance is provided. Al and Mg elements are added into the plating solution, so that an Fe-Al inhibition layer is formed to inhibit brittle failure of the steel plate caused by penetration of liquid zinc into the steel plate in the hot forming process; by adding Sn element, the Sn element reacts with Zn element in the plating solution to form fine Mg 2 Sn phase in the hot dip plating process, so that the surface hardness and the wear resistance of the plating layer can be improved; and by adding Mg element, the Mg element reacts with Zn element in the plating solution in the hot dip plating process to form Mg 2Zn11 and MgZn 2 phases, so that the corrosion resistance of the plating layer is further improved. The micro-morphology and spectral scanning of Zn-3.5wt.% Al-2.8wt.% Mg-0.8wt.% Sn-rich zinc-based coating are shown in FIG. 2. In the formation of zinc-aluminum-magnesium base alloy plating layer on the surface of high-strength steel, fe-Al inhibition layer with thickness not less than 0.5 μm is formed, and the Fe-Al inhibition layer comprises Fe 2Al5 phase.
The heat treatment method of the tin-rich zinc-based coating material comprises the following steps:
in order to obtain the liquid zinc infiltration condition of a coating of the steel plate after hot dip plating under the heat treatment process, the steel plate is put into a vertical resistance furnace for heat treatment experiments, and the heat treatment temperature is 400-930 ℃. The specific experimental steps are as follows:
Step 1: cutting a steel plate sample into 15mm multiplied by 15mm, and processing a round hole with the diameter of 3mm at the position 3mm away from the edge for taking an experimental sample;
Step 2: heating the vertical furnace to 930 ℃, measuring the position corresponding to the temperature in the hearth, and placing a graphite crucible filled with water below the vertical furnace;
step 3: placing the sample with the high-temperature alloy wire at a position corresponding to the temperature in the furnace body from the top of the vertical resistance furnace, and reaching the corresponding temperature according to the corresponding time in the measured temperature curve;
Step 4: and after the heat treatment time is up, opening a furnace door below the vertical furnace, cutting off alloy wires above the furnace door, and feeding the sample into a crucible for water cooling to finish water quenching.
The method for detecting the infiltration condition of liquid zinc after heat treatment of the tin-rich zinc-based coating material comprises the following steps:
step 1: taking each group of samples after heat treatment, and cutting the samples into a size suitable for a scanning electron microscope sample holder by using a linear cutting instrument;
Step 2: bonding each group of cut samples on a scanning electron microscope sample base by using conductive adhesive, and observing the section of a coating of the heat-treated samples by adopting a scanning electron microscope (SEM+EDS) provided with an X-ray spectrometer;
step 3: determining the phase composition of the plating layer and the cut section of the sample by adopting an X-ray diffractometer (XRD), wherein the scanning speed is 4 degrees/min;
Step 4: observing the element distribution of the cut section of the sample in the plating layer by adopting Electron Probe Microscopic Analysis (EPMA);
step 5: carrying out layer-by-layer analysis of surface chemical components on the cut sections of the plating layer and the sample by adopting a glow discharge emission atomic spectrometer (GDMS);
Step 6: a Transmission Electron Microscope (TEM) was used to observe more subtle tissue structures in the coating and in the cut section of the sample.
The method for detecting the mechanical properties of the steel plate after the heat treatment of the tin-rich zinc-based coating material comprises the following steps:
In order to obtain the cracking behavior of the base plate in the hot forming process of the steel plate after hot dip plating, a Gleeble 3500 thermal simulation tester is adopted to carry out a uniaxial hot stretching experiment on the steel plate, and the specific experimental steps are as follows:
Step 1: heating the heat-treated steel plate to a target temperature of 930 ℃ in a Gleeble 3500 thermal simulation testing machine at a heating speed of 10 ℃/s, preserving heat for 30s, and then carrying out 40% strain at a strain rate of 0.5s -1;
step 2: after the strain is finished, quenching the steel plate by using compressed air at a cooling speed exceeding 60 ℃/s to obtain a martensitic structure with ultra-high strength;
step 3: carrying out hot stretching on the steel plate along the rolling direction, breaking the steel plate after the hot stretching is finished, analyzing the fracture morphology of the steel plate, obtaining a crack sample of the steel plate, and identifying and analyzing the crack morphology and microstructure in the crack sample;
Step 4: preparing a crack sample from a hot-dip plated steel plate hot-tensile sample by adopting a metallographic sample preparation means, and carrying out analysis on crack morphology and microstructure after grinding and polishing the sample;
step 5: observing the morphology and the structure of the crack by adopting a scanning electron microscope (SEM+EDS) provided with an X-ray energy spectrometer;
Step 6: observing element distribution of the plating layer and the substrate at the crack by adopting Electron Probe Microscopic Analysis (EPMA);
Step 7: cutting and analyzing the microstructure of the interface between the coating at the crack and the substrate by adopting a dual-beam Focused Ion Beam (FIB) and a field emission transmission electron microscope (FE-TEM);
step 8: and analyzing the elongation and tensile strength of the steel plate coated with the tin-rich zinc-based coating after hot dip coating by combining a stress-strain curve provided on the Gleeble 3500 thermal simulation tester.
Referring to fig. 3, the hardness Hv of the zinc-aluminum-magnesium base alloy coating material of this embodiment is not lower than 150. The tin-rich zinc-based coating is coated on the hot stamping steel plate, so that the problems of decarburization and oxide peeling of the surface of the steel plate in the hot stamping processing process can be solved, and the corrosion resistance of the steel plate can be improved. Aiming at the situation that liquid zinc generated in the hot forming process permeates into a steel plate to cause brittle fracture of a matrix, an Al element is added to form an Fe-Al alloy layer, and the Fe-Al alloy layer can inhibit contact between the liquid zinc melted under the influence of high temperature and the steel plate matrix in the hot forming process, so that the brittle fracture of the steel plate matrix can be avoided in the hot forming process; in addition, sn element is introduced in the embodiment, so that the Sn element can be combined with Zn element in the plating solution in the hot dip plating process to generate a fine Mg 2 Sn phase, the abrasion loss between the surface of a formed part and a die in the hot forming process can be reduced, and cracks generated by abrasion can be further controlled to extend into a steel plate matrix.
Embodiment III:
this embodiment is substantially identical to the previous embodiment, except that:
In this embodiment, a zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel is a Zn-Al-Mg-Sn-Bi alloy having the following composition and weight percentage: 85.7wt.% Zn, al:3.5%; mg:2.8%; sn:4.0%, bi:4.0% and the balance of unavoidable impurities.
A preparation method of zinc-aluminum-magnesium-based alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel comprises the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: 85.7wt.% Zn; 3.5wt.% Al; 2.8wt.% of Mg, 4.0wt.% of Sn, 4.0wt.% of Bi, and the balance of unavoidable impurities, wherein Al blocks, mg blocks, sn blocks, bi blocks and Zn blocks are used as raw materials;
1) Preparing a covering agent:
The zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50wt.% CaCl 2, 45wt.% NaCl,5.0wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparation of Al-Bi intermediate alloy:
step 1: taking the rest Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: heating to 600-700 ℃, preserving heat until the Al blocks are completely melted, then gradually adding Bi blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Bi intermediate alloy;
6) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for 2 hours after the Zn blocks are completely melted, then starting adding the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; then adding the Al-Bi intermediate alloy prepared in the step 5), carrying out heat preservation for 1h, stirring to obtain Zn-Al-Mg-Sn-Bi alloy melt, pouring the melt into a mould, and cooling and forming to prepare a tin-rich zinc-based plating alloy material;
b. And (3) hot dip plating:
step1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn-Bi hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove the oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the mass percent concentration of NaOH of the mixed alkaline aqueous solution is 5 wt%, the mass percent concentration of NaCO 3 of the mixed alkaline aqueous solution is 5 wt%, and the mixed alkaline aqueous solution is placed into a constant-temperature water bath, heated to 80 ℃ and kept at a temperature, and the oil stains on the surface of steel are removed by using the prepared alkaline solution, so that the surface of the steel is subjected to alkaline washing treatment;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is 5wt.%, the urotropine mass percentage concentration of the acidic aqueous solution is 0.5wt.%, the surface of the steel subjected to alkali washing treatment is washed with deionized water and absolute ethyl alcohol in sequence and then dried, and then the steel is put into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to 630 ℃, the reduction atmosphere is the mixed gas atmosphere of N 2 and H 2, wherein the mixed gas contains 10vol.% of H 2, and the surface of the steel is continuously subjected to reduction treatment for 5-10min;
Step 7: after the reduction treatment of the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn-Bi hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
The hardness Hv of the zinc-aluminum-magnesium base alloy coating material of the embodiment is not lower than 150. The tin-rich zinc-based coating is coated on the hot stamping steel plate, so that the problems of decarburization and oxide peeling of the surface of the steel plate in the hot stamping processing process can be solved, and the corrosion resistance of the steel plate can be improved. Aiming at the situation that liquid zinc generated in the hot forming process permeates into a steel plate to cause brittle fracture of a matrix, an Al element is added to form an Fe-Al alloy layer, and the Fe-Al alloy layer can inhibit contact between the liquid zinc melted under the influence of high temperature and the steel plate matrix in the hot forming process, so that the brittle fracture of the steel plate matrix can be avoided in the hot forming process; in addition, sn element is introduced in the embodiment, so that the Sn element can be combined with Zn element in the plating solution in the hot dip plating process to generate a fine Mg 2 Sn phase, the abrasion loss between the surface of a formed part and a die in the hot forming process can be reduced, and cracks generated by abrasion can be further controlled to extend into a steel plate matrix. The Bi element is added in the embodiment, so that the mobility of the plating solution in the hot dip plating process can be effectively increased, the surface tension of the plating solution is reduced, the wettability is improved, and the surface quality and the mechanical property of the plating layer are improved.
In summary, the above embodiments suppress embrittlement of liquid metal during hot forming and provide a zn—al-Mg-based alloy plating material excellent in wear resistance, and a method of producing the same. The invention mainly adds new elements Sn and Bi into the traditional zinc-aluminum-magnesium coating. In the hot forming process of advanced high-strength steel, the embodiment of the invention can provide a restraining effect for embrittling a steel plate matrix caused by liquid zinc penetration; on the other hand, excellent wear-resistant coating can be provided, and the wear amount in the thermoforming process can be reduced. According to the embodiment of the invention, through hot dip plating experiments, heat treatment experiments, observation of the section structure of the coating, mechanical tensile property detection, hardness detection and friction experiment detection of the coating, an alloy coating material capable of inhibiting embrittlement of liquid metal and providing excellent wear resistance is provided for advanced high-strength steel.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (7)
1. A zinc aluminum magnesium base alloy coating material for inhibiting liquid metal from embrittling in the hot forming process of high-strength steel is characterized by being Zn-Al-Mg-Sn alloy or Zn-Al-Mg-Sn-Bi alloy, and having the following composition and weight percentage: al: 3.5-5.0%; mg: 2.6-4%; sn: 0.8-4.0%, bi: 0-4.0%, and the balance of Zn and unavoidable impurities; the zinc aluminum magnesium base alloy coating material is used for forming a zinc aluminum magnesium base alloy coating on the surface of a high-strength steel substrate, wherein the zinc aluminum magnesium base alloy coating is formed on the surface of the high-strength steel and comprises a Mg 2 Sn phase, a Mg 2Zn11 phase and a MgZn 2 phase, an Fe-Al inhibition layer with the thickness not less than 0.5 mu m is formed between a high-strength steel interface and the zinc aluminum magnesium base alloy coating, the Fe-Al inhibition layer comprises a Fe 2Al5 phase, and liquid zinc infiltration into the high-strength steel substrate is prevented in the hot forming process of the high-strength steel.
2. The zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel according to claim 1, wherein: the composition and weight percentage are as follows: zn: 83.0-96.9%; al: 3.5-5.0%; mg: 2.6-4%; sn: 0.8-4.0%; bi: 0-4.0%, and the balance of unavoidable impurities.
3. The zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel according to claim 2, wherein: the composition and weight percentage are as follows: zn: 83.0-93.7%; al:3.5%; mg: 2.8-4%; sn:0.8%; bi: 0-4.0%, and the balance of unavoidable impurities.
4. The zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel according to claim 1, wherein: the composition and weight percentage are as follows: al:3.5%; mg: 2.8-4%; sn: 0.8-4.0%; bi: 0-4.0%, and the balance of Zn and unavoidable impurities.
5. The zinc aluminum magnesium base alloy plating material for inhibiting liquid metal embrittlement during hot forming of high strength steel according to claim 1, wherein: the hardness Hv is not less than 150.
6. The preparation method of the zinc-aluminum-magnesium-based alloy coating material for inhibiting the brittleness caused by liquid metal in the hot forming process of high-strength steel is characterized by comprising the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: al: 3.5-5.0%; mg: 2.6-4%; sn: 0.8-4.0%, and the balance of Zn and unavoidable impurities, wherein Al blocks, mg blocks, sn blocks and Zn blocks are used as raw materials;
1) Preparing a covering agent:
the zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50 wt.% CaCl 2, 45 wt.% NaCl,5.0 wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of dehydrated 50 wt% CaCl 2, 45 wt% NaCl and 5 wt% KCl;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of dehydrated 50 wt% CaCl 2, 45 wt% NaCl and 5 wt% KCl;
Step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for at least 2 hours after the Zn blocks are completely melted, then starting to add the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for at least 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for at least 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; pouring the zinc-rich zinc-based coating alloy material into a mould for cooling and forming to prepare a tin-rich zinc-based coating alloy material;
b. And (3) hot dip plating:
step 1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove an oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the concentration of NaOH in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt percent, the concentration of NaCO 3 in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt percent, heating the mixed alkaline aqueous solution to not lower than 80 ℃ in a constant-temperature water bath, preserving heat, removing greasy dirt on the surface of steel by using the prepared alkaline solution, and performing alkaline washing treatment on the surface of the steel;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is not lower than 5 wt percent, the urotropine mass percentage concentration of the acidic aqueous solution is not lower than 0.5: 0.5 wt percent, washing the surface of the steel subjected to alkaline washing with deionized water and absolute ethyl alcohol in sequence, drying, and then putting the steel into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to be not lower than 630 ℃, the reduction atmosphere is the mixed gas atmosphere of N 2 and H 2, wherein the mixed gas contains not lower than 10 vol percent of H 2 in volume percent, and the surface of the steel is continuously subjected to reduction treatment for 5-10 min;
Step 7: after the reduction treatment in the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
7. The preparation method of the zinc-aluminum-magnesium-based alloy coating material for inhibiting the brittleness caused by liquid metal in the hot forming process of high-strength steel is characterized by comprising the following steps:
a. The preparation process of the hot-dip coating liquid comprises the following steps:
The preparation method comprises the following steps of weighing and preparing raw materials according to the following elements required by preparing a target zinc-aluminum-magnesium-based alloy coating material: al: 3.5-5.0%; mg: 2.6-4%; sn: 0.8-4.0%, bi is less than or equal to 4.0%, and the balance is Zn and unavoidable impurities, wherein Al blocks, mg blocks, sn blocks, bi blocks and Zn blocks are used as raw materials;
1) Preparing a covering agent:
the zinc plating solution is prevented from being oxidized in the preparation process of the zinc plating solution, and the adopted covering agent comprises the following components in percentage by mass: 50 wt.% CaCl 2, 45 wt.% NaCl,5.0 wt.% KCl;
2) Under the protection of a covering agent, smelting and preparing alloy in a resistance furnace according to the raw materials of a set formula;
3) Preparation of Al-Mg intermediate alloy:
Step 1: firstly, weighing a part of Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of dehydrated 50 wt% CaCl 2, 45 wt% NaCl and 5 wt% KCl;
step 2: heating to 600-700 ℃, preserving heat until all Al blocks are melted, then gradually adding a part of Mg blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Mg intermediate alloy;
4) Preparation of Mg-Sn intermediate alloy:
Step 1: taking the rest Mg blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of dehydrated 50 wt% CaCl 2, 45 wt% NaCl and 5 wt% KCl;
Step 2: heating to 600-700 ℃, preserving heat until Mg blocks are completely melted, then gradually adding Sn blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Mg-Sn intermediate alloy;
5) Preparation of Al-Bi intermediate alloy:
Step 1: taking the rest Al blocks, and then adding a covering agent, wherein the covering agent comprises the following components: a uniformly mixed solid powder of dehydrated 50 wt% CaCl 2, 45 wt% NaCl and 5 wt% KCl;
Step 2: heating to 600-700 ℃, preserving heat until the Al blocks are completely melted, then gradually adding Bi blocks prepared in advance, stirring, and cooling to room temperature after argon treatment to obtain an Al-Bi intermediate alloy;
6) Preparing a tin-rich zinc-based coating material:
Step 1: weighing Zn blocks, polishing, putting into a crucible, and then adding a covering agent, wherein the components are as follows: a uniformly mixed solid powder of 50wt.% CaCl 2, 45wt.% NaCl and 5wt.% KCl, which was dehydrated;
Step 2: placing the crucible into a resistance furnace, starting heating, raising the temperature to 600-700 ℃, keeping the temperature at 600-700 ℃ for at least 2 hours after the Zn blocks are completely melted, then starting to add the Al-Mg intermediate alloy prepared in the step 3), keeping the temperature for at least 0.5 hour, and stirring to obtain a Zn-Al-Mg alloy melt; then adding the Mg-Sn intermediate alloy prepared in the step 4) into the prepared Zn-Al-Mg alloy melt, preserving heat for at least 1h, and stirring to obtain a Zn-Al-Mg-Sn alloy melt; then adding the Al-Bi intermediate alloy prepared in the step 5), preserving heat for at least 1h, stirring to obtain Zn-Al-Mg-Sn-Bi alloy melt, pouring the melt into a mould, and cooling and forming to prepare a tin-rich zinc-based plating alloy material;
b. And (3) hot dip plating:
step1: c, placing the tin-rich zinc-based coating alloy material prepared in the step a into a zinc pot, and forming Zn-Al-Mg-Sn-Bi hot-dip coating liquid after melting;
step 2: polishing the surface of the steel to be coated by 400-2000 # abrasive paper to remove an oxide layer on the surface of the steel;
Step 3: preparing a mixed alkaline aqueous solution, wherein the concentration of NaOH in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt percent, the concentration of NaCO 3 in mass percent of the mixed alkaline aqueous solution is not lower than 5 wt percent, heating the mixed alkaline aqueous solution to not lower than 80 ℃ in a constant-temperature water bath, preserving heat, removing greasy dirt on the surface of steel by using the prepared alkaline solution, and performing alkaline washing treatment on the surface of the steel;
Step 4: preparing an acidic aqueous solution, wherein the HCl mass percentage concentration of the acidic aqueous solution is not lower than 5 wt percent, the urotropine mass percentage concentration of the acidic aqueous solution is not lower than 0.5: 0.5 wt percent, washing the surface of the steel subjected to alkaline washing with deionized water and absolute ethyl alcohol in sequence, drying, and then putting the steel into the acidic solution to remove rust on the surface of the steel;
Step 5: after the pickling process of the step 4 is completed, taking out the steel, cleaning the surface of the steel with deionized water and absolute ethyl alcohol in sequence, and drying;
Step 6: the steel plate subjected to the blow-drying in the step 5 is sent to a hot dip plating experiment simulator, the surface of the steel is subjected to reduction treatment, the reduction temperature is set to be not lower than 630 ℃, the reduction atmosphere is the mixed gas atmosphere of N 2 and H 2, wherein the mixed gas contains not lower than 10 vol percent of H 2 in volume percent, and the surface of the steel is continuously subjected to reduction treatment for 5-10 min;
Step 7: after the reduction treatment of the step 6 is completed, immersing the steel into the molten Zn-Al-Mg-Sn-Bi hot plating solution prepared in the step 1 for hot dip plating, and controlling the hot dip plating time to be 3-15s;
step 8: after the hot dip plating is finished, cooling treatment is carried out, the steel is immediately cooled by water after being extracted from the hot dip plating solution, the water cooling temperature is 20-30 ℃, and the zinc-aluminum-magnesium-based alloy coating is obtained on the surface of the steel.
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| JP7445128B2 (en) * | 2020-04-30 | 2024-03-07 | 日本製鉄株式会社 | Hot-dip Zn-Al-Mg coated steel with excellent workability and corrosion resistance |
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