CN114107737A - Zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn and preparation method thereof - Google Patents
Zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn and preparation method thereof Download PDFInfo
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- CN114107737A CN114107737A CN202111440098.9A CN202111440098A CN114107737A CN 114107737 A CN114107737 A CN 114107737A CN 202111440098 A CN202111440098 A CN 202111440098A CN 114107737 A CN114107737 A CN 114107737A
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 111
- 239000010959 steel Substances 0.000 title claims abstract description 111
- -1 Zinc-aluminum-magnesium Chemical compound 0.000 title claims abstract description 38
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 31
- 229910052746 lanthanum Inorganic materials 0.000 title claims abstract description 26
- 229910052720 vanadium Inorganic materials 0.000 title claims abstract description 26
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 25
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000007747 plating Methods 0.000 claims abstract description 71
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 26
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 19
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 18
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 15
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 6
- 238000000576 coating method Methods 0.000 claims description 49
- 239000011248 coating agent Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 33
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 238000000137 annealing Methods 0.000 claims description 15
- 238000005238 degreasing Methods 0.000 claims description 15
- 239000011572 manganese Substances 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- 238000007598 dipping method Methods 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 229910052793 cadmium Inorganic materials 0.000 claims description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000937 TWIP steel Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910000655 Killed steel Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000794 TRIP steel Inorganic materials 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000004886 process control Methods 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 29
- 238000005260 corrosion Methods 0.000 abstract description 29
- 238000009851 ferrous metallurgy Methods 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 23
- 150000003839 salts Chemical class 0.000 description 17
- 239000007921 spray Substances 0.000 description 17
- 229910018134 Al-Mg Inorganic materials 0.000 description 14
- 229910018467 Al—Mg Inorganic materials 0.000 description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 13
- 230000007935 neutral effect Effects 0.000 description 13
- 238000005452 bending Methods 0.000 description 9
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 9
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 6
- 239000011651 chromium Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 239000011253 protective coating Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 206010011416 Croup infectious Diseases 0.000 description 1
- 229910017708 MgZn2 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910007981 Si-Mg Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910008316 Si—Mg Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/26—Methods of annealing
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
- C23C2/18—Removing excess of molten coatings from elongated material
- C23C2/20—Strips; Plates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The invention relates to a zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn and a preparation method thereof, belonging to the technical field of ferrous metallurgy production. The invention provides a zinc-aluminum-magnesium alloy plating steel containing V, Ce, La and Mn, which comprises the following chemical components in percentage by mass: 0.5-5% of aluminum, 0.5-3.0% of magnesium, 0.05-1% of vanadium, 0.01-0.50% of cerium, 0.01-0.30% of lanthanum, 0.025-1.0% of Mn0.025%, and the balance of zinc and inevitable impurities; wherein Al/Mg is 1.0-1.5, and the total amount of vanadium, cerium and lanthanum is 0.03-1.0%. The zinc-aluminum-magnesium alloy coated steel provided by the invention not only meets the requirement of users on high corrosion resistance of the steel, but also meets the requirement of users on excellent stamping formability or high-strength steel, is especially suitable for the fields of household appliances and automobiles, and has good popularization and application prospects.
Description
Technical Field
The invention relates to a zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn and a preparation method thereof, belonging to the technical field of ferrous metallurgy production.
Background
The Zn-Al-Mg alloy coating has attracted wide attention abroad in the 80 s of the 20 th century, and becomes a research focus in the professional field of hot dip galvanizing and zinc alloy coating. From the research results of the same lines at home and abroad, the hot-dip galvanized Zn-Al-Mg alloy coated steel plate added with Mg has better corrosion resistance under the condition that the contents of Zn and Al of the coatings are at the same level, and the processing application performance (formability, weldability and paintability) of the material is excellent, so that the hot-dip galvanized Zn-Al-Mg alloy coated steel plate can replace the existing corresponding hot-dip galvanized or zinc alloy coated steel plate, and has very wide market demand prospect.
The hot dip Zn-Al-Mg alloy coated steel plate realizes industrial production and application in iron and steel companies such as Nissin iron, Nissin Steel, Thisen Krupp and the like in the early 21 st century, and is gradually popularized and applied to industries such as household appliances, automobile manufacturing and the like in the main application field at present in the building industry. The research on the Zn-Al-Mg alloy coating in China is late, and only enterprises such as precious steel, first steel, wine steel, climbing steel and the like put forward the hot dip coating Zn-Al-Mg alloy coating steel plate at present.
The existing hot dip Zn-Al-Mg alloy coated steel plate can be divided into three types of low aluminum (WAl is less than 5 percent), medium aluminum (WAl is more than or equal to 5 percent and less than 13 percent) and high aluminum (WAl is more than or equal to 47 percent and less than or equal to 57 percent). For different varieties of Zn-Al-Mg alloy coating steel plates, the contents of Al and Mg in the coatings are different, and the organizational structure and the quality performance of the coatings are different, so the application fields are different. CN105063532A discloses a high corrosion resistance single plating type zinc-aluminum-magnesium rare earth protective coating and a preparation process thereof, wherein the single plating type zinc-aluminum-magnesium rare earth protective coating process obtains a zinc-aluminum-magnesium alloy coating on the metal surface by a single hot dipping method. The plating layer and the metal matrix respectively keep the original performance, but have more than 99.9 percent of metallurgical bonding interface, and meanwhile, the plating layer has compact structure, stable components, no plating leakage, excellent corrosion resistance and the salt spray corrosion reaching 2060 h. The alloy plating layer has better corrosion resistance than the common hot-dip pure zinc plating layer, and the service life is prolonged. The single plating process can be repeatedly used and produced in an industrialized mode, overcomes the defects that metal and zinc-aluminum-magnesium alloy liquid are difficult to assist plating, an excellent bonding interface is difficult to form between the metal and the zinc-aluminum-magnesium alloy liquid, plating leakage is easy to generate and the like, can be widely applied to preparing zinc-aluminum-magnesium alloy plating liquid with the content of 5% -12% of Al and 1% -6% of Mg on the surface of metal, and the prepared co-permeation layer forms Zn/Al/MgZn2 ternary eutectic and various types of binary eutectic and is the main reason that the co-permeation layer has high corrosion resistance. The high corrosion resistance single plating type zinc-aluminum-magnesium rare earth protective coating adopts a medium aluminum component system.
CN109402547A provides a hot-dip coated steel sheet with excellent corrosion resistance and a manufacturing method thereof, the hot-dip coated steel sheet comprises a substrate and an Al-Zn-Si-Mg coating coated on the substrate, and the coating comprises the following chemical components in percentage by mass: al: 45% -65%, Si: 0.1-3%, Mg: 0.2-5%, Mn: 0.001-0.15%, Cr: 0.001 to 0.5 percent, and the balance of Zn and inevitable impurities. The manufacturing method comprises the following steps: (1) pretreating a steel plate; (2) immersing a steel plate into a plating liquid pool for hot dip plating, wherein the temperature of the plating liquid pool is 560-595 ℃; (3) and taking the steel plate out of the plating solution, and carrying out sectional cooling. The hot dip coating steel plate has excellent corrosion resistance, and has remarkable inhibiting effect on the development of white rust and red rust and the failure propagation of a treatment film from a notch. The hot dip coated steel sheet excellent in corrosion resistance is a high aluminum component system coating.
It can be seen that the high corrosion resistance zinc-aluminum-magnesium steel sheet is mainly a zinc-aluminum-magnesium steel sheet of medium-high aluminum composition system, and the corrosion resistance of the plating layer increases with the increase of the Al and Mg contents, but the formability and weldability are also reduced. In the field of household appliances and automobile application, in order to ensure that a Zn-Al-Mg alloy coating steel plate meets the punch forming requirements of users, the Zn-Al-Mg alloy coating steel plate has good formability, and the current Zn-Al-Mg alloy coating steel plate with a medium-high aluminum component system can not meet the requirements of the users. In the aspect of automobile plates, high-strength steel with higher strength has poor wettability of a plating solution and steel matrix due to more alloy elements in the steel matrix, and the use of zinc-aluminum-magnesium in the aspect of high-strength steel is seriously influenced. Therefore, it is important to provide a Zn-Al-Mg alloy-plated steel sheet having both high formability and corrosion resistance.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn with high formability and corrosion resistance and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows: firstly, providing a zinc-aluminum-magnesium alloy plating steel containing V, Ce, La and Mn, wherein the chemical components of the plating are as follows by mass percent: 0.5-5% of aluminum, 0.5-3.0% of magnesium, 0.05-1% of vanadium, 0.01-0.50% of cerium, 0.01-0.30% of lanthanum, 0.025-1.0% of manganese, less than or equal to 0.3% of other trace alloy elements, and the balance of zinc and inevitable impurities; wherein Al/Mg is 1.0-1.5, and the total amount of vanadium, cerium and lanthanum is 0.3-1.0%.
Further, the method comprises the following steps: the chemical composition of the plating layer satisfies at least one of the following conditions:
the coating contains 0.8-3.2% of aluminum, 0.8-2.5% of magnesium, 0.05-0.40% of vanadium, 0.03-0.30% of cerium, 0.02-0.20% of lanthanum and 0.10-1.0% of manganese;
Al/Mg is 1-1.2;
the total amount of vanadium, cerium and lanthanum is 0.10-0.35%.
Further, the method comprises the following steps: the total amount of the inevitable impurities is less than or equal to 0.010 percent, wherein lead is less than or equal to 0.002 percent, antimony is less than or equal to 0.002 percent, tin is less than or equal to 0.002 percent, arsenic is less than or equal to 0.002 percent, tellurium is less than or equal to 0.002 percent, and cadmium is less than or equal to 0.002 percent.
Further, the method comprises the following steps: the weight of the coating is 30-400 g/m2On a double-sided basis; preferably, the weight of the coating is 150-320 g/m2On a double-sided basis.
Further, the method comprises the following steps: the steel base of the steel is selected from at least one of IF steel, low-carbon aluminum killed steel, bake-hardening steel, QP steel, DP steel, TRIP steel and TWIP steel.
The manufacturing method of the zinc-aluminum-magnesium alloy coating steel comprises the following steps: the method comprises the following steps: degreasing and cleaning the steel base, continuously annealing, hot dipping and blowing by an air knife.
Further, the method comprises the following steps: controlling the hydrogen in the furnace to be more than or equal to 3.5 percent in percentage by volume in the continuous annealing process; preferably, the continuous annealing process controls 4.0-8.0% of hydrogen in the furnace in volume percentage.
Further, the method comprises the following steps: the temperature of the steel base in a zinc pot is controlled to be 420-520 ℃, the temperature of the plating solution in the hot dip plating process is 410-520 ℃, and the temperature difference between the temperature of the steel base in the zinc pot and the temperature of the plating solution is controlled to be +/-10 ℃.
Further, the method comprises the following steps: quickly cooling after plating, and controlling the temperature of the strip steel reaching the top steering roller to be less than or equal to 260 ℃; preferably, after plating, the strip steel is quickly cooled, and the temperature of the strip steel reaching the top turning roll is controlled to be 200-260 ℃.
The invention has the beneficial effects that: the zinc-aluminum-magnesium alloy coating steel provided by the invention adopts a low-aluminum component system, and a Zn-Al-Mg alloy coating steel plate with high corrosion resistance and high formability is produced by controlling coating components. The detection proves that the time of red rust of the zinc-aluminum-magnesium alloy coating steel is as long as 600h even more than 3200h under the condition of a neutral salt spray test, obvious cracks are not seen by naked eyes after 0T bending, the time of red rust of a bending part under the condition of the neutral salt spray test is 500h even more than 3000h, and the adhesiveness of the sprayed coating after spraying is excellent. The zinc-aluminum-magnesium alloy coated steel is particularly suitable for the fields of household appliances and automobiles, and has good popularization and application prospects.
Detailed Description
The invention provides a zinc-aluminum-magnesium alloy plating steel containing V, Ce, La and Mn, which comprises the following chemical components in percentage by mass: 0-5% of aluminum, 0.5-3.0% of magnesium, 0.05-1% of vanadium, 0.01-0.50% of cerium, 0.01-0.30% of lanthanum, 0.025-1.0% of manganese, less than or equal to 0.3% of other trace alloy elements, and the balance of zinc and inevitable impurities; wherein Al/Mg is 1.0-1.5, the total amount of vanadium, cerium and lanthanum is 0.3-1.0%, and the other trace alloy elements are selected from at least one of boron, silicon, titanium, calcium, manganese, molybdenum, chromium, niobium, yttrium and bismuth.
In order to ensure the corrosion resistance of Zn-Al-Mg alloy coating steel, a medium-high aluminum component system is mainly adopted in the field at present, but the forming performance and the welding performance of the steel are obviously reduced along with the increase of the content of Al and Mg, and the requirement of the fields of household appliances, automobiles and the like on the stamping forming performance is difficult to meet. Aiming at the problems, the invention improves the corrosion resistance of the plating layer under the condition of improving the ductility of the plating layer by optimizing the contents (content ratio) of Mg and Al and the addition of other alloy elements in the plating layer, wherein V provides heterogeneous nucleation points in the formation process of the plating layer, refines and reduces the grain size of the plating layer; ce and La increase the fluidity of the plating bath, reduce the surface tension of the plating bath, increase the wettability of the plating bath to the steel substrate, and improve the bonding effect of the plating layer and the steel substrate; mn can enhance the bonding effect of the plating layer and a steel base (especially Mn-containing high-strength steel) to form an Mn-rich intermetallic compound, so that the plating layer obtains good plasticity and toughness, and is easy for subsequent processing, thereby further meeting the use requirements of users on high corrosion resistance and high formability. However, the excessive contents of V, Ce, La and Mn can form oxide skin on the surface of the alloy plating solution, increase zinc slag and influence the surface quality of the plating layer.
In the process of preparing the plating layer, in order to ensure that the plating layer has good surface quality and performance, the process is limited, the thickness of the plating layer is controlled within a certain range due to the air knife capability and the fluidity of the plating solution, when the air knife pressure is too large, the surface quality and the thickness are not easy to control, and when the air knife flow is limited and the fluidity of the plating layer is certain, the plating layer cannot be controlled too thin; the wettability of the plating solution on the surfaces of different steel plates is different, and the plating solution can only form a plating layer with excellent adhesive force on the steel plate with good wettability; the annealing atmosphere is used for improving the good reducibility of the steel base surface, generally, the higher the H2 content is, the better the content is, but the higher the H2 content is, the higher the explosion risk is; the temperature of the plating solution needs to be ensured to be in a molten state and have good fluidity, the temperature range of the plating solution is improved by adding V, Mn, but the zinc oxide slag is increased easily when the temperature is too high; in order to ensure that the coating is completely solidified, the temperature of the steel plate needs to be reduced to be below a solidifying point before the first turning roll, the zinc aluminum magnesium is easy to oxidize, and the surface quality of the steel plate can be better due to quick cooling.
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
EXAMPLE 1 preparation of a Zinc-aluminum-magnesium alloy coated Steel product of the present invention
Coating weight 50g/m2(double-sided), the main components of the plating layer are: 0.8% of aluminum, 0.6% of magnesium, 0.10% of vanadium, 0.05% of lanthanum, 0.15% of cerium, 0.20% of manganese, 0.002% of lead, 0.001% of antimony, 0.001% of chromium, 0.001% of cadmium, 0.001% of tin and the balance of zinc; the steel base is DP steel.
The preparation method comprises the following steps: degreasing cleaning, continuous annealing, hot dipping, air knife blowing and cooling, wherein the degreasing cleaning is to clean after degreasing treatment, hydrogen in a furnace is controlled by 5.0% in the continuous annealing process according to volume percentage, the temperature of a steel plate entering a zinc pot is 450 ℃, the temperature of a plating solution in the hot dipping process is 440 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 260 ℃.
The test method comprises the following steps:
corrosion resistance: a neutral salt spray accelerated corrosion test is adopted, the test conditions and the method are executed according to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test, a test instrument is a salt spray corrosion test box, NaCl deionized water solution with the concentration of 50g/L, pH and the value of 6.5 is used as a corrosion medium, and the test temperature is 35 +/-2 ℃; the specification of the sample is 75mm multiplied by 150mm multiplied by 0.8mm, and the edge sealing with the size of 5mm is carried out by using a transparent adhesive tape so as to prevent the end part from being rusted to influence the result; the sample is placed at an angle of 15-25 degrees with the vertical direction. The time for the surface of the specimen to develop red rust was observed.
Formability: the test sample is bent at 0T (bent at 180 degrees, the radius of a bending core is 0), whether cracks appear is observed by naked eyes, the time of red rust appearing on the bent part is tested under the condition of a neutral salt spray test, and the neutral salt spray test condition and the method are executed according to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test.
Coating property: and (3) carrying out spraying and drying on the coated steel plate after degreasing, cleaning, vitrification or phosphorization, and then testing the bonding degree of the spraying coating and the steel plate by adopting a grid marking method, wherein if the coating does not fall off, the coating has good adhesiveness.
Through detection, the zinc-aluminum-magnesium alloy coating steel prepared by the embodiment has good surface quality, and has excellent corrosion resistance, formability and coating property. The time of red rust appearing under the neutral salt spray test condition is more than 70h, no obvious crack is seen after 0T bending, the time of red rust appearing on the bent part under the neutral salt spray test condition is more than 600h, the adhesiveness of the sprayed coating after spraying is excellent, and the requirement of a user is met.
EXAMPLE 2 preparation of a Zinc-aluminum-magnesium alloy coated Steel product of the present invention
Coating weight 150g/m2(double-sided), the main components of the plating layer are: 1.5 percent of aluminum, 1.5 percent of magnesium, 0.15 percent of vanadium, 0.10 percent of cerium, 0.10 percent of lanthanum, 0.15 percent of manganese, 0.001 percent of lead, 0.002 percent of stibium, 0.001 percent of chromium, 0.001 percent of cadmium, 0.001 percent of tin and the balance of zinc; the steel base is TWIP steel.
The preparation method comprises the following steps: degreasing cleaning, continuous annealing, hot dipping, air knife blowing and cooling, wherein the degreasing cleaning is to clean after degreasing treatment, the hydrogen in the furnace is controlled by 6.0% in the continuous annealing process according to the volume percentage, the temperature of a steel plate entering a zinc pot is 470 ℃, the temperature of a plating solution in the hot dipping process is 460 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 200 ℃.
The test method was the same as in example 1. Through detection, the zinc-aluminum-magnesium alloy coating steel prepared by the embodiment has good surface quality, and has excellent corrosion resistance, formability and coating property. The time of red rust occurrence under the neutral salt spray test condition is over 1800h, no obvious crack is seen after 0T bending, the time of red rust occurrence of a bending part under the neutral salt spray test condition is over 1700h, and the adhesion of the sprayed coating after spraying is excellent, thereby meeting the user requirements.
EXAMPLE 3 preparation of a Zinc-aluminum-magnesium alloy coated Steel product of the present invention
Coating weight 320g/m2(double-sided), the main components of the plating layer are: 3.2 percent of aluminum, 2.5 percent of magnesium, 0.10 percent of vanadium, 0.15 percent of lanthanum, 0.20 percent of cerium, 0.05 percent of manganese, 0.002 percent of lead, 0.001 percent of stibium, 0.001 percent of chromium, 0.002 percent of cadmium, 0.002 percent of tin and the balance of zinc; the steel base is QP steel.
The preparation method comprises the following steps: degreasing cleaning, continuous annealing, hot dipping, air knife blowing and cooling, wherein the degreasing cleaning is to clean after degreasing treatment, hydrogen in a furnace is controlled by 4.5% in the continuous annealing process according to the volume percentage, the temperature of a steel plate entering a zinc pot is 510 ℃, the temperature of a plating solution in the hot dipping process is 500 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 200 ℃.
The test method was the same as in example 1. Through detection, the zinc-aluminum-magnesium alloy coating steel prepared by the embodiment has good surface quality, and has excellent corrosion resistance, formability and coating property. The time of red rust occurrence under the neutral salt spray test condition is more than 3200h, no obvious crack is seen after 0T bending, the time of red rust occurrence of a bending part under the neutral salt spray test condition is more than 3000h, the adhesiveness of the sprayed coating after spraying is excellent, and the user requirements are met.
Comparative example
Coating weight 180g/m2(double-sided), the main components of the plating layer are: 1.6 percent of aluminum, 1.6 percent of magnesium, 0.001 percent of lead, 0.001 percent of stibium, 0.001 percent of chromium, 0.001 percent of cadmium, 0.001 percent of tin and the balance of zinc; the steel base is QP steel.
The preparation method comprises the following steps: degreasing cleaning, continuous annealing, hot dipping, air knife blowing and cooling, wherein the degreasing cleaning is to clean after degreasing treatment, hydrogen in a furnace is controlled by 3.5% in the continuous annealing process according to volume percentage, the temperature of a steel plate entering a zinc pot is 470 ℃, the temperature of a plating solution in the hot dipping process is 470 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 300 ℃.
The test method was the same as in example 1. Through detection, the zinc-aluminum-magnesium alloy coating steel prepared by the comparative example has poor surface quality, bright spot defects, and slightly poor corrosion resistance, formability and coating property. The time of red rust occurrence under the neutral salt spray test condition is more than 1400h, and the time of red rust occurrence under the neutral salt spray test condition of the bent part is more than 1100h, wherein the bent part has slight cracks after 0T bending.
It should be appreciated that the particular features, structures, materials, or characteristics described in this specification may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments and features of the various embodiments described in this specification can be combined and combined by one skilled in the art without contradiction.
Claims (10)
1. The zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn is characterized in that: the chemical components of the plating layer are as follows by mass percent: 0.5-5% of aluminum, 0.5-3.0% of magnesium, 0.05-1% of vanadium, 0.01-0.50% of cerium, 0.01-0.30% of lanthanum, 0.025-1.0% of manganese, less than or equal to 0.3% of other trace alloy elements, and the balance of zinc and inevitable impurities; wherein Al/Mg is 1.0-1.5, and the total amount of vanadium, cerium and lanthanum is 0.3-1.0%.
2. The zinc-aluminum-magnesium alloy coated steel product as set forth in claim 1, wherein: the chemical composition of the plating layer satisfies at least one of the following conditions:
the coating contains 0.8-3.2% of aluminum, 0.8-2.5% of magnesium, 0.05-0.40% of vanadium, 0.03-0.30% of cerium, 0.02-0.20% of lanthanum and 0.10-1.0% of manganese;
Al/Mg is 1-1.2;
the total amount of vanadium, cerium and lanthanum is 0.10-0.35%.
3. The zinc-aluminum-magnesium alloy coated steel product as set forth in claim 1, wherein: the total amount of the inevitable impurities is less than or equal to 0.010 percent, wherein lead is less than or equal to 0.002 percent, antimony is less than or equal to 0.002 percent, tin is less than or equal to 0.002 percent, arsenic is less than or equal to 0.002 percent, tellurium is less than or equal to 0.002 percent, and cadmium is less than or equal to 0.002 percent.
4. The zinc-aluminum-magnesium alloy coated steel product as set forth in claim 1, wherein: the weight of the coating is 30-400 g/m2On a double-sided basis; preferably, the weight of the coating is 150-320 g/m2On a double-sided basis.
5. The zinc-aluminum-magnesium alloy coated steel product as set forth in claim 1, wherein: the steel base of the steel is selected from at least one of IF steel, low-carbon aluminum killed steel, bake-hardening steel, QP steel, DP steel, TRIP steel and TWIP steel.
6. A method for producing a zinc-aluminum-magnesium alloy coated steel product as claimed in any one of claims 1 to 5, characterized by comprising: the method comprises the following steps: degreasing and cleaning the steel base, continuously annealing, hot dipping and blowing by an air knife.
7. The method of claim 6, wherein: controlling the hydrogen in the furnace to be more than or equal to 3.5 percent in percentage by volume in the continuous annealing process; preferably, the continuous annealing process controls 4.0-8.0% of hydrogen in the furnace in volume percentage.
8. The method of claim 6, wherein: the temperature of the steel base in a zinc pot is controlled to be 420-520 ℃, the temperature of the plating solution in the hot dip plating process is 410-520 ℃, and the temperature difference between the temperature of the steel base in the zinc pot and the temperature of the plating solution is controlled to be +/-10 ℃.
9. The method of claim 6, wherein: quickly cooling after plating, and controlling the temperature of the strip steel reaching the top steering roller to be less than or equal to 260 ℃; preferably, after plating, the strip steel is quickly cooled, and the temperature of the strip steel reaching the top turning roll is controlled to be 200-260 ℃.
10. A zinc-aluminum-magnesium alloy coated steel product obtained by the production method according to any one of claims 6 to 9.
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| PCT/CN2022/109957 WO2023098126A1 (en) | 2021-11-30 | 2022-08-03 | Zinc-aluminum-magnesium alloy coating steel containing v, ce, la and mn, and preparation method therefor |
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| CN116162824A (en) * | 2023-03-07 | 2023-05-26 | 保定奥琦圣新型金属材料制造有限公司 | Novel zinc-aluminum-magnesium alloy containing Mo and Cr and production method thereof |
| WO2023098126A1 (en) * | 2021-11-30 | 2023-06-08 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium alloy coating steel containing v, ce, la and mn, and preparation method therefor |
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| CN108588491A (en) * | 2018-06-05 | 2018-09-28 | 马鞍山钢铁股份有限公司 | A kind of hot dip galvanizing-Al-Mg clad steel sheets that immersion plating is excellent and production method |
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| CN114107737A (en) * | 2021-11-30 | 2022-03-01 | 攀钢集团攀枝花钢铁研究院有限公司 | Zinc-aluminum-magnesium alloy plated steel containing V, Ce, La and Mn and preparation method thereof |
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