CN114107864A - Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel and preparation method thereof - Google Patents

Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel and preparation method thereof Download PDF

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Publication number
CN114107864A
CN114107864A CN202111439478.0A CN202111439478A CN114107864A CN 114107864 A CN114107864 A CN 114107864A CN 202111439478 A CN202111439478 A CN 202111439478A CN 114107864 A CN114107864 A CN 114107864A
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China
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steel
aluminum
zinc
percent
magnesium alloy
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Inventor
董学强
郭太雄
冉长荣
徐接旺
王亮赟
尹晶晶
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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Pangang Group Panzhihua Iron and Steel Research Institute Co Ltd
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    • 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
    • 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
    • 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
    • C23C2/02—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
    • C23C2/14—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

Abstract

The invention relates to a Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel and a preparation method thereof, belonging to the technical field of ferrous metallurgy production. The invention provides a Ti and Bi containing zinc-aluminum-magnesium alloy plating steel, which comprises the following chemical components in percentage by mass: 1 to 5 percent of aluminum, 0.5 to 10 percent of magnesium, 0.001 to 0.5 percent of titanium, 0.01 to 1.0 percent of bismuth, and the balance of zinc and inevitable impurities; wherein Al/Mg is 0.5-2, and the total amount of titanium and bismuth is less than or equal to 0.6%. The zinc-aluminum-magnesium alloy coated steel provided by the invention can meet the requirements of users on both high corrosion resistance and formability of the steel, is particularly suitable for the fields of household appliances and automobiles, and has good popularization and application prospects.

Description

Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel and preparation method thereof
Technical Field
The invention relates to a Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel 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%, Zr: 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.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides a Ti and Bi-containing zinc-aluminum-magnesium alloy plated steel material with both 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 Ti and Bi-containing zinc-aluminum-magnesium alloy plating steel, wherein the chemical components of the plating are as follows by mass percent: 1 to 5 percent of aluminum, 0.5 to 10 percent of magnesium, 0.001 to 0.50 percent of titanium, 0.01 to 1.0 percent of bismuth, and the balance of zinc and inevitable impurities; wherein Al/Mg is 0.5-2, and the total amount of titanium and bismuth is less than or equal to 0.6%.
Further, the method comprises the following steps: the chemical composition of the plating layer satisfies at least one of the following conditions: the plating layer contains 1.5-3.5% of aluminum, 1.0-3.0% of magnesium, 0.01-0.30% of titanium and 0.05-0.40% of bismuth;
Al/Mg is 1-1.5;
the total amount of titanium and bismuth is 0.10-0.40%.
Further, the method comprises the following steps: the total of the inevitable impurities is less than or equal to 0.020%, wherein the lead content is less than or equal to 0.003%, the antimony content is less than or equal to 0.002%, and the tin content is less than or equal to 0.002%
Less than or equal to 0.002 percent, less than or equal to 0.002 percent of arsenic, less than or equal to 0.002 percent of tellurium and less than or equal to 0.002 percent of cadmium.
Further, the method comprises the following steps: the weight of the coating is 20-400 g/m2On a double-sided basis; preferably, the weight of the plating layer is 60-270 g/m2 in terms of double sides.
Further, the method comprises the following steps: the steel base of the steel is selected from at least one of low-carbon aluminum killed steel, IF steel, bake-hardening steel, SPCC, SEDDQ, QP steel, DP steel and TRIP steel; preferably, the IF steel is P-containing high-strength IF steel or Ti-containing IF steel.
The invention also provides a preparation method of the zinc-aluminum-magnesium alloy coating steel, which 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 3.0 percent in percentage by volume in the continuous annealing process; preferably, the continuous annealing process controls 4.5-6.0% of hydrogen in the furnace in volume percentage.
Further, the method comprises the following steps: the temperature of the steel base in the zinc pot is controlled to be 380-510 ℃, the temperature of the plating solution in the hot dipping process is 390-520 ℃, 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 +/-15 ℃.
Further, the method comprises the following steps: quickly cooling after plating, and controlling the temperature of the strip steel reaching a top steering roller to be less than or equal to 280 ℃; preferably, the strip steel is cooled quickly after being plated, and the temperature of the strip steel reaching the top turning roll is controlled to be 200-240 ℃.
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 coated steel product under the neutral salt spray test condition is as long as 500h even more than 4500h, no obvious crack is seen after 0T bending, the time of red rust of the bending part under the neutral salt spray test condition is 450h even more than 4000h, 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 Ti and Bi containing zinc-aluminum-magnesium alloy plating steel, which comprises the following chemical components in percentage by mass: 1 to 5 percent of aluminum, 0.5 to 10 percent of magnesium, 0.001 to 0.50 percent of titanium, 0.01 to 1.0 percent of bismuth, and the balance of zinc and inevitable impurities; wherein Al/Mg is 0.5-2, and the total amount of titanium and bismuth is less than or equal to 0.6%.
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 optimizes the contents of Mg and Al in the coating and the addition of other alloy elements, so that Ti provides heterogeneous nucleation points in the coating forming process, refines and reduces the grain size of the coating, improves the corrosion resistance of the coating under the condition of improving the ductility of the coating, but the increase of the content of Ti can increase the generation of zinc slag and reduce the coating quality; bi increases the fluidity of zinc liquid, increases the binding force of the plating layer, reduces the generation of zinc slag and enhances the formability of the plating layer, but Bi is easy to enrich at the texture grain boundary of the plating layer and is not beneficial to the improvement of corrosion resistance. The use requirements of users on high corrosion resistance and high formability can be met through the synergistic action of Ti and Bi.
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, and H is general2Higher contents are better, but H2The higher the 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 Ti and Bi, and the zinc oxide slag is increased 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 40g/m2(double-sided), the main components of the plating layer are: 0.5% of aluminum, 0.8% of magnesium, 0.01% of titanium, 0.05% of bismuth, 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 bake-hardening 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 3.2% in the continuous annealing process according to the volume percentage, the temperature of a steel plate entering a zinc pot is 410 ℃, the temperature of a plating solution in the hot dipping process is 400 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 280 ℃.
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 method comprises the steps of bending a sample by 0T (bending at 180 degrees, and the radius of a bending center is 0), observing whether cracks appear or not by naked eyes, observing the micro appearance of a bent part by using an optical mirror or a scanning electron microscope, measuring the width of the maximum crack, and testing the time of red rust appearing on the bent part under the condition of a neutral salt spray test, wherein 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 occurrence under the neutral salt spray test condition is more than 500h, no obvious crack is seen after 0T bending, fine cracks exist under the scanning electron microscope condition, the maximum crack width is 25 mu m, the time of red rust occurrence of a bending part under the neutral salt spray test condition is more than 450h, the adhesiveness of the sprayed coating after spraying is excellent, and the user requirements are met.
EXAMPLE 2 preparation of a Zinc-aluminum-magnesium alloy coated Steel product of the present invention
Coating weight 180g/m2(double-sided), the main components of the plating layer are: 2.0 percent of aluminum, 2.0 percent of magnesium, 0.20 percent of titanium, 0.15 percent of bismuth, 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 Ti-IF 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 4.5% in the continuous annealing process according to the 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 460 ℃, the plating solution is quickly cooled, and the temperature of the strip steel reaching a top steering roller is 240 ℃.
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 2500h, no obvious crack is seen after 0T bending, fine cracks exist under the scanning electron microscope condition, the maximum crack width is 10 mu m, the time of red rust occurrence of a bending part under the neutral salt spray test condition is more than 2000h, the adhesiveness of the sprayed coating after spraying is excellent, and the user requirements are met.
EXAMPLE 3 preparation of a Zinc-aluminum-magnesium alloy coated Steel product of the present invention
Coating weight of 350g/m2(double-sided), the main components of the plating layer are: 3.5 percent of aluminum, 3.0 percent of magnesium, 0.30 percent of titanium, 0.30 percent of bismuth, 0.10 percent of silicon, 0.001 percent of lead, 0.002 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 low-carbon aluminum killed 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 to be 6.0 percent in the continuous annealing process according to the volume percentage, the temperature of a steel plate entering a zinc pot is 500 ℃, 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 4000h, no obvious crack is seen by naked eyes after 0T bending, fine cracks exist under the scanning electron microscope condition, the maximum crack width is 20 mu m, the time of red rust occurrence of a bending part under the neutral salt spray test condition is more than 3500h, and the sprayed coating has excellent adhesiveness and meets the user requirements.
Comparative example
Coating weight 200g/m2(double-sided), the main components of the plating layer are: 1.8 percent of aluminum, 1.9 percent of magnesium, 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 Ti-Nb-IF steel.
The preparation method comprises the following steps: degreasing and cleaning, continuous annealing, hot dipping, air knife blowing and cooling, wherein the degreasing and cleaning is to rinse and clean after degreasing treatment, the hydrogen in the furnace is controlled by 3.5% in the continuous annealing process according to the volume percentage, the temperature of a steel plate entering a zinc pot is 460 ℃, 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 245 ℃.
The test method was the same as in example 1. The detection shows that the zinc-aluminum-magnesium alloy coating steel prepared by the comparative example has good surface quality, but has slightly poor corrosion resistance, formability and coating property. The time of red rust occurrence under the neutral salt spray test condition is more than 1500h, no obvious crack is seen after 0T bending, fine cracks exist under the scanning electron microscope condition, the maximum crack width reaches 50 mu m, and the time of red rust occurrence of the bending part under the neutral salt spray test condition is more than 1200 h.
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 Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel is characterized in that: the chemical components of the plating layer are as follows by mass percent: 1 to 5 percent of aluminum, 0.5 to 10 percent of magnesium, 0.001 to 0.50 percent of titanium, 0.01 to 1.0 percent of bismuth, and the balance of zinc and inevitable impurities; wherein Al/Mg is 0.5-2, and the total amount of titanium and bismuth is less than or equal to 0.6%.
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 plating layer contains 1.5-3.5% of aluminum, 1.0-3.0% of magnesium, 0.01-0.30% of titanium and 0.05-0.40% of bismuth;
Al/Mg is 1-1.5;
the total amount of titanium and bismuth is 0.10-0.40%.
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 0.020%, wherein lead is less than or equal to 0.003%, antimony is less than or equal to 0.002%, tin is less than or equal to 0.002%, arsenic is less than or equal to 0.002%, tellurium is less than or equal to 0.002%, and cadmium is less than or equal to 0.002%.
4. The zinc-aluminum-magnesium alloy coated steel product as set forth in claim 1, wherein: the weight of the coating is 20-400 g/m2On a double-sided basis; preferably, the weight of the coating is 60-270 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 low-carbon aluminum killed steel, IF steel, bake-hardening steel, SPCC, SEDDQ, QP steel, DP steel and TRIP steel; preferably, the IF steel is P-containing high-strength IF steel or Ti-containing IF steel.
6. A method of 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 for producing a zinc-aluminum-magnesium alloy coated steel product as claimed in claim 6, characterized in that: controlling the hydrogen in the furnace to be more than or equal to 3.0 percent in percentage by volume in the continuous annealing process; preferably, the continuous annealing process controls the hydrogen in the furnace from 4.5% to 6.0% by volume percent.
8. The method for producing a zinc-aluminum-magnesium alloy coated steel product as claimed in claim 6, characterized in that: the temperature of the steel base in the zinc pot is controlled to be 380-510 ℃, the temperature of the plating solution in the hot dipping process is 390-520 ℃, 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 +/-15 ℃.
9. The method for producing a zinc-aluminum-magnesium alloy coated steel product as claimed in claim 6, characterized in that: quickly cooling after plating, and controlling the temperature of the strip steel reaching a top steering roller to be less than or equal to 280 ℃; preferably, the strip steel is cooled quickly after being plated, and the temperature of the strip steel reaching the top turning roll is controlled to be 200-240 ℃.
10. The zinc-aluminum-magnesium alloy coating steel is characterized in that: a zinc-aluminium-magnesium alloy coated steel product according to any one of claims 6 to 9, when produced by a process.
CN202111439478.0A 2021-11-30 2021-11-30 Ti and Bi-containing zinc-aluminum-magnesium alloy coating steel and preparation method thereof Pending CN114107864A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199956A (en) * 1998-01-12 1999-07-27 Nisshin Steel Co Ltd Zinc-aluminum-magnesium alloy for hot dip coating excellent in corrosion resistance
JP2002020850A (en) * 2000-03-31 2002-01-23 Nippon Steel Corp Plated steel material having high corrosion resistance and excellent in workability, and its manufacturing method
CN110268087A (en) * 2017-01-27 2019-09-20 日本制铁株式会社 Plated steel material
CN111304573A (en) * 2020-03-20 2020-06-19 攀钢集团攀枝花钢铁研究院有限公司 Zinc-aluminum-magnesium alloy coated steel plate with excellent corrosion resistance and preparation method thereof
CN115478239A (en) * 2022-08-23 2022-12-16 马鞍山钢铁股份有限公司 Aluminum-zinc-magnesium coated steel plate with excellent forming performance and manufacturing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH11199956A (en) * 1998-01-12 1999-07-27 Nisshin Steel Co Ltd Zinc-aluminum-magnesium alloy for hot dip coating excellent in corrosion resistance
JP2002020850A (en) * 2000-03-31 2002-01-23 Nippon Steel Corp Plated steel material having high corrosion resistance and excellent in workability, and its manufacturing method
CN110268087A (en) * 2017-01-27 2019-09-20 日本制铁株式会社 Plated steel material
CN111304573A (en) * 2020-03-20 2020-06-19 攀钢集团攀枝花钢铁研究院有限公司 Zinc-aluminum-magnesium alloy coated steel plate with excellent corrosion resistance and preparation method thereof
CN115478239A (en) * 2022-08-23 2022-12-16 马鞍山钢铁股份有限公司 Aluminum-zinc-magnesium coated steel plate with excellent forming performance and manufacturing method thereof

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