A kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet and its production technology
阅读说明：本技术 一种汽车用高表面质量锌铝镁镀层钢板及其生产工艺 (A kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet and its production technology ) 是由 李建新 熊自柳 齐建军 刘宏强 孙力 周国平 弓俊杰 张鹏 董伊康 罗扬 王健 于 2019-09-12 设计创作，主要内容包括：本发明公开了一种汽车用高表面质量锌铝镁镀层钢板及其生产工艺,镀液化学成分组成及其质量百分含量为：Al+Mg：2～6%、Mg/Al：0.8～1.2%、Cr：0.1～0.6%、Ti：0.2～1.0%、Cu：0.5～2.5%,其余为Zn和不可避免的杂质；IF钢、BH钢、HSLA钢、DP钢基板采用美钢联工艺进行热浸镀生产,TRIP钢、Q&P钢基板采用美钢联工艺和森吉米尔法进行热浸镀生产。本发明在Zn-Al-Mg的基础上添加Ti、Cr、Cu元素,可以得到细化的镀层晶粒尺寸,提高镀层硬度,镀层性能：硬度120～150HV,表面质量：光度值0.69～0.89,具有良好的抗刮擦性能和镀层表面质量。(The invention discloses a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet and its production technologies, plating solution chemical component composition and its mass percentage are as follows: Al+Mg:2~6%, Mg/Al:0.8~1.2%, Cr:0.1~0.6%, Ti:0.2~1.0%, Cu:0.5~2.5%, remaining is Zn and inevitable impurity；IF steel, BH steel, HSLA steel, DP steel substrate carry out hot-dip production using U.S. steel connection technique, and TRIP steel, Q&P steel substrate carry out hot-dip production using U.S. steel connection technique and Sendzimir method.The present invention adds Ti, Cr, Cu element on the basis of Zn-Al-Mg, the coating crystallite dimension of available refinement improves coating hardness, coating performance: 120~150HV of hardness, surface quality: shading value 0.69~0.89 has good Scratch Resistance energy and coating surface quality.)
1. a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet, which is characterized in that the zinc-aluminum-magnesium clad steel sheet plating liquefaction It studies and is grouped as and its mass percentage are as follows: Al+Mg:2~6%, Mg/Al:0.8~1.2%, Cr:0.1~0.6%, Ti:0.2 ~1.0%, Cu:0.5~2.5%, remaining is Zn and inevitable impurity.
2. a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet according to claim 1, which is characterized in that the zinc Magnalium clad steel sheet substrate is deep-draw, ultra-deep punching, the high-intensitive, hot radical of superhigh intensity automobile steel or cold base Automobile Plate；It is described Zinc-aluminum-magnesium clad steel sheet steel grade is IF steel, BH steel, HSLA steel, DP steel, TRIP steel, Q&P steel.
3. a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet according to claim 1, which is characterized in that the zinc The coating performance of magnalium clad steel sheet: 120~150HV of hardness, surface quality: shading value 0.69~0.89.
4. the production work based on a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet described in claim 1-3 any one Skill, which is characterized in that
1) IF steel, BH steel, HSLA steel, DP steel substrate carry out hot-dip production using U.S. steel connection technique:
(1) continuous annealing atmosphere use hydrogen volume content for 3~25% nitrogen hydrogen mixeding gas, oxygen content≤20ppm, dew - 50~-30 DEG C of point；
(2) hot-dip temperature is 420~520 DEG C；
(3) it is cooled down after plating using nitrogen, 10~20 DEG C/s of cooling rate；
2) TRIP steel, Q&P steel substrate carry out hot-dip production using U.S. steel connection technique, continuous annealing process using degreasing, heating, Pre-oxidation, soaking, cooling, hot-dip, coating cooling technique:
(1) 500~800 DEG C of Pre oxidation, 10~60s of preoxidation time, pre-oxidation atmosphere are the gaseous mixture of nitrogen and air Body, oxygen content are 300~20000ppm；
(2) hydrogen volume percentage composition is 3~25% in soaking pit, 0~20ppm of oxygen content, dew point -50~-30 DEG C；
(3) hot-dip temperature is 420~520 DEG C；
(4) it is cooled down after plating using nitrogen, 10~20 DEG C/s of cooling rate；
3) TRIP steel, Q&P steel substrate carry out hot-dip production using Sendzimir method:
(1) direct combustion section controls micro-oxidizing atmosphere, coefficient of excess air 0.70~0.95, and CO volumn concentration is 1~5%, CO2Body Product percentage composition is 5~15%；
(2) soaking zone hydrogen volume percentage composition is 5~15%, O2Content≤20ppm；
(3) hot-dip temperature is 420~520 DEG C；
(4) it is cooled down after plating using nitrogen, 3~20 DEG C/s of cooling rate.
5. a kind of production technology of automobile great surface quality zinc-aluminum-magnesium clad steel sheet according to claim 4, feature It is, the IF steel, BH steel, HSLA steel, DP steel substrate obtain pickling volume through smelting, continuous casting, hot rolling, pickling, or smelted, Continuous casting, hot rolling, cold rolling obtain cold rolling coil.
6. a kind of production technology of automobile great surface quality zinc-aluminum-magnesium clad steel sheet according to claim 4, feature It is, the TRIP steel, Q&P steel substrate obtain pickling volume through smelting, continuous casting, hot rolling, pickling, or through smelting, continuous casting, heat It rolls, cold rolling obtains cold rolling coil.
7. a kind of production work of automobile great surface quality zinc-aluminum-magnesium clad steel sheet according to claim 4-6 any one Skill, which is characterized in that plating solution composition addition alloy is 6 component alloys of Zn, Al, Mg, Cu, Ti, Cr element, and element is in alloy Gu melt exists, Adding Way is to be slowly positioned in molten bath by artificial or robotic arm.
Technical field
The invention belongs to steel material surface protection technology fields, and in particular to a kind of automobile great surface quality zinc-aluminum-magnesium Clad steel sheet and its production technology.
Background technique
Zinc-aluminum-magnesium clad steel sheet is widely used in anti-corrosion material, has compared to traditional steel plate, heat zinc coating plate (GI, GA) There is better corrosion resisting property, and corrosion resisting property is 2-20 times or more of GI steel plate, and has in extreme environments such as acid rain, salt fogs There is preferable corrosion resistance.Therefore be widely used in agricultural, animal husbandry, freeway guardrail etc., in addition certain application fields can To replace stainless steel to use；The zinc-aluminum-magnesium coating of low-aluminum-content is widely used in automobile, household electric appliances, resistance to underfilm corrosion is good, With self-healing property, the secondary corrosion-resistant requirement such as sealing wax, japanning can be reduced, therefore before automobile industry has good application Scape.
The patented technology of zinc-aluminum-magnesium is relatively more, and major technique thinking is by the elements optimization such as control Zn, Al, Mg, Si, Re Coating Elemental redistribution, crystallite dimension and phase structure, improve coating corrosion resistance, and high temperature oxidation resistance etc. is related special Sharp mainly includes GAFAN(Zn-5%Al), GALVALUME(Zn-55%Al-1.6%Mg), ZAM(Zn-6%Al-3%Mg), SUPERDUMA(Zn-11%Al-3%Mg), DYMAZINC(Zn-0.2%Al-0.5%Mg), SUPERZINE(Zn-4.5%Al-0.1% Mg) etc..These patents mainly rest in the days such as day brand-new iron, Nippon Steel, An Saile meter tal fibre, Thyssen Krupp, Tata Steel Originally, in European, United States Steel Corporation's hand, production and application to China's zinc-aluminum-magnesium form patent barrier.
It is domestic in recent years to do a lot of work in the innovation of zinc-aluminum-magnesium product technology, zinc is improved by addition microalloy element The performance of magnalium achieves the progress of some novelties, but the problems such as zinc-aluminum-magnesium coated steel sheet surface quality color difference still It is huge challenge, hardly results in main engine plants' approval.Patent CN 108486415A adds Ti:0.01~0.05% using zinc-aluminum-magnesium, The elements such as Cd≤0.002%, Cr≤0.002%, and the coating of fine grain size has been obtained using the method for hot-dip, but not It is described hot-dip rear surface quality problems；Patent CN 108977695A adds Ti:0.1~0.2wt%, Sb using zinc-aluminum-magnesium: 0.1~0.2wt% effectively improves the comprehensive performance of alloy so that eutectic structure also becomes more tiny and fine and close, improves anti- Scratch resistant and corrosion resistance；Patent CN 105648273A adds W:0.3~0.5wt%, Ti:0.5~0.8wt% using zinc-aluminum-magnesium Equal elements improve hardness and Scratch Resistance energy；Patent CN 108642493A improves plating using zinc-aluminum-magnesium addition B, Cu, Ni, Mn Stability of the layer in atmospheric environment.
Therefore a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet is developed, the Automobile Plate hot-dip of zinc-aluminum-magnesium coating is solved Rear surface is of low quality, and the relatively low problem of coating hardness is of great significance.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of automobile great surface quality zinc-aluminum-magnesium clad steel sheet and its lifes Production. art.The elements such as Ti, Cr, Cu are added in the invention on the basis of Zn-Al-Mg, the coating crystallite dimension of available refinement, Coating hardness is improved, there is good Scratch Resistance energy, good coating surface quality solves zinc-aluminum-magnesium coating Automobile Plate heat Immersion plating rear surface is of low quality, the relatively low problem of coating hardness.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of automobile great surface quality zinc-aluminum-magnesium Clad steel sheet, the zinc-aluminum-magnesium clad steel sheet plating solution chemical component composition and its mass percentage are as follows: Al+Mg:2~6%, Mg/ Al:0.8~1.2%, Cr:0.1~0.6%, Ti:0.2~1.0%, Cu:0.5~2.5%, remaining is Zn and inevitable impurity.
Zinc-aluminum-magnesium clad steel sheet substrate of the present invention is deep-draw, ultra-deep punching, high-intensitive, superhigh intensity automobile steel heat Base or cold base Automobile Plate；The zinc-aluminum-magnesium clad steel sheet steel grade is IF steel, BH steel, HSLA steel, DP steel, TRIP steel, Q&P steel.
The coating performance of zinc-aluminum-magnesium clad steel sheet of the present invention: 120~150HV of hardness, surface quality: shading value 0.69 ~0.89.
The present invention also provides a kind of production technology of automobile great surface quality zinc-aluminum-magnesium clad steel sheet,
1) IF steel, BH steel, HSLA steel, DP steel substrate carry out hot-dip production using U.S. steel connection technique:
(1) continuous annealing atmosphere use hydrogen volume content for 3~25% nitrogen hydrogen mixeding gas, oxygen content≤20ppm, dew - 50~-30 DEG C of point；
(2) hot-dip temperature is 420~520 DEG C；
(3) it is cooled down after plating using nitrogen, 10~20 DEG C/s of cooling rate.
2) TRIP steel, Q&P steel substrate carry out hot-dip production using U.S. steel connection technique, continuous annealing process using degreasing, Heating, pre-oxidation, soaking, cooling, hot-dip, coating cooling technique:
(1) 500~800 DEG C of Pre oxidation, 10~60s of preoxidation time, pre-oxidation atmosphere are the gaseous mixture of nitrogen and air Body, oxygen content are 300~20000ppm；
(2) hydrogen volume percentage composition is 3~25% in soaking pit, 0~20ppm of oxygen content, dew point -50~-30 DEG C；
(3) hot-dip temperature is 420~520 DEG C；
(4) it is cooled down after plating using nitrogen, 10~20 DEG C/s of cooling rate.
3) TRIP steel, Q&P steel substrate carry out hot-dip production using Sendzimir method:
(1) direct combustion section controls micro-oxidizing atmosphere, coefficient of excess air 0.70~0.95, and CO volumn concentration is 1~5%, CO2 Volumn concentration is 5~15%；
(2) soaking zone hydrogen volume percentage composition is 5~15%, O2Content≤20ppm；
(3) hot-dip temperature is 420~520 DEG C；
(4) it is cooled down after plating using nitrogen, 3~20 DEG C/s of cooling rate.
IF steel of the present invention, BH steel, HSLA steel, DP steel substrate obtain pickling volume through smelting, continuous casting, hot rolling, pickling, or Person obtains cold rolling coil through smelting, continuous casting, hot rolling, cold rolling.
TRIP steel of the present invention, Q&P steel substrate obtain pickling volume through smelting, continuous casting, hot rolling, pickling, or smelted, Continuous casting, hot rolling, cold rolling obtain cold rolling coil.
Plating solution composition addition alloy of the present invention is 6 component alloys of Zn, Al, Mg, Cu, Ti, Cr element, and element is in alloy Gu melt exists, Adding Way is to be slowly positioned in molten bath by artificial or robotic arm
The beneficial effects of adopting the technical scheme are that the 1, present invention utilizes the skin effect of Cu element, work as coating When middle copper content is more than 1.66%, a large amount of tiny and stable ξ can be precipitated in ZnCu, and work as ξCuIt is uniformly poly- when content is more than 2% Collection inhibits steel plate to go out the aerial oxidation process of coating behind molten bath, avoids loose magnesia in zinc-aluminum-magnesium coating surface The generation of object to improve zinc-aluminum-magnesium coating surface quality, and can be improved corrosion resistance under high temperature and normal temperature condition.2, Ti of the present invention and Cr element can be formed other than being conducive to form tiny coating grain structure in coating on coating most surface layer Fine and close oxide, the ξ of protection surface layer enrichmentCuAutoxidation does not occur under the conditions of complex environment during military service, guarantees Coating has good corrosion resistance and great surface quality for a long time.3, the present invention adds Ti, Cr, Cu member on the basis of Zn-Al-Mg Element, the coating crystallite dimension of available refinement improve coating hardness, coating performance: 120~150HV of hardness, surface quality: Shading value 0.69~0.89 has good Scratch Resistance energy and coating surface quality.
Specific embodiment
Present invention will be explained in further detail combined with specific embodiments below.