CN104060209A - Galvalized aluminum magnesium steel plate and manufacture method thereof - Google Patents
Galvalized aluminum magnesium steel plate and manufacture method thereof Download PDFInfo
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- CN104060209A CN104060209A CN201310091401.8A CN201310091401A CN104060209A CN 104060209 A CN104060209 A CN 104060209A CN 201310091401 A CN201310091401 A CN 201310091401A CN 104060209 A CN104060209 A CN 104060209A
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Abstract
The invention discloses a galvalized aluminum magnesium steel plate, which comprises a substrate and a coating layer coating on the substrate, the coating layer comprises the following chemical element components: 1.9-3.9wt% of Al, 1.9-3.9wt% of Mg, and the balance of Zn and other inevitable impurities; and the mass percentage of Al to Mg is greater than or equal to 1. The invention also discloses a method for manufacturing the galvalized aluminum magnesium steel plate, which comprises the following steps: 1)manufacturing the substrate; 2)degreasing and cleaning the surface of the substrate; 3)continuously annealing; 4)galvalizing the substrate in a heat galvalizing pool; and 5)galvalizing and cooling. The galvalized aluminum magnesium steel plate has good corrosion resisting performance, clunging performance, weldability and manufacturability, can satisfy the plate usage requirement in automobile industry, building field and household electrical appliance industry, the manufacture method of the galvalized aluminum magnesium steel plate can avoid the scum problem of a plating liquid due to addition of Mg, production cost is reduced, and equipment life is prolonged.
Description
Technical field
The present invention relates to a kind of steel plate and manufacture method thereof, relate in particular to a kind of steel plate with coating and manufacture method thereof.
Background technology
The iron and steel that is described as industrial grain plays very important effect in the fields such as industry, agricultural, activity in production, daily life.But iron and steel is very easily corroded in air, not only can affects surface of steel plate attractive in appearance, and also failure conditions can occur through steel plate after a period of time.In surface of steel plate hot dip process last layer metallic zinc, can significantly reduce the erosion rate of steel plate.Pure zinc plays good anti-corrosion defencive function by insulation blocking effect and sacrificing protection interaction energy to steel product; but the product of having relatively high expectations for some solidity to corrosions; durable consumer goods such as automobile, household electrical appliance; Architectural Equipments such as factory building, covil construction and commercial building again; it is not enough that the erosion resistance of hot pure zinc plating steel plate will seem, can not meet the needed corrosion-resistant defencive function of the said products or facility.In order to make steel plate obtain better corrosion resisting property under the condition of identical thickness of coating (even more flash plating thickness), reduce production costs simultaneously, can improve steel plate coating performance and reduce Plate Production cost by add certain alloying element in zinc liquid, correspondingly, various new Plating Systems are developed in succession, for example, Galfan coating (Zn-5%Al-0.06%Re) and Galvalmue coating (Zn-55%Al-1.6%Si).Galfan coating has only improved 2-3 doubly compared to the solidity to corrosion of GI coating (the pure zinc coating of hot dip); And Galvalume coating compared to GI coating (the pure zinc coating of hot dip) although solidity to corrosion improved 6-7 doubly; but the sacrificing protection effect of Galvalume coating is also almost lost; and the hot dip process temperature in production technique is brought up to more than 600 ℃ significantly from 460 ℃ of left and right; increase the energy consumption of production process, increased the loss of hot-dip coating apparatus.
Find after deliberation, magnesium add the corrosion resisting property that can greatly improve Zn-based plating layer, but because the chemical property of MAGNESIUM METAL is very active, how to be added zinc pot, the generation that how to reduce scum silica frost is all that magnesium is introduced to the required technical problem facing of Zn-based plating layer.In order to address this problem, conventionally adopt the add-on that reduces magnesium to solve, the add-on of magnesium is controlled to 0.2% left and right, but has just sacrificed the solidity to corrosion of coating simultaneously.In addition, also have and consider to introduce other alloying element and solve the problem that plating solution scum silica frost and Mg add zinc pot.
Publication number is CN1398304A, open day is on February 19th, 2003, the Chinese patent literature that name is called " steel plate of the Zn-Al-Mg alloy of the high Al of hot dip process " discloses the Coated Steel that a kind of coating is Zn-Al-Mg alloy, the quality percentage composition of each chemical composition of this steel plate coating is: Al:10%～22%, Mg:1～5%, and select any one of following chemical composition: Ti:0.002～0.1%, B:0.001～0.045%, Si:0.005～0.5%, this coating shows by being blended in Al/Zn/Zn
2, in the metallographic structure of this coating, substantially there is not Zn in the metallographic structure that an Al crystalline phase in the matrix of Mg ternary eutectic structure forms
11mg
2phase.
Publication number is CN1632157A, open day is on June 29th, 2005, the Chinese patent literature that name is called " the zinc-aluminum-magnesium alloy coated steel production method that solidity to corrosion is good and zinc-aluminum-magnesium alloy coated steel " has related to zinc-aluminum-magnesium alloy coated steel and manufacture method thereof, in plating solution, the quality percentage composition of each chemical composition is: Al2.5%～20%, Mg1.5%～4.5%, Re0.01%～0.3%, all the other are Zn and inevitable impurity; And add appropriate Si and V at plating solution, and solvent is the aqueous solution, chemical constitution is ZnCl
2: 200g/l～1000g/l, NH
4cl:0g/l～200g/l, KCl:0g/l～100g/l, NaCl:0g/l～100g/l, rare earth chloride: 0g/l～100g/l, pH value is 3～4; Bath temperature is 450 ℃～580 ℃, and the plating time is 2s～300s.
Publication number is CN101558182A, open day is on October 14th, 2009, the Chinese patent literature that name is called " hot-dip zn-al alloy coated steel sheet and manufacture method thereof " provides a kind of hot-dip zn-al alloy coated steel sheet, and this alloy steel plate has the plating outward appearance of metalluster and good anti-blackening energy.The hot dip Zn-Al of this alloy steel plate is that in alloy layer, contained chemical composition is: Al:1.0～10wt%, and Mg:0.2～1.0wt%h and Ni:0.005～0.1wt%, surplus is Zn and other inevitable impurity.The manufacture method of this hot-dip steel plate is, first steel plate being impregnated in to melting Zn-Al is in alloy electroplating bath, then it is cooling from plating solution, to sling, and finally steel plate is cooled to 250 ℃, and speed of cooling is 1～15 ℃/sec.
In the disclosed technical scheme of above-mentioned these patent documentations, all added more metallic aluminium, and in coating, Al content is higher, the spot welding characteristics of Coated Steel is just poorer, and this can limit it in the application of auto industry field.
Summary of the invention
One of object of the present invention is to provide a kind of pot galvanize magnalium steel plate, and it,, by controlling solution composition, has improved solidity to corrosion, sticking power and the welding property of pot galvanize magnalium steel plate coating.
Another object of the present invention is to provide a kind of manufacture method of pot galvanize magnalium steel plate, and this manufacture method can solve the problem of adding magnesium and causing a large amount of scum silica frost in hot dip process, thereby has guaranteed the surface quality of steel plate.
To achieve these goals, the present invention proposes a kind of pot galvanize magnalium steel plate, it comprises substrate and wrap the coating on substrate, and the chemical element composition of this coating is:
Al 1.9-3.9wt%；
Mg 1.9-3.9wt%；
Surplus is Zn and other inevitable impurity;
And ratio >=1 of Al and the mass percent of Mg.
In the substrate coating of pot galvanize magnalium steel plate of the present invention, aluminium and magnesium elements have been added.Mg adds the solidity to corrosion that can significantly improve substrate coating, but when Mg content is less than 1.9%, the corrosion resisting property of coating improves also not obvious.Contriver finds through overtesting, increase along with Mg content, the corrosion resisting property of coating also can constantly promote, when the content of excessive Mg does not approach 4%, the effect that Mg improves for corrosion resistance of coating is tending towards saturated, at this moment, then add too much Mg and not only can cause temperature in hot dip process process to raise, also can make hot dipping plating solution produce a large amount of oxidation sludges.In addition, adding also of Al can improve substrate corrosion resistance coating, but contriver finds, when Al content is higher than 3.9% time, in hot dip process process, easily generate blocked up Fe-Al alloy layer, this can affect the processing characteristics in coating later stage, and Al content is higher, the spot welding characteristics of substrate coating is just poorer, and this can limit its Application in manufacture in relevant industries.
When controlling solution composition scope, it is very crucial that the ratio of the control quality percentage composition of Al and the quality percentage composition of Mg is more than or equal to 1, the a large amount of face slags that produce when Mg adds zinc liquid be could effectively reduce like this, thereby surface quality and the manufacturability energy of finished product substrate coating improved.
Correspondingly, the present invention also provides a kind of manufacture method of pot galvanize magnalium steel plate, and it comprises the following steps:
(1) manufacture substrate;
(2) substrate surface is carried out to cleaning by degreasing;
(3) continuous annealing;
(4) in hot dip pond, substrate is carried out to hot dip process;
(5) cooling after plating.
Further, in above-mentioned steps (4), the temperature in hot dip pond is 380～480 ℃.Too low bath temperature can cause the liquid fluidity variation of plating solution, thereby affect the surface quality of coating, too high bath temperature can cause substrate iron loss too high, and cause increasing and then making hot-dip coating apparatus corrosion aggravation of scum silica frost amount, hot dip process energy consumption increases, therefore, according to the setting range of each chemical composition in plating solution, the temperature in hot dip pond is controlled to 380～480 ℃.
Further, in above-mentioned steps (4), the hot dip process time is 3～10s.In order to obtain desirable substrate thickness of coating (two-sided 60g/m
2～400g/m
2) and good coating surface quality, the immersion plating time should be controlled to 3～10s.
Further, in above-mentioned steps (5), speed of cooling >=5 ℃/s.Speed of cooling is set in to the above too small alloy layer that causes of speed of cooling of can avoiding of 5 ℃/s blocked up and affect the adhesive ability of coating.
Adopt corrosion resistance nature and the surface quality of the pot galvanize magnalium steel plate of the technical program manufacture to be greatly better than existing pot galvanize product, and it also possesses good adhesive ability and welding property, can be widely used in industrial circles such as building work, household electrical appliances and automobile; In addition, the technical program has also solved the problem that adds a large amount of plating solution scum silica frost that Mg brings, reduced the bath temperature in hot dip process, reduced the equipment loss in hot dip pond, improve the work-ing life of hot dip production unit, thereby realized the decrement of plating solution metals resources consumption and the reduction of hot dip process energy consumption.
Accompanying drawing explanation
Fig. 1 has shown the temperature curve of embodiment 1 in hot dip process.
Fig. 2 is for detecting the energy spectrogram obtaining to the coating cross section of comparative example 4 by photoelectron spectrum equipment.
Embodiment
Below in conjunction with Figure of description and specific embodiment, pot galvanize magnalium steel plate of the present invention and manufacture method thereof are made to detailed description further, but this explanation does not form the improper restriction for technical solution of the present invention.
Embodiment 1-8
According to the following step, manufacture pot galvanize magnalium steel plate of the present invention, this steel plate comprises substrate and wraps the coating on substrate, the common IF steel that substrate employing thickness is 0.7mm:
(1) manufacture substrate:
(2) substrate surface is carried out to cleaning by degreasing;
(3) temperature rise rate is 15 ℃/s, and continuous annealing temperature is 780 ℃, and reducing atmosphere is 10vol%H
2+ N
2, dew point is-30 ℃, the recovery time is 60s;
(4) before immersion plating, at the temperature of high 10 ℃ than plating solution, being incubated 10s makes substrate plate temperature even, the bath temperature being controlled in hot dip pond is 380～480 ℃, substrate is put into hot dip pond and carry out hot dip process, the immersion plating time is 3～10s, wherein, in plating solution, each chemical element composition proportion is as shown in table 1, and bath temperature and immersion plating time are as shown in table 2;
(5) after plating, control substrate speed of cooling >=5 ℃/s.
Fig. 1 has shown in this case embodiment 1, the temperature curve in hot dip process.
The chemical composition quality per distribution ratio of table 1. embodiment 1-8 and comparative example 1-4 light plate coating
(wt%, surplus is Zn and other inevitable impurity)
In table 1, embodiment 1-8 is all pot galvanize magnalium steel plates of manufacturing by technical scheme of the present invention, the Coated Steel of comparative example 1-4 for adopting prior art to manufacture, the steel plate coating of comparative example 1-4 is respectively: pure zinc coating (GI), Zn-0.2%Al-3%Mg coating, Zn-5%Al coating and Zn-11%Al-3%Mg coating.
The correlation technique parameter of table 2. embodiment 1-8 in hot dip process
The Coated Steel of embodiment 1-8 and comparative example 1-4 is carried out to neutral salt spray test, the curved test of T and the test of hot dip product surface visual appearance, and check plating solution surface slag formational situation.Adopt neutral salt spray test to evaluate the corrosion resisting property of coating, requirement of experiment is carried out according to GB/T10125-1997.The combination degree of the curved test evaluation coating of T, requirement of experiment is carried out in accordance with the standard of GB232-82.In addition, contriver weighs plating solution slag production by formed the quantity of slag after the standing exposure of air 12h of the plating solution for embodiment 1-8 and comparative example 1-4, the face quantity of slag of pure steel plate galvanized of comparative example 1 of take is benchmark, measures respectively formed quantity of slag of plating solution of embodiment and other comparative examples compared to the multiple of benchmark value.The formational situation of the test result of above-mentioned test and the viewed plating solution face quantity of slag is all listed in table 3.
Table 3.
As shown in Table 3, the pot galvanize magnalium steel plate of embodiment 1-8 occurs that the time of 5% red rust appears in Coated Steel that the time of 5% red rust is all greater than comparative example 1-3, wherein, the pot galvanize magnalium steel plate of embodiment 3-4 occurs that the time of 5% red rust is that the more than 10 times of 5% red rust time appear in the pure steel plate galvanized of comparative example 1; Although there is pot galvanize magnalium steel plate that the time of 5% red rust is slightly larger than embodiment 1-8 and occur the time of 5% red rust in the Coated Steel of comparative example 4, but after the curved test of T, the steel plate coating of comparative example 4 can produce on a small quantity and peel off, and the grade of its appearance quality test is also only 2 grades.Yet the coating of the pot galvanize magnalium steel plate of embodiment 1-8 after the curved test of T does not all produce peeling phenomenon, meanwhile, the grade after its appearance quality is evaluated after tested has also all reached 1 grade.In addition, as shown in Table 3, the face quantity of slag of embodiment 1-8 is basic identical with formed quantity of slag of pure steel plate galvanized of comparative example 1; And the face quantity of slag of the Coated Steel of comparative example 2 is 75 times of formed the quantity of slag of pure steel plate galvanized of comparative example 1.The too much plating solution face quantity of slag can directly affect the manufacturability of coating surface quality and steel plate, and the face quantity of slag and the benchmark value of embodiment 1-8 are similar, and therefore, the pot galvanize magnalium steel plate of embodiment 1-8 all has good surface quality and manufacturability energy.
Fig. 2 is the energy spectrogram that the Coated Steel of comparative example 4 obtains through photoelectron spectrum device analysis, and comparative example 4 has adopted the coating of Zn-11%Al-3%Mg.By observing coating Cross Section Morphology and can knowing in conjunction with energy spectrogram, the steel plate of comparative example 4 has generated thicker Fe-Al alloy layer at its coating and basal body interface, the fragility of Fe-Al alloy layer is larger, will cause like this steel plate coating loss of adhesion, thus limited Coated Steel in automobile and the application of building work field.
Pot galvanize magnalium steel plate of the present invention coordinates with conventional hot plating technology flow process to obtain the pot galvanize magnalium steel plate of fine corrosion resistance by rational solution composition design, this steel plate also possesses good sticking power, welding property and manufacturability energy, the plate requirement such as car body, shell, inner panel and base plate in automotive industry not only can be met, the plate requirement such as casing in Lightgage Steel Joist, construction level panel, corrugated panel, rolling screen door and the household electric appliances in building field and panel can also be met.In addition, the manufacturing approach craft of pot galvanize magnalium steel plate of the present invention is simple, without carrying out scrap build, hot dip process energy consumption is less, hot-dip coating apparatus loss is lower, has avoided adding the problem of a large amount of plating solution scum silica frost that Mg brings, and has reduced the input of production cost, improve the work-ing life of operational outfit, can be applicable on a large scale the manufacturing of enterprise.
Be noted that above enumerate only for specific embodiments of the invention, obviously the invention is not restricted to above embodiment, have many similar variations thereupon.If all distortion that those skilled in the art directly derives or associates from content disclosed by the invention, all should belong to protection scope of the present invention.
Claims (5)
1. a pot galvanize magnalium steel plate, it comprises substrate and wraps the coating on substrate, it is characterized in that,
The chemical element composition of described coating is:
Al 1.9-3.9wt%；
Mg 1.9-3.9wt%；
Surplus is Zn and other inevitable impurity;
And ratio >=1 of Al and the mass percent of Mg.
2. the manufacture method of pot galvanize magnalium steel plate as claimed in claim 1, it comprises the following steps:
(1) manufacture substrate;
(2) substrate surface is carried out to cleaning by degreasing;
(3) continuous annealing;
(4) in hot dip pond, substrate is carried out to hot dip process;
(5) cooling after plating.
3. the manufacture method of pot galvanize magnalium steel plate as claimed in claim 2, is characterized in that, in step (4), the temperature in hot dip pond is 380-480 ℃.
4. the manufacture method of pot galvanize magnalium steel plate as claimed in claim 2, is characterized in that, in step (4), the hot dip process time is 3-10s.
5. the manufacture method of pot galvanize magnalium steel plate as claimed in claim 2, is characterized in that, in step (5), and speed of cooling >=5 ℃/s.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104328370A (en) * | 2014-11-11 | 2015-02-04 | 武汉钢铁(集团)公司 | Production method of hot-dip galvanized magnesium alloy steel plate |
| CN106916998A (en) * | 2017-04-21 | 2017-07-04 | 孙健 | A kind of super anticorrosive zinc base alloy layer steel band and its production method |
| CN110983224A (en) * | 2019-12-16 | 2020-04-10 | 首钢集团有限公司 | Hot-dip galvanized aluminum-magnesium coated steel and preparation method thereof |
| CN111270182A (en) * | 2020-03-20 | 2020-06-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot-dip Zn-Al-Mg alloy coated steel plate and preparation method thereof |
| CN111826598A (en) * | 2020-07-28 | 2020-10-27 | 攀钢集团研究院有限公司 | Wear-resistant corrosion-resistant zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN111850447A (en) * | 2020-07-28 | 2020-10-30 | 攀钢集团研究院有限公司 | High-performance zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN112680684A (en) * | 2020-11-23 | 2021-04-20 | 新冶高科技集团有限公司 | Hot-dip zinc-aluminum-magnesium alloy coating and preparation method thereof |
| CN114000081A (en) * | 2021-11-08 | 2022-02-01 | 浙江金洲管道科技股份有限公司 | Galvanizing method for steel pipe for nuclear power |
| CN115433893A (en) * | 2022-08-15 | 2022-12-06 | 马鞍山钢铁股份有限公司 | Method for reducing slag yield in low-aluminum zinc aluminum magnesium pot to be produced |
| CN116641009A (en) * | 2023-05-17 | 2023-08-25 | 宝山钢铁股份有限公司 | Zinc-based plated steel sheet having excellent corrosion resistance, hot stamped member, and method for manufacturing same |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104328370A (en) * | 2014-11-11 | 2015-02-04 | 武汉钢铁(集团)公司 | Production method of hot-dip galvanized magnesium alloy steel plate |
| CN106916998A (en) * | 2017-04-21 | 2017-07-04 | 孙健 | A kind of super anticorrosive zinc base alloy layer steel band and its production method |
| CN110983224B (en) * | 2019-12-16 | 2021-07-23 | 首钢集团有限公司 | Hot-dip galvanized aluminum-magnesium coated steel and preparation method thereof |
| CN110983224A (en) * | 2019-12-16 | 2020-04-10 | 首钢集团有限公司 | Hot-dip galvanized aluminum-magnesium coated steel and preparation method thereof |
| CN111270182A (en) * | 2020-03-20 | 2020-06-12 | 攀钢集团攀枝花钢铁研究院有限公司 | Hot-dip Zn-Al-Mg alloy coated steel plate and preparation method thereof |
| CN111826598A (en) * | 2020-07-28 | 2020-10-27 | 攀钢集团研究院有限公司 | Wear-resistant corrosion-resistant zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN111850447A (en) * | 2020-07-28 | 2020-10-30 | 攀钢集团研究院有限公司 | High-performance zinc-aluminum-magnesium coated steel plate and preparation method thereof |
| CN112680684A (en) * | 2020-11-23 | 2021-04-20 | 新冶高科技集团有限公司 | Hot-dip zinc-aluminum-magnesium alloy coating and preparation method thereof |
| CN112680684B (en) * | 2020-11-23 | 2023-02-07 | 新冶高科技集团有限公司 | Hot-dip zinc-aluminum-magnesium alloy coating and preparation method thereof |
| CN114000081A (en) * | 2021-11-08 | 2022-02-01 | 浙江金洲管道科技股份有限公司 | Galvanizing method for steel pipe for nuclear power |
| CN115433893A (en) * | 2022-08-15 | 2022-12-06 | 马鞍山钢铁股份有限公司 | Method for reducing slag yield in low-aluminum zinc aluminum magnesium pot to be produced |
| CN115433893B (en) * | 2022-08-15 | 2024-03-01 | 马鞍山钢铁股份有限公司 | Method for reducing slag rate in zinc-aluminum-magnesium pot with low aluminum series to be produced |
| CN116641009A (en) * | 2023-05-17 | 2023-08-25 | 宝山钢铁股份有限公司 | Zinc-based plated steel sheet having excellent corrosion resistance, hot stamped member, and method for manufacturing same |
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Application publication date: 20140924 |