CN101163811A - Galvannealed sheet steel and process for production thereof - Google Patents
Galvannealed sheet steel and process for production thereof Download PDFInfo
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- CN101163811A CN101163811A CNA2006800134781A CN200680013478A CN101163811A CN 101163811 A CN101163811 A CN 101163811A CN A2006800134781 A CNA2006800134781 A CN A2006800134781A CN 200680013478 A CN200680013478 A CN 200680013478A CN 101163811 A CN101163811 A CN 101163811A
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Abstract
The invention aims at providing galvannealed sheet steel excellent in corrosion resistance, workability, coatability and appearance and a process for the production thereof. The invention relates to a process for the production of galvannealed sheet steel which comprises subjecting an ultra low carbon steel sheet to surface cleaning and preplating with nickel, heating the resulting sheet rapidly either in the absence of oxygen or in a reducing atmosphere to a sheet temperature of 430 to 500 DEG C at a temperature rise rate of 30 DEG C/sec or above, plating the sheet in a plating bath of molten Zn, wiping the resulting sheet, heating the sheet rapidly to 470 to 600 DEG C at a temperature rise rate of 30 DEG C/sec or above, and then cooling the sheet either without soaking or after soaking for less than 15 seconds. The galvannealed steel sheet produced by the process is composed of an ultra low carbon steel sheet and a galvannealed layer formed on at least one side of the sheet which layer comprises by mass Fe: 8 to 13 %, Ni: 0.05 to 1.0%, and Al: 0.15 to 1.5% with the balance being Zn and unavoidable impurities, and has an Al/Ni ratio of 0.5 to 5.0, the mean thickness of G layer present on the interface of basis steel being 1 m or below and the dispersion of the thickness falling within +- 0.3 m.
Description
Technical field
The present invention relates to solidity to corrosion, processibility, coating all excellent be the alloyed hot-dip galvanized steel plate and the manufacture method thereof of raw sheet with the ultra-low carbon steel plate.In addition, the invention still further relates to the manufacture method of the very good hot-dip galvanized steel sheet of outward appearance.
Background technology
In the past, alloyed hot-dip galvanized steel plate, known as the automobile of the corrosion resistance excellent after the adhesivity of filming, the application or steel plate for building.In recent years,, require to have deep drawing quality, therefore use morely with the alloyed hot-dip galvanized steel plate of ultra-low carbon steel plate as raw sheet as the automobile purposes.In the case, the solidity to corrosion under the naked attitude and the solidity to corrosion of coating scratch portion may not can be described as fully.In addition, also there is following problem: add and suppress efflorescence (powdering) man-hour and suppress slabbing (surfacial spalling) to be difficult to realize simultaneously; Be easy to generate macroscopic irregularity during electrodeposition coating.
Open once to disclose in the flat 9-3417 communique the spy and containing zn-fe alloy layer on the steel plate, containing Fe:8～15%, Ni:0.1～2%, the alloyed hot-dip galvanized steel plate of corrosion resistance excellent below the Al:1% as the 2nd layer as the 1st layer.In addition, in No. 2783452 communique of Japanese Patent, once disclosed a kind of manufacture method of alloyed hot-dip galvanized steel plate of corrosion resistance excellent, it is characterized in that, carried out 0.2～2g/m on the surface of steel plate
2Preplating Ni after, quickly heat up to 430～500 ℃, in the Zn plating bath that contains 0.05～0.25%Al, carry out hot dip process, after wiping 470～550 ℃ of alloying heat treated of carrying out for 10～40 seconds.It is the calm steel plate of hot-rolled low carbon Al that above-mentioned spy opens flat 9-3417 communique and No. 2783452 communique of Japanese Patent disclosed, not about the knowledge opinion of the present invention as the ultra-low carbon steel plate of target.
The ultra-low carbon steel plate is compared with mild steel plate, and its difference is: the degree of cleaning height of ferrite crystal boundary, and alloying is carried out unevenly, and the Г layer is grown easily in addition, therefore, can not intactly continue to use the knowledge opinion of mild steel plate.In addition, open the knowledge opinion that does not also have in flat 9-3417 communique and No. 2783452 communique of Japanese Patent about processibility, application the spy.
In No. 2804167 communique of Japanese Patent, disclose and a kind ofly carried out hot dip process and carry out alloying by making in the bath that contains in the plating bath less than the Ni of 0.2% Al and 0.01～0.5%, thereby make coating contain Fe:8～13%, Al: less than 0.5%, the Zn of Ni:0.02～1% and its surplus, and the Г layer thickness at iron matrix (substrate iron) interface is the following alloyed hot-dip galvanized steel plate of 0.5 μ m.No. 2804167 communique of this patent is disclosed to be mild steel plate, not about the knowledge opinion of the present invention as the ultra-low carbon steel plate of target.Even wherein disclosed method for making is used for the ultra-low carbon steel plate, in fact also the Г layer thickness can not be controlled at below the 0.5 μ m, about solidity to corrosion, processibility, the coating of the present invention, also be inadequate fully as target.
No. 2800285 communique of Japanese Patent once disclosed to the firm and hard 20～70mg/m that executes of ultra-low carbon steel
2Plating Ni after, anneal, the manufacture method of the alloyed hot-dip galvanized steel plate of galvanizing, Alloying Treatment.But, when adopting this method, there is not the corrosion proof effect of improving, also insufficient about processibility in addition.
No. 3557810 communique of Japanese Patent once disclosed in the galvanizing that contains Al:0.1～0.2%, Ni:0.04～0.2% is bathed and carried out plating, and with 10～20 ℃/second heat-up rate alloying, by the sliding and all excellent alloyed hot-dip galvanized steel plate of coating on the surface of the ζ layer lining 1～40% of 1～10 μ m.But, this technology, processibility, particularly pulverability and solidity to corrosion are insufficient.
No. 3498466 communique of Japanese Patent once disclosed by add Ni in the galvanizing that contains Al is bathed, and then add at least a kind of plating bath that forms among Pb, Sb, Bi, the Sn and carry out plating, and carry out alloying with defined terms, thereby make coating contain among Al:0.1～0.25%, Fe:6～18%, Ni:0.05～0.3% and Pb, Sb, Bi, the Sn at least a kind: 0.001～0.01% alloyed hot-dip galvanized steel plate.But in this technology, plating bath is 4 yuan of systems, not only manages miscellaneously, and the scum silica frost that Ni and Al chemical combination form takes place easily in plating bath, is involved in occasion in the coating at it, just becomes the factor of solidity to corrosion deterioration, so undesirable.
In addition, add the ultra-low carbon steel plate of Ti, having can be in the stable extremely deep drawing quality and the ductile feature of excellence of obtaining of very wide composition range.But, this steel plate is implemented galvanizing, and then carry out the occasion of Alloying Treatment, and since the influence of Ti in the steel, being cleaned of crystal boundary, so alloying reaction is promoted at crystal boundary.Its result causes explosive reaction easily, carries out alloying easily, and pulverability worsens.
In order to address the above problem, once disclosed by with the compound together interpolation Nb of Ti, be controlled at the alloying reaction that crystal boundary produces, make the manufacture method (special public clear 61-32375 communique, spy open clear 59-67319 communique, spy are opened clear 59-74231 communique, the spy opens flat 5-106003 communique) of the alloyed hot-dip galvanized steel plate that pulverability improves thus.They all are the schemes with the further compound interpolation Nb of Ti, but therefore the interpolation cost height of this Nb exists uneconomic shortcoming.
Can improve the technology of the pulverability of the ultra-low carbon steel plate that adds Ti as not compound interpolation Nb, open the spy and to control steam atmosphere in once disclosing by the process of cooling after recrystallization annealing in the flat 10-287964 communique, make grain boundary oxidation, thus the method for the outburst of control during alloying reaction.This method is the control difficulty of oxidation not only, and causes detrimentally affect for easily the coating outward appearance.
Open the spy and once to disclose the Al concentration ratio that makes in the hot dipping plating bath in the flat 8-269665 communique and improve usually, be 0.12～0.2%, thereby make iron matrix-part, coating interface have the method for the high phase of Al concentration, but under this occasion, it is uneven that coating becomes easily, and outward appearance worsens easily.
In addition, alloyed hot-dip galvanized steel plate, as the occasion that the automobile exterior panel purposes is used, the outward appearance of alloyed hot-dip zinc-coated layer is inhomogeneous, and still the occasion as inhomogeneous and residual is a lot of behind painting dressing automobiles, therefore requires the outward appearance grade of high degree.It is more that wherein a lot of inhomogeneous results from the situation of last process such as the oxide film of plating raw sheet is inhomogeneous, trace ingredients is inhomogeneous, but be that its reason is difficult to specific situation substantially, and basic countermeasure is in the situation of difficulty.In the above-mentioned document of quoting, even openly be not used to obtain the pointer as the also permissible very good surface appearance of automobile exterior panel purposes of target as the present invention.
Summary of the invention
As described above, problem of the present invention provide a kind of solidity to corrosion, processibility, coating all excellent be the alloyed hot-dip galvanized steel plate and the manufacture method thereof of raw sheet with the ultra-low carbon steel plate.In addition, usually in the manufacturing of alloyed hot-dip galvanized steel plate, interface at iron matrix-coating in galvanizing is bathed forms Fe-Al-Zn alloy layer (so-called blocking layer), by heat treated subsequently, above-mentioned alloy layer is disappeared, meanwhile form Al dispersive zn-fe alloy layer, can make thus.At this, the Fe-Al-Zn alloy layer from the control of subsequently zn-fe alloy reaction with guarantee the viewpoint of plating adhesion, is undertaken important role.Yet, the Fe-Al-Zn alloy layer, its formation speed is subjected to the influence of the condition of surface of plating raw sheet, the liquid stream in the plating bath etc. very sensitively, meanwhile, the delicate difference of the thickness of Fe-Al-Zn alloy layer, can influence the alloying reaction behavior extremely sensitively with former state, it is inhomogeneous to bring out small coating outward appearance, therefore makes the very good alloyed hot-dip galvanized steel plate of outward appearance and is not easy.Therefore, the objective of the invention is to, the manufacture method of the extremely good alloyed hot-dip galvanized steel plate of outward appearance is provided.
Present inventors are based on above-mentioned Te Kaiping-No. 3417 communique and No. 2783452 disclosed technology opinion of communique of Japanese Patent, with the ultra-low carbon steel plate as raw sheet, the alloyed hot-dip galvanized steel plate of investigation solidity to corrosion, processibility, coating excellence, thus the present invention finished.Promptly, the present invention is all excellent alloyed hot-dip galvanized steel plate of a kind of solidity to corrosion, processibility, coating, it is characterized in that, having by quality % by the Zn of Fe:8～13%, Ni:0.05～1.0%, Al:0.15～1.5%, its surplus and the coating that unavoidable impurities constitutes on the one side at least of ultra-low carbon steel plate, the ratio of Al/Ni is 0.5～5.0, the mean thickness of the Г layer at iron matrix interface is below the 1 μ m, and its deviation (undulating quantity) is in ± 0.3 μ m.
In addition, the present invention is a kind of manufacture method of alloyed hot-dip galvanized steel plate, it is characterized in that, after annealed ultra-low carbon steel plate surface is cleaned, implements 0.1～1.0g/m
2Preplating Ni, after in non-oxidation or reducing atmosphere, quickly heating up to 430～500 ℃ of plate temperatures with the heat-up rate more than 30 ℃/second, in bathing, the galvanizing that contains Al:0.1～0.2 quality % carries out plating, through quickly heating up to 470～600 ℃ with the heat-up rate more than 30 ℃/second after the wiping, just cool off or after carrying out, cool off less than 15 seconds soaking maintenance without soaking time.
In addition, what present inventors discussed found that, as in galvanizing is bathed, the alloy layer that generates at the interface of iron matrix-coating, replace the Fe-Al-Zn alloy layer and when utilizing the Fe-Ni-Al-Zn alloy layer, the fluctuation that caused alloy layer such as the liquid stream in the condition of surface of plating raw sheet, the plating bath generates behavior tails off, meanwhile, with regard to the thickness deviation of alloy layer, its zn-fe alloy reflex action to the back less exerts an influence, the result can obtain extremely good surface appearance, thereby has finished the present invention.Promptly, the present invention is a kind of manufacture method of alloyed hot-dip galvanized steel plate, it is characterized in that, in galvanizing is bathed, after the iron matrix interface forms the Fe-Ni-Al-Zn alloy layer, by heat treated above-mentioned Fe-Ni-Al-Zn alloy layer is disappeared, meanwhile form Ni, Al dispersive zn-fe alloy layer.
According to the present invention, can provide solidity to corrosion, processibility, coating all excellent be the alloyed hot-dip galvanized steel plate and the manufacture method thereof of raw sheet with the ultra-low carbon steel plate.In addition, according to the present invention, can obtain can be used for the manufacture method of alloyed hot-dip galvanized steel plate automobile exterior panel etc., that outward appearance is extremely good.
Description of drawings
Fig. 1 is the analysis result of the relevant coating-iron matrix interface alloy layer that generates in galvanizing is bathed of the present invention of expression.
Fig. 2 is the analysis result of the coating-iron matrix interface alloy layer that generates in galvanizing is bathed of the existing method of expression.
Fig. 3 is the analysis result of the relevant alloyed hot-dip zinc-coated layer structure of the present invention of expression.
Fig. 4 is the analysis result of the alloyed hot-dip zinc-coated layer structure in the existing method of expression.
Fig. 5 be expression among the present invention, the figure of the preferable range of Al concentration and the pre-adhesion amount of Ni in the plating bath.
Embodiment
Below, describe the present invention in detail.
At first, the present invention is as the ultra-low carbon steel plate of object, can use to add Ti, Nb etc. single or compoundly and make the ultra-low carbon steel plate that solid solution carbon disappears and further add P, Mn, Si etc. and make ultra-low carbon steel plate that intensity improves etc.In addition, also can use Ni, Cu, the so-called ultra-low carbon steel plates of sneaking into element such as Sn, Cr that contain denier.
The ultra-low carbon steel plate that solid solution carbon is disappeared, at length say, can use by quality % contain below the C:0.005%, below the Si:0.03%, Mn:0.05～0.5%, below the P:0.02%, below the S:0.02%, Ti (and/or Nb): 0.001～0.2% ultra-low carbon steel plate.Even add the occasion of Ti (or Nb) singlely, the situation that contains the Nb (or Ti) below about 0.001% that sneaks into as unavoidable impurities also is defined as the ultra-low carbon steel plate that comprises.
In addition,, at length say as adding the ultra-low carbon steel plate that P improves intensity, can use contain that C:0.005% is following, Si:0.03% is following, Mn:0.05～0.5%, P:0.02%～0.1%, the following ultra-low carbon steel plate of S:0.02%.The raw sheet of the applicable high-strength and high-ductility galvannealed steel sheet that also spendable deep drawing quality is good in the automobile exterior panel purposes as 340MPa～390MPa level of these steel plates.In addition, can also use and in above-mentioned composition, further Mn is defined as 0.5～2.5%, further Si is defined as the steel plate below 0.5%.The applicable raw sheet of these steel plates as 390MPa～440MPa level high-strength and high-ductility galvannealed steel sheet that also spendable deep drawing quality is good in the automobile exterior panel purposes.
Secondly, narration is about the composition of coating, the reason that structure limits.Fe is defined as 8～13%, because less than down in limited time, solidity to corrosion worsens easily, surpasses the cause that last pulverability in limited time worsens easily.
Ni is defined as 0.05～1.0%, because less than down in limited time, solidity to corrosion worsens easily, surpasses the cause that last pulverability in limited time worsens easily.In addition, when requiring better pulverability, preferred Ni is 0.1～0.5%.
Al is defined as 0.15～0.5%, because less than down in limited time, pulverability and solidity to corrosion worsen easily, surpasses the cause that last coating in limited time and solidity to corrosion also worsen easily.In addition, when requiring better pulverability, preferred the following of Al is limited to 0.3%, in addition, when requiring better coating, is limited to 0.8% on the preferred Al.
In addition, the ratio of Al/Ni is defined as 0.5～5.0th,, surpasses the cause that last coating in limited time and solidity to corrosion also worsen easily because less than down in limited time, pulverability worsens easily.When requiring better pulverability, preferred the following of Al/Ni ratio is limited to 1.0.
The invention is characterized in that the mean thickness of the Г layer at iron matrix interface is below the 1 μ m, and its deviation is in ± 0.3 μ m.At this, as the method for the thickness of measuring the Г layer, following method all can, for example, in aqueous ammonium chloride solution,, adopt the constant current electrolysis that the quantitative electric current of Г layer peeled off method by after the part beyond the constant potential electrolytic dissolution Г layer; The coating section is corroded with nital (Nital) known corrosive fluids such as (alcohol+nitric acid), with the method for direct viewing such as opticmicroscope; Perhaps, method of trying to achieve etc. by X-ray diffraction intensity.In addition, the deviation of so-called Г layer is meant at the width of steel plate and measures several points～dozens of point, maximum value and minimum value to the difference of the mean value of Г layer in ± 0.3 μ m.Being limited to 1 μ m on the mean thickness of Г layer of the present invention, is bigger value, but for pulverability, processibility, above-mentioned deviation control is important, in addition, forms with above-mentioned suitable coating and to combine, and can obtain good performance.
Secondly, the method for making alloyed hot-dip galvanized steel plate of the present invention is narrated.
In the present invention, use annealed ultra-low carbon steel plate as raw sheet.At first, the surface to clean be necessary, be not particularly limited about this method, according to the situation of the dirt and the oxide film of raw sheet, individually or the known methods such as alkali degreasing, brushing processing, acid treatment that are used in combination get final product.Consider from the inhomogeneity viewpoint of plating Ni layer described later, preferably be used in combination alkali degreasing (for example the NaOH aqueous solution is handled) and acid treatment (for example aqueous sulfuric acid processing) in order.
In the present invention, implement 0.1～1.0g/m
2Preplating Ni.Though also depend on the above-mentioned pre-treatment that cleans, to prescribe a time limit less than following, the wettability of hot dip process after this is insufficient, and in addition, solidity to corrosion is also not enough.In limited time, pulverability worsens easily on surpassing.When requiring better pulverability, be limited to 0.8g/m on the preferred preplating Ni
2
Behind the preplating Ni, in non-oxidation or reducing atmosphere, quickly heat up to 430～500 ℃ of plate temperatures with the heat-up rate more than 30 ℃/second.This processing is necessary in order to ensure the wettability and the plating adhesion of hot dip process.When requiring better pulverability, the plate temperature upper limit of heating is preferably 480 ℃.
Galvanizing is bathed, the plating bath of using the Zn by Al:0.1～0.2% and unavoidable impurities and surplus thereof to constitute.When Al less than down in limited time, pulverability and solidity to corrosion worsen easily; When Al surpass last in limited time, coating and solidity to corrosion also worsen easily.In the present invention, initiatively do not add Ni in the plating bath, this point is different with patent documentation 5 and 6, because Ni source as coating, adopt preplating Ni layer, therefore following problems can not take place: the scum silica frost of the Ni-Al system that generates in the plating bath enters in the coating, causes coating to become inhomogeneous, as a result mis-behave etc.When requiring better pulverability, the Al concentration limit is preferably 0.12% in the plating bath.
Behind the plating and after wiping, by quickly heating up to 470～600 ℃, just cool off or after carrying out, cool off less than 15 seconds soaking maintenance without soaking time with the heat-up rate more than 30 ℃/second, carry out Alloying Treatment.This regulation is to suppressing the Г layer, particularly being extremely important to suppressing deviation.Especially during 30 ℃/second of heat-up rate less thaies, Г layer, its deviation all increase.After carrying out rapid heating, just cool off or be important carrying out the short period of time cooling off after (less than 15 seconds) soaking keeps without soaking time, in the case, if this condition of disengaging, Г layer, its deviation all increase.In addition, common ultra-low carbon steel plate preferably just cools off without soaking time.Because do not need soaking time this moment, so furnace apparatus is changeable, also need not slow down for soaking in addition, favourable from the viewpoint of productivity yet.In addition, the ultra-low carbon steel plate that interpolation P etc. improves intensity exists alloying to be inclined to slowly, and the soaking of therefore carrying out the short period of time as required keeps getting final product.When requiring better pulverability, preferably, just cool off or after carrying out, cool off, carry out Alloying Treatment less than 10 seconds soaking maintenance without soaking time by quickly heating up to 470～550 ℃ with the heat-up rate more than 30 ℃/second.
Then, the method that is used to obtain extremely good hot-dip galvanized steel sheet outward appearance is described.
The plating raw sheet that uses among the present invention, can use any raw sheet, but, be effective so use the ultra-low carbon steel plate that is suitable for as the automobile exterior panel purposes mostly because purpose of the present invention mainly is to obtain desired such utmost point good surface appearance in the automobile exterior panel purposes.
Fig. 1 represents the state of the interior alloy layer that forms of galvanizing bath among the present invention.Fig. 1 be with just carried out after just from galvanizing is bathed, proposing chilling sample the section landfill and grind, analyze by EPMA, measure the figure that the element (Ni, Al, Zn, Fe) of coating depth direction distributes.On iron matrix-coating interface, be formed with the alloy layer that constitutes by Fe-Ni-Al-Zn as can be known.In addition, in Fig. 2, as a comparison, express the situation that the common Fe-Al-Zn alloy layer of observing with same method is present in the iron matrix interface.
Secondly, Fig. 3 represents that the element (Ni, Al, Zn, Fe) of the coating depth direction after the heating Alloying Treatment among the present invention distributes.The Fe-Ni-Al-Zn alloy layer at such iron matrix-coating interface of being seen among Fig. 1 disappears, and becomes the zn-fe alloy layer of Ni, Al dispersive state.In addition, in Fig. 4, as a comparison, express the element (Ni, Al, Zn, Fe) that to have the coating depth direction after the sample heating Alloying Treatment of alloy layer of state of common Fig. 2 and distribute.
Among the present invention, in bathing, galvanizing forms the state of Fig. 1, then make it become the state of Fig. 3 by the heating Alloying Treatment, compared with occasion (i.e. operation from Fig. 2 to Fig. 4) through common operation, the reason that can obtain good surface appearance through such operation is not necessarily clear and definite, but can think by due to following such reason.That is, form the process of the interface alloy layer of Fig. 1, can think crystallization reaction via the Ni in plating bath, Al, Zn, Fe, but can infer, by containing Ni therein, Ni works as the crystallization nucleus, even the substrate raw sheet has some inhomogeneous, also has it by hidden effect.Can infer in addition, Fe-Ni-Al-Zn alloy layer and Fe-Al-Zn alloy layer are relatively, and be little to the dependency of alloy layer thickness to the barrier effect of zn-fe alloy reaction, and alloy layer thickness inhomogeneous is difficult to become inhomogeneous after the alloying.
Secondly, the manufacture method through the alloyed hot-dip galvanized steel plate of the state of Fig. 1 to Fig. 3 of the present invention as described above is more specifically described.The Al of iron matrix of the present invention-coating interface alloy layer supplies with from galvanizing is bathed.And Ni also can supply with from galvanizing is bathed, but in this occasion, need make and contain a large amount of Ni in the plating bath, because a large amount of scum silica frost that Ni-Al system takes place is therefore undesirable.For fear of this problem, preferred Ni supplies with the form of the pre-plating layer on steel plate.
Below, the concrete grammar of the occasion that adopts preplating Ni layer is narrated.
In the present invention, at first the surface to clean be necessary, be not particularly limited for this method, according to the situation of the dirt and the oxide film of raw sheet, individually or the known methods such as alkali degreasing, brushing processing, acid treatment that are used in combination get final product.Consider from the inhomogeneity viewpoint of plating Ni layer described later, preferably be used in combination alkali degreasing (for example the NaOH aqueous solution is handled) and acid treatment (for example aqueous sulfuric acid processing) in order.
In the present invention, implement 0.05～1.0g/m
2Preplating Ni.Prescribing a time limit less than following, the wettability of hot dip process thereafter is insufficient,, in the Zn plating bath, is difficult to form the such interface alloy layer of Fig. 1 in limited time on surpassing, and the result is difficult to obtain good surface appearance.
Behind preplating Ni, in non-oxidation or reducing atmosphere, quickly heat up to 430～500 ℃ of plate temperatures with the heat-up rate more than 30 ℃/second.This processing is necessary in order to ensure the wettability and the plating adhesion of hot dip process.
Galvanizing is bathed, the plating bath of using the Zn by Al:0.07～0.2% and unavoidable impurities and surplus thereof to constitute.Al is difficult to form the such interface alloy layer of Fig. 1 less than down in limited time, and the result is difficult to obtain good surface appearance.In limited time, alloying reaction postpones on Al surpasses, and is therefore undesirable.
In addition, be used to form the condition of the such interface alloy layer of Fig. 1, depend in pre-adhesion amount of Ni and the plating bath Al concentration these two.Use the ultra-low carbon steel plate, and preplating Ni amount carried out various changes, after quickly heating up to 460 ℃ with 50 ℃/second heat-up rates, be immersed in 455 ℃ the galvanizing bath of the Al that contains various concentration, take out after 3 seconds, cool off fast, whether checking has the Fe-Ni-Al-Zn alloy layer at iron matrix-coating interface, and it the results are shown in Fig. 5.Among the figure with " zero " expression be to confirm that the Fe-Ni-Al-Zn alloy layer is arranged, but can be observed when Al in the plating bath reduces the tendency that the upper limit of suitable preplating Ni amount also reduces.The straight line that is represented by dotted lines among the figure (is designated as Yg/m with preplating Ni amount
2, when Al concentration is designated as [X] % in the Zn plating bath, be the relation of Y=15 * [X]-1) following zone is preferred in the present invention zone.
Among the present invention, preferably behind the plating and after wiping, quickly heat up to 470～600 ℃ with the heat-up rate more than 30 ℃/second,, carry out Alloying Treatment by just cooling off without soaking time or after carrying out, cooling off less than 15 seconds soaking maintenance.This regulation when obtaining good surface appearance, guarantees that also on the alloying degree that suits and the plating adhesion be important.
Embodiment
Below, utilize embodiment to describe the present invention in detail.
(embodiment 1～13, and comparative example 1～11)
Table 1 is expressed the composition of the employed annealed ultra-low carbon steel plate of test.After carrying out pre-treatment according to the condition shown in the table 2, in the plating bath shown in the table 3, (bathe 60 ℃ of temperature, current density 30A/dm by electroplating
2) carry out preplating Ni.
Then, at 3%H
2+ N
2Atmosphere in, be heated to 450 ℃ with 50 ℃/second heat-up rates, be immersed in insulation immediately in 450 ℃ galvanizing is bathed, keep carrying out wiping after 3 seconds, thereby adjust the weight of coating per surface area, just just carry out alloying after the wiping with heat-up rate and temperature, the soaking time of stipulating.About cooling, carry out 10 seconds 2 ℃/second slow cooling after, carry out chilling with 20 ℃/second.Then, carrying out draft is 0.5% skin-pass.
With the various conditions shown in the table 4 (the Al concentration of the pre-adhesion amount of Ni, plating bath, the alloying condition) perparation of specimen.In addition, the weight of coating per surface area is 50g/m
2
The composition of the sample determination coating of employing table 4 and Г layer thickness the results are shown in table 5.Use dissolving with hydrochloric acid coating, obtain the concentration of each composition.In addition,, adopt the electrolytic stripping method to measure 10 points, obtain its mean value and maximum value, minimum value about the Г layer.About the deviation of Г layer, the arbitrary difference in maximum value-mean value, the mean value-minimum value surpasses 0.3 μ m, is labeled as " * ".
Table 6 expression performance evaluation result.Performance evaluation is carried out like that according to following.
(1) coating outward appearance: carry out visual observation, fully not defective such as plating be evaluated as " zero ", have the defective of not plating be evaluated as " △ ", do not plate defective serious be evaluated as " * ".
(2) processibility (pulverability): adopt the sample applied slushing oil, carry out the cylinder punching press (pull and stretch punching press) of Ф 40mm under than 2.2 condition at pull and stretch, its side of usefulness tape stripping is estimated according to the melanism degree.The melanism degree is 0～less than 20% be evaluated as " zero ", be 20%～less than 30% be evaluated as " △ ", be evaluated as " * " more than 30%.
(3) processibility (sliding): adopt the sample that has applied slushing oil, carry out flat board sliding test continuously.Under pressure appendix lotus 500kgf, carry out 5 times and slide continuously, estimate with the frictional coefficient of the 5th.Being evaluated as " zero ", being 0.15 of frictional coefficient less than 0.15～less than 0.2 be evaluated as " △ ", be evaluated as " * " more than 0.2.
(4) solidity to corrosion (the anti-red rust of coating scratch portion): the steel plate sample is implemented the three cation chemical conversion processing that automobile is used
※ 1, cationic electrodeposition coating
※ 2After (20 μ m), peel off coated film, coated side is exposed, carry out the corrosive cycle test with the strip of 5mm * 50mm
※ 3Estimate with the outward appearance after 10 days.Rust takes place or only take place being evaluated as of yellow rust " zero ", red rust less than 20% be evaluated as " △ ", red rust is be evaluated as " * " more than 20%.
(5) solidity to corrosion (anti-pierceability): will carry out carrying out covering of 40mm * 40mm after the sample smoothing of the crooked punching press of flanging (PVC one De is paid) U-shaped, and implement the three cation chemical conversion processing that automobile is used
※ 1, cationic electrodeposition coating
※ 2(20 μ m).Twisted plate and dull and stereotyped involutory with the liner (spacer) of 0.5mm, and make that having removed the not finish department that covers becomes Nei-Nei, has made car body flanging model.This sample is carried out the corrosive cycle test
※ 3Estimate with the outward appearance after 30 days.Red rust less than 20% be evaluated as " zero ", red rust be 20%～less than 50% be evaluated as " △ ", red rust is be evaluated as " * " more than 50%.
(6) coating: the steel plate sample is implemented the three cation chemical conversion processing that automobile is used
※ 1, cationic electrodeposition coating
※ 2Electrodeposition coating carries out under voltage 220V, rising (Upslope) 0.5 minute, 3 minutes condition of energising total, the counting test piece (number at the unusual position of the discharge trace in 70 * 150mm) etc., N/R being evaluated as " zero ", unusual position have 1～less than 3 be evaluated as " △ ", be evaluated as " * " more than 3 arranged.
※ 1: the SD5000 of Japanese ペ イ ソ ト corporate system;
※ 2: the PN120M of Japanese ペ イ ソ ト corporate system;
The dry 50 ℃ of 45%RH (1 hour) of dry 50 ℃ of 45%RH (3 hours) moistening 50 ℃ of 95%RH of (14 hours) of ※ 3:SST (6 hours) .
Table 1 test steel grade
| Composition (quality %) | |||||||
| C | Mn | Si | P | S | Ti | | |
| Steel grade | |||||||
| 1 | 0.0016 | 0.170 | 0.011 | 0.012 | 0.006 | 0.015 | 0.018 |
| Steel grade 2 | 0.0020 | 0.381 | 0.003 | 0.059 | 0.006 | - | 0.003 |
Table 2 pre-treatment condition
| Alkali degreasing is handled | NaOH liquid temperature dipping | 65 ℃ of 50g/ |
| Cleanup acid treatment | H 2SO 4Liquid temperature dipping | 30 ℃ of 100g/l 5 seconds |
The plating bath of table 3 preplating Ni
| Composition | Concentration |
| NiSO 4·6H 2O H 3BO 3 Na 2SO 4 pH | 300g/l 40g/l 100g/l 2.7 |
Table 4 sample is created conditions
| No | Steel grade | Plating Ni amount (g/m 2) | Al% in the zinc-plated bath | Alloying | Remarks | ||
| Heat-up rate (℃/second) | Temperature (℃) | Soaking time (second) | |||||
| 1 | 1 | 0.2 | 0.16 | 50 | 500 | 0 | Embodiment |
| 2 | 1 | 0.3 | 0.16 | 50 | 500 | 0 | Embodiment |
| 3 | 1 | 0.5 | 0.16 | 50 | 500 | 0 | |
| 4 | 1 | 1.0 | 0.16 | 50 | 500 | 0 | Embodiment |
| 5 | 1 | 0.3 | 0.10 | 50 | 500 | 0 | Embodiment |
| 6 | 1 | 0.3 | 0.14 | 50 | 500 | 0 | Embodiment |
| 7 | 1 | 0.3 | 0.18 | 50 | 500 | 0 | Embodiment |
| 8 | 1 | 0.3 | 0.18 | 50 | 550 | 0 | Embodiment |
| 9 | 1 | 0.3 | 0.16 | 70 | 500 | 0 | |
| 10 | 1 | 0.3 | 0.16 | 50 | 500 | 5 | Embodiment |
| 11 | 2 | 0.3 | 0.16 | 50 | 580 | 0 | Embodiment |
| 12 | 2 | 0.3 | 0.16 | 50 | 550 | 10 | Embodiment |
| 13 | 1 | 0.5 | 0.16 | 50 | 470 | 5 | |
| 1 | 1 | 0 | 0.16 | 50 | 500 | 0 | Comparative example |
| 2 | 1 | 0.05 | 0.16 | 50 | 500 | 0 | Comparative example |
| 3 | 1 | 3 | 0.16 | 50 | 500 | 0 | Comparative example |
| 4 | 1 | 0.3 | 0.08 | 50 | 500 | 0 | Comparative example |
| 5 | 1 | 0.3 | 0.25 | 50 | 500 | 0 | Comparative example |
| 6 | 1 | 0.3 | 0.25 | 50 | 550 | 20 | Comparative example |
| 7 | 1 | 0.3 | 0.16 | 20 | 500 | 0 | Comparative example |
| 8 | 1 | 0.3 | 0.16 | 50 | 500 | 20 | Comparative example |
| 9 | 2 | 0.3 | 0.16 | 50 | 550 | 20 | Comparative example |
| 10 | 1 | 0.5 | 0.16 | 50 | 460 | 20 | Comparative example |
| 11 | 1 | 0.5 | 0.16 | 50 | 610 | 0 | Comparative example |
Table 5 is for coating composition, the Г layer thickness of examination material
| No | Coating | Remarks | |||||
| Fe％ | Ni％ | Al％ | The Al/Ni ratio | Г layer thickness average value mu m | |
||
| 1 | 10.7 | 0.09 | 0.25 | 2.8 | 0.75 | ○ | Embodiment |
| 2 | 10.7 | 0.2 | 0.25 | 1.3 | 0.75 | ○ | Embodiment |
| 3 | 10.7 | 0.4 | 0.51 | 1.3 | 0.75 | ○ | |
| 4 | 10.8 | 0.8 | 0.7 | 0.9 | 0.75 | ○ | Embodiment |
| 5 | 11.5 | 0.2 | 0.15 | 0.75 | 0.82 | ○ | Embodiment |
| 6 | 11.1 | 0.2 | 0.19 | 0.95 | 0.78 | ○ | Embodiment |
| 7 | 9.5 | 0.2 | 0.6 | 3 | 0.45 | ○ | Embodiment |
| 8 | 11.3 | 0.2 | 0.6 | 3 | 0.78 | ○ | Embodiment |
| 9 | 10.6 | 0.4 | 0.51 | 1.3 | 0.75 | ○ | |
| 10 | 11.5 | 0.4 | 0.51 | 1.3 | 0.91 | ○ | Embodiment |
| 11 | 11 | 0.2 | 0.25 | 1.3 | 0.74 | ○ | Embodiment |
| 12 | 10.9 | 0.2 | 0.25 | 1.3 | 0.7 | ○ | Embodiment |
| 13 | 10.7 | 0.4 | 0.51 | 1.3 | 0.76 | ○ | Embodiment |
| 1 | 10.0 | Less than 0.01% | 0.25 | - | -(undetermined) | -(undetermined) | Comparative example |
| 2 | 10.5 | 0.02 | 0.25 | 12.5 | -(undetermined) | -(undetermined) | Comparative example |
| 3 | 11.5 | 2 | 0.65 | 0.3 | 1.05 | ○ | Comparative example |
| 4 | 11.5 | 0.2 | 0.12 | 0.6 | 1.21 | × | Comparative example |
| 5 | 7.9 | 0.2 | 1.52 | 7.6 | 0.4 | × | Comparative example |
| 6 | 11.5 | 0.2 | 1.52 | 7.6 | 1.29 | × | Comparative example |
| 7 | 10.8 | 0.4 | 0.51 | 1.3 | 0.92 | × | Comparative example |
| 8 | 12.1 | 0.4 | 0.51 | 1.3 | 1.13 | ○ | Comparative example |
| 9 | 11.5 | 0.2 | 0.25 | 1.3 | 0.8 | × | Comparative example |
| 10 | 10 | 0.4 | 0.51 | 1.3 | 0.65 | × | Comparative example |
| 11 | 13.1 | 0.4 | 0.51 | 1.3 | 1.51 | ○ | Comparative example |
Table 6 performance evaluation result
| No | The coating outward appearance | Processibility | Solidity to corrosion | Coating | Remarks | ||
| Efflorescence | Slide | The anti-red rust of | Anti-pierceability | ||||
| 1 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 2 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 3 | ○ | ○ | ○ | ○ | ○ | ○ | |
| 4 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 5 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 6 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 7 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 8 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 9 | ○ | ○ | ○ | ○ | ○ | ○ | |
| 10 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 11 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 12 | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 13 | ○ | ○ | ○ | ○ | ○ | ○ | |
| 1 | × | -(undetermined) | -(undetermined) | -(undetermined) | -(undetermined) | -(undetermined) | Comparative example |
| 2 | △ | -(undetermined) | -(undetermined) | × | -(undetermined) | × | Comparative example |
| 3 | ○ | × | ○ | ○ | × | △ | Comparative example |
| 4 | ○ | × | ○ | ○ | × | ○ | Comparative example |
| 5 | ○ | ○ | × | △ | ○ | × | Comparative example |
| 6 | ○ | × | ○ | ○ | × | △ | Comparative example |
| 7 | ○ | × | × | ○ | ○ | △ | Comparative example |
| 8 | ○ | × | ○ | ○ | △ | × | Comparative example |
| 9 | ○ | △ | ○ | ○ | ○ | △ | Comparative example |
| 10 | ○ | × | × | ○ | × | ○ | Comparative example |
| 11 | ○ | × | ○ | ○ | × | △ | Comparative example |
Such as shown above, sample has within the scope of the present invention obtained excellent characteristic.
(embodiment 14～22 and comparative example 12,13)
Table 7 is expressed the composition of the employed annealed ultra-low carbon steel plate of test.After condition shown in the employing table 2 is carried out pre-treatment, in the plating bath shown in the table 3, (bathe temperature 60 ℃, current density 30A/dm by electroplating
2) carry out preplating Ni.
Then, at 4%H
2+ N
2Atmosphere in be heated to 455 ℃ with 50 ℃/second heat-up rate, at insulation dipping in 450 ℃ galvanizing is bathed, keeps carrying out after 2.5 seconds the weight of wiping immediately with adjustment coating per surface area, just after the wiping just with 50 ℃ of/second intensifications, keep carrying out chilling with 50 ℃/second after 4 seconds.Carry out draft then and be 0.5% skin-pass.
(comparative example 14)
Table 7 is expressed the composition of the employed annealed ultra-low carbon steel plate of test.After condition shown in the employing table 2 is carried out pre-treatment, at 4%H
2+ N
2Heat-up rate with 20 ℃/second in the atmosphere is heated to 650 ℃, keep after 60 seconds, naturally cool to 455 ℃, be immersed in insulation in 450 ℃ galvanizing is bathed, keep carrying out after 2.5 seconds wiping to adjust the weight of coating per surface area, just after the wiping just with 50 ℃ of/second intensifications, keep carrying out chilling with 50 ℃/second after 4 seconds.Then, carrying out draft is 0.5% skin-pass.
Under the various conditions shown in the table 8 (the Al concentration of the pre-adhesion amount of Ni, plating bath, alloying condition), made sample.In addition, the weight of coating per surface area all is defined as 50g/m
2
The composition of the sample determination coating of employing table 8 and Г layer thickness the results are shown in table 9.Use dissolving with hydrochloric acid coating, obtain the concentration of each composition.In addition, adopt the electrolytic stripping method that the Г layer is measured 10 points, obtain its mean value and, maximum value, minimum value.About the deviation of Г layer, any in maximum value-minimum value, the mean value-minimum value surpasses 0.3 μ m, is labeled as " * ".
Table 10 expression performance evaluation result.Performance evaluation and previous example similarly carry out.Wherein, about processibility (efflorescence), carry out with stricter condition (pull and stretch is than 2.3).Metewands etc. are identical with previous example.In addition,, except the evaluation of previous example, also appended broken (the チ Star ピ Application ゲ of falling of low temperature here; Chipping) property.The broken property that falls of low temperature is carried out as described below.After the method for the assessment item (6) of employing front proceeds to electrodeposition coating, and then the inter coat coating 30 μ m and the finishing coat coating 40 μ m of coating polyester system, place then and (be of a size of 70mm * 150mm), above-mentioned application sample is cooled to-20 ℃ with dry ice, in 1 day with 2kgf/cm
2Air pressure will about 0.4g vertical injection of rubble (10), remove because of after the filming of the broken perk that falls, measure the maximum value of peel diameter.Peel diameter less than being evaluated as of 4mm " zero ", for 4mm～less than being evaluated as of 6mm " △ ", for 6mm above be evaluated as " * ".
Table 7 test steel grade
| Composition (quality %) | |||||||||||
| C | Mn | Si | P | S | Ti | Nb | Cu | Ni | Cr | Sn | |
| Steel grade 3 | 0.0011 | 0.12 | 0.009 | 0.010 | 0.005 | 0.017 | 0.02 | 0.075 | 0.03 | 0.04 | 0.01 |
| |
0.0010 | 0.09 | 0.006 | 0.007 | 0.003 | 0.064 | 0.001 | 0.02 | 0.02 | 0.02 | 0.001 |
| Steel grade 5 | 0.0016 | 0.058 | 0.005 | 0.009 | 0.004 | 0.037 | 0.001 | 0.098 | 0.039 | 0.043 | 0.014 |
| Steel grade 6 | 0.002 | 0.055 | 0.013 | 0.01 | 0.005 | 0.031 | 0.006 | 0.08 | 0.039 | 0.042 | 0.009 |
| Steel grade 7 | 0.003 | 1.652 | 0.323 | 0.081 | 0.006 | 0.009 | 0.024 | 0.124 | 0.039 | 0.059 | 0.013 |
Table 8 sample is created conditions
| No | Steel grade | Plating Ni amount (g/m 2) | Al% in the zinc plating bath | Alloying | Remarks | ||
| Heat-up rate (℃/second) | Temperature (℃) | Soaking time (second) | |||||
| 14 | 3 | 0.3 | 0.16 | 50 | 530 | 4 | Embodiment |
| 15 | 4 | 0.3 | 0.16 | 50 | 510 | 4 | Embodiment |
| 16 | 4 | 0.6 | 0.18 | 50 | 530 | 4 | Embodiment |
| 17 | 5 | 0.3 | 0.16 | 50 | 510 | 4 | Embodiment |
| 18 | 5 | 0.6 | 0.18 | 50 | 530 | 4 | Embodiment |
| 19 | 6 | 0.3 | 0.16 | 50 | 520 | 4 | |
| 20 | 6 | 0.6 | 0.18 | 50 | 540 | 4 | Embodiment |
| 21 | 7 | 0.3 | 0.16 | 50 | 550 | 4 | Embodiment |
| 22 | 7 | 0.6 | 0.18 | 50 | 570 | 4 | Embodiment |
| 12 | 3 | 1.1 | 0.1 | 50 | 480 | 4 | Comparative example |
| 13 | 4 | 1.1 | 0.11 | 50 | 470 | 4 | Comparative example |
| 14 | 4 | 0 | 0.18 | 50 | 580 | 4 | Comparative example |
Table 9 is for coating composition, the Г layer thickness of examination material
| No | Coating | Remarks | |||||
| Fe％ | Ni％ | Al％ | The Al/Ni ratio | Г layer thickness average value mu m | Deviation | ||
| 14 | 11.1 | 0.15 | 0.3 | 2 | 0.89 | ○ | Embodiment |
| 15 | 11 | 0.15 | 0.3 | 2 | 0.91 | ○ | Embodiment |
| 16 | 10.7 | 0.39 | 0.65 | 1.7 | 0.89 | ○ | Embodiment |
| 17 | 10.5 | 0.15 | 0.3 | 2 | 0.87 | ○ | Embodiment |
| 18 | 10.4 | 0.39 | 0.65 | 1.7 | 0.89 | ○ | Embodiment |
| 19 | 10.5 | 0.15 | 0.3 | 2 | 0.81 | ○ | |
| 20 | 10.5 | 0.39 | 0.65 | 1.7 | 0.8 | ○ | Embodiment |
| 21 | 10.1 | 0.15 | 0.3 | 2 | 0.7 | ○ | Embodiment |
| 22 | 10.1 | 0.39 | 0.65 | 1.7 | 0.65 | ○ | Embodiment |
| 12 | 11.5 | 0.7 | 0.3 | 0.4 | 1.0 | ○ | Comparative example |
| 13 | 11.5 | 0.7 | 0.3 | 0.4 | 0.99 | ○ | Comparative example |
| 14 | 10.6 | 0 | 0.45 | - | 0.85 | × | Comparative example |
Table 10 performance evaluation result
| No | The coating outward appearance | Processibility | Solidity to corrosion | Coating | The broken property that falls of low temperature | Remarks | ||
| Efflorescence | Slide | The anti-red rust of coating scratch | Anti-pierceability | |||||
| 14 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 15 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 16 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 17 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 18 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 19 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | |
| 20 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 21 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 22 | ○ | ○ | ○ | ○ | ○ | ○ | ○ | Embodiment |
| 12 | ○ | △ | ○ | ○ | ○ | ○ | △ | Comparative example |
| 13 | ○ | △ | ○ | ○ | ○ | ○ | △ | Comparative example |
| 14 | ○ | × | △ | ○ | ○ | × | △ | Comparative example |
As described above, sample has within the scope of the invention obtained excellent characteristic.
Then, the embodiment that is used to obtain extremely good GA outward appearance is described.
(embodiment 19～25 and comparative example 15～17)
Use cold rolling, the annealed raw sheet shown in the table 1, after the pre-treatment shown in carry out table 2, in the plating bath shown in the table 3, (bathe temperature 60 ℃, current density 30A/dm by electroplating
2) carry out preplating Ni.Then, at 3%H
2+ N
2Heat-up rate with 50 ℃/second in the atmosphere is heated to 460 ℃, at insulation dipping in 455 ℃ galvanizing is bathed, keeps carrying out after 3 seconds wiping to adjust the weight of coating per surface area immediately, and the weight of coating per surface area is 60g/m
2Heat Alloying Treatment with defined terms then.Cooling after the heating is carried out carrying out chilling with 20 ℃/second after 10 seconds 2 ℃/second the slow cooling.Then, carrying out draft is 0.5% skin-pass.In addition, observe the used sample of interface alloy layer, use the sample that is immersed in the galvanizing bath, keeps chilling after 3 seconds.
(comparative example 18)
With the cold rolling mistake of the composition identical, identical thickness of slab with the raw sheet 1 of table 1 but unannealed material as raw sheet, the alkali degreasing that only carries out in the described pre-treatment of table 2 is handled, annealing, the reduction carried out in 10% nitrogen atmosphere then 800 ℃ * 30 seconds are handled, be cooled to 460 ℃ then, be immersed in insulation in 455 ℃ galvanizing is bathed, keep carrying out after 3 seconds wiping to adjust the weight of coating per surface area, the weight of coating per surface area is 60g/m
2Then, heat Alloying Treatment with defined terms.Cooling after the heating, carry out 10 seconds 2 ℃/second slow cooling after, carry out chilling with 20 ℃/second.Then, carrying out draft is 0.5% skin-pass.In addition, observe the sample that the interface alloy layer is used, use the sample that is immersed in the galvanizing bath, keeps chilling after 3 seconds.
Embodiment 19～25, comparative example 15～18 are all as shown in table 11 like that, have adjusted galvanizing and have bathed Al concentration, preplating Ni amount.
Performance evaluation is carried out like that according to following.
1) iron matrix behind the galvanizing-coating interface alloy layer:, analyze the state of investigation alloy layer with sample section landfill, also grinding by EPMA.Have being evaluated as of Fe-Ni-Al-Zn alloy layer " zero ", being evaluated as except that this situation " * ".
2) coating outward appearance (visual): to the light of sample from the oblique direction luminescent lamp, observation has or not small uneven coating even.There is not uneven being evaluated as " zero ".
3) coating outward appearance (SEM observation): carry out the observation of 20 visual fields with 500 times multiplying powers, obtain in skin-pass by conquassation and the area occupation ratio of the part of smoothing, in the mean value of the poor or area occupation ratio of the mean value of area occupation ratio and maximum value and the difference of minimum value, a big side is less than being evaluated as " zero " at 10% o'clock, being more than 10% but less than being evaluated as " △ " at 20% o'clock, surpassing at 20% o'clock and be evaluated as " * ".
4) alloying degree: use dissolving with hydrochloric acid coating, obtain by chemical analysis and respectively become component, calculate the Fe% of coating.Fe% be 9～12% be evaluated as " zero ", situation in addition is evaluated as " * ".
5) plating adhesion: adopt the sample that has applied slushing oil, carry out the cylinder punching press (pull and stretch punching press) of Ф 40mm than 2.2 condition,, estimate according to the melanism degree with its side of tape stripping with pull and stretch.The melanism degree is 0～less than 20% be evaluated as " zero ", be 20%～less than 30% be evaluated as " △ ", be evaluated as " * " more than 30%.
Table 11 sample is created conditions and the interface alloy layer
| Raw sheet | Preplating Ni measures (g/m 2) | Al% in the bath | Fe-Ni-Al-Zn interface alloy | The alloying condition | Remarks | ||
| Temperature ℃ | Soaking time (second) | ||||||
| 19 | 1 | 0.05 | 0.15 | ○ | 500 | 0 | |
| 20 | 1 | 0.2 | 0.15 | ○ | 500 | 0 | Embodiment |
| 21 | 1 | 0.5 | 0.15 | ○ | 500 | 0 | Embodiment |
| 22 | 1 | 0.5 | 0.1 | ○ | 500 | 0 | Embodiment |
| 23 | 1 | 1 | 0.18 | ○ | 520 | 0 | Embodiment |
| 24 | 2 | 0.2 | 0.15 | ○ | 550 | 0 | Embodiment |
| 25 | 2 | 0.2 | 0.15 | ○ | 530 | 5 | Embodiment |
| 15 | 1 | 0.01 | 0.15 | ※ | - | - | Comparative example |
| 16 | 1 | 1.5 | 0.15 | × | 500 | 0 | Comparative example |
| 17 | 1 | 0.5 | 0.05 | × | 500 | 0 | Comparative example |
| 18 | 1 (unannealed) | 0.11 | × | - | 500 | Comparative example | |
※: comparative example 15, because not plating (plating) significantly takes place, so the specific of interface alloy layer is difficult.Therefore, the performance evaluation after also carry out GAization.
Table 12 performance evaluation result
| The coating outward appearance | The alloying degree | Plating adhesion | Remarks | ||
| Visual | SEM observes | ||||
| 19 | ○ | ○ | ○ | ○ | |
| 20 | ○ | ○ | ○ | ○ | Embodiment |
| 21 | ○ | ○ | ○ | ○ | Embodiment |
| 22 | ○ | ○ | ○ | ○ | Embodiment |
| 23 | ○ | ○ | ○ | ○ | Embodiment |
| 24 | ○ | ○ | ○ | ○ | Embodiment |
| 25 | ○ | ○ | ○ | ○ | Embodiment |
| 15 | - | - | - | - | Comparative example |
| 16 | × | × | ○ | ○ | Comparative example |
| 17 | △ | △ | ○ | △ | Comparative example |
| 18 | × | × | ○ | ○ | Comparative example |
As shown in table 12 such, sample has within the scope of the present invention obtained excellent characteristic.
Industrial applicibility
According to the present invention, to be mainly used in ultra-low carbon steel plate in the automobile purposes as raw sheet, can obtain having the alloyed hot-dip galvanized steel plate of excellent corrosion resistance, processability, coating, its value industrially is very big. In addition, according to the present invention, can obtain also the manufacture method applicable to alloyed hot-dip galvanized steel plate automobile exterior panel etc., that outward appearance is extremely good.
Among the present invention the expression number range " more than " and " following " comprise given figure.
Claims (4)
1. all excellent alloyed hot-dip galvanized steel plate of a solidity to corrosion, processibility, coating, it is characterized in that, having by quality % by the Zn of Fe:8～13%, Ni:0.05～1.0%, Al:0.15～1.5%, its surplus and the coating that unavoidable impurities constitutes on the one side at least of ultra-low carbon steel plate, the ratio of its Al/Ni is 0.5～5.0, the mean thickness of the Г layer at iron matrix interface is below the 1 μ m, and its deviation is in ± 0.3 μ m.
2. the manufacture method of an alloyed hot-dip galvanized steel plate is characterized in that, after annealed ultra-low carbon steel plate surface is cleaned, implements 0.1～1.0g/m
2Preplating Ni, after in non-oxidation or reducing atmosphere, quickly heating up to 430～500 ℃ of plate temperatures with the heat-up rate more than 30 ℃/second, in bathing, the galvanizing that contains Al:0.1～0.2 quality % carries out plating, through quickly heating up to 470～600 ℃ with the heat-up rate more than 30 ℃/second after the wiping, just cool off or after carrying out, cool off less than 15 seconds soaking maintenance without soaking time.
3. the manufacture method of an alloyed hot-dip galvanized steel plate is characterized in that, in galvanizing is bathed, after forming the Fe-Ni-Al-Zn alloy layer on the iron matrix interface, by heat treated, when described Fe-Ni-Al-Zn alloy layer is disappeared, form Ni, Al dispersive zn-fe alloy layer.
4. the manufacture method of an alloyed hot-dip galvanized steel plate is characterized in that, after surface of steel plate is cleaned, implements 0.05～1.0g/m
2Preplating Ni, after in non-oxidation or reducing atmosphere, quickly heating up to 430～500 ℃ of plate temperatures with the heat-up rate more than 30 ℃/second, in containing the zinc-plated bath that concentration is 0.07～0.2% Al, carry out hot dip process, and just just quickly heat up to 470～600 ℃ after the wiping with the heat-up rate more than 30 ℃/second, just cool off or after carrying out, cool off without soaking time less than 15 seconds soaking maintenance, wherein, preplating Ni amount (Y, g/m
2) and zinc-plated bath in Al concentration ([X], quality %) satisfy the relation of Y≤15 * [X]-1.
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| JP2005121831A JP4551268B2 (en) | 2005-04-20 | 2005-04-20 | Method for producing alloyed hot-dip galvanized steel sheet |
| JP121831/2005 | 2005-04-20 | ||
| JP239384/2005 | 2005-08-22 |
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|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104981346A (en) * | 2013-02-12 | 2015-10-14 | 塔塔钢铁艾默伊登有限责任公司 | Coated steel suitable for hot-dip galvanising |
| CN105112914A (en) * | 2015-08-31 | 2015-12-02 | 中国钢研科技集团有限公司 | Continuous hot-dip galvanizing device and continuous hot-dip galvanizing method |
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| JP2783452B2 (en) * | 1990-10-09 | 1998-08-06 | 新日本製鐵株式会社 | Manufacturing method of galvannealed steel sheet |
| JP2562747B2 (en) * | 1991-07-17 | 1996-12-11 | 新日本製鐵株式会社 | Method for producing hot dip galvanized steel sheet and alloyed hot dip galvanized steel sheet by pre-Ni alloy plating method |
| JPH073417A (en) * | 1993-06-18 | 1995-01-06 | Nippon Steel Corp | Highly corrosion resistant galvannealed steel sheet |
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- 2005-04-20 JP JP2005121831A patent/JP4551268B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104981346A (en) * | 2013-02-12 | 2015-10-14 | 塔塔钢铁艾默伊登有限责任公司 | Coated steel suitable for hot-dip galvanising |
| CN104981346B (en) * | 2013-02-12 | 2017-07-18 | 塔塔钢铁艾默伊登有限责任公司 | Coating steel substrate suitable for galvanizing by dipping |
| CN109371320A (en) * | 2013-05-01 | 2019-02-22 | 新日铁住金株式会社 | Galvanized steel plain sheet and its manufacturing method |
| US10294551B2 (en) | 2013-05-01 | 2019-05-21 | Nippon Steel & Sumitomo Metal Corporation | High-strength low-specific-gravity steel sheet having superior spot weldability |
| US10336037B2 (en) | 2013-05-01 | 2019-07-02 | Nippon Steel & Sumitomo Metal Corporation | Galvanized steel sheet and method for producing the same |
| CN105209655A (en) * | 2013-05-20 | 2015-12-30 | 新日铁住金株式会社 | Galvannealed steel plate and method for manufacturing same |
| US10040270B2 (en) | 2013-05-20 | 2018-08-07 | Nippon Steel & Sumitomo Metal Corporation | Galvannealed steel sheet and manufacturing method thereof |
| CN105112914A (en) * | 2015-08-31 | 2015-12-02 | 中国钢研科技集团有限公司 | Continuous hot-dip galvanizing device and continuous hot-dip galvanizing method |
| CN111989420A (en) * | 2018-05-16 | 2020-11-24 | 日本制铁株式会社 | Plated steel material |
| CN110318015A (en) * | 2019-08-16 | 2019-10-11 | 东北大学 | A kind of hot galvanizing method obtaining color plating on flat steel |
| CN110318015B (en) * | 2019-08-16 | 2020-09-29 | 东北大学 | Hot galvanizing method for obtaining color coating on flat steel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100580130C (en) | 2010-01-13 |
| JP4551268B2 (en) | 2010-09-22 |
| JP2006299341A (en) | 2006-11-02 |
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