CN101760712B - Production method for hot dip galvanized steel sheet in high manganese steel with great coating surface quality - Google Patents
Production method for hot dip galvanized steel sheet in high manganese steel with great coating surface quality Download PDFInfo
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- CN101760712B CN101760712B CN2009102543783A CN200910254378A CN101760712B CN 101760712 B CN101760712 B CN 101760712B CN 2009102543783 A CN2009102543783 A CN 2009102543783A CN 200910254378 A CN200910254378 A CN 200910254378A CN 101760712 B CN101760712 B CN 101760712B
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- 239000011248 coating agent Substances 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 title claims abstract description 26
- 229910001335 Galvanized steel Inorganic materials 0.000 title claims abstract description 19
- 239000008397 galvanized steel Substances 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229910000617 Mangalloy Inorganic materials 0.000 title abstract description 7
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 55
- 239000010959 steel Substances 0.000 claims abstract description 55
- 239000011572 manganese Substances 0.000 claims abstract description 47
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 32
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims description 54
- 230000003647 oxidation Effects 0.000 claims description 32
- 238000007254 oxidation reaction Methods 0.000 claims description 32
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- 239000011159 matrix material Substances 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical group [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 11
- 230000002829 reductive effect Effects 0.000 abstract description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 238000003618 dip coating Methods 0.000 abstract 2
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- 150000001875 compounds Chemical class 0.000 description 15
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- 229910052785 arsenic Inorganic materials 0.000 description 2
- 229910001566 austenite Inorganic materials 0.000 description 2
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- 229910018573 Al—Zn Inorganic materials 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
- C23C2/022—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating
- C23C2/0222—Pretreatment of the material to be coated, e.g. for coating on selected surface areas by heating in a reactive atmosphere, e.g. oxidising or reducing atmosphere
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
- C23C2/36—Elongated material
- C23C2/40—Plates; Strips
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- Coating With Molten Metal (AREA)
Abstract
The invention relates to a production method for hot dip galvanized steel sheet in high ductility and high strength used in vehicular body and structural material, the object is to provide a method of easily producing high manganese steel with great coating surface qualities such as hot-dip coating property, coating adherence or the like using high manganese steel as the coating material. The invention provides a method for producing high manganese hot dip zinc coating steel plates in great coating surface quality using high manganese steel as the base, and is characterized in that the high manganese steel is optionally oxidized in a manner of regulating the dew point, the heating temperature and the heating time of the ambient gas, forming internal oxide and porous surface oxide closely below the base, reduced in the reduction ambient gas, then subject to hot dip zinc coating. According to the invention, high manganese hot dip zinc coating steel plate with great coating surface quality such as hot dip coating property, coating adherence or the like can be easily produced.
Description
Technical field
The present invention relates to the method for manufacture of galvanizing high manganese steel sheet used in the vehicle body of automobile and structured material etc. with high ductibility and high-strength characteristic; More particularly, the present invention relates to the method for manufacture of the high mangaenese steel hot-dip galvanized steel sheet of great coating surface qualities such as hot dipping plating property and plating tackiness.
Background technology
Hot-dip galvanized steel sheet is widely used as automotive sheet owing to have superior corrosion resistance, weldableness and coating.
On the other hand, because the lighting of automobile from improving the angle of fuel efficiency and security, is constantly sought the high strength of body of a motor car and structured material, thereupon, developed multiple automobile high-strength steel.
But most of steel plate reduces owing to high strength makes ductility, and the result causes that a lot of restrictions are arranged when being processed into parts.
The ductility that causes for the HS that solves such steel plate reduces; Many researchs have been carried out; The result has proposed austenite (austenite) type high mangaenese steel; This type steel contains 7～35% manganese in steel, when viscous deformation takes place, in steel, induce twin crystal (TWIN) to occur, thereby improved ductility (patent documentation 1, patent documentation 2, patent documentation 3, patent documentation 4 etc.) epoch-makingly.
But, using such high mangaenese steel as plating in the raw-material hot-dip galvanized steel sheet, in order to ensure material and make surface active (reduction), in hydrogenous nitrogen atmosphere atmosphere gas, anneal.
Such atmosphere gas is reductibility atmosphere gas for plating starting material Fe, but for the element of oxidation easily such as the Mn of high mangaenese steel, Si, Al, is to work as oxidisability atmosphere gas.Therefore; In such atmosphere gas; When the high mangaenese steel that is added with a large amount of Mn was carried out full annealed, micro-moisture that contains in the atmosphere gas and oxygen can make these being selected property of alloying element oxidations (selective oxidation), the main oxide compound that generates Mn on matrix (plating starting material) surface.
Therefore, when the high mangaenese steel that will contain a large amount of Mn uses as the plating starting material, owing to before plating, form oxide on surface in the operation annealing process, so or the plating failure, even or coating also can take place man-hour and peel off adding in the plating success.
Up to now; In order to prevent above-mentioned galvanizing high manganese steel sheet plating failure; The prior art that had proposed already has following method: 1) of patent documentation 5; Add elements such as Sb, Sn, As, Te, prevent that alloying elements such as Mn, Si from forming oxide compound in surface diffusion, thereby carry out the method for plating; 2) of patent documentation 6, add Si, form very thin Si oxide skin on the surface, thereby suppress the formation of Mn oxide, thereby carry out the method for plating; 3) of patent documentation 7, before annealing, contain the Al material, thereby prevent the formation of Mn oxide, thereby carry out the method for plating through what vaccum gas phase sedimentation method (PVD) applied one deck 50nm to 1000nm.
But; In above-mentioned existing method 1) in; Units such as Sb that can not be through in containing the high mangaenese steel of 5～35% manganese, adding the trace below 0.05%, Sn, As, Te usually prevent the surface oxidation of the manganese that oxidisability is very strong, therefore, have to add a large amount of above-mentioned high price alloying elements; Cause expense to increase, therefore not ideal enough.
In above-mentioned existing method 2) in, therefore Si is stronger than the oxidisability of Mn, forms the oxide compound of stable film morphology, the problem that the wettability with fused zinc is difficult to improve occurs.
In addition; In above-mentioned existing method 3) in, must before the annealing of plating process, carry out the operation of vacuum vapor deposition, as oxidized easily by the Al of the plating material of vapour deposition; Therefore; In annealing operation subsequently, the effect of moisture and the oxygen of the Al of vapour deposition in annealing atmosphere gas is the al oxide of formation wettability difference down, so the plating property problem of variation on the contrary occurs.
As stated; In the prior art; When the high mangaenese steel that will contain a large amount of manganese uses as the plating starting material,, be difficult to guarantee the good plating property of hot-dip galvanized steel sheet and the good adhesive problem of plating so exist owing in annealing process, form thicker Mn oxide.
The prior art document:
Patent documentation:
Patent documentation 1:JP1992-259325
Patent documentation 2:WO93/013233
Patent documentation 3:WO99/001585
Patent documentation 4:WO02/101109
Patent documentation 5:KR 2007-0067593
Patent documentation 6:KR 2007-0067950
Patent documentation 7:KR 2007-0107138
Summary of the invention
The problem that invention will solve
The purpose of this invention is to provide a kind of with high mangaenese steel as the plating starting material, easily make the method for the high mangaenese steel hot-dip galvanized steel sheet of great coating surface qualities such as hot dipping plating property and plating tackiness.
The means of dealing with problems
Below the present invention will be described.
The present invention relates to a kind of is the method that matrix is made the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality with high mangaenese steel; It is characterized in that; Through dew point, Heating temperature and the heat-up time of adjustment atmosphere gas gas; Mode below next-door neighbour's matrix, to form subscale and porosity surface oxide compound is carried out selective oxidation to high mangaenese steel, then reduces processing in the atmosphere gas reducing, and carries out galvanizing then.
Preferably; The present invention relates to a kind of method of making the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality; It is characterized in that above-mentioned high mangaenese steel is formed as follows in weight %: below C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, the Nb:0.03%, below the V:0.1%, Fe and other unavoidable impurities of following, the surplus of S:0.01%; And; Is that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned high mangaenese steel at dew point; Forming the subscale of manganese, form the oxide on surface of porous manganese on the surface, be that the temperature with 800～850 ℃ heats in-40～-60 ℃ the reduction atmosphere gas at dew point then; Make oxide on surface reduction, be dipped in Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating.
The invention effect
As stated; According to the present invention; Can make hot-dip galvanized steel sheet, in addition with the high mangaenese steel that contains 5～35% manganese that can't galvanizing with usual method as the plating starting material; Also make the hot dip process steel plate as the plating starting material applicable to the general plow-steel that will contain alloying elements such as Si, Mn, Al (for example, IF plow-steel, two-phase complex tissue steel (DP), TRIP steel etc.).
Description of drawings
Fig. 1 is when being presented at 800 ℃ annealing temperature, the graphic representation that the thickness of oxide on surface (Mn oxide) changes with the variation of dew point.
The annealed material cross-section photograph of Fig. 2 formation degree of subscale when showing different dew point, (a) the expression dew point be-20 ℃ a situation, representes that (b) dew point is-40 ℃ a situation.
The photo of Fig. 3 variation of the surface shape of oxide on surface when showing different dew point, (a) the expression dew point is 0 ℃ a situation, and (b) the expression dew point be-20 ℃ a situation, and (c) the expression dew point is-40 ℃ a situation, representes that (d) dew point is-60 ℃ a situation.
Fig. 4 is for showing the process chart of existing galvanizing (GI) operation and galvanizing of the present invention (GI) operation.
Embodiment
Be elaborated in the face of the present invention down.
The present invention is when with high mangaenese steel being matrix manufacturing high mangaenese steel hot-dip galvanized steel sheet; Mode below next-door neighbour's matrix, to form subscale and porosity surface oxide compound is carried out selective oxidation to high mangaenese steel; Then in reduction atmosphere gas, reduce processing; Carry out galvanizing then, can produce the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality thus.
Dew point, Heating temperature and the heat-up time of the atmosphere gas gas when adjusting above-mentioned selective oxidation, form above-mentioned subscale and porosity surface oxide compound.
The inventor is in order to understand fully the occurrence cause of the high mangaenese steel plating failure that contains a large amount of manganese; The amount of increasing of material that the failure of high mangaenese steel plating takes place and oxide on surface is studied with the situation that the variation of the reductive condition of annealing atmosphere gas changes; The result is as shown in Figure 1; Along with the variation of the dew point of annealing atmosphere gas, the thickness of the Mn oxide that increase on the high mangaenese steel surface shows sizable difference, even change annealing conditions; Because the formation of the thicker Mn oxide of film-type, plating performance also can't be guaranteed.
But, be in-40 ℃ the annealing atmosphere gas under the annealed situation at dew point, as shown in Figure 2, can find to have formed the subscale of manganese.
When below next-door neighbour's matrix, forming subscale, this subscale has stoped the surface of the manganese of matrix to be increased, so the thickness attenuation of oxide on surface, and perhaps the shape of oxide on surface is not the continuous thin film shape, and shows alternate particle shape or netted.
But for high mangaenese steel, as shown in Figure 1, even can find that the thickness of oxide compound does not reduce yet, proportional on the contrary increase more than the critical dew point-40 that begins to form subscale ℃.
According to judge this be because high mangaenese steel and common carbon steel to compare manganese content very high, so even form the subscale of Mn oxide (MnO), a large amount of excessive manganese that exist also can increase on the surface, form oxide on surface.
But; Can know Fig. 3 of the shape of oxide on surface when showing different dew point, when not forming-60 ℃ (Fig. 3 (d)) of subscale, form very fine and close oxide on surface, and more than critical dew point-40 ℃ the time; Oxide on surface demonstrates the shape that the oxide compound of particle shape tangles mutually; Dew point is high more, and oxide particle is just thick more, and the gap between particle and the particle (pore, emptying aperture) is just big more.
That is to say, can know, when dew point is high, can form between the oxide particle oxide on surface that the existence owing to the gap interlinks.
Therefore; The inventor studies subscale and the scheme of porosity surface oxide compound of the below that can use next-door neighbour's matrix; Results verification, when heating than the higher dew point of critical dew point that begins to form subscale, alloying elements such as manganese are selected oxidation; Formation contains the porosity surface oxide compound of more emptying aperture; When in strong reducing property atmosphere gas, it being carried out successive thermal treatment, the emptying aperture of oxide on surface plays the effect of the diffusion path (diffusion path) that is used for reductive atmosphere gas gas, thereby easily oxide on surface is reduced.
Can give an example % meter by weight of an instance of the preferred high mangaenese steel that is suitable for has the high mangaenese steel of following composition among the present invention: below C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, the Nb:0.03%, below the V:0.1%, below the S:0.01%, Fe and other unavoidable impurities of surplus, this high mangaenese steel is well known in the art.
Therefore; As an instance; As shown in Figure 4, be that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned known high mangaenese steel at dew point, in matrix, to form the subscale of manganese; Form the oxide on surface of the porous manganese of easy reductive on the surface; Then continuously dew point be in-40～-60 ℃ the reduction atmosphere gas with 800～850 ℃ temperature heating, make the oxide on surface reduction, guarantee material character; Immerse Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating, the hot-dip galvanized steel sheet of the high mangaenese steel that can produce thus not can the plating failure, the plating tackiness is good.
As stated, in order to form the porosity surface oxide compound, in the selective oxidation operation, dew point is limited to-20～-40 ℃ through the subscale that forms matrix.
Above-mentioned dew point is during less than-40 ℃, because below critical dew point, so internal oxidation does not take place; And form fine and close oxide on surface, when dew point surpasses-40 ℃, form subscale; Also form the porosity surface oxide compound; But when surpassing-20 ℃, owing to form very thick oxide on surface, so in the limited reduction treatment time, be difficult to make oxide on surface to reduce fully.
The Heating temperature of above-mentioned selective oxidation operation is limited at 400～800 ℃.
When above-mentioned Heating temperature during less than 400 ℃, can not successfully form subscale,, reduction takes place that increase on the surface and oxidation when handling once more from the manganese in the matrix, be difficult to guarantee the wettability of fused zinc; When surpassing 800 ℃,, in the limited reduction treatment time, be difficult to reduction, so be non-preferred version owing to form thicker oxide on surface.
Be limited to the heat-up time of above-mentioned selective oxidation operation 10～40 seconds.
When the heat-up time of the less than in the time of 10 seconds that is used for above-mentioned selective oxidation, even under higher Heating temperature, also can't be completed into internal oxidation, the manganese of matrix takes place once more that increase on the surface and oxidation when reduction is handled, and wettability reduces; When surpass 40 seconds heat-up time, because excessive internal oxidation and formation oxide on surface need be carried out the reduction of long period, so be non-preferred version.
In addition; As stated, in order to make the porosity surface oxide compound reduction that selective oxidation forms and to guarantee material character, after selective oxidation; Continuously dew point be in-40～-60 ℃ the reduction atmosphere gas with 800～850 ℃ temperature heating, oxide on surface is reduced fully.
For the porosity surface oxide compound reduction that selective oxidation is formed, the reason that the dew point of reduction atmosphere gas is limited to-40～-60 ℃ is described below.
When the dew point of reduction atmosphere gas surpassed-40 ℃, the moisture in the reduction atmosphere gas and the ratio of oxygen were higher, are difficult to make Mn oxide to reduce fully; When dew point during less than-60 ℃, the manganese in the matrix increases and oxidation once more, is difficult to make oxide on surface to reduce fully.
Above-mentioned reduction temperature is high more, and reduction is just easy more, so be preferred version; But when surpassing 850 ℃, the problem that high temperature causes the strength degradation of steel can appear; During less than 800 ℃, make the required time of oxide on surface reduction longer, so preferably reduction temperature is defined as 800～850 ℃.
As stated, the high mangaenese steel that will carry out selective oxidation and reduction processing is dipped in the zinc-plated bath that Al concentration is 0.21～0.25wt% and carries out plating, makes the high mangaenese steel hot-dip galvanized steel sheet.
The Al concentration that above-mentioned plating is bathed can suitably be 0.23～0.25wt%.
When process reductive steel plate is dipped in the plating bath, the preferential and surface of steel plate reaction of the Al during plating is bathed, the Fe-Al-Zn layer of formation ductility; Play the effect of the growth of the Zn-Fe intermetallic compound that suppresses fragile; So it is favourable that the Al concentration that plating is bathed maintains higher level, but bathe Al concentration above 0.25% the time, generate the floating scum silica frost of Fe-Al easily when plating; Flow into coating layer and can cause macroscopic irregularity, so its upper limit is defined as 0.25%.
Below through embodiment the present invention is done explanation more specifically.
(embodiment)
As shown in table 1 below; Thickness is 1.2mm, contains C:0.6 weight %, Mn:18 weight %, Si:0.2 weight %, Al:1.5 weight %, Nb:0.03 weight %, V:0.1 weight %, S:0.008 weight %, the Fe of surplus and the high mangaenese steel of other impurity; In hydrogeneous 15%, surplus is that nitrogen, dew point are in 0 ℃～-60 ℃ the reduction atmosphere gas; Kept 10～40 seconds with 400 ℃～800 ℃ annealing temperature; Carry out the internal oxidation of manganese and the selective oxidation of surface oxidation; The oxide on surface that forms in the process with selective oxidation continuously is that-20～-75 ℃, Heating temperature are under 800～850 ℃ the reduction treatment condition at atmosphere gas gas dew point, carries out reduction in 40 seconds and handles, and is cooled to 460 ℃ with 15 ℃/second speed of cooling then; Being dipped in then and bathing temperature is that Al concentration that 460 ℃, plating are bathed is to carry out hot dip process during the galvanizing of 0.23wt% is bathed, and uses air knife (air knife) adjustment to make every plating adhesion amount be 60g/m
2, evaluation coating surface quality, that is, Mn surface degree of increasing, plating failure degree and plating tackiness, the result is shown in the following table 1.
For the sample No.1,12 in the following table 1,17 and 27, do not evaluate Mn surface degree of increasing.
Above-mentioned manganese surface degree of increasing carries out the composition analysis of depth direction with glow discharge spectrometry (GDS), and the surface of manganese is increased degree and carried out quantitative evaluation with the height of peak value (peak) and length (highly * degree of depth).
As for above-mentioned plating failure degree, the appearance behind the galvanizing is taken pictures handle and obtain the area of plating failure part after, with following baseline rated grade.
-1 etc.: the defective that does not have the plating failure
-2 etc.: the mean diameter of plating failure place is less than 1mm
-3 etc.: the mean diameter of plating failure place is 1～2mm
-4 etc.: the mean diameter of plating failure place is 2～3mm
-5 etc.: the mean diameter of plating failure place is more than the 3mm
In addition,, after having carried out the 0T-crooked test, adhesive tape test (taping test) is carried out in the outside portion of bending, the occurrence degree that coating is peeled off is estimated with following benchmark as for the plating tackiness of hot-dip galvanized steel sheet.
-1 etc.: do not have and peel off
-2 etc.: peel off less than 5%
-3 etc.: peel off 5～10%
-4 etc.: peel off 10～30%
-5 etc.: peel off more than 30%
Table 1:
As above shown in the table 1; Under the selective oxidation condition that the present invention proposes; Promptly in dew point is-20～-40 ℃ reduction atmosphere gas,, form oxide on surface with 40～-00 ℃ Heating temperatures heating 10～40 seconds; Be with 800～850 ℃ Heating temperature heating in-40～-60 ℃ the reduction atmosphere gas at dew point continuously; Make the oxide on surface reduction, (sample No.4～5,9～10,14～15,19～20,22～37,39～40,42～43) in this case, the subscale of formation manganese in matrix; Form the oxide on surface of the porous manganese of easy reductive on the surface; When reduction is handled, be reduced easily, the formation of subscale can prevent to increase once more and reoxidation from the manganese in the matrix, so can the plating failure can produce hot dip process the time, add the high manganese hot-dip galvanized steel sheet that the great coating surface quality that coating peels off does not take place man-hour.
On the other hand; Under the situation of only carrying out anneal (sample No.1) though or carry out the reduction of selective oxidation processing and successive and handle, internal oxidation does not take place in the dew point during selective oxidation below next-door neighbour's matrix under the situation beyond the present invention (sample No.2～3,6～8,11～13,16～18,21); Only form fine and close film-type oxide on surface; Also form very thickly even perhaps form the porosity surface oxide compound, thus the plating failure takes place, even the plating success; Unreduced oxide on surface also can cause coating to be peeled off adding man-hour on the interface, so be non-preferred version.
In addition; When the dew point of reductive condition and reduction temperature beyond the scope of the invention when (sample No.38,41,44); Owing in atmosphere gas, have excessive moisture and oxygen,, fail so plating can take place so the film-type oxide on surface that in the selective oxidation operation, forms is difficult to reduce fully; Perhaps coating takes place man-hour peel off adding, so be non-preferred version.
Claims (2)
1. one kind is the method that matrix is made the high mangaenese steel hot-dip galvanized steel sheet of great coating surface quality with high mangaenese steel,
It is characterized in that; Above-mentioned high mangaenese steel is formed as follows in weight %: below C:0.1～1.5%, Mn:5～35%, Si:0.1～3wt%, Al:0.01～3%, the Nb:0.03%, below the V:0.1%, Fe and other unavoidable impurities of following, the surplus of S:0.01%; And; Is that selective oxidation was carried out in the Heating temperature heating with 400～800 ℃ in 10～40 seconds in-20～-40 ℃ the reduction atmosphere gas with above-mentioned high mangaenese steel at dew point; Forming the subscale of manganese, form the oxide on surface of porous manganese on the surface, be that the temperature with 800～850 ℃ heats in-40～-60 ℃ the reduction atmosphere gas at dew point then; Make oxide on surface reduction, be dipped in Al concentration then and be in the zinc-plated bath of 0.21～0.25wt% and carry out plating.
2. the method for the high mangaenese steel hot-dip galvanized steel sheet of manufacturing great coating surface quality according to claim 1 is characterized in that, the Al concentration of above-mentioned zinc-plated bath is 0.23～0.25wt%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2008-0132593 | 2008-12-23 | ||
| KR1020080132593A KR101079472B1 (en) | 2008-12-23 | 2008-12-23 | Method for Manufacturing High Manganese Hot Dip Galvanizing Steel Sheet with Superior Surface Property |
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| CN101760712A CN101760712A (en) | 2010-06-30 |
| CN101760712B true CN101760712B (en) | 2012-08-22 |
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| JP4990345B2 (en) | 2012-08-01 |
| KR20100073819A (en) | 2010-07-01 |
| KR101079472B1 (en) | 2011-11-03 |
| JP2010150660A (en) | 2010-07-08 |
| CN101760712A (en) | 2010-06-30 |
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