CN1276990C - Zinc-base hot dip galvanized steel sheet excellent in retention of gloss - Google Patents
Zinc-base hot dip galvanized steel sheet excellent in retention of gloss Download PDFInfo
- Publication number
- CN1276990C CN1276990C CN02808369.5A CN02808369A CN1276990C CN 1276990 C CN1276990 C CN 1276990C CN 02808369 A CN02808369 A CN 02808369A CN 1276990 C CN1276990 C CN 1276990C
- Authority
- CN
- China
- Prior art keywords
- steel band
- district
- shrend
- coating
- plating bath
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000014759 maintenance of location Effects 0.000 title description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 title 1
- 239000008397 galvanized steel Substances 0.000 title 1
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 143
- 239000010959 steel Substances 0.000 claims abstract description 143
- 238000007747 plating Methods 0.000 claims abstract description 98
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims description 119
- 239000011248 coating agent Substances 0.000 claims description 114
- 238000000034 method Methods 0.000 claims description 73
- 238000007598 dipping method Methods 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 26
- 230000006866 deterioration Effects 0.000 claims description 20
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 14
- 229910052710 silicon Inorganic materials 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 42
- 229910018134 Al-Mg Inorganic materials 0.000 abstract description 11
- 229910018467 Al—Mg Inorganic materials 0.000 abstract description 11
- 239000010410 layer Substances 0.000 abstract description 6
- 239000002344 surface layer Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 95
- 238000001816 cooling Methods 0.000 description 51
- 239000002932 luster Substances 0.000 description 33
- 230000007423 decrease Effects 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 238000010276 construction Methods 0.000 description 18
- 239000007921 spray Substances 0.000 description 18
- 230000005496 eutectics Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000003628 erosive effect Effects 0.000 description 9
- 230000005021 gait Effects 0.000 description 8
- 239000012530 fluid Substances 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 5
- 238000005507 spraying Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002788 crimping Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007761 roller coating Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- 229910000521 B alloy Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007739 conversion coating Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000010583 slow cooling Methods 0.000 description 1
- 238000004441 surface measurement Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/06—Zinc or cadmium or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
- C23C2/24—Removing excess of molten coatings; Controlling or regulating the coating thickness using magnetic or electric fields
-
- 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
- C23C2/26—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating With Molten Metal (AREA)
- Laminated Bodies (AREA)
Abstract
Contact temperature between a plating layer and water flow is controlled through a watercooling step carried out after the plating layer is solidified. Thus, the temperature of band materials during a contact period with the water flow is properly controlled. A small amount of proper easy oxidation elements are further added to plating liquid to stabilize the oxidation state of Al and Mg in a surface layer of the plating layer. Thus, the descending of the surface gloss of a thin steel plate which is hot dipped and plated with Zn-Al-Mg is suppressed.
Description
Technical field
The present invention relates to a kind of technology that prevents the surface luster variation that during adopting the continuous hot-dipping production line to prepare hot dip process Zn-Al-Mg steel sheet, occurs sometimes.
Technical background
The JP.Hei-10-226865A that the application's applicant has, JP.Hei-10-306357A, USP6,235,410 (US6,235,410B1) and USP6,379,820 (US6,379,820B1) point out: the hot dipping plating bath by adopting a kind of Zn-Al-Mg system and give below the coating and prepare Zn base hot dip process steel sheet in metal construction, can obtain to have the erosion resistance that satisfies the Industrial products requirement fully and the plating steel sheet of appearance, the hot dipping plating bath of described Zn-Al-Mg system comprises Al:4.0-10%, Mg:1.0-4.0%, Ti:0.002-0.1%, B:0.001-0.045% the rest is Zn and unavoidable impurities, and the structure of described coating is included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase] and [Zn is single-phase].In disclosed specification sheets, provided the working condition that obtains described metal construction.
In the preparation process subsequently, during the hot dip process Zn base steel sheet higher to this Al content and Mg content processed, the inventor finds: according to preparation condition, deterioration took place in the surface luster of coating in 2-3 days.This gloss deterioration of coating makes just behind plating says pleasant coating surface from aesthetic, As time goes on (soon then 2-3 days, then need 4-7 days sometimes) faded and had the variegated of black a little.Can quantitatively determine the degree of fade (a kind of blackout) of outermost surface by surface measurements brightness.For example, just made afterwards surface brightness (L value) dropped to about L=72 for the coating surface of about L=82 in 7 days.Though the decline of this L value does not reduce the erosion resistance of product, do not damage plating steel-sheet physics and chemical quality yet,,, still do not wish to occur this decline from the angle of appearance.The decline of this surface luster is not evenly to take place in whole coating surface scope, but carries out with flecked decolouring form.This fact has especially been damaged aesthetic appearance.
Can think that the decline of this surface luster betides Al content and the higher plating steel sheet of Mg content, for example aforesaid hot dip process Zn-Al-Mg steel sheet especially.The state of oxidation that is enriched in Al in the degree of oxidation of Mg of coating outermost surface and the upper layer is likely the combined cause of this decline.So far, still unexposed any relevant mechanism or relevant report that suppresses the method for this decline that appears at the surface luster decline in this hot dip process Zn-Al-Mg steel sheet.
Purpose of the present invention
Therefore, the purpose of this invention is to provide the means that surface luster that inhibition particularly occurs descends in hot dip process Zn-Al-Mg steel sheet.
Disclosure of the Invention
In order to overcome the problems referred to above, the inventor has carried out test and research work widely.The result, we determine: the response characteristic that reason that surface luster descends is to carry out in the cooling step after plating coating surface and water during the water-cooled appears in the hot dip process steel sheet, a kind of method that prevents that surface luster from descending is in the water-cooled step of carrying out " controlling the temperature that contacts between coating and the current; " coating solidifies after broadly, suitably control " with the strip temperature of current period of contact " is very effective, and, also can stablize the state of oxidation of Al and Mg in the coating surface layer effectively by in plating bath, adding a small amount of suitable " easily oxidation element ".So-called " with the strip temperature of current period of contact " refer to coating solidify finish after, in cooling step, cool off the strip temperature when coating surface forms moisture film simultaneously.Particularly, it be current by on the coating surface that solidifies fully and coating formed in its surface the moisture film cooling time the coating temperature.
In other words, discovery according to the inventor, when steel band is to carry out continuous impregnating and taking-up in the hot dipping plating bath at aforesaid Zn-Al-Mg, and, make steel band by one steel band be carried out refrigerative shrend district continuously afterwards, make the coating surface that solidifies fully contact (a certain amount of water that can form water membrane in coating surface moment is provided simultaneously) with current simultaneously on coating surface, be lower than 105 ℃ by the control steel band in the temperature of shrend district inlet side, aforesaid deterioration takes place in the gloss that can suppress coating surface.
Though it is steel band depends on appointed condition in the temperature of shrend district inlet side, closely related with sheet gauge.When thickness of strips is big, may be not easy to control steel band and be lower than 105 ℃ in the temperature of shrend district inlet side.Find: in this case, by in plating bath, adding a small amount of and the chemical affinity very strong (being easy oxidation element) of oxygen and the element that the oxide compound of Al is had stabilization, then do not need to make steel band to be lower than 105 ℃ (temperature equals 105 ℃ or higher), can obtain similarly to suppress the effect of surface luster deterioration yet in the temperature of shrend district inlet side.This dvielement comprises for example rare earth element, Y, Zr and Si.In fact, the easy oxidation element of the about 0.002-0.05% of interpolation (quality) is just enough.
Therefore, the invention provides a kind of hot dip process Zn steel-sheet method that gloss keeps excellent performance for preparing, it comprises: steel band carries out continuous impregnating and taking-up in containing the Zn base hot dipping plating bath of Al:4.0-15% (quality) and Mg:1.0-4.0% (quality), on steel band, form the step of coating thus, and, make steel band continuously by a shrend district afterwards, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, be lower than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface gloss deterioration.Described Zn base hot dipping plating bath preferred package contains, in % (quality): Al:4.0-15%, and Mg:1.0-4.0%, Ti:0.001-0.1%, B:0.001-0.045% the rest is Zn and unavoidable impurities.
The present invention also provides a kind of hot dip process Zn steel-sheet method that gloss keeps excellent performance for preparing, it comprises: steel band is containing Al:4.0-15% (quality) and Mg:1.0-4.0% (quality), and add at least a rare earth element that is selected from of 0.002-0.05% (quality), Y, carry out continuous impregnating and taking-up in the Zn base hot dipping plating bath of the easy oxidation element of Zr and Si, on steel band, form the step of coating thus, and, make steel band continuously by a shrend district afterwards, this shrend district carries out refrigerative to steel band makes the coating surface that solidifies fully contact with current simultaneously, be not less than 105 ℃ but be not higher than 300 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface gloss deterioration.Described Zn base hot dipping plating bath preferred package contains, in % (quality): Al:4.0-15%, Mg:1.0-4.0%, Ti:0.001-0.1%, B:0.001-0.045%, at least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05% the rest is Zn and unavoidable impurities.
As a kind of hot dip process Zn steel sheet that adopts preceding method to obtain, it is a kind of by adopting a kind of hot dipping plating bath steel band to be carried out the hot dip process Zn steel sheet of the gloss maintenance excellent performance of hot dipping plating acquisition that the present invention also provides, described plating bath comprises, in % (quality):
Al:4.0-15%, and
Mg：1.0-4.0％，
Randomly,
Ti:0.001-0.1% and
B：0.001-0.045％，
Preferably,
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities, on steel sheet, form coating thus.Described coating has and is included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], perhaps be included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], [Zn phase] and/or [Zn
2The Mg phase] metal construction.
The accompanying drawing summary
Fig. 1 is that explanation is used to produce the route map according to the Mg of containing hot dip process Zn steel-sheet device of the present invention.
The preferred embodiments of the invention
Generally speaking, in this manual, when explanation hot dip process production line, use term " steel band ", and when the explanation product, use term " steel sheet." steel band and steel sheet have same characteristics.
Fig. 1 has carried out illustrative to being used to prepare Zn base hot dip process steel-sheet device.The steel band 2 of process furnace 1 that will be by remaining on preset temperature is sent in the plating bath 3 continuously.When from plating bath 3, coming out, make steel band pass through a wiping shower nozzle 4 of adjusting its coating weight, then, again by air spray refrigerating unit 5.Coating solidifies during by air spray refrigerating unit 5 fully.Next, steel band is by air- water cooling district 6a, 6b and an air-cooling zone 14, and described each cooling zone can work independently or work together, perhaps do not work, then, by a shrend district 7.Afterwards, steel band carries out skin-pass rolling on levelling machine 8, again by a tension level(l)er 9, through a detection step, and is crimped onto on the tension force crimping machine 10.When carrying out chromate treating or other this class chemical treatment, on roller coating machine 11, handle leaving tension level(l)er 9 steel bands, again by a drying zone 12 and an air-cooling zone 13, and be crimped onto on the tension force crimping machine 10.
As previously mentioned, when the steel sheet of the higher hot dip process Zn-Al-Mg of preparation Al and Mg content when (after this being called " the hot dip process Zn steel sheet that contains Mg "), consider from the surface property aspect, suitably control speed of cooling and the coating position of fully solidifying of coating before solidifying fully and be absolutely necessary.For this reason, the speed of sending into that must strict control steel band, and, need be according to sheet gauge strip temperature when accurately control is by air spray refrigerating unit 5.Next, in order on levelling machine 8, to carry out suitable skin-pass rolling, need to be adjusted to preset temp level (for example, not being higher than 70 ℃) at the strip temperature of smooth inlet side by (with air-cooling zone 14) and/or shrend district 7 implement cooling in air-water cooling district 6.The cooling intensity at place, described cooling zone changes according to the gait of march and the sheet gauge of band.Usually, at the air-water cooling district splash water or the aqueous solution,,, then provide the current that can form moisture film enough in moment on coating surface in the shrend district at air spray cooling zone injection air.Compare with the cooling step of at first mentioning, the shrend district of mentioning later can reach speed of cooling faster because current contact with coating surface.Therefore, irrelevant with the variation of cooling intensity, can implement effective cooling operation in the shrend district.Though in air-water cooling district 6, the water or the aqueous solution is with the airflow splash,, can not provide enough water on coating surface, to form moisture film.So this cooling mainly is the result who emits latent heat by evaporation.This be a kind of with in the shrend district by contact with current different heat radiation form, therefore, the speed of cooling difference.
Find: the gloss of coating surface keeps performance with in the difference of the strip temperature of shrend district inlet side and difference.When temperature is 105 ℃ or when higher, the surface luster deterioration takes place easily.Although its reason is not determined as yet, but, the inventor conclude reason relate to following factor as: strip temperature is 100 ℃ or when higher when entering the shrend district, a kind of appearance of boiling phenomenon has improved the reactivity of coating surface, and, under atmospheric pressure, when having water to exist, the characteristic of Al is in temperature difference during above and below about 110 ℃, is higher than this temperature, Al that is:
2O
3H
2O (or AlOOH) compound is stable, and when being lower than this temperature, Al
2O
33H
2O (or Al (OH)
3) compound is stable, the result, the Al compound that forms on the coating surface in the shrend district changes according to the inlet side temperature of steel strips.
The steel-sheet metal construction of the hot dip process Zn of the aforementioned Mg of containing is included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], [Zn phase] and/or [Zn
2The Mg phase] metal construction, by above-mentioned chemical reaction, the outermost surface of described ternary eutectic crystalline structure becomes a kind of easy oxidised form, and, it is believed that why Here it is can occur producing the reason of the surface luster deterioration of brightness flop in 2 or 3 days behind plating.
In a word, the inventor finds: as provide later embodiment confirmed like that, be adjusted to by the temperature of steel strips that will enter the shrend district and be lower than 105 ℃, then can significantly prevent to contain the steel sheet generation surface luster deterioration of the hot dip process Zn of Mg.In this case, during cooling operation before implementing to enter the shrend district, do not provide enough water to produce the moisture film that quenches as in the shrend district, to form to the coating surface that solidifies fully, but carry out the slow cooling operation, for example carry out air-water cooling (spraying) or air cooling (for example injection air cooling).This is because if before steel band enters the shrend district, implements to form as in the shrend district the hardening step of moisture film, the temperature of steel strips that then will enter the shrend district be adjusted to hang down 105 ℃ meaningless.According to the gait of march of sheet gauge and band, even can be, will be adjusted at the strip temperature of shrend district inlet side and be lower than 105 ℃ by air-water cooling.
But, when sheet gauge is thicker, the strip temperature at shrend district inlet side can not be adjusted to sometimes and be lower than 105 ℃.When though even sheet gauge is big, also can realize abundant cooling in air-water-cooled district by reducing the band gait of march,, this is undesirable, because this can produce zero pour control problem and can reduce productivity.Yet, as provide later embodiment confirmed, by making the coating surface that has just solidified fully have an amount of easily oxidation element, the chemical affinity of this element and oxygen is very strong and the oxide compound of Al had a kind of stabilization, for example rare earth element, Y, Zr or Si, even when the strip temperature of shrend district inlet side be 105 ℃ or when higher, also can effectively suppress the deterioration of surface luster.In the practice, the described easy oxidation element that adds about 0.002-0.05% (quality) is just enough.Although may there be other element that has with rare earth element, Y, Zr or Si similar effect,, do not have a kind ofly to be confirmed.
Described these easy oxidation elements have contain on the hot dip process Zn steel sheet of Mg the coating solidificating period or even solidifying after, be enriched in the characteristic of the outermost surface part of coating.Even when only adding in plating bath when a small amount of, these elements also can reach than higher concentration at the outermost surface place therefore.It is believed that can make these elements suppress in the shrend district to take place like this can disadvantageous surface reaction to retention of surface gloss.But, when the addition of these easy oxidation elements in plating bath is lower than 0.002% (quality), can not show described inhibition effect.Therefore, the addition of these easy oxidation elements in plating bath must be not less than 0.002% (quality).On the other hand, cause the solubleness in plating bath to descend when addition is too much, and, even even dissolving fully, it reaches capacity to restraining effect that surface luster descends, because the excessive part of described element is only separated out near the crystal boundary in the coating surface part.Therefore, the addition of these elements in plating bath is not higher than 0.10% (quality), is not higher than 0.08% (quality) under some situation, preferred 0.05% (quality), more preferably 0.03% (quality).
As previously mentioned, when the strip temperature of shrend district inlet side is 105 ℃ or when higher, the most effective by the effect of adding the inhibition surface luster deterioration that one or more easy oxidation elements produce.But, even when the strip temperature of shrend district inlet side is lower than 105 ℃, can safely one or more easy oxidation elements be added in the plating bath.
When the strip temperature of shrend district inlet side is 105 ℃ or when higher, should preferably control it and not be higher than 300 ℃, because when being higher than 300 ℃, the cooling load in shrend district is too big, and the temperature of skin-pass rolling inlet side is fully reduced.
In common production line, if thickness of strip is lower than 1.6mm, then can make the strip temperature of shrend district inlet side be lower than 105 ℃ with comparalive ease, thereby can guarantee that good gloss keeps performance.When thickness of strip is 1.6mm or when thicker, consider from the actually operating aspect, and compare by steel band being forced the cold-zone make the temperature of shrend district inlet side be lower than 105 ℃, add easy oxidation element and can guarantee better that gloss keeps performance.
The present invention prevents to contain the breakthrough that surface luster decline aspect takes place the hot dip process Zn steel sheet of Mg, therefore, can be used to take place the hot dip process Zn steel sheet that contains Mg that surface luster descends.The hot dip process Zn steel sheet of this Mg of containing has the excellent erosion resistance and a hot dip process Zn-Al-Mg steel sheet of appearance by what use that a kind of Zn base hot dipping plating bath obtains typically, described Zn base hot dipping plating bath contains basic component A l:4.0-10% and Mg:1.0-4.0%, add Ti:0.001-0.1% and B:0.001-0.045%, the rest is Zn and unavoidable impurities, the metal construction of the coating that is obtained is included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase] or at [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], [Zn phase] and/or [Zn
2The Mg phase] metal construction.At [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in comprise the preferred [Al/Zn/Zn of metal construction of [nascent Al crystalline phase]
2Mg ternary eutectic structure]+total amount of [nascent Al crystalline phase] is not less than 80% (volume) of metal construction, more preferably is not less than 95% (volume) of metal construction.Remaining part can comprise [Zn phase] and [Zn
2The Mg phase], add, in some cases, a spot of [Zn/Zn
2Mg two component eutectic body] and/or [Al//Zn
2Mg two component eutectic body].When adding Si, also may there be a spot of [Si phase], [Mg
2The Si phase], [Al/Mg
2Si two component eutectic body] etc.
Therefore, the invention provides the hot dip process Zn steel sheet that a kind of gloss that obtains by the hot dip process steel band keeps excellent performance, the hot dipping plating bath that uses during the hot dip process steel band contains, in % (quality):
Al：4.0-15％，
Mg：1.0-4.0％，
Ti：0.001-0.1％，
B：0.001-0.045％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities, on steel sheet, form coating thus.Described coating has and is included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], perhaps be included in [Al/Zn/Zn
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], [Zn phase] and/or [Zn
2The Mg phase] metal construction.Its constitutional features is: one or more easy oxidation enrichment of element are at the outmost surface layer of coating.
The Al in the plating bath according to the present invention, Mg, Ti, the addition of B etc., role and influence remain unchanged in the plating bath that adds a kind of easy oxidation element at least.It is favourable to add Ti and B, suppresses Zn because these elements rise
11Mg
2The generation of phase and the effect of growing up are when coating has the aforementioned Zn of comprising
2During the metal construction of Mg two component eutectic body, Zn
11Mg
2Its outward appearance and erosion resistance have disadvantageous effect relatively.For by adding Ti in plating bath, B or Ti-B alloy or compound obtain above-mentioned this effect, make to contain Ti:0.001-0.1% in the plating bath and B:0.001-0.045% is just enough.When content was higher than described scope, precipitated phase was grown up in coating, formed " projection " that impair appearance (be called butsu in the Japanese ") in coating.
Exist Al to improve plating steel-sheet erosion resistance in the coating, and can during preparation plating steel sheet, suppress the generation of firecoat.When Al content is lower than 1.0% (quality), improve the effect deficiency of erosion resistance, and the effect that suppresses the oxide based firecoat of generation Mg is also low.Preferably make Al content be not less than 4.0% (quality).On the other hand, when Al content surpasses 15% (quality), between coating and matrix steel sheet, significantly form the Fe-Al alloy layer, reduce the adhesion property of coating.Preferred Al content is 4.5-13.0% (quality), more preferably 5.0-10.0% (quality), most preferably 5.0-7.0% (quality).
Mg is present in the coating can produce uniform corrosion product on coating surface, and thus, it has the effect that significantly improves plating steel-sheet erosion resistance.When Mg content is lower than 1.0%, evenly produce the effect deficiency of this corrosion product.On the other hand, when Mg content surpassed 4.0%, the erosion resistance that Mg produced was improved effect and is reached capacity, and, can the oxide based firecoat of the undesirable Mg of easier appearance.Therefore, limiting Mg content is 1.0-4.0% (quality).Preferred Mg content is 1.5-4.0% (quality), and more preferably 2.0-3.5% (quality) most preferably is 2.5-3.5% (quality).
Find: when in the final stage that contains Mg hot dip process Zn steel sheet production line, when for example carrying out chemical treatment by the roller coating machine 11 of use shown in Fig. 1 bottom, the problem that aforesaid surface luster descends also can appear, and this with whether form chromate coating, chromate-free conversion coating, contain the organic resin film of chromic acid or contain silicate films or other this type of film of chromic acid irrelevant.It is the same with the phenomenon of surface luster decline to occur that (perhaps not occurring) brightness descends when not carrying out chemical treatment, according to working condition, exist the plated product of the film that produces by chemical treatment the phenomenon that (perhaps not occurring) brightness descends and surface luster descends after several days, also can occur.Find: the strip temperature according to the present invention by being controlled at shrend district inlet side and add at least a easy oxidation element in plating bath can overcome this problem equally.
More specifically, also at steel band through after the shrend district again in the situation by the chemical treatment district, as contain Mg hot dip process Zn steel-sheet method in aforementioned preparation in, be lower than 105 ℃ or in plating bath, add the easy oxidation element of 0.002-0.05% (quality) by the strip temperature that is controlled at shrend district inlet side, can suppress the chemically treated Mg of containing hot dip process Zn steel-sheet surface luster and descend.
Therefore, the invention provides the hot dip process Zn steel sheet that a kind of gloss that obtains by the hot dip process steel band keeps excellent performance, the hot dipping plating bath that uses during the hot dip process steel band contains, in % (quality):
Al：4.0-15％，
Mg：1.0-4.0％，
Ti：0.001-0.1％，
B：0.001-0.045％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities, on steel sheet, form coating thus, and described coating is carried out chemical treatment.
In device as shown in Figure 1, make and contain 6% (quality) Al that has an appointment in the zinc, about 3% (quality) Mg, the Zn base hot dipping plating bath of about 0.05% (quality) Ti and about 0.01% (quality) B, and, (thickness: 0.8-1.0mm), the metal construction of described coating is included in [Al/Zn/Zn to prepare the hot dip process Zn steel sheet that contains Mg with coating
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], [Zn phase] and [Zn
2Mg phase].At this moment, the strip temperature that exports a side at injection air water cooler 5 is 335 ℃ or lower, so that coating is solidified in water cooler fully, at air- water cooling district 6a, 6b, air-cooling zone 14 and shrend district 7, cooling conditions and band gait of march remain unchanged substantially.Strip temperature at shrend district 7 inlet sides is 100 ℃ or lower, and steel band is at about 70 ℃ or lower by the skin-pass rolling milling train.The hot dip process Zn steel-sheet that contains Mg that is obtained becomes face gloss excellence, does not observe the phenomenon that causes that gloss descends.
With aforementioned essentially identical condition under by 1.6mm or thicker steel band.Although the strip temperature at shrend district 7 inlet sides rises to about 120-150 ℃,, operation itself is no problem, and, prepared the hot dip process Zn steel sheet that contains Mg of surface luster with same excellence.But after 2 or 3 days, slight decline has taken place in described steel-sheet surface luster, 82 when observing some brightness L value and finishing from just making drop to two days later about 75.Afterwards, improved air-water cooling district 6a, the cooling power of 6b is so that be brought down below 105 ℃ with the strip temperature of shrend district 7 inlet sides.As a result, do not observe surface luster decline phenomenon again.
In addition, when carrying out chromate treating, whether the strip temperature that shrend district 7 inlet sides are depended in surface luster decline appears once more.Hence one can see that: when the mode of the mode of implementing chromate treating when not carrying out chromate treating is identical, surface deterioration can occur equally.
Based on the experience that obtains in the aforementioned embodiment, by testing the degree that coating surface gloss descends of having examined or check under various conditions.Laboratory method (Lab mehtod) the L value that adopts spectrophotometer to record is evaluated surface luster as brightness (L) with this brightness value.
At first, down during preparation hot dip process Zn-Al-Mg steel sheet, under following " cooling conditions ", carry out air-water cooling (spraying) and shrend (water flow jet), make the temperature of band when coating solidifies fully reduce to about 30 ℃ in following " plating condition ".When just having finished and the L value after the test of fixed temperature and humidity degree by measuring plating, evaluation is by the surface luster decline degree of the sample that intercepts on the plating steel sheet that obtains, wherein, in the test of fixed temperature and humidity degree, with the sample after the plating just in controlled thermohygrostat (thermohygrostat), 60 ℃ of temperature kept 20 hours under the condition of relative humidity 90%.
The plating condition
The hot rolled strip that handled steel band: 2.0mm is thick
Plating bath is formed: Al=9.0% (quality), Mg=2.3% (quality), surplus=Zn
Bath temperature: 430 ℃
Coating weight: 90g/m
2
Band gait of march: 80m/min
Cooling conditions
(1) air-water cooling
Nozzle: two-fluid spray nozzle
Fluid: water (pressure=12.5kPa)+air (pressure=4.0kPa)
Spray water flow: as shown in table 1
Spray air flow: as shown in table 1
Fog particles mean radius: about 50 μ m
Strip temperature during the spraying beginning: as shown in table 1
Strip temperature when spraying finishes: as shown in table 1
(2) shrend
Aqueous stream injectors: 7 row's shower nozzles, 10 flat burners are drawn together in every package, at each nozzle interval 150mm of strip width direction
Fluid: water (pressure=2.5kgf/cm
2)
Discharge: as shown in table 1
Strip temperature when water flow jet begins: as shown in table 1
Strip temperature when water flow jet finishes: as shown in table 1
Table 1 shows the plating steel sheet that obtains down at aforementioned condition, different strip temperatures (strip temperature of shrend inlet region one side) when water flow jet begins when plating just finishes and through the L value measuring result after the fixed temperature and humidity degree test in 20 hours.Carry out microscopic examination by cross section, detect the metal construction of coating each plating steel-sheet coating.All be included in [Al/Zn/Zn in the metal construction of each steel sheet coating
2Mg ternary eutectic structure] matrix in [nascent Al crystalline phase], also comprise [Zn phase] and [Zn sometimes
2The Mg phase] (after this be called " Zn
2Mg system " metal construction).
Table 1
Plating bath is formed: Al=9.0% (quality), Mg=2.3% (quality), surplus=Zn
| Numbering | Cooling conditions | Surface luster | The embodiment type | |||||||
| Air-water cooling | Shrend | The L value behind the plating just | L value after the constant temperature stationary temperature test in 20 hours | |||||||
| Spray water flow m 3/h | Spray air flow m 3/min | Strip temperature when beginning to spray ℃ | Strip temperature when stopping to spray ℃ | Discharge m 3/h | Strip temperature when current begin to spray ℃ | Strip temperature when water flow jet stops | ||||
| A-1 | ||||||||||
| 10 | 1000 | 198 | 131 | 150 | 92 | 30 | 82 | 82 | The | |
| A-2 | ||||||||||
| 10 | 1000 | 280 | 207 | 150 | 101 | 30 | 82 | 81 | The present invention | |
| A-3 | 8 | 600 | 280 | 223 | 150 | 112 | 30 | 82 | 74 | |
| A-4 | ||||||||||
| 4 | 600 | 280 | 245 | 150 | 132 | 31 | 81 | 70 | Reference examples | |
Can be found out by table 1 result: when the strip temperature of shrend inlet side was higher than 105 ℃, along with temperature raises, the downtrending of brightness L value was stronger.On the contrary, when described temperature was lower than 105 ℃, the brightness after the plating just was along with the prolongation of time remains unchanged, and confirmed to have obtained that gloss keeps excellent performance contains Mg hot dip process Zn steel sheet.
Under the following conditions, adopt the coating identical to solidify the postcooling condition, prepare and contain Mg hot dip process Zn steel sheet, and the decline situation of its surface luster is detected with embodiment 2.The results are shown in the table 2.
The plating condition
The hot rolled strip that handled steel band: 3.2mm is thick
Plating bath is formed: Al=6.3% (quality), Mg=3.2% (quality), Ti=0.008% (quality), B=0.002% (quality), surplus=Zn
Bath temperature: 390 ℃
Coating weight: 120g/m
2
The band gait of march: its changing conditions is as shown in table 2
Cooling conditions
(1) gas cooling (only using the cooling of air spray water cooler)
Nozzle: tabular nozzle, its slit width 5mm
Gas: air (pressure=4kPa)
Air flow quantity: as shown in table 2
Strip temperature when air cooling begins: as shown in table 2
Strip temperature when air cooling finishes: as shown in table 2
(2) shrend
Aqueous stream injectors: 7 row's shower nozzles, 10 flat burners are drawn together in every package, at each nozzle interval 150mm of strip width direction
Fluid: water (pressure=2.2kgf/cm
2)
Discharge: as shown in table 2
Strip temperature when water flow jet begins: as shown in table 2
Strip temperature when water flow jet finishes: as shown in table 2
Table 2
Plating bath is formed: Al=6.3% (quality), Mg=3.2% (quality), Ti=0.008% (quality), B=0.002% (quality), surplus=Zn
| Numbering | Band gait of march m/min | Cooling conditions | Surface luster | The embodiment type | ||||||
| Air cooling | Shrend | The L value behind the plating just | L value after the fixed temperature and humidity degree test in 20 hours | |||||||
| Air flow quantity m 3/min | Strip temperature when beginning to cool down ℃ | Cooling strip temperature ℃ at the end | Discharge m 3/h | Strip temperature when current begin to spray ℃ | Strip temperature when water flow jet stops ℃ | |||||
| B-1 | 23 | 0 | - | - | 120 | 82 | 30 | 81 | 81 | The present invention |
| B-2 | 31 | 2500 | 167 | 126 | 120 | 82 | 30 | 81 | 81 | The present invention |
| B-3 | 40 | 2500 | 185 | 140 | 120 | 102 | 30 | 81 | 80 | The present invention |
| B-4 | 40 | 1200 | 185 | 158 | 120 | 118 | 30 | 81 | 73 | Reference examples |
| B-5 | 56 | 2500 | 212 | 164 | 120 | 131 | 31 | 81 | 71 | Reference examples |
Can be found out by table 2 result: the same with embodiment 2, in the present embodiment, when the strip temperature of shrend inlet side was higher than 105 ℃, along with temperature raises, the downtrending of brightness L value was stronger.But, when described temperature is lower than 105 ℃, the brightness after the plating just even after through 20 hours fixed temperature and humidity degree test, also remain unchanged.Carry out microscopic examination by cross section, detected the metal construction of coating each plating steel-sheet coating.All obtained a kind of " Zn in each steel sheet bar none
2Mg system " metal construction.
Under the following conditions, the coating surface after the shrend of the sample that is numbered B-2 and B-5 among the embodiment 3 has been carried out chemical treatment.Adopt the method among the embodiment 2, measured described sample chemical treatment just after and the brightness after testing through 20 hours fixed temperature and humidity degree.The results are shown in the table 3.
Chemical treatment conditions A
Coating process: spraying and squeezing roller method
Treatment soln: Zinchrome 3387N, Nihon Parkerizing Co., the Ltd. (total concn of chromium in the solution: 10g/L) of producing
Chromiumcoating weight: 10mg/m
2
Chemical treatment conditions B
Coating process: rolling method
Treatment soln: the Zinchrome 3387N (total concn of chromium in the solution: 20g/L) of adding the Zirconium tetrafluoride of 1g/L
Chromiumcoating weight: 40mg/m
2
Chemical treatment conditions C
Coating process: rolling method
Treatment soln: mainly contain the trimagnesium phosphate of 50g/L, the potassium fluotitanate of 10g/L and the organic acid aqueous solution of 3g/L
Metal parts coating wt: 50mg/m
2
Chemical treatment conditions D
Coating adopts following two step method to form
Bottom
Coating process: spray and squeezing roller method
Treatment soln: the Zinchrome 3387N (total concn of chromium in the solution: 10g/L)
Chromiumcoating weight: 10mg/m
2
Top layer
Coating process: rolling method
Organic coating: urethane resin (thickness: 1.5 μ m)
Table 3
| Coating after the chemical treatment | Chemical treatment conditions | Surface luster | The embodiment type | |
| The L value after the chemical treatment just | L value after the fixed temperature and humidity degree test in 20 hours | |||
| No.B-2 | A | 81 | 81 | The present invention |
| No.B-4 | A | 81 | 72 | Reference examples |
| No.B-3 | B | 81 | 80 | The present invention |
| No.B-5 | B | 81 | 70 | Reference examples |
| No.B-3 | C | 81 | 81 | The present invention |
| No.B-4 | C | 81 | 73 | Reference examples |
| No.B-2 | D | 81 | 81 | The present invention |
| No.B-5 | D | 81 | 72 | Reference examples |
Can find out by table 3 result: when the strip temperature of shrend inlet side is 105 ℃ or when higher, no matter whether carry out chemical treatment, along with the prolongation of time, brightness L all descends.On the contrary, when described temperature was lower than 105 ℃, the brightness after the plating just remained unchanged.
Under following plating condition and cooling conditions, carry out plating, wherein, in plating bath, added one or more easy oxidation elements.Each coating surface glossy decline situation is detected.The results are shown in the table 4.
The plating condition
The hot rolled strip that handled steel band: 1.6mm is thick
Plating bath is formed: as shown in table 4
Bath temperature: 450 ℃
Coating weight: 190g/m
2
Band gait of march: 60-120m/min
Cooling conditions
(1) air-water cooling
Nozzle: two-fluid spray nozzle
Fluid: water (pressure=1.0-3.5kgf/cm
2)+air (pressure=2.5-5.0kgf/cm
2)
Spray water flow: 0-8m
3/ h
Spray air flow: 0-600m
3/ h
Fog particles mean radius: 10-30 μ m
(2) gas cooling
Nozzle: tabular nozzle, its slit width 5mm
Gas: air (pressure=4kPa)
Air flow quantity: 0-3500m
3/ min
(3) shrend
Aqueous stream injectors: 7 row's shower nozzles, 10 flat burners are drawn together in every package, at each nozzle interval 150mm of strip width direction
Fluid: water (pressure=3.0kgf/cm
2)
Discharge: 180m
3/ h
Strip temperature when water flow jet begins: as shown in table 4
Table 4
| Numbering | Plating bath is formed (% (quality), surplus Zn) | The strip temperature of shrend district inlet side ℃ | Chemical treatment | Surface luster | The embodiment type | ||||||
| Al | Mg | Ti | B | Easy oxidation element | The L value after plating or the chemical treatment just | L value after the fixed temperature and humidity degree test in 20 hours | |||||
| Type | Content | ||||||||||
| C-1 | 13.8 | 2.2 | 0.046 | 0.020 | Y | 0.030 | 198 | Do not have | 81 | 80 | The present invention |
| C-2 | 8.2 | 2.9 | 0.012 | 0.005 | Y | 0.009 | 96 | Do not have | 82 | 82 | The present invention |
| C-3 | 9.4 | 3.3 | 0.009 | 0.010 | La Ce | 0.007 0.010 | 155 | Do not have | 82 | 81 | The present invention |
| C-4 | 4.5 | 1.3 | 0.037 | 0.038 | Zr | 0.028 | 237 | Do not have | 81 | 80 | The present invention |
| C-5 | 6.1 | 3.3 | 0.024 | 0.009 | Zr | 0.003 | 131 | Do not have | 82 | 81 | The present invention |
| C-6 | 10.3 | 3.7 | 0.005 | 0.006 | Zr | 0.029 | 103 | Do not have | 82 | 82 | The present invention |
| C-7 | 7.8 | 3.2 | 0.011 | 0.002 | Si | 0.041 | 138 | Do not have | 82 | 82 | The present invention |
| C-8 | 6.3 | 3.0 | 0.050 | 0.003 | Si | 0.023 | 100 | Do not have | 82 | 82 | The present invention |
| C-9 | 5.2 | 2.6 | 0.008 | 0.004 | Si | 0.004 | 83 | Do not have | 82 | 82 | The present invention |
| C-10 | 5.6 | 2.5 | 0.006 | 0.001 | Zr | 0.001 | 146 | Do not have | 81 | 72 | Reference examples |
| C-11 | 11.5 | 2.0 | 0.073 | 0.015 | La | 0.001 | 174 | Do not have | 81 | 66 | Reference examples |
| C-12 | 6.1 | 3.3 | 0.024 | 0.009 | Zr | 0.003 | 131 | (Type B) arranged | 82 | 81 | The present invention |
| C-13 | 13.8 | 2.2 | 0.046 | 0.020 | Y | 0.030 | 198 | (C type) arranged | 81 | 80 | The present invention |
| C-14 | 6.3 | 3.0 | 0.050 | 0.003 | Si | 0.023 | 100 | (C type) arranged | 82 | 82 | The present invention |
| C-15 | 5.6 | 2.5 | 0.006 | 0.001 | Zr | 0.001 | 146 | (Type B) arranged | 81 | 73 | Reference examples |
| C-16 | 4.4 | 1.8 | - | - | Zr | 0.021 | 109 | Do not have | 82 | 82 | The present invention |
| C-17 | 6.3 | 2.9 | - | - | Y Si | 0.005 0.012 | 145 | Do not have | 82 | 82 | The present invention |
| C-18 | 5.7 | 3.2 | - | - | Si | 0.028 | 167 | (Type B) arranged | 81 | 81 | The present invention |
As shown in table 4, except at least a easy oxidation element of interpolation in plating bath, under all identical condition of other condition, prepare and the similar plating steel sheet of plating steel sheet of in embodiment 2 and 3, reducing to about 71 through brightness value L after the test of 20 hours constant temperature and constant humidity degree, but at this moment, by adding the decline that easy oxidation element has suppressed brightness L value.When to add Si be numbered the containing Mg hot dip process Zn steel-sheet coating surface layer segment and adopt ESCA to carry out elementary composition analysiss of C-7 the time, find: nearly all Si all is enriched in the outermost surface part of coating, and does not almost have the Si existence in coating inside.The esca analysis result of the plating steel sheet (numbering C-10) that brightness L value in the test of 20 hours constant temperature and constant humidity degree is descended does not have the result of the plating steel sheet (numbering C-5) of decline to compare with brightness L value, and discovery: Mg is tending towards being present in a large number the outmost surface layer segment of previous plating steel sheet coating.
Table 4 comprises shrend coating is carried out chemically treated example (numbering C-12 to C-15).The decline degree of brightness L value is different according to whether adding easy oxidation element, and can see: when adding easy oxidation element, the decline of brightness L value has obtained inhibition.
As previously mentioned, the present invention can effectively prevent and contain the exclusive surface luster decline phenomenon of Mg hot dip process Zn steel sheet.Therefore, can provide the good and gloss of erosion resistance keep performance also excellent contain Mg hot dip process Zn steel sheet.
Claims (9)
1. one kind prepares the hot dip process Zn steel-sheet method that gloss keeps excellent performance, and it comprises:
Steel band carries out continuous impregnating and taking-up in containing the Zn base hot dipping plating bath of Al:4.0-15 quality % and Mg:1.0-4.0 quality %, form the step of coating thus on steel band, and,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is lower than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface glossy deterioration.
2. one kind prepares the hot dip process Zn steel-sheet method that gloss keeps excellent performance, and it comprises:
Steel band carries out continuous impregnating and taking-up in Zn base hot dipping plating bath, on steel band, form the step of coating thus, described Zn base hot dipping plating bath contains, in quality %: Al:4.0-15%, Mg:1.0-4.0%, Ti:0.001-0.1%, B:0.001-0.045% the rest is Zn and unavoidable impurities; And,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is lower than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface glossy deterioration.
3. one kind prepares the hot dip process Zn steel-sheet method that gloss keeps excellent performance, and it comprises:
Steel band is containing Al:4.0-15 quality % and Mg:1.0-4.0 quality %, and carry out continuous impregnating and taking-up in the Zn base hot dipping plating bath of at least a easy oxidation element that is selected from rare earth element, Y, Zr and Si that adds 0.002-0.05 quality %, on steel band, form the step of coating thus, and
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is not less than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface glossy deterioration.
4. one kind prepares the hot dip process Zn steel-sheet method that gloss keeps excellent performance, and it comprises:
Steel band carries out continuous impregnating and taking-up in Zn base hot dipping plating bath, on steel band, form the step of coating thus, described Zn base hot dipping plating bath comprises, in quality %: Al:4.0-15%, Mg:1.0-4.0%, Ti:0.001-0.1%, B:0.001-0.045%, at least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05% the rest is Zn and unavoidable impurities; And,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is not less than 105 ℃ but be not higher than 300 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating gloss deterioration.
5. the hot dip process Zn steel-sheet method that keeps excellent performance according to any one the preparation gloss among the claim 1-4, it further comprises a step that makes the steel band that passes through the shrend district by the chemical treatment district.
6. one kind forms the hot dip process Zn steel sheet that gloss that coating obtains keeps excellent performance thereon thus by adopting a kind of hot dipping plating bath that steel band is carried out the hot dipping plating, and described plating bath comprises, in quality %:
Al：4.0-15％，
Mg：1.0-4.0％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities,
Described steel sheet obtains by the method that may further comprise the steps:
Steel band carries out continuous impregnating and taking-up in described hot dipping plating bath, form the step of coating thus on steel band; And,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is not less than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppresses the step of coating surface glossy deterioration.
7. one kind forms the hot dip process Zn steel sheet that gloss that coating obtains keeps excellent performance thereon thus by adopting a kind of hot dipping plating bath that steel band is carried out the hot dipping plating, and described plating bath comprises, in quality %:
Al：4.0-15％，
Mg：1.0-4.0％，
Ti：0.001-0.1％，
B：0.001-0.045％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities,
Described steel sheet obtains by the method that may further comprise the steps:
Steel band carries out continuous impregnating and taking-up in described hot dipping plating bath, form the step of coating thus on steel band; And,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein be not less than 105 ℃ but be not higher than 300 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppress the step of coating surface gloss deterioration.
8. one kind by adopting a kind of hot dipping plating bath that steel band is carried out the hot dipping plating, form coating thus thereon and coating is carried out chemical treatment, and the gloss that obtains keeps the hot dip process Zn steel sheet of excellent performance, and described plating bath comprises, in quality %:
Al：4.0-15％，
Mg：1.0-4.0％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities,
Described steel sheet obtains by the method that may further comprise the steps:
Steel band carries out continuous impregnating and taking-up in described hot dipping plating bath, form the step of coating thus on steel band,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein is not less than 105 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppress coating surface glossy deterioration step and
Make the step of steel band by the chemical treatment district by the shrend district.
9. one kind by adopting a kind of hot dipping plating bath that steel band is carried out the hot dipping plating, form coating thus thereon and coating is carried out chemical treatment, and the gloss that obtains keeps the hot dip process Zn steel sheet of excellent performance, and described plating bath comprises, in quality %:
Al：4.0-15％，
Mg：1.0-4.0％，
Ti：0.001-0.1％，
B：0.001-0.045％，
At least a easy oxidation element that is selected from rare earth element, Y, Zr and Si: 0.002-0.05%, and
The rest is Zn and unavoidable impurities,
Described steel sheet obtains by the method that may further comprise the steps:
Steel band carries out continuous impregnating and taking-up in described hot dipping plating bath, form the step of coating thus on steel band,
Afterwards, make steel band continuously by a shrend district, cool off steel band the coating surface that solidifies is fully contacted with current in this shrend district, wherein be not less than 105 ℃ but be not higher than 300 ℃ by the control steel band in the temperature of shrend district inlet side this moment, suppress coating surface gloss deterioration step and
Make the step of steel band by the chemical treatment district by the shrend district.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2002/007485 WO2004009863A1 (en) | 2002-07-24 | 2002-07-24 | Zinc-base hot dip galvanized steel sheet excellent in retention of gloss |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1503853A CN1503853A (en) | 2004-06-09 |
| CN1276990C true CN1276990C (en) | 2006-09-27 |
Family
ID=30490773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN02808369.5A Expired - Lifetime CN1276990C (en) | 2002-07-24 | 2002-07-24 | Zinc-base hot dip galvanized steel sheet excellent in retention of gloss |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP1524326B1 (en) |
| CN (1) | CN1276990C (en) |
| AT (1) | ATE484605T1 (en) |
| AU (1) | AU2002323927B2 (en) |
| CA (1) | CA2444460C (en) |
| DE (1) | DE60238001D1 (en) |
| ES (1) | ES2350921T3 (en) |
| NZ (1) | NZ528816A (en) |
| WO (1) | WO2004009863A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105492646A (en) * | 2013-07-12 | 2016-04-13 | 奥钢联钢铁公司 | Method for improving adherence |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100666693B1 (en) | 2004-11-23 | 2007-01-11 | 삼성전자주식회사 | Monolithic duplexer |
| CN102330043B (en) * | 2011-08-03 | 2013-03-13 | 马鞍山鼎泰稀土新材料股份有限公司 | Steel wire hot dipping rare earth zinc alloy and hot dipping method |
| CN103361588B (en) * | 2012-03-30 | 2016-04-06 | 鞍钢股份有限公司 | Production method of low-aluminum low-magnesium zinc-aluminum-magnesium coated steel plate and coated steel plate thereof |
| JP5097305B1 (en) * | 2012-04-25 | 2012-12-12 | 日新製鋼株式会社 | Black plated steel plate |
| WO2013160566A1 (en) | 2012-04-25 | 2013-10-31 | Arcelormittal Investigacion Y Desarrollo, S.L. | Method for producing a metal sheet having oiled zn-al-mg coatings, and corresponding metal sheet |
| WO2014059475A1 (en) | 2012-10-17 | 2014-04-24 | Bluescope Steel Limited | Method of producing metal-coated steel strip |
| TWI653362B (en) * | 2012-10-17 | 2019-03-11 | 澳大利亞商布魯史寇普鋼鐵有限公司 | Method of producing metal-coated steel strip |
| KR20150070230A (en) * | 2012-10-18 | 2015-06-24 | 블루스코프 스틸 리미티드 | Method of producing metal coated steel strip |
| ES2676045T5 (en) | 2013-12-20 | 2022-04-29 | Arcelormittal | Production process of a ZnAlMg coated sheet with optimized creepage and corresponding sheet |
| KR101767788B1 (en) * | 2015-12-24 | 2017-08-14 | 주식회사 포스코 | Plating steel material having excellent friction resistance and white rust resistance and method for manufacturing same |
| WO2017170967A1 (en) * | 2016-03-31 | 2017-10-05 | 日新製鋼株式会社 | Method for producing molten aluminum-plated steel wire |
| KR102031466B1 (en) | 2017-12-26 | 2019-10-11 | 주식회사 포스코 | Zinc alloy coated steel having excellent surface property and corrosion resistance, and method for manufacturing the same |
| KR102425278B1 (en) * | 2018-05-16 | 2022-07-27 | 닛폰세이테츠 가부시키가이샤 | plated steel |
| CN108977695B (en) * | 2018-09-30 | 2020-12-01 | 济南大学 | Titanium and antimony-containing hot-dip galvanized aluminum magnesium alloy and preparation method thereof |
| TWI691615B (en) * | 2019-04-10 | 2020-04-21 | 中國鋼鐵股份有限公司 | Zinc-coated steel sheet and method of forming the same |
| CN113025937B (en) * | 2021-02-07 | 2023-03-17 | 首钢集团有限公司 | Hot-dip galvanized steel plate and preparation method thereof |
| CN112941417A (en) * | 2021-03-03 | 2021-06-11 | 靖江新舟合金材料有限公司 | Alloy coated steel plate and production method thereof |
| CN113512691B (en) * | 2021-03-11 | 2023-05-09 | 首钢集团有限公司 | Zinc-aluminum-magnesium coated steel and preparation method thereof |
| CN113604765B (en) * | 2021-10-09 | 2022-01-04 | 天津市弘仁金属材料有限公司 | Steel strip hot dipping method |
| CN115261703A (en) * | 2022-06-08 | 2022-11-01 | 日照宝华新材料有限公司 | Manufacturing method of high-corrosion-resistance steel plate for photovoltaic support |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2754126B2 (en) * | 1992-11-26 | 1998-05-20 | 新日本製鐵株式会社 | Hot-dip Zn-Al plated steel sheet with excellent appearance, blackening resistance over time and corrosion resistance |
| JP3148542B2 (en) * | 1995-01-11 | 2001-03-19 | 新日本製鐵株式会社 | Hot-dip galvanized steel sheet with excellent glare resistance |
| JPH10265926A (en) * | 1997-03-25 | 1998-10-06 | Nisshin Steel Co Ltd | Production of hot dip zn-al-mg coated steel strip excellent in corrosion resistance and appearance |
| JP3888784B2 (en) * | 1998-09-21 | 2007-03-07 | 日新製鋼株式会社 | Edge wrinkle prevention method for hot-dip Zn-based plated steel sheet |
| JP2001295015A (en) * | 2000-02-09 | 2001-10-26 | Nisshin Steel Co Ltd | HOT DIP HIGH Al-CONTAINING Zn-Al-Mg BASE METAL COATED STEEL SHEET |
| JP2002080952A (en) * | 2000-06-29 | 2002-03-22 | Nisshin Steel Co Ltd | Home building material excellent in corrosion resistance, and home building member |
| JP2002146504A (en) * | 2000-08-22 | 2002-05-22 | Nisshin Steel Co Ltd | Material for electrical equipment and member for electrical equipment having excellent corrosion resistance and whisker resistance |
| JP2002187234A (en) * | 2000-12-21 | 2002-07-02 | Nisshin Steel Co Ltd | Non-chromium coated steel plate having excellent corrosion resistance |
| JP4064634B2 (en) * | 2001-02-02 | 2008-03-19 | 日新製鋼株式会社 | Hot-dip Zn-based plated steel sheet with good gloss retention and method for producing the same |
-
2002
- 2002-07-24 CA CA002444460A patent/CA2444460C/en not_active Expired - Lifetime
- 2002-07-24 CN CN02808369.5A patent/CN1276990C/en not_active Expired - Lifetime
- 2002-07-24 DE DE60238001T patent/DE60238001D1/en not_active Expired - Lifetime
- 2002-07-24 ES ES02755638T patent/ES2350921T3/en not_active Expired - Lifetime
- 2002-07-24 NZ NZ528816A patent/NZ528816A/en not_active IP Right Cessation
- 2002-07-24 EP EP02755638A patent/EP1524326B1/en not_active Expired - Lifetime
- 2002-07-24 AT AT02755638T patent/ATE484605T1/en not_active IP Right Cessation
- 2002-07-24 AU AU2002323927A patent/AU2002323927B2/en not_active Expired
- 2002-07-24 WO PCT/JP2002/007485 patent/WO2004009863A1/en active IP Right Grant
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105492646A (en) * | 2013-07-12 | 2016-04-13 | 奥钢联钢铁公司 | Method for improving adherence |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2444460C (en) | 2008-01-22 |
| CA2444460A1 (en) | 2004-01-24 |
| ATE484605T1 (en) | 2010-10-15 |
| AU2002323927B2 (en) | 2005-08-25 |
| WO2004009863A1 (en) | 2004-01-29 |
| DE60238001D1 (en) | 2010-11-25 |
| CN1503853A (en) | 2004-06-09 |
| AU2002323927A1 (en) | 2004-02-09 |
| EP1524326A4 (en) | 2006-09-13 |
| EP1524326A1 (en) | 2005-04-20 |
| ES2350921T3 (en) | 2011-01-28 |
| EP1524326B1 (en) | 2010-10-13 |
| NZ528816A (en) | 2005-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1276990C (en) | Zinc-base hot dip galvanized steel sheet excellent in retention of gloss | |
| CN1265013C (en) | Steel sheet hot dip coated with Zn-Al-Mg having high Al content | |
| CN100338252C (en) | Zinc-plated steel sheet excellent in corrosion resistance after coating and clarity of coating thereon | |
| CN1639376A (en) | Surface treated steel plate and method for production thereof | |
| CN1070932C (en) | High-corrosion-resistant Zn-Mg series electro-plated steel plate and production method thereof | |
| CN1809650A (en) | Hot press-formed article and method for its manufacture | |
| CN1074054C (en) | Cold-rolled steel sheet and hot-dipped galvanized steel sheet excellent in uniform workability, and process for producing the sheets | |
| KR101819393B1 (en) | Hot dip zinc alloy plated steel material having excellent weldability and press formability and method for manufacturing same | |
| CN1024141C (en) | Steel sheets for porcelain enameling and method of producing same | |
| CN1145645A (en) | Hot-dip aluminized sheet, process for producing the sheet, and alloy layer control device | |
| CN1236093C (en) | Ferritic stainless steel sheet excellent in press formability and workability and method for production thereof | |
| CN1831171A (en) | Aluminum alloy heat sinks of heat exchanger and heat exchanger | |
| KR101647229B1 (en) | HOT DIP Zn ALLOY PLATED STEEL WIRE HAVING EXCELLENT ANTI-CORROSION AND METHOD FOR MANUFACTURING THE STEEL WIRE USING THE SAME | |
| CN1207424C (en) | Galvannealed sheet steel and method for production thereof | |
| KR20070112874A (en) | Galvannealed sheet steel and process for production thereof | |
| CN1131339C (en) | Zinc coated steel plate and mfg. method thereof | |
| KR101568474B1 (en) | HOT DIP Zn ALLOY PLATED STEEL SHEET HAVING EXCELLENT BLACKENING-RESISTANCE AND SURFACE APPEARANCE AND METHOD FOR MANUFACTURING THE SAME | |
| CN114761603B (en) | Aluminum-based alloy-plated steel sheet excellent in workability and corrosion resistance, and method for producing same | |
| TWI780824B (en) | Manufacturing method of hot-dip galvanized steel sheet, steel sheet and vehicle component | |
| CN1784504A (en) | Non-oriented silicon steel sheet having excellent core loss and its production method | |
| KR101560934B1 (en) | GI Steel Plate Having Excellent Surface Smoothness and Method for preparing the Same, and Solution of Zn melts for the GI Steel Plate | |
| CN1701130A (en) | Steel sheet plated by hot dipping with alloyed zinc with excellent adhesion and process for producing the same | |
| JP7497339B2 (en) | Hot-dip galvanized steel sheet and its manufacturing method | |
| JP2727598B2 (en) | Alloyed hot-dip galvanized steel sheet excellent in workability and paintability and method for producing the same | |
| JP2560662B2 (en) | Equipment for producing hot-dip galvanized steel sheets with few surface defects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060927 |
|
| CX01 | Expiry of patent term |