EP1524326B1 - Feuerverzinktes galvanisiertes zinkbasis-stahlblech mit ausgezeichneter beibehaltung des glanzes - Google Patents

Feuerverzinktes galvanisiertes zinkbasis-stahlblech mit ausgezeichneter beibehaltung des glanzes Download PDF

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EP1524326B1
EP1524326B1 EP02755638A EP02755638A EP1524326B1 EP 1524326 B1 EP1524326 B1 EP 1524326B1 EP 02755638 A EP02755638 A EP 02755638A EP 02755638 A EP02755638 A EP 02755638A EP 1524326 B1 EP1524326 B1 EP 1524326B1
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Prior art keywords
plating layer
dip
water
plating
strip
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French (fr)
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EP1524326A4 (de
EP1524326A1 (de
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Atsushi Komatsu
Takao Tsujimura
Atsushi Steel & Tech. Dev. Lab. ANDOH
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Nippon Steel Nisshin Co Ltd
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Nisshin Steel Co Ltd
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    • 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

Definitions

  • This invention relates to a technology for preventing surface luster degradation that sometimes occurs during production of hot-dip Zn-Al-Mg plated steel sheet using a continuous hot-dip plating line.
  • JP.Hei-10-226865A , JP.Hei-10-306357A , USP No. 6,235,410 ( US6,235,410 B1 ) and USP. No. 6,379,820 ( US 6,379,820 B1 ) owned by the applicant of this application teach that a plated steel sheet having corrosion resistance and surface appearance sufficient to meet the requirements of an industrial product can be obtained manufacturing a hot dip Zn-base plated steel sheet using a hot-dip Zn-Al-Mg-system bath composed of Al: 4.0 - 10 %, Mg: 1.0 - 4.0 %, Ti: 0.002 - 0.1 %, B: 0.001 - 0.045 % and the balance of Zn and unavoidable impurities, and imparting to the plating layer a metallic structure including [primary crystal Al phase] and [Zn single phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure].
  • the inventors experienced that, depending on the production conditions, the surface luster of the plating layer deteriorated within two to three days. This surface luster degradation of the plating layer discolors the aesthetically pleasing plated surface just after plating to a somewhat blackish interference color with passage of time (as quickly as 2 - 3 days but sometimes taking 4 - 7 days).
  • This degradation of surface luster can be considered to be peculiar to plated steel sheets having relatively high Al and Mg content like the hot-dip Zn-Al-Mg plated steel sheets mentioned above.
  • the degree of oxidation of Mg concentrated in the outermost surface layer of the plating and the oxidized state of the surface layer Al are most likely complexly involved as causes of the degradation. No reports have been published to date regarding the mechanism of the surface luster degradation occurring in such a hot-dip Zn-Al-Mg plated steel sheet or regarding a method for inhibiting the degradation.
  • Prior art document WO 01/59171 A1 discloses a steel sheet hot dip coated with Zn-Al-Mg having a high A1 content, a hot dip coating layer having a chemical composition of wt-%: more than 10 % and 22 % or less Al, 1 to 5 % Mg and optionally in addition 0.002 to 0.1 % Ti, 0.001 to 0.045 % B, 0.005 to 0.5 % Si. Furthermore the hot dip coating layer has a metal structure composed of a base of a ternary eutectic structure of Al/Zn/Zn 2 Mg and primary crystal phases of A1 being included in the base.
  • Prior art document JP 2002 187234 A discloses a non-chromium coated steel plate having excellent corrosion resistance whereby the galvanized layer is composed of in wt%: 4-22 % Al, 1-4 % Mg, 0-0,1 % Ti, 0-0.045 % B and 0-0,5 % Si. According to table 1 Ti + B and/or Si may singly or in combination be added to the Zn-Al-Mg coating composition and in this way a steel plate with a corresponding plating layer thereon is formed.
  • An object of the present invention is therefore to provide means for inhibiting the degradation of surface luster that appears as a problem peculiar to hot-dip Zn-Al-Mg plated steel sheet.
  • the object of the invention is solved by a method as stated in claim 1 or 2.
  • the inventors carried out extensive experimentation and research directed to overcoming the foregoing problem.
  • that one way to prevent the surface luster degradation is to "control the contact temperature between the plating layer and the water stream" in the water cooling step after plating layer solidification, that, by extension, it is effective to suitably control the "strip temperature during contact with the water stream," and that it is also effective to stabilize the oxidation state of plating surface layer Al and Mg by incorporating a small amount of a suitable "readily oxidizing element" in the plating bath.
  • strip temperature during contact with the water stream is meant the strip temperature at the time cooling is conducted while forming a water film on the plating layer surface in the cooling step after completion of plating layer solidification. Specifically, it is the plating layer temperature when a water stream is passed onto the completely solidified plating layer and the plating layer is being cooled with a water film formed on the surface of the plating layer.
  • the strip temperature on the water quenching zone entry side depends strongly on the sheet thickness. When the strip thickness is great, controlling the strip temperature on the water quenching zone entry side to lower than 105°C may not be easy. It was found that in such a case, similar inhibition of surface luster degradation can be achieved without lowering the strip temperature on the water quenching zone entry side to lower than 105 °C (i.e., with the temperature at 105 °C or higher) by adding to the plating bath a small amount of an element that has a very powerful affinity for oxygen (that is a readily oxidizing element) and that has a stabilizing effect on Al oxides.
  • Such elements include, for example, the rare earth elements, Y, Zr and Si. In actual practice, it suffices to add about 0.002 - 0.05 mass % of the readily oxidizing element.
  • the present invention provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 4.0 - 15 mass % and Mg: 1.0 - 4.0 mass %, thereby forming a plating layer thereon, and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, degradation of the plating layer luster being inhibited at this time by controlling strip temperature on the water quenching zone entry side to lower than 105 °C.
  • the hot-dip Zn base bath is preferably composed of, in mass %, Al: 4.0 - 15 %, Mg: 1.0 - 4.0 %, Ti: 0.001 - 0.1 %, B: 0.001 - 0.045 % and the balance of Zn and unavoidable impurities.
  • the present invention further provides a method of producing a hot-dip Zn plated steel sheet excellent in luster-retaining property comprising a step of continuously immersing and withdrawing steel strip into/from a hot-dip Zn base bath containing Al: 4.0 - 15 mass % and Mg: 1.0 - 4.0 mass % and added with 0.002 - 0.05 mass % of at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si, thereby forming a plating layer thereon, and a step of thereafter continuously passing the steel strip through a water quenching zone that effects cooling while bringing the completely solidified plating layer surface into contact with a water stream, degradation of the plating layer surface luster being inhibited at this time by controlling strip temperature on the water quenching zone entry side to not lower than 105 °C and not higher than 300 °C.
  • the hot-dip Zn base bath is preferably composed of, in mass %, Al: 4.0 - 15 %, Mg: 1.0 - 4.0 %, Ti: 0.001 - 0.1 %, B: 0.001 - 0.045 %, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 - 0.05 %, and the balance of Zn and unavoidable impurities.
  • the methods of the present invention further provide a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass %, Al: 4.0 - 15% and Mg: 1.0 - 4.0%, optionally, Ti: 0.001- 0.1 % and B: 0.001 - 0.045 %, preferably, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 - 0.05 %, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon.
  • the plating layer has a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure].
  • FIG. 1 is a line diagram schematically illustrating a facility for producing Mg-containing hot-dip Zn plated steel sheet according to the present invention.
  • steel strip is used when explaining the hot-dip plating line and the term “steel sheet” is used when explaining the product.
  • steel strip and steel sheet have the same characteristics.
  • FIG. 1 schematically illustrates a facility used to produce a hot dip Zn-base plated steel sheet.
  • a steel strip 2 passed through a furnace 1 to be maintained at a prescribed temperature is continuously fed into a plating bath 3.
  • the steel strip Upon exiting the plating bath 3, the steel strip passes through a wiping nozzle 4 that regulates its coating weight and then through an air-jet cooler 5.
  • the plating layer is completely solidified during passage through the air-jet cooler 5.
  • the strip next passes through air-water cooling zones 6a, 6b and an air cooling zone 14, any of which may be operated alone or in combination with the others, or not be operated, and then through a water quenching zone 7.
  • Mg-containing hot-dip Zn plated steel sheet when producing a hot-dip Zn-Al-Mg plated steel sheet containing relatively large amounts of Al and Mg (hereinafter called "Mg-containing hot-dip Zn plated steel sheet"), appropriate control of the cooling rate up to complete plating layer solidification and of the solidification completion position is essential from the aspect of surface property.
  • the strip feeding speed must be strictly controlled and the strip temperature at the time of passage through the air-jet cooler 5 needs to be exactly controlled in accordance with the sheet thickness.
  • the strip temperature at the skin pass entry side needs to be adjusted to a prescribed level (e.g., not more than 70 °C) by cooling conducted at the air-water cooling zones 6 (and the air cooling zone 14) and/or the water quenching zone 7.
  • the cooling load at these cooling zones varies with the strip running speed and the sheet thickness.
  • water or a water solution is sprayed at the air-water cooling zones, air is jetted at the air-jet cooling zone, and, at the water quenching zone, a water stream adequate for momentarily forming a water film on the plating layer surface is supplied.
  • the latter mentioned water quenching zone can achieve a faster cooling rate owing to the contact of the water stream with the plating layer surface. Efficient cooling operation can therefore be conducted at the water quenching zone irrespective of variation in cooling load.
  • water or a water solution is sprayed together with an air stream at air-water cooling zone 6, not enough water is supplied to form a water film on the plating layer surface.
  • the cooling is therefore chiefly the result of latent heat extraction by evaporation. This is a different form of heat removal from that by contact with a water stream as in the water quenching zone and therefore differs in cooling rate.
  • the luster-retaining property of the plating surface differs depending on strip temperature on the water quenching zone entry side.
  • the temperature is 105 °C or higher, surface luster degradation readily occurs. While the reason for this is not certain, the inventors concluded that the causes involve such factors as that the reactivity of the plating layer surface is enhanced by the occurrence of a kind of boiling phenomenon when the strip temperature is 100 °C or higher upon entering the water quenching zone and that the behavior of Al under atmospheric pressure in the presence of water differs above and below about 110°C, i.e., Al 2 O 3 •H 2 O (or AlOOH) compound is stable above this temperature while Al 2 O 3 •3H 2 O (or Al(OH) 3 ) compound is stable below this temperature, so that the Al compound formed on the plating layer surface in the water quenching zone differs depending on the entry side steel strip temperature.
  • an Mg-containing hot-dip Zn plated steel sheet of the foregoing type having a metallic structure including [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] the outermost surface of the ternary eutectic crystal structure is changed into a readily oxidizing form by the aforesaid chemical reaction and this is believed to be why surface luster degradation that produces a change in brightness occurs within two or three days after plating.
  • the inventors discovered that, as demonstrated by the Examples set out later, the surface luster degradation of an Mg-containing hot-dip Zn plated steel sheet can be substantially prevented by regulating the temperature of the steel strip entering the water quenching zone to lower than 105 °C.
  • the cooling operation before entry into to the water quenching zone needs to be conducted not by supplying enough water to the completely solidified plating surface to form a water film that produces quenching, as is done in the water quenching zone, but by a mild cooling operation such as by air-water cooling (mist spraying) or air cooling (e.g. air-jet cooling).
  • These readily oxidizing elements have a property of concentrating at the outermost surface layer portion of the plating layer during the solidification process of the plating layer of the Mg-containing hot-dip Zn plated steel sheet, or even after solidification. These elements can therefore reach a relatively high concentration at the outermost surface layer portion even when added to the plating bath in only a small amount. This is thought to enable them to inhibit surface reactions in the water quenching zone which adversely affect the surface luster-maintaining property.
  • these readily oxidizing elements are added to the plating bath at less than 0.002 %, however, they do not manifest the inhibiting effect. They must therefore be added so as to make their content in the plating bath composition not less than 0.002 mass %.
  • amounts added in excess have poor solubility in the plating bath and even if dissolved only saturate the surface luster degradation inhibiting effect because the elements simply precipitate in excess near the grain boundaries in the plating surface layer portion.
  • the amount added is therefore such that the content in the plating bath becomes not more than 0.10 mass %, in some cases not more than 0.08 mass %, preferably 0.05 mass %, more preferably 0.03 mass %.
  • the surface luster degradation preventing effect produced by addition of one or more readily oxidizing elements is acts most effectively when, as explained in the foregoing, the strip temperature on the water quenching zone entry side is 105 °C or higher. Even when the strip temperature on the water quenching zone entry side is lower than 105 °C, however, one or more readily oxidizing elements can be added to the plating bath to stay on the safe side.
  • the strip temperature on the water quenching zone entry side is 105 °C or higher, it should preferably be controlled to not higher than 300 °C because at higher than 300 °C the cooling load in the water quenching zone becomes so large as to prevent sufficient lowering of the temperature on the skin pass entry side.
  • the strip temperature on the water quenching zone entry side can be relatively easily made lower than 105 °C so as to ensure good luster-retaining property.
  • the strip thickness is 1.6 mm or greater, it is, from the aspect of actual operation, better to ensure luster-retaining property by addition of a readily oxidizing element than by forcibly cooling the steel strip so as to have a temperature on the water quenching zone entry side of lower than 105 °C.
  • the present invention offers a breakthrough in prevention of surface luster degradation in Mg-containing hot-dip Zn plated steel sheets and is therefore used with Mg-containing hot-dip Zn plated steel sheets that experience surface luster degradation.
  • Such an Mg-containing hot-dip Zn plated steel sheet is typically a hot-dip Zn-Al-Mg plated steel sheet exhibiting excellent corrosion resistance and surface appearance obtained by using a hot-dip Zn base bath composed of Al: 4.0 - 15% and Mg: 1.0 - 4.0 % as basic components, plus Ti: 0.001 - 0.1 % and B: 0.001 - 0.045 %, and the balance of Zn and unavoidable impurities, and imparting the plating layer with a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [A
  • the metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] is preferably one in which the total amount of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] + [primary crystal Al phase] accounts for not less than 80 vol. % of the metallic structure, more preferably for not less than 95 vol. % thereof.
  • the balance can consist of [Zn phase] and [Zn 2 Mg phase], plus, in some cases, small amounts of [Zn/Zn 2 Mg binary eutectic crystal] and/or [Al/Zn 2 Mg binary eutectic crystal].
  • Si small amounts of [Si phase], [Mg 2 Si phase], [Al/Mg 2 Si binary eutectic crystal] and the like may also be present.
  • the present invention thus provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass %, Al: 4.0 - 15%, Mg: 1.0 - 4.0%, Ti: 0.001 - 0.1% B: 0.001 - 0.045 %, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 - 0.05 %, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon.
  • the plating layer has a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure] or [primary crystal Al phase], [Zn phase] and/or [Zn 2 Mg phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure]. It has a structural characteristic in the point that the one or more readily oxidizing elements are concentrated in the outermost surface layer portion of the plating layer.
  • Al present in the plating layer improves the corrosion resistance of the plated steel sheet and operates to inhibit dross generation during plated steel sheet production.
  • the Al content is preferably made not less than 4.0 mass %.
  • the Al content exceeds 15 mass %, pronounced growth of an Fe-Al alloy layer at the interface between the plating layer and the base steel sheet degrades plating adherence.
  • the Al content is preferably 4.5 - 13.0 mass %, more preferably 5.0 - 10.0 mass %, and most preferably 5.0 - 7.0 mass %.
  • Mg present in the plating layer generates a uniform corrosion product on the plating layer surface and, by this, operates to markedly enhance the corrosion resistance of the plated steel sheet.
  • the Mg content is therefore defined as 1.0 - 4.0 mass%.
  • the Mg content is preferably 1.5 - 4.0 mass %, more preferably 2.0 - 3.5 mass %, most preferably 2.5 - 3.5 mass %.
  • the aforesaid surface luster degradation problem also occurs when chemical treatment is applied at the final stage of the Mg-containing hot-dip Zn plated steel sheet production line such as by using the roll coater 11 shown at the bottom of FIG. 1 , irrespective of whether a chromate coating, a chromate-free conversion coating, an organic resin film containing chromium acid, or a silicate film containing chromium acid or other such film is formed.
  • the phenomenon of a decline in brightness and surface luster degradation after a few days also occurs (or does not occur) in a plated product having a film produced by chemical treatment, just as it does (or does not) when chemical treatment is not conducted. It was found that this problem can be similarly overcome by controlling the aforesaid strip temperature on the water quenching zone entry side and adding at least one readily oxidizing element to the plating bath in accordance with the present invention.
  • the surface luster degradation of the chemically treated Mg-containing hot-dip Zn plated steel sheet can be inhibited by, as in the foregoing method of producing an Mg-containing hot-dip Zn plated steel sheet, controlling the strip temperature on the water quenching zone entry side to lower than 105 °C or adding 0.002 - 0.05 mass % of a readily oxidizing element to the plating bath.
  • the present invention thus provides a hot-dip Zn plated steel sheet excellent in luster-retaining property obtained by hot-dip plating a steel strip using a hot-dip plating bath comprising, in mass %, Al: 4.0 - 15%, Mg: 1.0 - 4.0%, Ti: 0.001 - 0.1% B: 0.001 - 0.045 %, at least one readily oxidizing element selected from among rare earth elements, Y, Zr and Si: 0.002 - 0.05 %, and the balance of Zn and unavoidable impurities, thereby forming a plating layer thereon, and chemically treating the plating layer.
  • a hot-dip Zn base bath containing about 6 mass % of Al, about 3 mass % of Mg, about 0.05 mass % of Ti and about 0.01 mass % of B in zinc was constituted in a facility like that shown in FIG. 1 and an Mg-containing hot-dip Zn plated steel sheets (thickness: 0.8 - 1.0 mm) were manufactured to have a plating layer with a metallic structure including of [primary crystal Al phase], [Zn phase] and [Zn2Mg phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure].
  • the strip temperature on the outlet side of the air-jet cooler 5 was made 335 °C or lower so as to complete solidification of the plating layer in the cooler, the cooling conditions and strip running speed were made substantially constant in the air-water cooling zones 6a, 6b, the air cooling zone 14 and the water quenching zone 7, the strip temperature on the water quenching zone 7 entry side was made 100 °C or lower, and the steel strip was passed through the skin pass mill at about 70 °C or lower.
  • the surface luster of the Mg-containing hot-dip Zn plated steel sheet obtained was excellent and no phenomenon causing degradation thereof was observed.
  • the degree of plating layer surface luster degradation was investigated by conducting tests under various conditions.
  • the surface luster was assessed as the brightness (L) measured as the Lab method L value using a spectrophotometer.
  • Water stream projector 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width
  • Water flow As shown in Table 1
  • the L values of plated steel sheets obtained under the foregoing conditions at different strip temperatures at start of stream projection (strip temperature on the water quenching entry side) measured just after plating and after the 20-hour constant temperature and humidity test are shown in Table 1.
  • the metallic structures of the plating layers were examined by microscopically observing a cross-section of the plating layer of each plated steel sheet.
  • the plating layer of every steel sheet had a metallic structure including [primary crystal Al phase] in a matrix of [Al/Zn/Zn 2 Mg ternary eutectic crystal structure], sometimes further including [Zn phase] and [Zn 2 Mg phase] (hereinafter called "Zn 2 Mg-system" metallic structure).
  • Mg-containing hot-dip Zn plated steel sheets produced under the following conditions using the same cooling conditions after plating layer solidification as in Example 2 were examined for state of surface luster degradation. The results are shown in Table 2.
  • Strip running speed Varied as shown in Table 2
  • Nozzle Plate-like nozzle with slit of 5 mm width
  • Airflow As shown in Table 2
  • Water stream projector 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width
  • Water flow As shown in Table 2
  • Example 3 Nos. B-2 to B-5 of Example 3 were subjected to chemical treatment of their water-quenched plating surfaces under the conditions set out below. Their brightnesses just after chemical treatment and after a 20-hour constant temperature and humidity test were measured by the method of Example 2. The results are shown in Table 3.
  • Spray and wringer roll method Processing solution: Zinchrome 3387N from Nihon Parkerizing Co., Ltd. (solution total chromium concentration: 10 g/L) Chromium coating weight: 10 mg/m 2
  • Roll coating method Processing solution: Aqueous solution composed mainly of 50 g/L of magnesium phosphate, 10 g/L of potassium fluorotitanate and 3 g/L of organic acid Metallic component coating weight: 50 mg/m 2
  • Plating was conducted under the following plating conditions and cooling conditions with one or more readily oxidizing elements added to the plating bath. Each plating was examined for surface luster degradation. The results are shown in Table 4.
  • Hot-rolled steel strip of 1.6 mm thickness Plating bath composition As shown in Table 4 Plating bath temperature: 450 °C Coating weight: 190 g/m 2 Strip running speed: 60 -120 m/min
  • Nozzle Plate-like nozzle with slit of 5 mm width
  • Water stream projector 7 header rows each consisting of 10 flat spray nozzles spaced at 150 mm intervals in the direction of strip width
  • Water flow 180 m 3 /h
  • Strip temperature at start of water stream projection As shown in Table 4 Table 4 No.
  • Plating bath composition (mass %, balance Zn) Strip temperature on the water quenching entry side °C Chemical treatment Surface luster Example type Al Mg Ti B Readily oxidizing element L value just after plating or chemical treatment L value after 20-h constant temperature humidity test Type Content C-1 13.8 2.2 0.046 0.020 Y 0.030 198 No 81 80 Invention C-2 8.2 2.9 0.012 0.005 Y 0.009 96 No 82 82 Invention C-3 9.4 3.3 0.009 0.010 La 0.007 155 No 82 81 Invention Ce 0.010 C-4 4.5 13 0.037 0.038 Zr 0.028 237 No 81 80 Invention C-5 6.1 3.3 0.024 0.009 Zr 0.003 131 No 82 81 Invention C-6 10.3 3.7 0.005 0.006 Zr 0.029 103 No 82 82 Invention C-7 7.8 3.2 0.011 0.002 Si 0.041 138 No 82 82 Invention C-8 6.3 3.0
  • Table 4 includes cases in which the water-quenched plating layer was chemically treated (No. C-12 to No. C-15).
  • the degree of decline in brightness L value differs depending on whether or not a readily oxidizing element is added and it can be seen that a readily oxidizing element was added, decrease in brightness L value was inhibited.
  • the present invention can effectively prevent the phenomenon of surface luster degradation that is peculiar to Mg-containing hot-dip Zn plated steel sheets. It is therefore capable of providing Mg-containing hot-dip Zn plated steel sheet that is good in corrosion resistance and also excellent in luster-retaining property.

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Claims (2)

  1. Ein Verfahren zum Erzeugen eines feuerverzinkten Stahlblechs mit exzellenter glanzbeibehaltender Eigenschaft, wobei das Verfahren aufweist:
    einen Schritt zum kontinuierlichen Tauchen und Herausnehmen von Stahlstreifen in/aus einem Bad zum Feuerverzinken, das in Massen% besteht aus: Al: 4,0 - 15 % Mg: 1,0 - 4,0 % Ti: 0,001 - 0,1 % B: 0,001 - 0,045 %
    der Differenz aus Zink und unvermeidbaren Verunreinigungen,
    dadurch eine Platierungsschicht darauf bildend;
    einen Schritt zum danach kontinuierlichen Leiten des Stahlstreifens durch eine Wasserabkühlzone, die Kühlung bewirkt, während die komplett verfestigte Platierungsschichtoberfläche in Kontakt mit einem Wasserstrom gebracht wird, wobei eine Degradation von dem Glanz der Platierungsschicht zu dieser Zeit verhindert wird durch Steuern der Streifentemperatur auf der Eintrittsseite der Wasserabkühlzone auf weniger als 105°C und falls gewünscht einem Schritt des Leitens des Stahlstreifens der durch die Wasserabkühlzone geleitet wurde, durch eine chemische Behandlungszone.
  2. Ein Verfahren zum Erzeugen eines feuerverzinkten Stahlblechs mit exzellenter glanzbeibehaltender Eigenschaft, wobei das Verfahren aufweist:
    einen Schritt zum kontinuierlichen Tauchen und Herausnehmen von Stahlstreifen in/aus einem Bad zum Feuerverzinken, das in Massen% besteht aus: Al: 4,0 - 15 % Mg: 1,0 - 4,0 % Ti: 0,001 - 0,1 % B: 0,001 - 0,045 %
    wenigstens einem leicht oxidierenden Element, ausgewählt aus seltenen Erdenelementen, Y, Zr und Si:
    0,002 - 0,05 % und
    der Differenz aus Zink und unvermeidbaren Verunreinigungen,
    dadurch eine Platierungsschicht darauf bildend;
    einen Schritt zum danach kontinuierlichen Leiten des Stahlstreifens durch eine Wasserabkühlzone, die Kühlung bewirkt, während die komplett verfestigte Platierungsschichtoberfläche in Kontakt mit einem Wasserstrom gebracht wird, wobei eine Degradation von dem Glanz der Platierungsschicht zu dieser Zeit verhindert wird durch Steuern der Streifentemperatur auf der Eintrittsseite der Wasserabkühlzone auf nicht weniger als 105°C und nicht höher als 300°C und falls gewünscht einem Schritt des Leitens des Stahlstreifens der durch die Wasserabkühlzone geleitet wurde, durch eine chemische Behandlungszone.
EP02755638A 2002-07-24 2002-07-24 Feuerverzinktes galvanisiertes zinkbasis-stahlblech mit ausgezeichneter beibehaltung des glanzes Expired - Lifetime EP1524326B1 (de)

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CN103361588B (zh) * 2012-03-30 2016-04-06 鞍钢股份有限公司 低铝低镁系锌铝镁镀层钢板生产方法及其镀层钢板
JP5097305B1 (ja) * 2012-04-25 2012-12-12 日新製鋼株式会社 黒色めっき鋼板
WO2013160566A1 (fr) 2012-04-25 2013-10-31 Arcelormittal Investigacion Y Desarrollo, S.L. Procédé de réalisation d'une tôle à revêtements znalmg huilés et tôle correspondante.
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CN108977695B (zh) * 2018-09-30 2020-12-01 济南大学 一种含钛和锑的热浸镀锌铝镁合金及其制备方法
TWI691615B (zh) * 2019-04-10 2020-04-21 中國鋼鐵股份有限公司 鍍鋅鋼片及其製造方法
CN113025937B (zh) * 2021-02-07 2023-03-17 首钢集团有限公司 一种热浸镀锌钢板及其制备方法
CN112941417A (zh) * 2021-03-03 2021-06-11 靖江新舟合金材料有限公司 一种合金镀层钢板及其生产方法
CN113512691B (zh) * 2021-03-11 2023-05-09 首钢集团有限公司 一种锌铝镁镀层钢及其制备方法
CN113604765B (zh) * 2021-10-09 2022-01-04 天津市弘仁金属材料有限公司 一种钢带热浸镀方法
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CN1276990C (zh) 2006-09-27
AU2002323927B2 (en) 2005-08-25
AU2002323927A1 (en) 2004-02-09
EP1524326A4 (de) 2006-09-13
CA2444460C (en) 2008-01-22
WO2004009863A1 (ja) 2004-01-29
ES2350921T3 (es) 2011-01-28
EP1524326A1 (de) 2005-04-20
CA2444460A1 (en) 2004-01-24
NZ528816A (en) 2005-10-28
CN1503853A (zh) 2004-06-09
ATE484605T1 (de) 2010-10-15

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