WO2019186645A1 - 溶融Ａｌ系めっき鋼板の製造方法、および溶融Ａｌ系めっき鋼板 - Google Patents

溶融Ａｌ系めっき鋼板の製造方法、および溶融Ａｌ系めっき鋼板 Download PDF

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WO2019186645A1
WO2019186645A1 PCT/JP2018/012124 JP2018012124W WO2019186645A1 WO 2019186645 A1 WO2019186645 A1 WO 2019186645A1 JP 2018012124 W JP2018012124 W JP 2018012124W WO 2019186645 A1 WO2019186645 A1 WO 2019186645A1
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molten
plating bath
steel sheet
plated steel
concentration
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PCT/JP2018/012124
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English (en)
French (fr)
Japanese (ja)
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伸也 古川
康太郎 石井
服部　保徳
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日新製鋼株式会社
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Priority to CN201880091677.7A priority Critical patent/CN112041477A/zh
Priority to EP18912021.5A priority patent/EP3778979A1/de
Priority to PCT/JP2018/012124 priority patent/WO2019186645A1/ja
Priority to US16/982,786 priority patent/US20210002752A1/en
Priority to KR1020207029744A priority patent/KR102420305B1/ko
Publication of WO2019186645A1 publication Critical patent/WO2019186645A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C22C21/04—Modified aluminium-silicon alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C3/00—Removing material from alloys to produce alloys of different constitution separation of the constituents of alloys
    • C22C3/005—Separation of the constituents of alloys
    • 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
    • C23C2/003—Apparatus
    • C23C2/0034—Details related to elements immersed in bath
    • C23C2/00342—Moving elements, e.g. pumps or mixers
    • C23C2/00344—Means for moving substrates, e.g. immersed rollers or immersed bearings
    • 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
    • C23C2/003—Apparatus
    • C23C2/0038—Apparatus characterised by the pre-treatment chambers located immediately upstream of the bath or occurring locally before the dipping process
    • C23C2/004—Snouts
    • 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
    • C23C2/325—Processes or devices for cleaning the bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the present invention relates to a method for producing a molten Al-based plated steel sheet having fine spangles.
  • the molten aluminum-based plated steel sheet (molten Al-based plated steel sheet) is obtained by applying a plating mainly composed of aluminum to the surface layer of a steel sheet by a melting method in order to improve the corrosion resistance and heat resistance of the steel sheet.
  • Hot-dip Al-based plated steel sheets are widely used mainly for heat-resistant applications such as automobile exhaust gas members and combustion equipment members.
  • a spangle pattern due to dendrites (dendritic crystals) that are solidified structures of aluminum appears on the surface of the plating layer.
  • the spangle pattern is a unique geometric pattern or floral pattern, and each region (spangle) forming the spangle pattern is made of the dendrite.
  • Spangle grows in the process of solidification of aluminum after plating.
  • the growth proceeds by first generating spangle nuclei, then growing a primary dendrite arm from the spangle nuclei, and subsequently generating a secondary dendrite arm from the primary dendrite arm. Since the growth of the dendrite arm stops when the adjacent spangles collide with each other, the number of spangles increases as the number of spangle nuclei in the plating layer increases, and the spangle size per piece becomes finer.
  • spangles does not adversely affect the quality such as corrosion resistance of hot-dip Al-plated steel sheets, but in the market, hot-dip Al-plated steel sheets with a fine spangle size and an unobtrusive surface skin are preferred. It is rare.
  • Ti, Zr are added to the plating bath in order to increase the amount of substances acting as spangle nuclei for the purpose of forming fine spangles.
  • Nb, B, boride such as aluminum boride (AlB 2 , AlB 12 ), titanium carbide (TiC), titanium boride (TiB 2 ), or titanium aluminide (TiAl 3 ) has been proposed. Yes.
  • Such a manufacturing method is described in, for example, Patent Documents 1 to 3.
  • Japanese Patent Publication Japanese Patent Laid-Open No. 2004-115908 (published on April 15, 2004)” Japanese Patent Publication “Japanese Patent Laid-Open No. 2006-22409 (published Jan. 26, 2006)” Japanese Patent Gazette “Patent No. 3751879 (issued on December 16, 2005)” Japanese Patent Gazette “Patent No. 5591414 (issued on September 17, 2014)”
  • B and aluminum boride (AlB 2 , AlB 12 ) have a small specific gravity difference from the aluminum bath and have a low sedimentation property to the bath bottom.
  • AlB 2 , AlB 12 aluminum boride
  • Patent Document 4 discloses a molten Al-based plated steel sheet having a B content of 0.002 to 0.080 mass%.
  • B is unevenly distributed on the surface of the plated layer of the molten Al-based plated steel sheet, improving the slidability between the plated layer and the mold, and improving the galling resistance of the plated layer. To do.
  • the present invention has been made in view of the above-described conventional problems, and its purpose is to produce a molten Al-based plated steel sheet in which fine spangles are stably formed on the surface of the plated layer in the molten Al-based plated steel sheet. It is to provide a method.
  • the inventors of the present invention have made extensive studies, and when a molten Al-based plated steel sheet is obtained using a molten Al-based plating bath in which appropriate amounts of B (boron) and K (potassium) coexist, an excellent spangle refinement effect is obtained.
  • the present invention has been completed.
  • the composition of a molten Al-based plating bath containing aluminum as a main component is added to a master alloy containing B, and the B concentration is 0.005% by mass.
  • the gas concentration is supplied to the molten Al-based plating bath, and the floating concentration on the molten Al-based plating bath is reduced by removing the suspended matter on the bath surface. It is characterized by lowering.
  • a gas is supplied into the molten Al-based plating bath by blowing a gas into the molten Al-based plating bath. Also good.
  • the molten Al-based plating bath is used at or near the bath surface of the molten Al-based plating bath using a stirring mechanism. Gas may be supplied into the molten Al-based plating bath by stirring.
  • the stirrer which has a stirring blade may be sufficient as the said stirring mechanism.
  • the stirring mechanism is a drive roll including a rotating portion that can rotate around an axis by external power, and the molten Al-based plating bath
  • the gas may be supplied into the molten Al-based plating bath by immersing a part of the rotating part and rotating the rotating part.
  • the molten Al-based plated steel sheet according to an aspect of the present invention is a molten Al-based plated steel sheet manufactured by the method for manufacturing a molten Al-based plated steel sheet, and the average B concentration is 0.005% by mass on the surface of the base steel sheet.
  • the present invention is characterized by having a molten Al-based plating layer having a composition having an average K concentration of greater than 0% by mass and less than 0.0005% by mass.
  • the number of spangle crystal nuclei existing on the surface of the hot-dip Al-based plating layer is 100 or more per 1 cm 2 of the surface area of the hot-melt Al-based plating layer.
  • FIG. 1 shows the optical microscope photograph after grind
  • FIG. 1 shows typically the aluminum pot in the plating equipment which manufactures a fusion
  • FIG. 5 is a figure which shows the optical microscope photograph after grind
  • the molten Al-based plated steel sheet is generally manufactured by immersing and passing the base steel sheet in a molten Al-based plating bath containing aluminum as a main component to form a molten Al-based plated layer on the surface of the base steel sheet.
  • a molten Al-based plating bath containing aluminum as a main component to form a molten Al-based plated layer on the surface of the base steel sheet.
  • an Al—Fe alloy layer is also formed between the steel substrate of the base steel sheet and the molten Al-based plating layer (interface) by mutual diffusion of Al and Fe.
  • dendrites grown from spangle crystal nuclei exist on the surface of the molten Al-based plating layer. The density of the spangle crystal nuclei on the surface of the molten Al-based plating layer will be described later.
  • the base steel plate can be selected from various steel types depending on the application, including steel types that have been conventionally used as a plating base plate for hot-dip Al-based plated steel plates.
  • a stainless steel plate may be applied to the base steel plate.
  • the thickness of the base steel plate can be set to 0.4 to 3.2 mm, for example.
  • a base-material steel plate is meant including a base-material steel strip.
  • Al-Fe alloy layer is mainly composed of an Al—Fe intermetallic compound.
  • Si is preferably added to the molten Al-based plating bath, and the Al—Fe-based alloy layer formed by the Al-based plating bath containing Si contains a large amount of Si.
  • an Al—Fe alloy layer containing no Si and a so-called Al—Fe—Si alloy layer containing Si are collectively referred to as an Al—Fe alloy layer. Since the Al—Fe-based alloy layer is composed of a brittle intermetallic compound, when the thickness is increased, the adhesion of the plating layer is lowered, which becomes a factor that impairs press workability.
  • the thickness of the Al—Fe-based alloy layer is preferably as thin as possible.
  • excessively thinning increases the process load and becomes uneconomical.
  • the average thickness of the Al—Fe alloy layer may be in the range of 0.5 ⁇ m or more.
  • composition of molten Al-based plating layer The chemical composition of the molten Al-based plating layer is almost the same as the plating bath composition. Therefore, the composition of the plating layer can be controlled by adjusting the plating bath composition.
  • the molten Al-based plating layer is a plating layer formed on the surface of the base steel plate and includes an Al—Fe-based alloy layer.
  • the aluminum oxide layer on the outermost surface of the hot-dip Al-based plated steel sheet is not particularly problematic because it is a very thin layer, but is included in the hot-melt Al-based plating layer.
  • the film layer such as an organic film
  • this film layer is naturally not contained in a hot-dip Al type plating layer.
  • the “average concentration” of the molten Al-based plating layer is the average of the depth direction from the surface of the base steel plate to the outer surface of the molten Al-based plating layer in the molten Al-based plated steel plate.
  • the molten Al-based plating layer contains Al as a main component and contains at least B and K, but other elements may be present.
  • Si is an additive element necessary for suppressing the growth of the Al—Fe alloy layer during hot dip plating. Further, when Si is added to the Al-based plating bath, the melting point of the plating bath is lowered, which is effective for reducing the plating temperature. When the Si content in the plating bath is less than 1.0% by mass, a thick Al-Fe alloy layer is formed by interdiffusion between Al and Fe during hot dipping. It becomes. On the other hand, when it is set as Si content exceeding 12.0 mass%, a plating layer will harden
  • Fe is mixed from a base steel plate or a constituent member of a hot-dip plating tank, and the Fe content of the molten Al-based plated layer is usually 0.05% by mass or more.
  • the Fe content is allowed up to 3.0% by mass, but more preferably 2.5% by mass or less.
  • elements such as Sr, Na, Ca, Sb, P, Mg, Cr, Mn, Ti, Zr, and V may be intentionally added to the molten Al plating bath as necessary. Yes, and sometimes mixed from raw materials. Even in the hot-dip Al-plated steel sheet which is the subject of the comparative example of the present invention, there is no problem even if these conventionally generally accepted elements are contained.
  • Sr 0 to 0.2%
  • Na 0 to 0.1%
  • Ca 0 to 0.1%
  • Sb 0 to 0.6%
  • P 0 to 0% by mass 0.2%
  • Mg 0 to 5.0%
  • Cr 0 to 1.0%
  • Mn 0 to 2.0%
  • Ti 0 to 0.5%
  • Zr 0 to 0.5%
  • V A content range of 0 to 0.5% can be exemplified.
  • the balance other than the above elements may be Al and inevitable impurities.
  • the hot-dip Al-based plated steel sheet in the comparative example of the present invention is a hot-dip Al-based plating having a composition in which the average B concentration is 0.005 mass% or more and the average K concentration is 0.0004 mass% or more on the surface of the base steel plate. It is characterized by having a layer.
  • spangle crystal nuclei As shown in FIG. 5, the size of each spangle is not constant and is not uniform. However, for example, when viewed with an optical microscope, spangle crystal nuclei can be distinguished.
  • the number of spangle crystal nuclei existing in a certain visual field area is measured, the number of spangle crystal nuclei per the visual field area can be obtained. Based on this, the number of spangle crystal nuclei per field area can be converted into a rough number of spangle crystal nuclei per 1 cm 2 of surface area of the molten Al-based plating layer.
  • this measurement method is merely an example, and measurement by other methods is not excluded.
  • the molten Al-based plated layer of the molten Al-based plated steel sheet is not limited to being provided on both sides, and may be provided on at least one side of the base steel sheet.
  • the molten Al-based plated steel sheet in the comparative example of the present invention can be manufactured by a melting method using a plating bath in which the B and K concentrations are adjusted.
  • the method for producing a molten Al-based plated steel sheet in a comparative example of the present invention includes a plating step of immersing and passing a base steel sheet in a molten Al-based plating bath containing aluminum as a main component.
  • the B concentration is 0.005% by mass or more and the K concentration is 0.0004% by mass or more.
  • the average concentration of each component of the molten Al-based plating layer after the plating step is almost the same as the composition of the molten Al-based plating bath. Therefore, with this configuration, a hot-dip Al-based plated steel sheet having a hot-alloyed plated layer having a composition with an average B concentration of 0.005% by mass or more and an average K concentration of 0.0004% by mass or more can be produced. .
  • a composition adjustment step is performed in which the concentration of each element in the molten Al plating bath is adjusted to adjust the composition of the molten Al plating bath.
  • the composition of the molten Al-based plating bath in the composition adjusting step can be adjusted as follows.
  • the B concentration of the molten Al-based plating bath is preferably adjusted by adding an aluminum mother alloy containing B. According to this, B can be suitably dispersed in the molten Al-based plating bath.
  • the B concentration of the molten Al-based plating bath may be adjusted, for example, by adding B alone or a boride such as aluminum boride such as AlB 2 or AlB 12 , and the method for adjusting the concentration is particularly limited. Not. When these raw materials are used, a treatment for uniformly dispersing B in the molten Al plating bath is required.
  • the K concentration of the molten Al-based plating bath is preferably adjusted by adding an aluminum mother alloy containing K. According to this, K can be suitably dispersed in the molten Al-based plating bath.
  • the K concentration of the molten Al-based plating bath may be adjusted by adding, for example, K alone or a compound such as KF, KBF 4 , or K 2 AlF 6 AlB 2. It is not limited. When these raw materials are used, it is necessary to uniformly disperse K in the molten Al plating bath.
  • the B concentration and the K concentration of the molten Al plating bath are adjusted by adding an aluminum mother alloy containing B and K. According to this, by adding the aluminum mother alloy, B and K can be suitably dispersed easily in the molten Al plating bath.
  • Embodiment 1 Embodiments of the present invention will be described below.
  • the various structure of the hot-dip Al type plated steel plate and its manufacturing method in embodiment of this invention has the structure similar to the structure of the comparative example mentioned above. The following description is for better understanding of the gist of the invention and does not limit the invention unless otherwise specified.
  • “A to B” indicates that A is B or more and B or less.
  • the present inventors have intensively studied and obtained a molten Al-based plated steel sheet using a molten Al-based plating bath in which appropriate amounts of B (boron) and K (potassium) coexist as described in the comparative example. And found a new finding that an excellent spangle refinement effect is manifested.
  • the present inventors tried to continuously manufacture the molten Al-based plated steel sheet of the above comparative example (continuous operation) aiming at practical application to a plating line in a factory.
  • the sink roll provided in the plating bath is black. It was found that the phenomenon that foreign matter adheres (wounds) occurs. The foreign matter eventually adhered (transferred) to the molten Al-based plated steel sheet in the plating bath, and plating defects occurred.
  • FIG. 2 is a cross-sectional view schematically showing an aluminum pot 4 and a pre-melt pot 6 in a plating facility for continuously producing a molten Al-based plated steel sheet.
  • a molten Al-based plating bath 3 is stored in an aluminum pot 4, and the base steel plate 1 is a snout that is a cylindrical facility from an annealing facility (not shown). 2 is cut off from the outside air and immersed in the molten Al-based plating bath 3.
  • a plurality of sink rolls 5 are provided in the molten Al-based plating bath 3, and the sink roll 5 advances the base steel plate 1 so that the base steel plate 1 passes through the molten Al-based plating bath 3. Guided.
  • the number of sink rolls 5 is not particularly limited. The problem is that black foreign substances adhere to such a sink roll 5.
  • the present invention has been made in view of the above problems, and a molten Al-based plating capable of continuously producing a molten Al-based plated steel sheet in which fine spangles are stably formed on the surface of the plating layer. It is a further object to provide a method for manufacturing a steel sheet.
  • the present inventors have reviewed various manufacturing processes (manufacturing conditions) for the cause of the occurrence of the black foreign matter in the continuous production of the molten Al-based plated steel sheet for a long time. Detailed investigations, such as analysis of products, and so on. As a result, the present inventors have come up with the present invention by discovering factors that cause black foreign matters and methods for removing the contaminants that cause the black foreign matters. This will be described in more detail below.
  • the black foreign matter adhering to the sink roll is mainly composed of impurities (alumina, aluminum carbide, graphite carbon, etc.) that are unavoidably present in the plating bath, and the K concentration in the foreign matter is the plating bath. It was confirmed that it was relatively higher than the inside.
  • impurities alumina, aluminum carbide, graphite carbon, etc.
  • the addition of K to the plating bath was performed using an aluminum mother alloy containing B and K in the manufacture of the hot-dip Al-based plated steel sheet of the comparative example.
  • the aluminum mother alloy will be described below.
  • KBF 4 is used to contain B in the form of AlB 2 or AlB 12 in Al. .
  • KBF 4 is added to molten Al and stirring is continued at a predetermined temperature, whereby B is taken into the molten Al in the form of AlB 2 or AlB 12 .
  • a compound mainly composed of KAlF 4 or K 3 AlF 6 is generated as a by-product.
  • These generated compounds have a specific gravity lighter than that of molten Al and are likely to float on the surface of the molten Al bath.
  • KBF 4 , KAlF 4 , and K 3 AlF 6 are collectively referred to as a flux for convenience.
  • the flux mixed in the Al—B master alloy has a B concentration of about 0.2% by weight in terms of K concentration per 4% by mass.
  • the present inventors generate black foreign matter even when KBF 4 , KAlF 4 , and K 3 AlF 6 themselves as the above flux are experimentally added to the plating bath instead of the Al—B master alloy. It was confirmed.
  • the mechanism by which the black foreign matter is generated in the continuous production of a hot-dip Al-based steel sheet for a long time is not clear, but the following can be said because the black foreign matter contains a large amount of K.
  • the impurities alumina, aluminum carbide, graphite carbon, etc.
  • the impurities alumina, aluminum carbide, graphite carbon, etc.
  • the K concentration in the plating bath that is, by removing the flux mixed in the plating bath together with the black foreign matter in advance, the generation of black foreign matter in the continuous production for a long time is prevented. It was suggested that it can be suppressed.
  • the present inventors examined a method for removing the flux mixed in the plating bath. As a result, it was found that coarse agglomerates such as graphite carbon, aluminum oxide, and Al—B—C compounds can be floated on the bath surface by stirring the plating bath so as to entrain gas. It is considered that the aggregates float on the bath surface due to oxidation of impurities or adhesion to bubbles.
  • an aluminum plating bath in which the amount of flux in the bath is reduced can be obtained.
  • the aluminum plating bath it is possible to reduce the generation of black foreign matters in continuous production for a long time, to prevent foreign matters from adhering to the sink roll immersed in the bath, and to prevent foreign matters from adhering to the surface of the plated steel sheet. It was found that plating defects due to adhesion can be suppressed.
  • the composition of a hot-dip Al-based plating bath containing aluminum as a main component is added to a master alloy containing B, and the B concentration is 0.005% by mass or more. And adjusting the K concentration to be greater than 0% by mass and less than 0.0005% by mass, and to the molten Al-based plating bath having the adjusted composition, Dipping and passing plating step.
  • composition adjustment process Prior to immersing and passing the base steel sheet in the molten Al-based plating bath, a composition adjustment step is performed in which the concentration of each element in the molten Al-based plating bath is adjusted to adjust the composition of the molten Al-based plating bath. .
  • the B concentration in the molten Al-based plating bath can be adjusted by adding a master alloy containing B, so that the B concentration in the molten Al-based plating bath can be 0.005% by mass or more (boron concentration adjusting step).
  • the mother alloy containing B include an Al—B alloy, an alloy of titanium and B (Ti—B alloy), an alloy of nickel and B (Ni—B alloy), and the like.
  • KBF 4 is used in the manufacturing process of the master alloy containing B, the flux containing K is mixed in the master alloy containing B.
  • the K concentration in the molten Al plating bath inevitably increases.
  • black foreign matter may be generated on the sink roll.
  • composition adjustment step of the present embodiment by stirring the plating bath so as to entrain the gas in the molten Al-based plating bath, and supplying the gas into the plating bath, graphite carbon, aluminum oxide, and A coarse aggregate such as an Al—B—C compound is floated on the bath surface.
  • This bath surface floating substance also contains a flux component mixed in the molten Al-based plating bath.
  • the amount of flux in the plating bath can be reduced by removing the bath surface floating matter. That is, K in the molten Al-based plating bath can be removed, and the K concentration in the plating bath can be reduced to be greater than 0% by mass and less than 0.0005% by mass (potassium concentration adjustment step).
  • the process of generating and removing bath surface suspended matter may be referred to as a flux removal process.
  • the method of stirring the plating bath so as to entrain gas in the molten Al-based plating bath is not particularly limited.
  • a method of blowing a gas such as air into a molten Al-based plating bath (bubbling), and (ii) the molten Al-based at or near the bath surface of the molten Al-based plating bath using a stirring mechanism examples thereof include a method of stirring the plating bath.
  • the specific aspect of the stirring mechanism is not particularly limited.
  • it may be a stirrer having a stirring blade such as a propeller stirrer, and may be a driving roll including a rotating part that can rotate around an axis by external power.
  • a driving roll When a driving roll is used, a part of the rotating part is immersed in the molten Al-based plating bath (with a part of the roll exposed from the bath surface), and the rotating part is rotated to obtain the molten Al-based plating bath. What is necessary is just to supply gas in a plating bath.
  • the molten Al-based plating bath may be stirred by combining a plurality of stirring mechanisms.
  • the time for stirring the molten Al-based plating bath can be, for example, 0.5 h to 5 h.
  • the flux removal processing time there is no particular limitation on the flux removal processing time as long as the floating matter on the bath surface can be generated and removed. Further, the flux removal processing may be performed in a plurality of times, in which case the flux removal processing time per time may be shortened.
  • FIG. 2 is a cross-sectional view schematically showing an aluminum pot 4 and a pre-melt pot 6 in a plating facility for continuously producing a molten Al-based plated steel sheet.
  • FIG. 2A shows a state in which the molten Al-based plating bath 3a in the premelt pot 6 is being stirred using the propeller stirrer 7.
  • FIG. (B) of FIG. 2 has shown the state which is stirring the molten Al type
  • illustration and description are abbreviate
  • a premelt pot 6 may be provided near the aluminum pot 4 in a plating facility.
  • an aluminum ingot and a mother alloy are melted, and a molten Al-based plating bath 3 for supplying to the aluminum pot 4 is produced.
  • a pre-treatment molten Al-based plating bath 3a containing a flux, whose composition is adjusted using, for example, an Al-4 mass% B master alloy in the premelt pot 6 is prepared. To do. Then, in the premelt pot 6, the pre-treatment molten Al-based plating bath 3a is stirred so that a gas (for example, air) is involved in the plating bath.
  • a gas for example, air
  • the plating bath is stirred at or near the bath surface of the pre-treatment molten Al-based plating bath 3a using a propeller stirrer 7.
  • a propeller stirrer 7 As shown in FIG. 2 (a), the plating bath is stirred at or near the bath surface of the pre-treatment molten Al-based plating bath 3a using a propeller stirrer 7.
  • a pipe 8 immersed in a pre-treatment molten Al plating bath 3a gas is blown into the plating bath and stirred.
  • the pre-treatment molten Al-based plating bath 3a may be agitated using a drive roll 22 (see FIG. 3) described later.
  • molten Al plating bath 3 having a reduced K concentration after the flux removal treatment is obtained.
  • This molten Al plating bath 3 is supplied to an aluminum pot 4.
  • the molten Al-based plating bath 3 after the flux removal treatment in the premelt pot 6 may be once cooled and solidified to form a solid substance (ingot), and the solid substance may be dissolved in the premelt pot 6 and used. It may be put into the aluminum pot 4.
  • the flux removing process is not limited to being performed in the premelt pot 6 installed in the vicinity of the aluminum pot 4.
  • the flux removal process may be performed in advance at a place away from the aluminum pot 4 to produce a molten Al-based plating bath 3, and the plating bath may be cooled and solidified to form an ingot, and the ingot may be used.
  • the flux removal treatment may be performed in the aluminum pot 4.
  • the aluminum pot 4 may be provided with a mechanism for supplying a gas to the plating bath so that the bath surface floating material can be removed.
  • a flux removal treatment can be performed while the base steel plate 1 passes through or passes through the molten Al-based plating bath 3 in the aluminum pot 4.
  • FIG. 1 is a view showing an optical micrograph after the surface of the molten Al-based plated steel sheet according to the present embodiment is polished so that a dendrite structure can be observed.
  • dendrites grown from spangle crystal nuclei exist on the surface of the molten Al-based plating layer.
  • the molten Al-based plated steel sheet produced using the plating bath has 100 spangle crystal nuclei per 1 cm 2 of the surface area of the plated layer. This can be done.
  • a molten Al-based plated steel sheet can be continuously produced for a long time, and the occurrence of a phenomenon that black foreign substances adhere to the sink roll can be suppressed.
  • a molten Al-based plated steel sheet in which fine spangles are stably formed on the surface of the plating layer can be continuously manufactured.
  • the B concentration of the molten Al-based plating bath is less than 0.005% by mass, a sufficient spangle refinement effect cannot be obtained on the molten Al-based plated steel sheet produced using the plating bath.
  • the B concentration of the molten Al-based plating bath exceeds 0.50% by mass, the spangle refinement effect of the molten Al-based plated steel plate produced using the plating bath is saturated. Therefore, superiority is not recognized even if the average B concentration is further increased.
  • concentration of a molten Al type plating bath is 0.005. It is preferable that the content be ⁇ 2.0% by mass.
  • the K concentration of the molten Al-based plating bath after reducing the flux amount in the plating bath is 0.0005% by mass or more
  • the molten Al-based plated steel sheet is continuously used for a long time using the plating bath.
  • a phenomenon occurs in which black foreign matter adheres to the sink roll. For this reason, a plating defect may generate
  • the B concentration of the molten Al-based plating bath is 0.02% by mass or more and 2.0% by mass or less, and the K concentration is greater than 0% by mass and less than 0.0005% by mass.
  • the molten Al-based plated steel sheet produced using the plating bath can have 300 or more spangle crystal nuclei existing per 1 cm 2 of the surface area of the plating layer. As a result, it is possible to manufacture a molten Al-based plated steel sheet having a more beautiful surface appearance.
  • the molten Al plating bath contains Al as a main component and contains at least B and K, but the composition may be adjusted so as to contain other elements. Specifically, similar to the comparative example described above, elements such as Si, Fe, Sr, Na, Ca, Sb, P, Mg, Cr, Mn, Ti, Zr, and V are required for the molten Al-based plating bath. Depending on the case, it may be added intentionally.
  • the balance other than the above elements may be Al and inevitable impurities.
  • the average concentration of each component of the molten Al plating layer after the plating step is substantially the same as the composition of the molten Al plating bath. Therefore, with the above-described configuration, the molten Al-based plating having a molten Al-based plating layer having a composition in which the average B concentration is 0.005% by mass or more and the average K concentration is greater than 0% by mass and less than 0.0005% by mass. Steel sheets can be manufactured.
  • the Al concentration is adjusted to 9% by mass using an Al-20 mass% Si master alloy, and a predetermined amount of Al-4 mass% B master alloy is added to the aluminum plating bath.
  • the B concentration was adjusted to 0 to 1%.
  • Table 1 shows the results of chemical analysis of the composition of the added Al-4 mass% B master alloy. The numbers in Table 1 indicate mass%.
  • Fe is inevitably mixed in the aluminum plating bath from the base steel plate and the constituent parts of the pot during continuous production.
  • the Fe concentration was adjusted to 2.0 mass%.
  • the composition was adjusted in this way and the plating bath No. shown in Table 2 was used. 1 to 10 molten Al plating baths were prepared. Since the abundance ratio of B and K in the Al-4 mass% B master alloy is constant, the plating bath No. 1 in which the K concentration in the plating bath is smaller than the lower limit of analysis limit. For 2, 3, and 4, the K concentration value obtained by ratio calculation is described. Also, the plating bath No. No. 1 contains no Al-4 mass% B master alloy.
  • a plating bath piece obtained by cooling and solidifying a part of the molten Al plating bath was dissolved by heating with a mixed acid (mixed solution of nitric acid 40 ml and hydrochloric acid 10 ml), and then ultrapure water was added to make a constant volume of 250 ml.
  • the solution after the constant volume obtained from the plating bath piece was used as a quantitative analysis solution for components in the plating bath. Then, about the said quantitative analysis solution, the following two types of quantitative analysis was performed and the composition of the component in a plating bath was calculated
  • Quantitative analysis of Si, B, and Fe was performed by inductively coupled plasma emission spectroscopy (ICP-AES method).
  • quantitative analysis of K was performed by inductively coupled plasma mass spectrometry (ICP-MS method).
  • composition of each molten Al plating bath in the following description was determined by performing the above quantitative analysis.
  • Table 3 summarizes the molten Al-based plating bath that has been subjected to the flux removal treatment and the molten Al-based plating bath that has not been subjected to the flux removal treatment.
  • Plating bath no By performing the flux removal treatment on 3 to 10, the K concentration was reduced to a trace amount (indicated as tr in the table). On the other hand, it can be seen that there is no change in the B concentration.
  • a cold-rolled annealed steel sheet having a thickness of 0.8 mm having the chemical composition shown in Table 4 was used as a base steel sheet.
  • the base steel plate is immersed in the molten Al-based plating bath and then pulled up to solidify the plating layer at a predetermined cooling rate, thereby producing a molten Al-based plated steel plate (test material).
  • Table 5 shows the conditions for producing the aluminum-plated steel sheet.
  • each test material was buffed and the extreme surface layer from the surface of the plating layer to a depth of 5 ⁇ m was smoothed so that the dendrite structure could be observed. Then, the number of spangle crystal nuclei existing per 1 cm 2 of the surface area of the plating layer was calculated with an optical microscope. The surface appearance was evaluated according to the following criteria, and a score of ⁇ or higher was regarded as acceptable.
  • FIG. 3 is a diagram schematically showing a test apparatus 10 that performs a roll wrapping test for black foreign matter in a plating bath used for manufacturing a molten Al-based plated steel sheet.
  • the plating pot is shown as a cross-sectional view in FIG.
  • the test apparatus 10 includes a support base 11, a motor 20 supported on the support base 11, and a fixture 30 that is also supported on the support base 11.
  • the motor 20 is connected to the drive roll 22 via the universal joint 21 and rotates the drive roll 22.
  • 2Two rotatable non-driving rolls 31 are pivotally supported on the fixture 30.
  • the two non-driving rolls 31 and the driving roll 22 are arranged side by side so as to contact each other.
  • the driving roll 22 rotates, the two non-driving rolls 31 also rotate in response to the rotation. ing.
  • a bundle of rolls composed of the two non-driven rolls 31 and the driven rolls 22 was immersed in a molten Al-based plating bath 41 stored in the plating pot 40 so as to be inclined with respect to the bath surface.
  • the bundle of rolls was immersed and the drive roll 22 was rotated for a predetermined time under the conditions shown in Table 6, and then the drive roll 22 was lifted.
  • FIG. 4 is a plan view showing the surface state of the drive roll 22 when black foreign matter is adhered. As shown in FIG. 4, when the black foreign material 22a adheres to the drive roll 22 and a bulge is formed, and the adhesion bath 22b adhering to the surface is broken, A black foreign object 22a may be confirmed.
  • the test apparatus 10 is used for each composition of the molten Al-based plating bath to perform a roll test of black foreign matter, and on the surface of the pulled drive roll 22, the adhesion area of the black foreign matter per surface area of 180 cm 2. was measured. Evaluation was made based on the following criteria, and a case where the adhesion area of black foreign matters on the surface of the drive roll 22 was less than 1 cm 2 (indicated by “ ⁇ ” in the column of “immersion roll” in Table 6) was regarded as acceptable. In addition, as an adhesion area of a black foreign material, the black foreign material 22a adhering under said adhesion bath 22b is included.
  • the invention example No. Using the molten Al-based plating bath after the flux removal treatment shown in 1 to 18, a molten Al-based plated steel sheet in which fine spangles are stably formed on the surface of the plating layer can be continuously produced.
  • the K concentration in the plating bath is within the range of the present invention, but the B concentration is outside the range of the present invention.
  • no black foreign matter is wound around the drive roll 22, but there are fewer spangle crystal nuclei per 1 cm 2 of the surface area of the aluminum plating layer in the manufactured molten Al-based plated steel sheet (for example, 10 or less). The spangle refinement effect was insufficient.
PCT/JP2018/012124 2018-03-26 2018-03-26 溶融Ａｌ系めっき鋼板の製造方法、および溶融Ａｌ系めっき鋼板 WO2019186645A1 (ja)

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CN201880091677.7A CN112041477A (zh) 2018-03-26 2018-03-26 熔融Al系镀覆钢板的制造方法以及熔融Al系镀覆钢板
EP18912021.5A EP3778979A1 (de) 2018-03-26 2018-03-26 Verfahren zur herstellung von feuerverzinktem, al-beschichtetem stahlblech und feuerverzinktes, al-beschichtetes stahlblech
PCT/JP2018/012124 WO2019186645A1 (ja) 2018-03-26 2018-03-26 溶融Ａｌ系めっき鋼板の製造方法、および溶融Ａｌ系めっき鋼板
US16/982,786 US20210002752A1 (en) 2018-03-26 2018-03-26 Hot-dip al-plated steel sheet production method, and hot-dip al-plated steel sheet
KR1020207029744A KR102420305B1 (ko) 2018-03-26 2018-03-26 용융 Al계 도금 강판의 제조방법, 및 용융 Al계 도금 강판

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KR102420305B1 (ko) 2022-07-13
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