US20200002818A1 - Al-based plated steel sheet - Google Patents

Al-based plated steel sheet Download PDF

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US20200002818A1
US20200002818A1 US16/485,703 US201816485703A US2020002818A1 US 20200002818 A1 US20200002818 A1 US 20200002818A1 US 201816485703 A US201816485703 A US 201816485703A US 2020002818 A1 US2020002818 A1 US 2020002818A1
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steel sheet
amount
zno
acetylacetonato
surface layer
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Shinichi Yamaguchi
Shintaro Yamanaka
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Nippon Steel Corp
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Nippon Steel Corp
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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/07—Aldehydes; Ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
    • C08K5/1575—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • 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
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc

Definitions

  • the present invention relates to an Al-plated steel sheet suitable for hot pressing capable of exhibiting sufficient formability (lubricity), corrosion resistance (corrosion resistance of painted steel), and the like during hot pressing.
  • a typical material with an excellent mechanical strength tends to have lowered formability and shape freezing properties during a forming process such as bending, so that the material is difficult to form into a complicated shape.
  • Technologies capable of overcoming such a formability problem include so-called hot pressing (also referred to as hot stamping, hot pressing, die quenching, and press hardening).
  • hot pressing a material (target to be subjected to a forming process) is first heated to a high temperature (austenite range), and cooled after the steel sheet softened by heating is subjected to press forming.
  • Such hot pressing in which a material is first heated to a high temperature to be softened, allows the material to be easily press-formed. Additionally, a quenching effect provided by cooling after the forming increases the mechanical strength of the material. The hot pressing can thus provide a molding article with good shape freezing properties and high mechanical strength.
  • a typical metallic coating on steel sheet can be made of a variety of materials such as organic materials and inorganic materials.
  • a zinc-plated steel sheet capable of sacrificial protection of steel sheet has been widely used as steel sheet for automobiles and the like in terms of anti-corrosion performance and steel sheet production technology (Patent Literature 1).
  • a heating temperature (700 degrees C. to 1000 degrees C.) for hot pressing is higher than decomposition temperatures for organic materials and boiling temperature of Zn (zinc).
  • Zn zinc
  • an Al (aluminum) metallic coating which is higher in boiling temperature than an organic material film and a Zn metallic coating, is preferably formed on steel sheet to be heated to a high temperature for hot pressing to provide a so-called Al-plated steel sheet. Formation of such an Al metallic coating prevents adhesion of scale onto a surface of steel sheet, eliminating the necessity of a descaling treatment or the like with improved productivity.
  • the Al metallic coating also provides an anti-corrosion effect to improve corrosion resistance of painted steel.
  • an Al-plated steel sheet with an Al metallic coating formed on steel of a predetermined steel composition is subjected to hot pressing (see, for instance, Patent Literature 3).
  • One of the challenges of an Al-plating material for hot pressing as disclosed in Patent Literature 3 is to improve the formability during hot pressing.
  • There are some problems regarding the formability during hot pressing For instance, an Fe—Al—Si plating layer generated during heating bites into a mold due to the hardness thereof or cumulates on the mold due to the large friction coefficient thereof. Such problems would result in damages on a surface of a product, impairing the appearance quality.
  • a coating layer containing zinc oxide (ZnO) is stuck on a plating surface (see, for instance, Patent Literature 4).
  • the method disclosed in Patent Literature 4 includes: sticking a coating layer onto a surface of steel sheet, the coating layer containing a binder consisting of a resin component, a silane coupler, or the like so that ZnO is prevented from falling off; and volatilizing an organic solvent component of the binder at a temperature of 300 degrees C. to 500 degrees C. during hot pressing so that only ZnO remains.
  • This method is said to allow voids to be generated by combustion and evaporation of the organic solvent, causing ZnO to be in point-contact with the molding metal for improved lubricity.
  • an oxide such as ZnO is used to improve temperature-rise properties during in-furnace heating or infrared heating, chemical convertibility after heat pressing, and corrosion resistance of painted steel as well as lubricity during hot pressing (see, for instance, Patent Literatures 5 to 8).
  • Patent Literature 4 International Publication No. WO 2009/131233
  • Patent Literature 8 International Publication No. WO 2014/181653
  • Patent Literatures 4 to 8 a surface layer containing ZnO formed on an Al-plating improves the slidability during hot pressing.
  • studies by the inventors have proven that when an Al-plated steel sheet is heated on a conveyor for preheating and transportation prior to hot pressing, a ZnO metallic coating disappears from a stacked portion of the steel sheet in contact with the conveyor, lowering the hot slidability of this portion and, consequently, making the formability (lubricity) insufficient as a whole.
  • an object of the invention is to provide an Al-plated steel sheet suitable for hot pressing capable of reducing loss of ZnO from a contact area with a conveyor during heating to provide sufficient formability (lubricity) during hot pressing, corrosion resistance (corrosion resistance of painted steel), and the like.
  • the inventors first researched the reasons for disappearance of the ZnO metallic coating at the stacked portion in contact with the conveyor.
  • an organic resin component or Al present in a plating surface is usually combined with oxygen in atmosphere to be oxidized.
  • the stacked portion of the plated steel sheet in contact with the conveyor is supplied with less oxygen, so that ZnO is reduced by Al to be oxidized.
  • ZnO is reduced to metal Zn as a result of adverse response of oxidation of the organic resin component or Al present in the plating surface and, consequently, the metal Zn disappears by vaporization.
  • a surface layer formed on an Al-plating layer on the steel surface can reduce loss of ZnO at the contact area with the conveyor during heating and, consequently, provide sufficient formability during hot pressing, corrosion resistance, and the like, the surface layer containing ZnO particles, an organic resin (binder), and an Al-oxidizer (an oxidizer supplying oxygen to Al) for reducing loss of ZnO.
  • the inventors have made the invention based on the above findings.
  • the outline of the invention is as follows.
  • an Al-plated steel sheet for hot pressing includes:
  • the surface layer containing:
  • acetylacetonato in an amount in a range from 10 mass % to 30 mass %, both inclusive, with respect to a total mass of the surface layer, in which
  • a mean particle size of the ZnO particles is in a range from 0.10 ⁇ m to 5.00 ⁇ m, both inclusive, and
  • an amount of coating of the ZnO particles is in a range from 0.5 g/m 2 to 10.0 g/m 2 , both inclusive, in terms of metal Zn.
  • the Al-plating layer and the surface layer are formed on each of the opposite surfaces of the base.
  • the Al-plated steel sheet according to the above aspect is improved in components of the surface layer (outermost layer) and the amount of coating of the ZnO particles (a component of the surface layer). As a result of the improvement, the Al-plated steel sheet according to the aspect achieves sufficient formability (lubricity) during hot pressing, corrosion resistance (corrosion resistance of painted steel), and the like.
  • FIG. 1 schematically illustrates a cross section of an Al-plated steel sheet according to an exemplary embodiment with a surface provided with an Al-plating layer and a surface layer.
  • FIG. 2 schematically illustrates a cross section of the Al-plated steel sheet according to the exemplary embodiment with opposite surfaces each provided with the Al-plating layer and the surface layer.
  • an Al-plated steel sheet (hereinafter, occasionally simply referred to as “steel sheet”) suitable for hot pressing according to an exemplary embodiment of the invention. It should be noted that the invention is by no means limited to the exemplary embodiment. Components according to the exemplary embodiment include components replaceable or easily conceivable for those skilled in the art or components substantially the same as such replaceable or easily conceivable components. Furthermore, a variety of configurations according to the exemplary embodiment may be combined by those skilled in the art as desired within a scope of obviousness.
  • FIG. 1 illustrates an exemplary Al-plated steel sheet according to the exemplary embodiment of the invention.
  • An Al-plated steel sheet 100 according to the exemplary embodiment of the invention includes a base 101 , an Al-plating layer 103 formed on a surface of the base 101 , and a surface layer 107 formed on a surface of the Al-plating layer 103 .
  • the surface layer 107 contains acetylacetonato and ZnO particles 109 united by an organic resin 111 .
  • the Al-plating layer 103 and the surface layer 107 may be formed on each of opposite surfaces of the base 101 (see FIG. 2 ). Each layer will be described below in detail.
  • the base 101 (a member for forming the Al-plating layer 103 ) for the Al-plated steel sheet 100 is a member configured to exhibit an excellent mechanical strength (i.e., a variety of properties against mechanical deformation and destroy such as tensile strength, yield point, extensibility, durability during a drawing process, hardness, impact value, endurance strength, and creep strength) during hot pressing subsequent to formation of the plating layer.
  • a member added with C (carbon) or alloy element for enhancement of hardenability is used.
  • an automobile part produced by hot-pressing the Al-plated steel sheet 100 which is produced by forming the Al-plating layer 103 and the surface layer 107 as described later, exhibits an excellent mechanical strength.
  • the base 101 for the Al-plated steel sheet 100 may be any typical member with an excellent mechanical strength.
  • the base 101 may be a member containing, but not limited to, the following components.
  • the base 101 contains, in mass %, C: not less than 0.01% nor more than 0.5%, Si: 2.0% or less, Mn: not less than 0.01% nor more than 3.5%, P: 0.1% or less, S: 0.05% or less, Al: not less than 0.001% nor more than 0.1%, and N: 0.01% or less.
  • the base 101 may selectively further contain, in mass %, one of or two or more of Ti: not less than 0.005% nor more than 0.1%, B: not less than 0.0003% nor more than 0.01%, Cr: not less than 0.01% nor more than 1.0%, Ni: not less than 0.01% nor more than 5.0%, Mo: not less than 0.005% nor more than 2.0%, and Cu: not less than 0.005% nor more than 1.0%, in addition to elements such as W, V, Nb, and Sb. Furthermore, the balance of the base 101 consists of Fe and inevitable impurities. Detailed description will be made below on components added to the base 101 . A unit % of each component means mass % throughout the description below.
  • Si which is added as a deoxidizer or the like, is an element inevitably contained in a steel-smelting process.
  • an excessive addition of Si lowers ductility during hot rolling of a steel manufacturing process and, consequently, degrades the resulting surface texture, so that the content of Si is preferably 2.0% or less.
  • Si is a reinforcing element capable of improving the mechanical strength of the base 101
  • Si may be added for the purpose of ensuring the desired mechanical strength as well as C.
  • Si contained in an amount of less than 0.01% is less effective in improving the strength, so that the mechanical strength is unlikely to be sufficiently improved.
  • Si is an oxidizable element, Si contained in an amount exceeding 0.6% lowers wettability during Al-melt plating, possibly causing failure in plating. Accordingly, Si is preferably added in an amount of 0.01% to 0.6%, both inclusive. It should be noted that the content of Si is further preferably in a range from 0.05% to 0.5%, both inclusive.
  • Mn not less than 0.01% nor more than 3.5%
  • Manganese (Mn) which is added as a deoxidizer or the like, is an element inevitably contained in a steel-smelting process.
  • Mn Manganese
  • the content of Mn is thus preferably 3.5% or less.
  • reducing the content of Mn to less than 0.01% increases processes and costs, so that the content of Mn is preferably 0.01% or more.
  • the content of Mn is preferably in a range from 0.01% to 3.5%, both inclusive.
  • Mn is an element capable of enhancing the hardenability while being a reinforcing element for the base 101 .
  • Mn is also effective in reducing the hot shortness associated with S (sulfur), which is one of the inevitable impurities, to a lower level.
  • S sulfur
  • Mn contained in an amount of 0.5% or more can improve the hardenability and reduce the hot shortness.
  • Mn contained in an amount exceeding 3% would lower the strength due to an excessive increase in residual ⁇ phase.
  • Mn is more preferably added in an amount of 0.5% to 3%, both inclusive. It should be noted that the content of Mn is further preferably in a range from 1% to 2%, both inclusive.
  • Phosphorus (P) which is a solid-solution reinforcing element while being an inevitably contained element, is capable of improving the strength of the base 101 with relatively low costs.
  • a lower limit of the content of P is preferably 0.001% in terms of economic smelting limit.
  • P contained in an amount exceeding 0.1% would lower the toughness of the base 101 .
  • the content of P is preferably in a range from 0.001% to 0.1%, both inclusive. It should be noted that the content of P is further preferably in a range from 0.01% to 0.08%, both inclusive.
  • S Sulfur
  • an upper limit is preferably 0.05%.
  • a reduction in the content of S possibly increases manufacturing costs, so that a lower limit of the content of S is preferably 0.001%.
  • the content of S is further preferably in a range from 0.01% to 0.02%, both inclusive.
  • Aluminum (Al) is an element that impairs a plating performance while being a component contained as a deoxidizer in the base 101 . Accordingly, an upper limit of the content of Al is preferably 0.1%. Meanwhile, a lower limit of the content of Al is not limited but is preferably, for instance, 0.001% in terms of economic smelting limit. It should be noted that the content of Al is further preferably in a range from 0.01% to 0.08%, both inclusive.
  • the content of N may be fixed with reference to respective contents of Ti, Al, and the like. Meanwhile, an excessive content of N possibly increases manufacturing costs due to an increase in the respective contents of Ti, Al, and the like, so that an upper limit of the content of N is preferably 0.01%.
  • Ti not less than 0.005% nor more than 0.1%
  • B not less than 0.0003% nor more than 0.01%
  • Cr not less than 0.01% nor more than 1.0%
  • Ni not less than 0.01% nor more than 5.0%
  • Mo not less than 0.005% nor more than 2.0%
  • Cu not less than 0.005% nor more than 1.0%
  • Titanium (Ti) is not only a reinforcing element for the base 101 but also an element capable of improving the heat resistance of the Al-plating layer 103 formed on the surface of the base 101 .
  • Ti contained in an amount of less than 0.005% fails to sufficiently improve the strength and heat resistance.
  • Ti added in an excessive amount would form, for instance, carbide or nitride, softening the base 101 .
  • Ti contained in an amount exceeding 0.1% is highly unlikely to achieve the desired mechanical strength. Accordingly, Ti is more preferably added in an amount of 0.005% to 0.1%, both inclusive. It should be noted that the content of Ti is further preferably in a range from 0.03% to 0.08%, both inclusive.
  • Boron (B) is an element that works during quenching, exhibiting an effect in improving the strength of the base 101 .
  • B contained in an amount of less than 0.0003% fails to exhibit a sufficient effect in improving the strength. Meanwhile, B contained in an amount exceeding 0.01% would form an inclusion (e.g., BN and carbon boride) in the base 101 , increasing the shortness and, consequently, lowering fatigue strength. Accordingly,
  • B is more preferably added in an amount of 0.0003% to 0.01%, both inclusive. It should be noted that the content of B is further preferably in a range from 0.001% to 0.008%, both inclusive.
  • Chrome (Cr) has an effect in reducing generation of AlN, which causes separation of the Al-plating layer 103 , in an interface between the Al-plating layer 103 and the base 101 when the Al-plating layer 103 is alloyed to form an Al—Fe alloy layer.
  • Cr is not only an element capable of improving wear resistance but also an element capable of enhancing hardenability.
  • Cr contained in an amount of less than 0.01% fails to sufficiently exhibit the above effects.
  • Cr contained in an amount exceeding 1.0% not only saturates the above effects but also increases the manufacturing costs of the steel sheet. Accordingly, Cr is more preferably added in an amount of 0.01% to 1.0%, both inclusive. It should be noted that the content of Cr is further preferably in a range from 0.5% to 1.0%, both inclusive.
  • Ni not less than 0.01% nor more than 5.0%
  • Nickel (Ni) has an effect in improving hardenability during hot pressing. Ni also has an effect in enhancing the corrosion resistance of the base 101 . However, Ni contained in an amount of less than 0.01% fails to sufficiently exhibit the above effects. Meanwhile, Ni contained in an amount exceeding 5.0% not only saturates the above effects but also increases the manufacturing costs of the steel sheet. Accordingly, Ni is more preferably added in an amount of 0.01% to 5.0%, both inclusive.
  • Molybdenum (Mo) has an effect in improving hardenability during hot pressing. Mo also has an effect in enhancing the corrosion resistance of the base 101 . However, Mo contained in an amount of less than 0.005% fails to sufficiently exhibit the above effects. Meanwhile, Mo contained in an amount exceeding 2.0% not only saturates the above effects but also increases the manufacturing costs of the steel sheet. Accordingly, Mo is more preferably added in an amount of 0.005% to 2.0%, both inclusive.
  • Copper (Cu) has an effect in improving hardenability during hot pressing. Cu also has an effect in enhancing the corrosion resistance of the base 101 . Cu contained in an amount of less than 0.005% fails to sufficiently exhibit the above effects. Meanwhile, Cu contained in an amount exceeding 1.0% not only saturates the above effects but also increases the manufacturing costs of the steel sheet. Accordingly, Cu is more preferably added in an amount of 0.005% to 1.0%, both inclusive.
  • elements such as tungsten (W), vanadium (V), niobium (Nb), antimony (Sb) may be selectively added to the above base 101 according to the exemplary embodiment. These elements may each be added in any content in a known range.
  • the balance of the base 101 consists of iron (Fe) and inevitable impurities.
  • the inevitable impurities include components inherently present in a material and components naturally mixed during the manufacturing process, which are not deliberately contained in the base 101 .
  • the base 101 containing the above components exhibits a mechanical strength of approximately 1500 MPa or more after quenched by heating for hot pressing or the like. In spite of such an excellent mechanical strength, the steel sheet can be easily press-formed by hot pressing as the steel sheet is thermally softened. Furthermore, when cooled from a high temperature after pressed, the base 101 exhibits a high mechanical strength. The mechanical strength can be maintained or improved even when the thickness is reduced for weight reduction.
  • the Al-plating layer 103 is formed on at least one of opposite surfaces of the base 101 .
  • the Al-plating layer 103 is formed by, but not limited to, hot dip coating.
  • the Al-plating layer 103 is not limited as long as it consists mainly of Al.
  • the wording “consisting mainly of Al” herein means that Al is contained in an amount of 50 mass % or more.
  • the content of Al (the main component) is preferably 70 mass % or more, which means that Al-plating layer 103 preferably contains Al in an amount of 70 mass % or more.
  • Components other than Al are not limited but Si may be contained at a predetermined concentration.
  • the Al-plating layer 103 is configured to prevent corrosion of the base 101 .
  • the Al-plating layer 103 is also configured to prevent scale (oxide of iron) from being generated on the steel surface during preheating for hot pressing.
  • scale oxide of iron
  • the presence of the Al-plating layer 103 on at least one of opposite surfaces of the base 101 can eliminate the necessity of processes such as descaling, surface cleaning, and surface treatment and, consequently, improves the productivity of automobile parts and the like.
  • a melting point of the Al-plating layer 103 is higher than that of the metallic coating of an organic material or any other metallic material (e.g., Zn material), the Al-plating layer 103 can be processed at a high temperature during hot pressing.
  • Al contained in the Al-plating layer 103 is sometimes partly or fully alloyed with Fe in the base 101 during hot dip coating or hot pressing.
  • the Al-plating layer 103 is not always in the form of a single layer with fixed components.
  • the Al-plating layer 103 sometimes includes a partially alloyed layer (alloy layer) or a steel-aluminum gradient alloy layer with variation in concentration gradient from the surface thereof.
  • the surface layer 107 is formed on the Al-plating layer 103 .
  • the surface layer 107 contains the ZnO particles 109 with a mean particle size in a range from 0.10 ⁇ m to 5.00 ⁇ m, both inclusive, and the organic resin 111 .
  • An amount of coating of the ZnO particles 109 needs to be in a range from 0.5 g/m 2 to 10.0 g/m 2 , both inclusive, in terms of metal Zn. It should be noted that for the configuration where the Al-plating layer 103 is formed on each of the opposite surfaces of the base 101 , the surface layer 107 may be formed on the Al-plating layer 103 on at least one of the opposite surfaces.
  • the surface layer 107 may be formed using, for instance, a solution prepared by blending the above components in a variety of solvents such as water and organic solvent.
  • the ZnO particles 109 come into point-contact with the mold with a lowered kinematic friction coefficient, thus improving formability.
  • the ZnO particles 109 with a mean particle size of less than 0.10 ⁇ m fail to sufficiently improve formability due to an excessive number of contact points between the ZnO particles 109 and the mold.
  • the ZnO particles 109 with a mean particle size exceeding 5.00 ⁇ m lowers weldability.
  • the ZnO particles 109 with a small particle size are crushed upon application of a welding pressure, ensuring sufficient power distribution points.
  • the ZnO particles 109 have a large mean particle size of more than 5 ⁇ m the ZnO particles 109 are unlikely to be crushed upon application of a welding pressure. As a result, sufficient power distribution points cannot be ensured, so that dust is easily caused to lower weldability.
  • a method of determining the mean particle size of the ZnO particles 109 is not limited.
  • the mean particle size may be determined by: observing any selected ten or more of the ZnO particles 109 at 2000-fold magnification with a SEM (Scanning Electron Microscope) or the like; and measuring and averaging maximum particle sizes of these particles.
  • the mean particle size of the ZnO particles 109 may be determined using a particle size distribution measuring device.
  • the amount of coating of the ZnO particles 109 on the Al-plating layer 103 may be measured by a calibration curve method using XRF (X-ray Fluorescence).
  • amount of coating herein means an amount of coating measured before the steel sheet is set and heated on the conveyor for hot pressing.
  • the organic resin 111 which is a component of the surface layer 107 , is not limited as long as the organic resin 111 functions as a binder capable of keeping the ZnO particles 109 within the metallic coating.
  • the organic resin 111 is configured be combusted to disappear during preheating for hot pressing, so that the subsequent processes, such as pressing and welding, are performed without any influence thereof.
  • the organic resin 111 may be an aqueous chemical agent.
  • a cation resin which is mildly alkaline and stable as well as ZnO, is preferably usable and examples of the cation resin include cationic urethane resin and cationic acrylic resin.
  • a ratio of the concentration (g/kg) of the organic resin in the chemical agent is not limited according to the exemplary embodiment.
  • Exemplary resins usable as the organic resin 111 according to the exemplary embodiment of the invention include a cationic urethane resin (manufactured by DKS Co. Ltd., trade name: SUPERFLEX 650).
  • the content of the organic resin 111 with respect to the surface layer 107 as a whole is preferably in a range from, in mass %, 10% to 60%, both inclusive. At a content of less than 10%, the organic resin 111 fails to sufficiently function as a binder, making the metallic coating easy to separate before preheating. It should be noted that the content of the organic resin 111 is preferably 15% or more so that the organic resin 111 stably functions as a binder. Meanwhile, a content of the organic resin 111 exceeding 60% results in unignorable emission of unpleasant odor.
  • the surface layer 107 especially, acetylacetonato contained as an oxidizer for oxidizing Al in the surface layer 107 is considerably important.
  • the contact area of the Al-plated steel sheet 100 with the conveyor suffers from oxidation of the organic resin 111 and Al in the plating surface, which is accompanied by reduction of ZnO to metal Zn and, consequently, vaporization of the metal Zn.
  • addition of acetylacetonato, which is more reducible (i.e., more unlikely to be oxidized) than ZnO, to the surface layer 107 reduces the above behavior of ZnO and, consequently, reduces the loss of ZnO.
  • addition of acetylacetonato to the surface layer 107 reduces the loss of ZnO contributable to lubricity, allowing for stable formability during hot pressing and corrosion resistance.
  • Acetylacetonato may be added by itself or added in the form of an acetylacetonato complex (acetylacetonato metal salt).
  • the acetylacetonato complex include copper complex, manganese complex, nickel complex, zinc complex, titanium complex, and vanadyl complex.
  • zinc acetylacetonato (zinc complex) is preferable, since it functions by itself as a ZnO source that generates ZnO.
  • the amount in terms of acetylacetonato is determined as follows. First, a predetermined area of the surface layer 107 is removed using fuming nitric acid, and a weight of the surface layer 107 is measured before and after the removal to calculate a metallic coating amount of coating. Subsequently, the removed metallic coating is well stirred in a known amount of a 30-degrees-C.
  • a concentration of the acetylacetonato in the solution is measured by a calibration curve method based on liquid chromatography, and an amount of the acetylacetonato contained in the metallic coating is calculated from the amount of the solution, while a ratio of the acetylacetonato is calculated from the metallic coating amount of coating.
  • the surface layer 107 may be formed on the Al-plating layer 103 by, but not limited to, a method including: preparing a solution or solvent where the above main components (i.e., ZnO particles 109 , organic resin 111 , and acetylacetonato) are dissolved; applying this solution or solvent on the Al-plating layer 103 using a known device such as roll coater and spray; and drying the applied solution or solvent.
  • the applied solution or solvent may be dried by, but not limited to, a variety of techniques such as hot-air heating, IH (Induction Heating), NIR (Near InfraRed) heating, and resistance heating.
  • a heating temperature for drying is preferably determined as desired, considering a glass transition temperature (Tg) of the organic resin 111 (binder).
  • the Al-plated steel sheet 100 according to the exemplary embodiment exhibits an excellent lubricity during hot pressing without loss of ZnO metallic coating at the contact area of the surface layer 107 (outermost layer) with the conveyor, achieving, for instance, excellent formability during hot pressing and excellent corrosion resistance after hot pressing. Furthermore, the Al-plated steel sheet 100 according to the exemplary embodiment is less adhesive to a mold due to the presence of the highly lubricative surface layer 107 . If the Al-plating layer 103 is accidentally powdered by heating, adhesion of the powder (e.g., Al—Fe powder) to a mold used for subsequent pressing would be reduced by the presence of the highly lubricative surface layer 107 . Thus, the Al-plated steel sheet 100 according to the exemplary embodiment can be hot-pressed without the necessity of removal of Al—Fe powder adhering to the mold, achieving excellent productivity.
  • the powder e.g., Al—Fe powder
  • a cold-rolled steel sheet (balance: Fe and inevitable impurities, thickness: 1.4 mm) with chemical components shown in Table 1 was used.
  • the Al-plating layer 103 was formed on each of opposite surfaces of the cold-rolled steel sheet by Sendzimir process.
  • An annealing temperature for forming the Al-plating layer 103 was approximately 800 degrees C.
  • a typical Al-plating bath was used.
  • an amount of the Al-plating layer 103 adhering to the base 101 was adjusted to 160 g/m 2 per each surface by gas wiping.
  • the surface layer 107 was formed by applying on the Al-plating layer 103 a solution prepared by blending a dispersant of the ZnO particles 109 (manufactured by SAKAI CHEMICAL INDUSTRY CO., LTD., trade name: DIF-3ST4S), a cationic urethane resin (manufactured by DKS Co. Ltd., trade name: SUPERFLEX 650) as the organic resin 111 , and acetylacetonato using a roll coater, and drying the solution such that a sheet temperature reached 80 degrees C.
  • the organic resin 111 was not used and cyclopentasiloxane with ZnO particles 109 being dispersed was applied and then dried at 80 degrees C.
  • Zn Amount of Coating means a value (unit: g/m 2 ) of a total amount of coating of the ZnO particles 109 per square meter in terms of the mass of metal Zn, the value being measured by a calibration curve method using XRF.
  • the content of acetylacetonato, the particle size of the ZnO particles 109 , and the ZnO amount of coating were identified as follows.
  • the surface layer 107 was partly removed using fuming nitric acid as described above and a concentration of the removed acetylacetonato was measured by a calibration curve method based on liquid chromatography.
  • the ZnO particles 109 were observed at 2000-fold magnification with a scanning electron microscope manufactured by JEOL Ltd. (trade name: JSM-7800F) and respective maximum particle sizes of 20 of the ZnO particles 109 were measured and averaged. The average value was defined as the particle size of the ZnO particles 109 .
  • the ZnO amount of coating was measured with an X-ray fluorescence analyzer manufactured by Rigaku Corporation (trade name: ZSX Primus) under the following conditions.
  • an analytical curve was created in advance that represented a relationship between ZnO amount of coating and intensity of X-ray fluorescence in terms of metal Zn content and the amount of coating was determined with reference to the analytical curve.
  • each sample steel sheet was subjected to a hot mold-pulling test. More specifically, each 30 mm ⁇ 350 mm sample steel sheet was put in a furnace and heated at 900 degrees C. for 6 minutes while sandwiched between two SiC plates (60 mm width ⁇ 200 mm length ⁇ 30 mm thickness) and taken out of the furnace. A flat mold (50 mm width ⁇ 40 mm length) of SKD11 was then pressed against opposite surfaces of the steel sheet at approximately 700 degrees C. for a pulling process. The steel sheet was sandwiched between by the SiC plates at both sides thereof with supply of oxygen through the surfaces being sufficiently cut in order to simulate the situation where the ZnO metallic coating disappeared at the stacked portion in contact with the conveyor under more severer conditions.
  • a pressing load and a pulling load were measured and a value calculated by pulling load/(2 ⁇ pressing load) was defined as a hot friction coefficient. It should be noted that a smaller kinematic friction coefficient means a higher lubricity for hot working, and a kinematic friction coefficient of less than 0.52 is evaluated to pass in Table 3.
  • Each 120 mm ⁇ 200 mm sample steel sheet was put in a furnace and placed on an in-furnace SiC mount with an evaluation surface of the steel sheet in contact with the mount.
  • the steel sheet was then heated in the furnace at 900 degrees C. for 6 minutes with a SUS304 block (50 mm ⁇ 50 mm ⁇ 70 mm) having been heated to 900 degrees C. placed thereon.
  • the steel sheet was sandwiched between a stainless steel mold for rapid cooling. The cooling rate was approximately 150 degrees C./second.
  • each steel sheet having been cooled was cut from a center thereof into a 70 mm ⁇ 150 mm piece.
  • each 70 mm ⁇ 150 mm steel sheet with a thermocouple welded thereto was put in an air atmosphere furnace whose temperature was set to 900 degrees C., and a temperature of the steel sheet was measured until it reached 900 degrees C. to calculate an average temperature-rise rate.
  • the average temperature-rise rate was 5 degrees C./second.
  • Evaluation of corrosion resistance of painted steel was performed by a method in accordance with JASO M609 instituted by Society of Automotive Engineers of Japan, Inc. Specifically, a film was cross-cut in advance with a cutter, and a width (maximum value on one side) of swelling of the film from the cross cut was measured after the elapse of 180 cycles of a corrosion test (60 days). A smaller width of swelling of the film means a higher corrosion resistance and a width equal to or less than 5 mm is evaluated to pass in Table 3.
  • the prepared sample steel sheets were each put in a furnace and heated therein at 900 degrees for 6 minutes.
  • the sample steel sheets were then each sandwiched by a stainless steel mold for rapid cooling immediately after taken out of the furnace.
  • the cooling rate was approximately 150 degrees C./second.
  • Each cooled steel sheet was cut into a 30 ⁇ 50 mm piece for measurement of a suitable current range for spot welding (maximum current to minimum current).
  • the measurement conditions are as follows. A current value achieving a nugget diameter of 3 ⁇ (t)0.5 was defined as the minimum current, whereas a current causing expulsion was defined as the maximum current.
  • electrode made of chrome copper, DR (40R/6-mm-diameter tip end)
  • a larger value means a higher spot weldability and a spot weldability of 1.0 kA or more is evaluated to pass in Table 3.
  • Each sample steel sheet was punched into a diameter of 30 mm, and stacked on a 70 mm ⁇ 70 mm in-furnace SiC mount while a 50 mm ⁇ 50 mm ⁇ 70 mm SUS304 block having been heated to 900 degrees C. was placed thereon. The steel sheet in this state was then heated in a furnace at 900 degrees C. for 6 minutes, and sandwiched by a stainless steel mold for rapid cooling immediately after taken out of the furnace. Values of Zn amount of coating before and after the heating were measured with XRF. The Zn amount of coating was measured in terms of Zn and a ZnO residual ratio was calculated in terms of Zn.
  • a sample with a Zn residual ratio of 75% or more and a Zn residual amount of 0.40 g/m 2 or more is evaluated to pass in Table 3.

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