WO2017179665A1 - 表面処理鋼帯及び表面処理鋼帯の製造方法 - Google Patents
表面処理鋼帯及び表面処理鋼帯の製造方法 Download PDFInfo
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- WO2017179665A1 WO2017179665A1 PCT/JP2017/015160 JP2017015160W WO2017179665A1 WO 2017179665 A1 WO2017179665 A1 WO 2017179665A1 JP 2017015160 W JP2017015160 W JP 2017015160W WO 2017179665 A1 WO2017179665 A1 WO 2017179665A1
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- zinc phosphate
- coating layer
- lubricating
- steel strip
- base steel
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
- C23C22/12—Orthophosphates containing zinc cations
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
- C10M169/044—Mixtures of base-materials and additives the additives being a mixture of non-macromolecular and macromolecular compounds
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- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
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- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- 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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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- 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
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- 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
- C23C28/04—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 only coatings of inorganic non-metallic material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M143/00—Lubricating compositions characterised by the additive being a macromolecular hydrocarbon or such hydrocarbon modified by oxidation
- C10M143/02—Polyethene
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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- C10M2201/065—Sulfides; Selenides; Tellurides
- C10M2201/066—Molybdenum sulfide
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- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
- C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
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- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
- C10M2209/084—Acrylate; Methacrylate
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- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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Definitions
- the present invention relates to a surface-treated steel strip and a method for producing the surface-treated steel strip.
- Patent Document 1 the treatment as disclosed in Patent Document 1 is often carried out in the state of a steel strip in practice.
- the object to be treated is a steel strip
- roll feedability (roll slip resistance) and mold galling resistance at the time of multi-stage press molding under high surface pressure are performances that are in a trade-off relationship with each other.
- both the above-described roll slip resistance and mold galling resistance are required.
- the present invention has been made in view of the above problems, and the object of the present invention is a surface capable of realizing both roll slip resistance and mold galling resistance which are contradictory performances. It is providing the manufacturing method of a treated steel strip and a surface-treated steel strip.
- the static friction coefficient of the surface-treated steel strip in which irregularities due to the zinc phosphate crystal are formed on the surface of the lubricant film layer is based on the static friction coefficient of the lubricant film layer alone. Also grows.
- the static friction coefficient of the surface-treated steel strip has a correlation with the area ratio of zinc phosphate crystals exposed from the surface of the lubricating coating layer (hereinafter sometimes referred to as the exposed area ratio). That is, by controlling the exposed area ratio of the zinc phosphate crystal, it is possible to control the static friction coefficient of the surface-treated steel strip.
- a base steel plate Formed in an island shape on the surface of the base steel sheet, a zinc phosphate coating layer made of acicular zinc phosphate crystals; A lubricating coating layer containing at least a lubricating component, covering the surface of the base steel sheet and a part of the zinc phosphate coating layer; With The surface-treated steel strip, wherein the area ratio of the zinc phosphate crystals exposed on the surface of the lubricating coating layer is 25% to 90%.
- the adhesion amount of the zinc phosphate coating layer is a single-sided per 1.5g / m 2 ⁇ 15.0g / m 2, [1] or the surface treated steel strip according to any one of [2].
- the adhesion amount of the lubricant coating layer is a single-sided per 1.0g / m 2 ⁇ 12.0g / m 2, the surface treated steel strip according to any one of claims 1 to 3.
- the lubricating coating layer comprises an alkali metal silicate having a molar ratio of 2 to 5 represented by SiO 2 / M 2 O (M is an alkali metal), and an average particle size of 0.1 ⁇ m to 3.
- a polymer wax composed of at least one of polyethylene wax or polypropylene wax that is 0 ⁇ m,
- the solid content of the alkali metal silicate is 60% to 90% by mass, and the solid content of the polymer wax is 5% by mass to the total solid content of the lubricating coating layer.
- FIG. 1 is an explanatory diagram for explaining the surface-treated steel strip according to the present embodiment
- FIGS. 2A and 2B are explanatory diagrams schematically showing the configuration of the surface-treated steel strip according to the present embodiment. is there.
- the surface-treated steel strip 10 according to the present embodiment is obtained by subjecting the base steel plate 101 to a high lubrication treatment as will be described in detail below.
- the surface-treated steel strip 10 is unwound by a pinch roll 1 from a coiled state in a slit process positioned at the front stage of multistage plastic working, and is predetermined. Is continuously passed in the plate passing direction X.
- the surface-treated steel strip 10 that has been passed through is processed into a target product through multi-stage pressing using a mold 2 corresponding to the target product.
- the static friction coefficient of the surface-treated steel strip 10 is lowered.
- the surface-treated steel strip 10 has a certain static friction coefficient. It is important to have Therefore, in the surface-treated steel strip 10 according to the present embodiment, as shown in FIGS. 2A and 2B, the surface of the base steel plate 101 that is a base material is subjected to a surface treatment that will be described in detail below. A surface treatment layer composed of two layers is formed.
- the surface-treated steel strip 10 includes a base steel plate 101 as a base material, a zinc phosphate coating layer 103 formed on the base steel plate 101, and phosphoric acid. And a lubricating coating layer 105 formed on the zinc coating layer 103.
- the zinc phosphate coating layer 103 and the lubricating coating layer 105 may be formed only on one surface of the base steel plate 101 as shown in FIG. 2A, or the base steel plate as shown in FIG. 2B. 101 may be formed on two surfaces facing each other.
- the base steel plate 101 is used as a base material of the surface-treated steel strip 10.
- the base steel plate 101 according to the present embodiment is not particularly limited, and it is possible to use a known steel plate capable of realizing characteristics required for an object manufactured through a subsequent multistage plastic working process.
- a known steel plate capable of realizing characteristics required for an object manufactured through a subsequent multistage plastic working process.
- the manufacturing method and material of such a known steel sheet There is no particular limitation on the manufacturing method and material of such a known steel sheet, and various known processes such as hot rolling, pickling, cold rolling, annealing, temper rolling, etc. from the normal slab manufacturing process. It may be manufactured appropriately.
- the base steel plate 101 may be not only a carbon steel plate but also a special steel plate such as a stainless steel plate or a high alloy steel plate.
- An example of such a base steel plate 101 is a hot-rolled steel plate having the following chemical components.
- the hot-rolled steel sheet as an example of the base steel sheet 101 is, in mass%, C: 0.070% to 0.080%, Si: 0.030% to 0.080%, Mn 1.15% to 1.30%, P: 0.015% to 0.028%, S: 0.000% to 0.040%, with the balance being Fe and impurities.
- the zinc phosphate coating layer 103 plays a role of enhancing the adhesion between the base steel plate 101 and the lubricating coating layer 105.
- This zinc phosphate coating layer 103 is an aggregate of acicular zinc phosphate crystals composed of zinc phosphate acicular crystals deposited on the surface of the base steel plate 101 by a chemical reaction. The deposited zinc phosphate needle-like crystals do not completely cover the surface of the base steel plate 101, as schematically shown in FIGS. 2A and 2B. The zinc phosphate crystals remain uncoated.
- the zinc phosphate coating layer 103 is divided into a plurality of locations on the surface of the base steel plate 101 and appears in a state independent of each other.
- the state of the zinc phosphate coating layer 103 that is divided into a plurality of locations on the surface of the base steel plate 101 and appears in an independent state is referred to as an “island shape”.
- the zinc phosphate coating layer 103 is formed on a base steel plate 101 that has been surface tempered using a specific surface conditioner, and further includes a phosphorous that forms the zinc phosphate coating layer 103. Since the base steel plate 101 is heated in the zinc acid coating layer forming step, the base steel plate 101 is composed of zinc phosphate needle-like crystals having a larger ratio of grain sizes in the major axis direction and the minor axis direction. Adhesion amount of the zinc phosphate coating layer 103 is preferably in a per side 1.5g / m 2 ⁇ 15.0g / m 2.
- Adhesion amount of the zinc phosphate coating layer 103 is more preferably a per side 3.0g / m 2 ⁇ 15.0g / m 2.
- the lubricating coating layer 105 can be reliably adhered to the base steel plate 101, and the zinc phosphate coating can be formed even at a high surface pressure.
- the lubricant film layer 105 can be more reliably held until the final step of the molding process without the layer 103 disappearing.
- the zinc phosphate needle-like crystals constituting the zinc phosphate coating layer 103 have an average particle size in the major axis direction of 25 ⁇ m to 70 ⁇ m and an average particle size in the minor axis direction of 3 ⁇ m to 10 ⁇ m. It is preferable that The average particle diameter of the zinc phosphate needle-like crystals is more preferably 25 ⁇ m to 50 ⁇ m in the major axis direction and 3 ⁇ m to 5 ⁇ m in the minor axis direction. Since the zinc phosphate crystals constituting the zinc phosphate coating layer 103 have such an average particle size, it is possible to more reliably realize the above adhesion.
- the zinc phosphate needle-like crystal constituting the zinc phosphate coating layer 103 according to the present embodiment is a needle-like crystal whose ratio of the average particle diameter in the major axis direction and the minor axis direction is 2.5 or more. It is preferable. By precipitating zinc phosphate needle-like crystals having such an average particle diameter, it is possible to more reliably realize adhesion between the base steel plate 101 and the lubricating coating layer 105.
- the zinc phosphate coating layer 103 can be formed using a known processing solution that contains zinc phosphate and can precipitate needle crystals of zinc phosphate.
- a treatment liquid is not particularly limited.
- a reaction type zinc phosphate treatment liquid for plastic working more specifically, a reaction type in which the treatment time for complete coating is 20 seconds or more
- Zinc phosphate treatment solution for plastic working Zinc phosphate treatment solution for plastic working.
- the zinc phosphate treatment liquid as described above may be brought into contact with the base steel plate 101 by a spray method or an immersion method, or a reaction including the zinc phosphate treatment liquid as described above.
- the electrolytic treatment may be performed using a tank.
- the zinc phosphate treatment may be finished before the zinc phosphate crystals completely cover the entire surface of the base steel plate 101.
- the contact time and electrolysis time of the base steel plate 101 and the zinc phosphate treatment solution may be limited to a short time. That is, the treatment may be completed in a shorter time than the instructed treatment time using a commercially available zinc phosphate treatment solution for plastic working.
- Whether or not the zinc phosphate crystals precipitated by the above treatment are island-like can be determined by observing the surface of the base steel plate 101 after the zinc phosphate treatment with a microscope. Specifically, when the surface of the base steel plate 101 after the zinc phosphate treatment is observed with a scanning electron microscope (SEM) and the area of the flat portion obtained by both image processing is 30% or more. May be determined that the zinc phosphate crystals are formed in an island shape. The observation of the zinc phosphate crystal may be performed before or after the formation of the lubricating film layer 105 described later.
- SEM scanning electron microscope
- the zinc phosphate crystal is observed through the lubricating coating layer 105, SEM observation at a high acceleration voltage is performed. Specifically, by setting the acceleration voltage to 20 kV or more, the crystal of zinc phosphate can be observed through the lubricating coating layer 105, and the area ratio of the flat portion can be obtained. In addition, in the observation before forming the lubricating film layer 105, the zinc phosphate crystal can be observed even at a lower acceleration voltage.
- the surface of the base steel plate 101 is tempered with a surface conditioner containing titanium colloid.
- Zinc phosphate crystals are precipitated from the surface of the base steel plate 101 to which no surface conditioning agent component is adhered, but since the titanium colloid is coarse colloidal particles, the surface of the exposed base steel plate 101 is widened. Will be suppressed.
- a surface refining treatment with a surface conditioner containing a titanium colloid, it becomes possible to more reliably precipitate zinc phosphate needle-like crystals having the above preferred average particle size ratio. .
- the lubricating coating layer 105 is located on the surface of the base steel plate 101 and covers the surface of the base steel plate 101 and at least a part of the zinc phosphate coating layer 103. In addition, at least a part of the zinc phosphate crystal is exposed on the surface.
- This lubricating film layer 105 is a layer containing at least a lubricating component, and preferably comprises a binder component and a lubricating component.
- the island-shaped zinc phosphate crystal as described above is formed, so that the lubricating component and the binder component contained in the lubricating coating layer 105 are as shown in FIG. 2A and FIG. As schematically shown in 2B, it is held between island-like zinc phosphate crystals.
- a high surface pressure is applied to the surface of the surface-treated steel strip 10 during multi-stage plastic working (for example, during multi-stage press working)
- the lubricating component held between the island-like zinc phosphate crystals is changed to the base steel plate 101. It flows out between molds. As a result, the static friction coefficient of the lubricating coating layer 105 is lowered, so that the lubricating performance is exhibited and the mold galling resistance is realized.
- Adhesion amount of the lubricating film layer 105 is a single-sided per 1.0g / m 2 ⁇ 12.0g / m 2, the area ratio of the zinc phosphate crystals exposed on the surface of the lubricating film layer 105 (per unit area Area ratio) is 25% to 90%.
- the adhesion amount of the lubricating coating layer 105 is less than 1.0 g / m 2 , the amount of the lubricating component held as the lubricating coating layer 105 is insufficient, and sufficient mold galling resistance cannot be realized. It is not preferable. Moreover, when the adhesion amount of the lubricating coating layer 105 exceeds 12.0 g / m 2 , the amount of the lubricating component held as the lubricating coating layer 105 becomes excessive, and roll slip resistance cannot be realized. It is not preferable.
- the adhesion amount per one side of the lubricating coating layer 105 is more preferably 2.0 g / m 2 to 9.0 g / m 2 .
- the adhesion amount of the lubricating coating layer 105 is also affected by the adhesion amount of the zinc phosphate coating layer 103. That is, when the adhesion amount of the zinc phosphate coating layer 103 is small, the amount of the lubricant coating layer 105 that can be retained is also reduced. Conversely, when the adhesion amount of the zinc phosphate coating layer 103 is large, the lubricant coating layer 105 that can be retained The amount also increases. For example, when the adhesion amount of the zinc phosphate coating layer 103 is 1.5 g / m 2 to 8.0 g / m 2 , the adhesion amount of the lubricating coating layer 105 is 1.0 g / m 2 to 6.0 g / m 2.
- the adhesion amount of the zinc phosphate coating layer 103 is more than 8.0 g / m 2 to 15.0 g / m 2
- the adhesion amount of the lubricating coating layer 105 is more than 6.0 g / m 2. It is preferably about 12.0 g / m 2 .
- Adhesion amount of the zinc phosphate coating layer 103 if the per side 1.5g / m 2 ⁇ 8.0g / m 2, the lubricating layer deposition amount of about 1.0g / m 2 ⁇ 6.0g / m 2
- the layer 105 can be suitably adhered to the base steel plate 101, and the zinc phosphate coating layer 103 is not lost even in the molding process under high surface pressure, and the lubricating coating layer 105 is held until the final process of the molding process. Is possible.
- the adhesion amount of the zinc phosphate coating layer 103 is more than 8.0 g / m 2 to 15.0 g / m 2
- the adhesion amount of the lubricating coating layer 105 is more than 6.0 g / m 2 to 12.0 g / m. It is preferably about 2 .
- the lubricating film layer 105 has a molar ratio represented by SiO 2 / M 2 O (M is an alkali metal selected from Li, Na, K, etc.) as the binder component. And an alkali metal silicate having an average particle diameter of 0.1 ⁇ m to 3.0 ⁇ m, and a polymer wax composed of at least one of polyethylene wax and polypropylene wax. Is preferred.
- the lubricating component can be appropriately retained in the film, and in addition, a strong continuous film excellent in heat resistance can be formed on the surface of the steel strip. It becomes possible to form. As a result, it is possible to develop a seizure resistance function that prevents direct metal contact between the surface-treated steel strip and the mold according to the present embodiment, a rust resistance function due to a barrier property of a dense alkaline film, and the like. It becomes.
- the molar ratio is less than 2
- the film strength cannot be sufficiently obtained and the plastic working performance is deteriorated, which is not preferable.
- the molar ratio represented by SiO 2 / M 2 O in the alkali metal silicate is more preferably 3-4.
- the expansion of the lubricating coating layer 105 can be suppressed, and the plastic processing performance of the lubricating coating layer 105 can be further improved.
- the average particle size of the polymer wax is less than 0.1 ⁇ m, the oil diffusion from the interface of the polymer wax into the film becomes remarkable and the oil resistance of the film deteriorates.
- the average particle diameter of the molecular wax is more than 3.0 ⁇ m, it is not preferable because dispersion of the polymer wax in the chemical solution becomes poor and it becomes difficult to form a uniform film.
- the average particle size of the polymer wax is more preferably 0.5 ⁇ m to 1.5 ⁇ m.
- the lubricating component By using the polymer wax having the average particle diameter as described above as the lubricating component, the lubricating component can be easily filled in the concave and convex portions of the zinc phosphate crystal, and as a result, the zinc phosphate crystal is formed into the lubricating coating layer. It becomes easy to expose from the surface of 105.
- the solid content of the alkali metal silicate is preferably 60% by mass to 90% by mass with respect to the total solid content of the lubricating coating layer 105, and the solid content of the polymer wax is lubricating. It is preferably 5% by mass to 40% by mass with respect to the total solid content mass of the coating layer 105.
- the solid content of the alkali metal silicate is less than 60% by mass, the continuity of the glassy film formed by the alkali metal silicate is poor, and a film strength that can withstand plastic working is obtained. Since possibility falls, it is not preferable. Moreover, when the solid content of the alkali metal silicate is more than 90% by mass, the obtained film strength is saturated and disadvantageous in terms of cost, which is not preferable.
- the solid content of the alkali metal silicate is more preferably 70% by mass to 80% by mass with respect to the total solid content of the lubricant film 105.
- the solid content of the polymer wax is less than 5% by mass, the amount of the lubricating component retained by the lubricating coating layer 105 is insufficient, and the possibility that sufficient lubricating performance is exhibited is reduced. Absent. Further, when the solid content of the polymer wax is more than 40% by mass, the amount of the lubricating component held by the lubricating coating layer 105 becomes excessive, and the possibility that sufficient roll slip resistance is exhibited is reduced. Therefore, it is not preferable.
- the solid content of the polymer wax is more preferably 3% by mass to 10% by mass with respect to the total solid content of the lubricating coating layer 105.
- the lubricating coating layer 105 can be formed by coating using a lubricating treatment agent in which the above lubricating component is mixed in a binder component solution or dispersion as described above.
- a solvent to be used any of water, an organic solvent, and a mixture thereof may be used.
- an aqueous solvent water or a mixed solvent of water and a water-miscible organic solvent such as alcohol
- the binder component for example, alkali metal silicate
- the binder component for example, alkali metal silicate
- the lubricating film layer 105 having a solid content as described above can be formed by adding a lubricating component (for example, a polymer wax) in an amount of from 40% to 40% by mass and applying and drying appropriately. .
- a known surfactant may be added to the lubricating treatment agent.
- a viscosity adjusting agent may be added as long as the strength of the lubricating coating layer 105 is not affected.
- the viscosity modifier those generally used can be used, and examples thereof include organic polymer-based organic compounds such as hydroxyethyl cellulose, carboxymethyl cellulose, polyacrylic acid amide, sodium polyacrylate, polyvinyl pyrrolidone, and polyvinyl alcohol. A sticky agent etc. are mentioned.
- the content thereof is preferably less than 10% by mass with respect to the total solid mass of the lubricating coating layer 105.
- the lubricant When applying the lubricant to the base substrate 3 and the zinc phosphate coating layer 103, a known method such as dipping, shower ringer or roll coating can be used. In addition, it is only necessary that the surfaces of the base substrate 3 and the zinc phosphate coating layer 103 be sufficiently covered with the lubricant, and the temperature and application time of the lubricant are not particularly limited. Further, the drying temperature of the lubricant is not particularly limited, and may be appropriately set according to the components contained in the lubricant.
- the area ratio of the zinc phosphate crystals exposed on the surface of the lubricating coating layer 105 is less than 25%, the degree of suppression of the reduction in the static friction coefficient of the lubricating coating layer 105 becomes insufficient, and sufficient roll resistance Since slipperiness cannot be realized, it is not preferable.
- the area ratio of the zinc phosphate crystal exposed on the surface of the lubricating coating layer 105 is more than 90%, the degree of suppression of the reduction in the static friction coefficient of the lubricating coating layer 105 becomes excessive, and sufficient resistance This is not preferable because mold galling cannot be realized.
- the area ratio of the zinc phosphate crystals exposed on the surface of the lubricating coating layer 105 is more preferably 30% to 60%.
- the amount of adhesion of the lubricating coating layer 105 and the area ratio of the zinc phosphate crystals exposed on the surface of the lubricating coating layer 105 are in the above ranges, so that the static friction coefficient of the lubricating coating layer 105 according to this embodiment is Is from 0.10 to 0.20.
- the static friction coefficient of the lubricating coating layer 105 is more preferably 0.12 to 0.15.
- the area ratio of the zinc phosphate crystal (zinc phosphate coating layer 103) exposed on the surface of the lubricating coating layer 105 In order to set the area ratio of the zinc phosphate crystal (zinc phosphate coating layer 103) exposed on the surface of the lubricating coating layer 105 to 25% to 90%, 1.5 g / m 2 to 15 per side.
- 0.0 g / m 2 of the zinc phosphate coating layer 103 needs to be island-shaped, and for this purpose, a method of increasing the temperature of the zinc phosphate treatment or extending the treatment time can be considered.
- the temperature of the zinc phosphate treatment bath is water, it is practically difficult to raise the treatment temperature to 100 ° C. or higher.
- the crystals of the zinc phosphate coating that precipitates when the treatment time is extended are steel.
- the band surface is densely formed, and the zinc phosphate coating layer 103 is not island-shaped.
- an increase in the temperature of the zinc phosphate treatment bath raises the energy cost because it is necessary to raise the temperature of the entire treatment bath.
- productivity is lowered when the zinc phosphate treatment is performed in a zinc phosphate treatment bath having a certain length for extending the treatment time.
- high surface pressure moldability mold galling resistance (simulated by L-shaped press molding) is conventional. Is maintained at the same level.
- FIGS. 3A and 3B has a configuration in which steam generated by the heater 21 is applied to the surface of the base steel plate 101 passed through the zinc phosphate treatment bath 20.
- steam generated by the heating of the heater 21 is stirred by the stirrer 22 and applied to the surface of the base steel plate 101.
- the zinc phosphate coating layer 103 When the zinc phosphate coating layer 103 is formed, if the treatment temperature is increased by performing partial heating in the zinc phosphate treatment bath 20 and applying steam to the surface of the base steel plate 101, the zinc phosphate coating It is possible to easily form the zinc phosphate coating layer 103 in an island shape without making the entire treatment bath 20 extremely high temperature and in a short treatment time without impairing the productivity.
- the steam temperature is preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
- the steam temperature is preferably 200 ° C. or lower.
- the zinc phosphate coating per side 1.5g / m 2 ⁇ 15.0g / m 2 to the steel strip when exposed to steam on the surface of the base steel sheet 101 in the zinc phosphate treatment bath 20 is formed in an island shape so as The reason is not clear.
- the growth of the zinc phosphate crystal from a part of the growth point of the zinc phosphate crystal was inhibited, and the zinc phosphate film was formed in an island shape, whereas it was formed in an island shape.
- the zinc phosphate crystal rises to 100 ° C. or more and is activated by steam, and the growth thereof is further promoted by contact with the zinc phosphate treatment solution in the zinc phosphate treatment bath 20, and 1.5 g per side. It is estimated that a zinc phosphate film of / m 2 to 15.0 g / m 2 can be formed in an island shape.
- apparatus for forming a single-sided per 1.5g / m 2 ⁇ 15.0g / m zinc phosphate coating layer 103 of 2 into an island shape is not particularly limited.
- a type in which steam is directly applied to the base steel plate 101 or a type in which steam is directly applied to the base steel plate 101 after mixing with the zinc phosphate treatment liquid may be used.
- the steam generated from the heater 21 installed on the wall surface of the zinc phosphate treatment bath 20 may be stirred by the stirrer 22 so that the steam is applied to the base steel plate 101 simultaneously with the zinc phosphate treatment liquid.
- the zinc phosphate coating layer 103 can be formed into an island shape, but the maximum amount of the zinc phosphate coating layer 103 deposited by spraying steam is used. Is about 15.0 g / m 2 .
- the lubricating coating layer 105 makes it possible to reliably adhere the base steel sheet 101, a high surface Even in the molding process under pressure, the zinc phosphate coating layer 103 does not disappear, and the lubricating coating layer 105 can be more reliably held until the final step of the molding process.
- the average particle size of the zinc phosphate crystals constituting the zinc phosphate coating layer 103 and the average particle size of the polymer wax contained in the lubricating coating layer 105 are determined by a field emission scanning electron microscope (Field Emission Scanning Microscope: FE-SEM) can be used to measure by a known measuring method such as observing the steel sheet surface at a low acceleration voltage.
- FE-SEM Field Emission Scanning Microscope
- the adhesion amount per one side of the zinc phosphate coating layer 103 and the lubricating coating layer 105 can be measured by a known measuring method such as a gravimetric method.
- the thickness of the zinc phosphate coating layer 103 and the lubricating coating layer 105 can be measured by observing the cross section of the surface-treated steel strip using an electron microscope such as SEM. Can also be measured by the following method. First, components (for example, Si) and zinc phosphate crystal component of the surface of the surface-treated steel strip 10 are grown along the depth direction from the surface using a glow discharge emission spectroscopy (GDS). The emission spectrum intensity of (for example, Zn) is measured. By such measurement, two peaks corresponding to each component can be obtained in the emission spectrum.
- the thickness corresponding to the 50% value of each of the peak intensities of the two components Si is a 50% value on the base steel plate side, and Zn is a 50% value on the surface layer side of the steel strip
- the thickness can be 105.
- the surface of the surface-treated steel strip 10 is observed with an electron microscope such as SEM, and the zinc phosphate crystals detected in the field of view are detected.
- the area can be obtained by specifying the area by a known method.
- the static friction coefficient of the lubricating coating layer 105 can be measured by various test methods such as a round bead pull-out test described in detail below.
- FIG. 4 is a flowchart showing an example of the flow of the method for manufacturing the surface-treated steel strip 10 according to the present embodiment.
- pretreatment such as degreasing and cleaning is performed on the steel strip around which the predetermined base steel plate 101 is wound up, as necessary. (Preprocessing step S101).
- the surface of the base steel plate 101 is tempered with a surface conditioner containing titanium colloid (tempering step S103).
- a surface conditioner containing titanium colloid adheres to the surface of the base steel plate 101.
- needle-like crystals of zinc phosphate are deposited on the surface of the base steel sheet 101 after the surface tempering by the method described above (zinc phosphate coating layer forming step S105).
- needle-like crystals of zinc phosphate are deposited in the form of islands on the surface of the base steel plate 101 to form the zinc phosphate coating layer 103.
- the zinc phosphate coating layer 103 can be suitably formed in an island shape by depositing zinc phosphate using the apparatus shown in FIGS. 3A and 3B.
- a lubricating coating agent is applied on the base steel plate 101 and the zinc phosphate coating layer 103 and dried under appropriate drying conditions to form the lubricating coating layer 105 (lubricating coating layer forming step S107).
- the surface-treated steel strip 10 as shown to FIG. 2A and 2B will be manufactured.
- post-treatment step S109 After, it is possible to carry out a known post-treatment on the manufactured surface-treated steel strip 10 as necessary (post-treatment step S109).
- the surface-treated steel strip and the method for producing the surface-treated steel strip according to the present invention will be specifically described with reference to Examples and Comparative Examples.
- the Example shown below is an example to the last of the manufacturing method of the surface treatment steel strip and surface treatment steel strip which concern on this invention, Comprising:
- the manufacturing method of the surface treatment steel strip and surface treatment steel strip which concerns on this invention is the following It is not limited to the example shown in.
- the description “%” means “% by mass” unless otherwise specified.
- the amount of adhesion means the amount of adhesion per one side.
- Zinc phosphate treatment of steel plate Zinc phosphate treatment by immersion treatment on both sides of a cut plate (300 mm x 300 mm) of SPH590 steel plate (hot rolled steel plate with tensile strength of 590 MPa or more) with a thickness of 3.2 mm went.
- steam generated from a heater installed on the wall surface of the apparatus is stirred with a stirrer on both surfaces of the steel plate during the dipping process, so that steam at 100 ° C. to 120 ° C. is applied for 5 seconds. I was hit.
- the amount of zinc phosphate crystals attached was adjusted by changing the immersion time between 5 seconds and 120 seconds, and the zinc phosphate-treated steel sheets shown in Table 1 were obtained.
- the amount of zinc phosphate crystals deposited was determined by the change in the mass of the steel sheet before and after the zinc phosphate treatment.
- Procedure Procedure (1) Apply general rust preventive oil to both sides of the sample so that the adhesion amount is 1.5 g / m 2 .
- Step (3) Repeat the process for the L-shaped sample ironed in step (2) until the die galling occurs on the steel sheet surface while further reducing the clearance at -0.25 pitch.
- Procedure (1) Apply general rust preventive oil to both sides of the sample so that the adhesion amount is 1.5 g / m 2 .
- Procedure (2) Both sides of the steel plate are pressed with a round bead (R5) and sandwiched with a load of 1 [kN], the steel plate is pulled out, and the static friction coefficient when it is pulled out is calculated.
- Evaluation results Table 1 above shows the evaluation results when lubricating coatings were formed on various zinc phosphate-treated steel sheets with different zinc phosphate crystal adhesion amounts.
- No. 1 has a preferable zinc phosphate coating layer and a lubricating coating layer and satisfies the exposed area ratio of zinc phosphate crystals.
- Nos. 2-4, 6-10, 12-15, 17-18, and 20 exhibited sufficient performance to achieve both mold galling resistance and roll slip resistance.
- NO. Nos. 1 and 19 had low coefficient of static friction, resulting in inferior mold galling resistance and roll slip resistance. Even if the adhesion amount of the zinc phosphate coating layer and the upper lubricating coating satisfy the preferable conditions, the average particle size in the major axis direction or the average particle size in the minor axis direction of the zinc phosphate crystal is outside the scope of the present invention. . Nos. 11, 24, 29, 30, and 31 had low coefficient of static friction and poor roll slip resistance. No. with many zinc phosphate crystals exposed. No. 5 resulted in inferior mold galling resistance because the lubricating film itself was small. NO. No. 16 had a small exposed area ratio of zinc phosphate crystals and a static friction coefficient of not more than 0.10.
- the comparative example (No. 30) shown in FIG. 7 has an adhesion amount of 1.9 g / m 2 of an island-like zinc phosphate coating layer, a major axis of 100 ⁇ m, a minor axis of 20 ⁇ m, and an adhesion amount of a lubricating coating layer (chemical 2-1) of 3.3 g. / m 2 , the zinc phosphate exposed area ratio is 10%, and in the comparative example (No. 31) shown in FIG.
- the deposited amount of the island-like zinc phosphate coating layer is 4.5 g / m 2
- the major axis is 200 ⁇ m
- the minor axis is 50 ⁇ m.
- the adhesion amount of the lubricating film layer (chemical solution 2-1) is 3.3 g / m 2
- the zinc phosphate exposed area ratio is 24%.
- the present invention example (No. 14) shown in FIG. 9 has an adhesion amount of island-like zinc phosphate coating layer of 8.0 g / m 2 , major axis of 64 ⁇ m, minor axis of 7 ⁇ m, and adhesion amount of lubricating coating layer (chemical 2-1) 3.7.
- the example of the present invention shown in FIG. 10 is an adhesion amount of island-like zinc phosphate coating layer of 8.0 g / m 2 , major axis 31 ⁇ m, minor axis 4 ⁇ m, lubricating coating
- the adhesion amount of the layer (chemical solution 2-1) is 3.7 g / m 2
- the zinc phosphate exposed area ratio is 60%.
- the zinc phosphate crystals are made more acicular (sharp).
- the bulkiness of the zinc phosphate crystals was increased, and many heads of the zinc phosphate crystals appeared from the lubricating coating layer.
- the coefficient of static friction increased.
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Abstract
Description
(A)母材である素地鋼鈑の表面に潤滑皮膜層を形成する前に、素地鋼板の表面にリン酸亜鉛結晶を島状に析出させる。このとき、リン酸亜鉛結晶の一部が潤滑皮膜層の表面から露出(突出)するように、リン酸亜鉛結晶の形状を制御する。これにより、最終的に、リン酸亜鉛結晶による凹凸が潤滑皮膜層の表面から露出(突出)した形態の表面処理鋼帯を得る。
(B)リン酸亜鉛結晶は潤滑性を有しないため、リン酸亜鉛結晶による凹凸が潤滑皮膜層の表面に形成された表面処理鋼帯の静止摩擦係数は、潤滑皮膜層単体の静止摩擦係数よりも大きくなる。表面処理鋼帯の静止摩擦係数は、潤滑皮膜層の表面から露出しているリン酸亜鉛結晶の面積率(以下、露出面積率と称す場合がある)と相関関係にある。すなわち、リン酸亜鉛結晶の露出面積率を制御することにより、表面処理鋼帯の静止摩擦係数を制御することが可能である。
(C)表面処理鋼帯を一対のピンチロールの間に挟んだ状態で搬送するとき、表面処理鋼帯にはピンチロールによって圧力(面圧)が加わるが、その圧力は潤滑皮膜層から露出したリン酸亜鉛結晶を潰すほど高くない。言い換えれば、ピンチロールによって潤滑皮膜層の表面の凹凸は平坦化されない。そのため、ピンチロール下での表面処理鋼帯の静止摩擦係数は大きな値のまま維持される。その結果、ピンチロール下での表面処理鋼帯の滑りが抑制されるので、ピンチロール下(低面圧下)での耐ロール滑り性が向上する。
(D)一方、ピンチロールの下流側に設置されたプレス装置により表面処理鋼帯に多段プレス成形を施すとき、表面処理鋼帯に非常に大きな圧力(面圧)が加わるため、潤滑皮膜層から露出したリン酸亜鉛結晶が潰れて、潤滑皮膜層の表面の凹凸が平坦化される。これにより、プレス装置下での表面処理鋼帯の静止摩擦係数は、潤滑皮膜層が本来有する静止摩擦係数となる。その結果、プレス装置下では表面処理鋼帯の本来の潤滑性(摺動性)が発揮されるので、プレス装置下(高面圧下)での耐型かじり性が向上する。
本発明は、上記の知見に基づいて完成されたものであり、その要旨は以下の通りである。
素地鋼板と、
前記素地鋼板の表面に島状に形成された、針状のリン酸亜鉛結晶からなるリン酸亜鉛皮膜層と、
前記素地鋼板の表面と前記リン酸亜鉛皮膜層の一部とを被覆した、潤滑成分を少なくとも含む潤滑皮膜層と、
を備え、
前記潤滑皮膜層の表面に露出している前記リン酸亜鉛結晶の面積率は、25%~90%である、表面処理鋼帯。
[2]
前記リン酸亜鉛結晶は、長軸方向の平均粒径が25μm~70μmであり、短軸方向の平均粒径が3μm~10μmである、[1]に記載の表面処理鋼帯。
[3]
前記リン酸亜鉛皮膜層の付着量は、片面当たり1.5g/m2~15.0g/m2である、[1]または[2]の何れか1項に記載の表面処理鋼帯。
[4]
前記潤滑皮膜層の付着量は、片面当たり1.0g/m2~12.0g/m2である、請求項1~3の何れか1項に記載の表面処理鋼帯。
[5]
前記潤滑皮膜層は、SiO2/M2O(Mは、アルカリ金属である。)で表わされるモル比が2~5であるケイ酸アルカリ金属塩と、平均粒径が0.1μm~3.0μmであるポリエチレンワックス又はポリプロピレンワックスの少なくとも何れか一方からなる高分子ワックスと、を含み、
前記潤滑皮膜層の全固形分質量に対して、前記ケイ酸アルカリ金属塩の固形分含有量は60質量%~90質量%であり、前記高分子ワックスの固形分含有量は、5質量%~40質量%である、[1]~[4]の何れか1項に記載の表面処理鋼帯。
[6]
チタンコロイドを含む表面調整剤を利用して素地鋼板の表面の調質を行う調質ステップと、
表面調質の施された前記素地鋼板の表面にリン酸亜鉛の針状結晶を島状に成長させて、当該素地鋼板の表面にリン酸亜鉛皮膜層を形成するリン酸亜鉛皮膜層形成ステップと、
潤滑成分を少なくとも含む潤滑処理剤を、付着量が片面当たり1.0g/m2~12.0g/m2となるように前記素地鋼板及び前記リン酸亜鉛皮膜層の表面に塗布して、潤滑皮膜層を形成し、前記潤滑皮膜層の表面に露出している前記リン酸亜鉛結晶の面積率を、25%~90%とする潤滑皮膜層形成ステップと、
を含む、表面処理鋼帯の製造方法。
[7]
前記リン酸亜鉛皮膜層形成ステップにおいて、前記素地鋼板を加熱する、[6]に記載の表面処理鋼帯の製造方法。
[8]
前記素地鋼板を蒸気をあてて加熱する、[7]に記載の表面処理鋼帯の製造方法。
まず、図1~図2Bを参照しながら、本発明の一実施形態に係る表面処理鋼帯について、詳細に説明する。図1は、本実施形態に係る表面処理鋼帯について説明するための説明図であり、図2A及び図2Bは、本実施形態に係る表面処理鋼帯の構成を模式的に示した説明図である。
素地鋼板101は、表面処理鋼帯10の母材として用いられる。本実施形態に係る素地鋼板101については特に限定されるものではなく、後段の多段塑性加工処理を経て製造される目的物に求める特性が実現可能な公知の鋼板を使用することが可能である。かかる公知の鋼板の製造方法や材質についても特に限定されるものではなく、通常の鋳片製造工程から、熱間圧延、酸洗、冷間圧延、焼鈍、調質圧延等といった公知の各種工程を適宜経て製造されたものでよい。また、かかる素地鋼板101は、炭素鋼板のみならず、ステンレス鋼板や高合金鋼板などの特殊鋼板であってもよいことは言うまでもない。
リン酸亜鉛皮膜層103は、素地鋼板101と潤滑皮膜層105との密着性を高める役割を担う。このリン酸亜鉛皮膜層103は、素地鋼板101の表面に化学反応で析出したリン酸亜鉛の針状結晶で構成されている、針状のリン酸亜鉛結晶の集合体である。析出したリン酸亜鉛の針状結晶は、図2A及び図2Bに模式的に示したように、素地鋼板101の表面を完全に被覆しているわけではなく、素地鋼板101の表面の一部は、リン酸亜鉛の結晶で被覆されずに残っている状態となっている。その結果、リン酸亜鉛の針状結晶は、素地鋼板101の表面に島状に分布することとなり、リン酸亜鉛の針状結晶が存在していない素地鋼板101の表面は、平坦部として存在することとなる。なおリン酸亜鉛皮膜層103は、素地鋼板101の表面において複数の箇所に分割されて、互いに独立した状態で現れる。本発明では、このように素地鋼板101の表面において複数の箇所に分割されて、互いに独立した状態で現れるリン酸亜鉛皮膜層103の状態を、「島状」と呼ぶ。
潤滑皮膜層105は、図2A及び図2Bに模式的に示したように、素地鋼板101の表面上に位置して、素地鋼板101の表面とリン酸亜鉛皮膜層103の少なくとも一部とを被覆するとともに、リン酸亜鉛結晶の少なくとも一部が表面に露出している層である。この潤滑皮膜層105は、潤滑成分を少なくとも含む層であり、好ましくは、バインダー成分と潤滑成分とからなる。
本実施形態に係る潤滑皮膜層105では、図2A及び図2Bに示したように、リン酸亜鉛結晶(リン酸亜鉛皮膜層103)の一部が潤滑皮膜層105の表面の一部に露出していることにより、潤滑皮膜層105の静止摩擦係数の低下が程良く抑制される。その結果、鋼帯から鋼板を巻き解く際の耐ロール滑り性をも実現することが可能となる。
続いて、本実施形態に係る表面処理鋼帯10で実現される各種の物性値の測定方法について、簡単に説明する。
続いて、図4を参照しながら、本実施形態に係る表面処理鋼帯10の製造方法について説明する。図4は、本実施形態に係る表面処理鋼帯10の製造方法の流れの一例を示したフローチャートである。
板厚3.2mmのSPH590鋼板(引張強度590MPa以上の熱延鋼板)の切り板(300mm×300mm)の両面に対して、浸漬処理にてリン酸亜鉛処理を行った。その際に本実施例に対しては浸漬処理中に鋼板の両面に対して、装置の壁面に設置したヒーターより発生する蒸気を撹拌機で撹拌することにより100℃~120℃の蒸気を5秒間あてた。浸漬時間を5秒~120秒の間で変化させてリン酸亜鉛結晶の付着量を調整し、表1に示すリン酸亜鉛処理鋼板を得た。リン酸亜鉛結晶の付着量は、リン酸亜鉛処理前後の鋼板の質量変化により求めた。
下記に示すバインダー成分、潤滑成分及び極圧添加剤を純水(脱イオン水)に添加し、十分に撹拌して分散させ、純水で固形分量が20%になるように希釈して、塗布に用いる薬液を調整した。この薬液を、上記のリン酸亜鉛処理鋼板の表面にバーコーターにより片面ずつ塗布し、60℃で乾燥させて、潤滑皮膜を表面に形成し、潤滑処理鋼板を作成した。潤滑皮膜の付着量は、潤滑皮膜形成前後の鋼板の質量変化から算出した。
A)バインダー成分
・メタケイ酸ナトリウム(SiO2/Na2Oのモル比:4)
・アクリル系樹脂(モノマー組成:アクリル酸8%、メタクリル酸52%、アクリル酸ブチル40%)
B)潤滑成分
・有機高分子化合物:ポリエチレンワックス(分子量20000、平均粒径3μm)
・固体潤滑剤:二硫化モリブデン(平均粒径2μm)
・石けん:ステアリン酸ナトリウム
C)極圧添加剤
・亜リン酸エステル
D)固形分含有量
・潤滑皮膜層の全固形分量に対するメタケイ酸ナトリウムの固形分量:88%
・潤滑皮膜層の全固形分量に対するポリエチレンワックスの固形分量:5%
A)バインダー成分
・メタケイ酸ナトリウム(SiO2/Na2Oのモル比:5)
・アクリル系樹脂(モノマー組成:アクリル酸8%、メタクリル酸52%、アクリル酸ブチル40%)
B)潤滑成分
・有機高分子化合物:ポリエチレンワックス(分子量2000、平均粒径0.5μm)
・固体潤滑剤:二硫化モリブデン(平均粒径2μm)
・石けん:ステアリン酸ナトリウム
C)極圧添加剤
・亜リン酸エステル
D)固形分含有量
・潤滑皮膜層の全固形分量に対するメタケイ酸ナトリウムの固形分量:80%
・潤滑皮膜層の全固形分量に対するポリエチレンワックスの固形分量:5%
A)バインダー成分
・メタケイ酸ナトリウム(SiO2/Na2Oのモル比:2)
・アクリル系樹脂(モノマー組成:アクリル酸8%、メタクリル酸52%、アクリル酸ブチル40%)
B)潤滑成分
・有機高分子化合物:ポリエチレンワックス(分子量10000、平均粒径1.0μm)
・固体潤滑剤:二硫化モリブデン(平均粒径2μm)
・石けん:ステアリン酸ナトリウム
C)極圧添加剤
・亜リン酸エステル
D)固形分含有量
・潤滑皮膜層の全固形分量に対するメタケイ酸ナトリウムの固形分量:60%
・潤滑皮膜層の全固形分量に対するポリエチレンワックスの固形分量:30%
リン酸亜鉛処理後の鋼板表面を、加速電圧5kV、500倍の倍率でSEMにより観察した。表面に露出しているリン酸亜鉛結晶の面積率は、画像を2値化し、結晶部分の面積で算出した。また、表面に露出している結晶を4個以上の任意で選択して長軸と短軸の長さを測定し、平均結晶サイズを算出し、リン酸亜鉛の結晶サイズとした。
a-1)耐型かじり性
高面圧下での多段塑性加工を模擬するために、図5に概要を示すように、L字型プレス成形設備を使用し、潤滑処理鋼板のL曲げ加工サンプルの側面に対して下記の手順にて多段しごき加工を行い、その潤滑性能を評価した。この際、成形回数が2回以下で鋼板表面にかじりが発生する場合には、多段成形が出来ていないため、3回以上かじりが発生しない鋼板を合格とした。なお、2回以下でかじりが発生したものを×とし、3回以上かじりが発生しなかったものを○と表記した。
手順(1) 一般防錆油を、付着量が1.5g/m2となるように、サンプルの両面に塗布する。
手順(2) ポンチとダイのクリアランスを、板厚-0.25(板厚減少幅=0.15mm)になるようにセットして、サンプルに最初のしごき加工(L次成形)を実施する。
手順(3) 手順(2)でしごき加工したL字型サンプルに対し、クリアランスを更に-0.25ピッチで縮めながら、鋼板表面に型かじりが発生するまで繰り返し、型かじりが発生したしごき回数を求める。
高面圧下での耐ロール送り性を模擬するために、図6に概要を示すように丸型ビードで鋼板の表裏面を挟み、鋼板を引き抜く時の荷重から静止摩擦係数を算出した。静止摩擦係数が0.09以下では、鋼板を送り出すための力を加えることが出来ず、実ラインでの通板が困難であること、及び、静止摩擦係数が0.20超過では、鋼板を送り出すために要する力が大きくなりすぎて、実ラインでの通板が困難であること、をそれぞれ確認している。従って、静止摩擦係数が0.10以上0.20以下である鋼板を合格とした。なお、静止摩擦係数が当該範囲内を外れるものを×と表記し、当該範囲内にあるものを○と表記した。
手順(1) 一般防錆油を、付着量が1.5g/m2となるように、サンプルの両面に塗布する。
手順(2) 丸型ビード(R5)で鋼板の両面を押しつけて荷重1[kN]で挟み、鋼板を引き抜き、引き抜く際の静止摩擦係数を算出する。
上記表1は、リン酸亜鉛結晶の付着量が異なる各種のリン酸亜鉛処理鋼板に潤滑皮膜を形成した場合の評価結果を示したものである。
2 金型
10 表面処理鋼帯
20 リン酸亜鉛処理浴
21 ヒータ
22 攪拌機
101 素地鋼板
103 リン酸亜鉛皮膜層
105 潤滑皮膜層
Claims (8)
- 素地鋼板と、
前記素地鋼板の表面に島状に形成された、針状のリン酸亜鉛結晶からなるリン酸亜鉛皮膜層と、
前記素地鋼板の表面と前記リン酸亜鉛皮膜層の一部とを被覆した、潤滑成分を少なくとも含む潤滑皮膜層と、
を備え、
前記潤滑皮膜層の表面に露出している前記リン酸亜鉛結晶の面積率は、25%~90%である、表面処理鋼帯。 - 前記リン酸亜鉛結晶は、長軸方向の平均粒径が25μm~70μmであり、短軸方向の平均粒径が3μm~10μmである、請求項1に記載の表面処理鋼帯。
- 前記リン酸亜鉛皮膜層の付着量は、片面当たり1.5g/m2~15.0g/m2である、請求項1または2の何れか1項に記載の表面処理鋼帯。
- 前記潤滑皮膜層の付着量は、片面当たり1.0g/m2~12.0g/m2である、請求項1~3の何れか1項に記載の表面処理鋼帯。
- 前記潤滑皮膜層は、SiO2/M2O(Mは、アルカリ金属である。)で表わされるモル比が2~5であるケイ酸アルカリ金属塩と、平均粒径が0.1μm~3.0μmであるポリエチレンワックス又はポリプロピレンワックスの少なくとも何れか一方からなる高分子ワックスと、を含み、
前記潤滑皮膜層の全固形分質量に対して、前記ケイ酸アルカリ金属塩の固形分含有量は60質量%~90質量%であり、前記高分子ワックスの固形分含有量は、5質量%~40質量%である、請求項1~4の何れか1項に記載の表面処理鋼帯。 - チタンコロイドを含む表面調整剤を利用して素地鋼板の表面の調質を行う調質ステップと、
表面調質の施された前記素地鋼板の表面にリン酸亜鉛の針状結晶を島状に成長させて、当該素地鋼板の表面にリン酸亜鉛皮膜層を形成するリン酸亜鉛皮膜層形成ステップと、
潤滑成分を少なくとも含む潤滑処理剤を、付着量が片面当たり1.0g/m2~12.0g/m2となるように前記素地鋼板及び前記リン酸亜鉛皮膜層の表面に塗布して、潤滑皮膜層を形成し、前記潤滑皮膜層の表面に露出している前記リン酸亜鉛結晶の面積率を、25%~90%とする潤滑皮膜層形成ステップと、
を含む、表面処理鋼帯の製造方法。 - 前記リン酸亜鉛皮膜層形成ステップにおいて、前記素地鋼板を加熱する、請求項6記載の表面処理鋼帯の製造方法。
- 前記素地鋼板を蒸気をあてて加熱する、請求項7に記載の表面処理鋼帯の製造方法。
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KR101697891B1 (ko) * | 2013-02-08 | 2017-01-18 | 제이에프이 스틸 가부시키가이샤 | 아연계 도금 강판용 표면 처리액과 표면 처리 피막 부착 아연계 도금 강판 및 그 제조 방법 |
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2017
- 2017-04-13 TW TW106112376A patent/TWI629377B/zh not_active IP Right Cessation
- 2017-04-13 US US16/093,369 patent/US20190211456A1/en not_active Abandoned
- 2017-04-13 CN CN201780023567.2A patent/CN109072447B/zh not_active Expired - Fee Related
- 2017-04-13 KR KR1020187031755A patent/KR102133749B1/ko active IP Right Grant
- 2017-04-13 WO PCT/JP2017/015160 patent/WO2017179665A1/ja active Application Filing
- 2017-04-13 EP EP17782478.6A patent/EP3444378A4/en not_active Withdrawn
- 2017-04-13 JP JP2017533369A patent/JP6246984B1/ja active Active
- 2017-04-13 MX MX2018012427A patent/MX2018012427A/es unknown
- 2017-04-13 BR BR112018070898A patent/BR112018070898A2/pt not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2005290552A (ja) * | 2004-03-08 | 2005-10-20 | Nisshin Steel Co Ltd | 耐食性,塗膜密着性,接着性に優れた化成処理鋼板 |
JP2013104125A (ja) * | 2011-11-16 | 2013-05-30 | Nippon Steel & Sumitomo Metal Corp | 高潤滑表面処理鋼板 |
Non-Patent Citations (1)
Title |
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See also references of EP3444378A4 * |
Also Published As
Publication number | Publication date |
---|---|
TWI629377B (zh) | 2018-07-11 |
EP3444378A1 (en) | 2019-02-20 |
EP3444378A4 (en) | 2019-12-18 |
CN109072447A (zh) | 2018-12-21 |
KR102133749B1 (ko) | 2020-07-14 |
US20190211456A1 (en) | 2019-07-11 |
JPWO2017179665A1 (ja) | 2018-04-19 |
TW201739936A (zh) | 2017-11-16 |
CN109072447B (zh) | 2020-09-01 |
KR20180131597A (ko) | 2018-12-10 |
MX2018012427A (es) | 2019-03-01 |
BR112018070898A2 (pt) | 2019-02-05 |
JP6246984B1 (ja) | 2017-12-13 |
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