WO2015115469A1 - 表面処理鋼板 - Google Patents
表面処理鋼板 Download PDFInfo
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- WO2015115469A1 WO2015115469A1 PCT/JP2015/052331 JP2015052331W WO2015115469A1 WO 2015115469 A1 WO2015115469 A1 WO 2015115469A1 JP 2015052331 W JP2015052331 W JP 2015052331W WO 2015115469 A1 WO2015115469 A1 WO 2015115469A1
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- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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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
- C23C28/30—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
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- 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
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/10—Electrophoretic coating characterised by the process characterised by the additives used
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/714—Inert, i.e. inert to chemical degradation, corrosion
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
Definitions
- the present invention relates to a surface-treated steel sheet.
- a Zn-plated steel plate has a steel plate (hereinafter referred to as a base material steel plate) as a base material and a Zn plating layer formed on the surface of the base material steel plate.
- chemical conversion treatment is often performed on the surface of the Zn-plated layer for the purpose of improving corrosion resistance and gloss.
- the corrosion of the Zn-plated steel sheet subjected to the chemical conversion treatment includes the following first to fourth stages.
- white rust which is a corrosion product of Zn
- Zn around the corroded portion is dissolved before Fe in the base steel plate, thereby protecting the base steel plate electrochemically (sacrificial corrosion protection).
- Patent Literature 1 and Non-Patent Literature 1 listed below disclose an electrical Zn-plated steel plate in which Zn is plated on a base steel plate surface by an electroplating method.
- an electro-Zn-plated steel sheet as in Patent Literature 1 and Non-Patent Literature 1, emphasis is often placed on preventing the occurrence of white rust.
- Patent Document 2 discloses a surface-treated steel sheet for electronic device parts.
- Ni and Zn are plated on one side of the base steel sheet, and Ni, Sn, and Zn are plated on the other side.
- the corrosion resistance is improved by performing alloying treatment by heating after the base steel sheet is plated with the above metal.
- the occurrence of white rust in a Zn-plated steel sheet whose surface has been subjected to chemical conversion treatment is determined by the interaction between Zn and the chemical substance subjected to chemical conversion treatment. Therefore, it is considered that there is no relationship between the occurrence of white rust and the amount of deposited Zn plating in the Zn-plated steel sheet that has been subjected to chemical conversion treatment.
- the amount of deposited Zn plating is small, white rust occurs earlier than when the amount of deposited Zn plating is large.
- the adhesion amount of Zn plating is 2 g / m 2 or less
- Zn precipitates in a granular form on the base material steel plate, so that a portion not covered with Zn occurs on the surface of the base material steel plate.
- the base material steel plate and the chemical conversion treatment layer are in contact. Therefore, corrosion advances by interaction with a base material steel plate and a chemical conversion treatment layer, and a chemical conversion treatment layer is destroyed. Thereby, since a Zn plating layer is no longer covered with a chemical conversion treatment layer, white rust is formed.
- This invention is made
- a surface-treated steel sheet according to an aspect of the present invention includes a base steel sheet, a surface treated layer formed on at least one side of the base steel sheet and having an oxide layer and a metal layer, and the surface treated layer. And a chemical conversion treatment layer formed on the surface.
- the surface treatment layer containing a Zn in the deposited amount 0.30 ⁇ 2.00g / m 2, and Ni deposition amount is equal to or less than the amount of adhered and the Zn in 0.03 ⁇ 2.00g / m 2
- Fe atoms by performing glow discharge emission analysis on a range in which the surface of the chemical conversion treatment layer is a measurement start position and the measurement end position is 1 ⁇ m in the depth direction from the surface of the surface treatment layer, Fe atoms, When the distribution curves of the emission intensity of Zn atoms and Ni atoms are respectively obtained, the emission intensity of the Fe atoms is 20% or less of the maximum emission intensity of the Fe atoms at the interface between the oxide layer and the metal layer. is there.
- the emission intensity of the Ni atoms is 20% or less of the maximum emission intensity of the Ni atoms.
- the second range which is equal to or greater than% has an overlap.
- the Zn adhesion amount in the surface treatment layer is 0.80 to 1.20 g / m 2
- the Ni adhesion amount in the surface treatment layer is It may be not less than 0.07 g / m 2 and not more than half of the deposited amount of Zn.
- the surface treatment layer may further contain Sn of 10% or less of the amount of Zn deposited.
- an average thickness of the surface-treated layer may be 0.30 ⁇ m or less.
- the surface-treated steel sheet of the present embodiment can be used for applications that are required not to generate white rust.
- it can be used for a back plate of home appliances, parts of home appliances, bearing covers, and the like.
- the surface-treated steel sheet 1 of this embodiment is formed on the surface of the base material steel plate 2, the surface treatment layer 3 formed on at least one side of the base material steel plate 2, and the surface treatment layer 3. And a chemical conversion treatment layer 4.
- the surface treatment layer 3 is a plating layer containing Zn and Ni.
- the adhesion amount of Zn in the surface treatment layer 3 is 0.30 to 2.00 g / m 2
- the adhesion amount of Ni is 0.03 to 2.00 g / m 2 .
- the adhesion amount of Ni is below the adhesion amount of Zn.
- the surface treatment layer 3 has an oxide layer on the surface side and a metal layer on the base steel plate 2 side. Zn and Ni are alloyed by an alloying process to be described later, and a Zn—Ni alloy layer is formed in the metal layer of the surface treatment layer 3. In the surface treatment layer 3, the Zn concentration varies depending on the depth from the surface of the surface treatment layer 3. In the metal layer of the surface treatment layer 3, the Zn concentration is maximized.
- the adhesion amount of Zn plating is 3 g / m 2
- the variation in the corrosion resistance of the surface-treated steel sheet is large. Therefore, the effect of this embodiment can be confirmed even when the Zn plating adhesion amount is 3 g / m 2 .
- the effect of the present embodiment is remarkably exhibited when the amount of deposited Zn plating is 2 g / m 2 or less.
- the adhesion amount of Zn plating is 1.2 g / m 2 or less, excellent corrosion resistance can be obtained as compared with the case where only the surface of the base steel plate 2 is plated with Zn.
- the amount of Zn plating attached is preferably 0.5 g / m 2 or more, and more preferably 0.8 g / m 2 or more.
- Ni contained in the surface treatment layer 3 has an effect of suppressing corrosion of the surface treatment layer 3. Therefore, when the surface treatment layer 3 contains Ni, the corrosion resistance of the surface-treated steel sheet 1 is improved as compared with the case where the surface treatment layer 3 is made of only Zn and the case where the surface treatment layer 3 is made of only an Fe—Zn alloy. To do. However, when the adhesion amount of Ni plating is too large, since the ionization tendency of the surface treatment layer 3 is lower than that of Fe, the sacrificial anticorrosive effect of Zn is lost. On the other hand, when the adhesion amount of Ni plating is too small, the corrosion suppressing effect by the surface treatment layer 3 is reduced, and Fe in the base steel sheet 2 is excessively diffused.
- the amount of Ni plating is 0.03 to 2.00 g / m 2 .
- adhesion of Ni plating is preferably from 0.05 g / m 2 or more, 0.07 g / m 2 or more is more preferable.
- Zn and Ni contained in the surface treatment layer 3 are alloyed by heat treatment.
- the heat treatment if the amount of Ni plating on the surface treatment layer 3 is large, it may not be alloyed with Zn. Even when Zn and Ni are alloyed, the proportion of Ni in the surface treatment layer 3 is increased. In such a case, since the ionization tendency of the surface treatment layer 3 is lower than the ionization tendency of the base steel plate 2, the sacrificial anticorrosive effect of Zn cannot be obtained. Therefore, the base material steel plate 2 is corroded and the corrosion resistance is lowered.
- the amount of Ni plating attached to the surface treatment layer 3 is set to be equal to or less than the amount of Zn plating attached. Particularly stable corrosion resistance is obtained when the amount of Ni plating is less than half of the amount of Zn plating.
- Ni when Ni is present alone, corrosion of the surface treatment layer 3 may be promoted, so Ni needs to be included in the surface treatment layer 3 as an alloy.
- the surface treatment layer 3 may contain Sn in addition to Ni and Zn.
- Sn has an effect of suppressing corrosion of the surface treatment layer 3. However, if Sn is present alone, corrosion may be accelerated. Further, when Sn is contained in the surface treatment layer 3 as an alloy with Zn, the Zn—Sn alloy crystal is less likely to grow than the Zn crystal, so that the coverage of the base steel plate 2 is enhanced. In addition, since a Zn—Sn alloy has a lower melting point than Zn, it is easily alloyed with Ni. For the reasons described above, Sn needs to be included in the surface treatment layer 3 as an alloy with another metal.
- the adhesion amount of Sn plating is 10% or less of the adhesion amount of Zn plating.
- a more preferable amount of Sn plating is 0.05 g / m 2 or less.
- the preferable adhesion amount of Sn plating is 0.04 g / m 2 or less.
- An even more preferable amount of Sn plating is 0.03 g / m 2 or less.
- the surface-treated layer 3 when the formation of the Zn—Ni alloy layer is insufficient, the surface-treated layer 3 cannot sufficiently cover the base material steel sheet 2, so that sufficient corrosion resistance cannot be obtained.
- the concentration of Fe and Ni in the vicinity of the surface of the surface treatment layer 3 is increased. In such a case, since the sacrificial anticorrosive effect of Zn cannot be obtained, sufficient corrosion resistance cannot be obtained.
- the well-known chemical conversion treatment layer 4 for Zn plating can be utilized.
- the chemical conversion treatment layer 4 in order to improve the coverage of the base material steel plate 2 and the surface treatment layer 3 by the chemical conversion treatment layer 4, the chemical conversion treatment layer 4 can contain a resin such as polyester, polyurethane, epoxy, phenol, and modified polyolefin.
- the chemical conversion treatment layer 4 can contain silica, silane oligomer, organic titanate, tannate, phosphate, vanadyl compound, guanidyl compound, and the like.
- the chemical conversion treatment layer 4 may include a pigment and a dye.
- the chemical conversion treatment layer 4 In order to improve the slidability of the surface-treated steel sheet 1, the chemical conversion treatment layer 4 can contain a wax or the like.
- the alloying state of Zn and Ni in the surface treatment layer 3 can be confirmed by glow discharge emission analysis (GDS). Specifically, measurement is performed from the surface of the chemical conversion treatment layer 4 toward the inside of the base steel plate 2 by GDS, and a depth of 1 ⁇ m from the surface of the surface treatment layer 3 (interface between the surface treatment layer 3 and the chemical conversion treatment layer 4). Analyze to the position.
- GDS glow discharge emission analysis
- the interface between the surface treatment layer 3 and the chemical conversion treatment layer 4 and the interface between the oxide layer of the surface treatment layer 3 and the metal layer of the surface treatment layer 3 are determined based on the GDS measurement results as follows.
- FIG. 2 shows measurement result 5 of the emission intensity of Zn atoms by GDS.
- the horizontal axis of FIG. 2 is the measurement depth (depth) from the surface of the chemical conversion treatment layer 4.
- the vertical axis in FIG. 2 represents the emission intensity of Zn atoms emitted from the sample by sputtering the sample in a glow discharge environment.
- the maximum emission intensity of Zn atoms in the measurement range is X
- the minimum emission intensity of Zn atoms in the measurement range is Y
- the depth position where the emission intensity (Z) of the Zn atoms is represented by the following formula (1):
- An interface 6 between the surface treatment layer 3 and the chemical conversion treatment layer 4 is used.
- Z (XY) ⁇ 0.25 + Y (1)
- the interface between the oxide layer of the surface treatment layer 3 and the metal layer of the surface treatment layer 3 is determined based on the measurement result of the emission intensity of oxygen atoms using GDS.
- the method for determining the interface between the oxide layer of the surface treatment layer 3 and the metal layer of the surface treatment layer 3 is either the maximum emission intensity of oxygen atoms in the chemical conversion treatment layer 4 or the maximum emission intensity of oxygen atoms in the surface treatment layer 3. It depends on whether it is expensive.
- FIG. 3 shows a measurement result 7 of the emission intensity of oxygen atoms by GDS when the maximum emission intensity of oxygen atoms in the surface treatment layer 3 is higher than the maximum emission intensity of oxygen atoms in the chemical conversion treatment layer 4.
- FIG. 4 shows measurement results 9 of the emission intensity of oxygen atoms by GDS and Zn when the maximum emission intensity of oxygen atoms in the chemical conversion treatment layer 4 is higher than the maximum emission intensity of oxygen atoms in the oxide layer of the surface treatment layer 3. Measurement result 10 of the emission intensity of atoms is shown.
- the diffusion state of Fe and Ni in the vicinity of the surface of the surface treatment layer 3 is determined based on the measurement result of the emission intensity of Fe atoms and Ni atoms using GDS.
- the emission intensity of Fe atoms at the interface between the oxide layer of the surface treatment layer 3 and the metal layer of the surface treatment layer 3 is the maximum emission intensity of Fe atoms in the measurement range. 20% or less.
- Ni is also the same as Fe, and when alloying is suitably performed, the emission intensity of Ni atoms at the interface between the oxide layer of the surface treatment layer 3 and the metal layer of the surface treatment layer 3 is measured. It is 20% or less of the maximum emission intensity of Ni atoms in the range.
- FIG. 5 shows the measurement result 12 of the emission intensity of Zn atoms and the emission intensity of Ni atoms when the surface-treated steel sheet of the present invention was analyzed by GDS from the surface when the alloying of Zn and Ni was sufficiently performed. It is the schematic diagram which showed the measurement result 13.
- FIG. FIG. 5 shows the measurement result 12 of the emission intensity of Zn atoms and the emission intensity of Ni atoms when the surface-treated steel sheet of the present invention was analyzed by GDS from the surface when the alloying of Zn and Ni was sufficiently performed. It is the schematic diagram which showed the measurement result 13.
- the fact that the emission intensity of Zn atoms and the emission intensity of Ni atoms overlap each other at 60% or more of the maximum value As shown in FIG. 5, the fact that the light emission intensity of Zn atoms and the light emission intensity of Ni atoms have an overlap at a portion of 60% or more of the maximum value means that the Zn—Ni alloy layer is formed by thermal diffusion. means.
- the measurement result 12 of the emission intensity of Zn atoms is 60% or more of the maximum value in the depth position range from x 1 to x 3 .
- the measurement result 13 of the emission intensity of Ni atoms is not less than 60% of the maximum value. That is, in the case of FIG. 5, the measurement results of the emission intensity of Zn atoms and Ni atoms are both 60% or more of the respective maximum values in the range of the depth position from x 2 to x 3 .
- the measurement result 14 of the emission intensity of Zn atoms is 60% or more of the maximum value in the range of the depth position from x 5 to x 6 .
- the measurement results 15 of the emission intensity of Ni atoms is not less than 60% of the maximum value. That is, in the case of FIG. 6, the depth position where the measurement result 14 of the Zn atom emission intensity is 60% or more of the maximum value and the measurement result 15 of the Ni atom emission intensity 15 is 60% or more of the maximum value. It does not overlap with the depth position.
- the alloy state of Sn and other metals is determined based on the measurement result of the emission intensity of Sn atoms using GDS. If any one or more of Zn, Ni, and Fe are detected together with Sn in the measurement result of the emission intensity of Sn atoms, it is determined that Sn exists in an alloy state with the metal detected together with Sn. be able to.
- the surface treatment layer 3 of this embodiment contains Ni 2 Zn 11 .
- Ni 2 Zn 11 When X-ray diffraction analysis is performed on the surface treatment layer 3 of the present embodiment, from data indicating a correspondence relationship between the diffraction X-ray intensity and the diffraction angle 2 ⁇ obtained by irradiating the sample with X-rays, Whether or not Ni 2 Zn 11 is present in the surface treatment layer 3 can be identified.
- the peak of diffraction X-ray intensity caused by Ni 2 Zn 11 has a diffraction angle 2 ⁇ in the range of 34.5 ° to 35.2 °, in the range of 39.6 ° to 40.3 °, and 49.7 ° to 50.50.
- the diffraction angle 2 ⁇ is 39.6 ° to 40 °. It is preferable to have a diffraction X-ray intensity peak in at least one of the range of .3 ° and the range of 78.7 ° to 79.2 °.
- the diffraction angle 2 ⁇ is diffracted into at least one of a range of 39.6 ° to 40.3 ° and a range of 78.7 ° to 79.2 °.
- the surface-treated steel sheet 1 of this embodiment has more excellent corrosion resistance.
- the diffraction angle 2 ⁇ is in the range of 39.6 ° to 40.3 ° and the diffraction angle 2 ⁇ is in the range of 78.7 ° to 79.79. No peak of diffraction X-ray intensity was obtained in the range of 2 °.
- corrosion resistance was inferior.
- the average thickness of the surface treatment layer 3 is preferably 0.30 ⁇ m or less. This is because when the average thickness of the surface treatment layer is 0.30 ⁇ m or less, stress is not accumulated during processing and cracks are unlikely to occur.
- the steel plate used as the base material steel plate 2 is not particularly limited, a general cold-rolled steel plate or a hot-rolled steel plate can be used.
- the surface treatment layer 3 of the surface-treated steel sheet 1 of this embodiment has a very small amount of plating per unit area, the surface treatment layer 3 has a low degree of roughness in order to uniformly coat the base material steel sheet 2. It is preferable to use the base material steel plate 2. If the roughness Ra of the base steel plate 2 is less than 0.4 ⁇ m, particularly stable corrosion resistance can be obtained. Since the surface treatment layer 3 of the present embodiment has an extremely small amount of plating per unit area, the surface roughness is substantially the same before and after the formation of the surface treatment layer 3.
- An electroplating method is used as a method for plating the base material steel plate 2 with Ni.
- a plating bath for plating Ni (Ni plating bath) is not particularly limited, but a known plating bath can be used. For example, a watt bath, a borofluoride bath, a sulfamic acid bath, a nickel sulfate bath, and a nickel chloride bath can be used.
- the bath temperature of the Ni plating bath is preferably 55 to 65 ° C.
- a gloss additive or the like may be added to the Ni plating bath.
- the gloss additive is not particularly limited, and commercially available secondary gloss additives (smoothing agents) such as 1-4 butynediol, formaldehyde, coumarin and propargyl alcohol can be used.
- An electroplating method is used as a method for plating Sn.
- the plating bath for plating Sn (Sn plating bath) is not particularly limited, but a known plating bath can be used.
- a ferrostan bath, a halogen bath, a borofluoride bath, and a sulfuric acid bath can be used.
- the bath temperature of the Sn plating bath is preferably 55 to 65 ° C.
- the Sn plating bath of this embodiment may contain a gloss additive and the like.
- the gloss additive is not particularly limited, but commercially available gloss additives such as phenol sulfonic acid, cresol sulfonic acid, ⁇ -naphthol, dihydroxydiphenyl sulfone, ethoxylated-naphthol, methoxybenzaldehyde, polyalkylene oxide, gelatin and polyalkylene glycol. Can be used.
- the plating bath for plating Zn is not particularly limited, but a known plating bath can be used.
- a sulfuric acid bath, a chloride bath, an acidic ammonia bath, a zincate bath, a cyan bath, and the like can be used.
- the Zn plating bath of this embodiment preferably contains an organic additive. This is because the orientation of Ni 2 Zn 11 is appropriately changed by containing the organic additive.
- Organic additives to be added to the Zn plating bath include phenolsulfonic acid, ethoxylated naphthol, polyethylene glycol, gelatin, sulfonic acid compounds, succinic acid, polyoxyethylene naphthyl ether, benzaldehyde, citric acid, citric acid salts, and aromatics. Family aldehydes.
- phenolsulfonic acid and ethoxylated naphthol are particularly preferable.
- the Zn plating bath of this embodiment may contain a trace amount of metal elements.
- the metal element include Cr, Co, Ni, Sn, Pb, Cu, and Ag.
- the added metal element is alloyed with Ni, Zn or Sn contained in the surface treatment layer 3 by heating, the kind and amount of the metal element to be added so that the ionization tendency of the surface treatment layer 3 does not become lower than that of the steel plate. It is necessary to select.
- Sn is co-deposited on the surface treatment layer 3 because the Zn plating bath contains a small amount of Sn. Thereby, the corrosion resistance of the surface treatment layer 3 is improved, and the coverage of the base steel plate 2 by the surface treatment layer 3 is improved, which is particularly preferable.
- the Zn plating bath of this embodiment preferably has a bath temperature of 55 to 65 ° C. This is because the orientation of Ni 2 Zn 11 is appropriately changed by limiting the bath temperature of the Zn plating bath to 55 to 65 ° C. When the bath temperature of the Zn plating bath is lower than 55 ° C. and higher than 65 ° C., the orientation of Ni 2 Zn 11 does not change, which is not preferable.
- a Zn—Sn alloy plating bath may be used instead of the above Zn plating bath.
- the Zn—Sn alloy plating bath preferably contains an organic additive as well as the Zn plating bath.
- the organic additive that can be added to the Zn—Sn alloy plating bath is the same as that of the Zn plating bath.
- the bath temperature of the Zn—Sn alloy plating bath is preferably 55 to 65 ° C.
- the alloying treatment is performed after the above-described Zn plating or Zn—Sn alloy plating.
- the heating temperature for the alloying treatment is 320 ° C. to 400 ° C.
- the heating temperature for the alloying treatment is set in the range of 320 to 400 ° C.
- said heating temperature means the highest ultimate temperature of the surface treatment steel plate 1 at the time of alloying process.
- the alloying process in the manufacturing method of the surface-treated steel sheet 1 of the present embodiment it is preferable to hold a temperature of 320 ° C. or higher for 0.2 to 2 seconds. This is because holding the temperature of 320 ° C. or more for 0.2 to 2 seconds appropriately changes the orientation of Ni 2 Zn 11 .
- the holding time at a temperature of 320 ° C. or higher is less than 0.2 seconds, the orientation of Ni 2 Zn 11 does not change, which is not preferable.
- the holding time at a temperature of 320 ° C. or higher exceeds 2 seconds, it is not preferable because the corrosion resistance deteriorates due to excessive diffusion of Fe.
- the manufacturing method of the surface-treated steel sheet 1 of this embodiment it is preferable to perform the cooling process by immersing the surface-treated steel sheet 1 in water after performing the alloying process.
- the cooling treatment is not performed, variations in the cooling rate at the surface-treated steel sheet 1 are likely to occur.
- the surface-treated steel sheet 1 is cooled by being immersed in water in a state where the temperature is 320 ° C. or higher.
- the temperature of the surface-treated steel sheet 1 is made 100 ° C. or less faster than the method of cooling the surface-treated steel sheet 1 in the air and the method of cooling the surface-treated steel sheet 1 by spraying mist.
- the crystal orientation in the surface treatment layer 3 can be easily aligned in a certain direction.
- the temperature of the water in which the surface-treated steel sheet 1 is immersed is preferably 45 to 95 ° C.
- the time from the alloying treatment to the cooling treatment is 0 to 3 seconds. If the time from the alloying treatment to the cooling treatment exceeds 3 seconds, the orientation of Ni 2 Zn 11 does not change appropriately, which is not preferable. Incidentally, by performing the cooling process after the alloying treatment, the orientation of the Ni 2 Zn 11 changes, a finding that revealed for the first time by the present invention.
- the cold rolled annealed steel plates (original plate 1 and original plate 2) of ultra-low carbon steel whose components are shown in Table 1 were used as the base material steel plate.
- the cold-rolled annealed steel sheet has a thickness of 0.5 mm.
- a surface treatment layer was formed on the surface of the base steel plate using the plating bath described in Table 2. After the surface treatment layer was formed, the time until reaching the heating temperature was heated for 10 seconds by energization heating. Immediately after heating, it was cooled by immersion in water within 3 seconds. The water temperature was in the range of 45-95 ° C. When the water temperature was lower than 45 ° C., the orientation of Ni 2 Zn 11 did not change appropriately.
- Treatment agent 1 and treatment agent 2 were used to form the chemical conversion treatment layer.
- Table 3 shows the composition of the treating agent 1.
- the treatment agent 1 is a drug described as Example 22 in Japanese Patent No. 4776458.
- Treatment agent 2 is a mixture of treatment agent 1 and water-based urethane resin Takelac (registered trademark) W5100 (manufactured by Mitsui Chemicals Co., Ltd.) having the same mass as the solid content, and titanium nickel so that the solid content becomes 2% as a pigment. It is a medicine mixed with antimony yellow.
- the treatment agent 1 and the treatment material 2 were attached on the surface treatment layer in the attachment amounts shown in Tables 4 to 6.
- the heating temperature was 150 ° C., and the heating time to 150 ° C. was 10 seconds. Then, it stood to cool and formed the chemical conversion treatment layer.
- the surface treatment layer is dissolved with hydrochloric acid, and Ni, Zn, and Sn contained in the solution are quantified with a high frequency inductively coupled plasma emission spectrometer (ICP), and Ni plating, Zn plating, and Sn plating per unit area are adhered. By calculating the amount, the adhesion amount of Ni plating, Zn plating, and Sn plating was measured.
- ICP inductively coupled plasma emission spectrometer
- the average thickness of the surface treatment layer was calculated by dividing the adhesion amount of Ni plating, Zn plating and Sn plating determined by ICP by the density of each metal and adding them together.
- GDS ⁇ Glow discharge emission analysis
- the diffusion state of Fe in the vicinity of the surface of the surface treatment layer was determined based on the measurement result of Fe atoms at the interface between the oxide layer of the surface treatment layer and the metal layer of the surface treatment layer using GDS.
- the emission intensity of Fe atoms at the interface was 20% or less of the maximum emission intensity of Fe atoms in the measurement range
- the diffusion state of Fe atoms in the vicinity of the surface of the surface treatment layer was within the standard.
- the emission intensity of Fe atoms at the interface exceeds 20% of the maximum emission intensity of Fe atoms in the measurement range, the diffusion state of Fe in the vicinity of the surface of the surface treatment layer is determined to be out of the standard.
- the diffusion state of Ni in the vicinity of the surface of the surface treatment layer was determined based on the emission intensity of Ni atoms at the interface between the oxide layer of the surface treatment layer and the metal layer of the surface treatment layer using GDS.
- the emission intensity of Ni atoms at the interface was 20% or less of the maximum emission intensity of Ni atoms in the measurement range
- the diffusion state of Ni in the vicinity of the surface of the surface treatment layer was within the standard.
- the emission intensity of Ni atoms at the interface exceeds 20% of the maximum emission intensity of Ni atoms in the measurement range, the Ni diffusion state in the vicinity of the surface of the surface treatment layer is determined to be out of the standard.
- the alloy state of Zn and Ni was judged based on the measurement results of Zn atoms and Ni atoms using GDS. From the above measurement results, the depth range (first range) in which the emission intensity of Zn atoms is 60% or more of the maximum emission intensity of Zn atoms, and the emission intensity of Ni atoms is 60% or more of the maximum emission intensity of Ni atoms. A depth range (second range) was determined. When the first range and the second range overlap, the alloy state of Zn and Ni is assumed to be within the standard. On the other hand, when the first range and the second range do not overlap, the alloy state of Zn and Ni is determined to be out of the standard.
- X-ray diffraction analysis In order to investigate the presence of Ni 2 Zn 11 in the surface-treated steel sheet, diffraction lines of 39.6 ° to 40.3 ° and diffraction lines of 78.7 ° to 79.2 ° were examined by X-ray diffraction analysis. . Specifically, X-ray diffraction analysis was performed by a parallel beam method using Cu as a tube and a Xe proportional detector as a detector. As measurement conditions, voltage: 45 kV, current: 40 mA, measurement angle: 10 ° to 90 °, slit: 1/2 °, step size: 0.1 °, incident angle: 2 ° were used.
- diffraction angle 2 ⁇ is in the range of 39.6 ° to 40.3 ° or diffraction angle 2 ⁇ is in the range of 78.7 ° to 79.2 °
- 1 of the maximum X-ray diffraction intensity in the measurement range When a peak having an intensity of at least% was present, it was judged that a peak was present within the range. For example, when examining the presence of a peak in a diffraction line of 39.6 ° to 40.3 °, first, a base line connecting two points of 39.1 ° and 40.8 ° was drawn. Next, the maximum X-ray diffraction intensity in the measurement range (a range where the diffraction angle 2 ⁇ is 10 to 90 °) was obtained. When a peak having an intensity of 1% or more of the maximum X-ray diffraction intensity in the measurement range exists in the range of 39.6 ° to 40.3 °, it is determined that the peak exists within the range. .
- the corrosion resistance was evaluated by a method standardized in JIS Z 2371. In this method, the corrosion resistance is evaluated by the time from spraying salt water until white rust or red rust is generated. In the evaluation of corrosion resistance, an unprocessed flat plate whose end face was sealed was used as a test piece. Five test pieces treated in the same manner were prepared, and the occurrence of white rust or red rust was confirmed every 3 hours after spraying salt water. When white rust or red rust occurred in at least one of the five test pieces, the time was defined as the rust generation time.
- the corrosion resistance may be evaluated based on the time until white rust occurs.
- the surface-treated steel sheet of the present invention has a very small amount of Zn plating, the time from when white rust occurs until red rust occurs may be short. In such a case, occurrence of red rust may be confirmed without confirming the occurrence of white rust. Therefore, the corrosion resistance was evaluated based on the time until the occurrence of white rust or red rust.
- Corrosion resistance is evaluated by comparing the time until the occurrence of white rust or red rust on each specimen and the time until the occurrence of white rust or red rust when the Zn plating adhesion amount is 20 g / m 2 (reference material). went. That is, in the case of the examples and comparative examples shown in Table 4, the corrosion resistance was evaluated by comparing the time until the occurrence of white rust or red rust with the reference material 1. In the case of the Examples and Comparative Examples shown in Table 5, the corrosion resistance was evaluated by comparing the time until the occurrence of white rust or red rust with the reference material 2. In the case of the Examples and Comparative Examples shown in Table 6, the corrosion resistance was evaluated by comparing the time until the occurrence of white rust or red rust with the reference material 3.
- the time until white rust or red rust in the reference material to generate a T 1 is generated and T 2.
- T 1 -T 2 time difference
- the example or the comparative example has the same corrosion resistance as the case where the amount of deposited Zn plating is 20 mg / m 2. It was evaluated as Excellent.
- the example or comparative example is inferior to the corrosion resistance when the amount of Zn plating deposited is 20 mg / m 2 , It was evaluated as Good as having corrosion resistance that is not a problem in practice.
- the time difference (T 1 -T 2 ) exceeds 12 hours, the example or the comparative example is poorer in corrosion resistance than the case where the deposited amount of Zn plating is 20 mg / m 2. It was evaluated.
- Tables 4 to 9 show the production methods and test results of each surface-treated steel sheet.
- the reference material 1 and the reference material 3 were rusted 60 hours after spraying salt water, and the reference material 2 was rusted 84 hours after spraying salt water.
- Comparative Example 1-3 since the amount of Zn plating adhered was small, it was considered that the coverage of the base steel plate by the surface treatment layer was low and rust was generated early.
- Comparative Example 1-4 since Ni and Zn were not alloyed, the coverage of the base material steel plate by the surface treatment layer was low, and it is considered that rust occurred early.
- Comparative Example 1-5 the alloying of Ni and Zn was inadequate, so the coverage of the base steel plate with the surface treatment layer was low, and it is considered that rust occurred early.
- Comparative Examples 1-6 and 1-7 it is considered that the orientation of Ni 2 Zn 11 did not change appropriately because the heating temperature for the alloying treatment was insufficient.
- Comparative Example 1-8 since Fe and Ni were diffused to the vicinity of the surface of the chemical conversion treatment layer, it is considered that rust was generated early.
- Comparative Example 1-12 since the holding time of 320 ° C. or higher was 0.1 second, the orientation of Ni 2 Zn 11 did not change appropriately, and rust was considered to have occurred early.
- Comparative Example 1-13 since the holding time of 320 ° C. or higher was 5.0 seconds, it is considered that Fe and Ni were diffused to the vicinity of the chemical conversion treatment layer surface. Thereby, since the coverage of the base material steel plate by the surface treatment layer was low, it is considered that rust was generated early.
- Example 2-1 to 2-4 shown in Table 5 the time until the occurrence of rust was 72 hours or more after the salt water was sprayed.
- Comparative Examples 2-1 to 2-3 rust was generated by 72 hours after spraying salt water.
- the reason is considered as follows. Since Comparative Example 2-1 does not have Ni plating, the coverage of the base steel plate by the surface treatment layer is low, and it is considered that rust occurred early.
- Comparative Example 2-2 Fe and Ni are diffused to the vicinity of the surface of the chemical conversion treatment layer, and the coverage of the base steel sheet by the surface treatment layer is low, so it is considered that rust was generated early.
- Example 3-1 to 3-15 shown in Table 6 the time until the occurrence of rust was 48 hours or more after the salt water was sprayed.
- Comparative Examples 3-1 to 3-3 rust was generated by 45 hours after spraying salt water.
- Sn plating using the Sn plating bath (1) was performed between the Ni plating and the Zn plating.
- Zn—Sn alloy plating using the Zn—Sn alloy plating bath (1) shown in Table 2 was performed.
- the reason that rust occurred by 45 hours is considered to be as follows.
- Comparative Example 3-1 since alloying treatment was not performed, Sn having a lower ionization tendency than the base steel plate remained in the surface treatment layer, and it is considered that rust was generated earlier.
- Comparative Example 3-2 since the heating temperature related to the alloying treatment was insufficient, the orientation of Ni 2 Zn 11 did not change appropriately, and it is considered that rust occurred early.
- Comparative Example 3-3 the amount of Ni plating deposited was small, and the corrosion resistance of Ni was not fully exhibited, so it is considered that rust occurred early.
- Example 3-11 The reason why the corrosion resistance of Example 3-11 was inferior to that of Example 3-1 and Example 3-10 was that the surface roughness of the base steel sheet was high, and therefore the surface treatment layer and the chemical conversion treatment layer This is thought to be due to the low coverage of the base material steel plate due to.
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Abstract
Description
本願は、2014年1月28日に、日本に出願された特願2014-13525号に基づき優先権を主張し、その内容をここに援用する。
Znめっき鋼板では、耐食性の向上及び光沢性の向上などを目的として、Znめっき層の表面に化成処理が施されることが多い。
第1段階では、Znの腐食生成物である白錆が発生する。
第2段階では、腐食した部位の周辺のZnが、母材鋼板中のFeよりも先に溶け出すことにより、母材鋼板を電気化学的に保護(犠牲防食)する。
第4段階では、白錆が母材鋼板の表面から消失することにより、母材鋼板が露出する。これにより、母材鋼板中のFeが腐食し、Feの腐食生成物である赤錆が発生する。
実際には、上記の各段階の現象が並行して起こることにより、腐食が進行する。Znめっきの付着量が多いほど、上記の第2段階と第3段階における腐食の進行は抑制される。
電気Znめっき鋼板では、特許文献1及び非特許文献1のように白錆の発生の防止に重点を置くことが多い。
しかしながら、実際には、Znめっきの付着量が少ない場合には、Znめっきの付着量が多い場合と比べて、白錆が早く発生する。
上記の特許文献2に記載されている電子機器部品用表面処理鋼板では、NiとZnとの合金化処理が十分ではないため、好ましい耐食性を得られない場合がある。
(1)本発明の一態様に係る表面処理鋼板は、母材鋼板と、前記母材鋼板の少なくとも片面に形成され、且つ酸化物層及び金属層を有する表面処理層と、前記表面処理層の表面に形成された化成処理層と、を備えている。前記表面処理層は、付着量が0.30~2.00g/m2のZnと、付着量が0.03~2.00g/m2で且つ前記Znの付着量以下であるNiとを含有し、前記化成処理層の表面を測定開始位置とし、前記表面処理層の表面から深さ方向に1μmの位置を測定終了位置とする範囲に対してグロー放電発光分析を行うことにより、Fe原子、Zn原子及びNi原子の発光強度の分布曲線をそれぞれ得た場合に、前記酸化物層と前記金属層との界面において、前記Fe原子の発光強度が前記Fe原子の最大発光強度の20%以下である。また、前記界面において、前記Ni原子の発光強度が前記Ni原子の最大発光強度の20%以下である。また、前記深さ方向に関して、前記Zn原子の発光強度が前記Zn原子の最大発光強度の60%以上である第1の範囲と、前記Ni原子の発光強度が前記Ni原子の最大発光強度の60%以上である第2の範囲とが、重なりを有する。
表面処理層3は、ZnとNiとを含むめっき層である。表面処理層3におけるZnの付着量は、0.30~2.00g/m2であり、Niの付着量は、0.03~2.00g/m2である。
また、本実施形態の表面処理鋼板1では、Niの付着量は、Znの付着量以下である。
なお、表面処理層3において、Znの濃度は、表面処理層3の表面からの深さに依存して変化する。表面処理層3の金属層において、Znの濃度は最大となる。
特に、Znめっきの付着量が1.2g/m2以下の場合には、母材鋼板2の表面にZnのみをめっきした場合と比べて、優れた耐食性を得ることができる。
より安定的に耐食性を得る観点から、Znめっきの付着量は0.5g/m2以上が好ましく、0.8g/m2以上がより好ましい。
しかしながら、Niめっきの付着量が多すぎる場合には、表面処理層3のイオン化傾向がFeよりも低くなるため、Znの犠牲防食効果が失われる。
一方、Niめっきの付着量が少なすぎる場合には、表面処理層3による腐食抑制効果が低減し、母材鋼板2中のFeが過剰に拡散してしまう。
より安定的に耐食性を得る観点から、Niめっきの付着量は0.05g/m2以上が好ましく、0.07g/m2以上がより好ましい。
上述の理由から、表面処理層3におけるNiめっきの付着量は、Znめっきの付着量以下とする。
特に安定した耐食性が得られるのは、Niめっきの付着量が、Znめっきの付着量の半分以下の場合である。
ただし、Snが単体で存在すると、腐食を促進してしまうことがある。また、SnがZnとの合金として表面処理層3に含まれる場合は、Zn-Sn合金の結晶はZnの結晶よりも成長しにくいため、母材鋼板2の被覆性が高まる。また、Zn-Sn合金はZnよりも融点が低いため、Niと合金化し易くなる。
上述の理由から、Snは表面処理層3中に他の金属との合金として含まれる必要がある。
より好ましいSnめっきの付着量は、0.05g/m2以下である。さらに好ましいSnめっきの付着量は、0.04g/m2以下である。よりさらに好ましいSnめっきの付着量は、0.03g/m2以下である。
一方、合金化が過剰に行われた場合には、表面処理層3の表面近傍におけるFe及びNiの濃度が高くなってしまう。このような場合には、Znの犠牲防食効果が得られないため、十分な耐食性が得られない。
例えば、化成処理層4による母材鋼板2及び表面処理層3の被覆性を高めるため、化成処理層4は、ポリエステル、ポリウレタン、エポキシ、フェノール及び変性ポリオレフィンなどの樹脂を含むことができる。表面処理鋼板1の防錆性を高めるために、化成処理層4は、シリカ、シランオリゴマー、有機チタネート、タンニン酸塩、リン酸塩、バナジル化合物及びグアニジル化合物などを含むことができる。
化成処理層4を着色するために、化成処理層4は、顔料及び染料を含むことができる。
表面処理鋼板1の摺動性を向上するために、化成処理層4はワックスなどを含むことができる。
図2に、GDSによるZn原子の発光強度の測定結果5を示す。図2の横軸は、化成処理層4の表面からの測定深度(深さ)である。図2の縦軸は、グロー放電環境下で、試料をスパッタリングすることで、試料から放出されるZn原子の発光強度である。
測定範囲におけるZn原子の最大発光強度をX、測定範囲におけるZn原子の最小発光強度をYとしたとき、Zn原子の発光強度(Z)が以下の(1)式で表される深さ位置を、表面処理層3と化成処理層4との界面6とする。
Z=(X-Y)×0.25+Y・・・(1)
表面処理層3の酸化物層と表面処理層3の金属層との界面は、GDSを用いた、酸素原子の発光強度の測定結果に基づき決定する。表面処理層3の酸化物層と表面処理層3の金属層との界面の決定方法は、化成処理層4における酸素原子の最大発光強度と表面処理層3における酸素原子の最大発光強度とのいずれが高いかによって異なる。
図3に、表面処理層3における酸素原子の最大発光強度が、化成処理層4における酸素原子の最大発光強度よりも高い場合における、GDSによる酸素原子の発光強度の測定結果7を示す。
測定範囲における最大発光強度をL、測定範囲における最小発光強度をMとしたとき、酸素原子の発光強度(N)が以下の(2)式で表される深さ位置を、表面処理層3の酸化物層と表面処理層3の金属層との界面6とする。
N=(L-M)×0.5+M・・・(2)
図4に、化成処理層4における酸素原子の最大発光強度が表面処理層3の酸化物層における酸素原子の最大発光強度よりも高い場合における、GDSによる酸素原子の発光強度の測定結果9及びZn原子の発光強度の測定結果10を示す。
測定範囲における最大発光強度をL’、測定範囲における最小発光強度をM’としたとき、酸素原子の発光強度(N’)が以下の(3)式で表される深さ位置を、表面処理層の酸化物層と表面処理層の金属層との界面11とする。
N’=(L’-M’)×0.25+M’・・・(3)
表面処理層3の表面近傍におけるFe及びNiの拡散状態は、GDSを用いた、Fe原子およびNi原子の発光強度の測定結果に基づき決定する。
合金化が好適に行われていた場合には、表面処理層3の酸化物層と表面処理層3の金属層との界面におけるFe原子の発光強度が、測定範囲におけるFe原子の最大発光強度の20%以下である。
NiについてもFeと同様であり、合金化が好適に行われていた場合には、表面処理層3の酸化物層と表面処理層3の金属層との界面におけるNi原子の発光強度が、測定範囲におけるNi原子の最大発光強度の20%以下である。
図5及び図6を参照して、ZnとNiとの合金化の進行状態を、GDSを用いたZn原子及びNi原子の発光強度の測定結果に基づき決定する方法について説明する。
図5は、ZnとNiとの合金化が十分に行われた場合の本発明の表面処理鋼板を表面からGDSで分析した際のZn原子の発光強度の測定結果12及びNi原子の発光強度の測定結果13を示した模式図である。図6は、ZnとNiとの合金化が不十分である場合の本発明の表面処理鋼板を表面からGDSで分析した際のZn原子の発光強度の測定結果14及びNi原子の発光強度の測定結果15を示した模式図である。
図5では、深さ位置がx1からx3の範囲において、Zn原子の発光強度の測定結果12が最大値の60%以上である。深さ位置がx2からx4の範囲において、Ni原子の発光強度の測定結果13が最大値の60%以上である。つまり、図5の場合には、深さ位置がx2からx3の範囲において、Zn原子及びNi原子の発光強度の測定結果は、共にそれぞれの最大値の60%以上である。
図6では、深さ位置がx5からx6の範囲において、Zn原子の発光強度の測定結果14が最大値の60%以上である。深さ位置がx7からx8の範囲において、Ni原子の発光強度の測定結果15が最大値の60%以上である。つまり、図6の場合には、Zn原子の発光強度の測定結果14が最大値の60%以上である深さ位置と、Ni原子の発光強度の測定結果15が最大値の60%以上である深さ位置とは重複しない。
Snと他の金属との合金状態は、GDSを用いたSn原子の発光強度の測定結果に基づき決定する。Sn原子の発光強度の測定結果において、Snと共にZn、Ni、Feのいずれか一つ以上が検出されれば、Snが、Snと共に検出された金属との合金状態で存在していると判断することができる。
本実施形態の表面処理層3に対してX線回折分析を行った場合には、上記のNi2Zn11に起因する回折X線強度のピークのうち、回折角2θが39.6°~40.3°の範囲と78.7°~79.2°の範囲との少なくとも一方に、回折X線強度のピークを有することが好ましい。表面処理層3に対してX線回折分析を行った場合に、回折角2θが39.6°~40.3°の範囲と78.7°~79.2°の範囲との少なくとも一方に回折X線強度のピークを有することにより、本実施形態の表面処理鋼板1は、より優れた耐食性を有する。
なお、NiとZnとを同時に溶融状態にしためっき浴で溶融めっきした試験材、Niをプレめっきして、その後溶融Znめっきを施した試験材及びNiとZnとを電気めっきした試験材では、Znめっきの付着量及びNiめっきの付着量が本実施形態の範囲内であっても、回折角2θが39.6°~40.3°の範囲及び回折角2θが78.7°~79.2°の範囲に回折X線強度のピークは得られなかった。また、これらの試験材では、本実施形態の表面処理鋼板1と比べて耐食性が劣っていた。
本実施形態の表面処理層3は、単位面積当たりのめっき付着量が極めて少ないため、表面処理層3の形成前後で表面粗度はほぼ同じである。
Niめっき浴の浴温度は、55~65℃であることが好ましい。
Niめっき浴に、光沢添加剤などを添加してもよい。光沢添加剤は、特に限定されないが、1-4ブチンジオール、ホルムアルデヒド、クマリン及びプロパルギルアルコールなど、市販されている二次光沢添加剤(平滑化剤)を用いることができる。
Snめっき浴の浴温度は、55~65℃であることが好ましい。
本実施形態のSnめっき浴は、光沢添加剤などを含有してもよい。光沢添加剤は、特に限定されないが、フェノールスルホン酸、クレゾールスルホン酸、β-ナフトール、ジヒドロキシジフェニルスルホン、エトキシ化-ナフトール、メトキシベンズアルデヒド、ポリアルキレンオキシド、ゼラチン及びポリアルキレングリコールなど、市販の光沢添加剤を用いることができる。
本実施形態のZnめっき浴は、有機添加剤を含有することが好ましい。有機添加剤を含有することにより、Ni2Zn11の配向性が適切に変化するためである。Znめっき浴に添加する有機添加剤としては、フェノールスルホン酸、エトキシ化ナフトール、ポリエチレングリコール、ゼラチン、スルホン酸系化合物、コハク酸、ポリオキシエチレンナフチルエーテル、ベンズアルデヒド、くえん酸、くえん酸の塩及び芳香族アルデヒドが挙げられる。Znめっき浴に添加する有機添加剤としては、これらの中でも、特にフェノールスルホン酸及びエトキシ化ナフトールが好ましい。
特に、上記の金属元素の中でも、Znめっき浴が微量のSnを含有することにより、表面処理層3にSnが共析する。これにより、表面処理層3の耐食性が向上し、表面処理層3による母材鋼板2の被覆性が向上するので、特に好ましい。
Znめっき浴の浴温度を55℃未満及び65℃超にした場合には、Ni2Zn11の配向性に変化が生じないため好ましくない。
Zn-Sn合金めっき浴も、Znめっき浴と同様に有機添加剤を含有することが好ましい。なお、Zn-Sn合金めっき浴に添加することのできる有機添加剤は、Znめっき浴の場合と同様である。
Zn-Sn合金めっき浴の浴温度は55~65℃であることが好ましい。
この温度範囲で合金化処理を行うことにより、本実施形態の表面処理鋼板1の製造方法により製造された表面処理鋼板1は、優れた耐食性を有する。その理由は定かではないが、この温度範囲で合金化処理を行うことにより、Ni2Zn11の配向性が適切に変化するため、優れた耐食性を有すると考えられる。
上記の理由から、合金化処理に係る加熱温度は320~400℃の範囲とする。
なお、上記の加熱温度とは、合金化処理時における、表面処理鋼板1の最高到達温度を意味する。
320℃以上の温度の保持時間が0.2秒未満の場合には、Ni2Zn11の配向性に変化が生じないため好ましくない。320℃以上の温度の保持時間が2秒を越える場合には、Feが過度に拡散することにより、耐食性が劣化するため好ましくない。
本実施形態の冷却処理によれば、表面処理鋼板1を大気中で冷却する方法及び表面処理鋼板1にミストを吹きかけて冷却する方法に比べて、表面処理鋼板1の温度をより速く100℃以下の温度に冷却することができる。表面処理鋼板1の温度が100℃以下の場合には、表面処理層3において、結晶核生成及び結晶成長が進行しない。そのため、本実施形態の冷却処理によれば、表面処理層3中の結晶の方位を一定方向に揃えやすい。
本実施形態の冷却処理において、表面処理鋼板1を浸漬する水の温度は、45~95℃であることが好ましい。表面処理鋼板1を浸漬する水の温度を上述の範囲に限定することにより、Ni2Zn11の配向性が、耐食性を発揮するのに適した配向性となる。
なお、合金化処理を行った後に冷却処理を行うことにより、Ni2Zn11の配向性が変化することは、本発明によって初めて明らかになった知見である。
表1に成分を示す極低炭素鋼の冷延焼鈍鋼板(原板1及び原板2)を母材鋼板として用いた。この冷延焼鈍鋼板の板厚は0.5mmである。
表2に記載のめっき浴を用いて、母材鋼板の表面に表面処理層を形成した。表面処理層を形成した後、通電加熱により、加熱温度に到達するまでの時間を10秒間として加熱した。加熱した直後、3秒以内に水に浸漬して冷却した。水温は45~95℃の範囲とした。なお、水温が45℃未満の場合には、Ni2Zn11の配向性が適切に変化しなかった。
化成処理層の形成には処理剤1及び処理剤2を用いた。処理剤1の組成を表3に示す。なお、処理剤1は特許4776458号公報に実施例22として記載されている薬剤である。
処理剤2は処理剤1に固形分で同質量となる水系ウレタン樹脂タケラック(登録商標)W5100(三井化学株式会社製)を混合し、さらに顔料として全固形分の2%となるようにチタンニッケルアンチモン黄を混合した薬剤である。
処理剤1及び処理材2を、表4~表6に示す付着量で表面処理層の上に付着させた。加熱温度を150℃とし、150℃までの到達時間を10秒間として加熱した。その後、放冷し、化成処理層を形成した。
表面処理層を塩酸で溶解し、その溶解液中に含まれる Ni、Zn及びSnを高周波誘導結合プラズマ発光分光装置(ICP)で定量し、単位面積当たりのNiめっき、Znめっき及びSnめっきの付着量を算出することにより、Niめっき、Znめっき、及びSnめっきの付着量を測定した。
ICPにより定量したNiめっき、Znめっき及びSnめっきの付着量を、各金属の密度で割り、それらを足し合わせることにより、表面処理層の平均厚みを算出した。
表面処理鋼板の構造は、GDA750(株式会社リガク製)をGDS装置として用いて測定した。GDSでは、化成処理層の表面を測定開始位置とし、表面処理層の表面から母材鋼板に向かって深さ1μmの位置を測定終了位置とした。
GDSを用いた酸素原子の測定結果から、表面処理層の酸化物層と表面処理層の金属層との界面を決定した。
表面処理層の表面近傍におけるFeの拡散状態は、GDSを用いた、表面処理層の酸化物層と表面処理層の金属層との界面におけるFe原子の測定結果に基づいて判断した。
上記界面におけるFe原子の発光強度が、測定範囲におけるFe原子の最大発光強度の20%以下である場合には、表面処理層の表面近傍におけるFe原子の拡散状態が基準内であるとした。一方、上記界面におけるFe原子の発光強度が、測定範囲におけるFe原子の最大発光強度の20%を越える場合には、表面処理層の表面近傍におけるFeの拡散状態が基準外であるとした。
表面処理層の表面近傍におけるNiの拡散状態は、GDSを用いた、表面処理層の酸化物層と表面処理層の金属層との界面におけるNi原子の発光強度に基づいて判断した。
上記界面におけるNi原子の発光強度が、測定範囲におけるNi原子の最大発光強度の20%以下である場合には、表面処理層の表面近傍におけるNiの拡散状態が基準内であるとした。一方、上記界面におけるNi原子の発光強度が、測定範囲におけるNi原子の最大発光強度の20%を越える場合には、表面処理層の表面近傍におけるNiの拡散状態が基準外であるとした。
ZnとNiとの合金状態は、GDSを用いたZn原子及びNi原子の測定結果に基づいて判断した。上記測定結果から、Zn原子の発光強度がZn原子の最大発光強度の60%以上である深さ範囲(第1の範囲)と、Ni原子の発光強度がNi原子の最大発光強度の60%以上である深さ範囲(第2の範囲)とを求めた。
第1の範囲と第2の範囲とが重なりを有している場合には、ZnとNiとの合金状態が基準内であるとした。一方、第1の範囲と第2の範囲とが重なりを有していない場合には、ZnとNiとの合金状態が基準外であるとした。
表面処理鋼板中のNi2Zn11の存在を調べるために、X線回折分析により、39.6°~40.3°の回折線及び78.7°~79.2°の回折線を調べた。
具体的には、管球にCu、検出器にXe比例検出器を用い、平行ビーム法によりX線回折分析を行った。測定条件としては、電圧:45kV、電流:40mA、測定角:10°~90°、スリット:1/2°、ステップサイズ:0.1°、入射角:2°を用いた。
ピークの検出に当たっては、まず、それぞれの範囲(回折角2θが39.6°~40.3°の範囲または回折角2θが78.7°~79.2°の範囲)において、回折角2θの下限マイナス0.5°から、回折角2θの上限プラス0.5°に向かって直線(ベースライン)を引いた。次に、測定範囲(回折角2θが10°~90°の範囲)における、最大のX線回折強度を求めた。
例えば、39.6°~40.3°の回折線においてピークの存在を調べる際には、まず、39.1°と40.8°との2点を結ぶベースラインを引いた。次に、測定範囲(回折角2θが10~90°の範囲)における、最大のX線回折強度を求めた。そして、39.6°~40.3°の範囲に、測定範囲における最大のX線回折強度の1%以上の強度を有するピークが存在した場合には、その範囲内にピークが存在すると判断した。
耐食性は、JIS Z 2371で規格されている方法により評価した。この方法では、塩水を噴霧してから、白錆または赤錆が発生するまでの時間により耐食性を評価する。
耐食性の評価では、端面をシールした無加工の平板を試験片として用いた。
同じように処理した試験片を合計で5つ用意し、白錆または赤錆の発生を、塩水を噴霧してから3時間ごとに確認した。5つのうち少なくとも1つの試験片において、白錆または赤錆が発生した場合には、その時間を錆発生時間とした。
つまり、表4に示されている実施例及び比較例の場合には、白錆または赤錆発生までの時間を、基準材1と比較することにより耐食性を評価した。表5に示されている実施例及び比較例の場合には、白錆または赤錆発生までの時間を、基準材2と比較することにより耐食性を評価した。表6に示されている実施例及び比較例の場合には、白錆または赤錆発生までの時間を、基準材3と比較することにより耐食性を評価した。
上記の時間の差(T1-T2)が12時間以内である場合には、その実施例又は比較例は、Znめっきの付着量が20mg/m2である場合の耐食性よりは劣るが、実用上問題ない耐食性を有しているとして、Goodと評価した。
上記の時間の差(T1-T2)が12時間を越える場合には、その実施例又は比較例は、Znめっきの付着量が20mg/m2である場合よりも耐食性が劣るとして、Poorと評価した。
比較例1-1は、Niめっきを有さないため、表面処理層による母材鋼板の被覆性が低く、錆が早く発生したと考えられる。
比較例1-2は、Niめっきの付着量が多かったため、母材鋼板よりイオン化傾向の高いNiが表面処理層内に残存し、錆が早く発生したと考えられる。
比較例1-4は、NiとZnとが合金化されていなかったため、表面処理層による母材鋼板の被覆性が低く、錆が早く発生したものと考えられる。
比較例1-5は、NiとZnとの合金化が不十分だったため、表面処理層による母材鋼板の被覆性が低く、錆が早く発生したものと考えられる。
比較例1-8は、FeおよびNiが化成処理層の表面近傍まで拡散してしまっていたため、錆が早く発生したものと考えられる。
比較例1-13は、320℃以上の保持時間が5.0秒であったため、FeおよびNiが化成処理層表面近傍まで拡散していたものと考えられる。それにより、表面処理層による母材鋼板の被覆性が低かったため、錆が早く発生したものと考えられる。
比較例2-1は、Niめっきを有さないため、表面処理層による母材鋼板の被覆性が低く、錆が早く発生したと考えられる。
比較例2-2は、FeおよびNiが化成処理層の表面近傍まで拡散しており、表面処理層による母材鋼板の被覆性が低かったため、錆が早く発生したものと考えられる。
なお、実施例3-5~3-9及び比較例3-1では、NiめっきとZnめっきとの間に、Snめっき浴(1)によるSnめっきを行った。
また、実施例3-15及び比較例3-2では、Niめっきを行った後、表2に示したZn-Sn合金めっき浴(1)によるZn-Sn合金めっきを行った。
比較例3-1~3-3において、45時間までに錆びが発生した理由は以下のためと考えられる。
比較例3-2は、合金化処理に係る加熱温度が不十分であったため、Ni2Zn11の配向性が適切に変化せず、錆が早く発生したものと考えられる。
比較例3-3は、Niめっきの付着量が少なく、Niの有する耐食性が十分に発揮されなかったため、錆が早く発生したものと考えられる。
なお、実施例3-11の耐食性が、実施例3-1及び実施例3-10の耐食性よりも劣っていたのは、母材鋼板の表面粗度が高いため、表面処理層及び化成処理層による母材鋼板の被覆性が低かったためと考えられる。
2 母材鋼板
3 表面処理層
4 化成処理層
5 Zn原子の発光強度の測定結果
6 表面処理層と化成処理層との界面
7 酸素原子の発光強度の測定結果
8 表面処理層中の酸化物層と金属層との界面
9 酸素原子の発光強度の測定結果
10 Zn原子の発光強度の測定結果
11 表面処理層中の酸化物層と金属層との界面
12 Zn原子の発光強度の測定結果
13 Ni原子の発光強度の測定結果
14 Zn原子の発光強度の測定結果
15 Ni原子の発光強度の測定結果
Claims (5)
- 母材鋼板と;
前記母材鋼板の少なくとも片面に形成され、且つ酸化物層及び金属層を有する表面処理層と;
前記表面処理層の表面に形成された化成処理層と;
を備え、
前記表面処理層は、付着量が0.30~2.00g/m2のZnと、付着量が0.03~2.00g/m2で且つ前記Znの付着量以下であるNiとを含有し、
前記化成処理層の表面を測定開始位置とし、前記表面処理層の表面から深さ方向に1μmの位置を測定終了位置とする範囲に対してグロー放電発光分析を行うことにより、Fe原子、Zn原子及びNi原子の発光強度の分布曲線をそれぞれ得た場合に、
前記酸化物層と前記金属層との界面において、前記Fe原子の発光強度が前記Fe原子の最大発光強度の20%以下であり、
前記界面において、前記Ni原子の発光強度が前記Ni原子の最大発光強度の20%以下であり、且つ、
前記深さ方向に関して、前記Zn原子の発光強度が前記Zn原子の最大発光強度の60%以上である第1の範囲と、前記Ni原子の発光強度が前記Ni原子の最大発光強度の60%以上である第2の範囲とが、重なりを有する、
ことを特徴とする表面処理鋼板。 - 前記表面処理層に対してX線回折分析を行うことにより、回折X線強度と回折角2θとの対応関係を示す測定データを得た場合に、
前記回折角2θが39.6°~40.3°の範囲と前記回折角2θが78.7°~79.2°の範囲との少なくとも一方に前記回折X線強度のピークが現れる
ことを特徴とする請求項1記載の表面処理鋼板。 - 前記表面処理層中の前記Znの付着量が、0.80~1.20g/m2であり;
前記表面処理層中の前記Niの付着量が、0.07g/m2以上でかつ前記Znの付着量の半分以下である;
ことを特徴とする請求項1記載の表面処理鋼板。 - 前記表面処理層が、前記Znの付着量の10%以下のSnをさらに含有する
ことを特徴とする請求項1記載の表面処理鋼板。 - 前記表面処理層の平均厚みが0.30μm以下である
ことを特徴とする請求項1記載の表面処理鋼板。
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