JP4767752B2 - Ni-plated steel sheet excellent in slidability and manufacturing method thereof - Google Patents
Ni-plated steel sheet excellent in slidability and manufacturing method thereof Download PDFInfo
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- JP4767752B2 JP4767752B2 JP2006131304A JP2006131304A JP4767752B2 JP 4767752 B2 JP4767752 B2 JP 4767752B2 JP 2006131304 A JP2006131304 A JP 2006131304A JP 2006131304 A JP2006131304 A JP 2006131304A JP 4767752 B2 JP4767752 B2 JP 4767752B2
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- 229910000831 Steel Inorganic materials 0.000 title claims description 42
- 239000010959 steel Substances 0.000 title claims description 42
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 238000007747 plating Methods 0.000 claims description 64
- 239000010410 layer Substances 0.000 claims description 56
- 239000000654 additive Substances 0.000 claims description 32
- 230000000996 additive effect Effects 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 15
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 230000002378 acidificating effect Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002344 surface layer Substances 0.000 claims description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 8
- 238000009792 diffusion process Methods 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910018104 Ni-P Inorganic materials 0.000 description 3
- 229910018536 Ni—P Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000009713 electroplating Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910018100 Ni-Sn Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 229910018532 Ni—Sn Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
本発明は、主に電池缶等の用途に用いられる摺動性に優れたＮｉメッキ鋼板およびその製造方法に関する。 The present invention relates to a Ni-plated steel sheet excellent in slidability used mainly for applications such as battery cans and a method for producing the same.
一般に電池缶用の素材として、Ｎｉメッキされた鋼板が使用される。従来Ｎｉメッキは、缶に加工した後のいわゆるバレルメッキによって行われてきたが、缶内面へのＮｉメッキの付着が十分ではなく品質上の不安定性の問題があることから、先メッキ鋼板を缶に加工する方法に置き換わりつつある。先メッキ鋼板の場合、Ｎｉメッキ層が硬く延展性に乏しいことから、プレス加工性に劣り、また加工時にメッキが剥離して耐食性が劣化しやすい等の問題があった。 In general, a Ni-plated steel sheet is used as a material for a battery can. Conventionally, Ni plating has been carried out by so-called barrel plating after processing into a can, but since the Ni plating adheres to the inner surface of the can and is not sufficient, there is a problem of instability in quality. It is being replaced by the method of processing. In the case of a pre-plated steel sheet, since the Ni plating layer is hard and poor in spreadability, the press workability is inferior, and the plating is peeled off during processing and the corrosion resistance is liable to deteriorate.
この問題に対し、Ｎｉメッキ後熱処理することでメッキと地鉄の界面にＦｅ−Ｎｉ拡散層を形成して密着性を向上させると同時に、Ｎｉを再結晶、軟質化してメッキ層の延展性を向上させる方法が知られており、プレス加工性や耐食性は大幅に改善される（例えば特許文献１〜４）。
To solve this problem, heat treatment after Ni plating forms a Fe-Ni diffusion layer at the interface between the plating and the base iron to improve adhesion, and at the same time recrystallizes and softens Ni to increase the spreadability of the plating layer. A method of improving is known, and press workability and corrosion resistance are greatly improved (for example,
しかしながら、前述の従来技術では、Ｎｉメッキ層が再結晶、軟質化している結果として、電池製造過程において電池缶を高速搬送する際、電池缶外面どおしの接触における摺動性が必ずしも十分でなく、缶の流れ性が劣り生産性を悪化させる場合がある。また、プレス加工においても、金型との摺動性が十分でなく、プレス性を悪化させる場合もある。 However, in the above-described prior art, as a result of the Ni plating layer being recrystallized and softened, when the battery can is conveyed at high speed during the battery manufacturing process, the slidability in contact between the outer surfaces of the battery can is not always sufficient. In some cases, the flowability of the can is poor and the productivity is deteriorated. Also in the press working, the slidability with the mold is not sufficient, and the pressability may be deteriorated.
特許文献５では、Ｎｉメッキ後、更にＮｉ−Ｐ合金メッキを施して熱処理することにより、Ｆｅ−Ｎｉ拡散層と再結晶、軟質化したＮｉメッキ層の上層に更に硬質なＮｉ−Ｐ合金メッキ層を有する耐食性と耐疵つき性に優れたＮｉメッキ鋼板が示されている。また特許文献６では、最表層に光沢Ｎｉ層あるいは、光沢Ｎｉ−Ｃｏ合金メッキ層を有する電池缶用メッキ鋼板が示されてされている。特許文献７では、電池缶外面に相当する面に、Ｆｅ−Ｎｉ拡散層、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有し、更にその上層にロール圧延された光沢添加剤含有Ｎｉメッキ層または半光沢剤含有Ｎｉメッキ層を有することを特徴とする電池缶用Ｎｉメッキ鋼板が示されている。 In Patent Document 5, after Ni plating, Ni-P alloy plating is further performed and heat treatment is performed, so that a Ni-P alloy plating layer that is harder on the Fe-Ni diffusion layer and the recrystallized and softened Ni plating layer. A Ni-plated steel sheet having excellent corrosion resistance and scratch resistance is shown. Patent Document 6 discloses a plated steel sheet for battery cans having a bright Ni layer or a bright Ni-Co alloy plating layer as the outermost layer. In Patent Document 7, the surface corresponding to the outer surface of the battery can has an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer that is recrystallized and softened on the upper layer, and is further rolled to the upper layer. Further, there is shown a Ni-plated steel sheet for battery cans characterized by having a bright additive-containing Ni plating layer or a semi-brightening agent-containing Ni plating layer.
特許文献８では、電池缶外面に相当する面に、Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層を有し、更にその上層に未再結晶の軟質Ｎｉメッキ層を有することを特徴とする電池缶用Ｎｉメッキ鋼板が示されている。 In Patent Document 8, a Fe-Ni diffusion layer and a recrystallized and softened Ni plating layer are provided on the surface corresponding to the outer surface of the battery can, and an unrecrystallized soft Ni plating layer is provided on the upper layer. A Ni-plated steel sheet for battery cans is shown.
以上の特許文献５〜８の従来技術は一定の摺動性改善効果があるものの、高速、連続プレスにおける、油膜低下時の摺動性については必ずしも十分ではなく、プレス金型の磨耗やそれに伴うプレスコストの増大が問題となっている。 Although the conventional techniques of Patent Documents 5 to 8 described above have a certain slidability improving effect, the slidability at the time of oil film lowering is not necessarily sufficient in a high-speed, continuous press, and wear of the press die and associated with it Increased press cost is a problem.
本発明は、高速、連続プレスにおける、油膜低下時にも良好な摺動性を発現し、プレス金型の磨耗を抑制できるような摺動性に優れたＮｉメッキ鋼板およびその製造方法を提供することを目的とする。 The present invention provides a Ni-plated steel sheet that exhibits good slidability even when the oil film is lowered in a high-speed, continuous press and has excellent slidability that can suppress wear of a press die, and a method for producing the same. With the goal.
本発明者らは、Ｎｉメッキ鋼板の表層を光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層のいずれかとし、さらにその上層に、前記Ｎｉメッキ鋼板をアノード電解処理することにより酸化膜を形成することで、摺動性が顕著に改善されることを見出した。 The present inventors made the surface layer of the Ni-plated steel sheet either a gloss additive or a semi-gloss additive-containing Ni plating layer or a Ni alloy plating layer, and further anodic electrolytic treatment of the Ni-plated steel sheet on the upper layer It has been found that slidability is significantly improved by forming an oxide film.
すなわち本発明の要旨とするところは、表層が光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層のいずれかからなるＮｉメッキ鋼板において、前記Ｎｉメッキ鋼板の表層に前記Ｎｉメッキ鋼板をアノード電解処理することにより形成した酸化膜を有することを特徴とする摺動性に優れたＮｉメッキ鋼板である。 That is, the gist of the present invention is that, in a Ni-plated steel sheet whose surface layer is composed of either a gloss additive or a semi-gloss additive-containing Ni plating layer or a Ni alloy plating layer, the surface of the Ni-plated steel sheet is the Ni-plated steel sheet. This is a Ni-plated steel sheet having excellent slidability, characterized in that it has an oxide film formed by subjecting to anodic electrolysis.
また、表層が光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層のいずれかからなるＮｉメッキ鋼板の表層に、前記Ｎｉメッキ鋼板をアノード電解処理することにより酸化膜を形成することを特徴とする摺動性に優れたＮｉメッキ鋼板の製造方法である。前記酸化膜厚みは５ｎｍ以上であることが望ましい。 Further, an oxide film is formed by subjecting the Ni-plated steel sheet to an anodic electrolytic treatment on the surface layer of the Ni-plated steel sheet, the surface layer of which is either a bright additive, a semi-bright additive-containing Ni plated layer, or a Ni alloy plated layer. This is a method for producing a Ni-plated steel sheet excellent in slidability characterized by the following. The oxide film thickness is preferably 5 nm or more.
本発明により、摺動性に優れたＮｉメッキ鋼板が得られる。 By this invention, the Ni plating steel plate excellent in slidability is obtained.
以下図面を用いて本発明を詳細に説明する。図１は、市販のサッカリン系光沢添加剤を含有したワット浴から電析させた厚み２μｍの光沢添加剤含有Ｎｉメッキ層を有するＮｉメッキ鋼板を用い、７０℃の５ｇ／ｌ硫酸水溶液中で５Ａ／ｄｍ2の電流密度にてアノード電解し、処理時間を変更して種々の酸化膜厚みのサンプルを製造し、その酸化膜厚みと摺動性（摩擦係数）の関係を示したものである。図１において、酸化膜厚みは、ＡＥＳ（オージェ電子分析）により表層から深さ方向の元素分析を行い、Ｏ強度がアトミック％で５％となる深さを酸化膜厚みとした。また摺動性は、油膜切れ状態を模擬するため、２０ｍｇ／ｍ2の極薄塗油したサンプルを１０ｍｍ幅の平板金型で加重１２００ｋｇにて圧着し、５００ｍｍ／ｍｉｎにて引き抜き、摩擦係数を測定したものである。 Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows the use of a Ni-plated steel sheet having a gloss additive-containing Ni plating layer having a thickness of 2 μm, electrodeposited from a watt bath containing a commercially available saccharin-based gloss additive, in a 5 g / l sulfuric acid aqueous solution at 70 ° C. Samples with various oxide film thicknesses are produced by changing the treatment time by anodic electrolysis at a current density of / dm 2 , and the relationship between the oxide film thickness and slidability (friction coefficient) is shown. In FIG. 1, the oxide film thickness was determined by conducting elemental analysis in the depth direction from the surface layer by AES (Auger electron analysis), and the depth at which the O intensity was 5% in atomic% was defined as the oxide film thickness. In addition, in order to simulate the state of oil film slidability, a sample coated with 20 mg / m 2 of ultra-thin oil is pressure-bonded with a 10 mm-wide flat plate mold at a load of 1200 kg, and drawn at 500 mm / min. It is measured.
この図から明らかなように、アノード電解処理を施したものは、極めて良好な摺動性を示した。酸化膜厚みとしては５ｎｍ以上、特に１０ｎｍ以上の領域で良好であった。酸化膜厚みの上限は特に限定されないが、１００ｎｍを超えると外観が不安定になりやすいので、５〜１００ｎｍとするのがよい。 As is clear from this figure, those subjected to the anodic electrolysis treatment showed extremely good slidability. The oxide film thickness was good in the region of 5 nm or more, particularly 10 nm or more. The upper limit of the thickness of the oxide film is not particularly limited, but since the appearance tends to be unstable when it exceeds 100 nm, it is preferably 5 to 100 nm.
以上のような作用は、Ｎｉメッキ鋼板の表層が光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層のいずれかである場合に得られるものである。前記メッキ層は、適度に硬質（具体的にはビッカース硬度で３００〜６００程度）であるため、メッキ層が延伸しにくく、厳しい加工時も粗度が低下しにくく油膜保持能が維持されるとともに、前記Ｎｉメッキ層を表層に有する鋼板をアノード電解処理することにより形成した酸化膜は、メッキ層との密着性に優れ、固体潤滑作用を有することから、極めて良好な摺動性が得られるものと考えられる。 The effects as described above are obtained when the surface layer of the Ni-plated steel sheet is either a gloss additive, a semi-gloss additive-containing Ni plating layer, or a Ni alloy plating layer. Since the plating layer is moderately hard (specifically, about 300 to 600 in terms of Vickers hardness), the plating layer is difficult to stretch, and the roughness is hardly lowered even during severe processing, and the oil film retaining ability is maintained. The oxide film formed by subjecting the steel plate having the Ni plating layer to the anodic electrolysis treatment has excellent adhesion to the plating layer and has a solid lubricating action, so that extremely good slidability can be obtained. it is conceivable that.
アノード電解処理の方法としては特に限定されず、水溶液中で、常温〜８０℃の温度にて、０．１〜１００Ａ／ｄｍ2のアノード電解を行なえばよい。ただし、ここで注意が必要なのは、水溶液として強酸性水溶液を用いた場合、アノード電解によってＮｉメッキ層のエッチングが優先して起こり、酸化膜が形成されないため、酸性水溶液の場合には弱酸性水溶液とする必要がある。弱酸性水溶液としては、硫酸、塩酸、硝酸、リン酸等を単独あるいは複合で１０ｇ／ｌ未満の濃度とすることが望ましい。また前記濃度では電解質濃度が低く通電が安定しない場合があるため、さらに支持電解質として中性塩を複合添加することが望ましい。アルカリ性水溶液中では、適度な酸化膜厚みを得るのに長時間反応が必要であることから、生産性を考慮すると、中性あるいは弱酸性水溶液中での処理が望ましい。また、アルカリ性水溶液中での処理は反応速度が遅いものの均一に反応が進行しやすく、外観が安定しやすいといった利点もあることから、中性あるいは弱酸性水溶液中での処理に引き続いてアルカリ性水溶液中での処理を行うことも好適に用いられる。 The method of the anodic electrolysis is not particularly limited, and anodic electrolysis of 0.1 to 100 A / dm 2 may be performed in an aqueous solution at a temperature of normal temperature to 80 ° C. However, it should be noted here that when a strong acidic aqueous solution is used as the aqueous solution, the etching of the Ni plating layer occurs preferentially by anodic electrolysis, and no oxide film is formed. There is a need to. As the weakly acidic aqueous solution, it is desirable that sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid and the like be used alone or in combination to have a concentration of less than 10 g / l. In addition, since the electrolyte concentration is low at the above concentration, current conduction may not be stable, and it is desirable to add a neutral salt as a supporting electrolyte. In an alkaline aqueous solution, a long-time reaction is required to obtain an appropriate oxide film thickness. Therefore, in consideration of productivity, treatment in a neutral or weakly acidic aqueous solution is desirable. In addition, the treatment in an alkaline aqueous solution has the advantage that the reaction proceeds slowly and the appearance is easy to stabilize even though the reaction rate is slow. Therefore, following the treatment in a neutral or weakly acidic aqueous solution, It is also suitably used to perform the processing in (1).
中性あるいは弱酸性水溶液中での処理の場合、アノード電解の電流密度によっては耐食性が低下する場合がある。これを防止するためには電流密度として、２０Ａ／ｄｍ2以上、好ましくは３０Ａ／ｄｍ2以上とすればよい。またこの高電流密度でのアノード電解の場合、処理浴温度が低いと酸化膜が形成されにくい場合があることから、高めの温度、具体的には５０〜８０℃、好ましくは６０〜８０℃での処理が望ましい。 In the case of treatment in a neutral or weakly acidic aqueous solution, the corrosion resistance may be lowered depending on the current density of anode electrolysis. In order to prevent this, the current density may be 20 A / dm 2 or more, preferably 30 A / dm 2 or more. In the case of anodic electrolysis at this high current density, an oxide film may be difficult to be formed if the treatment bath temperature is low. Therefore, at a higher temperature, specifically 50 to 80 ° C., preferably 60 to 80 ° C. Is desirable.
アノード電解処理に先立っては、必要に応じてアルカリ脱脂処理や酸洗活性化処理等の前処理を行ってもよい。 Prior to the anode electrolytic treatment, pretreatment such as alkali degreasing treatment or pickling activation treatment may be performed as necessary.
本発明の鋼板は、Ｎｉメッキ以降にアノード電解処理を行って製造するものであり、アノード電解処理する表面が光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層のいずれかであれば、特にその工程は問わない。 The steel sheet of the present invention is manufactured by performing anodic electrolytic treatment after Ni plating, and the surface to be subjected to anodic electrolytic treatment is either a gloss additive, a semi-gloss additive-containing Ni plating layer, or a Ni alloy plating layer. The process is not particularly limited.
ただし、光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ層、Ｎｉ合金メッキ層は、厳しい加工時に、メッキ層が割れて耐食性が低下する懸念がある。これを回避する、本発明におけるもっとも好ましい形態は、鋼板にＮｉメッキを施した後、熱処理を行い、前記Ｎｉメッキ層の一部または全てをＦｅ−Ｎｉ拡散層とし、次いで光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ、Ｎｉ合金メッキのいずれかを施し、その後アノード電解処理するものである。アノード電解処理の前後のいずれでもロール圧延による形状の矯正と表面粗度の調整を行なうこともできる。また、光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ、Ｎｉ合金メッキのいずれかを施す前にロール圧延を行なうこともできる。ロール圧延は、ダルまたは鏡面ロールにて、伸び率０．１〜３％程度の処理が適用できる。 However, the gloss additive or semi-gloss additive-containing Ni plating layer or Ni alloy plating layer has a concern that the plating layer is broken and the corrosion resistance is lowered during severe processing. In order to avoid this, the most preferable mode in the present invention is that the steel plate is Ni-plated and then heat-treated to make a part or all of the Ni-plated layer an Fe-Ni diffusion layer, and then a gloss additive or semi-gloss Either additive-containing Ni plating or Ni alloy plating is applied, followed by anodic electrolytic treatment. It is possible to correct the shape by roll rolling and adjust the surface roughness either before or after the anode electrolytic treatment. Further, roll rolling can be performed before any of the gloss additive, the semi-gloss additive-containing Ni plating, or the Ni alloy plating is performed. Roll rolling can be applied with a dull or mirror roll with an elongation of about 0.1 to 3%.
また、上記の実施形態の場合、光沢添加剤あるいは半光沢添加剤含有Ｎｉメッキ、Ｎｉ合金メッキのいずれかは、片面にのみ施すこともできる。この場合、アノード電解処理は、前記メッキが施された面にのみ実施してもよいし、両面に実施してもよい。 In the case of the above-described embodiment, either the gloss additive, the semi-gloss additive-containing Ni plating, or the Ni alloy plating can be applied only to one side. In this case, the anodic electrolytic treatment may be performed only on the plated surface or on both surfaces.
（実施例１〜８および比較例１）
未再結晶のＮｂ，Ｔｉ−ＳＵＬＣ鋼に脱脂、酸洗の前処理の後、無光沢ワット浴による電気メッキでＮｉを２μｍ形成した。次いで無酸化雰囲気にて、８００℃、６０ｓｅｃ保持し、前記Ｎｉメッキ層のおよそ半分をＦｅ−Ｎｉ拡散層とした。更に脱脂、酸洗の後、市販のアセチレン系半光沢添加剤を含有したワット浴による電気メッキで半光沢Ｎｉを０．５μｍ形成した。次いで表１に示す条件にて、各種水溶液中、各種条件下でアノード電解処理を行った。いずれも処理後水洗乾燥した。なお、実施例７，８では［１］に示す条件のアノード電解処理の後、水洗し、引き続き［２］に示す条件のアノード電解処理を行い、水洗乾燥した。いずれのサンプルも伸び率１．２％の調質圧延を行い供試材とした。比較例１ではアノード電解処理を行わなかった。
(Examples 1-8 and Comparative Example 1)
Non-recrystallized Nb, Ti-SULC steel was degreased and pickled, and then Ni was formed by electroplating in a matte watt bath. Subsequently, it was kept at 800 ° C. for 60 seconds in a non-oxidizing atmosphere, and approximately half of the Ni plating layer was used as an Fe—Ni diffusion layer. Further, after degreasing and pickling, 0.5 μm of semi-gloss Ni was formed by electroplating using a Watt bath containing a commercially available acetylene-based semi-gloss additive. Next, anode electrolytic treatment was performed under various conditions in various aqueous solutions under the conditions shown in Table 1. All were washed and dried after treatment. In Examples 7 and 8, the anode electrolytic treatment under the condition shown in [1] was followed by washing with water, followed by the anode electrolytic treatment under the condition shown in [2], followed by washing with water and drying. All samples were subjected to temper rolling with an elongation of 1.2% to obtain test materials. In Comparative Example 1, no anodic electrolytic treatment was performed.
（実施例９および比較例２）
Ｎｉメッキ、熱処理を先の例と同様に施し、更に脱脂、酸洗の後、電気Ｓｎメッキを０．１μｍ施し、無酸化雰囲気にて４５０℃×６０ｓｅｃの熱処理を行い、表層にＮｉ−Ｓｎ合金層を形成した。
(Example 9 and Comparative Example 2)
Ni plating and heat treatment are performed in the same manner as the previous example, and after degreasing and pickling, electro Sn plating is performed to 0.1 μm, and heat treatment is performed at 450 ° C. × 60 sec in a non-oxidizing atmosphere, and a Ni—Sn alloy is formed on the surface layer. A layer was formed.
次いで表１に示す条件にて、アノード電解処理を行い、水洗乾燥した。伸び率１．２％の調質圧延を行い供試材とした。比較例２ではアノード電解処理を行わなかった。 Next, anodic electrolytic treatment was performed under the conditions shown in Table 1, followed by washing with water and drying. Temper rolling was performed at an elongation rate of 1.2% to obtain a test material. In Comparative Example 2, the anode electrolytic treatment was not performed.
（実施例１０および比較例３）
Ｎｉメッキ、熱処理を先の例と同様に施し、更に脱脂、酸洗の後、亜リン酸添加ワット浴による電気メッキでＰ５％のＮｉ−Ｐメッキを１μｍ形成した。次いで表１に示す条件にて、アノード電解処理を行い、水洗乾燥した。伸び率１．２％の調質圧延を行い供試材とした。比較例３ではアノード電解処理を行わなかった。
(Example 10 and Comparative Example 3)
Ni plating and heat treatment were performed in the same manner as in the previous example, and after degreasing and pickling, 1 μm of P—5% Ni—P plating was formed by electroplating using a phosphite-added watt bath. Next, anodic electrolytic treatment was performed under the conditions shown in Table 1, followed by washing with water and drying. Temper rolling was performed at an elongation rate of 1.2% to obtain a test material. In Comparative Example 3, the anode electrolytic treatment was not performed.
（性能評価方法）
（１）酸化膜厚み；ＡＥＳ（オージェ電子分析）により表層から深さ方向の元素分析を行い、Ｏ強度がアトミック％で５％となる深さを酸化膜厚みとした。
（２）摺動性；２０ｍｇ／ｍ2の極薄塗油したサンプルを１０ｍｍ幅の平板金型で加重１２００ｋｇにて圧着し、５００ｍｍ／ｍｉｎにて引き抜き、摩擦係数を測定した。０．１３未満を「○」、０．１３〜０．１７未満を「△」、０．１７以上を「×」と評価した。
（３）メッキ損傷；前記と同様の引抜を連続１０回行い、メッキ表面の損傷をＳＥＭ観察した。顕著な損傷のないものを「○」、あるものを「×」と評価した。
(Performance evaluation method)
(1) Thickness of oxide film: Elemental analysis in the depth direction from the surface layer was performed by AES (Auger electron analysis), and the depth at which the O intensity was 5% in atomic% was defined as the oxide film thickness.
(2) Sliding property: A sample coated with 20 mg / m 2 of ultrathin oil was pressure-bonded with a flat plate mold having a width of 10 mm at a load of 1200 kg, extracted at 500 mm / min, and the coefficient of friction was measured. Less than 0.13 was evaluated as “◯”, less than 0.13 to 0.17 was evaluated as “Δ”, and 0.17 or more was evaluated as “x”.
(3) Plating damage: The same drawing as described above was carried out 10 times continuously, and the damage of the plating surface was observed by SEM. Those with no significant damage were evaluated as “◯”, and those with some as “×”.
本発明の実施例では、良好な性能を示した。 The examples of the present invention showed good performance.
本発明により、高速、連続プレスにおける油膜低下時にも良好な摺動性を発現するＮｉメッキ鋼板が得られるため、プレス金型の磨耗を抑制できるなど、産業上の利用価値は多大である。 According to the present invention, a Ni-plated steel sheet that exhibits good slidability even when the oil film is lowered in a high-speed, continuous press can be obtained.
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