JP2007297696A - Ni-PLATED STEEL SHEET HAVING EXCELLENT SLIDABILITY AND CONTACT RESISTANCE AND ITS PRODUCTION METHOD - Google Patents
Ni-PLATED STEEL SHEET HAVING EXCELLENT SLIDABILITY AND CONTACT RESISTANCE AND ITS PRODUCTION METHOD Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 56
- 239000010959 steel Substances 0.000 title claims abstract description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000010410 layer Substances 0.000 claims abstract description 66
- 238000009792 diffusion process Methods 0.000 claims abstract description 21
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 19
- 239000002344 surface layer Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000005868 electrolysis reaction Methods 0.000 claims description 13
- 230000002378 acidificating effect Effects 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 39
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 8
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910018104 Ni-P Inorganic materials 0.000 description 2
- 229910018536 Ni—P Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007921 spray 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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- 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
Abstract
Description
本発明は、主に電池缶等の用途に用いられる摺動性と接触抵抗に優れた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 and contact resistance 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。この鋼板は、摺動性は良好であるが、接触抵抗が高いといった問題があった。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が、この鋼板も、摺動性は良好であるが、接触抵抗が高いといった問題があった。以上のように摺動性と接触抵抗はトレードオフの関係となりやすい。 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. This steel sheet has good sliding properties but has a problem of high contact resistance. In Patent Document 6, a plated steel sheet for battery cans having a bright Ni layer or a bright Ni-Co alloy plating layer as the outermost layer is shown, but this steel sheet also has good sliding properties. There was a problem that contact resistance was high. As described above, slidability and contact resistance tend to be in a trade-off relationship.
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おり、この鋼板は、摺動性は十分であるが、接触抵抗については、積極的に改善しようという思想はなく、いかに悪化しないようにするかに主眼が置かれていた。 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. A Ni-plated steel sheet for battery cans characterized by having a bright additive-containing Ni-plated layer or a semi-brightener-containing Ni-plated layer is shown. With regard to, there was no idea of positive improvement, and the main focus was on how to prevent deterioration.
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おり、この鋼板は、摺動性は厳しい条件下では十分でなく、また接触抵抗については、積極的に改善しようという思想はなく、いかに悪化しないようにするかに主眼が置かれていた。 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. Ni-plated steel sheet for battery cans is shown, and this steel sheet is not sufficient for slidability under severe conditions, and there is no idea to positively improve contact resistance. The main focus was on how to keep it from getting worse.
本発明は、摺動性と接触抵抗に優れたＮｉメッキ鋼板を提供することを目的とする。特に接触抵抗については、従来の悪化させない、という思想でなく積極的に改善する手法を提供することを目的とする。 An object of this invention is to provide the Ni plating steel plate excellent in slidability and contact resistance. In particular, an object of the present invention is to provide a method for positively improving contact resistance, not the conventional idea of not deteriorating.
本発明者らは、摺動性改善の手段として、Ｎｉ合金メッキや、光沢添加剤、半光沢添加剤含有Ｎｉメッキを用いると、メッキ層の導電性が低下しやすいため、接触抵抗改善には限界があることを知見した。そこで、他の方法を検討したところ、Ｎｉメッキ鋼板の表層をＦｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉ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、摺動性は顕著に改善されるとともに、接触抵抗も悪化しないばかりでなく、意外にも改善される領域があることを見出した。 The present inventors use Ni alloy plating, gloss additive, or semi-gloss additive-containing Ni plating as means for improving slidability, because the conductivity of the plating layer is likely to be lowered. I found that there was a limit. Therefore, when other methods were examined, the surface layer of the Ni-plated steel sheet was either an Fe-Ni diffusion layer, a recrystallized / softened Ni-plated layer, or a non-recrystallized soft Ni-plated layer, and the upper layer thereof, By forming an oxide film by subjecting the Ni-plated steel sheet to anodic electrolysis, the slidability is remarkably improved, the contact resistance is not deteriorated, and there is an unexpectedly improved region. I found it.
すなわち本発明の要旨とするところは、表層がＦｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉ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と接触抵抗に優れたＮｉメッキ鋼板である。 That is, the gist of the present invention is that the Ni-plated steel sheet is a Ni-plated steel sheet whose surface layer is one of an Fe-Ni diffusion layer, a recrystallized soft Ni-plated layer, and a non-recrystallized soft Ni-plated layer. A Ni-plated steel sheet excellent in slidability and contact resistance, characterized in that it has an oxide film formed by subjecting the Ni-plated steel sheet to anodic electrolysis on the surface layer.
また、表層がＦｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉ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と接触抵抗に優れたＮｉメッキ鋼板の製造方法である。前記酸化膜厚みは５〜２００ｎｍであることが望ましい。 Further, the surface of the Ni-plated steel plate, the surface layer of which is any one of a Fe—Ni diffusion layer, a recrystallized / softened Ni-plated layer, and a non-recrystallized soft Ni-plated layer, is subjected to anodic electrolytic treatment of the Ni-plated steel plate This is a method for producing a Ni-plated steel sheet excellent in slidability and contact resistance, characterized in that an oxide film is formed. The thickness of the oxide film is preferably 5 to 200 nm.
本発明の鋼板は、表層に酸化膜を有しながら、接触抵抗を改善するという、一見奇異な特性を有する。この理由は、Ｆｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉメッキ層のいずれかからなる表層に、アノード電解処理により形成された酸化膜は、電子伝導性を有するとともに、その摺動性改善効果に起因して、鋼板表層と接触端子との接触状態を安定化させるはたらきがあることによると推定される。実用的な観点からも、接触による導通が取られる場合には、多かれ少なかれ必ず表面のミクロな摺動が伴うため、適切な酸化膜を表層に形成することで、摺動性と接触抵抗が改善されたＮｉメッキ鋼板を得ることができるのである。 The steel sheet of the present invention has a seemingly strange property of improving contact resistance while having an oxide film on the surface layer. The reason for this is that the oxide film formed by anodic electrolytic treatment on the surface layer composed of any one of the Fe-Ni diffusion layer, the recrystallized and softened Ni plated layer, and the non-recrystallized soft Ni plated layer is electrically conductive. It is presumed that there is a function to stabilize the contact state between the steel plate surface layer and the contact terminal due to the effect of improving the slidability. From a practical point of view, when contact conduction is achieved, there is always more or less micro sliding of the surface, so the formation of an appropriate oxide film on the surface layer improves the slidability and contact resistance. The obtained Ni-plated steel sheet can be obtained.
本発明により、摺動性と接触抵抗に優れたＮｉメッキ鋼板が得られる。 By this invention, the Ni plating steel plate excellent in slidability and contact resistance is obtained.
以下図面を用いて本発明を詳細に説明する。図１および図２は、Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなる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）および接触抵抗の関係を求めたものである。図１，２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。また図１の摺動性は、ｈｅｉｄｏｎ１４型試験装置を用い、完全無塗油条件にて、鋼板サンプルを１０ｍｍφステンレス球で２００ｇの荷重で連続１０回摺動した場合の摩擦係数を求めたものである。さらに図２における接触抵抗は、山崎精機研究所製電気接点シュミレータＣＲＳ−１を用い、荷重２０ｇにおける鋼板サンプルの接触抵抗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 and FIG. 2 show a current density of 5 A / dm 2 in a 5 g / l sulfuric acid aqueous solution at 70 ° C. using a Ni-plated steel sheet comprising a Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened thereon. In this example, samples having various oxide film thicknesses were produced by changing the processing time by anodic electrolysis, and the relationship between the oxide film thickness, slidability (friction coefficient), and contact resistance was obtained. In FIGS. 1 and 2, 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, the slidability in FIG. 1 is obtained by calculating the coefficient of friction when a steel plate sample is slid continuously 10 times with a load of 200 g with a 10 mmφ stainless steel ball under a completely oil-free condition using a heidon 14 type test apparatus. is there. Furthermore, the contact resistance in FIG. 2 measured the contact resistance of the steel plate sample in the load of 20 g using Yamazaki Seiki Laboratory electric contact simulator CRS-1.
これら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、また接触抵抗も大きく劣化しないばかりでなく、酸化膜厚み５〜２００ｎｍの領域では、アノード電解処理を施さないものよりも良好な接触抵抗を示す。またこれら図から、摺動性、接触抵抗が極めて良好な、好ましい酸化膜厚み範囲としては１０〜１００ｎｍ、更により好ましい範囲としては１０〜３０ｎｍであることもわかる。 As is apparent from these figures, those subjected to the anodic electrolysis showed extremely good slidability and the contact resistance was not greatly deteriorated. In addition, in the region having an oxide film thickness of 5 to 200 nm, the anodic electrolysis was performed. It shows better contact resistance than those not subjected to. From these figures, it can also be seen that the slidability and contact resistance are very good, the preferred oxide film thickness range is 10 to 100 nm, and the still more preferred range is 10 to 30 nm.
以上のような作用は、Ｎｉメッキ鋼板の表層がＦｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉメッキ層のいずれかである場合に得られるものであり、例えば、Ｎｉ合金メッキや、光沢添加剤、半光沢添加剤含有Ｎｉメッキが表層にある場合には、この効果は得られない。 The action as described above is obtained when the surface layer of the Ni-plated steel sheet is any one of an Fe-Ni diffusion layer, a recrystallized and softened Ni plated layer, and an unrecrystallized soft Ni plated layer, For example, this effect cannot be obtained when Ni alloy plating, gloss additive, or semi-gloss additive-containing Ni plating is present on the surface layer.
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。 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, etc. 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.
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。 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Ｆｅ−Ｎｉ拡散層、再結晶軟質化されたＮｉメッキ層、未再結晶の軟質Ｎｉメッキ層のいずれかであれば、特にその工程は問わない。例えば、Ｎｉメッキして直後にアノード電解処理を施してもよいし、Ｎｉメッキとアノード電解処理の工程の間に、熱処理によるＦｅ−Ｎｉ拡散層の形成あるいはＮｉの再結晶軟質化処理を実施してもよい。また、Ｎｉメッキ後に熱処理によるＦｅ−Ｎｉ拡散層の形成あるいはＮｉの再結晶軟質化処理行い、さらにその上層にＮｉメッキを施してその後アノード電解処理を実施してもよい。また、いずれの場合でも、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。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。 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 Fe-Ni diffusion layer, recrystallized soft Ni plated layer, non-recrystallized soft Ni. The process is not particularly limited as long as it is any of the plating layers. For example, anodic electrolytic treatment may be performed immediately after Ni plating, or an Fe—Ni diffusion layer is formed by heat treatment or Ni recrystallization softening treatment is performed between the steps of Ni plating and anodic electrolytic treatment. May be. Alternatively, after Ni plating, an Fe—Ni diffusion layer may be formed by heat treatment or Ni recrystallization softening treatment may be performed, and Ni plating may be applied to the upper layer, followed by anodic electrolytic treatment. In any case, it is possible to correct the shape by roll rolling and adjust the surface roughness either before or after the anode electrolytic treatment. Roll rolling can be applied with a dull or mirror roll with an elongation of about 0.1 to 3%.
アノード電解処理は片面にのみ施すこともできる。例えば電池缶用途の場合は、缶外面になる面に、より摺動性、接触抵抗が求められることから、この面にのみ施すことも可能である。 The anodic electrolytic treatment can be applied only to one side. For example, in the case of a battery can application, since the slidability and contact resistance are required on the surface that becomes the outer surface of the can, it can be applied only to this surface.
（実施例１〜６および比較例１，２）
Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるＮｉ拡散メッキ層を有する、Ｎｂ，Ｔｉ−ＳＵＬＣ鋼のＮｉメッキ鋼板を原板として用いた。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５，６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０．２％の調質圧延を行い供試材とした。比較例１では同一原板にアノード電解処理を行わずに調質圧延のみを行った。比較例２では、同一原板に更に半光沢添加剤含有Ｎｉメッキを施し更に調質圧延を行った。
(Examples 1 to 6 and Comparative Examples 1 and 2)
A Ni-plated steel plate of Nb, Ti-SULC steel having a Ni-diffusion plated layer composed of an Fe-Ni diffusion layer and a recrystallized and softened Ni-plated layer as an upper layer was used as the original plate. Under the conditions shown in Table 1, anodic electrolysis was performed in various aqueous solutions under various conditions. All were washed and dried after treatment. In Examples 5 and 6, the anode electrolytic treatment under the conditions shown in [1] was followed by washing with water, followed by the anode electrolytic treatment under the conditions shown in [2], followed by washing and drying. All samples were subjected to temper rolling with an elongation rate of 0.2% to obtain test materials. In Comparative Example 1, only the temper rolling was performed on the same original plate without performing the anode electrolytic treatment. In Comparative Example 2, Ni plating containing a semi-gloss additive was further applied to the same original plate, and temper rolling was further 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；ｈｅｉｄｏｎ１４型試験装置を用い、完全無塗油条件にて、鋼板サンプルを１０ｍｍφステンレス球で２００ｇの荷重で連続１０回摺動し、平均の動摩擦係数を求めた。０．３未満を「○」、０．３以上を「×」と評価した。
（３）接触抵抗；山崎精機研究所製電気接点シュミレータＣＲＳ−１を用い、荷重２０ｇにおける鋼板サンプルの接触抵抗を測定した３０ｍΩ未満を「○」、３０ｍΩ以上を「×」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: Using a heidon 14 type test apparatus, a steel plate sample was slid continuously 10 times with a load of 200 g with a 10 mmφ stainless steel ball under completely oil-free conditions, and an average dynamic friction coefficient was obtained. Less than 0.3 was evaluated as “◯”, and 0.3 or more was evaluated as “x”.
(3) Contact resistance: Using an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Laboratories, the contact resistance of a steel sheet sample at a load of 20 g was evaluated as “◯”, and 30 mΩ or more was evaluated as “×”.
本発明の実施例では、摺動性、接触抵抗とも、良好な性能を示した。 In the examples of the present invention, both the slidability and the contact resistance showed good performance.
（実施例７〜１０および比較例３，４）
Ｆｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるＮｉ拡散メッキ層を有する、Ｎｂ，Ｔｉ−ＳＵＬＣ鋼のＮｉメッキ鋼板を原板として用いた（メッキのＮｉ量は１０ｇ／ｍ2）。表２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１１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０．２％の調質圧延を行い供試材とした。比較例４では同一原板にアノード電解処理を行わずに調質圧延のみを行った。
(Examples 7 to 10 and Comparative Examples 3 and 4)
A Ni-plated steel plate of Nb, Ti-SULC steel having a Ni-diffusion plated layer consisting of an Fe-Ni diffusion layer and a recrystallized and softened Ni-plated layer on the upper layer was used as the original plate (the Ni amount of plating was 10 g / m 2 ). Under the conditions shown in Table 2, anodic electrolysis was performed in various aqueous solutions under various conditions. All were washed and dried after treatment. In Example 11, 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 rate of 0.2% to obtain test materials. In Comparative Example 4, only the temper rolling was performed on the same original plate without performing the anode electrolytic treatment.
性能評価は先の例と同様に行なった。またあわせて耐食性評価を次のように行なった。平板サンプルのエッジをテープシールし、ＪＩＳＺ２３７１の塩水噴霧試験を２４Ｈｒ行い、画像解析にて赤錆面積率を評価した。 The performance evaluation was performed in the same manner as in the previous example. In addition, the corrosion resistance was evaluated as follows. The edge of the flat plate sample was tape-sealed, a salt spray test of JISZ2371 was conducted for 24 hours, and the red rust area ratio was evaluated by image analysis.
表２に示す実施例では、摺動性、接触抵抗に加えて耐食性も良好な性能を示した。 In the examples shown in Table 2, in addition to the slidability and contact resistance, the corrosion resistance was good.
本発明により、摺動性、接触抵抗に優れたＮｉメッキ鋼板が得られるため、電池、電池缶の高性能化、低コスト化に資するものである。 According to the present invention, a Ni-plated steel sheet excellent in slidability and contact resistance can be obtained, which contributes to high performance and low cost of batteries and battery cans.
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| JPS61113794A (en) * | 1984-11-08 | 1986-05-31 | Sumitomo Metal Ind Ltd | Manufacture of blackening-treated steel plate |
| JPS61124580A (en) * | 1984-11-22 | 1986-06-12 | Nippon Steel Corp | Production of solar heat absorption plate |
| JPH01119651A (en) * | 1987-10-30 | 1989-05-11 | Nippon Steel Corp | Plated steel sheet excellent in spot weldability |
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| JP2014112552A (en) * | 2014-02-06 | 2014-06-19 | Gs Yuasa Corp | Battery |
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