JP2007254847A - METHOD FOR MANUFACTURING HIGH PURITY Ni-DIFFUSION PLATED STEEL SHEET - Google Patents
METHOD FOR MANUFACTURING HIGH PURITY Ni-DIFFUSION PLATED STEEL SHEET Download PDFInfo
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- 238000009792 diffusion process Methods 0.000 title claims abstract description 65
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 47
- 239000010959 steel Substances 0.000 title claims abstract description 47
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 12
- 238000007747 plating Methods 0.000 claims abstract description 41
- 239000012535 impurity Substances 0.000 claims abstract description 26
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000005096 rolling process Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 13
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 239000010960 cold rolled steel Substances 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 abstract description 41
- 239000002344 surface layer Substances 0.000 abstract description 11
- 239000000243 solution Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 230000002950 deficient Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910000655 Killed steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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、未焼鈍冷延鋼板にＮｉメッキした後、拡散焼鈍処理を行い、鋼板の再結晶焼鈍と拡散層の形成を行い、Ｆｅ−Ｎｉ拡散層のみからなるか、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるＮｉ拡散メッキ層を有したＮｉ拡散メッキ鋼板の製造方法に関し、形成されたＮｉ拡散メッキ層の不純物を極限まで低下させる方法に関する。 In the present invention, Ni plating is performed on an unannealed cold-rolled steel sheet, followed by diffusion annealing treatment, recrystallization annealing of the steel sheet and formation of a diffusion layer, and only the Fe-Ni diffusion layer or the Fe-Ni diffusion layer Further, the present invention relates to a method of manufacturing a Ni diffusion plated steel sheet having a Ni diffusion plating layer made of a recrystallized and softened Ni plating layer, and a method of reducing impurities in the formed Ni diffusion plating layer to the limit.
電池缶等に用いられるＮｉメッキ鋼板素材について、プレス加工時のメッキ密着性や、電池缶としての耐食性を向上させる目的で、未焼鈍冷延鋼板に、対極を純Ｎｉとした無光沢ワット浴による電気メッキを行いＮｉメッキ層を形成した後、拡散焼鈍処理を行い、鋼板の再結晶焼鈍と拡散層の形成を行い、Ｆｅ−Ｎｉ拡散層のみからなるか、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるＮｉ拡散メッキ層を有したＮｉ拡散メッキ鋼板とした後、調質圧延を行うＮｉ拡散メッキ鋼板の製造方法が知られている（例えば特許文献１、特許文献２、特許文献３）。 For Ni-plated steel sheet materials used in battery cans, etc., with a matte Watt bath with pure Ni as the counter electrode for unannealed cold-rolled steel sheets for the purpose of improving plating adhesion during press working and corrosion resistance as battery cans After forming the Ni plating layer by electroplating, the diffusion annealing treatment is performed, the recrystallization annealing of the steel sheet and the formation of the diffusion layer are performed, and it consists only of the Fe—Ni diffusion layer, or the Fe—Ni diffusion layer and its upper layer. There is known a method for producing a Ni diffusion plated steel sheet that is subjected to temper rolling after forming a Ni diffusion plated steel sheet having a Ni diffusion plating layer made of a recrystallized and softened Ni plating layer (for example, Patent Document 1, Patent Document 2 and Patent Document 3).
特許文献１、２の鋼板は良好な性能を有するも、その適用範囲が拡大するにつれて、表面の接触抵抗値が高い場合がある、電池の特性を悪くする場合がある、といった新たな課題が発生し、これらの不良の原因は、Ｎｉ拡散メッキ層、特に最表層付近に濃化する不純物が原因となっていた。 Although the steel sheets of Patent Documents 1 and 2 have good performance, new problems such as the contact resistance value of the surface may be high and the characteristics of the battery may be deteriorated as the application range is expanded. These defects are caused by impurities concentrated in the Ni diffusion plating layer, particularly in the vicinity of the outermost layer.
上記課題に対し、本発明者は、Ｎｉ拡散メッキ表層に濃化する不純物の特定を検討したところ、メッキ液中の不純物に加えて、原板である鋼板の不可避的不純物あるいは材質発現のために添加する元素（具体的には、Ｍｎ、Ｓｉ、Ｐ、Ｔｉ、Ｎｂ、Ｓ、等の易酸化成分）が、微量ではあるが、拡散焼鈍中にＮｉメッキ層の微小欠陥部や結晶粒界部を通じて表層に濃化することを見出し、これらの効果的な除去方法として拡散焼鈍処理後の酸水溶液による処理が有効であり、極めて高純度のＮｉ拡散メッキ層を有するＮｉ拡散メッキ鋼板が製造できることを見出し本発明に至った。すなわち本発明の要旨とするところは、未焼鈍冷延鋼板に、対極を純Ｎｉとした無光沢ワット浴による電気メッキを行いＮｉメッキ層を形成した後、拡散焼鈍処理を行い、鋼板の再結晶焼鈍と拡散層の形成を行い、Ｆｅ−Ｎｉ拡散層のみからなるか、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるＮｉ拡散メッキ層を有したＮｉ拡散メッキ鋼板とした後、調質圧延を行うＮｉ拡散メッキ鋼板の製造方法において、
拡散焼鈍後、調質圧延前に酸水溶液による処理を行い、上記Ｎｉ拡散メッキ鋼板のＮｉ拡散メッキ層表層に濃化した不純物を除去することを特徴とする高純度Ｎｉ拡散メッキ鋼板の製造方法である。
In response to the above problems, the present inventor examined the identification of impurities concentrated on the Ni diffusion plating surface layer. In addition to impurities in the plating solution, the present inventors added them for the inevitable impurities or material expression of the original steel plate. Although there are trace amounts of elements (specifically, easily oxidizable components such as Mn, Si, P, Ti, Nb, S, etc.), during diffusion annealing, they pass through minute defects and crystal grain boundaries in the Ni plating layer. It has been found that the surface layer is concentrated, and as an effective removal method thereof, the treatment with the acid aqueous solution after the diffusion annealing treatment is effective, and it has been found that a Ni diffusion plated steel sheet having an extremely high purity Ni diffusion plating layer can be produced. The present invention has been reached. In other words, the gist of the present invention is that an unannealed cold-rolled steel sheet is electroplated with a matte Watt bath with pure Ni as the counter electrode to form a Ni-plated layer, and then subjected to diffusion annealing treatment to recrystallize the steel sheet. Ni diffusion plating with annealing and diffusion layer formation, consisting only of Fe-Ni diffusion layer, or Ni diffusion plating layer consisting of Fe-Ni diffusion layer and recrystallized and softened Ni plating layer thereon In the manufacturing method of the Ni diffusion plating steel sheet that performs temper rolling after making the steel sheet,
In the method for producing a high-purity Ni diffusion-plated steel sheet, characterized in that after diffusion annealing, treatment with an acid aqueous solution is performed before temper rolling, and impurities concentrated on the surface of the Ni diffusion-plated layer of the Ni diffusion-plated steel sheet are removed. is there.
本発明により、未焼鈍冷延鋼板にＮｉメッキした後、拡散焼鈍処理を行い、鋼板の再結晶焼鈍と拡散層の形成を行うＮｉ拡散メッキ鋼板の製造方法において、Ｎｉ拡散メッキ層の不純物を極限まで低下させることが可能となり、接触抵抗、電池特性、等を改善することが可能となる。 According to the present invention, after Ni plating is performed on an unannealed cold-rolled steel sheet, diffusion annealing treatment is performed to recrystallize the steel sheet and form a diffusion layer. The contact resistance, battery characteristics, etc. can be improved.
（未焼鈍冷延鋼板）
本発明に用いられるメッキ原板としての未焼鈍冷延鋼板は、電池缶等の加工を受けることを考慮した成分系が望ましく、具体的にはＴｉ，Ｎｂを単独あるいは複合添加した極低炭素鋼板、または低炭素Ａｌキルド鋼板であることが望ましい。
(Unannealed cold-rolled steel sheet)
The unannealed cold-rolled steel sheet as the plating base plate used in the present invention is preferably a component system that takes into account the processing of battery cans and the like, specifically, an ultra-low carbon steel sheet with Ti or Nb added alone or in combination, Or it is desirable that it is a low carbon Al killed steel plate.
（Ｎｉメッキ）
Ｎｉメッキとしては、その不純物を最小化する観点から、対極を純Ｎｉとした無光沢ワット浴による電気メッキ法が必要である。ワット浴はＮｉの析出効率が高いため、不純物が共析することが少ない。光沢添加剤あるいは半光沢添加剤を含有した浴では、前記添加剤起因のＣ、Ｓ等不純物が共析することから好ましくなく、無光沢ワット浴が必要である。ワット浴の場合、Ｎｉイオン補給をかねる対極として金属Ｎｉが用いられ、この際，Ｎｉの溶解、イオン化を促進する目的で、微量の不純物（Ｓ，Ｐ，Ｃ等）を含有させた金属Ｎｉが用いられることもあるが、本発明においては好ましくなく、前記不純物を含有させない純Ｎｉを対極とすることが必要である。Ｎｉメッキは、両面とも、片面のみ、表裏差厚のいずれでも可能である。
(Ni plating)
As the Ni plating, from the viewpoint of minimizing the impurities, an electroplating method using a matte Watt bath with a counter electrode made of pure Ni is necessary. Since the Watt bath has high Ni deposition efficiency, impurities are less likely to co-deposit. In a bath containing a glossy or semi-glossy additive, impurities such as C and S resulting from the additive are not preferable, and a matte watt bath is required. In the case of the Watt bath, metallic Ni is used as a counter electrode that also replenishes Ni ions. At this time, metallic Ni containing a small amount of impurities (S, P, C, etc.) is used for the purpose of promoting dissolution and ionization of Ni. Although it may be used, it is not preferable in the present invention, and it is necessary to use pure Ni that does not contain the impurities as a counter electrode. Ni plating can be performed on both sides, only on one side, or on both sides.
（拡散焼鈍処理）
Ｎｉメッキ後の拡散焼鈍処理において、鋼板の再結晶焼鈍とＮｉ拡散メッキ層の形成を行なう。Ｎｉ拡散メッキ層とは、Ｆｅ−Ｎｉ拡散層のみからなるか、またはＦｅ−Ｎｉ拡散層とその上層に再結晶軟質化されたＮｉメッキ層からなるものである。拡散焼鈍条件として具体的には、不活性ガスまたは還元性のガス雰囲気中で７００〜８５０℃程度の温度で均熱時間２０〜６０ｓｅｃ程度の処理を行う。ここで、最終的に得られる鋼板の耐食性を考慮した場合には、Ｎｉメッキ層の一部のみをＦｅ−Ｎｉ拡散層とし、表層に再結晶軟質化したＮｉメッキ層を残存させておくことが望ましい。
(Diffusion annealing treatment)
In the diffusion annealing treatment after Ni plating, recrystallization annealing of the steel plate and formation of the Ni diffusion plating layer are performed. The Ni diffusion plating layer is composed of only an Fe—Ni diffusion layer, or an Fe—Ni diffusion layer and an Ni plating layer recrystallized and softened on the Fe—Ni diffusion layer. Specifically, the diffusion annealing is performed in an inert gas or reducing gas atmosphere at a temperature of about 700 to 850 ° C. for a soaking time of about 20 to 60 seconds. Here, when considering the corrosion resistance of the finally obtained steel sheet, only a part of the Ni plating layer may be an Fe—Ni diffusion layer, and the re-softened Ni plating layer may remain on the surface layer. desirable.
（酸水溶液による処理）
上記の処理を行うと、メッキ液中の不純物に加えて、原板である鋼板の不可避的不純物あるいは材質発現のために添加する元素（具体的には、Ｍｎ、Ｓｉ、Ｐ、Ｔｉ、Ｎｂ、Ｓ、等の易酸化成分）が、微量ではあるが、Ｎｉメッキ層の微小欠陥部や結晶粒界部を通じてＮｉ拡散メッキ表層に濃化するため、これらを除去することが必要である。
(Treatment with acid aqueous solution)
When the above treatment is performed, in addition to impurities in the plating solution, inevitable impurities of the steel plate that is the original plate or elements added for material development (specifically, Mn, Si, P, Ti, Nb, S However, it is necessary to remove these components because they are concentrated in the Ni diffusion plating surface layer through the minute defect portion and the crystal grain boundary portion of the Ni plating layer.
除去方法としては、酸水溶液による処理が必要であり、具体的には硫酸、塩酸、硝酸、有機酸等の単独あるいは混合水溶液が用いられる。前記水溶液に４０〜８０℃で５〜１００秒程度浸漬する方法が有効である。より好ましい処理としては、硫酸水溶液中で鋼板の極性をカソードとして電解する。さらに好ましくは、硫酸水溶液中で鋼板の極性を切り替えながら電解し、最後の極性をカソードとして処理する。硫酸水溶液としては、１０〜２００ｇ／ｌ程度の濃度で、常温〜６０℃程度の温度が用いられる。電解の際の電流密度としては、１Ａ／ｄｍ2〜２０Ａ／ｄｍ2程度が望ましく、処理時間としては１〜６０秒が望ましい。なお、電解の場合、アノード処理のみの電解では耐食性が悪化する場合があり好ましくない。 As the removal method, treatment with an aqueous acid solution is required, and specifically, a single or mixed aqueous solution of sulfuric acid, hydrochloric acid, nitric acid, organic acid or the like is used. A method of immersing in the aqueous solution at 40 to 80 ° C. for about 5 to 100 seconds is effective. As a more preferable treatment, electrolysis is performed in a sulfuric acid aqueous solution with the polarity of the steel sheet as the cathode. More preferably, electrolysis is performed while switching the polarity of the steel sheet in an aqueous sulfuric acid solution, and the final polarity is treated as a cathode. As the sulfuric acid aqueous solution, a temperature of about room temperature to about 60 ° C. is used at a concentration of about 10 to 200 g / l. The current density during electrolysis is preferably about 1 A / dm 2 to 20 A / dm 2 , and the processing time is preferably 1 to 60 seconds. In the case of electrolysis, the corrosion resistance may be deteriorated by electrolysis only by anodizing, which is not preferable.
このような方法によってＮｉ拡散メッキ表層に濃化した微量不純物は効果的に除去できる。 Trace impurities concentrated on the Ni diffusion plating surface layer by such a method can be effectively removed.
前記のような電解法は、浸漬法よりも低温、短時間処理が可能であり、生産性や設備へのダメージの点で有利である。 The electrolytic method as described above can be processed at a lower temperature and for a shorter time than the dipping method, and is advantageous in terms of productivity and damage to equipment.
（調質圧延）
上記の不純物除去処理の後に、ロール圧延によって形状を矯正するとともに粗度を調整することも可能である。なお、不純物除去処理の前にロール圧延を行ってしまうと、その後に酸水溶液による処理を行っても、効果的な除去が困難となるため好ましくない。
(Temper rolling)
After the impurity removal treatment, the shape can be corrected by roll rolling and the roughness can be adjusted. In addition, if roll rolling is performed before the impurity removal treatment, even if treatment with an aqueous acid solution is performed thereafter, effective removal becomes difficult, which is not preferable.
板厚０．３ｍｍの冷延、未再結晶鋼板（ＮｂＴｉ−ＳＵＬＣ鋼）をメッキ原板とした。アルカリ脱脂、酸洗処理の後、無光沢ｗａｔｔ浴（硫酸Ｎｉ：３００ｇ／ｌ、塩化Ｎｉ：７０ｇ／ｌ、ホウ酸：７０ｇ／ｌ）を用い、対極を純Ｎｉ板とし、０．３ｍ／ｓｅｃの液流速にて６０℃で１８ｇ／ｍ2のＮｉを電析させた。ただし実施例５および比較例４では９ｇ／ｍ2のＮｉを電析させた。その後、拡散焼鈍処理を行った。無酸化雰囲気にて、８００℃まで昇温し、４０ｓｅｃの均熱の後、室温まで冷却することで、Ｆｅ−Ｎｉ拡散層の上層に再結晶軟質化したＮｉ層を有するＮｉ拡散メッキ鋼板を製造した。ただし実施例５および比較例４では同条件で表層までＦｅ−Ｎｉ拡散層を有するＮｉ拡散メッキ鋼板を製造した。 A cold-rolled, non-recrystallized steel plate (NbTi-SULC steel) having a thickness of 0.3 mm was used as a plating original plate. After alkaline degreasing and pickling treatment, a matte watt bath (sulfuric acid Ni: 300 g / l, Ni chloride: 70 g / l, boric acid: 70 g / l) is used, and the counter electrode is a pure Ni plate, 0.3 m / sec. 18 g / m 2 of Ni was electrodeposited at 60 ° C. with a liquid flow rate of However, in Example 5 and Comparative Example 4, 9 g / m 2 of Ni was electrodeposited. Thereafter, a diffusion annealing treatment was performed. In a non-oxidizing atmosphere, heated to 800 ° C, soaked for 40 seconds, and then cooled to room temperature to produce a Ni diffusion plated steel sheet having a recrystallized and softened Ni layer on top of the Fe-Ni diffusion layer did. However, in Example 5 and Comparative Example 4, a Ni diffusion plated steel sheet having an Fe—Ni diffusion layer up to the surface layer was manufactured under the same conditions.
その後、表１に示す各種条件での処理を行った。表中の極性で「Ａ」は鋼板をアノードとして電解したことを意味し、「Ｃ」は鋼板をカソードとして電解したことを意味する。「ＡＣ」はアノード→カソードと繰り返したことを意味する。またカッコ内の数値は電解の電流密度Ａ／ｄｍ2を示す。各処理の後、水洗乾燥し、ダルロールにて伸び率０．３％の調質圧延を行いサンプルを完成した。 Then, the process on various conditions shown in Table 1 was performed. In the table, “A” means that the steel plate was electrolyzed as an anode, and “C” means that the steel plate was electrolyzed as a cathode. “AC” means repetition of anode → cathode. Numerical values in parentheses indicate electrolysis current density A / dm 2 . After each treatment, it was washed with water and dried, and temper rolled with an elongation of 0.3% using a dull roll to complete a sample.
性能評価は以下のように行った。 The performance evaluation was performed as follows.
（表面不純物）：ＳＥＭにより５０００〜２００００倍の倍率にて表面観察を行うとともに、ＥＤＳによって元素定性を行い、結晶粒界あるいはその近傍に不純物（Ｎｉ、Ｆｅ以外の元素、Ｍｎ、Ｓｉ、Ｐ、Ｔｉ、Ｎｂ、Ｓ、Ｏ等）の濃化スポットがあるかどうか確認した。１０視野観察して、ないものを「○」、数視野にあるものを「△」、全視野にあるものを「×」と評価した。 (Surface impurities): The surface is observed by SEM at a magnification of 5000 to 20000 times, and element qualification is performed by EDS, and impurities (elements other than Ni and Fe, Mn, Si, P, (Ti, Nb, S, O, etc.) were confirmed to have a concentrated spot. Ten fields of view were observed, and those that were not present were evaluated as “◯”, those in several fields as “Δ”, and those in all fields as “×”.
（接触抵抗）：鋼板サンプルをプレス加工し、通常のＬＲ０６型アルカリマンガン電池用の缶を製造し、６０℃９５％ＲＨに２０日間放置した後、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５０ｇにて正極端子部外面の接触抵抗を測定した。１０ｍΩ未満を「○」、１０ｍΩ以上２０ｍΩ未満を「△」、２０ｍΩ以上を「×」と評価した。 (Contact resistance): A steel plate sample was pressed to produce a can for an ordinary LR06 type alkaline manganese battery, and left at 60 ° C. and 95% RH for 20 days. Then, an electrical contact simulator CRS-1 manufactured by Yamazaki Seiki Lab. The contact resistance of the outer surface of the positive electrode terminal portion was measured at a load of 50 g. Less than 10 mΩ was evaluated as “◯”, 10 mΩ or more and less than 20 mΩ was evaluated as “Δ”, and 20 mΩ or more was evaluated as “X”.
（耐食性）：５％ＮａＣｌ＋５％Ｈ2Ｏ2水溶液に常温で３時間浸漬し、赤錆発生状況を目視観察した。錆発生がほとんどないものを「○」、僅かにあるものを「△」、全面錆発生を「×」と評価した。 (Corrosion resistance): It was immersed in a 5% NaCl + 5% H 2 O 2 aqueous solution at room temperature for 3 hours, and the occurrence of red rust was visually observed. The case where there was almost no rust was evaluated as “◯”, the case where there was a little rust was evaluated as “△”, and the entire surface was evaluated as “×”.
表１に結果を示すが、本発明例では表層不純物が少なく接触抵抗値、耐食性も良好であった。 The results are shown in Table 1. In the examples of the present invention, there were few surface layer impurities, and the contact resistance value and the corrosion resistance were good.
本発明の方法を用いて製造したＮｉ拡散メッキ鋼板は、表層の不純物が極めて少なく、この鋼板を用いて製造した電池缶、あるいは電池の性能改善に大きく寄与するため、産業上極めて有用である。 The Ni diffusion plated steel sheet produced by using the method of the present invention is extremely useful industrially because it has very few impurities on the surface layer and greatly contributes to improving the performance of battery cans or batteries produced using this steel sheet.
Claims (4)
拡散焼鈍後、調質圧延前に酸水溶液による処理を行い、上記Ｎｉ拡散メッキ鋼板のＮｉ拡散メッキ層表層に濃化した不純物を除去することを特徴とする高純度Ｎｉ拡散メッキ鋼板の製造方法。 After electroplating an unannealed cold-rolled steel sheet with a matte Watt bath with pure Ni as the counter electrode to form a Ni plating layer, a diffusion annealing treatment is performed to recrystallize the steel sheet and form a diffusion layer. A Ni diffusion plated steel sheet having only a Ni diffusion layer or a Ni diffusion plating layer consisting of an Fe-Ni diffusion layer and an Ni plating layer recrystallized and softened thereon is subjected to temper rolling. In the manufacturing method of Ni diffusion plated steel sheet,
A method for producing a high-purity Ni diffusion-plated steel sheet, characterized by performing treatment with an acid aqueous solution after diffusion annealing and before temper rolling to remove impurities concentrated on the surface of the Ni diffusion-plated layer of the Ni diffusion-plated steel sheet.
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| CN113195795A (en) * | 2018-12-27 | 2021-07-30 | 日本制铁株式会社 | Ni-plated steel sheet and method for producing Ni-plated steel sheet |
| CN114746584A (en) * | 2019-12-20 | 2022-07-12 | 日本制铁株式会社 | Ni-plated steel sheet and method for producing Ni-plated steel sheet |
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