JP5443790B2 - Method for producing nickel plating material - Google Patents
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- JP5443790B2 JP5443790B2 JP2009055828A JP2009055828A JP5443790B2 JP 5443790 B2 JP5443790 B2 JP 5443790B2 JP 2009055828 A JP2009055828 A JP 2009055828A JP 2009055828 A JP2009055828 A JP 2009055828A JP 5443790 B2 JP5443790 B2 JP 5443790B2
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 272
- 238000007747 plating Methods 0.000 title claims description 147
- 229910052759 nickel Inorganic materials 0.000 title claims description 136
- 239000000463 material Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000002253 acid Substances 0.000 claims description 26
- 238000009713 electroplating Methods 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 28
- 238000010306 acid treatment Methods 0.000 description 19
- 238000002845 discoloration Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 11
- 230000007797 corrosion Effects 0.000 description 11
- 238000005260 corrosion Methods 0.000 description 11
- 238000004090 dissolution Methods 0.000 description 11
- 229910017604 nitric acid Inorganic materials 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 8
- 229910000881 Cu alloy Inorganic materials 0.000 description 7
- 239000000956 alloy Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000001845 chromium compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- YDLQKLWVKKFPII-UHFFFAOYSA-N timiperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCC(N2C(NC3=CC=CC=C32)=S)CC1 YDLQKLWVKKFPII-UHFFFAOYSA-N 0.000 description 1
- 229950000809 timiperone Drugs 0.000 description 1
Description
本発明は、ニッケルめっき材の製造方法に関し、特に、素材上にニッケルめっき皮膜が形成されたニッケルめっき材の製造方法に関する。 The present invention relates to a method for manufacturing a nickel plating material, and more particularly to a method for manufacturing a nickel plating material in which a nickel plating film is formed on a material.
従来、金属部材の表面にニッケルめっきが施されたニッケルめっき材は、プリント配線基板、電池容器、電池用端子などの材料として広く使用されているが、その用途によって、耐酸性（耐食性）が求められる場合がある。 Conventionally, nickel plating materials with nickel plating on the surface of metal members have been widely used as materials for printed wiring boards, battery containers, battery terminals, etc., but acid resistance (corrosion resistance) is required depending on the application. May be.
ニッケルめっき材の耐酸性（耐食性）を向上させる方法として、クロム酸系表面処理剤でニッケルめっき材を処理して、クロム化合物を含む保護膜をニッケルめっき皮膜の表面に形成する方法（例えば、特許文献１〜３参照）や、モリブデン化合物などの複数の化合物を含む表面処理剤でニッケルめっき材を処理して、クロム化合物を含む保護膜と同等の耐食性および耐変色性を有する保護膜をニッケルめっき皮膜の表面に形成する方法（例えば、特許文献４参照）が提案されている。 As a method of improving the acid resistance (corrosion resistance) of a nickel plating material, a method of forming a protective film containing a chromium compound on the surface of a nickel plating film by treating the nickel plating material with a chromic acid-based surface treatment agent (for example, a patent Treat the nickel plating material with a surface treatment agent containing a plurality of compounds such as a molybdenum compound, and then plating the protective film having the same corrosion resistance and discoloration resistance as the protective film containing a chromium compound. A method of forming on the surface of the film (for example, see Patent Document 4) has been proposed.
しかし、クロム化合物などを含む保護膜をニッケルめっき皮膜の表面に形成する方法では、ニッケルめっき皮膜を形成した後に保護膜を形成する処理が必要であり、ニッケルめっき材の製造コストが高くなる。また、保護膜の材料に有害物質が含まれる場合には、徐害や安全対策などを行う必要があり、ニッケルめっき材の製造コストが高くなる。さらに、ニッケルめっき皮膜の表面に保護膜を形成することにより、ニッケルめっき材の表面の濡れ性が損なわれる場合がある。 However, in the method of forming a protective film containing a chromium compound or the like on the surface of the nickel plating film, a process for forming the protective film after forming the nickel plating film is necessary, and the manufacturing cost of the nickel plating material is increased. In addition, when the protective film material contains a harmful substance, it is necessary to take gradual harm, safety measures, and the like, which increases the manufacturing cost of the nickel plating material. Furthermore, the wettability of the surface of the nickel plating material may be impaired by forming a protective film on the surface of the nickel plating film.
したがって、本発明は、このような従来の問題点に鑑み、耐酸性（耐食性）に優れたニッケルめっき材を簡易且つ安価に製造することができる、ニッケルめっき材の製造方法を提供することを目的とする。 Therefore, in view of such conventional problems, an object of the present invention is to provide a method for producing a nickel plating material that can easily and inexpensively produce a nickel plating material excellent in acid resistance (corrosion resistance). And
本発明者らは、上記課題を解決するために鋭意研究した結果、ニッケルめっき液を使用して電気めっきを行うことにより、ニッケルめっき皮膜を素材上に形成した後に、酸素を含む雰囲気中において、ニッケルめっき皮膜の表面に酸溶液を注ぎかけることにより、耐酸性（耐食性）に優れたニッケルめっき材を簡易且つ安価に製造することができることを見出し、本発明を完成するに至った。 As a result of earnest research to solve the above-mentioned problems, the present inventors have performed electroplating using a nickel plating solution, and after forming a nickel plating film on the material, in an atmosphere containing oxygen, It has been found that a nickel plating material excellent in acid resistance (corrosion resistance) can be easily and inexpensively produced by pouring an acid solution onto the surface of the nickel plating film, and the present invention has been completed.
すなわち、本発明によるニッケルめっき材の製造方法は、ニッケルめっき液を使用して電気めっきを行うことにより、ニッケルめっき皮膜を素材上に形成する工程と、酸素を含む雰囲気中において、ニッケルめっき皮膜の表面に酸溶液を注ぎかける工程とを備えたことを特徴とする。このニッケルめっき材の製造方法において、ニッケルめっき皮膜を素材上に形成する工程と、ニッケルめっき皮膜の表面に酸溶液を注ぎかける工程とを、それぞれ複数回行うのが好ましい。また、酸素を含む雰囲気が大気雰囲気であるのが好ましく、酸溶液がニッケルめっき液であるのが好ましく、酸溶液をシャワー状に注ぎかけるのが好ましい。 That is, the method for producing a nickel plating material according to the present invention includes a step of forming a nickel plating film on a material by performing electroplating using a nickel plating solution, and a nickel plating film in an atmosphere containing oxygen. And a step of pouring an acid solution on the surface. In this method for producing a nickel plating material, it is preferable that the step of forming the nickel plating film on the material and the step of pouring the acid solution on the surface of the nickel plating film are performed a plurality of times. The atmosphere containing oxygen is preferably an air atmosphere, the acid solution is preferably a nickel plating solution, and the acid solution is preferably poured into a shower.
本発明によれば、ニッケルめっき液を使用して電気めっきを行うことにより、ニッケルめっき皮膜を素材上に形成した後に、酸素を含む雰囲気中において、ニッケルめっき皮膜の表面に酸溶液を注ぎかけることにより、耐酸性（耐食性）に優れたニッケルめっき材を簡易且つ安価に製造することができる。 According to the present invention, after the nickel plating film is formed on the material by electroplating using the nickel plating solution, the acid solution is poured onto the surface of the nickel plating film in an oxygen-containing atmosphere. Thus, a nickel plating material excellent in acid resistance (corrosion resistance) can be easily and inexpensively manufactured.
本発明によるニッケルめっき材の製造方法の実施の形態では、ニッケルめっき液を使用して電気めっきを行うことによりニッケルめっき皮膜を素材上に形成する工程（ニッケルめっき皮膜形成工程）と、大気雰囲気のような酸素を含む雰囲気中において、ニッケルめっき皮膜の表面に酸溶液をシャワー状に注ぎかける工程（酸処理工程）とを、それぞれ複数回繰り返した後、素材上に形成されたニッケルめっき皮膜を水洗し、乾燥して、ニッケルめっき材を得る。 In the embodiment of the method for producing a nickel plating material according to the present invention, a step of forming a nickel plating film on a material by performing electroplating using a nickel plating solution (nickel plating film forming step), and an atmospheric atmosphere In an atmosphere containing oxygen, the step of pouring the acid solution onto the surface of the nickel plating film in a shower (acid treatment process) was repeated several times, and then the nickel plating film formed on the material was washed with water. And drying to obtain a nickel plating material.
ニッケルめっき皮膜を形成する素材（母材）は、一般に電気電子部材などに使用される金属素材であればよく、銅や銅合金の素材などの電気が導通する素材を使用することができる。 The material (base material) for forming the nickel plating film may be a metal material generally used for electric and electronic members and the like, and materials that conduct electricity such as copper and copper alloy materials can be used.
電気めっきによりニッケルめっき皮膜を素材上に形成する前に、一般的な前処理として、アルカリ脱脂、水洗、酸洗浄および水洗を順次行うのが好ましい。このような前処理により、ニッケルめっき皮膜と素材との間の金属結合性（金属間結合力）を向上させることができる。 Before the nickel plating film is formed on the material by electroplating, it is preferable to sequentially perform alkaline degreasing, water washing, acid washing and water washing as a general pretreatment. By such pretreatment, the metal bondability (intermetallic bond strength) between the nickel plating film and the material can be improved.
ニッケルめっき液としては、一般的なスルファミン浴、ワット浴、硫酸浴などを使用することができ、特別な添加物を使用する必要はない。 As the nickel plating solution, a general sulfamine bath, watt bath, sulfuric acid bath or the like can be used, and it is not necessary to use a special additive.
電気めっきにおける電流密度は、３〜２０Ａ／ｄｍ２であるのが好ましく、５〜１０Ａ／ｄｍ２があるのがさらに好ましい。電流密度が３Ａ／ｄｍ２より低いと、生産性が悪いため、工業的な使用に適さず、２０Ａ／ｄｍ２を超えると、めっき焼けが生じて、剥離などの問題が生じる。 Current density in electroplating is preferably from 3~20A / dm 2, and more preferably is 5~10A / dm 2. If the current density is lower than 3 A / dm 2 , the productivity is poor, so that it is not suitable for industrial use. If the current density exceeds 20 A / dm 2 , plating burn occurs and problems such as peeling occur.
酸溶液として、電気めっきに使用したニッケルめっき液などの酸性水溶液を使用することができる。電気めっきに使用したニッケルめっき液をそのまま使用することにより、酸性水溶液を別途用意する必要がなくなり、非常に簡素な設備により低コストで耐酸性（耐食性）に優れたニッケルめっき材を製造することができる。 An acidic aqueous solution such as a nickel plating solution used for electroplating can be used as the acid solution. By using the nickel plating solution used for electroplating as it is, there is no need to prepare an acidic aqueous solution separately, and it is possible to produce a nickel plating material with excellent acid resistance (corrosion resistance) at a low cost with very simple equipment. it can.
ニッケルめっき皮膜の表面に酸溶液をシャワー状に注ぎかける酸処理は、空気などの酸素を含む雰囲気中で行う。この酸処理により、クロム化合物を含む保護膜をニッケルめっき皮膜の表面に形成しなくても、ニッケルめっき皮膜の耐酸性（耐食性）を向上させることができる。また、ニッケルめっき皮膜形成工程と酸処理工程とを複数回繰り返すことにより、ニッケルめっき皮膜の耐酸性（耐食性）をさらに向上させることができる。 The acid treatment in which the acid solution is poured in a shower shape on the surface of the nickel plating film is performed in an atmosphere containing oxygen such as air. By this acid treatment, the acid resistance (corrosion resistance) of the nickel plating film can be improved without forming a protective film containing a chromium compound on the surface of the nickel plating film. Moreover, the acid resistance (corrosion resistance) of the nickel plating film can be further improved by repeating the nickel plating film forming step and the acid treatment step a plurality of times.
このように、酸素が存在する雰囲気中で酸処理を行うと、表面のニッケルめっき皮膜の表面の一部が酸溶液に溶解する反応が促進される。この溶解は、ニッケルめっき皮膜の表面の微細な凹凸の凸部や、結晶方位などによって酸溶液に溶解し易い部分から優先的に進むと考えられる。また、ニッケルめっき皮膜形成工程と酸処理工程とをそれぞれ複数回繰り返すことにより、最終的に得られるニッケルめっき皮膜中に、結晶方位などにより酸に溶解し易い部分が少なくなると考えられる。最終的に得られるニッケルめっき皮膜は、酸処理を行わない場合と比べて、表面粗さが小さく、平滑な表面になっている。 Thus, when acid treatment is performed in an atmosphere in which oxygen is present, a reaction in which a part of the surface of the nickel plating film on the surface is dissolved in the acid solution is promoted. It is considered that this dissolution preferentially proceeds from a portion that is easily dissolved in an acid solution due to a fine uneven projection on the surface of the nickel plating film or a crystal orientation. Moreover, it is thought that the part which is easy to melt | dissolve in an acid by a crystal orientation etc. in the nickel plating film finally obtained by repeating a nickel plating film formation process and an acid treatment process several times each is considered. The finally obtained nickel plating film has a small surface roughness and a smooth surface as compared with the case where acid treatment is not performed.
なお、酸素が存在する雰囲気中において酸溶液を注ぎかける酸処理の代わりに、ニッケルめっき皮膜が形成された素材を酸溶液やアルカリ溶液中に浸漬しても、十分な耐酸性（耐食性）のニッケルめっき材を得ることができない。 Nickel with sufficient acid resistance (corrosion resistance) even if the material on which the nickel plating film is formed is immersed in an acid solution or an alkali solution instead of the acid treatment in which an acid solution is poured in an oxygen-containing atmosphere. A plating material cannot be obtained.
以下、本発明によるニッケルめっき材の製造方法の実施例について詳細に説明する。 Hereinafter, the Example of the manufacturing method of the nickel plating material by this invention is described in detail.
［実施例１］
まず、厚さ０．２ｍｍで５０ｍｍ角の大きさの銅合金素材（Ｃ１０２０Ｒ材）に、一般的な電析の前処理として、アルカリ脱脂、水洗、酸洗浄および水洗を順次を行った。
[Example 1]
First, alkaline degreasing, water washing, acid washing, and water washing were sequentially performed on a copper alloy material (C1020R material) having a thickness of 0.2 mm and a size of 50 mm square as a general pretreatment for electrodeposition.
次に、４９５ｇ／Ｌのスルファミン酸ニッケルと、２０ｇ／Ｌの塩化ニッケルと、３５ｇ／Ｌのホウ酸を含有する水溶液からなるめっき液（ｐＨ３．９）を使用する一般的なスルファミン浴中に、上記の前処理を行った銅合金素材を入れ、めっき液温度５０℃、電流密度６Ａ／ｄｍ２で電気めっきを（１回当りの電気めっき時間として）９６秒間行って、銅合金素材上にニッケルめっき皮膜を形成した。 Next, in a general sulfamine bath using a plating solution (pH 3.9) composed of an aqueous solution containing 495 g / L nickel sulfamate, 20 g / L nickel chloride, and 35 g / L boric acid, The copper alloy material subjected to the above pretreatment is put in, electroplating is performed at a plating solution temperature of 50 ° C. and a current density of 6 A / dm 2 (as electroplating time per time) for 96 seconds, and nickel is deposited on the copper alloy material. A plating film was formed.
次に、ニッケルめっき皮膜を形成した銅合金素材を浴中から取り出し、大気中（温度２５℃）において、ニッケルめっき皮膜の表面に上記のめっき液を１Ｌ／分の流量でシャワー状に注ぎかけて酸処理を（１回当りの酸処理時間として）５秒間行った。 Next, the copper alloy material on which the nickel plating film is formed is taken out from the bath, and the above plating solution is poured into the surface of the nickel plating film at a flow rate of 1 L / min in the atmosphere (at a temperature of 25 ° C.). Acid treatment was performed for 5 seconds (as acid treatment time per one time).
次に、上記の酸処理を行った銅合金素材を再び浴中に入れ、上記の電気めっきを９６秒間行って、さらにニッケルめっき皮膜を形成した後、このニッケルめっき皮膜を形成した銅合金素材を浴中から取り出し、上記の酸処理を５秒間行った。このようにして、上記の９６秒間の電気めっきと５秒間の酸処理をそれぞれ６回ずつ繰り返した。 Next, the copper alloy material that has been subjected to the acid treatment is again placed in the bath, the electroplating is performed for 96 seconds, and a nickel plating film is further formed. The product was taken out from the bath and subjected to the above acid treatment for 5 seconds. In this way, the electroplating for 96 seconds and the acid treatment for 5 seconds were repeated 6 times each.
次に、銅合金素材上に形成されたニッケルめっき皮膜を水洗した後、乾燥して、ニッケルめっき材を得た。 Next, the nickel plating film formed on the copper alloy material was washed with water and then dried to obtain a nickel plating material.
得られたニッケルめっき材のニッケルめっき皮膜の厚さと表面粗さを求めた。ニッケルめっき皮膜の厚さは、蛍光Ｘ線膜厚計（ＳＩＩナノテクノロジー社製の蛍光Ｘ線膜厚計ＳＦＴ３２００）により測定した。ニッケルめっき材の表面粗さについては、超深度表面形状測定顕微鏡（株式会社キーエンス製のＶＫ−８５００）を使用して、倍率２０００倍、測定エリア０．１５ｍｍ×０．１１ｍｍで測定した結果から、ＪＩＳ Ｂ０６０１に基づいて表面粗さを示すパラメータである算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを算出した。その結果、ニッケルめっき皮膜の厚さは１．２μｍ、算術平均粗さＲａは０．１μｍ、最大高さＲｙは２．１μｍ、十点平均粗さＲｚは１．４μｍであった。 The thickness and surface roughness of the nickel plating film of the obtained nickel plating material were determined. The thickness of the nickel plating film was measured with a fluorescent X-ray film thickness meter (fluorescent X-ray film thickness meter SFT3200 manufactured by SII Nano Technology). About the surface roughness of the nickel-plated material, from an ultra-deep surface shape measurement microscope (VK-8500 manufactured by Keyence Corporation), the result of measurement at a magnification of 2000 times and a measurement area of 0.15 mm × 0.11 mm, Based on JIS B0601, arithmetic average roughness Ra, maximum height Ry, and ten-point average roughness Rz, which are parameters indicating surface roughness, were calculated. As a result, the thickness of the nickel plating film was 1.2 μm, the arithmetic average roughness Ra was 0.1 μm, the maximum height Ry was 2.1 μm, and the ten-point average roughness Rz was 1.4 μm.
また、得られたニッケルめっき材を１０質量％の硝酸水溶液（２３℃）に入れ、マグネチックスターラーの回転数を３００ｒｐｍにして攪拌しながら３００秒浸漬させた後、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を蛍光Ｘ線膜厚計（ＳＩＩナノテクノロジー社製の蛍光Ｘ線膜厚計ＳＦＴ３２００）により測定した。その結果、外観の変色はなく、ニッケルめっき皮膜の厚さの減少量は０．２μｍであった。なお、ニッケルめっき皮膜の厚さの減少量が０．４μｍ以下であれば、耐酸性（耐食性）に優れているといえる。 Moreover, after putting the obtained nickel plating material in a 10 mass% nitric acid aqueous solution (23 degreeC) and making it stir for 300 seconds, stirring the rotation speed of a magnetic stirrer at 300 rpm, the discoloration of an external appearance is observed with the naked eye. At the same time, the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured by a fluorescent X-ray film thickness meter (fluorescent X-ray film thickness meter SFT3200 manufactured by SII Nano Technology). As a result, there was no discoloration of the appearance and the amount of decrease in the thickness of the nickel plating film was 0.2 μm. In addition, if the reduction amount of the thickness of a nickel plating film is 0.4 micrometer or less, it can be said that it is excellent in acid resistance (corrosion resistance).
［実施例２］
１回当りの電気めっき時間を２００秒にした以外は、実施例１と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．１μｍ、十点平均粗さＲｚは１．６μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなく、ニッケルめっき皮膜の厚さの減少量は０．２μｍであった。
[Example 2]
After obtaining a nickel plating material by the same method as in Example 1 except that the electroplating time per time was 200 seconds, the thickness of the nickel plating film, the arithmetic average roughness Ra, the maximum height Ry, Ten-point average roughness Rz was determined. As a result, the nickel plating film had a thickness of 2.5 μm, an arithmetic average roughness Ra of 0.2 μm, a maximum height Ry of 2.1 μm, and a ten-point average roughness Rz of 1.6 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance and the amount of decrease in the thickness of the nickel plating film was 0.2 μm.
［実施例３］
１回当りの電気めっき時間を４００秒にした以外は、実施例１と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．１μｍ、十点平均粗さＲｚは１．６μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなく、ニッケルめっき皮膜の厚さの減少量は０．２μｍであった。
[Example 3]
After obtaining a nickel plating material by the same method as in Example 1 except that the electroplating time per time was 400 seconds, the thickness of the nickel plating film, the arithmetic average roughness Ra, the maximum height Ry, Ten-point average roughness Rz was determined. As a result, the thickness of the nickel plating film was 5 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.1 μm, and the ten-point average roughness Rz was 1.6 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance and the amount of decrease in the thickness of the nickel plating film was 0.2 μm.
［比較例１］
電流密度を１０Ａ／ｄｍ２とし、めっき液による酸処理の代わりに純水をシャワー状に注ぎかけた以外は、実施例１と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．１μｍ、最大高さＲｙは４．１μｍ、十点平均粗さＲｚは３．２μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色があり、ニッケルめっき皮膜の厚さの減少量は０．９μｍであった。
[Comparative Example 1]
A nickel plating material was obtained by the same method as in Example 1 except that the current density was 10 A / dm 2 and pure water was poured into the shower instead of the acid treatment with the plating solution. Thickness, arithmetic average roughness Ra, maximum height Ry, and ten-point average roughness Rz were determined. As a result, the nickel plating film had a thickness of 2.5 μm, an arithmetic average roughness Ra of 0.1 μm, a maximum height Ry of 4.1 μm, and a ten-point average roughness Rz of 3.2 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, the appearance was discolored, and the decrease in the thickness of the nickel plating film was 0.9 μm.
［比較例２］
電流密度を１０Ａ／ｄｍ２とし、めっき液をシャワー状に５秒間注ぎかける酸処理の代わりに、強アルカリ水溶液（５０ｇ／ＬのＮａＯＨ水溶液）に５秒間浸漬させた以外は、実施例１と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．１μｍ、最大高さＲｙは２．５μｍ、十点平均粗さＲｚは２．０μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色があり、ニッケルめっき皮膜の厚さの減少量は０．９μｍであった。
[Comparative Example 2]
Similar to Example 1, except that the current density was 10 A / dm 2 and the plating solution was immersed in a strong alkaline aqueous solution (50 g / L NaOH aqueous solution) for 5 seconds instead of being poured into a shower for 5 seconds. After obtaining the nickel plating material by the method, the thickness, arithmetic average roughness Ra, maximum height Ry, and ten-point average roughness Rz of the nickel plating film were determined. As a result, the thickness of the nickel plating film was 2.5 μm, the arithmetic average roughness Ra was 0.1 μm, the maximum height Ry was 2.5 μm, and the ten-point average roughness Rz was 2.0 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, the appearance was discolored, and the decrease in the thickness of the nickel plating film was 0.9 μm.
［比較例３］
めっき液による酸処理の代わりに純水をシャワー状に注ぎかけた以外は、実施例１と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは１．２μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．３μｍ、十点平均粗さＲｚは１．９μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなかったが、ニッケルめっき皮膜の厚さの減少量は１．０μｍであった。
[Comparative Example 3]
The nickel plating material was obtained by the same method as in Example 1 except that pure water was poured into the shower instead of the acid treatment with the plating solution, and then the thickness of the nickel plating film, the arithmetic average roughness Ra, The maximum height Ry and the ten-point average roughness Rz were determined. As a result, the thickness of the nickel plating film was 1.2 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.3 μm, and the ten-point average roughness Rz was 1.9 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance, but the decrease in the thickness of the nickel plating film was 1.0 μm.
［比較例４］
めっき液による酸処理の代わりに純水をシャワー状に注ぎかけた以外は、実施例２と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．８μｍ、十点平均粗さＲｚは２．１μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなかったが、ニッケルめっき皮膜の厚さの減少量は１．０μｍであった。
[Comparative Example 4]
The nickel plating material was obtained by the same method as in Example 2 except that pure water was poured into the shower instead of the acid treatment with the plating solution, and then the thickness of the nickel plating film, the arithmetic average roughness Ra, The maximum height Ry and the ten-point average roughness Rz were determined. As a result, the thickness of the nickel plating film was 2.5 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.8 μm, and the ten-point average roughness Rz was 2.1 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance, but the decrease in the thickness of the nickel plating film was 1.0 μm.
［比較例５］
めっき液による酸処理の代わりに純水をシャワー状に注ぎかけた以外は、実施例３と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．６μｍ、十点平均粗さＲｚは１．８μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなかったが、ニッケルめっき皮膜の厚さの減少量は１．０μｍであった。
[Comparative Example 5]
A nickel plating material was obtained by the same method as in Example 3 except that pure water was poured into a shower instead of the acid treatment with the plating solution, and then the thickness of the nickel plating film, the arithmetic average roughness Ra, The maximum height Ry and the ten-point average roughness Rz were determined. As a result, the thickness of the nickel plating film was 5 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.6 μm, and the ten-point average roughness Rz was 1.8 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance, but the decrease in the thickness of the nickel plating film was 1.0 μm.
［比較例６］
電流密度を１０Ａ／ｄｍ２とし、めっき液をシャワー状に注ぎかける酸処理の代わりに、めっき液中５秒間通電を停止することにより、ニッケルめっき皮膜をめっき液に浸漬する酸処理を行った以外は、実施例２と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．７μｍ、十点平均粗さＲｚは２．３μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色があり、ニッケルめっき皮膜の厚さの減少量は１．０μｍであった。
[Comparative Example 6]
The current density was set to 10 A / dm 2 and instead of the acid treatment in which the plating solution was poured into a shower, the current treatment was stopped for 5 seconds in the plating solution, thereby performing an acid treatment for immersing the nickel plating film in the plating solution. After obtaining a nickel plating material by the same method as in Example 2, the thickness, arithmetic average roughness Ra, maximum height Ry, and ten-point average roughness Rz of the nickel plating film were determined. As a result, the thickness of the nickel plating film was 2.5 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.7 μm, and the ten-point average roughness Rz was 2.3 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, the appearance was discolored, and the amount of decrease in the thickness of the nickel plating film was 1.0 μm.
［比較例７］
電流密度を６Ａ／ｄｍ２とした以外は、比較例６と同様の方法により、ニッケルめっき材を得た後、ニッケルめっき皮膜の厚さ、算術平均粗さＲａ、最大高さＲｙ、十点平均粗さＲｚを求めた。その結果、ニッケルめっき皮膜の厚さは２．５μｍ、算術平均粗さＲａは０．２μｍ、最大高さＲｙは２．６μｍ、十点平均粗さＲｚは２．１μｍであった。また、実施例１と同様の方法により、外観の変色を肉眼で観察するとともに、ニッケルめっき皮膜の硝酸への溶解による厚さの減少量を測定した。その結果、外観の変色はなかったが、ニッケルめっき皮膜の厚さの減少量は０．５μｍであった。
[Comparative Example 7]
Except for the current density of 6 A / dm 2 , the nickel plating material was obtained by the same method as in Comparative Example 6, and then the thickness of the nickel plating film, the arithmetic average roughness Ra, the maximum height Ry, and the ten-point average The roughness Rz was determined. As a result, the thickness of the nickel plating film was 2.5 μm, the arithmetic average roughness Ra was 0.2 μm, the maximum height Ry was 2.6 μm, and the ten-point average roughness Rz was 2.1 μm. In addition, the discoloration of the appearance was observed with the naked eye by the same method as in Example 1, and the amount of decrease in thickness due to dissolution of the nickel plating film in nitric acid was measured. As a result, there was no discoloration of the appearance, but the amount of decrease in the thickness of the nickel plating film was 0.5 μm.
これらの実施例および比較例におけるニッケルめっき材の製造条件および特性をそれぞれ表１および表２に示す。 Tables 1 and 2 show the production conditions and properties of the nickel plating materials in these examples and comparative examples, respectively.
なお、各々の実施例および比較例で得られたニッケルめっき材の表面を走査電子顕微鏡（ＳＥＭ）により５０００倍で観察したところ、実施例１〜３、比較例３〜５および７では、１〜３μｍ程度の結晶粒が全面に認められ、比較例１、２および６では、０．５〜１μｍ程度の結晶粒が全面に認められた。 In addition, when the surface of the nickel plating material obtained by each Example and the comparative example was observed by 5000 time with the scanning electron microscope (SEM), in Examples 1-3, Comparative Examples 3-5, and 7, Crystal grains of about 3 μm were observed on the entire surface, and in Comparative Examples 1, 2, and 6, crystal grains of about 0.5 to 1 μm were observed on the entire surface.
また、各々の実施例および比較例で得られたニッケルめっき材の表面をＥＳＣＡ（化学分析用電子分光法）で分析したところ、定性分析では、Ｎｉ、Ｏ、Ｃの元素が検出された。また、Ｎｉのピークをピーク分離することにより、表面近傍のニッケル、ニッケル水酸化物、ニッケル酸化物の比率を調べたが、それぞれの実施例および比較例の間で大きな差は認められなかった。
Moreover, when the surface of the nickel plating material obtained in each Example and Comparative Example was analyzed by ESCA (electron spectroscopy for chemical analysis), Ni, O, and C elements were detected in the qualitative analysis. Further, the ratio of nickel, nickel hydroxide and nickel oxide in the vicinity of the surface was examined by separating the Ni peak, but no significant difference was observed between the respective examples and comparative examples.
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| JPS581076A (en) * | 1981-06-26 | 1983-01-06 | Nisshin Steel Co Ltd | Surface treatment method of high nickel-iron alloy steel |
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