JPH03100187A - Highly corrosion resistant nickel plating method - Google Patents
Highly corrosion resistant nickel plating methodInfo
- Publication number
- JPH03100187A JPH03100187A JP1234794A JP23479489A JPH03100187A JP H03100187 A JPH03100187 A JP H03100187A JP 1234794 A JP1234794 A JP 1234794A JP 23479489 A JP23479489 A JP 23479489A JP H03100187 A JPH03100187 A JP H03100187A
- Authority
- JP
- Japan
- Prior art keywords
- nickel plating
- plating
- tri
- nickel
- corrosion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 217
- 238000007747 plating Methods 0.000 title claims abstract description 136
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 134
- 230000007797 corrosion Effects 0.000 title claims abstract description 68
- 238000005260 corrosion Methods 0.000 title claims abstract description 68
- 238000000034 method Methods 0.000 title claims description 45
- 239000002245 particle Substances 0.000 claims description 7
- 241000270708 Testudinidae Species 0.000 claims 1
- 239000010419 fine particle Substances 0.000 abstract description 17
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 abstract description 4
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 abstract description 2
- 229960002327 chloral hydrate Drugs 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 238000005406 washing Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005282 brightening Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 229910018487 Ni—Cr Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- -1 Sulfonic acid sodium salts Chemical class 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- VXFDQYQEGQQDOJ-UHFFFAOYSA-N nickel Chemical compound [Ni].[Ni].[Ni].[Ni] VXFDQYQEGQQDOJ-UHFFFAOYSA-N 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/625—Discontinuous layers, e.g. microcracked layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、高耐食ニッケルめっき方法に関し、更に詳細
には、高耐食性と優れた光沢外観を共に要求される自動
車、オートバイ等の部品に対する高耐食ニッケルめっき
方法に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a highly corrosion-resistant nickel plating method, and more particularly, to high corrosion-resistant nickel plating for parts of automobiles, motorcycles, etc. that require both high corrosion resistance and excellent glossy appearance. Regarding a corrosion-resistant nickel plating method.
［従来の技術］
屋外の風雨に晒される自動車、オートバイ等の部品には
、一般にその耐食性、優れた金属外観などの面からニッ
ケル・クロムめっきが採用されている。[Prior Art] Nickel-chromium plating is generally used for parts of automobiles, motorcycles, etc. that are exposed to outdoor wind and rain due to its corrosion resistance and excellent metal appearance.
通常のニッケル・クロムめっきにおいては、最表面のク
ロム層の不働態化により防食しているが、クロム皮膜の
欠陥（クラック・ボア）の発生を完全に防ぐことはでき
ず、また、たとえ可能となっても、めっき徨のスリキズ
等による欠陥の発生は防ぐことができないので、欠陥の
部分から腐食が開始し、この最表面に近いニッケルの腐
食は、被めっき部品の目立った外観の低下を招いていた
。In normal nickel-chromium plating, corrosion is prevented by passivating the outermost chromium layer, but it is not possible to completely prevent defects (cracks and bores) in the chrome film, and even if it is possible, However, it is not possible to prevent defects from occurring due to scratches on the plating, so corrosion starts from the defective area, and this corrosion of nickel near the outermost surface causes a noticeable deterioration in the appearance of the plated parts. was.
このような問題を解決し、ニッケルめっきの膜厚を低下
させながら耐食性を持たせる高耐食ニッケルめっきプロ
セスとして、３重ニッケルプロセス及びマイクロポーラ
スクロムやマイクロクラッククロムプロセスがすでに開
発されている。A triple nickel process and a microporous chromium or microcrack chromium process have already been developed as highly corrosion-resistant nickel plating processes that solve these problems and provide corrosion resistance while reducing the thickness of the nickel plating.
［発明が解決しようとする課題］
高耐食ニッケルめっきプロセスのうち、マイクロポーラ
スクロムあるいはマイクロクラッククロム法は、めっき
面の最表面のクロムに微孔や微細なりラック等の欠陥を
作成することにより、腐食電流密度を微小化し、腐食速
度を遅らせる方法であるが、いずれも初期の微細な腐食
孔も時間の経過とともに大きくなり、いわゆる「霜降り
」等の外観上目立った腐食孔となる欠点を有する。[Problems to be Solved by the Invention] Among the highly corrosion-resistant nickel plating processes, the microporous chromium or microcrack chromium method creates defects such as micropores and fine racks in the outermost chromium of the plating surface. These methods reduce the corrosion current density and slow the corrosion rate, but they all have the disadvantage that the initially minute corrosion holes become larger over time, resulting in visually noticeable corrosion holes such as so-called "marbling".
一方、３重ニッケル（トリニッケル）プロセスは、電位
の貴なニッケルめっき層（半光沢ニッケルめっき層）の
上に電位がこれより卑なニッケルめっき層（光沢ニッケ
ルめっき層）を施す二重ニッケルプロセスを改良したも
ので、半光沢ニッケル層と光沢ニッケル層の間に、イオ
ウ含量が高く、光沢ニッケル層より電位が卑なニッケル
めっき（以下、これを「トリニッケルめっき」という）
を施し、この電位が卑なトリニッケルめっき層を犠牲皮
膜として利用して光沢ニッケル層と素地の防蝕をおこな
う゛ものである。On the other hand, the triple nickel (tri-nickel) process is a double nickel process in which a nickel plating layer with a lower potential (bright nickel plating layer) is applied on top of a nickel plating layer with a noble potential (semi-bright nickel plating layer). This is an improved nickel plating between the semi-bright nickel layer and the bright nickel layer, which has a high sulfur content and has a lower potential than the bright nickel layer (hereinafter referred to as "tri-nickel plating").
The tri-nickel plating layer, which has a lower potential, is used as a sacrificial film to protect the bright nickel layer and the substrate from corrosion.
しかし、この方法も、−度この犠牲皮膜であるトリニッ
ケルめっき層に腐食が到達すると、トリニッケルめっき
層の腐食が早く、目立つ大きなビットが発生するという
問題があった。したがって、めっき外観が低下せず、し
かも優れた耐食性を有するニッケルめっきプロセスの開
発が望まれていた。However, this method also has the problem that once the corrosion reaches the tri-nickel plating layer, which is the sacrificial film, the tri-nickel plating layer corrodes quickly, resulting in noticeable large bits. Therefore, it has been desired to develop a nickel plating process that does not deteriorate the plating appearance and has excellent corrosion resistance.
［課題を解決するための手段］
本発明者らは、上記課題を解決すべく、種々研究をおこ
なった結果、トリニッケルプロセスの大きなビットが発
生するという欠点は、トリニッケルめっき層に対する腐
食電流を微細化すれば防げることに想い到った。そして
、更に研究をおこない、腐食電流の微細化は、トリニッ
ケルめっき層に非電導微粒子を共祈せしめることにより
達成できることを見出した。[Means for Solving the Problems] In order to solve the above problems, the present inventors have conducted various studies and found that the drawback of the tri-nickel process that large bits occur is that the corrosion current to the tri-nickel plating layer is reduced. I realized that it could be prevented by miniaturizing it. Further research was conducted and it was discovered that the corrosion current could be reduced by incorporating non-conductive fine particles into the tri-nickel plating layer.
更にまた、トリニッケルめっき層を電位の異なる二層で
構成し、その電位のより卑なトリニッケルめっき層にの
み非電導性微粒子を共祈せしめればより以上に優れた耐
食性及び外観が得られることを見出した。Furthermore, if the tri-nickel plating layer is composed of two layers with different potentials, and non-conductive fine particles are applied only to the tri-nickel plating layer with the lower potential, even more excellent corrosion resistance and appearance can be obtained. I discovered that.
本発明は、これら知見に基いて完成されたものであり、
その第１の目的は、半光沢ニッケルめっき、非電導性微
粒子を共祈せしめたトリニッケルめっき及び光沢ニッケ
ルめっきを順秋施すことを特徴とする高耐食ニッケルめ
っき方法を提供するものである。The present invention was completed based on these findings,
The first object is to provide a highly corrosion-resistant nickel plating method characterized by sequentially applying semi-bright nickel plating, tri-nickel plating containing non-conductive fine particles, and bright nickel plating.
また、本発明の他の目的は、半光沢ニッケルめっき、非
電導性微粒子を共祈し、電位が相対的に卑な第１トリニ
ッケルめっき、電位が相対的に貴な第２トリニッケルめ
っき及び光沢ニッケルめっきを順次施すことを特徴とす
る高耐食ニッケルめっき方法を提供するものである。Another object of the present invention is to combine semi-bright nickel plating, non-conductive fine particles, first tri-nickel plating with a relatively base potential, second tri-nickel plating with a relatively noble potential, and The present invention provides a highly corrosion-resistant nickel plating method characterized by sequentially applying bright nickel plating.
本発明の第１の高耐食ニッケルめっき方法を実施するに
は、まず被めっき素材に半光沢ニッケルめっきを施すこ
とが必要である。In order to carry out the first highly corrosion-resistant nickel plating method of the present invention, it is first necessary to apply semi-bright nickel plating to the material to be plated.
本発明方法を実施することのできる被めっき素材には特
に制限はなく、鉄鋼、亜鉛、アルミニウム、銅、銅合金
その他の金属素地やＡＢＳ樹脂その他のプラスチック素
地上に、通常の方法により前処理をしたのち、必要であ
れば、銅などの下地めっきを施したもののいずれをも採
用することができる。There are no particular restrictions on the materials to be plated to which the method of the present invention can be applied, and metal substrates such as steel, zinc, aluminum, copper, copper alloys, and plastic substrates such as ABS resin are pretreated by a conventional method. After that, if necessary, it is possible to use any one coated with a base plating of copper or the like.
また、半光沢ニッケルめっきには、イオウ共祈量が、例
えば０．００５％以下と極めて少なく、電位の貴な半光
沢ニッケルめっき層を形成するために用いられる公知ニ
ッケルめっき浴のいずれをも採用することができ、利用
できる光沢剤としては、抱水クロラール、ホルマリン、
クマリン等を挙げることができる。またこれらに代えて
、例えば、Ｎ２Ｅ、ＢＴＬ （荏原ニーシライト■製）
などの市販のものを利用することもできる。In addition, for semi-bright nickel plating, any known nickel plating bath that has an extremely low sulfur content of 0.005% or less and is used to form a high-potential semi-bright nickel plating layer is used. Available brighteners include chloral hydrate, formalin,
Examples include coumarin. In addition, instead of these, for example, N2E, BTL (manufactured by Ebara Nishilight ■)
You can also use commercially available products such as.
この半光沢ニッケルめっきの好ましい条件は、次の通り
である。The preferred conditions for this semi-bright nickel plating are as follows.
範囲
最適値
ＮｌＳＯ４・６８．０ １００〜４００ ｇ／ｌ
２８０ ｇ／ｌＮｉＣｌ２・６Ｈ，０３０〜 ６０
ｇ／ｌ ４５ ｇ／１１（３８０，２０〜 ６０
ｇ／ｌ ４０ ｇ／ｌ光沢剤 適量
適量
ｐＨ３，５〜５．５ ４．２
めっき温度 ４０〜６５℃ ５５℃陰極電流密
度 １〜ＩＯＡ／ｄａ′２４ Ａ／ｄａ２撹拌 □
空気、機械 空気、機械
この半光沢ニッケル層の膜厚は、かなり薄くすることも
可能であるが、プラスチック素材へのめっきの場合には
、熱衝撃を緩和するために１０μｍ以上とすることが望
ましい。Range optimum value NlSO4・68.0 100-400 g/l
280 g/l NiCl2・6H, 030~60
g/l 45 g/11 (380,20~60
g/l 40 g/l brightener appropriate amount
Appropriate amount pH 3.5-5.5 4.2 Plating temperature 40-65℃ 55℃ Cathode current density 1-IOA/da'24 A/da2 Stirring □
Air, Machinery Air, Machinery The thickness of this semi-bright nickel layer can be made quite thin, but when plating on plastic materials, it is preferably 10 μm or more to alleviate thermal shock. .
次いで、非電導性微粒子を共祈させつつトリニッケルめ
っきを施す。Next, tri-nickel plating is applied while the non-conductive fine particles are mixed together.
このトリニッケルめっきに用いられる浴は、電析するニ
ッケルめっき層の電位が光沢ニッケルめっき層より卑で
、しかも撹拌可能なものであれば良く、例えば、特公昭
６２−５２０３９号に開示のチアゾールまたはチアゾリ
ンを添加剤として利用し、空気撹拌を行なうトリニッケ
ル浴が挙げられる。また、市販の空気撹拌可能なトリニ
ッケルストライク浴（例えば、荏原ニーシライト■製
Ｔｒｉ−Ｎｉ ＴＡ）を利用することもできる。これ
らにより、イオウ含量が０．０５〜０．５％程度の電位
が卑なニッケルめっき層が得られる。The bath used for this tri-nickel plating may be any bath as long as the potential of the nickel plating layer to be deposited is less base than that of the bright nickel plating layer and that it can be stirred. Examples include tri-nickel baths that utilize thiazoline as an additive and perform air agitation. Moreover, a commercially available air-stirable tri-nickel strike bath (for example, Tri-Ni TA manufactured by Ebara Nisilite ■) can also be used. As a result, a nickel plating layer having a sulfur content of about 0.05 to 0.5% and having a base potential can be obtained.
他方、このトリニッケルめっき浴に添加され、ニッケル
めっき層に共祈される非電導性微粒子としては、好まし
くは粒径０．０３〜５μｍの硫酸バリウム、ケイ酸アル
ミニウム、ケイ酸ジルコニウム、酸化ジルコニウム、硫
酸ストロンチウム、酸化チタン、ガラス粉末、フッ化カ
ルシウム等が挙げられ、市販品としては、ＤＮ−ＭＰ、
５Ｙ−１０５，５Ｙ−１０６，５Ｙ−１０８等を利用
することができる。On the other hand, the non-conductive fine particles added to the tri-nickel plating bath and intermixed with the nickel plating layer include barium sulfate, aluminum silicate, zirconium silicate, zirconium oxide, and preferably have a particle size of 0.03 to 5 μm. Examples include strontium sulfate, titanium oxide, glass powder, calcium fluoride, etc. Commercially available products include DN-MP,
5Y-105, 5Y-106, 5Y-108, etc. can be used.
この非電導性微粒子は、種類及びその粒径によっても変
化するが、一般にはトリニッケルめっき液中に０．５〜
５０ｇ／ｌ、好ましくは１〜 Ｌｏｇ／ｌ添加される。These non-conductive fine particles vary depending on the type and particle size, but generally 0.5~
50 g/l, preferably 1 to Log/l.
このトリニッケルめっきは、０．３〜０．６ｍ’／ｍ程
度の撹拌下、４０〜６５℃程度、１〜１０Ａ／ｄｍ”程
度の条件で約０．５〜５分間おこなわれる。 なお、ト
リニッケルめっきの好ましい組成を示せば次の通りであ
る。This tri-nickel plating is performed for about 0.5 to 5 minutes under conditions of about 40 to 65°C and about 1 to 10 A/dm'' under stirring at about 0.3 to 0.6 m'/m. The preferred composition of nickel plating is as follows.
（以下余白）
範囲
最適値
Ｎ１５Ｏ，・６Ｈ，０１００〜４００ ｇ／ｌ
２８０ ｇ／ｌＮｉＣ１，・６Ｈ，０３０〜 ６０
ｇ／ｌ ４５ ｇ／ＩＨｓＢＯｓ ２
０〜６０ ｇ／ｌ ４Ｇ ｇ／ｌ光沢剤 適
量 適量
ｐＨ２，０〜３．５ ３．０
めっき温度 ４０〜６５℃ ５５℃陰極電流密
度 １〜ＩＯＡ／ｄ膳２４ Ａ／ｄａ２撹拌 空
気 空気
更に、被めっき物に装飾性を持たせるために光沢ニッケ
ルめっきが施される。 この光沢ニッケルめっき被膜は
イオウ含量が
０．０２〜０．０７％であり、６μｍ程度以上の膜厚が
あれば、その目的は達成される。(Left below) Optimal range N15O, 6H, 0100~400 g/l
280 g/lNiC1,・6H,030~60
g/l 45 g/IHsBOs 2
0 to 60 g/l 4G g/l brightener Appropriate amount Appropriate amount pH 2,0 to 3.5 3.0 Plating temperature 40 to 65°C 55°C Cathode current density 1 to IOA/d 24 A/da2 Stirring Air Air Furthermore, Bright nickel plating is applied to give the plated object a decorative appearance. This bright nickel plating film has a sulfur content of 0.02 to 0.07%, and if the film has a thickness of about 6 μm or more, the purpose is achieved.
この光沢ニッケルには、公知の光沢剤、例えば−次光沢
剤として、１．５−１．６−又は２．５−ナフタリンジ
スルホン酸ソーダ、１゜３．６−ナフタリントリスルホ
ン酸ソーダ、ベンゼンスルホン酸ソーダ及びサッカリン
酸ソーダなどの芳香族スルホンイミド類、及びスルフィ
ン酸類が単独又は組み合わせて使用され、また、光沢・
レベリングを付与する目的で、１．４−ブチンジオール
を代表とするアセチレン系不飽和アルコール及びその誘
導体、及びビニルスルホン酸ソーダζアリルスルホン酸
ソーダなどのエチレン系不飽和スルホン酸塩、あるいは
、ピリジン系スルホン酸ソーダ塩が使用される。 また
これらに代えて、。６１、“６３（荏原ニーシライト■
製）等の市販の光沢ニッケル用光沢剤を利用しても良い
。This bright nickel may be coated with known brightening agents, such as -sodium 1.5-1.6- or 2.5-naphthalene disulfonate, sodium 1゜3.6-naphthalene trisulfonate, and benzenesulfone. Aromatic sulfonimides such as acid soda and sodium saccharinate, and sulfinic acids are used alone or in combination, and also have gloss and
For the purpose of imparting leveling, acetylenically unsaturated alcohols and their derivatives such as 1,4-butynediol, ethylenically unsaturated sulfonates such as sodium vinylsulfonate ζallylsulfonate, or pyridine-based Sulfonic acid sodium salts are used. Also, instead of these. 61, “63 (Ebara Nishi Light ■
Commercially available brightening agents for bright nickel, such as those manufactured by Co., Ltd., may also be used.
（以下余白）
範囲
最適値
ＮｉＳＯ４・６）１．０ １００〜４００ ｇ／ｌ
２８０ ｇ／ｌＮｉＣ１□・６Ｈ，０４０〜 ７０
ｇ／ｌ ５５ ｇ／ＩＨ３Ｂ０３ ２０〜
６０ ｇ／ｌ ４０ ｇ／ｌ光沢剤 適量
適量
ｐ Ｈ３，５〜５．５ ４．２
めっき温度 ４０〜６５℃ ５５℃陰極電流密
度 １〜１０Ａ／ｄａ２４ Ａ／ｄａ２撹拌 空気
、機械 空気、機械
叙上の方法によっても相当程度の耐食性が得られるが、
より高度な耐食性を得るためには本発明の第二の高耐食
トリニッケルめっき法を採用することが好ましい。すな
わち、第一の高耐食ニッケルめっき方法においては、ト
リニッケルめっき層における非電導性微粒子の共祈量は
重量％で約５％程度でしかなく、表面積の割合では、ニ
ッケル面の方が多いので、腐食の分散効果はあるものの
、Ｓ共祈量の多い層の腐食の広がりを防止することには
限界がある。これに対し、本発明の第２の高耐食ニッケ
ルめっき方法ではトリニッケル層を電位が相対的に卑な
第１層と相対的に貴な第２層とからなる二層構造とし、
しかも第１層に微粒子を共祈せしめて腐食電流の分散化
を図るものであるため、より高度な耐食性が得られる。(Left below) Optimal range NiSO4/6) 1.0 100-400 g/l
280 g/lNiC1□・6H, 040~70
g/l 55 g/IH3B03 20~
60 g/l 40 g/l brightener appropriate amount
Appropriate amount pH 3.5~5.5 4.2 Plating temperature 40~65℃ 55℃ Cathode current density 1~10A/da24 A/da2 Stirring Air, machine Air, machine A considerable degree of corrosion resistance can also be obtained by the above methods. However,
In order to obtain higher corrosion resistance, it is preferable to employ the second highly corrosion-resistant tri-nickel plating method of the present invention. In other words, in the first highly corrosion-resistant nickel plating method, the amount of non-conductive fine particles in the tri-nickel plating layer is only about 5% by weight, and the nickel surface has more in terms of surface area. Although it has the effect of dispersing corrosion, there is a limit to preventing the spread of corrosion in layers with a high amount of S. In contrast, in the second highly corrosion-resistant nickel plating method of the present invention, the tri-nickel layer has a two-layer structure consisting of a first layer with a relatively base potential and a second layer with a relatively noble potential,
Moreover, since the first layer is made to contain fine particles to disperse the corrosion current, a higher degree of corrosion resistance can be obtained.
ニッケルめっきにおけるめっき皮膜の電位は、めっき皮
膜中のイオウ含量に依存することが知られているので、
上記のように電位の異なる二層のトリニッケルめっき層
を得るためには、トリニッケル皮膜中のイオウ含量を調
整することが必要である。このためには、第１層のイオ
ウ含量が０．１２〜０．２５％程度となるようにトリニ
ッケルめっきをおこない、次いで第２層のイオウ含量が
０．０５〜０．１２％程度となるようにトリニッケルめ
っきをおこなうことが好ましい。It is known that the potential of the plating film in nickel plating depends on the sulfur content in the plating film.
In order to obtain two tri-nickel plating layers with different potentials as described above, it is necessary to adjust the sulfur content in the tri-nickel film. For this purpose, tri-nickel plating is performed so that the sulfur content of the first layer is approximately 0.12 to 0.25%, and then the sulfur content of the second layer is approximately 0.05 to 0.12%. It is preferable to perform tri-nickel plating.
二のような、第１層と第２層の間の電位の条件を満たし
、かつ第１層において添加された微粒子を共祈させるた
めには、まず空気撹拌下、非電導性微粒子を添加してト
リニッケルめっきをおこなうことが必要であり、この各
条件を満たすトリニッケルめっき浴としては、前記第１
の高耐食ニッケルめっき方法で用いられたものを採用す
ることができる。In order to satisfy the potential conditions between the first layer and the second layer as described in 2, and to make the particles added in the first layer work together, first add non-conductive particles under air agitation. It is necessary to perform tri-nickel plating using the above conditions, and the tri-nickel plating bath that satisfies each of these conditions is the first
The material used in the highly corrosion-resistant nickel plating method can be adopted.
次いで、第１トリニッケルめっき層よりイオウ含量の低
いトリニッケルめっき層が電析するように第２のトリニ
ッケルめっきをおこなう。Next, second tri-nickel plating is performed so that a tri-nickel plating layer having a lower sulfur content than the first tri-nickel plating layer is deposited.
この第２のトリニッケルめっきにおいては、空気撹拌等
は必要ではなく、逆に第１のトリニッケルめっきから汲
み込まれる非電導性微粒子を有効に除去するために静止
状態の浴の方が望ましい。 この第２トリニッケル浴組
成は第１トリニッケル浴組成とほぼ同一で良く、また、
光沢剤としては、第１トリニッケルと同じものでも良い
が、トリライト（荏原ニーシライト−製）等の市販の静
止トリニッケル用光沢剤を用いても良い。In this second tri-nickel plating, air agitation or the like is not necessary, and on the contrary, a static bath is preferable in order to effectively remove non-conductive fine particles drawn in from the first tri-nickel plating. This second tri-nickel bath composition may be approximately the same as the first tri-nickel bath composition, and
The brightening agent may be the same as the first tri-nickel, but a commercially available brightening agent for static tri-nickel such as Trilite (manufactured by Ebara Nishilight) may also be used.
本方法におけるトリニッケル第１層とトリニッケル第２
層をそれぞれ相対的に卑及び責とするためには、そのイ
オウ含量を、その差が少なくとも０．０５％以上とする
ことが好ましい。 また、トリニッケル第１層と第２層
の膜厚はそれぞれ０．５〜１．５μｍ、０．５〜１．０
μｍとすることが好ましい。Tri-nickel first layer and tri-nickel second layer in this method
In order to make the layers relatively non-basic and non-basic, respectively, it is preferred that the difference in sulfur content between the layers be at least 0.05%. In addition, the film thicknesses of the trinickel first layer and second layer are 0.5 to 1.5 μm and 0.5 to 1.0 μm, respectively.
It is preferable to set it to μm.
トリニッケル第１層の膜厚が０．５μｍ以下の場合、共
祈微粒子量が減少することがあり、また、１．５μｍ以
上の場合、横方向への過剰な腐食が生じることがあるの
でいずれも好ましくない。If the thickness of the tri-nickel first layer is less than 0.5 μm, the amount of co-particles may decrease, and if it is more than 1.5 μm, excessive corrosion in the lateral direction may occur. I also don't like it.
本発明の第２の高耐食ニッケルめっき方法における、他
の半光沢ニッケルめっき及び光沢ニッケルめっきは第１
の高耐食ニッケルめっき方法と同様に実施することがで
き、また、本方法が適用できる被めっき素材も同一であ
る。In the second highly corrosion-resistant nickel plating method of the present invention, other semi-bright nickel plating and bright nickel plating are
This method can be carried out in the same manner as the highly corrosion-resistant nickel plating method, and the materials to be plated to which this method can be applied are also the same.
本発明方法により高耐食ニッケルめっきが施された被め
っき素材は、更に必要に応じ仕上げめっきが施される。The material to be plated which has been subjected to highly corrosion-resistant nickel plating by the method of the present invention is further subjected to finish plating as necessary.
仕上げめっきは、屋外使用部品の場合一般にはクロムで
あるが、これのみに限定されず、池の金属、例えば金、
金合金等を採用することも可能である。Finish plating is generally chrome for outdoor parts, but is not limited to, but can also be metal such as gold,
It is also possible to use gold alloy or the like.
［作用］
本発明方法により優れた耐食性が得られる理由は未だ明
確ではないが、次のように推定される。[Function] Although the reason why excellent corrosion resistance is obtained by the method of the present invention is not yet clear, it is presumed as follows.
すなわち、トリニッケルめっき層に非電導性微粒子を共
祈させることによりその上の光沢ニッケルめっき層の共
祈微粒子に起因する欠陥、例えば微小クラック、粒界等
が生じる。That is, by causing non-conductive fine particles to coexist in the tri-nickel plating layer, defects such as microcracks and grain boundaries caused by the coplanar fine particles in the bright nickel plating layer thereon occur.
そして、腐食環境下におかれとき、これらの欠陥にそっ
て腐食が開始し、電位が最も卑なトリニッケルめっき層
が攻撃される。When placed in a corrosive environment, corrosion begins along these defects and attacks the tri-nickel plating layer, which has the lowest potential.
しかし、従来の三重ニッケルプロセスと異なり本発明に
よるめっき被膜にはトリニッケルめっき層に到る数多く
の欠陥があるので、各腐食箇所当りの腐食電流は分散さ
れて極めて微弱なものとなり、目に見えるような大きな
腐食孔は生じず、この結果、高耐食性と優れた外観を保
つことができるものと考えられる。However, unlike the conventional triple nickel process, the plating film according to the present invention has many defects in the tri-nickel plating layer, so the corrosion current per corrosion point is dispersed and becomes extremely weak, making it visible to the naked eye. It is thought that such large corrosion holes do not occur, and as a result, high corrosion resistance and excellent appearance can be maintained.
特に、本発明の第二の方法によれば、第３図に示すよう
に腐食が第１トリニッケルめっき層と第２トリニッケル
めっき層に更に分散されるので、より優れた効果が得ら
れるものと考えられる。In particular, according to the second method of the present invention, corrosion is further dispersed in the first tri-nickel plating layer and the second tri-nickel plating layer, as shown in FIG. 3, so that better effects can be obtained. it is conceivable that.
［発明の効果］
従来の三重ニッケルプロセスにクロムめっきを施した素
材では、約２サイクルの加速腐食試験で大きな腐食孔が
発生し、外観が低下するが、本発明の高耐食ニッケルめ
っき方法とクロムめっきを組合せ施した素材では目立つ
ような腐食孔は発生せず、外観は低下しなかった。[Effects of the Invention] With materials chromium plated using the conventional triple nickel process, large corrosion holes occur after approximately two cycles of accelerated corrosion testing, deteriorating the appearance, but with the highly corrosion resistant nickel plating method of the present invention No noticeable corrosion holes occurred in the material that was combined with plating, and the appearance did not deteriorate.
特に、第二の高耐食ニッケルめっき方法とクロムめっき
を施した素材は、加速腐食試験１０サイクルを経ても極
めてわずかな腐食孔が発生するに留まり、優れた高耐食
性が得られ、しかもその外観はほとんど低下しなかった
。In particular, the second highly corrosion-resistant nickel plating method and the chromium-plated material produced only a very small number of corrosion holes even after 10 cycles of the accelerated corrosion test, resulting in excellent high corrosion resistance and the appearance of the material. There was almost no decline.
したがって本発明は、屋外の厳しい条件下で長期間使用
される物品、例えば自動車部品の耐食めっき方法として
極めて優れたものである。Therefore, the present invention is extremely excellent as a corrosion-resistant plating method for articles that are used outdoors for a long period of time under severe conditions, such as automobile parts.
［実施例］
次に実施例を挙げ、本発明を更に具体的に説明するが、
本発明はこれら実施例に何ら制約されるものではない。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these examples in any way.
実施例 １゜
常法により電導化処理後、銅めっきされたＡＢＳ樹脂板
（１０ｃｐｓ Ｘ ５ ｅｌｍ ）をテスト板として用
い、下記工程でめっきをほどこし、耐食性試験片Ａを得
た。用いたニッケルめっき浴組成及び条件を第１表に、
クロムめっき浴組成を第２表に示す。Example 1 A copper-plated ABS resin plate (10 cps x 5 elm) was used as a test plate after being made conductive by a conventional method, and plated in the following steps to obtain a corrosion resistance test piece A. The composition and conditions of the nickel plating bath used are shown in Table 1.
The composition of the chromium plating bath is shown in Table 2.
めっき工程：
１．酸洗
１０％重量硫酸水溶液
時間１０秒
温 度 室温
水 洗
半光沢ニッケルめっき
微粒子共祈（第１）トリニッケル
めっき
光沢ニッケルめっき
水 洗
クロムめっき
水 洗
乾 燥
３゜
２゜
４゜
条
件
無水クロム酸（ＣｒＯ２） ２５０ ｇ／ｌ三価
クロム（Ｃｒ”） ２．０ ｇ／ｌ硫 酸
２．５ ｇ／ｌ温 度
４５ °Ｃ陰極電流密度
１５ Ａ／ｄａ２時 間
３ 分実施例２
下に示すめっき工程とする以外は、実施例１と同様にし
て耐食性試験片を得た。 用いたニッケルめっき浴組成
及び条件を第３表に示す
めっき工程：
１、 Ｍ洗
１０％重量硫酸水溶液
時間ｉｏ秒
温 度 室温
２、水洗
３、 半光沢ニッケルめつき
４、第１トリニッケルめつき
析）
第２トリニッケルめっき
光沢ニッケルめっき
水 洗
クロムめっき
水 洗
乾 燥
（以下余白）
（微粒子共
実施例３
実施例１及び２で得られた試験片について、膜厚測定及
びＣＡＳＳ試験（ＪＩＳ ０２０１）をおこない、その
膜厚と耐食性を評価した。膜厚測定の結果を第４表に、
耐食性試験の結果を第４図及び第５図に示す。Plating process: 1. Pickling 10% weight sulfuric acid aqueous solution Time 10 seconds Temperature Room temperature water Washing semi-bright nickel plating with fine particles (1st) Tri-nickel plating Bright nickel plating water Washing chromium plating water Washing drying 3°2°4° conditions Chromic acid anhydride (CrO2) 250 g/l Trivalent chromium (Cr”) 2.0 g/l Sulfuric acid 2.5 g/l Temperature
45 °C cathode current density
15 A/da 2 hours
3 minutes Example 2 A corrosion resistance test piece was obtained in the same manner as in Example 1 except for the plating process shown below. The nickel plating bath composition and conditions used are shown in Table 3. Plating process: 1. M washing 10% weight sulfuric acid aqueous solution Time io seconds Temperature room temperature 2 Water washing 3 Semi-bright nickel plating 4 First tri-nickel plating (Analysis) 2nd tri-nickel plating Bright nickel plating water Washing Chromium plating water Washing Drying (Hereafter the margin) (Example 3 with fine particles Film thickness measurement and CASS test (JIS 0201) ) to evaluate the film thickness and corrosion resistance.The results of the film thickness measurement are shown in Table 4.
The results of the corrosion resistance test are shown in Figures 4 and 5.
第 ４ 表
半成ツケｈ（１！１））ワニツケ）第２トツニツケル逼
りお訃ワニフヶ１メ乙チと一タ警りロム実施ＩＦ（Ｉ
Ａ ７．０μｍ １．５μｍ６．５μｍ ０
．５μｍ
Ｆ １２．０μｍ
１．０μｍ ８．０μｍ Ｏ，２５μｍ4th table half completed h (1! 1)) Wanitsuke) 2nd Totsunikkelu and deceased Wanifuga 1 me Ochi and Ichita alarm ROM implementation IF (I
A 7.0μm 1.5μm6.5μm 0
．． 5μm F 12.0μm 1.0μm 8.0μm O, 25μm
第１図及び第２図は、本発明の高耐食トリニッケルめっ
き方法により得られるニッケルめっき皮膜の構成を示す
図面である。
第３図は、第２図に示す構成のニッケルめっき皮膜につ
いての腐食電流密度の分散を模式的に示した図である。
第４図及び第５図は、本発明の高耐食性トリニッケルめ
っき方法を施した試験片及び比較試験片についてＣＡＳ
Ｓ試験をおこなったときのサイクル数とレイティングナ
ンバーの関係を示す図面である。
以 上
耐食性試験の結果のうち、第４図は全ニッケル膜厚を１
５μにしたものを、第５図では全ニッケルのめっき膜厚
を２０μとしたものを示すが、この結果から、本発明方
法によれば、従来の三重ニッケルプロセスに比べ優れた
耐食性が得られることは明らかである。FIGS. 1 and 2 are drawings showing the structure of a nickel plating film obtained by the highly corrosion-resistant tri-nickel plating method of the present invention. FIG. 3 is a diagram schematically showing the dispersion of corrosion current density for the nickel plating film having the configuration shown in FIG. 2. Figures 4 and 5 show CAS results for test pieces and comparative test pieces subjected to the highly corrosion-resistant tri-nickel plating method of the present invention.
It is a drawing showing the relationship between the number of cycles and the rating number when performing the S test. Among the results of the above corrosion resistance test, Figure 4 shows that the total nickel film thickness is 1
Figure 5 shows a case where the total nickel plating film thickness was 20μ, and the results show that the method of the present invention provides superior corrosion resistance compared to the conventional triple nickel process. is clear.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1234794A JPH03100187A (en) | 1989-09-12 | 1989-09-12 | Highly corrosion resistant nickel plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1234794A JPH03100187A (en) | 1989-09-12 | 1989-09-12 | Highly corrosion resistant nickel plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03100187A true JPH03100187A (en) | 1991-04-25 |
| JPH0514035B2 JPH0514035B2 (en) | 1993-02-24 |
Family
ID=16976497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1234794A Granted JPH03100187A (en) | 1989-09-12 | 1989-09-12 | Highly corrosion resistant nickel plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03100187A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102953094A (en) * | 2011-08-26 | 2013-03-06 | 比亚迪股份有限公司 | Semi-bright nickel electroplating solution additive, semi-bright nickel electroplating solution and semi-bright nickel electroplating method |
| WO2013094766A1 (en) * | 2011-12-22 | 2013-06-27 | オーエム産業株式会社 | Plated article and manufacturing method therefor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6232278A (en) * | 1985-08-02 | 1987-02-12 | Suzuki Motor Co Ltd | Fuel injection engine |
| JPS6252039A (en) * | 1985-07-02 | 1987-03-06 | エービー テトラ パック | Outflow edge of packaging vessel |
-
1989
- 1989-09-12 JP JP1234794A patent/JPH03100187A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6252039A (en) * | 1985-07-02 | 1987-03-06 | エービー テトラ パック | Outflow edge of packaging vessel |
| JPS6232278A (en) * | 1985-08-02 | 1987-02-12 | Suzuki Motor Co Ltd | Fuel injection engine |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102953094A (en) * | 2011-08-26 | 2013-03-06 | 比亚迪股份有限公司 | Semi-bright nickel electroplating solution additive, semi-bright nickel electroplating solution and semi-bright nickel electroplating method |
| WO2013094766A1 (en) * | 2011-12-22 | 2013-06-27 | オーエム産業株式会社 | Plated article and manufacturing method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0514035B2 (en) | 1993-02-24 |
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