JPS5844754B2 - Hard nickel plating method - Google Patents
Hard nickel plating methodInfo
- Publication number
- JPS5844754B2 JPS5844754B2 JP5766376A JP5766376A JPS5844754B2 JP S5844754 B2 JPS5844754 B2 JP S5844754B2 JP 5766376 A JP5766376 A JP 5766376A JP 5766376 A JP5766376 A JP 5766376A JP S5844754 B2 JPS5844754 B2 JP S5844754B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- nickel
- present
- temperature
- hardness
- 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.)
- Expired
Links
Description
【発明の詳細な説明】
本発明は、クロムのようなその廃水が公害の原因となる
金属を用いずに、高硬度の金属めっきを行なう方法に関
するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for plating high hardness metals without using metals whose waste water causes pollution, such as chromium.
さらに詳しくいえば、本発明はなんら還元剤を必要とし
ない電解ニッケルめっき法により、従来のクロムめっき
法により得られるものに匹敵する高い硬度の金属めっき
層を得る方法に関するものである。More specifically, the present invention relates to a method for obtaining a metal plating layer of high hardness comparable to that obtained by conventional chromium plating methods by electrolytic nickel plating method that does not require any reducing agent.
これまで、硬質めっき法としては、クロムめっきが工業
的に広く利用されていた。Until now, chromium plating has been widely used industrially as a hard plating method.
このもの（ま、硬度が高く、耐食性、耐摩耗性のすぐれ
ためつき層を形成するという長所を有するが、電流効率
が低い上に、有害な廃水を生じ公害の原因となるという
致命的な欠陥を有しているため、これに代るべき新らし
いめっき法の出現が大いに要望されている。This one (well, it has the advantage of being highly hard and forming a matting layer with excellent corrosion resistance and abrasion resistance, but it has the fatal flaw that it has low current efficiency and generates harmful waste water, causing pollution. Therefore, there is a great demand for a new plating method to replace this.
この要望にこたえるべく、その後ニッケルーホウ素合金
めっき、ニッケルーリン合金めっきが研究されたが、こ
れらのめつき層は硬化するのに５００〜６００’Ｃとい
う高い温度における熱処理を必要とするため、熱に対し
不安定な金属基材やプラスチックのような低い軟化点の
材料に適用できない上に、ホウ素やリンの含有量により
硬化温度が変化し、条件制御が困難であるという欠点が
あり、工業的方法としてはまだ満足すべきものではなか
った。In order to meet this demand, nickel-boron alloy plating and nickel-phosphorus alloy plating were subsequently researched, but these plating layers require heat treatment at a high temperature of 500 to 600'C to harden. In addition, it cannot be applied to materials with low softening points such as unstable metal substrates and plastics, and the curing temperature changes depending on the boron and phosphorus content, making it difficult to control the conditions. The method was still not satisfactory.
本発明者らは、これら従来の硬質めっき法のもつ欠点を
克服し、有害金属を用いることなく、シかも低温度の熱
処理で高い硬度を得ることができる新規な硬質めっき法
を開発すべく鋭意研究を重ねた結果、アルカリ性のニッ
ケルキレート含有浴を用いて電解めっきした場合は、８
０〜４００℃好ましくは１００℃〜３００℃という低い
温度における熱処理により非常に高い硬度のめっき層を
形成しうろことを見出し、この知見に基づいて本発明を
なすに至った。The present inventors have worked diligently to overcome the drawbacks of these conventional hard plating methods and to develop a new hard plating method that can obtain high hardness through low-temperature heat treatment without using harmful metals. As a result of repeated research, we found that when electrolytically plated using an alkaline nickel chelate containing bath,
It has been discovered that a plating layer with extremely high hardness can be formed by heat treatment at a low temperature of 0 to 400°C, preferably 100 to 300°C, and based on this knowledge, the present invention has been accomplished.
すなわち、本発明は所定の基材を水溶性ニッケル塩及び
キレート形成化合物を含有するアルカリ性水溶液中にお
いて電析処理したのち、８０〜４００℃において熱処理
することを特徴とする硬質ニッケルめっき法を提供する
ものである。That is, the present invention provides a hard nickel plating method characterized in that a predetermined base material is electrodeposited in an alkaline aqueous solution containing a water-soluble nickel salt and a chelate-forming compound, and then heat-treated at 80 to 400°C. It is something.
本発明方法において用いられるニッケル電析浴中の水溶
性ニッケル塩としては、例えば塩化ニッケル、硝酸ニッ
ケル、硫酸ニッケルなどがある。Examples of water-soluble nickel salts in the nickel electrodeposition bath used in the method of the present invention include nickel chloride, nickel nitrate, and nickel sulfate.
これらの塩は、０．２５〜２．０モルの濃度で用いられ
る。These salts are used in concentrations of 0.25 to 2.0 molar.
また、キレート形成化合物の例としては、エチレンジア
ミン、エチレンジアミン四酢酸塩、各種アミノ酸塩、グ
リシン酸などがあげられる。Furthermore, examples of chelate-forming compounds include ethylenediamine, ethylenediaminetetraacetate, various amino acid salts, and glycinic acid.
これらは単独あるいは２種以上混合し、通常は０．２５
〜２．０モルの範囲の濃度で用いられる。These may be used alone or in combination of two or more, and are usually 0.25
Used at concentrations ranging from ~2.0 molar.
本発明の電析浴には、前記の水溶性ニッケル塩とキレー
ト形成化合物に加えて、酒石酸塩０．０２〜２．０モル
、塩化アンモニウム０．７５〜２．０モルなどを補助成
分として添加し、全体をアルカリ性に調節する。In addition to the above-mentioned water-soluble nickel salt and chelate-forming compound, the electrodeposition bath of the present invention contains 0.02 to 2.0 mol of tartrate, 0.75 to 2.0 mol of ammonium chloride, etc. as auxiliary components. and adjust the overall alkalinity.
本発明の電解は、室温〜８０℃の温度、１〜１０Ａ／ｄ
−の電流密度で行われる。The electrolysis of the present invention is carried out at a temperature of room temperature to 80°C, 1 to 10 A/d.
- carried out at a current density of -.
本発明方法によりめっき可能な基材としては、銅、鉄、
亜鉛などの金属、青銅、黄銅などの合金、各種プラスチ
ックをあげることができる。Substrates that can be plated by the method of the present invention include copper, iron,
Examples include metals such as zinc, alloys such as bronze and brass, and various plastics.
本発明方法においては、硬化のための熱処理を従来の方
法の場合に比べかなり低い温度で行いうるので、従来の
方法ではめつきできなかった基材についても施こすこと
ができる。In the method of the present invention, heat treatment for curing can be performed at a considerably lower temperature than in conventional methods, so it can be applied to substrates that could not be plated using conventional methods.
本発明方法においては、電析処理した基材を真空中、８
０°Ｃ〜４００℃好ましくは１００００〜３００℃の範
囲の温度で３０分間〜１０時間程度熱処理して硬化させ
ることができる。In the method of the present invention, the electrodeposited substrate is placed in vacuum for 8
It can be cured by heat treatment at a temperature in the range of 0°C to 400°C, preferably 10,000 to 300°C, for about 30 minutes to 10 hours.
従来のニッケルーホウ素系合金やニッケルーリン系合金
のめつきにおいては、５００〜６００℃という高い温度
で熱処理することによりはじめて硬化することができる
が、本発明方法においては、４００°Ｃよりも高い温度
に加熱すると硬度はむしろ急激に低下する。In conventional plating of nickel-boron alloys and nickel-phosphorus alloys, hardening can only be achieved by heat treatment at a high temperature of 500 to 600°C, but in the method of the present invention, plating at temperatures higher than 400°C When heated to a certain temperature, the hardness decreases rather rapidly.
これは、本発明方法においては電析された金属の組織の
吸蔵水素が安定な状態に固定され、それによって硬化が
達成されるが、さらに高い温度に加熱すると吸蔵水素が
容易に放出し軟化するためであると考えられる。This is because in the method of the present invention, the occluded hydrogen in the structure of the electrodeposited metal is fixed in a stable state, thereby achieving hardening, but when heated to a higher temperature, the occluded hydrogen is easily released and softens. This is thought to be due to the
このように、水素を安定に吸蔵させる手段としては、炭
素、窒素などの元素を共析させ、それらの元素間の相互
作用により格子欠陥内に固定させる方法がとられ、した
がって炭水化物、アンモニア、エチレンジアミンなどを
電析浴中に共存させるのが好ましい。In this way, a method for stably storing hydrogen is to eutectoid elements such as carbon and nitrogen and fix them in lattice defects through interactions between these elements. It is preferable to coexist in the electrodeposition bath.
このようにして得られる硬質めっき層は、従来法による
硬質クロムめっきに匹敵する機械的性質を有する。The hard plating layer thus obtained has mechanical properties comparable to hard chromium plating by conventional methods.
本発明方法は、有毒廃水を排出することなく、しかもめ
つき浴の濃度、温度などや電解条件の側割が容易であり
、熱硬化温度が低いので従来のクロムめっきに代わる効
果的な硬質めっき法として有用である。The method of the present invention does not discharge toxic waste water, and the concentration, temperature, etc. of the plating bath and electrolysis conditions can be easily adjusted, and the heat curing temperature is low, making it an effective hard plating alternative to conventional chrome plating. Useful as a law.
次に実施例により本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例 １
塩化ニッケル０．５Ｍとエチレンジアミン２．０Ｍを水
ｌｌ中に溶解し、めっき液をｐＨ８に調整した。Example 1 0.5 M of nickel chloride and 2.0 M of ethylenediamine were dissolved in 1 liter of water, and the plating solution was adjusted to pH 8.
陽極材料として、ニッケル板を用い、陰極にめっきをし
ようとする銅板（１０ＸＩ ＯＯＸｌｍｍ）を懸吊し、
電流密度１０Ａ／ｄｍ’、浴温６０℃の条件で５０分間
めっき処理し、５０μの膜厚とした。A nickel plate is used as the anode material, and a copper plate (10XI OOXlmm) to be plated on the cathode is suspended.
Plating was carried out for 50 minutes at a current density of 10 A/dm' and a bath temperature of 60° C., resulting in a film thickness of 50 μm.
この電析ニッケル硬度はＨｖ４５０である。The hardness of this electrodeposited nickel is Hv450.
このものを２００°Ｃ１時間の加熱にあってＨｖ８５０
．２時間の加熱ではＨｖｌＯＯＱ、８時間加熱後の硬さ
はＨｖ８００を得た。When heated at 200°C for 1 hour, Hv850
．． After heating for 2 hours, HvlOOQ was obtained, and after heating for 8 hours, hardness was Hv800.
比較のためサージェント浴からのクロムめつき浴温５５
℃、５０ Ａ ／ ｄ ｍの電解条件で５０μ膜厚のも
のについて行った。For comparison, chrome plating bath temperature 55 from Sargent bath
The test was carried out on a film having a thickness of 50 μm under electrolytic conditions of 50 A/dm at ℃.
電析後はＨｖ１０５０．２００℃１時間の加熱にあって
Ｈｖ１０３０．２時間でＩ（ｖｌｏ００１８時間の加熱
にあってＨｖ９００であった。After electrodeposition, it was heated at Hv 1050.200° C. for 1 hour and Hv 1030.2 hours I (vlo00) and Hv 900 after heating for 18 hours.
また通常一般に用いられているワット浴からの電析物と
比較するため同上記と同条件で２５分間電解を施し、５
０μの膜厚について加熱による硬さの変化は、電析後Ｉ
（ｖ３８０．２０００Ｃ１時間加熱Ｈｖ３５０．２時間
３５０．８時間の加熱にあってＨｖ３００であった。In addition, in order to compare with the deposits from the commonly used Watt bath, electrolysis was performed for 25 minutes under the same conditions as above.
For a film thickness of 0μ, the change in hardness due to heating is I after electrodeposition.
(V380.2000C 1 hour heating Hv 350.2 hours 350.8 hours heating, Hv 300.
実施例 ２
実施例１と同じめっき液を用い、浴温６０℃、電流密度
６ Ａ／ ｄ ｍ″の電解条件下で、銅板（６０Ｘ５０
Ｘ１ｍｍ）を、ニッケルめっきし、５０μの膜厚のめつ
き層を得た。Example 2 Using the same plating solution as in Example 1, a copper plate (60×50
1 mm) was nickel plated to obtain a plated layer with a thickness of 50 μm.
このものを１Ｏ−３Ｔｏｒｒの真空中、室温、２５０°
Ｃ及び６００℃において１時間熱処理し、その硬さを測
定した。This material was placed in a vacuum of 1O-3 Torr at room temperature at 250°
It was heat-treated at 600° C. and 600° C. for 1 hour, and its hardness was measured.
その結果を添付図面に曲線Ａとして示す。The results are shown as curve A in the accompanying drawings.
また比較のために、塩化ニッケル０．２５Ｍ、エチレン
ジアミン１．０Ｍ、水酸化ナトリウム１．０Ｍ及びホウ
水素化ナトリウム５ｍＭを水ｌｌ中に溶解した無電解め
っき液を用いて、めっきしたものについて同じように熱
処理し、得られた試料の硬さを曲線Ｂとして示す。For comparison, similar results were obtained using an electroless plating solution containing 0.25M nickel chloride, 1.0M ethylenediamine, 1.0M sodium hydroxide, and 5mM sodium borohydride dissolved in 1 liter of water. The hardness of the obtained sample is shown as curve B.
この結果から明らかなように、本発明方法によるめっき
層は２５０℃付近の熱処理で最大硬さになるの；こ対し
、従来の無電解めっき層は、６ｏ。As is clear from this result, the plating layer formed by the method of the present invention reaches its maximum hardness when heat treated at around 250°C; on the other hand, the conventional electroless plating layer has a hardness of 6o.
℃以上において最大硬さになる。Maximum hardness occurs above ℃.
添付図面は、本発明方法及び従来法により得ためつき層
の熱処理温度と硬さとの関係を示すグラフである。The accompanying drawing is a graph showing the relationship between heat treatment temperature and hardness of the laminated layer obtained by the method of the present invention and the conventional method.
Claims (1)
化合物を含有するアルカリ性水溶液中において電析処理
したのち、８０〜４００’Ｃにおいて熱処理することを
特徴とする硬質ニッケルめっき法。 ２ 水溶性ニッケル塩が塩化ニッケルである特許請求の
範囲第１項記載の方法。 ３ キレート形成化合物がエチレンジアミンである特許
請求の範囲第１項記載の方法。[Scope of Claims] 1. Hard nickel plating characterized in that a predetermined base material is electrodeposited in an alkaline aqueous solution containing a water-soluble nickel salt and a chelate-forming compound, and then heat-treated at 80 to 400'C. Law. 2. The method according to claim 1, wherein the water-soluble nickel salt is nickel chloride. 3. The method of claim 1, wherein the chelate-forming compound is ethylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5766376A JPS5844754B2 (en) | 1976-05-19 | 1976-05-19 | Hard nickel plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5766376A JPS5844754B2 (en) | 1976-05-19 | 1976-05-19 | Hard nickel plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS52140433A JPS52140433A (en) | 1977-11-24 |
| JPS5844754B2 true JPS5844754B2 (en) | 1983-10-05 |
Family
ID=13062131
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5766376A Expired JPS5844754B2 (en) | 1976-05-19 | 1976-05-19 | Hard nickel plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5844754B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6062765U (en) * | 1983-10-05 | 1985-05-02 | ウシオ電機株式会社 | tubular halogen incandescent light bulb |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2671013B2 (en) * | 1988-06-16 | 1997-10-29 | ディップソール株式会社 | Method for supplying nickel ions in alkaline nickel or nickel alloy plating |
-
1976
- 1976-05-19 JP JP5766376A patent/JPS5844754B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6062765U (en) * | 1983-10-05 | 1985-05-02 | ウシオ電機株式会社 | tubular halogen incandescent light bulb |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS52140433A (en) | 1977-11-24 |
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