JP2007077463A - Nickel-boron composite plating liquid, composite plating method using the liquid, and composite plated parts using the method - Google Patents

Nickel-boron composite plating liquid, composite plating method using the liquid, and composite plated parts using the method Download PDF

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JP2007077463A
JP2007077463A JP2005268202A JP2005268202A JP2007077463A JP 2007077463 A JP2007077463 A JP 2007077463A JP 2005268202 A JP2005268202 A JP 2005268202A JP 2005268202 A JP2005268202 A JP 2005268202A JP 2007077463 A JP2007077463 A JP 2007077463A
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nickel
boron
plating
composite plating
composite
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JP4892678B2 (en
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Ikuo Shoji
郁夫 荘司
Susumu Arai
進 新井
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Gunma University NUC
Shinshu University NUC
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Shinshu University NUC
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Abstract

<P>PROBLEM TO BE SOLVED: To manufacture machine parts excellent in wear resistance by a composite plating process. <P>SOLUTION: The plating liquid is prepared by mixing boron particles (or boron compounds) therein. A nickel-boron composite plated film is prepared by a composite plating method by using the plating liquid, thereby increasing the boron content in the nickel-boron composite plated film. Machine parts excellent in wear resistance can be manufactured by the composite plated film. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、ニッケル−ホウ素複合めっきの更なる高機能化を目的として、当該めっきに好適な複合めっき液とその液を使用した複合めっき方法およびその方法を使用した複合めっき部品に関するものであり、この複合めっきにより耐摩耗性にすぐれた機械部品等を製造することができる。   The present invention relates to a composite plating solution suitable for the plating, a composite plating method using the solution, and a composite plated part using the method for the purpose of further enhancing the functionality of the nickel-boron composite plating. With this composite plating, it is possible to manufacture machine parts having excellent wear resistance.

従来より、ニッケル−ホウ素合金めっきは熱処理後の硬さがビッカ−ス硬度で１０００に達する等、様々な特性を持つめっきであり、ギヤ等の機械摺動部品の耐摩耗性を向上させる目的で、広く使用されている。
しかし、公知の方法によって作製したニッケルーホウ素合金めっき膜は、めっき膜中のホウ素含有量が少ないため、機械摺動部品の耐摩耗性が十分でなく、当該業界では更なるめっき膜の耐摩耗性等の向上が求められている。
前記したニッケル−ホウ素合金めっきは、現在、特許文献１にも示すような電気めっき法や、これとは別の無電解めっき法により作製されている。 Conventionally, nickel-boron alloy plating is a plating with various properties such that the hardness after heat treatment reaches 1000 in Vickers hardness, and for the purpose of improving the wear resistance of mechanical sliding parts such as gears. Widely used.
However, the nickel-boron alloy plating film produced by a known method has a low boron content in the plating film, so the wear resistance of the mechanical sliding parts is not sufficient, and the plating film has further wear resistance in the industry. There is a need for improvements in properties.
The nickel-boron alloy plating described above is currently produced by an electroplating method as shown in Patent Document 1 or an electroless plating method different from this.

特開平１０−２４５６９３号公報Japanese Patent Laid-Open No. 10-245893

ところで、現在ニッケル−ホウ素合金めっきのために使用するめっき液は、ニッケルめっき液中に水溶性のホウ素化合物を溶解させたものである。このようなタイプのめっき液からはせいぜいホウ素含有量２５原子％未満までのニッケル−ホウ素複合金めっきの作製が可能であるものの、ホウ素含有量２５原子％以上のニッケル−ホウ素複合めっきを作ることはできなかった。特に、ホウ素が粒子の状態でめっき膜中に存在するような複合めっき法は現在まで皆無であり、このため耐摩耗性に優れた特性を有するニッケル−ホウ素複合めっきの開発が求められている。
また、ニッケル−ホウ素複合めっきの熱処理後の相構造は金属ニッケルと金属間化合物（Ｎｉ3 Ｂ）から成るため、ホウ素含有量を２５原子％以上にすることができれば、熱処理後、Ｎｉ3 ＢとＮｉ2 Ｂ等から成る相構造の新規合金膜が作製可能となり、機械摺動部品の耐摩耗性等をさらに向上させることが期待できる。 By the way, the plating solution currently used for nickel-boron alloy plating is obtained by dissolving a water-soluble boron compound in a nickel plating solution. Although it is possible to produce a nickel-boron composite gold plating with a boron content of less than 25 atomic% from such a type of plating solution, it is not possible to produce a nickel-boron composite plating with a boron content of 25 atomic% or more. could not. In particular, there has been no composite plating method in which boron is present in the plating film in the state of particles, and therefore, development of nickel-boron composite plating having characteristics excellent in wear resistance has been demanded.
Moreover, since the phase structure after the heat treatment of the nickel-boron composite plating is composed of metallic nickel and an intermetallic compound (Ni 3 B), if the boron content can be 25 atomic% or more, Ni 3 B and A new alloy film having a phase structure made of Ni 2 B or the like can be produced, and it can be expected to further improve the wear resistance of the machine sliding parts.

本発明者らは、ニッケルーホウ素複合めっき中のホウ素含有量を増やすためのめっき液について種々の研究を進めてきたが、めっき膜中に難溶性のホウ素微粒子（約６００ｎｍ）を取り込むことができる新しい工法の開発に成功した。これにより従来のめっき法において、ホウ素の含有限界であった２５原子％以上にホウ素を含有するニッケル−ホウ素複合めっき膜を作成することができた。
本工法は、めっき液中に微小（少なくとも粒径は１μｍ以下）なホウ素粒子をめっき液中に高濃度で混入しためっき液を作り、そのめっき液を使用して複合めっき法によりニッケルーホウ素複合めっき膜を作製する。
なお、複合めっきとはめっき浴中に難溶性の微粒子を懸濁させた状態でめっきを行い、金属膜中に難溶性の微粒子を取り込んだ複合膜を作製するめっき法である。
本発明によれば、高濃度でホウ素粒子を含有するニッケル−ホウ素複合めっき膜を作製することが可能であり、さらに２５原子％以上のホウ素を含有するニッケル−ホウ素複合めっき膜を作製することが可能である。その後作製されたニッケル−ホウ素複合めっき膜を熱処理等を施すことにより、合金化を促進させ、膜の物性・特性を変化させることもできる。まためっき浴中へ添加剤（たとえばブチンジオールとサッカリン等）を加えることにより膜の表面形態を平滑にすることもできる。 The present inventors have made various studies on the plating solution for increasing the boron content in the nickel-boron composite plating, but it is possible to incorporate hardly soluble boron fine particles (about 600 nm) into the plating film. Succeeded in developing a new construction method. Thereby, in the conventional plating method, a nickel-boron composite plating film containing boron at 25 atomic% or more, which was the limit of boron content, could be produced.
This method creates a plating solution in which fine boron particles (at least particle size of 1 μm or less) are mixed in the plating solution at a high concentration in the plating solution, and the plating solution is used to form a nickel-boron composite by a composite plating method. A plating film is produced.
The composite plating is a plating method in which plating is performed in a state where hardly soluble fine particles are suspended in a plating bath to produce a composite film in which the hardly soluble fine particles are taken into the metal film.
According to the present invention, a nickel-boron composite plating film containing boron particles at a high concentration can be produced, and further a nickel-boron composite plating film containing 25 atomic% or more of boron can be produced. Is possible. The nickel-boron composite plating film produced thereafter is subjected to heat treatment or the like, thereby promoting alloying and changing the physical properties and characteristics of the film. Further, the surface morphology of the film can be made smooth by adding additives (for example, butynediol and saccharin) to the plating bath.

このため、本発明が採用した技術解決手段は、
ニッケルめっき液にホウ素粒子を添加したことを特徴とするニッケルーホウ素複合めっき液である。
また、前記ホウ素粒子の径は１マイクロメートル以下であることを特徴とするニッケルーホウ素複合めっき液である。
また、前記に記載のニッケルーホウ素複合めっき液に基材を入れ、電解めっきあるいは無電解めっきによりめっきすることを特徴とするニッケルーホウ素複合めっき方法である。
また、前記方法によって作成したニッケル−ホウ素複合めっき膜である。
また、前記ニッケル−ホウ素複合めっき膜を熱処理したことを特徴とするニッケル−ホウ素複合めっき膜である。
また、前記に記載のめっき方法によりニッケル−ホウ素複合めっき膜で皮膜した機械部品である。
また、前記ニッケル−ホウ素複合めっき膜を熱処理したことを特徴とする機械部品である。
また、前記に記載の機械部品の材料は銅、黄銅、ステンレス、アルミ、チタン、導電性樹脂の何れかであることを特徴とする機械部品である。 For this reason, the technical solution means adopted by the present invention is:
A nickel-boron composite plating solution characterized in that boron particles are added to a nickel plating solution.
Moreover, the diameter of the said boron particle is 1 micrometer or less, It is a nickel-boron composite plating liquid characterized by the above-mentioned.
Moreover, the nickel-boron composite plating method is characterized in that a substrate is put into the nickel-boron composite plating solution described above and plated by electrolytic plating or electroless plating.
Moreover, it is the nickel-boron composite plating film produced by the said method.
The nickel-boron composite plating film is characterized by being heat-treated.
Moreover, it is a machine part coated with a nickel-boron composite plating film by the plating method described above.
The nickel-boron composite plating film is heat treated.
Further, the material of the machine part described above is any one of the machine parts characterized in that it is any one of copper, brass, stainless steel, aluminum, titanium, and conductive resin.

本発明では、
ａ：本工法のニッケル−ホウ素複合めっき法により、ニッケル中にホウ素粒子が分散した構造の複合めっき層を形成することができる。
ｂ：上記複合めっき層をさらに熱処理を行うことで硬度等の機械的物性値を向上させ、機械部品の耐摩耗性を向上することができる。
ｃ：本工法によればホウ素含有量２５原子％以上の合金膜も作製可能であり、熱処理により例えばＮｉ3 ＢとＮｉ2 Ｂ等から成る新規合金膜が作製可能である。
ｄ：本めっき液を使用しためっき法は、電解めっき、無電解めっきのいずれにも適用できるが、電解めっき法を使用することで無電解めっき法と比べて成膜速度の向上を図ることができ、さらにめっき製品の製造コストも減少させることができる。 In the present invention,
a: A composite plating layer having a structure in which boron particles are dispersed in nickel can be formed by the nickel-boron composite plating method of this method.
b: By further heat-treating the composite plating layer, mechanical property values such as hardness can be improved, and wear resistance of mechanical parts can be improved.
c: According to this method, an alloy film having a boron content of 25 atomic% or more can be produced, and a new alloy film made of, for example, Ni 3 B and Ni 2 B can be produced by heat treatment.
d: The plating method using this plating solution can be applied to both electrolytic plating and electroless plating. However, by using the electrolytic plating method, it is possible to improve the deposition rate compared to the electroless plating method. In addition, the manufacturing cost of the plated product can be reduced.

本発明は、
ニッケルーホウ素複合めっきの更なる高機能化を目的として、複合めっき法によりニッケルーホウ素複合めっき膜を作製することを特徴とする。
本発明では、従来のめっき法において、ホウ素の含有限界であった２５原子％以上のホウ素を含有するニッケルーホウ素複合めっき膜を作製することが可能であり、さらに熱処理等を施すことにより、合金化を促進させ、膜の物性・特性を変化させることもできる。まためっき浴中へ添加剤を加えることにより膜の表面形態を平滑にすることもできる。 The present invention
A nickel-boron composite plating film is produced by a composite plating method for the purpose of further enhancing the functionality of the nickel-boron composite plating.
In the present invention, it is possible to produce a nickel-boron composite plating film containing 25 atomic% or more of boron, which was the limit of boron content in the conventional plating method, and by applying heat treatment or the like, It is also possible to promote the formation and change the physical properties and characteristics of the film. Moreover, the surface form of the film can be smoothed by adding an additive to the plating bath.

以下、図面を参照して本発明に係る実施例を説明する。
図１、図２は本発明による電解めっき法によるめっき膜生成の説明図、図３はめっき層の断面図である。
図１、図２において、１はニッケルめっき液を入れる容器、２はニッケルめっき液、３は同めっき液中にいれる陽極電極、４は陰極電極を兼ねためっき基材、５は攪拌翼、６は電源である。なお、図１は電極を垂直にしたもの、図２は基材側となる電極を容器の底に寝かせて配置したものである。
ニッケルめっき液中には、粒径が少なくとも１μｍ未満のホウ素の微小な粒子を懸濁してある。
なお、めっき基材としては、銅、黄銅、ステンレス、アルミ、チタン等の材料の他に導電性合成樹脂等を使用する。
上記のような状態で通電すると、図３に示すように公知の原理により基材４上にホウ素粒子が混入しためっき膜（複合めっき膜）７が生成される。こうしてめっき膜が生成された基材を、従来と同様の手法で熱処理することで、従来には得ることができなかった、高い耐久性を有するニッケル−ホウ素複合めっき膜を得ることができる。 Embodiments according to the present invention will be described below with reference to the drawings.
1 and FIG. 2 are explanatory views of the production of a plating film by the electrolytic plating method according to the present invention, and FIG. 3 is a sectional view of a plating layer.
1 and 2, 1 is a container for containing a nickel plating solution, 2 is a nickel plating solution, 3 is an anode electrode contained in the plating solution, 4 is a plating base material also serving as a cathode electrode, 5 is a stirring blade, 6 Is the power supply. Note that FIG. 1 is a view in which the electrodes are vertical, and FIG. 2 is a view in which the electrodes on the base material side are placed on the bottom of the container.
In the nickel plating solution, fine particles of boron having a particle size of at least less than 1 μm are suspended.
In addition, as a plating substrate, a conductive synthetic resin or the like is used in addition to materials such as copper, brass, stainless steel, aluminum, and titanium.
When energized in the above state, a plating film (composite plating film) 7 in which boron particles are mixed on the substrate 4 is generated according to a known principle as shown in FIG. By heat-treating the base material on which the plating film is formed in the same manner as in the past, a nickel-boron composite plating film having high durability, which could not be obtained conventionally, can be obtained.

〔実施例１〕 本実施例では、めっき液として、基本浴（１ＭＮｉＳＯ4 ・６Ｈ2 Ｏ＋０．２ＭＮｉＣｌ2 ・６Ｈ2 Ｏ＋０．５ＭＨ3 ＢＯ3 ）にホウ素粒子（粒サイズ：０．９μ以下）を２０ｇ／リットル添加した浴（浴１）、基本浴に粒子サイズ：６００ｎｍ以下のホウ素を２０ｇ／リットル添加した浴（浴２）、さらに浴１および浴２に０．００２５Ｍブチン１，４ジオールと０．０１Ｍサッカリンナトリウムを添加した浴３および浴４を調製した。電析試験として、電流規制法によりめっき液温度２５°Ｃ、通電量６０Ｃ／ｃｍ2 の条件にて銅板またはステンレス板上にめっき層を作製した。電極配置は垂直配置とした。作製しためっき層の成分分析をＩＣＰ法にて分析したところ、浴１，浴２，浴３および浴４から得られたニッケル−ホウ素複合膜はそれぞれ、ホウ素含有量５．５，４．１，３．７，１．９原子％であった。また、浴１および浴２から得られためっき層に比べ浴３および浴４から得られためっき層は平滑な表面形態であった。 Example 1 In this example, 20 g of boron particles (grain size: 0.9 μm or less) were added to a basic bath (1MNiSO 4 .6H 2 O + 0.2MNiCl 2 .6H 2 O + 0.5MH 3 BO 3 ) as a plating solution. / L added bath (Bath 1), a basic bath added with 20 g / L of boron having a particle size of 600 nm or less (Bath 2), and Bath 1 and Bath 2 with 0.0025 M butyne 1,4 diol and 0. Bath 3 and bath 4 with the addition of 01M sodium saccharin were prepared. As an electrodeposition test, a plating layer was prepared on a copper plate or a stainless steel plate under the conditions of a plating solution temperature of 25 ° C. and an energization amount of 60 C / cm 2 by a current regulation method. The electrode arrangement was a vertical arrangement. When the component analysis of the produced plating layer was analyzed by the ICP method, the nickel-boron composite films obtained from the bath 1, bath 2, bath 3 and bath 4 were boron content 5.5, 4.1, respectively. 3.7 and 1.9 atomic%. In addition, the plating layers obtained from bath 3 and bath 4 were smoother than the plating layers obtained from bath 1 and bath 2.

以上、本発明の実施例について説明したが、本発明では、従来のめっき法において、ホウ素含有限界であった２５原子パーセント以上のホウ素を含有するニッケルーホウ素複合めっき膜を作製することが可能であり、熱処理等を施すことにより、合金化を促進させ、膜の物性・特性を変化させることもできる。
まためっき基材としては、銅、黄銅、ステンレス、アルミニウム、チタン等の他に導電性合成樹脂等を材料とした機械部品（ギヤ、ロッド等）を対象とする。
さらにめっき浴槽中の基材は垂直、横、斜め等種々の状態で配置することができる。
まためっき浴中へ添加剤を加えることにより膜の表面形態を平滑にすることもできる。
また機械部品とは広義の意味であり、広くめっきされた部品を含むこととする。
また本発明はその精神また主要な特徴から逸脱することなく、他の色々な形で実施することができる。そのため前述の実施例は単なる例示に過ぎず、限定的に解釈してはならない。更に特許請求の範囲の均等範囲に属する変形や変更は全て本発明の範囲内のものである。 As mentioned above, although the Example of this invention was described, in this invention, in the conventional plating method, it is possible to produce the nickel-boron composite plating film containing 25 atomic percent or more boron which was the boron content limit. Yes, by performing heat treatment or the like, alloying can be promoted and the physical properties and characteristics of the film can be changed.
Moreover, as a plating base material, it is intended for machine parts (gear, rod, etc.) made of conductive synthetic resin or the like in addition to copper, brass, stainless steel, aluminum, titanium or the like.
Furthermore, the base material in the plating bath can be arranged in various states such as vertical, horizontal, and diagonal.
Moreover, the surface form of the film can be smoothed by adding an additive to the plating bath.
In addition, mechanical parts have a broad meaning and include parts that are widely plated.
In addition, the present invention can be implemented in various other forms without departing from the spirit and main features thereof. For this reason, the above-described embodiments are merely examples, and should not be interpreted in a limited manner. Further, all modifications and changes belonging to the equivalent scope of the claims are within the scope of the present invention.

本発明は、機械部品、摺動部品表面への硬質層の形成方法としての利用が可能である。   The present invention can be used as a method for forming a hard layer on the surface of a machine part or a sliding part.

本発明に係るニッケル−ホウ素複合めっきの構成図である。It is a block diagram of the nickel-boron composite plating which concerns on this invention. 同ニッケル−ホウ素複合めっきの他の例の構成図である。It is a block diagram of the other example of the nickel-boron composite plating. 同ニッケル−ホウ素複合めっきによるめっき層の断面図である。It is sectional drawing of the plating layer by the nickel-boron composite plating.

符号の説明Explanation of symbols

１ ニッケルめっき液を入れる容器
２ ニッケルめっき液
３ 同めっき液中にいれる陽極電極
４ 陰極電極を兼ねためっき基材
５ 攪拌翼
６ 電源
７ めっき膜
DESCRIPTION OF SYMBOLS 1 Container which puts nickel plating liquid 2 Nickel plating liquid 3 Anode electrode put in the same plating liquid 4 Plating base material which served as cathode electrode 5 Stirring blade 6 Power supply 7 Plating film

Claims (8)

ニッケルめっき液にホウ素粒子またはニッケル−ホウ素化合物を添加したことを特徴とするニッケルーホウ素複合めっき液。 A nickel-boron composite plating solution, wherein boron particles or a nickel-boron compound is added to a nickel plating solution. 前記ホウ素粒子またはニッケル−ホウ素化合物の径は１マイクロメートル以下であることを特徴とする請求項１に記載のニッケルーホウ素複合めっき液。 The nickel-boron composite plating solution according to claim 1, wherein the boron particles or the nickel-boron compound has a diameter of 1 micrometer or less. 前記請求項１または請求項２に記載のニッケルーホウ素複合めっき液に基材を入れ、電解めっきあるいは無電解めっきによりめっきすることを特徴とするニッケルーホウ素複合めっき方法。 A nickel-boron composite plating method, wherein a substrate is placed in the nickel-boron composite plating solution according to claim 1 or 2 and plated by electrolytic plating or electroless plating. 前記請求項３の方法によって作製したニッケル−ホウ素複合めっき膜。 A nickel-boron composite plating film produced by the method of claim 3. 前記請求項４のニッケル−ホウ素複合めっき膜を熱処理したことを特徴とするニッケル−ホウ素複合めっき膜。 A nickel-boron composite plating film obtained by heat-treating the nickel-boron composite plating film according to claim 4. 前記請求項３に記載のめっき方法によりニッケル−ホウ素複合めっき膜で皮膜した機械部品。 A machine part coated with a nickel-boron composite plating film by the plating method according to claim 3. 前記請求項６によるニッケル−ホウ素複合めっき膜を熱処理したことを特徴とする機械部品。 A mechanical part obtained by heat-treating the nickel-boron composite plating film according to claim 6. 前記請求項６または請求項７に記載の機械部品の材料は銅、黄銅、ステンレス、アルミ、チタン、導電性樹脂の何れかであることを特徴とする機械部品。


The mechanical part material according to claim 6 or 7 is any one of copper, brass, stainless steel, aluminum, titanium, and conductive resin.


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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013211264A (en) * 2012-03-02 2013-10-10 Shinshu Univ Negative electrode material for lithium ion battery
JP2020146804A (en) * 2019-03-14 2020-09-17 株式会社東京精密 Nickel electroformed blade and method for producing nickel electroformed blade

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Publication number Priority date Publication date Assignee Title
JPS5060436A (en) * 1973-09-26 1975-05-24
JPH08218179A (en) * 1995-02-08 1996-08-27 Mazda Motor Corp Wear resistant sliding member
JPH10245693A (en) * 1997-03-03 1998-09-14 Murata Mfg Co Ltd Electroplating bath for nickel and nickel alloy and electroplating method

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5060436A (en) * 1973-09-26 1975-05-24
JPH08218179A (en) * 1995-02-08 1996-08-27 Mazda Motor Corp Wear resistant sliding member
JPH10245693A (en) * 1997-03-03 1998-09-14 Murata Mfg Co Ltd Electroplating bath for nickel and nickel alloy and electroplating method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013211264A (en) * 2012-03-02 2013-10-10 Shinshu Univ Negative electrode material for lithium ion battery
JP2020146804A (en) * 2019-03-14 2020-09-17 株式会社東京精密 Nickel electroformed blade and method for producing nickel electroformed blade
JP7442974B2 (en) 2019-03-14 2024-03-05 株式会社東京精密 Nickel electroformed blade and manufacturing method of nickel electroformed blade

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