JP2008088491A - Composite plating material and method of manufacturing the same - Google Patents
Composite plating material and method of manufacturing the same Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
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- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は、複合めっき材およびその製造方法に関し、特に、スイッチやコネクタなどの接点や端子部品などの材料として使用される複合めっき材およびその製造方法に関する。 The present invention relates to a composite plating material and a method for manufacturing the same, and more particularly to a composite plating material used as a material for contacts and terminal parts such as switches and connectors and a method for manufacturing the same.
従来、スイッチやコネクタなどの接点や端子部品などの材料として、摺動過程における加熱による銅や銅合金などの導体素材の酸化を防止するために、導体素材に銀めっきを施した銀めっき材が使用されている。 Conventionally, as a material for contacts and terminal parts such as switches and connectors, a silver plating material in which the conductor material is silver-plated to prevent oxidation of the conductor material such as copper and copper alloy due to heating in the sliding process has been used. in use.
しかし、銀めっきは、軟質で摩耗し易く、一般に摩擦係数が高いため、耐摩耗性が低いという問題がある。この問題を解消するため、銀マトリクス中に黒鉛粒子を分散させた複合材の皮膜を電気めっきにより導体素材上に形成して耐摩耗性を向上させる方法が提案されている（例えば、特許文献１参照）。また、炭素粒子の分散に適した湿潤剤が添加されためっき浴を使用することにより、炭素粒子を含む銀めっき皮膜を製造する方法が提案されている（例えば、特許文献２参照）。さらに、ゾル−ゲル法によって炭素粒子を金属酸化物などでコーティングして、銀と炭素粒子の複合めっき液中における炭素粒子の分散性を高め、めっき皮膜中に複合化する炭素粒子の量を増大する方法が提案されている（例えば、特許文献３参照）。 However, silver plating is soft and easy to wear, and generally has a high coefficient of friction, and thus has a problem of low wear resistance. In order to solve this problem, a method of improving wear resistance by forming a composite film in which graphite particles are dispersed in a silver matrix on a conductor material by electroplating has been proposed (for example, Patent Document 1). reference). In addition, a method for producing a silver plating film containing carbon particles by using a plating bath to which a wetting agent suitable for dispersion of carbon particles is added has been proposed (for example, see Patent Document 2). Furthermore, the carbon particles are coated with a metal oxide or the like by a sol-gel method to increase the dispersibility of the carbon particles in the composite plating solution of silver and carbon particles, and increase the amount of carbon particles to be combined in the plating film. A method has been proposed (see, for example, Patent Document 3).
しかし、特許文献１〜３の方法により製造された複合めっき材であっても、耐摩耗性が比較的低いため、特許文献１〜３の方法により製造された複合めっき材よりもめっき皮膜中の炭素粒子の含有量が多く、優れた耐摩耗性の複合めっき材を提供することが望まれている。 However, even the composite plating material manufactured by the method of Patent Documents 1 to 3 has a relatively low wear resistance, so that it is more in the plating film than the composite plating material manufactured by the method of Patent Documents 1 to 3. It is desired to provide a composite plating material having a high carbon particle content and excellent wear resistance.
したがって、本発明は、このような従来の問題点を鑑み、めっき皮膜中の炭素粒子の含有量が多く、優れた耐摩耗性の複合めっき材を提供することを目的とする。 Accordingly, the present invention has been made in view of such conventional problems, and an object thereof is to provide a composite plating material having a high content of carbon particles in the plating film and having excellent wear resistance.
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、溶媒中に炭素粒子を添加した電気泳動浴に素材を浸漬して電気泳動を行うことにより、素材上に炭素粒子の堆積層を形成した後、この炭素粒子の堆積層を形成した素材を銀めっき液に浸漬して銀めっきを施すことにより、めっき皮膜中の炭素粒子の含有量が多く、優れた耐摩耗性の複合めっき材を提供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 diligent research to solve the above-mentioned problems, the present inventors have carried out electrophoresis by immersing the material in an electrophoretic bath in which carbon particles are added to a solvent, thereby performing a deposition layer of carbon particles on the material. After the material is formed, the material on which the deposited layer of carbon particles is formed is immersed in a silver plating solution to perform silver plating, thereby increasing the content of carbon particles in the plating film and providing excellent wear-resistant composite plating. The present inventors have found that a material can be provided and have completed the present invention.
すなわち、本発明による複合めっき材の製造方法は、溶媒中に炭素粒子を添加した電気泳動浴に素材を浸漬して電気泳動を行うことにより、素材上に炭素粒子の堆積層を形成した後、この炭素粒子の堆積層を形成した素材を銀めっき浴に浸漬して銀めっきを施すことを特徴とする。 That is, in the method for producing a composite plating material according to the present invention, after forming a deposition layer of carbon particles on the material by immersing the material in an electrophoresis bath in which carbon particles are added in a solvent and performing electrophoresis, The material on which the deposited layer of carbon particles is formed is dipped in a silver plating bath to perform silver plating.
この複合めっき材の製造方法において、溶媒が有機溶媒であるのが好ましく、炭素粒子が、酸化処理を行った後にシランカップリング処理を施した炭素粒子であるのが好ましい。また、シランカップリング処理が、炭素粒子を有機溶媒中に分散させて懸濁させた後にシランカップリング剤を添加する処理であるのが好ましく、酸化処理が、炭素粒子を水中に懸濁させた後に酸化剤を添加する湿式酸化処理であるのが好ましい。さらに、銀めっき浴が、硝酸銀と硫酸アンモニウムを含むアンモニア浴、またはシアン銀カリウムとシアン化カリウムを含むシアン浴であるのが好ましい。 In this method for producing a composite plating material, the solvent is preferably an organic solvent, and the carbon particles are preferably carbon particles that have been subjected to silane coupling treatment after oxidation treatment. Further, the silane coupling treatment is preferably a treatment in which carbon particles are dispersed and suspended in an organic solvent and then a silane coupling agent is added, and the oxidation treatment suspends the carbon particles in water. A wet oxidation treatment in which an oxidizing agent is added later is preferable. Further, the silver plating bath is preferably an ammonia bath containing silver nitrate and ammonium sulfate, or a cyan bath containing potassium cyanogen potassium and potassium cyanide.
また、本発明による複合めっき材は、銀層中に炭素粒子を含有する複合材から複合めっき皮膜が素材上に形成され、この複合めっき皮膜中の炭素粒子の含有量が３．０質量％以上であることを特徴とする。 In the composite plating material according to the present invention, a composite plating film is formed on a material from a composite material containing carbon particles in a silver layer, and the content of the carbon particles in the composite plating film is 3.0% by mass or more. It is characterized by being.
本発明によれば、めっき皮膜中の炭素粒子の含有量が多く、優れた耐摩耗性の複合めっき材を製造することができる。この複合めっき材は、スイッチやコネクタなどの端子の高寿命化に十分に対応可能な材料として使用することができる。 According to the present invention, it is possible to produce a composite plating material having a high content of carbon particles in the plating film and having excellent wear resistance. This composite plating material can be used as a material that can sufficiently cope with the extension of the service life of terminals such as switches and connectors.
本発明による複合めっき材の製造方法の実施形態では、酸化処理を行った後にシランカップリング処理を施した炭素粒子を有機溶媒中に分散させた電気泳動浴に、素材を浸漬して電気泳動を行うことにより、素材上に炭素粒子の堆積層を形成した後、この炭素粒子の堆積層を形成した素材を銀めっき液に浸漬して電気めっきを行うことにより、炭素粒子の堆積層を覆うように銀めっき層を形成する。このように銀めっき層を形成すると、炭素粒子間（炭素粒子の堆積層の空隙中）に銀が入り込んで、銀層中に炭素粒子を含む複合材からなる複合めっき皮膜が素材上に形成される。 In the embodiment of the method for producing a composite plating material according to the present invention, the material is immersed in an electrophoresis bath in which carbon particles that have been oxidized and then subjected to silane coupling treatment are dispersed in an organic solvent. After forming a carbon particle deposition layer on the material, the material on which the carbon particle deposition layer is formed is immersed in a silver plating solution to perform electroplating to cover the carbon particle deposition layer. A silver plating layer is formed on the substrate. When a silver plating layer is formed in this way, silver enters between carbon particles (in the voids of the carbon particle deposition layer), and a composite plating film made of a composite material containing carbon particles in the silver layer is formed on the material. The
本発明による複合めっき材の製造方法の実施形態では、まず、酸化処理により炭素粒子の表面に吸着している親油性有機物を除去する。このような親油性有機物として、アルカンやアルケンなどの脂肪酸炭化水素や、アルキルベンゼンなどの芳香族炭化水素が含まれる。炭素粒子の酸化処理として、湿式酸化処理の他、Ｏ２ガスなどによる乾式酸化処理を使用することができるが、量産性の観点から湿式酸化処理を使用するのが好ましく、湿式酸化処理によって表面積が大きい炭素粒子を均一に処理することができる。 In the embodiment of the method for producing a composite plating material according to the present invention, first, the lipophilic organic matter adsorbed on the surface of the carbon particles is removed by oxidation treatment. Such lipophilic organic substances include fatty acid hydrocarbons such as alkanes and alkenes, and aromatic hydrocarbons such as alkylbenzenes. As the oxidation treatment of carbon particles, a dry oxidation treatment using O 2 gas or the like can be used in addition to the wet oxidation treatment, but it is preferable to use a wet oxidation treatment from the viewpoint of mass productivity. Large carbon particles can be treated uniformly.
湿式酸化処理の方法としては、炭素粒子を水中に懸濁させた後に適量の酸化剤を添加する方法などを使用することができる。酸化剤としては、硝酸、過酸化水素、過マンガン酸カリウム、過硫酸カリウム、過塩素酸ナトリウムなどの酸化剤を使用することができる。炭素粒子に付着している親油性有機物は、添加された酸化剤により酸化されて水に溶けやすい形態になり、炭素粒子の表面から適宜除去されると考えられる。また、この湿式酸化処理を行った後、ろ過を行い、さらに炭素粒子を水洗することにより、炭素粒子の表面から親油性有機物を除去する効果をさらに高めることができる。 As a wet oxidation method, a method of adding an appropriate amount of an oxidizing agent after suspending carbon particles in water can be used. As the oxidizing agent, oxidizing agents such as nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, and sodium perchlorate can be used. It is considered that the lipophilic organic substance adhering to the carbon particles is oxidized by the added oxidizing agent to be easily dissolved in water, and is appropriately removed from the surface of the carbon particles. Moreover, after performing this wet oxidation process, the effect which removes lipophilic organic substance from the surface of a carbon particle can be further heightened by filtering, and also washing | cleaning a carbon particle with water.
上記の酸化処理により炭素粒子の表面から脂肪族炭化水素や芳香族炭化水素などの親油性有機物を除去することができ、３００℃加熱ガスによる分析によれば、酸化処理後の炭素粒子を３００℃で加熱して発生したガス中には、アルカンやアルケンなどの親油性脂肪族炭化水素や、アルキルベンゼンなどの親油性芳香族炭化水素が殆ど含まれてない。酸化処理後の炭素粒子中に脂肪族炭化水素や芳香族炭化水素が若干含まれていても、炭素粒子を銀めっき液に分散させることができるが、炭素粒子中に分子量１６０以上の炭化水素が含まれず且つ炭素粒子中の分子量１６０未満の炭化水素の３００℃加熱発生ガス強度（パージ・アンド・トラップ・ガスクロマトグラフ質量分析強度）が５，０００，０００以下になるのが好ましい。 Lipophilic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles by the above oxidation treatment, and according to the analysis with 300 ° C. heating gas, the carbon particles after the oxidation treatment are converted to 300 ° C. The gas generated by heating in step 3 hardly contains lipophilic aliphatic hydrocarbons such as alkanes and alkenes and lipophilic aromatic hydrocarbons such as alkylbenzenes. Even if aliphatic hydrocarbons and aromatic hydrocarbons are slightly contained in the oxidized carbon particles, the carbon particles can be dispersed in the silver plating solution. However, hydrocarbons having a molecular weight of 160 or more are contained in the carbon particles. It is preferred that the hydrocarbons not contained and having a molecular weight of less than 160 in the carbon particles have a 300 ° C. heat generation gas intensity (purge and trap gas chromatograph mass spectrometry intensity) of 5,000,000 or less.
次に、酸化処理を行った炭素粒子にシランカップリング処理を施す。このシランカップリング処理の方法として、酸化処理を行った炭素粒子を有機溶媒中に分散させて懸濁させ、この懸濁液に適量のシランカップリング剤を添加する方法を使用することができる。シランカップリング剤としては、有機官能基としてビニル基、エポキシ基、アミノ基、メルカプト基などを有し、加水分解基としてメトキシ基、エトキシ基、イソプロポキシ基などを有するシランカップリング剤を使用することができる。このようなシランカップリング処理を施すことにより、炭素粒子の表面電位が変化して、ゼータ電位の等電点をｐＨ６〜１０に変化させることができる。このシランカップリング処理後の炭素粒子は、ｐＨ６〜１０の液中で正に帯電するため、負に帯電した素材に接近し易くなって、電気泳動の際の陰極との親和性が向上し、その結果、素材に堆積される炭素粒子の量を増大させることができると考えられる。 Next, the carbon particles subjected to the oxidation treatment are subjected to silane coupling treatment. As a method for this silane coupling treatment, a method can be used in which the oxidized carbon particles are dispersed and suspended in an organic solvent, and an appropriate amount of a silane coupling agent is added to this suspension. As the silane coupling agent, a silane coupling agent having a vinyl group, an epoxy group, an amino group, a mercapto group, or the like as an organic functional group and a methoxy group, an ethoxy group, an isopropoxy group, or the like as a hydrolysis group is used. be able to. By performing such silane coupling treatment, the surface potential of the carbon particles is changed, and the isoelectric point of the zeta potential can be changed to pH 6-10. Since the carbon particles after the silane coupling treatment are positively charged in a liquid having a pH of 6 to 10, it becomes easy to approach a negatively charged material, and the affinity with the cathode during electrophoresis is improved. As a result, it is considered that the amount of carbon particles deposited on the material can be increased.
次に、酸化処理およびシランカップリング処理を行った炭素粒子を有機溶媒に添加することによって、有機溶媒中に炭素粒子が懸濁して分散した電気泳動浴を作製し、この電気泳動浴を使用して電気泳動を行うことにより、素材上に炭素粒子の堆積層を形成する。この炭素粒子の堆積層は、素材に電気的に吸着されて強固に固定され、めっき液に浸漬しても素材から脱離しない。電気泳動浴に使用する有機溶媒は、アルコール類またはケトン類の有機溶媒であるのが好ましく、この有機溶媒に若干量の水を添加してもよい。また、有機溶媒に添加する炭素粒子の量は、１〜５０ｇ／Ｌであるのが好ましい。１ｇ／Ｌ未満であると、炭素粒子の堆積層が薄くなって複合めっき皮膜中の炭素粒子の量が低下し、５０ｇ／Ｌを超えると、炭素粒子の堆積層が脆くなって素材上に維持することができなくなるからである。なお、素材とめっき膜との密着性を向上させるために、電気泳動によって素材上に炭素粒子の堆積層を形成する前に、素材上にＡｇストライクめっきなどの下地めっきを施してもよい。 Next, an electrophoretic bath in which carbon particles are suspended and dispersed in an organic solvent is prepared by adding carbon particles that have undergone oxidation treatment and silane coupling treatment to an organic solvent, and this electrophoretic bath is used. By performing electrophoresis, a deposited layer of carbon particles is formed on the material. The deposited layer of carbon particles is electrically adsorbed to the material and firmly fixed, and does not desorb from the material even when immersed in the plating solution. The organic solvent used in the electrophoresis bath is preferably an alcohol or ketone organic solvent, and a slight amount of water may be added to the organic solvent. The amount of carbon particles added to the organic solvent is preferably 1 to 50 g / L. If it is less than 1 g / L, the carbon particle deposition layer becomes thin and the amount of carbon particles in the composite plating film decreases, and if it exceeds 50 g / L, the carbon particle deposition layer becomes brittle and is maintained on the material. It is because it becomes impossible to do. In order to improve the adhesion between the material and the plating film, a base plating such as Ag strike plating may be applied to the material before forming the carbon particle deposition layer on the material by electrophoresis.
次に、炭素粒子の堆積層を形成した素材を銀めっき浴に浸漬して電気めっきを行うことにより、炭素粒子の堆積層を覆うように銀めっき層を形成する。このように銀めっき層を形成すると、炭素粒子間（炭素粒子の堆積層の空隙中）に銀が入り込んで、銀層中に炭素粒子が入り込んだ構造の複合めっき皮膜が素材上に形成される。銀めっき浴としては、硝酸銀と硫酸アンモニウムからなるアンモニア浴、またはシアン銀カリウムとシアン化カリウムからなるシアン浴を使用することができる。 Next, the material on which the deposited layer of carbon particles is formed is immersed in a silver plating bath and electroplated to form a silver plated layer so as to cover the deposited layer of carbon particles. When the silver plating layer is formed in this manner, silver enters between the carbon particles (in the voids of the carbon particle deposition layer), and a composite plating film having a structure in which the carbon particles enter the silver layer is formed on the material. . As the silver plating bath, an ammonia bath composed of silver nitrate and ammonium sulfate, or a cyan bath composed of potassium cyanogen silver and potassium cyanide can be used.
このようにして、銀層中に３．０質量％以上、好ましくは３．０〜４．０質量％の炭素粒子を含有する複合材からなる複合めっき皮膜が素材上に形成された複合めっき材を製造することができる。この複合めっき材の複合めっき皮膜の厚さは、２〜１０μｍであるのが好ましい。２μｍ未満では耐摩耗性が不十分であり、１０μｍを越えると生産効率が悪くなるからである。 Thus, the composite plating material in which the composite plating film which consists of a composite material containing 3.0 mass% or more, preferably 3.0-4.0 mass% of carbon particles in a silver layer was formed on the raw material. Can be manufactured. The thickness of the composite plating film of this composite plating material is preferably 2 to 10 μm. If the thickness is less than 2 μm, the wear resistance is insufficient, and if it exceeds 10 μm, the production efficiency deteriorates.
以下、本発明による複合めっき材およびその製造方法の実施例について詳細に説明する。 Hereinafter, examples of the composite plating material and the manufacturing method thereof according to the present invention will be described in detail.
炭素粒子として平均粒径３μｍの鱗片状黒鉛粒子（エスイーシー社製のカーボンＳＧＰ−３）を用意し、この黒鉛粒子６質量％を３Ｌの純水中に添加し、この混合溶液を攪拌しながら５０℃に昇温させた。次に、この混合溶液に酸化剤として０．１モル／Ｌの過硫酸カリウム水溶液１．２Ｌを徐々に滴下した後、２時間攪拌して酸化処理を行い、その後、ろ紙によりろ別を行い、水洗を行った。 As the carbon particles, scaly graphite particles having an average particle diameter of 3 μm (carbon SGP-3 manufactured by ESC) were prepared, 6% by mass of the graphite particles were added to 3 L of pure water, and the mixed solution was stirred while stirring. The temperature was raised to ° C. Next, 1.2 L of a 0.1 mol / L potassium persulfate aqueous solution as an oxidizing agent was gradually added dropwise to the mixed solution, and then the mixture was stirred for 2 hours for oxidation treatment, and then filtered with a filter paper. Washed with water.
この酸化処理の前後の炭素粒子について、パージ・アンド・トラップ・ガスクロマトグラフ質量分析装置（日本分析工業ＪＨＳ−１００）（島津製作所製のＧＣＭＡＳ ＱＰ−５０５０Ａ）を使用して、３００℃加熱発生ガスの分析を行ったところ、上記の酸化処理により、炭素粒子に付着していたノナン、デカン、３−メチル−２−ヘプテンなどの親油性脂肪族炭化水素や、キシレンなどの親油性芳香族炭化水素が除去され、水分散性の良好な炭素粒子が得られているのがわかった。 About the carbon particles before and after this oxidation treatment, a purge and trap gas chromatograph mass spectrometer (Nippon Analytical Industries JHS-100) (GCMAS QP-5050A manufactured by Shimadzu Corporation) As a result of the analysis, lipophilic aliphatic hydrocarbons such as nonane, decane and 3-methyl-2-heptene and lipophilic aromatic hydrocarbons such as xylene adhering to the carbon particles by the oxidation treatment described above were obtained. It was found that carbon particles with good water dispersibility were obtained.
次に、上記の湿式酸化処理を行った炭素粒子１０質量％をトルエン中に分散させて懸濁させ、この炭素粒子の懸濁液を１２０℃に加熱して攪拌しながら、シランカップリング剤として３−アミノプロピルトリメトキシシラン（トルエンの１体積％）を添加した後、６時間攪拌してシランカップリング処理を行った。その後、炭素粒子をトルエンで洗浄し、１２０℃で２４時間乾燥させた。このように酸化処理およびシランカップリング処理を施した炭素粒子の表面電位について、ゼータ電位計（大塚電子製のＥＬＳ−８０００ＫＷ）を用いて測定したところ、等電点はｐＨ１０であった。 Next, 10% by mass of the carbon particles subjected to the above-described wet oxidation treatment are dispersed and suspended in toluene, and the suspension of the carbon particles is heated to 120 ° C. while stirring and used as a silane coupling agent. After 3-aminopropyltrimethoxysilane (1% by volume of toluene) was added, the mixture was stirred for 6 hours to perform silane coupling treatment. Thereafter, the carbon particles were washed with toluene and dried at 120 ° C. for 24 hours. The surface potential of the carbon particles subjected to oxidation treatment and silane coupling treatment as described above was measured using a zeta potentiometer (ELS-8000 KW manufactured by Otsuka Electronics Co., Ltd.), and the isoelectric point was pH 10.
また、めっき膜の密着性を向上させるために、素材としての厚さ０．３ｍｍの銅板上に、下地めっきとしてＡｇストライクめっきとＡｇめっきを施した。Ａｇストライクめっきは、硝酸銀０．０３ｇ／Ｌと硝酸アンモニウム０．８ｇ／Ｌとピロリン酸ナトリウム０．４ｇ／Ｌとからなる組成のＡｇストライクめっき浴中において、液温２５℃、電流密度５Ａ／ｄｍ２で行った。Ａｇめっきは、硝酸銀４０ｇ／Ｌと硝酸アンモニウム１２０ｇ／Ｌとピロリン酸ナトリウム２０ｇ／Ｌとからなる組成のＡｇめっき浴中において、液温２５℃、電流密度１．５Ａ／ｄｍ２で行い、厚さ１μｍのＡｇめっき皮膜を形成した。 Moreover, in order to improve the adhesiveness of a plating film, Ag strike plating and Ag plating were performed as a base plating on a copper plate having a thickness of 0.3 mm as a material. Ag strike plating is performed in an Ag strike plating bath having a composition of 0.03 g / L silver nitrate, 0.8 g / L ammonium nitrate, and 0.4 g / L sodium pyrophosphate, with a liquid temperature of 25 ° C. and a current density of 5 A / dm 2. I went there. Ag plating is performed in an Ag plating bath having a composition of 40 g / L silver nitrate, 120 g / L ammonium nitrate, and 20 g / L sodium pyrophosphate at a liquid temperature of 25 ° C. and a current density of 1.5 A / dm 2 , and a thickness of 1 μm. The Ag plating film was formed.
次に、アセトン８０質量％と純水２０質量％からなる溶媒中に、上述した酸化処理およびシランカップリング処理を施した炭素粒子１０ｇ／Ｌを添加して電気泳動浴とし、この電気泳動浴に上述した下地めっきを施した素材を浸漬し、定電圧２０Ｖを印加して電気泳動を行うことにより、素材上に厚さ５μｍの炭素粒子の堆積層を形成した。 Next, 10 g / L of the carbon particles subjected to the above-described oxidation treatment and silane coupling treatment are added to a solvent composed of 80% by mass of acetone and 20% by mass of pure water to form an electrophoresis bath. The material subjected to the base plating described above was immersed, and electrophoresis was performed by applying a constant voltage of 20 V, thereby forming a 5 μm thick carbon particle deposition layer on the material.
次に、炭素粒子の堆積層を形成した素材にＡｇめっきを施した。このＡｇめっきは、硝酸銀４０ｇ／Ｌと硝酸アンモニウム１２０ｇ／Ｌとピロリン酸ナトリウム２０ｇ／Ｌとからなる組成のＡｇめっき浴中において、液温２５℃、電流密度１．５Ａ／ｄｍ２で行い、厚さ５μｍのＡｇめっき皮膜を形成した。 Next, Ag plating was applied to the material on which the deposited layer of carbon particles was formed. This Ag plating is performed in an Ag plating bath having a composition of 40 g / L silver nitrate, 120 g / L ammonium nitrate, and 20 g / L sodium pyrophosphate at a liquid temperature of 25 ° C. and a current density of 1.5 A / dm 2. A 5 μm Ag plating film was formed.
このようにして、素材としての厚さ０．３ｍｍの銅板上に、下地めっきとしてのＡｇストライクめっきとＡｇめっきを介して、厚さ５μｍの炭素粒子の堆積層を形成し、この炭素粒子の堆積層を覆うように厚さ５μｍのＡｇめっき皮膜を形成することにより、複合めっき材を作製した。 In this way, a deposited layer of carbon particles having a thickness of 5 μm is formed on a copper plate having a thickness of 0.3 mm as a material through Ag strike plating and Ag plating as base plating, and deposition of the carbon particles is performed. A composite plating material was produced by forming an Ag plating film having a thickness of 5 μm so as to cover the layer.
得られた複合めっき材（素材を含む）から切り出した試験片を銀および炭素の分析用にそれぞれ用意し、試験片中の銀の含有量（Ｘ質量％）をＩＣＰ装置（ジャーレル・アッシュ社製のＩＲＩＳ／ＡＲ）を用いてプラズマ分光分析法によって求めるとともに、試験片中の炭素の含有量（Ｙ質量％）を微量炭素・硫黄分析装置（堀場製作所製のＥＭＩＡ−Ｕ５１０）を用いて燃焼赤外線吸収法によって求め、めっき皮膜中の炭素の含有量をＹ／（Ｘ＋Ｙ）として算出したところ、めっき皮膜中の炭素の含有量は４．０質量％であった。 Test pieces cut out from the obtained composite plating material (including raw materials) were prepared for analysis of silver and carbon, respectively, and the content (X mass%) of silver in the test pieces was determined using an ICP device (manufactured by Jarrel Ash). (IRIS / AR), and the content of carbon in the test piece (Y mass%) is determined by combustion infrared using a trace carbon / sulfur analyzer (EMIA-U510 manufactured by Horiba, Ltd.). The carbon content in the plating film was 4.0% by mass when calculated by the absorption method and the carbon content in the plating film was calculated as Y / (X + Y).
また、得られた複合めっき材から切り出した２つの試験片の一方をインデント加工（Ｒ３ｍｍ）して圧子とするとともに、他方を評価試料とし、圧子を一定の荷重（０．５Ｎ）で評価試料に押し当てながら、素材が露出するまで往復摺動動作（摺動距離１０ｍｍ、摺動速度２．５Ｈｚ）を継続して、複合めっき材の摩耗状態を確認することにより、耐摩耗性の評価を行った。その結果、１００万回以上の往復摺動動作後でも素材が露出することはなかった。 In addition, one of the two test pieces cut out from the obtained composite plating material is indented (R3 mm) to form an indenter, the other is used as an evaluation sample, and the indenter is used as an evaluation sample with a constant load (0.5 N). While pressing, continue the reciprocating sliding operation (sliding distance 10 mm, sliding speed 2.5 Hz) until the material is exposed, and evaluate the wear resistance by checking the wear state of the composite plating material. It was. As a result, the material was not exposed even after a reciprocating sliding operation of 1 million times or more.
また、比較例として、電気泳動を行わないで、実施例と同様の酸化処理およびシランカップリング処理を施した炭素粒子を銀めっき液に添加して銀めっきを行った以外は、実施例と同様の方法により複合めっき材を作製し、実施例と同様の方法により、めっき皮膜中の炭素の含有量を算出し、耐摩耗性の評価を行った。その結果、めっき皮膜中の炭素の含有量は１．９質量％であり、４８万回の往復摺動動作後に素材が露出した。 Further, as a comparative example, the same as in the example, except that the electroplating was not performed, and the carbon particles subjected to the same oxidation treatment and silane coupling treatment as in the example were added to the silver plating solution to perform silver plating. A composite plating material was prepared by the method described above, and the carbon content in the plating film was calculated by the same method as in the examples, and the wear resistance was evaluated. As a result, the carbon content in the plating film was 1.9% by mass, and the material was exposed after 480,000 reciprocating sliding operations.
実施例および比較例で得られた複合めっき材から切り出した試験片の断面を収束イオンビーム（ＦＩＢ）で加工した後、走査電子顕微鏡（ＳＥＭ）により撮影した断面のＳＥＭ写真（倍率５０００倍）をそれぞれ図１および図２に示す。図２に示すように、比較例では、表面近傍部と比べて素材近傍部で炭素粒子の量が減少し、膜厚方向の炭素粒子の分布が不均一であるのに対し、図１に示すように、実施例では、素材近傍部でも炭素粒子の量が減少せず、炭素粒子が膜厚方向に均一に分散していることがわかる。 After processing the cross section of the test piece cut out from the composite plating material obtained in the example and the comparative example with a focused ion beam (FIB), an SEM photograph (magnification 5000 times) of the cross section taken with a scanning electron microscope (SEM). They are shown in FIGS. 1 and 2, respectively. As shown in FIG. 2, in the comparative example, the amount of carbon particles is reduced in the vicinity of the material compared to the vicinity of the surface, and the distribution of carbon particles in the film thickness direction is non-uniform, whereas that shown in FIG. Thus, in the Example, it turns out that the quantity of carbon particles does not decrease even in the vicinity of the material, and the carbon particles are uniformly dispersed in the film thickness direction.
Claims (7)
A composite plating film is formed on a material from a composite material containing carbon particles in a silver layer, and the content of carbon particles in the composite plating film is 3.0% by mass or more. Wood.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101041395B1 (en) | 2008-10-28 | 2011-06-14 | 한국기계연구원 | Manufacturing Method for Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| KR101041396B1 (en) | 2008-10-28 | 2011-06-14 | 한국기계연구원 | Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| KR101041394B1 (en) | 2011-03-02 | 2011-06-14 | 한국기계연구원 | A composite material with Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| KR101297971B1 (en) | 2008-04-18 | 2013-08-19 | 주식회사 엘지화학 | Metohd of modificating carobn fiber using electrophoresis |
| CN113394017A (en) * | 2021-06-10 | 2021-09-14 | 北京工业大学 | Method for sintering neodymium iron boron by electroplating electrophoresis in cooperation with deposition diffusion |
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| KR101297971B1 (en) | 2008-04-18 | 2013-08-19 | 주식회사 엘지화학 | Metohd of modificating carobn fiber using electrophoresis |
| KR101041395B1 (en) | 2008-10-28 | 2011-06-14 | 한국기계연구원 | Manufacturing Method for Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| KR101041396B1 (en) | 2008-10-28 | 2011-06-14 | 한국기계연구원 | Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| KR101041394B1 (en) | 2011-03-02 | 2011-06-14 | 한국기계연구원 | A composite material with Multi-functional Hybrid Fiber by Simultaneous Multi-component Deposition |
| CN113394017A (en) * | 2021-06-10 | 2021-09-14 | 北京工业大学 | Method for sintering neodymium iron boron by electroplating electrophoresis in cooperation with deposition diffusion |
| CN113394017B (en) * | 2021-06-10 | 2023-11-03 | 北京工业大学 | Method for diffusion sintering of neodymium iron boron through electroplating and electrophoresis collaborative deposition |
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