JP4669967B2 - Manufacturing method of composite plating material - Google Patents
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- JP4669967B2 JP4669967B2 JP2005195718A JP2005195718A JP4669967B2 JP 4669967 B2 JP4669967 B2 JP 4669967B2 JP 2005195718 A JP2005195718 A JP 2005195718A JP 2005195718 A JP2005195718 A JP 2005195718A JP 4669967 B2 JP4669967 B2 JP 4669967B2
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- 239000000463 material Substances 0.000 title claims description 48
- 239000002131 composite material Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 15
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- -1 fatty acid hydrocarbons Chemical class 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
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Description
本発明は、複合めっき材の製造方法に関し、特に、銀層中に炭素粒子を含有する複合材からなる皮膜が素材上に形成され、スイッチやコネクタなどの摺動接点部品などの材料として使用される複合めっき材の製造方法に関する。 The present invention relates to a method for producing a composite plating material, and in particular, a film made of a composite material containing carbon particles in a silver layer is formed on the material, and is used as a material for sliding contact parts such as switches and connectors. The present invention relates to a method for producing a composite plating material.
従来、スイッチやコネクタなどの摺動接点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 sliding contact 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、摺動により剥離し易いという問題がある。この問題を解消するため、耐熱性、磨耗性、潤滑性などに優れた黒鉛やカーボンブラックなどの炭素粒子のうち、黒鉛粒子を銀マトリクス中に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、黒鉛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、黒鉛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 therefore has a problem that it is easily peeled off by sliding. In order to solve this problem, among the carbon particles such as graphite and carbon black, which have excellent heat resistance, wear resistance, lubricity, etc., a conductive material is obtained by electroplating a composite film in which graphite particles are dispersed in a silver matrix. A method of improving the wear resistance by forming the above has been proposed (for example, see Patent Document 1). In addition, a method for producing a silver plating film containing graphite particles by using a plating bath to which a wetting agent suitable for the dispersion of graphite 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および2の方法では、銀めっき液中に炭素粒子を分散させるための分散剤や湿潤剤を添加する必要があり、分散剤として使用する界面活性剤などが炭素粒子の表面だけでなくめっき皮膜の表面にも吸着して、めっき皮膜の生成に悪影響を及ぼす場合がある。また、特許文献3の方法では、分散剤を使用していないが、金属酸化物などのコーティングの材質によって、使用可能なめっき液が限定され、例えば、シアン系めっき液や強酸性のめっき液を使用することができない。
However, in the methods of
また、特許文献1〜3の方法により製造された複合めっき材は、摩擦係数が比較的高く、接点や端子の高寿命化に対応することができないという問題があり、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炭素粒子の含有量や表面の炭素粒子の量を増大させて、さらに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。 Moreover, the composite plating material manufactured by the method of patent documents 1-3 has a comparatively high friction coefficient, and there exists a problem that it cannot respond to the lifetime improvement of a contact and a terminal, The method of patent documents 1-3 It is desired to provide a composite plating material with even better wear resistance by increasing the content of carbon particles and the amount of carbon particles on the surface than the composite plating material produced by the above method.
したがって、本発明は、このような従来の問題点に鑑み、分散剤などの添加物を使用することなく且つ炭素粒子の表面をコーティングすることなく、銀めっき液中に炭素粒子を良好に分散させて、炭素粒子の含有量および表面の炭素粒子の量が多く、耐摩耗性に優れた複合めっき材の製造方法を提供することを目的とする。 Therefore, in view of such a conventional problem, the present invention can disperse carbon particles well in a silver plating solution without using an additive such as a dispersant and without coating the surface of the carbon particles. Thus, an object of the present invention is to provide a method for producing a composite plating material having a high content of carbon particles and a large amount of carbon particles on the surface 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、電解処理により炭素粒子の表面の親油性有機物を除去し、この親油性有機物を除去した炭素粒子を銀めっき液に添加することにより炭素粒子を銀めっき液中に均一に分散させ、この銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子が均一に分散した複合材からなる皮膜が素材上に形成され、炭素粒子の含有量および表面の炭素粒子の量が多く、耐摩耗性に優れた複合めっき材を製造することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors have removed the lipophilic organic substance on the surface of the carbon particles by electrolytic treatment, and added the carbon particles from which the lipophilic organic substance has been removed to the silver plating solution. By uniformly dispersing the carbon particles in the silver plating solution and performing electroplating using this silver plating solution, a film made of a composite material in which the carbon particles are uniformly dispersed in the silver layer is formed on the material. As a result, the inventors have found that a composite plating material having a large amount of carbon particles and a large amount of carbon particles on the surface and having excellent wear resistance can be produced, and the present invention has been completed.
すなわち、本発明による複合めっき材の製造方法は、電解処理を行った炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子を含有する複合材からなる皮膜を素材上に形成することを特徴とする。この複合めっき材の製造方法において、電解処理が、導電塩を含む水中に炭素粒子を懸濁させた後に電気分解を行う処理であるのが好ましく、銀めっき液がシアン系銀めっき液であるのが好ましい。 That is, the method for producing a composite plating material according to the present invention comprises a composite material containing carbon particles in a silver layer by performing electroplating using a silver plating solution to which carbon particles subjected to electrolytic treatment are added. A film is formed on the material. In this method for producing a composite plating material, the electrolytic treatment is preferably a treatment in which electrolysis is performed after suspending carbon particles in water containing a conductive salt, and the silver plating solution is a cyan-based silver plating solution. Is preferred.
また、本発明による炭素粒子は、銀層中に炭素粒子を含有する複合材からなる皮膜を素材上に形成するための電気めっきに使用する銀めっき液に添加される炭素粒子であって、電解処理を行った炭素粒子であることを特徴とする。 The carbon particles according to the present invention are carbon particles added to a silver plating solution used for electroplating for forming a film made of a composite material containing carbon particles in a silver layer on the material, It is the carbon particle which processed. It is characterized by the above-mentioned.
本発明によれば、分散剤などの添加物を使用することなく且つ炭素粒子の表面をコーティングすることなく、銀めっき液中に炭素粒子を良好に分散させて、炭素粒子の含有量および表面の炭素粒子の量が多く、耐摩耗性に優れた複合めっき材を製造することができる。この複合めっき材は、スイッチやコネクタなどの摺動接点部品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, carbon particles can be dispersed well in a silver plating solution without using an additive such as a dispersant and without coating the surface of the carbon particles, so that the content of the carbon particles and the surface A composite plating material having a large amount of carbon particles and excellent wear resistance can be produced. This composite plating material can be used as a material that can sufficiently cope with the long life of sliding contact parts 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の形態では、電解処理を行った炭素粒子を添加した銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子が均一に分散した複合材からなる皮膜を素材上に形成する。分散剤を使用しないで炭素粒子を銀めっき液中に添加して懸濁させただけでは、めっき皮膜中に炭素粒子を取り込ませることができないが、この実施の形態のように、炭素粒子を銀めっき液中に投入する前に電解処理を施すことにより、分散剤を使用しなくても炭素粒子の分散性を向上させることができる。 In the embodiment of the method for producing a composite plating material according to the present invention, the carbon particles are uniformly dispersed in the silver layer by performing electroplating using a silver plating solution to which carbon particles subjected to electrolytic treatment are added. A film made of a composite material is formed on the material. If carbon particles are simply added and suspended in the silver plating solution without using a dispersant, the carbon particles cannot be taken into the plating film. However, as in this embodiment, the carbon particles are silver. By performing the electrolytic treatment before being put into the plating solution, the dispersibility of the carbon particles can be improved without using a dispersant.
本発明による複合めっき材の製造方法の実施の形態では、炭素粒子を銀めっき液に添加する前に、電解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、(ノナンやデカンなどの)アルカンや、(メチルヘプテンなどの)アルケンのような脂肪酸炭化水素や、(キシレンなどの)アルキルベンゼンのような芳香族炭化水素が含まれる。 In the embodiment of the method for producing a composite plating material according to the present invention, before adding the carbon particles to the silver plating solution, the lipophilic organic substance adsorbed on the surface of the carbon particles is removed by electrolytic treatment. Such lipophilic organic substances include fatty acid hydrocarbons such as alkanes (such as nonane and decane), alkenes (such as methylheptene), and aromatic hydrocarbons such as alkylbenzene (such as xylene).
炭素粒子の電解処理として、導電塩を含む水中に炭素粒子を懸濁させた後に白金電極やカーボン電極などの陰極および陽極を挿入して通電することにより電気分解を行う方法を使用することができ、水中に添加する炭素粒子の量を1〜20重量%にするのが好ましい。炭素粒子に付着している親油性有機物は、陽極に接触して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、この電解処理を行った後、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 the electrolytic treatment of carbon particles, a method can be used in which carbon particles are suspended in water containing a conductive salt and then electrolyzed by inserting a cathode and an anode such as a platinum electrode or a carbon electrode and energizing them. The amount of carbon particles added to water is preferably 1 to 20% by weight. The lipophilic organic substance adhering to the carbon particles is considered to be oxidized from the anode to be easily dissolved in water and appropriately removed from the surface of the carbon particles. Moreover, after performing this electrolytic treatment, the effect of removing lipophilic organic substances from the surface of the carbon particles can be further enhanced by performing filtration and washing the carbon particles with water.
上記の電解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、電解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。電解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・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。炭素粒子中に分子量の大きな炭化水素が含まれると、炭素粒子の表面が強い親油性の炭化水素で被覆され、水溶液である銀めっき溶液中で炭素粒子が互い凝集し、めっき皮膜中に炭素粒子が複合化しなくなると考えられる。 Lipophilic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles by the above electrolytic treatment. According to the analysis with a 300 ° C. heating gas, the carbon particles after the electrolytic treatment can be removed at 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. The carbon particles can be dispersed in the silver plating solution even if the carbon particles after the electrolytic treatment contain some aliphatic hydrocarbons or aromatic hydrocarbons. 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 gas chromatograph mass spectrometry intensity) of 5,000,000 or less. When hydrocarbons with a large molecular weight are contained in the carbon particles, the surfaces of the carbon particles are coated with strong lipophilic hydrocarbons, and the carbon particles aggregate together in the silver plating solution, which is an aqueous solution, and the carbon particles in the plating film Will not be combined.
このような電解処理により脂肪酸炭化水素と芳香族炭化水素を除去した炭素粒子を銀めっき液に懸濁させて電気めっきを行う際に、銀めっき液としてシアン系銀めっき液を使用するのが好ましい。従来の方法では、シアン系銀めっきを使用する場合には、界面活性剤を添加する必要があったが、本発明による複合めっき材の製造方法の実施の形態では、界面活性剤を添加しなくても銀めっき液中に炭素粒子が均一に分散した複合めっき液を得ることができるので、界面活性剤を添加する必要はない。 When electroplating by suspending carbon particles from which fatty acid hydrocarbons and aromatic hydrocarbons have been removed by such electrolytic treatment in a silver plating solution, it is preferable to use a cyan-based silver plating solution as the silver plating solution. . In the conventional method, when cyan silver plating is used, it is necessary to add a surfactant. However, in the embodiment of the method for producing a composite plating material according to the present invention, no surfactant is added. However, since a composite plating solution in which carbon particles are uniformly dispersed in the silver plating solution can be obtained, it is not necessary to add a surfactant.
また、シアン系銀めっき液を使用すると、炭素粒子の含有量および表面の炭素粒子の量が多いめっき皮膜を得ることができる。めっき皮膜中の炭素粒子の含有量が多くなるのは、銀めっき液に界面活性剤を添加しないことにより、銀めっき結晶の成長過程において界面活性剤が成長面に吸着しないので、銀マトリクス中に炭素粒子が取り込まれ易くなるためであると考えられる。また、めっき皮膜の表面の炭素粒子の量が多くなるのは、銀めっき液に界面活性剤を添加しないことにより、めっき後の水洗の際に、(洗剤が汚れを落とす働きと同様に)炭素粒子が表面から脱落または除去され難くなるためであると考えられる。 When a cyan silver plating solution is used, a plating film having a large carbon particle content and a large amount of carbon particles on the surface can be obtained. The amount of carbon particles in the plating film increases because the surfactant is not adsorbed on the growth surface during the growth process of the silver plating crystal because the surfactant is not added to the silver plating solution. This is probably because carbon particles are easily taken up. Also, the amount of carbon particles on the surface of the plating film increases because the surfactant is not added to the silver plating solution, so that when washing with water after plating (as the detergent removes dirt) This is thought to be because the particles are less likely to fall off or be removed from the surface.
このように炭素粒子を電解処理した後に銀めっき液に添加することにより、分散剤などの添加物を使用することなく且つ炭素粒子の表面をコーティングすることなく、銀めっき液中に炭素粒子を良好に分散させることができ、この銀めっき液を使用して電気めっきを行うことにより、銀層中に炭素粒子が分散した複合材からなる皮膜が素材上に形成され、炭素粒子の含有量および表面の炭素粒子の量が多く、耐摩耗性に優れた複合めっき材を製造することができる。 By adding the carbon particles to the silver plating solution after electrolytic treatment in this way, the carbon particles are excellent in the silver plating solution without using an additive such as a dispersant and without coating the surface of the carbon particles. By performing electroplating using this silver plating solution, a film made of a composite material in which carbon particles are dispersed in a silver layer is formed on the material, and the content and surface of the carbon particles Therefore, a composite plating material having a large amount of carbon particles and having excellent wear resistance can be produced.
なお、皮膜中の炭素粒子の含有量が多いほど複合めっき材の耐摩耗性が向上するが、上述した複合めっき材の製造方法の実施の形態により製造された複合めっき材では、皮膜中の炭素粒子の含有量を1.0重量%以上、好ましくは1.5重量%以上にすることができ、皮膜の表面の炭素粒子の量を10面積%以上、好ましくは20面積%以上にすることができるので、耐摩耗性に優れた複合めっき材を得ることができる。 The higher the carbon particle content in the film, the better the wear resistance of the composite plating material. However, in the composite plating material manufactured according to the embodiment of the method for manufacturing a composite plating material described above, the carbon in the film The content of particles can be 1.0% by weight or more, preferably 1.5% by weight or more, and the amount of carbon particles on the surface of the film can be 10% by area or more, preferably 20% by area or more. Therefore, a composite plating material having excellent wear resistance can be obtained.
以下、本発明による複合めっき材の製造方法の実施例について詳細に説明する。 Hereinafter, the Example of the manufacturing method of the composite plating material by this invention is described in detail.
[実施例1〜3]
炭素粒子として平均粒径5μmの鱗片状黒鉛粒子(エスイーシー社製のカーボンSN−5)6重量%を3Lの純水中に添加した後、pHをアルカリ性にするために水酸化カリウムを添加し、この混合溶液を、電極として白金電極を使用して電流密度1A/cm2で攪拌しながら8時間電解した。その後、ろ紙によりろ別し、水洗した。
[Examples 1 to 3]
After adding 6% by weight of scaly graphite particles having an average particle diameter of 5 μm (carbon SN-5 manufactured by ESC) as carbon particles in 3 L of pure water, potassium hydroxide is added to make the pH alkaline, This mixed solution was electrolyzed for 8 hours while stirring at a current density of 1 A / cm 2 using a platinum electrode as an electrode. Then, it was separated by filter paper and washed with water.
この電解処理の前後の炭素粒子について、パージ・アンド・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、表2に示すパージ・アンド・トラップ条件および表3に示すCGMS分析条件で、300℃加熱発生ガスの分析を行った。その結果を表3に示すとともに、電解処理前の炭素粒子の分析結果を図1、電解処理後の炭素粒子の分析結果を図2に示す。表3、図1および図2からわかるように、上記の電解処理により、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ているのがわかる。 For the carbon particles before and after this electrolytic treatment, a purge and gas chromatograph mass spectrometer (Nippon Analytical Industries JHS-100) (GCMAS QP-5050A manufactured by Shimadzu Corporation) was used, and the purge and gas chromatograph shown in Table 2 was used. Under the trap conditions and the CGMS analysis conditions shown in Table 3, analysis of the gas generated by heating at 300 ° C. was performed. The results are shown in Table 3, the analysis results of carbon particles before electrolytic treatment are shown in FIG. 1, and the analysis results of carbon particles after electrolytic treatment are shown in FIG. As can be seen from Table 3, FIG. 1 and FIG. 2, by the above electrolytic treatment, lipophilic aliphatic hydrocarbons such as nonane, decane and 3-methyl-2-heptene attached to the carbon particles, xylene and the like It can be seen that the lipophilic aromatic hydrocarbons have been removed.
次に、上記の電解処理を行った炭素粒子40g/L(実施例1)、80g/L(実施例2)、120g/L(実施例3)を、それぞれ100g/Lのシアン銀カリウムと120g/Lのシアン化カリウムと4mg/Lのシアン化セレン酸カリウムとからなるシアン銀めっき液中に添加して分散および懸濁させることにより、銀と炭素粒子の複合めっき液を作製した。これらの複合めっき液を使用して、それぞれ液温25℃、電流密度1A/dm2で電気めっきを行い、素材としての銅板上に膜厚5μmの銀と炭素粒子の複合めっき皮膜が形成された複合めっき材を作製した。 Next, 40 g / L (Example 1), 80 g / L (Example 2), and 120 g / L (Example 3) of the carbon particles subjected to the above-described electrolytic treatment were converted into 100 g / L cyanogen potassium potassium and 120 g, respectively. A composite plating solution of silver and carbon particles was prepared by adding and dispersing and suspending in a cyan silver plating solution composed of / L potassium cyanide and 4 mg / L potassium cyanide selenate. Using these composite plating solutions, electroplating was performed at a liquid temperature of 25 ° C. and a current density of 1 A / dm 2 , respectively, and a composite plating film of silver and carbon particles having a film thickness of 5 μm was formed on a copper plate as a material. A composite plating material was produced.
得られた複合めっき材(素材を含む)から切り出した試料をAgおよびCの分析用にそれぞれ用意し、試料中のAgの含有量(X重量%)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、試料中のCの含有量(Y重量%)を微量炭素・硫黄分析装置(堀場製作所製のEMIA−U510)を用いて赤外線吸収法によって求め、めっき皮膜中のC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Cの含有量は1.5〜2.2重量%であった。 Samples cut out from the obtained composite plating materials (including raw materials) were prepared for analysis of Ag and C, respectively, and the content (X wt%) of Ag in the samples was determined using an ICP device (IRIS made by Jarrel Ash). / AR), and the C content (Y wt%) in the sample is determined by an infrared absorption method using a trace carbon / sulfur analyzer (EMIA-U510 manufactured by Horiba, Ltd.). When the content of C in the plating film was calculated as Y / (X + Y), the content of C in the plating film was 1.5 to 2.2% by weight.
また、得られた複合めっき材から切り出した試験片の表面を表面観察することにより、めっき皮膜の表面の炭素粒子の量(面積%)を算出した。このめっき皮膜の表面の炭素粒子の量は、試験片の表面を超深度形状顕微鏡(キーエンス社製のVK−8500)により対物レンズ倍率100倍で超深度画像として撮影した画像を、PC上で画像解析アプリケーション(SCION CORPORATION社製のSCION IMAGE)を使用して、白黒で取り込んで階調を二値化し、銀の部分と炭素粒子の部分に分離して、画像全体のピクセル数Xに対する炭素粒子の部分のピクセル数Yの比Y/Xとして算出した。その結果、めっき皮膜の表面の炭素粒子の量は28〜32面積%であった。 In addition, the amount (area%) of carbon particles on the surface of the plating film was calculated by observing the surface of the test piece cut out from the obtained composite plating material. The amount of carbon particles on the surface of the plating film is an image obtained by photographing the surface of the test piece as an ultra-deep image at an objective lens magnification of 100 times with an ultra-deep shape microscope (VK-8500 manufactured by Keyence Corporation) on a PC. Using an analysis application (SCION IMAGE, SCION IMAGE), the image is captured in black and white, the gradation is binarized, and separated into a silver part and a carbon particle part. It calculated as ratio Y / X of the pixel number Y of the part. As a result, the amount of carbon particles on the surface of the plating film was 28 to 32 area%.
また、得られた複合めっき材から切り出した試験片と、めっき液として120g/Lのシアン銀カリウムと100g/Lのシアン化カリウムからなる浴組成のシアン系銀めっき浴を使用して厚さ0.3mmの銅板上に厚さ5μmの銀めっき皮膜を形成した銀めっき材との間の摩擦係数を求めた。この摩擦係数(μ)は、得られた複合めっき材から切り出した試験片をインデント加工(R3mm)して凸形状の圧子とするとともに、平板状の銀めっき材をベース側の評価試料とし、ロードセルを使用して、圧子を加重3Nで評価試料の表面に押し付けながら移動速度60mm/分で滑らせ、水平方向にかかる力(F)を測定し、μ=F/Nから算出した。その結果、摩擦係数は0.26〜0.34であった。 In addition, using a test piece cut out from the obtained composite plating material and a cyan silver plating bath having a bath composition of 120 g / L potassium cyanide cyanide and 100 g / L potassium cyanide as a plating solution, a thickness of 0.3 mm The coefficient of friction with the silver plating material which formed the silver plating film | membrane with a thickness of 5 micrometers on the copper plate of this was calculated | required. The coefficient of friction (μ) is obtained by indenting (R3 mm) a test piece cut out from the obtained composite plating material into a convex indenter, and using a flat silver plating material as a base side evaluation sample. , The indenter was slid at a moving speed of 60 mm / min while pressing the indenter against the surface of the evaluation sample with a weight of 3 N, the force (F) applied in the horizontal direction was measured, and calculated from μ = F / N. As a result, the friction coefficient was 0.26 to 0.34.
[比較例1]
電解処理を行わなかった以外は、実施例2と同様の方法により、銀めっき材を作製し、めっき皮膜中の炭素粒子の含有量、めっき皮膜の表面の炭素粒子の量および摩擦係数を求めた。その結果、炭素粒子の含有量および表面の炭素粒子の量は0重量%および0面積%であり、炭素粒子の複合化が認められなかった。また、摩擦係数は1.23であり、実施例1〜3と比べて非常に高い値であった。
[Comparative Example 1]
A silver plating material was prepared by the same method as in Example 2 except that the electrolytic treatment was not performed, and the content of carbon particles in the plating film, the amount of carbon particles on the surface of the plating film, and the friction coefficient were obtained. . As a result, the content of carbon particles and the amount of carbon particles on the surface were 0% by weight and 0% by area, and no composite of carbon particles was observed. Moreover, the friction coefficient was 1.23, which was a very high value as compared with Examples 1 to 3.
なお、表3および図1に示す300℃加熱発生ガスの分析結果から、本比較例のように電解処理を行わなかった場合には、親油性脂肪族炭化水素および親油性芳香族炭化水素を示すピークが多数みられ、黒鉛粒子に親油性脂肪族炭化水素および親油性芳香族炭化水素に付着しているのがわかる。また、本比較例のように電解処理を行わなかった黒鉛粒子は、めっき液中で凝集して均一に懸濁させることができなかった。 In addition, from the analysis result of 300 degreeC heating generation gas shown in Table 3 and FIG. 1, when an electrolytic treatment is not performed like this comparative example, lipophilic aliphatic hydrocarbon and lipophilic aromatic hydrocarbon are shown. It can be seen that many peaks are observed, and the graphite particles are adhered to the lipophilic aliphatic hydrocarbon and the lipophilic aromatic hydrocarbon. Further, the graphite particles not subjected to the electrolytic treatment as in this comparative example could not be aggregated and suspended uniformly in the plating solution.
[比較例2]
めっき液中に界面活性剤として炭素粒子分散効果が高いラウリル硫酸ナトリウム5ml/Lを添加した以外は、比較例1と同様の方法により、複合めっき材を作製し、めっき皮膜中の炭素粒子の含有量、めっき皮膜の表面の炭素粒子の量および摩擦係数を求めた。その結果、炭素粒子の含有量および表面の炭素粒子の量は1.1重量%および5面積%であり、実施例1〜3と比べて非常に少なかった。また、摩擦係数は1.23であり、実施例1〜3と比べて高い値であった。
[Comparative Example 2]
A composite plating material was prepared in the same manner as in Comparative Example 1 except that 5 ml / L of sodium lauryl sulfate, which has a high carbon particle dispersion effect, was added as a surfactant to the plating solution, and the inclusion of carbon particles in the plating film The amount, the amount of carbon particles on the surface of the plating film, and the friction coefficient were determined. As a result, the content of carbon particles and the amount of carbon particles on the surface were 1.1% by weight and 5% by area, which was very small compared to Examples 1 to 3. Moreover, the friction coefficient was 1.23, which was a higher value than Examples 1-3.
実施例1〜3および比較例1、2の結果を表4に示す。 Table 4 shows the results of Examples 1 to 3 and Comparative Examples 1 and 2.
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