JP6911164B2 - Composite plating material - Google Patents
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- JP6911164B2 JP6911164B2 JP2020002293A JP2020002293A JP6911164B2 JP 6911164 B2 JP6911164 B2 JP 6911164B2 JP 2020002293 A JP2020002293 A JP 2020002293A JP 2020002293 A JP2020002293 A JP 2020002293A JP 6911164 B2 JP6911164 B2 JP 6911164B2
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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 sliding contact parts such as switches and connectors.
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、摺動過程における発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-plated material in which the conductor material is silver-plated in order to prevent oxidation of the conductor material such as copper or copper alloy due to heat generation 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、摺動により摩耗して素材が露出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、耐摩耗性、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 easily worn, and generally has a high friction coefficient, so that there is a problem that the material is easily worn by sliding and exposed. In order to solve this problem, among carbon particles such as graphite and carbon black, which have excellent heat resistance, wear resistance, lubricity, etc., a composite material film in which graphite particles are dispersed in a silver matrix is conducted by electroplating. A method of forming on a material to improve wear resistance has been proposed (see, for example, Patent Document 1). Further, a method of producing a silver plating film containing graphite particles by using a plating bath to which a wetting agent suitable for dispersing graphite particles is added has been proposed (see, for example, Patent Document 2). Furthermore, the sol-gel method coats the carbon particles with a metal oxide or the like to improve the dispersibility of the carbon particles in the composite plating solution of silver and carbon particles, and increase the amount of carbon particles complexed 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が占める割合を増大させて、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。
However, the composite plating material produced by the methods of
このような複合めっき材を製造する方法として、酸化処理を行った炭素粒子を添加したシアン系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方法（例えば、特許文献４参照）、銅または銅合金からなる母材の表面を被覆する銀めっき層の下層側の第一の銀めっき層の結晶粒径を上層部の第二の銀めっき層の結晶粒径よりも大きくする方法（例えば、特許文献５参照）、素材上に形成された第１の銀めっき層上に０．５質量％以上のアンチモンを含む第２の銀めっき層を形成する方法（例えば、特許文献６参照）などが提案されている。 As a method for producing such a composite plating material, an oxidation-treated carbon particle-added cyan-based silver plating solution is used for electroplating to perform electroplating from the composite material containing carbon particles in the silver layer. (For example, see Patent Document 4), the crystal grain size of the first silver-plated layer on the lower side of the silver-plated layer covering the surface of the base material made of copper or a copper alloy is set to the upper layer. A method of increasing the crystal grain size of the second silver-plated layer of the portion (see, for example, Patent Document 5), containing 0.5% by mass or more of antimony on the first silver-plated layer formed on the material. A method of forming a second silver-plated layer (see, for example, Patent Document 6) has been proposed.
しかし、特許文献４〜６の方法により製造されためっき材は、挿抜可能な接続端子などの材料として使用すると、雄端子と雌端子の接点部間の摺動によって、最表層が摩耗して粗大な摩耗粉が発生し、この粗大な摩耗粉が接点部間に介在して、接点部間の垂直荷重が増大し、摩耗粉の凝着を促進するため、接点部間の摩擦係数が上昇し易くなる。 However, when the plating material produced by the methods of Patent Documents 4 to 6 is used as a material such as a connectable terminal that can be inserted and removed, the outermost layer is worn and coarse due to sliding between the contact portion between the male terminal and the female terminal. Abrasion powder is generated, and this coarse wear debris intervenes between the contact portions to increase the vertical load between the contact portions and promote the adhesion of the wear debris, so that the friction coefficient between the contact portions increases. It will be easier.
したがって、本発明は、このような従来の問題点に鑑み、挿抜可能な接続端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動による摩擦係数の上昇を抑制することができる、複合めっき材を提供することを目的とする。 Therefore, in view of such conventional problems, the present invention suppresses an increase in the friction coefficient due to sliding between the contact portion between the male terminal and the female terminal when used as a material such as a connectable terminal that can be inserted and removed. It is an object of the present invention to provide a composite plating material capable of providing a composite plating material.
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、挿抜可能な接続端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動によって発生する摩耗粉を小さくすれば、雄端子と雌端子の接点部間の摺動による摩擦係数の上昇を抑制することができる、複合めっき材を提供することを見出し、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 found that when used as a material such as a connectable terminal that can be inserted and removed, the wear debris generated by sliding between the contact portion between the male terminal and the female terminal is generated. We have found that we can provide a composite plating material that can suppress an increase in the friction coefficient due to sliding between the contact portions of the male terminal and the female terminal if the size is reduced, and have completed the present invention.
すなわち、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において、この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成されたビッカース硬さＨＶ１８０のＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで１，０００回の往復摺動動作を行った後に、摺動端部の摩耗粉をテープで貼り付けて採取したときに、そのテープ上の摩耗粉の輪郭に外接する長方形の面積が最小となる長方形の短辺の長さの最大値が１００μｍ以下であることを特徴とする。 That is, the composite plating material according to the present invention is a composite plating material in which a composite plating film made of a composite material containing carbon particles in a silver layer is formed on the material, and a test piece cut out from the composite plating material is formed into a flat plate. AgSb of Vickers hardness HV180 in which a 20 μm-thick AgSb plating film containing 2% by mass of Sb was formed on a material that was embossed with a hemisphere with an inner R = 1.0 mm as a test piece and indented. The plated material is an indented test piece, and while the indented test piece is pressed against the flat plate-shaped test piece with a constant load of 2N by a sliding wear tester, the sliding distance is 10 mm and the sliding speed is 1,000 mm / s. Short of the rectangle that minimizes the area of the rectangle that circumscribes the contour of the wear debris on the tape when the wear debris at the sliding end is attached with tape and collected after performing the reciprocating sliding operation once. The maximum value of the side length is 100 μm or less.
この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成されたビッカース硬さＨＶ１８０のＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで１，０００回の往復摺動動作を行った後に、摺動端部の摩耗粉をテープで貼り付けて採取したときに、そのテープ上の摩耗粉の輪郭に外接する長方形の面積が最小となる長方形の短辺の長さに対する長辺の長さの比であるアスペクト比が３．０以上の摩耗粉の数の割合が３０％以上であるのが好ましい。 The test piece cut out from this composite plating material is used as a flat plate-shaped test piece, and a hemispherical embossed material having an inner R = 1.0 mm as an indenting process contains 2% by mass of Sb and has a thickness of 20 μm. A Vickers hardness HV180 AgSb plating material on which a plating film is formed is used as an indented test piece, and the sliding wear tester presses the indented test piece against the flat plate-shaped test piece with a constant load of 2N while sliding distance. After performing 1,000 reciprocating sliding operations at a sliding speed of 10 mm and a sliding speed of 3 mm / s, when the wear debris at the sliding end is affixed with tape and collected, the contour of the wear debris on the tape is displayed. The ratio of the number of wear debris having an aspect ratio of 3.0 or more, which is the ratio of the length of the long side to the length of the short side of the rectangle that minimizes the area of the circumscribing rectangle, is preferably 30% or more.
また、この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成されたビッカース硬さＨＶ１８０のＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで往復摺動動作を行ったときの１，０００回の往復摺動動作の各々の往路の摩擦係数の平均値が０．７以下であるのが好ましい。 Further, the test piece cut out from this composite plating material is used as a flat plate-shaped test piece, and the material is indented by hemispherical embossing with an inner R = 1.0 mm and contains 2% by mass of Sb in a thickness of 20 μm. The AgSb plating material with Vickers hardness HV180 on which the AgSb plating film was formed was used as an indented test piece, and the sliding wear tester pressed the indented test piece against the flat plate-shaped test piece with a constant load of 2N while sliding. It is preferable that the average value of the friction coefficient of each outbound route of 1,000 reciprocating sliding operations when the reciprocating sliding operation is performed at a moving distance of 10 mm and a sliding speed of 3 mm / s is 0.7 or less.
さらに、上記の複合めっき材において、複合めっき皮膜の厚さが０．３〜２０μｍであるのが好ましく、複合めっき皮膜中の炭素含有量が０．３〜１０質量％であるのが好ましい。また、摩耗粉中の炭素含有量が１〜３０質量％であるのが好ましい。また、素材が銅または銅合金からなるのが好ましく、複合めっき皮膜と素材との間にニッケルめっき皮膜を形成してもよい。 Further, in the above-mentioned composite plating material, the thickness of the composite plating film is preferably 0.3 to 20 μm, and the carbon content in the composite plating film is preferably 0.3 to 10% by mass. Further, the carbon content in the abrasion powder is preferably 1 to 30% by mass. Further, the material is preferably made of copper or a copper alloy, and a nickel plating film may be formed between the composite plating film and the material.
本発明によれば、挿抜可能な接続端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動による摩擦係数の上昇を抑制することができる、複合めっき材を提供することができる。 According to the present invention, there is provided a composite plating material capable of suppressing an increase in friction coefficient due to sliding between a contact portion between a male terminal and a female terminal when used as a material such as a connectable terminal that can be inserted and removed. be able to.
本発明による複合めっき材の実施の形態は、酸化処理を行った炭素粒子（好ましくは平均粒径１〜１５μｍの鱗片状黒鉛）を添加したスルホン酸系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（好ましくは銅または銅合金からなる）素材上に形成することによって製造することができる。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、このように、炭素粒子を銀めっき液中に投入する前に酸化処理を施すことにより、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 composite plating material according to the present invention, electroplating is performed using a sulfonic acid-based silver plating solution to which oxidized carbon particles (preferably scaly graphite having an average particle size of 1 to 15 μm) are added. Thereby, it can be produced by forming a film made of a composite material containing carbon particles in the silver layer on a material (preferably made of copper or a copper alloy). It is not possible to incorporate carbon particles into the plating film simply by adding the carbon particles to the silver plating solution and suspending them. In this way, the carbon particles are oxidized before being put into the silver plating solution. By applying the above, the dispersibility of the carbon particles can be improved.
本発明による複合めっき材の実施の形態を製造するためには、炭素粒子を銀めっき液に添加する前に、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のが好ましい。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族炭化水素や、（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 order to produce the embodiment of the composite plating material according to the present invention, it is preferable to remove the lipophilic organic matter adsorbed on the surface of the carbon particles by an oxidation treatment before adding the carbon particles to the silver plating solution. .. Such lipophilic organics include alkanes (such as nonane and decane), aliphatic hydrocarbons such as alkenes (such as methylheptene), and aromatic hydrocarbons such as alkylbenzene (such as xylene).
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。 As the oxidation treatment of carbon particles, in addition to the wet oxidation treatment, a dry oxidation treatment using O 2 gas or the like can be used, but from the viewpoint of mass productivity, the wet oxidation treatment is preferably used, and the surface area is increased by the wet oxidation treatment. Large carbon particles can be treated uniformly.
湿式酸化処理の方法としては、導電塩を含む水中に炭素粒子を懸濁させた後に陰極や陽極となる白金電極などを挿入して電気分解を行う方法や、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が、生産性を考慮すると後者の方法を使用するのが好ましい。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、過硫酸ナトリウム、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分散し易い形態になり、炭素粒子の表面から適宜除去されると考えられる。また、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 method of wet oxidation treatment, carbon particles are suspended in water containing a conductive salt and then electrolyzed by inserting a platinum electrode serving as a cathode or an anode, or carbon particles are suspended in water. A method of adding an appropriate amount of an oxidizing agent can be used later, but the latter method is preferably used in consideration of productivity. As the oxidizing agent, an oxidizing agent such as nitric acid, hydrogen peroxide, potassium permanganate, potassium persulfate, sodium persulfate, and sodium perchlorate can be used. It is considered that the lipophilic organic matter adhering to the carbon particles is oxidized by the added oxidizing agent to be easily dispersed in water, and is appropriately removed from the surface of the carbon particles. Further, by performing the wet oxidation treatment, filtering, and further washing the carbon particles with water, the effect of removing lipophilic organic substances from the surface of the carbon particles can be further enhanced.
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・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。 By the above oxidation treatment, aliphatic organic substances such as aliphatic hydrocarbons and aromatic hydrocarbons can be removed from the surface of the carbon particles, and according to the analysis with a heating gas at 300 ° C., the carbon particles after the oxidation treatment are removed at 300 ° C. The gas generated by heating in the above contains almost no lipophilic aliphatic hydrocarbons such as alkanes and alkanes and lipophilic aromatic hydrocarbons such as alkylbenzene. Even if the carbon particles after the oxidation treatment contain some aliphatic hydrocarbons or aromatic hydrocarbons, the carbon particles can be dispersed in the silver plating solution, but the carbon particles contain hydrocarbons having a molecular weight of 160 or more. It is preferable that the intensity of the gas generated by heating at 300 ° C. (purge and gas chromatograph mass analysis intensity) of the hydrocarbon which is not contained and has a molecular weight of less than 160 in the carbon particles is 5,000,000 or less. When a hydrocarbon having a large molecular weight is contained in the carbon particles, the surface of the carbon particles is coated with a strong lipophilic hydrocarbon, and the carbon particles aggregate with each other in a silver plating solution which is an aqueous solution, and the carbon particles are contained in the plating film. Is considered to be uncomplicated.
このような酸化処理により脂肪族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、銀めっき液としてスルホン酸系銀めっき液を使用するのが好ましい。このスルホン酸銀として、メタンスルホン酸銀、アルカノールスルホン酸銀、フェノールスルホン酸銀などを使用することができる。また、スルホン酸系銀めっき液は、Ａｇイオン源としてのスルホン酸銀と、錯化剤としてのスルホン酸を含み、光沢剤などの添加剤を含んでもよい。この銀めっき液中のＡｇ濃度は、５〜１５０ｇ／Ｌであるのが好ましく、１０〜１２０ｇ／Ｌであるのがさらに好ましく、２０〜１００ｇ／Ｌであるのが最も好ましい。 When carbon particles from which aliphatic hydrocarbons and aromatic hydrocarbons have been removed by such an oxidation treatment are suspended in a silver plating solution for electroplating, a sulfonic acid-based silver plating solution is used as the silver plating solution. Is preferable. As the silver sulfonate, silver methanesulfonate, silver alkanol sulfonate, silver phenol sulfonate and the like can be used. Further, the sulfonic acid-based silver plating solution contains silver sulfonate as an Ag ion source and sulfonic acid as a complexing agent, and may contain an additive such as a brightener. The Ag concentration in the silver plating solution is preferably 5 to 150 g / L, more preferably 10 to 120 g / L, and most preferably 20 to 100 g / L.
また、銀めっき液中の炭素粒子の量は、１０〜１００ｇ／Ｌであるのが好ましく、２０〜９０ｇ／Ｌであるのがさらに好ましい。銀めっき液中の炭素粒子の量が１０ｇ／Ｌ未満であると、複合めっき層中の炭素粒子の含有量を十分に多くすることができないおそれがあり、１００ｇ／Ｌより多くしても、複合めっき層中の炭素粒子の含有量を多くすることはできない。 The amount of carbon particles in the silver plating solution is preferably 10 to 100 g / L, and more preferably 20 to 90 g / L. If the amount of carbon particles in the silver plating solution is less than 10 g / L, the content of carbon particles in the composite plating layer may not be sufficiently increased, and even if it is more than 100 g / L, the composite The content of carbon particles in the plating layer cannot be increased.
また、電気めっきの際の電流密度は、１〜２０Ａ／ｄｍ２であるのが好ましく、２〜１５Ａ／ｄｍ２であるのがさらに好ましい。Ａｇ濃度や電流密度が低過ぎると、複合めっき皮膜の形成が遅くなって効率的でなく、Ａｇ濃度や電流密度が高過ぎると、複合めっき皮膜の外観にムラが生じ易い。 The current density during electroplating is preferably from 1 to 20A / dm 2, and even more preferably 2~15A / dm 2. If the Ag concentration or current density is too low, the formation of the composite plating film is delayed and inefficient, and if the Ag concentration or current density is too high, the appearance of the composite plating film tends to be uneven.
本発明による複合めっき材の実施の形態を製造するために、酸化処理を行った炭素粒子を使用すると、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。また、スルホン酸系銀めっき液を使用すると、表面の炭素粒子が占める割合が多いめっき皮膜を得ることができる。めっき皮膜の表面の炭素粒子が占める割合が多くなるのは、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 carbon particles subjected to oxidation treatment are used in order to produce an embodiment of the composite plating material according to the present invention, composite plating in which carbon particles are uniformly dispersed in a silver plating solution without adding a surfactant. Since the liquid can be obtained, it is not necessary to add a surfactant. Further, when a sulfonic acid-based silver plating solution is used, a plating film in which carbon particles on the surface occupy a large proportion can be obtained. The ratio of carbon particles on the surface of the plating film is increased by not adding a surfactant to the silver plating solution, so that the carbon particles (similar to the detergent's function of removing stains) during washing with water after plating. Is thought to be because it is difficult for the particles to fall off or be removed from the surface.
このように炭素粒子を酸化処理した後に銀めっき液に添加することにより、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、表面の炭素粒子が占める割合が多く、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 the oxidation treatment in this way, the carbon particles can be satisfactorily dispersed in the silver plating solution, and 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 carbon particles on the surface occupy a large proportion, so that a composite plating material having excellent wear resistance can be produced.
また、本発明による複合めっき材の実施の形態は、銀層中に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において、この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成された（ビッカース硬さＨＶが１８０の）ＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで１，０００回の往復摺動動作を行った後に、摺動端部の摩耗粉をテープで貼り付けて採取したときに、そのテープ上の摩耗粉の輪郭に外接する長方形の面積が最小となる長方形の短辺の長さ（短径）の最大値が１００μｍ以下（好ましくは１〜１００μｍ、さらに好ましくは１０〜１００μｍ、最も好ましくは３０〜１００μｍ）である。このように摩耗粉の短径が短いと、摩耗粉が小さくなり（摩耗粉の長径に対して短径が短くなれば摩耗粉が細長くなり）、複合めっき材を挿抜可能な接合端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動による摩擦係数の上昇を抑制することができる。 Further, in the embodiment of the composite plating material according to the present invention, in a composite plating material in which a composite plating film made of a composite material containing carbon particles in a silver layer is formed on the material, a test cut out from the composite plating material is performed. A plate-shaped test piece was used as a flat plate-shaped test piece, and a 20 μm-thick AgSb plating film containing 2% by mass of Sb was formed on a hemispherical embossed material having an inner R = 1.0 mm as an indenting process (Vickers). AgSb-plated material (with a hardness HV of 180) is used as an indented test piece, and the sliding wear tester presses the indented test piece against the flat plate-shaped test piece with a constant load of 2N while sliding for a sliding distance of 10 mm. After performing 1,000 reciprocating sliding movements at a speed of 3 mm / s, when the wear debris at the sliding end is attached with tape and collected, a rectangular shape that circumscribes the contour of the wear debris on the tape. The maximum value of the length (minor axis) of the short side of the rectangle having the smallest area is 100 μm or less (preferably 1 to 100 μm, more preferably 10 to 100 μm, and most preferably 30 to 100 μm). When the minor axis of the abrasion powder is short in this way, the abrasion powder becomes smaller (when the minor axis is shorter than the major axis of the abrasion powder, the abrasion powder becomes elongated), and a material such as a joint terminal into which a composite plating material can be inserted and removed. When used as, it is possible to suppress an increase in the friction coefficient due to sliding between the contact portions of the male terminal and the female terminal.
この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成された（ビッカース硬さＨＶが１８０の）ＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで１，０００回の往復摺動動作を行った後に、摺動端部の摩耗粉をテープで貼り付けて採取したときに、これらの摩耗粉のうちのテープ上の摩耗粉の輪郭に外接する長方形の面積が最小となる長方形の短辺の長さ（短径）が長い方から２０個の摩耗粉を選んで、その短辺の長さ（短径）に対する長辺の長さ（長径）の比であるアスペクト比が３．０以上の摩耗粉の数の割合が３０％以上であるのが好ましく、４０％以上であるのがさらに好ましく、４５％以上であるのが最も好ましい。このように細長い摩耗粉の数の割合が多いと、複合めっき材を挿抜可能な接合端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動による摩擦係数の上昇をさらに抑制することができる。 The test piece cut out from this composite plating material is used as a flat plate-shaped test piece, and a hemispherical embossed material having an inner R = 1.0 mm as an indenting process contains 2% by mass of Sb and has a thickness of 20 μm AgSb. The AgSb plating material on which the plating film was formed (Vickers hardness HV is 180) was used as the indented test piece, and the indented test piece was pressed against the flat plate-shaped test piece with a constant load of 2N by a sliding wear tester. After performing 1,000 reciprocating sliding operations at a sliding distance of 10 mm and a sliding speed of 3 mm / s, when the wear debris at the sliding end is attached with tape and collected, these wear debris Select 20 pieces of wear debris from the one with the longest short side length (minor axis) of the rectangle that minimizes the area of the rectangle circumscribing the contour of the wear debris on our tape, and the length of the short side (minor axis). The ratio of the number of wear debris having an aspect ratio of 3.0 or more, which is the ratio of the length (major axis) of the long side to the minor axis), is preferably 30% or more, more preferably 40% or more. Most preferably, it is 45% or more. When the ratio of the number of elongated abrasion powders is large in this way, when the composite plating material is used as a material such as a removable joint terminal, the friction coefficient increases due to sliding between the contact portion between the male terminal and the female terminal. It can be further suppressed.
また、この複合めっき材から切り出した試験片を平板状試験片とするとともに、インデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成された（ビッカース硬さＨＶが１８０の）ＡｇＳｂめっき材をインデント付き試験片とし、摺動摩耗試験機により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓで往復摺動動作を行ったときの１，０００回の往復摺動動作の各々の往路の摩擦係数の平均値が０．７以下であるのが好ましく、０．１〜０．５であるのがさらに好ましい。 Further, the test piece cut out from this composite plating material is used as a flat plate-shaped test piece, and the material is indented by hemispherical embossing with an inner R = 1.0 mm and contains 2% by mass of Sb in a thickness of 20 μm. The AgSb plating material on which the AgSb plating film was formed (Vickers hardness HV is 180) was used as an indented test piece, and the indented test piece was pushed onto the flat plate-shaped test piece with a constant load of 2N by a sliding wear tester. The average value of the friction coefficient of each outbound route of 1,000 reciprocating sliding operations when the reciprocating sliding operation is performed at a sliding distance of 10 mm and a sliding speed of 3 mm / s while hitting is 0.7 or less. Is preferable, and 0.1 to 0.5 is more preferable.
さらに、上記の複合めっき材において、複合めっき皮膜の厚さは０．３〜２０μｍであるのが好ましく、１〜１５μｍであるのがさらに好ましく、１．５〜１２μｍであるのが最も好ましい。複合めっき皮膜の厚さが０．３μｍ未満であると、複合めっき材の耐摩耗性が十分でなく、２０μｍを超えると、銀の量が多くなり、複合めっき材の製造コストが高くなる。また、複合めっき皮膜中の炭素含有量は０．３〜１０質量％であるのが好ましく、０．４〜５質量％であるのがさらに好ましく、０．５〜３質量％であるのが最も好ましい。また、摩耗粉中の炭素含有量は１〜３０質量％であるのが好ましく、１．２〜２５質量％であるのがさらに好ましい。このような炭素含有量の摩耗粉の複合めっき材を挿抜可能な接続端子などの材料として使用した際に、雄端子と雌端子の接点部間の摺動による摩耗粉の成長を抑制することができる。また、素材が銅または銅合金からなるのが好ましく、複合めっき皮膜と素材との間にニッケルめっき皮膜を形成してもよい。 Further, in the above-mentioned composite plating material, the thickness of the composite plating film is preferably 0.3 to 20 μm, more preferably 1 to 15 μm, and most preferably 1.5 to 12 μm. If the thickness of the composite plating film is less than 0.3 μm, the wear resistance of the composite plating material is not sufficient, and if it exceeds 20 μm, the amount of silver increases and the production cost of the composite plating material increases. The carbon content in the composite plating film is preferably 0.3 to 10% by mass, more preferably 0.4 to 5% by mass, and most preferably 0.5 to 3% by mass. preferable. The carbon content in the abrasion powder is preferably 1 to 30% by mass, more preferably 1.2 to 25% by mass. When such a composite plating material of wear powder having a carbon content is used as a material such as a connectable terminal that can be inserted and removed, it is possible to suppress the growth of wear powder due to sliding between the contact portion between the male terminal and the female terminal. can. Further, the material is preferably made of copper or a copper alloy, and a nickel plating film may be formed between the composite plating film and the material.
以下、本発明による複合めっき材の実施例について詳細に説明する。 Hereinafter, examples of the composite plating material according to the present invention will be described in detail.
［実施例１］
素材として厚さ０．２ｍｍのＣｕ−Ｎｉ−Ｓｎ−Ｐ合金からなる板材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の板材）（ＤＯＷＡメタルテック株式会社製のＮＢ１０９ＥＨ）を用意し、この素材をカソード、（チタンのメッシュ素材を白金めっきした）チタン白金メッシュ電極板をアノードとして使用して、錯化剤としてスルホン酸を含むスルホン酸系Ａｇストライクめっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＳＴ）中において、電流密度５Ａ／ｄｍ２で３０秒間電気めっき（Ａｇストライクめっき）を行った。
[Example 1]
As a material, a plate material made of a Cu-Ni-Sn-P alloy having a thickness of 0.2 mm (containing 1.0% by mass of Ni, 0.9% by mass of Sn, and 0.05% by mass of P, and the balance is Cu. A copper alloy plate material) (NB109EH manufactured by DOWA Metal Tech Co., Ltd.) is prepared, and this material is used as a cathode, and a titanium platinum mesh electrode plate (platinum-plated titanium mesh material) is used as an anode to make a complexing agent. Electroplating (Ag strike plating) was performed for 30 seconds at a current density of 5 A / dm 2 in a sulfonic acid-based Ag strike plating solution (Dyne Silver GPE-ST manufactured by Daiwa Kasei Co., Ltd.) containing sulfonic acid.
また、炭素粒子として平均粒径５．０μｍの鱗片状（板状）の黒鉛粒子を用意した。なお、実施例および比較例において、炭素粒子の平均粒径は、炭素粒子０．５ｇを０．２重量％のヘキサメタリン酸ナトリウム溶液５０ｇに分散させ、さらに超音波により分散させた後、レーザー光散乱粒度分布測定装置を用いて体積基準分布の粒径を測定し、累積分布で５０％の粒径を平均粒径とすることにより求めた。 Further, as carbon particles, scaly (plate-shaped) graphite particles having an average particle size of 5.0 μm were prepared. In the examples and comparative examples, the average particle size of the carbon particles was such that 0.5 g of the carbon particles were dispersed in 50 g of a 0.2 wt% sodium hexametaphosphate solution, further dispersed by ultrasonic waves, and then scattered by laser light. The particle size of the volume-based distribution was measured using a particle size distribution measuring device, and the average particle size was 50% of the cumulative distribution.
次に、上記の黒鉛粒子８０ｇを純水１３５０ｇ中に投入して５０℃まで加熱し、ｐＨが１２になるように水酸化カリウムを加えた後、酸化剤として過硫酸カリウム２７ｇを純水６００ｇに溶かした液を添加し、６０分間撹拌して湿式酸化処理を行った。このように湿式酸化処理を行った炭素粒子を、吸引ろ過により分離し、水で洗浄した後、乾燥した。 Next, 80 g of the above graphite particles were put into 1350 g of pure water, heated to 50 ° C., potassium hydroxide was added so that the pH became 12, and then 27 g of potassium persulfate was added to 600 g of pure water as an oxidizing agent. The dissolved liquid was added, and the mixture was stirred for 60 minutes for wet oxidation treatment. The carbon particles subjected to the wet oxidation treatment in this manner were separated by suction filtration, washed with water, and then dried.
次に、錯化剤としてスルホン酸を含むＡｇ濃度３０ｇ／Ｌのスルホン酸系銀めっき液（大和化成株式会社製のダインシルバーＧＰＥ−ＰＬ（無光沢））中に、上記の酸化処理を行った炭素粒子を３０ｇ／Ｌになるように添加し、攪拌して分散させた。 Next, the above oxidation treatment was carried out in a sulfonic acid-based silver plating solution containing sulfonic acid as a complexing agent and having an Ag concentration of 30 g / L (Dyne Silver GPE-PL (matte) manufactured by Daiwa Kasei Co., Ltd.). Carbon particles were added so as to be 30 g / L, and the mixture was stirred and dispersed.
次に、上記のＡｇストライクめっきした素材をカソード、Ａｇ電極板をアノードとして使用して、上記の酸化処理を行った炭素粒子を添加した銀めっき液中において、スターラにより４００ｒｐｍで撹拌しながら、温度２５℃、電流密度３Ａ／ｄｍ２で２５０秒間電気めっきを行い、銀めっき層中に炭素粒子を含有する複合めっき皮膜（Ａｇ−Ｃめっき皮膜）が素材上に形成された複合めっき材を作製した。 Next, using the above-mentioned Ag strike-plated material as a cathode and the Ag electrode plate as an anode, the temperature is set in a silver plating solution to which the above-mentioned oxidation-treated carbon particles are added while stirring at 400 rpm with a stirrer. Electroplating was performed at 25 ° C. and a current density of 3 A / dm 2 for 250 seconds to prepare a composite plating material in which a composite plating film (Ag-C plating film) containing carbon particles in the silver plating layer was formed on the material. ..
この複合めっき材の複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを蛍光Ｘ線膜厚計（株式会社日立ハイテクサイエンス製のＦＴ９４５０）で測定したところ、５μｍであった。 The thickness of the composite plating film (within a diameter of 1.0 mm at the center of the composite plating material) of this composite plating material was measured with a fluorescent X-ray film thickness meter (FT9450 manufactured by Hitachi High-Tech Science Co., Ltd.) and found to be 5 μm.
また、この複合めっき材（素材を含む）から切り出した（５ｍｍ×５ｍｍの大きさで約５ｇの重量の）試料をＡｇおよびＣの分析用にそれぞれ用意し、一方の試料を溶解して試料中の銀含有量（Ｘ重量％）を誘導結合プラズマ発光分光分析装置（ＩＣＰ−ＯＥＳ）（株式会社日立ハイテクサイエンス製のＳＰＳ５１００）によって求めるとともに、他方の試料中の炭素含有量（Ｙ重量％）を微量炭素・硫黄分析装置（株式会社堀場製作所製のＥＭＩＡ−８１０Ｗ）を用いて赤外線吸収法によって求め、複合めっき皮膜中の炭素含有量をＹ／（Ｘ＋Ｙ）として算出したところ、複合めっき皮膜中の炭素含有量は１．５重量％であった。 In addition, a sample (5 mm × 5 mm in size and about 5 g in weight) cut out from this composite plating material (including the material) was prepared for analysis of Ag and C, respectively, and one sample was dissolved in the sample. The silver content (X% by weight) of the sample is determined by an induction coupling plasma emission spectroscopic analyzer (ICP-OES) (SPS5100 manufactured by Hitachi High-Tech Science Co., Ltd.), and the carbon content (Y% by weight) in the other sample is determined. It was determined by the infrared absorption method using a trace carbon / sulfur analyzer (EMIA-810W manufactured by Horiba Seisakusho Co., Ltd.), and the carbon content in the composite plating film was calculated as Y / (X + Y). The carbon content was 1.5% by weight.
また、この複合めっき材から切り出した試験片を平板状試験片（評価試料）とするとともに、４０ｍｍ×１０ｍｍ×０．２ｍｍのＣｕ−Ｎｉ−Ｓｎ−Ｐ合金からなる板材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の板材）（ＤＯＷＡメタルテック株式会社製のＮＢ１０９ＥＨ）にインデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に（後述する比較例２と同様の方法により）２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成された（ビッカース硬さＨＶが１８０の）ＡｇＳｂめっき材をインデント付き試験片（圧子）とし、摺動摩耗試験機（株式会社山崎精機研究所製のＣＲＳ−Ｇ２０５０−ＤＷＡ）により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当てながら、１，０００回の往復摺動動作（摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓ）を行った後、摺動端部の摩耗粉をカーボンテープ（日新ＥＭ株式会社製の幅１２ｍｍのＳＥＭ用カーボン両面テープ）で採取した。この摩耗粉の採取は、カーボンテープを３０ｍｍの長さに切断し、このカーボンテープを、往復摺動動作の往路の終点（一方の摺動端部）に、カーボンテープの長手方向が往復摺動動作の方向に垂直な方向になり且つその一方の摺動端部がカーボンテープの幅と長さのそれぞれの中心になるように貼り付けた後に剥がすことによって行った。このようにして採取された摩耗粉を卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により加速電圧５ｋＶで電子線を照射して倍率５０倍で観察し、これらの摩耗粉のうちのテープ上の摩耗粉の輪郭（卓上電子顕微鏡写真上の摩耗粉の輪郭）に外接する長方形の面積が最小となる長方形の短辺の長さ（短径）が長い方から２０個の摩耗粉を選んで、それぞれの摩耗粉について、短径と、長径（その長方形の長辺の長さ）を測定し、短径に対する長径の比（長径／短径（アスペクト比））を算出した。その結果、摩耗粉の短径の最大値は６４μｍであり、アスペクト比が３．０以上の摩耗粉の数の割合は５０％であった。また、それぞれの摩耗粉について、電子プローブマイクロアナライザ（ＥＰＭＡ）（日本電子株式会社製のＪＸＡ８１００）により加速電圧１５ｋＶで電子線を照射して倍率１０００倍、ビーム径１０μｍで観察し、このＥＰＭＡに付属する波長分散型（ＷＤＳ）Ｘ線分光器により炭素含有量を測定した。その結果、それぞれの摩耗粉中の炭素含有量は１．５〜９．３質量％であった。 Further, the test piece cut out from this composite plating material is used as a flat plate-shaped test piece (evaluation sample), and a plate material (1.0% by mass) made of a Cu—Ni—Sn—P alloy of 40 mm × 10 mm × 0.2 mm. Inner R = 1.0 mm as indent processing on a copper alloy plate containing Ni, 0.9% by mass Sn and 0.05% by mass P, and the balance being Cu) (NB109EH manufactured by DOWA Metal Tech Co., Ltd.) A 20 μm-thick AgSb plating film containing 2% by mass of Sb was formed on the hemispherical embossed material (by the same method as in Comparative Example 2 described later) (Vickers hardness HV is 180). The AgSb plating material is used as an indented test piece (indenter), and the indented test piece is placed on a flat plate-shaped test piece with a constant load of 2N using a sliding wear tester (CRS-G2050-DWA manufactured by Yamazaki Seiki Laboratory Co., Ltd.). After performing 1,000 reciprocating sliding operations (sliding distance 10 mm, sliding speed 3 mm / s) while pressing, carbon tape (width manufactured by Nissin EM Co., Ltd.) is applied to the wear debris at the sliding end. It was collected with a 12 mm SEM carbon double-sided tape). To collect the wear debris, the carbon tape is cut to a length of 30 mm, and the carbon tape is reciprocally slid in the longitudinal direction of the carbon tape at the end point (one sliding end) of the outward path of the reciprocating sliding operation. This was done by sticking the carbon tape so that it was perpendicular to the direction of operation and having one of the sliding ends at the center of the width and length of the carbon tape, and then peeling it off. The wear debris collected in this way is observed by irradiating an electron beam with an acceleration voltage of 5 kV with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Co., Ltd.) at a magnification of 50 times, and on the tape of these wear debris. Select 20 pieces of wear powder from the one with the longest short side length (minor axis) of the rectangle that minimizes the area of the rectangle circumscribing the contour of the wear powder (outline of the wear powder on the tabletop electron micrograph). For each wear debris, the minor axis and the major axis (the length of the long side of the rectangle) were measured, and the ratio of the major axis to the minor axis (major axis / minor axis (aspect ratio)) was calculated. As a result, the maximum value of the minor axis of the wear debris was 64 μm, and the ratio of the number of wear debris having an aspect ratio of 3.0 or more was 50%. In addition, each wear debris was observed by irradiating an electron beam with an electron probe microanalyzer (EPMA) (JXA8100 manufactured by Nippon Denshi Co., Ltd.) at an acceleration voltage of 15 kV at a magnification of 1000 times and a beam diameter of 10 μm, and attached to this EPMA. The carbon content was measured by a wavelength dispersive (WDS) X-ray spectrometer. As a result, the carbon content in each wear powder was 1.5 to 9.3% by mass.
また、この複合めっき材から切り出した試験片を平板状試験片（評価試料）とするとともに、４０ｍｍ×１０ｍｍ×０．２ｍｍのＣｕ−Ｎｉ−Ｓｎ−Ｐ合金からなる板材（１．０質量％のＮｉと０．９質量％のＳｎと０．０５質量％のＰを含み、残部がＣｕである銅合金の板材）（ＤＯＷＡメタルテック株式会社製のＮＢ１０９ＥＨ）にインデント加工として内側Ｒ＝１．０ｍｍの半球状の打ち出し加工をした素材に（後述する比較例２と同様の方法により）２質量％のＳｂを含有する厚さ２０μｍのＡｇＳｂめっき皮膜が形成された（ビッカース硬さＨＶが１８０の）ＡｇＳｂめっき材をインデント付き試験片（圧子）とし、摺動摩耗試験機（株式会社山崎精機研究所製のＣＲＳ−Ｇ２０５０−ＤＷＡ）により、平板状試験片にインデント付き試験片を一定の荷重２Ｎで押し当て（すなわち垂直抗力を２Ｎに保ち）ながら、往復摺動動作（摺動距離１０ｍｍ、摺動速度３ｍｍ／ｓ）を１，０００回継続して、平板状試験片の摩耗状態を確認する摩耗試験を行うことにより、耐摩耗性の評価を行った。その結果、１，０００回の往.復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路の中央部において水平方向にかかる力Ｆを測定し、平板状試験片とインデント付き試験片との間の動摩擦係数（μ）をμ＝Ｆ／Ｎ（Ｎは垂直抗力）から算出したところ、その平均値は０．３７であり、上記の往復摺動動作のうちの最初の往復摺動動作の往路の中央部において水平方向にかかる力Ｆを測定し、平板状試験片とインデント付き試験片との間の動摩擦係数（μ）をμ＝Ｆ／Ｎ（Ｎは垂直抗力）から算出したところ、０．１２であった。 Further, the test piece cut out from this composite plating material is used as a flat plate-shaped test piece (evaluation sample), and a plate material (1.0% by mass) made of a Cu—Ni—Sn—P alloy of 40 mm × 10 mm × 0.2 mm. Inner R = 1.0 mm as indent processing on a copper alloy plate containing Ni, 0.9% by mass Sn and 0.05% by mass P, and the balance being Cu) (NB109EH manufactured by DOWA Metaltech Co., Ltd.) A 20 μm-thick AgSb plating film containing 2% by mass of Sb was formed on the hemispherical embossed material (by the same method as in Comparative Example 2 described later) (Vickers hardness HV is 180). The AgSb plating material is used as an indented test piece (indenter), and the indented test piece is placed on a flat plate-shaped test piece with a constant load of 2N using a sliding wear tester (CRS-G2050-DWA manufactured by Yamazaki Seiki Laboratory Co., Ltd.). While pressing (that is, keeping the vertical drag force at 2N), the reciprocating sliding operation (sliding distance 10 mm, sliding speed 3 mm / s) is continued 1,000 times to check the wear state of the flat plate-shaped test piece. Abrasion resistance was evaluated by conducting a test. As a result, the material was not exposed after 1,000 reciprocating and reciprocating sliding operations, and the force F applied in the horizontal direction at the center of each of the 1,000 reciprocating sliding operations was measured to form a flat plate. The coefficient of dynamic friction (μ) between the test piece and the indented test piece was calculated from μ = F / N (N is the normal force), and the average value was 0.37. The force F applied in the horizontal direction at the center of the outward path of the first reciprocating sliding motion was measured, and the coefficient of dynamic friction (μ) between the flat plate-shaped test piece and the indented test piece was μ = F / N (N). Was calculated from the normal force) and was 0.12.
［実施例２］
複合めっき皮膜を形成する際の電気めっき時間を１２０秒とした以外は、実施例１と同様の方法により、複合めっき皮膜（Ａｇ−Ｃめっき皮膜）が素材上に形成された複合めっき材を作製した。
[Example 2]
A composite plating material in which a composite plating film (Ag-C plating film) is formed on a material is produced by the same method as in Example 1 except that the electroplating time for forming the composite plating film is 120 seconds. did.
この複合めっき材の複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、２μｍであった。また、この複合めっき材の複合めっき皮膜中の炭素含有量を実施例１と同様の方法により算出したところ、０．７重量％であった。また、この複合めっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は９９μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は５５％、摩耗粉中の炭素含有量は１．４〜１１．８質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数の平均値と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ０．２５および０．０８であった。 The thickness of the composite plating film (within a diameter of 1.0 mm at the center of the composite plating material) of this composite plating material was measured by the same method as in Example 1 and found to be 2 μm. Moreover, when the carbon content in the composite plating film of this composite plating material was calculated by the same method as in Example 1, it was 0.7% by weight. Further, the maximum value of the minor axis of the wear debris of this composite plating material, the ratio of the number of the wear debris having an aspect ratio of 3.0 or more, and the carbon content in the wear debris are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the wear debris is 99 μm, the ratio of the number of wear debris with an aspect ratio of 3.0 or more is 55%, and the carbon content in the wear debris is 1.4 to 11.8 mass%. there were. In addition, the material was not exposed after 1,000 reciprocating sliding movements, and the average value of the friction coefficient in each outbound route of 1,000 reciprocating sliding movements and the friction coefficient in the outbound route of the first reciprocating sliding movement. Was calculated by the same method as in Example 1 and found to be 0.25 and 0.08, respectively.
［実施例３］
複合めっき皮膜を形成する際の電気めっき時間を５００秒とした以外は、実施例１と同様の方法により、複合めっき皮膜（Ａｇ−Ｃめっき皮膜）が素材上に形成された複合めっき材を作製した。
[Example 3]
A composite plating material in which a composite plating film (Ag-C plating film) is formed on a material is produced by the same method as in Example 1 except that the electroplating time for forming the composite plating film is 500 seconds. did.
この複合めっき材の複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、１０μｍであった。また、この複合めっき材の複合めっき皮膜中の炭素含有量を実施例１と同様の方法により算出したところ、２．１重量％であった。また、この複合めっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は６０μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は５５％、摩耗粉中の炭素含有量は４．６〜２１．２質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数の平均値と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ０．３２および０．１８であった。 The thickness of the composite plating film (within a diameter of 1.0 mm at the center of the composite plating material) of this composite plating material was measured by the same method as in Example 1 and found to be 10 μm. Moreover, when the carbon content in the composite plating film of this composite plating material was calculated by the same method as in Example 1, it was 2.1% by weight. Further, the maximum value of the minor axis of the wear debris of this composite plating material, the ratio of the number of the wear debris having an aspect ratio of 3.0 or more, and the carbon content in the wear debris are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the wear debris is 60 μm, the ratio of the number of wear debris with an aspect ratio of 3.0 or more is 55%, and the carbon content in the wear debris is 4.6 to 21.2 mass%. there were. In addition, the material was not exposed after 1,000 reciprocating sliding movements, and the average value of the friction coefficient in each outbound route of 1,000 reciprocating sliding movements and the friction coefficient in the outbound route of the first reciprocating sliding movement. Was calculated by the same method as in Example 1 and found to be 0.32 and 0.18, respectively.
［実施例４］
素材をカソード、Ｎｉ電極板をアノードとして使用して、８０ｇ／Ｌのスルファミン酸ニッケルと４５ｇ／Ｌのホウ酸からなるニッケルめっき浴中において、液温５５℃、電流密度４Ａ／ｄｍ２で攪拌しながら３０秒間電気めっき（Ｎｉめっき）を行って、素材上に厚さ０．５μｍのＮｉめっき皮膜を形成した後に、Ａｇストライクめっきを行い、複合めっき被膜を形成する際の電気めっき時間を２５０秒とした以外は、実施例３と同様の方法により、複合めっき皮膜（Ａｇ−Ｃめっき皮膜）が素材上に形成された複合めっき材を作製した。
[Example 4]
Using the material as the cathode and the Ni electrode plate as the anode, the mixture was stirred in a nickel plating bath consisting of 80 g / L nickel sulfamate and 45 g / L boric acid at a liquid temperature of 55 ° C. and a current density of 4 A / dm 2. While electroplating (Ni plating) for 30 seconds, a Ni plating film with a thickness of 0.5 μm is formed on the material, and then Ag strike plating is performed, and the electroplating time for forming the composite plating film is 250 seconds. A composite plating material in which a composite plating film (Ag—C plating film) was formed on the material was produced by the same method as in Example 3.
この複合めっき材の複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、５μｍであった。また、この複合めっき材の複合めっき皮膜中の炭素含有量を実施例１と同様の方法により算出したところ、１．５重量％であった。また、この複合めっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は６４μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は５０％、摩耗粉中の炭素含有量は１．５〜９．３質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数の平均値と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ０．３５および０．１２であった。 The thickness of the composite plating film (within a diameter of 1.0 mm at the center of the composite plating material) of this composite plating material was measured by the same method as in Example 1 and found to be 5 μm. Moreover, when the carbon content in the composite plating film of this composite plating material was calculated by the same method as in Example 1, it was 1.5% by weight. Further, the maximum value of the minor axis of the wear debris of this composite plating material, the ratio of the number of the wear debris having an aspect ratio of 3.0 or more, and the carbon content in the wear debris are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the wear debris is 64 μm, the ratio of the number of wear debris with an aspect ratio of 3.0 or more is 50%, and the carbon content in the wear debris is 1.5 to 9.3 mass%. there were. In addition, the material was not exposed after 1,000 reciprocating sliding movements, and the average value of the friction coefficient in each outbound route of 1,000 reciprocating sliding movements and the friction coefficient in the outbound route of the first reciprocating sliding movement. Was calculated by the same method as in Example 1 and found to be 0.35 and 0.12, respectively.
［比較例１］
実施例１と同様の方法により、Ａｇストライクめっきを行った後に、炭素粒子を添加しない銀めっき液を使用して電気めっき時間を１，０００秒とした以外は、実施例３と同様の方法により、Ａｇめっき皮膜が素材上に形成されたＡｇめっき材を作製した。
[Comparative Example 1]
By the same method as in Example 1, after performing Ag strike plating, the electroplating time was set to 1,000 seconds using a silver plating solution to which carbon particles were not added. , An Ag plating material having an Ag plating film formed on the material was produced.
このＡｇめっき材のＡｇめっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、２０μｍであった。また、このＡｇめっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は２８０μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は５％、摩耗粉中の炭素含有量は０．８質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数の平均値と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ１．５７および５．６であった。 The thickness of the Ag plating film (within a diameter of 1.0 mm at the center of the central portion) of the Ag plating material was measured by the same method as in Example 1 and found to be 20 μm. Further, the maximum value of the minor axis of the wear debris of this Ag plating material, the ratio of the number of the wear debris having an aspect ratio of 3.0 or more, and the carbon content in the wear debris are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the wear debris was 280 μm, the ratio of the number of wear debris having an aspect ratio of 3.0 or more was 5%, and the carbon content in the wear debris was 0.8% by mass. In addition, the material was not exposed after 1,000 reciprocating sliding movements, and the average value of the friction coefficient in each outbound route of 1,000 reciprocating sliding movements and the friction coefficient in the outbound route of the first reciprocating sliding movement. Was calculated by the same method as in Example 1 and found to be 1.57 and 5.6, respectively.
［比較例２］
３ｇ／Ｌのシアン化銀カリウムと９０ｇ／Ｌのシアン化カリウムを含むシアン系Ａｇストライクめっき液を使用して、電流密度５Ａ／ｄｍ２で３０秒間電気めっきを行った以外は、実施例１と同様の方法により、Ａｇストライクめっきを行い、シアン化銀とシアン化ナトリウムとアンチモンと６０ｇ／ＬのＡｇを含むＡｇ濃度６０ｇ／Ｌのシアン系ＡｇＳｂめっき液（日進化成株式会社製）を使用して、このシアン系ＡｇＳｂめっき液に炭素粒子を添加しないで、電流密度１Ａ／ｄｍ２で２，４００秒間電気めっきを行った以外は、実施例１と同様の方法により、ＡｇＳｂめっき皮膜が素材上に形成されたＡｇＳｂめっき材を作製した。このＡｇＳｂめっき材のＡｇＳｂめっき皮膜を卓上電子顕微鏡（株式会社日立ハイテクノロジーズ製のＴＭ４０００Ｐｌｕｓ）により加速電圧１５ｋＶで電子線を照射して倍率１０００倍で観察し、この卓上電子顕微鏡に付属するエネルギー分散型Ｘ線分析装置（ＥＤＸ）（Ｏｘｆｏｒｄ社製のＡＺｔｅｃ Ｏｎｅ）により、ＡｇＳｂめっき皮膜中のＳｂ含有量を求めたところ、２質量％であった。
[Comparative Example 2]
Same as Example 1 except that electroplating was performed at a current density of 5 A / dm 2 for 30 seconds using a cyanide Ag strike plating solution containing 3 g / L of silver potassium cyanide and 90 g / L of potassium cyanide. By the method, Ag strike plating is performed, and a cyanide AgSb plating solution (manufactured by Nikkei Seisei Co., Ltd.) containing silver cyanide, sodium cyanide, antimony, and 60 g / L Ag at an Ag concentration of 60 g / L is used. An AgSb plating film was formed on the material by the same method as in Example 1 except that electroplating was performed at a current density of 1 A / dm 2 for 2,400 seconds without adding carbon particles to this cyanide AgSb plating solution. The AgSb plating material was prepared. The AgSb plating film of this AgSb plating material is irradiated with an electron beam at an acceleration voltage of 15 kV with a desktop electron microscope (TM4000Plus manufactured by Hitachi High-Technologies Corporation) and observed at a magnification of 1000 times. The Sb content in the AgSb plating film was determined by an X-ray analyzer (EDX) (AZtec One manufactured by Oxford) and found to be 2% by mass.
このＡｇＳｂめっき材のＡｇＳｂめっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、２０μｍであった。また、このＡｇＳｂめっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は２１６μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は０％、摩耗粉中の炭素含有量は０．７質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ１．３７および０．１２であった。 The thickness of the AgSb plating film (within a diameter of 1.0 mm at the center of the central portion) of the AgSb plating material was measured by the same method as in Example 1 and found to be 20 μm. Further, the maximum value of the minor axis of the wear powder of this AgSb plating material, the ratio of the number of wear powders having an aspect ratio of 3.0 or more, and the carbon content in the wear powder are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the wear debris was 216 μm, the ratio of the number of wear debris having an aspect ratio of 3.0 or more was 0%, and the carbon content in the wear debris was 0.7 mass%. Further, the material is not exposed after 1,000 reciprocating sliding operations, and the friction coefficient in each outward path of 1,000 reciprocating sliding operations and the friction coefficient in the outward path of the first reciprocating sliding operation are shown in Examples. When calculated by the same method as in 1, it was 1.37 and 0.12, respectively.
［比較例３］
比較例２と同様の方法により、Ａｇストライクめっきを行い、シアン化銀カリウム（ＫＡｇ（ＣＮ）２）とシアン化カリウム（ＫＣＮ）とセレノシアン酸カリウム（ＫＳｅＣＮ）とを含む水溶液からなるシアン系銀めっき液に、実施例１と同様の酸化処理を行った炭素粒子（鱗片状黒鉛粒子）を添加して、８０ｇ／Ｌの炭素粒子と８０ｇ／ＬのＡｇを含むシアン系銀めっき液を用意し、このシアン系銀めっき液を使用し、電流密度を３Ａ／ｄｍ２とし、電気めっき時間を２５０秒間とした以外は、実施例１と同様の方法により、複合めっき皮膜（Ａｇ−Ｃめっき皮膜）が素材上に形成された複合めっき材を作製した。
[Comparative Example 3]
Ag strike plating is performed by the same method as in Comparative Example 2 to prepare a cyanide silver plating solution consisting of an aqueous solution containing potassium cyanide (KAg (CN) 2 ), potassium cyanide (KCN), and potassium selenocyanate (KSeCN). , Carbon particles (scaly graphite particles) subjected to the same oxidation treatment as in Example 1 were added to prepare a cyanide silver plating solution containing 80 g / L of carbon particles and 80 g / L of Ag, and this cyanide was prepared. A composite plating film (Ag-C plating film) was applied on the material by the same method as in Example 1 except that a silver-based plating solution was used, the current density was 3 A / dm 2, and the electroplating time was 250 seconds. A composite plating material formed in 1 was produced.
この複合めっき材の複合めっき皮膜（の中央部分の直径１．０ｍｍの範囲）の厚さを実施例１と同様の方法により測定したところ、５μｍであった。また、この複合めっき材の複合めっき皮膜中の炭素含有量を実施例１と同様の方法により算出したところ、１．５重量％であった。また、この複合めっき材の摩耗粉の短径の最大値と、アスペクト比が３．０以上の摩耗粉の数の割合と、摩耗粉中の炭素含有量を実施例１と同様の方法により求めたところ、摩耗粉の短径の最大値は１２０μｍ、アスペクト比が３．０以上の摩耗粉の数の割合は２０％、摩耗粉中の炭素含有量は１．５〜６．０質量％であった。また、１，０００回の往復摺動動作後に素材の露出はなく、１，０００回の往復摺動動作の各々の往路における摩擦係数と、最初の往復摺動動作の往路における摩擦係数を実施例１と同様の方法により算出したところ、それぞれ０．９５および０．２４であった。 The thickness of the composite plating film (within a diameter of 1.0 mm at the center of the composite plating material) of this composite plating material was measured by the same method as in Example 1 and found to be 5 μm. Moreover, when the carbon content in the composite plating film of this composite plating material was calculated by the same method as in Example 1, it was 1.5% by weight. Further, the maximum value of the minor axis of the wear debris of this composite plating material, the ratio of the number of the wear debris having an aspect ratio of 3.0 or more, and the carbon content in the wear debris are determined by the same method as in Example 1. As a result, the maximum value of the minor axis of the abrasion powder is 120 μm, the ratio of the number of abrasion powders having an aspect ratio of 3.0 or more is 20%, and the carbon content in the abrasion powder is 1.5 to 6.0% by mass. there were. Further, the material is not exposed after 1,000 reciprocating sliding operations, and the friction coefficient in each outward path of 1,000 reciprocating sliding operations and the friction coefficient in the outward path of the first reciprocating sliding operation are shown in Examples. When calculated by the same method as in 1, it was 0.95 and 0.24, respectively.
これらの実施例および比較例のめっき材の製造条件および特性を表１〜表３に示す。また、実施例１と比較例２の複合めっき材の摺動磨耗試験後の摩耗粉の５０倍の卓上電子顕微鏡写真をそれぞれ図１および図２に示す。 Tables 1 to 3 show the production conditions and characteristics of the plating materials of these Examples and Comparative Examples. Further, FIG. 1 and FIG. 2 show tabletop electron micrographs of the composite plating materials of Example 1 and Comparative Example 2 which are 50 times as much as the wear powder after the sliding wear test.
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