JP7470321B2 - Sn-graphene composite plating film metal terminal and its manufacturing method - Google Patents
Sn-graphene composite plating film metal terminal and its manufacturing method Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims description 149
- 238000007747 plating Methods 0.000 title claims description 148
- 239000002131 composite material Substances 0.000 title claims description 72
- 229910052751 metal Inorganic materials 0.000 title claims description 33
- 239000002184 metal Substances 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 103
- 239000000463 material Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 15
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 8
- 238000009713 electroplating Methods 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 32
- 238000005259 measurement Methods 0.000 description 21
- 239000000758 substrate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001237 Raman spectrum Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 8
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 8
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 241000150258 Prospect Hill orthohantavirus Species 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 4
- 229920000218 poly(hydroxyvalerate) Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000002733 tin-carbon composite material Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001652 electrophoretic deposition Methods 0.000 description 2
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000007542 hardness measurement Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000007888 film coating Substances 0.000 description 1
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- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000013074 reference sample Substances 0.000 description 1
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- 239000000523 sample Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
- Manufacturing Of Electrical Connectors (AREA)
Description
本発明は、Ｓｎ－グラフェン複合めっき膜金属製端子とその製造方法に関する。 The present invention relates to a metal terminal made of Sn-graphene composite plating film and a method for manufacturing the same.
従来から、車載電装部材であるワイヤーハーネスの端子材料には、約９割が銅合金表面に錫（Ｓｎ、スズ）膜を被覆したＳｎめっき材、約１割が金（Ａｕ），パラジウム（Ｐｄ）のような貴金属めっき材が用いられている。
また、ＥＶ／ＰＨＶ用充電装置の端子電極材料として、すべでの金属の中に導電性が最も高い貴金属純銀（Ａｇ）めっき材の使用が進めているが、全ての端子材を貴金属であるＡｇめっきにするのは、コスト上および資源上に現実的に不可能である。一方、グラフェンは銀よりも導電性が高く、優れた潤滑性と熱安定性を有することが知られている。しかし、グラフェンは単体での使用ができないため、ほかの材料に複合させるしかない。また、通常の市販のグラフェン粉末は、殆ど酸化グラフェンが主体となり、水溶液中に分散しにくいので、作業と製造コストなどで実用に困難である。
Conventionally, about 90% of terminal materials for wire harnesses, which are in-vehicle electrical components, are Sn-plated materials in which a tin (Sn) film is coated on the surface of a copper alloy, and about 10% are precious metal-plated materials such as gold (Au) and palladium (Pd).
In addition, the use of precious metal pure silver (Ag) plating materials, which have the highest electrical conductivity of all metals, is being promoted as the terminal electrode material for charging devices for EVs/PHVs. However, it is practically impossible to plate all terminal materials with Ag, which is a precious metal, in terms of cost and resources. On the other hand, graphene is known to have higher electrical conductivity than silver and excellent lubricity and thermal stability. However, graphene cannot be used alone, so it must be combined with other materials. In addition, most commercially available graphene powders are mainly graphene oxide, which is difficult to disperse in aqueous solutions, making it difficult to put into practical use due to the work and manufacturing costs.
現行の一般端子としたＳｎめっき材は、低コストではんだ濡れ性や加工性が優れるが、Ｓｎ金属が融点は低く極めて軟質（２０－５０Ｈｖ）であるため、耐熱性と耐摩耗性が低いといった課題がある。そして、耐摩耗性を向上させるため、固体潤滑剤である黒鉛粉末や二硫化モリブデン、テフロン（登録商標）粒子など非金属材料との複合化に関する研究が報告されたが、いずれ耐摩耗性の改善効果が低く、加えて導電性の低下を招いていた。 The Sn-plated materials currently used for general terminals are low cost and have excellent solder wettability and workability, but because Sn metal has a low melting point and is extremely soft (20-50 Hv), it has issues such as low heat resistance and wear resistance. To improve wear resistance, research has been reported on combining it with non-metallic materials such as solid lubricants such as graphite powder, molybdenum disulfide, and Teflon (registered trademark) particles, but all of these have only a small effect on improving wear resistance and also result in a decrease in conductivity.
特許文献１には、基体上に、カーボンナノチューブ、フラーレン及び／又はグラフェン含有コーティングを製造方法について記載されているが、スズを含有するグラフェン等の具体的構造については記載がない。 Patent Document 1 describes a method for producing a coating containing carbon nanotubes, fullerenes, and/or graphene on a substrate, but does not describe the specific structure of tin-containing graphene, etc.
しかしながら、上述のようなめっき材では自動車の電子制御が高度化に対応したワイヤーハーネスの高性能化・高耐久性化や、ＥＶ／ＰＨＶの更なる拡大に対応する充電装置の端子の高性能化、高耐久性化には不十分であるといった問題があった。そこで本発明は、低コスト且つ耐摩耗性、耐熱性の向上を実現する金属製端子を提供することを目的とする。 However, there is a problem in that the plating materials described above are insufficient for improving the performance and durability of wire harnesses to accommodate the increasingly sophisticated electronic controls in automobiles, or for improving the performance and durability of charging device terminals to accommodate the further expansion of EVs/PHVs. Therefore, the object of the present invention is to provide a metal terminal that is low cost and has improved abrasion resistance and heat resistance.
上記課題を解決する本発明は以下の通りである。
（１）電気接続用（または通電用）の金属製端子材と、前記金属製端子材の表面をめっきしたＳｎ－グラフェン複合めっき膜と、を備えることを特徴とするＳｎ－グラフェン複合めっき膜金属製端子である。
「金属製端子材の表面をめっきしたＳｎ－グラフェン複合めっき膜」とは、Ｓｎ－グラフェン複合めっき膜が、金属製端子材の表面の少なくても一部分をめっき（被覆）した状態を含む。
（２）前記Ｓｎ－グラフェン複合めっき膜は、Ｓｎ層と、前記Ｓｎ層中に分散した、前記Ｓｎが積層型グラフェンに分散したＳｎ分散積層型グラフェンと、を含むことを特徴とする（１）に記載のＳｎ－グラフェン複合めっき膜金属製端子である。
「Ｓｎ分散積層型グラフェン」について、その「グラフェン」がグラフェンシートである場合には、そのグラフェンシートがＳｎ（片）ナノ結晶を分散して含んだり、Ｓｎ（片）ナノ結晶を含んだグラフェンがＳｎ－グラフェン粒子となったりする場合を含むことを意味する。
（３）前記Ｓｎ－グラフェン複合めっき膜中の前記Ｓｎ分散積層型グラフェン濃度は、１０～８０体積％であることを特徴とする（２）に記載のＳｎ－グラフェン複合めっき膜金属製端子である。
（４）前記Ｓｎ分散積層型グラフェン中のＳｎ濃度は、５～９５質量％であることを特徴とする（２）又は（３）の何れか１つに記載のＳｎ－グラフェン複合めっき膜金属製端子である。
（５）前記金属製端子の材質は銅又は銅合金を含むことを特徴とする（１）～（４）の何れか１つに記載のＳｎ－グラフェン複合めっき膜金属製端子である。
金属製端子基材の材質が銅又は銅合金を含むことが好ましいのは、銅又は銅合金は高導電性と高強度であり、自動車端子・電子部品の電気接続材料として広く使用されているためである。また、導電性の金属材料であれば、アルミ合金や鉄鋼材料などでもよい。
（６）前記グラフェンの粒子を製造するためにグラファイトから剥離した積層型グラフェンフレークを製造するグラフェン製造工程と、製造された前記積層型グラフェンフレークを含むＳｎめっき浴を用いたグラフェン粒子の泳動電着Ｓｎの電気めっきを同時に行うハイブリッドめっき工程と、を含み、前記電気めっきの条件は、電流密度が０．１～１０Ａ／ｄｍ２、めっき浴の温度が５～３０℃であることを特徴とするＳｎ－グラフェン複合めっき膜金属製端子の製造方法である。
（７）前記めっき浴は工業用硫酸浴、スルホン酸浴又はアルカリ浴であることを特徴とする（６）に記載のＳｎ－グラフェン複合めっき膜金属製端子の製造方法である。
The present invention that solves the above problems is as follows.
(1) A Sn-graphene composite plating film metal terminal comprising: a metal terminal material for electrical connection (or for current flow); and a Sn-graphene composite plating film formed by plating a surface of the metal terminal material.
The term "Sn-graphene composite plating film plated on the surface of a metal terminal material" includes a state in which at least a portion of the surface of a metal terminal material is plated (covered) with the Sn-graphene composite plating film.
(2) The Sn-graphene composite plating film metal terminal according to (1), wherein the Sn-graphene composite plating film includes an Sn layer, and Sn-dispersed laminated graphene in which the Sn is dispersed in the Sn layer.
Regarding "Sn-dispersed laminated graphene," when the "graphene" is a graphene sheet, it means that the graphene sheet contains dispersed Sn (flake) nanocrystals, and the graphene containing Sn (flake) nanocrystals becomes Sn-graphene particles.
(3) The Sn-graphene composite plating film metal terminal according to (2), wherein a concentration of the Sn-dispersed laminated graphene in the Sn-graphene composite plating film is 10 to 80 volume %.
(4) The Sn-graphene composite plating film metal terminal according to any one of (2) or (3), characterized in that a Sn concentration in the Sn-dispersed laminated graphene is 5 to 95 mass %.
(5) The Sn-graphene composite plating film metal terminal according to any one of (1) to (4), wherein the material of the metal terminal contains copper or a copper alloy.
The reason why the material of the metal terminal substrate preferably contains copper or a copper alloy is that copper or a copper alloy has high electrical conductivity and high strength and is widely used as an electrical connection material for automobile terminals and electronic components. Also, any conductive metal material such as aluminum alloy or steel material may be used.
(6) A method for producing a metal terminal having a Sn-graphene composite plating film, comprising: a graphene production step of producing stacked graphene flakes peeled from graphite in order to produce the graphene particles; and a hybrid plating step of simultaneously performing electroplating of Sn by electrophoretic electrodeposition of the graphene particles using a Sn plating bath containing the produced stacked graphene flakes, wherein the electroplating conditions are a current density of 0.1 to 10 A/ dm2 and a plating bath temperature of 5 to 30°C.
(7) The method for producing a Sn-graphene composite plating film metal terminal according to (6), wherein the plating bath is an industrial sulfuric acid bath, a sulfonic acid bath, or an alkaline bath.
本発明によれば、高性能化・高耐久性化したワイヤーハーネスやＥＶ／ＰＨＶに対応する充電装置の端子の高性能化、高耐久性化に応じた低コスト且つ耐摩耗性、耐熱性の向上を実現する金属製端子を提供することができる。 The present invention can provide metal terminals that are low cost and have improved wear resistance and heat resistance in response to the high performance and durability of wire harnesses and terminals of charging devices compatible with EVs/PHVs.
以下、図面を参照しつつ本発明の実施の形態について説明する。本発明は、以下の実施形態に限定されるものではなく、発明の範囲を逸脱しない限りにおいて、変更、修正、改良を加え得るものである。 The following describes an embodiment of the present invention with reference to the drawings. The present invention is not limited to the following embodiment, and may be changed, modified, or improved without departing from the scope of the invention.
図１には、金属合金基材２の表面が、Ｓｎ－グラフェン複合めっき膜８によりめっきされた、Ｓｎ－グラフェン複合めっき膜金属製端子１の断面の模式図を示した。Ｓｎ－グラフェン複合めっき膜８は、Ｓｎ層６と、Ｓｎ層６中に分散した、Ｓｎ（錫、スズ）４が積層型グラフェン３に分散した団子状なＳｎ分散積層型グラフェン５とシート状のグラフェンフレーク７、を含む。積層型グラフェン３に分散したＳｎ４は、Ｓｎのいわば極小片（ナノ結晶）として分散している。団子状な積層型グラフェン３とシート状のグラフェンフレーク７は電解剥離工程により作製したグラフェンは例えば積層して形成されたものであり、めっき液中での分散状態による異なる集合体である。一方、Ｓｎ分散積層型グラフェン５の生成は、団子状な積層型グラフェン３は純Ｓｎより導電しやすく、また表面エネルギーが大きいので、めっきにおけるＳｎ結晶の核形成過程は成長過程より速いためであると考えられる。 Figure 1 shows a schematic diagram of a cross section of a metal terminal 1 made of a Sn-graphene composite plating film, in which the surface of a metal alloy substrate 2 is plated with a Sn-graphene composite plating film 8. The Sn-graphene composite plating film 8 includes a Sn layer 6, a dumpling-shaped Sn-dispersed stacked graphene 5 in which Sn (tin) 4 is dispersed in the stacked graphene 3, and a sheet-shaped graphene flake 7. The Sn 4 dispersed in the stacked graphene 3 is dispersed as so-called very small pieces (nanocrystals) of Sn. The dumpling-shaped stacked graphene 3 and the sheet-shaped graphene flakes 7 are different aggregates depending on the dispersion state in the plating solution, and the dumpling-shaped stacked graphene 3 and the sheet-shaped graphene flakes 7 are formed by stacking graphene produced by an electrolytic peeling process, for example. On the other hand, the generation of the Sn-dispersed stacked graphene 5 is thought to be due to the fact that the dumpling-shaped stacked graphene 3 is more conductive than pure Sn and has a large surface energy, so the nucleation process of Sn crystals in plating is faster than the growth process.
Ｓｎ－グラフェン複合めっき膜８中のＳｎ分散積層型グラフェン５の濃度は、端子として嵌合する際の凝着を抑制し、耐摩耗性を向上する同時に、めっき膜の導電性を保持する観点から、１０～８０体積％が好ましく、２０～６０体積％がさらに好ましい。
Ｓｎ－グラフェン複合めっき膜７は、さらに積層型でないグラフェンシート（Ｓｎ分散積層型グラフェン７）を含んでもよい。めっき層全体の耐摩耗性を向上するためである。Ｓｎ－グラフェン複合めっき膜７に含まれる積層型でないグラフェン濃度は、２～５０質量％が好ましく、５～３０質量％がさらに好ましい。
The concentration of Sn-dispersed laminated graphene 5 in the Sn-graphene composite plating film 8 is preferably 10 to 80% by volume, and more preferably 20 to 60% by volume, from the viewpoints of suppressing adhesion when fitting as a terminal and improving wear resistance, while at the same time maintaining the conductivity of the plating film.
The Sn-graphene composite plating film 7 may further include a non-laminated graphene sheet (Sn-dispersed laminated graphene 7) in order to improve the wear resistance of the entire plating layer. The concentration of the non-laminated graphene contained in the Sn-graphene composite plating film 7 is preferably 2 to 50 mass %, more preferably 5 to 30 mass %.
金属合金基材２としてはアルミ合金、鉄―ニッケル合金（例えば４２アロイ）、ＳＵＳ類材料等を使用することができるが、端子全体の導電性の観点からＣｕ（銅）又はＣｕ（銅）合金が好ましい。
Ｓｎ－グラフェン複合めっき膜の作製には、Ｓｎの電気めっきとグラフェン（Ｇｒａｐｈｅｎｅ）粒子の泳動電着とを組み合わせたハイブリッドめっき法を利用することができる。なお、グラフェン粒子とは、グラフェンシートを数枚～数十枚で積層して団子状またフレーク状として存在することである。
The metal alloy substrate 2 may be made of an aluminum alloy, an iron-nickel alloy (eg, 42 alloy), or a stainless steel material, but is preferably made of Cu (copper) or a Cu (copper) alloy in terms of electrical conductivity of the entire terminal.
The Sn-graphene composite plating film can be produced by a hybrid plating method that combines electroplating of Sn with electrophoretic deposition of graphene particles. Note that graphene particles are graphene sheets that are stacked in a ball or flake shape with several to several tens of sheets.
（Ｓｎ－グラフェン複合めっき膜の作製）
Ｃｕ合金板（２０×５０×０．２ｍｍ）を基材（金属製端子材）とし、前処理としてアルカリ電解脱脂および酸洗いを行った。ハイブリッドめっきは、硫酸系光沢Ｓｎめっき浴を基本液とし、電解剥離したグラフェン分散液を１５ｍｌ／Ｌ添加しためっき液を用い、ハイブリッド電気めっき法によりＳｎ－グラフェン複合めっき膜を作製した。
すなわちハイブリッドめっきは、グラフェン分散液に含まれる、電解剥離したグラフェンの粒子を泳動電着する過程と、Ｓｎによって金属製端子材の電気めっきを行う過程と、を含む。Ｓｎによる電気めっき条件の要素としては、電流密度、めっき浴の液温、（撹拌）、めっき時間等を考慮した。
(Preparation of Sn-graphene composite plating film)
A Cu alloy plate (20 × 50 × 0.2 mm) was used as a substrate (metal terminal material), and alkaline electrolytic degreasing and pickling were performed as pretreatment. For hybrid plating, a plating solution was used in which a sulfuric acid-based gloss Sn plating bath was used as a base solution and 15 ml/L of electrolytically peeled graphene dispersion was added, and a Sn-graphene composite plating film was produced by a hybrid electroplating method.
That is, the hybrid plating includes a process of electrophoretic deposition of the electrolytically peeled graphene particles contained in the graphene dispersion, and a process of electroplating the metal terminal material with Sn. As factors of the electroplating conditions with Sn, the current density, the liquid temperature of the plating bath, (stirring), plating time, etc. were considered.
Ｃｕ合金基材に対する前処理として、アルカリ電解脱脂と酸洗いを行ったが、処理条件は特に規定しない。一方、電解剥離は次のようにして行った。グラファイトを水溶液中に浸漬し、強力の電場作用および電気化学反応によりグラファイトを層状に分解し、積層型のグラフェンフレークを作製した。 As pretreatment for the Cu alloy substrate, alkaline electrolytic degreasing and pickling were performed, but the treatment conditions were not specified. On the other hand, electrolytic stripping was performed as follows. Graphite was immersed in an aqueous solution, and the graphite was decomposed into layers by the action of a strong electric field and an electrochemical reaction, producing stacked graphene flakes.
めっき条件の電流密度、液温、めっき時間を次のようにして、Ｃｕ合金板上にＳｎ－グラフェン複合めっき膜（実施例１～６）を作製した。電流密度０．１Ａ／ｄｍ２、液温５℃、３０ｍｉｎ（実施例１）、電流密度０．５Ａ／ｄｍ２、液温１０℃、１５ｍｉｎ（実施例２）、電流密度０．１Ａ／ｄｍ２、液温１０℃、１０ｍｉｎ（実施例３）、電流密度１．０Ａ／ｄｍ２、液温１５℃、１０ｍｉｎ（実施例４）、電流密度０．１Ａ／ｄｍ２、液温１０℃、２０ｍｉｎ（実施例５）、電流密度０．５Ａ／ｄｍ２、液温５℃、３０ｍｉｎ（実施例６）、電流密度１．０Ａ／ｄｍ２、液温５℃、２０ｍｉｎ（実施例７）、電流密度１Ａ／ｄｍ２、液温１０℃、めっき時間１０ｍｉｎ（実施例８）。
一方、Ｓｎ－グラフェン複合めっき膜の作製において、グラフェン分散液を添加ないめっき液を用い、電流密度１．０Ａ／ｄｍ２、液温１０℃でＳｎ（純Ｓｎ）めっき膜（比較例１）を作製した。
純Ｓｎめっきは光沢のある平滑な膜が得られた一方、Ｓｎ－グラフェン複合めっきは半光沢で凹凸のある膜が得られた。
The plating conditions of current density, solution temperature, and plating time were as follows, and Sn-graphene composite plating films (Examples 1 to 6) were produced on Cu alloy plates. Current density 0.1 A/ dm2 , liquid temperature 5°C, 30 min (Example 1), current density 0.5 A/ dm2 , liquid temperature 10°C, 15 min (Example 2), current density 0.1 A/ dm2 , liquid temperature 10°C, 10 min (Example 3), current density 1.0 A/ dm2 , liquid temperature 15°C, 10 min (Example 4), current density 0.1 A/ dm2 , liquid temperature 10°C, 20 min (Example 5), current density 0.5 A/ dm2 , liquid temperature 5°C, 30 min (Example 6), current density 1.0 A/ dm2 , liquid temperature 5°C, 20 min (Example 7), current density 1 A/ dm2 , liquid temperature 10°C, plating time 10 min (Example 8).
On the other hand, in the preparation of the Sn-graphene composite plating film, a plating solution containing no graphene dispersion was used, and a Sn (pure Sn) plating film (Comparative Example 1) was prepared at a current density of 1.0 A/dm 2 and a solution temperature of 10°C.
Pure Sn plating produced a glossy, smooth film, while Sn-graphene composite plating produced a semi-glossy, uneven film.
図２には、電流密度０．１Ａ／ｄｍ２、液温５℃、めっき時間３０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例１）の表面のＦＥ－ＳＥＭを、（ａ）×１Ｋ、（ｂ）×５Ｋ、（ｃ）×１０Ｋ、（ｄ）×３０Ｋ、（ｅ）×５０Ｋのそれぞれの倍率で示した。
図２（ａ）から、Ｓｎ（Ｓｎ膜）でめっき（被覆）されたＣｕ合金板１２の表面上に、Ｓｎ分散積層型グラフェン１５が存在していたことが分かった。（ｄ）から、Ｓｎ分散積層型グラフェン１５には、グラフェン（グラフェンシート）１３が含まれていたことが分かった。そして、（ｅ）から、Ｓｎ（１４、１４´、１４´´等）がグラフェン（グラフェンシート）１３に分散していたことが分かった。
なお、ＦＥ－ＳＥＭ観察と、後出するエネルギー分散型Ｘ線分析（ＥＤＳ）の分析条件は次のようであった。装置名：電界放出型走査電子顕微鏡（ＦＥ－ＳＥＭ、日本電子／ＪＸＡ－８２３０）、加速電圧７．０ｋＶであった。エネルギー分散型Ｘ線分析（ＥＤＳ）では、面分析を行った。また、面分析の際に写真の全面または示された領域で分析した。
FIG. 2 shows FE-SEM images of the surface of the Sn-graphene composite plating film (Example 1) produced at a current density of 0.1 A/dm 2 , a solution temperature of 5° C., and a plating time of 30 min, at magnifications of (a) ×1K, (b) ×5K, (c) ×10K, (d) ×30K, and (e) ×50K.
2(a) shows that Sn-dispersed stacked graphene 15 was present on the surface of Cu alloy plate 12 plated (coated) with Sn (Sn film). (d) shows that graphene (graphene sheet) 13 was included in Sn-dispersed stacked graphene 15. (e) shows that Sn (14, 14', 14'', etc.) was dispersed in graphene (graphene sheet) 13.
The analysis conditions for FE-SEM observation and energy dispersive X-ray analysis (EDS) described later were as follows: Instrument name: Field emission scanning electron microscope (FE-SEM, JEOL/JXA-8230), acceleration voltage was 7.0 kV. In energy dispersive X-ray analysis (EDS), area analysis was performed. In addition, the area analysis was performed over the entire surface or the indicated area of the photograph.
図３には、電流密度０．５Ａ／ｄｍ２、液温１０℃、めっき時間１５ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例２）の表面のＦＥ－ＳＥＭを、（ａ）×１Ｋ、（ｂ）×５Ｋ、（ｃ）×１０Ｋ、（ｄ）×３０Ｋ、（ｅ）×５０Ｋのそれぞれの倍率で示した。
図３（ｃ）、（ｄ）から、Ｓｎ（２４、２４´、２４´´等）がグラフェン（グラフェンシート）２３に分散していたことが分かった。なお、（ｄ）から（ｃ）に向けて引かれた直線は、（ｄ）の拡大箇所を示したものである。
FIG. 3 shows FE-SEM images of the surface of the Sn-graphene composite plating film (Example 2) produced at a current density of 0.5 A/dm 2 , a solution temperature of 10° C., and a plating time of 15 min, at magnifications of (a) ×1K, (b) ×5K, (c) ×10K, (d) ×30K, and (e) ×50K.
3(c) and (d), it was found that Sn (24, 24', 24" etc.) was dispersed in the graphene (graphene sheet) 23. The straight line drawn from (d) to (c) indicates an enlarged portion of (d).
図４には、電流密度０．１Ａ／ｄｍ２、液温１０℃、めっき時間１０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例３）の表面のＦＥ－ＳＥＭを、（ａ）×１Ｋ、（ｂ）×５Ｋ、（ｃ）×１０Ｋ、（ｄ）×３０Ｋのそれぞれの倍率で示した。
図４（ａ）から、Ｓｎ（Ｓｎ膜）にめっき（被覆）されたＣｕ合金板３２の表面上に、Ｓｎ分散積層型グラフェン３５が存在していたことが分かった。（ｄ）から、Ｓｎ分散積層型グラフェン３５には、グラフェン（グラフェンシート）３３が含まれていたことが分かった。そして、同（ｄ）から、Ｓｎ（３４、３４´、３４´´等）がグラフェン（グラフェンシート）３３に分散していたことが分かった。
FIG. 4 shows FE-SEM images of the surface of the Sn-graphene composite plating film (Example 3) produced at a current density of 0.1 A/dm 2 , a solution temperature of 10° C., and a plating time of 10 min, at magnifications of (a) ×1K, (b) ×5K, (c) ×10K, and (d) ×30K.
4(a) shows that Sn-dispersed laminated graphene 35 was present on the surface of Cu alloy plate 32 plated (coated) with Sn (Sn film). 4(d) shows that graphene (graphene sheet) 33 was included in Sn-dispersed laminated graphene 35. 4(d) shows that Sn (34, 34', 34'', etc.) was dispersed in graphene (graphene sheet) 33.
図５には、電流密度１Ａ／ｄｍ２、液温１０℃、めっき時間１０ｍｉｎでにより作製したＳｎ－グラフェン複合めっき膜（実施例８）の表面のＦＥ－ＳＥＭを、（ａ）×１Ｋ、（ｂ）×５Ｋ、（ｃ）×１０Ｋ、（ｄ）×３０Ｋのそれぞれの倍率で示した。
表面がＳｎでおおわれているが、粒径が少し小さくなっていることが分かった。ドーム部分の下にはグラフェンがあると推定された。後述の断面SIMS像にはSn殻の下に積層型のグラフェンが確認される。
FIG. 5 shows FE-SEM images of the surface of a Sn-graphene composite plating film (Example 8) produced at a current density of 1 A/dm 2 , a solution temperature of 10° C., and a plating time of 10 min, at magnifications of (a) ×1K, (b) ×5K, (c) ×10K, and (d) ×30K.
It was found that the surface was covered with Sn, but the particle size was slightly smaller. It was assumed that graphene was present under the dome part. The cross-sectional SIMS image shown below confirms stacked graphene under the Sn shell.
図６には、Ｓｎ－グラフェン複合めっき膜（実施例８）の表面のラマン分析測定について、（ａ）測定部分（Ｓｎ分散積層型グラフェン）、（ｂ）ラマンスペクトル結果、及び（ｃ）めっき液中のグラフェンのラマンスペクトル結果を、それぞれ示した。
同（ｃ）のラマンスペクトルのピークと同（ｂ）のラマンスペクトルのピークは一致した。グラフェンのラマンスペクトルは、Ｄ、Ｇ（Ｃ六環の欠陥構造に由来するＤ－ｂａｎｄ、Ｃ原子のｓｐ２結合の存在を示唆するＧ－ｂａｎｄ）及び２Ｄとして特徴的なピークが検出された。グラファイトに特有なＤバンドとＧバンド（Ｄ／Ｇ＜１）が検出され、特にグラフェンの証とした２Ｄバンドのピークも示されたため、測定部分にはグラフェンが存在していたことが分かった。なお、Ｄバンドは欠陥構造に由来し、ＧバンドはＣ原子のｓｐ２結合の存在を示唆していた。
なお、、その測定条件は次のようであった。機種名：レーザーラマン分光光度計（ＮＲＳ－３３００）、測定範囲：２５４．８９６ｃｍ－１～３８９９．８７ｃｍ－１、中心波数：２３０１．０１ｃｍ－１、励起波長：５３２．０８ｎｍ、レーザ゛強度：７．９ｍＷであった。
FIG. 6 shows the Raman analysis measurement of the surface of the Sn-graphene composite plating film (Example 8), including (a) the measured portion (Sn-dispersed laminated graphene), (b) the Raman spectrum result, and (c) the Raman spectrum result of graphene in the plating solution.
The peaks of the Raman spectrum of (c) and (b) were consistent. In the Raman spectrum of graphene, characteristic peaks were detected as D, G (D-band derived from the defect structure of the C hexacyclic ring, G-band suggesting the presence of sp 2 bonds of C atoms) and 2D. The D band and G band (D/G<1) specific to graphite were detected, and in particular, the peak of the 2D band, which is evidence of graphene, was also shown, indicating that graphene was present in the measured portion. The D band was derived from the defect structure, and the G band suggested the presence of sp 2 bonds of C atoms.
The measurement conditions were as follows: Model name: Laser Raman spectrophotometer (NRS-3300), measurement range: 254.896 cm -1 to 3899.87 cm -1 , central wave number: 2301.01 cm -1 , excitation wavelength: 532.08 nm, laser intensity: 7.9 mW.
図７には、（ａ）電流密度１．０Ａ／ｄｍ２、液温１５℃、めっき時間１０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例４）の表面の黒色の粒子（Ｓｎ分散積層型グラフェン１５に類似すると推定したもの）のラマンスペクトル結果、（ｂ）（ａ）の表面において黒色の粒子以外の部分のラマンスペクトル結果を、それぞれ示した。
（ａ）から、Ｃ六環の欠陥構造に由来するＤ－ｂａｎｄ、Ｃ原子のｓｐ２結合の存在を示唆するＧ－ｂａｎｄ及びグラフェンの証とした２Ｄ－ｂａｎｄとして特徴的なピークが検出され、グラフェンとの複合化をできたことがわかる。なお、ここでは、強度比Ｄ／Ｇ＞１なので、めっき膜表面に顔を出したグラフェンは一部酸化グラフェンになったと推察される。一方、（ｂ）から、めっき膜の平ら部分には、グラフェンに帰属するピークが検出されていないため、その場所は単なるSn膜であることが分かった。
FIG. 7 shows (a) a Raman spectrum result of black particles (estimated to be similar to Sn-dispersed laminated graphene 15) on the surface of a Sn-graphene composite plating film (Example 4) produced at a current density of 1.0 A /dm 2 , a solution temperature of 15° C., and a plating time of 10 min, and (b) a Raman spectrum result of the part other than the black particles on the surface of (a).
From (a), characteristic peaks were detected as the D-band derived from the defect structure of the C hexagon, the G-band suggesting the presence of sp2 bonds of C atoms, and the 2D-band proving graphene, and it can be seen that a composite with graphene was successfully formed. Here, since the intensity ratio D/G>1, it is presumed that some of the graphene exposed on the plating film surface became graphene oxide. On the other hand, from (b), no peaks belonging to graphene were detected in the flat part of the plating film, and therefore it was found that the area was simply a Sn film.
図８には、（ａ）電流密度１．０Ａ／ｄｍ２により作製した純Ｓｎめっき膜（比較例１）のＧＤ－ＯＥＳ測定の結果、（ｂ）電流密度０．５Ａ／ｄｍ２、液温１０℃により作製したＳｎ－グラフェン複合めっき膜（実施例２）および実施例８のＧＤ－ＯＥＳ測定の結果を、それぞれ示した。（ｂ）から、炭素は最表面が一番多かったが、破線領域で囲まれた内部およびめっき界面からも検出され、炭素はグラフェン由来であるから、グラフェンすなわちＳｎ分散積層型グラフェンが内部にも存在していたことが分かった。（ｃ）には破線は示していないが、（ｂ）と同様であった。
なお、ＧＤ－ＯＥＳの測定条件は次のようであった。機種名：グロー放電発光表面分析装置（ＧＤ－ＯＥＳ、堀場ＧＤ－ｐｒｏｆｉｌｅｒ ２－ＭＮ），測定面積：直径８ｍｍ．ガスフロー：窒素ガスであった。
8 shows (a) the result of GD-OES measurement of a pure Sn plating film (Comparative Example 1) produced at a current density of 1.0 A/ dm2 , and (b) the result of GD-OES measurement of a Sn-graphene composite plating film (Example 2) produced at a current density of 0.5 A/ dm2 and a solution temperature of 10°C (Example 8). From (b), carbon was most abundant on the outermost surface, but it was also detected inside the area surrounded by the dashed line and at the plating interface, and since carbon is derived from graphene, it was found that graphene, i.e., Sn-dispersed stacked graphene, was also present inside. (c) does not show the dashed line, but is similar to (b).
The measurement conditions for the GD-OES were as follows: Model name: glow discharge optical emission surface analyzer (GD-OES, Horiba GD-profiler 2-MN), Measurement area: diameter 8 mm, Gas flow: nitrogen gas.
図９には、電流密度０．１Ａ／ｄｍ２、液温１０℃、めっき時間１０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例５）の表面について、（ａ）ＳＥＭ観察の結果、（ｂ）（ａ）を拡大したＳＥＭ観察の結果、（ｃ）（ａ）のＸＲＤ測定の結果、（ｄ）（ｂ）のＸＲＤ測定の結果を、それぞれ示した。
（ｃ）、（ｄ）から、Ｓｎ以外に多くの炭素を検出し、純Ｓｎめっきと比べてＣの濃度が顕著に高いため、Ｓｎ－グラフェン複合めっき膜が形成されたことが分かった。また、（ｃ）から、Ｃの濃度は２．４９質量％で１９．１原子％、Ｓｎの濃度は９７．５１質量％で８０．９原子％、（ｄ）から、Ｃの濃度は０．７１質量％で６．２１原子％、Ｓｎの濃度は９９．２９質量％で９３．８原子％であることが分かった。
FIG. 9 shows ( a) the results of SEM observation, (b) the results of SEM observation with an enlargement of (a), (c) the results of XRD measurement of (a), and (d) the results of XRD measurement of (b), for the surface of a Sn-graphene composite plating film (Example 5) produced at a current density of 0.1 A/dm 2 , a solution temperature of 10° C., and a plating time of 10 min.
From (c) and (d), a lot of carbon was detected in addition to Sn, and the C concentration was significantly higher than that of pure Sn plating, indicating that a Sn-graphene composite plating film was formed. Also, from (c), it was found that the C concentration was 2.49 mass% and 19.1 atomic %, and the Sn concentration was 97.51 mass% and 80.9 atomic %, and from (d), it was found that the C concentration was 0.71 mass% and 6.21 atomic %, and the Sn concentration was 99.29 mass% and 93.8 atomic %.
図１０には、電流密度０．５Ａ／ｄｍ２、液温５℃、めっき時間３０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例６）の表面について、（ａ）ＳＥＭ観察の結果、（ｂ）（ａ）を拡大したＳＥＭ観察の結果、（ｃ）（ａ）のＸＲＤ測定の結果、（ｄ）（ｂ）のＸＲＤ測定の結果を、それぞれ示した。
（ｃ）から、Ｃの濃度は６．２３質量％で３８．０原子％、Ｓｎの濃度は９３．７７質量％で６２．０原子％、（ｄ）から、Ｃの濃度は、０．４４質量％で３．９原子％、Ｓｎの濃度は９９．５６質量％で９６．１原子％であることが分かった。
FIG. 10 shows ( a) the results of SEM observation, (b) the results of SEM observation with an enlargement of (a), (c) the results of XRD measurement of (a), and (d) the results of XRD measurement of (b), for the surface of a Sn-graphene composite plating film (Example 6) produced at a current density of 0.5 A/dm 2 , a solution temperature of 5° C., and a plating time of 30 min.
From (c), it was found that the C concentration was 6.23 mass% or 38.0 atomic %, the Sn concentration was 93.77 mass% or 62.0 atomic %, and from (d), the C concentration was 0.44 mass% or 3.9 atomic %, and the Sn concentration was 99.56 mass% or 96.1 atomic %.
図１１には、電流密度０．５Ａ／ｄｍ２、液温５℃、めっき時間３０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例６）の別の表面について（ａ）ＳＥＭ観察の結果、（ｂ）（ａ）を拡大したＳＥＭ観察の結果、（ｃ）（ａ）のＸＲＤ測定の結果、（ｄ）（ｂ）のＸＲＤ測定の結果を、それぞれ示した。
（ｃ）から、Ｃの濃度は２２．８４質量％で６８原子％、Ｏの濃度は３．７２質量％で３８．０原子％、Ｓｎの濃度は７３．４３質量％で２３．７４原子％、（ｄ）から、Ｃの濃度は１．５２質量％で１２．５原子％、Ｓｎの濃度は９８．４８質量％で８７．４原子％であることが分かった。
FIG. 11 shows (a) the results of SEM observation, (b) the results of SEM observation with an enlargement of (a), (c) the results of XRD measurement of (a), and (d) the results of XRD measurement of (b), for another surface of a Sn-graphene composite plating film (Example 6) produced at a current density of 0.5 A/dm 2 , a solution temperature of 5° C., and a plating time of 30 min.
From (c), it was found that the C concentration was 22.84 mass% or 68 atomic %, the O concentration was 3.72 mass% or 38.0 atomic %, and the Sn concentration was 73.43 mass% or 23.74 atomic %, and from (d), the C concentration was 1.52 mass% or 12.5 atomic %, and the Sn concentration was 98.48 mass% or 87.4 atomic %.
図１２には、電流密度１．０Ａ／ｄｍ２、液温５℃、めっき時間２０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例７）の表面について、（ａ）ＳＥＭ観察の結果、（ｂ）（ａ）を拡大したＳＥＭ観察の結果、（ｃ）（ａ）のＸＲＤ測定の結果、（ｄ）（ｂ）のＸＲＤ測定の結果を示した。
（ｃ）から、Ｃの濃度は０．４２質量％で３．７原子％、Ｓｎの濃度は９９．５８質量％で９６．３原子％、（ｄ）から、Ｃの濃度は０．６７質量％で５．９原子％、Ｓｎの濃度は９９．３３質量％で９４．１原子％であることが分かった。
FIG. 12 shows ( a) the results of SEM observation, (b) the results of SEM observation with an enlargement of (a), (c) the results of XRD measurement of (a), and (d) the results of XRD measurement of (b), for the surface of a Sn-graphene composite plating film (Example 7) produced at a current density of 1.0 A/dm 2 , a solution temperature of 5° C., and a plating time of 20 min.
From (c), it was found that the C concentration was 0.42 mass% or 3.7 atomic %, the Sn concentration was 99.58 mass% or 96.3 atomic %, and from (d), the C concentration was 0.67 mass% or 5.9 atomic %, and the Sn concentration was 99.33 mass% or 94.1 atomic %.
以上の図９～１２に基づき、また、耐摩耗性向上と導電性保持の観点から、Ｃの濃度やＳｎの濃度を定めることができる。 Based on Figures 9 to 12 above, and from the standpoint of improving wear resistance and maintaining electrical conductivity, the C concentration and Sn concentration can be determined.
図１３には、電流密度０．５Ａ／ｄｍ２、液温５℃、めっき時間２０ｍｉｎにより作製したＳｎ－グラフェン複合めっき膜（実施例7）によりめっき（被覆）された端子について、（ａ）断面ＳＩＭ像（ＦＩＢ加工）、（ｂ）（ａ）を拡大した断面ＳＩＭ像を、それぞれ示した。（ａ）から、粒子状の大きなＳｎ分散積層型グラフェン粒子４５が、Ｃｕ合金基板１２を被覆したＳｎ－グラフェン複合めっき膜に嵌っていることが分かった。（ｂ）から、Ｓｎ分散積層型グラフェン粒子４５にＳｎ４６が入っている。 13 shows (a) a cross-sectional SIM image (processed by FIB ) and (b) a cross-sectional SIM image enlarged from (a) of a terminal plated (coated) with a Sn-graphene composite plating film (Example 7) produced at a current density of 0.5 A/dm 2 , a solution temperature of 5° C., and a plating time of 20 min. (a) shows that a large Sn-dispersed laminated graphene particle 45 is embedded in the Sn-graphene composite plating film coating the Cu alloy substrate 12. (b) shows that Sn 46 is embedded in the Sn-dispersed laminated graphene particle 45.
図１４には、図１２（ｂ）の拡大図を示した。Ｃｕ合金基板の上にＣｕ－Ｓｎ合金層が積層し、Ｓｎ－グラフェン複合めっき層（膜）中にＧｒａｐｈｅｎｅ ｆｌａｋｅが多い場所を確認することができた。 Figure 14 shows an enlarged view of Figure 12(b). A Cu-Sn alloy layer was laminated on top of the Cu alloy substrate, and it was possible to confirm areas with many graphene flakes in the Sn-graphene composite plating layer (film).
比較例１、実施例８、実施例２、実施例３に対して次のようにして硬度（ビッカース硬度）を測定した。なお、めっき膜厚は、５imになるように、めっき時間を調整した。測定条件は、島津製製作所製、型式：ＨＭＶ－１ＡＤＷＪを使用し、測定荷重は１Ｎでそれぞれ５つの試験片に対する硬度、それらの平均値を表１に示した。表１から、実施例８／比較例１＝７４．９／４４．７＝１．６８、実施例２／比較例１＝５３．８／４４．７＝１．２０、実施例３／比較例１＝７６．７１．７２／４４．７＝１．７２となった。これらから次のことが分かった。いずれも、グラフェンとの複合化によりＳｎめっき膜は硬くなった。 The hardness (Vickers hardness) of Comparative Example 1, Example 8, Example 2, and Example 3 was measured as follows. The plating time was adjusted so that the plating film thickness was 5 im. The measurement conditions were as follows: Shimadzu Corporation, Model: HMV-1ADWJ, and the measurement load was 1 N. The hardness and average value of five test pieces are shown in Table 1. From Table 1, Example 8/Comparative Example 1 = 74.9/44.7 = 1.68, Example 2/Comparative Example 1 = 53.8/44.7 = 1.20, and Example 3/Comparative Example 1 = 76.71.72/44.7 = 1.72. From these, the following was found. In all cases, the Sn plating film became harder when composited with graphene.
図１５には、表１の硬さの測定結果をグラフに示した。 Figure 15 shows a graph of the hardness measurement results in Table 1.
図１６は実施例１～５、比較例１の導電率の測定結果を示した。なお、表１は実施例１～５及び比較例１のそれぞれの導電率を５回測定で平均した数値データを示した。測定方法を簡潔に説明すると次のようである。機種名：抵抗計／シート抵抗測定器（ナプソンＲＴ－７０Ｖ／ＲＧ－７Ｇ）、４端子法によりバルク抵抗式で５点測定し、その平均値を図１５に示した。その結果により、Ｓｎ－複合めっきは純Ｓｎと同じレベルの導電性を保持できたことがわかる。 Figure 16 shows the measurement results of the conductivity of Examples 1 to 5 and Comparative Example 1. Table 1 shows the numerical data obtained by averaging the conductivity of each of Examples 1 to 5 and Comparative Example 1, measured five times. The measurement method is briefly explained as follows: Model name: Resistance meter/sheet resistance meter (Napson RT-70V/RG-7G), 5 points were measured using the bulk resistance type with the four-terminal method, and the average value is shown in Figure 15. The results show that the Sn-composite plating was able to maintain the same level of conductivity as pure Sn.
図１７には、純Ｓｎめっき膜とＳｎ―グラフェン複合めっき膜の摩耗試験結果の一例を示す。Ｓｎ－Ｃ複合めっき（すなわちＳｎ－グラフェン複合めっき膜）と純Ｓｎめっきは、それぞれ１Ａ／ｄｍ２で作製しためっき膜を使用した。グラフより、純Ｓｎめっきは初期に大きな摩擦係数の上昇が現れ、相手材のＡｇめっき膜とは凝着現象が発生したことに対し、Ｓｎ－Ｃ複合めっき膜は初期に摩擦係数の上昇が見られなく、摩耗における凝着現象に抑制できたことがわかる。また、摩耗の全体領域においてもＳｎ－Ｃ複合めっきの摩擦係数は純Ｓｎめっきより低く、耐摩耗性が向上されたことがわかる。また、摩耗試験の条件は次のようであった。評価装置：直線往復式摩擦摩耗試験機（Ｏｐｔｉｍａｌ Ｉｎｓｔｒｕｍｅｎｔｓ－ＳＲＶ－４）、荷重５Ｎ、摺動距離２００μｍ、周波数１Ｈｚ、２５℃、乾式（潤滑油なし）。相手材（Ｅｍｂｏｓｓ）は市販の一般Ａｇめっき（１１０Ｈｖ）材、凸部分は半径５ｍｍのものを基準試料として用いた。 FIG. 17 shows an example of the wear test results of the pure Sn plating film and the Sn-graphene composite plating film. The Sn-C composite plating (i.e., the Sn-graphene composite plating film) and the pure Sn plating were prepared at 1 A/ dm2 . From the graph, it can be seen that the pure Sn plating showed a large increase in the friction coefficient at the beginning and adhesion occurred with the Ag plating film of the mating material, whereas the Sn-C composite plating did not show an increase in the friction coefficient at the beginning, and adhesion during wear was suppressed. In addition, it can be seen that the friction coefficient of the Sn-C composite plating was lower than that of the pure Sn plating in the entire wear region, and wear resistance was improved. In addition, the wear test conditions were as follows. Evaluation device: linear reciprocating friction wear tester (Optimal Instruments-SRV-4), load 5N, sliding distance 200 μm, frequency 1 Hz, 25 °C, dry (without lubricant). The mating material (Emboss) was a commercially available general Ag-plated material (110 Hv), and the convex portion had a radius of 5 mm, which was used as a reference sample.
自動車特に更なる拡大が予想されるＥＶ／ＰＨＶの電子制御の高度化に伴うワイヤーハーネスの高性能化、高耐久性化を実現することができる。 This will enable wire harnesses to achieve higher performance and durability in line with the increasing sophistication of electronic control in automobiles, particularly EVs and PHVs, which are expected to continue to expand.
１：Ｓｎ－グラフェン複合めっき膜金属製端子
２：金属合金基材
３、１３、２３、３３：積層型グラフェン
５、１５、３５、４５：Ｓｎ分散積層型グラフェン
６、２６：Ｓｎ層
７：シート状のグラフェンフレーク
８：Ｓｎ－グラフェン複合めっき膜
１２、３２：Ｓｎによりめっき（被覆）されたＣｕ合金基板
１３、２３：グラフェン（グラフェンシート）
１４、１４´、１４´´、２４、２４´、２４´´、３４、３４´、３４´´、４６：Ｓｎ
４２：Ｃｕ合金基板
1: Sn-graphene composite plating film metal terminal 2: Metal alloy substrate 3, 13, 23, 33: Laminated graphene 5, 15, 35, 45: Sn-dispersed laminated graphene 6, 26: Sn layer 7: Sheet-shaped graphene flakes 8: Sn-graphene composite plating film 12, 32: Cu alloy substrate plated (coated) with Sn 13, 23: Graphene (graphene sheet)
14, 14', 14'', 24, 24', 24'', 34, 34', 34'', 46: Sn
42: Cu alloy substrate
Claims (5)
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| JP2014001126A (en) | 2012-05-25 | 2014-01-09 | National Institute For Materials Science | Method for manufacturing separated graphene film |
| JP2014164965A (en) | 2013-02-24 | 2014-09-08 | Furukawa Electric Co Ltd:The | Method of manufacturing terminal, terminal material for use in manufacturing method, terminal manufactured by manufacturing method, terminal connection structure of wire and manufacturing method therefor, and copper or copper alloy plate material for terminal |
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| US20090026086A1 (en) | 2007-07-27 | 2009-01-29 | Aruna Zhamu | Electrochemical method of producing nano-scaled graphene platelets |
| JP2014001126A (en) | 2012-05-25 | 2014-01-09 | National Institute For Materials Science | Method for manufacturing separated graphene film |
| JP2014164965A (en) | 2013-02-24 | 2014-09-08 | Furukawa Electric Co Ltd:The | Method of manufacturing terminal, terminal material for use in manufacturing method, terminal manufactured by manufacturing method, terminal connection structure of wire and manufacturing method therefor, and copper or copper alloy plate material for terminal |
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