JP2008231530A - Surface coating material - Google Patents
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- JP2008231530A JP2008231530A JP2007074931A JP2007074931A JP2008231530A JP 2008231530 A JP2008231530 A JP 2008231530A JP 2007074931 A JP2007074931 A JP 2007074931A JP 2007074931 A JP2007074931 A JP 2007074931A JP 2008231530 A JP2008231530 A JP 2008231530A
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- 239000000463 material Substances 0.000 title claims abstract description 179
- 239000011248 coating agent Substances 0.000 title claims abstract description 50
- 238000000576 coating method Methods 0.000 title claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 116
- 229910052751 metal Inorganic materials 0.000 claims abstract description 63
- 239000002184 metal Substances 0.000 claims abstract description 63
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 40
- 239000000956 alloy Substances 0.000 claims abstract description 40
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 238000007747 plating Methods 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 32
- 239000002109 single walled nanotube Substances 0.000 claims description 23
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 22
- 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 claims description 21
- 229910003472 fullerene Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 14
- 238000007772 electroless plating Methods 0.000 claims description 13
- 238000009713 electroplating Methods 0.000 claims description 11
- 239000002048 multi walled nanotube Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 8
- 125000000524 functional group Chemical group 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- 125000003277 amino group Chemical group 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 239000002245 particle Substances 0.000 description 26
- 238000011156 evaluation Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 20
- 239000002134 carbon nanofiber Substances 0.000 description 13
- 239000002131 composite material Substances 0.000 description 12
- 239000002116 nanohorn Substances 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000002041 carbon nanotube Substances 0.000 description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 238000009832 plasma treatment Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- OGKAGKFVPCOHQW-UHFFFAOYSA-L nickel sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O OGKAGKFVPCOHQW-UHFFFAOYSA-L 0.000 description 2
- -1 peanut-type Chemical compound 0.000 description 2
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012022 methylating agents Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 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
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002072 nanorope Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
本発明は、電気・電子部品等の接点部品、コネクター部品等に有用な導電性、潤滑性、耐摩耗性、及び耐食性に優れる表面被覆材、及びその形成方法に関する。 The present invention relates to a surface coating material excellent in conductivity, lubricity, wear resistance, and corrosion resistance useful for contact parts such as electric / electronic parts, connector parts, and the like, and a method for forming the same.
従来から、導電性を必要とするコネクター用途に金属からなるめっきをコーティングした構成部品を使うことは知られている。このようなコネクター用途には耐摩耗性が必要とされる。耐摩耗性を向上するために、耐摩耗性を有する粒子として剛性率が高い粒子を複合すると、複合コネクター表面の硬度を向上させることができるが、その反面金属と該粒子との界面でウィスカーが発生するという問題を生ずる。
ウィスカーが発生する金属としてＳｎ、Ｚｎ、Ｃｄ、Ｆｅ、Ａｇ等の金属が知られており、その成長にも潜伏期間があり、最も発生し易く成長速度の大きいものがＳｎである。
Conventionally, it is known to use metal-plated components for connector applications that require electrical conductivity. Wear resistance is required for such connector applications. In order to improve the wear resistance, if the particles having high rigidity are combined as the particles having wear resistance, the hardness of the composite connector surface can be improved. On the other hand, whiskers are formed at the interface between the metal and the particles. This causes a problem that occurs.
Metals such as Sn, Zn, Cd, Fe, and Ag are known as metals that generate whiskers. Their growth has a latent period, and Sn is the most easily generated and has a high growth rate.
一方、金属マトリックス中にカーボンナノファイバー等の炭素構造材料を配合して複合化し、種々の特性を改良する試みがなされている。
特許文献１には、コーティング層が金属マトリックス中に分布された電気伝導性を有する粒子、潤滑性を有する粒子、磨耗耐性を有する粒子および温度耐久性を増加させる性質を有する粒子を組み合わせた電気コネクターまたは電気スイッチ素子が開示されている。
特許文献２には、カーボンナノファイバーの含量や複合体の大きさをコントロール可能で、量産に向く金属・カーボンナノファイバー複合体およびその製造方法を提供することを目的として、溶融状態の金属にカーボンナノファイバーが混入され、該複合物が粒子化され、かつ固化されて成る金属・カーボンナノファイバー複合体が開示されている。
特許文献３には、金属にカーボンナノ材料を複合する複合めっきにおいて、表面を平滑に仕上げることのできる複合めっき技術を提供することを目的として、硫酸ニッケルと塩化ニッケルを主成分とするワット浴に、光沢剤と、ポリアクリル酸と、カーボンナノファイバーとを混合して複合めっき液を調製し、このめっき液に金属材料を投入し、電解めっき処理を施すことで、ニッケルに繊維状カーボンナノ材料を複合させた複合めっき層からなる繊維状ナノカーボン・金属複合材料が開示されている。
On the other hand, attempts have been made to improve various properties by compounding a carbon matrix material such as carbon nanofiber into a metal matrix.
Patent document 1 discloses an electrical connector in which a coating layer is a combination of particles having electrical conductivity distributed in a metal matrix, particles having lubricity, particles having wear resistance, and particles having a property of increasing temperature durability. Or an electrical switch element is disclosed.
In Patent Document 2, the content of carbon nanofibers and the size of the composite can be controlled, and in order to provide a metal / carbon nanofiber composite suitable for mass production and a method for producing the composite, carbon in the molten state is used. A metal / carbon nanofiber composite is disclosed in which nanofibers are mixed, and the composite is made into particles and solidified.
Patent Document 3 discloses a watt bath mainly composed of nickel sulfate and nickel chloride for the purpose of providing a composite plating technique capable of finishing the surface smoothly in composite plating in which a carbon nanomaterial is combined with a metal. A composite plating solution is prepared by mixing brighteners, polyacrylic acid, and carbon nanofibers. A metal material is added to the plating solution, and electrolytic plating treatment is performed. There has been disclosed a fibrous nanocarbon / metal composite material comprising a composite plating layer in which is combined.
特許文献１において、前記潤滑性を有する粒子として、ＰＴＦＥ、ポリイミド及びポリアミド、炭素含有粒子、本質的に純粋な炭素およびグラファイト、セラミック粒子、二硫化モリブデン及び窒化ホウ素、並びに潤滑手段含有カプセル、例えばポリフェニルエーテル又は有機潤滑手段を含有するカプセルが例示されている。前記磨耗耐性を有する粒子として、セラミック粒子、例えば酸化アルミニウム、酸化ジルコニウム、炭化珪素、窒化ホウ素および窒化チタン、並びに炭素質ナノチューブが例示されている。しかしながら、実施例において磨耗耐性等を有する粒子として評価されているのはすべてグラファイトのみである。
特許文献２において、金属と微細炭素繊維とでは比重が大きく異なることやカーボンナノファイバーが溶融湯金属に濡れ難いという性質があることから、微細炭素繊維を均一に溶融金属中に分散する技術が開示されているが、炭素材としてカーボンナノファイバーのみが対象とされている。
特許文献３において、金属にカーボンナノ材料を複合化する複合して表面を平滑に仕上げることのできる複合めっき技術が開示されているが、カーボンナノ材料として繊維状ナノカーボンが開示されているのみである。
従って、潤滑性、耐摩耗性と耐食性を向上して、ウィスカーの発生を抑制する複合めっき材はまだ見出されていない。
In Patent Document 1, as the particles having lubricity, PTFE, polyimide and polyamide, carbon-containing particles, essentially pure carbon and graphite, ceramic particles, molybdenum disulfide and boron nitride, and lubricating means-containing capsules such as poly Capsules containing phenyl ether or organic lubricating means are illustrated. Examples of the wear-resistant particles include ceramic particles such as aluminum oxide, zirconium oxide, silicon carbide, boron nitride and titanium nitride, and carbonaceous nanotubes. However, in the examples, only graphite is evaluated as particles having wear resistance and the like.
Patent Document 2 discloses a technique for uniformly dispersing fine carbon fibers in molten metal because the specific gravity is greatly different between metal and fine carbon fiber and carbon nanofibers are difficult to wet with molten metal. However, only carbon nanofibers are targeted as carbon materials.
Patent Document 3 discloses a composite plating technique capable of complexing a carbon nanomaterial with a metal to finish the surface smoothly, but only a fibrous nanocarbon is disclosed as a carbon nanomaterial. is there.
Therefore, a composite plating material that improves lubricity, wear resistance, and corrosion resistance and suppresses the generation of whiskers has not yet been found.
本発明者らは、上記従来技術に鑑みて、低い剛性率を有する炭素構造材料を表面被覆材に含有させることにより、該炭素構造材料がコネクター等の接点で弾性変形することで潤滑性・耐摩耗性を同時に向上させ、さらにめっき金属内部で発生する内部応力に対して弾性限界が大きい粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで、表面被覆材の耐食性を向上させ、ウィスカー発生を抑制すること等を見出し、本発明を完成するに至った。 In view of the above prior art, the present inventors have included a carbon structural material having a low rigidity in the surface coating material, so that the carbon structural material is elastically deformed at a contact point such as a connector, thereby improving lubricity and resistance. At the same time, the wear resistance is improved, and the particles with a large elastic limit against the internal stress generated inside the plated metal are deformed. As a result, the inventors have found that the generation of whiskers is suppressed, and the present invention has been completed.
すなわち、本発明の第１の態様は、（１）少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材、に関する発明である。
また、本発明の第１の態様の表面被覆材においては、下記（２）ないし（７）の態様とすることが可能である。
（２）前記炭素構造材料のアスペクト比が１以上で３００未満である。
（３）前記炭素構造材料が少なくとも単層カーボンナノチューブ、２〜１０層の多層カーボンナノチューブ、カーボンナノホーン、及びフラーレンから選択される１種又は２種以上である。
（４）前記炭素構造材料が、アミノ基、ヒドロキシル基、メトキシ基、アミド基、及びメチル基から選択される１種又は２種以上の官能基で修飾されている。
（５）前記金属がNi、Sn、Cｒ、Au、Ag、Cu、Pt、Pd、In、Bi、及びZnから選択される１種又は２種以上、又は前記合金がこれらの金属から選択される２種以上を含む合金である。
（６）前記表面被覆材が前記炭素構造材料１〜３０体積％、及び金属又は合金７０〜９９体積％からなる。
（７）前記炭素構造材料が表面被覆材の最表面層に面積割合で少なくとも５％以上存在している。
That is, the first aspect of the present invention is an invention relating to (1) a surface coating material in which a carbon structural material having at least a rigidity of 0.01 to 0.6 TPa is dispersed in a metal or alloy matrix. is there.
Moreover, in the surface coating material of the 1st aspect of this invention, it is possible to set it as the aspect of following (2) thru | or (7).
(2) The aspect ratio of the carbon structural material is 1 or more and less than 300.
(3) The carbon structural material is at least one selected from single-walled carbon nanotubes, 2 to 10 multi-walled carbon nanotubes, carbon nanohorns, and fullerenes.
(4) The carbon structural material is modified with one or more functional groups selected from an amino group, a hydroxyl group, a methoxy group, an amide group, and a methyl group.
(5) The metal is one or more selected from Ni, Sn, Cr, Au, Ag, Cu, Pt, Pd, In, Bi, and Zn, or the alloy is selected from these metals An alloy containing two or more kinds.
(6) The surface covering material comprises 1 to 30% by volume of the carbon structural material and 70 to 99% by volume of a metal or alloy.
(7) The carbon structural material is present in the outermost surface layer of the surface covering material in an area ratio of at least 5% or more.
本発明の第２の態様は、（８）少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料をめっき液中に添加して、撹拌下に電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材を形成することを特徴とする、表面被覆材の形成方法、に関する発明である。
本発明の第３の態様は、（９）少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料をめっき液中に添加して、撹拌下に無電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材を形成することを特徴とする、表面被覆材の形成方法、に関する発明である。
本発明の第４の態様は、（１０）少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料と、金属又は合金粉末からなる混合粉末を焼結させることにより基材上に前記炭素構造材料が金属又は合金間に分散している表面被覆材を形成することを特徴とする、表面被覆材の形成方法、に関する発明である。
In the second aspect of the present invention, (8) at least a carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa is added to the plating solution, and the above-described substrate is electroplated with stirring on the substrate. The invention relates to a method for forming a surface covering material, characterized in that a surface covering material in which a carbon structural material is dispersed in a metal or alloy matrix is formed.
In the third aspect of the present invention, (9) at least a carbon structural material having a rigidity in the range of 0.01 to 0.6 TPa is added to the plating solution, and electroless plating is performed on the substrate with stirring. The invention relates to a method for forming a surface covering material, characterized in that the surface covering material in which the carbon structural material is dispersed in a metal or alloy matrix is formed.
According to a fourth aspect of the present invention, (10) at least a carbon structural material having a rigidity in a range of 0.01 to 0.6 TPa and a mixed powder composed of a metal or alloy powder is sintered on a base material. The invention relates to a method for forming a surface covering material, characterized in that a surface covering material in which the carbon structural material is dispersed between metals or alloys is formed.
本発明の少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材は、接点で弾性変形することで潤滑性と耐摩耗性が向上し、また表面被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制すると共に導電性にも優れた特性を有する。 The surface covering material in which the carbon structural material having at least a rigidity of 0.01 to 0.6 TPa of the present invention is dispersed in a metal or alloy matrix is lubricated and wear-resistant by elastically deforming at a contact point. The surface coating material is improved by the effect of internal strain relaxation on the plated metal due to deformation of particles made of carbon structural material that has a large elastic limit against internal stress generated inside the surface coating metal. The corrosion resistance is improved, whisker generation is suppressed, and the conductivity is excellent.
〔１〕第１の態様の表面被覆材
本発明の第１の態様の表面被覆材は、少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料が金属又は合金マトリックス中に分散している、ことを特徴とする。
（１）炭素構造材料の種類
炭素構造材料としては、一般に単層カーボンナノチューブ（以下、ＳＷＣＮＴということがある。）、多層カーボンナノチューブ、カーボンナノホーン、フラーレン、フラーレン重合物、フラーレン誘導体、カーボンナノファイバー、活性炭素等が挙げられるが、本発明で使用する炭素構造材料としては、これらの中でも単層カーボンナノチューブ、多層カーボンナノチューブ、カーボンナノホーン、カーボンナノファイバー、フラーレン、フラーレン重合物、及びフラーレン誘導体が好ましい。
（ｉ）カーボンナノチューブ
カーボンナノチューブとは、グラファイトの１枚面を巻いた筒状形状を有するものをいい、１層に巻かれたものを単層カーボンナノチューブ、２層に巻かれたものを２層カーボンナノチューブ、多層に巻かれたものを多層カーボンナノチューブという。
[1] Surface coating material according to the first aspect In the surface coating material according to the first aspect of the present invention, at least a carbon structural material having a rigidity of 0.01 to 0.6 TPa is dispersed in a metal or alloy matrix. It is characterized by that.
(1) Types of carbon structural materials Carbon structural materials are generally single-walled carbon nanotubes (hereinafter sometimes referred to as SWCNTs), multi-walled carbon nanotubes, carbon nanohorns, fullerenes, fullerene polymers, fullerene derivatives, carbon nanofibers, Examples of the carbon structural material used in the present invention include single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, carbon nanofibers, fullerenes, fullerene polymers, and fullerene derivatives.
(I) Carbon nanotubes Carbon nanotubes have a cylindrical shape in which one surface of graphite is wound. Single-walled carbon nanotubes are wound in one layer, and two layers are wound in two layers. Carbon nanotubes and those wound in multiple layers are called multi-walled carbon nanotubes.
（ii）カーボンナノホーン
カーボンナノホーンとはグラファイトの１枚面が円錐状に巻かれた形状を有しており、１層に巻かれたものを単層カーボンナノホーンといい、２層に巻かれたものを２層カーボンナノホーンといい、３層以上の多層に巻かれたものを多層カーボンナノホーンという。
（iii）フラーレン
フラーレンとは炭素原子からなるクラスターで、炭素の同素体であり、通常はＣ３６、Ｃ６０、Ｃ７０、Ｃ７６、Ｃ７８、Ｃ８０、Ｃ８２、Ｃ８４などから選ばれる。フラーレン重合物とは、２個のＣ60が結合して出来た二量体や、さらに密に結合した落花生型などのＣ120、３個が結合したトリマーのＣ180やｎ個が結合したポリマーなども合成されている。
フラーレン誘導体とは前記フラーレンが官能基化修飾されたものであれば特に限定しないが、本発明では−ＯＨ、−ＯＳＯ３Ｈ、−ＣＯＯＨ、−ＳＯ３Ｈ、−ＯＰＯ（ＯＨ）３の官能基の内、少なくとも１つ以上含むものが好ましい。
（iv）カーボンナノファイバー
カーボンナノファイバーとは直径が１ｎｍないし５００ｎｍであり、長さが１μｍ以上の成分組成が炭素５０％以上であるものとし、ロッド状でも中空状でもよい。
(Ii) Carbon nanohorn A carbon nanohorn has a shape in which one surface of graphite is wound in a conical shape, and one wound in one layer is called a single-layer carbon nanohorn and is wound in two layers. Is called a two-layer carbon nanohorn, and a multi-layered carbon nanohorn is a multi-layer carbon nanohorn.
(Iii) Fullerene Fullerene is a cluster composed of carbon atoms and is an allotrope of carbon, and is usually selected from C 36 , C 60 , C 70 , C 76 , C 78 , C 80 , C 82 , C 84 and the like. Fullerene polymer The two dimers or the C 60 was able to bond, further tightly bound C 120, such as peanut-type, three are C 180 and n-number of trimers bound is bonded polymer Etc. are also synthesized.
The fullerene derivative is not particularly limited as long as the fullerene is functionally modified, but in the present invention, functional groups of —OH, —OSO 3 H, —COOH, —SO 3 H, —OPO (OH) 3 are used. Of these, those containing at least one are preferred.
(Iv) Carbon nanofiber The carbon nanofiber has a diameter of 1 nm to 500 nm, a component composition with a length of 1 μm or more is 50% or more of carbon, and may be rod-shaped or hollow.
（２）炭素構造材料の剛性率
本発明で使用する炭素構造材料は、少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料である。剛性率が０．０１未満では、潤滑性と耐摩耗性及び耐食性の向上が不十分であり、剛性率が０．６を超えると金属の内部応力に対して変形できなくなるという不都合を生ずる。好ましい剛性率は、０．３０〜０．５５ＴＰａの範囲である。
このような炭素構造材料を使用することにより、潤滑性と耐摩耗性が向上すると共に、被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制し、導電性にも優れた特性を有する。
（ｉ）炭素構造材料の剛性率の測定法
本発明における剛性率は、参考文献１（Wong E W, Sheehan P E and Lieber C M 1997 Science 277 1971）に記載された下式から算出される剛性率Ｇである。具体的には、剛性率Ｇは、各種炭素構造材料のヤング率を測定し、ポアソン比を０．２として下式から算出される。
Ｇ＝Ｅ／［２（１＋γ）］
Ｅ:ヤング率、
γ:ポアソン比（下記参考文献２から、上式におけるポアソン比はすべて０．２と推定した。）
＊参考文献２：VOLUME 79, NUMBER 7 PHYSICALREVIEW LETTERS 18 AUGUST 1997
Elastic Properties of Carbon Nanotubes and Nanoropes Jian Ping Lu
(2) Stiffness of carbon structural material The carbon structural material used in the present invention is a carbon structural material having a rigidity of at least 0.01 to 0.6 TPa. If the rigidity is less than 0.01, improvement in lubricity, wear resistance and corrosion resistance is insufficient, and if the rigidity exceeds 0.6, there is a disadvantage that the metal cannot be deformed by internal stress. A preferable rigidity is in the range of 0.30 to 0.55 TPa.
By using such a carbon structural material, lubricity and wear resistance are improved, and particles made of the carbon structural material having a large elastic limit against internal stress generated inside the coating metal are deformed. The surface coating material is improved in corrosion resistance by influencing the plated metal such as internal strain relaxation, whisker generation is suppressed, and the conductivity is excellent.
(I) Method of measuring rigidity of carbon structural material The rigidity in the present invention is the rigidity G calculated from the following equation described in Reference Document 1 (Wong EW, Sheehan PE and Lieber CM 1997 Science 277 1971). is there. Specifically, the rigidity G is calculated from the following equation by measuring the Young's modulus of various carbon structural materials and setting the Poisson's ratio to 0.2.
G = E / [2 (1 + γ)]
E: Young's modulus
γ: Poisson ratio (From Reference Document 2 below, all Poisson ratios in the above equation were estimated to be 0.2)
* Reference 2: VOLUME 79, NUMBER 7 PHYSICALREVIEW LETTERS 18 AUGUST 1997
Elastic Properties of Carbon Nanotubes and Nanoropes Jian Ping Lu
（ii）炭素構造材料の剛性率
本発明で使用する炭素構造材料のうち単層カーボンナノチューブ、多層カーボンナノチューブ、カーボンナノホーン、及びフラーレンの剛性率を表１に示す。尚、これらの測定に使用した炭素構造材料を以下に示す。
（ｉ）フラーレン
フロンティアカーボン（株）製、商品名：フラーレンＣ６０−ＳＵＨ
（ii）カーボンナノホーン
ＮＥＣ（株）製、カーボンナノホーン
（iii）単層カーボンナノチューブ、
Sun Nanotech Co Ltd製、商品名：SUNNANO(SWNT)
（iv）２ないし１０層の多層カーボンナノチューブ
Sun Nanotech Co Ltd製、商品名：SUNNANO(B-MWNT)
（ｖ）気相成長炭素繊維
昭和電工（株）製、商品名：ＶＧＣＦ
（vi）活性炭素
米国スーぺリア・グラファイト社製、商品名：ＣＧＣ鱗片状黒鉛No2935
(Ii) Stiffness of carbon structural material Table 1 shows the rigidity of single-walled carbon nanotubes, multi-walled carbon nanotubes, carbon nanohorns, and fullerenes among the carbon structural materials used in the present invention. The carbon structural materials used for these measurements are shown below.
(I) Fullerene Frontier Carbon Co., Ltd., trade name: Fullerene C60-SUH
(Ii) carbon nanohorn manufactured by NEC Corporation, carbon nanohorn (iii) single-walled carbon nanotube,
Product name: SUNNANO (SWNT), manufactured by Sun Nanotech Co Ltd
(Iv) 2 to 10 multi-walled carbon nanotubes
Product name: SUNNANO (B-MWNT), manufactured by Sun Nanotech Co Ltd
(V) Vapor growth carbon fiber Showa Denko Co., Ltd., trade name: VGCF
(Vi) Activated carbon Product name: CGC scaly graphite No2935, manufactured by Superior Graphite, USA
（３）炭素構造材料の形状
本発明で使用する炭素構造材料のアスペクト比が１以上で３００未満が好ましい。
炭素構造材料のアスペクト比が３００を超えると長すぎて絡まり分散性が悪くなる場合がある。炭素構造材料のアスペクト比は、より好ましくは1〜１００であり、特に好ましくは1〜１０である。
また、炭素構造材料の最大長さが１０ｎｍ以上の炭素構造材料を５０質量％含むことが望ましい。炭素構造材料の最大長さが１０ｎｍ以上の炭素構造材料を５０質量％含むことにより表面での炭素構造材料の脱落がより効果的に防止される。このようなアスペクト比、と炭素構造材料の長さは、走査電子顕微鏡（ＳＥＭ）を用いて測定することが可能である。
(3) Shape of carbon structural material The aspect ratio of the carbon structural material used in the present invention is preferably 1 or more and less than 300.
If the aspect ratio of the carbon structural material exceeds 300, the carbon structure material may be too long and entangled, resulting in poor dispersibility. The aspect ratio of the carbon structural material is more preferably 1 to 100, and particularly preferably 1 to 10.
In addition, it is desirable that the carbon structural material includes 50% by mass of a carbon structural material having a maximum length of 10 nm or more. By including 50% by mass of the carbon structural material having a maximum length of 10 nm or more, the carbon structural material is more effectively prevented from falling off at the surface. Such an aspect ratio and the length of the carbon structural material can be measured using a scanning electron microscope (SEM).
（４）炭素構造材料の官能基による修飾
炭素構造材料は、アミノ基、ヒドロキシル基、メトキシ基、アミド基、及びメチル基から選択される１種以上の官能基で修飾されていることが望ましい。
炭素構造材料をこのような官能基で修飾することにより、炭素構造材料をめっき液中に添加して、撹拌下に電解めっき又は無電解めっきにより基材上に前記炭素構造材料を金属又は合金マトリックス中に分散させて表面被覆材を形成する際に、炭素構造材料が金属又は合金への親和性を増加させて、マトリックス中への分散をより容易にする。
炭素構造材料へのこのような修飾方法は下記方法により行うことができる。
尚、炭素構造材料このような官能基を付与するタイミングは、電解めっき又は無電解めっきを行う直前が望ましい。
（ｉ）ヒドロキシル基
プラズマ処理、又は酸化剤等の反応試薬により形成できる。
（ii）アミノ基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成した後、SOCl2を用いてヒドロキシル基を塩素に置換する。さらにこの塩素部分をアンモニアを用いてアミノ基に置換する。
（iii）メトキシ基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成し、塩基の存在下、ヒドロキシル基にヨードメタンや硫酸ジメチルなどのメチル化剤を反応させてメトキシ基を形成する。
（iv）アミド基
大気中において、４００℃ないし５４０℃で熱処理によりカルボキシル基を形成し、SOCl2でカルボキシル基のヒドロキシル基を塩素に置換する。さらにアンモニアを用いてこの塩素部分をアミノ基に置換することにより、アミド基を形成する。
（ｖ）メチル基
プラズマ処理、又は酸化剤等の反応試薬によりヒドロキシル基を形成し、メタノールと酸触媒下で反応させてメチル基を形成する。
(4) Modification of carbon structural material with functional group The carbon structural material is desirably modified with one or more functional groups selected from an amino group, a hydroxyl group, a methoxy group, an amide group, and a methyl group.
By modifying the carbon structural material with such a functional group, the carbon structural material is added to the plating solution, and the carbon structural material is placed on the substrate by electrolytic plating or electroless plating under stirring. When dispersed in to form a surface coating, the carbon structural material increases the affinity for the metal or alloy, making it easier to disperse into the matrix.
Such a modification method to the carbon structural material can be performed by the following method.
It is desirable that the carbon structural material be provided with such a functional group immediately before electrolytic plating or electroless plating.
(I) Hydroxyl group It can be formed by a plasma treatment or a reaction reagent such as an oxidizing agent.
(Ii) Amino group After a hydroxyl group is formed by a plasma treatment or a reaction reagent such as an oxidizing agent, the hydroxyl group is substituted with chlorine using SOCl 2 . Furthermore, this chlorine part is substituted with an amino group using ammonia.
(Iii) Methoxy group A hydroxyl group is formed by a plasma treatment or a reaction reagent such as an oxidant, and a methoxy group is formed by reacting the hydroxyl group with a methylating agent such as iodomethane or dimethyl sulfate in the presence of a base.
(Iv) Amide group A carboxyl group is formed by heat treatment at 400 ° C. to 540 ° C. in the atmosphere, and the hydroxyl group of the carboxyl group is replaced with chlorine with SOCl 2 . Furthermore, an amide group is formed by substituting this chlorine part with an amino group using ammonia.
(V) Methyl group A hydroxyl group is formed by a plasma treatment or a reaction reagent such as an oxidizing agent, and reacted with methanol under an acid catalyst to form a methyl group.
〔２〕金属又は合金
本発明の表面被覆材のマトリックスを構成する金属又は合金に使用可能である金属として、特に限定されるものではないが、好ましい金属又は合金として、Ni、Sn、Cｒ、Au、Ag、Cu、Pt、Pd、In、Bi、及びZnから選択される１種もしくは２種以上、又は合金としてこれらの金属から選択される２種以上を含む合金が挙げられる。
すなわち、電気・電子部品等の接点部品は常温下で接触抵抗が低いことは勿論のこと、自動車用の電気・電子部品等の接点部品に使用されるものについては、良好な耐熱性を有していると共に高温下でも接触抵抗を低く維持できることが要求される。また、コネクター部品に使用される表面被覆材については、コネクター部品を接続するときの負荷、すなわち挿入力が低減する材料であることが望まれている。そして、接点部品を構成する表面被覆材については、一般的に長期的な安定性を有することが望まれている。
このような観点からも上記例示した金属又は合金が好適に使用できる。
[2] Metal or alloy The metal that can be used in the metal or alloy constituting the matrix of the surface coating material of the present invention is not particularly limited, but preferred metals or alloys include Ni, Sn, Cr, Au , Ag, Cu, Pt, Pd, In, Bi, and Zn, or an alloy containing two or more selected from these metals as an alloy.
That is, contact parts such as electric / electronic parts have low contact resistance at room temperature, and those used for contact parts such as electric / electronic parts for automobiles have good heat resistance. In addition, the contact resistance is required to be kept low even at high temperatures. Further, it is desired that the surface covering material used for the connector part is a material that reduces a load when the connector part is connected, that is, an insertion force. And it is generally desired for the surface covering material constituting the contact parts to have long-term stability.
From such a viewpoint, the metal or alloy exemplified above can be preferably used.
〔３〕表面被覆材
（１）表面被覆材の形成
本発明の表面被覆材は、電解めっき法、無電解めっき法、焼結法等により炭素構造材料を金属又は合金マトリックス中へ分散させることにより形成されるがこれらの具体的方法については後述する。
[3] Surface coating material (1) Formation of surface coating material The surface coating material of the present invention is obtained by dispersing a carbon structural material in a metal or alloy matrix by an electrolytic plating method, an electroless plating method, a sintering method, or the like. Although formed, these specific methods will be described later.
（２）表面被覆材中の前記炭素構造材料と、金属又は合金の体積割合
本発明の表面被覆材は、それぞれ炭素構造材料が１〜３０体積％、及び金属又は合金が７０〜９９体積％からなることが好ましい。
このような体積割合とすることにより、表面被覆材が接点で適度に弾性変形して潤滑性と耐摩耗性が向上し、また表面被覆剤金属内部で発生する内部応力に対して弾性限界が大きい炭素構造材料からなる粒子が変形することにより、めっき金属に内部歪緩和などの影響を与えることで表面被覆材の耐食性を向上させ、更にウィスカー発生を抑制する。
上記体積割合の表面被覆材は、例えば電解めっき浴もしくは無電解めっき浴の溶液中の金属と炭素構造材料の配合割合を該体積割合とすればよく、また焼結法により表面被覆材を形成するときはそれぞれの粒子の配合割合を前記体積割合とすればよい。
(2) Volume ratio of the carbon structural material and metal or alloy in the surface coating material The surface coating material of the present invention has a carbon structural material of 1 to 30% by volume and a metal or alloy of 70 to 99% by volume, respectively. It is preferable to become.
By setting such a volume ratio, the surface coating material is appropriately elastically deformed at the contact point to improve lubricity and wear resistance, and the elastic limit is large against internal stress generated inside the surface coating metal. The deformation of the particles made of the carbon structural material improves the corrosion resistance of the surface coating material by affecting the plated metal such as internal strain relaxation, and further suppresses the occurrence of whiskers.
The above-mentioned volume ratio of the surface coating material may be, for example, the mixing ratio of the metal and the carbon structural material in the solution of the electrolytic plating bath or the electroless plating bath, and the surface coating material is formed by a sintering method. In some cases, the mixing ratio of each particle may be the volume ratio.
（３）表面被覆材の最表面層における炭素構造材料の面積割合
炭素構造材料は、表面被覆材の最表面層に面積割合で少なくとも５％以上存在していることが望ましい。
このような割合とすることにより、表面被覆材において上記した潤滑性、耐摩耗性、耐食性、及びウィスカー発生の抑制効果が効果的に発揮される。より好ましい表面被覆材の最表面層における炭素構造材料の面積割合は５ないし１０％である。
尚、上記表面被覆材の最表面層における炭素構造材料の面積割合はめっき又は粉末焼結を行う際の金属（金属イオンの状態で存在する）と炭素構造材料の配合割合から推定可能である。すなわち、該炭素構造材料の面積割合は、電解めっきと無電解めっきを行う場合には浴中の金属もしくは合金と炭素構造材料の配合割合、又は粉末焼結を行う場合には金属もしくは合金粉末と炭素構造材料粉末の配合割合（体積ベース）の２／３乗を目安に推定することが可能である。
尚、このような面積割合であることの確認は、走査電子顕微鏡（ＳＥＭ）を用いて確認することが可能である。
(3) Area ratio of carbon structural material in outermost surface layer of surface covering material It is desirable that the carbon structural material is present in the outermost surface layer of the surface covering material in an area ratio of at least 5% or more.
By setting it as such a ratio, the above-mentioned lubricity, wear resistance, corrosion resistance, and whisker generation suppressing effect are effectively exhibited in the surface coating material. The area ratio of the carbon structural material in the outermost surface layer of the surface covering material is more preferably 5 to 10%.
In addition, the area ratio of the carbon structural material in the outermost surface layer of the surface covering material can be estimated from the blending ratio of the metal (present in the state of metal ions) and the carbon structural material when performing plating or powder sintering. That is, the area ratio of the carbon structural material is the blending ratio of the metal or alloy in the bath and the carbon structural material when performing electroplating and electroless plating, or the metal or alloy powder when performing powder sintering. It is possible to estimate using the 2/3 power of the mixing ratio (volume basis) of the carbon structural material powder as a guide.
In addition, confirmation of such an area ratio can be confirmed using a scanning electron microscope (SEM).
〔４〕第２の態様における電解めっきによる表面被覆材の形成方法
この表面被覆材の形成方法は、少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料をめっき液中に添加して、撹拌下に電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材を形成することを特徴とする。
具体例としては、めっき浴中にめっき液を調製すると共に、上記した所定量の炭素構造材料を金属又は合金マトリックス中分散させて撹拌下に、アノードとカソードである基材間に印加してめっきを行うことにより、炭素構造材料が金属又は合金マトリックス中に分散している、表面被覆材を形成することができる。めっき液に炭素構造材料を含む以外は公知の電解めっき方法を採用してめっきを行うことができる。
〔５〕第３の態様における無電解めっきによる表面被覆材の形成方法
この表面被覆材の形成方法は、少なくとも剛性率が０．０１〜０．６ＴＰａの範囲にある炭素構造材料をめっき液中に添加して、撹拌下に無電解めっきにより基材上に前記炭素構造材料が金属又は合金マトリックス中に分散している表面被覆材を形成することを特徴とする。
具体例としては、無電解めっき浴中に無電解めっき液を調製すると共に、所定量の炭素構造材料を撹拌下に分散させながら、還元剤の存在下に金属イオンを還元して基材上に金属又は合金と共に炭素構造材料をめっきすることにより表面被覆材を形成することができる。めっき液に炭素構造材料を含む以外は公知の無電解めっき方法を採用してめっきを行うことができる。
[4] Method for forming surface coating material by electrolytic plating in second aspect This method for forming a surface coating material is to add a carbon structural material having a rigidity of at least 0.01 to 0.6 TPa to the plating solution. Then, a surface coating material in which the carbon structural material is dispersed in a metal or alloy matrix is formed on the base material by electrolytic plating under stirring.
As a specific example, a plating solution is prepared in a plating bath, and the above-mentioned predetermined amount of carbon structural material is dispersed in a metal or alloy matrix and applied between the anode and cathode substrates while stirring. By performing the above, it is possible to form a surface coating material in which the carbon structural material is dispersed in the metal or alloy matrix. Except for including a carbon structural material in the plating solution, a known electrolytic plating method can be employed for plating.
[5] Method for Forming Surface Coating Material by Electroless Plating in Third Aspect This method for forming a surface coating material includes at least a carbon structural material having a rigidity in a range of 0.01 to 0.6 TPa in a plating solution. In addition, a surface coating material in which the carbon structural material is dispersed in a metal or alloy matrix is formed on the substrate by electroless plating under stirring.
As a specific example, while preparing an electroless plating solution in an electroless plating bath and dispersing a predetermined amount of carbon structural material with stirring, metal ions are reduced in the presence of a reducing agent on the substrate. A surface covering material can be formed by plating a carbon structural material together with a metal or an alloy. Except for including a carbon structural material in the plating solution, a known electroless plating method can be employed for plating.
〔６〕第４の態様における粉末焼結法による表面被覆材の形成方法
この表面被覆材の形成方法は、少なくとも剛性率が０．０１ないし０．６ＴＰａの範囲にある炭素構造材料と、金属又は合金粉末からなる混合粉末を焼結させることにより基材上に前記炭素構造材料が金属又は合金間に分散している表面被覆材を形成することを特徴とする。上記粉末焼結させる温度条件は、金属又は合金が焼結する温度にまで加熱することにより、金属又は合金が融着現象を生じさせて炭素構造材料に焼結する温度である。
[6] Method for Forming Surface Coating Material by Powder Sintering Method in Fourth Embodiment This method for forming a surface coating material comprises a carbon structural material having at least a rigidity of 0.01 to 0.6 TPa, a metal or A surface coating material in which the carbon structural material is dispersed between a metal or an alloy is formed on a base material by sintering a mixed powder made of an alloy powder. The temperature condition for the powder sintering is a temperature at which the metal or alloy is heated to a temperature at which the metal or alloy is sintered to cause the metal or alloy to cause a fusing phenomenon and sinter into the carbon structural material.
以下に実施例により本発明をより具体的に説明するが本発明はこれらの方法に限定されるものではない。
本実施例１ないし５に使用した炭素構造材料を以下に示す。
（１）炭素構造材料
（ｉ）フラーレン
フロンティアカーボン（株）製、商品名：フラーレンＣ６０−ＳＵＨ
（ii）カーボンナノホーン
ＮＥＣ（株）製、カーボンナノホーン
（iii）単層カーボンナノチューブ、
Sun Nanotech Co Ltd製、商品名：SUNNANO(SWNT)
（iv）２ないし１０層の多層カーボンナノチューブ
Sun Nanotech Co Ltd製、商品名：SUNNANO(B-MWNT)
（ｖ）気相成長炭素繊維
昭和電工（株）製、商品名：ＶＧＣＦ
（vi）活性炭素
米国スーペリア・グラファイト社製、商品名：ＣＧＣ鱗片状黒鉛No2935
The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these methods.
The carbon structural materials used in Examples 1 to 5 are shown below.
(1) Carbon structural material (i) Fullerene Frontier Carbon Co., Ltd., trade name: Fullerene C60-SUH
(Ii) carbon nanohorn manufactured by NEC Corporation, carbon nanohorn (iii) single-walled carbon nanotube,
Product name: SUNNANO (SWNT), manufactured by Sun Nanotech Co Ltd
(Iv) 2 to 10 multi-walled carbon nanotubes
Product name: SUNNANO (B-MWNT), manufactured by Sun Nanotech Co Ltd
(V) Vapor growth carbon fiber Showa Denko Co., Ltd., trade name: VGCF
(Vi) Activated carbon Product name: CGC scaly graphite No2935, manufactured by Superior Graphite, USA
（２）炭素構造材料の剛性率とアスペクト比
炭素構造材料の剛性率とアスペクト比を表１に示す。
（ｉ）アスペクト比の測定
アスペクト比と最大粒径は走査電子顕微鏡（ＳＥＭ）を用いてそれぞれの炭素構造材料を１０個ずつ観察し、最大サイズと最小サイズを測定して、その平均値からアスペクト比を求めた。
（ii）剛性率の測定
参考文献（Wong E W, Sheehan P E and Lieber C M 1997 Science 277 1971）に記載の方法を採用した。先ず各種ナノカーボンのヤング率を測定し、ポアソン比を０．２として下式から剛性率Ｇを算出した。
Ｇ＝Ｅ／［２（１＋γ）］
E:ヤング率、γ:ポアソン比
(2) Stiffness and aspect ratio of carbon structural material Table 1 shows the rigidity and aspect ratio of the carbon structural material.
(I) Measurement of aspect ratio The aspect ratio and the maximum particle diameter were measured with 10 pieces of each carbon structural material using a scanning electron microscope (SEM), the maximum size and the minimum size were measured, and the average value was calculated from the average value. The ratio was determined.
(Ii) Measurement of rigidity modulus The method described in the reference (Wong EW, Sheehan PE and Lieber CM 1997 Science 277 1971) was adopted. First, the Young's modulus of various nanocarbons was measured, and the rigidity G was calculated from the following equation with a Poisson's ratio of 0.2.
G = E / [2 (1 + γ)]
E: Young's modulus, γ: Poisson's ratio
[実施例１]
ニッケルマトリックス中に炭素構造材料が分散している表面被覆剤を調製して、摺動性の評価を行った。
（１）サンプルの調製
ＮｉＳＯ４・６Ｈ２Ｏ、ＮｉＣｌ２・６Ｈ２Ｏ、Ｈ３ＢＯ３をそれぞれ１：０．２：０．５の質量割合で溶解されているNiめっき浴１リットル（L）中に、表２に示す割合の炭素構造材料を分散させ、攪拌しながら、２０℃、５３ＲＨで２Ａ／ｄｍ２の電流密度で通電して接点材にめっきを行った。
（２）評価方法
動摩擦係数の測定
バウデン型摩擦試験器を用い、荷重２９４ｍＮ、摺動距離１０ｍｍ、摺動速度１００Ｍ／ｍｉｎ、摺動回数１回の条件下で測定。なお、相手材としては、板厚０.２５ｍｍの黄銅条にリフローＳｎめっきを１μｍ施したのち、０.５ｍｍＲに張り出し加工を行ったものを用いた。
（３）評価結果
評価結果をまとめて表２に示す。
表２から、単層カーボンナノチューブ、２〜１０層の多層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆材中の体積割合が１〜３０体積％において、ブランクと比較して動摩擦係数が低下しており、摺動性の向上が確認された。
[Example 1]
A surface coating agent in which a carbon structural material is dispersed in a nickel matrix was prepared, and the slidability was evaluated.
(1) Preparation of sample 1 liter of Ni plating bath in which NiSO 4 · 6H 2 O, NiCl 2 · 6H 2 O, and H 3 BO 3 are dissolved at a mass ratio of 1: 0.2: 0.5 (L ), The carbon structural material in the ratio shown in Table 2 was dispersed, and while stirring, the contact material was plated by energizing at 20 ° C. and 53 RH at a current density of 2 A / dm 2 .
(2) Evaluation Method Measurement of Dynamic Friction Coefficient Using a Bowden friction tester, measurement was performed under the conditions of a load of 294 mN, a sliding distance of 10 mm, a sliding speed of 100 M / min, and a sliding frequency of once. As the mating material, a brass strip having a thickness of 0.25 mm was subjected to reflow Sn plating of 1 μm and then subjected to an overhanging process to 0.5 mmR.
(3) Evaluation results Table 2 summarizes the evaluation results.
From Table 2, for single-walled carbon nanotubes, 2- to 10-walled multi-walled carbon nanotubes, carbon nanohorns, and fullerenes, the coefficient of dynamic friction is lower than that of the blank when the volume ratio in the surface coating is 1 to 30% by volume. The improvement of slidability was confirmed.
[実施例２]
ニッケルマトリックス中に炭素構造材料が分散している表面被覆剤を調製して耐食性の評価をフェロキシル試験に基づいて行った。
（１）サンプルの調製
実施例１に記載したと同様の方法で評価用のサンプルを調製した。
（２）評価方法
フェロキシル試験は、JIS H B617付属書３の規定に準じて行った。
すなわち、試験紙をフェロシアン化カリウム、フェリシアン化カリウム及び塩化ナトリウムの混合液に浸し、めっき面にはり付けて、めっき面のピンホール発生の有無を観察した。
（３）評価結果
評価結果をまとめて表３に示す。
尚、表中ピンホールが確認されない場合は○、ピンホールが確認された場合は×印で表示した。
表３から、単層カーボンナノチューブ、２〜１０層の多層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆材中の体積割合１ないし３０体積％の場合に、ブランクと比較して耐食性が向上することが確認された。
[Example 2]
A surface coating agent in which a carbon structural material was dispersed in a nickel matrix was prepared, and corrosion resistance was evaluated based on a ferroxyl test.
(1) Preparation of sample A sample for evaluation was prepared in the same manner as described in Example 1.
(2) Evaluation method The ferroxyl test was conducted according to the provisions of JIS H B617 Annex 3.
That is, the test paper was immersed in a mixed solution of potassium ferrocyanide, potassium ferricyanide, and sodium chloride and adhered to the plated surface, and the presence or absence of pinholes on the plated surface was observed.
(3) Evaluation results Table 3 summarizes the evaluation results.
In the table, the case where no pinhole was confirmed was indicated by ○, and the case where a pinhole was confirmed was indicated by ×.
From Table 3, for single-walled carbon nanotubes, 2- to 10-layered multi-walled carbon nanotubes, carbon nanohorns, and fullerenes, the corrosion resistance is improved compared to the blank when the volume ratio in the surface coating material is 1 to 30% by volume. It was confirmed.
[実施例３]
電解めっきによりスズマトリックス中に炭素構造材料が分散している表面被覆剤を調製して、ウィスカーの成長評価試験を行った。
（１）サンプルの調製
Ｈ2ＳＯ4・６Ｈ2Ｏ、ＳｎＳＯ4・６Ｈ2Ｏが1：1の質量割合で溶解されているＳｎめっき浴１L中に表４に示す配合割合の炭素構造材料を分散させ、攪拌しながら、２０℃、相対湿度５２％の条件下で接点材へ２Ａ／ｄｍ２の電流密度で通電してめっきを行った。
（２）評価方法
短絡を引き起こすウィスカーの成長し易さを調べた。すなわち、上記で調製したサンプルを温度５０℃のエアバス内に1ヶ月放置した後、ウィスカーの発生の有無を顕微鏡観察により調べた。
（３）評価結果
評価結果をまとめて表４に示す。
表４から、単層カーボンナノチューブ、２〜１０層の多層カーボンナノチューブ、カーボンナノホーン、及びフラーレンについて、表面被覆剤中の体積割合１ないし３０体積％において、ウィスカーの発生が観察されなかった。
[Example 3]
A surface coating agent in which a carbon structural material is dispersed in a tin matrix was prepared by electrolytic plating, and a whisker growth evaluation test was performed.
(1) Preparation of sample Carbon structural materials having the blending ratios shown in Table 4 in 1 L of Sn plating bath in which H 2 SO 4 .6H 2 O and SnSO 4 .6H 2 O are dissolved at a mass ratio of 1: 1. While being dispersed and stirred, the contact material was plated at a current density of 2 A / dm 2 under conditions of 20 ° C. and a relative humidity of 52%.
(2) Evaluation method The ease of growth of whiskers that cause a short circuit was examined. That is, after the sample prepared above was left in an air bath at a temperature of 50 ° C. for 1 month, the presence or absence of whisker generation was examined by microscopic observation.
(3) Evaluation results Table 4 summarizes the evaluation results.
From Table 4, with respect to single-walled carbon nanotubes, 2 to 10 multi-walled carbon nanotubes, carbon nanohorns, and fullerenes, no occurrence of whiskers was observed at a volume ratio of 1 to 30% by volume in the surface coating agent.
[実施例４、比較例１]
無電解めっきによりニッケルマトリックス中にＳＷＣＮＴが分散している表面被覆材を調製して、摺動性、腐食性、及びウィスカーの成長評価試験を行った。
（１）サンプルの調製
実施例４として、下記組成のＳＷＣＮＴ１０体積％含む無電解ニッケルめっき液を常法に従って調製した。また、比較例１としてＳＷＣＮＴのみを含まない下記組成のめっき液を調製した。
ＳＷＣＮＴ以外に無電解ニッケルめっき液は、硫酸ニッケル７水和物２５ｇ／Ｌ、次亜リン酸ナトリウム一水和物２０ｇ／Ｌ、ＤＬ−リンゴ酸２５ｇ／Ｌ、乳酸１０ｇ／Ｌ、酢酸５ｇ／Ｌ、安定化剤としてモリブデン５０ｍｇ／Ｌ及びビスマス０．５ｍｇ／Ｌを含む水溶液である。
被めっき試験片として、ＳＰＣＣ−ＳＢの鉄板（サイズ：０．３ｍｍ×５０ｍｍ×５０ｍｍ）を用い、上記各無電解ニッケルめっき液１Ｌ中に、下記めっき条件のもとで浸漬し、無電解ニッケルめっきを行った。
めっき液のｐＨ：４．９、浴温：９０℃、撹拌：空気撹拌、めっき時間：２０分間
（２）評価方法
得られた無電解ニッケルめっき表面被覆材について、摺動性、腐食性、及びウィスカーの発生を評価した。尚、摺動性は前記実施例１、腐食性は前記実施例２、ウィスカー発生の評価は前記実施例３にそれぞれ記載した方法と同じである。
（３）評価結果
評価結果をまとめて表５に示す。表５からＳＷＣＮＴ１０体積％含む表面被覆剤は、摺動性、腐食性、及びウィスカー発生の抑制に優れていることが確認できた。
[Example 4, Comparative Example 1]
A surface coating material in which SWCNT is dispersed in a nickel matrix was prepared by electroless plating, and slidability, corrosivity, and whisker growth evaluation tests were performed.
(1) Preparation of Sample As Example 4, an electroless nickel plating solution containing 10% by volume of SWCNT having the following composition was prepared according to a conventional method. Moreover, the plating solution of the following composition which does not contain only SWCNT as the comparative example 1 was prepared.
In addition to SWCNT, electroless nickel plating solution is nickel sulfate heptahydrate 25 g / L, sodium hypophosphite monohydrate 20 g / L, DL-malic acid 25 g / L, lactic acid 10 g / L, acetic acid 5 g / L An aqueous solution containing 50 mg / L molybdenum and 0.5 mg / L bismuth as a stabilizer.
An SPCC-SB steel plate (size: 0.3 mm x 50 mm x 50 mm) was used as the test piece to be plated, and immersed in 1 L of the above electroless nickel plating solution under the following plating conditions. Went.
PH of plating solution: 4.9, bath temperature: 90 ° C., stirring: air stirring, plating time: 20 minutes (2) Evaluation method About the obtained electroless nickel plating surface coating material, slidability, corrosivity, and The occurrence of whiskers was evaluated. Note that the slidability is the same as the method described in Example 1, the corrosivity is the same as in Example 2, and the evaluation of whisker generation is the same as that described in Example 3.
(3) Evaluation results Table 5 summarizes the evaluation results. From Table 5, it was confirmed that the surface coating agent containing 10% by volume of SWCNT was excellent in slidability, corrosivity, and suppression of whisker generation.
[実施例５、比較例２]
焼結によりニッケル粒子間にＳＷＣＮＴを分散させた表面被覆材を調製して、摺動性、腐食性、及びウィスカーの成長評価試験を行った。
（１）サンプルの調製
（ｉ）無電解還元による焼結用ニッケル粒子の調製
下記組成で、含む無電解ニッケルめっき液を常法に従って調製した。
無電解ニッケルめっき液は、硫酸ニッケル７水和物 ２５ｇ／Ｌ、次亜リン酸ナトリウム一水和物 ２０ｇ／Ｌ、ＤＬ−リンゴ酸 ２５ｇ／Ｌ、乳酸 １０ｇ／Ｌ、酢酸 ５ｇ／Ｌ、安定化剤としてモリブデン５０ｍｇ／Ｌ及びビスマス０．２ｍｇ／Ｌからなる水溶液である。上記各無電解ニッケルめっき浴１Ｌ中で、下記めっき条件のもとで無電解還元によるニッケル粒子を作製した。
めっき液のｐＨ：４．９、浴温：９０℃、撹拌：空気撹拌、めっき時間：２０分間
（ii）ニッケル粒子とＳＷＣＮＴとの焼結
得られたＮｉ粒子とＳＷＣＮＴを体積比９０：１０の割合で混合したものを、ＳＰＣＣ−ＳＢの鉄板（サイズ：０．３ｍｍ×５０ｍｍ×５０ｍｍ）の上部に乗せ、Ａｒガス雰囲気中１０００℃で熱処理を行い、Ｎｉ／ＳＷＣＮＴからなる表面被覆材を形成した。また比較例２としてＳＷＣＮＴを含まないＮｉ粒子のみを同条件で熱処理、焼結して上記と同じＳＰＣＣ−ＳＢの鉄板上に表面被覆材を形成した。
（２）評価方法
得られた表面被覆材について、摺動性、腐食性、及びウィスカー発生を評価した。尚、摺動性は実施例１、腐食性は実施例２、ウィスカー発生の評価は実施例３にそれぞれ記載した方法と同じである。
[Example 5, Comparative Example 2]
A surface coating material in which SWCNTs were dispersed between nickel particles was prepared by sintering, and slidability, corrosiveness, and whisker growth evaluation tests were performed.
(1) Preparation of sample (i) Preparation of nickel particles for sintering by electroless reduction An electroless nickel plating solution containing the following composition was prepared according to a conventional method.
Electroless nickel plating solution is nickel sulfate heptahydrate 25 g / L, sodium hypophosphite monohydrate 20 g / L, DL-malic acid 25 g / L, lactic acid 10 g / L, acetic acid 5 g / L, stabilized It is an aqueous solution consisting of molybdenum 50 mg / L and bismuth 0.2 mg / L as an agent. In each electroless nickel plating bath 1L, nickel particles were produced by electroless reduction under the following plating conditions.
PH of the plating solution: 4.9, bath temperature: 90 ° C., stirring: air stirring, plating time: 20 minutes (ii) Sintering of nickel particles and SWCNT The obtained Ni particles and SWCNT were in a volume ratio of 90:10 What was mixed at a ratio was placed on top of an SPCC-SB iron plate (size: 0.3 mm × 50 mm × 50 mm) and heat treated at 1000 ° C. in an Ar gas atmosphere to form a surface coating material made of Ni / SWCNT. . In Comparative Example 2, only Ni particles not containing SWCNTs were heat-treated and sintered under the same conditions to form a surface coating material on the same SPCC-SB iron plate as described above.
(2) Evaluation method About the obtained surface coating material, sliding property, corrosivity, and whisker generation | occurrence | production were evaluated. Note that the slidability is the same as the method described in Example 1, the corrosiveness is Example 2, and the evaluation of whisker generation is the same as the method described in Example 3.
（３）評価結果
評価結果をまとめて表６に示す。表６からＳＷＣＮＴ１０体積％含む表面被覆材は、摺動性、腐食性、及びウィスカー発生の抑制等に優れていることが確認できた。
(3) Evaluation results Table 6 summarizes the evaluation results. From Table 6, it was confirmed that the surface covering material containing 10% by volume of SWCNT was excellent in slidability, corrosivity, suppression of whisker generation, and the like.
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