JPH0816262B2 - Electrical wire - Google Patents
Electrical wireInfo
- Publication number
- JPH0816262B2 JPH0816262B2 JP62002137A JP213787A JPH0816262B2 JP H0816262 B2 JPH0816262 B2 JP H0816262B2 JP 62002137 A JP62002137 A JP 62002137A JP 213787 A JP213787 A JP 213787A JP H0816262 B2 JPH0816262 B2 JP H0816262B2
- Authority
- JP
- Japan
- Prior art keywords
- coating
- film
- copper
- electric wire
- sample
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000010408 film Substances 0.000 claims description 35
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 34
- 229910052802 copper Inorganic materials 0.000 claims description 34
- 239000010949 copper Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 3
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 2
- 239000011368 organic material Substances 0.000 claims description 2
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 18
- 230000007797 corrosion Effects 0.000 description 18
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 10
- 239000010936 titanium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- -1 and further On top Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Landscapes
- Insulated Conductors (AREA)
- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、銅を基材とする電線に関し、特に耐熱
性、耐蝕性、耐摩耗性、を付与するために基材表面に被
覆を施した電線に関するものである。Description: TECHNICAL FIELD The present invention relates to an electric wire using copper as a base material, and in particular, has a coating on the surface of the base material in order to impart heat resistance, corrosion resistance, and wear resistance. It is related to the electric wire.
［従来の技術］ 電気部品、機械部品、電線などでは、電気伝導性の良
い銅を基材とする部材が多く使用されている。そのよう
な部材は、使用環境に応じて、耐熱性、耐食性、耐摩耗
性が要求される。[Prior Art] In electrical parts, mechanical parts, electric wires, and the like, members having copper as a base material having good electric conductivity are often used. Such members are required to have heat resistance, corrosion resistance, and wear resistance depending on the use environment.
ところが、銅は、耐熱性、耐食性、耐摩耗性が劣って
いる。そこで、それらの特性を付与するために、銅の表
面に銅以外の金属または半金属の化合物からなる膜を被
覆したものが用いられている。たとえば、昭和60年10月
17日に国内公表されたレイケム社出願の公表特許公報昭
60−501783号公報には、高温下で使用される電気ワイヤ
に対して耐熱性を付与するためにその表面に酸化物また
は窒化物などを被覆したものが開示されている。その被
覆を形成する化合物の例としてはアルミニウム、ケイ
素、チタン、タンタルの酸化物または窒化物が挙げられ
ている。However, copper is inferior in heat resistance, corrosion resistance, and wear resistance. Therefore, in order to impart those properties, a copper surface coated with a film made of a compound of a metal other than copper or a metalloid is used. For example, October 1985
Published Patent Gazette of Raychem Co., Ltd. published in Japan on the 17th
Japanese Patent Laid-Open No. 60-501783 discloses a wire whose surface is coated with oxide or nitride in order to impart heat resistance to an electric wire used under high temperature. Examples of compounds forming the coating include aluminum, silicon, titanium, tantalum oxides or nitrides.
酸化物は耐熱性、耐摩耗性、耐食性に対して優れた特
性を示すので、酸化物を被覆した電気ワイヤは耐熱性、
耐摩耗性、耐食性に優れたものとなる。Since oxides have excellent heat resistance, wear resistance, and corrosion resistance, electric wires coated with oxides have excellent heat resistance,
It has excellent wear resistance and corrosion resistance.
［発明が解決しようとする問題点］ 上述のように示されているとおり、Al2O3,SiO2などの
酸化物は、耐熱性、耐食性、耐摩耗性については良好な
性質を示すことが知られている。しかし、これらの酸化
物は、銅に対する密着性があまり良くない。そのため、
たとえば酸化物を被覆して電気ワイヤを腐食環境下で長
期間使用した場合、酸化物が銅の表面からはく離し、そ
の部分から腐食が進行することがある。[Problems to be Solved by the Invention] As described above, oxides such as Al 2 O 3 and SiO 2 may exhibit good heat resistance, corrosion resistance, and wear resistance. Are known. However, these oxides do not have very good adhesion to copper. for that reason,
For example, when the electric wire is coated with an oxide and the electric wire is used for a long time in a corrosive environment, the oxide may be peeled off from the surface of the copper, and corrosion may progress from that portion.
そこで、この発明は、これらの酸化物と銅との密着性
を高めることによって、長期間にわたって優れた耐熱
性、耐食性、耐摩耗性を発揮する、電線を提供すること
を目的とする。Therefore, an object of the present invention is to provide an electric wire that exhibits excellent heat resistance, corrosion resistance, and wear resistance over a long period of time by increasing the adhesion between these oxides and copper.
［問題点を解決するための手段］ この発明に従って電線は、少なくともその表面が銅ま
たは銅合金である基材の表面の上に、Ti化合物からなる
第１の被膜を形成し、さらにその被膜の上に、Al2O3、S
iO2、MgO、BeO、ZrO2、CaO、Ta2O5を含む群から選ばれ
た酸化物からなる第２の被膜を形成したものである。[Means for Solving the Problems] According to the present invention, an electric wire is formed by forming a first coating film made of a Ti compound on at least the surface of a substrate whose surface is copper or copper alloy, and further On top, Al 2 O 3 , S
The second coating is formed of an oxide selected from the group including iO 2 , MgO, BeO, ZrO 2 , CaO, and Ta 2 O 5 .
［発明の作用効果］ 銅に対して密着性の良い化合物としては、TiN,TiCな
どのTi化合物がある。しかし、TiN,TiCなどのTi化合物
は、酸化物に比較して耐熱性、耐食性、耐摩耗性に劣る
ことが実験により認められる。また、Ti化合物は、Al2O
3,SiO2,MgO,BeO,ZrO2,CaO,Ta2O5などの酸化物に対して
良好な密着性を呈することも実験により認められる。こ
の発明は、このような本願発明者等の知見に基づくもの
である。[Advantageous Effects of the Invention] Examples of compounds having good adhesion to copper include Ti compounds such as TiN and TiC. However, it is confirmed by experiments that Ti compounds such as TiN and TiC are inferior in heat resistance, corrosion resistance and wear resistance to oxides. Further, the Ti compound is Al 2 O.
It is also confirmed by experiments that good adhesion is exhibited to oxides such as 3 , SiO 2 , MgO, BeO, ZrO 2 , CaO, and Ta 2 O 5 . The present invention is based on the findings of the present inventors.
したがって、銅に対して密着性が良い、TiNまたはTiC
などのTi化合物を第１の被膜として銅基材の表面に形成
し、その上に耐熱性、耐食性、耐摩耗性に優れた、Al2O
3,SiO2,MgO,BeO,ZrO2,CaO,Ta2O5などの酸化物を第２の
被膜として形成する。そうすると、中間層として存在す
るTi化合物は、母材である銅基材と密着性が良く、ま
た、その上に形成された酸化物とも密着性が良いため、
被覆物全体が母材に対して良好な密着性を示す。また、
表層部を形成している酸化物が優れた耐熱性、耐食性、
耐摩耗性を発揮するので、電線は、長期にわたって優れ
た耐熱性、耐食性、耐摩耗性を呈する。Therefore, TiN or TiC, which has good adhesion to copper
A Ti compound such as Al is formed on the surface of the copper substrate as the first coating, and Al 2 O, which has excellent heat resistance, corrosion resistance, and wear resistance
An oxide such as 3 , SiO 2 , MgO, BeO, ZrO 2 , CaO, Ta 2 O 5 is formed as the second coating. Then, the Ti compound present as the intermediate layer has good adhesiveness to the copper base material as the base material, and also has good adhesiveness to the oxide formed thereon,
The entire coating shows good adhesion to the base material. Also,
Oxide forming the surface layer has excellent heat resistance, corrosion resistance,
Since it exhibits wear resistance, the electric wire exhibits excellent heat resistance, corrosion resistance, and wear resistance over a long period of time.
この発明において、第１の被覆としてのTi化合物およ
び第２の被膜としての酸化物は、真空蒸着法、イオンプ
レーティング、スパッタ、熱CVD、プラズマCVD等の気相
薄膜成長法によって形成されることが望ましい。気相薄
膜成長法によると、腐食の進行に悪影響を及ぼすピンホ
ールの発生がほとんどなく、強い密着力をもつ被覆が得
られるという利点がある。In the present invention, the Ti compound as the first coating and the oxide as the second coating are formed by a vapor phase thin film growth method such as vacuum deposition method, ion plating, sputtering, thermal CVD, plasma CVD and the like. Is desirable. According to the vapor phase thin film growth method, there is an advantage that a pinhole which has a bad influence on the progress of corrosion is hardly generated and a coating having a strong adhesion can be obtained.
さらに、第２の被膜としての酸化物の上に有機物から
なる被覆を形成して、電気絶縁性あるいは耐食性を向上
させるようにしてもよい。Further, a coating made of an organic material may be formed on the oxide as the second coating so as to improve the electric insulation or the corrosion resistance.
［実施例１］ 長さが30mm、幅が20mm、厚さが3mmの無酸素銅の板の
表面に、以下に示すように被覆を形成したサンプルを作
製した。Example 1 A sample was prepared in which a coating was formed on the surface of an oxygen-free copper plate having a length of 30 mm, a width of 20 mm and a thickness of 3 mm as shown below.
サンプルＡ（比較例） 銅板にプラズマCVD法により、膜厚５μｍのAl2O3膜を
形成したもの。Sample A (Comparative Example) A copper plate on which an Al 2 O 3 film having a film thickness of 5 μm was formed by a plasma CVD method.
サンプルＢ（比較例） 銅板にプラズマCVD法により、膜厚５μｍのSiO2膜を
形成したもの。Sample B (Comparative Example) A copper plate on which a SiO 2 film having a thickness of 5 μm is formed by a plasma CVD method.
サンプルＣ（比較例） 銅板にプラズマCVD法により、膜厚５μｍのMgO膜を形
成したもの。Sample C (Comparative Example) A copper plate on which an MgO film having a thickness of 5 μm is formed by a plasma CVD method.
サンプルＤ（比較例） 銅板にプラズマCVD法により、膜厚５μｍのTiC膜を形
成したもの。Sample D (Comparative Example) A copper plate on which a TiC film having a thickness of 5 μm is formed by a plasma CVD method.
サンプルＥ（比較例） 銅板にプラズマCVD法により、膜厚５μｍのTiN膜を形
成したもの。Sample E (Comparative Example) A copper plate on which a TiN film having a thickness of 5 μm is formed by a plasma CVD method.
サンプルＦ（本発明例） 銅板にプラズマCVD法により、膜厚１μｍのTiN膜を形
成し、その上に膜厚４μｍのAl2O3膜を形成したもの。Sample F (Example of the present invention) A TiN film having a film thickness of 1 μm is formed on a copper plate by a plasma CVD method, and an Al 2 O 3 film having a film thickness of 4 μm is formed thereon.
サンプルＧ（本発明例） 銅板にプラズマCVD法により、膜厚１μｍのTiC膜を形
成し、その上に膜厚４μｍのAl2O3膜を形成したもの。Sample G (Inventive Example) A copper plate on which a TiC film having a film thickness of 1 μm was formed by a plasma CVD method, and an Al 2 O 3 film having a film thickness of 4 μm was formed on the TiC film.
サンプルＨ（本発明例） 銅板にプラズマCVD法により、膜厚１μｍのTiC膜を形
成し、その上に膜厚４μｍのMgO膜を形成したもの。Sample H (Inventive Example) A TiC film having a film thickness of 1 μm is formed on a copper plate by a plasma CVD method, and an MgO film having a film thickness of 4 μm is formed on the TiC film.
サンプルＩ（本発明例） 銅板にプラズマCVD法により、膜厚１μｍのTiN膜を形
成し、その上に膜厚４μｍのSiO2膜を形成したもの。Sample I (Inventive Example) A TiN film having a film thickness of 1 μm is formed on a copper plate by a plasma CVD method, and a SiO 2 film having a film thickness of 4 μm is formed thereon.
第１図に示すように、銅板２上に被覆３が形成されて
いる各サンプル１の被膜表面の上に、直径10mmφ、長さ
40mmの銅棒５を立てて瞬間接着剤４で接着する。その
後、銅棒５が倒れるまで矢印Ａで示す水平方向に力を加
える。そのとき銅棒５がサンプル１から離れた後、はく
離部分を観察し、どの界面ではく離を起こすかを調べ
た。その結果を第１表に示す。As shown in FIG. 1, on the coating surface of each sample 1 in which the coating 3 is formed on the copper plate 2, the diameter is 10 mmφ and the length is
A 40 mm copper rod 5 is set up and bonded with an instant adhesive 4. Then, force is applied in the horizontal direction indicated by arrow A until the copper rod 5 falls. At that time, after the copper rod 5 was separated from the sample 1, the peeled portion was observed to examine at which interface the peeling occurred. The results are shown in Table 1.
以上の結果から、まず中間層としてTiCまたはTiN膜を
形成し、さらにその上にAl2O3,SiO2,MgO膜を形成した場
合、２つの瞬間の密着力および銅板とTi化合物膜との間
の密着力は、接着剤による密着力よりも大きいことが認
められる。 From the above results, when a TiC or TiN film was first formed as an intermediate layer and then an Al 2 O 3 , SiO 2 , MgO film was formed thereon, the adhesive force between two moments and the copper plate and the Ti compound film were It is recognized that the adhesion force between the two is greater than the adhesion force due to the adhesive.
［実施例２］ 実施例１と同様のサンプルを使用して、60％HNO3溶液
中に常温で24時間浸けた後、サンプル表面に腐食状態を
観察した。その結果を第２表に示す。Example 2 Using the same sample as in Example 1, the sample was immersed in a 60% HNO 3 solution at room temperature for 24 hours, and then a corrosion state was observed on the surface of the sample. Table 2 shows the results.
以上の結果から明らかなように、Al2O3,SiO2,MgO膜を
直接銅板上に形成したサンプルA,B,Cでは、著しく腐食
が進行した。これは被膜と銅板との密着性が極めて悪い
ため、膜に一部ピンホールが存在すると、そのピンホー
ルからHNO3溶液が被膜と銅板との界面へ容易に浸入し、
腐食が進行したものと考えられる。 As is clear from the above results, in Samples A, B, and C in which the Al 2 O 3 , SiO 2 , and MgO films were formed directly on the copper plate, the corrosion progressed remarkably. This is because the adhesion between the coating and the copper plate is extremely poor, so if there are some pinholes in the film, the HNO 3 solution easily penetrates into the interface between the coating and the copper plate from the pinholes,
It is considered that the corrosion has progressed.
一方、中間層にTiCまたはTiN膜を形成し、さらにその
上にAl2O3,SiO2,MgO膜を形成したサンプルF,G,H,Iは、
耐食性が良好であることがわかった。On the other hand, the samples F, G, H, I in which a TiC or TiN film is formed in the intermediate layer, and Al 2 O 3 , SiO 2 , and MgO films are further formed thereon are
It was found that the corrosion resistance was good.
第１図は、この発明の実施例で示した試験方法を示す断
面図である。 図において、１はサンプル、２は銅板、３は被膜、４は
接着剤、５は銅棒を示す。FIG. 1 is a sectional view showing the test method shown in the embodiment of the present invention. In the figure, 1 is a sample, 2 is a copper plate, 3 is a coating, 4 is an adhesive, and 5 is a copper rod.
Claims (5)
る基材の表面の上に、Ti化合物からなる第１の被膜を形
成し、 さらに前記第１の被膜の上に、Al2O3,SiO2,MgO,BeO,ZrO
2,CaO,Ta2O5を含む群から選ばれた酸化物からなる第２
の被膜を形成した、電線。1. A first coating made of a Ti compound is formed on at least the surface of a substrate whose surface is copper or a copper alloy, and Al 2 O 3 , SiO 2 , MgO, BeO, ZrO
Second oxide consisting of oxides selected from the group including 2 , CaO and Ta 2 O 5
An electric wire that has a coating of.
許請求の範囲第１項記載の電線。2. The electric wire according to claim 1, wherein the Ti compound is TiN or TiC.
て形成されている、特許請求の範囲第１項または第２項
記載の電線。3. The electric wire according to claim 1, wherein the first coating film is formed by a vapor phase thin film growth method.
て形成されている、特許請求の範囲第１項ないし第３項
のいずれかに記載の電線。4. The electric wire according to claim 1, wherein the second coating film is formed by a vapor phase thin film growth method.
なる、特許請求の範囲第１項ないし第４項のいずれかに
記載の電線。5. The electric wire according to any one of claims 1 to 4, wherein an organic material coating is provided on the second coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002137A JPH0816262B2 (en) | 1987-01-08 | 1987-01-08 | Electrical wire |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62002137A JPH0816262B2 (en) | 1987-01-08 | 1987-01-08 | Electrical wire |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63171867A JPS63171867A (en) | 1988-07-15 |
| JPH0816262B2 true JPH0816262B2 (en) | 1996-02-21 |
Family
ID=11520948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62002137A Expired - Lifetime JPH0816262B2 (en) | 1987-01-08 | 1987-01-08 | Electrical wire |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0816262B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5079089A (en) * | 1988-07-28 | 1992-01-07 | Nippon Steel Corporation | Multi ceramic layer-coated metal plate and process for manufacturing same |
| DE4336664A1 (en) * | 1993-10-27 | 1995-05-04 | Demetron Gmbh | Workpieces made of non-corrosion-resistant metals with coatings applied using the PVD process |
| CN119320930B (en) * | 2024-10-24 | 2025-08-15 | 华南理工大学 | Preparation method of thermal shock resistant alumina coating |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57120667A (en) * | 1981-01-17 | 1982-07-27 | Sumitomo Electric Ind Ltd | Lamination coating material |
| JPS60258462A (en) * | 1984-06-05 | 1985-12-20 | Nippon Kogaku Kk <Nikon> | Soft metallic base material having hardened surface |
-
1987
- 1987-01-08 JP JP62002137A patent/JPH0816262B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63171867A (en) | 1988-07-15 |
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