JPS599167A - Thin metallic film - Google Patents
Thin metallic filmInfo
- Publication number
- JPS599167A JPS599167A JP57117281A JP11728182A JPS599167A JP S599167 A JPS599167 A JP S599167A JP 57117281 A JP57117281 A JP 57117281A JP 11728182 A JP11728182 A JP 11728182A JP S599167 A JPS599167 A JP S599167A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- corrosion resistance
- metallic film
- thin metallic
- halogen
- 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.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 20
- 150000002367 halogens Chemical class 0.000 claims abstract description 19
- 229910000531 Co alloy Inorganic materials 0.000 claims abstract 2
- 239000010409 thin film Substances 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 238000005260 corrosion Methods 0.000 abstract description 18
- 230000007797 corrosion Effects 0.000 abstract description 18
- 150000002739 metals Chemical class 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 150000004820 halides Chemical class 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 229910000990 Ni alloy Inorganic materials 0.000 abstract description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052731 fluorine Inorganic materials 0.000 abstract 1
- 229910052740 iodine Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000004381 surface treatment Methods 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 239000012496 blank sample Substances 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010297 mechanical methods and process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910020630 Co Ni Inorganic materials 0.000 description 1
- 229910002440 Co–Ni Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- ANOBYBYXJXCGBS-UHFFFAOYSA-L stannous fluoride Chemical compound F[Sn]F ANOBYBYXJXCGBS-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
- G11B5/62—Record carriers characterised by the selection of the material
- G11B5/64—Record carriers characterised by the selection of the material comprising only the magnetic material without bonding agent
- G11B5/65—Record carriers characterised by the selection of the material comprising only the magnetic material without bonding agent characterised by its composition
- G11B5/656—Record carriers characterised by the selection of the material comprising only the magnetic material without bonding agent characterised by its composition containing Co
Landscapes
- Physical Vapour Deposition (AREA)
- Magnetic Record Carriers (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、耐腐食性のすぐれた薄膜金属に関するＯ
従来、表面処理により耐腐食性が改善された金属として
ｄｌ、表面に酸化物等による不動態膜が形成されたもの
、また、各種の有機系や無機系の防錆剤で表面処理され
たもの等がある。しかし、これらの例は、金属が大きな
バルク状の場合に限られており、金属が、蒸着等の方法
やその他の機械的な方法で形成された薄膜状の場合には
、その金属の持つ物理的性質がそこなわれやすいという
不都合があった。たとえば金属のバルクが表面積に対し
て非常に小さな場合、すなわち、蒸着等で形成された薄
膜状の場合には、不動態膜の形成を試みると、不動態膜
部分の性質の寄与が大きくなり、本来の金属としての性
質がそこなわれるものであるのさらに、金属としての物
理的性質（電気伝導性や磁気的性質）を利用しようとす
る場合にも、せない不都合があった。言い換えると、犬
き々バルク状の金属においては問題にならなかったこと
でも、薄膜状の金属の場合には、表面処理の程度が、金
属の天来の性質に大きな影響を与えるということである
。このような表面処理が重要になる薄膜金庫の厚みは約
１０１１０１ｌ下である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thin film metal with excellent corrosion resistance. Conventionally, as a metal whose corrosion resistance has been improved by surface treatment, a passive film of oxide or the like is formed on the surface of dl. There are also those whose surface has been treated with various organic and inorganic rust preventive agents. However, these examples are limited to cases where the metal is in the form of a large bulk, and when the metal is in the form of a thin film formed by methods such as vapor deposition or other mechanical methods, the physical properties of the metal There was a disadvantage that the physical properties were easily damaged. For example, when the bulk of the metal is very small relative to its surface area, in other words, when it is in the form of a thin film formed by vapor deposition, when attempting to form a passive film, the contribution of the properties of the passive film becomes large; In addition to damaging the original properties of metals, there are also disadvantages when attempting to utilize the physical properties of metals (electrical conductivity and magnetic properties). In other words, the degree of surface treatment has a significant impact on the natural properties of metals, even though this would not be a problem in the case of metals in the form of a thin film. . The thickness of a thin film safe for which such surface treatment becomes important is approximately 101101 l or less.
以上のような、不都合な点をかんがみ、本発明者等は、
極めてＲ１？ｔのハロゲン元素を、金属の表面に導入す
ることにより、金属が薄膜状の場合においても、その金
属本来の性質が失なわれずに、すぐれた耐腐食性を有す
ることを見い出したものである。In view of the above disadvantages, the inventors of the present invention
Extremely R1? It was discovered that by introducing a halogen element of t into the surface of a metal, the metal retains its original properties and has excellent corrosion resistance even when the metal is in the form of a thin film. .
以下本発明の詳細な説明する〇
実施例
ポリエチレンテレナタレー１− （Ｐ Ｅ Ｔ ）フィ
ルム上に、通常の蒸着法によりＣｏ−Ｎｉ合金薄膜を形
成したのこの薄膜金属に以下のような各種の方法で、そ
の表面にハロゲン元素を極めて微°微導入した。The present invention will be described in detail below.Example 1-A Co-Ni alloy thin film was formed on a polyethylene terenatal (PET) film by a conventional vapor deposition method. Then, a very small amount of halogen element was introduced onto the surface.
ａ１ハロゲンのガス中に放置３、
ｂ１希薄なハロゲン化水素水溶液に浸漬もしくは溶液を
塗布後、水洗し乾燥。a1 Leave in halogen gas 3, b1 Immerse in dilute aqueous hydrogen halide solution or apply the solution, then wash with water and dry.
Ｃ１希薄なハロゲン化物の溶液に浸漬もしくは溶液を塗
布後、溶媒で洗浄し乾燥。C1 After immersing in or applying the solution to a dilute halide solution, wash with a solvent and dry.
ハロゲン化物としては、アルカリ金属やアルカリ土類金
属等の各種の金属のノ・ロゲン化物、またその他の例と
（７て、・・ロゲン化第−錫（ＳｎＸ２）等があり、又
、溶媒としてけノ・ロゲン化物を溶かすものであれば、
水、有機溶媒等が適用可能である。Examples of halides include halogenides of various metals such as alkali metals and alkaline earth metals, as well as other examples (7), such as tin halogenide (SnX2), and as solvents. If it is something that dissolves kenorogenide,
Water, organic solvents, etc. are applicable.
ただし、以」二のハロゲン元素の導入に際しては、その
処理時間、処理濃度等を極めて注意深く制御する必要が
あり、処理条件が激しすぎれば、処理中に、金属へのハ
ロゲンの導入が進みすき、所期の目的を達し得ない。例
えばノ・ロゲン化物溶液による処理においては、その濃
度は一般に０．１〜１１０００ｐｐ程度で充分であり、
浸漬時間も大ていの場合数秒間で処理を終える。又、ノ
・ロゲンのガスで処理する場合には、ガスと接触する時
間の制御や、温度制御プラズマ中での処理等との組み合
わせもｎＪ能である。However, when introducing the second halogen element, it is necessary to control the treatment time, treatment concentration, etc. extremely carefully; if the treatment conditions are too harsh, the introduction of halogen into the metal may progress during the treatment. , the intended purpose cannot be achieved. For example, in treatment with a chloride solution, a concentration of about 0.1 to 11,000 pp is generally sufficient;
In most cases, the immersion time is just a few seconds. Furthermore, in the case of treatment with a gas of no or gen, the combination with control of the contact time with the gas, treatment in a temperature-controlled plasma, etc. is also an nJ function.
このようにして、得られたサンプルを６０°Ｃ７９０％
ＲＨでの耐腐食性試験にかけたところ、いずれの方法で
作成したサンプルも、ブランクのものより耐腐食性が同
士ｊ〜でいた。In this way, the obtained sample was heated at 60°C, 790%
When subjected to a corrosion resistance test at RH, the samples prepared by either method had a corrosion resistance that was better than that of the blank.
すなわち、未処理のものが２「１の面１腐食性試験後、
ひっかきテストにおいて剥離が見られたのに対し、ハロ
ゲン元素を表面に微量導入したものにおいては、ひっか
きテストにおいて剥離が見られるまでの耐腐食性試験の
期間は３日から１０）Ｉｔで延長される。That is, after the untreated one surface 1 corrosion test of 2"1,
While peeling was observed in the scratch test, the period of corrosion resistance test until peeling was observed in the scratch test was extended by 3 days to 10) for those with a small amount of halogen element introduced to the surface. .
とのひっかきテストは、レコード釧に一定の荷重をかけ
、薄膜金属の表面をひっかき、金属のケズレ（削れ）や
刷Ｉ Ｉｆを見るテストである。The scratch test is a test in which a certain load is applied to a record hook, the surface of a thin metal film is scratched, and the scratches (scratches) and impressions of the metal are observed.
以上の例の中でも、ハロゲンとしてＦを用いた場合に、
耐腐食性の向上は顕著であっｆｒ、。たとえば、実施例
１において、５ｎＸ２溶液による処理の場合、ひっかき
テストをパスする耐腐食性試験のＦ１ａ１ｄ：、それぞ
れＦの場合、１０ Ｆｌ 、 Ｃｅノ場合８山Ｂｒの場
合７日、■の場合６日であった。Among the above examples, when F is used as the halogen,
The improvement in corrosion resistance is remarkable. For example, in Example 1, in the case of treatment with a 5nX2 solution, the corrosion resistance test that passes the scratch test F1a1d:, 10 Fl for F, 8 for Ce, 7 days for Br, 6 for ■ It was day.
本発明は、特に、金属の磁性を利用する場合の薄膜金属
において有効である。本実施例のコバルト−ニッケル合
金は磁性相であり、このまま磁気テープとして利ＩＩＩ
できる。磁気テープとしての記録特性を見ると、本発明
におけるサンプルにおいては、ブランクのサンプルと比
較して出力のダウンは殆んど見られながらだ。一方、通
常の有機系防錆材で処理された場合においては、本発明
のハロゲン元素の導入による場合と同等の面１腐食性を
保つためには、出力のダウン（３〜５ｄＢ）がさけられ
なかった。The present invention is particularly effective in thin film metals that utilize the magnetism of metals. The cobalt-nickel alloy of this example is in a magnetic phase and can be used as a magnetic tape as it is.
can. Looking at the recording characteristics as a magnetic tape, in the sample according to the present invention, there is almost no decrease in output compared to the blank sample. On the other hand, when treated with a normal organic rust preventive material, a reduction in output (3 to 5 dB) must be avoided in order to maintain surface 1 corrosion resistance equivalent to that obtained by introducing the halogen element of the present invention. There wasn't.
伺は加えるに、本発明の効果として、この例のごとく、
磁気テープとして利用する場合、走行性の改善がなされ
る。すなわち、ブランクのサンプルの薄膜金属面の摩擦
係数は、０．５〜０．６であるが、ハロゲン元素を導入
した場合、摩擦係数は０．２６〜０．３と半減するもの
である。In addition, as an effect of the present invention, as in this example,
When used as a magnetic tape, running properties are improved. That is, the friction coefficient of the thin film metal surface of the blank sample is 0.5 to 0.6, but when a halogen element is introduced, the friction coefficient is halved to 0.26 to 0.3.
寸だ、ハロゲン元素として、単独使用の実施例を示した
が、２種以−にのｆＪ１用も、もちろんｖ１能であるう
中でも、ＦとＣＩと併用した場合、その機構は不明であ
るが顕著な効果が見られた。すなわち、ＳｎＦ２とＳ
ｎＣ（１２の混合溶液による処理によって、ひっかきテ
ストをパスする耐腐食性試験の［］数は１２０まで延長
された。Although we have shown an example of its use alone as a halogen element, it is also used for fJ1 in two or more types, and of course it has v1 function, but when used in combination with F and CI, the mechanism is unknown. A remarkable effect was seen. That is, SnF2 and S
By treatment with a mixed solution of nC (12), the number of corrosion resistance tests passing the scratch test was extended to 120.
実施例２
ＰＥＴ上に、Ｃｏ、 Ｆｅ、 Ｃｒ 、 Ａｌ 、 Ｚ
ｎ 、Ｃｕ 、 Ｓｎ。Example 2 Co, Fe, Cr, Al, Z on PET
n, Cu, Sn.
Ｉｎ、Ｎｉおよびそり、らの合金を蒸着し、実施例１と
同様の方法で表向に、ハロゲン元素を導入した。An alloy of In, Ni, and the like was deposited, and a halogen element was introduced onto the surface in the same manner as in Example 1.
実施例１と同様、耐腐食性の向上が見られた。Similar to Example 1, improvement in corrosion resistance was observed.
実施例３ 機械的方法で作成された金属箔においてもＦｅ。Example 3 Fe also in metal foils made by mechanical methods.
Ｎｉ、Ｃｏおよびそれらの合金においても、実施例１と
同様の耐腐食性の向−１−の効果が見られた。Ni, Co, and their alloys also showed the same positive effect on corrosion resistance as in Example 1.
以上述べたように、薄膜金属の表面にハロゲンが導入さ
れた場合、耐腐食性の顕著な向上が見られる。しか（７
、その機構については今のところ、詳細は不明である。As described above, when halogen is introduced into the surface of a thin film metal, a significant improvement in corrosion resistance is observed. Only (7)
However, the details of the mechanism are currently unknown.
すなわち、）・ロゲン元素が金属薄膜表面にどのような
形で含まれているかについては、種々の「り能ｆｆｌ：
ｔノ・ロゲンイオンもしく１゜ハロゲン化物）が考え
られ、また、それらの金属薄膜との結合様式についても
不明である。In other words, the form in which the )-rogen element is contained on the surface of the metal thin film is determined by various methods.
Possible ions are t-halogen ions or 1° halides, and the mode of their bonding with the metal thin film is also unknown.
また導入されたハロゲンの量についても４＋＠微量が各
種の分析法によって観測されるにすぎず、また、ハロゲ
ンが分布する範囲は、金属表面から数〜数百オングスト
ロームオーダーの領域にすぎないと推定される。そのよ
うな極めて、薄い・・ロゲン含有層のため、金属本来の
１／Ｉ′質をいんぺいすることが々いものと考えられる
。すなわち、電気伝導度。Furthermore, only a trace amount of 4+@ has been observed using various analytical methods regarding the amount of introduced halogen, and it is estimated that the range in which halogen is distributed is on the order of several to several hundred angstroms from the metal surface. be done. It is thought that such an extremely thin rogen-containing layer often destroys the 1/I' quality inherent in the metal. i.e. electrical conductivity.
磁気的性質等の評価においては、未処理のものと殆んど
区別できなかった。In evaluation of magnetic properties, etc., it was almost indistinguishable from untreated material.
以−に、本発明は、金属としての性質を失なわず、すぐ
れた耐腐食性を有する薄膜金属を提供するものである。In summary, the present invention provides a thin film metal that does not lose its properties as a metal and has excellent corrosion resistance.
Claims (5)
薄膜金属。(1) It has a halogen element on the surface! Characteristic thin film metal.
ことを特徴とする特許請求の範囲第１項記載の薄膜金属
。(2) The thin film metal according to claim 1, wherein the halogen element is at least one of F and 04.
の範囲第１項記載の薄膜金属。(3) The thin film metal according to claim 1, wherein the metal is a magnetic metal.
る特許請求の範囲第３項記載の薄膜金属。(4) The thin film metal according to claim 3, wherein the magnetic metal is a cobalt-based alloy.
ル合金であることを特徴とする特許請求の範囲第４項記
載の薄膜金属０(5) The thin film metal 0 according to claim 4, characterized in that it is a Cacobaltoni Nochel alloy based on Coba)Ii)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57117281A JPS599167A (en) | 1982-07-05 | 1982-07-05 | Thin metallic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57117281A JPS599167A (en) | 1982-07-05 | 1982-07-05 | Thin metallic film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS599167A true JPS599167A (en) | 1984-01-18 |
Family
ID=14707858
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57117281A Pending JPS599167A (en) | 1982-07-05 | 1982-07-05 | Thin metallic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS599167A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6326090A (en) * | 1986-07-18 | 1988-02-03 | Fujitsu General Ltd | Picture transmission system using excess period |
-
1982
- 1982-07-05 JP JP57117281A patent/JPS599167A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6326090A (en) * | 1986-07-18 | 1988-02-03 | Fujitsu General Ltd | Picture transmission system using excess period |
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