JPS6111459B2 - - Google Patents
Info
- Publication number
- JPS6111459B2 JPS6111459B2 JP9132079A JP9132079A JPS6111459B2 JP S6111459 B2 JPS6111459 B2 JP S6111459B2 JP 9132079 A JP9132079 A JP 9132079A JP 9132079 A JP9132079 A JP 9132079A JP S6111459 B2 JPS6111459 B2 JP S6111459B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- cobalt
- magnetic thin
- potential
- cobalt magnetic
- 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
Links
- 229910017052 cobalt Inorganic materials 0.000 claims description 61
- 239000010941 cobalt Substances 0.000 claims description 61
- 239000010409 thin film Substances 0.000 claims description 60
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 56
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000005260 corrosion Methods 0.000 claims description 9
- 230000007797 corrosion Effects 0.000 claims description 9
- 238000007654 immersion Methods 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000000758 substrate Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000010408 film Substances 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- PQMFVUNERGGBPG-UHFFFAOYSA-N (6-bromopyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Br)=N1 PQMFVUNERGGBPG-UHFFFAOYSA-N 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 description 18
- 239000008151 electrolyte solution Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 7
- 230000001747 exhibiting effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007743 anodising Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229920006267 polyester film Polymers 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011521 glass 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/14—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates
- H01F41/20—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for applying magnetic films to substrates by evaporation
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Magnetic Record Carriers (AREA)
- Thin Magnetic Films (AREA)
- Physical Vapour Deposition (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
本発明は、耐蝕性に優れたコバルト磁性薄膜の
製造方法に関する。
磁性薄膜は、コバルトを真空蒸着法、イオンプ
レーテイング法、スパツタリング法等の方法によ
つて高分子ガラス、セラミツクス、金属等の基板
上に形成させたものである。
コバルトは、同じ遷移金属である鉄やニツケル
と同様に腐蝕しやすい金属である。厚さが数mm以
上のコバルト板が腐蝕しやすいのと同様に真空蒸
着等の減圧下で形成させたコバルト薄膜も腐蝕し
やすい。
本発明は、特に磁性材料としてコバルト薄膜を
形成させた場合の腐蝕性を問題とするものであ
る。
通常、コバルト金属を真空蒸着等の方法によつ
て高分子等の基板上に形成させた場合、純粋なコ
バルトからなるコバルト薄膜を形成している。こ
のコバルト薄膜をホウ砂0.02M/とホウ酸0.1M/
を含む30℃の水溶液（以後、電解質溶液と呼
ぶ）に浸漬した時に浸漬してから１〜２分後に純
コバルトの自然電極電位である−0.5V〜−0.55V
付近（飽和甘汞電極に対して、対SCEと以後書
く）の電位を示す。このコバルト薄膜を例えば
100℃で熱処理すると、主にその表面が酸化され
て電解質溶液に浸漬した場合、その浸漬した瞬間
は−0.50Vよりプラスの電位を示すが、浸漬３分
経過後は、−0.3V以下の値しか示さない。
ここで、電解質溶液は、１の蒸留水中に0.02
モル（Ｍ）のホウ砂と0.1モル（Ｍ）のホウ酸を
含む水溶液であり、窒素ガスで10分間程バブリン
グ処理して、水溶液中に溶解している酸素を窒素
で置換した溶液である。電解質溶液は、被熱処理
コバルト磁性薄膜を浸漬している間撹拌せずに静
置しておくものとする。薄膜の電位を測定する場
合は、リード線として金線を用い、導電性塗料で
薄膜上に接触固定させ、常温硬化樹脂で金線を固
定して測定した。基板が高分子フイルム等の場合
は、試料をガラスプレパラート上に常温硬化樹脂
で数ケ所固定して、試料が動かないようにした。
一方、本発明のコバルト磁性薄膜の製造方法
は、電解質溶液に浸漬した時に、浸漬してから３
分経過後の被熱処理コバルト磁性薄膜の示す自然
電極電位が飽和甘汞電極に対してマイナス0.30V
より正の電位を示すものである。
このように、−0.30Vより正の電位を示すコバ
ルトは、コバルト板等のコバルト金属を電解質溶
液中で陽極酸化処理することによつて得られるこ
とは公知である。
しかし、本発明のように減圧下で作製したコバ
ルト薄膜は、膜の厚さが数100〜数1000Åである
ので電解処理を行うと、電解質溶液中に溶解し
て、薄膜形状を維持することが困難になつたりす
る。それ故、本発明のコバルト磁性薄膜は、陽極
酸化のような公知の方法によつて、コバルト磁性
薄膜の耐蝕性を向上させるものではない。
本発明のコバルト磁性の製造方法は、陽極酸化
処理を施さずに、陽極酸化処理を施したものと同
様に、高い電位を示す薄膜を得ることによつて耐
蝕性を向上させるものである。陽極酸化処理は、
溶液中で形成されるが、本発明の薄膜は溶液中で
形成されたものでないので、高い電位を示す薄膜
の組織等は溶液中で形成したものとは異なつてい
る点が多いものと思われる。
すなわち本発明のコバルト磁性薄膜の製造方法
は、減圧下酸素雰囲気中で作製したコバルト薄膜
を熱処理したもので、しかもこの熱処理コバルト
薄膜が30℃の電解質溶液中で示す浸漬してから３
分経過後の自然電極電位が−0.30V（対SCE）よ
り高い電位を示す磁性薄膜である。
このような磁性薄膜は、熱処理する前の状態で
浸漬してから３分経過後の自然電極電位（対
SCE）が−0.40Vより正の電位を示す場合には、
ほとんど熱処理後、−0.30Vより正の電位を示す
ことから熱処理する前の電位が−0.40Vより正の
電位を有することが望ましい。しかし本発明では
熱処理する前の電位を特に問題とするものではな
く、熱処理した後のコバルト磁性薄膜の示す電位
（対SCE）が−0.30Vより正の電位を示す薄膜に
限定されるものである。
このように、熱処理後−0.30Vより正の電位を
示す薄膜は次のようにして得られた。
第１図に簡単にコバルト磁性薄膜の形成方法
（装置）を示した。図において、１は巻出しロー
ル２からキヤン３の周囲を経て巻取りリール４に
巻取られる基板フイルム、５はコバルトの蒸発
源、６はマスク、θは斜め蒸着する場合の入射角
である。入射角10゜以上、酸素導入下、ポリエス
テルフイルムを連続的に走行させ、電子ビームに
よりコバルトを加熱蒸発させて、コバルトの連続
磁性薄膜を得た。この磁性薄膜を122℃の熱ロー
ラに沿わせて連続的に加熱処理を行つた。
本発明のコバルト磁性薄膜は、熱処理を行う前
に示す電解質溶液に浸漬３分経過時の自然電極電
位が−0.50Vより高い電位（より正の電位）であ
ればあるほど一般に熱処理後もより高い電位を示
す。
以上のように本発明の製造方法によるコバルト
磁性薄膜は、電解質溶液に浸漬した時、浸漬後３
分経過後の自然電極電位が−0.30Vより正の電位
を示すことに特徴を有するものである。
このように−0.30Vより正の電位を示すコバル
ト磁性薄膜はこの値より低い電位を示す薄膜より
も一段と耐蝕性に優れているものであつた。
例えば、加熱処理後の自然電極電位の異なる各
サンプルを60℃、90％相対湿度条件下に３時間放
置した結果を次表に示す。
The present invention relates to a method for manufacturing a cobalt magnetic thin film with excellent corrosion resistance. The magnetic thin film is formed by forming cobalt on a substrate of polymer glass, ceramics, metal, or the like by a method such as a vacuum evaporation method, an ion plating method, or a sputtering method. Cobalt, like the transition metals iron and nickel, is a metal that corrodes easily. Just as a cobalt plate with a thickness of several millimeters or more is easily corroded, a cobalt thin film formed under reduced pressure, such as by vacuum evaporation, is also easily corroded. The present invention particularly deals with the problem of corrosion when a cobalt thin film is formed as a magnetic material. Usually, when cobalt metal is formed on a substrate such as a polymer by a method such as vacuum evaporation, a cobalt thin film made of pure cobalt is formed. This cobalt thin film is coated with 0.02M/0.02M of borax and 0.1M/0.1M/0 of boric acid.
-0.5V to -0.55V, which is the natural electrode potential of pure cobalt, 1 to 2 minutes after immersion in a 30℃ aqueous solution containing
It shows the potential near (hereinafter written as vs. SCE with respect to the saturated Amane electrode). For example, if this cobalt thin film is
When heat treated at 100℃, the surface is mainly oxidized, and when immersed in an electrolyte solution, it exhibits a potential more positive than -0.50V at the moment of immersion, but after 3 minutes of immersion, the value is less than -0.3V. only show. Here, the electrolyte solution is 0.02% in 1% distilled water.
This is an aqueous solution containing mol (M) of borax and 0.1 mol (M) of boric acid, and is a solution in which oxygen dissolved in the aqueous solution is replaced with nitrogen by bubbling with nitrogen gas for about 10 minutes. The electrolyte solution is left standing without stirring while the heat-treated cobalt magnetic thin film is immersed. When measuring the potential of a thin film, a gold wire was used as a lead wire, and a conductive paint was used to contact and fix the gold wire on the thin film, and the gold wire was fixed with a resin that cured at room temperature. When the substrate was a polymer film or the like, the sample was fixed at several places on a glass preparation with room-temperature curing resin to prevent the sample from moving. On the other hand, in the method for producing a cobalt magnetic thin film of the present invention, when immersed in an electrolyte solution,
After a minute has passed, the natural electrode potential of the heat-treated cobalt magnetic thin film is -0.30V with respect to the saturated electrode.
It shows a more positive potential. It is known that cobalt having a potential more positive than -0.30V can be obtained by anodizing cobalt metal such as a cobalt plate in an electrolyte solution. However, the cobalt thin film produced under reduced pressure as in the present invention has a thickness of several hundred to several thousand angstroms, so when electrolytically treated, it dissolves in the electrolyte solution and cannot maintain its thin film shape. It becomes difficult. Therefore, the cobalt magnetic thin film of the present invention does not improve the corrosion resistance of the cobalt magnetic thin film by known methods such as anodic oxidation. The method for producing cobalt magnetism of the present invention improves corrosion resistance by obtaining a thin film that exhibits a high potential, similar to that obtained by anodizing, without anodizing. The anodizing treatment is
Although it is formed in a solution, the thin film of the present invention is not formed in a solution, so it is thought that the structure of the thin film exhibiting a high potential is different from that formed in a solution in many ways. . That is, in the method for producing a cobalt magnetic thin film of the present invention, a cobalt thin film produced in an oxygen atmosphere under reduced pressure is heat-treated, and the heat-treated cobalt thin film is immersed in an electrolyte solution at 30°C.
This is a magnetic thin film whose natural electrode potential is higher than -0.30V (vs. SCE) after a minute has elapsed. Such a magnetic thin film has a natural electrode potential (relative to
SCE) shows a potential more positive than −0.40V,
Since the potential is more positive than -0.30V after the heat treatment, it is desirable that the potential before the heat treatment is more positive than -0.40V. However, in the present invention, the potential before heat treatment is not a particular issue, and the potential of the cobalt magnetic thin film after heat treatment (vs. SCE) is limited to a thin film in which the potential (vs. SCE) is more positive than -0.30V. . Thus, a thin film exhibiting a more positive potential than -0.30 V after heat treatment was obtained in the following manner. FIG. 1 briefly shows a method (apparatus) for forming a cobalt magnetic thin film. In the figure, 1 is a substrate film that is wound from an unwinding roll 2 around a can 3 to a take-up reel 4, 5 is a cobalt evaporation source, 6 is a mask, and θ is an incident angle in the case of oblique evaporation. A polyester film was run continuously under oxygen introduction at an incident angle of 10° or more, and cobalt was heated and evaporated by an electron beam to obtain a continuous magnetic thin film of cobalt. This magnetic thin film was subjected to continuous heat treatment by placing it along a heated roller at 122°C. The cobalt magnetic thin film of the present invention generally has a higher potential after heat treatment as the natural electrode potential after 3 minutes of immersion in the electrolyte solution is higher than -0.50V (more positive potential). Indicates potential. As described above, when the cobalt magnetic thin film produced by the production method of the present invention is immersed in an electrolyte solution,
It is characterized in that the natural electrode potential after a minute has passed is more positive than -0.30V. As described above, the cobalt magnetic thin film exhibiting a potential more positive than -0.30V had a much better corrosion resistance than the thin film exhibiting a potential lower than this value. For example, the following table shows the results of heat-treated samples with different natural electrode potentials left at 60°C and 90% relative humidity for 3 hours.
【表】
コバルト磁性薄膜の加熱条件は、コバルト磁性
薄膜の製造条件に依存するが、例えばポリエステ
ルフイルム上に形成した場合、60℃から加熱して
いつた場合、被加熱処理コバルト磁性薄膜の自然
電極電位は温度とともに上昇しはじめ約90〜120
℃でほぼ一定値に落ちつく。
製造条件によつて熱処理後に示す自然電極電位
（浸漬後３分値、対SCE）が−0.3Vより高い電位
を示す温度は異なるが、熱処理温度は90℃以上で
効果が大きいことから熱処理は90℃以上で行うも
のとする。
以上のように熱処理後の自然電極電位が−
0.30V（浸漬後３分値、対SCE）より高い電位を
示すコバルト磁性薄膜は、上表に示すように耐蝕
性に優れているものである。
以下に具体例を示す。
例 １
厚さ５μｍ、長さ500mのポリエステルテープ
をキヤン温度65℃、斜め蒸着の入射角30゜（第１
図のθの値）、加速電圧10KVの電子ビーム加熱条
件下で蒸着を行い、100mの長さにコバルトを真
空蒸着させた。
次に同一条件下で酸素ガスを0.25/minで導
入してコバルト薄膜を作製した。
以上２つの条件下で作製したコバルト薄膜を約
110℃の加熱ローラに沿わせて20m/minの走行速
度で加熱処理した。
この２つのサンプルの内、前者のサンプルを
Ａ、後者のそれをＢと呼ぶ。
ホウ砂0.02M/とホウ酸0.1M/を含む30℃の
水溶液にこのサンプルＡ，Ｂをそれぞれ浸漬した
ところ、第２図に示す自然電極電位の時間依存性
が見られた。浸漬後３分値の電位はサンプルＡが
−0.42V（対SCE）、サンプルＢが−0.22V（対
SCE）であつた。
この２つのコバルト磁性薄膜を60℃、90％相対
湿度雰囲気下に３時間放置した結果、サンプルＡ
によるものはフイルム全体に茶褐色の錆を発生し
たが、サンプルＢによるものは薄茶色に変色した
だけであつた。
例 ２
例１と同一のポリエステルフイルムをキヤン温
度60℃、入射角35゜、加速電圧30KV、酸素導入
量0.7/minの条件下で100mの長さにコバルトを
蒸着させた。得られたコバルト磁性薄膜を100℃
の加熱ローラに沿わせて20m/minの走行速度で
加熱処理した。コバルト薄膜を例１に示した電解
質溶液で自然電極電位を測定したところ、その３
分値は−0.44V（対SCE）であつた。このコバル
ト磁性薄膜を60℃、90％相対湿度条件下に３時間
放置した結果、茶褐色に錆を発生し耐蝕性が悪か
つた。これはコバルトが蒸着時に十分酸素に触れ
なかつたことが原因と考えられる。
以上のように−0.30Vより正の電位を示す被熱
処理コバルト磁性薄膜は、耐蝕性に優れ、磁気テ
ープ等の実用上の応用に対して益するところが大
である。
なお、本発明では、電子ビーム加熱によるコバ
ルト磁性薄膜についてのみ記したが、単に蒸着法
による薄膜形成法に限定されるものではなく、本
発明で述べた電解質溶液中での自然電極電位の３
分値がマイナス0.30V（対SCE）より正の電位を
示し、１気圧より低圧下で形成させた後、熱処理
されたコバルト磁性薄膜であればよいものであ
る。
本発明で記述した−0.30Vより正の電位または
高い電位とは、例えば−0.25V、0.0V、＋0.05V等
の電位のことである。またコバルト磁性薄膜の上
にさらに金属、半導体、誘電体等の異物質を形成
した後の熱処理した場合、コバルト磁性薄膜のみ
の電位を測定することは困難であるが、この場
合、異物質を形成する前に熱処理して−0.30Vよ
り正の電位をコバルト磁性薄膜が示す場合は、こ
のようなコバルト磁性薄膜も本発明に含まれるも
のである。[Table] The heating conditions for a cobalt magnetic thin film depend on the manufacturing conditions of the cobalt magnetic thin film, but for example, when it is formed on a polyester film and heated from 60℃, the natural electrode potential of the cobalt magnetic thin film to be heated is starts to rise with temperature, about 90 to 120
It settles down to an almost constant value at °C. The temperature at which the natural electrode potential (value for 3 minutes after immersion, vs. SCE) shows a potential higher than -0.3V after heat treatment differs depending on the manufacturing conditions, but the heat treatment temperature is 90℃ or higher because the effect is large at 90℃ or higher. The test shall be carried out at temperatures above ℃. As mentioned above, the natural electrode potential after heat treatment is -
Cobalt magnetic thin films exhibiting a potential higher than 0.30V (value for 3 minutes after immersion, vs. SCE) have excellent corrosion resistance, as shown in the table above. A specific example is shown below. Example 1 A polyester tape with a thickness of 5 μm and a length of 500 m was deposited at a can temperature of 65°C and an incident angle of 30° for oblique evaporation (first
Cobalt was vacuum-deposited over a length of 100 m using electron beam heating conditions with an accelerating voltage of 10 KV. Next, under the same conditions, oxygen gas was introduced at 0.25/min to fabricate a cobalt thin film. The cobalt thin film produced under the above two conditions was approximately
Heat treatment was carried out at a running speed of 20 m/min along a heating roller at 110°C. Of these two samples, the former sample is called A, and the latter sample is called B. When samples A and B were respectively immersed in an aqueous solution containing 0.02M/borax and 0.1M/boric acid at 30°C, the time dependence of the natural electrode potential as shown in FIG. 2 was observed. The potential for 3 minutes after immersion is -0.42V (vs. SCE) for sample A and -0.22V (vs. SCE) for sample B.
SCE). As a result of leaving these two cobalt magnetic thin films in an atmosphere of 60℃ and 90% relative humidity for 3 hours, sample A
Sample B produced brownish rust all over the film, but Sample B only had a light brown discoloration. Example 2 Cobalt was deposited on the same polyester film as in Example 1 to a length of 100 m under conditions of a can temperature of 60°C, an incident angle of 35°, an accelerating voltage of 30 KV, and an oxygen introduction rate of 0.7/min. The obtained cobalt magnetic thin film was heated to 100℃.
Heat treatment was carried out at a running speed of 20 m/min along a heating roller. When the natural electrode potential of a cobalt thin film was measured using the electrolyte solution shown in Example 1, Part 3
The minute value was -0.44V (vs. SCE). When this cobalt magnetic thin film was left at 60° C. and 90% relative humidity for 3 hours, brownish rust developed and its corrosion resistance was poor. This is thought to be because cobalt was not sufficiently exposed to oxygen during vapor deposition. As described above, the heat-treated cobalt magnetic thin film exhibiting a potential more positive than -0.30V has excellent corrosion resistance and is of great benefit for practical applications such as magnetic tapes. In the present invention, only the cobalt magnetic thin film formed by electron beam heating is described, but the method is not limited to the thin film formation method simply by vapor deposition, and the natural electrode potential in the electrolyte solution described in the present invention is 3.
A cobalt magnetic thin film that exhibits a potential more positive than minus 0.30 V (vs. SCE) and that has been formed at a pressure lower than 1 atm and then heat-treated may be used. The potential more positive or higher than -0.30V described in the present invention refers to potentials such as -0.25V, 0.0V, +0.05V, etc., for example. Furthermore, if heat treatment is performed after forming a foreign substance such as a metal, semiconductor, or dielectric on a cobalt magnetic thin film, it is difficult to measure the potential of only the cobalt magnetic thin film; If the cobalt magnetic thin film exhibits a potential more positive than -0.30 V after being heat treated before being heated, such a cobalt magnetic thin film is also included in the present invention.
第１図は本発明のコバルト磁性薄膜の製造方法
を実施した製造装置の要部の概略構成図、第２図
は電解質溶液中でのコバルト磁性薄膜の自然電極
電位の時間依存性を示す図である。
１…基板フイルム、５…コバルトの蒸発源。
Figure 1 is a schematic configuration diagram of the main parts of a manufacturing apparatus that implements the method of manufacturing a cobalt magnetic thin film of the present invention, and Figure 2 is a diagram showing the time dependence of the natural electrode potential of a cobalt magnetic thin film in an electrolyte solution. be. 1... Substrate film, 5... Cobalt evaporation source.
Claims (1)
バルトの薄膜を形成した後、この薄膜を熱処理し
てコバルト磁性薄膜を形成し、このコバルト磁性
薄膜をホウ砂0.02M/とホウ酸0.1M/を含む30
℃の水溶液に浸漬して、浸漬してから３分経過後
の前記コバルト磁性薄膜の示す自然電極電位が飽
和甘汞電極に対してマイナス0.30Vより正の電位
を示すコバルト磁性薄膜を選択するようにした耐
蝕性コバルト磁性薄膜の製造方法。1. After forming a cobalt thin film on a substrate film under reduced pressure in an oxygen atmosphere, this thin film is heat-treated to form a cobalt magnetic thin film, and this cobalt magnetic thin film is coated with 0.02M/borax and 0.1M/boric acid. including 30
Select a cobalt magnetic thin film that is immersed in an aqueous solution at ℃ and whose natural electrode potential after 3 minutes of immersion is more positive than -0.30 V with respect to the saturated electrode. A method for producing a corrosion-resistant cobalt magnetic thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9132079A JPS5615015A (en) | 1979-07-18 | 1979-07-18 | Corrosion-resistant cobalt magnetic thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9132079A JPS5615015A (en) | 1979-07-18 | 1979-07-18 | Corrosion-resistant cobalt magnetic thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5615015A JPS5615015A (en) | 1981-02-13 |
| JPS6111459B2 true JPS6111459B2 (en) | 1986-04-03 |
Family
ID=14023159
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9132079A Granted JPS5615015A (en) | 1979-07-18 | 1979-07-18 | Corrosion-resistant cobalt magnetic thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5615015A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3614644B2 (en) * | 1998-02-27 | 2005-01-26 | 松下電器産業株式会社 | Manufacturing method of laminate |
-
1979
- 1979-07-18 JP JP9132079A patent/JPS5615015A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5615015A (en) | 1981-02-13 |
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