JPH0551661B2 - - Google Patents
Info
- Publication number
- JPH0551661B2 JPH0551661B2 JP61039640A JP3964086A JPH0551661B2 JP H0551661 B2 JPH0551661 B2 JP H0551661B2 JP 61039640 A JP61039640 A JP 61039640A JP 3964086 A JP3964086 A JP 3964086A JP H0551661 B2 JPH0551661 B2 JP H0551661B2
- Authority
- JP
- Japan
- Prior art keywords
- base material
- hoop
- tin film
- substrate
- ion beam
- 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
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- Physical Vapour Deposition (AREA)
Description
【発明の詳細な説明】
〔技術分野〕
この発明は、耐蝕性に優れ、かつ、装飾性に優
れたTiN膜を表面に有するフープ状基材、こと
に鉄系の合金からなるフープ状基材の製造方法に
関する。[Detailed Description of the Invention] [Technical Field] The present invention relates to a hoop-shaped substrate having a TiN film on its surface that has excellent corrosion resistance and excellent decorative properties, particularly a hoop-shaped substrate made of an iron-based alloy. Relating to a manufacturing method.
フープ状基材の表面に耐蝕性および装飾性に優
れた皮膜を形成することが求められている。
There is a need to form a film with excellent corrosion resistance and decorative properties on the surface of a hoop-shaped substrate.
TiNは、高硬度で耐蝕性に優れ、かつ、特有
の金色をしているため、このTiNの薄膜を基材
表面に形成して基材の硬度を上げたり、耐蝕性を
付与したり、金色の装飾を施したりすることが行
われている。 TiN has high hardness, excellent corrosion resistance, and a unique golden color. Therefore, a thin TiN film can be formed on the surface of a substrate to increase its hardness, impart corrosion resistance, and give it a golden color. It is also decorated with decorations.
基材上にTiN薄膜（0.1〜10μｍ）を形成する方
法として、従来から、CVD法あるいはPVD法
（イオンプレーテイング、スパツタリング等）が
用いられている。 Conventionally, the CVD method or the PVD method (ion plating, sputtering, etc.) has been used to form a TiN thin film (0.1 to 10 μm) on a substrate.
ところが、これらの方法には、つぎのような問
題があつた。すなわち、CVD法では基材温度を
一般に1000℃程度の高温に加熱する必要があり、
鉄系の合金板などを基材として用いた場合、基材
が熱処理効果によつて変形してしまうという問題
がある。他方、PVD法では、通常200〜400℃で
処理されるので、基材の変形といつた問題はない
が、HCD（ホロカソード）法、RF励起法、ARE
（活性化反応蒸着）法などの従来のイオンプレー
テイング法では、真空度が10-2〜10-4Torr程度
と低いため、雰囲気ガス分子との衝突により失わ
れるエネルギーが大きくて緻密な膜が得られにく
く、膜の耐蝕性、密着性に問題が生じる場合があ
る。さらに、基材にバイアス電圧をかける必要が
あり、特に、フープ状基材表面にTiN膜を形成
するには生産性の点を考慮するとバツチ法ではな
く連続法により行うことが求められるが、連続処
理を行う場合に設備が複雑化する問題もある。ス
パツタリング法では、比較的緻密な膜が得られる
のであるが、生成速度が遅く、膜の色が黒ずみや
すい。色調調整にやはりバイアス電圧をかけねば
ならなかつた。 However, these methods have the following problems. In other words, in the CVD method, it is necessary to heat the base material to a high temperature, generally around 1000℃.
When an iron-based alloy plate or the like is used as a base material, there is a problem that the base material is deformed due to the heat treatment effect. On the other hand, in the PVD method, the treatment is usually carried out at 200 to 400°C, so there is no problem such as deformation of the base material, but the HCD (holocathode) method, RF excitation method, ARE
In conventional ion plating methods such as (activated reactive vapor deposition), the degree of vacuum is as low as 10 -2 to 10 -4 Torr, so a large amount of energy is lost through collisions with atmospheric gas molecules, making it difficult to form dense films. It is difficult to obtain, and problems may arise in the corrosion resistance and adhesion of the film. Furthermore, it is necessary to apply a bias voltage to the substrate, and in particular, when forming a TiN film on the surface of a hoop-shaped substrate, a continuous method is required, rather than a batch method, from the viewpoint of productivity. There is also the problem that the equipment becomes complicated when processing. Although a relatively dense film can be obtained using the sputtering method, the production rate is slow and the color of the film tends to darken. It was still necessary to apply a bias voltage to adjust the color tone.
他方、イオン注入法により基材を改質する方法
も提案されている。たとえば、特公昭54−28379
号公報や特開昭58−181864号公報では、刃または
パンチといつた被処理物に高エネルギーイオンビ
ームを照射し、イオンを被処理物中に打ち込んで
処理する方法が記載されている。しかし、イオン
注入法は、加速エネルギーが数十KeV〜数百
KeV程度と高く、照射物が表面上にはほとんど
堆積せず、ある程度の深さの位置に注入物の量的
ピークがある。このため、イオン注入法による生
成物は、耐蝕性や装飾性に乏しい。しかも、イオ
ンビーム電流は小さいもの（最大でも１ｍＡ程
度）であり、フープ状基材を対象とする場合には
処理に時間がかかるという問題もある。また、イ
オン注入では、基板温度の上昇が大きいため、冷
却装置が必要となり、装置が複雑になる。 On the other hand, a method of modifying the base material by ion implantation has also been proposed. For example, Tokuko Sho 54-28379
JP-A No. 58-181864 discloses a method of irradiating a workpiece such as a blade or punch with a high-energy ion beam to drive the ions into the workpiece. However, in the ion implantation method, the acceleration energy ranges from tens of KeV to hundreds of keV.
It is as high as KeV, and the irradiated material is hardly deposited on the surface, and there is a quantitative peak of the irradiated material at a certain depth. Therefore, products produced by ion implantation have poor corrosion resistance and decorative properties. Moreover, the ion beam current is small (approximately 1 mA at most), and when a hoop-shaped base material is targeted, there is a problem that processing takes time. Furthermore, in ion implantation, the temperature of the substrate increases significantly, so a cooling device is required, making the device complex.
この発明は、このような事情に鑑みて、フープ
状基材上に耐蝕性、耐摩耗性、密着性および装飾
性に優れた、均一なTiN膜を迅速、安価に形成
できるような生産性の向上した製造方法を提供す
ることを目的としている。
In view of these circumstances, this invention aims to improve productivity by quickly and inexpensively forming a uniform TiN film with excellent corrosion resistance, abrasion resistance, adhesion, and decorative properties on a hoop-shaped substrate. The aim is to provide improved manufacturing methods.
この発明者らは、このような目的を達成するた
めに、鋭意検討した結果、イオンビーム法を用い
真空中でTiを蒸発させるとともに、連続的に送
り出しているフープ状基材表面に比較的緩い加速
電圧で窒素イオンビームを照射すると、基材表面
に耐蝕性、耐摩耗性、密着性および装飾性に優れ
たTiNを効率よく得ることができるということ
を見出し、この発明を完成するに至つた。
In order to achieve this objective, the inventors conducted extensive research and found that while evaporating Ti in vacuum using the ion beam method, they also deposited a relatively loose layer onto the surface of the hoop-shaped base material that is continuously fed out. They discovered that TiN, which has excellent corrosion resistance, abrasion resistance, adhesion, and decorative properties, can be efficiently obtained on the surface of a substrate by irradiating a nitrogen ion beam at an accelerating voltage, leading to the completion of this invention. .
したがつて、この発明は、真空中にフープ状基
材を連続的に送り出すように配置して、Tiを蒸
発させると同時に、前記基材表面に加速電圧0.3
〜2.0KeVで窒素イオンビームを照射し、前記基
材表面にTiNを膜を形成する、TiN膜を有する
フープ状基材の製造方法を要旨とする。この場
合、窒素イオンビームの加速電圧を0.3〜2.0KeV
にまで高めることは、たとえば、真空度を10-5〜
10-6Torr程度に高めることで簡単に達成できる。 Therefore, in the present invention, a hoop-shaped base material is arranged to be continuously sent out in a vacuum, and at the same time Ti is evaporated and an accelerating voltage of 0.3 is applied to the surface of the base material.
The summary is a method for manufacturing a hoop-shaped base material having a TiN film, in which a nitrogen ion beam is irradiated at ~2.0 KeV to form a TiN film on the surface of the base material. In this case, the acceleration voltage of the nitrogen ion beam is set to 0.3 to 2.0 KeV.
For example, increasing the vacuum level to 10 -5 ~
This can be easily achieved by increasing the temperature to around 10 -6 Torr.
以下に、この発明を、その１実施例をあらわす
図面を参照しつつ詳しく説明する。 Hereinafter, the present invention will be explained in detail with reference to the drawings showing one embodiment thereof.
第１図は、この発明にかかる製造方法を実施す
るのに用いられるTiN膜形成装置の１例をあら
わす。図にみるように、このTiN膜形成装置は、
真空槽（真空チヤンバー）１内にフープ状基材
（またはフープ状基板）２が配置されるようにな
つている。このフープ状基材２は、送り出しプー
リ１１と巻き取りプーリ１２の間の、膜形成が行
われる空間部分で、たわみが生じないように配置
された状態で、矢印方向へ一定速度で巻き取れる
ようになつている。基材２の対面する位置には、
電子ビーム蒸発源３が設けられている。この蒸発
源３には、金属チタン４が載せられ電子ビームに
よる加熱によつて蒸発させられるようになつてい
る。真空槽１壁面には、基材２に銃口を向けて２
つのイオン銃５，６が設けられている。一方のイ
オン銃５は、Ar+イオンビームを基材２に照射し
てボンバード処理を行うようになつており、基材
２の進行方向（図中、矢印方向）に対して比較的
後方の基材２表面に照準が合わせられている。鉄
系の合金基板は表層が不動態としての酸化物層と
なつている。表面には有機系物質も付着している
こともある。これらの物質は成膜後のTiN膜に
対して密着清不良と言う問題を生じさせる。そこ
で、このような物質をエツチング除去するため
に、上記のAr+イオンビームの照射が行われる。
もう一方のイオン銃６は、一般に、窒素ガスを
N2 +イオンビームとして基材２に照射するように
なつており、前述のイオン銃５より基材２の進行
方向に対して前方の基材２表面に照準が合わせら
れている。さらに、真空槽１内には、水晶振動子
７（レートセンサ）が前述のAr+イオンビームお
よびN2 +イオンビームが当たらない位置に設けら
れている。この水晶振動子７は、レートコントロ
ーラ（IC−6000）８との組み合わせによつて金
属チタンの蒸発量を制御するためのものである。
図示していないが、このTiN膜形成装置には、
真空槽１内に真空にするための排気手段が設けら
れているのは、言うまでもない。 FIG. 1 shows an example of a TiN film forming apparatus used to carry out the manufacturing method according to the present invention. As shown in the figure, this TiN film forming equipment
A hoop-shaped base material (or hoop-shaped substrate) 2 is disposed within a vacuum chamber (vacuum chamber) 1 . This hoop-shaped base material 2 is placed in a space between the delivery pulley 11 and the take-up pulley 12 where film formation is performed, so that it can be wound at a constant speed in the direction of the arrow while being arranged so as not to bend. It's getting old. At the facing position of the base material 2,
An electron beam evaporation source 3 is provided. Metal titanium 4 is placed on this evaporation source 3 and is evaporated by heating with an electron beam. A gun is placed on the wall of the vacuum chamber 1 with the gun muzzle facing the base material 2.
Two ion guns 5 and 6 are provided. One ion gun 5 is designed to perform bombardment treatment by irradiating the base material 2 with an Ar + ion beam, and targets a base relatively rearward with respect to the traveling direction of the base material 2 (arrow direction in the figure). The aim is on the surface of material 2. The surface layer of the iron-based alloy substrate is a passive oxide layer. Organic substances may also be attached to the surface. These substances cause a problem of poor adhesion to the TiN film after it has been formed. Therefore, in order to remove such substances by etching, the above-mentioned Ar + ion beam irradiation is performed.
The other ion gun 6 generally uses nitrogen gas.
The base material 2 is irradiated with the N 2 + ion beam, and the above-mentioned ion gun 5 is aimed at the surface of the base material 2 in front of the base material 2 in its traveling direction. Further, in the vacuum chamber 1, a crystal oscillator 7 (rate sensor) is provided at a position where the Ar + ion beam and the N 2 + ion beam described above do not hit. This crystal oscillator 7 is used in combination with a rate controller (IC-6000) 8 to control the amount of evaporation of metallic titanium.
Although not shown, this TiN film forming apparatus includes:
Needless to say, the vacuum chamber 1 is provided with exhaust means for creating a vacuum.
つぎに、この発明にかかる製造方法を上記形成
装置を用いた場合を例にとつて詳しく説明する。
それは、以下のようである。 Next, the manufacturing method according to the present invention will be explained in detail using the above-mentioned forming apparatus as an example.
It is as follows.
真空槽１内の所定位置にフープ状基材２をセ
ツトするとともに、電子ビーム蒸発源３上に金
属チタン４を載せる。 A hoop-shaped substrate 2 is set at a predetermined position in a vacuum chamber 1, and a titanium metal 4 is placed on an electron beam evaporation source 3.
真空槽１内を排気手段で排気して１×10-5
Torrにする。 Evacuate the inside of vacuum chamber 1 with an exhaust means to 1×10 -5
Set to Torr.
基材２を一定速度で矢印方向に徐々に巻き取
る。これと同時に、Ar+イオンビームおよび
N2 +イオンビームを加速電圧0.3〜2.0KeVで基
材２表面へそれぞれのイオン銃５，６から照射
する。 The base material 2 is gradually wound up in the direction of the arrow at a constant speed. At the same time, Ar + ion beam and
An N 2 + ion beam is irradiated onto the surface of the base material 2 from each of the ion guns 5 and 6 at an acceleration voltage of 0.3 to 2.0 KeV.
この結果、蒸発した金属チタンは、たとえば、
以下のような式、
2Ti＋N2.+＋e-→2TiN
であらわされるように、TiNに変化する、そし
て、イオンビームエネルギーによつて密着性、緻
密性、耐摩耗性に優れるTiN膜が基材２表面に
連続的に形成される。TiN膜形成時の基材の温
度は、200℃以下である。膜は、蒸発源と基材間
の距離、蒸発のパワー、イオンビームのパワーを
適切な値に設定することにより、１〜30Å／ｓの
速度で成長させることができる。イオンビームの
パワーをあまり強くすると基材内に食い込んでし
まうので好ましくない。 As a result, the evaporated titanium metal is e.g.
As expressed by the following formula, 2Ti + N2. formed continuously. The temperature of the base material during TiN film formation is 200°C or less. The film can be grown at a rate of 1 to 30 Å/s by setting the distance between the evaporation source and the substrate, the evaporation power, and the ion beam power to appropriate values. It is not preferable to increase the power of the ion beam too much because it will dig into the base material.
つぎに、実施例を詳しく説明する。 Next, examples will be explained in detail.
（実施例）
電子ビームパワー6KV×200mAの電子ビーム
蒸発源を基材からの距離340mmに配置するととも
に、イオンビーム源としての0.5KeV×40mAの
イオン銃を基材からの距離450mmに配置した第１
図の装置を用い、基材としてのマルテンサイト系
ステンレス材表面にTiN膜を形成した。なお、
基材の温度は最高で80℃であつた。(Example) An electron beam evaporation source with an electron beam power of 6 KV x 200 mA was placed at a distance of 340 mm from the base material, and an ion gun of 0.5 KeV x 40 mA as an ion beam source was placed at a distance of 450 mm from the base material. 1
Using the apparatus shown in the figure, a TiN film was formed on the surface of a martensitic stainless steel material as a base material. In addition,
The maximum temperature of the substrate was 80°C.
このようにして得たTiN膜形成基板と、従来
の形成法で得たTiN膜形成基板とを、それぞれ
40℃、３％NaCl水溶液に浸漬して放置したとこ
ろ、実施例で得たTiN膜形成基板は、３日後で
も異常が検出されなかつた。これに対し、従来の
形成法（真空度10-3Torr程度のイオンプレーテ
イング法）で得たTiN膜形成基板は、１日で錆
の発生が検出された。実施例で得たTiN膜形成
基板は、テープテストの結果でも密着性に異常が
なかつた。さらに、ビツカース硬度は、2000〜
2500の高硬度であつた。金色の色度調整も容易で
あつた。 The TiN film formed substrate obtained in this way and the TiN film formed substrate obtained by the conventional formation method were
When the TiN film-formed substrate obtained in the example was left immersed in a 3% NaCl aqueous solution at 40° C., no abnormality was detected even after 3 days. On the other hand, on the TiN film-formed substrate obtained by the conventional formation method (ion plating method at a vacuum level of about 10 -3 Torr), rust was detected within one day. The TiN film-formed substrate obtained in the example had no abnormality in adhesion even as a result of a tape test. Furthermore, the Bitkers hardness is 2000 ~
It had a high hardness of 2500. It was also easy to adjust the chromaticity of gold.
この発明にかかる製造方法は、上記実施例に限
定されない。たとえば、基材もフープ状であれば
板状に限らない。ボンバード処理にもちいられる
ガスは、Arなどの希ガス類に限らずN2などでも
構わない。 The manufacturing method according to the present invention is not limited to the above embodiments. For example, the base material is not limited to a plate shape as long as it is hoop-shaped. The gas used for the bombardment process is not limited to rare gases such as Ar, but may also be N 2 or the like.
この発明のTiN膜を有するフープ状基材の製
造方法は、以上のように、鉄系の合金からなるフ
ープ状基材を真空中に連続的に送り出すように配
置して、Tiを蒸発させると同時に、前記基材表
面に加速電圧0.3〜2.0KeVで窒素イオンビームを
照射し、前記基材表面にTiNを膜を形成するよ
うになつているので、従来より、高真空側で処理
でき、N2ガス量が少なくすみ、かつ、基材にバ
イアス電圧をかける必要がなく、連続処理である
のに装置が複雑にならない。したがつて、フープ
状基材上に耐蝕性、密着性および装飾性に優れた
TiN膜を効率よく、かつ、安価で得ることがで
きる。
As described above, the method for producing a hoop-shaped substrate having a TiN film according to the present invention involves arranging a hoop-shaped substrate made of an iron-based alloy to be continuously fed into a vacuum to evaporate Ti. At the same time, the surface of the base material is irradiated with a nitrogen ion beam at an acceleration voltage of 0.3 to 2.0 KeV to form a TiN film on the surface of the base material. 2The amount of gas is small, there is no need to apply a bias voltage to the substrate, and the equipment does not become complicated even though it is a continuous process. Therefore, it has excellent corrosion resistance, adhesion and decorative properties on the hoop-shaped substrate.
A TiN film can be obtained efficiently and at low cost.
特に、この発明では、イオンのエネルギーが小
さく、成膜スピードが速いことから、基材の温度
上昇が小さく、冷却装置を要しないので、装置が
簡単で製造コストも安価になる。しかも、このよ
うに温度上昇が少ないとともに、巻き取りプーリ
などで基材を巻き取るので、基材にたわみが生じ
ず、その結果、均一な膜の形成が可能になる。 In particular, in this invention, since the ion energy is low and the film formation speed is high, the temperature rise of the base material is small and no cooling device is required, so the device is simple and the manufacturing cost is low. Moreover, since the temperature rise is small and the base material is wound up using a winding pulley, the base material does not bend, and as a result, a uniform film can be formed.
第１図はこの発明にかかる、TiN膜を有する
フープ状基材の製造方法を実施するのに用いられ
るTiN膜形成装置の１実施例を説明する概略説
明図である。
１……真空槽、２……フープ状基材、３……電
子ビーム蒸発源、４……金属チタン、５，６……
イオン銃。
FIG. 1 is a schematic explanatory diagram illustrating one embodiment of a TiN film forming apparatus used to carry out the method of manufacturing a hoop-shaped base material having a TiN film according to the present invention. 1... Vacuum chamber, 2... Hoop-shaped base material, 3... Electron beam evaporation source, 4... Metallic titanium, 5, 6...
ion gun.
Claims (1)
連続的に送り出し、巻き取るように配置して、
Tiを蒸発させると同時に、前記基材表面に加速
電圧0.3〜2.0KeVで窒素イオンビームを照射し、
前記基材表面にTiN膜を形成する、TiN膜を有
するフープ状基材の製造方法。1. A hoop-shaped base material made of an iron-based alloy is continuously fed into a vacuum, arranged so as to be wound up,
At the same time as evaporating Ti, the surface of the base material is irradiated with a nitrogen ion beam at an acceleration voltage of 0.3 to 2.0 KeV,
A method for manufacturing a hoop-shaped base material having a TiN film, the method comprising forming a TiN film on the surface of the base material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3964086A JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3964086A JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1236361A Division JPH0686657B2 (en) | 1989-09-11 | 1989-09-11 | Thin film forming equipment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62199763A JPS62199763A (en) | 1987-09-03 |
| JPH0551661B2 true JPH0551661B2 (en) | 1993-08-03 |
Family
ID=12558688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3964086A Granted JPS62199763A (en) | 1986-02-25 | 1986-02-25 | Formation of tin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62199763A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2611309B2 (en) * | 1988-02-23 | 1997-05-21 | 日新電機株式会社 | Method of manufacturing high hardness TiN film |
| JPH03177570A (en) * | 1989-12-05 | 1991-08-01 | Raimuzu:Kk | Production of combined hard material |
| CN111893439A (en) * | 2020-08-11 | 2020-11-06 | 苏州众智泽智能科技有限公司 | Method for preparing personal ornaments with titanium nitride hard coating |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58181864A (en) * | 1982-04-16 | 1983-10-24 | Sumitomo Electric Ind Ltd | Surface treatment method |
| JPS6115967A (en) * | 1984-06-29 | 1986-01-24 | Sumitomo Electric Ind Ltd | Surface treatment |
| JPS61195971A (en) * | 1985-02-25 | 1986-08-30 | Kobe Steel Ltd | Formation of wear resisting film |
-
1986
- 1986-02-25 JP JP3964086A patent/JPS62199763A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62199763A (en) | 1987-09-03 |
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