JPH0725566B2 - Amorphous oxide coating material and sliding member - Google Patents
Amorphous oxide coating material and sliding memberInfo
- Publication number
- JPH0725566B2 JPH0725566B2 JP1224486A JP22448689A JPH0725566B2 JP H0725566 B2 JPH0725566 B2 JP H0725566B2 JP 1224486 A JP1224486 A JP 1224486A JP 22448689 A JP22448689 A JP 22448689A JP H0725566 B2 JPH0725566 B2 JP H0725566B2
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- JP
- Japan
- Prior art keywords
- film
- zirconium
- coating material
- zrb
- amorphous oxide
- 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.)
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、優れた摺動特性を有するコーティング材及び
摺動部材を提供するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial field of use] The present invention provides a coating material and a sliding member having excellent sliding properties.
［従来の技術］ 摺動部材には、鉄，ステンレス，超硬合金等の金属が広
く用いられている。金属の摺動部材は、ほとんどの場
合、摩擦，摩耗を低減するため、潤滑油を用いて、使用
されている。したがって、潤滑油を用いることのできな
い条件下、たとえば、真空中あるいは電子製品等の高度
のクリーン度を要求される場合や衛生上の問題で潤滑油
を使用できない場合、従来の金属の摺動材料では大きな
問題があった。[Prior Art] Metals such as iron, stainless steel, and cemented carbide are widely used for sliding members. In most cases, metal sliding members are used with lubricating oil to reduce friction and wear. Therefore, under the condition that the lubricating oil cannot be used, for example, when a high degree of cleanliness is required in vacuum or electronic products, or when the lubricating oil cannot be used due to hygiene problems, the conventional metal sliding material is used. Then there was a big problem.
最近、無潤滑剤下で、利用できる摺動材料として耐熱
性，耐食性に優れた炭化ケイ素，窒化ケイ素，ジルコニ
ア等のファインセラミックスの摺動材が使用され始めて
きている。しかし、セラミックスは脆性材料であるた
め、割れ、欠け等が生じ易く、ハンドリングがむずかし
いといった問題を有している。Recently, fine ceramic sliding materials such as silicon carbide, silicon nitride, and zirconia, which have excellent heat resistance and corrosion resistance, have begun to be used as sliding materials that can be used without a lubricant. However, since ceramics is a brittle material, there is a problem that cracking, chipping and the like are likely to occur and handling is difficult.
また、金属にセラミックスをコーティングしたものとし
て、超硬合金にTiCやTiN等の高硬度のセラミックスをコ
ーティングした耐摩耗性の高い切削工具が開発されてい
る。Further, as a metal coated with ceramics, a cutting tool with high wear resistance has been developed in which cemented carbide is coated with high hardness ceramics such as TiC and TiN.
［発明の解決しようとする課題］ 本発明の目的は、従来の金属あるいはセラミックスの摺
動部材の有していた高摩擦，低潤滑，低耐摩耗等の欠点
を解消しようとするものである。[Problems to be Solved by the Invention] An object of the present invention is to eliminate the drawbacks such as high friction, low lubrication, low wear resistance and the like which the sliding members made of conventional metals or ceramics have.
［課題を解決するための手段］ 本発明は、前述の課題を解決すべくなされたものであ
り、Ｂ（ホウ素）とSi（ケイ素）のうち少なくとも１種
とZrとを特定の割合で含む酸化物を主成分とし、スパッ
タリング法により形成される摺動特性に優れたコーティ
ング材及び金属基体上に掛かるコーティング材を形成し
た摺動部材を提供するものである。[Means for Solving the Problems] The present invention has been made to solve the above problems, and includes an oxidation that contains at least one of B (boron) and Si (silicon) and Zr in a specific ratio. The present invention provides a sliding member which is mainly composed of a material and which has a coating material formed by a sputtering method and which has excellent sliding characteristics, and a coating material which hangs on a metal substrate.
本発明のコーティング材の母材としては、金属，セラミ
ックス，ガラス，プラスチック等が使用でき、特に、母
材強度が高く、摺動部材として使用しやすい、超硬合金
やステンレス等の金属を使用することが好ましい。As the base material of the coating material of the present invention, metal, ceramics, glass, plastic or the like can be used, and particularly, a metal such as cemented carbide or stainless steel having high base material strength and easy to use as a sliding member is used. It is preferable.
表１は、具体的に本発明の非晶質酸化物コート材に最適
な各種非晶質酸化物膜の性質を示したものである。それ
ぞれ表に挙げた組成のターゲットを用いて、反応性スパ
ッタリングにより製膜したものである。結晶性は、薄膜
Ｘ線回折により観測した。又、耐擦傷性は、砂消しゴム
による擦り試験の結果で、○は傷が殆どつかなかったも
の、×は容易に傷が生じたものである。Table 1 shows the properties of various amorphous oxide films most suitable for the amorphous oxide coating material of the present invention. Each film was formed by reactive sputtering using the target having the composition shown in the table. Crystallinity was observed by thin film X-ray diffraction. The scratch resistance is the result of a rubbing test with a sand eraser. O indicates that scratches were scarce, and X indicates that scratches occurred easily.
耐摩耗性は、テーバー試験（摩耗輪CS-10F、加重500g、
1000回転）の結果、ヘイズ４％以内のものを○、ヘイズ
４％超のものを×とした。耐酸性は0.1N H2SO4中に240
時間浸漬した結果、TV（可視光透過率）、RV（可視光反
射率）の浸漬前に対する変化率が１％以内のものを○、
１〜４％のものを△、膜が溶解して削減したしまったも
のを×とした。耐アルカリ性は0.1N NaOH中に240時間浸
漬した結果、TV，RVの浸漬前に対する変化率が１％以内
のものを○、膜が溶解してしまったものを×とした。煮
沸テストは、１気圧下、100℃の水に２時間浸漬した
後、TV，RVの浸漬前に対する変化率が１％以内であると
き○、１％超のとき×とした。Abrasion resistance is measured by Taber test (wear wheel CS-10F, weight 500g,
As a result of 1000 rotations, those having a haze of 4% or less were evaluated as ◯, and those having a haze of more than 4% were evaluated as x. Acid resistance is 240 in 0.1 NH 2 SO 4.
As a result of immersion for a period of time, the change rate of T V (visible light transmittance) and R V (visible light reflectance) within 1% before immersion was evaluated as ○,
The content of 1 to 4% was evaluated as Δ, and the content of the film dissolved and reduced was evaluated as ×. As for the alkali resistance, as a result of immersion in 0.1 N NaOH for 240 hours, the change rate of T V and R V within 1% before immersion was evaluated as ○, and the film dissolved was evaluated as ×. In the boiling test, after immersion in water at 100 ° C. under 1 atm for 2 hours, the change rate of T V and R V before immersion was 1% or less, and when it was more than 1%, x.
本発明のZrBXOY膜において、Ｘ＞0.10であれば膜が非晶
質化し、低摩擦で高耐摩耗性の膜となる。又、B2O3膜は
吸湿性で空気中の水分を吸収して溶けてしまうので、Zr
BXOY膜においてＸ≦３であり、特に、耐酸性の高いＸ＜
2.3が好ましい。ZrBXOY膜中のZrに対するＯ（酸素）の
原子比は特に限定されないが、多すぎると膜構造が粗に
なりボソボソの膜になってしまうこと、あまり少ないと
膜が金属的になり潤滑性が低下するなどの理由により、
ZrO2とB2O3の複合系となる量程度であることが好まし
い。即ち、複合酸化物をZrO2＋XBO1.5と表すと、ＢがZr
に対して原子比でＸ含まれる時に、Ｙ＝Ｚ＋1.5X程度で
あることが好ましい。In the ZrB X O Y film of the present invention, if X> 0.10, the film becomes amorphous and becomes a film with low friction and high wear resistance. Also, the B 2 O 3 film is hygroscopic and absorbs moisture in the air to dissolve, so Zr
In the B X O Y film, X ≦ 3, and in particular, X <with high acid resistance
2.3 is preferred. The atomic ratio of O (oxygen) to Zr in the ZrB X O Y film is not particularly limited, but if it is too large, the film structure becomes rough and becomes a rugged film, and if it is too small, the film becomes metallic and lubricated. For reasons such as deterioration in sex
It is preferable that the amount is such that a composite system of ZrO 2 and B 2 O 3 can be obtained. That is, when the complex oxide is expressed as ZrO 2 + X BO 1.5 , B is Zr
On the other hand, when X is contained in the atomic ratio, it is preferable that Y = Z + 1.5X.
ZrSiZOY膜に関しては、Ｚ≧0.05であれば膜が非晶質化
し、低摩擦で高耐摩耗性の膜となる。又、Ｚ≧19だと、
耐アルカリ性が悪くなる。又、Ｙは、ZrBXOY膜について
述べたのと同様の理由により、SiがZrに対してＺ含まれ
る時に、Ｙ＝２＋2Z程度であることが好ましい。For the ZrSi Z O Y film, film is amorphized if Z ≧ 0.05, a high wear resistance of the membrane with low friction. If Z ≧ 19,
Alkali resistance deteriorates. For the same reason as described for the ZrB X O Y film, Y is preferably about Y = 2 + 2Z when Si is included in Zr relative to Zr.
ZrBXSiZOY膜に関しては、Ｘ＋Ｚ≧0.05であれば膜が非
晶質化し、低摩擦で高耐摩耗性の膜となる。またＸ＋Ｚ
≦19であれば耐アルカリ性も良好であるので、ZrBxSizO
y膜においては、0.05≦Ｘ＋Ｚ≦19である。ただし、上
述のように、B2O3は吸湿性で空気中の水分を吸収して溶
けてしまうため、ZrBxSizOy膜中にあまり多く含有され
ない方が良い。具体的には、膜中において、ZrO2＜25mo
l％，かつSiO2＜25mol％で残りがB2O3となる程B2O3が含
まれていると化学的耐久性が不十分となる。即ち、ZrBx
SizOy膜中のZr:B:Si（原子比）を1:x:zとすると、1/
（１＋ｘ＋ｚ）＜0.25かつZ/（１＋ｘ＋ｚ）＜0.25、即
ち、ｘ＋ｚ−３＞０かつｘ−3z＋１＞０の組成は化学的
耐久性が好ましくない。With respect to the ZrB X Si Z O Y film, if X + Z ≧ 0.05, the film becomes amorphous and becomes a film with low friction and high wear resistance. Also X + Z
If ≤19, the alkali resistance is also good, so ZrB x Si z O
In the y film, 0.05 ≦ X + Z ≦ 19. However, as described above, B 2 O 3 is hygroscopic and absorbs water in the air to be melted. Therefore, it is preferable that B 2 O 3 is not contained in the ZrB x Si z O y film in a large amount. Specifically, in the film, ZrO 2 <25mo
If the content of B 2 O 3 is such that l% and SiO 2 <25 mol% and the balance becomes B 2 O 3 , the chemical durability becomes insufficient. That is, ZrB x
If Zr: B: Si (atomic ratio) in the Si z O y film is 1: x: z, then 1 /
The chemical durability is not preferable in the composition of (1 + x + z) <0.25 and Z / (1 + x + z) <0.25, that is, x + z-3> 0 and x-3z + 1> 0.
本発明の非晶質酸化物コート材は、あまり薄いと十分に
コート材としての機能が発揮されないため、50Å以上、
好ましくは100Å以上の膜厚で形成されるのが好まし
い。又、あまり厚いと膜はがれが起こる可能性があるた
め、数10μｍ以下で形成されるのが好ましい。Since the amorphous oxide coating material of the present invention does not exhibit the function as a coating material sufficiently when it is too thin, 50 Å or more,
It is preferable that the film is formed with a film thickness of 100 Å or more. Further, if it is too thick, film peeling may occur, so it is preferable to form the film with a thickness of several tens of μm or less.
本発明においては、スパッタ法が他の製法に比べて高付
着力の膜ができるので用いられる。In the present invention, the sputtering method is used because it can form a film having a higher adhesive force than other manufacturing methods.
たとえば、本発明の非晶質酸化物コートは次のように作
成できる。ZrBXOY膜の場合、ジルコニウム−ホウ素系の
ターゲット（例えば、ZrB2,Zr-ZrB2，ZrB2‐Ｂ等）を用
いて、又、ZrSiZOY膜の場合、ジルコニウム−ケイ素系
のターゲット（例えば、ZrSi2,Zr-ZrSi2，ZrSi2‐Si
等）を用いて、又、ZrBXSiZOY膜の場合、ジルコニウム
−ホウ素−ケイ素系のターゲット（例えば、ZrB2‐ZrSi
2,Zr-ZrB2‐ZrSi2，ZrB2‐ZrSi2‐Si等）を用いてAr＋O
2の混合雰囲気中で１×10-3〜１×10-2Torr程度の真空
中でスパッタリングすると均一な膜を成膜できる。For example, the amorphous oxide coat of the present invention can be made as follows. In the case of a ZrB X O Y film, a zirconium-boron-based target (for example, ZrB 2 , Zr-ZrB 2 , ZrB 2 -B, etc.) is used, and in the case of a ZrSi Z O Y film, a zirconium-silicon-based target is used. Target (eg ZrSi 2 , Zr-ZrSi 2 , ZrSi 2 -Si
Etc., and in the case of ZrB X Si Z O Y film, a zirconium-boron-silicon based target (for example, ZrB 2 -ZrSi
2 , Zr-ZrB 2 -ZrSi 2 , ZrB 2 -ZrSi 2 -Si etc.)
A uniform film can be formed by sputtering in a mixed atmosphere of 2 in a vacuum of about 1 × 10 −3 to 1 × 10 −2 Torr.
［作用］ Zrの酸化物にＢかつ／又はSiを添加すると、Ｂかつ／又
はSiが、かかる酸化物の格子を破壊し、かかる酸化物の
結晶粒の成長を妨げ、膜をより非晶質にすると考えられ
る。 [Operation] When B and / or Si is added to the oxide of Zr, the B and / or Si breaks the lattice of the oxide, prevents the growth of crystal grains of the oxide, and makes the film more amorphous. It is thought to be.
膜表面の凹凸は微結晶の集合である膜よりも非晶質の膜
の方が少ないと考えられ、その結果、本発明の非晶質膜
は摩擦係数が小さくなっていると考えられる。このた
め、本発明の非晶質膜は、潤滑性に優れており、引っか
かりが少ないため摩擦により疵つきにくく、高耐擦傷性
能及び高耐摩耗性能が得られるものと考えられる。It is considered that the unevenness of the film surface is smaller in the amorphous film than in the film that is an aggregate of microcrystals, and as a result, the amorphous film of the present invention has a smaller friction coefficient. Therefore, it is considered that the amorphous film of the present invention has excellent lubricity and is less likely to be scratched due to friction because it is less likely to be caught, and high scratch resistance and high wear resistance can be obtained.
［実施例］ 前述のスパッタ法で成膜した本発明の各種非晶質酸化物
膜（各々膜厚1000Å）の摩擦係数を表２に示す。[Examples] Table 2 shows friction coefficients of various amorphous oxide films of the present invention (each having a film thickness of 1000Å) formed by the above-described sputtering method.
摩擦係数は、ステンレス基板上に各種膜をスパッタコー
トした平板と、φ6mmのステンレス球との、直線運動で
摩擦力を測定し、摩擦係数を算出した。このとき荷重は
50gとした。The friction coefficient was calculated by measuring the friction force by linear movement between a flat plate obtained by sputter-coating various films on a stainless steel substrate and a stainless ball having a diameter of 6 mm. At this time the load is
50g.
耐摩耗性は、ガラス基板上に各種膜をスパッタコートし
たサンプルについて、テーパー試験（摩耗輪CS-10F,荷
重500g,1000回転）の結果、ヘイズ４％以内のものを
○，ヘイズ４％超のものを×とした。As for abrasion resistance, as a result of a taper test (wear wheel CS-10F, load 500g, 1000 rotations), a sample with various films sputter-coated on a glass substrate was rated as ○ for haze within 4% and over 4% for haze. The thing was marked as x.
本発明のコーティング膜の摩擦係数は、表１に示すよう
に0.1〜0.15と小さい。耐摩耗性も良い。The friction coefficient of the coating film of the present invention is as small as 0.1 to 0.15 as shown in Table 1. Good wear resistance.
［発明の効果］ 本発明のコート材は、優れた摺動性能を有するととも
に、高耐久性（耐酸，耐アルカリ，耐水等の耐薬品性な
らびに耐候性）を有しているため、母材を腐食等から保
護する保護コートの効果も認められる。 EFFECT OF THE INVENTION The coating material of the present invention has excellent sliding performance and high durability (chemical resistance such as acid resistance, alkali resistance, water resistance and weather resistance). The effect of a protective coat that protects from corrosion etc. is also recognized.
本発明のコート材は、摺動部材や、工具、治具、耐摩耗
性が要求される各種用途に使用できる。The coating material of the present invention can be used for sliding members, tools, jigs, and various applications requiring abrasion resistance.
Claims (5)
酸化物（ZrBXOY）を主成分とし、ホウ素のジルコニウム
に対する原子比Ｘが0.10＜Ｘ≦３であり、酸素のジルコ
ニウムに対する原子比Ｙが２＜Ｙ≦6.5であって、スパ
ッタリング法により形成されることを特徴とする非晶質
酸化物コート材。1. An oxide (ZrB X O Y ) containing Zr (zirconium) and B (boron) as a main component, the atomic ratio X of boron to zirconium is 0.10 <X ≦ 3, and oxygen to zirconium is an atom. An amorphous oxide coating material having a ratio Y of 2 <Y ≦ 6.5 and formed by a sputtering method.
酸化物（ZrBXOY）を主成分とし、ホウ素のジルコニウム
に対する原子比Ｘが0.10＜Ｘ＜2.3であり、酸素のジル
コニウムに対する原子比Ｙが２＜Ｙ≦5.5であって、ス
パッタリング法により形成されることを特徴とする非晶
質酸化物コート材。2. An oxide (ZrB X O Y ) containing Zr (zirconium) and B (boron) as a main component, the atomic ratio X of boron to zirconium is 0.10 <X <2.3, and oxygen is an atom of zirconium. An amorphous oxide coating material having a ratio Y of 2 <Y ≦ 5.5 and formed by a sputtering method.
酸化物（ZrSiZOY）を主成分とし、ケイ素のジルコニウ
ムに対する原子比Ｚが0.05≦Ｚ＜19であり、酸素のジル
コニウムに対する原子比Ｙが2.1≦Ｙ＜40であって、ス
パッタリング法により形成されることを特徴とする非晶
質酸化物コート材。Wherein a main component of Zr oxide containing zirconium () and Si (the silicon) (ZrSi Z O Y), the atomic ratio Z to silicon zirconium is the 0.05 ≦ Z <19, atoms to zirconium oxygen An amorphous oxide coating material having a ratio Y of 2.1 ≦ Y <40 and formed by a sputtering method.
（ケイ素）を含む酸化物（ZrBXSiZOY）を主成分とし、
ホウ素のジルコニウムに対する原子比をX,ケイ素のジル
コニウムに対する原子比をZ,酸素のジルコニウムに対す
る原子比をＹとすると、0.05≦Ｘ＋Ｚ≦19（ただしＸ＋
Ｚ−３＞０かつＸ−3Z＋１＞０の組成は除く）であり、
２＜Ｙ＜40であって、スパッタリング法により形成され
ることを特徴とする非晶質酸化物コート材。4. Zr (zirconium), B (boron) and Si
An oxide (ZrB X Si Z O Y ) containing (silicon) as a main component,
When the atomic ratio of boron to zirconium is X, the atomic ratio of silicon to zirconium is Z, and the atomic ratio of oxygen to zirconium is Y, 0.05 ≦ X + Z ≦ 19 (where X +
Z-3> 0 and X-3Z + 1> 0 are excluded),
An amorphous oxide coating material, wherein 2 <Y <40 and is formed by a sputtering method.
請求項１〜４のいずれか１項記載の非晶質酸化物コート
材を形成した摺動部材又は工具。5. A substrate made of metal or ceramics,
A sliding member or tool formed with the amorphous oxide coating material according to any one of claims 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1224486A JPH0725566B2 (en) | 1989-03-07 | 1989-09-01 | Amorphous oxide coating material and sliding member |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5300989 | 1989-03-07 | ||
| JP1-53009 | 1989-03-07 | ||
| JP1224486A JPH0725566B2 (en) | 1989-03-07 | 1989-09-01 | Amorphous oxide coating material and sliding member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03218939A JPH03218939A (en) | 1991-09-26 |
| JPH0725566B2 true JPH0725566B2 (en) | 1995-03-22 |
Family
ID=26393693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1224486A Expired - Fee Related JPH0725566B2 (en) | 1989-03-07 | 1989-09-01 | Amorphous oxide coating material and sliding member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0725566B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6033228A (en) * | 1983-07-27 | 1985-02-20 | Hitachi Ltd | Glass composition for silicon carbide ceramics |
| IL84025A0 (en) * | 1986-10-03 | 1988-02-29 | Ppg Industries Inc | Organosiloxane/metal oxide coating compositions and their production |
-
1989
- 1989-09-01 JP JP1224486A patent/JPH0725566B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03218939A (en) | 1991-09-26 |
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