JP3225576B2 - Sliding machine parts coated with self-healing hard solid lubricant film - Google Patents
Sliding machine parts coated with self-healing hard solid lubricant filmInfo
- Publication number
- JP3225576B2 JP3225576B2 JP03726092A JP3726092A JP3225576B2 JP 3225576 B2 JP3225576 B2 JP 3225576B2 JP 03726092 A JP03726092 A JP 03726092A JP 3726092 A JP3726092 A JP 3726092A JP 3225576 B2 JP3225576 B2 JP 3225576B2
- Authority
- JP
- Japan
- Prior art keywords
- boron
- film
- self
- carbon
- healing
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5006—Boron compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
Description
【０００１】[0001]
【産業上の利用分野】本発明は、大気中で使用される摺
動ないし摩擦を伴う機械部品であって、耐摩耗性及び摺
動特性を向上させる目的で、摩擦係数が低く且つ自己修
復性を有する硬質固体潤滑膜で被覆した摺動機械部品に
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a mechanical component which is used in the atmosphere and has sliding or friction, and has a low coefficient of friction and a self-healing property for the purpose of improving abrasion resistance and sliding characteristics. A sliding machine component coated with a hard solid lubricating film having the following.
【０００２】[0002]
【従来の技術】自動車や各種産業機械等を構成する鋼や
超硬合金等の金属質材料やセラミック質材料からなる機
械部品のなかには、常に相手材との摩擦ないし摺動にさ
らされる部材がある。これらは摩耗を減らし且つ摺動特
性を改善するために潤滑油等を常に供給しているが、潤
滑状態の悪化はそく機械全体の寿命低下や動力効率の低
下につながる。2. Description of the Related Art Among mechanical parts made of metallic materials such as steel and cemented carbide and ceramic materials constituting automobiles and various industrial machines, there are members which are always exposed to friction or sliding with a partner material. . These always supply lubricating oil and the like in order to reduce wear and improve sliding characteristics. However, deterioration of the lubrication state leads to a reduction in the life of the entire machine and a reduction in power efficiency.
【０００３】そこで、これら機械部品の表面特性を改善
し、耐摩耗性及び摺動特性を向上させる試みが広く行わ
れている。その一つの方法は、基材表面を硬質被膜で被
覆して、摩耗を少なくするというものである。例えば、
湿式法による硬質金属被膜の形成、溶融塩や流動層、熱
処理炉、プラズマ等を用いた窒化、浸炭、ホウ化、クロ
マイジング等の拡散硬化処理、ＰＶＤ法やＣＶＤ法を用
いた金属又はセラミックスの被覆処理、等が挙げられ
る。しかし、これらの方法は摩擦係数を低下させるもの
ではないので、硬化処理を施された基材側の耐摩耗性改
善には有効であるが、摺動の相手材にとってはより苛酷
な摩擦を受けることになり、相手材との相性を十分配慮
しなければ使用できないという欠点がある。[0003] Attempts have been made to improve the surface characteristics of these mechanical parts and to improve the wear resistance and sliding characteristics. One such method is to coat the substrate surface with a hard coating to reduce wear. For example,
Hard metal coating formation by wet method, molten salt and fluidized bed, heat treatment furnace, diffusion hardening treatment such as nitriding, carburizing, boring, chromizing using plasma, metal or ceramics using PVD method or CVD method Coating treatment and the like. However, since these methods do not lower the friction coefficient, they are effective for improving the abrasion resistance of the hardened substrate side, but suffer more severe friction for the sliding partner. As a result, there is a disadvantage that it cannot be used unless the compatibility with the partner material is sufficiently considered.
【０００４】他の表面特性の改善方法として、基材表面
に固体潤滑材料の被膜を設けて、摩擦係数を下げる方法
がある。固体潤滑材料としては、一般に黒鉛や二硫化モ
リブデン等が知られているが、これらは硬度が極めて低
いため容易に摩耗消滅してしまうので、硬質で且つ摩擦
係数の小さい材料が望まれている。そこで、かかる硬質
固体潤滑材料の一つとして、ポリテトラフルオロエチレ
ン等のフッ素樹脂の微粉を分散させた、いわゆる分散メ
ッキが開発された。フッ素樹脂は摩擦係数が低いものの
低硬度であるため機械部品への適用範囲は限られていた
が、上記の方法は硬質金属中に分散させることで、高い
硬度と低い摩擦係数を同時に実現した点で優れている。
しかしながら、この硬質固体潤滑材料も金属マトリック
スの硬度がヌープ硬度で高々１０００kg／mm2程度であ
るため、厳しい摩擦に対しての耐摩耗性は十分とは言え
なかった。[0004] As another method for improving the surface characteristics, there is a method in which a coating of a solid lubricating material is provided on the base material surface to lower the friction coefficient. Graphite, molybdenum disulfide, and the like are generally known as solid lubricating materials. However, since these materials are extremely low in hardness and easily worn away, they are desired to be hard and have a small friction coefficient. Therefore, as one of such hard solid lubricating materials, a so-called dispersion plating in which fine powder of a fluororesin such as polytetrafluoroethylene is dispersed has been developed. Fluororesin has a low coefficient of friction but low hardness, so its application to mechanical parts was limited.However, the above method realized high hardness and low coefficient of friction simultaneously by dispersing it in hard metal. Is excellent.
However, this hard solid lubricating material also has a Knoop hardness of at most about 1000 kg / mm 2 in the metal matrix, so that the wear resistance against severe friction was not sufficient.
【０００５】最近になって、ホウ素又は酸化ホウ素被膜
からなる自己修復性固体潤滑膜の概念が、Ali Erdemir
によりLubrication Engineering，vol.47, 3, P168〜17
3及びP179〜184（1991）や、Advanced Materials and P
rocesses，vol.7, P40〜42（1991）等に紹介された。ホ
ウ素やその酸化物は、それ自身の硬度がヌープ硬度で２
０００kg／mm2以上と高く耐摩耗性に優れるだけでな
く、その表面が大気中の酸素や水分と反応して最外表面
から順にホウ酸（Ｈ3ＢＯ3）／酸化ホウ素（Ｂ2Ｏ3）／
ホウ素（Ｂ）の層が形成され、最外表面のホウ酸は黒鉛
や二硫化モリブデンのように自己潤滑性を有する。同時
にホウ酸は硬度が低いという欠点を持つが、例えホウ酸
の層が摩耗して失われても、下地の酸化ホウ素が大気中
の水分と更に反応して次々とホウ酸に変化するため、自
己修復性を発現する。More recently, the concept of a self-healing solid lubricating film comprising a boron or boron oxide coating has been described by Ali Erdemir.
By Lubrication Engineering, vol.47, 3, P168-17
3 and P179-184 (1991), Advanced Materials and P
rocesses, vol.7, pp.40-42 (1991). Boron and its oxides have a Knoop hardness of 2
2,000 kg / mm 2 or more, which is not only excellent in abrasion resistance, but also its surface reacts with oxygen and moisture in the atmosphere and boric acid (H 3 BO 3 ) / boron oxide (B 2 O 3 ) /
A layer of boron (B) is formed, and boric acid on the outermost surface has self-lubricating properties like graphite and molybdenum disulfide. At the same time, boric acid has the disadvantage of low hardness, but even if the boric acid layer is worn away and lost, the underlying boron oxide reacts further with atmospheric moisture and changes into boric acid one after another, Develop self-healing properties.
【０００６】しかしながら、上記刊行物にはホウ素の持
つ自己修復性を利用した固体潤滑膜として、(1)硬質基
材へのホウ素のイオン注入、(2)他のセラミックスとの
イオンビームによるミキシング、及び(3)ホウ素の低級
酸化物被膜の３種類のみが提案されているに過ぎない。
これらの手法はいずれも有効な手段ではあるが、(1)及
び(2)はイオンビームを利用するプロセスであるからコ
スト高になり、工業的には問題があるばかりでなく、複
雑形状の部品への処理には適さない欠点がある。又、
(3)の低級酸化物の合成は実験室レベルでは可能であっ
ても、工業レベルでの生産ではより安定な酸化ホウ素の
生成を避けることが困難であり、実現は不可能であると
言っても過言ではない。However, the above publication discloses a solid lubricating film utilizing the self-healing property of boron, (1) boron ion implantation into a hard substrate, (2) ion beam mixing with other ceramics, And (3) Only three types of lower oxide coatings of boron have been proposed.
Both of these methods are effective means, but (1) and (2) are processes that use an ion beam, which increases the cost, is not only industrially problematic, but also involves parts with complex shapes. There is a disadvantage that it is not suitable for processing. or,
Although the synthesis of the lower oxide of (3) is possible at the laboratory level, it is difficult to avoid the production of more stable boron oxide at the production level at the industrial level, and it is impossible to realize it. Not too much.
【０００７】[0007]
【発明が解決しようとする課題】本発明はかかる従来の
事情に鑑み、高硬度でありながら摩擦係数が低く、自己
修復性を備えた硬質固体潤滑膜を、金属質やセラミック
質の基材上に工業的に低コストプロセスで被覆した摺動
機械部品を提供することを目的とする。SUMMARY OF THE INVENTION In view of the above circumstances, the present invention has a high hardness, a low coefficient of friction,
A hard solid lubricating film with reparability is applied to metallic or ceramic
Coated with low-cost process on quality substrate
The purpose is to provide mechanical parts .
【０００８】[0008]
【課題を解決するための手段】上記目的を達成するた
め、本発明が提供する基材上に硬質固体潤滑膜を設けた
摺動機械部品は、少なくとも硬質固体潤滑膜の最外表面
層がホウ素を１０〜４０原子％添加したダイヤモンド状
炭素又は非晶質炭素からなることを特徴する、自己修復
性硬質固体潤滑膜で被覆した摺動機械部品である。In order to achieve the above object , a hard solid lubricating film is provided on a substrate provided by the present invention .
The self-healing sliding machine component is characterized in that at least the outermost surface layer of the hard solid lubricating film is made of diamond-like carbon or amorphous carbon containing 10 to 40 atomic% of boron.
This is a sliding machine part covered with a conductive hard solid lubricant film .
【０００９】又、本発明における自己修復性硬質固体潤
滑膜の製造方法は、基材上にプラズマＣＶＤ法又はイオ
ンプレーティング法により、少なくとも最外表面層とし
てホウ素を３〜５０原子％添加したダイヤモンド状炭素
膜又は非晶質炭素膜を形成することを特徴とする。Further, the method for producing a self-healing hard solid lubricating film according to the present invention is characterized in that a diamond containing at least 3 to 50 atomic% of boron as an outermost surface layer on a substrate by a plasma CVD method or an ion plating method. A carbon film or an amorphous carbon film.
【００１０】[0010]
【作用】本発明者らは、ホウ素の示す自己修復性と潤滑
性に注目し、機械部品等の基材上に設ける硬質固体潤滑
膜について鋭意研究を重ねる中から、ホウ素を添加する
硬質固体膜の材質としてダイヤモンド状炭素又は非晶質
炭素（アモルファスカーボン）を用いることによって、
金属質やセラミック質の基材上に安価で且つ優れた特性
の自己修復性硬質固体潤滑膜を形成できることを見いだ
した。The present inventors have focused on the self-healing properties and lubricity exhibited by boron, and have been conducting intensive research on hard solid lubricating films provided on substrates such as mechanical parts. By using diamond-like carbon or amorphous carbon (amorphous carbon) as the material of
It has been found that a self-healing hard solid lubricating film having low cost and excellent properties can be formed on a metallic or ceramic base material.
【００１１】ダイヤモンド状炭素又は非晶質炭素は、い
ずれも硬度が高く耐摩耗性に優れているが、ホウ素を添
加することにより大気中でホウ酸が生成されるので摩擦
係数が小さく優れた固体潤滑膜となり、且つ含有される
ホウ素が大気中で酸化ホウ素を経てホウ酸に変化する反
応により自己修復性を示す。又、ダイヤモンド状炭素膜
又は非晶質炭素膜は、プラズマＣＶＤ法あるいはイオン
プレーティング法により、大きな面積の基材表面に安価
に被膜形成でき、容易に極めて平滑な膜表面が得られる
利点がある。Although diamond-like carbon and amorphous carbon are both high in hardness and excellent in wear resistance, boric acid is generated in the atmosphere by adding boron, so that a solid having a small friction coefficient and excellent It becomes a lubricating film and exhibits self-healing properties due to a reaction in which the contained boron changes into boric acid via boron oxide in the atmosphere. In addition, a diamond-like carbon film or an amorphous carbon film can be formed on a large-area substrate surface at low cost by a plasma CVD method or an ion plating method, and has an advantage that an extremely smooth film surface can be easily obtained. .
【００１２】これに対して、結晶質のダイヤモンド被膜
にホウ素を添加することも考えられるが、気相合成ダイ
ヤモンド膜はダイヤモンド微結晶の成長面が表面に露出
するため極めて表面が粗くなり、低い摩擦係数が得られ
ない。又、ダイヤモンド膜の形成には、処理面積が小さ
いことやコストが高い等のマイナス要因も存在する。更
に、立方晶の窒化ホウ素膜も、表面に酸化ホウ素が生成
することが予想されるが、既に公知となっている形成方
法はいずれもコスト的に厳しく、合成が困難であること
もあって、現実的には使用が難しい。On the other hand, it is conceivable to add boron to the crystalline diamond film, but the vapor phase synthetic diamond film is extremely rough because the growth surface of the diamond microcrystals is exposed on the surface, and the friction is low. The coefficient cannot be obtained. Further, the formation of the diamond film has negative factors such as a small processing area and a high cost. Furthermore, the cubic boron nitride film is also expected to generate boron oxide on the surface, but any of the known formation methods are costly and difficult to synthesize, Realistically difficult to use.
【００１３】かかる本発明のホウ素を添加したダイヤモ
ンド状炭素膜又は非晶質炭素膜の摩擦係数は、ＴｉＢ2
やＴａＢ2等のホウ化物セラミックスや、ホウ素をイオ
ン注入したＴｉＮやＴｉＣ等の他のセラミックス等の摩
擦係数よりも小さくなることが分かった。その原因は明
らかではないが、大気中での摩擦摩耗現象においては、
酸化物の形成を伴う酸化摩耗が主として起こっているこ
とが第一の原因であると考えられる。[0013] The coefficient of friction of the boron-added diamond-like carbon film or amorphous carbon film of the present invention is TiB 2
And TaB and boride ceramics such as 2, boron was found to be smaller than the friction coefficient of such other ceramics such as ion-implanted TiN or TiC. Although the cause is not clear, in the friction wear phenomenon in the atmosphere,
It is considered that the first cause is mainly oxidative wear accompanied by oxide formation.
【００１４】即ち、ＴｉＢ2等のホウ化物セラミックス
やホウ素をイオン注入したＴｉＮ等のセラミックスで
は、摺動面においてホウ素以外の金属の酸化物も酸化ホ
ウ素と同時に生成する。例えば、ＴｉＢ2の摺動面に生
じる酸化物には、Ｂ2Ｏ3だけでなく、ＴｉＯ2等の硬質
粒子も含まれる。そのため、Ｂ2Ｏ3の表面に形成される
ホウ酸により得られる低い摩擦係数を、これら硬質粒子
が悪化させているものと思われる。これに対して、本発
明のホウ素を含むダイヤモンド状炭素又は非晶質炭素の
被膜は、炭素とホウ素と水素からなるので、炭素の酸化
物及び水素の酸化物は容易に大気中に放出されて、摺動
面に形成される酸化物は酸化ホウ素のみとなり、摺動を
妨げる働きを持った硬質粒子が存在しないため、極めて
小さな摩擦係数がえられるものと考えられる。That is, in a boride ceramic such as TiB 2 or a ceramic such as TiN into which boron has been ion-implanted, an oxide of a metal other than boron is generated simultaneously with the boron oxide on the sliding surface. For example, oxides generated on the sliding surface of TiB 2 include not only B 2 O 3 but also hard particles such as TiO 2 . Therefore, it is considered that these hard particles deteriorate the low friction coefficient obtained by boric acid formed on the surface of B 2 O 3 . On the other hand, since the coating of diamond-like carbon or amorphous carbon containing boron of the present invention is composed of carbon, boron and hydrogen, oxides of carbon and oxides of hydrogen are easily released into the atmosphere. On the other hand, the oxide formed on the sliding surface is only boron oxide, and there is no hard particle having a function of hindering the sliding. Therefore, it is considered that an extremely small friction coefficient can be obtained.
【００１５】ダイヤモンド状炭素又は非晶質炭素中への
ホウ素の添加量については、３〜５０原子％の範囲と
し、特に１０〜４０原子％の範囲が好ましい。その理由
は、ホウ素の添加量が３原子％未満では図１に示す潤滑
性や自己修復性等のホウ素添加の効果が全く発現され
ず、逆に５０原子％を越えるとダイヤモンド状炭素膜又
は非晶質炭素膜としての特性が少なくなり、図２に示す
ように被膜の硬度が低下するからである。The amount of boron to be added to diamond-like carbon or amorphous carbon is in the range of 3 to 50 at%, particularly preferably 10 to 40 at%. The reason is that if the amount of boron is less than 3 atomic%, the effects of boron addition such as lubricity and self-healing properties shown in FIG. 1 are not exhibited at all, whereas if it exceeds 50 atomic%, the diamond-like carbon film or non- This is because the properties of the amorphous carbon film are reduced, and the hardness of the film is reduced as shown in FIG.
【００１６】ダイヤモンド状炭素又は非晶質炭素にホウ
素を添加した本発明の自己修復性硬質固体潤滑膜を安価
に且つ大きな面積に被覆する方法としては、プラズマＣ
ＶＤ法又はイオンプレーティング法を利用することが好
ましい。これらの方法はダイヤモンド状炭素膜又は非晶
質炭素膜の形成方法として公知であるが、その中にホウ
素を添加するため、炭素源とは別にホウ素源を同時に供
給する必要がある。As a method for coating the self-healing hard solid lubricating film of the present invention in which boron is added to diamond-like carbon or amorphous carbon over a large area at low cost, plasma C
It is preferable to use the VD method or the ion plating method. These methods are known as a method for forming a diamond-like carbon film or an amorphous carbon film. However, in order to add boron therein, it is necessary to simultaneously supply a boron source separately from a carbon source.
【００１７】例えばプラズマＣＶＤ法では、炭化水素等
の炭素含有ガスと共に、ジボランや三塩化ホウ素等のホ
ウ素含有ガスを供給し、マイクロ波や直流放電等により
励起させたプラズマ中で分解等の化学反応を起こさせ、
基材表面にホウ素を含むダイヤモンド状炭素又は非晶質
炭素の被膜を生成させる。又、イオンプレーティング法
では、固体黒鉛等を電子ビームあるいはアーク放電等に
より蒸発、昇華させると同時に、金属ホウ素を蒸発、昇
華あるいはスパッタさせ、炭素原子とホウ素原子をイオ
ン化して電界で加速し、基材表面に付着させ被膜を形成
する。For example, in the plasma CVD method, a boron-containing gas such as diborane or boron trichloride is supplied together with a carbon-containing gas such as a hydrocarbon, and a chemical reaction such as decomposition is performed in a plasma excited by microwaves or direct current discharge. Awaken
A film of diamond-like carbon or amorphous carbon containing boron is formed on the substrate surface. In the ion plating method, solid graphite or the like is evaporated and sublimated by an electron beam or arc discharge, and at the same time, metal boron is evaporated, sublimated or sputtered, and carbon atoms and boron atoms are ionized and accelerated by an electric field. A film is formed by adhering to the substrate surface.
【００１８】[0018]
【実施例１】基材として高速度鋼（ＳＫＨ９）を用い、
その表面を最大粗さ０.１μｍ以下に研磨ラッピングし
た後、有機溶剤で脱脂した。この基材１を図３に示すプ
ラズマＣＶＤ装置の真空槽２に入れ、電極３に取り付け
た。次に、真空槽２の内部を真空排気装置４により１×
１０-5Ｔｏｒｒ以下まで排気した後、ガス供給装置５か
らアルゴンガスを導入して、真空槽２内の圧力を０.１
Ｔｏｒｒとした。直流電源６から電極３に−５００Ｖの
負の電圧を与え、真空槽２内にプラズマを発生させて基
材１の表面を１０分間クリーニングした。Example 1 High speed steel (SKH9) was used as a substrate.
After polishing and lapping the surface to a maximum roughness of 0.1 μm or less, the surface was degreased with an organic solvent. The substrate 1 was placed in the vacuum chamber 2 of the plasma CVD apparatus shown in FIG. Next, the inside of the vacuum chamber 2 is evacuated to 1 × by the vacuum exhaust device 4.
After evacuating to 10 −5 Torr or less, argon gas was introduced from the gas supply device 5 to reduce the pressure in the vacuum chamber 2 to 0.1.
Torr. A negative voltage of -500 V was applied to the electrode 3 from the DC power supply 6 to generate plasma in the vacuum chamber 2 to clean the surface of the substrate 1 for 10 minutes.
【００１９】その後、電極３に−５００Ｖの電圧を供給
したまま、アルゴンガスの供給を減らし、代わりにメタ
ンガスをガス供給装置５から徐々に供給して、真空槽２
内の圧力を０.１Ｔｏｒｒに維持した。アルゴンガスの
供給が完全にゼロとなった時から１５分間はメタンガス
のみを供給し、次の１５分間はメタンガスと共に水素で
希釈したジボランガスをメタンガスに対して２体積％添
加して供給し、その後すべてのガスの供給を停止して直
流電源６を切った。Thereafter, the supply of argon gas is reduced while the voltage of -500 V is being supplied to the electrode 3, and instead, methane gas is gradually supplied from the gas supply device 5 to the vacuum tank 2.
The internal pressure was maintained at 0.1 Torr. From the time when the supply of argon gas becomes completely zero, only methane gas is supplied for 15 minutes, and for the next 15 minutes, diborane gas diluted with hydrogen is added together with methane gas at 2% by volume to methane gas, and then supplied. Was stopped and the DC power supply 6 was turned off.
【００２０】上記操作によるダイヤモンド状炭素（ＤＬ
Ｃ）膜の成膜中は、プラズマ中の荷電粒子の衝突により
基材１の温度は約２００℃まで上昇しているので、約３
０分間冷却して基材１の温度が１００℃以下になってか
ら真空槽２の排気を停止し、ガス供給装置５から大気又
は不活性ガスを導入した後、真空槽２を開いて基材１を
取り出した。基材１の表面には合計膜厚１.２μｍのＤ
ＬＣ膜が形成されており、その表面側に深さ０.３μｍ
まで１５原子％のホウ素が添加されていた。The diamond-like carbon (DL)
C) During the film formation, the temperature of the base material 1 has risen to about 200 ° C. due to the collision of charged particles in the plasma.
After cooling for 0 minute and the temperature of the substrate 1 became 100 ° C. or less, the evacuation of the vacuum chamber 2 was stopped, and air or an inert gas was introduced from the gas supply device 5. 1 was taken out. The surface of the base material 1 has a total thickness of 1.2 μm D
An LC film is formed and has a depth of 0.3 μm on the surface side.
Up to 15 atomic percent boron has been added.
【００２１】比較のため、同じ基材の上に下記の被膜を
それぞれ形成した試料も準備した： (１)ホウ素をイオン注入したＴｉＮ膜 (２)ホウ素をイオン注入したＴｉＣ膜 (３)イオンプレーティング法により成膜したＴｉＢ2膜 (４)プラズマＣＶＤ法により成膜したＴｉＢ2膜 尚、膜厚はいずれも１.２μｍに調節した。For comparison, samples having the following films formed on the same substrate were also prepared: (1) TiN film implanted with boron (2) TiC film implanted with boron (3) ion plating TiB 2 film Incidentally was formed by TiB 2 layer (4) plasma CVD deposited by plating method, none of the thickness was adjusted to 1.2 [mu] m.
【００２２】上記本発明試料と各比較試料について、ピ
ンオンディスク式摩擦摩耗試験機により大気中で摩擦係
数を測定した。試験条件としては、相手材をＳＵＪ２か
らなる直径１０ｍｍのボールとし、摺動状態は無潤滑
で、摺動速度を０.１ｍ／秒及び押し付け荷重を１Ｎと
した。試験結果を下記表１に示した。The friction coefficient of the sample of the present invention and each of the comparative samples were measured in the atmosphere using a pin-on-disk friction and wear tester. The test conditions were as follows: a mating material was a ball made of SUJ2 having a diameter of 10 mm, the sliding state was non-lubricated, the sliding speed was 0.1 m / sec, and the pressing load was 1 N. The test results are shown in Table 1 below.
【００２３】[0023]
【表１】試 料 の 被 膜 摩 擦 係 数 本発明のホウ素添加ＤＬＣ膜 ０.０４〜０.０６ ホウ素イオン注入ＴｉＮ膜 ２.１〜２.３ ホウ素イオン注入ＴｉＣ膜 ２.３〜２.５ イオンプレーティングＴｉＢ2膜 １.５〜１.８ プラズマＣＶＤＴａＢ2膜 １.４〜１.７ 表１の結果から分かるように、他のセラミックスにホウ
素を注入した被膜あるいはホウ化物セラミックスの被膜
よりも、本発明によるホウ素を添加したＤＬＣ膜の方が
低い摩擦係数を示す。TABLE 1 boronizing DLC film 0.04 to 0.06 boron ion implantation TiN film 2.1 to 2.3 boron ion implantation TiC film of the film friction engagement several invention specimen from 2.3 to 2. 5 Ion-plating TiB 2 film 1.5-1.8 Plasma CVD TaB 2 film 1.4-1.7 As can be seen from the results in Table 1, a film obtained by implanting boron into other ceramics or a film formed from boride ceramics Also, the boron-added DLC film according to the present invention shows a lower coefficient of friction.
【００２４】[0024]
【実施例２】基材としてＷＣ−Ｃｏ系超硬合金を用い、
その表面を最大粗さ０.１μｍ以下に研磨ラッピングし
た後、有機溶剤で脱脂した。この基材１を図４に示すイ
オンプレーティング装置の真空槽２に入れ、電極３に取
り付けた。次に、真空槽２の内部を真空排気装置４によ
り１×１０-5Ｔｏｒｒ以下まで排気した後、加熱用ヒー
ター７により基材１を５００℃まで加熱した。更に、ガ
ス供給装置５からアルゴンガスと水素ガスの混合ガス
（混合体積比１：１）を導入して、真空槽２内の圧力を
０.１Ｔｏｒｒとした。直流電源６から電極３に−１０
００Ｖの負の電圧を与え、真空槽２内にプラズマを発生
させて基材１の表面を１０分間クリーニングした。Embodiment 2 Using a WC-Co cemented carbide as a base material,
After polishing and lapping the surface to a maximum roughness of 0.1 μm or less, the surface was degreased with an organic solvent. The substrate 1 was placed in the vacuum chamber 2 of the ion plating apparatus shown in FIG. Next, after the inside of the vacuum chamber 2 was evacuated to 1 × 10 −5 Torr or less by the vacuum evacuation device 4, the substrate 1 was heated to 500 ° C. by the heater 7 for heating. Further, a mixed gas of argon gas and hydrogen gas (mixing volume ratio of 1: 1) was introduced from the gas supply device 5, and the pressure in the vacuum chamber 2 was set to 0.1 Torr. -10 from DC power supply 6 to electrode 3
A negative voltage of 00 V was applied to generate plasma in the vacuum chamber 2 to clean the surface of the substrate 1 for 10 minutes.
【００２５】その後、電極３に−１０００Ｖの電圧を供
給したまま、真空槽２内の圧力が１×１０-3Ｔｏｒｒに
なるようにガスの供給を減らした。この状態で、炭素蒸
発源８の固体黒鉛から炭素を、及びホウ素蒸発源９の金
属ホウ素からホウ素をそれぞれ蒸発させ、炭素とホウ素
の原子比率が８：２となるように炭素とホウ素の蒸発速
度を調整しながら、基材１の表面にホウ素を含む非晶質
炭素（ＡＣ）膜の形成を３０分間行った。その後、炭素
とホウ素の蒸発を停止させ、ガスの供給と直流電圧の供
給を止め、加熱用ヒーター７を切って基材１を冷却した
後、真空槽２を開いて基材１を取り出した。基材１の表
面には合計膜厚２.５μｍのホウ素添加ＡＣ膜が形成さ
れており、ホウ素添加量は２０原子％であった。Thereafter, while the voltage of -1000 V was supplied to the electrode 3, the supply of gas was reduced so that the pressure in the vacuum chamber 2 became 1 × 10 -3 Torr. In this state, carbon is evaporated from the solid graphite of the carbon evaporation source 8 and boron is evaporated from the metallic boron of the boron evaporation source 9, and the evaporation rates of carbon and boron are adjusted so that the atomic ratio of carbon and boron becomes 8: 2. While adjusting the conditions, an amorphous carbon (AC) film containing boron was formed on the surface of the substrate 1 for 30 minutes. Thereafter, the evaporation of carbon and boron was stopped, the supply of the gas and the supply of the DC voltage were stopped, the heater 7 was turned off to cool the substrate 1, and then the vacuum tank 2 was opened to take out the substrate 1. A boron-added AC film having a total film thickness of 2.5 μm was formed on the surface of the substrate 1, and the boron addition amount was 20 atomic%.
【００２６】比較のため、同じ基材の上にホウ素を含ま
ない下記の被膜をそれぞれ形成した試料も準備した： (１)イオンプレーティング法により成膜したＡＣ膜 (２)イオンプレーティング法により成膜したＴｉＮ膜 (３)イオンプレーティング法により成膜したＣｒＮ膜 尚、(１)の成膜条件はホウ素の供給を除いて上記と同じ
であり、(２)及び(３)はＴｉ又はＣｒの蒸発源のみを用
い且つ成膜中の雰囲気ガスとして窒素ガスを使用した。
又、膜厚はいずれも２.５μｍに調節した。For comparison, samples were also prepared in which the following coatings each containing no boron were formed on the same substrate, respectively: (1) AC film formed by ion plating (2) Ion plating TiN film formed (3) CrN film formed by ion plating method The film forming conditions of (1) are the same as above except for the supply of boron, and (2) and (3) are Ti or Only a Cr evaporation source was used, and nitrogen gas was used as an atmosphere gas during film formation.
The thickness of each film was adjusted to 2.5 μm.
【００２７】上記本発明試料と各比較試料について、実
施例１と同じ方法及び条件で摩擦係数を測定し、その結
果を下記表２に示した。The friction coefficient of the sample of the present invention and each comparative sample were measured by the same method and under the same conditions as in Example 1. The results are shown in Table 2 below.
【表２】試 料 の 被 膜 摩 擦 係 数 本発明のホウ素添加ＡＣ膜 ０.０５〜０.０６ ホウ素無添加ＡＣ膜 ０.０８〜０.１ イオンプレーティングＴｉＮ膜 ２.４〜２.９ イオンプレーティングＣｒＮ膜 １.８〜２.３ 表２の結果から分かるように、他のセラミックスよりも
本発明によるホウ素を添加したＡＣ膜の方が低い摩擦係
数を示す。TABLE 2 boronizing AC film 0.05 to 0.06 boron-free additive AC film of the film friction engagement several invention specimen 0.08-0.1 ion plating TiN film 2.4 to 2. 9 Ion-plating CrN film 1.8 to 2.3 As can be seen from the results in Table 2, the AC film to which boron is added according to the present invention has a lower coefficient of friction than other ceramics.
【００２８】[0028]
【実施例３】実施例１と同様のプラズマＣＶＤ法によ
り、ホウ素添加ＤＬＣ膜に添加するホウ素の量を変化さ
せた複数の試料を作製した。又、実施例２と同様のイオ
ンプレーティング法により、ホウ素添加ＡＣ膜に添加す
るホウ素の量を変化させた複数の試料を作製した。得ら
れた各試料について、実施例１と同じ条件で摩擦係数を
測定した結果を図１に示す。更に、添加量の異なるホウ
素添加ＤＬＣ膜の各試料について、ヌープ硬度を測定し
た結果を図２に示す。Example 3 By the same plasma CVD method as in Example 1, a plurality of samples were produced in which the amount of boron added to the boron-added DLC film was changed. Further, by the same ion plating method as in Example 2, a plurality of samples were prepared in which the amount of boron added to the boron-added AC film was changed. FIG. 1 shows the results of measuring the coefficient of friction of each of the obtained samples under the same conditions as in Example 1. Further, FIG. 2 shows the results of measuring the Knoop hardness of each sample of the boron-added DLC film having different addition amounts.
【００２９】図１及び図２の結果から、ＤＬＣ膜又は非
晶質炭素膜中のホウ素添加量が３原子％以上になれば摩
擦係数が急激に小さくなるが、ホウ素添加量が５０原子
％を越えると被膜の硬度が急減するので、ホウ素添加量
は３〜５０原子％の範囲とすべきことが分かる。From the results shown in FIGS. 1 and 2, the friction coefficient sharply decreases when the boron content in the DLC film or the amorphous carbon film becomes 3 atomic% or more. If it exceeds, the hardness of the coating decreases sharply, so that it is understood that the boron addition amount should be in the range of 3 to 50 atomic%.
【００３０】[0030]
【発明の効果】本発明によれば、膜中に含まれるホウ素
が大気中において摺動表面で自然にホウ酸に変化するこ
とにより自己修復性を備えると共に、摩擦係数が小さく
且つ高硬度な硬質固体潤滑膜で被覆された摺動機械部品
を、工業的に低コストで提供することができる。According to the present invention, the boron contained in the film is spontaneously changed to boric acid on the sliding surface in the atmosphere .
A sliding machine part having a self-healing property and a small friction coefficient and coated with a hard solid lubricating film having high hardness.
And it may be provided in industrially low cost.
【００３１】又、本発明の摺動機械部品は、その自己修
復性固体潤滑膜が高硬度でありながら従来材料にない低
い摩擦係数を長期間にわたって発揮することができるの
で、特に無潤滑下での耐摩耗性及び摺動特性を向上させ
るうえで極めて有効である。Further, the sliding machine component of the present invention is capable of self-repairing.
Even though the resilient solid lubrication film has a high hardness, it can exhibit a low friction coefficient unlike conventional materials for a long period of time, so it is extremely effective especially in improving wear resistance and sliding characteristics without lubrication. is there.
【図１】ホウ素添加したダイヤモンド状炭素膜と非晶質
炭素膜における、ホウ素添加量と摩擦係数の関係を示す
グラフである。FIG. 1 is a graph showing the relationship between the amount of added boron and the friction coefficient in a boron-added diamond-like carbon film and an amorphous carbon film.
【図２】ホウ素添加したダイヤモンド状炭素膜におけ
る、ホウ素添加量とヌープ硬度の関係を示すグラフであ
る。FIG. 2 is a graph showing the relationship between the amount of boron added and Knoop hardness in a boron-added diamond-like carbon film.
【図３】実施例１で用いたプラズマＣＶＤ装置の模式図
である。FIG. 3 is a schematic view of a plasma CVD apparatus used in Example 1.
【図４】実施例２で用いたイオンプレーティング装置の
模式図である。FIG. 4 is a schematic diagram of an ion plating apparatus used in Example 2.
１ 基材 ２ 真空槽 ３ 電極 ４ 真空排気装置 ５ ガス供給装置 ６ 直流電源 ７ 加熱用ヒーター ８ 炭素蒸発源 ９ ホウ素蒸発源 DESCRIPTION OF SYMBOLS 1 Base material 2 Vacuum tank 3 Electrode 4 Vacuum exhaust device 5 Gas supply device 6 DC power supply 7 Heating heater 8 Carbon evaporation source 9 Boron evaporation source
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ１０Ｎ 50:08 (56)参考文献 特開 平１−184718（ＪＰ，Ａ) 特開 平１−201463（ＪＰ，Ａ) 特開 平５−73900（ＪＰ，Ａ) 特開 平５−114275（ＪＰ，Ａ) 特開 昭61−167548（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 31/02 C10M 103/00 - 103/02 C23C 14/06 C23C 16/26 - 16/27 G11B 5/725 ──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. 7 Identification code FI C10N 50:08 (56) References JP-A-1-184718 (JP, A) JP-A-1-201463 (JP, A) JP-A-5-73900 (JP, A) JP-A-5-114275 (JP, A) JP-A-61-167548 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 31 / 02 C10M 103/00-103/02 C23C 14/06 C23C 16/26-16/27 G11B 5/725
Claims (1)
械部品において、少なくとも硬質固体潤滑膜の最外表面
層がホウ素を１０〜４０原子％添加したダイヤモンド状
炭素又は非晶質炭素からなることを特徴する、自己修復
性硬質固体潤滑膜で被覆した摺動機械部品。1. A sliding machine having a hard solid lubricating film provided on a base material
In a mechanical part , at least the outermost surface layer of the hard solid lubricating film is made of diamond-like carbon or amorphous carbon to which 10 to 40 atomic% of boron is added, and is coated with a self-healing hard solid lubricating film. Moving machine parts .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03726092A JP3225576B2 (en) | 1992-01-28 | 1992-01-28 | Sliding machine parts coated with self-healing hard solid lubricant film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03726092A JP3225576B2 (en) | 1992-01-28 | 1992-01-28 | Sliding machine parts coated with self-healing hard solid lubricant film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05208806A JPH05208806A (en) | 1993-08-20 |
| JP3225576B2 true JP3225576B2 (en) | 2001-11-05 |
Family
ID=12492691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03726092A Expired - Lifetime JP3225576B2 (en) | 1992-01-28 | 1992-01-28 | Sliding machine parts coated with self-healing hard solid lubricant film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3225576B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6572935B1 (en) * | 1999-03-13 | 2003-06-03 | The Regents Of The University Of California | Optically transparent, scratch-resistant, diamond-like carbon coatings |
| JP2001003169A (en) * | 1999-06-18 | 2001-01-09 | Sanyo Electric Co Ltd | Treatment of carbon coating film, carbon coating film and parts having carbon coating film |
| BR0105474A (en) | 2001-09-26 | 2003-09-23 | Fundacao De Amparo A Pesquisa | Deposition process of hydrogenated amorphous carbon film, hydrogenated amorphous carbon film and hydrogenated amorphous carbon film coated article |
| US9062274B2 (en) | 2009-07-03 | 2015-06-23 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Low friction sliding member |
| TW201216331A (en) * | 2010-10-05 | 2012-04-16 | Applied Materials Inc | Ultra high selectivity doped amorphous carbon strippable hardmask development and integration |
| US9624975B2 (en) | 2014-03-21 | 2017-04-18 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Sliding member and sliding machine |
| JP6528936B2 (en) * | 2014-03-27 | 2019-06-12 | 日立金属株式会社 | Method of manufacturing coated tool |
| CH709665A2 (en) * | 2014-05-16 | 2015-11-30 | Nivarox Sa | clockwork without lubrication in contact torque. |
| JP6586618B2 (en) * | 2014-08-07 | 2019-10-09 | 国立大学法人豊橋技術科学大学 | DLC film forming method and DLC film forming apparatus |
| US10619739B2 (en) | 2015-07-31 | 2020-04-14 | Nippon Piston Ring Co., Ltd | Piston ring |
| EP3171230B1 (en) * | 2015-11-19 | 2019-02-27 | Nivarox-FAR S.A. | Timepiece component with improved tribology |
| CN108165343A (en) * | 2018-02-22 | 2018-06-15 | 大连圣多教育咨询有限公司 | A kind of self-restoring lubricating oil additive and preparation method |
| CN108165342A (en) * | 2018-02-22 | 2018-06-15 | 大连圣多教育咨询有限公司 | A kind of self-restoring lubricating oil and preparation method |
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1992
- 1992-01-28 JP JP03726092A patent/JP3225576B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05208806A (en) | 1993-08-20 |
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