JP2000008155A - Hard carbon film coated member - Google Patents
Hard carbon film coated memberInfo
- Publication number
- JP2000008155A JP2000008155A JP17901398A JP17901398A JP2000008155A JP 2000008155 A JP2000008155 A JP 2000008155A JP 17901398 A JP17901398 A JP 17901398A JP 17901398 A JP17901398 A JP 17901398A JP 2000008155 A JP2000008155 A JP 2000008155A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- hard carbon
- carbon film
- outermost layer
- coated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 84
- 239000010410 layer Substances 0.000 claims abstract description 190
- 239000000463 material Substances 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 36
- 239000001301 oxygen Substances 0.000 claims abstract description 36
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 18
- 239000010959 steel Substances 0.000 claims abstract description 18
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 13
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 239000011247 coating layer Substances 0.000 claims abstract description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 7
- 150000004767 nitrides Chemical class 0.000 claims abstract description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 5
- 229910000861 Mg alloy Inorganic materials 0.000 claims abstract description 4
- -1 S i Inorganic materials 0.000 claims abstract description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011195 cermet Substances 0.000 claims abstract description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000758 substrate Substances 0.000 claims description 22
- 230000003746 surface roughness Effects 0.000 claims description 19
- 238000007733 ion plating Methods 0.000 claims description 16
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 14
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 11
- CXOWYMLTGOFURZ-UHFFFAOYSA-N azanylidynechromium Chemical compound [Cr]#N CXOWYMLTGOFURZ-UHFFFAOYSA-N 0.000 claims description 7
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 2
- 238000004080 punching Methods 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 51
- 238000000034 method Methods 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000523 sample Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000000576 coating method Methods 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910003460 diamond Inorganic materials 0.000 description 4
- 239000010432 diamond Substances 0.000 description 4
- 238000010891 electric arc Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000005553 drilling Methods 0.000 description 2
- 238000004453 electron probe microanalysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- SJKRCWUQJZIWQB-UHFFFAOYSA-N azane;chromium Chemical group N.[Cr] SJKRCWUQJZIWQB-UHFFFAOYSA-N 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
(57)【要約】
【課題】 中間層と硬質炭素膜との間の密着性を向上さ
せようとするものである。
【解決手段】 基材上に複数の被膜層を積層してなり、
上記基材を、超硬合金、サーメット、鋼材、窒化ケイ
素、ジルコニア、炭化ケイ素、アルミナ、アルミニウム
合金、マグネシウム合金、又はチタン合金のいずれかか
ら選び、上記被膜層の最外層を硬質炭素層から形成し、
上記基材と最外層の間の中間層のうち、最外層に内接す
る中間層を、４族の金属、５族の金属、６族の金属、Ｓ
ｉ、Ａｌ、又はＧｅの中から選ばれる１種又は複数種の
金属を含む金属の炭化物、窒化物、又は炭窒化物とし、
上記最外層とこの中間層との界面部に存在する酸素濃度
を、最大値で３ａｔ％、又は、界面を基準に±５０ｎｍ
の範囲の平均値で２ａｔ％以下とする。(57) [Problem] To improve adhesion between an intermediate layer and a hard carbon film. SOLUTION: A plurality of coating layers are laminated on a base material,
The base material is selected from cemented carbide, cermet, steel, silicon nitride, zirconia, silicon carbide, alumina, aluminum alloy, magnesium alloy, or titanium alloy, and the outermost layer of the coating layer is formed from a hard carbon layer. And
Among the intermediate layers between the base material and the outermost layer, the intermediate layer inscribed in the outermost layer is formed of a Group 4 metal, a Group 5 metal, a Group 6 metal, S
i, Al, or metal carbide, nitride or carbonitride containing one or more metals selected from Ge,
The oxygen concentration existing at the interface between the outermost layer and the intermediate layer is set to a maximum value of 3 at% or ± 50 nm with respect to the interface.
Is 2 at% or less as an average value in the range.
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、表面に硬質炭素
膜を被覆した工具、金型、機械部品に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a tool, a mold, and a machine part whose surface is coated with a hard carbon film.
【０００２】[0002]
【従来の技術】硬質炭素膜は、ダイヤモンド構造を一部
に有するアモルファス状の炭素膜又は水素化炭素膜で、
アモルファスカーボン（ａ−Ｃ、ａ−Ｃ：Ｈ）、ｉ−Ｃ
（アイ・カーボン）、ダイヤモンド状炭素（Diamond li
ke carbon ；ＤＬＣ）等とも呼ばれている。2. Description of the Related Art A hard carbon film is an amorphous carbon film or a hydrogenated carbon film partially having a diamond structure.
Amorphous carbon (aC, aC: H), iC
(Eye carbon), diamond-like carbon (Diamond li)
Also known as ke carbon (DLC).
【０００３】この硬質炭素膜は、一般にヌープ硬度が１
０００〜６０００と高硬度で耐摩耗性に優れている。多
くの相手材料に対する無潤滑での摩擦係数は、０．０５
〜０．２と極めて低く、軟質金属の離型性にも優れてい
る。化学的にも安定で、多くの酸、アルカリに対して極
めて高い耐食性を有する。また、電気抵抗率は１０6〜
１０14Ω％ｃｍと高い絶縁性を有し、赤外線に対して高
い透過性を有する等の、ダイヤモンドに類似した特性を
多く有する。これらの優れた性質を生かして、この硬質
炭素膜は、種々の分野への応用が期待されている。特
に、耐摩耗性部品、摺動部品、電気・電子部品、赤外線
光学部品、成型・成形部品等へのコーティングに関して
開発が進められている。特に近年、ビデオ部品やビデオ
テープの潤滑性、耐擦傷性を向上させるための保護コー
ティング、ハンダやアルミニウム等の軟質金属の溶着防
止の離型性コーティング等での実用化が著しい。This hard carbon film generally has a Knoop hardness of 1
It has high hardness of 000 to 6000 and excellent wear resistance. The coefficient of friction without lubrication for many mating materials is 0.05
It is extremely low, such as 0.2, and is excellent in the releasability of soft metals. It is chemically stable and has extremely high corrosion resistance to many acids and alkalis. The electric resistivity is 10 6 or more.
It has many properties similar to diamond, such as high insulating property of 10 14 Ω% cm and high transmittance to infrared rays. Taking advantage of these excellent properties, this hard carbon film is expected to be applied to various fields. In particular, the development of coatings on wear-resistant parts, sliding parts, electric / electronic parts, infrared optical parts, molded / molded parts, and the like has been promoted. In particular, in recent years, practical application of a protective coating for improving lubricity and abrasion resistance of video parts and video tapes, and a releasable coating for preventing welding of soft metals such as solder and aluminum has been remarkable.
【０００４】硬質炭素膜の形成には種々の手法がある。
例えば、結晶質ダイヤモンド薄膜を形成する手法として
は、マイクロ波プラズマＣＶＤ法、ＥＣＲプラズマＣＶ
Ｄ法、フィラメント法等に準ずる手法が知られている。
この他、硬質炭素膜を形成する方法として、高周波や直
流放電等の各種プラズマ源を用いたプラズマＣＶＤ法、
炭素又は炭化水素イオンを用いるイオンビーム蒸着法、
固体炭素源からスパッタリングやアーク放電にて炭素を
気化し、基体上に成膜する手法があげられる。これらの
各手法は、対象基材や用途、処理数等により使い分けら
れている。There are various methods for forming a hard carbon film.
For example, as a method of forming a crystalline diamond thin film, microwave plasma CVD, ECR plasma CV
Methods based on the D method, the filament method and the like are known.
In addition, as a method of forming a hard carbon film, a plasma CVD method using various plasma sources such as high frequency or DC discharge,
Ion beam evaporation using carbon or hydrocarbon ions,
There is a method of vaporizing carbon from a solid carbon source by sputtering or arc discharge to form a film on a substrate. Each of these methods is properly used depending on the target base material, the application, the number of treatments, and the like.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、硬質炭
素膜は非常に高い内部応力を有しており、その応力のた
め剥離が起こりやすく、厚膜化が困難である等の問題を
有する。このため、硬質炭素膜はその膜厚が１．５μｍ
を超えるものを得るのは極めて困難で、かつ、適用可能
な基材材料も限られていた。However, the hard carbon film has a very high internal stress, and has a problem that peeling easily occurs due to the stress and it is difficult to make the film thick. Therefore, the hard carbon film has a thickness of 1.5 μm
It is extremely difficult to obtain a material having a particle size exceeding the limit, and applicable substrate materials are also limited.
【０００６】この問題を解決するため、特公平５−８２
４７２号公報に、基材と硬質炭素膜の間に金属炭化物や
金属窒化物等の中間層を導入する方法が開示されてい
る。しかし、工具等の厳しい環境下で使用される用途に
おいて、中間層と硬質炭素膜との間の密着性が十分なも
のが得られず、実用化に際して問題を有していた。To solve this problem, Japanese Patent Publication No. 5-82
No. 472 discloses a method of introducing an intermediate layer such as a metal carbide or a metal nitride between a substrate and a hard carbon film. However, in applications used in harsh environments such as tools, sufficient adhesion between the intermediate layer and the hard carbon film could not be obtained, which had a problem in practical use.
【０００７】そこで、この発明は、中間層と硬質炭素膜
との間の密着性を向上させようとするものである。Therefore, the present invention is to improve the adhesion between the intermediate layer and the hard carbon film.
【０００８】[0008]
【課題を解決するための手段】この発明は、基材上に複
数の被膜層を積層してなり、上記基材は、超硬合金、サ
ーメット、鋼材、窒化ケイ素、ジルコニア、炭化ケイ
素、アルミナ、アルミニウム合金、マグネシウム合金、
又はチタン合金のいずれかから選ばれ、上記被膜層の最
外層は硬質炭素層からなり、上記基材と最外層の間の中
間層のうち、最外層に内接する中間層は、４族の金属、
５族の金属、６族の金属、Ｓｉ、Ａｌ、又はＧｅの中か
ら選ばれる１種又は複数種の金属を含む金属の炭化物、
窒化物、又は炭窒化物であり、上記最外層とこの中間層
との界面部に存在する酸素濃度が、最大値で３ａｔ％、
又は、界面を基準に±５０ｎｍの範囲の平均値で２ａｔ
％以下とすることにより、上記の課題を解決したもので
ある。According to the present invention, a plurality of coating layers are laminated on a substrate, and the substrate is made of cemented carbide, cermet, steel, silicon nitride, zirconia, silicon carbide, alumina, Aluminum alloy, magnesium alloy,
Or a titanium alloy, the outermost layer of the coating layer is made of a hard carbon layer, and of the intermediate layers between the base material and the outermost layer, the intermediate layer inscribed in the outermost layer is a Group 4 metal. ,
Group 5 metals, Group 6 metals, carbides of metals containing one or more metals selected from Si, Al, or Ge,
Nitride or carbonitride, the oxygen concentration present at the interface between the outermost layer and the intermediate layer is 3 at% at maximum,
Alternatively, 2 at an average value in a range of ± 50 nm with respect to the interface.
% Or less solves the above problem.
【０００９】硬質炭素層からなる最外層と中間層の界面
部の酸素濃度を所定値に限定したので、硬質炭素層と中
間層の界面にＣＯやＣＯ2 が形成されるのを抑制するこ
とができ、両者の密着性を向上させることができる。Since the oxygen concentration at the interface between the outermost layer made of the hard carbon layer and the intermediate layer is limited to a predetermined value, it is possible to suppress the formation of CO and CO 2 at the interface between the hard carbon layer and the intermediate layer. It is possible to improve the adhesion between the two.
【００１０】[0010]
【発明の実施の形態】以下、この発明の実施形態を図面
を参照して説明する。この発明にかかる硬質炭素膜被覆
部材は、基材上に複数の被膜層を積層した部材である。Embodiments of the present invention will be described below with reference to the drawings. The hard carbon film-coated member according to the present invention is a member in which a plurality of coating layers are laminated on a base material.
【００１１】上記基材は、超硬合金、サーメット、鋼
材、窒化ケイ素、ジルコニア、炭化ケイ素、アルミナ、
アルミニウム合金、マグネシウム合金、又はチタン合金
のいずれかから選ばれる。上記鋼材としては、工具鋼、
高速度鋼、軸受鋼、ステンレス鋼、炭素鋼、Ｍｎ鋼、Ｍ
ｎ−Ｃｒ鋼、Ｃｒ鋼、Ｃｒ−Ｍｏ鋼、Ｎｉ−Ｃｒ鋼、Ｎ
ｉ−Ｃｒ−Ｍｏ鋼等の鋼材や窒化鋼等があげられる。[0011] The base material is a cemented carbide, cermet, steel, silicon nitride, zirconia, silicon carbide, alumina,
It is selected from any of an aluminum alloy, a magnesium alloy, and a titanium alloy. The steel materials include tool steel,
High speed steel, bearing steel, stainless steel, carbon steel, Mn steel, M
n-Cr steel, Cr steel, Cr-Mo steel, Ni-Cr steel, N
Examples thereof include steel materials such as i-Cr-Mo steel and nitrided steel.
【００１２】上記被膜層のうち最外層は硬質炭素膜から
なる硬質炭素層で構成される。この硬質炭素層は非晶質
であり、高周波や直流放電等の各種プラズマ源を用いた
プラズマＣＶＤ法、炭素又は炭化水素イオンを発生させ
る炭化水素ガスを用いるイオンビーム蒸着法、固体炭素
源からスパッタリングやアーク放電にて炭素を気化する
カソードアークイオンプレーティング法等によって成膜
される。The outermost layer of the above coating layers is formed of a hard carbon layer made of a hard carbon film. This hard carbon layer is amorphous, and is plasma CVD using various plasma sources such as high frequency or direct current discharge, ion beam evaporation using hydrocarbon gas generating carbon or hydrocarbon ions, and sputtering from solid carbon source. Or by a cathode arc ion plating method of vaporizing carbon by arc discharge.
【００１３】上記基材と最外層の間に構成される被膜
層、すなわち、中間層は、１層に限られず、２層以上の
多層であってもよい。この中間層は、上記基材の表面を
硬質化すると共に、硬質炭素層と基材との密着性を高め
る機能を有する。この機能を発揮するために、最外層に
内接する中間層は、４族の金属、５族の金属、６族の金
属、Ｓｉ、Ａｌ、又はＧｅの中から選ばれる１種又は複
数種の金属を含む金属の炭化物、窒化物、又は炭窒化物
から構成される。これらの具体例としては、炭化チタ
ン、窒化チタン、炭窒化チタン、炭化タングステン、窒
化クロム等があげられる。なお、上記の４族、５族、６
族は、周期律表の族を表すものであり、かつ、ＩＵＰＡ
Ｃ無機化学命名法改訂版（１９８９年）の標記法に従っ
たものである。具体的には、上記の４族金属とは、Ｔ
ｉ、Ｚｒ、Ｈｆ等をいい、５族金属とは、Ｖ、Ｎｂ、Ｔ
ａ等をいい、６族金属とは、Ｃｒ、Ｍｏ、Ｗ等をいう。The coating layer formed between the substrate and the outermost layer, ie, the intermediate layer, is not limited to one layer, but may be a multilayer of two or more layers. The intermediate layer has a function of hardening the surface of the base material and increasing the adhesion between the hard carbon layer and the base material. In order to exhibit this function, the intermediate layer inscribed in the outermost layer is made of one or more kinds of metals selected from Group 4 metals, Group 5 metals, Group 6 metals, Si, Al, or Ge And metal carbides, nitrides, or carbonitrides containing Specific examples thereof include titanium carbide, titanium nitride, titanium carbonitride, tungsten carbide, chromium nitride and the like. In addition, the above-mentioned 4th, 5th, 6th
The tribe represents the tribe of the periodic table, and IUPA
C In accordance with the notation of the inorganic chemical nomenclature revised edition (1989). Specifically, the group 4 metal is T
i, Zr, Hf, etc., and the Group 5 metals include V, Nb, T
a and the like, and the Group 6 metal refers to Cr, Mo, W and the like.
【００１４】この中間層は、高周波や直流放電等の各種
プラズマ源を用いたプラズマＣＶＤ法、熱ＣＶＤ法、イ
オンプレーティング法、固体蒸発源からスパッタリング
やアーク放電にて対象原子を気化するカソードアークイ
オンプレーティング法等によって成膜される。This intermediate layer is formed by a plasma CVD method using various plasma sources such as high frequency or DC discharge, a thermal CVD method, an ion plating method, and a cathode arc which vaporizes target atoms by sputtering or arc discharge from a solid evaporation source. The film is formed by an ion plating method or the like.
【００１５】上記の中間層の膜厚は、０．０５〜５μｍ
が好ましく、０．２〜３μｍがより好ましい。０．０５
μｍ未満の場合、上記基材の凹凸をカバーしきれなかっ
たり、ピンホールが残存する場合が生ずる。さらに、中
間層そのものに耐摩耗性向上の効果をあまり期待できな
い。一方、５μｍを超える場合、中間層そのものの内部
応力が高くなり、中間層が剥離しやすくなる。The thickness of the intermediate layer is 0.05 to 5 μm.
Is preferably, and more preferably 0.2 to 3 μm. 0.05
If it is less than μm, the irregularities of the base material may not be completely covered, or pinholes may remain. Furthermore, the effect of improving the wear resistance of the intermediate layer itself cannot be expected. On the other hand, if it exceeds 5 μm, the internal stress of the intermediate layer itself becomes high, and the intermediate layer is easily peeled.
【００１６】上記最外層に内接される中間層としての好
ましい例としては、炭化チタン、窒化チタン、炭窒化チ
タン、炭化タングステンからなる層があげられ、この場
合の上記中間層の厚みは、膜厚０．０５〜５μｍが好ま
しく、０．２〜３μｍがより好ましい。これらの層は、
コーティング膜や粉末成形体の主成分として、工具や金
型等に幅広く適用されているものであり、硬質炭素層に
対する親和性に優れ、高い密着強度を得ることができ
る。このため、硬質炭素層の寿命が長くなり、また、硬
質炭素層が摩耗して無くなった場合でも、さらにこれら
の中間層によって耐摩耗性を維持することができる。上
記中間層の膜厚の好ましい理由は、上記と同様の理由で
ある。Preferred examples of the intermediate layer inscribed in the outermost layer include a layer made of titanium carbide, titanium nitride, titanium carbonitride, and tungsten carbide. The thickness is preferably 0.05 to 5 μm, more preferably 0.2 to 3 μm. These layers
As a main component of a coating film or a powder compact, it is widely applied to tools, dies, and the like, has excellent affinity for a hard carbon layer, and can achieve high adhesion strength. Therefore, the life of the hard carbon layer is prolonged, and even when the hard carbon layer is worn away, the wear resistance can be further maintained by these intermediate layers. Preferred reasons for the thickness of the intermediate layer are the same as those described above.
【００１７】上記中間層として少なくとも２層を形成す
る場合、上記最外層に内接される好ましい中間層とし
て、炭化チタン、炭化タングステンからなる層を、上記
基材に外接する中間層として、窒化チタンからなる層を
好ましい組み合わせの例としてあげることができる。こ
の場合の上記の両中間層の厚みは、膜厚０．０５〜５μ
ｍが好ましく、０．２〜３μｍがより好ましい。炭化チ
タンや炭化タングステンは上記のとおり、工具や金型等
に幅広く適用されている材料であり、硬質炭素層に対す
る親和性に優れる。また、窒化チタンは、各種コーティ
ング膜との親和性に優れている。すなわち、上記の中間
層の組み合わせは、基材と中間層、中間層同士又は中間
層と最外層との密着性を特に高めることが可能となる。
上記中間層の各膜厚の好ましい理由は、上記と同様の理
由である。When at least two layers are formed as the intermediate layer, a layer made of titanium carbide and tungsten carbide is preferably used as an intermediate layer inscribed in the outermost layer, and a layer made of titanium nitride is used as an intermediate layer inscribed in the base material. Can be given as an example of a preferable combination. In this case, the thickness of the two intermediate layers is 0.05 to 5 μm.
m is preferable, and 0.2 to 3 μm is more preferable. As described above, titanium carbide and tungsten carbide are materials widely used for tools, molds, and the like, and have excellent affinity for a hard carbon layer. Further, titanium nitride has excellent affinity with various coating films. That is, the combination of the above-described intermediate layers can particularly enhance the adhesion between the base material and the intermediate layer, between the intermediate layers, or between the intermediate layer and the outermost layer.
Preferred reasons for the thickness of the intermediate layer are the same as those described above.
【００１８】上記基材として、上記の鋼材、アルミニウ
ム合金又はチタン合金のいずれかを用いる場合、上記の
中間層のうち少なくとも１層は、膜厚０．０５〜２０μ
ｍの窒化クロムからなる層とするのが好ましい。基材と
しての鋼材は、工具や金型、機械部品等多く使用されて
おり、アルミニウム合金やチタン合金は、近年の軽量化
の流れに従い、自動車部品を始めとする多くの機械部品
に適用が広がっている。これらの鋼材、アルミニウム合
金又はチタン合金は、超硬合金や各種セラミックス材料
に比べ、硬さの点で劣る。この欠点を補うため、中間層
に硬質の材料を導入するのである。When any of the above-mentioned steel, aluminum alloy or titanium alloy is used as the substrate, at least one of the intermediate layers has a thickness of 0.05 to 20 μm.
Preferably, the layer is made of m chromium nitride. Steel materials as base materials are widely used for tools, molds, mechanical parts, and the like, and aluminum alloys and titanium alloys have been applied to many mechanical parts, including automobile parts, in accordance with the recent trend of weight reduction. ing. These steel materials, aluminum alloys or titanium alloys are inferior in hardness as compared with cemented carbides and various ceramic materials. To compensate for this disadvantage, a hard material is introduced into the intermediate layer.
【００１９】この中間層に用いられる材料としては、比
較的靱性があり、厚膜化も容易な窒化クロムが好まし
い。中間層として窒化クロムからなる層を用いる場合、
その膜厚は、上記の中間層の好ましい膜厚と異なり、
０．０５〜２０μｍが好ましい。上限が上記の中間層の
好ましい膜厚より厚いのは、窒化クロムは、他の中間層
を形成する材料に比べ、比較的靱性があり、厚膜化が容
易だからである。また、膜厚が０．０５μｍ未満の場合
は、上記基材の凹凸をカバーしきれなかったり、ピンホ
ールが残存する場合が生ずる。一方、２０μｍを超える
場合、応力の蓄積による剥離が起こりやすくなる。基材
の硬度を十分に補う点を考慮すれば、０．５μｍ以上と
するのがより好ましく、経済性の面から１０μｍ以下と
するのがより好ましい。The material used for the intermediate layer is preferably chromium nitride, which is relatively tough and easy to be thick. When using a layer made of chromium nitride as the intermediate layer,
The thickness is different from the preferred thickness of the above-mentioned intermediate layer,
0.05-20 μm is preferred. The upper limit is larger than the preferred thickness of the intermediate layer because chromium nitride has relatively toughness and is easy to be made thicker than the other materials forming the intermediate layer. If the film thickness is less than 0.05 μm, the irregularities of the base material may not be completely covered or pinholes may remain. On the other hand, if it exceeds 20 μm, peeling due to accumulation of stress tends to occur. In consideration of sufficiently supplementing the hardness of the base material, the thickness is more preferably 0.5 μm or more, and more preferably 10 μm or less from the viewpoint of economy.
【００２０】上記の硬質炭素層から構成される最外層と
上記中間層との界面部に存在する酸素濃度は、最大値で
３ａｔ％以下がよく、２ａｔ％以下が好ましい。また、
上記の最外層と中間層とにより形成される界面を基準に
±５０ｎｍの範囲における酸素濃度の平均値は、２ａｔ
％以下がよく、１ａｔ％以下が好ましい。酸素濃度が最
大値で３ａｔ％より多い場合、又は、±５０ｎｍの範囲
における酸素濃度の平均値が２ａｔ％より多い場合は、
最外層である硬質炭素層と中間層の界面にＣＯやＣＯ2
が形成され易く、最外層が剥離しやすい。The concentration of oxygen present at the interface between the outermost layer composed of the hard carbon layer and the intermediate layer is preferably at most 3 at%, and more preferably at most 2 at%. Also,
The average value of the oxygen concentration in a range of ± 50 nm based on the interface formed by the outermost layer and the intermediate layer is 2 at.
% Or less, and preferably 1 at% or less. When the maximum oxygen concentration is more than 3 at%, or when the average oxygen concentration in the range of ± 50 nm is more than 2 at%,
CO or CO 2 is placed at the interface between the outermost hard carbon layer and the intermediate layer.
Are easily formed, and the outermost layer is easily peeled off.
【００２１】上記界面部の酸素濃度を低下させる方法
は、任意の方法を採用することができる。例えば、上記
基材表面上に上記中間層を成膜し、減圧等することによ
り大気中の酸素濃度を低下させる。この状態で硬質炭素
膜を成膜することにより、上記界面部の酸素濃度を低下
させることができる。Any method can be adopted as the method for lowering the oxygen concentration at the interface. For example, the oxygen concentration in the atmosphere is reduced by forming the intermediate layer on the surface of the base material and reducing the pressure. By forming the hard carbon film in this state, the oxygen concentration at the interface can be reduced.
【００２２】なお、酸素濃度の定量には、オージェ電子
分光法、Ｘ線光電子分光法又は２次イオン質量分析法等
が適用できる。オージェ電子分光法やＸ線光電子分光法
は、最小検出限界が約１ａｔ％程度であり、深さ方向の
分解能は数ｎｍである。また、２次イオン質量分析法の
最小検出限界は数ｐｐｍ程度であり、深さ方向の分解能
は数ｎｍである。深さ方向に元素分析を行う場合、上層
又は下層の構成元素の深さに対する濃度の変化率が最も
大きいところ、あるいは、上層又は下層の構成元素が定
常値の約半分の濃度になっているところを界面とする。The oxygen concentration can be determined by Auger electron spectroscopy, X-ray photoelectron spectroscopy or secondary ion mass spectrometry. Auger electron spectroscopy and X-ray photoelectron spectroscopy have a minimum detection limit of about 1 at% and a resolution in the depth direction of several nm. The minimum detection limit of the secondary ion mass spectrometry is about several ppm, and the resolution in the depth direction is several nm. When performing elemental analysis in the depth direction, where the rate of change of the concentration of the constituent elements in the upper or lower layer with respect to the depth is the largest, or where the concentration of the constituent elements in the upper or lower layer is about half the steady-state value Is the interface.
【００２３】ここで、上記の酸素濃度の最大値とは、上
記の方法により規定される界面の近傍の酸素濃度の最大
値、詳しくは、この界面の上下方向±５０ｎｍの範囲内
の酸素濃度の最大値をいう。また、上記の酸素濃度の平
均値とは、上記の方法により規定される界面を基準に±
５０ｎｍの範囲における酸素濃度の平均値をいう。Here, the maximum value of the oxygen concentration is the maximum value of the oxygen concentration in the vicinity of the interface defined by the above method, more specifically, the maximum value of the oxygen concentration in the range of ± 50 nm in the vertical direction of the interface. Refers to the maximum value. Further, the average value of the oxygen concentration is ± with respect to the interface defined by the above method.
It means the average value of the oxygen concentration in the range of 50 nm.
【００２４】離型性、摺動性が要求される用途の場合、
上記部材の表面の平滑性が強く要求される。この平滑な
表面を得るのに適した硬質被膜の製造法としては、メタ
ンやベンゼン、アセチレン、等の炭化水素ガスを原料と
するイオン化蒸着法やプラズマＣＶＤ法、固体炭素を原
料としたカソードアークイオンプレーティング法でマク
ロパーティクルの飛来を押えたタイプのものが好まし
い。また、中間層の形成方法は、特に限定されるもので
なく、例えば、比較的表面粗さの小さいホロカソードイ
オンプレーティング法、熱電子式アーク放電型イオンプ
レーティング法、マクロパーティクルの飛来を抑えたカ
ソードアークイオンプレーティング法、各種スパッタリ
ング法等をあげられる。For applications requiring release and slidability,
The smoothness of the surface of the member is strongly required. Examples of a method for producing a hard coating suitable for obtaining a smooth surface include ionization vapor deposition using a hydrocarbon gas such as methane, benzene, and acetylene, plasma CVD, and cathode arc ion using solid carbon as a raw material. It is preferable to use a plating method in which macro particles are prevented from flying by a plating method. The method for forming the intermediate layer is not particularly limited. For example, a hollow cathode ion plating method having a relatively small surface roughness, a thermionic arc discharge ion plating method, and suppression of macroparticles are prevented. Cathodic arc ion plating method, various sputtering methods and the like.
【００２５】このとき、上記の最外層表面の表面粗さ
を、Ｒａで０．１μｍ以下、又は、Ｒｍａｘで１．０μ
ｍ以下とすることが好ましく、Ｒａで０．０５μｍ以
下、又は、Ｒｍａｘで０．５μｍ以下とすることがより
好ましい。上記の最外層表面の表面粗さが、Ｒａで０．
１μｍ以下、又は、Ｒｍａｘで１．０μｍ以下であると
焼き付き等が発生しにくいため、好ましい。また、Ｒａ
又はＲｍａｘの下限は、表面粗さのない状態、すなわ
ち、０である。At this time, the surface roughness of the outermost layer surface is 0.1 μm or less in Ra or 1.0 μm in Rmax.
m or less, more preferably 0.05 μm or less for Ra, or 0.5 μm or less for Rmax. The surface roughness of the surface of the outermost layer is Ra of 0.
When it is 1 μm or less, or Rmax is 1.0 μm or less, it is preferable because image sticking or the like hardly occurs. Also, Ra
Alternatively, the lower limit of Rmax is a state without surface roughness, that is, 0.
【００２６】上記中間層のうち少なくとも１層を、固体
蒸発源を原料とするカソードアークイオンプレーティン
グ法で形成し、中間層及び最外層を形成した後の最外層
表面の表面粗さを、Ｒａで０．１〜１μｍ、又は、Ｒｍ
ａｘで１．０〜１０μｍとすることができる。この場
合、粗い表面が求められる一部の工具、金型、機械部品
に適用することができる。このカソードアークイオンプ
レーティング法を用いれば表面粗さの大きいものが得ら
れる。このため、上記中間層以外に、最外層を形成する
際にもこのカソードアークイオンプレーティング法を用
い、最外層表面の表面粗さを、Ｒａで０．１〜１μｍ、
又は、Ｒｍａｘで１．０〜１０μｍとすることができ
る。At least one of the intermediate layers is formed by a cathode arc ion plating method using a solid evaporation source as a raw material, and the surface roughness of the outermost layer after forming the intermediate layer and the outermost layer is Ra. 0.1 to 1 μm or Rm
ax can be 1.0 to 10 μm. In this case, the present invention can be applied to some tools, molds, and mechanical parts requiring a rough surface. If this cathode arc ion plating method is used, a material having a large surface roughness can be obtained. For this reason, in addition to the intermediate layer, when forming the outermost layer, the cathode arc ion plating method is used, and the surface roughness of the outermost layer surface is 0.1 to 1 μm in Ra.
Or, it can be 1.0 to 10 μm in Rmax.
【００２７】最外層の表面粗さを大きくする方法として
は、上記カソードアークイオンプレーティング法以外の
方法を用いる場合であっても、中間層の膜厚を厚くした
り、基材表面の粗さそのものをあらかじめ大きくしてお
く方法を採用することができる。すなわち、上記基材表
面の表面粗さを、Ｒａで０．１〜５μｍ、又は、Ｒｍａ
ｘで１．０〜５０μｍとし、この基材表面に中間層及び
最外層を形成させて、その最外層表面の表面粗さが、Ｒ
ａで０．１〜５μｍ、又は、Ｒｍａｘで１．０〜５０μ
ｍとしてもよい。As a method for increasing the surface roughness of the outermost layer, even when a method other than the above-described cathode arc ion plating method is used, the thickness of the intermediate layer may be increased or the surface roughness of the substrate may be increased. A method of increasing the size in advance can be adopted. That is, the surface roughness of the substrate surface is 0.1 to 5 μm in Ra, or Rma
x is set to 1.0 to 50 μm, and an intermediate layer and an outermost layer are formed on the surface of the base material.
0.1 to 5 μm for a, or 1.0 to 50 μm for Rmax
m may be used.
【００２８】従来の硬質炭素膜では、基材表面が粗い
と、被覆された硬質炭素膜の応力が局所的に集中して剥
離しやすい問題があったが、本発明のように、界面部の
酸素濃度に配慮することにより、被膜の密着性が格段に
向上し、基材表面が粗い場合においても、被覆が可能と
なった。In the conventional hard carbon film, if the surface of the base material is rough, there is a problem that the stress of the coated hard carbon film is locally concentrated and easily peeled off. By taking into account the oxygen concentration, the adhesion of the coating was significantly improved, and coating was possible even when the substrate surface was rough.
【００２９】上記のような表面粗さの大きい被膜は、離
型性、耐焼き付き性、摩擦係数低減等の点からは、表面
粗さが小さい硬質炭素膜より性能が劣る傾向にあるが、
それでも、一般のＰＶＤ膜被膜品や、未コート品よりは
るかに優れた特性を有する。したがって、焼き付きが問
題となる工具、耐焼き付き性や離型性が要求される金
型、摩擦抵抗を低減させる機械部品に適用することがで
きる。また、被加工物の仕上がり表面の粗さを大きくす
ることを目的とする金型には最適である。A coating having a large surface roughness as described above tends to be inferior to a hard carbon film having a small surface roughness in terms of releasability, seizure resistance, reduction of friction coefficient, and the like.
Nevertheless, it has properties far superior to general PVD film coated products and uncoated products. Therefore, the present invention can be applied to a tool in which seizure is a problem, a mold in which seizure resistance and releasability are required, and a mechanical part for reducing frictional resistance. Further, it is most suitable for a mold aiming at increasing the roughness of a finished surface of a workpiece.
【００３０】上記の各硬質炭素膜被覆部材は、その表面
粗さが大きいものであっても、小さいものであっても、
従来の単層の硬質炭素膜や、界面の酸素量に配慮されて
いない硬質炭素膜を適用できなかった各種の工具、金
型、機械部品として使用することができ、十分な密着性
と耐久性が得られる。例えば、ドリル、エンドミル、切
削用チップ、カッター刃、メタルソー等を上記の各硬質
炭素膜被覆部材によって形成することにより、上記の特
性を有する工具を得ることができる。また、モールド成
型用金型、曲げ用金型、絞り用金型、引き抜き用金型、
打ち抜き用金型、粉末成型用金型等を上記の各硬質炭素
膜被覆部材によって形成することにより、上記の特性を
有する金型を得ることができる。さらに、産業用機械部
品、輸送用機械部品、家電製品用機械部品等を上記の各
硬質炭素膜被覆部材によって形成することにより、上記
の特性を有する機械部品を得ることができる。Each of the above hard carbon film-coated members has a large or small surface roughness.
It can be used as various tools, dies, and machine parts that could not be used with conventional single-layer hard carbon films or hard carbon films that did not consider the amount of oxygen at the interface, with sufficient adhesion and durability Is obtained. For example, a tool having the above characteristics can be obtained by forming a drill, an end mill, a cutting tip, a cutter blade, a metal saw, and the like with the above-described hard carbon film-coated members. In addition, mold mold, bending mold, drawing mold, drawing mold,
A die having the above characteristics can be obtained by forming a die for punching, a die for powder molding, and the like with the above-described hard carbon film covering members. Furthermore, by forming an industrial machine component, a transport machine component, a machine component for home electric appliances, and the like with the above-described hard carbon film-coated members, a machine component having the above characteristics can be obtained.
【００３１】[0031]
【実施例】〔実施例１〕平板上の超硬合金基材上に、中
間層を介して硬質炭素層を形成した。まず、基板表面側
にイオンプレーティング法により厚さ０．５μｍの窒化
チタン層を成膜し、次いで、その上層に同じくイオンプ
レーティング法により厚さ０．５μｍの炭化チタン層を
成膜した。これをいったん大気に出した後、硬質炭素成
膜用の成膜装置にセットし、到達真空度が２×１０-6Ｔ
ｏｒｒの条件下で排気を行った後、イオン蒸着法によっ
て硬質炭素層を１．０μｍ成膜した。得られた硬質炭素
層の密着強度が４８Ｎであった。なお、密着強度はスク
ラッチ試験法によって測定した。また、図１に、硬質炭
素膜と炭化チタンとの界面付近の深さ方向の元素分析の
結果を示す。分析にはＸ線光電子分光法（ＸＰＳ法）を
適用した。なお、被膜は、あらかじめ斜め研磨をして、
硬質炭素膜を０．２μｍ以下まで薄くした部分で分析を
行った。図１の横軸は、界面からの距離に換算してお
り、負は表面側（硬質炭素層側）、正は基板側（中間層
である炭化チタン層側）とした。EXAMPLES Example 1 A hard carbon layer was formed on a cemented carbide substrate on a flat plate via an intermediate layer. First, a titanium nitride layer having a thickness of 0.5 μm was formed on the substrate surface side by an ion plating method, and then a titanium carbide layer having a thickness of 0.5 μm was formed thereon by the same ion plating method. After this was once released to the atmosphere, it was set in a film forming apparatus for forming a hard carbon film, and the ultimate vacuum was 2 × 10 −6 T.
After evacuation was performed under orr conditions, a hard carbon layer was formed to a thickness of 1.0 μm by ion vapor deposition. The adhesive strength of the obtained hard carbon layer was 48N. The adhesion strength was measured by a scratch test. FIG. 1 shows the results of elemental analysis in the depth direction near the interface between the hard carbon film and titanium carbide. X-ray photoelectron spectroscopy (XPS method) was applied for the analysis. In addition, the film is polished diagonally in advance,
The analysis was performed at the portion where the hard carbon film was thinned to 0.2 μm or less. The abscissa in FIG. 1 is converted into the distance from the interface, and the negative is the surface side (hard carbon layer side), and the positive is the substrate side (titanium carbide layer side which is an intermediate layer).
【００３２】〔比較例１〕真空到達度を２×１０-5Ｔｏ
ｒｒとした以外は、実施例１と同様にして、超硬合金基
材上に、窒化チタン層、炭化チタン層、硬質炭素層を順
に形成した。得られた硬質炭素層の密着強度は１３Ｎで
あった。また、図２に、硬質炭素膜と炭化チタンとの界
面付近の深さ分析の結果を示す。分析法及び、図１中の
横軸の意味は、実施例１に記載の通りである。[Comparative Example 1] Degree of vacuum reached 2 × 10 -5 To
A titanium nitride layer, a titanium carbide layer, and a hard carbon layer were sequentially formed on a cemented carbide substrate in the same manner as in Example 1 except that rr was used. The adhesion strength of the obtained hard carbon layer was 13N. FIG. 2 shows the result of depth analysis near the interface between the hard carbon film and titanium carbide. The analysis method and the meaning of the horizontal axis in FIG. 1 are as described in Example 1.
【００３３】結果 硬質炭素層の密着強度は、実施例１の方が大きかった。
また、図１及び図２より、実施例１の方が界面の酸素濃
度が小さかった。 As a result, the adhesion strength of the hard carbon layer was higher in Example 1.
1 and 2, the oxygen concentration at the interface was smaller in Example 1 than in FIG.
【００３４】〔実施例２、比較例２〕平板状の超硬合金
基材上に、中間層を介して硬質炭素層を成膜した。中間
層のうち、硬質炭素層に内接する中間層には、炭化ケイ
素、炭窒化チタン、窒化クロムからなる層を形成した。
各層の成膜方法、膜厚は、表１に記載のとおりである。
中間層のうち、基材に外接する中間層としては、試料１
〜２及び比較試料１〜２においては、窒化チタンからな
る層を熱ＣＶＤ法によって１．０μｍの膜厚で形成し
た。試料３〜６及び比較試料３〜６は、硬質炭素層に内
接する中間層を基材に外接する中間層とした。上記の各
中間層の形成後、界面部の酸素濃度（界面±５０ｎｍの
平均の酸素濃度、及び、界面付近の酸素濃度の最大値）
が表１に示す値となるように、真空到達度、基板温度、
大気解放の有無、大気解放後の中間層表面のクリーニン
グの有無等の種々の条件を変化させて表１に示す膜厚を
有する硬質炭素層を形成した。得られた硬質炭素層につ
いて、スクラッチ試験法によって密着強度の測定を行っ
た。その結果を表１に示す。なお、上記の界面部の酸素
濃度は、オージェ電子分光法により、硬質炭素層／中間
層界面の深さ方向の元素分析で行うことにより測定し
た。実施例２及び比較例２の結果、表１より界面の酸素
濃度が小さいものは、密着強度が高い傾向にあることが
わかった。Example 2, Comparative Example 2 A hard carbon layer was formed on a plate-shaped cemented carbide substrate via an intermediate layer. Among the intermediate layers, a layer made of silicon carbide, titanium carbonitride, and chromium nitride was formed as an intermediate layer inscribed in the hard carbon layer.
The film formation method and film thickness of each layer are as described in Table 1.
Sample 1 was used as the intermediate layer circumscribing the base material among the intermediate layers.
In Comparative Examples 1 and 2 and Comparative Samples 1 and 2, a layer made of titanium nitride was formed to a thickness of 1.0 μm by a thermal CVD method. In Samples 3 to 6 and Comparative Samples 3 to 6, the intermediate layer inscribed in the hard carbon layer was used as the intermediate layer inscribed in the base material. After the formation of each of the above-mentioned intermediate layers, the oxygen concentration at the interface (the average oxygen concentration at the interface ± 50 nm and the maximum value of the oxygen concentration near the interface)
Is the value shown in Table 1 so that the vacuum reach, the substrate temperature,
Various conditions such as the presence or absence of release to the atmosphere and the presence or absence of cleaning of the surface of the intermediate layer after release to the atmosphere were changed to form a hard carbon layer having a film thickness shown in Table 1. About the obtained hard carbon layer, the adhesion strength was measured by a scratch test method. Table 1 shows the results. The oxygen concentration at the above interface was measured by Auger electron spectroscopy by elemental analysis in the depth direction of the hard carbon layer / intermediate layer interface. As a result of Example 2 and Comparative Example 2, it was found from Table 1 that those having a low oxygen concentration at the interface tended to have high adhesion strength.
【００３５】[0035]
【表１】 [Table 1]
【００３６】〔実施例３、比較例３〕平板状の基材上
に、中間層を介して硬質炭素膜を成膜した。基材として
は、表２〜６に示すように、超硬合金、ＳＫＨ５１、Ｓ
ＫＤ１１、ＳＵＳ３０４を用いた。中間層のうち、硬質
炭素層に内接する中間層には、炭化チタン、窒化チタ
ン、炭窒化チタン、炭化タングステン、窒化クロムから
なる層を形成した。各層の成膜方法、膜厚は、表２〜６
に記載のとおりである。中間層のうち、基材に外接する
中間層としては、試料１１〜２０、２６〜３０及び比較
試料５〜８、１１〜１２においては、窒化チタンからな
る層を形成した。各層の成膜方法、膜厚は、表２〜６に
記載のとおりである。試料１〜１０、２１〜２５及び比
較試料１〜４、９〜１０は、硬質炭素層に内接する中間
層を基材に外接する中間層とした。上記の各中間層の形
成後、界面部の酸素濃度（界面±５０ｎｍの平均の酸素
濃度、及び、界面付近の酸素濃度の最大値）が表１に示
す値となるように、真空到達度、基板温度、大気解放の
有無、大気解放後の中間層表面のクリーニングの有無等
の種々の条件を変化させて表２〜６に示す膜厚を有する
硬質炭素層を形成した。得られた硬質炭素層について、
スクラッチ試験法によって密着強度の測定を行った。そ
の結果を表２〜６に示す。なお、上記の界面部の酸素濃
度は、オージェ電子分光法により、硬質炭素層／中間層
界面の深さ方向の元素分析で行うことにより測定した。Example 3, Comparative Example 3 A hard carbon film was formed on a flat base material via an intermediate layer. As a base material, as shown in Tables 2 to 6, cemented carbide, SKH51, S
KD11 and SUS304 were used. Among the intermediate layers, a layer made of titanium carbide, titanium nitride, titanium carbonitride, tungsten carbide, and chromium nitride was formed as an intermediate layer inscribed in the hard carbon layer. Tables 2 to 6 show the film formation method and film thickness of each layer.
It is as described in. Among the intermediate layers, as the intermediate layer circumscribing the substrate, a layer made of titanium nitride was formed in Samples 11 to 20, 26 to 30 and Comparative Samples 5 to 8 and 11 to 12. The film forming method and film thickness of each layer are as described in Tables 2 to 6. In Samples 1 to 10, 21 to 25 and Comparative Samples 1 to 4, 9 to 10, the intermediate layer inscribed in the hard carbon layer was the intermediate layer inscribed in the base material. After the formation of each of the above-mentioned intermediate layers, the degree of vacuum reach, and the oxygen concentration at the interface (the average oxygen concentration at the interface ± 50 nm and the maximum value of the oxygen concentration near the interface) are as shown in Table 1. Various conditions such as the substrate temperature, the presence / absence of release to the atmosphere, and the presence / absence of cleaning of the surface of the intermediate layer after release to the atmosphere were changed to form hard carbon layers having the film thicknesses shown in Tables 2 to 6. About the obtained hard carbon layer,
The adhesion strength was measured by a scratch test method. The results are shown in Tables 2 to 6. The oxygen concentration at the above interface was measured by Auger electron spectroscopy by elemental analysis in the depth direction of the hard carbon layer / intermediate layer interface.
【００３７】[0037]
【表２】 [Table 2]
【００３８】[0038]
【表３】 [Table 3]
【００３９】[0039]
【表４】 [Table 4]
【００４０】[0040]
【表５】 [Table 5]
【００４１】[0041]
【表６】 [Table 6]
【００４２】〔実施例４、比較例４〕実施例２の試料３
及び比較例２の比較試料４における中間層及び硬質炭素
層を、超硬合金製のアルミ合金穴開け用ドリルに被覆処
理した。その結果、界面の酸素濃度の高いものに対し、
酸素濃度の低いドリルは、５倍の寿命を有することを確
認した。Example 4, Comparative Example 4 Sample 3 of Example 2
The intermediate layer and the hard carbon layer in Comparative Sample 4 of Comparative Example 2 were coated with an aluminum alloy drill for making hard metal. As a result, for those with high oxygen concentration at the interface,
It was confirmed that the drill having a low oxygen concentration had a five-fold life.
【００４３】〔実施例５、比較例５〕実施例２の試料１
及び比較例２の比較試料２における中間層及び硬質炭素
層を、ＳＫＤ１１製のアルミ合金曲げ金型に被覆処理し
た。その結果、界面の酸素濃度の高いものに対し、酸素
濃度の低い金型は、８倍の寿命を有することを確認し
た。Example 5, Comparative Example 5 Sample 1 of Example 2
The intermediate layer and the hard carbon layer in Comparative Sample 2 of Comparative Example 2 were coated on an aluminum alloy bending mold made of SKD11. As a result, it was confirmed that a mold having a low oxygen concentration has a life eight times longer than a mold having a high oxygen concentration at the interface.
【００４４】〔実施例６、比較例６〕実施例２の試料５
及び比較例２の比較試料５における中間層及び硬質炭素
層を、ＳＵＪ２製のベアリングに被覆処理した。界面の
酸素濃度が高いものに対し、酸素濃度が低いベアリング
は、４倍の寿命を有することを確認した。Example 6, Comparative Example 6 Sample 5 of Example 2
The intermediate layer and the hard carbon layer in Comparative Sample 5 of Comparative Example 2 were coated on a SUJ2 bearing. It was confirmed that a bearing having a low oxygen concentration had a life four times as long as a bearing having a high oxygen concentration at the interface.
【００４５】〔実施例７、比較例７〕ＳＫＨ５１製のア
ルミ合金穴開け用ドリルにおいて、表７に示す未コード
リール及び硬質炭素膜をイオン化蒸着法又はカソードア
ークイオンプレーティング法で被覆したドリルで、穴開
け時の切削抵抗を比較した。製膜方法及び膜厚は表７に
示すとおりである。未コードリールと比較して、硬質炭
素膜を被覆したものは、いずれも切削抵抗が２割前後小
さくなった。特に、実施例７の各試料の表面粗さの小さ
いドリルは、切削抵抗の大幅な低減が確認できた。Example 7 and Comparative Example 7 In a drill for drilling an aluminum alloy made of SKH51, a non-cored reel and a hard carbon film shown in Table 7 were coated by an ionization vapor deposition method or a cathode arc ion plating method. And the cutting resistance at the time of drilling were compared. The film forming method and film thickness are as shown in Table 7. The cutting resistance of each of those coated with the hard carbon film was reduced by about 20% as compared with the uncord reel. In particular, it was confirmed that the drill having a small surface roughness of each sample of Example 7 had a large reduction in cutting resistance.
【００４６】[0046]
【表７】 [Table 7]
【００４７】〔実施例８、比較例８〕アルミ合金に刻印
するＳＫＤ１１製の刻印ローラにおいて、刻印後にアル
ミ合金表面を粗面に仕上げるため、刻印ローラ表面の粗
さを大きくする処理（ブラスト処理）を施した。各試料
及び比較試料に対して、粗さ加工性と被加工物アルミの
ローラへの付着量を表８に示す。ここで、アルミの付着
量は、電子プローブ微小部分析法（ＥＰＭＡ法）により
分析し、下記の式により得られる値で表した。 （（Ａｌ強度）／（全元素の強度の和））／（（比較例
３のＡｌ強度）／（比較例３の全元素の強度の和）） なお、ここで、ＥＰＭＡ法に適用した入射電子線の加速
エネルギーは、１５ｋｅＶとした。未コートで基材表面
を粗くしたものでも、粗さ加工性は良好であるが、被加
工物のアルミがローラに付着しやすい傾向がある。Example 8 and Comparative Example 8 In a marking roller made of SKD11 for marking an aluminum alloy, a process of increasing the roughness of the surface of the marking roller in order to finish the surface of the aluminum alloy after marking (blasting). Was given. Table 8 shows the roughness workability and the amount of aluminum adhered to the roller for each sample and comparative sample. Here, the adhesion amount of aluminum was analyzed by an electron probe micropart analysis method (EPMA method) and represented by a value obtained by the following equation. ((Al intensity) / (sum of all element strengths)) / ((Al intensity of comparative example 3) / (sum of intensity of all elements of comparative example 3)) Here, the incident light applied to the EPMA method was used. The acceleration energy of the electron beam was set to 15 keV. Even if the surface of the base material is roughened without being coated, the workability of the roughness is good, but the aluminum of the workpiece tends to easily adhere to the roller.
【００４８】[0048]
【表８】 [Table 8]
【００４９】[0049]
【発明の効果】この発明によれば、硬質炭素層からなる
最外層と中間層の界面部の酸素濃度を限定したので、硬
質炭素層の界面にＣＯやＣＯ2 が形成されるのが抑制さ
れ、両者の密着性を向上させることができる。According to the present invention, since the oxygen concentration at the interface between the outermost layer made of the hard carbon layer and the intermediate layer is limited, the formation of CO and CO 2 at the interface of the hard carbon layer is suppressed. And the adhesion between the two can be improved.
【図１】実施例１における硬質炭素層と炭化チタン層の
界面付近の深さ方向の元素分析結果を示すグラフFIG. 1 is a graph showing the results of elemental analysis in the depth direction near the interface between a hard carbon layer and a titanium carbide layer in Example 1.
【図２】実施例１における硬質炭素層と炭化チタン層の
界面付近の深さ方向の元素分析結果を示すグラフFIG. 2 is a graph showing the results of elemental analysis in the depth direction near the interface between the hard carbon layer and the titanium carbide layer in Example 1.
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Claims (11)
素、ジルコニア、炭化ケイ素、アルミナ、アルミニウム
合金、マグネシウム合金、又はチタン合金のいずれかか
ら選ばれ、 上記被膜層の最外層は硬質炭素層からなり、 上記基材と最外層の間の中間層のうち、最外層に内接す
る中間層は、４族の金属、５族の金属、６族の金属、Ｓ
ｉ、Ａｌ、又はＧｅの中から選ばれる１種又は複数種の
金属を含む金属の炭化物、窒化物、又は炭窒化物であ
り、上記最外層とこの中間層との界面部に存在する酸素
濃度が、最大値で３ａｔ％、又は、界面を基準に±５０
ｎｍの範囲の平均値で２ａｔ％以下である硬質炭素膜被
覆部材。1. A laminate comprising a plurality of coating layers laminated on a substrate, wherein the substrate is made of cemented carbide, cermet, steel, silicon nitride, zirconia, silicon carbide, alumina, aluminum alloy, magnesium alloy, or titanium. The outermost layer of the coating layer is formed of a hard carbon layer, and the intermediate layer inscribed in the outermost layer among the intermediate layers between the base material and the outermost layer is a Group 4 metal, Group 6 metal, Group 6 metal, S
i, Al, or a carbide, nitride, or carbonitride of a metal containing one or more metals selected from Ge, and the concentration of oxygen present at the interface between the outermost layer and the intermediate layer Is 3 at% at the maximum or ± 50 based on the interface.
A member coated with a hard carbon film having an average value of 2 at% or less in a range of nm.
０．０５〜５μｍの炭化チタン、窒化チタン、炭窒化チ
タン、又は、炭化タングステンからなる層である請求項
１に記載の硬質炭素膜被覆部材。2. The hard carbon according to claim 1, wherein the intermediate layer inscribed in the outermost layer is a layer made of titanium carbide, titanium nitride, titanium carbonitride, or tungsten carbide having a thickness of 0.05 to 5 μm. Membrane-coated members.
０．０５〜５μｍの炭化チタン又は炭化タングステンか
らなる層であり、上記基材に外接する中間層が、膜厚
０．０５〜５μｍの窒化チタンからなる層である請求項
１又は２に記載の硬質炭素膜被覆部材。3. The intermediate layer inscribed in the outermost layer is a layer of titanium carbide or tungsten carbide having a thickness of 0.05 to 5 μm, and the intermediate layer inscribed in the base material has a thickness of 0.05 to 5 μm. The hard carbon film-coated member according to claim 1 or 2, which is a layer made of titanium nitride having a thickness of 5 µm.
チタン合金のいずれかであり、上記中間層のうち少なく
とも１層が膜厚０．０５〜２０μｍの窒化クロムからな
る層である請求項１乃至３のいずれかに記載の硬質炭素
膜被覆部材。4. The substrate according to claim 1, wherein the base material is any one of a steel material, an aluminum alloy and a titanium alloy, and at least one of the intermediate layers is a layer made of chromium nitride having a thickness of 0.05 to 20 μm. 4. The member coated with a hard carbon film according to any one of 3.
法、プラズマＣＶＤ法、または、カソードアークイオン
プレーティング法によって形成され、上記最外層表面の
表面粗さは、Ｒａで０．１μｍ以下、又は、Ｒｍａｘで
１．０μｍ以下である請求項１乃至４のいずれかに記載
の硬質炭素膜被覆部材。5. The outermost hard carbon layer is formed by an ion deposition method, a plasma CVD method, or a cathode arc ion plating method, and the surface roughness of the outermost layer surface is 0.1 μm or less in Ra. The hard carbon film-coated member according to any one of claims 1 to 4, wherein Rmax is 1.0 µm or less.
ソードアークイオンプレーティング法で形成され、上記
最外層表面の表面粗さは、Ｒａで０．１〜１μｍ、又
は、Ｒｍａｘで１．０〜１０μｍである請求項１乃至４
のいずれかに記載の硬質炭素膜被覆部材。6. At least one of the intermediate layers is formed by a cathodic arc ion plating method, and the outermost layer has a surface roughness of 0.1 to 1 μm in Ra or 1.0 in Rmax. 5 to 10 μm.
A member coated with a hard carbon film according to any one of the above.
ークイオンプレーティング法によって形成され、上記最
外層表面の表面粗さは、Ｒａで０．１〜１μｍ、又は、
Ｒｍａｘで１．０〜１０μｍである請求項１乃至４のい
ずれかに記載の硬質炭素膜被覆部材。7. The outermost hard carbon layer is formed by a cathodic arc ion plating method, and the outermost layer surface has a surface roughness of 0.1 to 1 μm in Ra, or
The hard carbon film-coated member according to any one of claims 1 to 4, wherein Rmax is 1.0 to 10 m.
１〜５μｍ、又は、Ｒｍａｘで１．０〜５０μｍであ
り、上記最外層表面の表面粗さが、Ｒａで０．１〜５μ
ｍ、又は、Ｒｍａｘで１．０〜５０μｍである請求項１
乃至４のいずれかに記載の硬質炭素膜被覆部材。8. The substrate having a surface roughness of Ra of 0.
1 to 5 μm, or 1.0 to 50 μm in Rmax, and the surface roughness of the outermost layer surface is 0.1 to 5 μm in Ra.
m or 1.0 to 50 μm in Rmax.
5. The member coated with a hard carbon film according to any one of items 1 to 4.
ッター刃、又は、メタルソーのいずれかが、請求項１乃
至８のいずれかの硬質炭素膜被覆部材から形成される工
具。9. A tool wherein any one of a drill, an end mill, a cutting tip, a cutter blade, and a metal saw is formed from the hard carbon film-coated member according to any one of claims 1 to 8.
り用金型、引き抜き用金型、打ち抜き用金型、又は、粉
末成型用金型のいずれかが、請求項１乃至８のいずれか
の硬質炭素膜被覆部材から形成される金型。10. The mold of any one of claims 1 to 8, wherein one of a mold, a bending mold, a drawing die, a drawing die, a punching die, and a powder molding die. A mold formed from such a hard carbon film-coated member.
は、家電製品用機械部品のいずれかが、請求項１乃至８
のいずれかの硬質炭素膜被覆部材から形成される機械部
品。11. The mechanical part for industrial use, the mechanical part for transport, or the mechanical part for home appliances,
A mechanical part formed from the member coated with a hard carbon film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17901398A JP2000008155A (en) | 1998-06-25 | 1998-06-25 | Hard carbon film coated member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17901398A JP2000008155A (en) | 1998-06-25 | 1998-06-25 | Hard carbon film coated member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000008155A true JP2000008155A (en) | 2000-01-11 |
Family
ID=16058601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17901398A Pending JP2000008155A (en) | 1998-06-25 | 1998-06-25 | Hard carbon film coated member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000008155A (en) |
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