JPH06951B2 - High adhesion diamond coated member - Google Patents
High adhesion diamond coated memberInfo
- Publication number
- JPH06951B2 JPH06951B2 JP61036161A JP3616186A JPH06951B2 JP H06951 B2 JPH06951 B2 JP H06951B2 JP 61036161 A JP61036161 A JP 61036161A JP 3616186 A JP3616186 A JP 3616186A JP H06951 B2 JPH06951 B2 JP H06951B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- diamond
- adhesion
- amorphous carbon
- outer layer
- 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
- 229910003460 diamond Inorganic materials 0.000 title claims description 46
- 239000010432 diamond Substances 0.000 title claims description 46
- 239000010410 layer Substances 0.000 claims description 88
- 239000002184 metal Substances 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 12
- 150000004767 nitrides Chemical class 0.000 claims description 8
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 150000001247 metal acetylides Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 description 26
- 239000011247 coating layer Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 238000005520 cutting process Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000012808 vapor phase Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 101100433727 Caenorhabditis elegans got-1.2 gene Proteins 0.000 description 1
- 229910000997 High-speed steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- -1 cemented carbide Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Physical Vapour Deposition (AREA)
- Chemical Vapour Deposition (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、切削工具，耐摩耗工具又は研削工具などの工
具部材、核融合炉の炉壁に代表される原子炉用部材並び
にヒートシンク又はスピーカーの振動板などのエレクト
ロニクス部材として応用できる高密着性ダイヤモンド被
覆部材に関するものである。Description: TECHNICAL FIELD The present invention relates to tool members such as cutting tools, wear-resistant tools or grinding tools, reactor members typified by a reactor wall of a fusion reactor, and heat sinks or speakers. The present invention relates to a high-adhesion diamond coating member applicable as an electronic member such as a diaphragm.
（従来の技術） 気相からダイヤモンドを合成する方法としては、スパッ
タ法、イオンプレーティング法，蒸着法とイオン注入法
を組合わせたイオンビーム蒸着法，熱フラメント又は熱
電子放射材を利用した化学蒸着法，マイクロ波又は高周
波を利用したプラズマ化学蒸着法などがある。(Prior Art) As a method of synthesizing diamond from a vapor phase, sputtering method, ion plating method, ion beam vapor deposition method combining vapor deposition method and ion implantation method, chemistry using thermal fragment or thermionic emission material There are a vapor deposition method, a plasma chemical vapor deposition method using microwave or high frequency, and the like.
これらの気相合成法によって基材の表面にダイヤモンド
の被覆層を形成する場合、超硬合金，サーメット又は工
具鋼などのように鉄族金属を含む基材の表面に直接ダイ
ヤモンドの被覆層を形成すると、この基材の鉄族金属が
ダイヤモンド合成のための供給炭化水素ガスの分解の触
媒として作用すること、又はダイヤモンド合成のための
供給水素ガスを吸収することなどから被覆層の質を低下
させるという問題がある。これらの問題を解決するもの
として、基材とダイヤモンドの被覆層との間に金属の炭
化物や窒化物の中間層を介在させてなるダイヤモンド被
覆部材が多数提案されている。しかしながら、これらの
中間層を介在させてなるダイヤモンド被覆部材は、金属
の炭化物や窒化物の中間層の表面にダイヤモンドの被覆
層が付着しているものであり、共有結合で、他の物質と
は殆んど反応しないダイヤモンドの被覆層と中間層との
密着性は悪く、剥離しやすいという問題がある。When a diamond coating layer is formed on the surface of a substrate by these vapor phase synthesis methods, a diamond coating layer is formed directly on the surface of a substrate containing an iron group metal such as cemented carbide, cermet or tool steel. Then, the iron group metal of the base material acts as a catalyst for the decomposition of the hydrocarbon gas supplied for diamond synthesis, or absorbs the hydrogen gas supplied for diamond synthesis, thereby deteriorating the quality of the coating layer. There is a problem. As a solution to these problems, many diamond-coated members have been proposed in which an intermediate layer of metal carbide or nitride is interposed between a substrate and a diamond coating layer. However, the diamond coating member formed by interposing these intermediate layers has a diamond coating layer attached to the surface of the intermediate layer of metal carbide or nitride, and is covalently bonded to other substances. There is a problem in that the adhesion between the diamond coating layer and the intermediate layer, which hardly reacts with each other, is poor and peeling easily occurs.
このような問題点を、更に解決しようと試みたものに特
開昭５９−９３８６９号公報がある。Japanese Patent Laid-Open No. 59-93869 discloses an attempt to further solve such a problem.
（発明が解決しようとする問題点） 特開昭５９−９３８６９号公報は、被膜の３０体積％〜
９５体積％をダイヤモンドもしくはダイヤモンド状の相
が占め、残部を鉄族金属又は無機硬質金属化合物が占め
たダイヤモンドを含有する硬質被膜で基材表面を被覆し
たダイヤモンド含有被覆部材である。この特開昭５９−
９３８６９号公報は、他の物質と殆んど反応しないダイ
ヤモンドを鉄族金属又は無機硬質金属化合物と混合又は
分散させてなる被覆層にすることにより、ダイヤモンド
粒子を保持する面積が増大して被覆層中のダイヤモンド
粒子と基材との密着性を高めているものと思われる。し
かしながら、鉄族金属を含有したダイヤモンド被覆層
は、前述の如く、鉄族金属の影響でダイヤモンドの質を
低下させるという問題及びダイヤモンドの生成速度を低
下させるという問題がある。また、無機硬質金属化合物
を含有したダイヤモンド被覆層は、無機硬質金属化合物
とダイヤモンド粒子との混合物からなる被覆層であっ
て、被覆層内の各粒子間の密着性が悪いこと、又は無機
硬質金属化合物粒子とダイヤモンド粒子との間に気孔が
生じることにより被覆層内強度が低いという問題があ
る。(Problems to be Solved by the Invention) Japanese Patent Application Laid-Open No. 59-93869 discloses that 30% by volume of a coating film
A diamond-containing coated member is obtained by coating the surface of a substrate with a hard coating containing diamond in which 95% by volume is occupied by diamond or a diamond-like phase and the balance is occupied by an iron group metal or an inorganic hard metal compound. This JP-A-59-
Japanese Patent No. 93869 discloses a coating layer in which diamond, which hardly reacts with other substances, is mixed or dispersed with an iron group metal or an inorganic hard metal compound to increase the area for holding the diamond particles. It seems that the adhesion between the diamond particles and the base material is enhanced. However, as described above, the diamond coating layer containing the iron group metal has a problem that the quality of the diamond is deteriorated by the effect of the iron group metal and a diamond generation rate is decreased. The diamond coating layer containing an inorganic hard metal compound is a coating layer made of a mixture of an inorganic hard metal compound and diamond particles, and the adhesion between the particles in the coating layer is poor, or the inorganic hard metal is There is a problem that the strength in the coating layer is low due to the formation of pores between the compound particles and the diamond particles.
本発明は、上述のような問題点を解決したもので、具体
的には、基材と結晶質ダイヤモンド状構造の外層との間
に、外層を形成しやすく、しかも、外層との密着性がす
ぐれている中間層を介在させてなるダイヤモンド被覆部
材の提供を目的とするものである。The present invention has solved the above-mentioned problems, specifically, it is easy to form an outer layer between the substrate and the outer layer of the crystalline diamond-like structure, and moreover, the adhesion with the outer layer is It is an object of the present invention to provide a diamond-coated member having an excellent intermediate layer interposed.
（問題点を解決するための手段） 一般に、ダイヤモンドは、他の物質との濡れ性が著しく
悪いこと、及びダイヤモンド中への他原子の拡散が少な
いことから基材の表面に密着性の高いダイヤモンドの被
覆層を形成するのが非常に困難である。そこで、本発明
者らは、ダイヤモンドの被覆層を形成しやすい物質、及
びダイヤモンドの被覆層との密着性を高める物質につい
て検討した所、カーボン、特に非晶質カーボン状構造か
らなる物質の表面には、ダイヤモンドの被覆層が形成し
やすくなり、密着性もすぐれるという知見を得て、本発
明を完成するに至ったものである。(Means for Solving Problems) Generally, diamond has a very poor wettability with other substances, and the diffusion of other atoms into the diamond is small, so that diamond having high adhesion to the surface of the substrate is used. It is very difficult to form the coating layer. Therefore, the present inventors have examined a substance that easily forms a diamond coating layer and a substance that enhances adhesion to the diamond coating layer, and found that carbon, particularly a substance having an amorphous carbon-like structure The present invention has been completed based on the knowledge that the diamond coating layer is easily formed and the adhesion is excellent.
すなわち、本発明の高密着性ダイヤモンド被覆部材は、
基材の表面に結晶質ダイヤモンド状構造の外層を形成し
てなる被覆部材であって、前記基材と前記外層との間に
１層又は多層で構成される中間層を介在させ、該中間層
は、該外層に隣接する非晶質カーボン状構造の層と該非
晶質カーボン状構造の層に隣接する密着補助層とからな
り、該密着補助層が周期律表4a,5a,6a族の金属又はSiの
炭化物，窒化物，酸化物，ホウ化物もしくは、Alの窒化
物，ホウ化物，酸化物及びこれらの相互固溶体の中の少
なくとも１種でなる単層あるいは２種以上でなる多層か
らなることを特徴とするものである。That is, the high adhesion diamond coating member of the present invention,
A covering member comprising an outer layer having a crystalline diamond-like structure formed on a surface of a base material, wherein an intermediate layer composed of one layer or multiple layers is interposed between the base material and the outer layer, and the intermediate layer Is composed of an amorphous carbon-like structure layer adjacent to the outer layer and an adhesion auxiliary layer adjacent to the amorphous carbon-like structure layer, and the adhesion auxiliary layer is a metal of Group 4a, 5a, 6a of the periodic table. Or a single layer of at least one of Si carbide, nitride, oxide, boride or Al nitride, boride, oxide and mutual solid solution thereof, or a multi-layer consisting of two or more kinds. It is characterized by.
ここで用いる基材は、後述する製造条件に耐えることが
可能な材質ならば特別に制限されるものではなく、例え
ば、各種の金属，合金，焼結ハイス、超硬合金，サーメ
ット又はセラミックスなどを用途によって使い分けるこ
とができる。The base material used here is not particularly limited as long as it is a material that can withstand the manufacturing conditions described later, and for example, various metals, alloys, sintered high speed steel, cemented carbide, cermet or ceramics, etc. It can be used properly depending on the application.
これらの基材と外層との間に介在させる中間層は、外層
に隣接する中間層が非晶質カーボン状構造の層によって
形成されていることを特徴とするもので、使用する基材
の材質又は本発明の被覆部材の用途もしくは形状により
各種の構造にすることができる。The intermediate layer interposed between the base material and the outer layer is characterized in that the intermediate layer adjacent to the outer layer is formed by a layer having an amorphous carbon-like structure. Alternatively, various structures can be formed depending on the use or shape of the covering member of the present invention.
例えば、中間層が外層に隣接する非晶質カーボン状構造
の層と密着補助層とからなり、この密着補助層が周期律
表４ａ，５ａ，６ａ族の金属又はＳｉの炭化物，窒化
物，酸化物，ホウ化物もしくはＡｌの窒化物，ホウ化
物，酸化物及びこれらの相互固溶体の中の少なくとも１
種でなる単層あるいは２種以上の多層からなるものであ
る。この場合は、基材と外層との間に非晶質カーボン状
構造の層と密着補助層が介在し、基材に密着補助層が隣
接し、外層に非晶質カーボン状構造の層が隣接している
もので、密着補助層との密着性にすぐれる基材、例え
ば、鉄族金属又は鉄族金属を含有した合金、及び各種の
セラミックでなる基材に適用することができる。For example, the intermediate layer is composed of a layer having an amorphous carbon-like structure adjacent to the outer layer and an adhesion auxiliary layer, and the adhesion auxiliary layer is a metal of Group 4a, 5a, 6a of the periodic table or Si carbide, nitride, or oxide. At least one of the following compounds, borides or Al nitrides, borides, oxides and their mutual solid solutions.
It is composed of a single layer consisting of one kind or a multilayer consisting of two or more kinds. In this case, the amorphous carbon-like structure layer and the adhesion auxiliary layer are interposed between the base material and the outer layer, the adhesion auxiliary layer is adjacent to the base material, and the amorphous carbon-like structure layer is adjacent to the outer layer. However, it can be applied to a base material having excellent adhesion to the adhesion auxiliary layer, for example, a base material made of an iron group metal or an alloy containing an iron group metal, and various ceramics.
その他の中間層の構成としては、中間層が非晶質カーボ
ン状構造の層と金属又は合金の層とでなる場合、もしく
は非晶質カーボン状構造の層と密着補助層と金属又は合
金の層とでなる場合など各種の構成にすることができ
る。As the structure of the other intermediate layer, when the intermediate layer is composed of a layer having an amorphous carbon-like structure and a metal or alloy layer, or a layer having an amorphous carbon-like structure, an adhesion auxiliary layer and a metal or alloy layer It is possible to have various configurations such as
これらの中間層の内、非晶質カーボン状構造とは、ダイ
ヤモンドの結晶構造を含有していないか、もしくはラマ
ン分光分析においてダイヤモンドの結晶構造を示す１３
３２cm-1の波数における回折線が確認できるかできない
か程度のカーボン、特に非晶質カーボンを示すもので、
さらに具体的には、例えばラマン分光分析における波数
が１１５０cm-1，１３６０cm-1，１５００cm-1又は１５
６０cm-1の内少なくとも１種の回折線が確認できるよう
な非晶質カーボンであることが好ましい。Among these intermediate layers, the amorphous carbon-like structure does not contain a diamond crystal structure or shows a diamond crystal structure in Raman spectroscopic analysis.
It shows carbon, especially amorphous carbon, to the extent that diffraction lines at a wave number of 32 cm -1 can be confirmed or not,
More specifically, for example, wave number 1150 cm -1 in the Raman spectroscopic analysis, 1360 cm -1, 1500 cm -1 or 15
Amorphous carbon is preferably such that at least one kind of diffraction line of 60 cm -1 can be confirmed.
これらの中間層の表面に形成する外層は、結晶質ダイヤ
モンド状構造からなり、この結晶質ダイヤモンド状構造
とは、ダイヤモンドの結晶構造を少なくとも含有してい
るもので、例えばラマン分光分析においてダイヤモンド
の結晶構造を示す１３３２cm-1の波数における回折線が
明確なもので、この１３３２cm-1の波数の回折線又はこ
の回折線の他に非晶質カーボン状構造を示す回折線が混
在していてもよい。The outer layer formed on the surface of these intermediate layers is composed of a crystalline diamond-like structure, and this crystalline diamond-like structure contains at least the crystal structure of diamond, for example, the crystal of diamond in Raman spectroscopic analysis. The diffraction line at the wave number of 1332 cm -1 showing the structure is clear, and the diffraction line of the wave number of 1332 cm -1 or the diffraction line showing the amorphous carbon-like structure may be mixed in addition to this diffraction line. .
これらの非晶質カーボン状構造の層は、外層との密着性
及び耐剥離性から１００Å〜２０μｍの厚さであること
が好ましく、外層は、耐摩耗性及び耐剥離性から０．１
μｍ〜１００μｍ厚さであることが好ましい。また、非
晶質カーボン状構造の層と外層は、ラマン分光分析にお
いて、ダイヤモンドの結晶構造を示す１３３２cm-1の波
数での回折線強度が連続的に強くなるような連続的な層
であってもよい。These layers having an amorphous carbon-like structure preferably have a thickness of 100 Å to 20 μm from the viewpoint of the adhesion to the outer layer and the peel resistance, and the outer layer has a thickness of 0.1 to 20 from the wear resistance and the peel resistance.
The thickness is preferably 100 μm to 100 μm. In addition, the amorphous carbon-like layer and the outer layer are continuous layers in which the diffraction line intensity at the wave number of 1332 cm −1 , which shows the crystal structure of diamond in Raman spectroscopy, continuously increases. Good.
本発明の高密着性ダイヤモンド被覆部材は、次のような
方法によって製造することができる。まず、各種の基材
の表面を必要に応じて研摩洗浄した後、密着補助層を形
成する必要がある場合は、化学蒸着法（ＣＶＤ法）又は
物理蒸着法（ＰＶＤ法）により基材の表面に形成し、次
いで、例えば熱フイラメントＣＶＤ法，マイクロ波プラ
ズマＣＶＤ法，高周波プラズマＣＶＤ法又は磁界分離に
よるイオンビーム蒸着法などにより非晶質カーボン状構
造の層と外層を形成することができる。The highly adherent diamond-coated member of the present invention can be manufactured by the following method. First, when it is necessary to form an adhesion auxiliary layer after polishing and cleaning the surfaces of various base materials as necessary, the surface of the base material is formed by a chemical vapor deposition method (CVD method) or a physical vapor deposition method (PVD method). Then, the layer of amorphous carbon-like structure and the outer layer can be formed by, for example, a thermal filament CVD method, a microwave plasma CVD method, a high frequency plasma CVD method or an ion beam vapor deposition method by magnetic field separation.
非晶質カーボン状構造の層と外層の形成は、ダイヤモン
ドの気相合成法に使われるＨ２ガス，不活性ガス，炭化
水素ガスの内、供給炭化水素ガスの濃度をコントロール
することによって行なうことができ、その他反応ガスの
全圧又は加熱反応温度などによってもコントロールする
ことができる。例えば、具体的には、非晶質カーボン状
構造の層の形成は、反応容器内の炭化水素ガス濃度を３
vol％以上、好ましくは５vol％以上〜２０vol％以下に
すること、反応ガスの全圧を１００Ｔｏｒｒ以上、好ま
しくは１００Ｔｏｒｒ以上〜７６０Ｔｏｒｒ以下にする
こと、及び反応温度を８５０℃未満、好ましくは３００
℃以上〜８５０℃未満にすることによって作製すること
ができる。これに対して、外層の形成は、反応容器内の
炭化水素ガス濃度を３vol％未満、好ましくは０．１vol
％以上〜１vol％以下にすること、反応ガスの全圧を１
００Ｔｏｒｒ未満、好ましくは１０Ｔｏｒｒ以上〜１０
０Ｔｏｒｒ未満にすること、及び反応温度を８５０℃以
上、好ましくは８５０℃以上〜１１００℃以下にするこ
とによって作製することができる。The formation of the amorphous carbon-like layer and the outer layer is performed by controlling the concentration of the supplied hydrocarbon gas among H 2 gas, inert gas and hydrocarbon gas used in the vapor phase synthesis method of diamond. It can also be controlled by the total pressure of the reaction gas or the heating reaction temperature. For example, specifically, the formation of a layer having an amorphous carbon-like structure is performed by adjusting the hydrocarbon gas concentration in the reaction vessel to 3
vol% or more, preferably 5 vol% or more to 20 vol% or less, the total pressure of the reaction gas is 100 Torr or more, preferably 100 Torr or more to 760 Torr or less, and the reaction temperature is less than 850 ° C., preferably 300
It can be produced by adjusting the temperature to not less than ℃ and less than 850 ℃. On the other hand, the formation of the outer layer is carried out when the hydrocarbon gas concentration in the reaction vessel is less than 3 vol%, preferably 0.1 vol.
% To 1 vol% or less, the total pressure of the reaction gas is 1
Less than 00 Torr, preferably 10 Torr or more to 10
It can be produced by setting the reaction temperature to less than 0 Torr and the reaction temperature to 850 ° C. or higher, preferably 850 ° C. or higher to 1100 ° C. or lower.
（作用） 本発明の高密着性ダイヤモンド被覆部材は、中間層とし
ての非晶質カーボン状構造の層が外層の合成を促進し、
外層の形成後には、中間層と外層との密着性を著しく高
めているものである。また、基材の材質又は形状によ
り、基材と非晶質カーボン状構造の層との密着性が劣る
場合は、基材と非晶質カーボン状構造との間に密着補助
層や金属層などの中間層を介在させると、基材と非晶質
カーボン状構造の層との密着性を高めることができる。(Function) In the high-adhesion diamond-coated member of the present invention, the layer having the amorphous carbon-like structure as the intermediate layer promotes the synthesis of the outer layer,
After forming the outer layer, the adhesion between the intermediate layer and the outer layer is remarkably enhanced. Further, when the adhesion between the base material and the layer of the amorphous carbon-like structure is poor due to the material or shape of the base material, an adhesion auxiliary layer or a metal layer between the base material and the amorphous carbon-like structure, etc. By interposing the intermediate layer, the adhesion between the substrate and the layer having the amorphous carbon-like structure can be enhanced.
（実施例） 実施例１ ＪＩＳ規格Ｋ１０相当で、形状がＳＰＰ４２２の超硬合
金を基材として、この基材をマイクロ波プラズマＣＶＤ
反応容器内に設置し、８vol％ＴｉＣｌ４−５vol％ＣＨ
４−８７vol％Ｈ２雰囲気中、圧力２０Ｔｏｒｒ，温度
１０００℃，保持時間３０分にて基材の表面にＴｉＣ層
を被覆した。次いで、反応容器内を真空排気した後、出
力３５０Ｗ，ガス圧力４０Ｔｏｒｒ，メタン濃度０．７
vol％残り水素、基材温度８７０℃で１時間保持してか
ら、更に基材温度９４０℃で２時間保持して本発明品No
１を得た。(Example) Example 1 A cemented carbide having a JIS standard K10 and a shape of SPP422 was used as a base material, and this base material was subjected to microwave plasma CVD.
Installed in the reaction vessel, 8vol% TiCl 4 -5vol% CH
A TiC layer was coated on the surface of the base material at a pressure of 20 Torr, a temperature of 1000 ° C., and a holding time of 30 minutes in a 4-87 vol% H 2 atmosphere. Then, after evacuation of the inside of the reaction vessel, output 350 W, gas pressure 40 Torr, methane concentration 0.7
Vol% remaining hydrogen, holding the substrate temperature 870 ° C for 1 hour, and then holding the substrate temperature 940 ° C for 2 hours
Got 1.
比較として、上記本発明品No１と同一基材，同一反応容
器を用いて、基材表面にＴｉＣ層を上記と同様にして被
覆した後、出力，圧力，メタン濃度を上記と同様にし
て、基材温度９２０℃で３時間保持にて比較品No１を得
た。For comparison, after using the same base material and the same reaction vessel as the product No. 1 of the present invention and coating the TiC layer on the surface of the base material in the same manner as above, the output, pressure and methane concentration were the same as above. Comparative product No. 1 was obtained by keeping the material temperature at 920 ° C. for 3 hours.
こうして得た本発明品No１と比較品No１を用いて被削材
Ａｌ−１８％Ｓｉ合金，切削速度４００m/min，送り速
度０．２mm/rev，切込み量１mmの条件で旋削試験を行な
ったところ、本発明品No１は１０分間切削後の逃げ面摩
耗量が０．０１mm以下の正常摩耗であったのに対して、
比較品No１は８分間切削時に被覆層が剥離してしまっ
た。Using the thus obtained invention product No. 1 and comparative product No. 1, a turning test was carried out under the conditions of a work material Al-18% Si alloy, a cutting speed of 400 m / min, a feed speed of 0.2 mm / rev and a depth of cut of 1 mm. While the product No. 1 of the present invention had normal wear of the flank wear amount after cutting for 10 minutes of 0.01 mm or less,
In comparative product No. 1, the coating layer peeled off during cutting for 8 minutes.
この本発明品No１と比較品No１の被覆層をラマン分光分
析によって調べた所、本発明品No１は外層が２．０μｍ
厚さで、第１図（ａ）の回折線の結晶質ダイヤモンド状
構造で、中間層が０．７μｍ厚さで第１図（ｃ）の回折
線の非晶質カーボン状構造と０．５μｍ厚さのＴｉＣ層
とからなっていた。また、比較品No１は、第１図（ａ）
の回折線とほぼ同様の結晶質ダイヤモンド状構造の被覆
層であった。When the coating layers of the present invention product No. 1 and the comparative product No. 1 were examined by Raman spectroscopy, the invention product product No. 1 had an outer layer of 2.0 μm.
The thickness is 0.5 μm with the crystalline diamond-like structure of the diffraction line of FIG. 1 (a) and the intermediate layer is 0.7 μm thick with the amorphous carbon-like structure of the diffraction line of FIG. 1 (c). It consisted of a thick TiC layer. The comparative product No. 1 is shown in Fig. 1 (a).
The coating layer had a crystalline diamond-like structure similar to that of the diffraction line.
（発明の効果） 以上の結果から、本発明の高密着性ダイヤモンド被覆部
材は、外層と基材との密着性が著しくすぐれていて、従
来のダイヤモンド被覆部材に対して数倍から数１０倍の
耐剥離性があり、それに伴って寿命も向上するものであ
る。このために、苛酷な重負荷の作用する切削工具とし
て、例えば旋削工具は勿論のことフライス工具，ドリ
ル，エンドミル，及びミクロンドリルなどの回転用工具
に応用でき、又印字ピンの先端もしくは紙や磁気テープ
などの切断用スリッターを含めた耐摩耗用工具にも応用
できる。さらに、ダイヤモンド自体が有している高電気
絶縁性及び高熱伝導性を利用してヒートシンクをはじめ
とするエレクトロニクス用部材並びに核融合炉の炉壁に
代表される原子炉用部材にと応用できる産業上有用な材
料である。(Effects of the Invention) From the above results, the high-adhesion diamond-coated member of the present invention has remarkably excellent adhesion between the outer layer and the substrate, and is several times to several tens of times that of the conventional diamond-coated member. It has resistance to peeling, and the life of the product is accordingly improved. For this reason, it can be applied as a cutting tool under a severe heavy load, for example, not only a turning tool but also a rotary tool such as a milling tool, a drill, an end mill, and a micron drill. It can also be applied to wear resistant tools including cutting slitters such as tape. Furthermore, by utilizing the high electrical insulation and high thermal conductivity of diamond itself, it can be applied to electronic components such as heat sinks and nuclear reactor components typified by the walls of fusion reactors. It is a useful material.
第１図は、実施例１で得た被覆部材の被覆層のラマン分
光分析における回折線である。 回折線（ａ）は、結晶質ダイヤモンド状構造の代表的回
折線 回折線（ｂ），（ｃ）は、非晶質カーボン状構造の代表
的回折線FIG. 1 is a diffraction line in a Raman spectroscopic analysis of the coating layer of the coating member obtained in Example 1. Diffraction lines (a) are typical diffraction lines of crystalline diamond-like structure Diffraction lines (b) and (c) are typical diffraction lines of amorphous carbon-like structure
Claims (3)
外層を形成してなる被覆部材であって、該基材と該外層
との間に１層又は多層で構成される中間層を介在させ、
該中間層は、該外層に隣接する非晶質カーボン状構造の
層と該非晶質カーボン状構造の層に隣接する密着補助層
とからなり、該密着補助層が周期律表4a,5a,6a族の金属
又はSiの炭化物，窒化物，酸化物，ホウ化物もしくはAl
の窒化物，ホウ化物，酸化物及びこれらの相互固溶体の
中の少なくとも１種でなる単層あるいは２種以上でなる
多層からなることを特徴とする高密着性ダイヤモンド被
覆部材。1. A covering member comprising an outer layer having a crystalline diamond-like structure formed on the surface of a substrate, wherein an intermediate layer composed of one layer or multiple layers is interposed between the substrate and the outer layer. Let
The intermediate layer is composed of a layer having an amorphous carbon-like structure adjacent to the outer layer and an adhesion auxiliary layer adjacent to the layer having an amorphous carbon-like structure, and the adhesion auxiliary layer comprises the periodic table 4a, 5a, 6a. Group metals or Si carbides, nitrides, oxides, borides or Al
A high-adhesion diamond-coated member comprising a single layer of at least one of the above-mentioned nitrides, borides, oxides, and a mutual solid solution thereof or a multilayer of two or more thereof.
〜20μｍの厚さであることを特徴とする特許請求の範囲
第１項記載の高密着性ダイヤモンド被覆部材。2. The layer of amorphous carbon-like structure is 100 Å
The high-adhesion diamond-coated member according to claim 1, which has a thickness of ˜20 μm.
ことを特徴とする特許請求の範囲第１項又は第２項記載
の高密着性ダイヤモンド被覆部材。3. The high-adhesion diamond-coated member according to claim 1 or 2, wherein the outer layer has a thickness of 0.1 μm to 100 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61036161A JPH06951B2 (en) | 1986-02-20 | 1986-02-20 | High adhesion diamond coated member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61036161A JPH06951B2 (en) | 1986-02-20 | 1986-02-20 | High adhesion diamond coated member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62196371A JPS62196371A (en) | 1987-08-29 |
| JPH06951B2 true JPH06951B2 (en) | 1994-01-05 |
Family
ID=12462040
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61036161A Expired - Lifetime JPH06951B2 (en) | 1986-02-20 | 1986-02-20 | High adhesion diamond coated member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06951B2 (en) |
Families Citing this family (27)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5462772A (en) * | 1957-06-27 | 1995-10-31 | Lemelson; Jerome H. | Methods for forming artificial diamond |
| US6083570A (en) * | 1987-03-31 | 2000-07-04 | Lemelson; Jerome H. | Synthetic diamond coatings with intermediate amorphous metal bonding layers and methods of applying such coatings |
| JPH07116606B2 (en) * | 1987-10-31 | 1995-12-13 | 住友電気工業株式会社 | Diamond coated carbon material |
| JP2564627B2 (en) * | 1988-10-11 | 1996-12-18 | 株式会社半導体エネルギー研究所 | Member covered with carbon film and manufacturing method thereof |
| US5204167A (en) * | 1989-02-23 | 1993-04-20 | Toshiba Tungaloy Co., Ltd. | Diamond-coated sintered body excellent in adhesion and process for preparing the same |
| US5334453A (en) * | 1989-12-28 | 1994-08-02 | Ngk Spark Plug Company Limited | Diamond-coated bodies and process for preparation thereof |
| US5075094A (en) * | 1990-04-30 | 1991-12-24 | The United States Of America As Represented By The Secretary Of The Navy | Method of growing diamond film on substrates |
| JP2624561B2 (en) * | 1990-05-11 | 1997-06-25 | 工業技術院長 | Amorphous hard carbon film coated diamond tool |
| CA2044543C (en) * | 1990-08-10 | 1999-12-14 | Louis Kimball Bigelow | Multi-layer superhard film structure |
| CA2060823C (en) * | 1991-02-08 | 2002-09-10 | Naoya Omori | Diamond-or diamond-like carbon-coated hard materials |
| JP2929779B2 (en) * | 1991-02-15 | 1999-08-03 | トヨタ自動車株式会社 | Water-repellent glass with carbon coating |
| US5147687A (en) * | 1991-05-22 | 1992-09-15 | Diamonex, Inc. | Hot filament CVD of thick, adherent and coherent polycrystalline diamond films |
| US5827613A (en) * | 1992-09-04 | 1998-10-27 | Tdk Corporation | Articles having diamond-like protective film and method of manufacturing the same |
| US5740941A (en) * | 1993-08-16 | 1998-04-21 | Lemelson; Jerome | Sheet material with coating |
| US5593719A (en) * | 1994-03-29 | 1997-01-14 | Southwest Research Institute | Treatments to reduce frictional wear between components made of ultra-high molecular weight polyethylene and metal alloys |
| US5725573A (en) * | 1994-03-29 | 1998-03-10 | Southwest Research Institute | Medical implants made of metal alloys bearing cohesive diamond like carbon coatings |
| US5731045A (en) * | 1996-01-26 | 1998-03-24 | Southwest Research Institute | Application of diamond-like carbon coatings to cobalt-cemented tungsten carbide components |
| US5605714A (en) * | 1994-03-29 | 1997-02-25 | Southwest Research Institute | Treatments to reduce thrombogeneticity in heart valves made from titanium and its alloys |
| US5984905A (en) | 1994-07-11 | 1999-11-16 | Southwest Research Institute | Non-irritating antimicrobial coating for medical implants and a process for preparing same |
| US5714202A (en) * | 1995-06-07 | 1998-02-03 | Lemelson; Jerome H. | Synthetic diamond overlays for gas turbine engine parts having thermal barrier coatings |
| US5616372A (en) * | 1995-06-07 | 1997-04-01 | Syndia Corporation | Method of applying a wear-resistant diamond coating to a substrate |
| US5688557A (en) * | 1995-06-07 | 1997-11-18 | Lemelson; Jerome H. | Method of depositing synthetic diamond coatings with intermediates bonding layers |
| US5780119A (en) * | 1996-03-20 | 1998-07-14 | Southwest Research Institute | Treatments to reduce friction and wear on metal alloy components |
| US5871805A (en) * | 1996-04-08 | 1999-02-16 | Lemelson; Jerome | Computer controlled vapor deposition processes |
| EP1067210A3 (en) * | 1996-09-06 | 2002-11-13 | Sanyo Electric Co., Ltd. | Method for providing a hard carbon film on a substrate and electric shaver blade |
| US8555921B2 (en) | 2002-12-18 | 2013-10-15 | Vapor Technologies Inc. | Faucet component with coating |
| JP2008100301A (en) * | 2006-10-17 | 2008-05-01 | Ngk Spark Plug Co Ltd | Diamond coated cutting insert and cutting tool |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6173882A (en) * | 1984-09-17 | 1986-04-16 | Sumitomo Electric Ind Ltd | Super hard layer coating material |
-
1986
- 1986-02-20 JP JP61036161A patent/JPH06951B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62196371A (en) | 1987-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH06951B2 (en) | High adhesion diamond coated member | |
| US4992082A (en) | Method of toughening diamond coated tools | |
| EP0378378B1 (en) | Making diamond composite coated cutting tools. | |
| US4988421A (en) | Method of toughening diamond coated tools | |
| US4707384A (en) | Method for making a composite body coated with one or more layers of inorganic materials including CVD diamond | |
| RU2138396C1 (en) | Diamond coated substrate | |
| CA2029873A1 (en) | Diamond-coated member and process for the preparation thereof | |
| US6268045B1 (en) | Hard material coating of a cemented carbide or carbide containing cermet substrate | |
| JP3214891B2 (en) | Diamond coated members | |
| US5607264A (en) | Tool with diamond cutting edge having vapor deposited metal oxide layer and a method of making and using such tool | |
| JPH0558067B2 (en) | ||
| JPH06262405A (en) | Coating part for tool | |
| JPH0583634B2 (en) | ||
| US20070214727A1 (en) | Coated Abrasives | |
| JPS6155591B2 (en) | ||
| JPS6312940B2 (en) | ||
| JP2797612B2 (en) | Artificial diamond coated hard sintering tool member with high adhesion strength | |
| JPH0542508B2 (en) | ||
| JPH0558066B2 (en) | ||
| JPH05295517A (en) | Multilayer-coated sintered alloy with crystal orientation | |
| JP3235206B2 (en) | Diamond cutting tool and manufacturing method thereof | |
| JP3371796B2 (en) | Surface coated cemented carbide cutting tool with excellent fracture resistance | |
| JPS59170264A (en) | Surface coated sintered hard alloy member for cutting tool | |
| JPS6257802A (en) | Parts coated with hard carbon | |
| JPH0582473B2 (en) |