JPS62226889A - Vapor phase synthesis method for filmy diamond - Google Patents
Vapor phase synthesis method for filmy diamondInfo
- Publication number
- JPS62226889A JPS62226889A JP6962186A JP6962186A JPS62226889A JP S62226889 A JPS62226889 A JP S62226889A JP 6962186 A JP6962186 A JP 6962186A JP 6962186 A JP6962186 A JP 6962186A JP S62226889 A JPS62226889 A JP S62226889A
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- substrate
- vapor phase
- phase synthesis
- film
- 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.)
- Granted
Links
- 239000010432 diamond Substances 0.000 title claims abstract description 69
- 229910003460 diamond Inorganic materials 0.000 title claims abstract description 67
- 239000012808 vapor phase Substances 0.000 title claims abstract description 21
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 69
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 10
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- 229910052582 BN Inorganic materials 0.000 claims abstract description 8
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 27
- 239000011247 coating layer Substances 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 238000007796 conventional method Methods 0.000 description 11
- 239000006061 abrasive grain Substances 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 3
- 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 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- -1 cermets Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241000022563 Rema Species 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
Landscapes
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
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
具部品、核融合炉の炉壁に代表される原子炉用部品、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
クス用部品並びにカメラ。Detailed Description of the Invention (Field of Industrial Application) The present invention is applicable to tool parts such as cutting tools, wear-resistant tools, or grinding tools, nuclear reactor parts such as the reactor wall of a nuclear fusion reactor, heat sinks, or speakers. Electronic parts such as diaphragms and cameras.
時計などの精ｖ、ａ械部品などの作成用として各種の産
業分野で応用できる膜状ダイヤモンドの気相合成法に関
するものである。The present invention relates to a method of vapor phase synthesis of film-like diamond, which can be applied in various industrial fields for the production of mechanical parts such as watches and other mechanical parts.
（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、イオンブレーティング法、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、熱電子放射材を利用
した化学蒸若法、マイクロ波、高周波又は直流を利用し
たプラズマ化学蒸着法などがある。(Prior art) Methods for synthesizing diamond from the gas phase include sputtering, ion blating, ion beam evaporation, which is a combination of vapor deposition and ion implantation, and chemical vapor deposition using a thermionic emitter. , plasma chemical vapor deposition using microwaves, high frequencies, or direct current.
これらのダイヤモンドの合成法において用いられる基板
は、基板の表面にダイヤモンドが析出され易いようにす
ると共に析出れたダイヤモンドの被覆層と基板との密看
性を高めるようにすることが試みられている。このため
の方法としては、１つに基板の材質を検討する方法があ
り、他の１つに基板の表面状態を検討する方法がある。Attempts have been made to make the substrate used in these diamond synthesis methods so that it is easy to deposit diamond on the surface of the substrate, and to improve the tightness between the deposited diamond coating layer and the substrate. . One method for this purpose is to examine the material of the substrate, and another method is to examine the surface condition of the substrate.
この内、後者に関しての代表的なものとしては、特開昭
６０−８６０９６号公報に開示されたものがある。Among these, a typical example of the latter is disclosed in Japanese Patent Application Laid-Open No. 60-86096.
（発明が解決しようとする問題点）
特開昭６０−８６０９６号公報は、炭化水素と水素との
混合ガスにプラズマを誘発せしめ、このプラズマ空間に
基板を設置し、該基板を３００〜１３００℃に加熱して
基板上にダイヤモンドを析出させるダイヤモンドの気相
合成法において、基板表面を高硬度粉末で摩擦または衝
突の処理を施して鋭利な表面傷を生成させていることを
特徴とする方法である。この特開昭６０−８６０９６号
公報における基板の表面処理は、高硬度粉末を直接摩擦
または衝突させる方法、もしくは高硬度粉末にワセリン
等の滑剤を混和させたもので摩擦させる方法であり、そ
の処理表面は鋭利な表面傷を生成させてなるものである
。この方法によると基板が曲面形状又は複雑な形状の場
合は、基板の表面に均一な傷を施すのが困難であり、そ
のために、基板の表面に均一な膜状のダイヤモンドを形
成できないという問題がある。また、この方法では、基
板の表面におけるダイヤモンドの核生成密度が低いため
に緻密で微細な膜状のダイヤモンドの形成が困難となり
、しかも基板とダイヤモンドの膜との密着性及び膜の強
度が劣るという問題がある。(Problems to be Solved by the Invention) JP-A-60-86096 discloses that plasma is induced in a mixed gas of hydrocarbon and hydrogen, a substrate is placed in this plasma space, and the substrate is heated at 300 to 1300°C. A method of diamond vapor phase synthesis in which diamond is precipitated on a substrate by heating the substrate to a temperature of be. The surface treatment of the substrate in this Japanese Patent Application Laid-open No. 60-86096 is a method of directly rubbing or colliding high hardness powder, or a method of rubbing with high hardness powder mixed with a lubricant such as vaseline. The surface is formed by producing sharp surface scratches. According to this method, if the substrate has a curved or complicated shape, it is difficult to make uniform scratches on the surface of the substrate, and therefore, there is a problem that a uniform diamond film cannot be formed on the surface of the substrate. be. In addition, with this method, the density of diamond nucleation on the surface of the substrate is low, making it difficult to form a dense and fine film of diamond, and furthermore, the adhesion between the substrate and the diamond film and the strength of the film are poor. There's a problem.
本発明は、上述のような問題点を解決したもので、Ａ体
重には、超音波を用いて、溶液を媒介にした硬質粒子に
より基板の表面を処理し、この表面処理した基板にダイ
ヤモンドを析出させることによって１ｉ＆密で微細な膜
状のダイヤモンドの被覆層を形成させることができるダ
イヤモンドの気相合成法の提供を目的とするものである
。The present invention solves the above-mentioned problems, and for weight A, the surface of the substrate is treated with hard particles mediated by a solution using ultrasonic waves, and diamond is applied to the surface-treated substrate. The object of the present invention is to provide a method for vapor phase synthesis of diamond, which can form a diamond coating layer in the form of a dense and fine film by precipitation.
（問題点を解決するための手段）
本発明者らは、基板の表面におけるダイヤモンドの核生
成密度を高める方法として、基板の表面処理法について
種々検討した結果、水、エタノール又はアセトンなどの
溶液を満たした容器中にダイヤモンド、立方晶窒化ホウ
素又は窒化ケイ素などの砥粒と共に基板を浸漬させた後
、溶液中に所定の出力の超音波を所定の時間入射させる
ことによって得た基板の表面にダイヤモンドを析出させ
ると緻密で微細な膜状のダイヤモンドの被覆層が形成さ
れるという知見を得ることによって本発明を完成するに
至ったものである。(Means for Solving the Problems) As a method for increasing the density of diamond nucleation on the surface of a substrate, the present inventors investigated various surface treatment methods for the substrate, and found that a solution such as water, ethanol, or acetone was used. After immersing the substrate with abrasive grains such as diamond, cubic boron nitride, or silicon nitride in a filled container, diamond is applied to the surface of the substrate obtained by injecting ultrasonic waves of a predetermined power into the solution for a predetermined time. The present invention was completed by obtaining the knowledge that a dense and fine film-like diamond coating layer is formed when the diamond is precipitated.
すなわち、本発明の膜状ダイヤモンドの気相合成法は、
炭素含有化合物ガスと水素ガスとが存在する雰囲気中で
基板の表面にダイヤモンドの被覆層を形成させるダイヤ
モンドの低圧気相合成法において、前記基板は硬質粒子
と共に溶液中に浸漬させた後、該溶液中に超音波を入射
させて処理したことを特徴とするものである。That is, the vapor phase synthesis method of film-like diamond of the present invention is as follows:
In a low-pressure vapor phase diamond synthesis method in which a diamond coating layer is formed on the surface of a substrate in an atmosphere containing carbon-containing compound gas and hydrogen gas, the substrate is immersed in a solution together with hard particles, and then the solution is immersed in the solution. It is characterized by being treated by injecting ultrasonic waves into it.
本発明の膜状ダイヤモンドの気相合成法における基板の
表面処理に用いる硬質粒子はダイヤモンド粉末、立方晶
窒化ホウ素粉末、炭化ケイ素粉末、酸化アルミニウム粉
末、酸化クロム粉末などの砥粒があり、その他、基板の
材質に合わせて、例えばガラス粉末、鉄粉末などの各種
の粉末を用いることができる。これらの硬質粒子の選定
基準としては、基板の材質よりも硬い材質のものならば
、特に制限されることなく用いることができ、特にダイ
ヤモンド粉末、立方晶窒化ホウ素粉末又は炭化ケイ素粉
末は高硬度粉末であることから好ましいものである。こ
れらの硬質粒子の大きさは、超音波の振幅の強さなどに
よっても異なるが、１１００ｐ以下の粒子の大きさのも
のを用いることができ、特に１０．ｍ以下の粒子の大き
さの硬質粒子を用いると基板の表面を均一に処理できる
ので好ましいものである。The hard particles used for surface treatment of the substrate in the vapor phase synthesis method of film-like diamond of the present invention include abrasive grains such as diamond powder, cubic boron nitride powder, silicon carbide powder, aluminum oxide powder, and chromium oxide powder; Various powders such as glass powder and iron powder can be used depending on the material of the substrate. The selection criteria for these hard particles is that any material that is harder than the material of the substrate can be used without any particular restriction. In particular, diamond powder, cubic boron nitride powder, or silicon carbide powder is a high-hardness powder. Therefore, it is preferable. The size of these hard particles varies depending on the amplitude of the ultrasonic wave, etc., but particles with a particle size of 1100p or less can be used, and in particular 10. It is preferable to use hard particles having a particle size of m or less because the surface of the substrate can be uniformly treated.
この硬質粒子と基板との両方を浸漬させるための溶液は
、硬質粒子及び基板との化学的反応が生じなく、しかも
硬質粒子が超音波の振幅によって自由に運動できるよう
な粘性のものならば、特に制限されなく、例えば水又は
エタノール、アセトンなどの各種の有機溶液を用いるこ
とができる。If the solution for immersing both the hard particles and the substrate has a viscosity that does not cause any chemical reaction with the hard particles and the substrate and allows the hard particles to move freely due to the amplitude of the ultrasonic waves, There are no particular limitations, and for example, water or various organic solutions such as ethanol and acetone can be used.
本発明で用いる基板は、従来のダイヤモンドの低圧気相
合成法の条件に耐えることができる材質ならば、特に制
限されるものでなく、用途に応じて、例えば各種の金属
９合金、超硬合金、サーメット又はセラミックスなどを
用いることができる。これらの基板の内、超硬合金、サ
ーメットなどの基板は、基板の表面に存在する鉄族金属
を除去した後に用いるか、又は基板の表面に炭化チタン
、窒化チタンなどの被覆層を形成した複合材料として用
いるのが好ましい、また、ステンレス。The substrate used in the present invention is not particularly limited as long as it can withstand the conditions of the conventional low-pressure vapor phase synthesis method for diamond. , cermet or ceramics can be used. Among these substrates, substrates made of cemented carbide, cermet, etc. are used after removing the iron group metal present on the surface of the substrate, or composite substrates are used after forming a coating layer of titanium carbide, titanium nitride, etc. on the surface of the substrate. Preferably used as material is also stainless steel.
炭素鋼などの各種の鉄系合金、ハステロイ、インコネル
などのニッケル系合金、ステライトなどのコバルト系合
金のように鉄族金属からなる基板の場合も炭化チタン、
窒化チタンなどの被覆層を基板の表面に形成させた複合
材料として用いるのが好ましい。Titanium carbide, titanium carbide,
It is preferable to use a composite material in which a coating layer such as titanium nitride is formed on the surface of a substrate.
溶液を満たした容器に基板と硬質粒子を浸漬させて、こ
の溶液に超音波を入射させることにより基板の表面を処
理する。このときの超音波の強度は、特に制限されるも
のではなく、溶液に超音波の振動エネルギーが伝搬され
て溶液と硬質粒子の運動が生じる強度にすればよい、ま
た、硬質粒子の分散性を高めるために活面活性剤を溶液
中に添加して、硬質粒子を均一に分散させることにより
基板の表面処理効果を高めることも好ましいことである
。このような処理を施した基板の表面は、例えば、砥粒
で摩擦又は研磨による表面傷のような幾何学的変化が生
じていなくてもよい、この処理を施す前の基板の表面は
、超硬合金、サーメット又はセラミックスからなる基板
の場合には焼肌面の状態又は研磨面の状態で表面処理を
施こせばよく、また金属や合金からなる基板の場合には
鍛造面、圧延面又は引抜き面など、その材料が加工され
てきた表面状態のまま、もしくは研磨面の状態で表面処
理を施こせばよい。The substrate and hard particles are immersed in a container filled with a solution, and ultrasonic waves are applied to the solution to treat the surface of the substrate. The intensity of the ultrasonic waves at this time is not particularly limited, and may be set to an intensity that causes the vibration energy of the ultrasonic waves to propagate into the solution and cause movement of the solution and the hard particles. It is also preferable to add a surfactant to the solution to enhance the surface treatment effect of the substrate by uniformly dispersing the hard particles. The surface of the substrate subjected to such treatment may be free of any geometrical changes, such as surface scratches caused by friction or polishing with abrasive grains.The surface of the substrate before this treatment is In the case of substrates made of hard metals, cermets, or ceramics, the surface treatment may be performed on a hardened surface or polished surface, and in the case of substrates made of metals or alloys, surface treatment may be performed on a forged surface, rolled surface, or drawn surface. The surface treatment may be performed on the surface of the material as it has been processed, such as a surface, or on the polished surface.
このように表面処理を施した基板を従来のダイヤモンド
気相合成用の反応容器内に設置して、炭素含有化合物ガ
スと水素ガスとを反応容器内に導入し、これらのガスを
熱電子放射材での加熱分解、又はマイクロ波、高周波、
直流などによるプラズマによって分解して基板表面にダ
イヤモンド被覆層を形成させればよい、このときのガス
の加熱分解又は分解条件は、従来の条件を用いればよく
、必要に応じて基板を加熱又は冷却することによって基
板を一定の温度に保持することも好ましいことである。The substrate that has been surface-treated in this way is placed in a conventional reaction vessel for diamond vapor phase synthesis, and carbon-containing compound gas and hydrogen gas are introduced into the reaction vessel, and these gases are used as a thermionic emitter material. thermal decomposition, or microwave, high frequency,
A diamond coating layer may be formed on the surface of the substrate by decomposition by plasma generated by direct current, etc. At this time, conventional gas thermal decomposition or decomposition conditions may be used, and the substrate may be heated or cooled as necessary. It is also preferable to maintain the substrate at a constant temperature by doing so.
ここで用いる炭素含有化合物ガスとは、メタンに代表さ
れる炭化水素系化合物、アセトンに代表されるケトン系
化合物、メチルアルコールに代表されるヒドロキシ系化
合物又はＣＣ１ａに代表されるハロゲン化炭素化合物で
ある。The carbon-containing compound gas used here is a hydrocarbon compound represented by methane, a ketone compound represented by acetone, a hydroxy compound represented by methyl alcohol, or a halogenated carbon compound represented by CC1a. .
（作用）
本発明の膜状ダイヤモンドの気相合成法は、基板の表面
に微細なダイヤモンド粒子が緻密な被覆層として形成さ
れ、しかも基板と被覆層との密着性が高くなるものであ
る。また、基板の表面に形成される被覆層は、結晶性の
すぐれたダイヤモンドからなっているものである。(Function) In the vapor phase synthesis method of film-like diamond of the present invention, fine diamond particles are formed as a dense coating layer on the surface of a substrate, and the adhesion between the substrate and the coating layer is increased. Further, the coating layer formed on the surface of the substrate is made of diamond with excellent crystallinity.
（実施例）
実施例１
１２００＃のダイヤモンド砥石で研磨したＷＣ−５％Ｃ
Ｏ超硬合金からなる基板を平均粒径３．０ｇｍダイヤモ
ンド砥粒と共にエチルアルコール溶液を満たした容器に
入れて、溶液内に超「波を入射させた。このときの各条
件は、エチルアルコールに対するダイヤモンド砥粒の濃
度がエチルアルコールｉｃｅあたり０．８ｇ、入射した
超音波の強さが０ 、３Ｗ／ａｍ２．周波数が４０ Ｋ
Ｈ２、入射時間が１時間であった。(Example) Example 1 WC-5%C polished with a 1200# diamond whetstone
A substrate made of O cemented carbide and diamond abrasive grains with an average particle size of 3.0 g were placed in a container filled with an ethyl alcohol solution, and a superwave was introduced into the solution. The concentration of diamond abrasive grains is 0.8 g per ethyl alcohol ice, the intensity of the incident ultrasonic wave is 0, 3 W/am2, and the frequency is 40 K.
H2, the injection time was 1 hour.
このような超音波処理を施した基板の表面にマイクロ波
を利用した従来と同様のプラズマＣｖＤ法によりダイヤ
モンド膜を形成させた。（本発明法）
比較として、上記の超音波処理を施さない上記と同質の
基板の表面に上記と同条件にしてダイヤモンド膜を形成
させた。（従来法）
本発明法によって得た試料と従来法によって得た試料を
それぞれ走査電子顕微鏡写真にて観察した結果１本発明
法による試料は第１図に示す如く緻密で微細な粒子から
なるダイヤモンド被覆層であるのに対して、従来法によ
る試料は第２図に示す如く殆んどダイヤモンドの膜が形
成しておらすその粒径も粗いものであった。A diamond film was formed on the surface of the substrate subjected to such ultrasonic treatment by a conventional plasma CvD method using microwaves. (Method of the Present Invention) For comparison, a diamond film was formed on the surface of a substrate of the same quality as above, which was not subjected to the above-mentioned ultrasonic treatment, under the same conditions as above. (Conventional method) As a result of observing the samples obtained by the method of the present invention and the samples obtained by the conventional method using scanning electron micrographs, it was found that the sample obtained by the method of the present invention was a diamond consisting of dense and fine particles, as shown in Figure 1. In contrast to the coating layer, the sample prepared by the conventional method had a mostly diamond film formed thereon, and its grain size was coarse, as shown in FIG.
実施例２
ＣＩＳ規格５ＰＧＮ４２２形状のＷＣ−６％Ｃｏ超硬合
金からなる基板を酸処理した後、平均粒径１．Ｏｐｍの
立方晶窒化ホウ素砥粒と共に水を満たした容器に入れて
、水中に超音波を入射した。このとさの各条件は、水に
対する立方晶窒化ホウ素砥粒の濃度が水１ｃｃあたり０
．５ｇ、入射した超音波の強さが０．４Ｗ／ｃ層２、周
波数が４０ＫＨ／、入射時間が１時間であった。Example 2 A substrate made of WC-6% Co cemented carbide having a shape of CIS standard 5PGN422 was acid-treated, and then the average grain size was 1. It was placed in a container filled with water together with Opm's cubic boron nitride abrasive grains, and ultrasonic waves were applied to the water. Each of these conditions is such that the concentration of cubic boron nitride abrasive grains in water is 0 per cc of water.
．． 5 g, the intensity of the incident ultrasonic waves was 0.4 W/c layer 2, the frequency was 40 KH/, and the incident time was 1 hour.
このような超音波処理を施した基板の表面にマイクロ波
を利用した従来と同様のプラズマＣＶＤ法によりダイヤ
モンド膜を形成させた。（本発明法）
比較として、Ｌ記の超音波処理を施さない上記と同質の
基板の表面に立方晶窒化ホウ素砥粒で研磨して傷を付け
た後上記と同条件にしてダイヤモンド膜を形成させた。A diamond film was formed on the surface of the substrate subjected to such ultrasonic treatment by a conventional plasma CVD method using microwaves. (Method of the present invention) For comparison, the surface of a substrate of the same quality as above without the ultrasonic treatment described in L was polished and scratched with cubic boron nitride abrasive grains, and then a diamond film was formed under the same conditions as above. I let it happen.
（従来法）
本発明法によって得た試料と従来法によって得た試料と
ダイヤモンド膜を形成させてない基板のままの試料を被
削材Ａｕ−１８％Ｓｉ合金、切削速度２００ ｍ／ｗｉ
ｎ 、切り込み埴０．５ｍｍ、送り速度０ 、２ ｔｉ
ｔｓ／ｒｅマの条件で旋削試験した所、本発明法による
試料のフランク摩耗量は、従来法による試料の約局で、
従来法による試料のフランク摩耗量は、基板のままの試
料の約埼であった。(Conventional method) A sample obtained by the method of the present invention, a sample obtained by the conventional method, and a sample with a substrate on which no diamond film was formed were cut using an Au-18% Si alloy as the work material and a cutting speed of 200 m/wi.
n, incision 0.5mm, feed speed 0, 2ti
When a turning test was conducted under the conditions of ts/rema, the amount of flank wear of the sample prepared by the method of the present invention was approximately that of the sample prepared by the conventional method.
The amount of flank wear of the sample obtained by the conventional method was approximately the same as that of the sample with the substrate intact.
実施例３
Ｓｉ単結晶の薄板からなる基板を平均粒径８、Ｏｐｍの
ＳｉＣ砥粒と共にヘキサン溶液を満たした容器に入れて
、溶液内に超音波を入射させた。このときの条件は、実
施例２と同条件で行なった。Example 3 A substrate made of a thin Si single crystal plate was placed in a container filled with a hexane solution together with SiC abrasive grains having an average grain size of 8 Opm, and ultrasonic waves were applied to the solution. The conditions at this time were the same as in Example 2.
この超音波処理を行なった基板の表面にマイクロ波を利
用した従来のプラズマＣＶＤ法の条件でダイヤモンド膜
を形成させた。（本発明法）比較として、同一基板の表
面をＳｉＣ砥粒で研磨して傷を付けた後、上記と同条件
にてダイヤモンド膜を形成させた。（従来法）
この本発明法による試料と従来法による試料の被覆層を
電子′！ｊＡ微鏡で観察した所、本発明法にょる試料は
、緻密で微細なダイヤモンドからなる被覆層であったの
に対して、従来法による試料は膜状のダイヤモンドが形
成されてなく、ダイヤモンドの粒子が疎らに付着してい
る状態であった。A diamond film was formed on the surface of the ultrasonic-treated substrate under conventional plasma CVD conditions using microwaves. (Method of the present invention) For comparison, the surface of the same substrate was scratched by polishing with SiC abrasive grains, and then a diamond film was formed under the same conditions as above. (Conventional method) The coating layers of the sample prepared by the method of the present invention and the sample prepared by the conventional method were separated using electronic '! When observed with a jA microscope, the sample prepared using the present invention method had a coating layer made of dense and fine diamonds, whereas the sample prepared using the conventional method did not have a film-like diamond layer formed on it. The particles were loosely attached.
（発明の効果）
以上の結果から、本発明の膜状ダイヤモンドの気相合成
法は、微細なダイヤモンドを緻密で膜状のダイヤモンド
からなる被覆層として形成させることができる方法であ
る。この本発明の膜状ダイヤモンドの気相合成法は、膜
状ダイヤモンドの析出速度が速くて、この膜状ダイヤモ
ンドからなる被覆層と基板との密着性がすぐれているも
のである。(Effects of the Invention) From the above results, the method for vapor phase synthesis of film-like diamond of the present invention is a method that can form fine diamonds as a covering layer made of dense film-like diamond. In the vapor phase synthesis method of film-like diamond of the present invention, the deposition rate of film-like diamond is fast, and the adhesion between the coating layer made of film-like diamond and the substrate is excellent.
このために、本発明の膜状ダイヤモンドの気相合成法は
、切削工具、＃摩耗工具又は研削工具などの工具部品、
核融合炉の炉壁に代表される原子炉用部品、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用部
品並びにカメラ、時計などの精密機械部品などに膜状ダ
イヤモンドを作製するのに応用できる各種の産業分野に
有用なダイヤモンドの気相合成法である。For this purpose, the vapor phase synthesis method of film-like diamond of the present invention can be applied to tool parts such as cutting tools, worn tools, or grinding tools.
Various industries where diamond film can be applied to the production of nuclear reactor parts such as the reactor walls of fusion reactors, electronic parts such as heat sinks or speaker diaphragms, and precision mechanical parts such as cameras and watches. This is a diamond vapor phase synthesis method useful in the field.
第１図は、実施例１で得た本発明の膜状ダイヤモンドの
気相合成法による試料を走査電子！１１微鏡により観察
した表面層のダイヤモンド粒子構造である。
第２図は、実施例１で得た従来法による試料を走査゛１
［子顕微鏡により観察した表面層のダイヤモンド粒子構
造である。Figure 1 shows a sample of the film-like diamond of the present invention obtained in Example 1 obtained by vapor phase synthesis using an electron beam scan. This is the diamond grain structure of the surface layer observed with a No. 11 microscope. Figure 2 shows the sample scanned by the conventional method obtained in Example 1.
[This is the diamond grain structure of the surface layer observed using a submicroscope.]
Claims (3)
気中で基板の表面にダイヤモンドの被覆層を形成させる
ダイヤモンドの低圧気相合成法において、前記基板は硬
質粒子と共に溶液中に浸炭させた後、該溶液中に超音波
を入射させて処理したことを特徴とする膜状ダイヤモン
ドの気相合成法。(1) In a low-pressure vapor phase diamond synthesis method in which a diamond coating layer is formed on the surface of a substrate in an atmosphere containing carbon-containing compound gas and hydrogen gas, the substrate is carburized in a solution together with hard particles. A method for vapor phase synthesis of film-like diamond, characterized in that the process is performed by injecting ultrasonic waves into the solution.
ホウ素粉末又は炭化ケイ素粉末の中の少なくとも１種で
あることを特徴とする特許請求の範囲第１項記載の膜状
ダイヤモンドの気相合成法。(2) The method for vapor phase synthesis of film-like diamond according to claim 1, wherein the hard particles are at least one of diamond powder, cubic boron nitride powder, and silicon carbide powder. .
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
の膜状ダイヤモンドの気相合成法。(3) The method for vapor phase synthesis of film-like diamond according to claim 1 or 2, wherein the solution is water, ethanol, or acetone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069621A JPH0643280B2 (en) | 1986-03-27 | 1986-03-27 | Vapor phase synthesis of film diamond |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61069621A JPH0643280B2 (en) | 1986-03-27 | 1986-03-27 | Vapor phase synthesis of film diamond |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62226889A true JPS62226889A (en) | 1987-10-05 |
| JPH0643280B2 JPH0643280B2 (en) | 1994-06-08 |
Family
ID=13408125
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61069621A Expired - Lifetime JPH0643280B2 (en) | 1986-03-27 | 1986-03-27 | Vapor phase synthesis of film diamond |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0643280B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0343846A2 (en) * | 1988-05-27 | 1989-11-29 | Xerox Corporation | Process for the preparation of polycrystalline diamond |
| JPH04132691A (en) * | 1990-09-25 | 1992-05-06 | Nec Corp | Production of diamond thin film by gaseous phase method using diamond fine powder as seed crystal |
| US5198070A (en) * | 1988-04-28 | 1993-03-30 | Jones Barbara L | Joining diamond bodies |
| US6110240A (en) * | 1996-05-31 | 2000-08-29 | Ngk Spark Plug Co., Ltd. | Superhard article with diamond coat and method of manufacturing same |
| JP2011514848A (en) * | 2008-03-10 | 2011-05-12 | モルガン アドバンスド セラミックス， インコーポレイテッド | Non-planar CVD diamond coated CMP pad conditioner and method of manufacturing the same |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5814536A (en) * | 1981-07-17 | 1983-01-27 | Matsushita Electric Ind Co Ltd | Treating method for surface of chemical compound semiconductor |
| JPS58126972A (en) * | 1982-01-22 | 1983-07-28 | Sumitomo Electric Ind Ltd | Diamond coated sintered hard alloy tool |
| JPS6076274A (en) * | 1983-09-30 | 1985-04-30 | Fuji Electric Co Ltd | Brazing method using aluminum |
| JPS6086096A (en) * | 1983-10-18 | 1985-05-15 | Natl Inst For Res In Inorg Mater | Precipitation of filmy diamond |
| JPS60204899A (en) * | 1984-03-28 | 1985-10-16 | Souzou Kagaku Gijutsu Kenkyusho:Kk | Surface treatment |
| JPS61121859A (en) * | 1984-11-15 | 1986-06-09 | Showa Denko Kk | Method of processing substrate for use in diamond synthesis by vapor phase method |
-
1986
- 1986-03-27 JP JP61069621A patent/JPH0643280B2/en not_active Expired - Lifetime
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5814536A (en) * | 1981-07-17 | 1983-01-27 | Matsushita Electric Ind Co Ltd | Treating method for surface of chemical compound semiconductor |
| JPS58126972A (en) * | 1982-01-22 | 1983-07-28 | Sumitomo Electric Ind Ltd | Diamond coated sintered hard alloy tool |
| JPS6076274A (en) * | 1983-09-30 | 1985-04-30 | Fuji Electric Co Ltd | Brazing method using aluminum |
| JPS6086096A (en) * | 1983-10-18 | 1985-05-15 | Natl Inst For Res In Inorg Mater | Precipitation of filmy diamond |
| JPS60204899A (en) * | 1984-03-28 | 1985-10-16 | Souzou Kagaku Gijutsu Kenkyusho:Kk | Surface treatment |
| JPS61121859A (en) * | 1984-11-15 | 1986-06-09 | Showa Denko Kk | Method of processing substrate for use in diamond synthesis by vapor phase method |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5198070A (en) * | 1988-04-28 | 1993-03-30 | Jones Barbara L | Joining diamond bodies |
| EP0343846A2 (en) * | 1988-05-27 | 1989-11-29 | Xerox Corporation | Process for the preparation of polycrystalline diamond |
| JPH04132691A (en) * | 1990-09-25 | 1992-05-06 | Nec Corp | Production of diamond thin film by gaseous phase method using diamond fine powder as seed crystal |
| US6110240A (en) * | 1996-05-31 | 2000-08-29 | Ngk Spark Plug Co., Ltd. | Superhard article with diamond coat and method of manufacturing same |
| JP2011514848A (en) * | 2008-03-10 | 2011-05-12 | モルガン アドバンスド セラミックス， インコーポレイテッド | Non-planar CVD diamond coated CMP pad conditioner and method of manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0643280B2 (en) | 1994-06-08 |
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