JPH075406B2 - Diamond-coated sintered body with excellent adhesion and method for producing the same - Google Patents
Diamond-coated sintered body with excellent adhesion and method for producing the sameInfo
- Publication number
- JPH075406B2 JPH075406B2 JP1110992A JP11099289A JPH075406B2 JP H075406 B2 JPH075406 B2 JP H075406B2 JP 1110992 A JP1110992 A JP 1110992A JP 11099289 A JP11099289 A JP 11099289A JP H075406 B2 JPH075406 B2 JP H075406B2
- Authority
- JP
- Japan
- Prior art keywords
- diamond
- sintered body
- base material
- coating
- coated sintered
- 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
- 239000010432 diamond Substances 0.000 title claims description 88
- 229910003460 diamond Inorganic materials 0.000 title claims description 88
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000000463 material Substances 0.000 claims description 86
- 239000011248 coating agent Substances 0.000 claims description 64
- 238000000576 coating method Methods 0.000 claims description 64
- 239000002344 surface layer Substances 0.000 claims description 31
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 13
- 239000012071 phase Substances 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 10
- 239000010410 layer Substances 0.000 claims description 9
- 239000012808 vapor phase Substances 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- 229910001882 dioxygen Inorganic materials 0.000 claims description 6
- 238000001308 synthesis method Methods 0.000 claims description 6
- 239000010408 film Substances 0.000 description 24
- 239000000758 substrate Substances 0.000 description 16
- 238000005520 cutting process Methods 0.000 description 14
- 229910021385 hard carbon Inorganic materials 0.000 description 12
- 239000010409 thin film Substances 0.000 description 12
- 239000000919 ceramic Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910052721 tungsten Inorganic materials 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 5
- 238000009832 plasma treatment Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 1
- 101000878595 Arabidopsis thaliana Squalene synthase 1 Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は、炭化タングステンを主成分とするセラミック
ス焼結体の基材の表面にダイヤモンド及び／又はダイヤ
モンド状カーボンの被膜を形成させてなる付着性にすぐ
れたダイヤモンド被覆焼結体及びその製造方法に関し、
具体的には、例えば切削工具材料，耐摩耗工具材料又は
装飾用材料などを主体に、電気産業，電子産業，精密機
器産業，事務機器産業などに用いられる部品用材料とし
て適する付着性にすぐれたダイヤモンド被覆焼結体及び
その製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention is an adhesion method in which a coating film of diamond and / or diamond-like carbon is formed on the surface of a base material of a ceramics sintered body containing tungsten carbide as a main component. Relates to a diamond-coated sintered body having excellent properties and a method for producing the same,
Specifically, it has excellent adhesiveness suitable as a material for parts used mainly in cutting tool materials, wear-resistant tool materials, decorative materials, etc. in the electrical industry, electronic industry, precision equipment industry, office equipment industry, etc. The present invention relates to a diamond-coated sintered body and a method for manufacturing the same.
（従来の技術） 従来から金属，合金又はセラミックスなどの焼結体でな
る基材の表面にダイヤモンド及び／又はダイヤモンド状
カーボンの被膜を形成してなるダイヤモンド被覆焼結体
の実用化への検討が行われている。このダイヤモンド被
覆焼結体は、ダイヤモンドが他の物質との濡れ性に劣る
ことから、ダイヤモンド及び／又はダイヤモンド状カー
ボンの被膜を基材の表面に、いかにすれば密着性及び付
着性を高めた状態に被覆することができるかという問題
が最大の課題となっている。特に、旋削工具，フライス
工具，ドリル，エンドミルなどの切削工具材料の場合
は、最も苛酷な条件で用いられるために被膜と基材との
密着性や付着性が一層重要な問題となる。(Prior Art) Conventionally, a study has been made on the practical application of a diamond-coated sintered body in which a coating of diamond and / or diamond-like carbon is formed on the surface of a base material made of a sintered body of metal, alloy, ceramics or the like. Has been done. Since this diamond-coated sintered body is inferior in wettability with other substances, a diamond and / or diamond-like carbon coating on the surface of the base material has improved adhesion and adhesion. The biggest problem is whether or not it can be coated. Particularly, in the case of cutting tool materials such as turning tools, milling tools, drills and end mills, the adhesion and adhesion between the coating and the base material become more important problems because they are used under the most severe conditions.
ダイヤモンドの被膜と基材との密着性を高めて、切削工
具材料として用いることが可能なダイヤモンド被膜焼結
体を多数提案されており、その内、基材の材質の方向か
ら検討した代表例として、特開昭62−57802号公報，特
開昭62−166904号公報及び特開昭63−99102号公報があ
り、基材の表面の加工歪から検討した代表例として特公
昭64−4586号公報がある。Many diamond coating sintered bodies that can be used as cutting tool materials by improving the adhesion between the diamond coating and the base material have been proposed. Among them, as a typical example examined from the direction of the material of the base material , JP-A-62-57802, JP-A-62-166904 and JP-A-63-99102, and JP-B-64-4586 as a representative example examined from the processing strain of the surface of the base material. There is.
（発明が解決しようとする問題点） 特開昭62−57802号公報には、気相により硬質炭素薄膜
を基材表面に析出させて被覆した硬質炭素被覆部品の該
硬質炭素薄膜と基材との中間にW2Cを主成分とするＷと
Ｃの化合物薄膜の中間層を厚さ0.1μｍ以上存在させて
なる硬質炭素被覆部品が開示されている。この同公報に
よる発明は、超硬合金やセラミックスでなる基材の表面
にCVD法（化学蒸着法）やPVD法（物理蒸着法）でもって
W2Cを主成分とするＷとＣの化合物薄膜の中間層を被覆
すると硬質炭素とW2Cの界面にはWCでなる拡散中間層が
形成され、その結果付着強度の向上を達成できたという
ものであるけれども、CVD法やPVD法でもって中間層を形
成した後、別の反応容器で硬質炭素薄膜を被覆するとい
う工程の煩雑さがあること、及び中間層の表面に不純物
が付着しやすいことから中間層と硬質炭素薄膜との密着
性が劣るという問題がある。(Problems to be Solved by the Invention) Japanese Patent Application Laid-Open No. 62-57802 discloses a hard carbon thin film and a base material of a hard carbon coated component in which a hard carbon thin film is deposited on a surface of a base material by a vapor phase and coated. In the middle of the above, there is disclosed a hard carbon-coated component having an intermediate layer of a compound thin film of W and C containing W 2 C as a main component and having a thickness of 0.1 μm or more. The invention according to this publication uses a CVD method (chemical vapor deposition method) or a PVD method (physical vapor deposition method) on the surface of a substrate made of cemented carbide or ceramics.
When an intermediate layer of a W and C compound thin film containing W 2 C as a main component was coated, a diffusion intermediate layer made of WC was formed at the interface between hard carbon and W 2 C, and as a result, improvement in adhesion strength could be achieved. However, after forming the intermediate layer by the CVD method or PVD method, the process of coating the hard carbon thin film in another reaction vessel is complicated, and impurities adhere to the surface of the intermediate layer. Since it is easy, there is a problem that the adhesion between the intermediate layer and the hard carbon thin film is poor.
特開昭62−166904号公報には、窒化ケイ素，炭化ケイ
素，酸化ジルコニウム，酸化アルミニウムを主成分とす
るセラミックス焼結体を基材とし、その表面に減圧下で
硬質炭素の薄膜を0.5〜50μｍ被覆してなるセラミック
ス焼結体加工用硬質炭素膜被覆切削工具が開示されてい
る。この同公報の発明は、変形抵抗の高いセラミックス
を基材とし、その表面に硬質炭素の薄膜を形成させるこ
とにより、難削材であるファインセラミックスの切削加
工を可能にしたというものであるけれど、例えば硬質炭
素の薄膜中にダイヤモンドを含有量が多くなればなるほ
ど基材と薄膜との密着性が劣化し、逆にダイヤモンドの
含有量が減少すればするほど耐摩耗性が低下するという
問題がある。Japanese Unexamined Patent Publication (Kokai) No. 62-166904 discloses a ceramic sintered body containing silicon nitride, silicon carbide, zirconium oxide, and aluminum oxide as a main component as a base material, and a hard carbon thin film of 0.5 to 50 μm on its surface under reduced pressure. A hard carbon film-coated cutting tool for processing a ceramics sintered body formed by coating is disclosed. The invention of this publication uses a ceramic having high deformation resistance as a base material, and by forming a thin film of hard carbon on the surface of the base material, fine ceramics, which is a difficult-to-cut material, can be cut. For example, as the content of diamond in the hard carbon thin film increases, the adhesion between the base material and the thin film deteriorates, and conversely, as the content of diamond decreases, the wear resistance decreases. .
特開昭63−99102号公報には、タングステンを基材と
し、該基材にダイヤモンドを１〜100μｍ被覆してなる
被覆タングステン工具が開示されている。この同公報の
発明は、超硬合金やセラミックスの基材表面にダイヤモ
ンド薄膜を形成した従来のダイヤモンド被覆工具が薄膜
と基材との接着強度に問題があったのに対し、タングス
テンを基材にすることにより接着強度の問題を解決した
というものであるけれども、タングステン自体が軟質で
あることから塑性変形しやすく、切削工具として用いて
も短寿命であるという問題がある。Japanese Unexamined Patent Publication No. 63-99102 discloses a coated tungsten tool in which tungsten is used as a base material and diamond is coated on the base material in an amount of 1 to 100 μm. In the invention of this publication, while the conventional diamond-coated tool in which a diamond thin film is formed on the surface of a cemented carbide or ceramic substrate has a problem in the adhesive strength between the thin film and the substrate, tungsten is used as the substrate. Although the problem of adhesive strength was solved by doing so, there is a problem that since tungsten itself is soft, it is easily plastically deformed and has a short life even when used as a cutting tool.
特開昭64−4586号公報には、ダイヤモンドの被膜を形成
するための超硬合金の基材表面に研削砥石により加工歪
を加え、加工歪付与前と加工歪付与後におけるそれぞれ
の加工歪をWC（100）結晶面のＸ線回折線の半価幅とし
て求め、その比を一定の値にした超硬合金の基材表面に
ダイヤモンドの被膜を形成させるという方法が開示され
ている。この同公報の発明は、前処理として、一定量の
加工歪を加えた超合金の基表面にダイヤモンドの被膜を
析出させると、ダイヤモンドの結晶核が著しく増大し、
その結果微細組織の被膜になり、かつ被膜と基材との密
着性がすぐれるというものであるけれども、基材である
超硬合金中にFe族金属を含んでいるために、ダイヤモン
ドの気相合成時の初期にグラファイトが生成しやすくて
ダイヤモンドの合成を阻害すること、又、たとえばダイ
ヤモンドの被膜を形成したとしても高温で使用した場合
にはダイヤモンドがグラファイトに変態して耐摩耗性が
劣化してまうという問題がある。In JP-A-64-4586, a processing strain is applied to the surface of a cemented carbide substrate for forming a diamond coating by a grinding wheel, and the respective processing strains before and after the processing strain is applied. A method has been disclosed in which a diamond coating is formed on the surface of a cemented carbide base material whose half-width of the X-ray diffraction line of the WC (100) crystal plane is determined and the ratio is kept constant. The invention of this publication, as a pretreatment, when a diamond coating is deposited on the base surface of the superalloy to which a certain amount of work strain has been applied, the crystal nuclei of the diamond significantly increase,
As a result, a film with a fine structure is formed and the adhesion between the film and the substrate is excellent.However, since the Fe-based metal is contained in the cemented carbide as the substrate, the vapor phase of diamond Graphite is likely to be generated in the early stage of the synthesis to hinder the synthesis of diamond. Moreover, even if a diamond coating is formed, if it is used at high temperature, the diamond transforms into graphite and wear resistance deteriorates. There is a problem of waiting.
本発明は、上記のような問題点を解決したもので、具体
的には、炭化タングステンを主成分とする硬質相からな
る焼結体の基材表面にダイヤモンドの被膜を形成してな
るダイヤモンド被覆焼結体の被膜の表面からのCr−Ｋα
線によるWC（100）面におけるＸ線回折線の半価幅を規
定することによって、被膜と基材との付着性をすぐれる
ようにしたダイヤモンド被覆焼結体及びその製造方法の
提供を目的とするものである。The present invention solves the above problems, and specifically, a diamond coating formed by forming a diamond coating on the surface of a base material of a sintered body composed of a hard phase containing tungsten carbide as a main component. Cr-Kα from the surface of the sintered body coating
The purpose of the present invention is to provide a diamond-coated sintered body in which the adhesion between the coating and the base material is improved by defining the half-value width of the X-ray diffraction line on the WC (100) plane by the X-ray and a manufacturing method thereof. To do.
（問題点を解決するための手段） 本発明者らは、気相合成法で形成するダイヤモンドの被
膜を基材に被覆する場合、基材の種類，被膜の厚さ及び
被膜の形成条件における被膜の基材への耐剥離性につい
て検討していた所、 炭化タングステンを主成分とする硬質相でなる焼結体の
基材の表面にダイヤモンドの被膜を形成したダイヤモン
ド被覆焼結体において、被膜を形成する前の基材の表面
における歪の大きさ、及び被膜の形成条件により被膜の
基材への耐剥離性が異なること、又この耐剥離性がダイ
ヤモンド被覆焼結体の被膜の表面からのCr−Ｋα線で測
定して得たWC（100）面におけるＸ線回折線の半価幅と
相関関係にあるという知見を得たものである。この知見
に基づいて、本発明を完成するに至ったものである。(Means for Solving the Problems) When the diamond coating formed by the vapor phase synthesis method is coated on a substrate, the present inventors will consider the type of the substrate, the thickness of the coating, and the coating conditions under which the coating is formed. When we examined the resistance to peeling of the base material to the base material, we found that the diamond-coated sintered body, in which the diamond coating was formed on the surface of the base material of the sintered body composed of a hard phase composed mainly of tungsten carbide, The peeling resistance of the coating to the base material differs depending on the magnitude of strain on the surface of the base material before formation and the film forming conditions, and this peeling resistance is different from the surface of the coating of the diamond-coated sintered body. It was found that there is a correlation with the half-value width of the X-ray diffraction line on the WC (100) plane obtained by measuring with the Cr-Kα ray. The present invention has been completed based on this finding.
すなわち、本発明の付着性にすぐれたダイヤモンド被覆
焼結体は、炭化タングステンを主成分とする硬質相と不
可避不純物とでなる焼結体の基材の表面にダイヤモンド
及び／又はダイヤモンド状カーボンの被膜を形成してな
るダイヤモンド被覆焼結体であって、該ダイヤモンド被
覆焼結体の該被膜の表面からのCr−Ｋα線によるWC（10
0）面におけるＸ線回折線の半価幅が２θで0.2゜〜0.4
゜であることを特徴とする被覆焼結体である。That is, the diamond-coated sintered body of the present invention having excellent adhesiveness is a coating of diamond and / or diamond-like carbon on the surface of the base material of the sintered body composed of a hard phase containing tungsten carbide as a main component and unavoidable impurities. A diamond-coated sintered body formed by forming WC (10 (10) by Cr-Kα rays from the surface of the coating of the diamond-coated sintered body.
The half-value width of the X-ray diffraction line on the (0) plane is 0.2 ° to 0.4 at 2θ.
The coated sintered body is characterized in that
この本発明のダイヤモンド被覆焼結体における硬質相
は、炭化タングステンのみからなる場合、又は炭化タン
グステンが硬質相中の少なくとも50vol％含有し、他に
周期律表4a,5a,6a族金属の炭化物，炭素化物及びこれら
の相互固溶体の中の少なくとも１種を含有している場合
である。これらの内、特に硬質相が90vol％以上の炭化
タングステンである場合、例えばWC又はWC−W2Cでなる
炭化タングステンのみからなる場合、もしくはこれらの
炭化タングステン90vol％以上と残り炭化モリブデンと
からなるWC−Mo2C,WC−W2C−Mo2CあるいはWC−（W,Mo）
Ｃでなる場合は、被膜と基材との密着性がすぐれると共
に、基材の強度もすぐれるので好ましいことである。The hard phase in the diamond-coated sintered body of the present invention, when consisting of only tungsten carbide, or tungsten carbide contains at least 50 vol% in the hard phase, in addition to the periodic table 4a, 5a, 6a group metal carbide, This is the case where it contains at least one of a carbonized material and a mutual solid solution thereof. Of these, particularly when the hard phase is 90 vol% or more of tungsten carbide, for example, it is composed of only tungsten carbide composed of WC or WC-W 2 C, or is composed of 90 vol% or more of these tungsten carbide and the remaining molybdenum carbide. WC−Mo 2 C, WC−W 2 C−Mo 2 C or WC− (W, Mo)
When it is C, the adhesion between the coating and the base material is excellent, and the strength of the base material is also excellent, which is preferable.
本発明のダイヤモンド被覆焼結体における基材は、前述
の硬質相の他に不可避不純物が混在しており、この不可
避不純物としては主として出発物質中に含有している不
純物と、出発物質の混合粉砕工程中に混入してくる不純
物とがあり、後者の不可避不純物としては、混合容器又
はボールなどから混入してくる、例えばCo,Ni,Fe,W,Cr,
Moなどがあり、これらの不可避不純物が基材中に0.5vol
％以下含有している場合でも基材と被膜との密着性の低
下が少なく、かえって基材の強度を補うという効果もあ
ることから実用可能である。これらの基材は、この基材
の表面から内部に向って多くとも10μｍまでの表面層に
存在する炭化タングステンの粒径がこの表面層を除い
た、さらに基材内部に存在する炭化タングステンの平均
粒径に比べて微細である構成にすると、基材と被膜との
密着性がよりすぐれること、及び被膜の膜質を高めるこ
とから、特に好ましいことである。The base material in the diamond-coated sintered body of the present invention contains unavoidable impurities in addition to the hard phase described above. As the unavoidable impurities, the impurities mainly contained in the starting material and the starting material are mixed and ground. There are impurities that are mixed in during the process, and as the latter unavoidable impurities, they are mixed in from the mixing container or balls, for example, Co, Ni, Fe, W, Cr,
Mo, etc., and these unavoidable impurities are 0.5vol in the substrate.
% Or less, the adhesiveness between the base material and the coating is not deteriorated so much, and the strength of the base material is complemented. In these base materials, the average particle size of tungsten carbide existing inside the base material is the same as the surface of the base material except for this surface layer, where the particle size of the tungsten carbide existing in the surface layer is at most 10 μm. It is particularly preferable to make the composition finer than the particle size because the adhesion between the base material and the coating film is better and the film quality of the coating film is improved.
又、表面層中の炭化タングステンの粒径が1.0μｍ以
下、好ましくは0.5μｍ以下の場合には基材と被膜との
密着性がより一層すぐれる傾向になることから好ましい
ことである。Further, when the particle size of tungsten carbide in the surface layer is 1.0 μm or less, preferably 0.5 μm or less, the adhesion between the base material and the coating tends to be more excellent, which is preferable.
本発明のダイヤモンド被覆焼結体における被膜は、電気
抵抗，光透過率，硬度などがダイヤモンドの性質又はダ
イヤモンドに近い性質を示すもので、具体的には、ラマ
ン分光分析した場合にダイヤモンドのラマン線であると
いわれている1333cm-1にピークを示すものである。さら
に詳述すると、この被膜はダイヤモンドのみからなる場
合、又はダイヤモンドと他に非晶質カーボンやガラス状
カーボンなどを含有している場合、もしくはダイヤモン
ドが含有していなくても従来からダイヤモンドに近い性
質を示すものであるといわれているダイヤモンド状カー
ボンからなる場合がある。特に、前述の表面層を有する
基材に形成された被膜の場合には、ラマン分光分析にお
けるダイヤモンドのラマン線であるといわれている1333
cm-1のピークが明確に表われた膜質のすぐれたものにな
る。この被膜の厚さは、用途及び形状によって異なり、
特に耐衝撃性よりも耐すきとり摩耗性を重要視するよう
な用途には、例えば３〜10μｍ厚さが好ましく、切削工
具材料として用途には、0.5〜７μｍ厚さが好ましく、
切削工具材料の中でもフライス用切削工具のように耐衝
撃性を重要視する用途及びドリルやエンドミル、あるい
は耐摩耗工具材料のスリッター，切断刃，裁断刃などの
ように鋭角な切刃を有する用途には、例えば0.5〜３μ
ｍ厚さと、被膜を薄くする構成にすることが好ましいこ
とである。The film in the diamond-coated sintered body of the present invention exhibits properties such as electric resistance, light transmittance, hardness, etc. of diamond or properties close to that of diamond. Specifically, when Raman spectroscopic analysis is performed, the Raman line of diamond is used. It has a peak at 1333 cm -1 , which is said to be. More specifically, if this coating consists of only diamond, or if it contains diamond and other amorphous carbon or glassy carbon, or if it does not contain diamond, it has properties similar to conventional diamond. It may be composed of diamond-like carbon which is said to indicate. Particularly, in the case of a film formed on a substrate having the above-mentioned surface layer, it is said to be Raman line of diamond in Raman spectroscopic analysis 1333.
The peak of cm -1 is clearly shown and the film quality is excellent. The thickness of this coating depends on the application and shape,
In particular, for applications where importance is attached to scrape abrasion resistance rather than impact resistance, for example, a thickness of 3 to 10 μm is preferable, and for use as a cutting tool material, a thickness of 0.5 to 7 μm is preferable.
For cutting tool materials such as milling tools, where impact resistance is important, and for drills and end mills, or wear resistant tool materials such as slitters, cutting blades, and cutting blades that have sharp cutting edges. Is, for example, 0.5 to 3μ
It is preferable that the thickness is m and the coating is thin.
本発明のダイヤモンド被覆焼結体における半価幅は、ク
ロムターゲット，グラファイト単結晶のモノクロメータ
を用いたディフラクトメータにより、被膜の表面からCr
−Ｋα線でもってWC（100）面におけるＸ線回折線を測
定し、この回折線のバックグランドとWC（100）面の回
折線ピークとの1/2の高さの部分の回折線の幅をもって
求めたものである。このようにして求めた半価幅が0.2
゜〜0.4を外れると、被膜の基材への耐剥離性が低下す
る。この半価幅の意味することは、明確ではないけれど
も基材の表面層の残留歪量及び基材の表面層中のWC粒径
などにより変動するものと考えられる。The full width at half maximum in the diamond-coated sintered body of the present invention is measured from the surface of the coating by using a diffractometer using a chromium target and a graphite monocrystal monochromator.
-The X-ray diffraction line on the WC (100) plane was measured with Kα rays, and the width of the diffraction line at a height half that of the background of this diffraction line and the peak of the diffraction line on the WC (100) plane. Was obtained with. The half width obtained in this way is 0.2
If the angle is out of the range of 0.4 to 0.4, the peeling resistance of the coating film to the base material deteriorates. Although not clear, the meaning of the half width is considered to vary depending on the residual strain amount of the surface layer of the base material and the WC grain size in the surface layer of the base material.
本発明のダイヤモンド被覆焼結体は、炭化タングステン
を主成分とする硬質相を形成するための出発物質を従来
の粉末治金法でもって焼結体とし、この焼結体の基材を
焼肌面の状態又は基材の表面に一定量の加工歪を加えた
状態にした後に、従来のマイクロ波プラズマ，高周波プ
ラズマ又は熱フイラメントによるプラズマ中でのダイヤ
モンドの合成方法の内、合成条件を選定してダイヤモン
ドの被膜を基材の表面に形成させることにより得ること
ができるけれども、次の方法で行うと被膜の形成前にお
ける基材の表面層の歪の大きさに関係なく基材と被膜と
の付着性がよりすぐれること及び製造が容易で、かつ安
定して作製することができるので好ましいことである。In the diamond-coated sintered body of the present invention, a starting material for forming a hard phase containing tungsten carbide as a main component is made into a sintered body by a conventional powder metallurgy method, and the base material of this sintered body is burned. After making the surface state or a state where a certain amount of processing strain is applied to the surface of the base material, select the synthesis condition from the conventional methods of synthesizing diamond in microwave plasma, high frequency plasma or plasma by thermal filament. Although it can be obtained by forming a diamond film on the surface of the base material by the following method, the following method can be used to form a diamond film on the surface of the base material regardless of the strain level of the surface layer of the base material before the formation of the film. It is preferable because it has better adhesiveness, is easy to manufacture, and can be stably manufactured.
すなわち、本発明の付着性にすぐれたダイヤモンド被覆
焼結体の製造方法は、炭化タングステンを主成分とする
硬質相と不可避不純物とでなる焼結体の基材を反応容器
内に設置し、該反応容器内を脱炭性雰囲気でもって昇温
して、該基材の表面層を脱炭した後、気相合成法により
ダイヤモンド及び／又はダイヤモンド状カーボンの被膜
を該基材の表面に形成すると共に、該表面層を炭化タン
グステンを主成分とする層にして得るダイヤモンド被覆
焼結体の製造方法であって、該ダイヤモンド被覆焼結体
の該被膜面からのCr−Ｋα線によるWC（100）面におけ
るＸ線回折線の半価幅が２θで0.2゜〜0.4゜になること
を特徴とする方法である。That is, the method for producing a diamond-coated sintered body having excellent adhesiveness of the present invention is to install a base material of a sintered body composed of a hard phase containing tungsten carbide as a main component and unavoidable impurities in a reaction vessel, After heating the inside of the reaction vessel in a decarburizing atmosphere to decarburize the surface layer of the base material, a coating film of diamond and / or diamond-like carbon is formed on the surface of the base material by a vapor phase synthesis method. And a method for producing a diamond-coated sintered body, wherein the surface layer is a layer containing tungsten carbide as a main component, comprising: WC (100) using Cr-Kα rays from the coating surface of the diamond-coated sintered body. The method is characterized in that the half-value width of the X-ray diffraction line on the plane is 0.2 ° to 0.4 ° at 2θ.
この本発明のダイヤモンド被覆焼結体の製造方法におけ
る基材は、炭化ステンを主成分とする出発物質を混合粉
砕後、ホットプレス焼結、又は普通焼結後に熱間静水圧
処理（HIP処理）することにより緻密な焼結体にするこ
とができる。こうして得た基材をダイヤモンドの気相合
成用の反応容器に設置し、この反応容器内を脱炭性雰囲
気でもって昇温して基材の表面から多くとも10μｍの内
部までの表面層を逸脱した後、気相合成法によるダイヤ
モンド被覆処理を行って、１度脱炭した表面層を再晶出
した炭化タングステン又は炭化タングステンを主成分と
する炭化物の層にすると共に、この表面層上にダイヤモ
ンド及び／又はダイヤモンド状カーボンの被膜を形成す
る方法である。The base material in the method for producing a diamond-coated sintered body of the present invention is a hot isostatic treatment (HIP treatment) after mixing and pulverizing a starting material containing carbide as a main component, hot pressing sintering, or normal sintering. By doing so, a dense sintered body can be obtained. The substrate thus obtained is placed in a reaction vessel for vapor phase synthesis of diamond, and the temperature in the reaction vessel is raised in a decarburizing atmosphere to deviate from the surface of the substrate to a surface layer of at most 10 μm inside. Then, a diamond coating treatment by a vapor phase synthesis method is performed to make the surface layer once decarburized into a layer of recrystallized tungsten carbide or a carbide containing tungsten carbide as a main component. And / or a method of forming a diamond-like carbon film.
このように基材の表面層を脱炭した後、被膜を施すこと
により再度表面層を炭化物として形成される再晶出炭化
タングステンは、表面層よりも基材内部の炭化タングス
テンに比べて微細粒径にすることができる。After decarburizing the surface layer of the base material in this way, the recrystallized tungsten carbide that is formed again as a carbide by coating the surface layer has finer grains than the tungsten carbide inside the base material rather than the surface layer. Can be diameter.
本発明のダイヤモンド被覆焼結体の製造方法における反
応容器内を脱炭性雰囲気にする場合は、種々のガス雰囲
気による方法で行うことができるが、後工程である被膜
の形成工程を連続的に行うために、例えば水素ガスと酸
素ガスとの混合ガス、又は水素ガスと酸素ガスと炭素の
供給源となりうるガスとの混合ガスからなる雰囲気であ
ることが好ましく、水素ガスと酸素ガスとの混合ガスの
場合には、混合割合によって爆発が起こるので注意する
必要があり、特に酸素ガス0.1〜5vol％と、残り水素ガ
スとの比率でなる脱炭性雰囲気でなる場合は、安全性が
高いこと、微細粒の炭化物でなる表面層になること、及
び表面層と被膜との耐剥離性にもすぐれていることから
好ましいことである。ここでいう炭素の供給源となりう
るガスとは、例えばメタン，エタン，プロパン，ブタ
ン，メタノール，エタノール，プロパノール，ブタノー
ル，メチルエーテル，エチルエーテルなどの炭素と水素
又は炭素と水素との酸素の含有した有機化合物を挙げる
ことができる。この脱炭性雰囲気でもって昇温する場合
は、基材の温度を500〜1200℃でプラズマ化処理をする
ことが好ましいことである。このときのプラズマ化処理
は、従来のマイロク波や高周波もしくは熱フイラメント
法などで行うことができ、このプラズマ化処理状態でも
って同一反応容器中で引続き従来の気相合成法によるダ
イヤモンド被覆処理を行うと、表面層と被膜間への不純
物の付着が殆どないことから好ましいことである。When a decarburizing atmosphere is used in the reaction container in the method for producing a diamond-coated sintered body of the present invention, it can be carried out by various gas atmospheres, but the subsequent step of forming a coating film is continuously performed. In order to carry out, it is preferable that the atmosphere is, for example, a mixed gas of hydrogen gas and oxygen gas, or a mixed gas of hydrogen gas, oxygen gas and a gas which can be a supply source of carbon, and a mixture of hydrogen gas and oxygen gas. In the case of gas, it is necessary to be careful because an explosion will occur depending on the mixing ratio, especially in a decarburizing atmosphere with a ratio of 0.1 to 5 vol% oxygen gas and the remaining hydrogen gas, the safety is high. It is preferable because it becomes a surface layer made of fine-grained carbide, and has excellent peeling resistance between the surface layer and the coating. The gas that can be the source of carbon as used herein includes, for example, carbon and hydrogen such as methane, ethane, propane, butane, methanol, ethanol, propanol, butanol, methyl ether, and ethyl ether, or oxygen containing carbon and hydrogen. Organic compounds can be mentioned. When the temperature is raised in the decarburizing atmosphere, it is preferable to perform the plasma treatment at a temperature of the base material of 500 to 1200 ° C. The plasma treatment at this time can be performed by a conventional myloch wave, high frequency or thermal filament method, etc., and the diamond coating treatment by the conventional vapor phase synthesis method is continuously performed in the same reaction vessel in this plasma treatment state. It is preferable because there is almost no adhesion of impurities between the surface layer and the coating.
（作用） 本発明の付着性にすぐれたダイヤモンド被覆焼結体は、
基材中の炭化タングステンが被膜との付着性を高める作
用をしていると共に、特に基材の表面層に残留している
適正な歪量、基材の表面層に存在する炭化タングステン
の粒径及び表面層の表面状態が被膜の基材への耐剥離性
を高めるという作用をしているものである。(Operation) The diamond-coated sintered body of the present invention having excellent adhesiveness is
Tungsten carbide in the base material has the function of increasing the adhesion to the coating film, and in particular the appropriate amount of strain remaining in the surface layer of the base material and the particle size of tungsten carbide present in the surface layer of the base material. Also, the surface state of the surface layer acts to enhance the peeling resistance of the coating film to the base material.
本発明の付着性にすぐれたダイヤモンド被覆焼結体の製
造方法は、脱炭性雰囲気での処理工程と気相合成法によ
るダイヤモンド被覆処理工程による熱処理が基材の表面
層を焼鈍する効果となり、基材の表面層に残留しうる歪
量の制御が容易であること、脱炭性雰囲気での処理工程
とダイヤモンド被覆処理工程により微細粒で再晶出した
炭化物、特に炭化タングステンでなる表面層が形成され
ること、またプラズマ処理中での脱炭性雰囲気とプラズ
マ処理中でのダイヤモンド被覆処理とを同一反応容器中
で連続的に行うことができ、その結果表面層と被膜との
界面に不純物を生じ難くし、しかもダイヤモンドの核生
成の促進を高め、緻密で微細粒でなる被膜を生成しやす
くしているものである。特に、本発明の製造方法による
と、被膜の形成前における基材表面状態、例えば焼結条
件で生じる基材の焼肌面に存在する歪の大きさや基材の
表面を研削などで加工したときの加工歪の大きさに影響
を受けることなく、付着性のすぐれたダイヤモンド被覆
焼結体が得られるものである。The method for producing a diamond-coated sintered body having excellent adhesiveness according to the present invention is a treatment step in a decarburizing atmosphere and a heat treatment by a diamond coating treatment step by a vapor phase synthesis method is an effect of annealing a surface layer of a base material, It is easy to control the amount of strain that can remain in the surface layer of the base material, and the surface layer made of carbide recrystallized with fine grains by the treatment step in the decarburizing atmosphere and the diamond coating treatment step, especially tungsten carbide It is possible to continuously form a decarburizing atmosphere during plasma treatment and a diamond coating treatment during plasma treatment in the same reaction vessel, and as a result, impurities are formed at the interface between the surface layer and the coating. Is less likely to occur, and in addition, the promotion of diamond nucleation is enhanced, and a dense and fine-grained film is easily produced. In particular, according to the manufacturing method of the present invention, when the surface state of the base material before the formation of the coating, for example, the magnitude of strain present on the burnt surface of the base material that occurs under sintering conditions or the surface of the base material is processed by grinding or the like. It is possible to obtain a diamond-coated sintered body having excellent adhesiveness without being affected by the magnitude of the processing strain.
（実施例） 実施例１ WC粉末,Mo2C粉末を出発物質として用いて超硬合金製ボ
ールと共に湿式でボールミル混合粉砕及び乾燥後、真空
中でホットプレス焼結し、平均粒径3.0μｍのWCを主成
分とする硬質相の焼結体を得た。この基材の表面を第１
表に示すような焼肌面又は研削面にした後、下記（Ａ）
の脱炭性雰囲気条件でもって脱炭処理し、引続き同一反
応容器の中で下記（Ｂ）のダイヤモンド被覆処理条件で
もって第１表に示した各試料を得た。（本発明品２のみ
95vol％WC−5vol％Mo2C配合組成、他は100％WC配合組
成）また、94wt％WC−6wt％Co組成超硬合金でなる焼肌
面状態の試料を比較品３の基材とし、同組成超硬合金
で、その表面を＃230のレジノイド砥石で研削した試料
を比較品４の基材とし、それぞれの基材表面に次の
（Ｂ）条件のダイヤモンド被覆処理を施して、約５μｍ
厚さのダイヤモンド被膜が被覆された比較品３及び比較
品４を得た。(Example) Example 1 WC powder and Mo 2 C powder were used as starting materials together with a cemented carbide ball in a wet ball mill, mixed and pulverized, dried, and hot-press sintered in vacuum to obtain an average particle size of 3.0 μm. A hard phase sintered body containing WC as a main component was obtained. The surface of this substrate is first
After making the burnt surface or ground surface as shown in the table, the following (A)
The decarburizing treatment was carried out under the decarburizing atmosphere condition of No. 1, and each sample shown in Table 1 was obtained under the following diamond coating treatment condition (B) in the same reaction vessel. (Invention product 2 only
95vol% WC-5vol% Mo 2 C blending composition, others 100% WC blending composition) In addition, 94wt% WC-6wt% Co composition cemented carbide as a base material of comparative product 3 Approximately 5 μm of the cemented carbide of the same composition, the surface of which was ground with a # 230 resinoid grindstone was used as the base material of Comparative Product 4, and each base material surface was subjected to the diamond coating treatment under the following condition (B).
Comparative products 3 and 4 coated with a diamond coating having a thickness were obtained.
（Ａ） 脱炭性雰囲気条件 ガス組成 99vol％H2−vol％O2 ガス圧力 60Torr 基材温度 930℃ マイロク波出力 0.7kw 処理時間 30min （Ｂ） ダイヤモンド被覆処理条件 ガス組成 98vol％H2−2vol％CH4 ガス圧力 80Torr 基材温度 1060℃ マイロク波出力 1.0kw 処理時間 120min 次に、第１表に示したそれぞれの試料の基材の表面層，
ダイヤモンドの被膜の状態を金属顕微鏡，走査型電子顕
微鏡で調べて、その結果を第１表に併記した。また、第
１表のそれぞれの試料と比較品３および比較品４をダイ
ヤモンドの被膜の表面からCr−Ｋα線による下記（Ｃ）
条件でもってＸ線回折を行い、WC（100）面にＸ線回折
線の半価幅を求めて、その結果を第２表に示した。(A) Decarburizing atmosphere condition Gas composition 99vol% H 2 −vol% O 2 Gas pressure 60Torr Substrate temperature 930 ℃ Milo wave output 0.7kw Treatment time 30min (B) Diamond coating treatment condition Gas composition 98vol% H 2 −2vol % CH 4 gas pressure 80Torr Base material temperature 1060 ℃ Milo wave output 1.0kw Treatment time 120min Next, the surface layer of the base material of each sample shown in Table 1,
The state of the diamond coating was examined with a metallographic microscope and a scanning electron microscope, and the results are also shown in Table 1. In addition, the respective samples in Table 1 and the comparative products 3 and 4 were measured by Cr-Kα radiation from the surface of the diamond coating below (C).
X-ray diffraction was performed under the conditions, the half-value width of the X-ray diffraction line on the WC (100) plane was determined, and the results are shown in Table 2.
（Ｃ） Ｘ線回折条件 ターゲット Cr 管電圧 45kv 管電流 35mA スケールレジン 400cps 時定数 1ses 走査速度 1/4゜/min チャート速度 10mm/min 発散スリット（DS） １゜ 受光スリット（RS） 0.3゜ R.S.M 0.8゜（モノクロメータ側） S.S 1゜ 走査範囲 55゜〜60゜ さらに、第１表のそれぞれの試料と比較品３および比較
品４を用いて、下記（Ｄ）条件でもって切削試験を行
い、その時の平均逃げ面摩耗量（VB）及びその損傷状態
を調べて、その結果を第２表に併記した。(C) X-ray diffraction conditions Target Cr tube voltage 45kv tube current 35mA scale resin 400cps time constant 1ses scanning speed 1/4 ° / min chart speed 10mm / min divergence slit (DS) 1 ° light receiving slit (RS) 0.3 ° RSM 0.8 ° (monochromator side) SS 1 ° Scanning range 55 ° to 60 ° Further, using each of the samples in Table 1 and Comparative Product 3 and Comparative Product 4, a cutting test was conducted under the following conditions (D). The average flank wear amount (V B ) and its damage state were examined, and the results are also shown in Table 2.
（Ｄ） 旋削試験条件 被削材 硬質カーボン チップ形状 SPGN 120308 切削速度 50m/min 送 り 0.1mm/rev 切込み量 1mm 切削時間 60min （発明の効果） 以上の結果から、本発明の付着性にすぐれたダイヤモン
ド被覆焼結体は、本発明から外れた比較のダイヤモンド
被覆焼結体及び超硬合金の基材でなる比較品に比べて、
被膜の基材への付着性がすぐれていること、切削工具材
料として用いた場合に、被膜の耐剥離性が著しくすぐれ
ていること、その結果耐摩耗性及び耐欠損性にすぐれる
という効果があり、耐摩耗性において約2.7〜6.8倍もす
ぐれるという効果がある。(D) Turning test conditions Work material Hard carbon Tip shape SPGN 120308 Cutting speed 50m / min Feed 0.1mm / rev Depth of cut 1mm Cutting time 60min (Effects of the Invention) From the above results, the diamond-coated sintered body of the present invention having excellent adhesion is compared with the comparative diamond-coated sintered body deviated from the present invention and the comparative product made of the cemented carbide base material. hand,
The film has excellent adhesion to the base material, and when used as a cutting tool material, the film has excellent peel resistance, resulting in excellent wear resistance and chipping resistance. There is an effect that the wear resistance is improved by about 2.7 to 6.8 times.
また、本発明の付着性にすぐれたダイヤモンド被覆焼結
体の製造方法は、被膜の成形前における基材の表面層の
歪の大きさに殆んど影響を受けなくなること、及び被膜
の成形後には微細粒の炭化タングステンでなる表面層を
有する基材となること、この結果被膜と基材への付着性
をより一層高めるという効果がある。Further, the method for producing a diamond-coated sintered body having excellent adhesiveness of the present invention is that it is almost unaffected by the magnitude of strain of the surface layer of the substrate before forming the coating, and that after forming the coating, Has an effect of forming a base material having a surface layer made of fine-grained tungsten carbide, and as a result, further improving the adhesion between the coating film and the base material.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭63−100182（ＪＰ，Ａ) 特開 昭63−53269（ＪＰ，Ａ) 特公 昭64−4586（ＪＰ，Ｂ２) ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-63-100182 (JP, A) JP-A-63-53269 (JP, A) JP-B-64-4586 (JP, B2)
Claims (6)
不可避不純物とでなる焼結体の基材の表面にダイヤモン
ド及び／又はダイヤモンド状カーボンの被膜を形成して
なるダイヤモンド被覆焼結体であって、該ダイヤモンド
被覆焼結体の該被膜の表面からのCr−Ｋα線によるWC
（100）面におけるＸ線回折線の半価幅が２θで0.2゜〜
0.4゜であることを特徴とする付着性にすぐれたダイヤ
モンド被覆焼結体。1. A diamond-coated sintered body having a coating film of diamond and / or diamond-like carbon formed on the surface of a base material of a sintered body comprising a hard phase containing tungsten carbide as a main component and inevitable impurities. The WC by Cr-Kα rays from the surface of the coating of the diamond-coated sintered body.
The half width of the X-ray diffraction line on the (100) plane is 0.2 ° at 2θ
A diamond-coated sintered body having excellent adhesion, which is 0.4 °.
ステンでなることを特徴とする特許請求の範囲第１項記
載の付着性にすぐれたダイヤモンド被覆焼結体。2. The diamond-coated sintered body according to claim 1, wherein the hard phase is 90 vol% or more of tungsten carbide.
て多くとも10μｍまでの表面層における炭化タングステ
ンの粒径が該表面層よりも内部に存在する炭化タングス
テンの平均粒径に比べて微細であることを特徴とする特
許請求の範囲第１項又は第２項記載の付着性にすぐれた
ダイヤモンド被覆焼結体。3. In the above-mentioned base material, the particle diameter of tungsten carbide in the surface layer of at most 10 μm from the surface of the base material to the inside is the average particle diameter of tungsten carbide existing inside the surface layer. The diamond-coated sintered body according to claim 1 or 2, characterized in that it is finer than the diamond-coated sintered body.
を特徴とする特許請求の範囲第１項，第２項又は第３項
記載の付着性にすぐれたダイヤモンド被覆焼結体。4. The diamond-coated sintered body according to claim 1, 2, or 3, wherein the coating has a thickness of 0.5 to 10 μm.
不可避不純物とでなる焼結体の基材を反応容器内に設置
し、該反応容器内を脱炭性雰囲気でもって昇温して、該
基材の表面層を脱炭した後、気相合成法によりダイヤモ
ンド及び／又はダイヤモンド状カーボンの被膜を該基材
の表面に形成すると共に、該表面層を炭化タングステン
を主成分とする層にして得るダイヤモンド被覆焼結体の
製造方法であって、該ダイヤモンド被覆焼結体の該被膜
の表面からのCr−Ｋα線によるWC（100）面におけるＸ
線回折線の半価幅が２θで0.2゜〜0.4゜になることを特
徴とする付着性にすぐれたダイヤモンド被覆焼結体の製
造方法。5. A base material of a sintered body, which comprises a hard phase containing tungsten carbide as a main component and unavoidable impurities, is placed in a reaction vessel, and the temperature in the reaction vessel is raised in a decarburizing atmosphere. After decarburizing the surface layer of the base material, a coating of diamond and / or diamond-like carbon is formed on the surface of the base material by a vapor phase synthesis method, and the surface layer is made a layer containing tungsten carbide as a main component. A method for producing a diamond-coated sintered body obtained by the method, comprising: X on a WC (100) plane by Cr-Kα rays from the surface of the coating of the diamond-coated sintered body.
A method for producing a diamond-coated sintered body having excellent adhesiveness, characterized in that the half-width of the line diffraction line is 0.2 ° to 0.4 ° at 2θ.
との混合ガス、又は水素ガスと酸素ガスと炭素の供給源
となりうるガスとの混合ガスからなることを特徴とする
特許請求の範囲第４項記載の付着性にすぐれたダイヤモ
ンド被覆焼結体の製造方法。6. The decarburizing atmosphere comprises a mixed gas of hydrogen gas and oxygen gas, or a mixed gas of hydrogen gas, oxygen gas, and a gas that can be a carbon source. A method for producing a diamond-coated sintered body having excellent adhesiveness as set forth in claim 4.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110992A JPH075406B2 (en) | 1989-04-28 | 1989-04-28 | Diamond-coated sintered body with excellent adhesion and method for producing the same |
| DE89121211T DE68910302T2 (en) | 1989-02-23 | 1989-11-16 | Diamond-coated sintered body with excellent adhesion and process for its production. |
| EP89121211A EP0384011B1 (en) | 1989-02-23 | 1989-11-16 | Diamond-coated sintered body excellent in adhesion and process for preparing the same |
| KR1019900002261A KR960001595B1 (en) | 1989-02-23 | 1990-02-22 | Diamond-coated sintered body excellent in adhesion and the |
| US07/623,493 US5100703A (en) | 1989-02-23 | 1990-12-07 | Diamond-coated sintered body excellent in adhesion and process for preparing the same |
| US07/798,972 US5204167A (en) | 1989-02-23 | 1991-11-29 | Diamond-coated sintered body excellent in adhesion and process for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1110992A JPH075406B2 (en) | 1989-04-28 | 1989-04-28 | Diamond-coated sintered body with excellent adhesion and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02293385A JPH02293385A (en) | 1990-12-04 |
| JPH075406B2 true JPH075406B2 (en) | 1995-01-25 |
Family
ID=14549656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1110992A Expired - Lifetime JPH075406B2 (en) | 1989-02-23 | 1989-04-28 | Diamond-coated sintered body with excellent adhesion and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075406B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2107547T3 (en) * | 1991-07-22 | 1997-12-01 | Sumitomo Electric Industries | HARD MATERIAL WITH DIAMOND COATING AND MANUFACTURING PROCEDURE FOR THIS MATERIAL. |
| JP5008789B2 (en) * | 2000-07-07 | 2012-08-22 | 住友電工ハードメタル株式会社 | Super hard sintered body |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0791651B2 (en) * | 1986-04-24 | 1995-10-04 | 三菱マテリアル株式会社 | Diamond coated tungsten carbide based cemented carbide cutting tool chip |
| JPS63100182A (en) * | 1986-04-24 | 1988-05-02 | Mitsubishi Metal Corp | Cutting tool tip made of diamond-coated tungsten carbide-based sintered hard alloy |
| JP2604160B2 (en) * | 1987-06-25 | 1997-04-30 | ヤマハ発動機株式会社 | Motorcycle frame structure |
-
1989
- 1989-04-28 JP JP1110992A patent/JPH075406B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02293385A (en) | 1990-12-04 |
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