JP2734157B2 - Manufacturing method of diamond coated tungsten carbide based cemented carbide cutting tool - Google Patents
Manufacturing method of diamond coated tungsten carbide based cemented carbide cutting toolInfo
- Publication number
- JP2734157B2 JP2734157B2 JP1433890A JP1433890A JP2734157B2 JP 2734157 B2 JP2734157 B2 JP 2734157B2 JP 1433890 A JP1433890 A JP 1433890A JP 1433890 A JP1433890 A JP 1433890A JP 2734157 B2 JP2734157 B2 JP 2734157B2
- Authority
- JP
- Japan
- Prior art keywords
- cemented carbide
- based cemented
- tungsten carbide
- carbide substrate
- diamond
- 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
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- Cutting Tools, Boring Holders, And Turrets (AREA)
- 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〕 この発明は、炭化タングステン（以下、WCと記す）基
超硬合金基体の表面に、均一で付着強度の高い人工ダイ
ヤモンドを析出させてなるダイヤモンド被覆炭化タング
ステン基超硬合金切削工具の製造法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a diamond obtained by depositing an artificial diamond having a uniform and high adhesive strength on the surface of a tungsten carbide (hereinafter abbreviated as WC) based cemented carbide substrate. The present invention relates to a method for manufacturing a coated tungsten carbide based cemented carbide cutting tool.
一般に、結合相形成成分としてCo:1〜25重量％を含有
し、残りが分散相形成成分としてWCと不可避不純物から
なる組成を有するWC基超硬合金基体表面に気相合成法に
より人工ダイヤモンドを析出させ、ダイヤモンド被覆WC
基超硬合金切削工具を製造する方法は知られており、上
記人工ダイヤモンドをWC基超硬合金基体表面に均一に強
固に密着させて工具寿命を延ばす工夫もいろいろなされ
ている。例えば、 （ａ） WC基超硬合金基体表面を砥石または砥粒を用い
て研摩し、WC基超硬合金基体表面粗さを平均:1.0μｍ以
下に制御し、人工ダイヤモンドを上記基体表面に強固に
密着させる方法（特開昭61−124573号公報参照）、 （ｂ） WC基超硬合金基体を化学エッチングすることに
より基体表面のCOを除去し、WCをCoよりも0.05〜0.5μ
ｍの段差で突き出したWC基超硬合金基体表面を形成し、
基体表面のWCに人工ダイヤモンド被膜が一層付きやすく
する方法（特開昭63−14869号公報参照）、 （ｃ） 表面研削したWC基超硬合金基体を熱処理するこ
とによりWC基超硬合金基体の表面粗さを0.3〜３μｍと
し、基体表面に形成された人工ダイヤモンドの耐剥離性
を向上させる方法（特開平１−246361号公報参照）、 などの方法が提案されている。Generally, artificial diamond is formed on the surface of a WC-based cemented carbide substrate having a composition consisting of WC and unavoidable impurities containing Co: 1 to 25% by weight as a binder phase forming component and the balance being a dispersed phase forming component. Precipitated, diamond coated WC
A method of manufacturing a base cemented carbide cutting tool is known, and various measures have been taken to extend the tool life by uniformly and firmly adhering the artificial diamond to the surface of a WC-based cemented carbide substrate. For example, (a) the surface of a WC-based cemented carbide substrate is polished using a grindstone or abrasive grains, the surface roughness of the WC-based cemented carbide substrate is controlled to an average of 1.0 μm or less, and an artificial diamond is firmly adhered to the surface of the substrate. (B) Chemical etching of the WC-based cemented carbide substrate to remove CO from the substrate surface, and to make WC 0.05 to 0.5 μm less than Co.
forming a WC-based cemented carbide substrate surface protruding with a step of m
A method of making an artificial diamond film more easily adhere to the WC on the surface of the substrate (see Japanese Patent Application Laid-Open No. 63-14869); A method has been proposed in which the surface roughness is set to 0.3 to 3 μm to improve the peeling resistance of the artificial diamond formed on the surface of the substrate (see JP-A-1-246361).
しかし、上記従来の製造法により製造されたダイヤモ
ンド被覆WC基超硬合金切削工具は、WC基超硬合金基体表
面に対するダイヤモンド被覆層の密着強度は十分でな
く、なお一層密着強度の優れたダイヤモンド被覆WC基超
硬合金切削工具が求められていた。However, the diamond-coated WC-based cemented carbide cutting tools manufactured by the conventional manufacturing method described above do not have sufficient adhesion strength of the diamond-coated layer to the surface of the WC-based cemented carbide substrate, and the diamond-coated diamond has excellent adhesion strength. There was a need for a WC-based cemented carbide cutting tool.
そこで、本発明者等は、ダイヤモンド被覆層のWC基超
硬合金基体表面に対する密着強度を向上せしめるべく研
究を行った結果、 WC基超硬合金基体の表面を研削する工程、 この表面研削したWC基超硬合金基体を非酸化性雰囲気
中で熱処理する工程、 この熱処理されたWC基超硬合金基体を化学エッチング
法により基体表面から３μｍ以上の深さにわたってCoを
除去し、Co不足層を形成する工程、 この表面Coが除去されたWC基超硬合金基体を微細硬質
粒子が浮遊分散した分散液中に浸漬し、この分散液に超
音波を作用させて上記表面Coが除去されたWC基超硬合金
基体表面を活性化させる工程、 上記表面活性化したWC基超硬合金基体表面に気相合成
法により人工ダイヤモンドを被覆する工程、 表面に人工ダイヤモンドを被覆したWC基超硬合金基体
を真空雰囲気中で熱処理する工程、 の各工程を経て製造されたダイヤモンド被覆WC基超硬合
金切削工具のダイヤモンド被覆層の密着強度は優れてい
るという知見を得たのである。Accordingly, the present inventors have conducted research to improve the adhesion strength of the diamond coating layer to the surface of the WC-based cemented carbide substrate, and as a result, a step of grinding the surface of the WC-based cemented carbide substrate. Heat-treating the base cemented carbide substrate in a non-oxidizing atmosphere, removing the Co from the heat-treated WC-based cemented carbide substrate to a depth of 3 μm or more from the substrate surface by a chemical etching method to form a Co-deficient layer Immersing the WC-based cemented carbide substrate from which the surface Co has been removed into a dispersion in which fine hard particles are suspended and dispersed, and applying ultrasonic waves to the dispersion to remove the WC-based substrate from which the surface Co has been removed. A step of activating the surface of the cemented carbide substrate, a step of coating the surface-activated WC-based cemented carbide substrate surface with artificial diamond by a vapor phase synthesis method, and a step of applying a WC-based cemented carbide substrate having the surface coated with artificial diamond. Vacuum atmosphere Adhesion strength heat-treated in air step, diamond-coated WC-based diamond coating layer of the cemented carbide cutting tool is manufactured through the respective steps of the is to obtain a finding that is superior.
この発明は、かかる知見にもとづいてなされたもの
で、この発明で用いるWC基超硬合金基体は、結合相形成
成分としてCo:1〜25重量％を含有し、残りWCおよび不可
避不純物からなる通常のWC基超硬合金であり、このWC基
超硬合金基体を表面粗さが平均1.0μｍ以下となるよう
に研削する。The present invention has been made based on such findings, and the WC-based cemented carbide substrate used in the present invention contains Co: 1 to 25% by weight as a binder phase forming component, and usually comprises WC and unavoidable impurities. The WC-based cemented carbide substrate is ground so that the surface roughness is 1.0 μm or less on average.
この表面研削されたWC基超硬合金を、非酸化性雰囲気
中、1000〜1500℃の所定の温度に所定時間保持の熱処理
を施したのち、化学エッチング法によりCoのみを溶出
し、基体表面から深さ３μｍ以上にわたってCoを除去
し、Co不足層を形成する。この場合、表面研削されたWC
基超硬合金基体の研削面を直接化学エッチングするより
も上記熱処理したのち化学エッチングする方がエッチン
グ速度が向上するので好ましい。After subjecting the surface-ground WC-based cemented carbide to a heat treatment for holding for a predetermined time at a predetermined temperature of 1000 to 1500 ° C. in a non-oxidizing atmosphere, only Co is eluted by a chemical etching method, and from the substrate surface, Co is removed over a depth of 3 μm or more to form a Co-deficient layer. In this case, the surface-ground WC
The chemical etching after the above heat treatment is more preferable than the chemical etching directly on the ground surface of the base cemented carbide substrate because the etching rate is improved.
一般に、WC基超硬合金基体を化学エッチング法により
結合相形成成分であるCoを除去し、基体表面にWCを突き
出し、このWCに気相合成法により人工ダイヤモンドを被
覆形成させる方法は上記〔従来の技術〕（ｂ）で述べた
如く公知ではあるが、上記従来法によるCo不足層の深さ
は0.5μｍ以下であり、この程度のCo不足層を形成して
もダイヤモンド被覆に悪影響を及ぼすCoの影響は回避で
きない。したがって、この発明では、化学エッチング法
により形成されるCo不足層の厚さを３μｍ以上とした。
上記Co不足層の厚さを３μｍ以上とするとWC基超硬合金
最表面のCo量は極めて微量となりダイヤモンド析出形成
に及ぼすCoの悪影響を軽減することができる。In general, the method of removing Co, which is a binder phase forming component, from a WC-based cemented carbide substrate by a chemical etching method, extruding WC on the substrate surface, and coating the WC with an artificial diamond by a vapor phase synthesis method is described above [Conventional method] As described in (b), it is known that the depth of the Co-deficient layer according to the conventional method described above is 0.5 μm or less. The effect of can not be avoided. Therefore, in the present invention, the thickness of the Co-deficient layer formed by the chemical etching method is set to 3 μm or more.
When the thickness of the Co-deficient layer is 3 μm or more, the amount of Co on the outermost surface of the WC-based cemented carbide becomes extremely small, so that the adverse effect of Co on diamond precipitation formation can be reduced.
つぎに、表面にCo不足層を有するWC基超硬合金基体
を、平均粒径:10〜30μｍの硬質粒子が分散した分散液
に浸漬し、この分散液に超音波を作用させて上記Co不足
層中のWC粒表面を活性化させる。この活性化処理を行う
と、非常に均質な密着性の良い残留応力の少ないダイヤ
モンド膜が形成される。Next, a WC-based cemented carbide substrate having a Co-deficient layer on the surface is immersed in a dispersion in which hard particles having an average particle size of 10 to 30 μm are dispersed, and the dispersion is subjected to ultrasonic waves to apply the Co-deficient material. Activate the WC grain surface in the layer. By performing this activation treatment, a very uniform diamond film having good adhesion and low residual stress is formed.
このようにして作製されたダイヤモンド被覆WC基超硬
合金を切削工具として用いても、３μｍ以上の厚さのCo
不足層があるとWC粒子の結合強度が低下し、切削中にWC
粒子が脱落することによりダイヤモンドも剥離する。そ
のため、上記Co不足層を有するダイヤモンド被覆WC基超
硬合金を１×10-5Torr以上の高真空中、液相が発生しな
い温度以下の温度（好ましくは、600〜900℃）で熱処理
することが必要である。かかる高真空中で熱処理するこ
とによりWC基超硬合金基体内部のCoが表面に向って固相
拡散し、Co不足層が消滅し、WC粒子の脱落によるダイヤ
モンドの剥離も解消される。この場合の熱処理雰囲気は
真空雰囲気であることが必要であり、例えば水素雰囲気
で行っても基体内部のCoは表面に向って移動しない。ま
た、この熱処理温度は液相が発生しない温度以下の温度
で行う必要があり、液相が発生する温度ではCoがダイヤ
モンドを食刻するので好ましくない。Even if the diamond-coated WC-based cemented carbide thus produced is used as a cutting tool,
If there is an insufficient layer, the bonding strength of the WC particles decreases,
As the particles fall off, the diamond also peels off. Therefore, the diamond-coated WC-base cemented carbide having the Co-deficient layer is heat-treated in a high vacuum of 1 × 10 −5 Torr or more at a temperature below the temperature at which no liquid phase is generated (preferably 600 to 900 ° C.). is required. By performing the heat treatment in such a high vacuum, Co in the WC-based cemented carbide substrate undergoes solid-phase diffusion toward the surface, the Co-deficient layer disappears, and the separation of diamond due to the falling off of WC particles is also eliminated. The heat treatment atmosphere in this case needs to be a vacuum atmosphere. For example, even in a hydrogen atmosphere, Co in the base does not move toward the surface. The heat treatment must be performed at a temperature lower than a temperature at which a liquid phase does not occur. At a temperature at which a liquid phase is generated, Co etches diamond, which is not preferable.
つぎに、この発明を実施例にもとづいて具体的に説明
する。Next, the present invention will be specifically described based on embodiments.
原料粉末として、いずれも0.5〜10μｍの範囲内の所
定の平均粒径を有するWC粉末およびCo粉末を用意し、こ
れら原料粉末を、 Co:6重量％、残り:WC となるように配合し、ボールミルで72時間湿式混合し、
乾燥したのち、1.5ton/cm2の圧力で圧粉体にプレス成形
し、この圧粉体を１×10-3Torrの真空中、1350〜1500℃
の範囲内の所定の温度に90分間保持の条件で焼結し、上
記配合組成と実質的に同一の成分組成をもったWC基超硬
合金基体を製造し、この基体表面に上下面および外周研
削機を用いて研削加工を施し、その形状をCIS（超硬工
具協会）規格SPP422のスローアウェイチップに形成し
た。As raw material powders, WC powder and Co powder each having a predetermined average particle size in the range of 0.5 to 10 μm are prepared, and these raw material powders are blended so that Co: 6% by weight and the balance: WC, Wet mix in a ball mill for 72 hours,
After drying, it is pressed into a green compact at a pressure of 1.5 ton / cm 2 and the green compact is heated to 1350-1500 ° C. in a vacuum of 1 × 10 −3 Torr.
Sintering for 90 minutes at a predetermined temperature within the range described above to produce a WC-based cemented carbide substrate having substantially the same composition as the above-mentioned composition, and the upper and lower surfaces and the outer periphery Grinding was performed using a grinding machine, and the shape was formed into a throw-away insert conforming to CIS (Carbide Tool Association) standard SPP422.
上記スローアウェイチップを、 （１） 水素雰囲気中、温度:1480℃,1時間保持の条件
で加熱処理する工程（以下、加熱処理工程という）、 （２） ５％硝酸水溶液にて化学エッチングし、スロー
アウェイチップ表面のCoを深さ:3μｍ以上にわたって除
去する工程（以下、化学エッチング工程という）、 （３） 平均粒径:15μｍのダイヤモンド粉末を純水に
浮遊分散させてなる分散液に浸漬し、1MHzの超音波をか
けて表面を活性化する工程（以下、表面活性化工程とい
う）、 （４） 金属Ｗフィラメントを備えた直径:120mmの石英
管反応容器内に装入し、 雰囲気圧力:30Torr、 基体温度 :700℃、 反応ガス :CH4/H2:1.0、 反応時間 :5時間、 の気相合成反応を行って、膜厚:3μｍのダイヤモンド被
覆層を形成する工程（以下、ダイヤモンド気相合成工程
という）、 （５） 10-5Torrの真空雰囲気中、温度:800℃、２時間
保持で熱処理し、基体内部のCoを表面に固相拡散せしめ
る工程（以下、真空熱処理工程という）、 の各工程を経て、第１表の本発明スローアウェイチップ
１を製造し、さらに第１表に示される上記ダイヤモンド
気相合成工程を除く各工程のうち少なくとも１工程を省
略した製造工程またはこの発明の条件から外れた条件を
含む製造工程を経て製造された比較スローアウェイチッ
プ１〜９をそれぞれ製造した（この製造工程においてこ
の発明の条件から外れた条件に※印を付して示した）。
第１表に示された製造法により製造された本発明スロー
アウェイチップ１および比較スローアウェイチップ１〜
９を用いて、 被削材 :Al−11％Si合金の丸棒、 切削速度:1000m/min、 切り込み:1.0mm、 送 り:0.1mm/rev、 の乾式連続切削試験、および、 被削材 :Al−11％Si合金の溝入り材、 切削速度:1200m/min、 切り込み:1.5mm、 送 り:0.3mm/rev、 の乾式フライス断続試験を行ない、それぞれダイヤモン
ド被覆層が剥離するまでの時間を測定し、それらの測定
結果も第１表に示した。(1) a step of heat-treating the throw-away chip in a hydrogen atmosphere at a temperature of 1480 ° C. for 1 hour (hereinafter, referred to as a heat treatment step); (2) a chemical etching with a 5% nitric acid aqueous solution; A step of removing Co on the surface of the throw-away tip over a depth of 3 μm or more (hereinafter referred to as a chemical etching step); (3) immersing in a dispersion of diamond powder having an average particle diameter of 15 μm suspended and dispersed in pure water. A step of activating the surface by applying 1 MHz ultrasonic waves (hereinafter referred to as a surface activating step); (4) charging into a 120 mm diameter quartz tube reaction vessel equipped with a metal W filament; 30 Torr, substrate temperature: 700 ° C., reaction gas: CH 4 / H 2 : 1.0, reaction time: 5 hours, performing a gas phase synthesis reaction to form a diamond coating layer having a thickness of 3 μm (hereinafter referred to as diamond Gas phase synthesis process), (5) In a 10 -5 Torr vacuum atmosphere, a heat treatment is performed at a temperature of 800 ° C. for 2 hours to allow Co in the substrate to solid-phase diffuse on the surface (hereinafter referred to as a vacuum heat treatment step). A manufacturing process in which the indexable insert 1 of the present invention shown in Table 1 was manufactured and at least one of the steps except the diamond vapor phase synthesis process shown in Table 1 was omitted or deviated from the conditions of the present invention. Comparative throw-away chips 1 to 9 manufactured through the manufacturing process including the conditions were manufactured respectively (conditions deviating from the conditions of the present invention in the manufacturing process are indicated by *).
Inventive throw-away chips 1 and comparative throw-away chips 1 to 1 manufactured according to the manufacturing methods shown in Table 1.
Work material: Al-11% Si alloy round bar, Cutting speed: 1000m / min, Depth of cut: 1.0mm, Feeding: 0.1mm / rev, Dry continuous cutting test and work material : Al-11% Si alloy grooved material, Cutting speed: 1200m / min, Depth of cut: 1.5mm, Feed: 0.3mm / rev, Was performed, and the time until the diamond coating layer peeled was measured. The measurement results are also shown in Table 1.
第１表の結果から、WC基超硬合金スローアウェイチッ
プを研削し、ついで、加熱処理工程、化学エッチング工
程、表面活性化工程を施したのちダイヤモンド気相合成
工程によりダイヤモンド被覆し、最終的に真空熱処理を
施すことにより初めて優れた耐剥離性を有するダイヤモ
ンド被覆WC基超硬合金スローアウェイチップが得られ、
上記工程のうちいずれの工程を省略しても良好な結果が
得られないことがわかる。From the results shown in Table 1, the WC-based cemented carbide indexable insert was ground, then subjected to a heat treatment step, a chemical etching step, and a surface activation step, and then coated with diamond by a diamond vapor phase synthesis step. Only by applying vacuum heat treatment, a diamond-coated WC-based cemented carbide indexable insert with excellent peel resistance can be obtained for the first time.
It can be seen that good results cannot be obtained even if any of the above steps is omitted.
この実施例ではWC基超硬合金を基体としたダイヤモン
ド被覆スローアウェイチップの製造法について述べた
が、この発明は上記スローアウェイチップの製造法に限
定されるものではなく、その他一般のダイヤモンド被覆
WC基超硬合金切削工具の製造にも適用可能であり、かか
る製造法により、従来よりも一層長寿命のダイヤモンド
被覆WC基超硬合金切削工具を提供することができる。In this embodiment, a method of manufacturing a diamond-coated indexable insert using a WC-based cemented carbide as a base has been described. However, the present invention is not limited to the method of manufacturing a throw-away insert described above.
The present invention is also applicable to the manufacture of WC-based cemented carbide cutting tools, and by such a production method, it is possible to provide a diamond-coated WC-based cemented carbide cutting tool having a longer life than before.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 // Ｃ０４Ｂ 41/87 Ｃ０４Ｂ 41/87 Ｈ ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 6 Identification code Agency reference number FI Technical indication // C04B 41/87 C04B 41/87 H
Claims (1)
有し、残りが分散相形成成分として炭化タングステンと
不可避不純物からなる組成を有する炭化タングステン基
超硬合金基体の表面に人工ダイヤモンドを被覆してなる
ダイヤモンド被覆炭化タングステン基超硬合金切削工具
の製造法において、 上記炭化タングステン基超硬合金基体の表面を研削する
工程、 上記表面研削された炭化タングステン基超硬合金基体を
非酸化性雰囲気中で熱処理する工程、 上記熱処理された炭化タングステン基超硬合金基体を化
学エッチング法により基体表面から深さ３μｍ以上にわ
たってCoを除去することによりCo不足層を形成する工
程、 Co不足層を有する炭化タングステン基超硬合金基体を微
細硬質粒子が浮遊分散した分散液中に浸漬し、この分散
液に超音波を作用させて上記炭化タングステン基超硬合
金基体のCo不足層表面を活性化させる工程、 表面活性化した炭化タングステン基超硬合金基体のCo不
足層表面に、気相合成法により人工ダイヤモンドを被覆
させる工程、 上記人工ダイヤモンドを被覆した炭化タングステン基超
硬合金基体を真空雰囲気中、液相が発生しない温度で熱
処理する工程、 の各工程を経て製造することを特徴とするダイヤモンド
被覆炭化タングステン基超硬合金切削工具の製造法。An artificial diamond is formed on the surface of a tungsten carbide-based cemented carbide substrate having a composition comprising, as a binder phase forming component, Co: 1 to 25% by weight and a balance comprising tungsten carbide and unavoidable impurities as a dispersed phase forming component. A step of grinding the surface of the tungsten carbide-based cemented carbide substrate, wherein the surface of the tungsten carbide-based cemented carbide substrate is non-oxidized. Heat-treating in a neutral atmosphere, forming a Co-deficient layer by removing Co over a depth of 3 μm or more from the surface of the heat-treated tungsten carbide-based cemented carbide substrate by a chemical etching method, The tungsten carbide-based cemented carbide substrate is immersed in a dispersion in which fine hard particles are suspended and dispersed. Activating the surface of the Co-deficient layer of the tungsten carbide-based cemented carbide substrate by acting on the surface of the tungsten carbide-based cemented carbide substrate. A step of heat-treating the tungsten carbide-based cemented carbide substrate coated with the artificial diamond in a vacuum atmosphere at a temperature that does not generate a liquid phase. Manufacturing method of hard alloy cutting tools.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1433890A JP2734157B2 (en) | 1990-01-24 | 1990-01-24 | Manufacturing method of diamond coated tungsten carbide based cemented carbide cutting tool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1433890A JP2734157B2 (en) | 1990-01-24 | 1990-01-24 | Manufacturing method of diamond coated tungsten carbide based cemented carbide cutting tool |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03219079A JPH03219079A (en) | 1991-09-26 |
| JP2734157B2 true JP2734157B2 (en) | 1998-03-30 |
Family
ID=11858281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1433890A Expired - Lifetime JP2734157B2 (en) | 1990-01-24 | 1990-01-24 | Manufacturing method of diamond coated tungsten carbide based cemented carbide cutting tool |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2734157B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69222138T2 (en) * | 1991-07-22 | 1998-01-22 | Sumitomo Electric Industries | DIAMOND-COVERED HARD MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
| DE69330052T2 (en) * | 1992-12-08 | 2001-11-15 | Osaka Diamond Industrial Co., Sakai | ULTRA-HARD FILM-COVERED MATERIAL AND THEIR PRODUCTION |
| GB9811213D0 (en) * | 1998-05-27 | 1998-07-22 | Camco Int Uk Ltd | Methods of treating preform elements |
| JP5070629B2 (en) * | 2009-04-01 | 2012-11-14 | トーカロ株式会社 | Loom member and manufacturing method thereof |
| JP5433897B2 (en) | 2009-10-22 | 2014-03-05 | 好孝 光田 | Diamond-like carbon film forming member and method for producing the same |
| CN115229192B (en) * | 2022-07-28 | 2024-03-29 | 廊坊西波尔钻石技术有限公司 | Method for compounding polycrystalline diamond compact |
-
1990
- 1990-01-24 JP JP1433890A patent/JP2734157B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03219079A (en) | 1991-09-26 |
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