JPH0782031A - Cubic boron nitride-containing sintered compact and its production - Google Patents
Cubic boron nitride-containing sintered compact and its productionInfo
- Publication number
- JPH0782031A JPH0782031A JP5181847A JP18184793A JPH0782031A JP H0782031 A JPH0782031 A JP H0782031A JP 5181847 A JP5181847 A JP 5181847A JP 18184793 A JP18184793 A JP 18184793A JP H0782031 A JPH0782031 A JP H0782031A
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- cubic boron
- boron nitride
- nitride
- sintered body
- 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
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、高硬度で、かつ高破壊
靭性値を有する立方晶窒化ホウ素含有焼結体およびその
製造方法に関し、具体的には、切削工具または耐摩耗工
具として最適な立方晶窒化ホウ素含有焼結体およびその
製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cubic boron nitride-containing sintered body having a high hardness and a high fracture toughness value, and a method for producing the same. Specifically, it is most suitable as a cutting tool or wear resistant tool. The present invention relates to a cubic boron nitride-containing sintered body and a method for manufacturing the same.
【０００２】[0002]
【従来の技術】立方晶窒化ホウ素は、ダイヤモンドに次
ぐ高い硬度と優れた熱伝導性を持ち、しかもダイヤモン
ドに比べて鉄との親和性が低いという工具材料としての
優れた長所を有している。この優れた長所を有している
立方晶窒化ホウ素と金属やセラミックスの結合相とでな
る立方晶窒化ホウ素含有焼結体についての検討が多数行
われており、その内、結合相成分組成および焼結体の組
織構造から提案されている代表的なものとして、特開昭
５６−１５６７３８号公報，特開昭５８−５８２４７号
公報，特開昭５８−６０６７８号公報，特開昭５８−６
０６７９号公報，特開昭５８−６０６８０号公報および
特開平２−２０８２５９号公報がある。2. Description of the Related Art Cubic boron nitride has the following advantages: high hardness second only to diamond and excellent thermal conductivity, and a lower affinity for iron than diamond. . Many studies have been carried out on cubic boron nitride-containing sintered compacts composed of cubic boron nitride and a binder phase of metal or ceramics, which have these excellent advantages. As typical ones proposed from the organization structure of the ties, JP-A-56-156738, JP-A-58-58247, JP-A-58-60678, and JP-A-58-6.
There are JP-A-0679, JP-A-58-60680 and JP-A-2-208259.
【０００３】[0003]
【発明が解決しようとする課題】特開昭５６−１５６７
３８号公報には、体積比で、２０〜８０％の立方晶窒化
ホウ素と、残り周期律表第４ａ，５ａ，６ａ族金属の炭
化物，窒化物，ホウ化物，ケイ化物もしくはこれらの混
合物または相互固溶体化合物の第１結合相と、Ａｌ，Ｓ
ｉ，Ｎｉ，Ｃｏ，Ｆｅまたはこれらを含む合金、化合物
の第２結合相とし、第１結合相，第２結合相が焼結体組
織中で連続した結合相をなし、前記周期律表第４ａ，５
ａ，６ａ族金属の化合物が結合相中の体積比で５０％以
上でなる高硬度工具用焼結体について記載されている。[Problems to be Solved by the Invention] JP-A-56-1567
No. 38, the volumetric ratio of cubic boron nitride is 20 to 80%, and the remaining periodic table 4a, 5a, 6a group metal carbides, nitrides, borides, silicides or mixtures thereof or mutual ones. First binder phase of solid solution compound, Al, S
i, Ni, Co, Fe or an alloy or a compound containing them, which is the second binder phase of the compound, and the first binder phase and the second binder phase form a continuous binder phase in the structure of the sintered body. , 5
It describes a sintered body for a high hardness tool in which a compound of group a, 6a metal is 50% or more by volume ratio in the binder phase.
【０００４】同公報に記載の高硬度工具用焼結体は、原
料として用いるミクロンまたはミクロン以下の微粉には
かなり多量の酸素を含有しており、超高圧下においては
酸素が焼結性を低下させるのに対し、非化学論量組成の
Ｔｉ，Ｚｒ，Ｈｆの炭化物，窒化物，炭窒化物を用い
て、ガス発生させないで焼結性を高めたというものであ
るが、第１結合相と第２結合相との組み合わせの仕方、
および第２結合相としてのＡｌ化合物の種類や粒径か
ら、耐摩耗性，体欠損性がまだ満足するまでに至ってい
なく、かつ破壊靭性値が低いという問題がある。The sintered body for a high hardness tool described in the above publication contains a considerably large amount of oxygen in micron or fine particles of micron or less used as a raw material, and oxygen deteriorates sinterability under ultrahigh pressure. On the other hand, a non-stoichiometric composition of Ti, Zr, and Hf carbides, nitrides, and carbonitrides was used to enhance the sinterability without generating gas. How to combine with the second bonding phase,
Also, there is a problem that abrasion resistance and body defectability are not yet satisfied due to the type and grain size of the Al compound as the second binding phase, and the fracture toughness value is low.
【０００５】特開平２−２０８２５９号公報には、立方
晶窒化ホウ素および／またはウルツ鉱型窒化ホウ素の硬
質相２０〜９０体積％と、残りが結合相と不可避不純物
とからなり、該結合相が周期律表の４ａ，５ａ，６ａ族
金属の窒化物およびこれらの相互固溶体の中の少なくと
も１種と、周期律表の４ａ，５ａ，６ａ族金属のホウ化
物およびこれらの相互固溶体の中の少なくとも１種と、
他に酸化アルミニウム，ホウ化アルミニウム，窒化アル
ミニウム，炭化ケイ素，窒化ケイ素の中の少なくとも１
種を含む高密度相窒化ホウ素反応焼結体について記載さ
れている。JP-A-2-208259 discloses that the hard phase of cubic boron nitride and / or wurtzite type boron nitride is 20 to 90% by volume, and the rest is a binder phase and inevitable impurities. At least one of nitrides of 4a, 5a and 6a metals of the periodic table and mutual solid solutions thereof, and at least one of borides of 4a, 5a and 6a metals of the periodic table and mutual solid solutions thereof. One kind,
At least one of aluminum oxide, aluminum boride, aluminum nitride, silicon carbide and silicon nitride
A dense phase boron nitride reactive sintered body including seeds is described.
【０００６】同公報に記載の高密度相窒化ホウ素反応焼
結体は、窒化ホウ素と周期律表の４ａ，５ａ，６ａ族の
金属およびこれらの２種以上の合金とを反応焼結して高
密度な窒化ホウ素焼結体としているのであるが、上述の
特開昭５６−１５６７３８号公報のような酸素に対する
積極的な配慮がなされていなく、高硬度な焼入網や合金
鋳鉄を被削材として切削した場合には、耐摩耗性，耐欠
損性が満足するに至っていないという問題がある。The high-density phase boron nitride reaction sintered body described in the above publication is highly sintered by reacting boron nitride with a metal of groups 4a, 5a, 6a of the periodic table and an alloy of two or more of these metals. Although the boron nitride sintered body has a high density, it does not give a positive consideration to oxygen as in the above-mentioned Japanese Patent Laid-Open No. 56-156738, and a high hardness quenching net or alloy cast iron is used as a work material. When it is cut as above, there is a problem that the wear resistance and the chipping resistance are not satisfied.
【０００７】特開昭５８−５８２４７号公報および特開
昭５８−６０６８０号公報には、０．１〜２μｍの平均
層厚さでなるＴｉ，Ｚｒ，Ｈｆ，Ｍｏのホウ化物で立方
晶窒化ホウ素を包囲し、他にセラミックスおよび金属の
含有した立方晶窒化ホウ素焼結体について記載されてお
り、特開昭５８−６０６７８号公報および特開昭５８−
６０６８０号公報には、０．１〜２μｍの平均層厚さで
なるＴｉ，Ｈｆ，Ｓｉの窒化物で立方晶窒化ホウ素を包
囲し、他にセラミックスおよび金属の含有した立方晶窒
化ホウ素焼結体について記載されている。In JP-A-58-58247 and JP-A-58-60680, cubic boron nitride is formed from a boride of Ti, Zr, Hf and Mo having an average layer thickness of 0.1 to 2 μm. And a cubic boron nitride sintered body containing ceramics and a metal are described in JP-A-58-60678 and JP-A-58-58.
Japanese Patent No. 60680 discloses a cubic boron nitride sintered body in which a cubic boron nitride is surrounded by a nitride of Ti, Hf, and Si having an average layer thickness of 0.1 to 2 μm, and other ceramics and a metal are contained. Is described.
【０００８】これら４件の公報に記載されている立方晶
窒化ホウ素焼結体は、立方晶窒化ホウ素粒子の表面を結
合相で包囲することにより、立方晶窒化ホウ素粒子の表
面における微小な凹み等によるボイドがなくなり、立方
晶窒化ホウ素と結合相との密着性に優れ、靭性と耐摩耗
性を兼ね備えた焼結体になっているというものである
が、破壊靭性値および高温時における耐欠損性がまだ充
分でなく、短寿命になるという問題がある。In the cubic boron nitride sintered bodies described in these four publications, the surface of the cubic boron nitride particles is surrounded by a binder phase so that minute recesses on the surface of the cubic boron nitride particles are formed. It is said that the sintered body has no voids caused by the above, has excellent adhesion between cubic boron nitride and the binder phase, and has both toughness and wear resistance, but it has a fracture toughness value and fracture resistance at high temperatures. However, there is a problem that the life is not sufficient and the life becomes short.
【０００９】本発明は、上述のような問題点を解決した
もので、具体的には、立方晶窒化ホウ素と反応焼結する
ような結合相前駆体物質を選定し、反応焼結により緻密
な焼結体にすると共に、結合相組成成分の選定およびそ
の粒径の調製から耐摩耗性を低下させずに、耐欠損性お
よび破壊靭性値を高めることに成功した立方晶窒化ホウ
素含有焼結体およびその製造方法の提供を目的とする。The present invention solves the above-mentioned problems. Specifically, a binder phase precursor substance that reacts with cubic boron nitride to react and sinter is selected. A cubic boron nitride-containing sintered body which was made into a sintered body and succeeded in increasing the fracture resistance and the fracture toughness value without lowering the wear resistance by selecting the binder phase composition component and adjusting the grain size thereof. And a method of manufacturing the same.
【００１０】[0010]
【課題を解決するための手段】本発明者らは、立方晶窒
化ホウ素と結合相とでなる焼結体の耐摩耗性および耐欠
損性の向上について検討していたところ、焼結体を作製
するための出発物質として、立方晶窒化ホウ素と反応焼
結する結合相前駆体物質、具体的には、Ｔｉの炭酸化
物，窒酸化物，炭窒酸化物の１種以上とＡｌとの結合相
前駆体物質を用いて、結合相前駆体物質と立方晶窒化ホ
ウ素とでもって反応焼結を起させると、緻密で耐摩耗
性，耐欠損性および破壊靭性値に優れた焼結体が得られ
るという知見を得て、本発明を完成するに至ったもので
ある。Means for Solving the Problems The inventors of the present invention have studied the improvement of wear resistance and fracture resistance of a sintered body composed of cubic boron nitride and a binder phase. As a starting material for this, a binder phase precursor material that reacts and sinters with cubic boron nitride, specifically, a binder phase of Al with at least one of Ti carbonate, nitrous oxide, and oxycarbonitride. When a precursor material is used and reactive sintering is carried out with a binder phase precursor material and cubic boron nitride, a dense sintered body having excellent wear resistance, fracture resistance and fracture toughness value can be obtained. The present invention has been completed based on the knowledge.
【００１１】すなわち、本発明の焼結体は、体積比で、
１０〜７０％の立方晶窒化ホウ素と、残りセラミックス
を主成分とする結合相と不可避不純物とからなる焼結体
であって、該結合相が焼結体の全体比で、酸化アルミニ
ウム５〜３０％と、窒化アルミニウムおよび／またはホ
ウ化アルミニウム３〜２０％と、炭化チタン，窒化チタ
ンまたは炭窒化チタンの中の１種以上１０〜４０％と、
ホウ化チタン３〜３０％とからなり、かつ該酸化アルミ
ニウムが１μｍ以下の粒径でなることを特徴とするもの
である。That is, the sintered body of the present invention has a volume ratio of
A sintered body comprising 10 to 70% of cubic boron nitride, a binder phase containing the remaining ceramics as a main component, and unavoidable impurities, the binder phase being 5 to 30% of aluminum oxide in a total ratio of the sintered body. %, Aluminum nitride and / or aluminum boride 3 to 20%, and one or more of titanium carbide, titanium nitride or titanium carbonitride 10 to 40%,
It is characterized in that it is composed of 3 to 30% of titanium boride and that the aluminum oxide has a particle diameter of 1 μm or less.
【００１２】本発明の焼結体における結合相は、酸化ア
ルミニウムと、窒化アルミニウムおよび／またはホウ化
アルミニウムと、炭化チタン，窒化チタンまたは炭窒化
チタンの中の１種以上と、ホウ化チタンとからなり、さ
らに必要に応じて周期律表４ａ，５ａ，６ａ族金属の炭
化物，窒化物，ホウ化物，ケイ化物およびこれらの相互
固溶体（但し、Ｔｉの炭化物，窒化物，炭窒化物は除
く）の中の１種以上を４０体積％以下またはＦｅ，Ｃ
ｏ，Ｎｉ，Ｃｒ，Ｍｏ，Ｗ等の金属、合金の中の１種以
上の含有したものである。この内、結合相中に金属，合
金を含有させる場合には、耐摩耗性の低下が顕著になる
ことから、結合相中の３０体積％以下、好ましくは１０
体積％以下である。The binder phase in the sintered body of the present invention comprises aluminum oxide, aluminum nitride and / or aluminum boride, one or more of titanium carbide, titanium nitride or titanium carbonitride, and titanium boride. In addition, if necessary, it is possible to add carbides, nitrides, borides, silicides of metals of groups 4a, 5a and 6a of the periodic table and their mutual solid solutions (excluding carbides, nitrides and carbonitrides of Ti). 40% by volume or less, or Fe, C
One or more kinds of metals and alloys such as o, Ni, Cr, Mo and W are contained. Of these, when a metal or alloy is contained in the binder phase, the wear resistance is markedly reduced, so that the content of the binder phase is 30% by volume or less, preferably 10% by volume or less.
Volume% or less.
【００１３】結合相の構成成分の内、酸化アルミニウム
が、焼結体の全体比で５体積％未満になると、耐摩耗性
および耐熱性の低下が著しく、逆に３０体積％を超えて
多くなると、靭性の低下が著しくなり、窒化アルミニウ
ムおよび／またはホウ化アルミニウムが３体積％未満に
なると、緻密な焼結体になり難く、逆に２０体積％を超
えて多くなると、強度および靭性の低下が著しくなり、
炭化チタン，窒化チタン，炭窒化チタンの１種以上が１
０体積％未満になると、強度および靭性の低下が著し
く、逆に４０体積％を超えて多くなると、他の結合相成
分含有量が相対的に少なくなり、耐熱性および耐摩耗性
の低下が著しく、ホウ化チタンが３体積％未満になる
と、高温における強度低下が著しく、逆に３０体積％を
超えて多くなると、あまり高くない温度領域での強度お
よび靭性の低下が著しくなる。Of the constituents of the binder phase, when the aluminum oxide content is less than 5% by volume of the sintered body, the wear resistance and heat resistance are significantly deteriorated, and conversely, the aluminum oxide content is more than 30% by volume. When the aluminum nitride and / or aluminum boride is less than 3% by volume, it becomes difficult to form a dense sintered body, and conversely, when it exceeds 20% by volume, the strength and toughness are deteriorated. Becomes noticeable,
1 or more of titanium carbide, titanium nitride, titanium carbonitride
If it is less than 0% by volume, the strength and toughness are remarkably deteriorated. On the contrary, if it is more than 40% by volume, the content of other binder phase components is relatively small, and the heat resistance and wear resistance are remarkably deteriorated. When the content of titanium boride is less than 3% by volume, the strength is significantly decreased at high temperature, and when it is more than 30% by volume, the strength and toughness are significantly decreased in a temperature range not so high.
【００１４】本発明の焼結体における立方晶窒化ホウ素
は、７０体積％を超えて多くなると、相対的に結合相が
３０体積％未満となり、結合相の組成成分を考慮した効
果が弱く、特に、できるだけ多くの立方晶窒化ホウ素の
粒子をホウ化チタンおよび／または窒化チタンのＴｉ化
合物で囲繞して焼結体の強度および靭性を高めるために
は、粒径との関係もあることながら、立方晶窒化ホウ素
の含有量は７０体積％が好ましく、逆に立方晶窒化ホウ
素が１０体積％未満になると、立方晶窒化ホウ素の高硬
度が充分に生かしきれなく、焼結体の耐摩耗性の低下が
顕著になる。If the cubic boron nitride content in the sintered body of the present invention exceeds 70% by volume, the binder phase will be relatively less than 30% by volume, and the effect in consideration of the composition components of the binder phase will be weak. In order to increase the strength and toughness of a sintered body by surrounding as many cubic boron nitride particles as possible with a titanium boride and / or titanium nitride Ti compound, the cubic particles have a relationship with the particle size, The content of cubic boron nitride is preferably 70% by volume, and conversely, when the content of cubic boron nitride is less than 10% by volume, the high hardness of cubic boron nitride cannot be fully utilized and the wear resistance of the sintered body decreases. Becomes noticeable.
【００１５】本発明の焼結体を作製するには、従来から
行われている各種の製造方法でもって作製することもで
きるが、次の方法で行うと緻密で高強度高靭性の焼結体
が得られやすく好ましいことである。The sintered body of the present invention can be manufactured by various conventional manufacturing methods. However, when the following method is used, the sintered body is dense and has high strength and high toughness. Is easily obtained, which is preferable.
【００１６】本発明の焼結体の製造方法は、立方晶窒化
ホウ素粉末と、Ｔｉの炭酸化物，窒酸化物，炭窒酸化物
の中の少なくとも１種の酸素含有化合物粉末と、Ａｌ粉
末とでなる混合粉末を圧粉成形体とする第１工程、必要
に応じて、該圧粉成形体を１×１０-3Ｔｏｒｒ以上の真
空中、７００℃〜１０００℃で熱処理する第２工程、次
いで圧力４〜６ＧＰａ，温度１４００〜１６００℃の超
高圧高温でもって反応焼結する第３工程とからなるもの
である。The method for producing a sintered body according to the present invention comprises a cubic boron nitride powder, at least one oxygen-containing compound powder of Ti carbonate, oxynitride and oxycarbonitride, and Al powder. The first step of forming the powder mixture into a powder compact, the second step of heat treating the powder compact at 700 ° C. to 1000 ° C. in a vacuum of 1 × 10 −3 Torr or more, if necessary. It comprises a third step of reacting and sintering at a pressure of 4 to 6 GPa and a temperature of 1400 to 1600 ° C. at ultrahigh pressure and high temperature.
【００１７】本発明の焼結体の製造方法における酸素含
有化合物粉末は、立方晶窒化ホウ素粉末とＡｌ粉末とに
よる反応焼結を行わせる重要な因子であり、具体的に
は、酸素含有化合物粉末とＡｌ粉末との反応焼結でもっ
て、酸素含有化合物粉末中の酸素とＡｌとが結合し、酸
化アルミニウムとなり、さらに酸素含有化合物粉末中の
酸素を除いた他の元素と立方晶窒化ホウ素との反応焼
結、または酸素含有化合物粉末中の酸素を除いた他の元
素と立方晶窒化ホウ素とＡｌとの反応焼結を行わせるこ
とにより、焼結体中の結合相として、酸化アルミニウム
と、窒化アルミニウムおよび／またはホウ化アルミニウ
ムと、炭化チタン，窒化チタン，炭窒化チタンの中の１
種以上と、ホウ化チタンとを含有するものである。The oxygen-containing compound powder in the method for producing a sintered body of the present invention is an important factor for performing reaction sintering with cubic boron nitride powder and Al powder. Specifically, the oxygen-containing compound powder is used. And Al powder, the oxygen and Al in the oxygen-containing compound powder are combined with each other to form aluminum oxide, and the other elements other than oxygen in the oxygen-containing compound powder are combined with cubic boron nitride. By performing reaction sintering or reaction sintering of cubic boron nitride and Al with other elements other than oxygen in the oxygen-containing compound powder, aluminum oxide and nitriding as a binder phase in the sintered body are obtained. Aluminum and / or aluminum boride and 1 of titanium carbide, titanium nitride, titanium carbonitride
It contains one or more seeds and titanium boride.
【００１８】この反応焼結によって得られる焼結体中の
立方晶窒化ホウ素は、立方晶窒化ホウ素と酸素含有化合
物との反応焼結によって形成されたホウ化チタンおよび
／または窒化チタンのＴｉ化合物により囲繞されること
になり、さらに反応焼結により形成された１μｍ以下の
微細な酸化アルミニウムが結合相中に分散し、強度およ
び靭性を一層高めることになる。この反応焼結の関係か
ら、立方晶窒化ホウ素は、平均粒径３μｍ以上のものが
好ましい。The cubic boron nitride in the sintered body obtained by this reactive sintering is the titanium compound of titanium boride and / or titanium nitride formed by the reactive sintering of cubic boron nitride and an oxygen-containing compound. As a result, the fine aluminum oxide particles having a size of 1 μm or less formed by reaction sintering are dispersed in the binder phase, and the strength and toughness are further enhanced. In view of this reaction sintering, the cubic boron nitride preferably has an average particle size of 3 μm or more.
【００１９】反応焼結を行わせるための酸素含有化合物
は、周期律表の４ａの金属であるＴｉ，Ｚｒ，Ｈｆの炭
酸化物，窒酸化物，炭窒酸化物を用いることも可能であ
るが、中でもＴｉの炭酸化物，窒酸化物，炭窒酸化物が
好ましい。この酸素含有化合物の酸素含有量は、同時に
用いるＡｌ粉末の含有量にも影響するが、酸素含有化合
物中の非金属元素を１モルとした場合に約０．８モル以
下、好ましくは０．６モル以下である。この酸素含有化
合物は、非化学量論組成からなることが好ましく、特
に、亜化学量論組成からなることが好ましい。As the oxygen-containing compound for carrying out the reactive sintering, it is possible to use the metal oxides of Ti, Zr and Hf which are metals 4a in the periodic table, such as carbon oxides, oxynitrides and oxycarbonitrides. Of these, Ti carbonates, oxynitrides, and oxycarbonitrides are preferable. The oxygen content of the oxygen-containing compound affects the content of Al powder used at the same time, but when the non-metal element in the oxygen-containing compound is 1 mol, the oxygen content is about 0.8 mol or less, preferably 0.6 mol or less. It is less than or equal to mol. The oxygen-containing compound preferably has a non-stoichiometric composition, and particularly preferably a substoichiometric composition.
【００２０】[0020]
【作用】本発明の焼結体は、反応焼結により形成された
１μｍ以下の粒径からなる酸化アルミニウムと、他の結
合相成分とによって、結合相の靭性および強度向上作用
をし、特に立方晶窒化ホウ素を囲繞した状態に形成され
るホウ化チタンおよび／または窒化チタンのＴｉ化合物
が立方晶窒化ホウ素と結合相と境界を緻密にする作用、
および結合を強化する作用をしている。The sintered body of the present invention has an effect of improving the toughness and strength of the binder phase by the aluminum oxide formed by the reaction sintering and having a grain size of 1 μm or less, and other binder phase components, and is particularly cubic. An action of titanium boride and / or a titanium compound of titanium nitride formed in a state of surrounding crystalline boron nitride to densify the boundary with cubic boron nitride, the bonding phase,
And acts to strengthen the bond.
【００２１】また、本発明の焼結体の製造方法は、出発
物質として用いる酸素含有化合物とＡｌと立方晶窒化ホ
ウ素が反応焼結を誘発する大きな役割をし、中でも酸素
含有化合物が酸素含有化合物とＡｌとの反応、酸素含有
化合物と立方晶窒化ホウ素との反応、Ａｌと立方晶窒化
ホウ素との反応という複合反応を誘発する作用をしてい
る。Further, in the method for producing a sintered body of the present invention, the oxygen-containing compound used as a starting material, Al and cubic boron nitride play a major role in inducing reactive sintering. Among them, the oxygen-containing compound is the oxygen-containing compound. It has the function of inducing a complex reaction of a reaction between Al and Al, a reaction between an oxygen-containing compound and cubic boron nitride, and a reaction between Al and cubic boron nitride.
【００２２】[0022]
【実施例】平均粒径４μｍのｃＢＮ粉末、平均粒径１μ
ｍの炭酸化物粉末，窒酸化物粉末，平均粒径１μｍのＡ
ｌ粉末，平均粒径１μｍのＴｉの炭化物粉末，窒化物粉
末，Ｈｆの炭化物粉末，Ｔａの窒化物粉末，Ｚｒの炭化
物粉末，平均粒径０．５μｍのＡｌ2Ｏ3粉末を用いて表
１に示す組成に配合し、これを超硬合金製ボールとメタ
ノール溶媒でもって混合粉砕して得た混合粉末を型押し
成形して圧粉体にした後、１×１０-5Ｔｏｒｒ、８５０
℃の条件で脱パラフィン処理し、次いで、超高圧高温装
置に設置し、５．５ＧＰａの圧力、１５００℃の温度、
３０分の保持時間の条件でもって焼結し、本発明品１〜
８および比較品１〜４を得た。Example: cBN powder having an average particle size of 4 μm, average particle size of 1 μ
m carbonate oxide powder, nitrous oxide powder, A with an average particle size of 1 μm
1 powder, Ti carbide powder, nitride powder, Hf carbide powder, Ta nitride powder, Zr carbide powder, and Al 2 O 3 powder having an average particle size of 0.5 μm having an average particle size of 1 μm. Compounded with the composition shown in Table 1 and mixed and crushed with a cemented carbide ball and a methanol solvent to obtain a mixed powder, which is pressed into a green compact, and then 1 × 10 −5 Torr, 850
Deparaffinization treatment under the condition of ℃, then installed in the ultra-high pressure high temperature apparatus, the pressure of 5.5GPa, the temperature of 1500 ℃,
Sintered under the condition of holding time of 30 minutes, the product of the present invention 1
8 and comparative products 1-4 were obtained.
【００２３】こうして得た本発明品１〜８および比較品
１〜４をＸ線回折により測定し、その組成成分を表２に
示した。また、これらの焼結体の硬さおよび破壊靭性値
を求めて表２に併記した。次に、顕微鏡でもって焼結体
の組織観察を行ったところ、本発明品１，４，６は、Ｔ
ｉ化合物が立方晶窒化ホウ素を囲繞した状態になってお
り、その平均層厚さは、約１μｍであった。また、本発
明品１〜８は、平均粒径０．１μｍ〜０．２μｍの酸化
アルミニウムが均一に分散していた。The products 1 to 8 of the present invention and the comparative products 1 to 4 thus obtained were measured by X-ray diffraction, and the composition components thereof are shown in Table 2. Further, the hardness and fracture toughness value of these sintered bodies were determined and shown in Table 2. Next, when the structure of the sintered body was observed with a microscope, the products of the present invention 1, 4, 6 were
The i compound was in a state of surrounding cubic boron nitride, and its average layer thickness was about 1 μm. Further, in the products 1 to 8 of the present invention, aluminum oxide having an average particle diameter of 0.1 μm to 0.2 μm was uniformly dispersed.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 次いで、本発明品１〜８および比較品１〜４を用いて、
下記条件による切削試験を行い、その結果を表３に示し
た。[Table 2] Then, using the present invention products 1 to 8 and the comparative products 1 to 4,
A cutting test was conducted under the following conditions, and the results are shown in Table 3.
【００２６】（Ａ）切削試験条件 被削材 ： ＳＣＭ４１５（ＨＲＣ６０．９〜６１．
７） 外周連続乾式切削 切削速度 ： １５０ｍ／ｍｉｎ 切込量 ： ０．５ｍｍ 送り ： ０．１ｍｍ／ｒｅｖ チップ形状： ＴＮＭＡ１６０４０８ ホルダー ： ＣＴＧＮＲ２０２０ 評価 ： 平均逃げ面摩耗量ＶB＝０．２ｍｍにな
るまでの切削時間または途中欠損の切削時間（なお、Ｖ
Bは５ｍｉｎごとに測定） （Ｂ）切削試験条件 被削材 ： ＦＣ３０（ＨB２１０〜２３０） 外周連続湿式切削 切削速度 ： ５００ｍ／ｍｉｎ 切り込み量： ０．５ｍｍ 送り ： ０．１５ｍｍ／ｒｅｖ チップ形状： ＴＮＭＡ１６０４０８ ホルダー ： ＣＳＢＮＲ２０２０ 評価 ： 平均逃げ面摩耗量ＶB＝０．２ｍｍにな
るまでの切削時間または途中欠損の切削時間（なお、Ｖ
Bは１０ｍｉｎごとに測定）(A) Cutting test conditions Work material: SCM415 (HRC60.9 to 61.
7) Peripheral continuous dry cutting Cutting speed: 150 m / min Depth of cut: 0.5 mm Feed: 0.1 mm / rev Tip shape: TNMA160408 Holder: CTGNR2020 Evaluation: Until average flank wear amount V B = 0.2 mm Cutting time or cutting time for intermediate defects (V
B is measured every 5min) (B) Cutting Test Conditions Workpiece: FC30 (H B 210~230) outer peripheral continuous wet cutting Cutting speed: 500 meters / min Depth of cut: 0.5mm Feed: 0.15 mm / rev chip shape : TNMA160408 Holder: CSBNR2020 Evaluation: Cutting time until the average flank wear amount V B = 0.2 mm or cutting time in the middle (V
(B is measured every 10 minutes)
【００２７】[0027]
【表３】 [Table 3]
【００２８】[0028]
【発明の効果】本発明の焼結体は、従来の立方晶窒化ホ
ウ素含有焼結体に比べて、破壊靭性値が高く、耐熱衝撃
性，高温での耐欠損性および耐酸化性等に優れているこ
とから、切削工具として用いた場合に長寿命となり、特
に立方晶窒化ホウ素がＴｉ化合物で囲繞された焼結体の
場合には、よりその効果が高くなる傾向にある。EFFECTS OF THE INVENTION The sintered body of the present invention has a higher fracture toughness value, superior thermal shock resistance, fracture resistance at high temperatures, and oxidation resistance, etc., as compared with the conventional cubic boron nitride-containing sintered body. Therefore, when it is used as a cutting tool, it has a long life, and particularly in the case of a sintered body in which cubic boron nitride is surrounded by a Ti compound, the effect tends to be higher.
Claims (8)
ウ素と、残りセラミックスを主成分とする結合相と不可
避不純物とからなる焼結体において、該結合相が焼結体
の全体比で、酸化アルミニウム５〜３０％と、窒化アル
ミニウムおよび／またはホウ化アルミニウム３〜２０％
と、炭化チタン，窒化チタンまたは炭窒化チタンの中の
１種以上１０〜４０％と、ホウ化チタン３〜３０％とか
らなり、かつ該酸化アルミニウムが１μｍ以下の粒径で
なることを特徴とする立方晶窒化ホウ素含有焼結体。1. A sintered body composed of 10 to 70% by volume of cubic boron nitride, a binder phase composed mainly of the remaining ceramics, and unavoidable impurities, wherein the binder phase is the entire ratio of the sintered body. And aluminum oxide 5 to 30% and aluminum nitride and / or aluminum boride 3 to 20%
And 10 to 40% of one or more of titanium carbide, titanium nitride or titanium carbonitride and 3 to 30% of titanium boride, and the aluminum oxide has a particle size of 1 μm or less. A cubic boron nitride-containing sintered body.
１〜２．０μｍのホウ化チタンおよび／または窒化チタ
ンのＴｉ化合物により囲繞されていることを特徴とする
請求項１記載の立方晶窒化ホウ素含有焼結体。2. The cubic boron nitride has an average layer thickness of 0.
The cubic boron nitride-containing sintered body according to claim 1, which is surrounded by a Ti compound of 1 to 2.0 μm of titanium boride and / or titanium nitride.
ウ素と、残りセラミックスを主成分とする結合相と不可
避不純物とからなる焼結体において、該結合相が焼結体
の全体比で、酸化アルミニウム５〜３０％と、窒化アル
ミニウムおよび／またはホウ化アルミニウム３〜２０％
と、炭化チタン，窒化チタンまたは炭窒化チタンの中の
１種以上１０〜４０％と、ホウ化チタン３〜３０％と、
周期律表４ａ，５ａ，６ａ族金属の炭化物，窒化物およ
びこれらの相互固溶体４０％以下（但し、Ｔｉの炭化
物，窒化物，炭窒化物は除く）からなり、かつ該酸化ア
ルミニウムが１μｍ以下の粒径でなることを特徴とする
立方晶窒化ホウ素含有焼結体。3. A sintered body comprising 10 to 70% by volume of cubic boron nitride, a binder phase containing the remaining ceramics as a main component, and unavoidable impurities, wherein the binder phase is the overall ratio of the sintered body. And aluminum oxide 5 to 30% and aluminum nitride and / or aluminum boride 3 to 20%
And 10 to 40% of one or more of titanium carbide, titanium nitride or titanium carbonitride, and 3 to 30% of titanium boride,
Consists of 40% or less (excluding Ti carbide, nitride and carbonitride) of carbides and nitrides of metals of groups 4a, 5a and 6a of the periodic table and mutual solid solutions thereof, and the aluminum oxide is 1 μm or less. A cubic boron nitride-containing sintered body characterized by having a grain size.
１〜２．０μｍのホウ化チタンおよび／または窒化チタ
ンのＴｉ化合物により囲繞されていることを特徴とする
請求項３記載の立方晶窒化ホウ素含有焼結体。4. The cubic boron nitride has an average layer thickness of 0.
The cubic boron nitride-containing sintered body according to claim 3, which is surrounded by a Ti compound of 1 to 2.0 μm of titanium boride and / or titanium nitride.
物，窒酸化物，炭窒酸化物の中の少なくとも１種の酸素
含有化合物粉末と、Ａｌ粉末とでなる混合粉末を圧粉成
形体とする第１工程、必要に応じて、該圧粉成形体を１
×１０-3Ｔｏｒｒ以上の真空中、７００℃〜１０００℃
で熱処理する第２工程、次いで圧力４〜６ＧＰａ，温度
１４００〜１６００℃の超高圧高温でもって反応焼結
し、体積比で、１０〜７０％の立方晶窒化ホウ素と、酸
化アルミニウム５〜３０％と、窒化アルミニウムおよび
／またはホウ化アルミニウム３〜２０％と、炭化チタ
ン，窒化チタンまたは炭窒化チタンの中の１種以上１０
〜４０％と、ホウ化チタン３〜３０％とからなり、かつ
該酸化アルミニウムが１μｍ以下の粒径でなる焼結体と
する第３工程からなる立方晶窒化ホウ素含有焼結体の製
造方法。5. A powder compact formed from a cubic boron nitride powder, a powder of Ti carbonate, at least one oxygen-containing compound powder of oxycarbonitride, and an Al powder. The first step, which is to
700 ° C to 1000 ° C in a vacuum of × 10 -3 Torr or more
In the second step of heat treatment in the next step, followed by reaction sintering at a pressure of 4 to 6 GPa and a temperature of 1400 to 1600 ° C. at an ultrahigh pressure and a high temperature, cubic boron nitride of 10 to 70% by volume and aluminum oxide of 5 to 30%. And 3 to 20% of aluminum nitride and / or aluminum boride and one or more of titanium carbide, titanium nitride or titanium carbonitride 10
-40% and titanium boride 3-30%, and a method for producing a cubic boron nitride-containing sintered body, which comprises a third step of forming a sintered body in which the aluminum oxide has a grain size of 1 µm or less.
中の酸素元素の含有比が０．２〜０．８モルでなること
を特徴とする請求項５記載の立方晶窒化ホウ素含有焼結
体の製造方法。6. The cubic boron nitride-containing sintered material according to claim 5, wherein the oxygen-containing compound powder has a content ratio of oxygen element in the non-metal element of 0.2 to 0.8 mol. Body manufacturing method.
物，窒酸化物，炭窒酸化物の中の少なくとも１種の酸素
含有化合物粉末と、Ａｌ粉末と、周期律表４ａ，５ａ，
６ａ族金属の炭化物，窒化物およびこれらの相互固溶体
の中の少なくとも１種の粉末とでなる混合粉末を圧粉成
形体とする第１工程、必要に応じて、該圧粉成形体を１
×１０-3Ｔｏｒｒ以上の真空中、７００℃〜１０００℃
で熱処理する第２工程、次いで圧力４〜６ＧＰａ，温度
１４００〜１６００℃の超高圧高温でもって反応焼結
し、体積比で、１０〜７０％の立方晶窒化ホウ素と、酸
化アルミニウム５〜３０％と、窒化アルミニウムおよび
／またはホウ化アルミニウム３〜２０％と、炭化チタ
ン，窒化チタンまたは炭窒化チタンの中の１種以上１０
〜４０％と、ホウ化チタン３〜３０％と、周期律表４
ａ，５ａ，６ａ族金属の炭化物，窒化物およびこれらの
相互固溶体４０％以下（但し、Ｔｉの炭化物，窒化物，
炭窒化物は除く）とからなり、かつ該酸化アルミニウム
が１μｍ以下の粒径でなる焼結体とする第３工程からな
る立方晶窒化ホウ素含有焼結体の製造方法。7. A cubic boron nitride powder, a carbon oxide of Ti, at least one oxygen-containing compound powder among oxycarbonitrides, an Al powder, and a periodic table 4a, 5a,
A first step of forming a powder compact with a mixed powder consisting of a carbide or nitride of a Group 6a metal and at least one kind of powder among these mutual solid solutions, and if necessary, the powder compact 1
700 ° C to 1000 ° C in a vacuum of × 10 -3 Torr or more
In the second step of heat treatment in the next step, followed by reaction sintering at a pressure of 4 to 6 GPa and a temperature of 1400 to 1600 ° C. at an ultrahigh pressure and a high temperature. And 3 to 20% of aluminum nitride and / or aluminum boride and one or more of titanium carbide, titanium nitride or titanium carbonitride 10
-40%, titanium boride 3-30%, and Periodic Table 4
Carbides and nitrides of a, 5a and 6a group metals and their mutual solid solutions of 40% or less (however, Ti carbides, nitrides,
(Excluding carbonitride) and a cubic boron nitride-containing sintered body comprising a third step of forming a sintered body having the aluminum oxide particle size of 1 μm or less.
中の酸素元素の含有比が０．２〜０．８モルでなること
を特徴とする請求項７記載の立方晶窒化ホウ素含有焼結
体の製造方法。8. The cubic boron nitride-containing sintered material according to claim 7, wherein the oxygen-containing compound powder has a content ratio of oxygen element in the non-metal element of 0.2 to 0.8 mol. Body manufacturing method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18184793A JP3476507B2 (en) | 1993-06-28 | 1993-06-28 | Method for producing cubic boron nitride-containing sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18184793A JP3476507B2 (en) | 1993-06-28 | 1993-06-28 | Method for producing cubic boron nitride-containing sintered body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0782031A true JPH0782031A (en) | 1995-03-28 |
| JP3476507B2 JP3476507B2 (en) | 2003-12-10 |
Family
ID=16107866
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP18184793A Expired - Fee Related JP3476507B2 (en) | 1993-06-28 | 1993-06-28 | Method for producing cubic boron nitride-containing sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3476507B2 (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635593B1 (en) | 1999-02-12 | 2003-10-21 | Sumitomo Electric Industries, Ltd. | High strength sintered impact having excellent resistance to cratering |
| WO2005056495A1 (en) | 2003-12-03 | 2005-06-23 | Diamond Innovations, Inc. | Cubic boron nitride sintered body and method for making the same |
| WO2010119962A1 (en) | 2009-04-17 | 2010-10-21 | 株式会社タンガロイ | Cubic boron nitride sintered compact and coated cubic boron nitride sintered compact |
| US7932199B2 (en) | 2004-02-20 | 2011-04-26 | Diamond Innovations, Inc. | Sintered compact |
| WO2012053375A1 (en) * | 2010-10-19 | 2012-04-26 | 住友電工ハードメタル株式会社 | Tool comprising sintered cubic boron nitride |
| WO2012105710A1 (en) | 2011-02-04 | 2012-08-09 | 株式会社タンガロイ | cBN SINTERED MATERIAL TOOL AND COATED cBN SINTERED MATERIAL TOOL |
| US8354353B2 (en) | 2008-09-17 | 2013-01-15 | Diamond Innovations, Inc. | Cubic boron nitride ceramic composites and methods of making thereof |
| US8500834B2 (en) | 2004-02-20 | 2013-08-06 | Diamond Innovations, Inc. | Sintered compact |
| WO2015060320A1 (en) | 2013-10-22 | 2015-04-30 | 株式会社タンガロイ | Cubic boron nitride sintered body, and coated cubic boron nitride sintered body |
| JP2015193072A (en) * | 2014-03-28 | 2015-11-05 | 三菱マテリアル株式会社 | Cutting tool comprising sintered body of cubic boron nitride |
| WO2019087481A1 (en) * | 2017-10-30 | 2019-05-09 | 住友電気工業株式会社 | Sintered body and cutting tool including same |
| US10744569B2 (en) * | 2016-03-07 | 2020-08-18 | Mitsubishi Materials Corporation | Surface-coated cubic boron nitride sintered material tool |
| GB2591616A (en) * | 2020-01-28 | 2021-08-04 | Element Six Uk Ltd | Polycrystalline cubic boron nitride material |
| CN114845975A (en) * | 2019-12-16 | 2022-08-02 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body and method for producing same |
| CN114867700A (en) * | 2019-12-16 | 2022-08-05 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6293669B2 (en) * | 2011-12-05 | 2018-03-14 | ダイヤモンド イノヴェーションズ インコーポレイテッド | Sintered cubic boron nitride cutting tool |
-
1993
- 1993-06-28 JP JP18184793A patent/JP3476507B2/en not_active Expired - Fee Related
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6635593B1 (en) | 1999-02-12 | 2003-10-21 | Sumitomo Electric Industries, Ltd. | High strength sintered impact having excellent resistance to cratering |
| WO2005056495A1 (en) | 2003-12-03 | 2005-06-23 | Diamond Innovations, Inc. | Cubic boron nitride sintered body and method for making the same |
| US8500834B2 (en) | 2004-02-20 | 2013-08-06 | Diamond Innovations, Inc. | Sintered compact |
| US7932199B2 (en) | 2004-02-20 | 2011-04-26 | Diamond Innovations, Inc. | Sintered compact |
| US8067323B2 (en) | 2004-02-20 | 2011-11-29 | Diamond Innovations, Inc. | Sintered compact |
| US8354353B2 (en) | 2008-09-17 | 2013-01-15 | Diamond Innovations, Inc. | Cubic boron nitride ceramic composites and methods of making thereof |
| JP5660034B2 (en) * | 2009-04-17 | 2015-01-28 | 株式会社タンガロイ | Cubic boron nitride sintered body and coated cubic boron nitride sintered body |
| WO2010119962A1 (en) | 2009-04-17 | 2010-10-21 | 株式会社タンガロイ | Cubic boron nitride sintered compact and coated cubic boron nitride sintered compact |
| WO2012053375A1 (en) * | 2010-10-19 | 2012-04-26 | 住友電工ハードメタル株式会社 | Tool comprising sintered cubic boron nitride |
| CN102712048A (en) * | 2010-10-19 | 2012-10-03 | 住友电工硬质合金株式会社 | Tool comprising sintered cubic boron nitride |
| JP5771883B2 (en) * | 2010-10-19 | 2015-09-02 | 住友電工ハードメタル株式会社 | Cubic boron nitride sintered tool |
| US8822361B2 (en) | 2010-10-19 | 2014-09-02 | Sumitomo Electric Hardmetal Corp. | Cubic boron nitride sintered body tool |
| WO2012105710A1 (en) | 2011-02-04 | 2012-08-09 | 株式会社タンガロイ | cBN SINTERED MATERIAL TOOL AND COATED cBN SINTERED MATERIAL TOOL |
| WO2015060320A1 (en) | 2013-10-22 | 2015-04-30 | 株式会社タンガロイ | Cubic boron nitride sintered body, and coated cubic boron nitride sintered body |
| US20160236988A1 (en) * | 2013-10-22 | 2016-08-18 | Tungaloy Corporation | Cubic boron nitride sintered body and coated cubic boron nitride sintered body |
| US9950962B2 (en) | 2013-10-22 | 2018-04-24 | Tungaloy Corporation | Cubic boron nitride sintered body and coated cubic boron nitride sintered body |
| JP2015193072A (en) * | 2014-03-28 | 2015-11-05 | 三菱マテリアル株式会社 | Cutting tool comprising sintered body of cubic boron nitride |
| US10744569B2 (en) * | 2016-03-07 | 2020-08-18 | Mitsubishi Materials Corporation | Surface-coated cubic boron nitride sintered material tool |
| WO2019087481A1 (en) * | 2017-10-30 | 2019-05-09 | 住友電気工業株式会社 | Sintered body and cutting tool including same |
| JPWO2019087481A1 (en) * | 2017-10-30 | 2020-09-24 | 住友電気工業株式会社 | Sintered body and cutting tools containing it |
| CN114845975A (en) * | 2019-12-16 | 2022-08-02 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body and method for producing same |
| CN114867700A (en) * | 2019-12-16 | 2022-08-05 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body |
| CN114867700B (en) * | 2019-12-16 | 2023-06-27 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body |
| CN114845975B (en) * | 2019-12-16 | 2023-08-22 | 住友电工硬质合金株式会社 | Cubic boron nitride sintered body and method for producing same |
| GB2591616A (en) * | 2020-01-28 | 2021-08-04 | Element Six Uk Ltd | Polycrystalline cubic boron nitride material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3476507B2 (en) | 2003-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100219930B1 (en) | Superhard composite member and its production | |
| JP5100927B2 (en) | Method for producing cubic boron nitride sintered body | |
| JP3476507B2 (en) | Method for producing cubic boron nitride-containing sintered body | |
| US7615185B2 (en) | Multicomponent ceramics powder, method of manufacturing multicomponent ceramics powder, sintered body, and method of manufacturing sintered body | |
| JPS58211862A (en) | Composite silicon nitride cutting tool also executing coating | |
| JP4065666B2 (en) | High crater resistance High strength sintered body | |
| JP2000247746A (en) | Cutting tool of cubic boron nitride-based sintered compact | |
| JP3949181B2 (en) | Diamond sintered body using hard alloy as binder and method for producing the same | |
| JP2007084382A (en) | Cubic boron nitride sintered compact, coated cubic boron nitride sintered compact, and cutting tool for quench-hardened steel comprising the same | |
| JP2005097646A (en) | Sintered alloy with gradient structure, and its production method | |
| JPH05310474A (en) | High-toughness boron nitride sintered compact with high-pressure phase | |
| JPH0881270A (en) | Ceramic sintered compact containing cubic boron nitride and cutting tool | |
| JPS644988B2 (en) | ||
| JPH07278719A (en) | Particulate plate crystal cemented carbide containing wc and its production | |
| JPH07172924A (en) | Highly tough sintered compact for tool and its production | |
| JP2000218411A (en) | Cubic boron nitride sintered body cutting tool | |
| JPS644989B2 (en) | ||
| JP2002194474A (en) | Tungsten carbide matrix super hard composite sintered body | |
| JP3976285B2 (en) | Cermet tool having a hard nitrided layer and method for producing the same | |
| JPS61197469A (en) | Manufacture of cubic boron nitride base sintering material for cutting tool | |
| JP2003081677A (en) | Dispersion-enhanced cbn-based sintered compact and method of producing the same | |
| JP3092887B2 (en) | Surface-finished sintered alloy and method for producing the same | |
| JP2001179508A (en) | Cutting tool | |
| JP2782524B2 (en) | High density phase boron nitride based reaction sintered body and method for producing the same | |
| JP2006291299A (en) | Hard metal, coated hard metal, and method for manufacturing them |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20030916 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R360 | Written notification for declining of transfer of rights |
Free format text: JAPANESE INTERMEDIATE CODE: R360 |
|
| R370 | Written measure of declining of transfer procedure |
Free format text: JAPANESE INTERMEDIATE CODE: R370 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| LAPS | Cancellation because of no payment of annual fees |