JPH07238338A - High strength touch cemented carbide and coated cemented carbide - Google Patents
High strength touch cemented carbide and coated cemented carbideInfo
- Publication number
- JPH07238338A JPH07238338A JP5297294A JP5297294A JPH07238338A JP H07238338 A JPH07238338 A JP H07238338A JP 5297294 A JP5297294 A JP 5297294A JP 5297294 A JP5297294 A JP 5297294A JP H07238338 A JPH07238338 A JP H07238338A
- Authority
- JP
- Japan
- Prior art keywords
- dispersed phase
- cemented carbide
- group
- carbide
- composite
- 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
Landscapes
- Powder Metallurgy (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、炭化タングステンを主
成分として含有する超硬合金に関し、具体的には、例え
ばバイト，ドリル，エンドミル，リーマ，ブローチに代
表される切削工具、絞り型，しごき型，鍛造型などの塑
性加工工具、打抜き型，スリッターなどの剪断工具に代
表される耐摩耗工具、時計枠，タイピンに代表される装
飾，耐蝕部品として適する高強度強靭性超硬合金に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a cemented carbide containing tungsten carbide as a main component, and specifically, for example, a cutting tool represented by a cutting tool, a drill, an end mill, a reamer, and a broach, a drawing die, and an ironing machine. Molds, forging dies and other plastic working tools, punching dies, wear-resistant tools typified by shearing tools such as slitters, watch frames, decorations typified by tie pins, and high-strength tough cemented carbide suitable for corrosion-resistant parts. is there.
【０００２】[0002]
【従来の技術】ＷＣ−Ｃｏ系合金にＴｉ，Ｚｒ，Ｈｆ，
Ｖ，Ｎｂ，Ｔａの炭化物を少量添加した超硬合金は、従
来から実用されており、例えばＷＣーＴａＣ（ＮｂＣ）
−Ｃｏ系超硬合金が鋳物，非鉄金属，非金属などの切削
工具として、またＷＣ−ＶＣ−Ｃｏ系超硬合金が鋼の倣
い切削工具，ドイル，エンドミルとして実用されてい
る。これらのＷＣ以外の炭化物は、焼結時のＷＣ粒成長
を抑制し、かつ冷却時にＷＣ粒界へ析出するため、超硬
合金の硬さおよび耐摩耗性を高め、高温での耐塑性変形
性を改善する効果がある。2. Description of the Related Art Ti, Zr, Hf,
Cemented carbides with small additions of V, Nb, and Ta carbides have been used for a long time, for example, WC-TaC (NbC).
-Co-based cemented carbide has been put to practical use as a cutting tool for castings, non-ferrous metals, non-metals, etc., and WC-VC-Co-based cemented carbide has been put to practical use as a steel copying cutting tool, doyle, and end mill. These carbides other than WC suppress the growth of WC grains during sintering and precipitate at the WC grain boundaries during cooling, thus increasing the hardness and wear resistance of the cemented carbide and the plastic deformation resistance at high temperatures. Has the effect of improving.
【０００３】しかしながら、例えば「粉体および粉末冶
金」１５（１９６８）１４に記載されているように、Ｗ
Ｃ以外の炭化物を少量添加した超硬合金は、焼結時にＷ
Ｃ以外の炭化物がＣｏ液相中に完全溶解し、冷却時に数
１０μｍもの粗大な樹枝状析出物となって晶出するため
に、強度，靭性ともに著しく低下するという問題があ
る。一方、ＷＣ以外の炭化物の添加量を溶解限以上に増
加させた超硬合金は、焼結時にＣｏ液相中に溶解しない
粒子が核となって均一に晶出するために、粗大な樹枝状
析出物の晶出を防止できるが、ＷＣ以外の炭化物を多量
に添加することにより、強度，靭性および耐すきとり摩
耗性を低下させるという問題がある。However, as described, for example, in "Powder and Powder Metallurgy" 15 (1968) 14, W
Cemented carbide containing a small amount of carbides other than C is
Since the carbides other than C are completely dissolved in the Co liquid phase and crystallize as coarse dendritic precipitates of several tens of μm upon cooling and crystallize, both strength and toughness are significantly reduced. On the other hand, the cemented carbide in which the addition amount of carbides other than WC is increased above the melting limit causes coarse dendritic grains because particles that do not dissolve in the Co liquid phase during crystallization form uniform nuclei. Although crystallization of precipitates can be prevented, the addition of a large amount of carbide other than WC causes a problem of lowering strength, toughness and scrape abrasion resistance.
【０００４】これらの問題を解決しようとしたＷＣーＣ
ｏ系超硬合金が多数提案されており、その代表的なもの
に、特開昭６１−１２４５４８号公報，特開平１−１９
１７６０号公報，特開平２−２２４３８号公報および特
開平２−１９０４３９号公報がある。WC-C which tried to solve these problems
Many o-type cemented carbides have been proposed, and representative ones thereof are Japanese Patent Laid-Open Nos. 61-124548 and 1-19.
1760, JP-A-2-22438 and JP-A-2-190439.
【０００５】[0005]
【発明が解決しようとする課題】ＷＣ−Ｃｏ系合金に、
ＷＣ以外の添加物を少量添加した超硬合金の内、特開昭
６１−１２４５４８号公報には、重量比で、ＷＣを主成
分とする硬質相７５〜９０％をＦｅ族およびＣｒ族のう
ちの１種以上１０〜２５％、ＨｆまたはＨｆ炭化物０．
１〜３．２％添加、硬質相の一部をＴａＣおよびＮｂＣ
の１種または２種０．１〜５％で置換した超硬合金につ
いて記載されている。また、特開平１−１９１７６０号
公報には、重量比で、Ｃｏ２〜５．５％、Ｔｉ，Ｔａ，
Ｎｂ，Ｖ，Ｃｒの炭化物のうちの１種以上０．２〜２
％、残りが炭化タングステンとする不可避不純物からな
る組成で、かつ炭化タングステンの平均粒系が０．３〜
１．２μｍでなるＴｉ合金切削用超硬合金について記載
されている。さらに、特開平２−２２４３８号公報に
は、重量比で、結合相形成成分としてのＣｏおよびＮｉ
の１種以上８〜２０％、Ｔｉ，Ｔａ，Ｎｂの炭化物の１
種以上０．２〜５％、残りが炭化タングステンと不可避
不純物からなる組成で、かつ炭化タングステンが炭化タ
ングステンに占める割合で、１μｍ以下の粒径５５〜７
０容量％、２〜４μｍの粒径２５〜４０容量％、１μｍ
以下の粒径と２〜４μｍの粒径の合計８０容量％以上で
なる超硬合金製エンドミルについて記載されている。そ
の他、特開平２−１９０４３９号公報には、粉末粒径１
〜１０μｍのＷＣを主成分とする系に、Ｎｉ１０〜３０
ｗｔ％、Ｃｒ3Ｃ2２ｗｔ％以下を含み、さらにＴａＣ，
ＴｉＣ，ＨｆＣの１種以上０．１〜２ｗｔ％を含む超硬
合金について記載されている。[Problems to be Solved by the Invention]
Among the cemented carbides containing a small amount of additives other than WC, JP-A-61-124548 discloses that a hard phase containing WC as a main component in a weight ratio of 75 to 90% is contained in Fe group and Cr group. 10 to 25% of Hf or Hf carbide 0.
Addition of 1 to 3.2%, part of hard phase is TaC and NbC
1 or 2 of the above-mentioned cemented carbides substituted by 0.1 to 5%. Further, in JP-A-1-191760, Co2 to 5.5% by weight ratio, Ti, Ta,
One or more of Nb, V and Cr carbides 0.2 to 2
%, The balance being tungsten carbide with the unavoidable impurities, and the average grain size of tungsten carbide is 0.3-
A cemented carbide for cutting a Ti alloy having a thickness of 1.2 μm is described. Further, in JP-A-2-22438, Co and Ni as binder phase forming components are used in a weight ratio.
1 or more of 8 to 20%, 1 of carbide of Ti, Ta, Nb
The composition is composed of 0.2 to 5% or more of the seeds, the balance being tungsten carbide and unavoidable impurities, and the ratio of tungsten carbide to tungsten carbide is 1 μm or less and the particle size is 55 to 7
0% by volume, particle size of 2 to 4 μm 25 to 40% by volume, 1 μm
The following describes a cemented carbide end mill having a total particle size of 2% to 2 μm and 80% by volume or more. In addition, in Japanese Patent Application Laid-Open No. 2-190439, powder particle size 1
Ni-10 to 30 in a system containing WC of 10 μm as a main component
wt%, Cr 3 C 2 2 wt% or less, TaC,
It describes a cemented carbide containing one or more of TiC and HfC in an amount of 0.1 to 2 wt%.
【０００６】これら４件の公報に記載されている超硬合
金は、組成成分または組成成分と炭化タングステンの粒
径の調整でもって、超硬合金の諸特性の向上を達成しよ
うとしたものではあるが、炭化タングステン以外の炭化
物による粗大な樹枝状析出物の晶出が生じて、やはり強
度および靭性を満足するには至っていないという問題が
ある。The cemented carbides described in these four publications are intended to improve various properties of the cemented carbide by adjusting the composition components or the grain sizes of the composition components and tungsten carbide. However, there is a problem that coarse dendritic precipitates are crystallized by carbides other than tungsten carbide, and the strength and toughness are still not satisfied.
【０００７】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、炭化タングステンを主成分とする
超硬合金中に、炭化タングステン以外の炭化物，窒化
物，炭窒化物でなる少量の分散相を微細で均一に分布さ
せて、略同組成の従来の超硬合金に比べて、略同一硬さ
に維持し、強度および靭性を顕著に高めた超硬合金の提
供を目的とするものである。The present invention has solved the above-mentioned problems. Specifically, in a cemented carbide containing tungsten carbide as a main component, carbides, nitrides, and carbonitrides other than tungsten carbide are used. The purpose of the present invention is to provide a cemented carbide in which a small amount of the dispersed phase is finely and uniformly distributed to maintain substantially the same hardness as compared with the conventional cemented carbide having substantially the same composition, and to significantly enhance the strength and toughness. It is what
【０００８】[0008]
【課題を解決するための手段】本発明者らは、ＷＣ−Ｃ
ｏ系合金に、ＷＣ以外の炭化物を少量添加した場合に生
じる粗大な樹枝状析出物の晶出の防止について検討して
いたところ、樹枝状析出物の晶出核として働く化合物粒
子を添加；分散させて均一微細な組織の分散相にするこ
と、この化合物としては樹枝状析出物と同一結晶構造お
よび近接した格子定数を有し、Ｃｏ液相中への溶解度が
低く、かつ合金特性を低下させないこと、これらを満足
するには、ＷＣーＣｏ系合金中に、炭化物，窒化物，炭
窒化物としての分散相に周期律表の４ａ族元素と周期律
表の５ａ族元素をある一定比の割合に存在させることで
達成することができ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。The present inventors have found that WC-C
When the prevention of crystallization of coarse dendritic precipitates that occurs when a small amount of carbides other than WC is added to the o-based alloy, compound particles that act as crystallization nuclei of dendritic precipitates were added; dispersion To form a dispersed phase with a uniform fine structure, this compound has the same crystal structure as the dendritic precipitate and a lattice constant close to it, has low solubility in the Co liquid phase, and does not deteriorate the alloy properties. In order to satisfy these, in the WC-Co alloy, the 4a group element of the periodic table and the 5a group element of the periodic table are provided in a certain ratio in the dispersed phase as carbides, nitrides, and carbonitrides. The present invention has been completed based on the finding that it can be achieved by allowing the presence of a certain proportion.
【０００９】すなわち、本発明の超硬合金は、Ｃｏおよ
び／またはＮｉを主成分とする結合相３〜３０重量％
と、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａの炭化物，窒化
物およびこれらの相互固溶体、並びにＴｉ，Ｚｒ，Ｈ
ｆ，Ｖ，Ｎｂ，Ｔａの１種以上とＷ，Ｍｏ，Ｃｒの１種
以上とを含む複合炭化物，複合窒化物，複合炭窒化物の
中から選ばれた１種以上の分散相（但し、分散相中には
Ｔｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素とＶ，Ｎ
ｂ，Ｔａの中の１種以上の５ａ族元素が含まれる）０．
０３〜５重量％と、残りが炭化タングステンからなる合
金であって、該分散相に含まれるＴｉ，Ｚｒ，Ｈｆの中
の１種以上の４ａ族元素が該分散相に含まれるＶ，Ｎ
ｂ，Ｔａの中の１種以上の５ａ族元素に対する重量百分
率で８５％以下でなることを特徴とするものである。That is, the cemented carbide of the present invention has a binder phase containing Co and / or Ni as a main component in an amount of 3 to 30% by weight.
And Ti, Zr, Hf, V, Nb, Ta carbides, nitrides and their mutual solid solutions, and Ti, Zr, H
One or more dispersed phases selected from among composite carbides, composite nitrides, and composite carbonitrides containing at least one of f, V, Nb, Ta and at least one of W, Mo, Cr (however, In the dispersed phase, one or more 4a group elements in Ti, Zr, and Hf and V, N
b, Ta containing one or more Group 5a elements).
It is an alloy consisting of 03 to 5% by weight and the balance tungsten carbide, and V, N in which at least one Group 4a element of Ti, Zr, and Hf contained in the dispersed phase is contained in the dispersed phase.
It is characterized by being 85% or less in weight percentage with respect to one or more group 5a elements of b and Ta.
【００１０】また、好ましくは、本発明の超硬合金は、
上述の結合相３〜３０重量％と、上述の分散相０．０３
〜５重量％と、残りが炭化タングステンからなる合金で
あって、該分散相に含まれるＴｉ，Ｚｒ，Ｈｆの中の１
種以上の４ａ族元素が該結合相に対する重量百分率で
０．２〜５％であり、該分散相に含まれるＶ，Ｎｂ，Ｔ
ａの中の１種以上の５ａ族元素が該結合相に対する重量
百分率で１〜１０％であることを特徴とするものであ
る。Also, preferably, the cemented carbide of the present invention comprises:
3 to 30% by weight of the above binder phase and 0.03 of the above dispersed phase
An alloy consisting of ˜5 wt% and the balance tungsten carbide, which is one of Ti, Zr and Hf contained in the dispersed phase.
The group 4a element or more is 0.2 to 5% by weight relative to the binder phase, and V, Nb, T contained in the dispersed phase.
One or more Group 5a elements in a are 1 to 10% in weight percentage with respect to the binder phase.
【００１１】さらに、特に好ましくは、本発明の超硬合
金は、上述の結合相３〜３０重量％と、上述の分散相
０．０３〜５重量％と、残りが炭化タングステンからな
る合金であって、該分散相に含まれるＴｉ，Ｚｒ，Ｈｆ
の中の１種以上の４ａ族元素が該分散相に含まれるＶ，
Ｎｂ，Ｔａの中の１種以上の５ａ族元素に対する重量百
分率で８５％いかでなり、かつ該分散相に含まれるＴ
ｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素が該結合相
に対する重量百分率で０．２〜５％であり、該分散相に
含まれるＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族元素が
該結合相に対する重量百分率で１〜１０％であることを
特徴とするものである。More preferably, the cemented carbide of the present invention is an alloy comprising 3 to 30% by weight of the binder phase described above, 0.03 to 5% by weight of the dispersed phase described above, and the balance tungsten carbide. And Ti, Zr, Hf contained in the dispersed phase
V containing one or more Group 4a elements in the dispersed phase,
The weight percentage of Nb and Ta with respect to at least one 5a group element is 85%, and T contained in the dispersed phase.
One or more 4a group elements in i, Zr, and Hf are 0.2 to 5% by weight with respect to the binder phase, and one or more of V, Nb, and Ta contained in the dispersed phase. It is characterized in that the group 5a element is 1 to 10% by weight relative to the binder phase.
【００１２】本発明の超硬合金における結合相は、具体
的には、例えばＣｏ，ＮｉまたはＣｏ−Ｎｉからなる場
合、もしくはこれらにＣｒ，Ｖ，Ｗなどが結合相に対し
て１０重量％以下含有している場合があり、特にＣｒや
Ｖが結合相中に含有している場合には、炭化タングステ
ンの粒成長抑制効果および耐蝕性効果を高めるので好ま
しいことである。この結合相が超硬合金全体に対して３
重量％未満になると、相対的に炭化タングステンが多く
なって強度および靭性の低下が顕著となり、逆に超硬合
金全体に対して３０重量％を超えて多くなると、硬さ，
耐摩耗性および耐塑性変形性の低下が顕著になるため
に、結合相は３〜３０重量％と定めたものである。Specifically, the binder phase in the cemented carbide of the present invention is, for example, Co, Ni or Co-Ni, or Cr, V, W or the like in an amount of 10% by weight or less based on the binder phase. It may be contained, and especially when Cr or V is contained in the binder phase, the grain growth suppressing effect and the corrosion resistance effect of tungsten carbide are enhanced, which is preferable. This binder phase is 3 for the whole cemented carbide
If the amount is less than 10% by weight, the amount of tungsten carbide is relatively increased, and the strength and toughness are significantly decreased. Conversely, if the amount is more than 30% by weight based on the whole cemented carbide, the hardness,
The binder phase is determined to be 3 to 30% by weight because the wear resistance and the plastic deformation resistance are significantly reduced.
【００１３】本発明の超硬合金における分散相は、具体
的には、例えばＴｉＣ，ＺｒＣ，ＨｆＣ，ＶＣ，Ｎｂ
Ｃ，ＴａＣ，ＴｉＮ，ＺｒＮ，ＨｆＮ，ＶＮ，ＮｂＮ，
ＴａＮ，Ｔｉ（Ｃ，Ｎ），Ｚｒ（Ｃ，Ｎ），Ｈｆ（Ｃ，
Ｎ），Ｖ（Ｃ，Ｎ），Ｎｂ（Ｃ，Ｎ），Ｔａ（Ｃ，
Ｎ），（Ｔｉ，Ｚｒ）Ｃ，（Ｔｉ，Ｚｒ）Ｎ，（Ｔｉ，
Ｚｒ）（Ｃ，Ｎ），（Ｔｉ，Ｔａ）Ｃ，（Ｔｉ，Ｗ）
Ｃ，（Ｔｉ，Ｗ）（Ｃ，Ｎ），（Ｔｉ，Ｔａ，Ｗ）Ｃ，
（Ｔｉ，Ｔａ，Ｎｂ，Ｗ）Ｃ，（Ｚｒ，Ｎｂ，Ｗ）Ｃ，
（Ｔｉ，Ｖ，Ｗ）Ｃ，（Ｔｉ，Ｔａ，Ｗ）（Ｃ，Ｎ），
（Ｈｆ，Ｔａ，Ｗ）（Ｃ，Ｎ）を挙げることができる。
これらの分散相は、（Ｔｉ，Ｔａ）Ｃ，（Ｔｉ，Ｔａ，
Ｗ）Ｃ，（Ｔｉ，Ｔａ，Ｎｂ，Ｗ）Ｃ，（Ｚｒ，Ｎｂ，
Ｗ）Ｃ，（Ｔｉ，Ｖ，Ｗ）Ｃ，（Ｔｉ，Ｔａ，Ｗ）
（Ｃ，Ｎ），（Ｈｆ，Ｔａ，Ｗ）（Ｃ，Ｎ）のように、
４ａ族元素と５ａ族元素を含んだ複合炭化物や複合炭窒
化物の場合は、これが単独で存在することもあり、その
他の炭化物，炭窒化物，窒化物の場合には２種以上存在
することになる。この分散相は、芯部とその周辺部との
組成成分が異なる２重構造になる傾向が強く、芯部には
４ａ族元素が、周辺部には５ａ族元素が多くなる傾向に
あり、化学量論組成になっている場合もあるが、ほとん
どが非化学量論組成からなっているものである。The dispersed phase in the cemented carbide of the present invention is specifically, for example, TiC, ZrC, HfC, VC, Nb.
C, TaC, TiN, ZrN, HfN, VN, NbN,
TaN, Ti (C, N), Zr (C, N), Hf (C,
N), V (C, N), Nb (C, N), Ta (C,
N), (Ti, Zr) C, (Ti, Zr) N, (Ti,
Zr) (C, N), (Ti, Ta) C, (Ti, W)
C, (Ti, W) (C, N), (Ti, Ta, W) C,
(Ti, Ta, Nb, W) C, (Zr, Nb, W) C,
(Ti, V, W) C, (Ti, Ta, W) (C, N),
(Hf, Ta, W) (C, N) can be mentioned.
These dispersed phases are (Ti, Ta) C, (Ti, Ta,
W) C, (Ti, Ta, Nb, W) C, (Zr, Nb,
W) C, (Ti, V, W) C, (Ti, Ta, W)
Like (C, N), (Hf, Ta, W) (C, N),
In the case of a complex carbide or complex carbonitride containing a 4a group element and a 5a group element, this may exist alone, and in the case of other carbides, carbonitrides, or nitrides, two or more kinds should exist. become. This dispersed phase has a strong tendency to have a double structure in which the composition components of the core part and the peripheral part thereof are different, and there is a tendency that the group 4a element is large in the core part and the group 5a element is large in the peripheral part. In some cases, it has a stoichiometric composition, but most of them have a non-stoichiometric composition.
【００１４】これらの分散相の内、（イ）Ｔｉ，Ｚｒ，
Ｈｆ，Ｖ，Ｎｂ，Ｔａの中の１種以上とＷとを含む複合
炭化物の存在した分散相、（ロ）超硬合金全体に対して
０．００１〜０．５重量％の窒素を含有した窒化物また
は炭窒化物の存在した分散相、（ハ）Ｚｒの炭化物，窒
化物，炭窒化物およびＺｒを含む複合炭化物，複合窒化
物，複合炭窒化物の中の１種以上の存在した分散相でな
ることが好ましく、特に（イ）と（ハ）の組合わされた
分散相の場合には、靭性の優れた超硬合金が得られ易く
好ましいことである。Of these dispersed phases, (a) Ti, Zr,
A dispersed phase in which a composite carbide containing at least one of Hf, V, Nb, and Ta and W was present, and (b) contained 0.001 to 0.5% by weight of nitrogen based on the whole cemented carbide. Dispersed phase in which nitride or carbonitride was present, (c) One or more existing dispersions in Zr carbide, nitride, carbonitride and complex carbide containing Zr, complex nitride, complex carbonitride It is preferable that the cemented carbide has a phase, and in particular, in the case of the dispersed phase in which (a) and (c) are combined, a cemented carbide having excellent toughness is easily obtained, which is preferable.
【００１５】分散相が超硬合金全体に対して０．０３重
量％未満になると、硬さ、耐摩耗性および耐塑性変形の
低下が著しく、逆に超硬合金全体に対して５重量％を超
えて多くなると、粗粒の樹枝状析出物が晶出し、強度お
よび靭性の低下が著しくなる。また、分散相中に存在す
るＴｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素が分散
相に存在するＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族元
素に対する重量百分率で８５％を超えて多くなると、粗
粒の樹枝状析出物が晶出し易くなって、強度および靭性
の低下が著しくなる。When the dispersed phase is less than 0.03% by weight with respect to the whole cemented carbide, the hardness, wear resistance and plastic deformation resistance are remarkably reduced, and conversely 5% by weight with respect to the whole cemented carbide. If the amount exceeds the above range, coarse dendritic precipitates are crystallized and the strength and toughness are significantly reduced. In addition, one or more 4a group elements of Ti, Zr, and Hf present in the dispersed phase are 85% by weight relative to one or more 5a group elements of V, Nb, and Ta present in the dispersed phase. If it exceeds the range, coarse dendritic precipitates are likely to crystallize, and the strength and toughness are significantly reduced.
【００１６】さらに、この分散相の粗粒化に対しては、
結合相量と相関があり、分散相に含まれるＴｉ，Ｚｒ，
Ｈｆの中の１種以上の４ａ族元素が結合相に対する重量
百分率で０．２％未満になると分散相の晶出核として働
く粒子数が減少し、不均一で粗粒な分散相になり易く、
その結果超硬合金の強度および靭性が低下し易く、逆に
５％を超えて多くなると分散相自体の脆化とその量の増
加により、超硬合金の強度および靭性が低下し易くな
る。一方、分散相に含まれるＶ，Ｎｂ，Ｔａの中の１種
以上の５ａ族元素が重量百分率で１％未満になると、不
均一で粗粒な分散相になり易く、超硬合金の強度，靭性
および耐組成変形性が低下し易く、逆に１０％を超えて
多くなると、樹枝状析出物を呈しなくなるものの分散相
過多による硬さ，耐摩耗性，強度および靭性が低下し易
くなる。この分散相の最大径は、５μｍ以下、好ましく
は３μｍ以下、特に好ましくは２μｍ以下で均一に分散
していることである。Further, for coarsening of the dispersed phase,
Ti, Zr, which is correlated with the amount of binder phase and contained in the dispersed phase,
When the weight percentage of one or more 4a group elements in Hf is less than 0.2% by weight with respect to the binder phase, the number of particles serving as crystallization nuclei of the dispersed phase decreases, and the dispersed phase tends to be non-uniform and coarse. ,
As a result, the strength and toughness of the cemented carbide are liable to decrease, and conversely, when the content exceeds 5%, the strength and toughness of the cemented carbide are apt to decrease due to embrittlement of the dispersed phase itself and an increase in the amount thereof. On the other hand, when the content of one or more Group 5a elements in V, Nb, and Ta contained in the dispersed phase is less than 1% by weight, an inhomogeneous, coarse-grained dispersed phase is likely to be formed, and the strength of the cemented carbide, If the toughness and compositional deformation resistance tend to decrease, and if it exceeds 10%, on the contrary, the dendritic precipitates do not appear, but the hardness, wear resistance, strength and toughness due to excessive dispersed phases tend to decrease. The maximum diameter of the dispersed phase is 5 μm or less, preferably 3 μm or less, particularly preferably 2 μm or less, and the particles are uniformly dispersed.
【００１７】以上のような分散相と、結合相と炭化タン
グステンとでなる本発明の超硬合金を基材とし、この基
材上に、硬質被膜、具体的には、例えば周期律表の４
ａ，５ａ，６ａ族金属の炭化物，窒化物，炭酸化物，窒
酸化物，ホウ化物およびこれらの相互固溶体，または酸
化アルミニウム，酸化ジルコニウム，（Ｔｉ，Ａｌ）
Ｎ，（Ｔｉ，Ａｌ）（Ｃ，Ｎ），（Ｔｉ，Ａｌ）（Ｎ，
Ｏ），（Ｔｉ，Ａｌ）（Ｃ，Ｎ，Ｏ），ダイヤモンド，
ダイヤモンド状カーボン，立方晶窒化ホウ素，硬質窒化
ホウ素の中の１種の単層もしくは２種以上の多層でなる
硬質被膜を被覆した被覆超硬合金として用いると耐摩耗
性の向上および長寿命化になることから、好ましいこと
である。この被覆超硬合金における硬質被膜は、総膜厚
さが０．１〜１５μｍ、好ましくは０．５〜１０μｍ、
基材に隣接する硬質被膜が分散相を形成している元素を
含んだ硬質被膜でなることが特に好ましいことである。A base material is the cemented carbide of the present invention composed of the dispersed phase as described above, a binder phase and tungsten carbide, and a hard coating, specifically, for example, 4 of the Periodic Table, on the base material.
Carbides, nitrides, carbonates, oxynitrides, borides and their mutual solid solutions of a, 5a and 6a group metals, or aluminum oxide, zirconium oxide, (Ti, Al)
N, (Ti, Al) (C, N), (Ti, Al) (N,
O), (Ti, Al) (C, N, O), diamond,
When used as a coated cemented carbide coated with a hard coating consisting of one single layer of diamond-like carbon, cubic boron nitride, or hard boron nitride, or a multilayer of two or more layers, it improves wear resistance and prolongs service life. Therefore, it is preferable. The hard coating in the coated cemented carbide has a total film thickness of 0.1 to 15 μm, preferably 0.5 to 10 μm,
It is particularly preferred that the hard coating adjacent to the substrate is a hard coating containing the elements forming the dispersed phase.
【００１８】本発明の超硬合金は、従来から行われてい
る粉末冶金法を応用することにより作製することができ
る。具体的には、例えばＣｏ，Ｎｉ，Ｗ，Ｃｒ3Ｃ2など
の結合相形成粉末と分散相形成粉末と炭化タングステン
粉末を混合粉砕して得た混合粉末を所定形状に成形して
圧粉成形体とし、これを真空または非酸化性雰囲気中で
１３００〜１５５０℃に加熱焼結することにより、本発
明の超硬合金を得ることができる。このときの分散相形
成粉末としては、周期律表の４ａ族金属，５ａ族金属の
炭化物，窒化物，炭窒化物をそれぞれ単独に用いてもよ
いが、ＷＣも含むこれらの相互固溶体を用いることも好
ましく、また、均一微細な分散相とするために、４ａ族
金属の酸化物粉末や硝酸塩を用いて、焼結時に還元，炭
化して分散相とすることも好ましく、特に、焼結を窒素
ガス雰囲気中で行うと、４ａ族金属が窒化されること、
およびその窒化物が安定して、分散相の晶出核として働
く粒子が増加して、より均一微細な分散相になり易く好
ましいことである。The cemented carbide of the present invention can be produced by applying a conventional powder metallurgy method. Concretely, for example, a mixed powder obtained by mixing and pulverizing a binder phase forming powder such as Co, Ni, W, Cr 3 C 2 and the like, a dispersed phase forming powder and a tungsten carbide powder is molded into a predetermined shape and compacted. The cemented carbide of the present invention can be obtained by forming a body and heating and sintering the body at 1300 to 1550 ° C in a vacuum or a non-oxidizing atmosphere. As the dispersed phase forming powder at this time, carbides, nitrides, and carbonitrides of 4a group metals and 5a group metals of the periodic table may be used individually, but mutual mutual solutions containing WC are also used. It is also preferable to use an oxide powder or nitrate of a group 4a metal to reduce and carbonize during sintering to obtain a dispersed phase in order to obtain a uniformly fine dispersed phase. When performed in a gas atmosphere, the group 4a metal is nitrided,
It is preferable that the nitride is stable and particles that act as crystallized nuclei of the dispersed phase increase to form a more uniform fine dispersed phase.
【００１９】こうして得た本発明の超硬合金を基材と
し、この基材上の硬質被膜を被覆する場合は、従来から
行われている化学蒸着法や物理蒸着法でもって被覆する
ことができる。When the thus obtained cemented carbide of the present invention is used as a substrate and a hard coating on this substrate is coated, it can be coated by a conventional chemical vapor deposition method or physical vapor deposition method. .
【００２０】[0020]
【作用】本発明の超硬合金は、分散相を構成している４
ａ族元素と５ａ族元素の比率が均一微細な分散相を形成
する作用として働き、具体的には、焼結時に４ａ族元素
の供給物質である、例えば４ａ族元素の炭化物，窒化
物，炭窒化物が分散相の晶出核として働き、５ａ族元素
の供給物質である、例えば５ａ族元素の炭化物を均一分
散させる作用をし、この均一微細な分散相が硬さ，耐摩
耗性，耐塑性変形性，強度および靭性を高める作用をし
ているものである。[Function] The cemented carbide of the present invention constitutes the dispersed phase.
The ratio of the a-group element to the 5a-group element acts as an action to form a uniform fine dispersed phase, and specifically, it is a feed material of the 4a-group element during sintering, for example, a carbide, a nitride or a charcoal of the 4a-group element. The nitride acts as a crystallization nucleus of the dispersed phase, and functions to uniformly disperse a carbide of the 5a group element, for example, a carbide of the 5a group element, and the uniformly fine dispersed phase has hardness, wear resistance, and resistance. It acts to enhance plastic deformability, strength and toughness.
【００２１】[0021]
【実施例１】市販されている平均粒径が１μｍのＷＣ、
１〜３μｍの範囲にあるＣｏ，Ｎｉ，Ｗ，Ｃｒ3Ｃ2，Ｖ
Ｃ，ＮｂＣ，ＴａＣ、０．５〜０．９μｍの範囲にある
ＴｉＮ，ＺｒＣ，ＺｒＮ，ＨｆＣ，（Ｗ，Ｔｉ）Ｃ［Ｗ
Ｃ／ＴｉＣ＝７０／３０］、０．０５μｍのＺｒＯ2お
よび試薬の硝酸ジルコニウム［ＺｒＯ （ＮＯ3）2］の各
粉末を用いて、表１に示す配合組成に秤量し、ステンレ
ス製ポットにアセトン溶媒と超硬合金製ボールと共に挿
入し、４８時間の混合粉砕後、乾燥して混合粉末を得
た。Example 1 Commercially available WC having an average particle size of 1 μm,
Co, Ni, W, Cr in the range of 1 to 3 μm3C2, V
C, NbC, TaC, in the range of 0.5 to 0.9 μm
TiN, ZrC, ZrN, HfC, (W, Ti) C [W
C / TiC = 70/30], ZrO of 0.05 μm2Oh
And reagent zirconium nitrate [ZrO (NO3)2] Each
Using the powder, weigh the compounding composition shown in Table 1 and
Insert the acetone solvent and cemented carbide balls into a stainless steel pot.
After mixing and pulverizing for 48 hours, dry to obtain mixed powder.
It was
【００２２】次にこれらの混合粉末を金型に充填し、１
ｔｏｎ／ｃｍ2の加圧でもって約５．５×９．５×２９
ｍｍの圧粉成形体を作製し、アルミナとカーボンの繊維
からなるシート上に設置して、表１に併記する雰囲気と
温度で各１時間、加熱保持することにより本発明品１〜
７および比較品１〜６を得た。こうして得た本発明品１
〜７および比較品１〜６のそれぞれの合金組成をＸ線回
折，顕微鏡，蛍光Ｘ線分析，ＸＭＡでもって調べて、そ
の結果を表２に示した。そして、＃２３０のダイヤモン
ド砥石で湿式研削加工し、４．０×８．０×２５．０ｍ
ｍの形状に仕上げて、各合金の試験片を作製した。Next, these mixed powders were filled in a mold, and 1
About 5.5 × 9.5 × 29 with a pressure of ton / cm 2.
mm powder compacts were prepared, placed on a sheet made of alumina and carbon fibers, and heated and held in the atmosphere and temperature shown in Table 1 for 1 hour each, to obtain the products of the present invention 1 to 1.
7 and comparative products 1-6 were obtained. Invention product 1 thus obtained
~ 7 and comparative products 1 to 6 were examined by X-ray diffraction, microscope, fluorescent X-ray analysis, and XMA, and the results are shown in Table 2. Then, wet-grinding is performed with a # 230 diamond grindstone to obtain 4.0 × 8.0 × 25.0 m.
After finishing to a shape of m, a test piece of each alloy was prepared.
【００２３】これら試験片を用いて抗折力（ＪＩＳ法）
を、また試験片の一面を１μｍのダイヤモンドペースト
でラップ加工して硬さ（荷重：２０ｋｇｆ）と破壊靭性
値：Ｋ1ｃ（ＩＭ法，荷重：２０ｋｇｆ）を測定し、そ
の結果を表３に示した。さらに、村上氏液でエッチング
した後、光学顕微鏡によって分散相の分布状態（凝集状
の直径）を観察し、その結果を表３に併記した。Using these test pieces, the transverse rupture strength (JIS method)
Also, the hardness (load: 20 kgf) and fracture toughness value: K 1 c (IM method, load: 20 kgf) were measured by lapping one surface of the test piece with 1 μm diamond paste, and the results are shown in Table 3. Indicated. Furthermore, after etching with Mr. Murakami's solution, the distribution state (aggregated diameter) of the dispersed phase was observed with an optical microscope, and the results are also shown in Table 3.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【実施例２】実施例１に示した各粉末を用いて、表４に
示す配合組成に秤量し、表４に示す焼結条件以外は実施
例１と同様の製造条件を経て焼結し、本発明品８〜１０
および本発明を外れた比較品７，８を得た。こうして得
た本発明品８〜１０および比較品７，８のそれぞれの合
金組成を実施例１と同様に調べて、その結果を表５に示
した。Example 2 Each powder shown in Example 1 was weighed to have a composition shown in Table 4, and sintered under the same manufacturing conditions as in Example 1 except for the sintering conditions shown in Table 4, Invention product 8 to 10
And the comparative products 7 and 8 which deviated from this invention were obtained. The alloy compositions of the inventive products 8 to 10 and the comparative products 7 and 8 thus obtained were examined in the same manner as in Example 1, and the results are shown in Table 5.
【００２８】また、実施例１と同様にして、本発明品８
〜１０および比較品７，８のそれぞれの合金組成を調べ
て、その結果を表６に示した。In the same manner as in Example 1, the product of the present invention 8
10 to 10 and comparative products 7 and 8 were examined for alloy compositions, and the results are shown in Table 6.
【００２９】[0029]
【表４】 [Table 4]
【００３０】[0030]
【表５】 [Table 5]
【００３１】[0031]
【表６】 [Table 6]
【００３２】[0032]
【発明の効果】本発明の超硬合金は、略近似した組成で
なる従来の超硬合金に比べて、硬さの低下がなく、（略
同程度の硬さ）強度が約１４〜６５％向上し、靭性が約
５〜１７％向上するという優れた効果を有するものであ
る。EFFECTS OF THE INVENTION The cemented carbide of the present invention does not show a decrease in hardness and has a strength of about 14 to 65% (about the same hardness) as compared with the conventional cemented carbide having an approximately similar composition. It has an excellent effect of improving the toughness by about 5 to 17%.
Claims (7)
結合相３〜３０重量％と、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎ
ｂ，Ｔａの炭化物，窒化物およびこれらの相互固溶体、
並びにＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａの１種以上と
Ｗ，Ｍｏ，Ｃｒの１種以上とを含む複合炭化物，複合窒
化物，複合炭窒化物の中から選ばれた１種以上の分散相
（但し、分散相中にはＴｉ，Ｚｒ，Ｈｆの中の１種以上
の４ａ族元素とＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族
元素が含まれる）０．０３〜５重量％と、残りが炭化タ
ングステンからなる超硬合金であって、該分散相に含ま
れるＴｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素が該
分散相に含まれるＶ，Ｎｂ，Ｔａの中の１種以上の５ａ
族元素に対する重量百分率で８５％以下でなることを特
徴とする高強度強靭性超硬合金。1. A binder phase containing Co and / or Ni as a main component in an amount of 3 to 30% by weight and Ti, Zr, Hf, V, N.
b, Ta carbides, nitrides and mutual solid solutions thereof,
And one or more selected from the group consisting of composite carbides, composite nitrides, and composite carbonitrides containing one or more of Ti, Zr, Hf, V, Nb, Ta and one or more of W, Mo, Cr. Dispersed phase (provided that the dispersed phase contains at least one group 4a element of Ti, Zr, and Hf and at least one group 5a element of V, Nb, and Ta) 0.03 to 5 A cemented carbide containing 1% by weight and the balance tungsten carbide, wherein V, Nb, Ta containing at least one Group 4a element in Ti, Zr, Hf contained in the dispersed phase is contained in the dispersed phase. One or more of 5a
A high-strength and tough cemented carbide, which is 85% or less in weight percentage with respect to the group element.
結合相３〜３０重量％と、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎ
ｂ，Ｔａの炭化物，窒化物およびこれらの相互固溶体、
並びにＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａの１種以上と
Ｗ，Ｍｏ，Ｃｒの１種以上とを含む複合炭化物，複合窒
化物，複合炭窒化物の中から選ばれた１種以上の分散相
（但し、分散相中にはＴｉ，Ｚｒ，Ｈｆの中の１種以上
の４ａ族元素とＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族
元素が含まれる）０．０３〜５重量％と、残りが炭化タ
ングステンからなる超硬合金であって、該分散相に含ま
れるＴｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素が該
結合相に対する重量百分率で０．２〜５％であり、該分
散相に含まれるＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族
元素が該結合相に対する重量百分率で１〜１０％である
ことを特徴とする高強度強靭性超硬合金。2. A binder phase containing Co and / or Ni as a main component in an amount of 3 to 30% by weight and Ti, Zr, Hf, V, N.
b, Ta carbides, nitrides and mutual solid solutions thereof,
And one or more selected from the group consisting of composite carbides, composite nitrides, and composite carbonitrides containing one or more of Ti, Zr, Hf, V, Nb, Ta and one or more of W, Mo, Cr. Dispersed phase (provided that the dispersed phase contains at least one group 4a element of Ti, Zr, and Hf and at least one group 5a element of V, Nb, and Ta) 0.03 to 5 % Of the cemented carbide, the balance of which is tungsten carbide, and one or more Group 4a elements of Ti, Zr, and Hf contained in the dispersed phase are 0.2 to 10% by weight with respect to the binder phase. 5%, and one or more group 5a elements of V, Nb, and Ta contained in the dispersed phase are 1 to 10% in weight percentage with respect to the binder phase. Hard alloy.
結合相３〜３０重量％と、Ｔｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎ
ｂ，Ｔａの炭化物，窒化物およびこれらの相互固溶体、
並びにＴｉ，Ｚｒ，Ｈｆ，Ｖ，Ｎｂ，Ｔａの１種以上と
Ｗ，Ｍｏ，Ｃｒの１種以上とを含む複合炭化物，複合窒
化物，複合炭窒化物の中から選ばれた１種以上の分散相
（但し、分散相中にはＴｉ，Ｚｒ，Ｈｆの中の１種以上
の４ａ族元素とＶ，Ｎｂ，Ｔａの中の１種以上の５ａ族
元素が含まれる）０．０３〜５重量％と、残りが炭化タ
ングステンからなる超硬合金であって、該分散相に含ま
れるＴｉ，Ｚｒ，Ｈｆの中の１種以上の４ａ族元素が該
分散相に含まれるＶ，Ｎｂ，Ｔａの中の１種以上の５ａ
族元素に対する重量百分率で８５％以下でなり、かつ該
分散相に含まれるＴｉ，Ｚｒ，Ｈｆの中の１種以上の４
ａ族元素が該結合相に対する重量百分率で０．２〜５％
であり、該分散相に含まれるＶ，Ｎｂ，Ｔａの中の１種
以上の５ａ族元素が該結合相に対する重量百分率で１〜
１０％であることを特徴とする高強度強靭性超硬合金。3. A binder phase containing Co and / or Ni as a main component in an amount of 3 to 30% by weight and Ti, Zr, Hf, V, N.
b, Ta carbides, nitrides and mutual solid solutions thereof,
And one or more selected from the group consisting of composite carbides, composite nitrides, and composite carbonitrides containing one or more of Ti, Zr, Hf, V, Nb, Ta and one or more of W, Mo, Cr. Dispersed phase (provided that the dispersed phase contains at least one group 4a element of Ti, Zr, and Hf and at least one group 5a element of V, Nb, and Ta) 0.03 to 5 A cemented carbide containing 1% by weight and the balance tungsten carbide, wherein V, Nb, Ta containing at least one Group 4a element in Ti, Zr, Hf contained in the dispersed phase is contained in the dispersed phase. One or more of 5a
The weight percentage relative to the group element is 85% or less, and one or more of 4 selected from Ti, Zr, and Hf contained in the dispersed phase.
Group a element is 0.2 to 5% by weight relative to the binder phase.
And one or more Group 5a elements of V, Nb, and Ta contained in the dispersed phase are 1 to 1 by weight percentage with respect to the binder phase.
High strength and toughness cemented carbide characterized by being 10%.
Ｎｂ，Ｔａの中の１種以上とＷとを含む複合炭化物が含
まれていることを特徴とする請求項１，２または３記載
の高強度強靭性超硬合金。4. The dispersed phase comprises Ti, Zr, Hf, V,
The high-strength toughness cemented carbide according to claim 1, characterized in that it contains a composite carbide containing at least one of Nb and Ta and W.
０．００１〜０．５重量％の窒素を含有した窒化物また
は炭窒化物が含まれていることを特徴とする請求項１，
２または３記載の高強度強靭性超硬合金。5. The dispersed phase contains a nitride or carbonitride containing 0.001 to 0.5% by weight of nitrogen with respect to the entire cemented carbide. ，
A high-strength and tough cemented carbide as described in 2 or 3.
炭窒化物およびＺｒを含む複合炭化物，複合窒化物，複
合炭窒化物の中の１種以上が含まれていることを特徴と
する請求項１，２または３記載の高強度強靭性超硬合
金。6. The dispersed phase is Zr carbide, nitride,
4. A high-strength, tough cemented carbide according to claim 1, characterized in that it contains at least one of a carbonitride and a composite carbide containing Zr, a composite nitride, and a composite carbonitride. .
の超硬合金を基材とし、該基材上に膜厚０．１〜１５μ
ｍの硬質被膜を被覆したことを特徴とする高強度強靭性
被覆超硬合金。7. A cemented carbide according to claim 1, 2, 3, 4, 5 or 6 as a base material, and a film thickness of 0.1 to 15 μm on the base material.
A high-strength and tough-coated cemented carbide characterized by being coated with a hard coating of m.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05297294A JP3474254B2 (en) | 1994-02-25 | 1994-02-25 | High-strength tough cemented carbide and its coated cemented carbide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05297294A JP3474254B2 (en) | 1994-02-25 | 1994-02-25 | High-strength tough cemented carbide and its coated cemented carbide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07238338A true JPH07238338A (en) | 1995-09-12 |
| JP3474254B2 JP3474254B2 (en) | 2003-12-08 |
Family
ID=12929814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05297294A Expired - Fee Related JP3474254B2 (en) | 1994-02-25 | 1994-02-25 | High-strength tough cemented carbide and its coated cemented carbide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3474254B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002239812A (en) * | 2001-02-20 | 2002-08-28 | Hitachi Tool Engineering Ltd | Coated cemented carbide tool |
| JP2006057155A (en) * | 2004-08-23 | 2006-03-02 | Tungaloy Corp | Particulate hard metal and manufacturing method therefor |
| JP2006063416A (en) * | 2004-08-30 | 2006-03-09 | Tungaloy Corp | Chromium-containing hard metal and coated hard metal thereof |
| JP2012196696A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Electric Ind Ltd | Rotating tool |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5952950B1 (en) | 2015-11-04 | 2016-07-13 | 株式会社エジュテックジャパン | Learning support system and program |
-
1994
- 1994-02-25 JP JP05297294A patent/JP3474254B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002239812A (en) * | 2001-02-20 | 2002-08-28 | Hitachi Tool Engineering Ltd | Coated cemented carbide tool |
| JP2006057155A (en) * | 2004-08-23 | 2006-03-02 | Tungaloy Corp | Particulate hard metal and manufacturing method therefor |
| JP2006063416A (en) * | 2004-08-30 | 2006-03-09 | Tungaloy Corp | Chromium-containing hard metal and coated hard metal thereof |
| JP2012196696A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Electric Ind Ltd | Rotating tool |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3474254B2 (en) | 2003-12-08 |
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