JP2020001990A - cBN sintered body and cutting tool - Google Patents
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Description
本発明は、靭性に優れた立方晶窒化ほう素（以下、「ｃＢＮ」で示す）基超高圧焼結体（以下、「ｃＢＮ焼結体」という）、および、これを工具基体とする切削工具（以下、「ＣＢＮ工具」という）に関する。 The present invention relates to a cubic boron nitride (hereinafter, referred to as “cBN”)-based ultrahigh-pressure sintered body (hereinafter, referred to as “cBN sintered body”) having excellent toughness, and a cutting tool using the same as a tool base. (Hereinafter referred to as “CBN tool”).
従来から、ｃＢＮ焼結体は、靭性に優れることが知られており、鋼、鋳鉄等の鉄系被削材の切削工具材料として広く用いられている。 Conventionally, cBN sintered bodies have been known to have excellent toughness, and have been widely used as cutting tool materials for iron-based work materials such as steel and cast iron.
例えば、特許文献１には、硬質相としてのｃＢＮを２０〜８０体積％含有し、残部が、周期律表の４ａ、５ａ、６ａの炭化物、窒化物、ほう化物等のセラミックス化合物を結合相としたｃＢＮ工具が記載されている。 For example, Patent Literature 1 discloses that a cBN as a hard phase is contained in an amount of 20 to 80% by volume, and the balance is made of a ceramic compound such as carbides, nitrides, and borides of 4a, 5a, and 6a in the periodic table as a binder phase. CBN tools are described.
また、例えば、特許文献２には、２０体積％以上８０体積％以下のｃＢＮ粒子と結合材とを有する複合焼結体であって、前記結合材は、周期律表第４ａ族元素、第５ａ族元素、第６ａ族元素の窒化物、炭化物、硼化物、酸化物、およびこれらの固溶体からなる群の中から選択された少なくとも一種と、Ｚｒ、Ｓｉ、Ｗ、Ｃｏ等の単体、化合物、および固溶体からなる群の中から選択された少なくとも１種と、Ａｌの化合物とからなり、前記複合焼結体中にＷ及び／又はＣｏが含有される場合には、該Ｗ及び／又はＣｏの合計質量は２．０質量％未満であり、かつ前記Ｚｒ、Ｓｉ等（以下、「Ｘ」とする。）のいずれか一以上を含有し、該Ｘはそれぞれ０．００５質量％以上２．０質量％未満であり、かつＸ／（Ｘ＋Ｗ＋Ｃｏ）が０．０１以上１．０以下を満たし、かつＡｌの質量が２．０質量％以上２０．０質量％以下であるｃＢＮ焼結体が記載されている。 Further, for example, Patent Document 2 discloses a composite sintered body having cBN particles of 20% by volume or more and 80% by volume or less and a binder, wherein the binder is a Group 4a element of the periodic table, a 5a Group elements, nitrides, carbides, borides and oxides of group 6a elements, and at least one selected from the group consisting of solid solutions thereof, and a simple substance such as Zr, Si, W and Co, a compound, and When at least one selected from the group consisting of a solid solution and a compound of Al, and when W and / or Co is contained in the composite sintered body, the total of W and / or Co The mass is less than 2.0% by mass, and contains at least one of the above-mentioned Zr, Si, etc. (hereinafter, referred to as “X”), and each X is 0.005% by mass or more and 2.0% by mass. % And X / (X + W + Co) is 0.01 or more It met .0 less, and cBN sintered body weight of Al is 20.0 mass% or less 2.0% by weight or more is described.
さらに、例えば、特許文献３には、立方晶窒化硼素粒子と結合相とを含む焼結体を工具基体とする立方晶窒化硼素焼結体切削工具において、前記焼結体は、立方晶窒化硼素粒子を４０容量％以上６０容量％未満およびＡｌが下限値で２質量％、上限値でＹをＡｌ含有割合（質量％）、Ｘを立方晶窒化硼素粒子含有割合（容量％）としたとき、Ｙ＝−０．１Ｘ＋１０の関係を満足する範囲となるように含有し、前記結合相は、少なくともＴｉ系化合物とＡｌ２Ｏ３と不可避不純物を含有し、前記Ａｌ２Ｏ３のうち、直径１０ｎｍ〜１００ｎｍの微粒Ａｌ２Ｏ３が結合相中に分散、生成しており、前記結合相の断面１μｍ×１μｍの領域において、前記微粒Ａｌ２Ｏ３が３０個以上生成していることを特徴とする立方晶窒化硼素焼結体切削工具が記載されている。 Furthermore, for example, Patent Document 3 discloses a cubic boron nitride sintered body cutting tool using a sintered body containing cubic boron nitride particles and a binder phase as a tool base, wherein the sintered body is cubic boron nitride. When the particles are 40% by volume or more and less than 60% by volume and Al is 2% by mass at the lower limit and Y is the Al content ratio (% by mass) and X is the cubic boron nitride particle content ratio (% by volume) at the upper limit value, Y = −0.1X + 10, and the binder phase contains at least a Ti-based compound, Al 2 O 3 and unavoidable impurities, and a diameter of 10 nm among the Al 2 O 3. Fine particles of Al 2 O 3 of １００100 nm are dispersed and generated in the binder phase, and 30 or more of the fine particles of Al 2 O 3 are generated in a region of a cross section of 1 μm × 1 μm of the binder phase. Cutting of cubic boron nitride sintered body Ingredients have been described.
特許文献１に記載されたｃＢＮ焼結体は、結合相としてセラミックス化合物を用いているため、Ｃｏ等の金属を結合相として用いた場合に比べて、強度、耐熱性、耐摩耗性の向上が認められる。しかし、このｃＢＮ焼結体は、切れ刃に高負荷が作用する断続切削加工用切削工具として用いた場合には、靱性が十分であるとはいえないため、チッピング、欠損等の異常損傷を発生し、短期間で寿命に至るという問題があった。 Since the cBN sintered body described in Patent Document 1 uses a ceramic compound as a binder phase, the strength, heat resistance, and abrasion resistance are improved as compared with a case where a metal such as Co is used as a binder phase. Is recognized. However, when this cBN sintered body is used as a cutting tool for intermittent cutting in which a high load acts on the cutting edge, it cannot be said that the toughness is sufficient, so that abnormal damage such as chipping and chipping occurs. However, there is a problem that the life is shortened in a short time.
特許文献２に記載されたｃＢＮ焼結体は、結合相の強度と靱性を高めるためにＷ及び／又はＣｏ、Ｓｉ又はＺｒを結合相中に所定量含有させているが、例えば、Ｗが焼結体中に占める割合が多いと焼結体の靱性が低下、Ｓｉが多いと結合材の拡散反応が過剰に抑制され、ｃＢＮ粒子と結合材および結合材同士の結合力が低下し、焼結体の靱性が低下する問題があった。また、混合時の分散性が悪いと局所的に添加物の濃度が高い部分が生じ、ｃＢＮ粒子と結合材との結合力の低下により焼結体の靱性が低下し、切削工具として使用した場合、破壊の起点となることによって耐欠損性が低下するという問題があった。 The cBN sintered body described in Patent Literature 2 contains a predetermined amount of W and / or Co, Si, or Zr in the binder phase in order to increase the strength and toughness of the binder phase. If the proportion of the binder in the binder is large, the toughness of the sintered body is reduced. If the content of Si is large, the diffusion reaction of the binder is excessively suppressed, and the bonding force between the cBN particles and the binder and the binder is reduced. There was a problem that the toughness of the body was reduced. In addition, when the dispersibility during mixing is poor, a portion where the concentration of the additive is locally high is generated, and the toughness of the sintered body is reduced due to a decrease in the bonding force between the cBN particles and the binder. However, there has been a problem that the fracture resistance is reduced due to the starting point of the fracture.
特許文献３に記載されたｃＢＮ焼結体は、平均粒径５〜１５ｎｍの超微粒Ａｌ２Ｏ３を用いることで粒径１００ｎｍ以下の微粒Ａｌ２Ｏ３の均一分散化をしているが、含有させるＡｌ２Ｏ３が少ない場合、微粒なためクラックを偏向させる効果はあるが、Ｔｉを主とするセラミックス結合相成分とＡｌ２Ｏ３のビッカース硬さは同程度のため、クラックを誘導させる効果が低減し、ｃＢＮ焼結体の破壊靭性が低下する虞があった。 The cBN sintered body described in Patent Literature 3 uniformly disperses fine Al 2 O 3 having a particle size of 100 nm or less by using ultrafine Al 2 O 3 having an average particle size of 5 to 15 nm. When the amount of Al 2 O 3 to be contained is small, cracks are deflecting due to fine grains, but the Vickers hardness of the ceramics binder phase component mainly composed of Ti and Al 2 O 3 are almost the same, so that cracks are induced. The effect may be reduced, and the fracture toughness of the cBN sintered body may be reduced.
本発明は、前記先行技術においてｃＢＮ焼結体が十分な靱性を確保できないという課題を解決するものであって、靱性の高いｃＢＮ焼結体およびこれを工具基体とするＣＢＮ工具を提供することを目的とする。 The present invention solves the problem that the cBN sintered body cannot secure sufficient toughness in the prior art, and provides a cBN sintered body having high toughness and a CBN tool using the same as a tool base. Aim.
本発明者は、ｃＢＮ焼結体及びこれを工具基体とするｃＢＮ工具について前記課題を解決すべく、ｃＢＮ焼結体中のＡｌ化合物粒子の分散と靱性の向上について鋭意検討を行った。その結果、微粒のイットリウム・アルミニウム・ガーネット（Ｙ３Ａｌ５Ｏ１２：ＹＡＧ）をｃＢＮ焼結体中に１体積％以上２０体積％以下含有し、かつ、結合相中に形成されるＹＡＧの平均粒径を２００ｎｍ以下とすることにより、ｃＢＮ焼結体内で生じたクラックの進展がＹ３Ａｌ５Ｏ１２粒子により迂回されること、すなわち、細かく迂回されることに加えて、結合相中でのクラックの細かな伝播の誘導を強くすることにより、靱性の高いｃＢＮ焼結体を得ることができること、また、このｃＢＮ焼結体を切削工具として使用すれば、刃先への負荷の大きい断続切削あたって刃先が欠損しにくいという優れた切削性能を有することを知見した。 The present inventor has made intensive studies on the dispersion of Al compound particles in a cBN sintered body and the improvement of toughness in order to solve the above-mentioned problems in a cBN sintered body and a cBN tool using the same as a tool base. As a result, fine yttrium aluminum garnet (Y 3 Al 5 O 12 : YAG) is contained in the cBN sintered body in an amount of 1% by volume or more and 20% by volume or less, and the average of YAG formed in the binder phase is obtained. By setting the particle size to 200 nm or less, the propagation of cracks generated in the cBN sintered body is diverted by the Y 3 Al 5 O 12 particles, that is, in addition to being diverted finely, It is possible to obtain a cBN sintered body having high toughness by strengthening the induction of the fine propagation of cracks. It has been found that the cutting edge has excellent cutting performance in which the cutting edge is not easily broken.
本発明は、前記知見に基づいてなされたものであって、
「（１）立方晶窒化硼素粒子と結合相とからなるｃＢＮ焼結体において、
前記結合相には、平均粒径が１０ｎｍ以上２００ｎｍ以下のＹ３Ａｌ５Ｏ１２が、前記焼結体に対する含有割合として１体積％以上２０体積％以下となるように分散していることを特徴とするｃＢＮ焼結体。
（２）前記（１）に記載のｃＢＮ焼結体を工具基体とすることを特徴とする切削工具。」
である。
The present invention has been made based on the above findings,
"(1) In a cBN sintered body composed of cubic boron nitride particles and a binder phase,
In the binder phase, Y 3 Al 5 O 12 having an average particle diameter of 10 nm or more and 200 nm or less is dispersed so as to be 1% by volume or more and 20% by volume or less with respect to the sintered body. CBN sintered body.
(2) A cutting tool, wherein the cBN sintered body according to (1) is used as a tool base. "
It is.
本発明は、焼結体中にＹ３Ａｌ５Ｏ１２の微粒子を分散させるため、ｃＢＮ焼結体中で生じたクラックの進展を細かく迂回させ、直線的な進展を抑えて靱性を高めるとともに、結合相の材料であるＴｉＮ、ＴｉＣに比してビッカース硬さが同程度のＡｌ２Ｏ３ではなく、ビッカース硬さが低いＹ３Ａｌ５Ｏ１２を使用することにより、焼結体中を進行するクラックの先端を硬さの低いＹ３Ａｌ５Ｏ１２へ誘導させることにより、その進展をより細かく迂回させ、より一層のｃＢＮ焼結体の靱性の向上がなされるという優れた効果を奏することができる。 The present invention disperses the fine particles of Y 3 Al 5 O 12 in the sintered body, finely circumvents the growth of cracks generated in the cBN sintered body, suppresses linear growth, and increases toughness. By using Y 3 Al 5 O 12 having a low Vickers hardness, instead of Al 2 O 3 having the same Vickers hardness as that of TiN or TiC, which is the material of the binder phase, it progresses in the sintered body. By inducing the tip of the crack to Y 3 Al 5 O 12 having a low hardness, the progress of the crack is more finely diverted, and an excellent effect that the toughness of the cBN sintered body is further improved is exhibited. Can be.
以下、本発明を詳細に説明する。なお、本明細書において、数値範囲を「〜」を用いて表現する場合、その範囲は上限および下限の数値を含むものである。 Hereinafter, the present invention will be described in detail. In this specification, when a numerical range is expressed by using “to”, the range includes upper and lower numerical values.
１．ｃＢＮ焼結体中の結合相に分散させるＹ３Ａｌ５Ｏ１２
（１）平均粒径
焼結体中に占めるＹ３Ａｌ５Ｏ１２粒の平均粒径は、１０ｎｍ以上２００ｎｍ以下とする。Ｙ３Ａｌ５Ｏ１２の平均粒径が、２００ｎｍを超えると、結合相中のＹ３Ａｌ５Ｏ１２粒子を起点とするクラックの発生や進展を生じやすくなるため、ｃＢＮ焼結体の靱性が低下する。したがって、結合相中に存在するＹ３Ａｌ５Ｏ１２の平均粒径の上限値は２００ｎｍとする。より好ましい上限値は１００ｎｍである。また、Ｙ３Ａｌ５Ｏ１２の粒径が１０ｎｍ未満であればクラックの進展を細かく迂回させ、直線的な進展を抑えることが十分でないことから、Ｙ３Ａｌ５Ｏ１２の粒径の下限値は１０ｎｍとした。
1. Y 3 Al 5 O 12 dispersed in the binder phase in the cBN sintered body
(1) Average particle size The average particle size of 12 Y 3 Al 5 O 12 particles occupying in the sintered body is set to 10 nm or more and 200 nm or less. If the average particle size of Y 3 Al 5 O 12 exceeds 200 nm, cracks originating from the Y 3 Al 5 O 12 particles in the binder phase tend to be generated and propagated, so that the toughness of the cBN sintered body is reduced. descend. Therefore, the upper limit of the average particle size of Y 3 Al 5 O 12 present in the binder phase is set to 200 nm. A more preferred upper limit is 100 nm. Further, if the particle size of Y 3 Al 5 O 12 is less than 10 nm, it is not sufficient to circumvent crack growth finely and to suppress linear growth, so the lower limit value of the particle size of Y 3 Al 5 O 12 is not sufficient. Was 10 nm.
（２）含有割合
焼結体中に占めるＹ３Ａｌ５Ｏ１２粒の含有割合は、１体積％（ｖｏｌ％）以上２０体積％以下とする。その理由は、１体積％未満であるとクラックを細かく迂回させてその進展を抑制することが十分にできずｃＢＮ焼結体の靱性を向上させるには十分な量ではなく、一方、２０体積％超えるとｃＢＮ焼結体中においてＹ３Ａｌ５Ｏ１２粒同士が接する確率が高くなり、隣り合ったＹ３Ａｌ５Ｏ１２粒が焼結時に粒成長し肥大なＹ３Ａｌ５Ｏ１２粒となり、その肥大なＹ３Ａｌ５Ｏ１２を起点としたクラックの発生が生じやすくなり、ｃＢＮ焼結体の靱性低下し、好ましくないからである。
(2) Content Ratio The content ratio of the Y 3 Al 5 O 12 grains in the sintered body is not less than 1% by volume (vol%) and not more than 20% by volume. The reason is that if it is less than 1% by volume, it is not possible to sufficiently circumvent cracks and to suppress the progress thereof, and it is not a sufficient amount to improve the toughness of the cBN sintered body. If it exceeds, the probability that the Y 3 Al 5 O 12 grains come into contact with each other in the cBN sintered body increases, and the adjacent Y 3 Al 5 O 12 grains grow during the sintering to become enlarged Y 3 Al 5 O 12 grains. This is because cracks starting from the enlarged Y 3 Al 5 O 12 easily occur, and the toughness of the cBN sintered body is reduced, which is not preferable.
２．Ｙ３Ａｌ５Ｏ１２の平均粒径と含有割合の測定方法
（１）Ｙ３Ａｌ５Ｏ１２の平均粒径
Ｙ３Ａｌ５Ｏ１２の存在は、Ｘ線回折（ＸＲＤ：ターゲットＣｕ）において、Ｙ３Ａｌ５Ｏ１２の回折ピークが現れることにより確認できる。
平均粒径は、ｃＢＮ焼結体の断面組織をオージェ電子分光（Ａｕｇｅｒ Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｇｒａｐｈｙ：以下、ＡＥＳという）装置を用いて、Ａｌ元素、Ｏ元素およびＹ元素のマッピング像を得て、Ａｌ元素、Ｏ元素およびＹ元素が重なる部位を画像処理によって抜き出し、当該部位をＹ３Ａｌ５Ｏ１２粒子と特定し、次いで、特定した各粒子に対して画像解析を行って平均粒径を求める。具体的には、結合相中のＹ３Ａｌ５Ｏ１２粒子を明確に判断するため、ＡＥＳを用いて得た同一視野におけるＡｌ元素、Ｏ元素およびＹ元素の各マッピング像は、対象元素が存在しない部位を黒、存在する部位を白とし、黒を０、白を２５５の２５６階調のモノクロにて取得し、各々のモノクロ像において各元素が存在する位置が白色となるように２値化処理する。２値化処理し得られた同一視野内におけるＡｌ元素、Ｏ元素およびＹ元素のマッピング像において、３元素が存在する、すなわち３元素の各マッピング像を比較しいずれも白色となる部位をＹ３Ａｌ５Ｏ１２粒子と特定する。
なお、Ｙ３Ａｌ５Ｏ１２粒同士が接触していると考えられる部分を切り離すような処理、例えば、画像処理法の1つであるウォーターシェッドを用いて接触していると思われるＹ３Ａｌ５Ｏ１２粒同士を分離する処理を、３元素の各マッピング像を比較しいずれも白色である部分を抜き出した後の像へ行ってもよい。
２値化処理後に得られた画像内のＹ３Ａｌ５Ｏ１２粒にあたる部分（白の部分）を粒子解析し、求めた最大長を各粒子の直径とする。最大長を求める粒子解析としては、例えば、１つのＹ３Ａｌ５Ｏ１２粒子に対してフェレ径を算出することより得られる２つの長さから大きい長さの値を最大長とし、その値を各粒子の直径とする。この直径を有する理想球体と仮定して計算より求めた体積を各粒子の体積として累積体積を求め、この累積体積を基に縦軸を体積百分率［％］、横軸を直径［μｍ］としてグラフを描画させ、体積百分率が５０％のときの直径をＹ３Ａｌ５Ｏ１２粒子の平均粒径とし、これを３観察領域に対して行い、その平均値をＹ３Ａｌ５Ｏ１２の平均粒径［μｍ］とした。粒子解析を行う際には、あらかじめＳＥＭにより分かっているスケールの値を用いて、１ピクセル当たりの長さ（μｍ）を設定しておく。画像処理に用いる観察領域としては、５.０μｍ×３.０μｍ程度の視野領域が望ましい。
2. The presence of Y 3 Al 5 average particle size and content The method of measurement of O 12 (1) Y 3 Al 5 average particle diameter Y 3 Al 5 O 12 of O 12 is, X-rays diffraction: In (XRD target Cu), This can be confirmed by the appearance of a diffraction peak of Y 3 Al 5 O 12 .
The average particle diameter is obtained by obtaining a mapping image of the Al element, the O element and the Y element using an Auger Electron Spectrograph (hereinafter, referred to as AES) apparatus for the cross-sectional structure of the cBN sintered body. A portion where the element and the Y element overlap is extracted by image processing, the portion is specified as Y 3 Al 5 O 12 particles, and then the specified particles are subjected to image analysis to obtain an average particle size. Specifically, in order to clearly determine the Y 3 Al 5 O 12 particles in the binder phase, the mapping images of the Al element, O element, and Y element in the same field of view obtained using AES show that the target element exists. The portions that do not exist are black, the portions that exist are white, black is 0, and white is acquired in monochrome with 256 gradations of 255, and binarized so that the position where each element exists in each monochrome image is white. To process. In the mapping image of the Al element, the O element, and the Y element in the same field of view obtained by the binarization processing, three elements are present, that is, a mapping image of each of the three elements is compared, and a portion where all become white is represented by Y 3 Specified as Al 5 O 12 particles.
In addition, a process of separating a portion where the Y 3 Al 5 O 12 grains are considered to be in contact with each other, for example, a Y 3 Al that seems to be in contact using a watershed which is one of image processing methods. The process of separating the 5 O 12 grains from each other may be performed on the image obtained by comparing the mapping images of the three elements and extracting the white portions.
A portion (white portion) corresponding to 12 Y 3 Al 5 O 12 particles in the image obtained after the binarization processing is subjected to particle analysis, and the obtained maximum length is defined as the diameter of each particle. As the particle analysis for obtaining the maximum length, for example, a value of a larger length from two lengths obtained by calculating a Feret diameter for one Y 3 Al 5 O 12 particle is set as the maximum length, and the value is set as the maximum length. The diameter of each particle. Assuming an ideal sphere having this diameter, the volume obtained by calculation is used as the volume of each particle to determine the cumulative volume. Based on this cumulative volume, the vertical axis represents the volume percentage [%], and the horizontal axis represents the diameter [μm]. Is drawn, and the diameter when the volume percentage is 50% is defined as the average particle size of the Y 3 Al 5 O 12 particles, and this is performed for three observation regions. The average value is the average particle size of the Y 3 Al 5 O 12 . The diameter was [μm]. When performing particle analysis, a length per pixel (μm) is set using a scale value known in advance by SEM. A viewing area of about 5.0 μm × 3.0 μm is desirable as an observation area used for image processing.
（２）含有割合
含有割合は、ＡＥＳを用いて、Ａｌ元素、Ｏ元素およびＹ元素のマッピング像を得て、Ａｌ元素、Ｏ元素およびＹ元素が重なる部位を画像処理によって抜き出し、当該部位をＹ３Ａｌ５Ｏ１２粒子と特定し、画像解析によりＹ３Ａｌ５Ｏ１２粒子が占める面積を算出して、Ｙ３Ａｌ５Ｏ１２粒子の面積割合を求める。これを少なくとも３画像に対して行い、算出した各Ｙ３Ａｌ５Ｏ１２粒子の面積割合の平均値をｃＢＮ焼結体に占めるＹ３Ａｌ５Ｏ１２の含有割合として求める。画像処理に用いる観察領域として、５．０μｍ×３．０μｍ程度の視野領域が望ましい。
(2) Content ratio The content ratio is obtained by using AES to obtain a mapping image of the Al element, the O element, and the Y element, extracting a portion where the Al element, the O element, and the Y element overlap by image processing, and extracting the portion with the Y component. 3 Al 5 O 12 particles are specified, the area occupied by the Y 3 Al 5 O 12 particles is calculated by image analysis, and the area ratio of the Y 3 Al 5 O 12 particles is determined. This is performed on at least three images, and the average value of the calculated area ratios of the respective Y 3 Al 5 O 12 particles is determined as the content ratio of Y 3 Al 5 O 12 in the cBN sintered body. A viewing area of about 5.0 μm × 3.0 μm is desirable as an observation area used for image processing.
３．ｃＢＮ焼結体中のｃＢＮ粒子の平均粒径と含有割合
本発明で用いるｃＢＮ粒子の平均粒径は、特に限定されるものではないが、０．２〜８．０μｍの範囲であることが好ましい。
これは、硬質なｃＢＮ粒子を焼結体内に含むことにより耐欠損性を高める効果に加えて、平均粒径が０．２〜８．０μｍのｃＢＮ粒子を焼結体内に分散させることにより、工具使用中に工具表面のｃＢＮ粒子が脱落して生じる刃先の凹凸形状を起点とする欠損、チッピングを抑制するだけでなく、工具使用中に刃先に加わる応力により生じるｃＢＮ粒子と結合相との界面から進展するクラック、あるいはｃＢＮ粒子が割れて進展するクラックの伝播を抑制することにより、優れた耐欠損性を有することができるためである。
ｃＢＮ焼結体に占めるｃＢＮ粒子の含有割合は、特に限定されるものではないが、４０体積％未満では、焼結体中に硬質物質が少なく、工具として使用した場合に、耐欠損性が低下することがあり、一方、７８体積％を超えると、焼結体中にクラックの起点となる空隙が生成し、耐欠損性が低下することがある。そのため、本発明が奏する効果をより一層発揮するためには、ｃＢＮ焼結体に占めるｃＢＮ粒子の含有割合は、４０〜７８体積％の範囲とすることが好ましい。
3. Average particle size and content ratio of cBN particles in cBN sintered body The average particle size of cBN particles used in the present invention is not particularly limited, but is preferably in the range of 0.2 to 8.0 µm. .
This is because, in addition to the effect of increasing the fracture resistance by including hard cBN particles in the sintered body, the cBN particles having an average particle size of 0.2 to 8.0 μm are dispersed in the sintered body, so that the tool is improved. In addition to suppressing chipping and chipping originating from the uneven shape of the cutting edge that occurs when cBN particles on the tool surface fall off during use, the interface between the cBN particles and the bonding phase generated by the stress applied to the cutting edge during use of the tool This is because excellent crack resistance can be obtained by suppressing the propagation of the crack that propagates or the crack that propagates by breaking the cBN particles.
The content ratio of the cBN particles in the cBN sintered body is not particularly limited, but if it is less than 40% by volume, the sintered body contains a small amount of hard material, and when used as a tool, the fracture resistance is reduced. On the other hand, if it exceeds 78% by volume, voids serving as crack starting points are formed in the sintered body, and the fracture resistance may be reduced. Therefore, in order to further exert the effect of the present invention, the content ratio of the cBN particles in the cBN sintered body is preferably in the range of 40 to 78% by volume.
ｃＢＮ粒子の平均粒径と含有割合は、以下のとおりにして求めることができる。
ｃＢＮ焼結体の断面組織をＳＥＭにてｃＢＮ焼結体組織を観察し、二次電子像を得る。得られた画像内のｃＢＮ粒子の部分を画像処理にて抜き出し、画像解析より求めた各粒子の最大長を基に平均粒径を算出する。
画像内のｃＢＮ粒子の部分を画像処理にて抜き出すにあたり、ｃＢＮ粒子と結合相とを明確に判断するため、画像は０を黒、２５５を白の２５６階調のモノクロで表示し、ｃＢＮ粒子部分の画素値と結合相部分の画素値の比が２以上となる画素値の像を用いてｃＢＮ粒が黒となるように２値化処理を行う。
ここで、ｃＢＮ粒子部分や結合相部分の画素値を求めるための領域として、０．５μｍ×０．５μｍ程度の領域内の平均値より求め、少なくとも同一画像内から異なる３個所より求めた平均の値を各々のコントラストとすることが望ましい。
なお、２値化処理後はｃＢＮ粒同士が接触していると考えられる部分を切り離すような処理、例えば、ウォーターシェッドを用いて接触していると思われるｃＢＮ粒同士を分離する。
２値化処理後に得られた画像内のｃＢＮ粒にあたる部分（黒の部分）を粒子解析し、求めた最大長を各粒子の直径とする。最大長を求める粒子解析としては、例えば、１つのｃＢＮ粒子に対してフェレ径を算出することより得られる２つの長さから大きい長さの値を最大長とし、その値を各粒子の直径とする。この直径を有する理想球体と仮定して計算より求めた体積を各粒子の体積として累積体積を求め、この累積体積を基に縦軸を体積百分率［％］、横軸を直径［μｍ］としてグラフを描画させ、体積百分率が５０％のときの直径をｃＢＮ粒子の平均粒径とし、これを３観察領域に対して行い、その平均値をｃＢＮの平均粒径［μｍ］とした。粒子解析を行う際には、あらかじめＳＥＭにより分かっているスケールの値を用いて、１ピクセル当たりの長さ（μｍ）を設定しておく。画像処理に用いる観察領域として、ｃＢＮ粒子の平均粒径が３μｍの場合、１５.０μｍ×１５.０μｍ程度の視野領域が望ましい。
The average particle size and the content ratio of the cBN particles can be determined as follows.
The cross-sectional structure of the cBN sintered body is observed with a SEM to obtain a secondary electron image. The portion of the cBN particles in the obtained image is extracted by image processing, and the average particle size is calculated based on the maximum length of each particle obtained by image analysis.
In extracting the cBN particle portion in the image by image processing, in order to clearly determine the cBN particle and the binding phase, the image is displayed in monochrome with 256 gradations of 0 for black and 255 for white, and the cBN particle portion. The binarization process is performed so that the cBN grains are black using an image of a pixel value in which the ratio of the pixel value of the pixel value to the pixel value of the combined phase portion is 2 or more.
Here, as a region for calculating the pixel value of the cBN particle portion or the bonded phase portion, the average value in a region of about 0.5 μm × 0.5 μm is obtained, and at least the average obtained from three different portions in the same image is obtained. It is desirable that the values be the respective contrasts.
In addition, after the binarization process, a process of separating a portion where cBN particles are considered to be in contact with each other, for example, separating cBN particles which are considered to be in contact with each other using a watershed.
The portion (black portion) corresponding to cBN grains in the image obtained after the binarization processing is subjected to particle analysis, and the obtained maximum length is defined as the diameter of each particle. As the particle analysis for obtaining the maximum length, for example, a value of a larger length from two lengths obtained by calculating the Feret diameter for one cBN particle is set as the maximum length, and the value is defined as the diameter of each particle. I do. Assuming an ideal sphere having this diameter, the volume obtained by calculation is used as the volume of each particle to determine the cumulative volume. Based on this cumulative volume, the vertical axis represents the volume percentage [%], and the horizontal axis represents the diameter [μm]. Was drawn, and the diameter when the volume percentage was 50% was defined as the average particle diameter of the cBN particles. This was performed for three observation regions, and the average value was defined as the average particle diameter of cBN [μm]. When performing particle analysis, a length per pixel (μm) is set using a scale value known in advance by SEM. When the average particle size of the cBN particles is 3 μm, a viewing area of about 15.0 μm × 15.0 μm is desirable as an observation area used for image processing.
ｃＢＮ焼結体に占めるｃＢＮ粒子の含有割合は、ｃＢＮ焼結体の断面組織をＳＥＭによって観察し、得られた二次電子像内のｃＢＮ粒子の部分を画像処理によって抜き出し、画像解析によってｃＢＮ粒子が占める面積を算出し、１画像内のｃＢＮ粒子が占める割合を求め、少なくとも３画像を処理し求めた値の平均値をｃＢＮ粒子の含有割合として求める。画像内のｃＢＮ粒子の部分を抜き出す画像処理は、ｃＢＮ粒の平均粒径の２値化処理後の像を得る手順と同様に行う。画像処理に用いる観察領域として、例えば、ｃＢＮ粒子の平均粒径０．３μｍの場合、５．０μｍ×３．０μｍ程度の視野領域が望ましい。 The content ratio of cBN particles in the cBN sintered body can be determined by observing the cross-sectional structure of the cBN sintered body by SEM, extracting a portion of the cBN particles in the obtained secondary electron image by image processing, and analyzing the cBN particles by image analysis. Is calculated, the ratio of cBN particles in one image is determined, and the average of the values obtained by processing at least three images is determined as the content ratio of cBN particles. Image processing for extracting a portion of the cBN particles in the image is performed in the same manner as the procedure for obtaining an image after the binarization processing of the average particle size of the cBN particles. For example, when the average particle diameter of the cBN particles is 0.3 μm, a viewing area of about 5.0 μm × 3.0 μm is desirable as the observation area used for image processing.
４．製造方法
本発明の製造方法の一例を以下に示す。
（１）結合相を構成する成分の原料粉末の準備
結合相を構成する原料粉末として、Ｙ３Ａｌ５Ｏ１２原料と結合相の主となる原料を用意する。Ｙ３Ａｌ５Ｏ１２原料として、平均粒径３〜５μｍのＹ３Ａｌ５Ｏ１２粉末を用意する。Ｙ３Ａｌ５Ｏ１２粉末は、所望の粒径に粉砕したＹ３Ａｌ５Ｏ１２原料粉とするため、例えば、超硬合金で内張りされた容器内に超硬合金製ボールとアセトンと共に充填し、蓋をした後にボールミルにより粉砕を行った後、遠心分離装置を用いて分級することにより、縦軸を体積百分率、横軸を粒子径とした場合のメディアン径Ｄ５０を粉砕したＹ３Ａｌ５Ｏ１２原料粉の平均粒径とし、その値が１０〜２００ｎｍのＹ３Ａｌ５Ｏ１２原料粉を得る。また、結合相の主となる原料としては、従来から知られている結合相形成原料粉末（ＴｉＮ粉末、ＴｉＣ粉末、ＴｉＣＮ粉末、ＴｉＡｌ３粉末）を準備する。
4. Manufacturing method One example of the manufacturing method of the present invention is shown below.
(1) Preparation of Raw Material Powder for Component Constituting Bound Phase As a raw material powder for forming the binding phase, a Y 3 Al 5 O 12 raw material and a main raw material of the binding phase are prepared. As a Y 3 Al 5 O 12 raw material, a Y 3 Al 5 O 12 powder having an average particle size of 3 to 5 μm is prepared. In order to make the Y 3 Al 5 O 12 powder into a Y 3 Al 5 O 12 raw material powder pulverized to a desired particle size, for example, a container lined with a cemented carbide is filled together with cemented carbide balls and acetone. , after pulverized by a ball mill after the lid and then classified using a centrifugal separator, the volume percent of the vertical axis and the horizontal axis grinding the median diameter D50 in the case of a particle diameter Y 3 Al 5 O an average particle size of 12 raw material powder, the value is obtained a Y 3 Al 5 O 12 material powder of 10 to 200 nm. Further, as a main raw material of the binder phase, a binder phase forming raw material powder (TiN powder, TiC powder, TiCN powder, TiAl 3 powder) conventionally known is prepared.
（２）粉砕・混合
これらの原料粉末を、例えば、超硬合金で内張りされた容器内に超硬合金製ボールとアセトンと共に充填し、蓋をした後にボールミルにより粉砕および混合を行う。
その後、硬質相として機能させる平均粒径０．２〜８．０μｍのｃＢＮ粉末を焼結後のｃＢＮ粒子の含有割合が所定の体積％となるように添加して、さらに、ボールミル混合を行う。
(2) Grinding / Mixing These raw material powders are filled together with cemented carbide balls and acetone into a container lined with a cemented carbide, for example, and after being covered, crushed and mixed by a ball mill.
Thereafter, cBN powder having an average particle size of 0.2 to 8.0 μm to function as a hard phase is added so that the content ratio of the cBN particles after sintering becomes a predetermined volume%, and further ball mill mixing is performed.
（３）成形、焼結
得られた焼結体原料粉末を、所定圧力で成形して成形体を作製し、これを真空下、１０００℃で仮焼結し、その後、超高圧焼結装置に装入して、例えば、圧力：５ＧＰａ、温度：１２００〜１６００℃の範囲内の所定の温度で焼結することにより、本発明のｃＢＮ焼結体を作製する。
(3) Forming and sintering The obtained raw material powder of the sintered body is formed at a predetermined pressure to form a formed body, which is temporarily sintered at 1000 ° C. under vacuum, and then is applied to an ultra-high pressure sintering apparatus. The cBN sintered body of the present invention is manufactured by charging and sintering at a predetermined temperature within a range of, for example, pressure: 5 GPa and temperature: 1200 to 1600 ° C.
５．ＣＢＮ工具
このように作製した本発明の、靭性に優れたｃＢＮ焼結体を工具基体とするｃＢＮ基超高圧焼結体製切削工具は、例えば、高硬度鋼の断続切削加工においても、耐欠損性に優れ、長期の使用にわたって優れた耐摩耗性を発揮する。
5. CBN Tool The cBN-based ultra-high pressure sintered compact cutting tool of the present invention produced using a cBN sintered compact having excellent toughness as a tool base according to the present invention is, for example, resistant to fracture even in intermittent cutting of high-hardness steel. Excellent wear resistance over a long period of use.
以下、本発明の実施例について記載する。 Hereinafter, examples of the present invention will be described.
本実施形態のｃＢＮ焼結体の製造では、結合相を構成するための原料粉末として、Ｙ３Ａｌ５Ｏ１２粉末を準備し、Ｙ３Ａｌ５Ｏ１２の粒径制御のため、ボールミルにて粉砕の処理を施した後、遠心分離法を用いて分級することにより所望の粒径範囲のＹ３Ａｌ５Ｏ１２原料粉を用意した。
すなわち、平均粒径３μｍのＹ３Ａｌ５Ｏ１２粉末を準備し、超硬合金で内張りされた容器内に超硬合金製ボールとアセトンと共に充填し、蓋をした後にボールミルを用いて粉砕を実施後、混合したスラリーを乾燥させた後、遠心分離装置を用いて分級することにより平均粒径が１０〜２００ｎｍのＹ３Ａｌ５Ｏ１２原料粉を得ることができる。
上記のように事前に準備したＹ３Ａｌ５Ｏ１２原料粉と、平均粒径が０．３μｍ〜０．９μｍのＴｉＮ粉末、ＴｉＣ粉末、ＴｉＣＮ粉末、ＴｉＡｌ３粉末を用意し、これら原料粉末の中から選ばれたいくつかの結合相構成用原料粉末（各原料粉末の体積％を表１に示す）と、硬質相用原料としてのｃＢＮ粉末の合量を１００体積％としたときの焼結後のｃＢＮ粒子の含有割合が４０〜７８体積％となるように配合し、湿式混合し、乾燥した。
次いで、得られた焼結体原料粉末を、成形圧１ＭＰａで直径：５０ｍｍ×厚さ：１．５ｍｍの寸法にプレス成形し、ついでこの成形体を、圧力：１Ｐａ以下の真空雰囲気中、１０００℃の範囲内の所定温度に保持して仮焼結し、その後、超高圧焼結装置に装入して、圧力：５ＧＰａ、温度：１４００℃の温度で焼結することにより、表２に示す本発明のｃＢＮ焼結体１〜１５（本発明焼結体１〜１５という）を作製した。なお、成形体に施す熱処理は、湿式混合時の溶媒を除去することが主な目的である。
また、上記作製工程は、超高圧焼結までの工程において原料粉末の酸化を防止することが好ましく、具体的には非酸化性の保護雰囲気中での取り扱いを実施することが好ましい。
本発明焼結体１のＸＲＤ図を図２に示す。
In the production of the cBN sintered body of the present embodiment, Y 3 Al 5 O 12 powder is prepared as a raw material powder for forming a binder phase, and is controlled by a ball mill to control the particle size of Y 3 Al 5 O 12 . After the pulverization treatment, the powder was classified by centrifugation to prepare a Y 3 Al 5 O 12 raw material powder having a desired particle size range.
That is, Y 3 Al 5 O 12 powder having an average particle size of 3 μm is prepared, filled in a vessel lined with cemented carbide together with cemented carbide balls and acetone, covered, and then ground using a ball mill. Thereafter, the mixed slurry is dried, and then classified by using a centrifugal separator, whereby Y 3 Al 5 O 12 raw material powder having an average particle diameter of 10 to 200 nm can be obtained.
Y 3 Al 5 O 12 raw material powder prepared in advance as described above, and TiN powder, TiC powder, TiCN powder, and TiAl 3 powder having an average particle diameter of 0.3 μm to 0.9 μm are prepared. Sintering when the total amount of several binder phase constituent raw material powders selected from the above (volume% of each raw material powder is shown in Table 1) and cBN powder as the hard phase raw material is 100 vol% It was blended so that the content ratio of the subsequent cBN particles was 40 to 78% by volume, wet-mixed and dried.
Next, the obtained sintered compact raw material powder is press-molded at a compacting pressure of 1 MPa to a size of diameter: 50 mm × thickness: 1.5 mm. Tentative sintering at a predetermined temperature within the range described above, and thereafter, the sintering was carried out in an ultrahigh pressure sintering apparatus, and sintering was performed at a pressure of 5 GPa and a temperature of 1400 ° C. Inventive cBN sintered bodies 1 to 15 (referred to as present invention sintered bodies 1 to 15) were produced. The main purpose of the heat treatment applied to the compact is to remove the solvent during wet mixing.
Further, in the above-mentioned manufacturing process, it is preferable to prevent oxidation of the raw material powder in the process up to ultrahigh pressure sintering, and specifically, it is preferable to carry out the handling in a non-oxidizing protective atmosphere.
FIG. 2 shows an XRD diagram of the sintered body 1 of the present invention.
比較のため、本発明において規定する範囲外のＹ３Ａｌ５Ｏ１２平均粒径、含有割合を検討すべく、Ｙ３Ａｌ５Ｏ１２を含まないおよび含む原料をボールミルを用いて粉砕し、遠心分離装置を用いて分級し、平均粒径０．３μｍ〜０．９μｍのＴｉＮ粉末、ＴｉＣＮ粉末、ＴｉＡｌ３粉末を用意し、これら原料粉末の中から選ばれたいくつかの結合相構成用原料粉末（各原料粉末の体積％を表３に示す）と、硬質相としてのｃＢＮ粉末との含量を１００体積％としたときの焼結後のｃＢＮ粒子の含有割合が５６〜６５体積％となるように配合し、湿式混合し、乾燥した。
その後、本発明焼結体１〜１５と同様な条件で成形体を作製し、熱処理し、この成形体を、本発明焼結体１〜１５と同様な条件で超高圧高温焼結することにより、表４に示す比較例のｃＢＮ焼結体（以下、比較例焼結体という）１〜５を作製した。
For comparison, in order to examine the average particle diameter and content of Y 3 Al 5 O 12 outside the range specified in the present invention, a raw material containing no and containing Y 3 Al 5 O 12 was pulverized using a ball mill and centrifuged. Classification was performed using a separation device to prepare TiN powder, TiCN powder, and TiAl 3 powder having an average particle diameter of 0.3 μm to 0.9 μm, and several raw material powders for forming a binder phase selected from these raw material powders (The volume percentage of each raw material powder is shown in Table 3) and the content ratio of cBN particles after sintering when the content of cBN powder as the hard phase is 100 volume% is 56 to 65 volume%. And wet-mixed and dried.
Thereafter, a compact is produced under the same conditions as the sintered bodies 1 to 15 of the present invention, heat-treated, and the compact is subjected to ultra-high pressure and high temperature sintering under the same conditions as the sintered bodies 1 to 15 of the present invention. Then, cBN sintered bodies of comparative examples (hereinafter, referred to as comparative sintered bodies) 1 to 5 shown in Table 4 were produced.
次に、上記で作製した本発明品１〜１５、比較品１〜５を、ワイヤー放電加工機で所定寸法に切断し、Ｃｏ：５質量％、ＴａＣ：５質量％、ＷＣ：残りの組成およびＩＳＯ規格ＣＮＧＡ１２０４０８のインサート形状をもったＷＣ基超硬合金製インサート本体のろう付け部（コーナー部）に、Ｃｕ：２６質量％、Ｔｉ：５質量％、Ａｇ：残りからなる組成を有するＡｇ合金のろう材を用いてろう付けし、上下面および外周研磨、ホーニング処理を施すことにより、ＩＳＯ規格ＣＮＧＡ１２０４０８のインサート形状をもつ本発明のｃＢＮ基超高圧焼結体切削工具（本発明工具という）１〜１５、および、比較例のｃＢＮ基超高圧焼結体切削工具（比較例工具という）１〜５を製造した。 Next, the inventive products 1 to 15 and the comparative products 1 to 5 prepared above were cut into predetermined dimensions by a wire electric discharge machine, and Co: 5% by mass, TaC: 5% by mass, WC: remaining composition and A brazing portion (corner portion) of a WC-based cemented carbide insert body having an insert shape conforming to ISO standard CNGA120408 has an Ag alloy having a composition consisting of 26% by mass of Cu, 5% by mass of Ti, and Ag: the remainder. By performing brazing using a brazing material, polishing the upper and lower surfaces and the outer periphery, and performing a honing process, the cBN-based ultrahigh-pressure sintered compact cutting tool of the present invention (referred to as a tool of the present invention) 1 having an insert shape of ISO standard CNGA120408. 15 and cBN-based ultrahigh-pressure sintered compact cutting tools (referred to as comparative example tools) 1 to 5 of Comparative Examples.
次いで、本発明工具１〜１５と比較工具１〜５に対して、以下の切削条件で切削加工を実施し、欠損に至るまでの工具寿命（回数）を測定した。
＜切削条件＞
被削材：浸炭焼き入れ鋼（ＪＩＳ・ＳＣＭ４１５、硬さ：ＨＲＣ５８〜６２）の長さ方向等間隔８本縦溝入り丸棒、
切削速度：２００ｍ／ｍｉｎ、
切り込み：０．１ｍｍ、
送り：０．１ｍｍ／ｒｅｖ
の条件での、高硬度鋼の乾式切削加工試験を実施。
各工具の刃先がチッピングあるいは欠損に至るまでの断続回数を工具寿命とし、断続回数５００回毎に刃先を観察し、刃先の欠損やチッピングの有無を確認した。
表５に、上記切削加工試験の結果を示す。
Next, cutting was performed on the present invention tools 1 to 15 and the comparative tools 1 to 5 under the following cutting conditions, and the tool life (number of times) until breakage was measured.
<Cutting conditions>
Work material: Carburized hardened steel (JIS SCM415, hardness: HRC58-62) Elongated round bar with 8 longitudinal grooves,
Cutting speed: 200m / min,
Notch: 0.1mm,
Feed: 0.1 mm / rev
Dry cutting test of high-hardness steel under the above conditions.
The number of interruptions until the cutting edge of each tool reached chipping or chipping was defined as the tool life, and the cutting edge was observed every 500 interruptions to confirm the presence or absence of chipping or chipping.
Table 5 shows the results of the cutting test.
表５に示される結果から、本発明工具は、比較例工具に比して、突発的な刃先の欠損、チッピングが発生することなく、工具寿命が延命化されており、靱性が向上したことが分かる。 From the results shown in Table 5, it can be seen that the tool of the present invention has a longer tool life and improved toughness without sudden chipping of the cutting edge and chipping as compared with the comparative example tool. I understand.
本発明の靱性に優れたｃＢＮ焼結体は、靱性が高くＣＢＮ工具の工具基体として用いると、欠損、破損を発生することなく長期の使用にわたって、優れた耐欠損性を発揮し、工具寿命の延命化が図られるものであることから、切削加工装置の高性能化、並びに切削加工の省力化および省エネ化、低コスト化に十分満足に対応できるものである。 The cBN sintered body having excellent toughness of the present invention, when used as a tool base of a CBN tool having high toughness, exhibits excellent chipping resistance over a long period of use without causing breakage or breakage, and has a long tool life. Since the life is prolonged, it is possible to satisfactorily cope with high performance of the cutting apparatus, labor saving and energy saving of the cutting processing, and cost reduction.
Claims (2)
平均粒径が１０ｎｍ以上２００ｎｍ以下のＹ３Ａｌ５Ｏ１２が、前記焼結体に対する含有割合として１体積％以上２０体積％以下となるように分散していることを特徴とするｃＢＮ焼結体。 In a cBN sintered body composed of cubic boron nitride particles and a ceramic binder phase,
A cBN sintered body characterized in that Y 3 Al 5 O 12 having an average particle size of 10 nm or more and 200 nm or less is dispersed so as to be 1% by volume or more and 20% by volume or less with respect to the sintered body. .
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| JPH11335159A (en) * | 1998-05-25 | 1999-12-07 | Kyocera Corp | High-strength, high-hardness alumina ceramics and its production |
| US20070134494A1 (en) * | 2003-12-03 | 2007-06-14 | Dole Stephen L | Cubic boron nitride sintered body and method for making the same |
| 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 |
| WO2017204152A1 (en) * | 2016-05-23 | 2017-11-30 | 三菱マテリアル株式会社 | Cubic boron nitride sintered compact cutting tool |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11335159A (en) * | 1998-05-25 | 1999-12-07 | Kyocera Corp | High-strength, high-hardness alumina ceramics and its production |
| US20070134494A1 (en) * | 2003-12-03 | 2007-06-14 | Dole Stephen L | Cubic boron nitride sintered body and method for making the same |
| 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 |
| WO2017204152A1 (en) * | 2016-05-23 | 2017-11-30 | 三菱マテリアル株式会社 | Cubic boron nitride sintered compact cutting tool |
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