JP2008517860A - 立方晶窒化硼素質焼結体およびそれを用いた切削工具 - Google Patents
立方晶窒化硼素質焼結体およびそれを用いた切削工具 Download PDFInfo
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- JP2008517860A JP2008517860A JP2006543713A JP2006543713A JP2008517860A JP 2008517860 A JP2008517860 A JP 2008517860A JP 2006543713 A JP2006543713 A JP 2006543713A JP 2006543713 A JP2006543713 A JP 2006543713A JP 2008517860 A JP2008517860 A JP 2008517860A
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- sintered body
- boron nitride
- cubic boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B27/00—Tools for turning or boring machines; Tools of a similar kind in general; Accessories therefor
- B23B27/14—Cutting tools of which the bits or tips or cutting inserts are of special material
- B23B27/148—Composition of the cutting inserts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
以下、本発明にかかるcBN質焼結体の実施形態について、図面を参照して詳細に説明する。
(第1の実施形態)
図1(a)は、本発明の第1の実施形態にかかるcBN質焼結体の組織を示す概略説明図である。図1(a)に示すように、このcBN質焼結体1は、cBN粒子2[図1(a)中の黒塗り部分]と結合相3とからなる。すなわち、cBN質焼結体1は、硬質相をなすcBN粒子2の周囲を結合相マトリックスである結合相3にて結合したものである。さらに、cBN粒子2と結合相3との間には、cBN粒子2と結合相3とを密着させる中間相4が存在している。
次に、本発明にかかるcBN質焼結体の第2の実施形態について説明する。なお、本実施形態においては、前述した第1の実施形態の構成と同一または同等な部分には同一の符号を付して説明は省略する。
次に、本発明にかかるcBN質焼結体の第3の実施形態について説明する。なお、本実施形態においては、前述した第1および第2の実施形態の構成と同一または同等な部分には同一の符号を付して説明は省略する。
次に、本発明にかかるcBN質焼結体の第4の実施形態について説明する。なお、本実施形態においては、前述した第1〜第3の実施形態の構成と同一または同等な部分には同一の符号を付して説明は省略する。
次に、本発明にかかるcBN質焼結体の第5の実施形態について説明する。なお、本実施形態においては、前述した第1〜第4の実施形態の構成と同一または同等な部分には同一の符号を付して説明は省略する。
なお、第2の実施形態にかかる比率IN/IcBN、比率Ic/IcBN、ピーク強度ICNとピーク強度Ic、INとの比などについても、上記と同様の条件を満足するのがよい。
次に、上記で説明した各実施形態におけるcBN質焼結体を備えた、本発明にかかる切削工具について、図面を参照して詳細に説明する。図10は、本発明にかかる切削工具の一実施形態を示す斜視図である。図10に示すように、切削工具である工具チップ12は、チップ本体13のコーナー部に設けられたチップ取付座に、所定の形状に切り出した工具用cBN質焼結体30が裏打ち板15を介してロウ付けされた構造を有している。工具用cBN質焼結体30は、上面と側面の交差稜線に切刃14が形成されている。
平均粒径2μmのcBN原料粉末、平均粒径1μmのTiC原料粉末、平均粒径1μmのTiN原料粉末、平均粒径1μmのTiCN原料粉末、平均粒径1μmのHfC原料粉末、平均粒径1μmのNbC原料粉末、平均粒径1.2μmの金属Al原料粉末、平均粒径0.8μmの金属Co原料粉末を用いて、表1に示す組成となるように調合し、この粉体を、アルミナ製ボールを用いたボールミルで16時間混合した。
上記で得られた各cBN質焼結体を研削後、鏡面加工し、金属顕微鏡で組織を観察した。その結果、黒色を示すcBN粒子と、茶褐色を示す窒化物および白色を示す炭化物を明確に区別することが可能であり、EPMA(電子プローブ微小分析)のWDS(波長分散型X線マイクロアナライザー)を用いて構成成分を確認することによって中間相および炭窒化物の区別も可能であった。さらに、画像解析法により、各化合物それぞれ20個以上について面積を測定し、その平均値をcBN粒子、炭化物、窒化物、中間相および炭窒化物の含有率としてそれぞれ測定した。その結果を表1に示す。
なお、炭窒化物については、X線回折ピークにて、その存在の有無を確認し、ピークが確認された場合には、標準試料(cBN粉末と炭窒化物粉末との混合粉末の成形体)に基づいて含有比率を算出した。
切削方法:旋削
被削材 :SCM415H浸炭焼き入れ鋼(HRC58〜62)、φ70mmの円柱形状
切削速度:200m/分
切り込み:0.2mm
送り :0.1mm/rev
切削時間:20分
測定項目:先端摩耗幅
切削方法:旋削
被削材 :SCM415H浸炭焼き入れ鋼(HRC58〜62)、八穴蓮根型材
切削速度:150m/分
切り込み:0.2mm
送り :0.2mm/rev
測定項目:欠損に至るまでの衝撃回数(上限40000回)
cBN:45体積%、TiN:42体積%、Al:15体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて芯材用成形体を作製した。次に、cBN:55体積%、TiC:35体積%、Al:10体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて表皮材用成形体を作製した。
平均粒径2μmのcBN原料粉末、平均粒径1μmのTiC原料粉末、平均粒径1μmのTiN原料粉末、平均粒径1μmのTiCN原料粉末、平均粒径1μmのHfC原料粉末、平均粒径1μmのTaC原料粉末、平均粒径1.2μmの金属Al原料粉末、平均粒径0.8μmの金属Co原料粉末を用いて、表3に示す組成となるように調合し、この粉体を、アルミナ製ボールを用いたボールミルで16時間混合し、混合した粉体を圧力98MPaで加圧成形した。
そして、各cBN質焼結体をCu−Kα線源を用い、2θ=30〜50°についてX線回折分析(XRD)にて分析し(Kα2除去を実施)、得られた回折強度チャートから炭化物および窒化物ピークを確認し、炭化物と窒化物ピーク強度比を計算した。結果は、表4に示した。
さらに、各cBN質焼結体を用いて、上記実施例Iと同様にして、JIS・CNGA120408に規定する形状のスローアウェイ型切削工具を作製した。ついで、断続切削試験における測定項目において、欠損に至るまでの衝撃回数を、上限40000回に代えて、60000回にした以外は、上記実施例Iと同様にして、連続切削試験と断続切削試験とを行った。これらの結果を表4に示す。
上記実施例IIと同様にして、芯材用成形体を作製した。次に、TiCを35体積%に代えて、30体積%にした以外は、上記実施例IIと同様にして、表皮材用成形体を作製した。ついで、この芯材用成形体と表皮材用成形体とを用い、上記実施例IIと同様にして、多芯構造の複合成形体を作成し、焼成してcBN複合焼結体を作製した。
平均粒径2.5μmのcBN原料粉末、平均粒径1.5μmのTiC原料粉末、平均粒径1.2μmのTiN原料粉末、平均粒径1μmのTiCN原料粉末、平均粒径1μmのNbC原料粉末、平均粒径1.1μmのTaC原料粉末、平均粒径0.9μmのNbN原料粉末、平均粒径1.2μmの金属Al原料粉末、平均粒径0.8μmの金属Co原料粉末を用いて、表5に示す組成となるように調合し、この粉体を、アルミナ製ボールを用いたボールミルで16時間混合した。
そして、上記実施例IIIと同様にして、X線回折分析(XRD)チャートから、炭化物ピーク、窒化物ピークおよびその他のピークを確認した。また、表6に示すピーク強度比を計算した。
また、金属顕微鏡を用いた組織観察をカラーで行い、結合相中の窒化物と炭化物との存在状態を確認し、ルーゼックス画像解析装置により、平均粒径dN、dC、dcBNを測定した。なお、dN、dC、dcBNの測定に際しては、組織写真にて観察される各相の個数はそれぞれ50個以上とした。
これらの測定結果を表6に併せて示す。
さらに、各cBN質焼結体を用いて、上記実施例Iと同様にして、JIS・CNGA120408に規定する形状をもったスローアウェイ型切削工具を作製した。ついで、断続切削試験における測定項目において、欠損に至るまでの衝撃回数を、上限40000回に代えて、60000回にした以外は、上記実施例Iと同様にして、連続切削試験と断続切削試験とを行った。これらの結果を表6に示す。
cBN:47体積%、TiN:39体積%、Al:14体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて芯材用成形体を作製した。次に、cBN:60体積%、TiC:30体積%、Al:10体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて表皮材用成形体を作製した。
平均粒径2μmのcBN原料粉末、平均粒径1μmのTiC原料粉末、平均粒径1μmのTiN原料粉末、平均粒径1μmのTiCN原料粉末、平均粒径1μmのTaC原料粉末、平均粒径1.2μmのZrC原料粉末、平均粒径1.1μmのZrN原料粉末、平均粒径0.9μmのWC原料粉末、平均粒径1.2μmの金属Al原料粉末、平均粒径0.8μmの金属Co原料粉末を用いて、表7に示す組成となるように調合し、この粉体を、アルミナ製ボールを用いたボールミルで16時間混合した。
そして、実施例IIIと同様にしてX線回折分析(XRD)にて、炭化物ピーク、窒化物ピークおよびその他のピークを確認した。また、表8に示すピーク強度比を計算した。
また、cBNについてはFe−Kα線を用いて、結合相のTiCとTiNについてはCu−Kα線を用いて、2θ≧100°に観測されるピーク、例えばcBNの(311)面に帰属されるピーク、および結合相の(422)面に帰属されるピークを用いてX線残留応力測定法(2θ−sin2φ法)によりcBN粒子および結合相にかかる残留応力を算出した。なお、この計算には、例えばcBN粒子については弾性定数E=712GPa、ポアソン比=0.215、TiNについては弾性定数E=250GPa、ポアソン比=0.19、TiCについては弾性定数E=400GPa、ポアソン比=0.19を用いた。
さらに、各cBN質焼結体を用いて、断続切削試験における測定項目において、欠損に至るまでの衝撃回数を、上限40000回に代えて、60000回にした以外は、上記実施例Iと同様にして、連続切削試験と断続切削試験とを行った。これらの結果を表8に示す。
cBN:50体積%、TiN:37体積%、Al:13体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて芯材用成形体を作製した。次に、cBN:60体積%、TiC:30体積%、Al:10体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて表皮材用成形体を作製した。
平均粒径1.5μmのcBN原料粉末、平均粒径1μmのTiC原料粉末、平均粒径1μmのTiN原料粉末、平均粒径1μmのTiCN原料粉末、平均粒径1μmのHfC原料粉末、平均粒径1μmのNbC原料粉末、平均粒径1.2μmの金属Al原料粉末、平均粒径0.8μmの金属Co原料粉末を用いて、表9に示す組成となるように調合し、この粉体を、アルミナ製ボールを用いたボールミルで16時間混合した。
得られた各切削工具に対して、実施例Iと同様にして、金属顕微鏡で組織観察を行い、各化合物の含有率を算出した。
実施例IIIと同様に、X線回折測定を行ない、その回折チャートから、IcBNを100としたときの各ピークのピーク強度比IcBN(=100)、IC、IN、IIL、ICNを算出した。
(硬質膜の膜厚)
硬質膜の膜厚は、表面被覆cBN質焼結体の破断面を走査型電子顕微鏡で観察して測定した。
(硬質膜のX線回折ピークにおける比[I(111)/I(200)])
X線回折分析にて硬質膜の(111)結晶面に帰属するピークの強度I(111)と、(200)結晶面に帰属するピーク強度I(200)を測定し、その比[I(111)/I(200)]の値を計算した。
(cBN質焼結体の圧縮残留応力)
実施例VIIと同様にしてcBN粒子および硬質膜にかかる残留応力を算出した。なお、硬質膜が多層膜からなる場合の残留応力は、最も厚く成膜した硬質膜の残留応力を用いて測定した。
断続切削試験における測定項目において、欠損に至るまでの衝撃回数を、上限40000回に代えて、60000回にした以外は、上記実施例Iと同様にして、連続切削試験と断続切削試験とを行った。
cBN:50体積%、TiN:35体積%、Al:15体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて芯材用成形体を作製した。次に、cBN:65体積%、TiC:25体積%、Al:10体積%の割合でそれぞれの粉末を混合し、有機バインダを添加して押出成形にて表皮材用成形体を作製した。
実施例IXと同様の方法で、表9の試料No.IX−1と同じcBN質焼結体を作製した。ついで、このcBN質焼結体を放電加工によって所定の形状に切り出し、フライス切削用の超硬合金製スローアウェイチップの刃先先端部に形成した切り込み段部にロウ付けした後、プラズマCVD法で膜厚0.2μmのダイヤモンドライクカーボン膜を成膜する以外は、実施例IXと同様にして切削工具を作製した(試料No.XI−1)。
切削方法:フライス
被削材 :Ti−16Al−4V合金
切削速度:500m/分
切り込み:1.0mm
送り :0.3mm/刃
測定項目:切削長1mに達した時の刃先の状態を走査型電子顕微鏡で確認
2 cBN粒子
3 結合相
4 中間相
5 炭化物
6 窒化物
7 炭窒化物
8 cBN質焼結体からなる繊維状の芯材
8a cBN質焼結体からなる繊維状の芯材(結合相が炭化物)
8b cBN質焼結体からなる繊維状の芯材(結合相が窒化物)
9 cBN質焼結体からなる表皮材
9a cBN質焼結体からなる表皮材(結合相が窒化物)
9b cBN質焼結体からなる表皮材(結合相が炭化物)
10 単芯繊維状構造のcBN質焼結体
10a 第1のcBN質焼結体
10b 第2のcBN質焼結体
11 多芯繊維状構造のcBN質焼結体
12 工具チップ
13 チップ本体
14 切刃部
15 裏打ち板
16 シート状構造体
16A cBN複合焼結体をシート状に並べたもの
16B 16Aの繊維方向を平行にして重ねたもの
16C 16Aの繊維方向を垂直にして重ねたもの
16D 16Aの繊維断面方向がシートの主面となるように配置したもの
17 芯材用成形体
18 表皮材用成形体
19 複合成形体
20 単芯繊維状構造の複合成形体
21 多芯繊維状構造の複合成形体
22 シート状複合成形体
23 ロール
30 工具用cBN質焼結体
31 すくい面
32 逃げ面
40 硬質膜
IcBN X線回折分析でのcBN粒子の最強回折ピーク
IN X線回折分析での(200)面に帰属される窒化物の回折ピーク
IC X線回折分析での(200)面に帰属される炭化物の回折ピーク
dc 芯材の直径
ds 表皮材の厚み
Claims (34)
- 立方晶窒化硼素粒子を結合相で結合した立方晶窒化硼素質焼結体であり、前記結合相は、周期律表第4,5および6族金属の群から選ばれる少なくとも1種の金属元素の炭化物と、周期律表第4,5および6族金属の群から選ばれる少なくとも1種の金属元素の窒化物とが共存している立方晶窒化硼素質焼結体。
- 立方晶窒化硼素粒子を周期律表第4,5および6族金属の群から選ばれる少なくとも1種の金属元素の炭化物からなる結合相で結合した立方晶窒化硼素質焼結体からなる繊維状の芯材の外周面を、立方晶窒化硼素粒子を周期律表第4,5および6族金属の群から選ばれる少なくとも1種の金属元素の窒化物からなる結合相で結合した立方晶窒化硼素質焼結体からなる表皮材によって被覆した単芯繊維状構造からなる立方晶窒化硼素質焼結体。
- 立方晶窒化硼素粒子を周期律表第4,5および6族金属の群から選ばれる少なくとも1種の金属元素の窒化物からなる結合相で結合した立方晶窒化硼素質焼結体からなる繊維状の芯材の外周面を、立方晶窒化硼素粒子を周期律表第4,5および6族金属から選ばれる少なくとも1種の金属元素の炭化物からなる結合相で結合した立方晶窒化硼素質焼結体からなる表皮材によって被覆した単芯繊維状構造からなる立方晶窒化硼素質焼結体。
- 前記単芯繊維状構造を複数本集束した多芯繊維状構造からなる請求項2または3記載の立方晶窒化硼素質焼結体。
- 前記炭化物を構成する金属元素および前記窒化物を構成する金属元素が同じ金属元素である請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記金属元素がチタン元素である請求項5記載の立方晶窒化硼素質焼結体。
- 立方晶窒化硼素質焼結体全体に対する前記炭化物の含有比率pCと、前記窒化物の含有比率pNとの比(pC/pN)が0.2〜3.0である請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記立方晶窒化硼素粒子の外周部に、周期率表第4、5および6族金属、鉄族金属およびAlから選ばれる少なくとも1種の金属元素の炭化物、窒化物、炭窒化物、硼化物、硼炭化物、硼窒化物および酸化物のうち、前記結合相成分以外の化合物を含む中間相が存在する請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 立方晶窒化硼素質焼結体全体に対する前記立方晶窒化硼素粒子の含有比率pcBNが45〜80面積%、前記炭化物の含有比率pCが2〜45面積%、前記窒化物の含有比率pNが3〜50面積%、前記中間相の含有比率pmが0〜25面積%である請求項8記載の立方晶窒化硼素質焼結体。
- 前記炭化物および窒化物の相互固溶体化合物である炭窒化物の含有比率が立方晶窒化硼素質焼結体全体に対して5質量%以下である請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- X線回折分析において、前記窒化物のピークと前記炭化物のピークとが共存している請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記X線回折分析において、前記炭化物の(200)面に帰属される回折ピークのピーク強度Icと、前記窒化物の(200)面に帰属される回折ピークのピーク強度INとの比(IC/IN)が0.2〜1.2である請求項11記載の立方晶窒化硼素質焼結体。
- 前記X線回折分析において、前記立方晶窒化硼素粒子の(111)面に帰属される回折ピークのピーク強度IcBNと、前記窒化物のピーク強度INとの比(IN/IcBN)が0.3〜1である請求項11記載の立方晶窒化硼素質焼結体。
- 前記X線回折分析において、前記立方晶窒化硼素粒子の(111)面に帰属される回折ピークのピーク強度IcBNと、前記炭化物のピーク強度Icとの比(Ic/IcBN)が0.1〜0.9である請求項11記載の立方晶窒化硼素質焼結体。
- 前記X線回折分析において、前記炭化物および窒化物の相互固溶体化合物である炭窒化物の(200)面に帰属される回折ピークのピーク強度ICNと、前記ピーク強度Ic、INとの比が、ICN<0.3IC、かつICN<0.3INである請求項11記載の立方晶窒化硼素質焼結体。
- 前記X線回折分析において、前記立方晶窒化硼素粒子の(111)面に帰属される回折ピークのピーク強度IcBNと、前記中間相の(101)面に帰属される回折ピークのピーク強度IILとの比(IIL/IcBN)が0.1〜0.8である請求項11記載の立方晶窒化硼素質焼結体。
- 前記立方晶窒化硼素質焼結体を断面観察したときに、前記立方晶窒化硼素粒子間に存在する前記炭化物の個々の面積を円に換算して求められる平均粒径dcと、前記窒化物の個々の面積を円に換算して求められる平均粒径dNとの比(dN/dc)が0.4〜1.2である請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記立方晶窒化硼素質焼結体を断面観察したときに、前記立方晶窒化硼素粒子の個々の面積を円に換算して求められる平均粒径dcBNが5μm以下であり、かつ前記炭化物の平均粒径dcが1〜3μm、前記窒化物の平均粒径dNが0.5〜2μmである請求項17記載の立方晶窒化硼素質焼結体。
- 前記立方晶窒化硼素粒子に圧縮の残留応力σcBNが300MPa以上残留している請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記結合相に圧縮の残留応力σbが残留しており、前記残留応力σcBNと前記残留応力σbとの比(σcBN/σb)が2〜5である請求項19記載の立方晶窒化硼素質焼結体。
- 前記結合相に残留している圧縮の残留応力σbが60〜300MPaである請求項20記載の立方晶窒化硼素質焼結体。
- 前記結合相のうち、前記窒化物にかかる圧縮の残留応力をσN、前記炭化物にかかる圧縮の残留応力をσCとしたとき、σCとσNとの比(σC/σN)が1.5〜5である請求項19記載の立方晶窒化硼素質焼結体。
- 前記窒化物にかかる圧縮の残留応力σNが30〜200MPa、前記炭化物にかかる圧縮の残留応力σCが100〜700MPaである請求項22記載の立方晶窒化硼素質焼結体。
- 前記立方晶窒化硼素質焼結体の表面に、周期律表第4、5および6族金属元素、AlおよびSiの群から選ばれる少なくとも1種の金属元素の炭化物、窒化物、硼化物、酸化物、炭窒化物およびこれらの固溶体、硬質炭素、並びに窒化硼素から選ばれる少なくとも1種からなる硬質膜を少なくとも1層被覆した請求項1〜3のいずれかに記載の立方晶窒化硼素質焼結体。
- 前記硬質膜が物理蒸着法(PVD法)によって形成されたものである請求項24記載の立方晶窒化硼素質焼結体。
- 前記硬質膜の総膜厚が0.1〜15μmである請求項24記載の立方晶窒化硼素質焼結体。
- 前記硬質膜に存在する圧縮の残留応力が0.1〜30GPaである請求項24記載の立方晶窒化硼素質焼結体。
- 前記硬質膜を被覆した状態での立方晶窒化硼素質焼結体の圧縮の残留応力が200MPa以上である請求項24記載の立方晶窒化硼素質焼結体。
- 前記硬質膜の少なくとも1層は、X線回折分析における(111)結晶面を示すピークの強度I(111)と、(200)結晶面を示すピークの強度I(200)との比[I(111)/I(200)]が0.7以上である請求項24記載の立方晶窒化硼素質焼結体。
- 請求項1〜3のいずれか記載の立方晶窒化硼素質焼結体からなり、すくい面と逃げ面との交差稜線部に形成された切刃を被切削物に当てて切削加工するための切削工具。
- 工具本体と、該工具本体の取付座にろう付けされた切刃チップとからなり、該切刃チップが前記立方晶窒化硼素質焼結体からなる請求項32記載の切削工具。
- 請求項32に記載の切削工具の前記すくい面と前記逃げ面との交差稜線部に形成された切刃を切削物に当てて切削加工を行う切削物の製造方法。
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JP2014050916A (ja) * | 2012-09-07 | 2014-03-20 | Nachi Fujikoshi Corp | 硬質皮膜被覆切削工具 |
JP2014184518A (ja) * | 2013-03-23 | 2014-10-02 | Kyocera Corp | 切削工具 |
WO2015199230A1 (ja) * | 2014-06-27 | 2015-12-30 | 京セラ株式会社 | 立方晶窒化硼素焼結体および切削工具 |
JP5909607B1 (ja) * | 2014-06-27 | 2016-04-26 | 京セラ株式会社 | 立方晶窒化硼素焼結体および切削工具 |
Also Published As
Publication number | Publication date |
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KR20070083529A (ko) | 2007-08-24 |
EP2792658B1 (en) | 2016-06-01 |
US7902098B2 (en) | 2011-03-08 |
WO2006046753A1 (en) | 2006-05-04 |
JP4927559B2 (ja) | 2012-05-09 |
EP1805120A1 (en) | 2007-07-11 |
EP2792658A1 (en) | 2014-10-22 |
JP2011219360A (ja) | 2011-11-04 |
JP5414744B2 (ja) | 2014-02-12 |
KR100955455B1 (ko) | 2010-04-29 |
EP1805120B1 (en) | 2016-06-01 |
US20070227297A1 (en) | 2007-10-04 |
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