WO2011059020A1 - 立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体並びにそれらの製造方法 - Google Patents

立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体並びにそれらの製造方法 Download PDF

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WO2011059020A1
WO2011059020A1 PCT/JP2010/070091 JP2010070091W WO2011059020A1 WO 2011059020 A1 WO2011059020 A1 WO 2011059020A1 JP 2010070091 W JP2010070091 W JP 2010070091W WO 2011059020 A1 WO2011059020 A1 WO 2011059020A1
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Prior art keywords
boron nitride
cubic boron
nitride sintered
sintered body
zro
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PCT/JP2010/070091
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English (en)
French (fr)
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祥 余越
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株式会社タンガロイ
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Application filed by 株式会社タンガロイ filed Critical 株式会社タンガロイ
Priority to IN3421DEN2012 priority Critical patent/IN2012DN03421A/en
Priority to US13/508,714 priority patent/US8814965B2/en
Priority to EP10829979.3A priority patent/EP2500332B1/en
Priority to CN201080051107.9A priority patent/CN102666435B/zh
Priority to JP2011540533A priority patent/JPWO2011059020A1/ja
Publication of WO2011059020A1 publication Critical patent/WO2011059020A1/ja

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Definitions

  • the present invention relates to a cubic boron nitride sintered body and a coated cubic boron nitride sintered body used for cutting tools and the like, and methods for producing them.
  • Patent Document 1 As a conventional technique of a cubic boron nitride sintered body used for a cutting tool or the like, there is a sintered body made of cubic boron nitride and aluminum oxide and / or aluminum nitride and titanium nitride (for example, Patent Document 1). reference.).
  • Patent Document 1 is not sufficient in wear resistance in processing in which the cutting edge temperature of a tool becomes high at the time of cutting, for example, high-speed processing of ordinary cast iron, and has not been able to sufficiently meet such requirements.
  • the present invention has been made to solve the above-mentioned problems, and has as its object to provide a cubic boron nitride sintered body and a coated cubic boron nitride sintered body excellent in wear resistance and a method for producing them. To do.
  • the inventor has studied the wear resistance of a cubic boron nitride sintered cutting tool in cutting of ordinary cast iron. As a result, when ⁇ -type Al 2 O 3 is included in the binder phase of the cubic boron nitride sintered body, the wear resistance of the cubic boron nitride sintered body is improved and is constant with respect to ⁇ -type Al 2 O 3 . It has been found that when ZrB 2 and ZrO are contained in the ratio, the wear resistance of the cubic boron nitride sintered body is further improved.
  • the cubic boron nitride sintered body of the present invention has cubic boron nitride: about 30 to about 70% by volume, and oxides, carbides, nitrides and borides of Ti, Al, Zr, Y, Ce, Mg, and Ca.
  • a binder phase consisting of at least one selected from these mutual solid solutions and unavoidable impurities: the remainder, containing ZrB 2 , ZrO 2 , ZrO and ⁇ -type Al 2 O 3, and ZrB 2
  • the X-ray diffraction intensity of the (101) plane of Izb the X-ray diffraction intensity of the (110) plane of ⁇ -type Al 2 O 3 is represented by Ia
  • the X-ray diffraction intensity of the (111) plane of ZrO is represented by Izo
  • (Izb / Ia) indicating the ratio of Izb to Ia satisfies 0.13 ⁇ (Izb / Ia) ⁇ 0.30
  • (Izo / Ia) indicating the ratio of Izo to Ia is 0.05 ⁇ (Izo / Ia) Cubic boron nitride sintered body satisfying ⁇ 0.20 .
  • the cubic boron nitride sintered body and the coated cubic boron nitride sintered body of the present invention are excellent in wear resistance.
  • the cubic boron nitride sintered body and the coated cubic boron nitride sintered body of the present invention are used as a cutting tool, there is an effect that the tool life can be extended.
  • the cubic boron nitride sintered body of the present invention has cubic boron nitride: about 30 to about 70% by volume, and oxides, carbides, nitrides and borides of Ti, Al, Zr, Y, Ce, Mg, and Ca. And at least one binder phase selected from these mutual solid solutions and inevitable impurities: the remainder.
  • the cubic boron nitride contained in the cubic boron nitride sintered body of the present invention has an effect of increasing the hardness of the cubic boron nitride sintered body. If the cubic boron nitride is less than about 30% by volume, sufficient hardness cannot be obtained, and cracks occur frequently during sintering, making sintering difficult.
  • Cubic boron nitride If it exceeds 70% by volume, the binder phase with excellent wear resistance is insufficient, and the cubic boron nitride undergoes reactive wear during cutting, resulting in a decrease in wear resistance. Therefore, cubic boron nitride: about 30 to about 70% by volume, binder phase and unavoidable impurities: balance. Among them, a cubic boron nitride sintered body composed of cubic boron nitride: 34 to 59% by volume and a binder phase and inevitable impurities: the balance is more preferable.
  • Examples of impurities inevitably contained in the cubic boron nitride sintered body of the present invention include WC, Co, Fe and the like. These are considered to be mixed in the manufacturing process.
  • the total amount of inevitable impurities in the cubic boron nitride sintered body of the present invention is 2% by volume or less with respect to the entire cubic boron nitride sintered body, and does not affect the characteristic values of the present invention.
  • other components that cannot be said to be inevitable impurities are within the range not impairing the characteristics of the cubic boron nitride sintered body of the present invention. May be contained in a small amount.
  • the binder phase contained in the cubic boron nitride sintered body of the present invention is selected from Ti, Al, Zr, Y, Ce, Mg, Ca oxides, carbides, nitrides, borides, and their mutual solid solutions. It consists of at least one kind.
  • the binder phase of the present invention has an action of firmly bonding cubic boron nitride and cubic boron nitride to improve wear resistance.
  • the cubic boron nitride sintered body of the present invention contains ZrB 2 , ZrO 2 , ZrO and ⁇ -type Al 2 O 3 , which are included as a binder phase.
  • the binder phase of the present invention preferably contains CeO 2 , Y 2 O 3 , MgO, CaO or the like added as a ZrO 2 stabilizer.
  • ZrO 2 means ZrO 2 of all crystal systems such as tetragonal ZrO 2 , monoclinic ZrO 2 , and cubic ZrO 2 .
  • the binder phase is more preferably composed of at least one selected from oxides, carbides, nitrides, borides and mutual solid solutions of Al, Zr, Y, Ce, Mg, Ca, More preferably, it is composed of at least one selected from Al, Zr oxides, borides, and their mutual solid solutions, and more preferably when they are composed of Al oxides, Zr oxides, and Zr borides.
  • the binder phase is particularly preferably composed of ⁇ -type Al 2 O 3 , ZrB 2, and cubic ZrO 2 and ZrO.
  • the wear resistance of the cubic boron nitride sintered body is improved, and at a constant ratio to ⁇ -type Al 2 O 3 .
  • the wear resistance is further improved.
  • the X-ray diffraction intensity of the (101) plane of ZrB 2 is expressed as Izb
  • the X-ray diffraction intensity of the (110) plane of ⁇ -type Al 2 O 3 is expressed as Ia
  • the X-ray diffraction intensity of the (111) plane of ZrO is expressed as Izo.
  • the X-ray diffraction intensity means the peak height of the X-ray diffraction peak on the crystal plane in the 2 ⁇ / ⁇ method.
  • the ratio of Izo to Ia is 0.05 or more
  • ZrO is dispersed in the structure of the cubic boron nitride sintered body, and ⁇ -type Al 2 O 3 and ⁇ -type Al in the binder phase are dispersed. Since a large amount of ZrO is contained in the grain boundary of 2 O 3 , the bond strength of these particles is increased and the wear resistance is improved.
  • (Izo / Ia) exceeds 0.20, the hardness of the cubic boron nitride sintered body decreases and the wear resistance decreases. Therefore, 0.05 ⁇ (Izo / Ia) ⁇ 0.20. Among them, 0.13 ⁇ (Izo / Ia) ⁇ 0.19 is more preferable.
  • the full width at half maximum of an X-ray diffraction peak is affected by the grain size of crystal grains.
  • the half width of the X-ray diffraction peak of the (111) plane of ZrO is 0.450 ° or more, since the wear resistance is improved.
  • the half width of the X-ray diffraction peak means the half width of the X-ray diffraction peak of the crystal plane in the 2 ⁇ / ⁇ method.
  • the half-value width of the X-ray diffraction peak of the (111) plane of ZrO being 0.450 ° or more indicates that ZrO is an extremely fine crystal grain. The dispersibility of ZrO is improved by making ZrO extremely fine.
  • ZrO is finely dispersed in the structure of the cubic boron nitride sintered body, and more ZrO is contained in the grain boundaries of ⁇ -type Al 2 O 3 and ⁇ -type Al 2 O 3.
  • the bond strength is increased, and the wear resistance is further improved.
  • the half width of the X-ray diffraction peak of the (111) plane of ZrO of the present invention does not exceed 1.000 °, practically, the half width of the X-ray diffraction peak of the (111) plane of ZrO Is more preferably in the range of 0.450 ° to 1.000 °, and more preferably in the range of 0.460 ° to 0.500 °.
  • the cubic ZrO 2 of the present invention can be obtained by sintering under high temperature and high pressure even if it is a cubic ZrO 2 obtained by adding a stabilizer such as CeO 2 , Y 2 O 3 , MgO and CaO. Any of the cubic ZrO 2 obtained is preferable.
  • the X-ray diffraction intensity of the (111) plane of cubic ZrO 2 that may be contained in the cubic boron nitride sintered body of the present invention is expressed as Izo 2, it indicates the ratio of Izo 2 to Ia (Izo 2 More preferably, / Ia) satisfies 0.15 ⁇ (Izo 2 /Ia) ⁇ 0.60.
  • the coating of the present invention has periodic table 4 (Ti, Zr, Hf, etc.), 5 (V, Nb, Ta, etc.), 6 (Cr, Mo, W, etc.) group elements, Al, Si oxides, carbides, nitrides And at least one selected from the group consisting of borides, borides and their mutual solid solutions. Specific examples include TiN, TiC, TiCN, TiAlN, TiSiN, CrAlN, and Al 2 O 3 .
  • the coating is preferably either a single layer or a laminate of two or more layers, and is also preferably an alternate laminated film in which thin films having different layer thicknesses of 5 to 200 nm are alternately laminated.
  • the average film thickness is less than 0.5 ⁇ m, the wear resistance is reduced, and when it exceeds 20 ⁇ m, the fracture resistance is reduced. Therefore, the average film thickness is preferably 0.5 to 20 ⁇ m, and more preferably 1 to 4 ⁇ m. If it exists, it is still more preferable.
  • the method for producing the cubic boron nitride sintered body is as follows: (A) Cubic boron nitride: about 30 to about 70% by volume, ⁇ -type Al 2 O 3 : about 25 to about 60% by volume, Al: about 2.5 to about 5.0% by volume, ZrO 2 : About 2.5 to about 5.0% by volume and at least one of TiN, TiC, TiCN, TiO 2 : 0 to about 15% by volume, and a mixture in which the total of these is 100% by volume is prepared Process, (B) enclosing the mixture in a container of an ultra-high pressure and high temperature generator; (C) sintering the mixture at a sintering temperature of 1300 to 1600 ° C. and a sintering pressure of 6.5 to 8 GPa; (D) The method of including the process of cooling the mixture which finished the process of (C) to normal temperature.
  • the cubic boron nitride sintered body of the present invention has a specific composition of cubic boron nitride: about 30 to about 70% by volume and ⁇ -type Al 2 O 3 : about 25 to about 60 volume. %, Al: about 2.5 to about 5.0 vol%, ZrO 2 : about 2.5 to about 5.0 vol%, and at least one of TiN, TiC, TiCN, TiO 2 : 0 to about Among them, preferably, cubic boron nitride: about 30 to 70% by volume, ⁇ -type Al 2 O 3 : about 25 to about 60% by volume, and Al: about 2.5 to about 5 0.0% by volume and ZrO 2 : about 2.5 to about 5.0% by volume, and the raw material powder whose total amount is 100% by volume is mixed by a ball mill, and the obtained mixed powder has a high melting point.
  • sintering temperature 1300-1600 ° C
  • sintering pressure 6.5 sintered at ⁇ 8 GPa
  • ZrO 2 powder of the raw material powder if the average particle size of the primary particles of ZrO 2 is 30 to 50 nm, fine ZrO 2 and ZrO are easily dispersed in the structure of the cubic boron nitride sintered body. effective.
  • the average primary particles of ZrO 2 of particle size 30 ⁇ 50 nm is used ZrO 2 powder secondary particles having an average particle diameter of 0.1 ⁇ 2 [mu] m aggregated if preferred.
  • the ZrO 2 powder is more stable than the high-purity ZrO 2 in that a stabilizer such as Y 2 O 3 , MgO, CaO, CeO 2 is added in an amount of 1 mol% to 16 mol% with respect to the entire ZrO 2.
  • Zirconia fluoride or stabilized zirconia (cubic ZrO 2 ) is more preferred because cubic ZrO 2 is contained in the cubic boron nitride sintered body of the present invention.
  • cubic boron nitride, Al, ZrO 2 and the like in the raw material powder react during sintering to produce ZrB 2 and ZrO in the cubic boron nitride sintered body, so that these components are sintered. Contained in the body.
  • the method for producing a coated cubic boron nitride sintered body of the present invention is a method for coating a surface of the cubic boron nitride sintered body obtained by the method for producing a cubic boron nitride sintered body of the present invention.
  • the coated cubic boron nitride sintered body of the present invention can be manufactured by coating the surface of the cubic boron nitride sintered body of the present invention with a conventional CVD method or PVD method.
  • X-ray diffraction intensity Ia, X-ray diffraction intensity Izo 2 of ZrO 2 (111) plane may be measured using a commercially available X-ray diffractometer.
  • an X-ray diffraction measurement of a 2 ⁇ / ⁇ concentrated optical system using a Cu-K ⁇ ray with an output of 50 kV and 250 mA was performed by an Rigaku Corporation X-ray diffractometer RINT-TTRIII, and Izb, Ia, Izo, Izo 2 and the half width of the X-ray diffraction peak of the ZrO (111) plane can be obtained.
  • the spacing between the ZrB 2 (101) plane, ZrO (111) plane, ⁇ -type Al 2 O 3 (110) plane, and cubic ZrO 2 (111) plane is the Powder Diffraction File PDF of the International Center for Diffraction Data. -2 Release 2004 (hereinafter referred to as PDF card).
  • ZrB 2 is a PDF card no. No. 34-0423 indicates that ZrO is the PDF card no.
  • ⁇ -type Al 2 O 3 is a PDF card no. From 10-0173, cubic ZrO 2 was converted to PDF card no. 49-1642 shows the black angle of each crystal plane.
  • cBN cubic boron nitride powder having an average particle size of 2 ⁇ m
  • ⁇ -type Al 2 O 3 powder having an average particle size of 0.1 ⁇ m
  • Al powder having an average particle size of 4 ⁇ m
  • the entire partially stabilized zirconia A partially stabilized zirconia powder (hereinafter referred to as PSZ) having an average particle size of 0.6 ⁇ m formed by agglomerating partially stabilized zirconia crystal particles (primary particles) having an average particle size of 40 nm to which 3 mol% of Y 2 O 3 has been added. Prepared).
  • the blended raw material powder is wet-mixed with a urethane-lined ball mill, the dried mixed powder is filled into a refractory metal capsule, sealed in a container of an ultra-high pressure and high temperature generator, and sintered under the sintering conditions shown in Table 3. did.
  • the cubic boron nitride sintered bodies of invention products 1 to 4 and comparative products 1 and 2 obtained as sintered bodies were polished.
  • the polished sintered body was subjected to X-ray diffraction measurement of a 2 ⁇ / ⁇ concentrated optical system using Cu-K ⁇ rays with an output of 50 kV and 250 mA, using an Rint-TTRIII manufactured by Rigaku Corporation.
  • X-ray diffraction peaks of cBN, ⁇ -type Al 2 O 3 , ZrB 2 , cubic ZrO 2 and ZrO were observed in invention products 1 to 4 and comparative products 1 and 2 .
  • invention products 1 to 4 and comparative products 1 and 2 were cubic boron nitride sintered bodies composed of cBN, ⁇ -type Al 2 O 3 , ZrB 2 , cubic ZrO 2 and ZrO. .
  • the invention products 1 to 4 the comparative products 1, 2, X-ray diffraction intensity Ia of (110) plane of ⁇ -type Al 2 O 3, of ZrB 2 (101) plane of the X-ray diffraction intensity Izb, of ZrO ( 111) plane of the X-ray diffraction intensity Izo, was measured half width of the X-ray diffraction peaks of cubic ZrO 2 (111) plane X-ray diffraction intensity Izo 2, ZrO of (111) plane.
  • Izb / Ia, Izo / Ia, and Izo 2 / Ia were determined from Ia, Izb, Izo, and Izo 2 .
  • the cross-sectional structure of the cubic boron nitride sintered bodies obtained by grinding the cubic boron nitride sintered bodies of the inventive products 1 to 4 and the comparative products 1 and 2 and then mirror-polishing them was obtained. Observation was performed in a 3000 ⁇ field of view.
  • image analysis was performed with a relatively black portion as a cubic boron nitride portion and a relatively white portion as a binder phase portion based on the color tone. In this case, when the color tone of the photograph is displayed in a histogram, two peaks are confirmed.
  • the cubic boron nitride portion and the binder phase portion are separated on the photograph by binarizing black and white with the peak and the midpoint of the peak as a threshold, and by measuring each area%, cubic boron nitride is measured. The area% of the binder phase was measured.
  • the area% in the sectional structure of the cubic boron nitride sintered body is Since it corresponds to the volume% of the cubic boron nitride part and the binder phase part contained in the cubic boron nitride sintered body, the volume% of each phase can be obtained.
  • Table 5 shows the volume% of cubic boron nitride and the volume% of the binder phase of Inventions 1 to 4 and Comparative Examples 1 and 2.
  • the cubic boron nitride sintered bodies of invention products 1 to 4 and comparative products 1 and 2 obtained as sintered bodies are cut into two triangular prism shapes having a hypotenuse of 3 mm, a base of 4.24 mm, and a thickness of 1.8 mm, and inserts.
  • a cutting tool was produced by brazing to a cemented carbide base metal having a shape SPGW120212. Further, the surface of the cutting tool of Invention 1 was coated with TiN having an average film thickness of 3 ⁇ m using a PVD apparatus, and this was designated as Invention 5. These cutting tools were subjected to cutting tests 1 and 2 shown below.
  • Table 6 shows the amount of flank wear on the tool edge after the cutting tests in Tests 1 and 2.

Abstract

　耐摩耗性に優れた立方晶窒化硼素焼結体を提供する。　立方晶窒化硼素：約３０～約７０体積％と、Ｔｉ、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる結合相および不可避的不純物：残部とから構成され、α型Ａｌ2Ｏ3とＺｒＢ2とＺｒＯ2とＺｒＯとを含有し、α型Ａｌ2Ｏ3の（１１０）面のＸ線回折強度をＩａ、ＺｒＢ2の（１０１）面のＸ線回折強度をＩｚｂ、ＺｒＯの（１１１）面のＸ線回折強度をＩｚｏと表したとき、Ｉａに対するＩｚｂの割合を示す（Ｉｚｂ／Ｉａ）が０．１３≦（Ｉｚｂ／Ｉａ）≦０．３０を満足し、Ｉａに対するＩｚｏの割合を示す（Ｉｚｏ／Ｉａ）が０．０５≦（Ｉｚｏ／Ｉａ）≦０．２０を満足することを特徴とする立方晶窒化硼素焼結体。

Description

立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体並びにそれらの製造方法
　本発明は、切削工具等に用いられる立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体並びにそれらの製造方法に関するものである。
　切削工具などに使われている立方晶窒化硼素焼結体の従来技術としては、立方晶窒化硼素と酸化アルミニウムおよび／または窒化アルミニウムと窒化チタンとからなる焼結体がある（例えば、特許文献１参照。）。
特開平８-１０９０７０号公報
　近年、加工能率を上げるため従来よりも切削条件が厳しくなる傾向があり、これまでより工具寿命を長くすることが求められてきた。上記特許文献１の発明は、切削加工時に工具の刃先温度が高くなる加工、例えば普通鋳鉄の高速加工などにおいて耐摩耗性が十分でなく、こうした要求に十分に応えられなくなってきた。
　本発明は、上記問題を解決するためになされたもので、耐摩耗性に優れた立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体並びにそれらの製造方法を提供することを目的とする。
　本発明者は、普通鋳鉄の切削加工における立方晶窒化硼素焼結体製切削工具の耐摩耗性について研究を行ってきた。その結果、立方晶窒化硼素焼結体の結合相にα型Ａｌ2Ｏ3を含有させると、立方晶窒化硼素焼結体の耐摩耗性が向上し、α型Ａｌ2Ｏ3に対して一定の割合でＺｒＢ2とＺｒＯを含有させると、さらに立方晶窒化硼素焼結体の耐摩耗性が向上するという知見が得られた。
　本発明の立方晶窒化硼素焼結体は、立方晶窒化硼素：約３０～約７０体積％と、Ｔｉ、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる結合相および不可避的不純物：残部とから構成され、ＺｒＢ2とＺｒＯ2とＺｒＯとα型Ａｌ2Ｏ3とを含有し、ＺｒＢ2の（１０１）面のＸ線回折強度をＩｚｂ、α型Ａｌ2Ｏ3の（１１０）面のＸ線回折強度をＩａ、ＺｒＯの（１１１）面のＸ線回折強度をＩｚｏと表したとき、Ｉａに対するＩｚｂの割合を示す（Ｉｚｂ／Ｉａ）が０．１３≦（Ｉｚｂ／Ｉａ）≦０．３０を満足し、Ｉａに対するＩｚｏの割合を示す（Ｉｚｏ／Ｉａ）が０．０５≦（Ｉｚｏ／Ｉａ）≦０．２０を満足する立方晶窒化硼素焼結体である。本発明の被覆立方晶窒化硼素焼結体は、本発明の立方晶窒化硼素焼結体の表面に被膜を被覆したものである。
　本発明の立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体は、耐摩耗性に優れる。本発明の立方晶窒化硼素焼結体および被覆立方晶窒化硼素焼結体を切削工具として用いると工具寿命を延長できるという効果を奏する。
　本発明の立方晶窒化硼素焼結体は、立方晶窒化硼素：約３０～約７０体積％と、Ｔｉ、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる結合相および不可避的不純物：残部とから構成される。本発明の立方晶窒化硼素焼結体に含まれる立方晶窒化硼素は、立方晶窒化硼素焼結体の硬さを高くする作用がある。立方晶窒化硼素が約３０体積％未満になると、十分な硬さが得られず、また焼結時にクラックが多発し焼結が困難となる。立方晶窒化硼素：７０体積％を超えると、耐摩耗性に優れた結合相が不足し、立方晶窒化硼素が切削加工時に反応摩耗することから耐摩耗性が低下する。そのため、立方晶窒化硼素：約３０～約７０体積％と、結合相および不可避的不純物：残部とした。その中でも立方晶窒化硼素：３４～５９体積％と、結合相および不可避的不純物：残部とからなる立方晶窒化硼素焼結体であるとさらに好ましい。
　本発明の立方晶窒化硼素焼結体に不可避的に含有される不純物としては、ＷＣ、Ｃｏ、Ｆｅなどが挙げられる。これらは製造工程で混入すると考えられる。本発明の立方晶窒化硼素焼結体における不可避的不純物の合計量は、立方晶窒化硼素焼結体全体に対して２体積％以下であり、本発明の特性値に影響を及ぼすことはない。なお、本発明においては、本発明の立方晶窒化硼素焼結体の特性を損なわない範囲で、立方晶窒化硼素と結合相と不可避的不純物のほかに、不可避的不純物とはいえない他の成分を少量含有してもよい。
　本発明の立方晶窒化硼素焼結体に含まれる結合相は、Ｔｉ、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる。本発明の結合相は立方晶窒化硼素と立方晶窒化硼素を強固に結合させ、耐摩耗性を向上させる作用がある。本発明の立方晶窒化硼素焼結体は、ＺｒＢ2とＺｒＯ2とＺｒＯとα型Ａｌ2Ｏ3とを含有するが、これらは結合相として含まれている。本発明の結合相には、ＺｒＯ2の安定化剤として添加されるＣｅＯ2、Ｙ2Ｏ3、ＭｇＯ、ＣａＯなどが含まれていても好ましい。なお、本発明においてＺｒＯ2とは、正方晶ＺｒＯ2、単斜晶ＺｒＯ2、立方晶ＺｒＯ2などすべての結晶系のＺｒＯ2を意味する。本発明においては、結合相はＡｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなると、より好ましく、Ａｌ、Ｚｒの酸化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなると、さらに好ましく、Ａｌの酸化物とＺｒの酸化物とＺｒの硼化物とからなると、さらに好ましく、その中でも、結合相は、α型Ａｌ2Ｏ3とＺｒＢ2と立方晶ＺｒＯ2とＺｒＯとからなると、特に好ましい。
　本発明の立方晶窒化硼素焼結体にα型Ａｌ2Ｏ3を含有させると、立方晶窒化硼素焼結体の耐摩耗性が向上し、α型Ａｌ2Ｏ3に対して一定の割合でＺｒＢ2とＺｒＯを存在せしめると、耐摩耗性がいっそう向上する。ＺｒＢ2の（１０１）面のＸ線回折強度をＩｚｂ、α型Ａｌ2Ｏ3の（１１０）面のＸ線回折強度をＩａ、ＺｒＯの（１１１）面のＸ線回折強度をＩｚｏと表したとき、Ｉａに対するＩｚｂの割合を示す（Ｉｚｂ／Ｉａ）が０．１３≦（Ｉｚｂ／Ｉａ）≦０．３０を満足し、Ｉａに対するＩｚｏの割合を示す（Ｉｚｏ／Ｉａ）が０．０５≦（Ｉｚｏ／Ｉａ）≦０．２０を満足すると耐摩耗性に優れる。なお、本発明においてＸ線回折強度とは、２θ／θ法における結晶面のＸ線回折ピークのピーク高さを意味する。
　Ｉａに対するＩｚｂの割合を示す（Ｉｚｂ／Ｉａ）が０．１３以上になると、ＺｒＢ2が立方晶窒化硼素焼結体の組織中に分散し、α型Ａｌ2Ｏ3と立方晶窒化硼素の粒界、立方晶窒化硼素と立方晶窒化硼素の粒界にＺｒＢ2が多く含まれるようになるので、これらの粒子の結合強度が高くなり、耐摩耗性が向上する。しかしながら、（Ｉｚｂ／Ｉａ）が０．３０を超えて大きくなると、立方晶窒化硼素焼結体の硬さが低下して耐摩耗性が低下する。そのため、０．１３≦（Ｉｚｂ／Ｉａ）≦０．３０とした。その中でも、０．１５≦（Ｉｚｂ／Ｉａ）≦０．２０であるとさらに好ましい。
　Ｉａに対するＩｚｏの割合を示す（Ｉｚｏ／Ｉａ）が０．０５以上になると、ＺｒＯが立方晶窒化硼素焼結体の組織中に分散し、結合相中のα型Ａｌ2Ｏ3とα型Ａｌ2Ｏ3の粒界にＺｒＯが多く含まれるようになるので、これらの粒子の結合強度が高くなり、耐摩耗性が向上する。しかしながら、（Ｉｚｏ／Ｉａ）が０．２０を超えて大きくなると、立方晶窒化硼素焼結体の硬さが低下して耐摩耗性が低下する。そのため、０．０５≦（Ｉｚｏ／Ｉａ）≦０．２０とした。その中でも０．１３≦（Ｉｚｏ／Ｉａ）≦０．１９であるとさらに好ましい。
　一般的にＸ線回折ピークの半値幅は結晶粒の粒径の影響を受ける。本発明においては、ＺｒＯの（１１１）面のＸ線回折ピークの半値幅が０．４５０°以上であると耐摩耗性を向上させるので、さらに好ましい。ここで、Ｘ線回折ピークの半値幅とは、２θ／θ法における結晶面のＸ線回折ピークの半値幅を意味する。ＺｒＯの（１１１）面のＸ線回折ピークの半値幅が０．４５０°以上になることは、ＺｒＯが極微細な結晶粒であることを示している。ＺｒＯが極微細化することでＺｒＯの分散性が向上する。そのため、立方晶窒化硼素焼結体の組織中にＺｒＯが細かく分散し、α型Ａｌ2Ｏ3とα型Ａｌ2Ｏ3の粒界にＺｒＯがさらに多く含まれるようになるので、これらの粒子の結合強度が高くなり、耐摩耗性がさらに向上する。しかしながら、本発明のＺｒＯの（１１１）面のＸ線回折ピークの半値幅が１．０００°を超えることはないので、実用的には、ＺｒＯの（１１１）面のＸ線回折ピークの半値幅は、０．４５０°～１．０００°の範囲であるとさらに好ましく、その中でも０．４６０°～０．５００°の範囲であるとさらに好ましい。
　本発明の立方晶窒化硼素焼結体に含まれるＺｒＯ2の一部または全部が立方晶ＺｒＯ2であると相変態を起こさず、立方晶窒化硼素焼結体にクラックが生じにくくなるので、さらに好ましい。本発明の立方晶ＺｒＯ2は、ＣｅＯ2、Ｙ2Ｏ3、ＭｇＯ、ＣａＯなどの安定化剤を添加して得られた立方晶ＺｒＯ2であっても、高温高圧下で焼結して得られた立方晶ＺｒＯ2であっても、いずれも好ましい。
　本発明の立方晶窒化硼素焼結体に含まれていてもよい立方晶ＺｒＯ2の（１１１）面のＸ線回折強度をＩｚｏ2と表したとき、Ｉａに対するＩｚｏ2の割合を示す（Ｉｚｏ2／Ｉａ）が０．１５≦（Ｉｚｏ2／Ｉａ）≦０．６０を満足すると、さらに好ましい。（Ｉｚｏ2／Ｉａ）が０．１５以上になると、立方晶ＺｒＯ2が立方晶窒化硼素焼結体の組織中に分散し、α型Ａｌ2Ｏ3と立方晶窒化硼素の粒界、立方晶窒化硼素と立方晶窒化硼素の粒界、α型Ａｌ2Ｏ3とα型Ａｌ2Ｏ3の粒界に立方晶ＺｒＯ2が多く含まれるようになるので、これらの粒子の結合強度が高くなり、耐摩耗性が向上する。しかしながら、（Ｉｚｏ2／Ｉａ）が０．６０を超えて大きくなると、立方晶窒化硼素焼結体の硬さが低下して耐摩耗性が低下する。そのため、０．１５≦（Ｉｚｏ2／Ｉａ）≦０．６０であると、さらに好ましい。その中でも０．４０≦（Ｉｚｏ2／Ｉａ）≦０．４９であるとさらに好ましい。
　本発明の立方晶窒化硼素焼結体の表面に被膜を被覆すると耐摩耗性が向上するので、さらに好ましい。本発明の被膜は、周期表４（Ｔｉ，Ｚｒ，Ｈｆ等），５（Ｖ，Ｎｂ，Ｔａ等），６（Ｃｒ，Ｍｏ，Ｗ等）族元素、Ａｌ、Ｓｉの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる。具体的には、ＴｉＮ、ＴｉＣ、ＴｉＣＮ、ＴｉＡｌＮ、ＴｉＳｉＮ、ＣｒＡｌＮ、Ａｌ2Ｏ3などを挙げることができる。被膜は単層または２層以上の積層のいずれも好ましく、組成が異なる層厚５～２００ｎｍの薄膜を交互に積層した交互積層膜も好ましい。被膜の平均膜厚は、０．５μｍ未満であると耐摩耗性が低下し、２０μｍを超えると耐欠損性が低下することから、０．５～２０μｍであると好ましく、その中でも１～４μｍであると、さらに好ましい。
　立方晶窒化硼素焼結体の製造方法は、
（Ａ）立方晶窒化硼素：約３０～約７０体積％と、α型Ａｌ2Ｏ3：約２５～約６０体積％と、Ａｌ：約２．５～約５．０体積％と、ＺｒＯ2：約２．５～約５．０体積％と、ＴｉＮ、ＴｉＣ、ＴｉＣＮ、ＴｉＯ2の少なくとも１種：０～約１５体積％とからなり、これらの合計が１００体積％となる混合物を準備する工程と、
（Ｂ）混合物を超高圧高温発生装置の容器内に封入する工程と、
（Ｃ）混合物を、焼結温度：１３００～１６００℃、焼結圧力：６．５～８ＧＰａにて焼結する工程と、
（Ｄ）（Ｃ）の工程を終えた混合物を常温に冷却する工程とを含む方法である。
　本発明の立方晶窒化硼素焼結体の製造方法として具体的には、配合組成が、立方晶窒化硼素：約３０～約７０体積％と、α型Ａｌ2Ｏ3：約２５～約６０体積％と、Ａｌ：約２．５～約５．０体積％と、ＺｒＯ2：約２．５～約５．０体積％と、ＴｉＮ、ＴｉＣ、ＴｉＣＮ、ＴｉＯ2の少なくとも１種：０～約１５体積％とからなり、その中でも好ましくは、立方晶窒化硼素：約３０～７０体積％と、α型Ａｌ2Ｏ3：約２５～約６０体積％と、Ａｌ：約２．５～約５．０体積％と、ＺｒＯ2：約２．５～約５．０体積％とからなり、これらの合計が１００体積％となる原料粉末をボールミルにて混合し、得られた混合粉末を高融点金属カプセルに充填した後、超高圧高温発生装置の容器内に封入し、焼結温度：１３００～１６００℃、焼結圧力：６．５～８ＧＰａにて焼結し、焼結工程を終えた後に常温まで冷却して焼結体を超高圧高温発生装置から取り出すとよい。なお、原料粉末のＺｒＯ2粉末については、ＺｒＯ2の一次粒子の平均粒径が３０～５０ｎｍであると立方晶窒化硼素焼結体の組織中に微細なＺｒＯ2やＺｒＯが分散しやすくなるという効果がある。しかしながら、取り扱いのしやすさから、平均粒径３０～５０ｎｍのＺｒＯ2の一次粒子が凝集した平均粒径０．１～２μｍの二次粒子のＺｒＯ2粉末を用いると好ましい。また、ＺｒＯ2粉末は、高純度ＺｒＯ2よりも、Ｙ2Ｏ3、ＭｇＯ、ＣａＯ、ＣｅＯ2などの安定化剤がＺｒＯ2全体に対して１モル％以上１６モル％以下添加された部分安定化ジルコニアまたは安定化ジルコニア（立方晶ＺｒＯ2）の方が本発明の立方晶窒化硼素焼結体に立方晶ＺｒＯ2が含まれるようになるので、さらに好ましい。本発明においては、原料粉末中の立方晶窒化硼素、Ａｌ及びＺｒＯ2などが焼結時に反応して、立方晶窒化硼素焼結体中にＺｒＢ2やＺｒＯを生ずることにより、これらの成分が焼結体中に含有される。
　本発明の被覆立方晶窒化硼素焼結体の製造方法は、本発明の立方晶窒化硼素焼結体の製造方法で得られた立方晶窒化硼素焼結体の表面に被膜を被覆する方法である。本発明の被覆立方晶窒化硼素焼結体は、本発明の立方晶窒化硼素焼結体の表面に従来のＣＶＤ法、ＰＶＤ法により被膜を被覆することで製造することができる。
　本発明の立方晶窒化硼素焼結体における、ＺｒＢ2（１０１）面のＸ線回折強度Ｉｚｂ、ＺｒＯ（１１１）面のＸ線回折強度ＩｚｏとＸ線回折ピークの半値幅、α型Ａｌ2Ｏ3（１１０）面のＸ線回折強度Ｉａ、ＺｒＯ2（１１１）面のＸ線回折強度Ｉｚｏ2は市販のＸ線回折装置を用いて測定することができる。例えば、株式会社リガク製Ｘ線回折装置ＲＩＮＴ－ＴＴＲIIIにより、出力：５０ｋＶ、２５０ｍＡのＣｕ－Ｋα線を用いた２θ／θ集中光学系のＸ線回折測定を行って、Ｉｚｂ、Ｉａ、Ｉｚｏ、Ｉｚｏ2およびＺｒＯ（１１１）面のＸ線回折ピークの半値幅を得ることができる。
　本発明における、ＺｒＢ2（１０１）面、ＺｒＯ（１１１）面、α型Ａｌ2Ｏ3（１１０）面、立方晶ＺｒＯ2（１１１）面の面間隔はInternational Centre for Diffraction DataのPowder Diffraction File PDF-2 Release 2004（以下、ＰＤＦカードという。）に記載されている。ＺｒＢ2はＰＤＦカードＮｏ．３４－０４２３により、ＺｒＯはＰＤＦカードＮｏ．５１－１１４９により、α型Ａｌ2Ｏ3はＰＤＦカードＮｏ．１０－０１７３により、立方晶ＺｒＯ2はＰＤＦカードＮｏ．４９－１６４２により、各結晶面のブラック角が分かる。
　市販の平均粒径２μｍの立方晶窒化硼素粉末（以下、ｃＢＮという。）、平均粒径０．１μｍのα型Ａｌ2Ｏ3粉末、平均粒径４μｍのＡｌ粉末、部分安定化ジルコニア全体に対して３ｍｏｌ％のＹ2Ｏ3が添加された平均粒径４０ｎｍの部分安定化ジルコニア結晶粒子（一次粒子）が凝集してできた平均粒径０．６μｍの部分安定化ジルコニア粉末（以下、ＰＳＺという。）を用意した。体積比でα型Ａｌ2Ｏ3：Ａｌ：ＰＳＺ＝８７．２：６．４：６．４の割合で配合し、それを粉末Ａとした。粉末Ａと立方晶窒化硼素粉末を表１に示す割合で配合した。最終的な配合組成は表２に示した。
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
　配合した原料粉末をウレタン内張りボールミルで湿式混合し、乾燥させた混合粉末を高融点金属カプセルに充填した後、超高圧高温発生装置の容器内に封入し、表３に示す焼結条件で焼結した。
Figure JPOXMLDOC01-appb-T000003
　焼結体として得られた発明品１～４、比較品１、２の立方晶窒化硼素焼結体を研磨した。研磨した焼結体について株式会社リガク製Ｘ線回折装置ＲＩＮＴ－ＴＴＲIIIにより、出力：５０ｋＶ、２５０ｍＡのＣｕ－Ｋα線を用いた２θ／θ集中光学系のＸ線回折測定を行った。その結果、発明品１～４、比較品１、２には、ｃＢＮ、α型Ａｌ2Ｏ3、ＺｒＢ2、立方晶ＺｒＯ2およびＺｒＯのＸ線回折ピークが観察された。このことから発明品１～４、比較品１、２は、ｃＢＮとα型Ａｌ2Ｏ3とＺｒＢ2と立方晶ＺｒＯ2とＺｒＯとからなる立方晶窒化硼素焼結体であることが分かった。さらに、発明品１～４、比較品１、２について、α型Ａｌ2Ｏ3の（１１０）面のＸ線回折強度Ｉａ、ＺｒＢ2の（１０１）面のＸ線回折強度Ｉｚｂ、ＺｒＯの（１１１）面のＸ線回折強度Ｉｚｏ、立方晶ＺｒＯ2の（１１１）面のＸ線回折強度Ｉｚｏ2、ＺｒＯの（１１１）面のＸ線回折ピークの半値幅を測定した。Ｉａ、Ｉｚｂ、Ｉｚｏ、Ｉｚｏ2から、Ｉｚｂ／Ｉａ、Ｉｚｏ／Ｉａ、Ｉｚｏ2／Ｉａを求めた。これらの結果を表４に示す。
Figure JPOXMLDOC01-appb-T000004
　発明品１～４、比較品１、２の立方晶窒化硼素焼結体を研削し、さらに鏡面研磨して得られた立方晶窒化硼素焼結体の断面組織を、走査型電子顕微鏡を用いて３０００倍視野にて観察した。走査型電子顕微鏡により得られた断面組織写真において、その色調を基準に相対的に黒い部分を立方晶窒化硼素部分とし、相対的に白い部分を結合相部分として画像解析を行った。この場合、当該写真の色調をヒストグラム表示すると二つのピークが確認される。そのピークとピークの中点を閾値として黒と白の二値化することにより立方晶窒化硼素部分と結合相部分を当該写真上で分け、それぞれの面積％を測定することにより、立方晶窒化硼素と結合相の面積％を測定した。発明品１～４、比較品１、２においては立方晶窒化硼素焼結体組織に恣意的な三次元的不均一を与えていないため、立方晶窒化硼素焼結体の断面組織における面積％は、立方晶窒化硼素焼結体に含まれる立方晶窒化硼素部分と結合相部分の体積％に一致するので、各相の体積％を求めることができる。発明品１～４、比較品１、２の立方晶窒化硼素の体積％と結合相の体積％を表５に示す。
Figure JPOXMLDOC01-appb-T000005
　焼結体として得られた発明品１～４、比較品１、２の立方晶窒化硼素焼結体を、２つの斜辺３ｍｍ×底辺４．２４ｍｍ×厚さ１．８ｍｍの三角柱形状に切り出し、インサート形状ＳＰＧＷ１２０４１２の超硬合金台金にロウ付けして切削工具を作製した。さらに、発明品１の切削工具の表面にＰＶＤ装置を用いて平均膜厚３μｍのＴｉＮを被覆したものを発明品５とした。これらの切削工具について下記に示す試験１、２の切削試験を行った。
［試験１］
被削材：普通鋳鉄
切削速度Ｖｃ：１０００ｍ／ｍｉｎ
切込みａｐ：０．０７ｍｍ
送りｆ：０．７０ｍｍ／ｒｅｖ
切削形態：湿式旋削加工
切削時間：１３分
［試験２］
被削材：普通鋳鉄
切削速度Ｖｃ：１０００ｍ／ｍｉｎ
切込みａｐ：０．０３ｍｍ
送りｆ：０．３５ｍｍ／ｒｅｖ
切削形態：湿式旋削加工
切削時間：２６分
　試験１、２の切削試験後の工具刃先逃げ面摩耗量を表６に示す。
Figure JPOXMLDOC01-appb-T000006
　表６に示されるように試験１および試験２において、発明品１～５は、比較品１、２よりも工具刃先逃げ面摩耗量が少なく、耐摩耗性に優れることが分かる。試験１の切削条件では発明品１～５は工具刃先逃げ面摩耗量が０．５２ｍｍになるまでさらに切削加工ができた。試験２の切削条件では発明品１～５は工具刃先逃げ面摩耗量が０．２４ｍｍになるまでさらに切削加工ができた。このことから、発明品１～５は比較品１、２よりも工具寿命が長いことが分かる。

Claims (16)

  1. 　立方晶窒化硼素：約３０～約７０体積％と、Ｔｉ、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる結合相および不可避的不純物：残部とから構成され、α型Ａｌ2Ｏ3とＺｒＢ2とＺｒＯ2とＺｒＯとを含有し、α型Ａｌ2Ｏ3の（１１０）面のＸ線回折強度をＩａ、ＺｒＢ2の（１０１）面のＸ線回折強度をＩｚｂ、ＺｒＯの（１１１）面のＸ線回折強度をＩｚｏと表したとき、Ｉａに対するＩｚｂの割合を示す（Ｉｚｂ／Ｉａ）が０．１３≦（Ｉｚｂ／Ｉａ）≦０．３０を満足し、Ｉａに対するＩｚｏの割合を示す（Ｉｚｏ／Ｉａ）が０．０５≦（Ｉｚｏ／Ｉａ）≦０．２０を満足することを特徴とする立方晶窒化硼素焼結体。
  2. 　（Ｉｚｂ／Ｉａ）が０．１５≦（Ｉｚｂ／Ｉａ）≦０．２０を満足する請求項１に記載の立方晶窒化硼素焼結体。
  3. 　（Ｉｚｏ／Ｉａ）が０．１３≦（Ｉｚｏ／Ｉａ）≦０．１９を満足する請求項１または２に記載の立方晶窒化硼素焼結体。
  4. 　ＺｒＯの（１１１）面のＸ線回折ピークの半値幅が０．４５０°以上である請求項１～３のいずれか１項に記載の立方晶窒化硼素焼結体。
  5. 　ＺｒＯの（１１１）面のＸ線回折ピークの半値幅が０．４５０°～１．０００°の範囲である請求項１～３のいずれか１項に記載の立方晶窒化硼素焼結体。
  6. 　ＺｒＯの（１１１）面のＸ線回折ピークの半値幅が０．４６０°～０．５００°の範囲である請求項１～３のいずれか１項に記載の立方晶窒化硼素焼結体。
  7. 　立方晶ＺｒＯ2を含有し、立方晶ＺｒＯ2の（１１１）面のＸ線回折強度をＩｚｏ2と表したとき、Ｉａに対するＩｚｏ2の割合を示す（Ｉｚｏ2／Ｉａ）が０．１５≦（Ｉｚｏ2／Ｉａ）≦０．６０を満足する請求項１～６のいずれか１項に記載の立方晶窒化硼素焼結体。
  8. 　（Ｉｚｏ2／Ｉａ）が０．４０≦（Ｉｚｏ2／Ｉａ）≦０．４９を満足する請求項７に記載の立方晶窒化硼素焼結体。
  9. 　立方晶窒化硼素焼結体が、立方晶窒化硼素：約３０～約７０体積％と、Ａｌ、Ｚｒ、Ｙ、Ｃｅ、Ｍｇ、Ｃａの酸化物、炭化物、窒化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる結合相および不可避的不純物：残部とから構成された立方晶窒化硼素焼結体である請求項１～８のいずれか１項に記載の立方晶窒化硼素焼結体。
  10. 　結合相が、Ａｌ、Ｚｒの酸化物、硼化物およびこれらの相互固溶体の中から選ばれた少なくとも１種からなる請求項１～９のいずれか１項に記載の立方晶窒化硼素焼結体。
  11. 　結合相が、Ａｌの酸化物とＺｒの酸化物とＺｒの硼化物とからなる請求項１～９のいずれか１項に記載の立方晶窒化硼素焼結体。
  12. 　結合相が、α型Ａｌ2Ｏ3とＺｒＢ2と立方晶ＺｒＯ2とＺｒＯとからなる請求項１～９のいずれか１項に記載の立方晶窒化硼素焼結体。
  13. 　請求項１～１２のいずれか１項に記載の立方晶窒化硼素焼結体の表面に被膜を被覆した被覆立方晶窒化硼素焼結体。
  14. （Ａ）立方晶窒化硼素：約３０～約７０体積％と、α型Ａｌ2Ｏ3：約２５～約６０体積％と、Ａｌ：約２．５～約５．０体積％と、ＺｒＯ2：約２．５～約５．０体積％と、ＴｉＮ、ＴｉＣ、ＴｉＣＮ、ＴｉＯ2の少なくとも１種：０～約１５体積％とからなり、これらの合計が１００体積％となる混合物を準備する工程と、
    （Ｂ）混合物を超高圧高温発生装置の容器内に封入する工程と、
    （Ｃ）混合物を、焼結温度：１３００～１６００℃、焼結圧力：６．５～８ＧＰａにて焼結する工程と、
    （Ｄ）（Ｃ）の工程を終えた混合物を常温に冷却する工程と
    を含むことを特徴とする立方晶窒化硼素焼結体の製造方法。
  15. 　混合物が、立方晶窒化硼素：約３０～約７０体積％と、α型Ａｌ2Ｏ3：約２５～約６０体積％と、Ａｌ：約２．５～約５．０体積％と、ＺｒＯ2：約２．５～約５．０体積％とからなるものである請求項１４に記載の立方晶窒化硼素焼結体の製造方法。
  16. 　請求項１４または１５に記載の方法で得られた立方晶窒化硼素焼結体の表面に被膜を被覆する被覆立方晶窒化硼素焼結体の製造方法。
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JPWO2016171155A1 (ja) * 2015-04-20 2018-02-15 住友電気工業株式会社 焼結体およびそれを含む切削工具
CN116375479A (zh) * 2015-04-20 2023-07-04 住友电气工业株式会社 烧结体和包含该烧结体的切削工具
KR101937061B1 (ko) * 2015-04-20 2019-01-09 스미토모덴키고교가부시키가이샤 소결체 및 그것을 포함하는 절삭 공구
US9988315B2 (en) 2015-04-20 2018-06-05 Sumitomo Electric Industries, Ltd. Sintered body and cutting tool including the same
WO2016171155A1 (ja) * 2015-04-20 2016-10-27 住友電気工業株式会社 焼結体およびそれを含む切削工具
JPWO2016194398A1 (ja) * 2015-05-29 2018-03-22 住友電工ハードメタル株式会社 焼結体および切削工具
KR20180015603A (ko) * 2015-05-29 2018-02-13 스미또모 덴꼬오 하드메탈 가부시끼가이샤 소결체 및 절삭 공구
US9856175B2 (en) 2015-05-29 2018-01-02 Sumitomo Electric Hardmetal Corp. Sintered compact and cutting tool
US9988314B2 (en) 2015-05-29 2018-06-05 Sumitomo Electric Hardmetal Corp. Sintered compact and cutting tool
KR102558333B1 (ko) * 2015-05-29 2023-07-20 스미또모 덴꼬오 하드메탈 가부시끼가이샤 소결체 및 절삭 공구
EP3156384A4 (en) * 2015-05-29 2017-08-09 Sumitomo Electric Hardmetal Corp. Sintered body and cutting tool
WO2016194398A1 (ja) 2015-05-29 2016-12-08 住友電工ハードメタル株式会社 焼結体および切削工具
CN108430950B (zh) * 2015-12-07 2021-03-30 株式会社泰珂洛 陶瓷烧结体
WO2017098937A1 (ja) * 2015-12-07 2017-06-15 株式会社タンガロイ セラミックス焼結体
JP6160986B1 (ja) * 2015-12-07 2017-07-12 株式会社タンガロイ セラミックス焼結体
CN108430950A (zh) * 2015-12-07 2018-08-21 株式会社泰珂洛 陶瓷烧结体
US10532951B2 (en) 2016-05-27 2020-01-14 Sumitomo Electric Industries, Ltd. Sintered material and cutting tool including same
WO2019244414A1 (ja) 2018-06-18 2019-12-26 住友電気工業株式会社 焼結体およびそれを含む切削工具
US11192827B2 (en) 2018-06-18 2021-12-07 Sumitomo Electric Industries, Ltd. Sintered material and cutting tool including same

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US8814965B2 (en) 2014-08-26
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EP2500332A1 (en) 2012-09-19
CN102666435A (zh) 2012-09-12
EP2500332A4 (en) 2013-05-01
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IN2012DN03421A (ja) 2015-10-23

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