JP2009220241A - Coated tool - Google Patents
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- JP2009220241A JP2009220241A JP2008069164A JP2008069164A JP2009220241A JP 2009220241 A JP2009220241 A JP 2009220241A JP 2008069164 A JP2008069164 A JP 2008069164A JP 2008069164 A JP2008069164 A JP 2008069164A JP 2009220241 A JP2009220241 A JP 2009220241A
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- zirconium
- aluminum oxide
- type aluminum
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 134
- 239000013078 crystal Substances 0.000 claims abstract description 80
- 150000003755 zirconium compounds Chemical class 0.000 claims abstract description 53
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 51
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000002245 particle Substances 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 41
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 40
- 238000002441 X-ray diffraction Methods 0.000 claims description 25
- 239000007789 gas Substances 0.000 description 68
- 230000015572 biosynthetic process Effects 0.000 description 25
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 22
- 238000004458 analytical method Methods 0.000 description 21
- 239000000758 substrate Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 18
- 238000005520 cutting process Methods 0.000 description 13
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 238000004453 electron probe microanalysis Methods 0.000 description 12
- 239000010936 titanium Substances 0.000 description 10
- 238000003754 machining Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000005211 surface analysis Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000009466 transformation Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000008602 contraction Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 230000001133 acceleration Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 229910003074 TiCl4 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 102220005308 rs33960931 Human genes 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 230000002730 additional effect Effects 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000010987 cubic zirconia Substances 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本願発明は、ジルコニウム含有酸化アルミニウム層を被覆した被覆工具でに関する。 The present invention relates to a coated tool coated with a zirconium-containing aluminum oxide layer.
特許文献１〜３は、酸化ジルコニウムを含有した酸化アルミニウム膜に関する技術が、特許文献４は、ＰＲ（１，０，１０）≧１．３である酸化アルミニウム膜に関する技術が開示されている。
本願発明は、α型酸化アルミニウム膜の機械強度を高め、皮膜硬度と伴に靭性と耐チッピング性に優れたジルコニウム含有酸化アルミニウム層を被覆した被覆工具を提供することである。 An object of the present invention is to provide a coated tool in which a mechanical strength of an α-type aluminum oxide film is increased and a zirconium-containing aluminum oxide layer excellent in toughness and chipping resistance along with film hardness is coated.
本願発明は、工具基体に、ジルコニウム含有酸化アルミニウム層を被覆した被覆工具であって、該ジルコニウム含有酸化アルミニウム層はα型酸化アルミニウム、ジルコニウム化合物を含有し、該ジルコニウム含有酸化アルミニウム層のα型酸化アルミニウムの結晶粒子は略膜厚方向に縦長に成長しており、該α型酸化アルミニウムの結晶粒子間を埋めるように該ジルコニウム化合物が存在し、該ジルコニウム化合物は、窒素含有量を質量％でＮｚ、酸素含有量をＯｚとしたとき、Ｎｚ＞Ｏｚであることを特徴とする被覆工具である。上記の構成を採用することによって、α型酸化アルミニウム膜の機械強度を高め、皮膜硬度と伴に靭性と耐チッピング性に優れたジルコニウム含有酸化アルミニウム層を被覆した被覆工具を得ることができる。 The present invention relates to a coated tool in which a tool base is coated with a zirconium-containing aluminum oxide layer, the zirconium-containing aluminum oxide layer containing α-type aluminum oxide and a zirconium compound, and the α-type oxidation of the zirconium-containing aluminum oxide layer. The aluminum crystal grains are grown vertically in a substantially film thickness direction, and the zirconium compound is present so as to fill the space between the α-type aluminum oxide crystal grains. The zirconium compound has a nitrogen content of Nz in mass%. The coated tool is characterized in that Nz> Oz when the oxygen content is Oz. By adopting the above-described configuration, it is possible to obtain a coated tool in which the mechanical strength of the α-type aluminum oxide film is increased and the zirconium-containing aluminum oxide layer excellent in toughness and chipping resistance along with the film hardness is coated.
本願発明の被覆工具における該ジルコニウム化合物は酸化ジルコニウムを含有し、該酸化ジルコニウムの結晶構造は単斜晶であり、α型酸化アルミニウムはＸ線回折強度比ＰＲ（１，０，１０）が１．３以上であることが好ましい。また、ジルコニウム含有酸化アルミニウム層のジルコニウム含有量が表面側に向かって多くなっていることが好ましく、更にジルコニウム含有量は、質量％で、０．５〜１５％であることが好ましい。 The zirconium compound in the coated tool of the present invention contains zirconium oxide, the crystal structure of the zirconium oxide is monoclinic, and the α-type aluminum oxide has an X-ray diffraction intensity ratio PR (1, 0, 10) of 1. It is preferably 3 or more. Further, the zirconium content of the zirconium-containing aluminum oxide layer is preferably increased toward the surface side, and the zirconium content is preferably 0.5 to 15% by mass.
本願発明により、α型酸化アルミニウム膜の機械強度を高め、皮膜硬度と伴に靭性と耐チッピング性に優れたジルコニウム含有酸化アルミニウム層を被覆した被覆工具を実現できる。 According to the present invention, it is possible to increase the mechanical strength of the α-type aluminum oxide film and realize a coated tool coated with a zirconium-containing aluminum oxide layer that is excellent in toughness and chipping resistance along with the film hardness.
本願発明による被覆工具におけるジルコニウム含有酸化アルミニウム層（以下、ＺＡ層と記す。）は、α型酸化アルミニウム、ジルコニウム化合物を含有している。また、このジルコニウム化合物は窒化ジルコニウム、酸化ジルコニウムを含有している。更に、ＺＡ層のα型酸化アルミニウムの結晶粒子は略膜厚方向に縦長に成長している。ＺＡ層のジルコニウム化合物が、α型酸化アルミニウムの結晶粒子間を埋めるように存在することにより、ＺＡ層の靭性が高くなり、耐チッピングに優れ工具寿命の長い、優れた工具特性を有する被覆工具を実現できる。この理由は、ＺＡ層のα型酸化アルミニウムは相変態による膜の収縮が発生することが無く安定しており、ＺＡ層のα型酸化アルミニウムの粒子間を埋めるように存在しているジルコニウム化合物は、酸化アルミニウムとの親和性に高く、酸化アルミニウムと比べ靭性の高い性質を有している。また、α型酸化アルミニウムとジルコニウム化合物は親和性が高いことより、α型酸化アルミニウムの結晶粒子の脱落を防ぎ、チッピングの発生を抑えられるため、ＺＡ層は優れた耐チッピング性を有する。α型酸化アルミニウムの粒子間を埋めるようにジルコニウム化合物が存在することにより、α型酸化アルミニウムの結晶粒径の粗大化を抑制することができ、靭性に劣るα型酸化アルミニウムの機械強度が上がり、ＺＡ層は優れた耐チッピング性を有する。ＺＡ層のジルコニウム化合物は、Ｎｚ＞Ｏｚであることから、酸化ジルコニウムの硬度と伴に靭性も上がる。酸化ジルコニウムは硬度が低く脆い欠点があるが、窒化ジルコニウムを含有し、Ｎｚ＞Ｏｚであることにより皮膜硬度と伴に靭性が改善され耐チッピング性に優れる。一方、Ｎｚ≦Ｏｚでは、靭性改善の効果を十分に得ることができない。本願発明による被覆工具は、α型酸化アルミニウム膜の機械強度が弱く、靭性に劣るという欠点を改善したものである。また、ジルコニウム化合物を含有した酸化アルミニウム被覆工具は、工具の刃先の温度が１０００℃以上に上昇する高速加工を行った場合、工具使用時の昇降温の繰り返しにより、酸化アルミニウム膜に存在する酸化ジルコニウムの相変態が原因の膨張や収縮により、皮膜にクラックが発生し酸化アルミニウム膜の結晶粒子が脱落し、強度が大きく低下し靭性や耐チッピングに劣る等の欠点を有するが、本願発明の被覆工具はこの点も改善した。 The zirconium-containing aluminum oxide layer (hereinafter referred to as ZA layer) in the coated tool according to the present invention contains α-type aluminum oxide and a zirconium compound. The zirconium compound contains zirconium nitride and zirconium oxide. Furthermore, the α-type aluminum oxide crystal grains of the ZA layer are grown vertically in a substantial film thickness direction. Since the zirconium compound of the ZA layer is present so as to fill in the space between the α-type aluminum oxide crystal grains, the toughness of the ZA layer is increased, the chipping resistance is excellent, the tool life is long, and the coated tool has excellent tool characteristics. realizable. This is because the α-type aluminum oxide of the ZA layer is stable without contraction of the film due to phase transformation, and the zirconium compound existing so as to fill in the space between the α-type aluminum oxide particles of the ZA layer is It has a high affinity with aluminum oxide and a toughness compared to aluminum oxide. In addition, the α-type aluminum oxide and the zirconium compound have high affinity, so that the crystal grains of the α-type aluminum oxide are prevented from falling off and the occurrence of chipping can be suppressed. Therefore, the ZA layer has excellent chipping resistance. The presence of the zirconium compound so as to fill in the space between the α-type aluminum oxide particles can suppress the coarsening of the crystal grain size of the α-type aluminum oxide, increasing the mechanical strength of the α-type aluminum oxide having poor toughness, The ZA layer has excellent chipping resistance. Since the zirconium compound in the ZA layer satisfies Nz> Oz, the toughness increases with the hardness of the zirconium oxide. Zirconium oxide has a drawback of low hardness and brittleness. However, it contains zirconium nitride and has Nz> Oz, whereby the toughness is improved along with the film hardness and the chipping resistance is excellent. On the other hand, if Nz ≦ Oz, the effect of improving toughness cannot be obtained sufficiently. The coated tool according to the present invention is an improvement of the drawback that the mechanical strength of the α-type aluminum oxide film is weak and the toughness is poor. In addition, an aluminum oxide-coated tool containing a zirconium compound has a zirconium oxide existing in the aluminum oxide film due to repeated heating and cooling when the tool is used when high-speed machining is performed in which the temperature of the tool edge rises to 1000 ° C. or higher. The coating tool of the present invention has the disadvantages that cracks are generated in the film due to expansion and contraction caused by the phase transformation of this, and the crystal particles of the aluminum oxide film fall off, the strength is greatly reduced, and the toughness and chipping resistance are poor. Also improved this point.
本願発明の被覆工具は、ＺＡ膜のα型酸化アルミニウムのＸ線回折強度比ＰＲ（１，０，１０）が１．３以上であることによって、（１，０，１０）面が基体表面の接線方向に配向するようになる。従って、ＺＡ膜のα型酸化アルミニウム表面の平均結晶粒子径を小さくすることが可能となり、皮膜表面の面粗さが小さくなって、耐チッピング性の改善に効果的に作用する。一方、ＰＲ（１，０，１０）が１．３未満では、上記の効果を得ることができない。
本願発明の被覆工具は、ＺＡ膜の窒化ジルコニウムが立方晶であり、酸化ジルコニウムが単斜晶であることから、窒化ジルコニウムと酸化ジルコニウムとα型の酸化アルミニウムは結晶系が異なるため、夫々単独の結晶粒が存在する。また、窒化ジルコニウムは、工具として使用した場合、大気中で高温に暴露されることにより酸化ジルコニウムに変化する。この酸化で生成した酸化ジルコニウムは、単斜晶の酸化ジルコニウムとなる。一方、成膜時に形成された酸化ジルコニウムも、単斜晶であることから、両者の酸化ジルコニウム同志は強い密着性をもち耐チッピング性に優れる。また、単斜晶の酸化ジルコニウムが｛１１１｝面のＸ線回折ピーク強度を最大であることによって、α型酸化アルミニウム粒子間を埋めるように存在する酸化ジルコニウムは、α型酸化アルミニウムに対して、より効果的に圧縮残留応力を加えることができ靭性と耐チッピング性に優れる。この圧縮残留応力を付加されたα型酸化アルミニウムの機械強度は、靭性と耐チッピング性をより効果的に改善することができる。上記の理由については、次のように考えられる。成膜後に存在する酸化ジルコニウムの結晶構造は、成膜時高温では正方晶であるが、冷却後に単斜晶へ相変態にすることよって｛１１１｝面のピーク強度が最大となり、これが酸化ジルコニウムの体積膨張による圧縮残留応力の付加効果を最大限に引き出すことになるからである。酸化ジルコニウムは、成膜温度が１０２０℃以上での成膜後、常温に冷却されると結晶構造が単斜晶に相変態する。この時に膜体積が膨張し、α型酸化アルミニウムの結晶粒子に圧縮残留応力を存在させ、この結晶粒子の圧縮残留応力により機械強度が上がり、靭性と耐チッピング性に優れるようになる。また、ジルコニウム化合物は、α型酸化アルミニウムの結晶粒子の成長方向が略膜厚方向に縦長に成長することを促す作用が得られる。またジルコニウム化合物は、α型酸化アルミニウムの結晶粒子の成長方向を略膜厚方向に対して垂直な方向、即ち、横長方向に成長することを抑制し、結晶粒子の粗大化を回避する作用も得られる。
In the coated tool of the present invention, when the X-ray diffraction intensity ratio PR (1,0,10) of α-type aluminum oxide of the ZA film is 1.3 or more, the (1,0,10) plane is the surface of the substrate. Oriented in the tangential direction. Accordingly, it becomes possible to reduce the average crystal particle diameter of the surface of the α-type aluminum oxide of the ZA film, and the surface roughness of the film surface is reduced, which effectively works to improve the chipping resistance. On the other hand, if PR (1, 0, 10) is less than 1.3, the above effect cannot be obtained.
In the coated tool of the present invention, the zirconium nitride of the ZA film is cubic and the zirconium oxide is monoclinic. Therefore, zirconium nitride, zirconium oxide, and α-type aluminum oxide have different crystal systems. There are crystal grains. Further, when used as a tool, zirconium nitride changes to zirconium oxide when exposed to high temperatures in the atmosphere. Zirconium oxide produced by this oxidation becomes monoclinic zirconium oxide. On the other hand, since zirconium oxide formed during film formation is also monoclinic, both zirconium oxides have strong adhesion and excellent chipping resistance. Further, since monoclinic zirconium oxide has the maximum X-ray diffraction peak intensity of the {111} plane, zirconium oxide present so as to fill in between the α-type aluminum oxide particles is Compressive residual stress can be applied more effectively, and the toughness and chipping resistance are excellent. The mechanical strength of the α-type aluminum oxide to which this compressive residual stress is added can improve toughness and chipping resistance more effectively. The above reason is considered as follows. The crystal structure of zirconium oxide present after film formation is tetragonal at a high temperature during film formation, but the peak intensity of the {111} plane is maximized by changing the phase to monoclinic after cooling, which is This is because the additional effect of compressive residual stress due to volume expansion is maximized. Zirconium oxide undergoes phase transformation to a monoclinic crystal when cooled to room temperature after film formation at a film formation temperature of 1020 ° C. or higher. At this time, the volume of the film expands, and the compressive residual stress is present in the α-type aluminum oxide crystal particles. The mechanical strength is increased by the compressive residual stress of the crystal particles, and the toughness and chipping resistance are improved. In addition, the zirconium compound has an effect of promoting the growth direction of the α-type aluminum oxide crystal grains to be vertically long in the substantially film thickness direction. In addition, the zirconium compound suppresses the growth direction of the α-type aluminum oxide crystal grains in a direction substantially perpendicular to the film thickness direction, that is, a laterally long direction, and also has an effect of avoiding the coarsening of the crystal grains. It is done.
本願発明の被覆工具は、ＺＡ層のジルコニウム含有量が表面側に向かって大きくなっていることが好ましい。この理由は、ＺＡ層の表面側のジルコニウム含有量が相対的に多く、基体側に向かって徐々に少なくすることによって、ＺＡ層の強度や密着性が高くなり、また酸化アルミニウムの結晶粒子の粗大化を防ぐことができ耐チッピング性が格段に高められるからである。更に、上記の様なジルコニウム含有量の組成傾斜により、窒化ジルコニウムと酸化ジルコニウムの相変態に伴う体積膨張がα型酸化アルミニウム結晶粒子に圧縮残留応力を印加する際に、ＺＡ層の基体側の応力印加を低く、最もチッピングの起点となり易い表面側の応力印加を高く制御することができる。この結果、耐欠損性に顕著な改善効果がみられる。一方、ＺＡ層の表面側のジルコニウム含有量が少なく基体側に多いと、基体側から容易に破壊し、チッピングの原因となる。これは、窒化ジルコニウムと酸化ジルコニウムが酸化アルミニウムに比べ皮膜硬度が低いためである。また、表面側の酸化アルミニウム結晶粒子の粗大化を防ぐことができず、更に残留応力による効果が少なく、靭性や耐チッピング性に劣ってしまうという不都合がある。 In the coated tool of the present invention, the zirconium content of the ZA layer is preferably increased toward the surface side. The reason for this is that the zirconium content on the surface side of the ZA layer is relatively large and gradually decreases toward the substrate side, so that the strength and adhesion of the ZA layer are increased, and the crystal grains of the aluminum oxide are coarse. This is because the chipping resistance can be remarkably enhanced. Furthermore, due to the composition gradient of the zirconium content as described above, when the volume expansion accompanying the phase transformation of zirconium nitride and zirconium oxide applies compressive residual stress to the α-type aluminum oxide crystal particles, the stress on the substrate side of the ZA layer The application of stress on the surface side, which is the lowest starting point and the most likely starting point for chipping, can be controlled to be high. As a result, a remarkable improvement effect is observed in the fracture resistance. On the other hand, if the zirconium content on the surface side of the ZA layer is small and large on the substrate side, it is easily broken from the substrate side and causes chipping. This is because zirconium nitride and zirconium oxide have lower film hardness than aluminum oxide. In addition, the aluminum oxide crystal particles on the surface side cannot be coarsened, and the effect of residual stress is small, resulting in inferior toughness and chipping resistance.
本願発明の被覆工具において、ＺＡ層のＺｒ量は０．５〜１５％が好ましい。Ｚｒ量が０．５％以上のとき、１０２０℃以上で成膜時に正方晶であった酸化ジルコニウムが成膜後、冷却時に単斜晶に相変態することにより窒化ジルコニウムと酸化ジルコニウムが膨張し、α型酸化アルミニウム結晶粒子に圧縮残留応力が印加して、耐欠損性が格段に高められる。Ｚｒ量が１５％以下のとき、ＺＡ層の結晶粒子間を埋めるように存在するジルコニウム化合物が適量であり、ＺＡ層全体の膜硬度と耐摩耗性が維持される。一方、ＺＡ層のＺｒ量が０．５％未満の場合には、ＺＡ層の酸化アルミニウムの粒子間を埋めるように存在するはずのジルコニウム化合物が少なく、靭性や耐チッピング性に劣ってしまう。１５％を超えて含有した場合には、酸化アルミニウムの結晶粒子間を埋めるように存在するジルコニウム化合物が過剰となり、皮膜硬度が低下して機械強度が低下してしまう。より好ましくは、３〜１０％である。Ｚｒ量が３〜１０％であることにより、α型酸化アルミニウムの結晶粒子間を埋めるように存在するジルコニウム化合物の量が最適となり、被覆工具として使用した場合、皮膜硬度の低下が少なく、靭性を高め、高速切削性に優れ耐チッピング性に優れた酸化アルミニウム膜被覆工具を実現できる。 In the coated tool of the present invention, the Zr amount of the ZA layer is preferably 0.5 to 15%. When the amount of Zr is 0.5% or more, zirconium nitride which has been tetragonal at the time of film formation at 1020 ° C. or higher is formed into a monoclinic crystal after cooling, whereby zirconium nitride and zirconium oxide expand, The compressive residual stress is applied to the α-type aluminum oxide crystal particles, and the fracture resistance is remarkably improved. When the amount of Zr is 15% or less, an appropriate amount of zirconium compound is present so as to fill the space between the crystal grains of the ZA layer, and the film hardness and wear resistance of the entire ZA layer are maintained. On the other hand, when the amount of Zr in the ZA layer is less than 0.5%, there are few zirconium compounds that should exist so as to fill in the space between the aluminum oxide particles in the ZA layer, and the toughness and chipping resistance are poor. If the content exceeds 15%, the zirconium compound present so as to fill the space between the aluminum oxide crystal particles becomes excessive, and the film hardness is lowered and the mechanical strength is lowered. More preferably, it is 3 to 10%. When the amount of Zr is 3 to 10%, the amount of zirconium compound present so as to fill in the space between the α-type aluminum oxide crystal particles is optimized, and when used as a coated tool, there is little decrease in film hardness, and toughness is reduced. It is possible to realize an aluminum oxide film-coated tool that is excellent in high-speed cutting performance and chipping resistance.
本願発明のＺＡ層の成膜において、例えば、化学蒸着法（以下、ＣＶＤ法と記す。）により、１０２０℃以上で成膜する時に、ジルコニウム化合物の原料ガスと酸化アルミニウムの原料ガスの比率を制御することにより、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物である窒化ジルコニウムと酸化ジルコニウムを存在させることができる。α型酸化アルミニウムを成膜した後、ＺＡ層成膜初期に原料ガスであるＡｌＣｌ３量を少なくし、ＺＡ層の窒化ジルコニウム、酸化ジルコニウムの原料ガスであるＺｒＣｌ４ガスを炉内に流し、酸化反応のためのＣＯガス量を少なくすることにより、ＺＡ層のα型酸化アルミニウムは、直下のα型酸化アルミニウムの結晶粒子と連続して成長する。そして原料ガスが少なくなった効果によりα型酸化アルミニウムの反応速度が低下し、結晶粒子間にジルコニウム化合物の起点が形成され、ＺＡ層のα型酸化アルミニウムの結晶粒子間にジルコニウム化合物を存在させることが可能となる。ここで使用する酸化ガスは１０２０℃以上で酸化力の弱い例えばＣＯガスを使用することが効果的である。酸化力の強いＯ２ガス、ＣＯ２ガスやＮ２Ｏガスでは窒化ジルコニウムが酸化されてしまい、酸化ジルコニウムの割合が多くなることから、Ｎｚ＞Ｏｚとすることができない。また、窒化ジルコニウム形成の窒素含有ガスとして窒素ガスやアンモニアガス使用する。ＺＡ層のジルコニウム化合物において、Ｎｚ＞Ｏｚの状態とするには、反応性の高いアンモニアガスを使用した方が効果的である。その後、膜の成長によりα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が形成される。また、酸化アルミニウムと酸化ジルコニウムの原料ガス混合した混合ガスと窒化ジルコニウムの原料ガスは炉内に導入する前に混合せず、炉内に導入後、反応炉内でガスを交差させ基体に到達する前に混ぜることで窒化ジルコニウムの酸化を防ぐことができる。これより、ジルコニウム化合物がα型酸化アルミニウムの結晶粒子間を埋めるように存在させることが可能となる。これは、本質的にアルミニウムと比較してジルコニウムの方が酸化物になり易いため、酸化ガスを少なくする効果によりジルコニウムは酸化アルミニウムからも酸素を奪い、酸化ジルコニウム膜の起点が、酸化アルミニウム膜とは別に、単独で形成しやすくなるためである。窒化ジルコニウムの原料ガスは、炉内に導入前に単独で混合され、炉内に導入後基体に到達する前に混合されるためＺＡ層内に単独に形成される。また、ＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在するには、成膜温度や成膜圧力により影響されるが、原料ガスのＡｌＣｌ３量を、ＺｒＣｌ４量の約４倍以下にし、酸化ガス量を酸化アルミニウム成膜時より少なくすることにより可能となる。更に、原料ガスのＡｌＣｌ３量を、ＺｒＣｌ４量と成膜温度の制御によりＺｒ量を制御可能となる。また、窒化ジルコニウムを効率よく存在させるためには、まず、酸化ジルコニウムと酸化アルミニウムの原料ガスを混合した混合ガスを反応炉内に分散させ、この混合ガスに窒化ジルコニウムの原料ガスを吹きかけることで得られる。また、ＺＡ層の成膜温度が１０２０℃以上であることにより、ジルコニウム化合物の成長速度が飛躍的に速くなりα型酸化アルミニウムの結晶粒子とは別に、単独で形成したジルコニウム化合物が存在可能となり、ＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が成長可能となる。成膜温度が１０２０℃以上であることにより、成膜時は酸化ジルコニウムの結晶構造が正方晶で成膜されるが、成膜後常温に冷却する時に酸化ジルコニウムの結晶構造が単斜晶に相変位する。 In the formation of the ZA layer of the present invention, for example, when the film is formed at a temperature of 1020 ° C. or higher by a chemical vapor deposition method (hereinafter referred to as a CVD method), the ratio of the zirconium compound source gas to the aluminum oxide source gas is controlled. As a result, zirconium nitride and zirconium oxide, which are zirconium compounds, can be present so as to fill the space between the α-type aluminum oxide crystal particles. After the formation of the α-type aluminum oxide, the amount of AlCl3 as a raw material gas is reduced at the initial stage of the formation of the ZA layer, and the zirconium nitride of the ZA layer and the ZrCl4 gas as the raw material gas of zirconium oxide are flown into the furnace. By reducing the amount of CO gas for this purpose, the α-type aluminum oxide of the ZA layer grows continuously with the crystal particles of the α-type aluminum oxide immediately below. The reaction rate of the α-type aluminum oxide is reduced due to the effect of reducing the source gas, the origin of the zirconium compound is formed between the crystal particles, and the zirconium compound is present between the crystal particles of the α-type aluminum oxide in the ZA layer. Is possible. As the oxidizing gas used here, it is effective to use, for example, CO gas having a low oxidizing power at 1020 ° C. or higher. Since O 2 gas, CO 2 gas, and N 2 O gas, which have strong oxidizing power, oxidize zirconium nitride and increase the proportion of zirconium oxide, Nz> Oz cannot be satisfied. Further, nitrogen gas or ammonia gas is used as a nitrogen-containing gas for forming zirconium nitride. In the zirconium compound of the ZA layer, it is more effective to use highly reactive ammonia gas in order to satisfy the state of Nz> Oz. Thereafter, a zirconium compound is formed so as to fill the space between the α-type aluminum oxide crystal grains by the growth of the film. Also, the mixed gas of the raw material gas of aluminum oxide and zirconium oxide and the raw material gas of zirconium nitride are not mixed before being introduced into the furnace, but after being introduced into the furnace, the gases are crossed in the reaction furnace to reach the substrate. Oxidation of zirconium nitride can be prevented by mixing in advance. Thus, the zirconium compound can be present so as to fill in the space between the α-type aluminum oxide crystal grains. This is because zirconium is inherently more likely to be an oxide than aluminum, so that zirconium also takes oxygen from the aluminum oxide due to the effect of reducing the oxidizing gas, and the starting point of the zirconium oxide film is the same as that of the aluminum oxide film. It is because it becomes easy to form separately. Zirconium nitride source gas is mixed alone before being introduced into the furnace, and after being introduced into the furnace and before reaching the substrate, it is formed alone in the ZA layer. In addition, the presence of a zirconium compound so as to fill in the space between the α-type aluminum oxide crystal particles of the ZA layer is affected by the film formation temperature and the film formation pressure, but the amount of AlCl 3 in the source gas is about 4 times the amount of ZrCl 4. This can be achieved by reducing the oxidization gas amount to less than that during aluminum oxide film formation. Furthermore, the amount of Zr can be controlled by controlling the amount of source gas AlCl3, the amount of ZrCl4, and the film formation temperature. In order to allow zirconium nitride to exist efficiently, first, a mixed gas in which a raw material gas of zirconium oxide and aluminum oxide is mixed is dispersed in a reaction furnace, and the raw material gas of zirconium nitride is sprayed on this mixed gas. It is done. In addition, when the film formation temperature of the ZA layer is 1020 ° C. or higher, the growth rate of the zirconium compound is remarkably increased, and separately from the α-type aluminum oxide crystal particles, a zirconium compound formed independently can exist. A zirconium compound can be grown so as to fill in the space between the α-type aluminum oxide crystal grains of the ZA layer. When the film formation temperature is 1020 ° C. or higher, the crystal structure of zirconium oxide is formed in a tetragonal crystal at the time of film formation, but the crystal structure of zirconium oxide becomes a monoclinic crystal when cooled to room temperature after film formation. Displace.
本願発明の被覆工具は、皮膜にＷ、Ｃｏ等の不可避の不純物を含む。これは成膜温度が高いことから皮膜中に基体成分であるＷやＣｏを含有するためである。また、３％以下のＢ、Ｈｆ、Ｃｒ等を含有していても良く、これは皮膜の原料であるＺｒに微量のＨｆが含まれることや、更に、３％以下のＢ、Ｈｆ、Ｃｒの添加により、結晶粒子径を制御することができるためである。またＺＡ層は、必ずしも最外層である必要はない。酸化膜の上層に、４ａ、５ａ、６ａ族元素の窒化物、炭窒化物、炭窒酸化物、酸化物を被覆することにより、例えば工具として使用した場合、使用した場所がわかりやすい識別効果が得られる。 The coated tool of the present invention contains inevitable impurities such as W and Co in the film. This is because the film formation temperature is high, so that the base component W or Co is contained in the film. Further, it may contain 3% or less of B, Hf, Cr, etc. This is because a small amount of Hf is contained in Zr which is a raw material of the film, and further, 3% or less of B, Hf, Cr. This is because the crystal grain size can be controlled by the addition. Further, the ZA layer is not necessarily the outermost layer. By covering the upper layer of the oxide film with nitrides, carbonitrides, carbonitride oxides, and oxides of group 4a, 5a, and 6a elements, for example, when used as a tool, it is possible to obtain an easy-to-understand identification effect. It is done.
（実施例１）
本発明例１の製造方法について述べる。質量％で、Ｃｏ：７％、Ｃｒ：０．６％、Ｚｒ：２．２％、Ｔａ：３．３％、Ｎｂ：０．２％、残ＷＣ及び不可避不純物の組成よりなる所定形状の切削工具用の超硬合金製基体をＣＶＤ成膜装置の炉内にセットした。ＣＶＤ成膜装置のガス導入配管は、２重管構造となっており、内側の管と外側の管からの２重になった吹き出し口から基体表面に、α型酸化アルミニウムを形成し、その後ＺＡ層を形成した。α型酸化アルミニウムは、２重管構造の外側の吹き出し口を使用してＡｌ金属小片を詰め３５０℃に保温した小筒中にＨ２ガスを流量３１０ｍｌ／分とＨＣｌガス１３０ｍｌ／分とを流すことにより発生させたＡｌＣｌ３ガスをＣＶＤ炉内に流し、１．５μｍ厚さを１０００℃と６６５０Ｐａで形成した。次に、ＺＡ層は、２重管構造の外側の吹き出し口を使用してＡｌ金属小片を詰め３５０℃に保温した小筒中にＨ２ガスを流量３１０ｍｌ／分とＨＣｌガス７５ｍｌ／分とを流すことにより発生させたＡｌＣｌ３ガスとＺｒ金属小片を詰め４５０℃に保温した小筒中にＨ２ガスを流量５００ｍｌ／分とＨＣｌガス３０ｍｌ／分を流すことにより発生させたＺｒＣｌ４ガス、Ｈ２ガスを２リットル／分、ＣＯガスを４００ｍｌ／分、ＨＣｌガスを１００ｍｌ／分とＨ２Ｓガスを１５ｍｌ／分を流し、２重管構造の内側の吹き出し口から、Ｈ２ガスに３％のＮＨ３ガスを混合した混合ガスを流量５００ｍｌ／分とＺｒ金属小片を詰め４５０℃に保温した小筒中にＨ２ガスを流量５００ｍｌ／分とＨＣｌガス２０ｍｌ／分を流すことにより発生させたＺｒＣｌ４ガスを炉内に流し、１０２０℃から１０６０℃まで３０分に５℃の速さで炉内温度を上昇させ６６５０Ｐａで反応させることにより１０μｍ厚さを被覆して本発明例１を作製した。本発明例１は、超硬合金基体表面に従来の技術で窒化チタン、炭窒化チタン、炭窒酸化チタンを成膜した後、その上にα型酸化アルミニウムとＺＡ層を形成したものである。
本発明例２〜１３は、ＺＡ層におけるジルコニウム含有量の影響を明らかにするため作成した。本発明例１と同じ基体、皮膜構成、皮膜厚さであり、ＺＡ層の成膜時のＡｌＣｌ３ガス量とＺｒＣｌ４ガス量と成膜温度が異なる条件で作製した。夫々の成膜温度は一定の炉内温度に保って成膜した。更に、本発明例１４はＺＡ層の酸化アルミニウムがＰＲ（１，０，１０）≧１．３であることの影響を明らかにするために作成した。本発明例１と同じ基体に、Ｔｉ（ＣＮ）まで成膜した。その後、Ｈ２キャリアーガスとＴｉＣｌ４ガスとＣＨ４ガスを原料に用い、１０００℃でＴｉＣを成膜した後、ＴｉＣｌ４ガスとＣＨ４を止め、Ｈ２キャリアーガスとＣＯ２ガスを１５分間流し、ＴｉＣ膜を酸化させた後、本発明例１と同じ成膜条件でＺＡ層を成膜した。
比較例１５、１６は、ＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるように存在するジルコニウム化合物の効果を明らかにするために作成した。比較例１５は、本発明例１と同じ基体に、同様の条件で酸化アルミニウムまで成膜した。その後、２重管構造の外側の吹き出し口を使用してＺＡ層を、Ａｌ金属小片を詰め３５０℃に保温した小筒中にＨ２ガスを流量３１０ｍｌ／分とＨＣｌガス７５ｍｌ／分とを流すことにより発生させたＡｌＣｌ３ガスとＺｒ金属小片を詰め４５０℃に保温した小筒中にＨ２ガスを流量５００ｍｌ／分とＨＣｌガス５０ｍｌ／分を流すことにより発生させたＺｒＣｌ４ガス、Ｈ２ガスを２リットル／分、ＣＯ２を１００ｍｌ／分、ＣＯガスを１００ｍｌ／分、ＨＣｌガスを１００ｍｌ／分とＨ２Ｓガスを１０ｍｌ／分をＣＶＤ炉内に流し、１０２０℃と６６５０Ｐａで反応させることにより１０μｍ厚さを被覆して作成した。また、２重管構造の内側の吹き出し口からはＨ２ガスを３０ｍｌ／分のみ流した。比較例１６は、成膜温度を９００℃と設定した以外は比較例１５と同様条件にして作成した。比較例１７は、本発明例１と同じ基体、皮膜構成であり、ＺＡ層の成膜時のＡｌＣｌ３ガス量とは同じであるが、ＺｒＣｌ４ガス量を減らし、２重管構造の内側の吹き出し口から、ＮＨ３ガスの代わりにＮ２ガスを２０００ｍｌ／分で炉内に流し、成膜温度を１０２０℃から１０６０℃まで３０分間に５℃の速さで温度を上昇させ、６６５０Ｐａで５μｍ厚さを被覆して作成した。比較例１８は、ＺＡ層の成膜温度を１０６０℃に一定に保ち作成した。本発明例、比較例の成膜条件を表１に示す。
Example 1
The manufacturing method of Example 1 of the present invention will be described. Cutting in a predetermined shape consisting of Co: 7%, Cr: 0.6%, Zr: 2.2%, Ta: 3.3%, Nb: 0.2%, residual WC and inevitable impurities in mass% A cemented carbide substrate for the tool was set in the furnace of the CVD film forming apparatus. The gas introduction pipe of the CVD film forming apparatus has a double pipe structure, and α-type aluminum oxide is formed on the substrate surface from the double outlet from the inner pipe and the outer pipe, and then ZA A layer was formed. α-type aluminum oxide is produced by flowing H2 gas at a flow rate of 310 ml / min and HCl gas of 130 ml / min into a small tube filled with Al metal pieces and kept at 350 ° C. using a blower outside the double tube structure. The generated AlCl 3 gas was flowed into the CVD furnace, and a thickness of 1.5 μm was formed at 1000 ° C. and 6650 Pa. Next, for the ZA layer, H2 gas is allowed to flow at a flow rate of 310 ml / min and HCl gas at 75 ml / min in a small tube filled with Al metal pieces and kept at 350 ° C. using the air outlet outside the double tube structure. The ZrCl4 gas and H2 gas generated by flowing H2 gas at a flow rate of 500 ml / min and HCl gas 30 ml / min into a small tube filled with AlCl3 gas and Zr metal pieces generated by the above and kept at 450 ° C. are 2 liters / min. , CO gas 400ml / min, HCl gas 100ml / min and H2S gas 15ml / min are flown, and the mixed gas of 3% NH3 gas mixed with H2 gas is flowed from the inside of the double pipe structure H2 gas was generated by flowing a flow rate of 500 ml / min and HCl gas of 20 ml / min into a small tube packed with Zr metal pieces at 500 ml / min and kept at 450 ° C. Flowing rCl4 gas into the furnace, it was prepared by coating a 10μm thickness of the present invention Example 1 by reacting 6650Pa to increase the furnace temperature at a rate of 5 ° C. to 30 minutes to 1060 ° C. from 1020 ° C.. In Invention Example 1, titanium nitride, titanium carbonitride, and titanium carbonitride oxide were formed on the surface of the cemented carbide substrate by a conventional technique, and then α-type aluminum oxide and a ZA layer were formed thereon.
Invention Examples 2 to 13 were prepared in order to clarify the influence of the zirconium content in the ZA layer. The same substrate, film configuration, and film thickness as Example 1 of the present invention were produced under the conditions that the AlCl3 gas amount and ZrCl4 gas amount during film formation of the ZA layer were different from the film formation temperature. Each film formation temperature was maintained at a constant furnace temperature. Furthermore, Invention Example 14 was prepared in order to clarify the influence of the fact that the aluminum oxide of the ZA layer satisfies PR (1, 0, 10) ≧ 1.3. A film of Ti (CN) was formed on the same substrate as Example 1 of the present invention. After that, TiC film was formed at 1000 ° C. using H2 carrier gas, TiCl4 gas and CH4 gas as raw materials, then TiCl4 gas and CH4 were stopped, H2 carrier gas and CO2 gas were allowed to flow for 15 minutes, and the TiC film was oxidized. Thereafter, a ZA layer was formed under the same film formation conditions as Example 1 of the present invention.
Comparative Examples 15 and 16 were prepared in order to clarify the effect of the zirconium compound existing so as to fill the space between the α-type aluminum oxide crystal grains of the ZA layer. In Comparative Example 15, a film of aluminum oxide was formed on the same substrate as Example 1 of the present invention under the same conditions. After that, by using the air outlet on the outside of the double tube structure, the H2 gas was flowed at a flow rate of 310 ml / min and HCl gas 75 ml / min into a small tube filled with Al metal pieces and kept at 350 ° C. ZrCl4 gas and H2 gas generated by flowing H2 gas at a flow rate of 500 ml / min and HCl gas 50 ml / min in a small tube filled with the generated AlCl3 gas and Zr metal pieces and kept at 450 ° C., 2 liters / min. CO2 is 100 ml / min, CO gas is 100 ml / min, HCl gas is 100 ml / min, and H2S gas is 10 ml / min in a CVD furnace and reacted at 1020 ° C. and 6650 Pa to cover a 10 μm thickness. did. Further, only 30 ml / min of H2 gas was allowed to flow from the blowout port inside the double pipe structure. Comparative Example 16 was created under the same conditions as Comparative Example 15 except that the film formation temperature was set to 900 ° C. Comparative Example 17 has the same substrate and coating structure as Example 1 of the present invention, and has the same amount of AlCl3 gas when the ZA layer is formed, but reduces the amount of ZrCl4 gas and blows out the inside of the double tube structure. Then, N2 gas is flowed into the furnace at 2000 ml / min instead of NH3 gas, and the film formation temperature is increased from 1020 ° C. to 1060 ° C. at a rate of 5 ° C. over 30 minutes, and a thickness of 5 μm is coated at 6650 Pa. And created. In Comparative Example 18, the film formation temperature of the ZA layer was kept constant at 1060 ° C. Table 1 shows the film forming conditions of the inventive example and the comparative example.
本発明例１のＺＡ層の結晶構造を同定するため、Ｘ線回折パターンを、理学電気（株）製のＸ線回折装置（ＲＵ−２００ＢＨ）で測定した。測定の結果、本発明例１のピーク位置は±０．２度の範囲内でＪＣＰＤＳカード番号１００１７３のＸ線回折パターンに一致し、α型酸化アルミニウムであることがわかった。また、本発明例１のピーク位置は±０．２度の範囲内でＪＣＰＤＳカード番号３５０７５３のＸ線回折パターンに一致し、立方晶の窒化ジルコニウムであることがわかった。また、本発明例１のピーク位置は±０．２度の範囲内でＪＣＰＤＳカード番号３７１４８４のＸ線回折パターンに一致し、単斜晶の酸化ジルコニウムであることがわかった。他の本発明例、比較例も同様に評価した。これらの評価結果を表２に示す。 In order to identify the crystal structure of the ZA layer of Invention Example 1, an X-ray diffraction pattern was measured with an X-ray diffractometer (RU-200BH) manufactured by Rigaku Corporation. As a result of the measurement, it was found that the peak position of Example 1 of the present invention coincided with the X-ray diffraction pattern of JCPDS card number 100173 within a range of ± 0.2 degrees and was α-type aluminum oxide. In addition, the peak position of Example 1 of the present invention coincided with the X-ray diffraction pattern of JCPDS card number 350753 within a range of ± 0.2 degrees, and it was found that the sample was cubic zirconium nitride. Further, the peak position of Example 1 of the present invention coincided with the X-ray diffraction pattern of JCPDS card number 371484 within a range of ± 0.2 degrees, and it was found that the sample was monoclinic zirconium oxide. Other invention examples and comparative examples were evaluated in the same manner. These evaluation results are shown in Table 2.
本発明例１のα型酸化アルミニウムの（１，０，１０）面における２θ値は７６．９度近傍である。表３にα型酸化アルミニウムの各結晶方位面に対する、面間距離ｄ、２θ値、標準Ｘ線回折強度Ｉ０をまとめたものを示した。また、表３に記載のｄ値とＩ０値は、ＡＳＴＭファイルの番号１０−１７３に記載の値を示す。２θ値はＣｕのＫα１線を用いた時に測定される値をｄ値から計算により求めた。表４は、Ｔｉ（ＣＮ）のｄ値、２θ値を示す。ＴｉＣのＩ０値はＡＳＴＭファイルの番号２９−１３６１に記載の値を、ＴｉＮのＩ０値はＡＳＴＭファイル３８−１４２０に記載の値を併記した。 The 2θ value in the (1,0,10) plane of the α-type aluminum oxide of Example 1 of the present invention is around 76.9 degrees. Table 3 shows a summary of the inter-plane distance d, 2θ value, and standard X-ray diffraction intensity I0 for each crystal orientation plane of α-type aluminum oxide. Further, the d value and the I0 value described in Table 3 indicate the values described in the ASTM file number 10-173. The 2θ value was obtained by calculation from the d value, which was measured when the Cu Kα1 line was used. Table 4 shows the d value and 2θ value of Ti (CN). The TiC I0 value is the value described in ASTM file number 29-1361, and the TiN I0 value is the value described in ASTM file 38-1420.
本願発明は、α型酸化アルミニウムの（０１２）面から（１，０，１０）面までの配向を定量的に評価するため、次式の等価Ｘ線回折強度比ＰＲ（ｈｋｌ）を、（化１）で定義した。但し、（ｈｋｌ）は、（０１２）、（１０４）、（１１０）、（１１３）、（０２４）、（１１６）、（１２４）、（０３０）、（１，０，１０）を示す。 In the present invention, in order to quantitatively evaluate the orientation of the α-type aluminum oxide from the (012) plane to the (1,0,10) plane, the equivalent X-ray diffraction intensity ratio PR (hkl) of the following equation is expressed as Defined in 1). However, (hkl) indicates (012), (104), (110), (113), (024), (116), (124), (030), (1, 0, 10).
ここで定義した等価Ｘ線回折強度比ＰＲ（ｈｋｌ）は、Ｉ（ｈｋｌ）、Ｉ０（ｈｋｌ）は計算に用いられる結晶方位面として、α型酸化アルミニウムの（ｈｋｌ）面からの実測Ｘ線回折強度であり、Ｉ０（ｈｋｌ）はＡＳＴＭファイルの番号１０−１７３に記載されている標準Ｘ線回折強度である。標準Ｘ線回折強度Ｉ０は、等方的に配向したα型酸化アルミニウム粉末粒子の（ｈｋｌ）面からのＸ線回折強度を表す。（化１）で定義されたＰＲ（ｈｋｌ）は、α型酸化アルミニウム膜の（ｈｋｌ）面からの実測Ｘ線回折ピーク強度の相対強度を示し、ＰＲ（ｈｋｌ）値が大きい程（ｈｋｌ）面からのＸ線回折ピーク強度が他のピーク強度よりも強いことす示す。この事は（ｈｋｌ）面が膜厚方向に対して垂直な方向即ち、基体接線方向に配向していることを示す。表３、４に示す様に、Ｔｉ（ＣＮ）の（２２２）面の２θ値である７６．９６度とα型酸化アルミニウムの（１，０，１０）面の２θ値である７６．８８度とは、その差が０．０８度であり、両者のＸ線回折ピークを分離することは出来ない。このため、Ｔｉ（ＣＮ）の（２２２）面は｛１１１｝面と結晶構造上同一であることを用いて、Ｔｉ（ＣＮ）の（２２２）面のＸ線回折強度を（化２）により求めた。（化３）により、この値を、実測された７６．９度近傍のＸ線回折強度Ｉ（７６．９度）から差し引くことにより、α型酸化アルミニウムの（１，０，１０）面のＸ線回折強度を求めた。 The equivalent X-ray diffraction intensity ratio PR (hkl) defined here is measured X-ray diffraction from the (hkl) plane of α-type aluminum oxide, where I (hkl) and I0 (hkl) are crystal orientation planes used for calculation. Intensity, and I0 (hkl) is a standard X-ray diffraction intensity described in ASTM file number 10-173. The standard X-ray diffraction intensity I0 represents the X-ray diffraction intensity from the (hkl) plane of the isotropically oriented α-type aluminum oxide powder particles. PR (hkl) defined in (Chemical Formula 1) indicates the relative intensity of the measured X-ray diffraction peak intensity from the (hkl) plane of the α-type aluminum oxide film, and the higher the PR (hkl) value, the (hkl) plane. It shows that the X-ray diffraction peak intensity from is stronger than other peak intensities. This indicates that the (hkl) plane is oriented in the direction perpendicular to the film thickness direction, that is, in the tangential direction of the substrate. As shown in Tables 3 and 4, 76.96 degrees that is the 2θ value of the (222) plane of Ti (CN) and 76.88 degrees that is the 2θ value of the (1,0,10) plane of α-type aluminum oxide. The difference is 0.08 degrees, and the X-ray diffraction peaks of the two cannot be separated. For this reason, using the fact that the (222) plane of Ti (CN) is the same as the {111} plane in terms of crystal structure, the X-ray diffraction intensity of the (222) plane of Ti (CN) is obtained by (Chemical Formula 2). It was. By subtracting this value from the actually measured X-ray diffraction intensity I (76.9 degrees) in the vicinity of 76.9 degrees, the X of the (1, 0, 10) plane of α-type aluminum oxide is obtained. The line diffraction intensity was determined.
ここで、Ｔｉ（ＣＮ）の標準Ｘ線回折強度Ｉ０（ｈｋｌ）はＴｉＣの値を採用した。ＴｉＮの標準Ｘ線回折強度Ｉ０（ｈｋｌ）を採用した場合、Ｔｉ（ＣＮ）のＩ（２２２）はＩ（１１１）の１２／７２倍となり（化２）による計算値よりも大きく、α型酸化アルミニウムのＩ（１，０，１０）は（化３）による計算値よりも小さくなる。（化２）、（化３）で求めたα型酸化アルミニウムのＩ（１，０，１０）値は、小さいめに求めた値であることがわかる。本発明例１のＰＲ（１，０，１０）は、３．２５であり、ＰＲ（１，０，１０）≧１．３であった。表５に本発明例１のα型酸化アルミニウムとＴｉ（ＣＮ）の（１１１）面のＸ線回折ピーク強度の実測値と計算後のα型酸化アルミニウムのＰＲ値を明記する。 Here, the value of TiC was adopted as the standard X-ray diffraction intensity I0 (hkl) of Ti (CN). When the standard X-ray diffraction intensity I0 (hkl) of TiN is adopted, I (222) of Ti (CN) is 12/72 times that of I (111), which is larger than the calculated value by (Chemical Formula 2), and α-type oxidation I (1, 0, 10) of aluminum is smaller than the calculated value by (Chemical Formula 3). It can be seen that the I (1, 0, 10) value of α-type aluminum oxide obtained in (Chemical Formula 2) and (Chemical Formula 3) is a value obtained to be smaller. PR (1, 0, 10) of Invention Example 1 was 3.25, and PR (1, 0, 10) ≧ 1.3. Table 5 clearly shows the measured value of the X-ray diffraction peak intensity of the (111) plane of the α-type aluminum oxide and Ti (CN) of Example 1 of the present invention and the calculated PR value of the α-type aluminum oxide.
ＺＡ層に含有するＺｒ量を、走査電子顕微鏡（日立製作所製Ｓ−４２００、以下、ＳＥＭと記す。）付属のＥＤＸ（堀場製作所製Ｓ−７９２Ｘ１）を用いて、ＺＡ層表面の２０μｍ角の領域を、２０ｋＶで測定することにより求めた。分析の結果、表２に示す様に本発明例１のＺｒ量は５％であった。本発明例１の膜表面のＳＥＭ写真を図１に、膜破断面のＳＥＭ写真を図２に、膜垂直研磨面のＳＥＭ写真を図３に示す。図１より、ＺＡ層のα型酸化アルミニウム結晶粒子の周りを、ジルコニウム化合物が取り囲んでいた。図２、図３より、ＺＡ層のα型酸化アルミニウムの結晶粒子と該ジルコニウム化合物間に隙間が無く、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していた。更に、α型酸化アルミニウムの結晶粒子は略膜厚方向に縦長に成長しており、α型酸化アルミニウムの結晶粒子が基体表面に対して平行な方向の成長が抑制され、ＺＡ層のα型酸化アルミニウム結晶粒子の粗大化が抑制されていた。図４は、α型酸化アルミニウムの結晶粒とジルコニウム化合物を点分析により定成分析したスポット１と分析スポット２の測定箇所である。α型酸化アルミニウムの結晶粒子である分析スポット２にはＡｌとＯのみ検出され、ＺｒやＮは検出されなかった。一方、α型酸化アルミニウムの結晶粒子間の分析スポット１はＡｌが検出されず、ＺｒとＮとＯが検出され、ＺＡ層のα型酸化アルミニウムの結晶粒子間にジルコニウム化合物が存在することがわかった。また、ＮとＯの含有量はＮ成分が多く、Ｎｚ＞Ｏｚであることがわかった。更に、ＺＡ層に含有されるジルコニウムの分布を電子プローブマイクロ分析装置（日本電子株式会社製ＪＸＡ−８５００Ｆ、以下、ＥＰＭＡと記す。）により倍率１０ｋ倍、加速電圧８ｋＶで面分析し、面分析した皮膜と同一の場所を、加速電圧８ｋＶ、ビーム径０．０２μｍの条件で線分析し測定した。本発明例１の面分析結果のうち、膜中のＡｌ量を測定したものを図５に、Ｚｒ量を測定したものを図６に、線分析結果を図７に示す。図５、図６は、膜垂直研磨面のＥＰＭＡ面分析結果であり、両図を対比すれば明らかなように、ＺＡ層のＡｌが多い所にはＺｒが少ないか若しくは検出されず、一方、Ｚｒの多い所にはＡｌが少ないか若しくは無いことから、α型酸化アルミニウムの結晶粒子の周りにジルコニウム化合物が存在した。図７は、図５、図６の中央部分の白線部についてＥＰＭＡ線分析を行なった結果であり、分析結果よりＡｌのピークが高い場所はＺｒのピークが低い若しくはピークが無かった。このように本発明例１は、図１〜図７に示すように、ＺＡ層のα型酸化アルミニウムとジルコニウム化合物間に隙間が無く、ＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していることが判った。
また、本発明例１の膜垂直研磨面の基体側から表面側まで順に６箇所の範囲について、ジルコニウム含有量を測定した。測定装置は、ＥＰＭＡを用い、条件は加速電圧５ｋＶ、１箇所分は、ビーム径を基体に対して縦方向の１μｍ、横方向に１０μｍの測定範囲とする面分析を行った。ジルコニウム含有量（ｗｔ％）は、Ａ基体側から表面側まで順に、１．０、２．０、３．５、４．５、５．０、５．０であった。これより、ジルコニウム含有量が表面側に向かって大きくなっていることが確認できた。表１の本発明例１のジルコニウム含有量は、表面側の値を示した。また、オージェ電子分析装置（日本電子株式会社製ＪＡＭＰ−９５００Ｆ、以下、ＡＥＳと記す。）を用いてジルコニウム含有酸化アルミニウム膜表面の高分解能２次電子像により、α型酸化アルミニウムの粒子間を同定した後、粒子間を埋めるような形態で存在する少なくともジルコニウム化合物の化学状態を分析した結果、本発明例１はジルコニウムが酸素元素と結合しているプロファイルと窒素元素と結合しているプロファイルを示し、ジルコニウムは酸化物と窒化物が存在していることがわかった。
The amount of Zr contained in the ZA layer is a 20 μm square region on the surface of the ZA layer using an EDX (S-792X1 manufactured by Horiba, Ltd.) attached to a scanning electron microscope (Hitachi S-4200, hereinafter referred to as SEM). Was determined by measuring at 20 kV. As a result of the analysis, as shown in Table 2, the amount of Zr in Invention Example 1 was 5%. The SEM photograph of the film surface of Example 1 of the present invention is shown in FIG. 1, the SEM photograph of the film fracture surface is shown in FIG. 2, and the SEM photograph of the film vertical polished surface is shown in FIG. From FIG. 1, the zirconium compound surrounded the α-type aluminum oxide crystal particles of the ZA layer. 2 and 3, there was no gap between the α-type aluminum oxide crystal particles of the ZA layer and the zirconium compound, and the zirconium compound was present so as to fill the space between the α-type aluminum oxide crystal particles. Furthermore, the α-type aluminum oxide crystal particles are grown vertically in the film thickness direction, and the growth of the α-type aluminum oxide crystal particles in the direction parallel to the substrate surface is suppressed, and the α-type oxidation of the ZA layer is suppressed. The coarsening of the aluminum crystal particles was suppressed. FIG. 4 shows the measurement locations of spot 1 and analysis spot 2 where the α-type aluminum oxide crystal grains and zirconium compound were subjected to point analysis by point analysis. Only Al and O were detected in the analysis spot 2 which is a crystal particle of α-type aluminum oxide, and Zr and N were not detected. On the other hand, in the analysis spot 1 between the α-type aluminum oxide crystal particles, Al is not detected, Zr, N, and O are detected, and it is found that a zirconium compound exists between the α-type aluminum oxide crystal particles of the ZA layer. It was. Further, it was found that the contents of N and O have a large N component and Nz> Oz. Further, the distribution of zirconium contained in the ZA layer was subjected to surface analysis by an electron probe microanalyzer (JXA-8500F manufactured by JEOL Ltd., hereinafter referred to as EPMA) at a magnification of 10 k and an acceleration voltage of 8 kV. The same place as the film was subjected to line analysis and measurement under the conditions of an acceleration voltage of 8 kV and a beam diameter of 0.02 μm. Of the surface analysis results of Example 1 of the present invention, FIG. 5 shows the measurement of Al content in the film, FIG. 6 shows the measurement of Zr content, and FIG. 7 shows the line analysis result. FIG. 5 and FIG. 6 show the EPMA surface analysis results of the film vertical polishing surface. As is clear from the comparison between the two figures, Zr is small or not detected in the place where the Al content of the ZA layer is large. Zirconium compounds were present around the α-type aluminum oxide crystal grains because there was little or no Al where Zr was high. FIG. 7 shows the results of EPMA line analysis performed on the white line portion at the center of FIGS. 5 and 6, where the Zr peak is low or absent at locations where the Al peak is higher than the analysis results. As described above, as shown in FIGS. 1 to 7, Example 1 of the present invention has no gap between the α-type aluminum oxide of the ZA layer and the zirconium compound, and fills the space between the α-type aluminum oxide crystal particles of the ZA layer. It was found that a zirconium compound was present.
Further, the zirconium content was measured in a range of 6 locations in order from the substrate side to the surface side of the film vertical polishing surface of Example 1 of the present invention. EPMA was used as the measuring apparatus, and the conditions were such that the acceleration voltage was 5 kV, and for one place, the beam diameter was 1 μm in the vertical direction and 10 μm in the horizontal direction with respect to the substrate. The zirconium content (wt%) was 1.0, 2.0, 3.5, 4.5, 5.0, 5.0 in order from the A substrate side to the surface side. From this, it was confirmed that the zirconium content increased toward the surface side. The zirconium content of Invention Example 1 in Table 1 is a value on the surface side. In addition, using an Auger electron analyzer (JAMP-9500F manufactured by JEOL Ltd., hereinafter referred to as AES), the particles between α-type aluminum oxide particles are identified by a high-resolution secondary electron image on the surface of the zirconium-containing aluminum oxide film. Then, as a result of analyzing the chemical state of at least the zirconium compound that exists in a form that fills the space between the particles, Example 1 of the present invention shows a profile in which zirconium is bonded to an oxygen element and a profile in which the nitrogen element is bonded. Zirconium was found to contain oxides and nitrides.
次に、本発明例２〜１４のＺＡ層を解析した。本発明例２〜１３はＸ線回折パターンよりＰＲ（１，０，１０）≧１．３のα型酸化アルミニウムと窒化ジルコニウムと単斜晶の｛１１１｝面の回折ピーク強度が最大である酸化ジルコニウムであった。本発明例１４のＺＡ層は、ＰＲ（１，０，１０）＜１．３のα型酸化アルミニウムであった。また、ジルコニウム含有量はＥＤＸ分析により、本発明例２と４〜１１、１４は、０．５％〜１５％、本発明例３は０．４％、本発明例１２、１３は夫々１６、２０％であった。またＥＰＭＡ点分析より、ＮとＯの含有量比は１より大きく、Ｎｚ＞Ｏｚであることがわかった。Ｚｒ分布をＥＰＭＡ面分析と線分析した結果、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していた。また、ジルコニウム含有量が基体側から表面側まで傾斜していなかった。ＡＥＳ分析の結果、Ｚｒが窒素及び酸素と結合しているプロファイルを示し、ジルコニウム窒化物と酸化物が存在していることがわかった。
一方、比較例１５、１６のＺＡ層の結晶構造は、ＰＲ（１，０，１０）≧１．３のα型酸化アルミニウムと単斜晶の｛１１１｝面の回折ピーク強度が最大である酸化ジルコニウムであったが、窒化物は検出されなかった。また、ＥＰＭＡ分析の結果、ジルコニウム含有量は、皮膜全体に渡って５％と略同じであった。ＥＰＭＡ分析によりＺｒ分布を面分析と線分析した結果、比較例１５はα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していた。比較例１６のＺＡ層は、成膜温度が９００℃であり酸化ジルコニウムの成長速度が遅く、原料ガスのＡｌＣｌ３量がＺｒＣｌ４量の約１．５倍であることから酸化アルミニウムの結晶粒子とは別に、単独に酸化ジルコニウムが存在することなく、α型酸化アルミニウムと酸化ジルコニウムが混在し、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していなかった。比較例１７、１８のＺＡ層を解析した所、Ｘ線回折パターンよりα型酸化アルミニウムと単斜晶の酸化ジルコニウムであり、｛１１１｝面の回折ピーク強度が最大であった。またＥＤＸ分析により、ジルコニウム含有量は５％と略同じであり、ＡＥＳ分析の結果、Ｚｒが窒素元素及び酸素元素と結合しているプロファイルを示し、Ｚｒの窒化物と酸化物が存在していることがわかった。しかし、ＥＰＭＡ分析によりＺｒ分布を面分析と線分析した結果、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在していたものの、α型酸化アルミニウムの結晶粒子間を埋める箇所の点分析の結果、ＮとＯの含有量比はＮｚ＜Ｏｚであった。比較例１７は、ジルコニウム含有量が基体側から表面側まで傾斜していた。
Next, the ZA layers of Invention Examples 2 to 14 were analyzed. In Examples 2 to 13 of the present invention, the diffraction peak intensity of the {111} plane of α-type aluminum oxide, zirconium nitride, and monoclinic crystal of PR (1, 0, 10) ≧ 1.3 is maximum from the X-ray diffraction pattern. It was zirconium. The ZA layer of Invention Example 14 was α-type aluminum oxide with PR (1, 0, 10) <1.3. Further, according to EDX analysis, the zirconium content was 0.5% to 15% for Invention Examples 2 and 4 to 11 and 14, 0.4% for Invention Example 3, and 16 for Invention Examples 12 and 13, respectively. 20%. From the EPMA point analysis, it was found that the content ratio of N and O was larger than 1, and Nz> Oz. As a result of analyzing the Zr distribution by EPMA surface analysis and line analysis, a zirconium compound was present so as to fill in the space between the α-type aluminum oxide crystal particles. Further, the zirconium content was not inclined from the substrate side to the surface side. As a result of AES analysis, it was found that Zr was bonded to nitrogen and oxygen, and zirconium nitride and oxide were present.
On the other hand, the crystal structures of the ZA layers of Comparative Examples 15 and 16 are such that the diffraction peak intensity of the {111} plane of α-type aluminum oxide and monoclinic crystal of PR (1, 0, 10) ≧ 1.3 is the maximum. Although it was zirconium, nitride was not detected. Further, as a result of EPMA analysis, the zirconium content was substantially the same as 5% throughout the film. As a result of surface analysis and line analysis of the Zr distribution by EPMA analysis, in Comparative Example 15, a zirconium compound was present so as to fill in between the crystal grains of the α-type aluminum oxide. The ZA layer of Comparative Example 16 has a film forming temperature of 900 ° C., the growth rate of zirconium oxide is slow, and the amount of AlCl 3 in the source gas is about 1.5 times the amount of ZrCl 4. Without the presence of zirconium oxide alone, α-type aluminum oxide and zirconium oxide were mixed, and no zirconium compound was present so as to fill in the space between the crystal grains of α-type aluminum oxide. When the ZA layers of Comparative Examples 17 and 18 were analyzed, α-type aluminum oxide and monoclinic zirconium oxide were found from the X-ray diffraction pattern, and the diffraction peak intensity on the {111} plane was maximum. Further, the EDX analysis shows that the zirconium content is substantially the same as 5%. As a result of the AES analysis, Zr shows a profile in which nitrogen and oxygen elements are bonded, and a nitride and an oxide of Zr are present. I understood it. However, as a result of surface analysis and line analysis of the Zr distribution by EPMA analysis, there was a zirconium compound so as to fill the space between the α-type aluminum oxide crystal particles, but the point where the space between the α-type aluminum oxide crystal particles was filled As a result of the analysis, the content ratio of N and O was Nz <Oz. In Comparative Example 17, the zirconium content was inclined from the substrate side to the surface side.
（実施例２）
本発明例１〜１４、比較例１５〜１８を下記の試験条件で評価した。切削加工に使用した被削材は、φ１６０でφ１２０まで２つ溝が入った炭素鋼Ｓ５０Ｃを用い、φ６０まで端面加工した。φ１２０までは湿式加工による断続切削をし、φ１２０からφ６０までは乾式加工による連続加工で評価した。評価は、刃先がチッピングもしくは欠損した時、または逃げ面最大摩耗幅ＶＢｍａｘが０．３０ｍｍ以上になった時の加工時間を工具寿命と判定した。刃先は倍率１００倍の光学顕微鏡で観察した。評価結果を表２に示した。
（試験条件）
被削材：Ｓ５０Ｃ、φ１６０、φ１２０まで２つ溝入り
加工方法：端面旋削加工、φ６０まで加工
工具形状：ＣＮＭＧ１２０４１２
切削速度：１８０ｍ／ｍｉｎ
送り：０．３０ｍｍ／回転
切り込み：１．０ｍｍ
切削液：φ１２０まで湿式加工、φ１２０からφ６０まで乾式加工
本発明例１〜１４は、何れも工具寿命が９分以上と、比較例１５〜１８に対して３倍以上長く格段に優れていた。これはＺＡ層において、α型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在しているため、皮膜硬度の低下が非常に少なく、機械特性に優れたからである。またＺＡ層の酸化ジルコニウムは単斜晶であることから、相変態による体積膨張や収縮による酸化アルミニウムの結晶粒子への影響が少なく、α型酸化アルミニウムの結晶粒子の脱落が無く、耐チッピング性に有効となり、ＺＡ層の残留応力が緩和され靭性に優れる効果が得られた。その結果、工具使用時に生じる刃先温度の急激な昇降温に対しても相変態を生じることなく、結晶粒子間の機械強度が高く結晶粒子の脱落によるチッピングが発生しなかった。本発明例１〜１４を比較すると、ＺＡ層のジルコニウム量が夫々０．４％、１６％、２０％の本発明例３、１２、１３は、工具寿命が９分であった。これに対して、ジルコニウム量が０．５〜１５％範囲内にある本発明例１、２と４〜１１は、工具寿命が１２分以上と１．２倍以上長く優れていた。これは、ＺＡ層のジルコニウム量が０．５％以上であることにより、ＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在し、酸化アルミニウムの結晶粒子間が高強度となったためである。Ｚｒ量が０．５、１％の本発明例４、５と、１２、１４、１５％の本発明例９〜１１は、工具寿命が１２から１４分であった。これに対して、３〜１０％の範囲の本発明例１、２、６、７、８は工具寿命が１７分以上と１．２倍以上長く、優れていた。ジルコニウム量は３〜１０％であることが、より好ましい結果を示した。
一方、比較例１５は６分間の断続切削した時に、刃先の欠損は発生しなかったものの膜に微小なチッピングが発生したため工具寿命に至った。これは窒化ジルコニウムを含有していないため、微小なチッピングが発生したためである。摩耗量の進行も大きく進行した。比較例１６は、２分間の切削で刃先が欠損した。これはＺＡ層のα型酸化アルミニウムの結晶粒子間を埋めるようにジルコニウム化合物が存在しておらず、皮膜硬度と機械的強度が劣化したためである。その結果、容易に膜がチッピングや欠損しやすく、刃先が欠損した。また刃先部の昇降温により、酸化ジルコニウムの相変態による体積膨張や収縮が起こり、酸化アルミニウムと酸化ジルコニウムの混合層全体にクラックや微小膜剥離が発生した。更に、α型酸化アルミニウム結晶粒子の粗大化によって結晶粒子が脱落し、皮膜全体が脆くなり靭性や耐チッピング性に劣った。比較例１７、１８はＮｚ＜Ｏｚであることにより酸化ジルコニウムの硬度が低く脆い欠点が現れ、靭性の改善が不十分なため耐チッピング性に劣った。
(Example 2)
Invention Examples 1 to 14 and Comparative Examples 15 to 18 were evaluated under the following test conditions. The work material used for the cutting was carbon steel S50C with two grooves up to φ120 and φ120, and the end face was processed to φ60. Up to φ120, intermittent cutting was performed by wet machining, and from φ120 to φ60 was evaluated by continuous machining by dry machining. In the evaluation, the tool life was determined as the tool life when the cutting edge was chipped or chipped or when the flank maximum wear width VBmax was 0.30 mm or more. The cutting edge was observed with an optical microscope having a magnification of 100 times. The evaluation results are shown in Table 2.
(Test conditions)
Work material: Two grooves up to S50C, φ160, φ120 Machining method: End face turning, machining to φ60 Tool shape: CNMG120212
Cutting speed: 180 m / min
Feed: 0.30mm / rotation Cut: 1.0mm
Cutting fluid: wet machining up to φ120, dry machining from φ120 to φ60 Each of Invention Examples 1 to 14 has a tool life of 9 minutes or longer, which is 3 times longer than Comparative Examples 15 to 18 and is remarkably excellent. This is because in the ZA layer, the zirconium compound exists so as to fill the space between the crystal grains of the α-type aluminum oxide, so that the coating hardness is hardly reduced and the mechanical properties are excellent. In addition, since the zirconium oxide in the ZA layer is monoclinic, there is little effect on the aluminum oxide crystal particles due to volume expansion and contraction due to phase transformation, and there is no dropout of the α-type aluminum oxide crystal particles, resulting in improved chipping resistance. It became effective and the residual stress of the ZA layer was relieved and the effect of having excellent toughness was obtained. As a result, phase transformation did not occur even when the temperature of the cutting edge temperature suddenly increased or decreased during use of the tool, and the mechanical strength between the crystal grains was high, and chipping due to dropping of the crystal grains did not occur. Comparing Invention Examples 1 to 14, Invention Examples 3, 12, and 13 in which the amount of zirconium in the ZA layer was 0.4%, 16%, and 20%, respectively, had a tool life of 9 minutes. On the other hand, Examples 1, 2, and 4 to 11 of the present invention in which the zirconium content is in the range of 0.5 to 15% were excellent in tool life of 12 minutes or more and 1.2 times or more. This is because when the amount of zirconium in the ZA layer is 0.5% or more, a zirconium compound exists so as to fill the space between the α-type aluminum oxide crystal particles in the ZA layer, and the strength between the aluminum oxide crystal particles is high. It is because it became. Inventive Examples 4 and 5 with Zr content of 0.5 and 1%, and Inventive Examples 9 to 11 with 12, 14, and 15%, the tool life was 12 to 14 minutes. On the other hand, the present invention examples 1, 2, 6, 7, and 8 in the range of 3 to 10% were excellent, with the tool life being 17 minutes or longer and 1.2 times or longer. A more preferable result was that the amount of zirconium was 3 to 10%.
On the other hand, in Comparative Example 15, when the intermittent cutting was performed for 6 minutes, although the chipping of the cutting edge did not occur, a minute chipping occurred in the film, which resulted in the tool life. This is because minute chipping occurred because it did not contain zirconium nitride. The progress of the wear amount also progressed greatly. In Comparative Example 16, the cutting edge was lost after cutting for 2 minutes. This is because the zirconium compound does not exist so as to fill the space between the α-type aluminum oxide crystal particles of the ZA layer, and the film hardness and mechanical strength deteriorate. As a result, the film was easily chipped and chipped, and the cutting edge was chipped. Further, the temperature rise and fall of the blade edge part caused volume expansion and contraction due to the phase transformation of zirconium oxide, and cracks and fine film peeling occurred in the entire mixed layer of aluminum oxide and zirconium oxide. Furthermore, the coarsening of the α-type aluminum oxide crystal particles caused the crystal particles to drop off, making the entire film brittle and inferior toughness and chipping resistance. In Comparative Examples 17 and 18, since Nz <Oz, the hardness of zirconium oxide was low and a brittle defect appeared, and the improvement in toughness was insufficient, resulting in poor chipping resistance.
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2017177292A (en) * | 2016-03-30 | 2017-10-05 | 三菱マテリアル株式会社 | Surface coated cutting tool |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5739168A (en) * | 1980-08-14 | 1982-03-04 | Sumitomo Electric Ind Ltd | Coated super hard alloy member and preparation thereof |
| JPH038785A (en) * | 1989-06-06 | 1991-01-16 | Mitsubishi Materials Corp | Silicon nitride-based cutting tool having excellent strength and toughness |
| JP2000144427A (en) * | 1998-11-05 | 2000-05-26 | Hitachi Metals Ltd | Aluminum oxide coated tool |
| JP2001152209A (en) * | 1999-11-22 | 2001-06-05 | Toshiba Tungaloy Co Ltd | High adhesion surface coated sintered member and its producing method |
| JP2002263914A (en) * | 2001-02-16 | 2002-09-17 | Sandvik Ab | α alumina coated cutting tool |
| JP2003145317A (en) * | 2001-09-03 | 2003-05-20 | Mitsubishi Materials Corp | Surface-coated cemented carbide cutting tool with excellent wear resistance and excellent adhesion and chipping resistance |
-
2008
- 2008-03-18 JP JP2008069164A patent/JP5229683B2/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5739168A (en) * | 1980-08-14 | 1982-03-04 | Sumitomo Electric Ind Ltd | Coated super hard alloy member and preparation thereof |
| JPH038785A (en) * | 1989-06-06 | 1991-01-16 | Mitsubishi Materials Corp | Silicon nitride-based cutting tool having excellent strength and toughness |
| JP2000144427A (en) * | 1998-11-05 | 2000-05-26 | Hitachi Metals Ltd | Aluminum oxide coated tool |
| JP2001152209A (en) * | 1999-11-22 | 2001-06-05 | Toshiba Tungaloy Co Ltd | High adhesion surface coated sintered member and its producing method |
| JP2002263914A (en) * | 2001-02-16 | 2002-09-17 | Sandvik Ab | α alumina coated cutting tool |
| JP2003145317A (en) * | 2001-09-03 | 2003-05-20 | Mitsubishi Materials Corp | Surface-coated cemented carbide cutting tool with excellent wear resistance and excellent adhesion and chipping resistance |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017177292A (en) * | 2016-03-30 | 2017-10-05 | 三菱マテリアル株式会社 | Surface coated cutting tool |
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