JP2008173737A - Aluminum oxide coated tool - Google Patents
Aluminum oxide coated tool Download PDFInfo
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- JP2008173737A JP2008173737A JP2007010935A JP2007010935A JP2008173737A JP 2008173737 A JP2008173737 A JP 2008173737A JP 2007010935 A JP2007010935 A JP 2007010935A JP 2007010935 A JP2007010935 A JP 2007010935A JP 2008173737 A JP2008173737 A JP 2008173737A
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 126
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000013078 crystal Substances 0.000 claims abstract description 67
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 37
- 239000010936 titanium Substances 0.000 claims abstract description 37
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 30
- 239000001301 oxygen Substances 0.000 claims abstract description 30
- 239000010410 layer Substances 0.000 claims description 153
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000460 chlorine Substances 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 26
- 238000000034 method Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 229910003074 TiCl4 Inorganic materials 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910009973 Ti2O3 Inorganic materials 0.000 description 2
- 229910009815 Ti3O5 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 239000002173 cutting fluid Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 2
- GQUJEMVIKWQAEH-UHFFFAOYSA-N titanium(III) oxide Chemical compound O=[Ti]O[Ti]=O GQUJEMVIKWQAEH-UHFFFAOYSA-N 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010730 cutting oil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102220097517 rs876659265 Human genes 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Landscapes
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
Description
本発明は、切削用及び耐摩耗用の酸化アルミニウム被覆工具に関するものである。 The present invention relates to an aluminum oxide coated tool for cutting and wear resistance.
α型酸化アルミニウム膜の間に酸素を含有する結合層を形成し、α型酸化アルミニウム膜を密着性良く成膜して、被覆工具に適用する技術が、下記の特許文献１〜５に開示されている。 The following Patent Documents 1 to 5 disclose a technique in which a bonding layer containing oxygen is formed between α-type aluminum oxide films, the α-type aluminum oxide film is formed with good adhesion, and applied to a coated tool. ing.
本願発明が解決しようとする課題は、α型酸化アルミニウム膜被覆工具の、内層膜との密着強度が高く、結晶粒径がより微細で耐クラック性と耐摩耗性とに優れたα型酸化アルミニウム膜を被覆した酸化アルミニウム被覆工具を実現することである。 The problem to be solved by the present invention is that the α-type aluminum oxide film-coated tool has high adhesion strength with the inner layer film, finer crystal grain size, and excellent crack resistance and wear resistance. It is to realize an aluminum oxide coated tool coated with a film.
本願発明の酸化アルミニウム被覆工具は、基体表面に、周期律表の４ａ、５ａ、６ａ族金属の炭化物、窒化物、炭窒化物、酸化物、酸炭化物、酸窒化物および酸炭窒化物のいずれか一種の単層皮膜又は二種以上の多層皮膜からなる内層膜と、結合層Ｂ、及び、少なくとも一層のα型酸化アルミニウム膜がこの順番で形成されており、該内層膜に、少なくともチタンと窒素及び炭素を含有する縦長柱状結晶粒からなり膜厚が２μｍ以上である皮膜Ｉが少なくとも一層形成されており、該結合層Ｂが少なくともチタンと窒素及び酸素元素を含有し、しかも、断面形状が針状である突起がα型酸化アルミニウム膜との界面に形成されている酸化アルミニウム被覆工具において、該結合層Ｂに含有されているチタン量に対する酸素量の比ＢＯ／ＢＴが０．００５〜０．０２５であり、且つ、該結合層Ｂに含有されているチタン量に対する窒素量の質量比ＢＮ／ＢＴと、該皮膜Ｉに含有されているチタン量に対する窒素量の質量比ＩＮ／ＩＴとの比、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．７〜２．５であることを特徴とする酸化アルミニウム被覆工具である。こうすることにより、緻密で機械強度が高く、しかも、断面形状が針状である突起がその表面に高密度に形成されている結合層Ｂが作製できるようになり、その結果、内層膜、結合層Ｂ、α型酸化アルミニウム膜間に格段に優れた密着強度を有する酸化アルミニウム被覆工具が実現でき、しかも、該針状突起が高密度に形成されていることにより、より微細な結晶粒径を有するα型酸化アルミニウム膜が形成できるようになり、耐クラック性と耐摩耗性が更に優れた酸化アルミニウム被覆工具を実現することができる。 The aluminum oxide-coated tool of the present invention has any of carbides, nitrides, carbonitrides, oxides, oxycarbides, oxynitrides, and oxycarbonitrides of the 4a, 5a, and 6a group metals of the periodic table on the substrate surface. An inner layer film composed of one kind of single-layer film or two or more kinds of multi-layer films, a bonding layer B, and at least one α-type aluminum oxide film are formed in this order, and the inner layer film includes at least titanium and At least one layer of a film I composed of vertically long columnar crystal grains containing nitrogen and carbon and having a film thickness of 2 μm or more is formed, the bonding layer B contains at least titanium, nitrogen and oxygen elements, and has a cross-sectional shape. In an aluminum oxide-coated tool in which needle-like protrusions are formed at the interface with the α-type aluminum oxide film, the ratio BO / BT of the amount of oxygen to the amount of titanium contained in the bonding layer B is 0. 005 / 0.025, and the mass ratio BN / BT of the nitrogen amount with respect to the titanium amount contained in the bonding layer B, and the mass ratio IN / of the nitrogen amount with respect to the titanium amount contained in the coating I It is an aluminum oxide-coated tool characterized in that the ratio to IT, (BN / BT) / (IN / IT), is 1.7 to 2.5. By doing so, it becomes possible to produce a bonding layer B having high density, high mechanical strength, and needles with cross-sectional shapes formed on the surface thereof at high density. An aluminum oxide-coated tool having a remarkably excellent adhesion strength between the layer B and the α-type aluminum oxide film can be realized, and the needle-like protrusions are formed at a high density, so that a finer crystal grain size can be obtained. The α-type aluminum oxide film can be formed, and an aluminum oxide-coated tool having further excellent crack resistance and wear resistance can be realized.
本願発明の酸化アルミニウム被覆工具は、結合層Ｂの塩素量が０．２質量％以下であることが好ましい。また、皮膜Ｉの窒素及び／又は炭素の一部が酸素元素に置換されており、該皮膜Ｉに含有されるチタン量ＩＴ質量％に対する窒素量ＩＮ質量％の比ＩＮ／ＩＴが０．０４０〜０．１１０、同炭素量ＩＣ質量％の比ＩＣ／ＩＴが０．１４５〜０．１８０であり、且つ、同酸素量ＩＯ質量％の比ＩＯ／ＩＴが０．０２以下であることが好ましい。また、α型酸化アルミニウム膜の膜厚をＡμｍ、同膜表面の平均結晶粒径をＤμｍとしたとき、Ａ≦２．５μｍの時はＤ≦０．８μｍ、２．５＜Ａ≦４．５μｍの時はＤ≦１．５μｍ、Ａ＞４．５μｍの時はＤ≦２．５μｍであることが好ましい。 In the aluminum oxide-coated tool of the present invention, the chlorine content of the bonding layer B is preferably 0.2% by mass or less. Further, a part of nitrogen and / or carbon of the film I is substituted with oxygen element, and the ratio IN / IT of the nitrogen amount IN mass% to the titanium amount IT mass% contained in the film I is 0.040 to It is preferable that the ratio IC / IT of 0.110 and the same carbon amount IC mass% is 0.145 to 0.180, and the ratio IO / IT of the same oxygen amount IO mass% is 0.02 or less. Further, when the film thickness of the α-type aluminum oxide film is A μm and the average crystal grain size of the film surface is D μm, when A ≦ 2.5 μm, D ≦ 0.8 μm, 2.5 <A ≦ 4.5 μm In this case, it is preferable that D ≦ 1.5 μm, and when A> 4.5 μm, D ≦ 2.5 μm.
本願発明により、内層膜とα型酸化アルミニウム膜間の密着性が高く、膜厚に比してα型酸化アルミニウム膜表面の結晶粒径がより微細であり、耐クラック性と耐摩耗性が更に優れた酸化アルミニウム被覆工具を実現できる。 According to the present invention, the adhesion between the inner layer film and the α-type aluminum oxide film is high, the crystal grain size on the surface of the α-type aluminum oxide film is finer than the film thickness, and the crack resistance and wear resistance are further improved. An excellent aluminum oxide coated tool can be realized.
本願発明の酸化アルミニウム被覆工具は、内層膜内に、少なくともチタンと窒素及び炭素を含有する縦長柱状結晶粒からなり膜厚が２μｍ以上である皮膜Ｉが少なくとも一層形成されており、結合層Ｂに含有されているチタン量に対する酸素量の比ＢＯ／ＢＴが０．００５〜０．０２５であり、且つ、該結合層Ｂに含有されているチタン量に対する窒素量の質量比ＢＮ／ＢＴと、該皮膜Ｉに含有されているチタン量に対する窒素量の質量比ＩＮ／ＩＴとの比、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．７〜２．５であることにより、内層膜とα型酸化アルミニウム膜間の密着性が更に高められるとともに、α型酸化アルミニウム膜の結晶粒径がより微細で耐クラック性と耐摩耗性とに優れた酸化アルミニウム被覆工具を実現することができる。その理由は、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）を１．７〜２．５に制御し、且つ、ＢＯ／ＢＴを０．００５〜０．０２５に制御することにより、結合層Ｂ中に含有される窒素量と酸素量の両者をより精密に制御でき、緻密で機械強度が高く、しかも、断面形状が針状である突起がその表面に高密度に形成されている結合層Ｂが作製できるためである。結合層Ｂ中の窒素含有量を精密に制御することにより、結合層Ｂ中に含有される酸素量の許容範囲が拡がるとともに、より精密に酸素含有量も制御できるようになる。元来、窒素、炭素、酸素のような軽元素の含有量を、結合層Ｂのようにその膜厚が数１００ｎｍ以下と薄い薄層中で定量分析することは困難であり、特に、窒素元素は、特性Ｘ線の波長がチタン元素の波長に重なるため、定量分析することが困難である。しかし、本願発明は、より波長分解能の高い電子プローブマイクロ分析機（以下、ＥＰＭＡと記す。）を用い、結合層Ｂ中の窒素含有量とチタン含有量の比（ＢＮ／ＢＴ）を測定するとともに、これを、膜厚が２μｍ以上と厚い皮膜Ｉの窒素含有量とチタン含有量の比（ＩＮ／ＩＴ）で割り、比較することにより、結合層Ｂ中の窒素含有量をより精密に制御できる。その理由は、結合層Ｂ近傍にあり、膜厚が２μｍ以上と厚い皮膜Ｉの（ＩＮ／ＩＴ）を測定し、これを基準にして、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）を１．７〜２．５に制御することにより、ＥＰＭＡ分析時の、窒素元素とチタン元素の特性Ｘ線の波長の重なりや、信号のベースの変動、ノイズ等の影響が相殺され、結合層Ｂ中の窒素含有量をより精密に測定できるためである。酸素原子の特性Ｘ線のピークは他の元素と重ならないため、比較的精密に測定できるが、結合層Ｂのチタン含有量に対する酸素含有量の比ＢＯ／ＢＴを測定し、これを０．００５〜０．０２５に制御することにより、ＥＰＭＡ分析時の、信号のベースの変動やノイズの影響を軽減でき、結合層Ｂ中の酸素含有量をより精密に制御できる。
このように、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）を１．７〜２．５に制御することにより、最適な酸素量を含有する結合層Ｂを成膜するために許容される、ＣＶＤ反応炉内の酸化ポテンシャルの範囲が拡がり、酸化ポテンシャルを比較的高くしても、結合層Ｂ中にＴｉ２Ｏ３やＴｉ３Ｏ５、ＴｉＯ２等が形成され難くなり、より安定して緻密で機械強度の高い結合層Ｂが形成できるようになる。しかも、ＢＯ／ＢＴを測定し、これを０．００５〜０．０２５に制御することにより、結合層Ｂ表面に存在する酸素原子と針状突起とがより多く、高密度に、且つ、均一に分布するようになり、これらを核にして、結合層Ｂの表面に形成されるα型酸化アルミニウムの結晶粒が、より高密度に、且つ、分散して形成されるため、α型酸化アルミニウム膜全体の結晶粒径がより微細になり、膜表面の平滑性がより高まると共に、膜自体の耐クラック性と耐摩耗性とが高くなる。
In the aluminum oxide-coated tool of the present invention, at least one layer of the coating I composed of longitudinal columnar crystal grains containing at least titanium, nitrogen and carbon is formed in the inner layer film, and the film thickness is 2 μm or more. The ratio of the amount of oxygen to the amount of titanium BO / BT is 0.005 to 0.025, and the mass ratio of the amount of nitrogen to the amount of titanium contained in the tie layer B is BN / BT, The ratio of the mass ratio IN / IT of the nitrogen content to the titanium content contained in the coating I, (BN / BT) / (IN / IT) is 1.7 to 2.5, so that the inner layer film and α It is possible to realize an aluminum oxide-coated tool in which the adhesion between the type aluminum oxide films is further enhanced and the α-type aluminum oxide film has a finer crystal grain size and is excellent in crack resistance and wear resistance. The reason is that (BN / BT) / (IN / IT) is controlled to 1.7 to 2.5 and BO / BT is controlled to 0.005 to 0.025. Both the amount of nitrogen and the amount of oxygen contained in can be controlled more precisely, and the bonding layer B is dense, has high mechanical strength, and has needle-shaped protrusions formed on its surface with high density. This is because it can be manufactured. By precisely controlling the nitrogen content in the bonding layer B, the allowable range of the oxygen content contained in the bonding layer B is expanded, and the oxygen content can be controlled more precisely. Originally, it is difficult to quantitatively analyze the content of light elements such as nitrogen, carbon and oxygen in a thin layer as thin as several hundred nm as in the bonding layer B. Is difficult to quantitatively analyze because the wavelength of characteristic X-rays overlaps with the wavelength of titanium element. However, the present invention uses an electron probe microanalyzer (hereinafter referred to as EPMA) with higher wavelength resolution and measures the ratio of the nitrogen content to the titanium content (BN / BT) in the bonding layer B. By dividing this by the ratio (IN / IT) of the nitrogen content to the titanium content (IN / IT) of the thick film I having a film thickness of 2 μm or more, the nitrogen content in the bonding layer B can be controlled more precisely. . The reason is that the (IN / IT) of the thick film I having a thickness of 2 μm or more is measured in the vicinity of the bonding layer B, and (BN / BT) / (IN / IT) is set to 1. By controlling to 7 to 2.5, influence of overlap of characteristic X-ray wavelengths of nitrogen element and titanium element, fluctuation of signal base, noise, etc. at the time of EPMA analysis is offset, and in the coupling layer B This is because the nitrogen content can be measured more precisely. Since the characteristic X-ray peak of oxygen atoms does not overlap with other elements and can be measured relatively accurately, the ratio BO / BT of the oxygen content to the titanium content of the bonding layer B is measured, and this is 0.005. By controlling to ˜0.025, it is possible to reduce the influence of the signal base and noise during EPMA analysis, and to control the oxygen content in the bonding layer B more precisely.
In this way, by controlling (BN / BT) / (IN / IT) to 1.7 to 2.5, the CVD allowed to form the bonding layer B containing the optimal amount of oxygen is allowed. Even if the range of the oxidation potential in the reactor is expanded and the oxidation potential is relatively high, Ti2O3, Ti3O5, TiO2 and the like are hardly formed in the bonding layer B, and the bonding layer is more stable, dense, and has high mechanical strength. B can be formed. Moreover, by measuring BO / BT and controlling it to 0.005 to 0.025, there are more oxygen atoms and needle-like protrusions present on the surface of the bonding layer B, and the density is high and uniform. Since the α-type aluminum oxide crystal grains formed on the surface of the bonding layer B using these as nuclei are formed with higher density and dispersion, the α-type aluminum oxide film The entire crystal grain size becomes finer, the smoothness of the film surface is further increased, and the crack resistance and wear resistance of the film itself are increased.
（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．７未満であると、結合層Ｂ中の窒素量が少なく、より容易に、且つ、急激に結合層Ｂが酸化されるため、結合層Ｂの機械強度が急激に低下する欠点が現れ、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が２．５を超えて大きいと、結合層Ｂ表面に存在する酸素原子と針状突起の密度が小さく、しかも、針状突起の長さが短くなり、α型酸化アルミニウムが形成されずκ型酸化アルミニウムが形成され易くなるとともに、例え、α型酸化アルミニウムが形成されても、結合層Ｂとの密着性が急激に低下するとともに、膜厚に比して結晶粒径の大きなα型酸化アルミニウムが形成される欠点が現れる。
ＢＯ／ＢＴが０．００５未満であると、結合層Ｂ中の酸素量が少なく、α型酸化アルミニウムが形成される基点となる酸素原子と針状突起とが結合層Ｂ表面に少ないため、α型酸化アルミニウムが形成され難くκ型酸化アルミニウムが形成され易く、例え、α型酸化アルミニウムが形成されても、結晶粒径が大きくなる欠点が現れる。一方、ＢＯ／ＢＴが０．０２５を超えて大きいと、結合層Ｂ内にＴｉ２Ｏ３やＴｉ３Ｏ５、ＴｉＯ２等が形成され易く、例え、形成されなくても、結合層Ｂ自体の機械強度が低くなり、結合層Ｂが破断し、皮膜が剥がれ易くなる欠点が現れる。
皮膜Ｉの膜厚が２μｍ未満であると、皮膜Ｉが縦長柱状結晶粒からなり、耐摩耗性と機械強度の両者が優れている効果が得られなくなり、工具寿命が短くなる欠点があらわれる。また、縦長柱状結晶粒からなる皮膜Ｉにかえて、粒状結晶粒からなる皮膜を用いた場合は、機械強度又は耐摩耗性のいずれかが大きく低下し、工具寿命が短くなる欠点が現れる。例えば、縦長柱状結晶粒からなるＴｉＣＮ膜にかえて、粒状結晶粒からなるＴｉＮ膜を用いると耐摩耗性が大きく低下し、同ＴｉＣ膜を用いると耐酸化性が低下することにより、耐摩耗性が大きく低下する。また、ＣＨ３ＣＮガスを用いずにＣＨ４ガスを用いて成膜した、縦長柱状結晶粒に比べて粗大な粒状結晶粒が多く含まれるＴｉＣＮ膜を用いると、耐摩耗性は若干優れるものの、機械強度が大きく低下し、工具として用いたときに、皮膜にチッピングや欠損が著しく生じやすくなり、工具寿命が大きく低下する欠点が現れる。
When (BN / BT) / (IN / IT) is less than 1.7, the amount of nitrogen in the bonding layer B is small, and the bonding layer B is oxidized more easily and rapidly. When the mechanical strength of (BN / BT) / (IN / IT) is larger than 2.5, the density of oxygen atoms and needle-like projections existing on the surface of the bonding layer B is small. In addition, the length of the needle-like projections is shortened, and α-type aluminum oxide is not formed, and κ-type aluminum oxide is easily formed. For example, even if α-type aluminum oxide is formed, adhesion with the bonding layer B is achieved. As a result, there is a drawback that α-type aluminum oxide having a crystal grain size larger than the film thickness is formed.
When BO / BT is less than 0.005, the amount of oxygen in the bonding layer B is small, and since there are few oxygen atoms and needle-like protrusions on the surface of the bonding layer B, the α-type aluminum oxide is formed. It is difficult to form type aluminum oxide, and κ type aluminum oxide is easily formed. For example, even if α type aluminum oxide is formed, there is a disadvantage that the crystal grain size becomes large. On the other hand, when BO / BT is larger than 0.025, Ti2O3, Ti3O5, TiO2 and the like are easily formed in the bonding layer B. For example, even if not formed, the mechanical strength of the bonding layer B itself is lowered, The bonding layer B breaks, and a defect that the film easily peels appears.
When the film thickness of the film I is less than 2 μm, the film I consists of vertically long columnar crystal grains, and the effect that both wear resistance and mechanical strength are excellent cannot be obtained, and there is a drawback that the tool life is shortened. In addition, when a film made of granular crystal grains is used instead of the film I made of vertically long columnar crystal grains, either mechanical strength or wear resistance is greatly reduced, resulting in a drawback that the tool life is shortened. For example, if a TiN film made of granular crystal grains is used instead of a TiCN film made of vertically long columnar crystal grains, the wear resistance is greatly reduced, and if the TiC film is used, the oxidation resistance is lowered, thereby reducing the wear resistance. Is greatly reduced. In addition, when a TiCN film formed using CH4 gas without using CH3CN gas and containing a large amount of coarse granular crystal grains as compared with longitudinal columnar crystal grains is used, although the wear resistance is slightly superior, the mechanical strength is improved. When used as a tool, chipping and chipping are prone to occur remarkably, and the tool life is greatly reduced.
本願発明の結合層Ｂは、例えば、ＣＶＤ装置の反応炉内に流すＨ２キャリヤーガス、ＴｉＣｌ４、ＣＨ４、Ｎ２、及び、ＣＯ２とＣＯの混合ガス、の各ガス流量を好適化し、α型酸化アルミニウム膜を成膜する温度近傍で反応させることにより成膜できる。これに対して、例えば、９５０℃以下で成膜すると、結合層Ｂの表面に断面が針状や棒状である突起が形成され難く、しかも、結合層Ｂを成膜した後に、α型酸化アルミニウム膜を成膜する略１０００℃以上まで昇温する過程で、結合層Ｂ表面の劣化が進むため、α型酸化アルミニウム膜の密着強度が大きく低下する欠点が現れる。このように、α型酸化アルミニウム膜を成膜する温度近傍で、結合層Ｂを成膜することが望ましいという意味で、本願発明の酸化アルミニウム被覆工具は、結合層Ｂ中に含有される塩素含有量が０．２質量％以下であることが好ましい。９５０℃以下で成膜すると、結合層Ｂ中に含有される塩素含有量が０．２質量％を超えて多くなり、結合層Ｂ自体の機械強度、及び、α型酸化アルミニウム膜の密着強度が低下する傾向が現れる。 The bonding layer B according to the present invention optimizes the gas flow rates of, for example, H2 carrier gas, TiCl4, CH4, N2, and a mixed gas of CO2 and CO flowing in the reactor of the CVD apparatus, and an α-type aluminum oxide film The film can be formed by reacting in the vicinity of the film forming temperature. On the other hand, for example, when the film is formed at a temperature of 950 ° C. or less, it is difficult to form protrusions having a needle-like or rod-like cross section on the surface of the bonding layer B. In the process of raising the temperature to approximately 1000 ° C. or higher when the film is formed, the surface of the bonding layer B is further deteriorated, which causes a drawback that the adhesion strength of the α-type aluminum oxide film is greatly reduced. Thus, in the sense that it is desirable to form the bonding layer B in the vicinity of the temperature at which the α-type aluminum oxide film is formed, the aluminum oxide-coated tool of the present invention contains chlorine contained in the bonding layer B. The amount is preferably 0.2% by mass or less. When the film is formed at 950 ° C. or less, the chlorine content contained in the bonding layer B exceeds 0.2% by mass, and the mechanical strength of the bonding layer B itself and the adhesion strength of the α-type aluminum oxide film are increased. A tendency to decline appears.
内層膜に、少なくともチタンと窒素及び炭素を含有する縦長柱状結晶粒からなり膜厚が２μｍ以上である皮膜Ｉが少なくとも一層形成されていることにより、内層膜自体の耐摩耗性と機械強度の両者がともに高まると共に、結合層Ｂの結晶粒径、及び、その上に成膜されるα型酸化アルミニウム膜の結晶粒径もより微細になる。内層膜中に、形成されている皮膜Ｉの膜厚が２μｍ未満であると、内層膜の厚さに比して結晶粒径が大きくなり、内層膜全体の機械強度が劣ると共に、その上に形成した結合層Ｂとα型酸化アルミニウム膜の結晶粒径も粗大になり、機械強度が大きく低下する欠点が現れる。ここで、縦長柱状結晶粒とは、基体表面に平行な結晶粒径に比べて、膜厚方向の結晶粒径が１．５倍以上大きく、膜厚方向に細長い結晶粒を云う。縦長柱状結晶粒からなる皮膜Ｉは、例えば、ＣＨ３ＣＮガスを用いて成膜する所謂ＭＴ−ＣＶＤ法により成膜できる。
以上の理由により、本願発明の酸化アルミニウム被覆工具を、基体表面に、周期律表の４ａ、５ａ、６ａ族金属の炭化物、窒化物、炭窒化物、酸化物、酸炭化物、酸窒化物および酸炭窒化物のいずれか一種の単層皮膜又は二種以上の多層皮膜からなる内層膜と、結合層Ｂ、及び、少なくとも一層のα型酸化アルミニウム膜がこの順番で形成されており、該内層膜に、少なくともチタンと窒素及び炭素を含有する縦長柱状結晶粒からなり膜厚が２μｍ以上である皮膜Ｉが少なくとも一層形成されており、該結合層Ｂが少なくともチタンと窒素及び酸素元素を含有し、しかも、断面形状が針状である突起がα型酸化アルミニウム膜との界面に形成されている酸化アルミニウム被覆工具において、該結合層Ｂに含有されているチタン量に対する酸素量の比ＢＯ／ＢＴが０．００５〜０．０２５であり、且つ、該結合層Ｂに含有されているチタン量に対する窒素量の質量比ＢＮ／ＢＴと、該皮膜Ｉに含有されているチタン量に対する窒素量の質量比ＩＮ／ＩＴとの比、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．７〜２．５であることを特徴とする酸化アルミニウム被覆工具とする。
本願発明の酸化アルミニウム被覆工具は、ＢＯ／ＢＴが０．０１０〜０．０２０であり、且つ、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．９〜２．３であることにより、更に、密着性が高く、結晶粒径の微細な酸化アルミニウム被覆工具が実現でき、好ましい。
従来は、結合層Ｂを成膜するときの酸素量のみを注目し、酸素量を制御することにより、結合層Ｂの特性を制御しようとしてきたが、十分に制御できず、優れた機械強度と密着強度とを有する結合層Ｂが実現出来ず、その結果、内層膜との密着強度が高く、結晶粒径がより微細で耐クラック性と耐摩耗性に優れたα型酸化アルミニウム膜を被覆した酸化アルミニウム被覆工具を安定して実現できなかった。
By forming at least one layer of the coating I consisting of longitudinal columnar crystal grains containing at least titanium, nitrogen and carbon on the inner layer film and having a thickness of 2 μm or more, both the wear resistance and mechanical strength of the inner layer film itself are obtained. Both increase, and the crystal grain size of the bonding layer B and the crystal grain size of the α-type aluminum oxide film formed thereon become finer. If the thickness of the film I formed in the inner layer film is less than 2 μm, the crystal grain size becomes larger than the thickness of the inner layer film, and the mechanical strength of the entire inner layer film is inferior. The formed bonding layer B and the α-type aluminum oxide film also have a coarse crystal grain size, and the mechanical strength is greatly reduced. Here, the vertically long columnar crystal grains refer to crystal grains that have a crystal grain size in the film thickness direction that is 1.5 times or more larger than the crystal grain diameter parallel to the substrate surface and that is elongated in the film thickness direction. The film I composed of vertically long columnar crystal grains can be formed by, for example, a so-called MT-CVD method in which a film is formed using CH3CN gas.
For the reasons described above, the aluminum oxide-coated tool of the present invention is applied to the substrate surface with carbides, nitrides, carbonitrides, oxides, oxycarbides, oxynitrides, and acids of the 4a, 5a, and 6a groups of the periodic table. An inner layer film composed of any one monolayer film or two or more multilayer films of carbonitride, a bonding layer B, and at least one α-type aluminum oxide film are formed in this order, and the inner layer film In addition, at least one layer of a film I composed of vertically long columnar crystal grains containing at least titanium, nitrogen and carbon and having a thickness of 2 μm or more is formed, and the bonding layer B contains at least titanium, nitrogen and oxygen elements, Moreover, in the aluminum oxide-coated tool in which the protrusion having a needle-like cross-sectional shape is formed at the interface with the α-type aluminum oxide film, the amount of oxygen relative to the amount of titanium contained in the bonding layer B The ratio BO / BT is 0.005 to 0.025, and the mass ratio BN / BT of the nitrogen amount relative to the titanium amount contained in the bonding layer B and the titanium amount contained in the coating I The ratio of nitrogen content to the mass ratio IN / IT, (BN / BT) / (IN / IT) is 1.7 to 2.5.
The aluminum oxide-coated tool of the present invention has a BO / BT of 0.010 to 0.020 and a (BN / BT) / (IN / IT) of 1.9 to 2.3, An aluminum oxide-coated tool having high adhesion and a fine crystal grain size can be realized, which is preferable.
Conventionally, attention has been paid only to the amount of oxygen when forming the bonding layer B, and the characteristics of the bonding layer B have been controlled by controlling the amount of oxygen. The bonding layer B having the adhesion strength cannot be realized, and as a result, the α-type aluminum oxide film having a high adhesion strength with the inner layer film, a finer crystal grain size, and excellent crack resistance and wear resistance is coated. An aluminum oxide coated tool could not be realized stably.
本願発明の酸化アルミニウム被覆工具は、結合層Ｂの塩素量が０．２質量％以下であることにより、結合層Ｂの機械強度が高く、しかも、結合層Ｂ表面に形成される断面が針状である突起がより高強度、且つ、高密度に形成されるため、α型酸化アルミニウム膜の密着強度が更に高くなり、更に優れた酸化アルミニウム被覆工具が実現でき、好ましい。結合層Ｂの塩素量が０．２質量％を超えて大きいと、０．２質量％以下の時よりも、結合層Ｂの機械強度が低下し、しかも、結合層Ｂ表面に形成される断面が針状である突起の機会強度が低下し、且つ、高密度に形成されない、α型酸化アルミニウム膜の密着強度が低下する傾向が現れる。
本願発明の酸化アルミニウム被覆工具は、皮膜Ｉの窒素及び／又は炭素の一部が酸素元素に置換されており、該皮膜Ｉに含有されるチタン量ＩＴ質量％に対する窒素量ＩＮ質量％の比ＩＮ／ＩＴが０．０４０〜０．１１０、同炭素量ＩＣ質量％の比ＩＣ／ＩＴが０．１４５〜０．１８０であり、且つ、同酸素量ＩＯ質量％の比ＩＯ／ＩＴが０．０２以下であることにより、皮膜Ｉの機械強度が更に高まるとともに、更に結晶粒径が微細なα型酸化アルミニウム膜が得られ、更に長寿命の優れた被覆工具が得られ、好ましい。皮膜Ｉに含有されるチタン量ＩＴ質量％に対する窒素量ＩＮ質量％の比ＩＮ／ＩＴが０．０４０〜０．１１０、同炭素量ＩＣ質量％の比ＩＣ／ＩＴが０．１４５〜０．１８０、の範囲外であると、同範囲内に比べて、皮膜Ｉの機械強度が低下するとともに、α型酸化アルミニウム膜の結晶粒径が大きくなり、工具寿命が短くなる傾向が現れる。
本願発明の酸化アルミニウム被覆工具は、α型酸化アルミニウム膜の膜厚をＡμｍ、同膜表面の平均結晶粒径をＤμｍとしたとき、Ａ≦２．５μｍの時はＤ≦０．８μｍ、２．５＜Ａ≦４．５μｍの時はＤ≦１．５μｍ、Ａ＞４．５μｍの時はＤ≦２．５μｍであることにより、更に優れた機械強度と摺動性を有する酸化アルミニウム膜が得られ、更に長寿命の優れた被覆工具が得られ、好ましい。α型酸化アルミニウム膜の膜厚と平均結晶粒径が上記範囲がであると、上記範囲内であるときに比べて、酸化アルミニウム膜の機械強度と摺動性とが低下し、工具寿命が短くなる傾向が現れる。
The aluminum oxide-coated tool of the present invention has a high mechanical strength of the bonding layer B due to the chlorine content of the bonding layer B being 0.2% by mass or less, and the cross section formed on the surface of the bonding layer B is needle-shaped. Since the protrusions are formed with higher strength and higher density, the adhesion strength of the α-type aluminum oxide film is further increased, and a further excellent aluminum oxide-coated tool can be realized, which is preferable. If the amount of chlorine in the bonding layer B exceeds 0.2% by mass, the mechanical strength of the bonding layer B is lower than that in the case of 0.2% by mass or less, and the cross section formed on the surface of the bonding layer B There is a tendency that the opportunity strength of the protrusions having a needle shape is lowered and the adhesion strength of the α-type aluminum oxide film which is not formed at a high density is lowered.
In the aluminum oxide-coated tool of the present invention, a part of nitrogen and / or carbon of the film I is substituted with oxygen element, and the ratio IN of the nitrogen amount IN mass% to the titanium amount IT mass% contained in the film I / IT is 0.040 to 0.110, the ratio IC / IT of the same carbon amount IC mass% is 0.145 to 0.180, and the ratio IO / IT of the same oxygen amount IO mass% is 0.02. The following is preferable because the mechanical strength of the coating I is further increased, an α-type aluminum oxide film having a finer crystal grain size is obtained, and a coated tool having a longer life is obtained. The ratio IN / IT of the nitrogen amount IN mass% to the titanium amount IT mass% contained in the coating I is 0.040 to 0.110, and the ratio IC / IT of the same carbon amount IC mass% is 0.145 to 0.180. If the value is outside the range, the mechanical strength of the coating I is lowered and the crystal grain size of the α-type aluminum oxide film is increased, and the tool life tends to be shortened.
The aluminum oxide-coated tool of the present invention has an α-type aluminum oxide film thickness of A μm and an average crystal grain size of the film surface of D μm. When A ≦ 2.5 μm, D ≦ 0.8 μm. When 5 <A ≦ 4.5 μm, D ≦ 1.5 μm, and when A> 4.5 μm, D ≦ 2.5 μm, thereby obtaining an aluminum oxide film having further excellent mechanical strength and slidability. In addition, a coated tool having an excellent long life is obtained, which is preferable. When the film thickness and average crystal grain size of the α-type aluminum oxide film are within the above ranges, the mechanical strength and slidability of the aluminum oxide film are reduced and the tool life is shortened compared to when the thickness is within the above range. The tendency to become appears.
本願発明のα型酸化アルミニウム膜は、必ずしも最外層である必要はなく、その上に更に少なくとも一層のチタン化合物、例えばＴｉＮ層等、やジルコニウム化合物、例えばＺｒＮ層等、を被覆しても良い。その場合、α型酸化アルミニウム膜の外層をショットブラスト、研磨等により除去した後、α型酸化アルミニウム膜表面の平均結晶粒径を測定する。また、α型酸化アルミニウム膜表面の結晶粒界が明確でない場合は、α型酸化アルミニウム膜表面を後述の電子プローブマイクロ分析機等により、結晶粒界を同定して、平均結晶粒径を求めても良い。また、弗化水素酸、又は、払酸と硝酸の混合液により、α型酸化アルミニウム膜表面をエッチングして、結晶粒界をより明確にして、測定してもよい。 The α-type aluminum oxide film of the present invention is not necessarily the outermost layer, and may be further coated with at least one titanium compound such as a TiN layer, or a zirconium compound such as a ZrN layer. In that case, after removing the outer layer of the α-type aluminum oxide film by shot blasting, polishing or the like, the average crystal grain size on the surface of the α-type aluminum oxide film is measured. If the crystal grain boundary on the surface of the α-type aluminum oxide film is not clear, the surface of the α-type aluminum oxide film is identified by an electron probe microanalyzer described later, and the average crystal grain size is obtained. Also good. Alternatively, the surface of the α-type aluminum oxide film may be etched with hydrofluoric acid or a mixed solution of hydrophobic acid and nitric acid to make the crystal grain boundary clearer and measured.
本願発明における被覆方法には既知の成膜方法を適用することが可能である。例えば、通常の熱化学蒸着法である熱ＣＶＤ法、プラズマを付加した化学蒸着法であるＰＡＣＶＤ法等を用いることができる。用途は切削工具に限るものではなく、耐摩耗材や金型、溶湯部品等でも良い。本願発明のα型酸化アルミニウム膜はα型酸化アルミニウム単相に限るものではなく、α型酸化アルミニウムを８０ｖｏｌ％以上含む膜を云い、他の酸化物、例えばα型酸化アルミニウムとκ型酸化アルミニウムとの混合膜やγ型酸化アルミニウム、θ型酸化アルミニウム、δ型酸化アルミニウム、χ型酸化アルミニウム等、他の酸化アルミニウムとの混合膜、あるいは、α型酸化アルミニウムと酸化ジルコニウム等他の酸化物との混合膜であっても同様の効果が得られる。また、本願発明のα型酸化アルミニウム膜は、Ｙ、Ｚｒ、Ｈｆ、Ｖ、Ｃｒ、Ｓ、Ｗ等の添加物や、不可避の元素が含有されていても良い。
次に本発明による被覆工具を実施例によって具体的に説明する。
A known film forming method can be applied to the coating method in the present invention. For example, a thermal CVD method that is a normal thermal chemical vapor deposition method, a PACVD method that is a chemical vapor deposition method to which plasma is added, or the like can be used. The application is not limited to cutting tools, but may be wear-resistant materials, molds, molten metal parts, and the like. The α-type aluminum oxide film of the present invention is not limited to an α-type aluminum oxide single phase, but refers to a film containing 80 vol% or more of α-type aluminum oxide. Other oxides such as α-type aluminum oxide and κ-type aluminum oxide Mixed film of γ-type aluminum oxide, θ-type aluminum oxide, δ-type aluminum oxide, χ-type aluminum oxide, etc. or other oxides such as α-type aluminum oxide and zirconium oxide The same effect can be obtained even with a mixed film. Further, the α-type aluminum oxide film of the present invention may contain additives such as Y, Zr, Hf, V, Cr, S, W, and inevitable elements.
Next, the coated tool according to the present invention will be specifically described with reference to examples.
（実施例１）
Ｃｏ：７質量％、Ｃｒ：０．６質量％、Ｚｒ：２．２質量％、Ｔａ：３．３質量％、Ｎｂ：０．２質量％、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超硬合金基体をＣＶＤ装置の反応炉内に設置し、基体の表面に、化学蒸着法によりＨ２キャリヤーガスとＴｉＣｌ４ガスとＮ２ガスとを原料ガスに用いて０．３μｍ厚さのＴｉＮを９００℃でまず形成した。続いて、ＴｉＣｌ４ガスを１ｖｏｌ％、ＣＨ３ＣＮガスを２ｖｏｌ％、Ｎ２ガスを４５ｖｏｌ％、ＣＯガスを０．８ｖｏｌ％、残Ｈ２キャリヤーガスで構成された原料ガスを毎分５５００ｍｌだけＣＶＤ装置の反応炉内に流し、成膜温度８５０℃、成膜圧力６．６ｋＰａの条件で６μｍ厚さのＴｉＣＮＯ膜を皮膜Ｉとして成膜した。その後、成膜温度を１０００℃に高め、成膜圧力６．６ｋＰａの条件で、ＴｉＣｌ４ガスを１ｖｏｌ％、ＣＨ４ガスを２ｖｏｌ％、Ｎ２ガスを６０ｖｏｌ％、残Ｈ２キャリヤーガスで構成された原料ガスを毎分５５００ｍｌで、２０分間ＣＶＤ装置の反応炉内に流すことにより、結合層Ｂの前半を形成した後、そのまま、同じ流量のＴｉＣｌ４、ＣＨ４、Ｎ２、Ｈ２のガスに加えて、更に、ＣＯ２とＣＯの混合ガスを７ｖｏｌ％追加して２０分間流すことにより結合層Ｂの後半を形成し、トータル厚さ０．１μｍの結合層Ｂを形成した。その後、１００５℃で、Ｈ２キャリヤーガス、ＡｌＣｌ３ガス、ＣＯ２とＣＯの混合ガス、および、Ｈ２Ｓガスを２７０分間、ＣＶＤ装置の反応炉内に流すことによりＡｌ２Ｏ３膜を成膜することにより、本発明例１を作製した。
そして、本発明例１と大略同じ基体と、皮膜構成、成膜方法を用いて、一部の皮膜の種類、又は成膜条件のみを変化させて以下の本発明例２〜２０と比較例２１〜２７を作製した。特に断らないかぎり、それらの基体と、皮膜構成、成膜方法は本発明例１と大略同じである。各試料の成膜条件の変更点を表１にまとめて示す。
(Example 1)
Co: 7% by mass, Cr: 0.6% by mass, Zr: 2.2% by mass, Ta: 3.3% by mass, Nb: 0.2% by mass, residual WC and inevitable impurities in a predetermined shape A cemented carbide substrate for a cutting tool is placed in a reaction furnace of a CVD apparatus, and a TiN film having a thickness of 0.3 μm is formed on the surface of the substrate by chemical vapor deposition using H2 carrier gas, TiCl4 gas, and N2 gas as source gases. Was first formed at 900 ° C. Subsequently, the source gas composed of 1 vol% of TiCl4 gas, 2 vol% of CH3CN gas, 45 vol% of N2 gas, 0.8 vol% of CO gas, and the remaining H2 carrier gas is 5500 ml / min in the reactor of the CVD apparatus. Then, a TiCNO film having a thickness of 6 μm was formed as a film I under conditions of a film forming temperature of 850 ° C. and a film forming pressure of 6.6 kPa. Thereafter, the raw material gas composed of TiCl4 gas at 1 vol%, CH4 gas at 2 vol%, N2 gas at 60 vol%, and the remaining H2 carrier gas under the conditions where the film forming temperature is increased to 1000 ° C. and the film forming pressure is 6.6 kPa. After forming the first half of the bonding layer B by flowing into the reactor of the CVD apparatus for 20 minutes at 5500 ml per minute, in addition to the TiCl4, CH4, N2 and H2 gases at the same flow rate, CO2 and The latter half of the bonding layer B was formed by adding 7 vol% of a mixed gas of CO and flowing for 20 minutes to form a bonding layer B having a total thickness of 0.1 μm. Thereafter, an Al2O3 film is formed by flowing an H2 carrier gas, an AlCl3 gas, a mixed gas of CO2 and CO, and an H2S gas at a temperature of 1005 [deg.] C. for 270 minutes in the reactor of the CVD apparatus. 1 was produced.
Then, the following examples of the present invention 2 to 20 and comparative example 21 are changed by using only the same substrate, film configuration, and film formation method as those of the present invention example 1 and changing only some kinds of films or film formation conditions. -27 were made. Unless otherwise specified, the substrates, the coating composition, and the film forming method are substantially the same as those of Example 1 of the present invention. Table 1 summarizes the changes in the film forming conditions for each sample.
まず、結合層Ｂ中に含有されているチタン量に対する窒素量比と、同酸素量比の影響を明らかにするため、結合層Ｂ前半に流すＣＨ４ガス量を１、１．５、２．５、３ｖｏｌ％、Ｎ２ガス量を５０、５５、６５、７０ｖｏｌ％に変更するとともに、結合層Ｂ後半に追加するＣＯ２とＣＯの混合ガス量を４、５、９、１０ｖｏｌ％に変更することにより、本発明例２〜５を作製した。また、結合層Ｂ中に含有される塩素量の効果を明らかにするため、内層膜を成膜した後、基体の温度を９６０℃に高めた後、結合層Ｂの前半と後半の両者を９６０℃で成膜した後、Ａｌ２Ｏ３膜を成膜することにより、本発明例６を作製した。
皮膜Ｉ、即ち、ＴｉＣＮＯ膜中に含有されているチタン量に対する含有窒素量比と、同炭素量比、及び、同酸素量比の影響を明らかにするため、本発明例として、ＴｉＣＮＯ膜の成膜温度を９３０、８９０、８１０、７８０℃、成膜時に流すＮ２ガス流量を３０、４０、５０、６０ｖｏｌ％、同ＣＯガス流量を２．０、１．５、０．２、０．１ｖｏｌ％に変更することにより、本発明例７〜１０を作製した。
Ａｌ２Ｏ３の各膜厚に於ける結晶粒径の影響を明らかにするため、成膜温度１００５℃で、Ａｌ２Ｏ３をそれぞれ１８０、２２５、４０５、４５０、７２０分間成膜することにより、Ａｌ２Ｏ３の結晶粒径がより微細である本発明例１１、１２、１４、１６、１８を作製するとともに、同成膜温度１０２０℃で、Ａｌ２Ｏ３をそれぞれ２２５、４０５、４５０分間成膜することにより、Ａｌ２Ｏ３の結晶粒径が若干大きい本発明例１３、１５、１７を作製した。
皮膜Ｉの膜厚の影響を明らかにするため、皮膜Ｉの成膜時間のみを短くし、皮膜Ｉの膜厚をそれぞれ４μｍ、２μｍと薄くした以外は、他の皮膜構成と成膜条件は本発明例１と同じである本発明例１９、２０を作製した。
First, in order to clarify the influence of the nitrogen amount ratio and the oxygen amount ratio with respect to the titanium amount contained in the bonding layer B, the amount of CH4 gas flowing in the first half of the bonding layer B is 1, 1.5, 2.5. 3 vol%, N2 gas amount is changed to 50, 55, 65, 70 vol%, and by changing the mixed gas amount of CO2 and CO added to the second half of the bonding layer B to 4, 5, 9, 10 vol%, Invention Examples 2 to 5 were produced. In order to clarify the effect of the amount of chlorine contained in the bonding layer B, after the inner layer film is formed, the temperature of the substrate is increased to 960 ° C., and then both the first half and the latter half of the bonding layer B are set to 960. After forming the film at ° C., an Al 2 O 3 film was formed to produce Inventive Example 6.
In order to clarify the influence of the nitrogen content ratio, the carbon content ratio, and the oxygen content ratio with respect to the titanium content contained in the coating I, that is, the TiCNO film, as an example of the present invention, a TiCNO film is formed. Membrane temperature is 930, 890, 810, 780 ° C, N2 gas flow rate is 30, 40, 50, 60 vol%, and CO gas flow rate is 2.0, 1.5, 0.2, 0.1 vol%. Inventive Examples 7 to 10 were prepared by changing to.
In order to clarify the influence of the crystal grain size on each film thickness of Al 2 O 3, Al 2 O 3 was deposited at a film forming temperature of 1005 ° C. for 180, 225, 405, 450 and 720 minutes, respectively. The present invention examples 11, 12, 14, 16, and 18 were produced, and Al2O3 was deposited at the same deposition temperature of 1020 ° C. for 225, 405, and 450 minutes, respectively. Inventive Examples 13, 15, and 17 were produced.
In order to clarify the influence of the film thickness, only the film formation time of the film I is shortened and the film thickness of the film I is reduced to 4 μm and 2 μm, respectively. Invention Examples 19 and 20 which are the same as Invention Example 1 were produced.
内層膜とα型酸化アルミニウム膜との間に、結合層Ｂが形成されている効果を明らかにするため、比較例として、内層膜を成膜し、基体の温度を１０００℃に高めた後、結合層Ｂを成膜せずに、直接、Ｈ２キャリヤーガスにＣＯ２、ＣＯ、ＡｌＣｌ３ガスをこの順序で、１５分間で加えていった後、Ａｌ２Ｏ３膜を成膜することにより、比較例２１を作製した。
結合層ＢのＢＯ／ＢＴ値の効果を明らかにするため、比較例として、結合層Ｂ後半を成膜するときに加えるＣＯ２とＣＯの混合ガス量をそれぞれ２ｖｏｌ％と１２ｖｏｌ％に変更して成膜した比較例２２と２３とを作製した。
結合層Ｂと皮膜Ｉ間の（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）値の効果を明らかにするため、比較例として、結合層Ｂ前半と後半の両者を成膜するときにもちいる、ＣＨ４ガス量とＮ２ガス量とをそれぞれ０．５と４０ｖｏｌ％に変更して成膜することにより、比較例２４を作製した。また、同、ＣＨ４ガス量とＮ２ガス量とをそれぞれ４と８０ｖｏｌ％に変更して成膜することにより、比較例２５を作製した。
皮膜Ｉの膜厚の影響を明らかにするため、比較例として、皮膜Ｉの成膜時間のみを短くし、皮膜Ｉの膜厚を１μｍと薄くした以外は、他の皮膜構成と成膜条件は本発明例１と同じである比較例２６を作製した。
皮膜Ｉが縦長柱状結晶粒からなる効果を明らかにするため、皮膜Ｉを、ＴｉＣｌ４ガスを３ｖｏｌ％、ＣＨ４ガスを２ｖｏｌ％、Ｎ２ガスを３０ｖｏｌ％、ＣＯガスを２ｖｏｌ％、残Ｈ２キャリヤーガスで構成された原料ガスを毎分５５００ｍｌだけＣＶＤ装置の反応炉内に流し、成膜温度１０００℃、成膜圧力７．９ｋＰａの条件で６μｍ厚さのＴｉＣＮＯ膜を皮膜Ｉとして成膜した以外は、他の皮膜構成と成膜条件は本発明例１と同じである本発明例２７を作製した。
In order to clarify the effect that the bonding layer B is formed between the inner layer film and the α-type aluminum oxide film, as a comparative example, after forming the inner layer film and raising the temperature of the substrate to 1000 ° C., Comparative Example 21 was fabricated by forming an Al2O3 film after adding CO2, CO, and AlCl3 gas in this order in this order for 15 minutes without forming the bonding layer B. did.
In order to clarify the effect of the BO / BT value of the bonding layer B, as a comparative example, the mixed gas amount of CO2 and CO added when forming the latter half of the bonding layer B was changed to 2 vol% and 12 vol%, respectively. Filmed Comparative Examples 22 and 23 were prepared.
In order to clarify the effect of the (BN / BT) / (IN / IT) value between the bonding layer B and the film I, as a comparative example, CH4 is used when both the first half and the second half of the bonding layer B are formed. Comparative Example 24 was produced by changing the gas amount and the N 2 gas amount to 0.5 and 40 vol%, respectively. Further, Comparative Example 25 was fabricated by changing the CH4 gas amount and the N2 gas amount to 4 and 80 vol%, respectively.
In order to clarify the influence of the film thickness of the film I, as a comparative example, other film configurations and film formation conditions are the same except that only the film formation time of the film I is shortened and the film thickness of the film I is reduced to 1 μm. Comparative Example 26, which is the same as Invention Example 1, was prepared.
In order to clarify the effect of coating I consisting of vertically long columnar crystal grains, coating I is composed of 3 vol% TiCl4 gas, 2 vol% CH4 gas, 30 vol% N2 gas, 2 vol% CO gas, and the remaining H2 carrier gas. Except that 5500 ml of the raw material gas was flown into the reactor of the CVD apparatus per minute, and a 6 μm thick TiCNO film was formed as film I under the conditions of a film forming temperature of 1000 ° C. and a film forming pressure of 7.9 kPa. Inventive Example 27 was produced in which the coating composition and film forming conditions were the same as in Inventive Example 1.
作製した膜のＸ線回折を理学電気（株）製のＸ線回折装置（ＲＵ−３００Ｒ）で、ＣｕのＫα１線（波長０．１５４０５ｎｍ）を用いて、２θ−θ法により２θが２０〜９０°の範囲内で測定した結果、いずれのＡｌ２Ｏ３膜も、ＪＣＰＤＳファイル番号１０−１７３記載の２θ値の±０．２５の範囲内にピークが現れ、α型酸化アルミニウム膜が形成されていることが確認された。
各試料を基体に垂直に破断し、その破断面を（株）日立製作所製の走査電子顕微鏡（以下、ＳＥＭと記す。）Ｓ−４２００型を用いて、１万倍で観察し、膜厚方向に細長い縦長柱状結晶粒からなる皮膜Ｉの、基体側から膜表面側までの領域を決定した。また、酸化アルミニウムの膜厚を測定した。
ＳＥＭを用いて、酸化アルミニウム膜の表面を倍率５、０００倍で観察し、これを０．８倍して、寸法８５ｍｍ×１１０ｍｍの大きさに印刷したＳＥＭ写真の表面に、上から２１ｍｍ、４２．５ｍｍ、６４ｍｍの各位置に横線を引くとともに更に対角線を２本、計５本を引き、各直線内にある結晶粒の数を求めて、化１により、酸化アルミニウム膜の平均粒径Ｄを求めた。測定した本発明例と比較例の酸化アルミニウム膜の膜厚と、酸化アルミニウム膜の平均結晶粒径を表２にまとめて示す。
X-ray diffraction of the prepared film was performed using an X-ray diffractometer (RU-300R) manufactured by Rigaku Denki Co., Ltd., using a Cu Kα1 ray (wavelength 0.15405 nm), and 2θ of 20 to 90 by the 2θ-θ method. As a result of measurement within the range of °, as for any Al2O3 film, a peak appears in the range of ± 0.25 of the 2θ value described in JCPDS file number 10-173, indicating that an α-type aluminum oxide film is formed. confirmed.
Each sample was fractured perpendicularly to the substrate, and the fractured surface was observed at a magnification of 10,000 using a scanning electron microscope (hereinafter referred to as SEM) S-4200 manufactured by Hitachi, Ltd. The region from the substrate side to the film surface side of the coating I composed of elongated vertically long columnar crystal grains was determined. Moreover, the film thickness of the aluminum oxide was measured.
Using the SEM, the surface of the aluminum oxide film was observed at a magnification of 5,000 times, and this was multiplied by 0.8, and the surface of the SEM photograph printed in a size of 85 mm × 110 mm was 21 mm, 42 mm from the top. .5mm and 64mm, draw a horizontal line and draw two diagonal lines, a total of five lines, to determine the number of crystal grains in each straight line. Asked. Table 2 summarizes the measured film thicknesses of the aluminum oxide films of the present invention and the comparative example and the average crystal grain size of the aluminum oxide films.
各試料の断面を鏡面研磨し、日本電子（株）製のＥＰＭＡ装置であるＪＸＡ−８５００Ｆを用いて、加速電圧８ｋＶ、スポット径１０ｎｍで、皮膜の断面を分析することにより、皮膜Ｉに含有されるチタン、炭素、酸素の各元素量を測定し、皮膜ＩのＩＣ／ＩＴとＩＯ／ＩＴを求めた。これらを表２に併せて示す。 It is contained in film I by mirror-polishing the cross section of each sample and analyzing the cross section of the film with an acceleration voltage of 8 kV and a spot diameter of 10 nm using JXA-8500F, an EPMA apparatus manufactured by JEOL Ltd. The amount of each element of titanium, carbon, and oxygen was measured, and IC / IT and IO / IT of coating I were determined. These are also shown in Table 2.
上記の研磨面に炭素を略１０ｎｍ厚だけ蒸着した後、皮膜Ｉに含有されるチタン量と窒素量を測定し、ＩＮ／ＩＴを求めた。そして、結合層Ｂに含有されるチタン、窒素、酸素、及び、塩素の各元素量を測定し、各試料のＢＯ／ＢＴ、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）、及び、塩素量を求めた。それらの結果を表２にあわせて示す。なお、上記の炭素は、結合層Ｂの直上にある酸化アルミニウム膜が分析時に帯電する事を避けるために、蒸着した。 After depositing carbon on the polished surface by a thickness of about 10 nm, the amount of titanium and the amount of nitrogen contained in the film I were measured to determine IN / IT. Then, the amount of each element of titanium, nitrogen, oxygen, and chlorine contained in the bonding layer B is measured, and the BO / BT, (BN / BT) / (IN / IT), and chlorine content of each sample are measured. Asked. The results are also shown in Table 2. The above carbon was deposited in order to prevent the aluminum oxide film immediately above the bonding layer B from being charged during analysis.
炭素を蒸着した上記研磨面の反射電子組成像を撮影し、本発明例と比較例の、結合層Ｂの針状突起長さを測定した。針状突起の長さは、倍率１０，０００で撮影した画面上で、結合層Ｂと酸化アルミニウム膜間の界面の長さが９５ｍｍの範囲内で１〜２本観察されるような異常な長さの突起は、針状突起長さの測定対象からはずし、他の針状突起長さの平均値を求めた。その結果、本発明例１〜２０と比較例２６、２７の結合層Ｂの、α型酸化アルミニウム膜側の界面に、特許文献３と同様の、断面が針状で長さが０．５μｍ以下である突起が多数形成されていが、比較例２１〜２５には針状突起が形成されていなかった。しかも、比較例２１、２３、２４の結合層Ｂはポアの多いチタン酸化物の層が形成されていた。 The backscattered electron composition images of the polished surface on which carbon was deposited were photographed, and the lengths of needle-like protrusions of the bonding layer B of the present invention example and the comparative example were measured. The length of the needle-like protrusions is an abnormal length such that one or two needles are observed on the screen photographed at a magnification of 10,000 within the range where the interface length between the bonding layer B and the aluminum oxide film is 95 mm. The protrusions were removed from the measurement target of the needle-like protrusion length, and the average value of the other needle-like protrusion lengths was obtained. As a result, at the interface on the α-type aluminum oxide film side of the bonding layers B of Invention Examples 1 to 20 and Comparative Examples 26 and 27, the cross section is needle-like and the length is 0.5 μm or less, similar to Patent Document 3. A large number of protrusions were formed, but the needle-like protrusions were not formed in Comparative Examples 21 to 25. In addition, in the bonding layers B of Comparative Examples 21, 23, and 24, a titanium oxide layer with a large amount of pores was formed.
次に、作製した本発明例と比較例の切削工具各５個を用いて、以下の切削条件１で被削材を連続切削し、逃げ面の摩耗量が０．２ｍｍに達した時点を工具寿命と判定した。逃げ面の摩耗量は光学顕微鏡を用いて倍率３５倍で観察した。
（切削条件１）
被削材：ＦＣ２５、硬さ、ＨＢ２３０
工具形状：ＣＮＭＡ１２０４１２
切削速度：３３０ｍ／ｍｉｎ
送り：０．３ｍｍ／回転
切り込み：２．０ｍｍ
切削液：水溶性切削油使用
上記の本発明例と比較例の切削工具各５個を以下の切削条件２で断続切削し、欠損に至るまでの断続切削可能回数を評価した。刃先先端の欠け状況は倍率５０倍の実体顕微鏡で観察した。
（切削条件２）
被削材：Ｓ５３Ｃ溝入材、硬さ、ＨＳ３８
切削速度：１９０ｍ／ｍｉｎ
送り：０．２ｍｍ／ｒｅｖ
切り込み：１．５ｍｍ
切削液：使用せず（乾式切削）
上記の方法で評価した、本発明例と比較例の工具寿命を、表２に併せて示す。
Next, using the five cutting tools of the present invention and the comparative example, the workpiece was continuously cut under the following cutting condition 1, and the point when the flank wear amount reached 0.2 mm was determined as the tool. Judged as life. The amount of wear on the flank surface was observed using an optical microscope at a magnification of 35 times.
(Cutting condition 1)
Work material: FC25, hardness, HB230
Tool shape: CNMA120204
Cutting speed: 330 m / min
Feed: 0.3 mm / rotation depth: 2.0 mm
Cutting fluid: Use of water-soluble cutting oil Five cutting tools of the present invention example and the comparative example were each intermittently cut under the following cutting conditions 2 to evaluate the number of times of intermittent cutting until the chipping occurred. The chipping state of the blade tip was observed with a stereomicroscope with a magnification of 50 times.
(Cutting condition 2)
Work material: S53C grooved material, hardness, HS38
Cutting speed: 190 m / min
Feed: 0.2mm / rev
Cutting depth: 1.5mm
Cutting fluid: Not used (dry cutting)
Table 2 shows the tool life of the inventive example and the comparative example evaluated by the above method.
表２より、皮膜Ｉの膜厚が６μｍ、酸化アルミニウムの膜厚が３μｍであり、結合層Ｂが形成されていない比較例２１の連続切削工具寿命が５０分であるのに対して、皮膜Ｉの膜厚が６μｍ、酸化アルミニウム膜厚が３μｍと同じであるが、針状突起を有する結合層Ｂが形成されている本発明例１〜１０の連続切削工具寿命は１３０分以上と、２．６倍以上長く格段に優れている。その理由は、結合層Ｂを形成することなく、内層膜の表面を酸化した後、α型酸化アルミニウム膜を成膜すると、内層膜の表面に針状突起を有する結合層Ｂが形成されず、しかも、内層膜の表面部分の機械強度が低下したため、内層膜とα型酸化アルミニウム膜間の密着強度が極端に低くなったためである。
本発明例１と同じ膜厚の皮膜Ｉと酸化アルミニウムが形成されているものの、結合層ＢのＢＯ／ＢＴが０．００３と小さい比較例２２の連続切削工具寿命が５０分であるのに対して、ＢＯ／ＢＴが０．００５である本発明例２の連続切削工具寿命は１７０分と、３倍以上長く格段に優れている。また、結合層ＢのＢＯ／ＢＴが０．０２８と大きい比較例２３の連続切削工具寿命が４０分であるのに対して、ＢＯ／ＢＴが０．０２５である本発明例５の連続切削工具寿命は１６０分と、４倍以上長く格段に優れている。その理由は、結合層ＢのＢＯ／ＢＴが０．００５未満だと、結合層Ｂ表面に形成される突起数が少ないため、α型酸化アルミニウム膜の密着強度が低く、しかも、結晶粒径が大きくなるためであり、０．０２５を超えて多いと、結合層Ｂ表面に形成される突起数が少なくなるとともに、結合層Ｂ自体の機械強度も低下し、結合層Ｂの内部からも破断し易くなり、その結果、α型酸化アルミニウム膜の密着強度が大幅に低下するためである。そこで、本願発明の結合層ＢのＢＯ／ＢＴを０．００５〜０．０２５とした。
本発明例１と同じ膜厚の皮膜Ｉと酸化アルミニウムが形成されており、結合層ＢのＢＯ／ＢＴが０．０１５であるものの、結合層Ｂと皮膜Ｉ間の（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．５と小さい比較例２４の連続切削工具寿命が５０分であるのに対して、同（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）比が１．７である本発明例２の連続切削工具寿命は１７０分と、３倍以上長く格段に優れている。また、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が２．７と大きい比較例２５の連続切削工具寿命が３０分であるのに対して、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）比が２．５である本発明例５の連続切削工具寿命は１６０分と５倍以上長く格段に優れている。その理由は、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）比が１．７未満であると、結合層Ｂ自体の機械強度が低くなり、結合層Ｂ自体の機械強度が低下し、結合層Ｂ内から破断し易くなると共に、結合層Ｂ表面に形成される針状突起数も少なくなるため、α型酸化アルミニウム膜の密着強度が低下するためである。また、針状突起数も少なくなるため、α型酸化アルミニウム膜の結晶粒径が大きくなるためでもある。一方、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）比が２．５を超えて大きくなると、結合層Ｂ表面に形成される針状突起数が少なくなり、α型酸化アルミニウム膜の密着強度が低くなるとともに、その結晶粒径が大きくなるためである。そこで、本願発明の（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）を１．７〜２．５とした。
本発明例１とほぼ同じ成膜条件で、ほぼ同じ皮膜が形成されているものの、皮膜Ｉの膜厚が１μｍと薄い比較例２６の連続切削工具寿命が８０分であるのに対して、皮膜Ｉの膜厚が２μｍ以上である本発明例１、１９、２０の連続切削工具寿命は１８０分以上と、２倍以上長く格段に優れている。その理由は、内層膜の一部を構成している縦長柱状結晶粒からなる皮膜Ｉの膜厚が２μｍ未満であると、内層膜の耐摩耗性が極端に低くなり、工具寿命が大きく低下するためである。そこで、本願発明の皮膜Ｉの膜厚を２μｍ以上とした。
本発明例１とほぼ同じ成膜条件、皮膜構成、膜厚が形成されているものの、皮膜Ｉの成膜に用いたガスの種類と成膜温度とが異なり、皮膜Ｉを形成する結晶粒が縦長柱状組織でない比較例２７の断続切削寿命は５００回と極端に短いのに対して、皮膜Ｉを形成する結晶粒が縦長柱状組織である本発明例１の断続切削寿命は１２００回と２倍以上長く格段に優れている。その理由は、内層膜の一部を構成している皮膜Ｉが縦長柱状結晶粒からなっていないと、内層膜の機械強度が極端に低下し、膜がチッピング又は破断しやすくなり、工具寿命が大きく低下するためである。そこで、本願発明の内層膜の一部を形成する皮膜Ｉを、少なくともチタンと窒素及び炭素を含有する縦長柱状結晶粒からなるとした。
From Table 2, the film thickness of the film I is 6 μm, the film thickness of the aluminum oxide is 3 μm, and the continuous cutting tool life of the comparative example 21 in which the bonding layer B is not formed is 50 minutes, whereas the film I In the present invention examples 1 to 10 in which the bonding layer B having needle-like protrusions is formed, the continuous cutting tool life is 130 minutes or longer, It is much better than 6 times longer. The reason for this is that if the α-type aluminum oxide film is formed after oxidizing the surface of the inner layer film without forming the bonding layer B, the bonding layer B having acicular protrusions on the surface of the inner layer film is not formed, Moreover, since the mechanical strength of the surface portion of the inner layer film has decreased, the adhesion strength between the inner layer film and the α-type aluminum oxide film has become extremely low.
Although the film I and the aluminum oxide having the same film thickness as the inventive example 1 are formed, the continuous cutting tool life of the comparative example 22 in which the BO / BT of the bonding layer B is as small as 0.003 is 50 minutes. Thus, the continuous cutting tool life of Inventive Example 2 in which BO / BT is 0.005 is 170 minutes, which is three times or more, which is remarkably excellent. Further, the continuous cutting tool life of Comparative Example 23 having a large BO / BT of 0.028 as the bonding layer B is 40 minutes, whereas the continuous cutting tool of Example 5 of the present invention in which BO / BT is 0.025. The service life is 160 minutes, which is 4 times longer and remarkably excellent. The reason is that when the BO / BT of the bonding layer B is less than 0.005, the number of protrusions formed on the surface of the bonding layer B is small, so the adhesion strength of the α-type aluminum oxide film is low, and the crystal grain size is If the amount exceeds 0.025, the number of protrusions formed on the surface of the bonding layer B decreases, the mechanical strength of the bonding layer B itself decreases, and the bonding layer B also breaks from the inside. This is because the adhesion strength of the α-type aluminum oxide film is greatly reduced as a result. Therefore, the BO / BT of the bonding layer B of the present invention is set to 0.005 to 0.025.
Although the film I and aluminum oxide having the same film thickness as Example 1 of the present invention are formed and the BO / BT of the bonding layer B is 0.015, (BN / BT) / (between the bonding layer B and the film I. Inventive example in which the ratio of (BN / BT) / (IN / IT) is 1.7 while the continuous cutting tool life of Comparative Example 24 having a small IN / IT) of 1.5 is 50 minutes. The continuous cutting tool life of No. 2 is 170 minutes, which is 3 times longer and remarkably excellent. In addition, the continuous cutting tool life of Comparative Example 25 having a large (BN / BT) / (IN / IT) of 2.7 is 30 minutes, whereas the (BN / BT) / (IN / IT) ratio is The continuous cutting tool life of Example 5 of the present invention, which is 2.5, is remarkably excellent at 160 minutes, which is 5 times longer. The reason is that when the ratio (BN / BT) / (IN / IT) is less than 1.7, the mechanical strength of the bonding layer B itself is lowered, the mechanical strength of the bonding layer B itself is lowered, and the bonding layer B This is because the adhesive strength of the α-type aluminum oxide film is lowered because it is easy to break from the inside and the number of needle-like protrusions formed on the surface of the bonding layer B is reduced. In addition, since the number of needle-like protrusions is reduced, the crystal grain size of the α-type aluminum oxide film is increased. On the other hand, when the ratio (BN / BT) / (IN / IT) exceeds 2.5, the number of needle-like protrusions formed on the surface of the bonding layer B decreases, and the adhesion strength of the α-type aluminum oxide film decreases. This is because the crystal grain size becomes large. Therefore, (BN / BT) / (IN / IT) of the present invention is set to 1.7 to 2.5.
Although substantially the same film was formed under substantially the same film formation conditions as Example 1 of the present invention, the film thickness of the film I was 1 μm, and the comparative cutting tool 26 of Comparative Example 26 had a continuous cutting tool life of 80 minutes, whereas the film The continuous cutting tool life of Invention Examples 1, 19, and 20 in which the film thickness of I is 2 μm or more is remarkably excellent as long as 180 minutes or more, which is twice or more. The reason is that when the film I of the longitudinally long columnar crystal grains constituting a part of the inner layer film has a film thickness of less than 2 μm, the wear resistance of the inner layer film becomes extremely low and the tool life is greatly reduced. Because. Therefore, the film thickness of the film I of the present invention is set to 2 μm or more.
Although almost the same film formation conditions, film configuration, and film thickness as Example 1 of the present invention were formed, the type of gas used for film formation of film I and the film formation temperature were different, and the crystal grains forming film I were The interrupted cutting life of Comparative Example 27, which is not a longitudinal columnar structure, is extremely short, 500 times, whereas the interrupted cutting life of Example 1 of the present invention in which the crystal grains forming the coating I are a longitudinal columnar structure is doubled to 1200 times. It is much better for a long time. The reason is that if the coating I constituting a part of the inner layer film is not composed of vertically long columnar crystal grains, the mechanical strength of the inner layer film is extremely lowered, the film is likely to be chipped or broken, and the tool life is shortened. This is because it greatly decreases. Therefore, the coating I forming a part of the inner layer film of the present invention is made of vertically long columnar crystal grains containing at least titanium, nitrogen and carbon.
本発明例内においても、本発明例１と同じ膜厚の皮膜Ｉと酸化アルミニウムが形成されており、結合層ＢのＢＯ／ＢＴが０．００５で（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．７である本発明例２の連続切削工具寿命が１７０分であるのに対して、ＢＯ／ＢＴが０．０１０で、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．９である本発明例３の連続切削工具寿命が２３０分と１．３倍以上長く更に優れている。また、ＢＯ／ＢＴ比が０．０２５で、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が２．５である本発明例５の連続切削工具寿命が１６０分であるのに対して、ＢＯ／ＢＴが０．０２０で、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が２．３である本発明例４の連続切削工具寿命が２２０分と１．３倍以上、長く更に優れている。そこで、本願発明は、結合層ＢのＢＯ／ＢＴが０．０１０〜０．０２０であり、且つ、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．９〜２．３であることが好ましい。その理由は、結合層ＢのＢＯ／ＢＴが０．０１０〜０．０２０であり、且つ、（ＢＮ／ＢＴ）／（ＩＮ／ＩＴ）が１．９〜２．３であることにより、結合層Ｂの、α型酸化アルミニウム膜側の表面に、針状突起がより多く形成されα型酸化アルミニウム膜の密着強度がより高くなるとともに、結合層Ｂ自体の機械強度もより高くなり、結合層Ｂ内部から更に破断し難くなり、内層膜〜α型酸化アルミニウム膜間の密着強度がより強くなり、より工具寿命の長い、更に優れたα型酸化アルミニウム被覆工具が得られるためである。 Also in the example of the present invention, the film I and aluminum oxide having the same film thickness as in Example 1 of the present invention are formed, and the BO / BT of the bonding layer B is 0.005 (BN / BT) / (IN / IT) The continuous cutting tool life of Inventive Example 2 in which the value is 1.7 is 170 minutes, while BO / BT is 0.010 and (BN / BT) / (IN / IT) is 1.9. The continuous cutting tool life of a certain example 3 of the present invention is 230 minutes, which is 1.3 times longer and further superior. In addition, while the BO / BT ratio is 0.025 and (BN / BT) / (IN / IT) is 2.5, the continuous cutting tool life of Example 5 of the present invention is 160 minutes, while BO / BT The continuous cutting tool life of Inventive Example 4 having BT of 0.020 and (BN / BT) / (IN / IT) of 2.3 is 220 minutes and 1.3 times or longer, which is further excellent. Therefore, in the present invention, BO / BT of the bonding layer B is preferably 0.010 to 0.020, and (BN / BT) / (IN / IT) is preferably 1.9 to 2.3. . The reason is that the BO / BT of the bonding layer B is 0.010 to 0.020 and (BN / BT) / (IN / IT) is 1.9 to 2.3. More acicular protrusions are formed on the surface of B on the α-type aluminum oxide film side, the adhesion strength of the α-type aluminum oxide film becomes higher, and the mechanical strength of the bonding layer B itself becomes higher, so that the bonding layer B This is because the inner layer film and the α-type aluminum oxide film become more difficult to break from the inside, the adhesion strength between the inner layer film and the α-type aluminum oxide film becomes stronger, and a further excellent α-type aluminum oxide-coated tool with a longer tool life can be obtained.
次に、結合層Ｂの塩素量が異なる本発明例６と本発明例１とを比較する。結合層Ｂの塩素量が０．４質量％と多い本発明例６の連続切削工具寿命が１５０分であるのに対して、結合層Ｂの塩素量が０．２質量％と少ない本発明例１の連続切削工具寿命は２４０分と、１．６倍以上長く、更に優れていた。そこで、本願発明は、結合層Ｂの塩素量が０．２質量％以下であることが好ましい。その理由は、層中の塩素量が０．２質量％を超えて多くなると結合層Ｂの硬度が低くなるとともに、結合層Ｂ表面に形成される針状突起数が少なくなるため、内層膜〜α型酸化アルミニウム膜間の密着強度が低くなるためである。 Next, Invention Example 6 and Invention Example 1 in which the amount of chlorine in the bonding layer B is different will be compared. While the continuous cutting tool life of the present invention example 6 having a large chlorine content of 0.4% by mass in the bonding layer B is 150 minutes, the present invention example having a low chlorine content of 0.2% by mass in the bonding layer B The continuous cutting tool life of No. 1 was 240 minutes, which was 1.6 times longer and was further excellent. Therefore, in the present invention, the chlorine content of the bonding layer B is preferably 0.2% by mass or less. The reason for this is that if the amount of chlorine in the layer exceeds 0.2% by mass, the hardness of the bonding layer B decreases, and the number of needle-like protrusions formed on the surface of the bonding layer B decreases. This is because the adhesion strength between the α-type aluminum oxide films is lowered.
皮膜Ｉに含有されているチタン量ＩＴ、窒素量ＩＮ、炭素量ＩＣ、及び、酸素量ＩＯ、が異なっている本発明例１、及び、７〜９内を比較する。皮膜ＩのＩＮ／ＩＴが０．０３９、ＩＣ／ＩＴが０．１８１、ＩＯ／ＩＴが０．０４０である本発明例７の連続切削工具寿命が１３０分であるのに対して、ＩＮ／ＩＴが０．０４０、ＩＣ／ＩＴが０．１８０、ＩＯ／ＩＴが０．０２０である本発明例８の連続切削工具寿命は２２０分と、１．６倍以上長く、更に優れている。また、ＩＮ／ＩＴが０．１１１、ＩＣ／ＩＴが０．１４４、ＩＯ／ＩＴが０．００１である本発明例１０の連続切削工具寿命が１４０分であるのに対して、ＩＮ／ＩＴが０．１１０、ＩＣ／ＩＴが０．１４５、ＩＯ／ＩＴが０．０１０である本発明例９の連続切削工具寿命は１４０分と、１．６倍以上長く、更に優れている。そこで、本願発明は、皮膜ＩのＩＮ／ＩＴが０．０４０〜０．１１０、ＩＣ／ＩＴが０．１４５〜０．１８０であり、ＩＯ／ＩＴが０．０２以下であることが好ましい。その理由は、皮膜ＩのＩＮ／ＩＴが０．０４０〜０．１１０、ＩＣ／ＩＴが０．１４５〜０．１８０であり、ＩＯ／ＩＴが０．０２以下であることにより、硬度と耐摩耗性、及び、機械強度がバランス良く優れている皮膜Ｉが得られ、より工具寿命の長い酸化アルミニウム被覆工具が得られるためである。皮膜ＩのＩＮ／ＩＴが０．０４０未満、ＩＣ／ＩＴとＩＯ／ＩＴとがそれぞれ０．１８０と０．０２を超えて多くなると、本発明例７のように皮膜Ｉの機械強度が低下する傾向が現れ、ＩＮ／ＩＴが０．１１０を超えて多く、ＩＣ／ＩＴが０．１４５未満になると、本発明例１０のように皮膜Ｉの硬度と耐摩耗性とが低下する傾向が現れる。 The present invention example 1 in which the amount of titanium IT, the amount of nitrogen IN, the amount of carbon IC, and the amount of oxygen IO contained in the coating I are different will be compared. The continuous cutting tool life of the present invention example 7 in which IN / IT of coating I is 0.039, IC / IT is 0.181, and IO / IT is 0.040 is 130 minutes, whereas IN / IT 0.040, IC / IT is 0.180, and IO / IT is 0.020. The continuous cutting tool life of Invention Example 8 is 220 minutes, which is 1.6 times or longer, which is even better. In addition, the continuous cutting tool life of Inventive Example 10 with IN / IT of 0.111, IC / IT of 0.144, and IO / IT of 0.001 is 140 minutes, whereas IN / IT is The continuous cutting tool life of Invention Example 9 having 0.110, IC / IT of 0.145, and IO / IT of 0.010 is 140 minutes, which is 1.6 times longer, which is further excellent. Therefore, in the present invention, it is preferable that IN / IT of the film I is 0.040 to 0.110, IC / IT is 0.145 to 0.180, and IO / IT is 0.02 or less. The reason is that the coating I has an IN / IT of 0.040 to 0.110, an IC / IT of 0.145 to 0.180, and an IO / IT of 0.02 or less. This is because the coating I having a good balance between mechanical properties and mechanical strength can be obtained, and an aluminum oxide-coated tool having a longer tool life can be obtained. When IN / IT of film I is less than 0.040 and IC / IT and IO / IT exceed 0.180 and 0.02, respectively, the mechanical strength of film I decreases as in Example 7 of the present invention. When a tendency appears and IN / IT exceeds 0.110 and IC / IT is less than 0.145, the hardness and wear resistance of the coating I tend to decrease as in Example 10 of the present invention.
α型酸化アルミニウムの膜厚と、同膜表面の平均結晶粒径が異なっている本発明例１１〜１８内を比較する。α型酸化アルミニウムの膜厚がともに２．５μｍであるものの、同膜表面の平均結晶粒径が１．０μｍである本発明例１３の連続切削工具寿命が１２０分であるのに対して、同膜表面の平均結晶粒径が０．８μｍと小さい本発明例１２の連続切削工具寿命は１９０分と、１．６倍長く、更に優れている。そこで、本願発明は、α型酸化アルミニウムの膜厚が２．５μｍ以下の時は、同膜表面の平均結晶粒径が０．８μｍ以下であることが好ましい。同膜厚がともに４．５μｍであるものの、平均結晶粒径が１．７μｍである本発明例１５の連続切削工具寿命が２２０分であるのに対して、平均結晶粒径が１．５μｍと小さい本発明例１４の連続切削工具寿命は３５０分と、１．６倍長く、更に優れている。そこで、本願発明は、α型酸化アルミニウムの膜厚が２．５μｍを超えて４．５μｍ以下の時は、同膜表面の平均結晶粒径が１．５μｍ以下であることが好ましい。同膜厚がともに５μｍであるものの、平均結晶粒径が２．７μｍである本発明例１７の連続切削工具寿命が２４０分であるのに対して、平均結晶粒径が１．７μｍと小さい本発明例１６の連続切削工具寿命は３８０分と、１．６倍長く、更に優れている。そこで、本願発明は、α型酸化アルミニウムの膜厚が４．５μｍを超えて大きい時は、同膜表面の平均結晶粒径が２．５μｍ以下であることが好ましい。
そこで、本願発明は、α型酸化アルミニウム膜の膜厚をＡμｍ、同膜表面の平均結晶粒径をＤμｍとしたとき、Ａ≦２．５μｍの時はＤ≦０．８μｍ、２．５＜Ａ≦４．５μｍの時はＤ≦１．５μｍ、Ａ＞４．５μｍの時はＤ≦２．５μｍであることが好ましい。これは、α型酸化アルミニウム膜の各膜厚Ａに対して、同膜表面の平均結晶粒径Ｄがより微細であることにより、α型酸化アルミニウム膜の機械強度が高まり耐クラック性が高まると共に、膜表面がより平滑になることにより摺動性が高まり、更に切削抵抗が小さくなるため、より工具寿命が長くなるためである。
The present invention examples 11 to 18 in which the film thickness of the α-type aluminum oxide and the average crystal grain size on the film surface are different will be compared. Although the α-type aluminum oxide film thickness is both 2.5 μm, the continuous cutting tool life of Inventive Example 13 in which the average crystal grain size on the film surface is 1.0 μm is 120 minutes, whereas The continuous cutting tool life of Inventive Example 12 having a small average crystal grain size of 0.8 μm on the film surface is 190 minutes, 1.6 times longer, and is further excellent. Therefore, in the present invention, when the film thickness of the α-type aluminum oxide is 2.5 μm or less, the average crystal grain size on the surface of the film is preferably 0.8 μm or less. Although the same film thickness is 4.5 μm, the continuous cutting tool life of Inventive Example 15 having an average crystal grain size of 1.7 μm is 220 minutes, whereas the average crystal grain size is 1.5 μm. The small continuous cutting tool life of Example 14 is 350 minutes, which is 1.6 times longer, and is even better. Therefore, in the present invention, when the film thickness of the α-type aluminum oxide exceeds 2.5 μm and is 4.5 μm or less, the average crystal grain size on the surface of the film is preferably 1.5 μm or less. Although the same film thickness is 5 μm, the continuous cutting tool life of the inventive example 17 having an average crystal grain size of 2.7 μm is 240 minutes, whereas the average crystal grain size is as small as 1.7 μm. The continuous cutting tool life of Invention Example 16 is 380 minutes, which is 1.6 times longer, and is further excellent. Therefore, in the present invention, when the film thickness of the α-type aluminum oxide is larger than 4.5 μm, the average crystal grain size on the surface of the film is preferably 2.5 μm or less.
Therefore, in the present invention, when the film thickness of the α-type aluminum oxide film is A μm and the average crystal grain size of the film surface is D μm, when A ≦ 2.5 μm, D ≦ 0.8 μm, 2.5 <A It is preferable that D ≦ 1.5 μm when ≦ 4.5 μm, and D ≦ 2.5 μm when A> 4.5 μm. This is because, with respect to each film thickness A of the α-type aluminum oxide film, the average crystal grain size D on the surface of the film is finer, so that the mechanical strength of the α-type aluminum oxide film increases and crack resistance increases. This is because the smoothness of the film surface increases the slidability and further reduces the cutting resistance, thereby further extending the tool life.
Claims (4)
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