CN100448600C - Pvc涂层刀具 - Google Patents
Pvc涂层刀具 Download PDFInfo
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- CN100448600C CN100448600C CNB031476783A CN03147678A CN100448600C CN 100448600 C CN100448600 C CN 100448600C CN B031476783 A CNB031476783 A CN B031476783A CN 03147678 A CN03147678 A CN 03147678A CN 100448600 C CN100448600 C CN 100448600C
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- 238000000576 coating method Methods 0.000 claims abstract description 36
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000002441 X-ray diffraction Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 239000011195 cermet Substances 0.000 claims description 5
- 230000005855 radiation Effects 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 abstract description 21
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 5
- 239000010935 stainless steel Substances 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 238000003801 milling Methods 0.000 abstract description 3
- 229910000760 Hardened steel Inorganic materials 0.000 abstract 1
- 238000003754 machining Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 56
- 239000010936 titanium Substances 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 13
- 239000001301 oxygen Substances 0.000 description 13
- 238000000151 deposition Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000003746 surface roughness Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 2
- 229910000997 High-speed steel Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910010038 TiAl Inorganic materials 0.000 description 2
- 229910010037 TiAlN Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 208000034189 Sclerosis Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 208000018875 hypoxemia Diseases 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000009304 pastoral farming Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000427 thin-film deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种刀具，由基底和含有至少一个具有X射线衍射图案的层的涂层构成。所述图案具有晶体结构和非晶态结构。所述层优选由(Ti，Al)(O，N)构成。该刀具特别适合于加工钢、硬化钢或不锈钢。优选是不锈钢的铣削。
Description
技术领域
本发明涉及一种通过排屑进行机加工的刀具，该刀具包括由硬质合金、金属陶瓷、陶瓷、基于立方氮化硼的材料或高速钢构成的基底和硬质耐磨耐火涂层。该涂层由一层或多层耐火化合物构成，其中至少一层包括含有由非晶态和结晶相构成的混合物的致密层，尤其是(Ti，AL)(O，N)层。
背景技术
US4474849披露了一种韧性和耐磨性优异的涂层硬质合金，它包括由硬质合金构成的基底和位于其上的至少一层，这些层中的至少一层由非晶态氧化铝构成。
US5330853披露了一种具有交替的第一和第二三元层的涂层表面，其中第一层TiAlNX其氮含量更高，并且明显比第二层TiAlNY薄。采用TiAl靶溅射来沉积这些层。
US5549975披露了由涂有(Ti，Me)N耐磨层的金属陶瓷本体构成的涂层刀具，其中Me至少是一种在700℃以上的温度下形成稳定氧化物的金属。该沉积工艺是蒸发和溅射的组合。
US5503912披露了一种由多层超薄层形成的涂层，这些超薄层包含由选自元素周期表中的IVa、Va和VIa系中的至少一种元素以及Al和B形成的至少一种氮化物或碳氮化物。整个化合物具有立方晶体X-射线衍射图案，但是其中一层在正常温度和正常压力下并且在均衡状态下具有立方晶体结构之外的晶体结构。该涂层实际上是TiN和AlN的层压体，并且每一层其厚度为0.2-50nm。
US5879823披露了一种涂层刀具，其最里面的层由IVB系金属-铝合金构成，并且其第二层是由通过物理气相沉积涂覆的氧化铝。
US6254984披露了一种多层涂层，它由多层第一层和多层第二层交替层叠构成的，第一层由元素周期表中的组4a、5a和6a的元素和AL的碳化物、氮化物和碳氮化物中的至少一种构成，而第二层由元素周期表中的组4a、5a和6a的元素和Al的氧化物、羰基化物、氮氧化物和碳氧氮化物中的至少一种构成。与第二层相邻的第一层在晶体取向中是连续的。在该说明书中还沉积有一层外部非晶态层以便提高抗氧化性。
US6071560披露了一种包含至少一层MeX的耐磨涂层，其中Me包含钛和铝，而X为氮或碳。在MeX层中，用X射线衍射法测量出的织构优选为(200)。
R.Luthier和F.Levy在J.Vac.Sci.Technol.，A9(1)(1991)102上报道了通过用由TiN-Al2O3构成的金属陶瓷靶中进行rf磁控管溅射已经形成TiAlON层。他们获得了一种由(Ti，Al)Nx和非晶(Ti，Al)O2构成的混合结构。由那些层所获得的XRD图案由源于结晶相的峰值与非晶态峰值构成。
K.Kawata、H.Sugimura和O.Takai在Thin Solid Films 390(2001)64上报道了已经采用等离子增强化学气相沉积(PAVAD)形成不同的Ti-Al-O-C-N层。
几个作者已经报道了在氧化作用之后的步骤期间或在高温下使用期间在(Ti，Al)N的顶部上会自然形成晶态或非晶态层，参见例如Münz等人，J.Vac.Sci.Technol.4(6)(1996)2717-2727。
发明内容
本发明的一个目的在于改善从现有技术中已知的几个性能，例如抗氧化性、表面韧性、层韧性和耐磨性。
现在已经发现，设有由一层或几层构成的涂层的涂层刀具与现有技术涂层相比其耐磨性和韧性得到改善，其中一层或至少一层具有与非晶体结构结合的晶体结构。
为实现上述目的，本发明提供一种刀具嵌入件，由基底和含有至少一个具有X射线衍射图案的层的涂层构成，所述图案具有窄峰值且高度为P的最高峰值的晶体结构以及宽峰值且高度为H的非晶态结构，其中H＞3B，P＞5B，0.75＜P/H＜3，其中B为Chebychev背景辐射，且此层的总厚度为0.3μm-20μm，其特征在于所述层由(Ti，Al)(O，N)构成，该构成使得在(TiXAl1-X)(OY，N1-Y)层中，0.20＜X＜0.70，0.15＜Y＜0.35。
附图说明
图1显示出从本发明的层中得出的X射线衍射图案，其中：
A-SPVII拟合曲线[1，2]
H-非晶态峰值的高度
P-涂层的最高晶态峰值的高度
B-背景水平面
图2显示出从本发明的试样中得出的断裂横断面的SEM显微照片；
图3显示出从具有不同氧含量的层中得到的θ-2θX射线衍射扫描曲线20°＜2θ＜90°。
具体实施方式
因此，本发明涉及一种由一涂层和一基底构成的刀具。该基底由硬质合金、金属陶瓷、高速钢或立方氮化硼构成。涂层由一层或几层构成，其中至少一层由与非晶态结构结合的晶体结构构成。所述层其厚度为0.3-20μm，优选为0.3-10μm。总涂层厚度为0.5-20μm。
参见图3，使用Cu Kα辐射
针对背景水平面B、非晶态峰值的高度H以及晶体结构的最高峰值的高度将该层的结构量化。采用SPVII曲线拟合算法[1，2]来提取非晶态峰值和晶态峰值的数据。
在20°＜2θ＜60°之间计算Chebychev背景辐射[1，2]B。
根据本发明，H＞3B，P＞5B并且0.75＜P/H＜3。
优选的是，所述层是具有与一种非晶态结构结合的晶体(Ti，Al)N-奥氏博尼特(NaCl)结构的(Ti，Al)(N，O)层。
在4°＜FWHM＜7°的情况下通过在20°＜2θ＜48°之间的宽峰值来识别该非晶态结构。该非晶态结构导致在30°＜2θ＜40°优选32°＜2θ＜38°处的布拉格反射，这与
-之间的原子距离相对应，并且最大H对准在
的原子距离处。
在使用Cu-Kα辐射进行的θ-2θ扫描中通过来自(111)-、(200)-和(200)面的反射识别出(Ti，Al)N的晶体NaCl结构，这些晶面分别与位置2θ＝37.5°、43.5°和63.5°相对应。
根据本发明的层可以直接沉积在基底上或沉积在现有技术中已知的一层或多层中间层上。同样还可以将其它层沉积在所述层的顶部上。
(Ti，Al)(O，N)层在它是单层时其特征还在于，具有一光滑表面，该表面具有少量小尺寸液滴并且用触针方法在2.5mm的长度上测量出的表面粗糙度Ra＜0.2μm。
(TixAl1-x)(Oy，N1-y)层的成分为采用量化EDX测量方法在以10kV的ZAF校正和25mm的工作距离的情况下为0.20＜x＜0.70并且0.15＜y＜0.35，优选为0.25＜x＜0.55并且0.20＜y＜0.30。
在由N2、O2和Ar构成的反应氛围中通过金属TiAl靶的电弧蒸发来沉积该层，在沉积期间的条件为，RMe＝Ti％at(Ti％at+Al％at)比为0.2＜RMe＜0.70，所采用的蒸发器电流IEVAP设定为6×100A，并且比例R气体＝O2/(N2+O2)设定为0.05＜R＜0.15，并且总压力P设定为1.0＜P＜10Pa。所施加的偏压U偏压为30＜U偏压＜-600V。
正确的工艺参数取决于所采用的涂布设备的设计。本领域普通技术人员能够确定已经获得所需要的结构，并且根据当前说明书来改进沉积条件。
根据本发明的涂层刀具尤其用于对钢、硬化钢或不锈钢进行机加工，优选对不锈钢进行铣削。
实施例1
在用于进行薄膜沉积的市售电弧蒸发沉积系统中沉积(Ti，Al)(O，N)层。
采用其成分为6wt％Co和94wt％WC的镜面抛光硬质合金基底来进行分析。用于切削试验的嵌入件在同一批中进行涂覆。
在沉积之前，在碱溶液的超声波浴中、在去离子水中并且在酒精中清洗这些基底。将基底安装在转动支架上。在阴极和基底之间的最小间距大约为100mm。
在实际涂布过程之前通过红外加热器对这些基底加热20分钟。
在变化的气体混合物R气体＝O2/(N2+O2)下进行随后的(Ti，Al)(O，N)沉积，其中R气体＝0、0.026、0.079、0.18和0.24。将蒸发器电流设定为6×100A，基底偏压为-120V并且总压力为2.0Pa。在涂布过程中用两个红外高温计测量出的温度为520℃。
所得到的涂层厚度为4.0μm。
基底电流密度为1.2mA/cm2。
XRD分析表明，所有薄膜具有立方奥氏博尼特结构。对于在涂布过程中具有低含量氧的层而言，也发现来自非晶态结构的宽峰值。采用EDX测量方法，对于和层中所测量的为10％at和22％at的氧含量分别对应的比例φO2/(φN2+φO2)＝0.079和0.18来说，该非晶态结构最为显著。
对于用低氧含量沉积的层，φO2/(φN2+φO2)＝0和0.026，分别导致涂层中氧含量为2％at和10％at，断面截面的SEM研究显示了柱状结构。随着图2中氧含量提高，该结构消失。非晶态峰值的强度H/B列在下表中。
通过纳米压痕来测量硬度和杨氏模量。结果列在下表中。随着层中氧含量的提高，硬度和杨氏模量下降，因此通过在过程中加入氧可以改善韧性。
利用reve测试来测量附着力和韧性。采用金刚石触针，负载范围是10-100N。所有的层都显示出良好的附着力(＞60N)，具有高氧含量的层比具有低氧量的层脆性较少。Reve测试显示本发明的层与没有氧而生长的层相比其韧性大大增强。
采用表面粗糙度仪器，利用触针表面光度仪来测量表面粗糙度Ra。利用AFM(原子力显微镜)对未涂布的基底的表面粗糙度进行测量，其Ra＜5nm，这不会影响层粗糙度参数的测量结果。很明显，当氧含量增加时，表面粗糙度下降，如表1所示。当层有氧和没有氧相比较时，表面粗糙度的差异明显。
表1(Ti，Al)(O，N)层的氧含量和性能
| 标号 | φO<sub>2</sub>/(φN<sub>2</sub>+φO<sub>2</sub>) | H[GPa] | E[GPa] | Ra[μm] | H/B | P/B | 结构 |
| 1a | 0 | 34.7 | 600 | 0.26 | 1.9 | 12.1 | 柱状 |
| 1b | 0.026 | 28.8 | 420 | 0.16 | 1.5 | 29.9 | 柱状 |
| 1c | 0.079 | 31.1 | 440 | 0.15 | 5.8 | 6.5 | 微细颗粒＜0.1μm |
| 1d | 0.18 | N/A | N/A | 0.12 | 4.7 | 20.2 | 微细颗粒＜0.1μm |
| 1e | 0.24 | N/A | N/A | 0.09 | 2.9 | 38.2 | 微细颗粒＜0.1μm |
实施例2
将与实施例1所用的同样类型的嵌入件用柱状结构的(Ti，Al)N-层以及(Ti，Al)(O，N)构成的非晶态和结晶结构的混合层构成的双层进行涂布。
按照与实施例1同样的方式对嵌入件在涂布之前进行预处理。在N2气氛下，在2.0Pa压力下进行涂布，从六个阴极蒸发TiAl。基底偏压为-120V，蒸发电流设定在6×100A。沉积温度是520℃。该层的厚度是2.0μm。
涂层的第二层与实施例1的1c相同。
涂层的总体厚度是4.0μm。
通过切线入射(gracing incidence)XRD扫描可以区分双层涂层和单层涂层。本领域的技术人员可以为这种分析设定参数。
此处该涂层称之为2a。
实施例3
在钢(SS1672，AISI-1042，DIN-CK45)的车削操作中使用具有不同涂层的并且其组成为6％wtCo、0.5％wtTaC和93.5％wtWC的硬质合金刀具嵌入件。
涂层：
将实施例1和实施例2中描述的涂层，以及现有技术中已知的两种涂层，也就是TiN和(Ti，Al)N涂层进行比较。
切削数据：
嵌入件几何形状SNUN120408
切削速度250m/分钟
切削深度1.5mm
进刀0.35mm
结果(刀具寿命)
| 1a | 20分钟 | 本发明范围之外 |
| 1b | 28分钟 | 本发明范围之外 |
| 1c | 32分钟 | 本发明 |
| 1d | 16分钟 | 本发明范围之外 |
| 1e | 10分钟 | 本发明范围之外 |
| 2a | 22分钟 | 本发明 |
| TiN | 12分钟 | 现有技术 |
| (Ti，Al)N | 18分钟 | 现有技术 |
实施例4
在不锈钢(SS2343，AISI-316，DIN-X5CrNiMo 17133)的方台肩铣削加工中，使用带有如实施例1和实施例2所述的不同涂层的并且其组成为13％wtCo和87％wtWC的硬质合金切削嵌入件。
切削数据
嵌入件几何形状XOMX090308TR-ME06
切削速度260m/分钟
切削深度3.0mm
进刀0.23mm
切削宽度5mm
刀具寿命标准是由制成的刀刃产生的切屑引起的切削刃的破坏。试验结果显示，具有实施例2所述的双层涂层的嵌入件与带有其它涂层的同样基底相比具有更长的刀具寿命。
以分钟计的结果(刀具寿命)
| 1a | 14 | 本发明范围之外 |
| 1b | 12 | 本发明范围之外 |
| 1c | 12 | 本发明 |
| 1d | 8 | 本发明范围之外 |
| 1e | 6 | 本发明范围之外 |
| 2a | 16 | 本发明 |
| TiN | 8 | 现有技术 |
| (Ti，Al)N | 14 | 现有技术 |
实施例5
在钢(SS1672，AISI-1042，DIN-CK45)的无底钻孔加工中，使用带有如实施例1和实施例2所述的不同涂层的并且其组成为10％wtCo和90％wtWC的硬质合金钻头。
切削数据
钻头类型SD25-6，0-32-6R5
切削速度80m/分钟
切削深度24mm
进刀0.16mm
以孔的数量计的结果(刀具寿命)
| 1a | 1000 | 本发明范围之外 |
| 1b | 1200 | 本发明范围之外 |
| 1c | 1600 | 本发明 |
| 1d | 600 | 本发明范围之外 |
| 1e | 200 | 本发明范围之外 |
| 2a | 1000 | 本发明 |
参考
[1]Bruker AXS(2000)
Topas V2.0：General profile and structure analysis software forpowder diffraction data.(用于粉末衍射数据的通用轮廓和结构分析软件)
-使用者手册，Bruker AXS，Karlsruhe，德国
[2]Cheary，R.W.，Coelho，A.A.(1992)
A fundamental parameters approach to x-ray line profile fitting(X射线线剖面装配的基本参数方法)
-J.Appl.Cryst.，25，109-121
Claims (6)
1.一种刀具嵌入件，由基底和含有至少一个具有X射线衍射图案的层的涂层构成，所述图案具有窄峰值且高度为P的最高峰值的晶体结构以及宽峰值且高度为H的非晶态结构，其中H＞3B，P＞5B，0.75＜P/H＜3，其中B为Chebychev背景辐射，且此层的总厚度为0.3μm-20μm，其特征在于所述层由(Ti，Al)(O，N)构成，该构成使得在(TiXAl1-X)(OY，N1-Y)层中，0.20＜X＜0.70，0.15＜Y＜0.35。
2.如权利要求1所述的刀具嵌入件，其特征在于：所述晶体结构是立方体。
3.如权利要求1所述的刀具嵌入件，其特征在于：所述晶体结构是奥氏博尼特结构。
4.如前述任一权利要求所述的刀具嵌入件，其特征在于：所述层是涂层的最外层。
5.如权利要求1-3中任一项所述的刀具嵌入件，其特征在于：所述基底是硬质合金或陶瓷。
6.如权利要求5所述的刀具嵌入件，其特征在于：所述陶瓷是金属陶瓷或立方氮化硼。
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| EP0908917B1 (en) * | 1997-10-10 | 2005-04-20 | Burle Technologies, Inc. | Secondary emission coating for photomultiplier tubes |
| JP3031907B2 (ja) * | 1998-03-16 | 2000-04-10 | 日立ツール株式会社 | 多層膜被覆部材 |
| DE69901985T2 (de) * | 1998-07-29 | 2002-12-05 | Toshiba Tungaloy Co. Ltd., Kawasaki | Aluminiumoxid-beschichteter Werkzeugteil |
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2002
- 2002-07-16 SE SE0202230A patent/SE526337C2/sv not_active IP Right Cessation
-
2003
- 2003-07-01 EP EP03014921A patent/EP1400293A3/en not_active Withdrawn
- 2003-07-02 US US10/610,650 patent/US20040076857A1/en not_active Abandoned
- 2003-07-10 JP JP2003195122A patent/JP2004050403A/ja active Pending
- 2003-07-16 CN CNB031476783A patent/CN100448600C/zh not_active Expired - Fee Related
- 2003-07-16 KR KR1020030048807A patent/KR20040010234A/ko not_active Application Discontinuation
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| US4997538A (en) * | 1988-06-24 | 1991-03-05 | Asulab S.A. | Process for depositing a black-colored coating on a substrate and a black-colored coating obtained using this process |
| EP0709353A2 (en) * | 1994-10-27 | 1996-05-01 | Sumitomo Electric Industries, Limited | Hard composite material for tools |
| CN1362309A (zh) * | 2000-12-28 | 2002-08-07 | 株式会社神户制钢所 | 切削工具用硬质被膜、硬质被膜覆盖的切削工具、硬质被膜的制造方法及硬质被膜形成用靶 |
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| Characterization of multilayer films of Ti-Al-O-C-N systemprepared by pulsed d.c. plasma-enhanced chemical vapordeposition. Kazuki Kawata et al.Thin Solid Films,Vol.390 No.1-2. 2001 |
| Characterization of multilayer films of Ti-Al-O-C-N systemprepared by pulsed d.c. plasma-enhanced chemical vapordeposition. Kazuki Kawata et al.Thin Solid Films,Vol.390 No.1-2. 2001 * |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20040010234A (ko) | 2004-01-31 |
| SE526337C2 (sv) | 2005-08-23 |
| US20040076857A1 (en) | 2004-04-22 |
| SE0202230L (sv) | 2004-01-17 |
| CN1481971A (zh) | 2004-03-17 |
| SE0202230D0 (sv) | 2002-07-16 |
| EP1400293A2 (en) | 2004-03-24 |
| EP1400293A3 (en) | 2006-04-12 |
| JP2004050403A (ja) | 2004-02-19 |
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