CN1061702C - 具有氧化物涂层的切削刀具 - Google Patents

具有氧化物涂层的切削刀具 Download PDF

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CN1061702C
CN1061702C CN95191221A CN95191221A CN1061702C CN 1061702 C CN1061702 C CN 1061702C CN 95191221 A CN95191221 A CN 95191221A CN 95191221 A CN95191221 A CN 95191221A CN 1061702 C CN1061702 C CN 1061702C
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B·朗伯格
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C30/00Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/02Pretreatment of the material to be coated
    • C23C16/0272Deposition of sub-layers, e.g. to promote the adhesion of the main coating
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/403Oxides of aluminium, magnesium or beryllium
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T407/00Cutters, for shaping
    • Y10T407/27Cutters, for shaping comprising tool of specific chemical composition

Abstract

本发明提供一种具有难熔的单或多层涂层的基体,其中,特殊层的特征在于受控的显微组织和相态组成,对涂覆过的基体表面来说具有在择优方向中优选生长的结晶面族。所述涂层包括一层或几层难熔的层,其中至少一层是在(104)方向具有α-Al2O3优选织构的致密的细晶粒层。本发明具有涂层的刀具显示出优良的表面精加工,当用于加工钢,铸铁,尤其是加工球墨铸铁时,与先有技术相比,大大地改进了耐磨损和韧性等特性。

Description

具有氧化物涂层的切削刀具
本发明涉及一种用于切削成形机械加工的具有涂层的切削刀具。
关于在切削刀具上的氧化铝的化学汽相淀积法(CVD)已有超过15年的工业实践。Al2O3及其它难熔材料的磨损性能已在文献中广泛地讨论过。
CVD技术也已用于生产其它金属氧化物、碳化物和氮化物的涂层,这些金属选自元素周期表中第ⅣB、ⅤB和ⅥB族的过渡金属。其中许多成分被发现作为耐磨损或保护性涂层的实际应用,但没有几种能象TiC、TiN和Al2O3那样极为注目地被公认。
具有各种类型Al2O3涂层,例如纯κ-Al2O3、κ-和α-Al2O3的混合物以及极粗粒化的α-Al2O3涂层的硬质合金切削刀具已以工业规模生产许多年。Al2O3以各种不同相态:α、κ、γ、β、θ等结晶。在耐磨损Al2O3-涂层的CVD中最经常发生的二种相态是热力学稳定的、六角形的α-相和亚稳的k-相。一般说来,κ-相是细粒化的,其粒度范围为0.5~2.0μm并常常显示出柱状涂敷形态。而且,κ-Al2O3涂层没有结晶缺陷并没有微孔或气孔。
α-Al2O3晶粒通常较粗大,根据沉积条件其粒径在1~6μm范围内。在这种情况下,多孔性和结晶缺陷更为常见。
在淀积到切削刀具上的CVD氧化铝涂层中常常存在α-和κ-相这两相。在工业规模生产的切削刀具中,总是将Al2O3涂敷在碳化物或陶瓷基质的TiC涂层上(参看如美国专利NO.3,837,896,新版美国专利No.29,420),因此TiC-表面和氧化铝涂层之间的界面化学反应尤其重要。由于这个原因,TiC层也应理解为包括具有化学结构式为TiCxNyOz的层,式中TiC中的碳完全或部分地被氧和/或氮取代。
例如在美国专利新版本No.29,420和美国专利NOS,4,399,168;4,018,631;4,490,191和4,463,033中证明了用氧化物涂敷硬质合金切削工刀的实践可进一步提高它的耐磨损性其本身是众所周知的。这些专利文献公开了氧化物涂敷体和例如硬质合金的TiC涂层进行怎样不同的预处理,则会增强随后淀积的氧化物层的粘附性。在美国专利No.3,736,107;5,071,696和5,137,774中进一步公开了氧化铝涂敷体,其中Al2O3层包括α,κ有关的α+κ组合物。
美国专利4,619,866叙述了一种在CVD淀积温度为1000~1050℃、浓度范围为0.01~0.2%时掺杂物例如硫化氢(H2S)的影响下,通过利用金属卤化物的水解反应生产快速生长的Al2O3层的方法。
在这些工艺条件下,主要产生Al2O3的两种相态,α-和κ相。结果生成的涂层由较小的κ-晶粒和较大的α-晶粒的混合物组成。这种工艺流程得到的涂层围绕涂敷体具有均匀的层厚分布。
瑞典专利申请9101953-9公开了一种使细粒的κ-氧化铝涂层生长的方法。
瑞典专利申请No.920 3852-0公开了一种获得一种细粒化的、(012)-织构的α-Al2O3涂层的方法。业已发现这种特殊的Al2O3涂层涂敷在硬质合金刀具上用于铸铁的机械加工尤其有效。
瑞典专利申请No.930 4283-6公开了一种具有涂层的基体,该涂层包括一层或多层难熔层,其中至少一层是在(110)方向上具有α-Al2O3织构的层。氧化铝层基本上没有涂却裂纹并包含长度为2-8μm和长/宽比为1-10的层状晶粒。
因此,本发明的一个目的是在硬基质或最好是在上述TiCxNyOz涂层上至少提供一层多晶型物α的单相Al2O3层,α相在使用适宜的成核和生长条件下具有理想的显微结构和结晶学织构,以致Al2O3层的所述特性被稳定化。
本发明的另一目的是提供一种在钢、不锈钢、铸铁和球墨铸铁的机加工中具有改进了切削性能的氧化铝涂层的切削工具刀片。
图1示出本发明典型的Al2O3涂层放大1000倍时扫描式电子显微镜(SEM)的顶视显微照相。
按照本发明提供一种切削刀具,它包括在其上淀积着耐磨损涂层的硬质合金基体。该涂层包括一层或几层难熔层,其中至少一层是致密的、细晶粒的和优选织构的多晶型物α的Al2O3层。
本发明的具有涂层的切削刀具,当用于机械加工钢或铸铁时尤其是如果表面用湿式喷砂法进一步被精加工整平过时,与先有技术相比较,显示出改进的耐磨损和韧性。
更具体地说,具有涂层的刀具包括优选在金属粘结相中至少有一种金属碳化物的烧结硬质合金、金属陶瓷或陶瓷体基质。涂层结构中个别的层可以是TiC或选自元素周期表第ⅣB、ⅤB和ⅥB族中的金属、B、Al和Si的相关碳化物、氮化物、碳氮化物、碳氧化物和碳氮氧化物,和/或它们的混合物。上述层中至少有一层是与基质接触。然而,涂层结构中至少有一层包含没有微孔和结晶缺陷的,细晶粒的致密的、单相α-Al2O3涂层。该涂层的优选织构,具有厚度d=0.5~25μm,平均晶粒度(S):
对0.5μm<d<2.5μm来说为0.5μm<S<1μm;
对2.5μm<d<25μm来说为0.5μm<s<4μm。
细晶粒的显微组织包括一个狭小的粒度分布。通常是80%的Al2O3晶粒所具有的粒度为平均粒度的±50%。
Al2O3涂层的粒度是由放大5000倍的SEM顶视显微照片来确定。在随意选择的方向上划出三条直线,沿直线晶粒边界之间的距离通过测量晶粒度而取得。
本发明的Al2O3层在(104)方向上具有最佳的晶体生长取向,该方向由X射线衍射(XRD)来测定。织构系数,TC,可由下式确定: TC ( hkl ) = I ( hkl ) I o ( hkl ) { 1 n Σ I ( hkl ) I o ( hkl ) } - 1
式中:
I(hkl)=(hkl)反射的测试强度
Io(hkl)=ASTM标准粉末图形衍射数据的标准强度
n=计算中使用的反射面数,使用的(hkl)反射面是:(012),(104),(110),(113),(024),(116)。
按照本发明用于(104)晶面族的TC大于1.5,优选大于2.5,更优选大于3.0。
按照本发明的被涂覆的基体还有一个特征是,在0.25mm的测量长度上难熔涂层的表面粗糙度(Ra)小于0.3μm。最好是,Al2O3层是暴露在最外面的一层。
按本发明织构的Al2O3涂层是通过在Al2O3成核之前精心控制CVD反应器气氛的氧化势而获得的。H2O或其它氧化性物质的总浓度水平应优选在5ppm以下。然而,Al2O3的成核是通过控制如下反应剂气体的顺序而开始进行的:CO2和CO在没有H2的气氛下例如存在N2和/或Ar的气氛中首先进入反应器中,然后再将H2和AlCl3送入反应器中。在成核期间,温度应为850~1100℃,优选950~1000℃。然而,精确条件在一定程度上取决于所用设备的设计。确定是否已获得必需的织构和涂层形态以及按照本说明书改进成核和淀积条件,如果需要,实施织构和涂层形态的数量等都在本领域熟练技术人员的权限范围内。
实施例1
A)其组成为6.5%Co、8.5%立方系碳化物以及其余为WC的硬质合金切削刀片,用厚度为5.5μm的TiCN涂覆。在相同的涂覆循环期间,随后的工艺步骤中,淀积6μm厚度的α-Al2O3层。在成核之前,载氢气体的氧化势,也就是,水蒸汽浓度明显地显示出低于5ppm的低水平(参看美国专利No.5,071,696)。
含有N2,CO2和C但不含氢的反应气体混合物首先送入CVD反应器中。反应气体按给定顺序逐一添加。在一个预定的时间后,将H2和AlCl3送入反应器。Al2O3的淀积期间,H2S作为一种掺杂剂而被使用。
在Al2O3淀积的各步骤中,气体混合物和其它工艺条件包括:步骤        1        2CO2         4%      4%AlCl3       4%      4%CO           2%      -H2S         -        0.2%HCl          1%      4%H2          余量     余量压力         55mbar   100mbar温度         1000℃   1000℃持续时间     1小时    7.5小时
XRD分析表明,Al2O3涂层的单一α相中(104)晶面族的织构系数TC(104)为3.2。
SEM研究表明,细晶粒的、厚度为6μm的Al2O3涂层具有2.1μm的平均粒度。
B)按照A)中所述方法在硬质合金基质A)上涂覆TiCN(5.5μm)和Al2O3(6μm),不同之处是按照先有技术进行Al2O3流程,结果在涂层中生成粗的α-和细的κ-Al2O3晶粒的混合物。
由A)和B)获得的具有涂层的刀具的刀片都用150目的Al2O3粉末进行湿式喷砂处理以获得光滑的涂层表面。
然后,在球墨铸铁(AISI 60-40-18,DIN GGG40)表面加工操作中就刀刃线和刀具的前倾面成片剥落情况对切削刀片进行试验。被加工的工件的形状应是在每旋转一周期间能使切削刀刃中断两次。
切削数据:
速度=150m/分钟,
切削深度=2.0mm,
走刀量=0.1mm/每转一周
这些刀片在工件表面进行切削。
试验结果可以表示为在获得成片剥落的切削中的刀刃线的百分数以及遭受剥落的刀具前倾面的面积相对于刀具前倾面和工件屑片之间总接触面积的百分数,并示于下表中。
                 成片剥落(%)
                 刀刃线    刀具前倾面A)单相/织构的α-Al2O3           5         6(按照本发明)B)α+κAl2O3       90        86
实施例2
在合金钢(AISI 1518,W-No.1,0580)表面加工操作中就刀刃线成片剥落情况对由A)和B)获得的切削刀片进行试验。被加工的工件形状应是在每旋转一周期间能使切削刀刃中断三次。
切削数据:
速度=130~220m/分钟,
切削深度=2mm
走刀量=0.2mm/每转一周
这些刀片在工件表面进行切削。
试验结果可以表示为在获得成片剥落的切削中刀刃线的百分数,并示于下表中。成片剥落(%)
                 刀刃线D)单相/织构的α-Al2O3             0                  (按照本发明)E)α+κAl2O3         28

Claims (7)

1.一种氧化物涂层刀具,它在刀具基体上至少部分涂有一层或多层,其中至少一层是氧化铝的难熔层,其特征在于,所述氧化铝层的厚度d=0.5~25μm,晶粒度(s)为:
对0.5μm<d<2.5μm来说为0.5μm<s<1μm,
对2.5μm<d<25μm来说为0.5μm<s<4μm;
并且包括在(104)方向具有织构的单相α-构成,织构系数大于1.5,织构系数被定义如下: TC ( hkl ) = I ( hkl ) I o ( hkl ) { 1 n Σ I ( hkl ) I o ( hkl ) } - 1
式中,
I(hkl)=(hkl)反射的测试强度,
Io(hkl)=ASTM标准粉末图形衍射数据的标准强度,
n=计算中使用反射面数,使用的(hkl)反射面是(012)、(104)、(110)、(113)、(024)、(116)。
2.根据权利要求1的氧化物涂层刀具,其中氧化铝层在(104)方向上的织构系数大于2.5。
3.根据权利要求1的氧化物涂层刀具,其中氧化铝层在(104)方向上的织构系数大于3.0。
4.权利要求1所述的氧化物涂层刀具,其特征在于,所述氧化铝层是暴露在最外面的一层。
5.上述权利要求中任一项所述的氧化物涂层刀具,其特征在于,所述氧化物铝层与TiCxNyOz层相接触。
6.权利要求5所述的氧化物涂层刀具,其特征在于,所述TiCxNyOz层是涂层的最面里的一层。
7.权利要求1所述的氧化物涂层刀具,其特征在于,所述基体是一种硬质合金、钛基碳氮化物或陶瓷的切削工具的刀片。
CN95191221A 1994-01-14 1995-01-12 具有氧化物涂层的切削刀具 Expired - Lifetime CN1061702C (zh)

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EP0738336B1 (en) 1999-04-21
AU1548095A (en) 1995-08-01
ATE179222T1 (de) 1999-05-15
DE69509218T3 (de) 2008-01-03
KR100348542B1 (ko) 2002-10-04
JPH09507528A (ja) 1997-07-29
JP4402171B2 (ja) 2010-01-20
US5766782A (en) 1998-06-16
BR9506948A (pt) 1997-09-09
EP0738336A1 (en) 1996-10-23
IL112206A (en) 1998-02-22
DE69509218D1 (de) 1999-05-27
SE9400089D0 (sv) 1994-01-14
EP0738336B2 (en) 2007-07-11
IL112206A0 (en) 1995-03-15
SE502223C2 (sv) 1995-09-18
CN1138881A (zh) 1996-12-25
USRE44870E1 (en) 2014-04-29
DE69509218T2 (de) 1999-08-19
WO1995019457A1 (en) 1995-07-20
SE9400089L (sv) 1995-07-15

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