CN1942605A - 硬质耐磨的氮化铝基涂层 - Google Patents
硬质耐磨的氮化铝基涂层 Download PDFInfo
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims 1
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- 229910052710 silicon Inorganic materials 0.000 abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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Abstract
本发明提出了一种硬质耐磨的组合物AlxSiyMezN氮化铝基涂层;x、y和z代表原子分数,其总和为0.95至1.05,其中Me是III至VIII族和Ib过渡金属的金属掺杂剂或其组合。涂覆期间,该金属提供的本征导电率比没有金属掺杂的涂层更高。硅含量为0.01≤y≤0.4,金属掺杂剂或掺杂剂Me的含量为0.001≤z≤0.08,优选0.01≤z≤0.05,最优选0.015≤z≤0.045。
Description
发明领域
本发明涉及一种硬质耐磨的氮化铝基涂层,用其涂布的制品和制备该涂层的方法。
发明背景
先有技术的说明
基于Al1-xTixN或基于Al1-xTixSiyN的层通常以Ti/Al化学计量接近最大硬度范围使用。TiAlN情况下,该化学计量相应于约为Al0.65Ti0.35N。如果铝比例超出该情况,例如选择75至85原子%金属,已知硬度和耐磨性急剧下降。已经预期并发现Al1-xCrxN和类似硬质材料具有相似的性质。
关于该软化的现有知识公开于T.Suzuki,Y.Makino,M.Samandi和S.Miyake,J.Mater.Sci.35(2000),4193,和A.Horling,L.Hultman,M.Oden,J.sjólen,L.Karlsson,Surf.Coat.Technol.191(2005)384,以及其中引用的参考文献。
典型的涂层进一步已知公开于JP-A-2003/225809。
发明概述
发明目的
因此本发明的第一目的是提供一种硬质涂层,其可使用阴极电弧蒸发技术和磁控溅射技术或两者组合容易地制备。
发明说明
本发明用权利要求1的涂层实现目的。本发明方法首先得到用本发明硬质涂层使用阴极电弧蒸发工艺涂布的制品,其中进行该方法时没有进一步处理腔室。另外,涂层参数出人意料地坚硬。
本发明溶液基于这样的事实,任何Al1-xMexN体系的Al含量进一步增加远远超过现有技术被称为最大硬度的组成,达到除氮以外的全部元素的约90原子%,令人吃惊地发现硬度再次升高。此外,已经发现在硅的存在下该趋势增强。然而,分别非常接近于纯AlN或Al1-ySiyN时,层硬度再次降低。这可用形成非导电层来解释,导致沉积期间抑制离子轰击。
更详细地,从下列相关附图说明获得本发明目的的特征和优点,附图中例如说明本发明方法。
附图简要说明
附图如下所述:
图1是本发明第一实施例靶在腔室中的排列示意图。
图2是本发明第二实施例靶在腔室中的排列示意图。
图3是Al0.91Si0.09N层的剖视图,表明了由于缺乏离子轰击不希望地形成不牢固的针状涂层材料;
图4是Al0.86Si0.09Cr0.05N层的剖视图,表明通过掺杂少量金属(在这种情况下为Cr)保持涂层导电性获得均匀和一致的精细结构;
图5是基于Al1-xCrxSi((1-x)/10)N体系的涂层化学计量的硬度图解。除了已知的初级硬度最大值外,在很高的(Al+Si)含量处观察到出乎意料的二级硬度最大值。没有加入硅的对比体系Al1-xCrxN的第二曲线(不是本发明)表明了类似性能,但是通常硬度更低;
图6是基于体系Al1-xZrxSi((1-x)/5)N涂层化学计量的硬度图解。该曲线表明加入低于8原子%掺杂剂甚至使该体系产生全域硬度(globalhardness)。
图7是使用直径5mm的固体碳化物钻头在下列试验条件下的金属钻孔试验图解:在软退火态下在冷加工钢X155CrVMo12-1(DIN1.2379)中钻不透孔,孔深度15毫米,vc=70米/分钟,进料=0.16毫米/转,内部冷却剂乳液7%。
图8是本发明组合物Al0.834Si0.123Cr0.044N0.994的典型涂层以沉积态,并在800℃下氮气气氛中热处理1小时后的掠入射X射线衍射图解。它示例性说明了该体系中同时存在六角形和立方体相。高温下退火前和退火后观察到衍射峰的类似性证明了纳米复合晶体结构的热稳定性。
本发明实施方案的详细说明
主要用弧蒸发技术沉积层。可以从单个靶或多个单独的靶制备AlN基底层。最佳层是Al1-xMexSiyN,其中最佳Me含量为1至3原子%,硅含量为3至10原子%(这相当于x=0.02至0.06,y=0.06至0.20)。
用图1描述单个阴极技术的实例。Al0.885Si0.10Cr0.015靶10用于主层制备,纯Cr靶20用于清洁过程,并用于粘合和任选的基底层体系,单独或与靶10结合使用。
双阴极体系示例于图2。电极30由AlSi合金或纯Al构成,金属电极40用于离子清洁,以形成任选的基底层,并在过程中和AlSi(Al)结合使用,以产生主要的Al1-xMexSiyN层。
当金属掺杂剂含量选择太低(明显小于1原子%)时,过程变得不稳定。在分别具有Al或AlSi金属纯度最小值为99.5重量%的纯AlN或AlSiN层情况下,其中表现出的杂质主要是Fe,处理期间电弧电压从30v增长-在2Pa的氮压力、100A弧电流下-至超过40V,其影响过程稳定性和涂层质量。加入导电氮化物和/或金属导电材料,稳定氮或氮基气体混合物气氛中AlSi和Al材料的蒸发过程。纯Al1-ySiyN层横截面与Al1-xCrxSiyN层的比较示于图3和4。该差异被认为是由于处理期间层的导电性不足所引起。薄膜生长期间不保持离子轰击导致晶粒变粗,使得机械性能差。在Al中存在1原子%Cr的CrAl靶情况下,已经测得处理期间电弧电压的增加不超过1V。存在3原子%Cr的材料表明在整个沉积期间没有明显的电压升高,产生均匀结构,其获得良好的机械性能,即对涂层使用非常重要的耐磨性。
图5表明了对于体系Al1-xCrxSiyN和Al1-xCrxN基于涂层化学计量的硬度图解,图6的(Al1-xZrxSiyN)表明了另一种可能的掺杂剂和更高的硅含量。
引人注目的发现是这些涂层的硬度保持稳定,甚至在高于沉积温度的温度退火时硬度增加,如表1所示。
该稳定性可用该材料的两相结构来解释,其包含六角形AlN相和另一种立方体相(图8)。在800℃惰性气氛中退火1小时后,该纳米复合体系实际上保持不变。这意味着该化合物作为用于加工应用涂层中的改进,其中在刀口出现高温。
样品号 | 原子%Al | 原子%Si | 原子%Cr | 密度[g/cm3] | 纳米硬度[GPa] | |
沉淀物 | 在800℃退火 | |||||
703 | 90.5 | 6.1 | 3.4 | 2.7 | 40.5 | 40.9 |
763 | 83.4 | 12.3 | 4.4 | 3.1 | 38.7 | 40.8 |
759 | 84.2 | 12.2 | 3.7 | 3.3 | 37.3 | 38.9 |
767 | 83.6 | 12.3 | 4.1 | 3.6 | 37.3 | 38.8 |
117 | 76.9 | 17.3 | 4.8 | 3.7 | 38.3 | 39.5 |
表1.硬质金属上的Al1-xCrxSiyN涂层的热稳定性。给出了除氮之外的组成;用Rutherford后向散射光谱法(RBS)分析,全部涂层中氮含量测定为50±1原子%。
在下表中表明了上述四个实施例的过程参数:
实施例1:双阴极方案(电弧法)
结构:靶1 Cr(部分屏蔽)
靶2 Al0.88Si0.12合金或共混物
涂层:Al0.85Si0.10Cr0.05N
涂层厚度:3.0μm
处理程序:
泵至高真空P<1×10-5hPa
真空中加热至处理温度,例如450℃
Ar等离子蚀刻,Ar流200sccm,偏压-750V,2分钟
弧金属离子蚀刻,偏压-1200V,Cr弧60A,
氩流15sccm,5分钟
粘附层,CrN、Cr电流120A,阴极2关闭
P(N2)1×10-2hPa,偏压-120V,5分钟
沉积,AlSi电流130A,Cr 50A,
P(N2)3×10-2hPa,偏压-75V
实施例2:单个阴极的解决方案(电弧法)
结构:靶1 Ti
靶2 Al0.90Si0.08Cr0.02合金或共混物
涂层:Al0.91Si0.06Cr0.03
涂层厚度:2.5μm
处理程序:
泵至高真空P<1×10-5hPaa,
真空中加热至处理温度例如450℃,
Ar等离子蚀刻,Ar流200sccm,偏压-750V,2分钟
弧金属离子蚀刻,偏压-900V,4分钟,Cr弧55A,
Ar流15sccm
粘附层,TiN,电流125A,P(N2)1×10-2hPa,
偏压-120V;阴极2关闭,2分钟
沉积AlSiCr 125A,Ti关闭,P(N2)=3×10-2hPa,偏压-75V
在上述沉积步骤之前任选的基底层:
Ti电流120A,阴极2关闭,P(N2)1.0×10-2hPa,偏压-75V,3分钟
实施例3:具有梯度中间层的单个阴极解决方案(电弧法)
结构:靶1 Cr
靶2 Al0.82Si0.15Cr0.03合金或共混物
涂层:Al0.84Si0.12Cr0.04N
涂层厚度:4.0μm
处理程序:
泵至高真空P<1×10-5hPa,
在真空下加热至处理温度,例如475℃
Ar等离子蚀刻,Ar流200sccm,偏压-750V,1分钟
弧金属离子蚀刻,偏压-1000V,5分钟,Cr弧60A,Ar流15sccm;
粘附层(任选的),CrN,Cr电流125A,阴极2关闭,P(N2)1×10-2hPa,偏压-120V,2分钟
分级中间层,Al1-xCrxSi((1-x)/7)N,P(N2)2×10-2hPa,偏压-75V;Cr125A->75A,AlSiCr 75->140A,5分钟
沉积,AlSiCr 130A,阴极1关闭,P(N2)=5×10-2hPa,偏压-40V
实施例4:具有梯度中间层的双阴极方案(电弧法)
结构:靶1Zr(部分屏蔽)
靶2Al0.82Si0.18合金或共混物
涂层:Al0.835Si0.140Zr0.025N
涂层厚度3.0μm
处理程序:
泵至高真空P<1×10-5hPa
真空中加热至处理温度,例如450℃
Ar等离子蚀刻,Ar流200sccm,偏压-750V,1分钟
弧金属离子蚀刻,偏压-1200V,5分钟,Zr弧70A,Ar流15sccm
粘附层(任选),ZrN,Zr电流120A,阴极2关闭,P(N2)1.8×10-2hPa,偏压-120V,2分钟
分级中间层,Al1-xZrxSi(1-x)/5.2)N,P(N2)2×10-2hPa,偏压-60V;Zr 125A->60A,AlSi 75->140A,10分钟
沉积AlSi电流140A,Zr 60A,P(N2)2.5×10-2hPa,偏压-60V
实施例5:单个阴极溅射方案(用弧粘结层进行溅射处理)
结构:靶1Cr(弧靶)
靶2Al0.82Si0.15Cr0.03合金或共混物(溅射磁控管)
涂层:Al0.81Si0.14Cr0.05N
涂层厚度:2.0μm
处理程序:
泵至高真空P<1×10-5hPa
真空中加热至处理温度,例如400℃
Ar等离子蚀刻,Ar流200sccm,偏压-750V,1分钟
弧金属离子蚀刻,偏压-1000V,5分钟,Cr弧60A,Ar流15sccm
粘结层(任选),CrN,Cr弧电流125A,阴极2关闭,
P(N2)1×10-2hPa,偏压-120V,2分钟
沉积,AlSiCr磁控管溅射靶10kW,阴极1(弧)关闭,
P(Ar+N2)=2.2×10-3hPa,P(N2)=5×10-4hPa,偏压-150V.
应该注意到实施本发明的实验条件通常公开于同一申请人的WO-A-02/50865和EP-A-1357577,这些文献包括在本申请公开内容中作为参考。
Claims (20)
1.一种硬质耐磨的组合物AlxSiyMezN氮化铝基涂层,其中x,y和z代表原子分数,其总和为0.95至1.05,其中Me是族III至VIII和Ib过渡金属元素或两种或更多种这些元素组合的金属掺杂剂,所述元素提供的本征导电率高于不含所述金属掺杂剂的涂层,其中硅含量为0.01≤y≤0.4,金属掺杂剂或掺杂剂Me的含量为0.001≤z≤0.08,优选0.01≤z≤0.05,最优选0.015≤z≤0.045。
2.权利要求1的硬质氮化铝基涂层,其中金属掺杂剂或掺杂剂组合物Me是族III至VI过渡金属的元素和Ce。
3.权利要求1的硬质氮化铝基涂层,其中金属掺杂剂或掺杂剂组合物Me是族VII、VIII或Ib过渡金属的元素,并优选这些族的第一排(Mn、Fe、Co、Ni、Cu)和Ag。
4.权利要求1至3中任一项的硬质氮化铝基涂层,其中所述金属掺杂剂或掺杂剂组合物Me原子分布在涂层中。
5.权利要求1至4中任一项的硬质氮化铝基涂层,其中所述金属掺杂剂或掺杂剂组合物Me以其氮化物化合物的形式含在涂层中。
6.权利要求1至4中任一项的硬质氮化铝基涂层,其中所述金属掺杂剂或掺杂剂组合物Me以金属形式含在涂层中。
7.权利要求1至6中任一项的硬质氮化铝基涂层,特征在于硅含量为0.05≤y≤0.20。
8.权利要求1至7中任一项的涂层,特征在于其包括加入量多达20at.%的一种或多种元素硼或碳或氧。
9.权利要求1至8中任一项的硬质氮化铝基涂层,特征在于组合物层对于至少一种包含的元素在厚度方向上化学分级的。
10.权利要求1至8中任一项的硬质氮化铝基涂层,特征在于其由化学不同的亚层序列组成,这些层一起形成多层或纳米层状结构。
11.权利要求1至10中任一项的硬质氮化铝基涂层,特征在于至少部分层具有包含至少两相的纳米复合结构。
12.一种包含权利要求1至11任一项中硬质氮化铝基涂层的制品,其中涂层沉积到基材例如冷加工或HSS工具钢、硬金属(WC/Co)、金属陶瓷、立方氮化硼、PCD、工程陶瓷上,所述制品适用于加工应用,例如钻孔、研磨、车削、铰孔、成丝、滚铣等。
13.权利要求12的制品,特征在于沉积所述涂层之前,粘性中间层沉积到所述层上,其中通过离子轰击清洁预处理所述基材。
14.权利要求12或13中任一项的制品,特征在于常规硬质材料的基底层包含过渡金属氮化物、碳氮化物或氧氮化物,其中所述基底层在沉积本发明的氮化铝基硬质涂层之前沉积。
15.权利要求14的制品,特征在于所述基底层至少为0.3μm厚,并且对于至少一种成分是化学分级的。
16.一种沉积权利要求1至11中任一项涂层的方法,特征在于所述涂层通过阴极电弧蒸发工艺沉积。
17.一种沉积权利要求1至11中任一项涂层的方法,特征在于所述涂层通过磁控溅射技术沉积。
18.一种沉积权利要求1至11中任一项涂层的方法,特征在于所述涂层通过阴极电弧蒸发和磁控溅射技术的组合沉积。
19.权利要求16至18中任一项的方法,其中所述沉积在真空沉积室中进行,所述真空沉积室中布置至少一个圆柱形阴极。
20.权利要求16至19中任一项的方法,其中在涂层处理期间,向要涂覆的基材和所述基材以及阳极的表面施加DC、或单极性脉冲DC、负偏压,并且沉积室内壁在整个涂覆过程期间保持本征导电。
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CA2562402A1 (en) | 2005-10-27 |
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