CN103484832B - 涂覆有硬质材料的本体 - Google Patents

涂覆有硬质材料的本体 Download PDF

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CN103484832B
CN103484832B CN201310308445.1A CN201310308445A CN103484832B CN 103484832 B CN103484832 B CN 103484832B CN 201310308445 A CN201310308445 A CN 201310308445A CN 103484832 B CN103484832 B CN 103484832B
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resistant material
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H·范丹比尔格
H·维斯特法
V·索特克
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Abstract

本发明涉及一种本体，该本体涂覆有硬质材料并且具有通过CVD施加的多个层，其中外层包括Ti1-xAlxN、Ti1-xAlxC和/或Ti1-xAlxCN，其中0.65≤x≤0.9，优选0.7≤x≤0.9，并且这个外层具有从100至1100MPa、优选从400至800MPa范围内的压缩应力，并且在该外层下安排了一个TiCN或Al2O3层。

Description

涂覆有硬质材料的本体
本申请是优先权日为2008年3月12日、发明名称为“涂覆有硬质材料的本体”的中国发明专利申请200980108495.7（国际申请号PCT/EP2009/000310）的分案申请。
技术领域
本发明涉及一种本体，该本体涂覆有硬质材料并且具有通过CVD施加的至少一个硬质材料层。
背景技术
用于切削加工的切削刀具必须满足就稳定性和强度而言的严格要求，特别是在通过高切削速度下的车削来切削加工硬质或韧性材料（例如淬硬钢或淬火钢）的过程中。该切削刀具的材料应该特别地是耐磨损的，这在过去已经致使烧结碳化物或金属陶瓷基质本体来配备一个表面涂层，其中最初钛的碳化物、氮化物或碳氮化物以及后来还有氧化铝层被用作磨损保护涂层。由不同的硬质材料所构成的多层磨损保护涂层也是已知的。例如，被安排在一个或多个中间层（如碳氮化钛或氮化钛）上的氧化铝层被称为减磨涂层。
WO03/085152A2披露了一种Ti-Al-N层的使用，该层可以通过PVD作为具有高达60%的铝含量的一个单相层来生产。然而，在更高的铝含量下，形成了立方体的和六边形的TiAlN的混合物，并且在甚至更高的铝含量下仅形成了更软的并且不耐磨的六边形的纤锌矿结构。
还已知单一相Ti1-xAlx-N硬质材料层（其中x=0.9）可以通过等离子体CVD来生产。然而，这种层构成的不令人满意的均质性以及该层的相对高的氯含量是不利的。
当使用PVD或等离子体CVD方法来生产Ti1-xAlxN硬质材料层时，这些层的使用限制在低于700℃的温度。一个缺点是复杂部件几何体的涂覆存在很多困难。PVD是一种定向的方法，其中复杂的几何体被不规则地涂覆。等离子体CVD要求高的等离子体均质性，因为该等离子体功率密度对该层的Ti/Al原子比率具有直接的影响。具有高的铝含量的单一相的立方体Ti1-xAlx-N层的生产通过工业中使用的PVD方法是不可能的。
通过一种常规的CVD方法在高于1000℃的温度下沉积TiAl也是不可能的，因为该亚稳的Ti1-xAlxN在这样高的温度下分解为TiN以及六边形的AlN。
最终，在US6,238,739B1中所描述的用于通过一种无等离子体辅助的热CVD方法在从550℃至650℃的范围内的温度下生产Ti1-xAlxN层（其中x在0.1至0.6的范围内）的方法中，表明了对于具有x≤0.6相对低的铝含量的一种限制。那里说明的方法中，氯化铝和氯化钛以及还有NH3和H2作为气体混合物使用。在这种涂层的情况下，同样，必须接受达12原子%的高的氯含量。
为了改进耐磨性和抗氧化性，WO2007/003648A1提出生产一种本体，该本体涂覆有硬质材料并且具有通过CVD的包含至少一个Ti1-xAlxN硬质材料层的一个单层或多层涂层系统，出于这个目的将该本体在从700℃至900℃的温度下通过没有等离子体激发的CVD在反应器中进行涂覆，并且将在升高的温度下被混合的卤化钛、卤化铝以及反应性氮化合物用作前体。这给出了一种本体，该本体具有一个单一相Ti1-xAlxN硬质材料层，该材料层有立方NaCl结构并且化学计量系数x为从>0.75至0.93；或具有一个多相层，该多相层包括Ti1-xAlxN（具有立方NaCl结构并且化学计量系数x为从>0.75至0.93）作为主相以及一种纤锌矿结构和/或TiNxNaCl结构作为另一个相。该氯含量是在从0.05原子%至0.9原子%的范围内。从该文件中还获知这个或这些Ti1-xAlxN硬质材料层可以包含按质量计高达30%的非晶相层组分。所得到的这些层的硬度是在从2500HV至3800HV的范围内。
为了改进一种高耐磨性下的Ti1-xAlxN硬质材料层的粘附性，DE102007000512（它不是一个在先的公开文件）也提出，施加在一个基质本体上的层系统包括施加在该本体上的氮化钛、碳氮化钛、或碳化钛的一个粘合层，接着是一个相梯度层并且最后是一个单一相或多相Ti1-xAlxN硬质材料层的一个外层。该相梯度层包括在其面向该粘合层的一侧上的一种TiN/h-AlN相混合物，并且随着层厚度的增加，具有增大的fcc-TiAlN比例（在大于50%的比例）、以及与此相关的同时的TiN和h-AlN相的比例的减小。
上述这些涂层的一个缺点是在中断性切削的情况下短的操作寿命，如具有切削中断的铣削、车削、以及钻孔、特别是当在切削过程中使用冷却润滑剂时。
发明内容
因此本发明的一个目的是提供一种本体，该本体涂覆有硬质材料并且具有改进的耐热性以及循环疲劳强度。
这个目的通过如权利要求1所述的涂覆有硬质材料的本体得以实现。该本体的特征在于，外层包括Ti1-xAlxN、Ti1-xAlxC和/或Ti1-xAlxCN，其中0.65≤x≤0.9、优选0.7≤x≤0.9，并且特征在于该外层具有从100至1100MPa、优选从400至800MPa范围内的压缩应力，并且特征在于在该外层之下安排了一个TiCN或Al2O3层。
已经发现通过CVD施加的Ti1-xAlxN、Ti1-xAlxC、或Ti1-xAlxCN的层是极度抗裂缝形成以及裂缝生长的，如现有技术中已知并且使用的其他涂层的情况下所遇到的情况。用作基质本体的烧结碳化物、金属陶瓷、或陶瓷具有比TiCN和Al2O3更低的膨胀系数，其结果是在从涂覆温度（对于TiCN是约900℃并且对于Al2O3是约1000℃）冷却时在这些硬质材料层中出现了拉伸应力。这些拉伸应力通过裂缝结构的形成而部分地解除。立方氮化钛铝或碳氮化钛铝（作为亚稳的晶系）在从这些涂覆温度冷却之后具有从100至1100MPa、优选从400至800MPa范围内的压缩应力，并且不形成裂缝结构，这总体上致使权利要求1中命名的这些层的这种组合被发现是极耐磨的。以这个同样非常耐磨的和抗氧化的氮化钛铝或碳氮化钛铝涂层作为具有压缩残余用力的外层的已知的TiCN的高耐磨性和Al2O3的低热导率以及高抗氧化性的组合，显著地改进了涉及高负荷变化以及高温度变化的应用中的切削耐久性。实例是具有中断或改变切口截面的铣削以及还有车削和钻孔，特别是当使用冷却润滑剂时。
在从属权利要求中说明了本发明的多个实施方案。
具体实施方式
因此，该Ti1-xAlxN层、该Ti1-xAlxC层、或该Ti1-xAlxCN层可以由一个单一相组成并且具有一种立方体结构，或由多个相组成并且包括一个立方体的主相连同具有纤锌矿结构的另一个相和/或具有NaCl结构的TiN。
上述氮化或碳氮化钛铝层可以具有按质量计高达30%的非晶相层的多种组分。该氮化钛铝或碳氮化钛铝层的氯含量优选是在从0.01原子%至3原子%的范围内。
在本发明的另一个实施方案中，也可以将一种包括多个层的多层涂层用作外层，这些层各自具有从1nm至5nm的厚度并且具有一种相同的或变化的、优选是交替的构成。该涂层中的这些单独的层是碳氮化钛铝以及氮化钛铝层，这些层的总厚度（它形成了最外面的涂层）是在从1μm至5μm的范围内。
也可以在进行涂覆时通过一种变化的气体气氛而在这些单独的层中创造一种梯度，其结果是在亚区中从内到外碳含量不断地增加或减小。施加到烧结碳化物、金属陶瓷、或一种陶瓷所构成的基质本体上的所有层的总厚度应该是在从5μm至25μm的范围内。
为了本发明的这些目的，该氮化钛铝或碳氮化钛铝层可以包含高达25%的六边形的AlN。
为了生产根据本发明的涂覆有硬质材料的本体，将一种烧结碳化物或金属陶瓷本体在从700℃至900℃的范围内的涂覆温度下引入一种气体气氛中，该气体气氛除多种载气外还包含用于涂覆TiCN或氯化铝的氯化钛、甲烷以及氨气和用于涂覆氧化铝的二氧化碳。在上述基质之一上或一个TiCN基底层（其上施加了一个Al2O3层）生产了一种粘合层之后，将氯化铝、氯化钛、氨、以及乙烯引入该气体气氛中以施加最外层。优选的层厚度是在从2至5μm的范围内。所有层的层厚度是从2至10μm、优选是从3至7μm。

Claims (12)

1.一种本体，该本体涂覆有硬质材料并且具有通过CVD施加的多个层，其特征在于，外层包括CVDTi1-xAlxN、Ti1-xAlxC和/或Ti1-xAlxCN，其中0.65≤x≤0.9，并且在于该外层具有从100至1100MPa范围内的压缩应力，并且在于在该外层下安排了一个TiCN层，在该TiCN层上施加了一个Al2O3层。
2.如权利要求1所述的涂覆有硬质材料的本体，其特征在于，0.7≤x≤0.9。
3.如权利要求1所述的涂覆有硬质材料的本体，其特征在于，该外层具有从400至800MPa范围内的压缩应力。
4.如权利要求1所述的涂覆有硬质材料的本体，其特征在于，该Ti1- xAlxN层、该Ti1-xAlxC层、或该Ti1-xAlxCN层由多个相组成并且包括一个立方主相连同具有纤锌矿结构的另一个相和/或包括TiN。
5.如权利要求1所述的涂覆有硬质材料的本体，其特征在于，该Ti1- xAlxN层、该Ti1-xAlxC层、或该Ti1-xAlxCN层由一个单一相组成并且具有一种立方结构。
6.如权利要求1-4中的任何一项所述的涂覆有硬质材料的本体，其特征在于，在该外层中存在着按质量计高达30%的非晶相层的多种组分。
7.如权利要求1至4中的任何一项所述的涂覆有硬质材料的本体，其特征在于，该外层包括多个层，这些层各自具有从1至5nm的厚度并且具有一种相同的或变化的构成，该构成是选自Ti1-xAlxN、Ti1-xAlxC以及Ti1- xAlxCN之中，并且其特征在于，该外层具有从1μm至5μm的总厚度。
8.如权利要求7所述的涂覆有硬质材料的本体，其特征在于，该变化的构成是交替的构成。
9.如权利要求1至4中的任何一项所述的涂覆有硬质材料的本体，其特征在于，已经被施加在一个基质本体上的所有层的总厚度是在从5μm至25μm的范围内，该基质本体是由烧结碳化物、金属陶瓷或一种陶瓷构成的。
10.如权利要求9所述的涂覆有硬质材料的本体，其特征在于，该基质本体是由烧结碳化物构成。
11.如权利要求9所述的涂覆有硬质材料的本体，其特征在于，该基质本体是由陶瓷构成。
12.如权利要求1至4中的任何一项所述的涂覆有硬质材料的本体，其特征在于，该Ti1-xAlxN层、该Ti1-xAlxC层、或该Ti1-xAlxCN层包含高达25%的六边形AlN。
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RU2010141751A (ru) 2012-04-20
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CA2717188A1 (en) 2009-09-17
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EP2250299B1 (de) 2014-10-22
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JP5832748B2 (ja) 2015-12-16
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RU2501887C2 (ru) 2013-12-20
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CN103484832A (zh) 2014-01-01
WO2009112116A1 (de) 2009-09-17
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PL2250299T3 (pl) 2015-03-31
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