CN1005995B - 多层包涂硬质合金制品 - Google Patents

多层包涂硬质合金制品 Download PDF

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CN1005995B
CN1005995B CN85104135.3A CN85104135A CN1005995B CN 1005995 B CN1005995 B CN 1005995B CN 85104135 A CN85104135 A CN 85104135A CN 1005995 B CN1005995 B CN 1005995B
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titanium
nitride
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中野登
飞冈正秋
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Sumitomo Electric Industries Ltd
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Priority to JP59094716A priority Critical patent/JPS60238481A/ja
Priority to US06/729,973 priority patent/US4746563A/en
Priority to AU42085/85A priority patent/AU578950B2/en
Priority to KR1019850003145A priority patent/KR890004787B1/ko
Priority to DE8585303397T priority patent/DE3580121D1/de
Priority to EP85303397A priority patent/EP0162656B1/en
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Abstract

有优良抗磨损性和韧性的多层包涂硬质合金含有硬质合金基质、与基质表面相接的内层和与内层相接的外层，内层是单层和／或叠层，该包涂层至少有钛的下述化合物之一：碳化物、氮化物，含碳氮化物、羧基氮化物、含氧氮化物、含硼氮化物和含硼碳化物；外层总厚度为５～２０微米叠层，由多层Ａｌ2Ｏ层构成，每层中都溶有氧化钛，或者至多３０％氧化钛共存，分别由０．０１～２微米中间层隔开，每层由ＴｉＣ、ＴｉＮ、ＴｉＣＮ、ＴｉＣＮＯ、ＴｉＮＯ、Ｔｉ的氧化物、Ｔｉ（Ｂ，Ｎ），Ｔｉ（Ｂ，Ｎ，Ｃ），ＳｉＣ、ＡｌＮ和ＡｌＯＮ。

Description

多层包涂硬质合金制品
本发明是关于具有优良抗磨损性和韧性的包涂硬质合金（Cemented Carbides）尤其是涉及适用于作切削工具的多层包涂的硬质合金该切削工具的切削速度可达很高，例如，在超过300米/分下，长期使用。
涂有主要含有一种抗磨损性能优良的硬质材料如TiC、Al2O3TiN等的单层或多层硬质合金至今仍被采用。尤其是，众所周知两层包涂硬质合金工具，其外层为Al2O3层，具有良好的抗磨损性能，因为Al2O3具有较高的抗热和抗氧化性能。对于这种切削工具所要求的切削条件近年来变的更加苛刻，而且对这种切削工具要求的较高抗磨损性能随着切削速度的增加而增加，如切削速度达300米/分以上。为了满足这一要求，人们一直在努力增加三氧化二铝层的厚度。
可是，三氧化二铝本身是易碎材料，这样增加它的膜厚度常导致韧性降低，因此，增加Al2O3厚度的硬质合金的切削工具因其韧性差而不能满足广泛地适用做具有耐磨和韧性的工具。
本发明的一个目的是提供一种新的抗磨性和韧性优良的硬质合金，从而可以克服上面已有技术中描述的缺点。
本发明的另一个目的是提供一涂有多层Al2O3的硬质合金，使其克服了韧性差的问题。
这些目的通过下列方法可以达到。多层包涂硬质合金含有硬质合金基质，与基质的表面相接的内层和与内层相接的外层，所说的内层至少是一层，该层主要由至少一种以下化合物构成;钛的碳化物、钛的氮化物、钛的含碳氮化物、钛的羧基氮化物、钛的含氧氮化物、钛的含硼氮化物和钛的含硼碳氮化物;所说的外层是总厚度为5～20微米的叠层，该层由多层Al2O3构成，每层Al2O3的厚度为0.01～2微米每层中都溶有氧化钛，或者与至少30%（体积）的氧化钛是共存的，每层分别由厚度为0.01～2微米的中间层隔开且每层至少含有以下一种化合物：TiC、TiN、TiCNO、TiCO、TiNO、Ti的氧化物，Ti（B、N）、Ti（B、N、C）、SiC、AlN和AlON。
为了提高抗磨损性，发明人在不降低其韧性下尽力增加Al2O3的层厚度，结果发现，使用具有Al2O3层和中间层的复合层是有效的。每个Al2O3层含有固溶体或混合结晶形式的氧化钛。本发明就是基于这一发现。
因此，本发明提供的多层包涂硬质合金含有硬质合金基质，与基质表面相接的内层和与内层相接的外层。所说的内层至少是一层，该层至少由以下一种化合物构成;钛的碳化物、钛的氮化物、钛的含碳化物、钛的羧基氮化物、钛的含氧氮化物、钛的含硼碳化物和钛的含硼碳氮化物;所说的外层是总厚度为5～20微米的叠层，该层由多层Al2O3层构成，每层厚度为0.01～2微米，每层中都溶有氧化钛，或者至多30%（体积）的氧化钛是共存的，每层Al2O3分别由厚度为0.01～2微米的中间层隔开，该中间层至少由以下一种化合物构成：
TiC、TiN、TiCN、TiCNO、TiCO、TiNO、Ti的氧化物、Ti（B、N）、Ti（B、N、C）、SiC、AlN和AlON。本发明一个可取实例中，上面描述的叠层的外层有一厚度为0.1～5微米的最外层，该层至少是由以下化合物中的一种构成：Ti、Zr和Hf的氮化物、BN和AlN。
防止加厚Al2O3包涂层而降低韧性的有效措施如下：
1）Al2O3包涂层不可由纯的Al2O3构成，而是由具有氧化钛或含有30%（体积）以下氧化钛的混合晶体结构的Al2O3固溶体所构成。
2）Al2O3包涂层为由Al2O3层构成的多层包涂结构，总厚度为5～20微米，每层Al2O3厚度为0.01～2微米并由厚度为0.01～2微米的中间层隔开，该中间层至少由以下一种化合物构成：TiC、TiCN、TiN、TiCNO、TiCO、TiNO、Ti的氧化物、Ti（B、N）、Ti（B、N、C）、SiC、AlN和AlON。
3）上面描述的多层含有厚度为0.1～5微米的最外层，该层是以下化合物中至少一种构成：Ti、Zr和Hf的氮化物、BN和AlN。
以上三个措施更详细的描述如下：
1）如果Al2O3颗粒大小恒定，其抗磨损性是随着本身的纯度增加的，而另一方面，其韧性不受纯度影响。然而发明人已经发现了一种方法，其中，通过稍微降低Al2O3的抗磨损性而使其韧性显著增加，就是通过把氧化钛溶解到Al2O3中形成通常的｛（AlTi）2O3｝。根据这一方法，稍微降低抗磨损性，而使其韧性显著地改善。因此，可以通过增加Al2O3的膜厚度来防止抗磨损性的降低，总体来说不会降低工具的韧性。以固溶体或氧化钛形式存在于Al2O3中的钛可起到增加上、下Al2O3层对其中间层的粘附性能的作用。
的确，理想的情况是氧化钛溶解在Al2O3中达到固溶体的限定值，可取的比例为（按体积比）0.01～0.1%;但是，如果是均匀沉积量达（按体积比）30%或以下，可取的是（按体积比）10～0.1%，也能达到类似的效果。用含有在通过化学气相沉积形成Al2O3期间同时加入卤化钛或有机钛化合物的方法，实现Ti氧化物在Al2O3中形成固溶体。
2）Ti氧化物在Al2O3膜中形成固溶体对于增加膜的韧性是有效的，而增加膜的厚度则导致Al2O3颗粒尺寸的增大，因此又降低了抗磨损性和韧性。尤其是，在切削工具的边缘经常出现粗糙颗粒或圆柱状晶体，Al2O3的增长速度较高，边缘部分会产生明显的磨损或损坏。发明人对这种问题进行了各种研究且发现这一问题可通过下面的结构解决，就是，用中间层将厚度为5～20微米的Al2O3分成很多层，使每层厚度为0.01～2微米。每个中间层厚度为0.01～2微米，该中间层至少由以下一种化合物构成：TiC、TiN、TiCN、TiCNO、TiCO、TiNO、Ti的氧化物、Ti（B、N）、Ti（B、N、C）、SiC、AlN和AlON。当用厚度为0.01～2微米中间层隔离每层Al2O3层时，不会产生颗粒增大，从而能保持住抗磨损性和韧性。如果厚度超过2微米，颗粒就会增大;反之，如果厚度小于0.01微米，Al2O3层的上、下中间层趋于粘结而产生Al2O3颗粒在中间层中漂浮的状态。在这种情况下，韧性有新改进，但不利的是抗磨性降低了。
如果Al2O3总厚度小于5微米，抗磨损性的增加是难以预料的，如果超过20微米，会发生显著的脱膜现象。膜的总厚度可取为5～10微米。当抗磨损性不作严格考虑时，总厚度可取为3微米或更大些。
中间层不仅之起到防止Al2O3颗粒尺寸增大的作用，而且也起到了在Al2O3中形成一种组合结构的作用，中间层彼此扩散和强化以致增加韧性。就是说，比Al2O3有较高强度和韧性的中间层能够防止Al2O3膜中的裂缝扩散或者减小裂缝的扩散速度，最终防止了来自基质内部扩散的裂缝。中间层厚度应为0.01～2微米。因为，如果小于0.01微米，就不能达到防止裂缝扩散的效果;同时，如果大于2微米，就会使Al2O3抗磨损性降低。尽管中间层以薄膜形成不以薄片结构形成，但偶尔在三氧化二铝层内表面也形成一种星散的（lsland-dolleol）结构。既使这种结构，本发明的效果和优点也能获得。
3）在本发明一个可取的实施例中，厚度为0.1～5微米的，至少由以下一种化合物构成的最外层：Ti、Zr和Hf的氮化物、BN和AlN都可提供在由中间层隔离的Al2O3的外层上。正如上面所述。
因为由Ti、Zr和Hf的氮化物、BN和AlN中至少一种构成的包涂层具有较高的韧性，所以，在冷却或切削时能够防止从表面或从包涂膜产生的裂缝扩散到基质的内部或表面，或者减小其扩散速度，从而防止切削工具因包涂层损失或脱膜造成不规则磨损或碎裂。
当使用BN时，尤其是包涂Hv硬度3000千克/毫米2或更高的硬BN膜时，限定下层膜的厚度最多为10微米，提供的切削工具有较高抗磨损性。
根据前面的详细描述，很明显，本发明的多层包涂超硬质合金具有优良的抗磨损性和韧性，而且能够用作高速切削材料，具有比已有技术中的材料更长的使用期。
下面给出的实施例是为了详细说明本发明，而没有对它们加以限定。
实施例1
由（按重量比）85%的WC、10%的（Ti、Ta、W）C、和5%的Co构成的硬质合金用作基质并在1000℃和10乇真空度充有一定气体的CVD容器内进行多层包涂，就是说，对于Al2O3层，该气流为（按体积比）5%的AlCl3、5%的CO2并以氢气平衡;对于TiC层、该气流为（按体积比）5%的TiCl4、10%的甲烷并以氢气平衡;对于TiN层，该气流为（按体积比）5%的TiCl4、10%的N2并以氢气平衡。并根据膜厚度控制适当的反应时间，这样获得多层包涂硬质合金（A、（B）和（C），各自的膜厚度结构如表1所示。
当形成Al2O3层时，涂上（按体积比）10%的TiCl4，使Ti溶解在Al2O3中，或涂上（按体积比）15%的TiCl4使（按体积比）5%的Ti2O3沉积在Al2O3中。
为了比较，涂有3微米TiC内层和5微米Al2O3外层的硬质合金（D）和另一涂有3微米TiC内层和10微米Al2O3外层的硬质合金（E）进行比较。（见表1）
然后将硬质试样（A）～（E）在下列条件＊进行切削实验：
切削速度300米/分
进料0.30毫米/转
切削深度2毫米
工件SCM435H（HB280）
参照试验结果，本发明的试样（A）、（B）和（C）以磨损0.3毫米计，所用的切削时间分别是10、11和18分钟;而比较试样（D）在1分钟内就被磨损坏了，比较试样（E）一开始就被损坏而无法使用。
实施例2
按重量比，由85%的WC、5%的（Ti·W）C、5%的TiN和5%的Co构成的硬质合金用作基质（硬质件：SNMG432）硬质件的侧面从表面到20微米厚的区域内是WC-Co相，而在其内部区域则是WC、Co和B1型固溶体之相。这种硬质合金涂有1微米SiC或TiC的内层和5个Al2O3薄层（溶有Ti），其总厚度10微米的外层;每层厚度为2微米，且由每层厚度为0.5微米的TiCNO、AlON或Ti（BN）的中间层所隔离，和1微米的TiN、ZrN、AlN或BN（六方形）的最外层。
在相同基质上包涂1微米SiC或TiCN内层，10微米Al2O3外层和1微米TiN最外层。以此制备对比试样。
得到的硬质试样在与实施例中类似条件下进行切削试验，获得结果如表2所示。
实施例3
实施例2的硬质合金，用等离子体CVD方法包涂1微米TiC内层、5微米Al2O3外层（溶有Ti）和其中间为0.5微米TiC中间层及厚度为3微米的硬BN最外层，其Hv硬度为3000千克/毫米2，然后在与实施例1相类似的条件下进行切削试验，可切削15分钟。

Claims (5)

1、一种硬质合金制品，该硬质合金制品含有硬质合金基质、与基质表面相接的内层和与内层相接的外层，所说的内层至少是一层，该层至少由一种以下化合物所构成：钛的碳化物、钛的氮化物、钛的含碳氮化物、钛的羧基氮化物、钛的含氧氮化物、钛的含硼氮化物和含硼碳氮化物;所说的外层是总厚度为5-20微米的叠层，该层由多个Al2O3层构成，每层Al2O3膜中都溶有氧化钛，或至多30%（体积）的氧化钛是共存的，每层Al2O3分别由厚度为0.01-2微米的中间层隔离，该中间层至少由以下一种化合物构成：TiC、TiN、TiCN、TiCNO、TiNO、Ti氧化物、Ti（BN）、Ti（B、N、C）、SiC、AlN和AlON。
2、按照权利要求1的硬质合金制品，其外层还包涂有厚度为0.1-5微米的最外层，该层至少由Ti、Zr和Hf的氮化物，BN和AlN中的一种所构成。
3、按照权利要求1的硬质合金制品，其中含有溶解或共存氧化钛的Al2O3膜是通过化学气相沉积法形成的，在气相沉积过程中添加卤化钛或有机钛化合物。
4、按照权利要求2的硬质合金制品，其中最外层是一层Hv硬度至少为3000千克/毫米2的硬BN膜。
5、按照权利要求1的硬质合金制品，其中氧化钛以0.01-0.1%的体积比例溶解在Al2O3膜中，形成如（AlTi）2O3固溶体。
CN85104135.3A 1984-05-14 1985-05-30 多层包涂硬质合金制品 Expired CN1005995B (zh)

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US06/729,973 US4746563A (en) 1984-05-14 1985-05-02 Multilayer coated cemented carbides
AU42085/85A AU578950B2 (en) 1984-05-14 1985-05-08 Multilayer coated cemented carbides
KR1019850003145A KR890004787B1 (ko) 1984-05-14 1985-05-09 다중층 피복 초경합금
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EP85303397A EP0162656B1 (en) 1984-05-14 1985-05-14 Multilayer coated cemented carbides
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EP0162656A3 (en) 1988-03-23
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US4746563A (en) 1988-05-24
EP0162656B1 (en) 1990-10-17
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DE3580121D1 (de) 1990-11-22
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EP0162656A2 (en) 1985-11-27
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