CN1202845A - 在硬质合金切削工具上固定的氧化物涂层 - Google Patents

在硬质合金切削工具上固定的氧化物涂层 Download PDF

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CN1202845A
CN1202845A CN96198584A CN96198584A CN1202845A CN 1202845 A CN1202845 A CN 1202845A CN 96198584 A CN96198584 A CN 96198584A CN 96198584 A CN96198584 A CN 96198584A CN 1202845 A CN1202845 A CN 1202845A
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罗伊·V·莱弗雷兹
约翰·博斯特
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Abstract

一种切削工具插件,包括具有至少两种耐磨涂层的硬质合金的基体,所述耐磨涂层包括外陶瓷涂层和该陶瓷涂层下面的具有氮碳原子比介于0.7和0.95的金属碳氮化物涂层,该涂层能使金属碳氮化物形成伸入陶瓷涂层的突出部分以改进陶瓷涂层的粘合力和疲劳强度。

Description

在硬质合金切削工具上 固定的氧化物涂层
                        发明领域
本发明涉及切削工具领域，尤其是涉及用于切削、铣、钻孔和其它用途如钻车、套孔、车螺纹以及开槽的陶瓷涂覆过的硬质合金刀具插件的涂层。
                        发明背景
涂层能改进切削工具的性能尤其是在碳化物或硬质合金切削工具上的陶瓷或氧化物涂层。自从碳化物切削工具插件已涂有例如氧化铝(Al2O3)陶瓷以来，一直在继续努力改进涂层与基体的粘合力。当开始将氧化铝涂层直接施加到碳化物或硬质合金型基体上时，氧化铝中的氧就会与基体发生反应而降低粘合力。
已知通过涂覆耐磨性的碳化物层可以改进由烧结硬质合金基体(用粘合剂金属粘结的金属碳化物)制成的工具插件的性能。见UK专利1,291,387和1,291,388，这些专利公开了涂覆具有改进粘合力的碳化物涂层的方法；尤其是，控制沉积该碳化物时所用气体的组份以使之能在与耐磨性碳化物介面上的烧结硬质金属中形成脱碳区。然而，被称作η层的脱碳区会导致最终引起破裂的硬化和脆化。还已知，可在烧结金属的基体上涂覆陶瓷或氧化物耐磨涂层(通常为氧化铝)。然而，正如早已阐述过的，直接涂于烧结金属体上的氧化物层会毁坏烧结金属的组织和结合能力。有许多专利都曾公开过使用碳化物、碳氮化物和/或氮化物的中间层。见US专利4,399,168和4,619,866。中间的碳化钛(TiC)层可改进韧性但仍有η层存在，结果限制了涂覆过的切削刀具插件在精加工中的使用。在TiC层之前先涂上氮化钛(TiN)层虽能消除η层但韧性仍然低于要求值。见US专利4,497,874。已提出用碳氮化钛(TiCN)中间层代替TiC中间层。见US专利4,619,866和4,399,168。还提出了在硬质合金基体和外面氧化物磨损层中间有一个由钽、铌和钒中的至少一种的碳化物或碳氧化物组成的薄表面氧化粘结层。见U.S专利4,490,191。
当用于提高涂层与胶合的碳化物基体的粘合力时，陶瓷涂层(Al2O3)对TiC和许多TiCN中间涂层并不能很好地粘合。由于热膨胀的不同，存在着分层的倾向。由热膨胀不同引起的应力，各涂层会完成得不一致。这些中间涂层的主要特征在于如图1所示介于中间涂层和氧化物层的直线界面。这一点将会导致弱粘接。通过使基体粗糙而稍稍提高粘合力，但是因粗糙产生的突出部分对于均匀性地完成来说其距离过大。
根据本发明，在硬质金切削工具上提供一种陶瓷涂层以提高耐磨性以及粘合强度。
                     发明概述
简单地说，根据本发明，可以提供一种包括至少具有两种耐磨涂层的硬质合金基体的切削工具插件。涂层之一是陶瓷涂层。陶瓷涂层下面的中间涂层是由氮碳原子比介于约0.7和约0.95的碳氮化物组成，借此碳氮化物涂层形成联锁陶瓷涂层的钉齿，因此改善了陶瓷涂层的粘合力和疲劳强度。优选的是，碳氮化物中的氮碳原子比按X-射线衍射法测定是在约0.75-0.95之间。
按照本发明的一个实施方案，硬质合金切削工具插件在硬质合金基体和氧化铝表面涂层之间具有两层中间涂层。靠近基体的涂层是1-4微米的氮化钛层。氮化钛层上面的涂层是2-4微米厚的碳氮化钛层和氧化铝涂层为1-10微米。
按最佳实施方案，切削工具插件的硬质合金基体具有如下的四种涂层：2微米氮化钛内涂层，3微米碳氮化钛中间涂层，6微米氧化铝中间涂层，和2微米的Ti(C，N)，即TiC、TiN、TiCxNy外涂层。
对于用在碳氮化物涂层中来说钛并非是唯一的合适金属。除了钛以外，所述金属还可包括锆、铪、钒、铌、钽、铬、钼和钨。
按照本发明，切削工具插件基体代表性地含有来自铁族的3％-30％的粘合剂金属，包括除铁以外的镍和钴及其混合物以及介于70％-97％选自碳化钨、碳化钛、碳化钽、碳化铌、碳化钼、碳化锆和碳化铪中的一种碳化物。除了碳化物以外，切削工具插件基体还可以包含氮化物。
按照最佳实施方案，切削工具插件基体具有粘合剂相富集的表面层，也就是说，表面层富集有高百分比的钴或其它粘合剂金属。
简短地说，根据本发明，可提供一种制造具有耐磨涂层的涂覆切削工具插件的方法，该方法包括的步骤有，通过调节用于所述涂层的化学气相淀积的反应物，沉积具有氮碳原子比在约0.7-约0.95之间的金属碳氮化物涂层，和直接在所述碳氮化物涂层上面沉积一陶瓷涂层，因而使所述碳氮化物的涂层和陶瓷涂层具有联锁的显微钉齿。
                    附图的简要说明
本发明的另外特征和其它目的以及优点在参照附图，根据下面详细的描述将会变得更清楚，在附图中：
图1是具有现有技术的氧化物涂层和中间涂层的硬质合金切削工具插件的精加工部分的显微照片；和
图2-4是本发明的具有中间涂层和氧化物涂层的硬质合金切削工具插件的精加工部分的显微照片。
                   最佳实施方案的描述
根据本发明，具有陶瓷或氧化物耐磨涂层的硬质合金切削工具具有新型的加强中间涂层。硬质合金基体具有涂有碳氮化钛涂层的薄金属氮化物涂层。耐磨陶瓷涂层涂覆在金属碳氮化物涂层上。使提供的金属碳氮化物中间层具有导致氧化物涂层的优越粘合力的氮碳原子比，这由于氧化物涂层和金属碳氮化物涂层间所形成的联锁钉齿。
设计出一种试验用来定量评价陶瓷涂覆的硬质合金切削工具插件的性能。该试验是在立式车床上完成。坏料是一种具有直径大于约4英寸的圆柱形棒材。该棒材具有4个轴向槽，其宽度为3/4英寸而沿棒材长度的深度为1.5英寸。该棒材是具有25-30HRC硬度的普通碳钢AISI-SAE 1045。待试验的刀具用于减小坯料的直径如下。
    进刀速度(每转一周的英寸或IPR) 切削深度(英寸)     速度(每分钟的表面切削英尺或SFM)
    0.020     0.05     500
很明显坯料每转一周，切削工具插件冲击槽的边缘四次。刀具的插件一直在运行直到观察到其击穿整个涂层或另外的损坏。采用下列描述的试验观察损坏的地方并且该损坏是较强烈磨损和切削损坏型前兆的磨损类型。
在下面的实施例中，通过使用X-射线衍射方法测量碳氮化钛中间层或涂层中的氮碳原子比以先检测碳氮化物层的点阵间距，然后计算氮与碳的原子比或以氮与碳为基础的氮的原子百分比。已知碳化钛的点阵间距是1.53埃而氮化钛的点阵间距是1.5埃。范围或差距是0.03埃。这样，发现了具有1.5073埃点阵间距的碳氮化钛层对于氮化钛和碳化钛来说其间距为0.0227埃。因此，碳氮化物层中的氮与碳原子比是用0.03除以0.0227或基于总碳和氮量为75.7％的氮。
               实施例1
               对比例
将K20材料(K20是一种按ISO标准ISO 513：1991(E)表示的用于机加工的硬质切削材料类型的牌号，所述标准是按适合于硬质合金切削材料使用的材料和加工条件的分类)的碳化钨基基体(94％的碳化钨，6％钴)在BernexProgrammat 250涂覆炉中按众所周知的程序加以涂覆。使用已知为化学气相淀积法(CVD)的涂覆法，其中使气体和液体(转化为气体)在800°-1100℃和50-900毫巴的低压下在待涂覆的基体上通过。用于涂覆硬质合金基体的反应如下：
TiN的CVD-使用H2+N2+四氯化钛(TiCl4)
TiCN的CVD-使用H2+N2+TiCl4+乙腈(CH3CN)或CH4
Al2O3的CVD-使用H2+HCl+氯化铝(AlCl3)+CO2+H2S
用于涂覆氮化钛层、碳氮化钛层和氧化物层的主要涂覆时间和气氛列于下面表I、II和III中。将气体反应物、AlCl3反应器的产物以及液体反应物引入炉中。
                   表I
  涂层   操作时间分 反应器压力毫巴   反应器温度℃
  TiN     60     160     920
  TiCN     420     60     870
  Al2O3     270     60     1005
                      表II
  涂层     气体反应物，升/分
    H2     N2     CO2   CH4    HCl   H2S
    TiN     14     9
    TiCN     14     8
    Al2O3     11     0.6     20   0.050
                     表III
  涂层 AlCl3气体发生器升/分     液体反应物毫升/分
    H2   HCl  CH3CN液体 TiCl4液体
  TiN     2.1
  TiCN     125     2.4
  Al2O3     1.9     0.8
碳氮化钛层的X-射线分析证实了1.516埃的点阵间距，根据上述的分析，表明碳氮化物层中的氮碳原子比为14∶30或以总碳和氮计，氮含量为46.7％。将按本例涂覆过的切削工具进行上述机加工试验。仅只14.5秒钟后，就发现了磨损。
图1是表示基体上面的一层或多层涂层的精加工部分的显微照片。注意碳氮化钛和氧化物层之间的界面几乎是一直线，也就是说，不存在联锁的钉齿。
                        实施例II
根据本发明，在碳化钨基的基体上在如上所述的涂覆炉中按表IV、V和VI所述的涂覆时间和气氛制备涂层。
                        表IV
  涂层   操作时间分 反应器压力毫巴 反应器温度℃
    TiN     60     160     920
    TiCN     240     80     1005
    Al2O3     540     60     1005
                         表V
  涂层     气体反应物升/分
    H2     N2     CO2     CH4     HCl     H2S
    TiN     14     9
    TiCN     11.3     8     0.6
    Al2O3     11     0.6     0.2     0.50
                     表VI
  涂层 AlCl3气体发生器升/分     液体反应物毫升/分
  H2   HCl CH3CN液体   TiCl4液体
  TiN     2.1
  TiCN     0.9
  Al2O3   1.9   0.8
表IV、V和VI除了表明操作时间，反应压力和温度外，还表明气体反应物、三氯化铝发生器反应物和液体反应物的速率。引入三氯化铝发生器的气体反应物流过能产生定量流入涂覆炉内的三氯化铝的铝金属屑。
碳氮化钛层的X-射线分析证实了1.5073埃的点阵间距，根据上述的分析，表明碳氮化物层中氮与碳之比为23∶30或以总碳和氮为基础的氮含量为75.7％。
使已涂覆过的切削工具插件进行上述机加工试验。切削试验表明180秒时无损坏。图2表明基体上的涂层精加工部分的显微照片。该显微照片说明穿透氧化层并将其固定在位的碳氮化钛层的钉齿或铰键。
                 实施例III
实施例III按实施例II同样进行制备，只是在碳氮化物层的沉积过程中涂覆炉中氮量低些。发现碳氮化钛层的点阵间距为1.509，该值表示氮碳原子比为21∶30或氮含量为70％。
在机加工试验中，仅在5英寸的切削长度后(估计为40-50秒)就显示损坏。示于图3中实施例II的氧化物和碳氮化钛层之间的铰键的显微结构虽存在但非常小。
                        实施例IV
实施例IV按实施例II同样进行制备，只是提高了氮的流速。碳氮化钛层的点阵间距为1.503埃，这表示氮碳原子比为27∶30或90％的氮。在机加工试验中切削工具插件在120秒钟后没有损坏。实施例IV的显微结构示于图4中且表明在碳氮化物层和氧化物层间延伸明显的钉齿或铰键。
                        实施例V
在下列实施例中，使按本发明涂覆的切削工具插件在下列切削条件下进行机加工试验。坯料是3000灰铸铁200BHN。使用试验的刀具以按下减少坯料直径。
    进刀速度(每旋转一周的英寸或IPR) 切削深度(英寸)     速度(每分钟的表面切削英尺或SFM)
    .022     .100     950
根据本发明，两种钢插件，每个刃口切削108个工件。进行对比，C-5氧化铝涂覆的刀具插件每个刃口切削50个工件。按照本发明，刀具插件改进100％。
                          实施例VI
在下面实施例中，机加工试验的坯料是ARMA钢250BHN。加工条件如下。
    进刀速度(每旋转一周的英寸或IPR) 切削深度(英寸)     速度(每分钟的表面切削英尺或SFM)
    .010     .100     1,200
根据本发明，使用刀具插件，每个刃口切削170个工件。进行比较，用C-5氧化铝涂覆的刀具插件，每个刃口可切削85件。按照本发明的刀具插件改进是100％。
按专利法要求已对我们的发明细节和特点进行了说明，要求专利证书保护的内容陈述在下面权利要求书中。

Claims (10)

1.一种包含硬质合金基体的切削工具插件，具有至少两种耐磨性涂层，包括外陶瓷涂层和该陶瓷涂层下的氮碳原子比介于0.7-0.95的金属碳氮化物的涂层，它能使金属碳氮化物形成伸入陶瓷涂层的突出部分，因而改进陶瓷涂层的粘合力和疲劳强度。
2.按权利要求1所述的切削工具插件，其中，金属碳氮化物，基于金属碳氮化物层的氮和碳总含量具有70％-90％的氮含量。
3.按权利要求1所述的切削工具插件，其中，金属碳氮化物按X-射线衍射测定具有介于0.75和0.95的氮与碳的原子比。
4.按权利要求1所述的切削工具插件，具有1-4微米厚的氮化钛涂层，2-4微米厚的碳氮化钛涂层，和1-10微米厚的氧化铝涂层。
5.按权利要求3所述的切削工具插件，具有2微米厚的氮化钛涂层，3微米厚的碳氮化钛涂层和具有Ti(C，N)2微米厚外涂层的6微米厚的氧化铝涂层。
6.按权利要求1所述的切削工具插件，其中，金属碳氮化物层中的金属选自元素周期表中IVB、VB和VIB族中的一种。
7.按权利要求6所述的切削工具插件，还包含一个由来自铁分族3％-30％的粘合剂金属和选自碳化钨、碳化钛、碳化钽、碳化铌、碳化钼、碳化锆和碳化铪的70％-约97％的碳化物所组成的基体。
8.按权利要求7所述的切削工具插件，其中，在基体中氮化物替代部分碳化物。
9.按权利要求6所述的切削工具插件，其中基体表面层富集粘合剂金属。
10.制造切削工具插件的方法，该方法包括的步骤有：涂覆氯化钛涂层、金属碳氮化物涂层和陶瓷涂层，所有这些涂层都是用化学气相淀积法，其中在碳氮化物层的化学气相淀积过程中要控制反应物以便使氮碳原子之比介于0.75-0.95，并其中，在其上沉积陶瓷涂层以便使碳氮化物层具有伸入陶瓷层而提高涂层粘合力的钉齿。
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