CN112313354A - 具有替代性粘结剂的硬质合金 - Google Patents
具有替代性粘结剂的硬质合金 Download PDFInfo
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- 239000011230 binding agent Substances 0.000 title claims abstract description 55
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 239000006104 solid solution Substances 0.000 claims abstract description 10
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 238000005520 cutting process Methods 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 11
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- 238000004519 manufacturing process Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
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- 239000000470 constituent Substances 0.000 claims description 4
- 239000012530 fluid Substances 0.000 claims description 3
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001247 metal acetylides Chemical class 0.000 abstract description 16
- 229910000765 intermetallic Inorganic materials 0.000 abstract description 4
- 229910003310 Ni-Al Inorganic materials 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 27
- 239000000203 mixture Substances 0.000 description 13
- 239000002002 slurry Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 8
- 238000005229 chemical vapour deposition Methods 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- 229910017052 cobalt Inorganic materials 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000005240 physical vapour deposition Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000943 NiAl Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010191 image analysis Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001005 Ni3Al Inorganic materials 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
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- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 239000008187 granular material Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
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- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 238000005482 strain hardening Methods 0.000 description 1
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- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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Abstract
本发明涉及包含η相和Ni‑Al粘结剂的硬质合金,其中所述粘结剂包含内嵌在包含Al和Ni的替代式固溶体基质中的金属间化合物
Description
背景技术
从二十年代起,本领域中已知基于WC且具有钴粘结剂的硬质合金。已知的在硬质合金中作为粘结金属的其它金属是铁和镍,然而迄今为止钴是最常用的。
由于钴对环境和健康的影响,一直努力在寻找钴的替代性粘结剂。然而,在不负面影响材料性能的情况下难以替换或限制钴的量。对于切削工具而言,基底性能对于所述工具的整体性能是重要的,甚至组成中的小变化都可能对性能有不利的影响。
镍表现出良好的对WC的润湿性,使得其适合于制造硬质合金。相比于WC-Co硬质合金,Ni在氧化和腐蚀条件下也表现出更好的性能。镍类硬质合金的主要缺点是其降低的机械强度。一个原因是相比于Co,Ni的堆垛层错能更高,这使得Ni的加工硬化相比于Co只是中等的。
为了克服WC-Ni硬质合金的性能缺陷,提出了不同方法以增加强度和/或硬度;例如通过在烧结期间抑制WC晶粒的生长来制造亚微米级或近纳米级的WC-Ni硬质合金(Hall-Petch关系);或向WC-Ni硬质合金的基质中添加一些促进高强度和/或高硬度的元素。
像这样的Ni-Al粘结剂对于硬质合金是已知的。Ni3Al是具有高硬度和熔点的金属间化合物。已有报道由内嵌在Ni3Al粘结剂中的WC制成的硬质合金具有高硬度和降低的韧性,使得他们不太适合用于切削工具基底。因此,为了实现具有目标性能(可比于钴)的粘结剂,需要优化NiAl粘结剂。
本发明的一个目的是能够制造具有替代性粘结剂相的硬质合金,所述硬质合金相比于具有钴粘结剂的基底具有相等或改善的性能。
附图说明
图1示出了根据本发明、即来自实施例的发明例1的粘结剂相的SEM图像。
具体实施方式
本发明涉及包含硬质合金基底的切削工具,所述硬质合金基底包含碳化钨和3至20重量%的粘结剂。所述粘结剂包含内嵌在替代式固溶体基质中的金属间化合物析出物,所述替代式固溶体基质包含Al/Ni重量比在0.03至0.10之间的Al和Ni且其中Ni和Al的总量在总粘结剂的70至95重量%之间。所述硬质合金还包含η相且所述硬质合金中的总碳含量C(重量%)低于值X,其中X通过以下方程式给出:
此方程式对于包含3至20重量%的量的粘结剂的硬质合金是有效的,其中所述粘结剂中Ni和Al的量适合地为粘结剂的70至95重量%且其中Al/Ni重量比在0.03至0.10之间。
已经发现通过降低所述硬质合金中的总碳含量使得微结构中存在η相,能够制造包含内嵌于Ni-Al替代式固溶体中的硬质相(主要是WC)的硬质合金,所述Ni-Al替代式固溶体包含精细分散于粘结剂基质中的析出物。这样的硬质合金的机械性质通过具有包含由析出物增强的易延展的粘结剂相的硬质相而结合了足够的硬度/韧性。
本文中,替代式固溶体意指其中溶剂和溶质原子随机位于相的晶体结构中的晶格位点中的固溶体。可能还存在例如C和N的元素,但其在间隙位点上。
粘结剂的量优选地在硬质合金的3至20重量%、优选地5至15重量%之间。
Al/Ni之间的重量比适合地在0.03至0.10之间且优选地在0.03至0.07之间。
Ni和Al的量适合地是所述粘结剂的从70至95重量%,优选地从80至95重量%。
所述粘结剂总是包含特定量的W和C,其在烧结工序期间在固结工序期间从WC溶解。确切的量依赖于所述硬质合金的整体组成。
所述硬质合金具有亚化学计量的碳含量,从而形成了η相。本文中,η相意指选自Me12C和Me6C的碳化物,其中Me选自W和一种以上粘结剂相金属。
所述η相的平均粒度适合地在0.1至10μm之间,优选地在0.1至3μm之间,更优选地在0.1至1μm之间。这可以用不同的方式测量,例如通过SEM/LOM图像上的平均线性截距法。
所述η相的分布应当尽可能均匀。
在本发明的一个实施方式中,所述η相的体积分数适合地在0.05至30体积%之间,优选地在0.5至15体积%之间,更优选地在0.8至8体积%之间,甚至更优选地在1至4体积%之间。
在本发明的一个实施方式中,所述η相以适合的量良好地分布,这是获得改善的性能所需的。通过将所述碳含量保持在特定限度内来实现分布良好的η相。这可以通过在制造期间小心地控制碳平衡实现。本文中,分布良好意指所述硬质合金不含大的粒子簇。
所述硬质合金中的总碳含量C(重量%)适合地低于值X,其中X通过以下方程式给出:
所述方程式对于包含3至20重量%的量的粘结剂的硬质合金是有效的,其中Ni和Al的量适合地为粘结剂的70至95重量%且其中Al/Ni重量比在0.03至0.10之间。
所述硬质合金中总碳含量的下限是其中除了WC、结合剂、(可能存在的γ相)以及η相之外的其它相会形成。在实践中,在硬质合金中需要的η相的最大量取决于切削工具的具体应用。过度增加η相的量可能导致所述硬质合金变脆。因此,作为指导,在所述硬质合金中不应该存在超过30体积%的η相,优选地不存在超过15体积%的η相。
如果所述总碳含量接近由方程式1给出的上限,存在所形成的η相不均匀分布、即位于大的簇中的风险。这对于特定应用而言可能是不期望的。在实现不想要的大的η相簇和实现作为目标的精细分布的η相之间的总碳含量的差异可能是非常小的。接近该限度需要监测微结构以确保避免不想要的大的簇。如本领域技术人员已知的,实现精细分布的η相时的限度取决于所述硬质合金的整体组成。
在本发明的一个实施方式中,所述硬质合金基本上不含Co,且在本文中,这意指没有添加Co作为原材料,且存在于所述硬质合金中的Co是杂质的水平,优选地小于1重量%。通常检测到少量的Co,因为一些制造设备像例如研磨体包含硬质合金且可能对整体组成造成少量贡献。
在本发明的一个实施方式中,所述硬质合金基本上不含Mo,且在本文中,这意指没有添加Mo作为原材料,且存在于所述硬质合金中的Mo是杂质的水平,优选地Mo低于1重量%。
此处Mo在材料中是不想要的,因为它可能溶解在WC中,改变其性能,或形成严重脆化的具有类似于粘结剂的粗糙结构的低碳化物。
所述WC的平均粒度适合地在0.2至10μm之间,优选地在0.2至5μm之间。
在本发明的一个实施方式中,所述硬质合金基底设置有耐磨的CVD(化学气相沉积)或PVD(物理气相沉积)涂层。
在本发明的一个实施方式中,所述硬质合金基底设置有耐磨的PVD涂层,适合地是选自Al、Si和元素周期表中的4、5和6族的一种以上元素的氮化物、氧化物、碳化物或其混合物。
在本发明的另一个实施方式中,所述硬质合金基底设置有耐磨的CVD涂层。
在本发明的另一个实施方式中,所述硬质合金基底设置有耐磨的CVD涂层,所述CVD涂层包含若干层,适合地至少包含碳氮化合物层和Al2O3层。
本文中,切削工具意指刀片、端铣刀或钻头。
本发明还涉及一种根据上文制造切削工具的方法,所述切削工具包含如上所述的硬质合金基底。所述方法包括以下步骤:
-提供形成硬质成分的包含WC的粉末
-提供形成所述粘结剂相的包含Al和Ni的粉末
-提供研磨液,
-将所述粉末研磨、干燥、压制并烧结成为硬质合金。
形成所述粘结剂相的原材料可以以纯金属、两种以上金属的合金或者以其碳化物、氮化物或碳氮化物形式添加。应当以使得烧结后所述粘结剂相具有如上所述的组成的量添加所述原材料。
所述形成硬质成分的粉末包含平均粒度优选地是0.2-10μm、更优选地是0.2-5μm的WC。
如果需要碳增加,可以通过添加炭黑来完成硬质合金中碳含量的改变。或者,如果需要碳减少,可以通过添加W或W2C来完成硬质合金中碳含量的改变。
可以使用在常规硬质合金制造中通常被用作研磨液的任何液体。所述研磨液优选地是水、醇或有机溶剂,更优选地是水或水与醇的混合物,最优选地是水与乙醇的混合物。浆料的性能取决于添加的研磨液的量。由于需要能量来干燥所述浆料,因此应当最小化液体的量以保持低成本。然而,需要添加足够的液体来实现可泵吸的浆料并避免系统的阻塞。并且,可以向浆料中添加本领域公知的其它化合物,例如分散剂、pH调节剂等。
也可任选地向所述浆料添加有机粘结剂从而在后续的喷雾干燥操作中促进粒化,也作为用于任何后续的压制和烧结操作中的压制剂。所述有机粘结剂可以是在本领域中常用的任何粘结剂。所述有机粘结剂可以是例如石蜡、聚乙二醇(PEG)、长链脂肪酸等。有机粘结剂的量适合地基于总的干粉末体积在15至25体积%之间,所述有机粘结剂的量并不包括在所述总的干粉末体积中。
所述浆料包含形成硬质成分的粉末和形成粘结剂相的粉末,以及可能存在的有机粘结剂,通过研磨操作将所述浆料在球磨机中或在立式球磨机中适当地混合。通过如下方式适当地完成所述研磨:首先形成包含金属粘结剂粉末、第一和第二粉末部分以及可能存在的有机粘结剂的浆料。随后将所述浆料在球磨机或立式球磨机中适当地研磨以获得均匀的浆料掺混物。
在干燥塔中通过适当的喷嘴将包含与有机液体和可能存在的有机粘结剂混合的粉末化材料的浆料雾化,其中小液滴立即被热气流例如在氮气流中干燥,以形成聚集的颗粒。对于小规模的实验,也可以使用其它干燥方法,例如盘式烘干。
随后通过压制操作例如单轴压制、多轴压制等由所述干燥的粉末/颗粒形成生胚。
接下来,根据任何常规的烧结方法例如真空烧结法、烧结HIP法、火花等离子体烧结法、气压烧结(GPS)法等将由根据本发明制成的粉末/颗粒形成的生胚烧结。
所述烧结适合地在液相温度下进行。确切的温度取决于所述粘结剂的确切组成。
在本发明的一个实施方式中,所述烧结温度在1350℃和1550℃之间。
在本发明的一个实施方式中,所述硬质合金基底设置有涂层。
在本发明的一个实施方式中,根据上文制成的硬质合金基底设置有使用CVD或PVD技术的耐磨涂层。
在本发明的一个实施方式中,所述硬质合金基底设置有耐磨的PVD涂层,适合地是选自Al、Si和元素周期表中的4、5和6族的一种以上元素的氮化物、氧化物、碳化物或其混合物。
在本发明的一个实施方式中,沉积了CVD涂层,包含通过MTCVD沉积的第一TiCN层和通过CVD沉积的第二α-Al2O3层。还可以沉积用于磨损检测的最外侧有色层,例如TiN层。
在本发明的一个实施方式中,沉积了CVD涂层,包含通过低压CVD沉积的(Al,Ti)N层。还可以沉积用于磨损检测的最外侧有色层,例如TiN层。
所述涂层还可以经历其它处理,例如涂刷、喷砂等。
本发明还公开了根据上述方法制成的硬质合金切削工具。
实施例1
根据表1中的组成,从由93.9重量%的Ni和5.3重量%的Al(NiAl-1)或94.4重量%的Ni和5.6重量%的Al(NiAl-2)组成的预合金NiAl材料、Cr3C2原材料和WC(平均粒度(FSSS)对WC0B而言是0.81-0.87μm,对WC2B而言是1.24-1.44μm,对WC5B而言是5.5-6.3μm)制备硬质合金。各原材料的量基于总的干粉末重量,其中余量是WC,除了在形成η相时必须添加少量的W以根据表1调节碳含量。
表1
与研磨液(水/乙醇)以及2重量%(由总的干粉末重量计算)的有机粘结剂(PEG)一起研磨所述粉末。随后将所形成的浆料进行盘式烘干并随后让干燥的粉末经历压制操作以形成生胚。
在400度下氢气中的脱粘步骤后,在真空中在1450℃的温度下将发明例1、比较例1和比较例2的样品生胚烧结1小时。在40mbar Ar+CO中在1410℃下将比较例3和比较例4烧结。
所述样品的性能示于表2。通过使用LECO WC-600仪器测量了以重量%表示的总碳含量,为了该分析,在分析前压碎所述样品。值的准确度是±0.01重量%。根据ASTM B294测量了HV3。根据Shetty测量了断裂韧性K1C。
通过平均线性截距法测量了析出物的尺寸,即析出物的平均粒度。
在表2中,通过具有相同放大率LOM图像上的图像分析确定了η相的量,其中所有样品具有相同的抛光和蚀刻,且其中使用了对所有测量具有相同设置的软件Image J。
表2
在扫描电子显微镜(SEM)下研究了烧结的坯体。发明例1的结果可见于图1。
在表2中,清晰可见发明例1相比于比较例3(纯Ni粘结剂)在相同的韧性下具有改善的硬度。
Claims (11)
2.根据权利要求1所述的切削工具,其中所述析出物的平均粒度在10和1000nm之间。
3.根据前述权利要求中任一项所述的切削工具,其中所述析出物的平均粒度在10和500nm之间。
4.根据前述权利要求中任一项所述的切削工具,其中Al/Ni之间的重量比适合地在0.03至0.07之间。
5.根据前述权利要求中任一项所述的切削工具,其中η相的体积分数在0.8体积%和8体积%之间。
6.根据前述权利要求中任一项所述的切削工具,其中Ni和Al的总量在总粘结剂的80至95重量%之间。
7.根据前述权利要求中任一项所述的切削工具,其中所述硬质合金基本上不含Co。
8.根据前述权利要求中任一项所述的切削工具,其中所述硬质合金基本上不含Mo。
9.一种制造根据权利要求1至7中任一项所述的切削工具的方法,所述方法包括以下步骤:
-提供形成硬质成分的包含WC的粉末,
-提供形成所述粘结剂相的包含Al和Ni的粉末,
-提供研磨液,
-将所述粉末研磨、干燥、压制并烧结成为硬质合金。
10.根据权利要求8所述的制造切削工具的方法,其中所述包含Al和Ni的粉末以预合金粉末形式添加。
11.根据权利要求8至9任一项所述的制造切削工具的方法,其中所述切削工具设置有耐磨的CVD或PVD涂层。
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