CN105980587A - 用于切削工具的新等级的组合物 - Google Patents
用于切削工具的新等级的组合物 Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 34
- 238000005520 cutting process Methods 0.000 title claims description 7
- 239000010941 cobalt Substances 0.000 claims abstract description 45
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 45
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 38
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 28
- 239000002184 metal Substances 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000011733 molybdenum Substances 0.000 claims abstract description 27
- 229910003470 tongbaite Inorganic materials 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 16
- 239000000956 alloy Substances 0.000 claims abstract description 16
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims abstract description 16
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011651 chromium Substances 0.000 claims description 25
- 239000011230 binding agent Substances 0.000 claims description 16
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 150000004767 nitrides Chemical class 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000001000 micrograph Methods 0.000 description 8
- 229910052738 indium Inorganic materials 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000930 thermomechanical effect Effects 0.000 description 3
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- 238000006073 displacement reaction Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 229910009043 WC-Co Inorganic materials 0.000 description 1
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 229910000963 austenitic stainless steel Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- AGVAZMGAQJOSFJ-WZHZPDAFSA-M cobalt(2+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+2].N#[C-].[N-]([C@@H]1[C@H](CC(N)=O)[C@@]2(C)CCC(=O)NC[C@@H](C)OP(O)(=O)O[C@H]3[C@H]([C@H](O[C@@H]3CO)N3C4=CC(C)=C(C)C=C4N=C3)O)\C2=C(C)/C([C@H](C\2(C)C)CCC(N)=O)=N/C/2=C\C([C@H]([C@@]/2(CC(N)=O)C)CCC(N)=O)=N\C\2=C(C)/C2=N[C@]1(C)[C@@](C)(CC(N)=O)[C@@H]2CCC(N)=O AGVAZMGAQJOSFJ-WZHZPDAFSA-M 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
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- 239000003966 growth inhibitor Substances 0.000 description 1
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- 230000008018 melting Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
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- 230000000630 rising effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
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Abstract
材料的硬质金属组合物，其按重量百分比计包含6‑15％的钴含量的合金；钴含量的5‑15％的钼含量，和钴含量的0‑15％的碳化铬含量，以及余量的碳化钨。
Description
技术领域
材料的硬质金属组合物，其按重量百分比计包含具有6-15％的钴含量的合金；钴含量5-15％的钼含量，和钴含量0-15％的碳化铬含量，以及余量的碳化钨。
发明内容
在一种实施方式中，材料的硬质金属组合物按重量百分比计包含具有6-15％的钴含量的合金；钴含量的5-15％的钼含量，和钴含量的0-15％的碳化铬含量，以及余量的碳化钨。
所述硬质金属组合物具有通过粘结相粘结的硬质相，所述硬质相由一种或多种选自钨、钛、铬、钒、钽、铌、钼的碳化物、氮化物或碳氮化物或等效材料或其组合组成。
所述硬质金属组合物具有选自钴、镍、铁、钼及其组合的粘结相。
在一种实施方式中，硬质金属组合物的铬含量为钴含量的5％-15％。
在一种实施方式中，钼为钴含量的15％，并且碳化铬为钴含量的15％。
在一种实施方式中，所述材料的硬度增加且韧性降低有限。
在一种实施方式中，所述材料的韧性对硬度之比增加至少5％。
在一种实施方式中，提供了材料的硬质金属组合物的切削工具，所述硬质金属组合物按重量百分比计包含6-15％的钴的合金；钴含量的5-15％的钼含量，和钴含量的0-15％的碳化铬含量，以及余量的碳化钨。
在一种实施方式中，提供了一种制备材料的硬质金属组合物的方法，所述方法包括以下步骤：提供具有6-15重量％的钴含量的合金；提供钴含量的5％-15％的钼；提供钴含量的0％-15％的碳化铬；提供余量的碳化钨；将钼、碳化铬、碳化钨和钴研磨成粉末混合物；和在压力下烧结该粉末混合物。
当参照附图解读时，将更好地理解前面的概述以及以下对实施方式的详细描述。应理解所描述的实施方式不限于所示的精确布置和手段。
附图说明
图1是1.0重量％的Mo、0.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图2是0.5重量％的Mo、1.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图3是1.5重量％的Mo、1.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图4是0.5重量％的Mo、0.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图5是1.5重量％的Mo、1.0重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图6是1.5重量％的Mo、0.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图7是1.0重量％的Mo、1.5重量％的Cr3C2在10重量％的Co中的细粒硬质合金材料中的电子显微镜图像。
图8是示出具有高铬含量的样品之间的收缩率差异的热机械分析(TMA)曲线。
图9是显示具有较低铬含量的样品之间的收缩率差异的热机械分析(TMA)曲线。
图10是例示测试变体的硬度和韧性之间关系的图。
图11是例示测试变体的硬度和韧性之间关系的图。
图12(a)和12(b)是表示钼添加量与硬度和Shetty断裂韧性的响应的曲线图。
发明详述
材料的硬质组合物，如硬质合金，适合作为金属切削应用的基体，是因为其提供了强度、硬度和韧性的独特组合。如在本文中所提到的，硬质金属组合物是指如下的复合材料，其通常具有由钨、钛、铬、钒、钽、铌、钼的一种或多种碳化物、氮化物或碳氮化物或等效材料或其组合组成的硬质相，所述硬质相通过粘结相或金属相粘结，所述粘结相或金属相通常为钴、镍、铁、钼或其呈不同比例的组合。硬质合金的硬度取决于硬质相的浓度和连续性(contiguity)。例如，碳化钨的浓度越高，硬度越大。
可以根据粘结相含量和WC粒度(grain size)来划分硬质合金等级。可将不同类型的等级定义为细、中、中粗和粗。在本文中所提到的，可将细等级定义为材料具有3％至20％的粘结剂含量和小于约1μm的粒度，将纳米、超细或亚微细等级定义为材料分别具有小于0.1μm，0.1-0.5μm和0.5-1μm的粒度。
可将材料的硬质组合物制作成备用压制(RTP)粉末以用于压制和烧结成组件。该材料可具有作为硬质相的碳化钨(WC)和作为粘合相的钴(Co)。已经发现钼在硬质合金的钴粘结剂中具有良好的溶解性。钼也已在金属陶瓷材料使用多年以提高韧性。钼的堆垛层错能量低，对于钴来说，这有可能增加其在较高温度下的抗蠕变性。
根据一个方面，钼(Mo)和碳化铬(Cr3C2)作为抑制剂和为了粘结相的合金化而添加。钼的晶粒生长抑制性能虽然不如铬强，但是能够以显著的量与铬一并添加到WC-Co合金中。
本发明涉及如下的细粒硬质合金，其具有碳化钨(WC)为作为硬质相和钴(Co)作为粘结相，具有6-15重量％的Co含量，为Co含量5-15％的钼含量和为Co含量0-15％的Cr3C2含量。
该组合物的一个优点在于，抑制了WC的晶粒生长，但不会降低粘结剂的强度，从而减少金属切削操作中刃的崩裂。
实施例1
对含有10重量％的Co的细粒硬质合金中的0.5-1.5重量％的Mo含量以及0.5-1.5重量％的Cr3C2含量的特性进行评估实验。一些变体显示有前途的断裂韧性对硬度之比，虽然这些值在测量方法的延伸(spread)范围内。
该实验的一个目的是研究Mo与Cr一起将如何影响细粒硬质合金的性能。为了这个目的，进行在含10重量％的Co的亚微米WC合金组合物中Mo和Cr含量不同的筛选试验。使样品随机，以便将主观人为错误的影响最小化。
通过在乙醇中将WC、Co、Mo、Cr3C2和PEG进行实验室研磨8小时，以制作100g份额的材料。通过50巴的静压烧结(sinter/HIP)，在1410℃下对所述材料进行烧结。对样品进行抛光，蚀刻，并测定Hc、Com、密度、HV30和K1c性质。因为K1c的测定灵敏性，所以在额外的抛光后对所有样品重新进行测量。
对所有样品的Cr、Mo和Co含量进行完整的X射线荧光(XRF)分析，以确认实际的组成和给出结果的精确评估。一些显微结构的SEM照片示于图1-7中。来自测试变体的金相结果示于表1中，其中试样1、7和8都为相同组成的重复。
表1
在样品3和10中，第三相沉淀在显微结构中是明显的。如表2所示的，烧结样品1、2、3、10和11的碳分析显示，这些样品中的碳含量与计算的配方相当。对于样品3和10，可以认为该沉淀不是由碳的缺乏所引起。
表2
| 1 | 3 | 10 | 5 | |
| 总的碳(％) | 5.46 | 5.51 | 5.50 | 5.45 |
| 配方的总的碳(％) | 5.50 | 5.59 | 5.52 | 5.55 |
参照图8和9，热机械分析(TMA)曲线显示具有高铬含量和低铬含量的样品之间的收缩率差异。如图8中所示，在高Cr含量(1-1.5重量％)下，位移曲线是非常尖锐和迅速的，最大速率在约1280℃。如图9中所示，对于低Cr含量样品(0.5重量％)，位移曲线具有一个在约1250℃且一个在约1330℃的两个单独的峰，这表明Mo含量以更为显著的方式影响收缩，并且熔化是一个较为滞后的性质。
测试变体的硬度和韧性之间的关系图示于图10和11中。以将Cr3C2含量标记为第一值且将Mo含量标记为第二值的方式，将不同组分的K1c和HV30示于表中。对于一些具有较高Mo添加量且具有相同硬度的组合物，观察到三个具有升高的K1c值的异常点。
可根据如下确定硬度对韧性之比：
＝(K1cH-K1cL)/K1cL
其中
K1cH是具有较高Mo含量的样品的平均K1c
K1cL是具有较低Mo含量的样品的平均K1c。
表3
参照表3，在样品3和10中，韧性增加了5.4％。对于样品6和8，百分比差异上升至8.7％。因此，实现了韧性对硬度之比的至少5％的增加。
在图12(A)和12(B)中示出了使用软件(Umetrics，Umse，SE)获得的表示Mo添加量与硬度和Shetty断裂韧性的响应的曲线图。结果表明，可以添加大量的Mo即高达1.5重量％的Mo而不显著减少韧性。这可由以下看出：随着Mo含量的增加，等韧性(iso-toughness)线是平的。
以上显示，可将较高量的Mo溶解在Co中。基于实现的Hc值，抑制效果也似乎是小的。应理解，变体的比较受制于它们粘结剂体积的微小差异。
实施例2
利用含有1.5重量％Mo和0.5重量％Cr3C2的具有η相的变体(EFP006)进行实验。图3是该样品的电子显微镜图像。
表4显示来自利用材料Mo+Cr+WC+Co合金(称为EFP006)和不添加Mo的参比(H10F参比(89.5％WC008，0.5％Cr3C2，10％的Co))进行的不锈钢的断续切削的实例。切削次数为直到未涂覆样品上出现刃崩裂为止。
表4
实施例3
对具有不同钴含量的变体进行实验。按钴含量比例以钴含量5-15％的范围决定钼添加量。
通过在乙醇/水中将粉末和PEG进行实验室研磨8小时来制作100g份额的材料。以Mo2C的形式添加钼。通过50巴的烧结/HIP，在1410℃下对所述材料进行烧结，然后将样品抛光，然后测定HV30和K1c性质。所用的配方以及硬度和韧性的测定示于表5中。
表5
可以看出，在所有情况下，与基线相比，Mo/Co比为0.05和0.15两者的Mo的添加量都产生硬度，和略微降低的韧性。因为关于10％粘结剂实例观察到了相似的材料性能响应，因此预期这些材料有相似的性能变化。
还已知，Co可以在烧结过程中溶解Mo，但冷却后残留的Mo可能导致降低的粘结剂延展性和较低的断裂韧性。因此，在碳化物等级组合物中包含Mo(以及还可能Cr)应本质上视为添加至硬质相，而不是向延展性粘结剂提供额外的成分。Co是硬质金属延展性的主要提供者，等级韧性由Co相对于其它所有成分的体积分数所决定。
应理解，设想了在所公开范围以及其它范围内的多种Co和Mo的组合，并且本申请不应仅限于那些公开的组合。
研究了在Co-Cr3C2-亚微米WC硬质金属中用Mo(最多～2体积％)部分代替Co对于等级韧性的影响。这些研究的结果显示，随着Co越来越多地被用Mo代替，硬度适度地增加，K1c略微下降。
由在奥氏体不锈钢管上的断续面切削的次数所表示的平均刃韧性随着Co越来越多地被Mo代替而降低。这与K1c的趋势一致。个体的切削寿命结果的扩展是相当宽的，这意味着外在因素可能有一定的影响。
钴是硬质金属的延展性的主要提供者。其它成分，如在Co中具有高溶解性的那些晶粒生长抑制剂的体积分数，不应视为在向所述等级提供延展性方面是与Co等效的。
尽管本发明的一种或多种实施方式关于其特定的方面进行了说明，但是许多其它变体和修改以及其它用途将对于本领域技术人员变得显而易见。因此优选本发明的一种或多种实施方式不由本文中的具体公开内容所限制，而是仅由所附权利要求书所限定。
Claims (12)
1.材料的硬质金属组合物，其按重量百分比计包含具有6-15％的钴含量的合金；所述钴含量的5-15％的钼含量，和所述钴含量的0-15％的碳化铬含量，以及余量的碳化钨。
2.根据权利要求1所述的硬质金属组合物，其中所述材料具有通过粘结相粘结的硬质相，所述硬质相由一种或多种选自钨、钛、铬、钒、钽、铌、钼的碳化物、氮化物或碳氮化物或等效材料或其组合组成。
3.根据权利要求1或2所述的硬质金属组合物，其中所述粘结相选自钴、镍、铁、钼及其组合。
4.根据前述权利要求中任一项所述的硬质金属组合物，其中铬含量为所述钴含量的5％-15％。
5.根据前述权利要求中任一项所述的硬质金属组合物，其中钼为所述钴含量的15％，碳化铬为所述钴含量的15％。
6.根据前述权利要求中任一项所述的硬质金属组合物，其中所述材料具有小于1μm的粒度。
7.根据前述权利要求中任一项所述的硬质金属组合物，其中所述材料的硬度增加且韧性降低有限。
8.根据前述权利要求中任一项所述的硬质金属组合物，其中所述材料的韧性对硬度之比增加至少5％。
9.材料的硬质金属组合物的切削工具，所述硬质金属组合物按重量百分比计包含6-15％的钴的合金；，所述钴含量的5-15％的钼含量，和所述钴含量的0-15％的碳化铬含量，以及余量的碳化钨。
10.一种制备材料的硬质金属组合物的方法，所述方法包括以下步骤：
提供具有6-15重量％的钴含量的合金；
提供所述钴含量的5％-15％的钼；
提供所述钴含量的0％-15％的碳化铬；
提供余量的碳化钨；
将钼、碳化铬、碳化钨和钴研磨成粉末混合物；和
在压力下烧结所述粉末混合物。
11.根据权利要求10所述的方法，其中提供所述钴含量的5％至约15％的铬。
12.根据权利要求10或11所述的方法，其中提供所述钴含量的15％的钼和所述钴含量的15％的碳化铬。
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