CN101209924A - 用于对韧性有要求的操作的陶瓷材料及由其制成的切削刀具 - Google Patents

用于对韧性有要求的操作的陶瓷材料及由其制成的切削刀具 Download PDF

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CN101209924A
CN101209924A CNA2007101605942A CN200710160594A CN101209924A CN 101209924 A CN101209924 A CN 101209924A CN A2007101605942 A CNA2007101605942 A CN A2007101605942A CN 200710160594 A CN200710160594 A CN 200710160594A CN 101209924 A CN101209924 A CN 101209924A
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埃里克·厄斯托尔斯
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Abstract

本发明涉及一种基于β－塞隆(Si6－zAlzOzN)、α－塞隆、包括TiN，Ti(C，N)或TiC的难熔硬质相、晶间非定形或部分结晶相、并且含有钇的陶瓷材料。β－塞隆相具有0.3－0.8的z值。难熔硬质相的含量为重量百分比10－20％。这种陶瓷材料特别有用于用作加工超耐热合金(HRSA)的切削刀片。

Description

用于对韧性有要求的操作的陶瓷材料及由其制成的切削刀具
技术领域
本发明涉及一种适合用于通过车削、钻削、铣削或者类似的成屑加工方法加工金属的陶瓷氮化硅基的材料。
背景技术
由于陶瓷材料高的热硬性，因此用于切削刀具应用的陶瓷材料适合用于加工在高温下具有高硬度、高拉伸强度并且低热扩散性的工件材料，并且尤其适合用于有时称为超耐热合金(HRSA)的自硬材料，例如一些类型的镍基的和钴基的材料。
氮化硅基的切削刀具通常用于加工灰口铸铁和HRSA。用于切削刀具的很多氮化硅基的材料利用氧化铝(Al2O3)作为烧结助剂而进行制造。铝和氧具有分别取代氮化硅晶体结构中的硅和氮的能力，从而形成所谓的塞隆陶瓷，这种陶瓷由Si-Al-O-N构成，有时另外还利用阳离子Men+进行稳定，其中Me可以选自大量的(稀土)金属和镧系元素，这些元素具有适当的离子半径(r＜1.0)，例如Y、Yb、Dy、Lu、Li、Ca、Mg、Sc等。
已经探测到了很多种塞隆相并且对其进行表征，见Izhevskiy V A，Genova L A，Bressiani J C和Aldinger F的文章“Progress in SiAlONceramics”(J.Eur.Ceram.Soc.20，2275-2295(2000))，但是用于切削刀具材料中的主要相仍然是α-塞隆相，RxSi12-(m+n)Al(m+n)OnN(16-n)(1.0＜m＜2.7；n＜1.2)，其中R是离子半径＜1.0的前述金属或者镧系元素，和β-塞隆：Si6-zAlzOzN8-z(0＜z＜4.2)。
在烧结时，所用原材料，通常为氮化硅、氧化铝和AlN或者某种塞隆多相与金属或镧系元素的氧化物一起的混合物，形成过渡熔体，α和β-塞隆相，并且可能还有其它的相，例如YAG(Y3Al5O12)、黄长石(Y2Si3O3N4)、B相(Y2SiAlO5N)、12H等从过渡熔体中结晶。在烧结之后，在晶粒之间留下非定形的或者部分结晶的晶间相。所产生的晶间相的量受到所用原材料的成分以及烧结条件的影响。
除了稳定α-塞隆相，金属离子还用作在烧结时形成塞隆晶体的催化剂，并且促进通常呈β相的细长塞隆晶粒的形成，但是也产生α-塞隆的细长晶粒，见Fang-Fang X、Shu-Lin W、Nordberg L-O和EkstrmT的文章“Nucleation and Growth of the Elongated α-SiAlON”(J.Eur.Ceram.Soc.17(13)1631-1638(1997))。还显然的是，所用金属离子的选择影响到无定形相的性质，见Sun E Y、Becher P F、PlucknettK P、Hsueh C-H、Alexander K B和Waters S B的文章“MicrostructuralDesign of Silicon Nitride with Improved Fracture Toughness II：Effects ofYttria and Alumina Additives”(J.Am.Ceram.Soc.81(11)2831-2840(1998))；Hong Z L、Yoshida H、Ikuhara Y、Sakuma T、Nishimura T和Mitomo M的文章“The effect of additives on sintering behavior andstrength retention in silicon nitride with RE-disilicate”(J.Eur.Ceram.Soc.22，527-534(2002))。
β-塞隆相中的z值影响烧结材料中的硬度、韧性和晶粒尺寸的分布，见Ekstrm T、Nygren M的文章“SiAlON ceramics”(J.Am.Ceram.Soc.75(2)，259-276(1992))。它还影响材料的切削刀具性能；较低的z值通常意味着更高的韧性和更低的抗缺口磨损性。
TiN目前在一些商业上可获得的用于切削刀具应用的塞隆中用作添加剂；其主要功能在于减小磨粒磨损并且提高断裂韧性，见Ayas E，Kara A，Mandal H，Turan S，Kara F的文章“Production of alpha-betaSiAlON-TiN/TiCN Composites”(Silicates Industrieis 69(7-8)287-292)，但是由于具有较高的热传导性，也可以利用它对于抗热冲击性能的有利的影响。
GB-A-2155007公开了一系列的适合用于金属切削刀具的塞隆材料，其中z值范围为从0到4.2，α塞隆的体积含量范围为从10％到70％，以及立方氮化物和碳化物颗粒加强添加剂的重量百分比范围为从0到45％。在车削钢材时，尝试了不同的组分。
WO 2005/016847公开了一种塞隆材料的制造方法及其成分，它作为烧结材料，包括体积百分比为10-90％的α塞隆和3-30％的立方氮化物或者碳化物相，例如SiC、Ti(C，N)、TiC、TiN等。
JP-A-2005231928公开了一种塞隆切削刀具材料，它包括＜＝30％的α塞隆以及β塞隆和6-30mol％的TiC、TiN、TiO2、Ti(C，N)和/或Ti(O，N)以及Al2O3。
US 5432132涉及一种用于制造烧结陶瓷物品的氮化硅基的合成物，特别是描述了具有提高的密度、硬度和断裂韧性特征的切削刀片。在氮化硅基的混合物中含有的氧化钇、氮化铝和氮化钛的量通过某种配方而相互关联，从而获得显著提高的抗磨损性。
发明内容
本发明的目的在于提供一种用于金属切削刀具的塞隆基陶瓷材料，它具有用于加工具有出众的韧性的金属、优选为超耐热合金的最优组分。
附图说明
图1示出根据本发明的塞隆材料的背向散射模式下的SEM图像，
其中
α-α塞隆
β-β塞隆
I-晶间相，以及
TiN-氮化钛
具体实施方式
本发明提供一种氮化硅基材料，除了晶间无定形相和/或结晶相，它包括：β-塞孔，即Si6-zAlzOzN，优选地0.3＜z＜0.8，α塞隆，即YxSi12-(m+n)Al(m+n)OnN(16-n)，其中如利用理论XRD光谱对测得的光谱的Rietveld精化方法测量到的α塞隆/(α塞隆+β塞隆)的重量比是0.2-0.4，见Rietveld，H.M.的文章“Line profiles of neutronpowder-diffraction peaks for structure refinement”，(Acta cryst.22，151-152(1967))；Rietveld，H.M.的文章“A profile refinement method fornuclear and magnetic structures”(J.Appl.Cryst.2，65-71(1969))；Hill，R.J.Howard，C.J.的文章“Quantitative phase analysis from neutronpowder diffraction data using the Rietveld method”(J.Appl.Cryst.20，467-474(1987))。
这种材料含有测量作为元素Y的重量百分比为3.5-6、优选为4-5％的钇。测量作为元素Al的铝的含量是5-7重量％。晶间相的量在3％和10％之间。这种材料也含有其它硬质的、基本惰性的成分、TiN、TiC或者Ti(C，N)或者其混合物，优选为晶粒尺寸为1-5μm的10-20wt-％、优选为13-17wt-％的TiN，或者，替代性地，优选为Ti(C，N)。此外，这种材料可以含有重量百分比达3％的YAG、B相或者黄长石。所述材料具有可以忽略的孔隙度。
这种材料一种特别有用于加工超耐热合金(HRSA)的切削刀片的材料。这种切削刀片可具有TiN、Ti(C，N)、Al2O3或者(Ti，Al)N或其任意组合的涂层。应用领域主要为要求高韧性的操作，这种操作具有锻造外皮(forged skin)、照明间歇和较不稳定的条件。
根据本发明的塞隆材料由粉末冶金方法，例如碾磨、压制和烧结制造。适当比例的氮化硅、氮化钛(或者碳化钛或者碳氮化钛)、氧化铝、氧化钇和氮化铝、多相体21R、12H、27R或者15H的粉末被碾磨并压制成坯体。坯体被置于烧结托盘上，而不嵌入粉末基床中并且单独地焙烧，并且然后在气体压力烧结炉中烧结。烧结的最终阶段在氮气压力下，在1700-1900℃的温度下进行。
在烧结之后，坯体被研磨成具有理想形状和尺寸的、用于金属切削的刀片。这些刀片可选地具有TiN、Ti(C，N)、Al2O3或者(Ti，Al)N或者如本领域已知的其任意组合的涂层。
实例
除了材料I、K和L，使用塞隆碾磨介质，将根据表A中的成分的粉末原材料在水中碾磨，这些材料都为商业可获得的塞隆切削刀具。将有机粘结剂混合到浆液中，浆液然后通过喷射干燥而颗粒化。
粉末被单轴向地冷压，从而形成坯体，然后坯体在650℃的温度下被分别地焙烧。焙灼后的坯体然后在1810℃的最大烧结温度下，在氮气压力下被烧结。
利用金相学方法分析这些材料。确定孔隙度。所有X射线衍射的孔隙度被用于利用理论XRD光谱对测得的光谱的Rietveld精化方法确定结晶相的z值和重量百分比(见Rietveld，H.M.的文章“Line profilesof neutron powder-diffraction peaks for structure refinement”(ActaCryst.22，151-152(1967)；Rietveld，H.M.的文章“A profile refinementmethod for nuclear and magnetic structures”(J.Appl.Cryst.2，65-71(1969)；Hill，R.J.Howard，C.J.的文章“Quantitative phase analysisfrom neutron powder diffraction data using the Rietveld method”(J.Appl.Cryst.20，467-474(1987))。Bruker公司的计算机程序Topasv2.1被用于上述精化。在图1中给出示出组分J的结构的SEM照片，其中：α-α塞隆；β-β塞隆；I-晶间相；以及TiN-氮化钛。这种图像被用于利用定量金相学方法来评估晶间相的量。结果总结于表B中。
表A：原材料的组分
组分，wt-％原材料                    元素成分
  材料   Si3N4   Al2O3   21R-F   Y2O3   wt-％   wt-％   wt-％
  A   70.09   1.87   9.35   5.14   13.55   5.9   4
  C   71.09   1.9   9.48   3.79   13.75   7   3.5
  D   81.07   2.16   10.81   5.95   0   6.9   4.7
  E   66.91   0   13.98   4.14   14.98   8.7   3.8
  F   77.07   2.04   10.14   5.63   5.11   6.9   4.7
  G   74.77   0   15.62   4.61   5   8.7   3.8
  I   N/A   N/A   N/A   N/A   0   2.2   8.5
  K   N/A   N/A   N/A   N/A   0   6.1   71)
  J   69.7   1.94   9.3   5.12   13.5   5.9   4
  L   68.6   14.8   10.9   5   0   13.6   3.9
1)Yb
表B：材料性能
  材料   测量到的z值   重量比alfa/(alfa+beta)   重量％alfa3)   孔隙度2)   晶间相(％)1)
  A   0.55   0.25   20   A04/B00   6
  C   0.6   0.21   18   A02/B00   4
  D   0.46   0.17   17.3   A02/B00   10
  E   0.55   0.56   45.9   A02/B02   2
  F   0.46   0.28   25.9   A02/B00   9
  G   0.6   0.64   59.5   A02/B00   3
  I   0.16   0.00   0   A02-06/B00   13
  K   0.59   0.30   30   A00/B00   11
  J   0.5   0.37   30   A02/B00   4
  L   1.4   0.00   0   A04/B00   10
1)在SEM图片中属于晶间相的面积与图片总面积的比值测量到的。
2)根据关于孔隙度金相学确定的ISO 4505标准。
3)可由X射线衍射方法探测到的在试样中结晶材料的比例表达的。
实例1
根据表1中的组分A、D、E、F、G和I的材料被研磨成ISORPGX120700T01020型刀片，并且使用280m/min的速度、0.2mm/rev的进给和2.5+2.5mm的切削深度，在对Inconel 718肩台进行双端面车削操作中进行测试。使用了冷却剂。在测试循环中运行刀片，其中一个测试循环相当于所述的端面车削操作。进行三次测试运行，每次利用一套新的刀片。记录下直至切削刃断裂或者出现1.0mm或更大的刀刃断裂或后刀面磨损深度(VB)时每个刀片承受的循环数目。作为所有三次测试运行的平均值的结果示于表1中。变型A显示出在抗后刀面磨损和抗切削刃断裂方面具有明显的优点，表明大约0.3-0.4、但是并不到0.5或更高的α/(α+β)塞隆比值是理想的，其中TiN含量为大约15wt-％(不具有TiN或者较低TiN含量的对照变型并不具有如此良好的性能)。因此，材料A被选择作为用于进一步的改进的基础。
表1
  材料   平均寿命长度(循环数)
  A   12
  D   4.3
  E   5.7
  F   8.7
  G   2
  I   9.5
  K   4.3
实例2
在表1中，根据具有增加的α塞隆含量的、作为对材料A的进一步改进的组分J的材料、材料A、具有降低的氧化钇含量的材料C被研磨成ISO RPGX120700T01020型刀片，并且使用280m/min的速度、0.2mm/rev的进给和2.5+2.5mm的切削深度，在对Inconel 718肩台进行双端面车削操作中进行测试。使用了冷却剂。在测试循环中运行刀片，其中一个测试循环相当于于所述的端面车削操作。进行三次测试运行，每次利用一套新的刀片。记录下直至切削刃断裂或者1.0mm或更大的后刀面磨损深度(VB)时每个刀片承受的循环数目。作为所有三次测试运行的平均值的结果示于表2中。组分非常接近于材料A的组分、但是具有显著较低Y2O3含量的材料C比材料A和J的性能显著变差。
表2
  材料   平均寿命长度(min)
  A   12.3
  J   12
  C   5
实例3
根据表1中的组分A、I、L和J的材料被研磨成ISORPGX120700T01020型刀片，并且使用250m/min的速度、0.2mm/rev的进给和2.5+2.5mm的切削深度，在对Inconel 718肩台进行双端面车削操作中进行测试。使用了冷却剂。此时，这批工件材料比用于实例1和2中的那批料显著得更加难以加工。因此，切削速度被降低，以便在切削刃断裂之前获得足够的信息。如在前面的实例中那样，在测试循环中运行刀片，其中一个测试循环相当于所述的端面车削操作。进行三次测试运行，每次利用一套新的刀片。记录下直至切削刃断裂或者1.0mm或更大的后刀面磨损深度(VB)时每个刀片承受的循环数目。作为所有三次测试运行的平均值的结果示于表3中。对于这批难以加工的材料中，具有更高的α塞隆含量的材料J比材料A的表现好得多，并且也比可在商业上获得的材料I和L工作得好。
表3
  材料   平均寿命长度(循环数)
  A   3
  J   11
  I   8
  L   6

Claims (8)

1.一种基于β-塞隆(Si6-zAlzOzN8-z)、α-塞隆、包括TiN，Ti(C，N)或TiC的难熔硬质相、晶间非定形或部分结晶相、并且含有钇的陶瓷材料，其特征在于：β-塞隆相具有0.3-0.8、优选为0.4-0.7的z值，且难熔硬质相的含量为重量百分比10-20％、优选为13-17％。
2.根据权利要求1的陶瓷材料，其特征在于，难熔硬质相是TiN。
3.根据权利要求1的陶瓷材料，其特征在于，难熔硬质相是Ti(C，N)。
4.根据权利要求1-3的陶瓷材料，其特征在于，α-塞隆/(α-塞隆+β-塞隆)的重量比为0.2-0.4。
5.根据权利要求1-3的陶瓷材料，其特征在于，钇的含量为重量百分比3.5-6％、优选为4-5％。
6.根据权利要求1-4的陶瓷材料，其特征在于，在SEM图片中属于晶间相的面积与图片总面积比值的测得的晶间相的量在3％和7％之间。
7.一种切削刀片，利用根据权利要求1-5的陶瓷材料制成。
8.根据权利要求6的切削刀片，具有TiN、Ti(C，N)、Al2O3或者(Ti，Al)N或者其任意组合的涂层。
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