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CN1845884A - SiAlON基材料 - Google Patents

SiAlON基材料 Download PDF

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Publication number
CN1845884A
CN1845884A CNA2004800226286A CN200480022628A CN1845884A CN 1845884 A CN1845884 A CN 1845884A CN A2004800226286 A CNA2004800226286 A CN A2004800226286A CN 200480022628 A CN200480022628 A CN 200480022628A CN 1845884 A CN1845884 A CN 1845884A
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China
Prior art keywords
sialon
described material
composition
preferably less
crystal boundary
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Granted
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CNA2004800226286A
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CN100448799C (zh
Inventor
B·比特利希
K·弗里德里希
U·莫莱
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Ceramtec GmbH
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Ceramtec GmbH
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    • C04B35/58—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 borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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Abstract

公知的Si3N4和SiAlON刀具材料在灰口铸铁(GG)上通常连续长时间切削时切削刃上开始非常迅速地卷起，这一点称为起始磨损。因此本发明提供了由一种α/β－SiAlON成分A和一种硬质材料成分B组成的材料混合物，所述混合物中含有70－97Vol％的成分A和3－30Vol％的成分B。

Description

SiAlON基材料
本发明的主题涉及一种SiAlON基材料及其制造方法和应用。
公知的Si3N4和SiAlON刀具材料在灰口铸铁(GG)上通常连续长时间切削时切削刃上开始非常迅速地卷起，这一点称为起始磨损。
因此，本发明的目的在于，克服已知刀具材料的这种缺点。
依据本发明，该目的通过提供一种由成分A和B组成的材料得以实现，其中，A表示α/β-SiAlON和B表示硬质材料。在此方面，本发明的材料含有70-97Vol％，最好80-95Vol％，特别优选84-91Vol％的成分A和3-30Vol％，最好5-20Vol％，特别优选9-16Vol％的成分B。
本发明所使用的成分A的原材料混合物由主要成分Si3N4、AlN、其他添加剂例如像Al2O3、Y2O3、Sc2O3、稀土金属的氧化物和少量含有Li、Ca、Mg、Sr的化合物组成。可比较的混合物已由DE 35 11 734 A1公开。本发明的材料由上述原材料混合物和添加的硬质材料在1800-2000℃温度下进行热处理和在最高温度保温0.5-5小时形成。
成分A由α-和β-SiAlON以及非晶形或者部分结晶的晶界相组成。在材料的烧结状态下烧结体内部的SiAlON相由10-90Vol％，优选12-60Vol％，特别优选15-50Vol％的α-SiAlON和90-10Vol％，优选88-40Vol％，特别优选85-50Vol％的β-SiAlON组成。α-和β-SiAlON成分的比例借助X射线衍射照片确定(根据Gazzara and Messier，J.Am.Ceram.Soc，Bull.56(1977))。
晶界相的含量小于10Vol％，优选小于5Vol％。晶界相可以是非晶形的，但优选应是部分结晶的。烧结体内部的A的组成已知可以通过制备参数，例如通过粉末混合物的的组成、炉内的烧结条件、坩埚材料、气体类型、温度和烧结时间改变。成分A内可以在烧结体表面和内部之间存在梯度，从而在所谓的烧成表面的α-SiAlON含量最高可以为100％。
如果烧结体的表面比内部冷却迅速或者表面的化学组成通过与大气反应进行改变的话，成分A内的梯度可以在确定条件下产生。富含α-SiAlON的表面导致一种具有韧性芯的硬质外层。
作为硬质材料成分B例如可以使用SiC、Ti(C、N)、TiC、TiN、元素周期表(PSE)第IVb、Vb和VIb族元素的碳化物和/或氮化物以及碳化钪和/或碳氧化钪或者所列举的硬质材料的混合物。硬质材料在热处理期间嵌入晶间和/或者晶内，也就是既嵌入SiAlON晶粒之间也嵌入内部并在热处理期间不变。所使用的硬质材料颗粒的尺寸因此不应超过其他结构成分α-和β-SiAlON晶粒的尺寸，否则硬质材料使本发明材料的机械特性变差。这意味着，硬质材料的平均粒度小于30μm，最好小于15μm，特别优选小于5μm。硬质材料颗粒可以是球状晶粒、片晶或者晶须，特别优选球状晶粒。
α-和β-SiAlON晶粒的最大尺寸应小于90μm，优选小于65μn，特别优选小于50μm。在公知的材料中通常追求小粒度，而在本发明的材料中令人惊异地表明，应用性能仅受粒度的次要影响。
为使非晶形晶界相结晶，可以并甚至优选进行热处理。根据公知技术，按照像粉末混合物的组成这种制备参数和像温度、气体组成、气压、时间、绝缘材料和坩埚材料这些烧结条件产生结晶相，特别优选含铝的黄长石或者二硅酸盐。
本发明的材料与已知材料相比的优点是其具有＞1550HV10的更高硬度并因此具有更高的耐磨强度。
此外，本发明的材料具有更高的热硬度，也就是说，即使在刀尖温度上升时在高切削速度下也具有更高的耐磨强度。
此外，玻璃相与所要加工工件材料的化学反应即使在高切削速度下也明显变小。
本发明的材料可以涂覆有例如像Al2O3、TiN或者TiC的降低磨损的已知涂层，从而提高耐磨强度。
依据本发明的材料可以按照本身已知的方法制造，如也是在通过粉末混合、成型、烧结和通过磨削的最终加工制造高效陶瓷组件，特别是SiAlON材料时使用。
烧结时的气氛应为惰性的并可以是N2或者由N2和例如像Ar其他惰性气体组成的混合气体。
下列附表中列出依据本发明材料组成的实施例。值得注意的是均为高硬度。
附表：实施例的组成和特性
称量kg   实施例1   实施例2   实施例3   实施例4   实施例5
Si3N4Y2O3AlNMgOAl2O3SiCTi(C、N)   5.660.320.290.010.030.69-   5.660.320.290.010.030.69-   5.350.300.270.010.031.04-   5.340.300.270.010.03-1.05   4.900.270.250.010.03-1.53
最高烧结温度保温时间最终密度与试样内部α+β相关的α-SiAlON硬质材料含量颜色硬度(HV10) 1940℃3h＞99.9％th28％10Vol％SiC灰-绿1730 1800℃1h＞99.9％th55％10Vol％SiC灰-绿1810 1800℃1h＞99.9％th58％15Vol％SiC灰-绿1820 1800℃1h99.9％th54％10Vol％TiCN灰-褐1810 1900℃3h99.9％th31％15Vol％TiCN灰-褐1790
在最终密度中：th.＝理论密度
已知的Si3N4-和SiAlON-刀具材料为浅灰色至深灰黑色，而本发明的材料在添加SiC时为灰绿色，在添加Ti(C、N)时为灰褐色。
本发明的材料作为刀具材料在加工灰口铸铁时通常连续长时间切削时令人惊异地没有出现已知刀具材料起始磨损的缺点，而是直至其耐用度结束仍保持锋利的切削刃。此外看出，本发明的材料即使在所谓的“条纹状磨损”时仍令人惊异地证明是具有优点的：切削具有特别是腐蚀性铸件砂皮的灰口铸铁时，迄今为止已知的刀具材料短时间后便形成深缺口。这种磨损主要是通过化学磨损，也就是刀具材料和工件材料之间的化学反应造成的。本发明的材料在明显更长的耐用度后才表现出这种磨损。
从图1和图2的两个曲线图中可以看出本发明的材料“新型刀具材料”相比于“参照物”由氮化硅组成材料的优点。图1说明主切削刃上的磨损宽度“VBH”取决于切削数量。在切削速度(车削件在切削刃上的圆周速度)“vc＝1000m/min”，进刀量“f＝0.5mm/U”和横向进刀(切削深度)“ap＝2.0mm”的情况下车削GG15的制动盘。
图2示出同样与氮化硅刀具相比在车削具有铸件砂皮的GG25合金灰口铸铁时，取决于切削数量的角的磨损宽度“VBE”。在切削速度(车削件在切削刃上的圆周速度)“vc＝800m/min”，进刀量“f＝0.5mm/U”和横向进刀(切削深度)“ap＝2.0mm”的情况下车削。
本发明材料除了作为刀具材料使用外，也可以设想在取决于高耐磨强度和任选出现材料的热和化学负荷的其他应用领域使用。例如本发明的材料可以设想有利地作为密封圈使用或者在燃油泵和冷却液泵上，在压缩机、涡轮增压器、换热器和空调机上使用。

Claims (21)

1.SiAlON基材料，其特征在于，该材料的原料混合物由α/β-SiAlON成分A和硬质材料成分B组成，组成为70-97Vol％，最好80-95Vol％，特别优选84-91Vol％的成分A和3-30Vol％，最好5-20Vol％，特别优选9-16Vol％的成分B。
2.按权利要求1所述的材料，其特征在于，成分A由α-和β-SiAlON以及非晶形或者部分结晶的晶界相组成。
3.按权利要求1或2所述的材料，其特征在于，在烧结状态下烧结体内部α-SiAlON的含量占整个SiAlON相的10-90Vol％，优选12-60Vol％，特别优选15-50Vol％，而β-SiAlON的含量则为90-10Vol％，优选88-40Vol％，特别优选85-50Vol％。
4.按权利要求1-3之一所述的材料，其特征在于，晶界相的含量小于10Vol％，优选小于5Vol％，而且晶界相为非晶形的。
5.按权利要求1-3之一所述的材料，其特征在于，晶界相的含量小于10Vol％，优选小于5Vol％，而且晶界相为部分结晶的。
6.按权利要求5所述的材料，其特征在于，晶界相含有结晶相，优选含铝的黄长石或者二硅酸盐。
7.按权利要求1-6之一所述的材料，其特征在于，该材料的烧结体具有一种从外向内下降的α-SiAlON梯度，而且在烧成表面的α-SiAlON含量最高可以为100％。
8.按权利要求1-7之一所述的材料，其特征在于，α-和β-SiAlON晶粒的最大尺寸小于90μm，优选小于65μm，特别优选小于50μm。
9.按权利要求1-8之一所述的材料，其特征在于，硬质材料成分B使用SiC、Ti(C、N)、TiC、TiN、元素周期表(PSE)第IVb、Vb和VIb族元素的碳化物和/或者氮化物以及碳化钪和/或者碳氧化钪或者所列举的硬质材料的混合物，它们在烧结后具有不变的状态。
10.按权利要求1-9之一所述的材料，其特征在于，硬质材料嵌入晶间和/或者晶内，也就是既嵌入SiAlON晶粒之间也嵌入其内部。
11.按权利要求1-10之一所述的材料，其特征在于，硬质材料的平均粒度小于30μm，优选小于15μm，特别优选小于5μm。
12.按权利要求11所述的材料，其特征在于，硬质材料晶粒为球状、针状或者碎片状。
13.按权利要求1-12之一所述的材料，其特征在于，其硬度＞1550HV10。
14.按权利要求1-13之一所述的材料，其特征在于，其涂覆有降低磨损的涂层像Al2O3、TiN或者TiC涂层。
15.一种制备根据权利要求1-14之一的SiAlON基材料的方法，通过粉末混合、成型、烧结和磨削制造，该方法在制造特别是由SiAlON材料组成的高效陶瓷成分时使用。
16.按权利要求15所述的方法，其特征在于，成分A是在1800-2000℃温度下进行热处理，在0.5-5小时的最高温度的保温时间期间形成的。
17.按权利要求15或16所述的方法，其特征在于，烧结气氛为惰性的并含有N2或者由N2和其他惰性气体，特别是氩组成的混合气体。
18.按权利要求1-14之一所述的材料，按照权利要求15-17所述的一种方法制造，作为刀具材料使用。
19.按权利要求1-14之一所述的材料，按照权利要求15-17所述的一种方法制造，作为加工灰口铸铁的刀具材料使用。
20.按权利要求1-14之一所述的材料，按照权利要求15-17所述的一种方法制造，作为密封圈使用。
21.按权利要求1-14之一所述的材料，按照权利要求15-17所述的一种方法制造，在燃油泵和冷却液泵、压缩机、涡轮增压器、换热器和空调机上使用。
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CF01 Termination of patent right due to non-payment of annual fee