CN1268576C - ZrO2－Al2O3复合陶瓷材料 - Google Patents
ZrO2－Al2O3复合陶瓷材料 Download PDFInfo
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- CN1268576C CN1268576C CNB2004100981564A CN200410098156A CN1268576C CN 1268576 C CN1268576 C CN 1268576C CN B2004100981564 A CNB2004100981564 A CN B2004100981564A CN 200410098156 A CN200410098156 A CN 200410098156A CN 1268576 C CN1268576 C CN 1268576C
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- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 61
- 239000013078 crystal Substances 0.000 claims description 46
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 11
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 238000005245 sintering Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 20
- 239000003381 stabilizer Substances 0.000 description 13
- 230000032683 aging Effects 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000006185 dispersion Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 8
- 239000002114 nanocomposite Substances 0.000 description 7
- 238000001513 hot isostatic pressing Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000005452 bending Methods 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 230000035882 stress Effects 0.000 description 5
- 229910052727 yttrium Inorganic materials 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- -1 cerium ion Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229910016341 Al2O3 ZrO2 Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000010987 cubic zirconia Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001272 pressureless sintering Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 150000000703 Cerium Chemical class 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000004807 localization Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000010010 raising Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003746 yttrium Chemical class 0.000 description 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 1
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Abstract
提供一种ZrO2-Al2O3复合陶瓷材料，其有优异的机械强度和韧性，并具有防止低温老化的能力。这种陶瓷材料包括平均粒径为0.1到0.8微米，且含10到12摩尔%的CeO2和0.005摩尔%到小于0.5摩尔%的Y2O3的ZrO2晶粒的第一相，和具有平均粒径为0.1到0.5微米Al2O3晶粒的第二相。ZrO2晶粒由90%或更多的四方ZrO2组成，复合陶瓷材料中的第二相含量为20到60体积%，优选30到50体积%。
Description
背景技术
1.发明领域
本发明涉及一种具有优异机械性能和防止低温老化能力的ZrO2-Al2O3复合陶瓷材料。
2.现有技术的公开
与典型的陶瓷材料如矾土、氮化硅和碳化硅相反，含2-3摩尔％Y2O3作为稳定剂的氧化钇稳定的四方二氧化锆多晶(Y-TZP)显示出优异的机械性能，例如高强度和高韧性，因此已经广泛地在实际中使用。近年来，正开始将Y-TZP陶瓷用作人造关节、假牙根、基牙、齿冠等等的生物材料。
然而，Y-TZP陶瓷的问题是在相对低温区域例如200到300进行从亚稳的四方ZrO2到单斜ZrO2的相变，同时伴随大约4.6％的体积膨胀。由于在Y-TZP陶瓷中受到这种体积膨胀而发展的微裂的影响，在机械性能方面出现相当大的损坏。另外，众所周知在潮湿条件下(例如体内环境)会进一步加速相变。作为这种Y-TZP陶瓷低温老化的主要原因的之一，认为将三价的钇离子填隙式地溶于四价锆离子的八配位位置，因此由化合价水平的差异在ZrO2晶格中产生氧致缺陷。
另一方面，含有二氧化铈作为稳定剂的二氧化铈稳定的四方二氧化锆多晶(Ce-TZP)也是为人们所熟知的。在这种情况中，因为将四价的铈离子溶入二氧化锆晶格，就不产生氧致缺陷。由许多的试验数据已经证明了在结晶学上该Ce-TZP陶瓷的低温老化未发生，另外，这种陶瓷显示出非常高的韧性。然而，有一个问题就是Ce-TZP陶瓷的机械强度和硬度比Y-TZP陶瓷的要低得多。因此，它已经成为实际应用中极大的障碍。
例如，象早期日本专利公告63-156063或63-123861所公开的那样，用二氧化铈和氧化钇两者作稳定剂来获得高强度ZrO2烧结体。这种ZrO2烧结体包括主要由四方ZrO2或四方ZrO2和立方ZrO2组成的部分稳定的氧化锆，其含有4到6摩尔％的二氧化铈(CeO2)和2到6摩尔％的氧化钇(YO1.5)作为稳定剂，和至少选自矾土、尖晶石和莫来石的第二相。在这种情况中，认为因为这种烧结体的ZrO2与仅含有氧化钇作为稳定剂的四方ZrO2相比具有更接近于立方晶体的结构也就是ZrO2的高温稳定相，所以改善了热稳定性。
然而，有另一个问题，就是在烧结过程中立方ZrO2晶粒在尺寸上比四方ZrO2容易变得更大。也就是说，ZrO2的晶粒反常生长容易发生。因此，难以确保足够的强度、硬度和可靠的耐磨性。另外，第二相如矾土和莫来石的存在使含氧化钇作为稳定剂的ZrO2基体难以完成烧结。因此，将需要专门的烧结技术如压力烧结或HIP来获得致密的烧结体。这导致生产费用增加并限制具有复杂形状的烧结体的生产。
发明概述
因此，本发明涉及一种ZrO2-Al2O3复合陶瓷材料，其机械强度和韧性优异，并且具有基本上克服低温老化问题的能力。
也就是说，本发明的陶瓷材料包括平均粒径为0.1到0.8微米，并且含有10到12摩尔％的CeO2和0.005摩尔％到小于0.5mol％的Y2O3的ZrO2晶粒的第一相，和包括具有平均粒径为0.1到0.5微米的Al2O3晶粒的第二相。ZrO2晶粒由90体积％或更多四方ZrO2组成，并且在复合陶瓷材料中第二相的含量在20到60体积％。
通常，一般认为作四方ZrO2的稳定剂需要2到3摩尔％的Y2O3。与此相反，需要的CeO2作为稳定剂与极少量的Y2O3结合使用对本发明来说是必要的。在这种情况中，有意义的是注意：通过添加Y2O3几乎不能期望达到稳定剂作用。就是说，本发明重要发现之一是通过10到12摩尔％的CeO2作为稳定剂与0.005到小于0.5摩尔％的Y2O3结合使用对显著地改善差的机械性能(是Ce-TZP陶瓷的主要缺点)是有效的，和同时防止低温老化(是Y-TZP陶瓷的主要缺点)。因此，本发明的工艺原理与传统的通过使用CeO2和Y2O3两者作为稳定剂改善Y-TZP陶瓷热稳定性的工艺原理不同。
本发明的这些还有其他的目的和优点通过本发明的详述和下面阐明的优选实施例将变得更加明显。
发明详述
以下详细说明本发明的ZrO2-Al2O3复合陶瓷材料和其生产方法。
使用含10到12摩尔％的CeO2和0.005摩尔％到小于0.5摩尔％的Y2O3的ZrO2晶粒作为第一相对本发明的ZrO2-Al2O3复合陶瓷材料来说是必要的。如前所述，CeO2作为稳定剂对于具有防止低温老化能力的四方ZrO2起着重要作用。当CeO2含量在10到12摩尔％时，第一相的ZrO2晶粒由90体积％或更多四方ZrO2组成。即使单斜ZrO2出现在第一相中，它的含量也是小于10体积％。在这时，没有立方ZrO2产生。因此，根据ZrO2的应力诱导相变效应能有效改善机械强度和韧性。另一方面，当CeO2含量小于10摩尔％时，单斜ZrO2数量相对增加，以致微裂纹在该复合陶瓷材料中容易扩大。这导致机械强度显著降低。当CeO2含量大于12摩尔％时，高温稳定相的立方ZrO2开始在复合陶瓷材料中出现。当由于立方ZrO2的产生而导致当四方ZrO2量小于90体积％时，不能获得足够的机械强度和韧性。
同时，已经知道使用2到3摩尔％的Y2O3作为四方ZrO2的稳定剂。另一方面，对本发明相对于ZrO2的总量使用极小限度即0.005到小于0.5摩尔％的Y2O3来说是必要的。因此，在本发明中，不能预料到Y2O3的稳定剂效果。换句话说，当将小于0.5摩尔％的Y2O3单独加入到ZrO2中时，单斜ZrO2成为主要的成分。因此，使用少量的Y2O3不能获得稳定剂效果。
然而，本发明者发现通过10到12摩尔％的CeO2与少量的Y2O3的结合使用，能同时解决低温老化的问题(是Y-TZP陶瓷的缺点)和机械强度差的问题(是Ce-TZP陶瓷的缺点问题)。在本发明中，当Y2O3的含量小于0.005摩尔％时，抑制ZrO2晶粒反常生长的效果变得不足，以致不能达到复合陶瓷材料机械强度和硬度的改善。另一方面，当Y2O3的含量远大于0.5摩尔％时，Y2O3的稳定剂效果逐渐地开始出现。这意味着低温老化成为问题。
如果CeO2作为四方ZrO2稳定剂与少量Y2O3结合使用，不希望受到理论束缚，人们相信如下所述晶粒反常生长抑制机制对于改善ZrO2-Al2O3复合陶瓷材料的机械性能起着重要作用。
陈等人(S.L.Hwang和I-w chen J.Am.cerams.Soc.73.3269c199))报道说研究了各种掺杂物对二氧化铈稳定的四方ZrO2晶粒生长的作用，因为掺杂物具有比Ce4+更小的化合价，所以晶粒生长的抑制作用增加。另外，据报导当掺杂物具有与Ce4+相同化合价时，通过具有离子半径比Ce4+更大的掺杂物进一步增加晶粒生长的抑制作用。因此，按照本发明，认为由于有具有比Ce4+更小化合价，和比Ce4+(0.97×10-1nm)更大的离子半径(1.019×10-1nm)的Y3+存在会引起晶粒生长抑制的作用。
而且，Ikuhara等(Y.Ikuhara，T.Sakuma，Ceramics，32，524(1997))报道说对于具有稳定晶粒间界结构和均匀晶粒粒径分布的Y-TZP陶瓷的晶粒间界进行了局部化组成分析，在晶粒间界附近具有几个纳米宽度的区域处观察到钇(Y)的离析。和Y-TZP陶瓷情况一样，有可能在Ce-TZP陶瓷中发生在晶粒间界附近钇相似的离析。认为在晶粒间界附近发生这样的分离会降低晶粒间界的迁移率和提高晶粒生长抑制的效果。
在本发明中，第一相的ZrO2晶粒具有0.1到0.8微米的平均粒径。当平均粒径大于0.8微米时，导致复合陶瓷材料机械强度和耐磨性降低或机械性能变化。另一方面，很难在复合陶瓷材料中获得具有小于0.1微米平均粒径的第一相。特别地，因为需要压力烧结或HIP处理来获得致密的烧结体，所以会出现性价比降低和生产率降低的问题。另外，为了在本发明的复合陶瓷材料中形成后面所述的“纳米复合结构”，要把Al2O3细晶粒有效地分散在ZrO2晶粒中会变得困难。
在本发明中，优选比第一相的平均粒径大二或更多倍的ZrO2晶粒数相对于分散在复合陶瓷材料中全部的ZrO2晶粒数的比例是10％或更小。这一比例可以通过使用上述定义的CeO2和Y2O3的量来获得。如果必要，第一相还可以含有氧化钛、氧化镁、氧化钙或少量的杂质。
另外，本发明的ZrO2-Al2O3复合陶瓷材料的第二相基本上是由平均粒径为0.1到0.5微米的Al2O3晶粒组成。当平均粒径小于0.1微米时，开始出现Al2O3晶粒的聚集，变得难以将Al2O3晶粒均匀地分散于第一相中。这导致机械特性的改变。另一方面，当平均粒径大于0.5微米时，陶瓷复合材料的耐磨性和硬度下降。尤其是，由于Al2O3晶粒不能有效地分散在第一相的ZrO2晶粒中，所以难于形成上述的陶瓷复合材料中的“纳米复合结构”。
另外，本发明的陶瓷复合材料基本上含有20到60体积％，优选30到50体积％的Al2O3晶粒。当Al2O3含量小于20体积％时，该陶瓷复合材料的机械强度和耐磨性不能得到足够的提高。而且，比第一相的平均粒径大二或更多倍的ZrO2晶粒数相对于分散在复合陶瓷材料中全部的ZrO2晶粒数的比例容易变得大于10％。另一方面，当Al2O3含量超过50体积％时，由于Al2O3晶粒聚集的增加而导致机械强度逐渐降低。当Al2O3含量超过60体积％时，由于Al2O3构成了基质相，导致机械强度和韧性显著降低。当陶瓷复合材料含有30到50％的第二相时，可能会得到具有均匀的机械强度和高度韧性的陶瓷复合材料。
在本发明中，优选A2O3细晶粒分散于ZrO2晶粒中在陶瓷复合材料中形成纳米复合结构。为了得到“纳米复合结构”，需要适度的ZrO2晶粒生长。然而，过量的晶粒生长会导致破坏机械强度、硬度和耐磨性。在本发明中，使用上面规定量的CeO2和Y2O3能达到ZrO2晶粒的适度生长。在这种情况中，也优选分散在ZrO2晶粒中的Al2O3晶粒数相对于分散在复合陶瓷材料中的全部Al2O3晶粒数的比例是2％或更多。
简要地说明通过将“纳米复合结构”引入复合陶瓷材料中所带来的优点。第一，通过形成“纳米复合”结构能显著加强第一相的ZrO2晶粒。另外，不存在异常晶粒生长的情况下均匀的细微结构会主要表现出优异的耐磨性。不希望受到这种理论的束缚，认为意想不到的改进的理由之一是基于因堆积位错而在ZrO2晶粒中形成亚晶粒间界，其在将ZrO2晶粒分成更细尺寸晶粒的假想中发挥作用。
也就是说，当将第二相的Al2O3细晶粒分散在第一相的ZrO2晶粒中时，由于在烧结过后的冷却工序中Al2O3与ZrO2二者之间热膨胀系数的不同，在每一个分散在ZrO2晶粒中的Al2O3细晶粒周围会局部产生剩余应力区域。受到该剩余应力区域的影响，在各个ZrO2晶粒中发生许多位错。然后位错彼此堆积，最终形成亚晶粒间界。亚晶粒间界带来更细的晶粒结构，其具有增加为引起从四方ZrO2到单斜ZrO2的应力诱导相变所需的临界应力的能力。结果，本发明的复合陶瓷材料显示出高机械强度和韧性以及优异耐磨性和硬度。
因此，为了防止低温老化，也为获得形成“纳米复合结构”来改善复合陶瓷材料的机械强度和韧性而所需的ZrO2晶粒的适当晶粒生长，确定本发明中规定的Y2O3和CeO2的添加量。
本发明的复合陶瓷材料是特别适于必需耐磨的应用中。例如，优选将本发明的复合陶瓷材料用于在WO 02/11780A1中所描述的人工关节。也就是说，当以复合陶瓷材料和聚乙烯之间的滑动接触提供人造关节的连接部分时，有可能显著地减少聚乙烯的磨损量。另外，当以复合陶瓷材料之间的滑动接触提供人造关节的连接部分时，能得到优异的耐磨性。因此，利用本发明的复合陶瓷材料对于得到具有在苛刻体内条件下连续长时间稳定地提供平滑连接运动的能力是有益的。
接下来，详细说明生产本发明的ZrO2-Al2O3复合陶瓷材料的方法。这种生产方法包括下列步骤：制备提供第一相的ZrO2晶粒的第一组分和提供第二相的Al2O3晶粒的第二组分；按照第二相在复合陶瓷材料中的含量为20到60体积％，更优选30-50体积％，将第一组分与第二组分混合；按所希望的形状模制所得到的混合物以获得生坯；在含氧气氛中在所需的烧结温度下烧结生坯。
按照在复合陶瓷材料的第一相中CeO2和Y2O3的含量分别为10到12摩尔％和0.005到小于0.5摩尔％制备第一组分，第一相是由90体积％或更多四方ZrO2组成。例如，作为第一组分，优选用通过使ZrO2与上规定量的CeO2和Y2O3形成固溶体而获得的四方ZrO2粉末。
可选择地，可以通过下述方法制备四方ZrO2粉末。也就是说，将含铈化合物如铈盐和含钇化合物如钇盐加入锆盐的水溶液中。然后，通过将如氨水这样的碱水溶液加入到所得到的混合物溶液中进行水解来获得沉淀。干燥沉淀物，在含氧气氛中例如在空气中煅烧，然后用湿式球磨机粉碎来获得具有所希望粒度分布的四方ZrO2粉末。
第二种组分是这样制备的，烧结之后将Al2O3晶粒分散在复合陶瓷材料中。例如，优选通过将碱水溶液例如氨水溶液加入到铝盐水溶液中进行水解来制备具有理想粒径分布的Al2O3粉末，干燥所得到的沉淀，在含氧气氛例如在空气中煅烧沉淀，利用湿式球磨机粉碎煅烧过的沉淀。可选择地，使用市售的Al2O3粉末。
优选在含氧气氛中烧结温度为1400到1500℃条件下进行烧结步骤。在烧结步骤中，使第一相的ZrO2晶粒的平均晶粒尺寸和第二相的Al2O3晶粒的平均晶粒尺寸分别满足0.1到0.8微米和0.1到0.5微米的条件是很重要的。更优选地，这样确定烧结条件，即分散在ZrO2晶粒中的Al2O3晶粒数相对于分散在复合陶瓷材料中全部的Al2O3晶粒数的比例是2％或更多。
换句话说，晶粒间界的迁移率也就是在含有以CeO2作为稳定剂的Ce-TZP陶瓷中的烧结指数比Y-TZP或氧化铝陶瓷高得多。因此，能利用无压烧结而无需使用压力烧结或HIP(热等静压)处理来致密地烧结含Ce-TZP陶瓷的复合陶瓷材料。然而，如果有必要的话，可以在烧结之后在含氧气氛中进行HIP处理。为了最大限度获得HIP处理的效果，经过烧结步骤而获得的复合陶瓷材料的烧结体优选具有95％或更大的相对密度。烧结步骤中在含氧气氛中的氧浓度没有特别地限制。可以使用氧气和如氩的惰性气体的混合气体。在这种情况中，优选氧的浓度相对于混合气体的总体积为大约5体积％或更多。
实施例
以下说明本发明的优选实施例。然而，无需说的是本发明并不局限于这些实施例。
<实施例1到20和对比例1到5>
实施例1到20中的每一个的ZrO2-Al2O3复合陶瓷材料是通过下述方法制造的。也就是说，使用具有比表面积为15m2/g和含列于表1或2中所需量的CeO2和Y2O3的四方ZrO2粉末，作为提供ZrO2晶粒的第一组分，即复合陶瓷材料的第一相。另一方面，使用具有平均粒径为0.2微米的α-Al2O3粉末，作为提供Al2O3晶粒的第二组分，即复合陶瓷材料的第二相。
接下来，将列于表1和2中所需量的α-Al2O3粉末加入到四方ZrO2粉末中，然后利用湿式球磨机在乙醇中混合24小时。干燥所得到的混合物以获得混合粉末。在10MPa压力下用具有直径大约为68mm的模具通过单轴挤压来模制该混合粉末以获得盘状的生坯。接下来，对生坯在147MPa压力下进行CIP(冷等静压)处理。最后，在1450℃的烧结温度下在空气中通过无压烧结烧结2小时以获得烧结体。
比较例1的ZrO2-Al2O3复合陶瓷材料是通过与实施例1相同的方法生产的，除了没有加入Y2O3以外。比较例2的ZrO2-Al2O3复合陶瓷材料是通过与实施例1相同的方法生产的，只是加入了1摩尔％的Y2O3。另外，比较例3到5的ZrO2-Al2O3复合陶瓷材料是通过与实施例1相同的方法生产的，除了Al2O3的含量没在本发明的范围内以外，如表2所列。
对于实施例1到20和比较例1到5中的每一个，烧结体具有的相对密度超过99％。从X射线衍射分析的结果，证实了各个烧结体的第一相由超过95体积％的四方ZrO2和其余的单斜ZrO2组成。没有X射线分布图显示存在立方ZrO2。从SEM(扫描电子显微镜)和TEM(透射电子显微镜)观察烧结体，证实了该烧结体具有纳米复合结构，其特征在于第二相的Al2O3细晶粒分散在第一相的ZrO2晶粒中。
如表1和2所列，从SEM和TEM观察测得的烧结体的第一和第二相的平均粒径分别为0.3到0.8微米，和0.2到0.5微米。而且，为了评价该复合陶瓷材料试样的机械性能，用烧结体制备具有4mm×3mm×40mm尺寸的试样。紧接着，利用试样在室温下测量3点的抗弯强度和断裂韧性。通过IF法确定断裂韧性。结果列在表3和4上。
另外，Al2O3分散比率(W1)，其定义为分散在ZrO2晶粒中的Al2O3晶粒数相对于分散在复合陶瓷材料中的全部Al2O3晶粒数的比率，ZrO2分散比率(W2)，其定义为比第一相的平均粒径大两或更多倍的ZrO2晶粒数相对于分散在复合陶瓷材料中的全部ZrO2晶粒数的比率，通过以下方法确定W1和W2。第一，通过抛光和热处理烧结体制备样品。然后，对样品进行SEM或TEM观察，来计算在视图区内第二相的全部Al2O3晶粒数(S1)，计算在相同视图区内分散在第一相的ZrO2晶粒中的Al2O3细晶粒数(n1)，计算在相同视图区内第一相的全部ZrO2晶粒数(S2)，计算在相同视图区内比第一相的平均粒径大二或更多倍的ZrO2晶粒数(n2)。通过将这些值代入以下方程式，计算出Al2O3和ZrO2的分散比率。结果示于表3和4中。
W1[％]＝(n1/S1)×100，
W2[％]＝(n2/S2)×100。
参考实施例1到15和比较例1和2中的每一个，进行压热试验以检查复合陶瓷材料存在还是不存在低温老化。也就是说，在121℃和1.15MPa的苛刻条件下进行100小时压热试验之后，测量单斜ZrO2数量，然后与试验前测量的单斜ZrO2数量相比较。结果示于表3中。
参考所有的实施例，如表1和2所示，Al2O3分散比率W1大于2％，和ZrO2分散比率W2小于10％。另外，观察到压热试验没有发生从四方ZrO2到单斜ZrO2的重大相变。
在比较例1中，ZrO2分散比率W2是15％。认为ZrO2分散比率W2的增加与抗弯强度显著降低有关。在比较例2中，通过压热试验可知单斜ZrO2的量从1.8体积％增加到25体积％。认为这种单斜ZrO2量的增加与断裂韧性显著下降有关。在比较例3和4中，因为复合陶瓷材料中的Al2O3含量小于20体积％，阻止ZrO2晶粒生长的效果不够，于是抗弯强度降低。另一方面，在比较例5中，因为Al2O3含量大于60体积％，抗弯强度显著降低。
如从上述实施例了解到的，本发明的ZrO2-Al2O3复合陶瓷材料的特征在于：通过10到12摩尔％作为稳定剂的CeO2与极少量(0.005到小于0.5摩尔％)的Y2O3结合使用同时阻止由ZrO2晶粒反常生长(即Ce-TZP陶瓷的主要的缺点)所引起的抗弯强度下降和与低温老化紧密相联的单斜ZrO2相变(即Y-TZP陶瓷主要的缺点)，来显示优异的机械强度和韧性。
因此，可以预料的是本发明的复合陶瓷材料可广泛地用于各种应用领域，例如，工业机器零件如光纤连接器的套圈、轴承和模具、切割工具如剪刀和锯条、固定物品、化学制品如机械焊接和采矿传动机构、体育器材、医疗设备如外科手术刀、生物材料部件如人造关节、人工骨、人造牙根、基牙和齿冠。
表1
| 原料 | 复合陶瓷材料 | ||||
| 第一相摩尔％) | 第二相(摩尔％) | 平均粒径(微米) | |||
| CeO2 | Y2O3 | Al2O3 | ZrO2 | Al2O3 | |
| 实施例1 | 10 | 0.020 | 30 | 0.69 | 0.38 |
| 实施例2 | 10 | 0.030 | 30 | 0.63 | 0.35 |
| 实施例3 | 10 | 0.170 | 30 | 0.45 | 0.31 |
| 实施例4 | 10 | 0.330 | 30 | 0.39 | 0.27 |
| 实施例5 | 10 | 0.470 | 30 | 0.37 | 0.30 |
| 实施例6 | 11 | 0.010 | 30 | 0.73 | 0.40 |
| 实施例7 | 11 | 0.070 | 30 | 0.55 | 0.30 |
| 实施例8 | 11 | 0.300 | 30 | 0.40 | 0.27 |
| 实施例9 | 11 | 0.370 | 30 | 0.39 | 0.27 |
| 实施例10 | 11 | 0.430 | 30 | 0.38 | 0.30 |
| 实施例11 | 12 | 0.005 | 30 | 0.78 | 0.43 |
| 实施例12 | 12 | 0.100 | 30 | 0.50 | 0.30 |
| 实施例13 | 12 | 0.230 | 30 | 0.42 | 0.27 |
| 实施例14 | 12 | 0.400 | 30 | 0.38 | 0.27 |
| 实施例15 | 12 | 0.490 | 30 | 0.37 | 0.30 |
| 对比例1 | 10 | 0 | 30 | 1.00 | 0.38 |
| 对比例2 | 12 | 1.000 | 30 | 0.35 | 0.28 |
表2
| 原料 | 复合陶瓷材料 | ||||
| 第一相(摩尔％) | 第二相(摩尔％) | 平均粒径(微米) | |||
| CeO2 | Y2O3 | Al2O3 | ZrO2 | Al2O3 | |
| 对比例3 | 10 | 0.45 | 0 | 2.5 | -- |
| 对比例4 | 10 | 0.45 | 10 | 1.00 | 0.25 |
| 实施例16 | 10 | 0.45 | 20 | 0.58 | 0.26 |
| 实施例17 | 10 | 0.45 | 30 | 0.35 | 0.28 |
| 实施例18 | 10 | 0.45 | 40 | 0.32 | 0.29 |
| 实施例19 | 10 | 0.45 | 50 | 0.29 | 0.30 |
| 实施例20 | 10 | 0.45 | 60 | 0.27 | 0.31 |
| 对比例5 | 10 | 0.45 | 70 | 0.26 | 0.32 |
表3
| 三点抗弯强度(MPa) | 断裂韧性(MPa.ml/2) | Al2O3分散比率W1(％) | ZrO2分散比率W2(％) | 压热试验单斜ZrO2的量(体积％) | ||
| 试验前 | 试验后 | |||||
| 实施例1 | 1050 | 18.8 | 3.4 | 7.8 | 4.1 | 4.2 |
| 实施例2 | 1100 | 18.6 | 3.1 | 7.0 | 3.8 | 3.7 |
| 实施例3 | 1240 | 18.4 | 3.3 | 4.2 | 3.6 | 3.7 |
| 实施例4 | 1290 | 18.2 | 3.1 | 2.5 | 4.2 | 4.1 |
| 实施例5 | 1280 | 18.0 | 2.5 | 2.1 | 3.9 | 4.0 |
| 实施例6 | 1120 | 15.5 | 3.3 | 8.5 | 3.1 | 3.2 |
| 实施例7 | 1230 | 15.4 | 3.0 | 6.0 | 2.9 | 2.8 |
| 实施例8 | 1330 | 15.2 | 3.2 | 2.7 | 3.3 | 3.5 |
| 实施例9 | 1310 | 15.0 | 3.1 | 2.4 | 3.4 | 3.3 |
| 实施例10 | 1290 | 14.8 | 2.6 | 2.2 | 3.2 | 3.1 |
| 实施例11 | 1200 | 11.5 | 3.2 | 9.3 | 2.6 | 2.5 |
| 实施例12 | 1350 | 11.3 | 3.1 | 5.0 | 2.9 | 2.8 |
| 实施例13 | 1400 | 11.2 | 3.2 | 3.2 | 2.3 | 2.5 |
| 实施例14 | 1400 | 11.1 | 3.1 | 2.3 | 2.7 | 2.8 |
| 实施例15 | 1450 | 11.1 | 2.5 | 2.0 | 2.8 | 2.6 |
| 对比例1 | 950 | 18.9 | 3.6 | 15.0 | 3.6 | 3.7 |
| 对比例2 | 1300 | 8.5 | 2.5 | 1.8 | 1.8 | 25.0 |
表4
| 三点抗弯强度(MPa) | 断裂韧性(MPa.ml/2) | Al2O3分散比率W1(％) | ZrO2分散比率W2(％) | |
| 对比例3 | 700 | 23.0 | -- | 25.2 |
| 对比例4 | 1010 | 22.3 | 3.0 | 13.3 |
| 实施例16 | 1170 | 21.0 | 2.9 | 4.8 |
| 实施例17 | 1290 | 18.9 | 2.8 | 2.1 |
| 实施例18 | 1340 | 16.0 | 2.6 | 1.8 |
| 实施例19 | 1270 | 12.5 | 2.3 | 1.6 |
| 实施例20 | 1100 | 8.5 | 2.1 | 1.5 |
| 对比例5 | 750 | 4.5 | 1.4 | 1.3 |
Claims (4)
1.一种ZrO2-Al2O3复合陶瓷材料，包含：
平均粒径为0.1到0.8微米，且含10到12摩尔％的CeO2和0.005摩尔％到小于0.5摩尔％的Y2O3的ZrO2晶粒的第一相，所述的ZrO2晶粒由90％体积或更多的四方ZrO2组成；和
平均粒径为0.1到0.5微米的Al2O3晶粒的第二相，所述的复合陶瓷材料中的第二相含量为20到60体积％。
2.根据权利要求1的复合陶瓷材料，其中所述的复合陶瓷材料中的第二相含量为30到50体积％。
3.根据权利要求1的复合陶瓷材料，其中所述的Al2O3晶粒分散在所述的ZrO2晶粒中的数相对于分散在复合陶瓷材料中的全部Al2O3晶粒数的比例为2％或更多。
4.根据权利要求1的复合陶瓷材料，其中比所述的第一相的平均晶粒尺寸大二或更多倍的所述ZrO2晶粒数相对于分散在复合陶瓷材料中的全部ZrO2晶粒数的比例为10％或更少。
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| US20020198602A1 (en) * | 2000-08-07 | 2002-12-26 | Masahiro Nawa | Artificial joint made from zirconia-alumina composite ceramic |
| KR100400263B1 (ko) * | 2001-07-04 | 2003-10-01 | 주식회사 코스마 | 와이어 본딩용 알루미나-지르코니아 복합체 캐필러리소결체 및 그의 제조 방법 |
| AU2003213529B2 (en) * | 2002-07-19 | 2005-01-20 | Panasonic Healthcare Holdings Co., Ltd. | ZrO2-AI2O3 composite ceramic material and production method thereof |
| US7148167B2 (en) * | 2003-08-28 | 2006-12-12 | Kyocera Corporation | Alumina/zirconia ceramics and method of producing the same |
-
2004
- 2004-08-16 AU AU2004203889A patent/AU2004203889B2/en not_active Ceased
- 2004-08-17 EP EP04019509A patent/EP1508554A3/en not_active Withdrawn
- 2004-08-20 US US10/921,841 patent/US7056851B2/en not_active Expired - Fee Related
- 2004-08-20 KR KR1020040065874A patent/KR100573758B1/ko not_active IP Right Cessation
- 2004-08-23 CN CNB2004100981564A patent/CN1268576C/zh not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| AU2004203889A1 (en) | 2005-03-10 |
| EP1508554A2 (en) | 2005-02-23 |
| US7056851B2 (en) | 2006-06-06 |
| EP1508554A3 (en) | 2008-01-23 |
| KR100573758B1 (ko) | 2006-04-24 |
| US20050079971A1 (en) | 2005-04-14 |
| CN1607196A (zh) | 2005-04-20 |
| KR20050020706A (ko) | 2005-03-04 |
| AU2004203889B2 (en) | 2006-02-23 |
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