CN111908923A - 一种高硬度氮化硅陶瓷及其制备方法 - Google Patents
一种高硬度氮化硅陶瓷及其制备方法 Download PDFInfo
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 145
- 239000000919 ceramic Substances 0.000 title claims abstract description 114
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 76
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 27
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 27
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 24
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 18
- 239000010432 diamond Substances 0.000 claims abstract description 18
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims description 131
- 238000000498 ball milling Methods 0.000 claims description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
- 238000007731 hot pressing Methods 0.000 claims description 29
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 25
- 238000003825 pressing Methods 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 229910002804 graphite Inorganic materials 0.000 claims description 20
- 239000010439 graphite Substances 0.000 claims description 20
- 238000005303 weighing Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 235000015895 biscuits Nutrition 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 5
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 5
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 5
- 238000000748 compression moulding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical group O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 4
- 239000007943 implant Substances 0.000 claims description 3
- 230000000399 orthopedic effect Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
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- 239000007787 solid Substances 0.000 description 19
- 238000001035 drying Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 12
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 12
- 238000011049 filling Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- 229910003443 lutetium oxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- -1 rare earth cation Chemical class 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
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Abstract
本发明涉及一种高硬度氮化硅陶瓷及其制备方法,以Si3N4作为主相,以SiC、TiC、ZrC、B4C和金刚石中的至少一种作为第二相,以Al2O3和稀土氧化物作为烧结助剂,以Li2O或/和LiF作为低温烧结助剂,经烧结后得到所述高硬度氮化硅陶瓷。
Description
技术领域
本发明涉及一种高硬度氮化硅陶瓷及其制备方法,具体涉及一种是以Si3N4为主相,Al2O3和La2O3为烧结助剂,Li2O或LiF为低温烧结助剂,SiC、TiC、ZrC、B4C或金刚石中的一种或多种为提高硬度的第二相,来制备高硬度的Si3N4陶瓷的方法,属于Si3N4陶瓷的制备领域。
背景技术
氮化硅陶瓷具有高强度、高硬度、高韧性等优异的力学性能,以及耐腐蚀、抗氧化、抗热震等多重化学和热力学稳定性,被誉为结构陶瓷的全能冠军。同时,氮化硅陶瓷由于具有优异的耐磨损性能和生物安全性,也逐渐被用作髋关节球头等骨科植入物。例如,专利(中国公开号CN 103435356A)公开了一种凝胶注模成型、无压烧结制备氮化硅人工陶瓷关节的方法。该专利指出氮化硅陶瓷与氧化铝或氧化锆制备的人工陶瓷关节相比,具有更高的可靠性,适合在人体内长期使用。但是该专利并没有对氮化硅陶瓷的硬度作具体的考察,这不利于对氮化硅陶瓷的摩擦磨损性能形成全面的认知。专利(中国公开号CN108585880A)公开了一种氮化硅陶瓷髋关节球头的制备方法,该专利虽对成型条件进行了一定的研究,但没有对氮化硅陶瓷的性能进行考察,这同样不利于深入理解氮化硅陶瓷力学性能与使用寿命的关系。
作为一种长寿命骨科植入物,氮化硅陶瓷需要具有优异的耐磨损性能。较高的硬度是优异耐磨损性能的保障。氮化硅陶瓷具有α和β两种常见的晶体结构。相比于β-Si3N4,α-Si3N4具有更高的本征硬度。
发明内容
为了提高氮化硅陶瓷的硬度,本发明人基于针对性地抑制α-βSi3N4相转变,使基体中更多地存留α-Si3N4,同时在氮化硅陶瓷基体中掺入硬度更高的第二相,协同提高氮化硅陶瓷硬度,提供了一种高硬度氮化硅陶瓷及其制备方法。
一方面,本发明提供了一种高硬度氮化硅陶瓷,以Si3N4作为主相,以SiC、TiC、ZrC、B4C和金刚石中的至少一种作为第二相,以Al2O3和稀土氧化物作为烧结助剂,以Li2O或/和LiF作为低温烧结助剂,经烧结后得到所述高硬度氮化硅陶瓷。优选,第二相选自SiC、TiC、ZrC、B4C和金刚石中的两种。以B4C和金刚石做为示例,二者质量比可为1:3~3:1,在此质量比范围内不同种类第二相可实现协同提高硬度。
本公开中,结合晶型控制和第二相掺杂两种方式来协同提高氮化硅陶瓷的硬度。具体来讲,采用二元或三元低熔点烧结助剂来降低烧结温度,以实现抑制α-Si3N4向β-Si3N4的相转变,获得以高硬度的α-Si3N4为主相的氮化硅材料;同时掺入TiC、SiC、B4C、ZrC或金刚石等硬度更高的第二相,一方面根据混合法则,可提高氮化硅陶瓷的硬度,另一方面,这些第二相的加入能够显著抑制氮化硅晶粒生长,获得细晶结构的氮化硅陶瓷,根据Hall-Petch效应,晶粒尺寸降低能够提高氮化硅陶瓷的硬度。
较佳的,所述稀土氧化物为La2O3、Sm2O3、Nd2O3和CeO2中的至少一种。氮化硅陶瓷的烧结以及α-Si3N4向β-Si3N4的相转变与所用稀土氧化物种类密切相关。稀土阳离子半径越大,阳离子场强越小,因而更容易在较低的温度下形成低粘度的液相,促进液相传质,实现致密化。
较佳的,所述主相、第二相、烧结助剂和低温烧结助剂的质量比为(69~90):(5~20):(4~6):(1~5)。
较佳的,所述烧结助剂中Al2O3和稀土氧化物的摩尔比(1~4):1,优选为5:3。烧结助剂选用该比例,更容易在烧结后形成结晶的晶间相,有助于硬度的提高。
较佳的,所述高硬度Si3N4陶瓷的维氏硬度为15.8~22.3GPa。
另一方面,本发明还提供了一种上述高硬度氮化硅陶瓷的制备方法,包括:
将α-Si3N4粉体、Al2O3粉体、稀土氧化物粉体、第二相和低温烧结助剂按照质量比称量并混合,再经压制成型例,得到素坯;
将所得素坯置于石墨热压模具中并放入碳管炉中,经过烧结,得到所述高硬度氮化硅陶瓷。
较佳的,所述α-Si3N4粉体的粒径为0.3~0.8μm;所述Al2O3粉体的粒径为0.1~0.4μm;所述稀土氧化物粉体的粒径为0.5~2μm;所述低温烧结助剂的粒径为0.5~1μm;所述第二相的粒径为0.5~3μm。
较佳的,所述混合的方式为球磨混合;所述压制成型的方式为干压预成型。
又,较佳的,优选地,所述球磨混合的转数为200~400rpm,球磨时间为4~6小时;所述干压预成型的压力为20~50MPa。
较佳的,所述烧结的方式为热压烧结;所述热压烧结的温度为1450~1550℃,保温时间为60~180分钟,烧结压力为30~60MPa。
再一方面,本发明还提供了一种上述高硬度氮化硅陶瓷在制备骨科植入物中的应用,以提高其使用寿命。
有益效果:
本发明中,通过采用Al2O3和La2O3、Sm2O3、Nd2O3和CeO2中的至少一种作为烧结助剂,Li2O或LiF为低温烧结助剂,可以显著降低烧结温度,抑制α-βSi3N4的相转变,使基体中主要保持硬度较高的α-Si3N4;另外,通过添加SiC、TiC、ZrC、B4C或金刚石中的一种或多种为提高硬度的第二相,利用其本征硬度比Si3N4高和抑制Si3N4晶粒长大的优势,从而得到高硬度的Si3N4陶瓷。
附图说明
图1为实施例2中所得Si3N4陶瓷的物相分析图;
图2为实施例3中所得Si3N4陶瓷的物相分析图;
图3为实施例10中所得Si3N4陶瓷的抛光面形貌图;
图4为实施例3所得Si3N4陶瓷的抛光面形貌图。
具体实施方式
以下通过下述实施方式进一步说明本发明,应理解,下述实施方式仅用于说明本发明,而非限制本发明。
在本公开中,在氮化硅陶瓷烧结过程中,引入低温烧结助剂显著降低了氮化硅陶瓷烧结温度,降低成本,抑制了α-Si3N4到β-Si3N4的相转变;同时引入高硬度的第二相,最终制备的高硬度的Si3N4陶瓷。
在本发明的一实施方式中,以α-氮化硅粉体作为原料,以La2O3粉体、Sm2O3、Nd2O3和CeO2中的至少一种以及Al2O3粉体为烧结助剂,Li2O粉体或/和LiF粉体为低温烧结助剂,以SiC、TiC、ZrC、B4C和金刚石中的一种或多种作为提高硬度的第二相,通过热压烧结,制备得到高硬度的Si3N4陶瓷。在可选的实施方式中,以氮化硅、烧结助剂、低温烧结助剂和第二相的总质量计为100wt%,所述Si3N4的含量可为69-90%。
在可选的实施方式中,以氮化硅、烧结助剂、低温烧结助剂和第二相的总质量计为100wt%,烧结助剂的总含量可为4-6wt%。优选地,Al2O3和稀土氧化物的摩尔比为5:3。若是烧结助剂总质量过高,会导致氮化硅陶瓷硬度降低。若是烧结助剂含量较低,难以实现低温致密。
在可选的实施方式中,以氮化硅、烧结助剂、低温烧结助剂和第二相的总质量计为100wt%,Li2O或/和LiF的含量可为1-5wt%。若是低温烧结助剂的含量过高,会由于低温助剂的大量挥发在氮化硅陶瓷中留下较多孔洞,不利于硬度的提高。若是低温烧结助剂含量较低,难以实现低温致密。
在可选的实施方式中,以氮化硅、烧结助剂、低温烧结助剂和第二相的总质量计为100wt%,第二相的含量可为5-20wt%。若是第二相的含量过高,将显著影响氮化硅陶瓷致密化,无法获得致密的烧结体。若是第二相含量较低,无法有效提高氮化硅陶瓷的硬度。
综上所述,本发明中能实现低温烧结制备得到高硬度氮化硅陶瓷是烧结助剂、低温烧结助剂以及第二相的含量具有密切的关联,是三者共同作用的结果。
以下示例性地说明高硬度氮化硅陶瓷的制备方法。
将Si3N4粉体、烧结助剂(氧化铝粉体和氧化镧粉体)、低温烧结助剂和第二相,按照(69-90):(4-6):(1-5):(5-20)的质量比例称量原料,再添加酒精配置成一定固含量的浆料。将所得浆料再进行球磨、烘干、过筛,得到原料粉体。配置得到的浆料的固含量可为60-70wt%。球磨过程中,控制球料比为1.5:1-2.5:1,球磨转数在200-400rpm之间,球磨时间在4-6h之间。其中,烘干的温度可为100℃-120℃,烘干时间可为2-4h。过筛目数可为100-325目。
将原料粉体经压制成型,得到素坯。其中,压制成型包括但不仅限于干压预成型等。干压预成型的压力可为20-50MPa。最后将预成型的素坯放入石墨热压模具中,并放入碳管炉中进行烧结。烧结的方式包括但不仅限于热压烧结等。其中,热压烧结的温度可为1450-1550℃。热压烧结的保温时间可为60-180min。热压烧结的烧结压力可为30~60MPa。热压烧结的气氛为氮气。
在本发明中,采用维氏硬度计测试得到Si3N4陶瓷的维氏硬度可为15.8~22.3GPa。采用阿基米德排水法测试得到Si3N4陶瓷的致密度可为98.1~99.5%。在本发明中,所得Si3N4陶瓷具有高硬度的优点,可用于制作髋关节球头,其使用寿命得到了很大的提升。
下面进一步例举实施例以详细说明本发明。同样应理解,以下实施例只用于对本发明进行进一步说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例,即本领域技术人员可以通过本文的说明做合适的范围内选择,而并非要限定于下文示例的具体数值。下述实施例和对比例中若无特殊说明,Si3N4的粒径为0.3-0.8μm,Al2O3的粒径为0.1-0.4μm,La2O3、Sm2O3、Nd2O3和CeO2的粒径为0.5-2μm,Li2O的粒径为0.5-1μm,LiF的粒径为0.5-1μm,第二相的粒径为0.5-3μm。
实施例1
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体90g,与1.37g Al2O3粉体、2.63g La2O3粉体、1克Li2O粉体和5克SiC粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入100℃恒温箱中烘2h,研磨,过100目筛;将所得粉体在20MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1300℃,30MPa压力下烧结60分钟,即得致密度为98.1%、维氏硬度为15.8GPa的Si3N4陶瓷。
实施例2
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体83g,与1.71g Al2O3粉体、3.29g La2O3粉体、2克LiF粉体和10克TiC粉体混合,配制成固含量为65wt%的浆料,200g Si3N4球为球磨介质,在300rpm下球磨5h,然后放入110℃恒温箱中烘4h,研磨,过200目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1400℃,40MPa压力下烧结60分钟,即得致密度为98.6%、维氏硬度为18.3GPa的Si3N4陶瓷。
实施例3
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体81g,与2.06g Al2O3粉体、3.94g La2O3粉体、3克Li2O粉体和10克ZrC粉体混合,配制成固含量为70wt%的浆料,150g Si3N4球为球磨介质,在400rpm下球磨4h,然后放入120℃恒温箱中烘4h,研磨,过325目筛;将所得粉体在40MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,50MPa压力下烧结180分钟,即得致密度为99.1%、维氏硬度为18.2GPa的Si3N4陶瓷。
实施例4
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体69g,与2.06g Al2O3粉体、3.94g La2O3粉体、5克LiF粉体、10克B4C和10克金刚石粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入120℃恒温箱中烘3h,研磨,过200目筛;将所得粉体在50MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1400℃,60MPa压力下烧结60分钟,即得致密度为99.5%、维氏硬度为22.3GPa的Si3N4陶瓷。
实施例5
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体85g,与1.71g Al2O3粉体、3.29g La2O3粉体、5克Li2O粉体和5克B4C粉体混合,配制成固含量为65wt%的浆料,200g Si3N4球为球磨介质,在300rpm下球磨5h,然后放入100℃恒温箱中烘3h,研磨,过200目筛;将所得粉体在40MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,60MPa压力下烧结120分钟,即得致密度为99.2%、维氏硬度为16.9GPa的Si3N4陶瓷。
实施例6
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体73g,与1.37g Al2O3粉体、2.63g La2O3粉体、3克LiF粉体和20克金刚石粉体混合,配制成固含量为70wt%的浆料,150g Si3N4球为球磨介质,在400rpm下球磨4h,然后放入110℃恒温箱中烘3h,研磨,过325目筛;将所得粉体在40MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,60MPa压力下烧结120分钟,即得致密度为99.1%、维氏硬度为20.4GPa的Si3N4陶瓷。
实施例7
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体76g,与1.71g Al2O3粉体、3.29g La2O3粉体、4克LiF粉体和15克TiC粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入110℃恒温箱中烘2h,研磨,过100目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1350℃,50MPa压力下烧结60分钟,即得致密度为98.7%、维氏硬度为19.3GPa的Si3N4陶瓷。
实施例8
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体80g,与1.37g Al2O3粉体、2.63g La2O3粉体、1克Li2O粉体和15克SiC粉体混合,配制成固含量为65wt%的浆料,200g Si3N4球为球磨介质,在300rpm下球磨5h,然后放入100℃恒温箱中烘3h,研磨,过100目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1350℃,50MPa压力下烧结180分钟,即得致密度为98.6%、维氏硬度为19.6GPa的Si3N4陶瓷。
实施例9
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体82g,与2.06g Al2O3粉体、3.94g La2O3粉体、2克Li2O粉体和10克金刚石粉体混合,配制成固含量为70wt%的浆料,150g Si3N4球为球磨介质,在400rpm下球磨4h,然后放入120℃恒温箱中烘3h,研磨,过100目筛;将所得粉体在50MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1300℃,50MPa压力下烧结180分钟,即得致密度为98.2%、维氏硬度为18.4GPa的Si3N4陶瓷。
实施例10
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体70g,与1.71g Al2O3粉体、3.29g La2O3粉体、5克LiF粉体和20克TiC粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入100℃恒温箱中烘4h,研磨,过325目筛;将所得粉体在20MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1400℃,40MPa压力下烧结120分钟,即得致密度为99.3%、维氏硬度为21.6GPa的Si3N4陶瓷。
实施例11
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体88g,与1.71g Al2O3粉体、3.29g La2O3粉体、2克Li2O粉体和5克ZrC粉体混合,配制成固含量为65wt%的浆料,200g Si3N4球为球磨介质,在300rpm下球磨5h,然后放入110℃恒温箱中烘2h,研磨,过200目筛;将所得粉体在50MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1400℃,40MPa压力下烧结120分钟,即得致密度为98.9%、维氏硬度为16.4GPa的Si3N4陶瓷。
实施例12
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体73g,与1.37g Al2O3粉体、2.63g La2O3粉体、3克LiF粉体和20克B4C粉体混合,配制成固含量为70wt%的浆料,150g Si3N4球为球磨介质,在400rpm下球磨4h,然后放入110℃恒温箱中烘2h,研磨,过200目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,40MPa压力下烧结120分钟,即得致密度为99.0%、维氏硬度为21.2GPa的Si3N4陶瓷。
实施例13
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体83g,与2.06g Al2O3粉体、3.94g La2O3粉体、1克LiF粉体、5克TiC和5克金刚石粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入120℃恒温箱中烘3h,研磨,过100目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1350℃,60MPa压力下烧结60分钟,即得致密度为98.4%、维氏硬度为18.5GPa的Si3N4陶瓷。
实施例14
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体71g,与2.06g Al2O3粉体、3.94g La2O3粉体、3克Li2O粉体和20克TiC粉体混合,配制成固含量为65wt%的浆料,200g Si3N4球为球磨介质,在300rpm下球磨5h,然后放入120℃恒温箱中烘2h,研磨,过325目筛;将所得粉体在40MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,30MPa压力下烧结180分钟,即得致密度为99.3%、维氏硬度为20.1GPa的Si3N4陶瓷。
实施例15
一种高硬度氮化硅陶瓷及其制备方法,包括以下步骤:
称取Si3N4粉体76g,与1.71g Al2O3粉体、3.29g La2O3粉体、4克Li2O粉体、10克TiC和5克ZrC粉体混合,配制成固含量为70wt%的浆料,150g Si3N4球为球磨介质,在200rpm下球磨5h,然后放入120℃恒温箱中烘4h,研磨,过325目筛;将所得粉体在30MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1450℃,60MPa压力下烧结120分钟,即得致密度为99.1%、维氏硬度为18.7GPa的Si3N4陶瓷。
实施例16
本实施例16中高硬度Si3N4陶瓷的制备过程基本参见实施例12,区别在于:B4C为10g,金刚石为10g。所得Si3N4陶瓷的致密度为99.1%,维氏硬度为21.5GPa。
实施例17
本实施例17中高硬度Si3N4陶瓷的制备过程基本参见实施例12,区别在于:B4C为15g,金刚石为5g。所得Si3N4陶瓷的致密度为99.2%,维氏硬度为21.3GPa。
实施例18
本实施例18中高硬度Si3N4陶瓷的制备过程基本参见实施例12,区别在于:B4C为5g,金刚石为15g。所得Si3N4陶瓷的致密度为99.0%,维氏硬度为21.4GPa。
对比例1
称取Si3N4粉体94g,与2.06g Al2O3粉体和3.94g La2O3粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入120℃恒温箱中烘3h,研磨,过200目筛;将所得粉体在50MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1750℃,60MPa压力下烧结180分钟,得到的Si3N4陶瓷的致密度为98.9%,维氏硬度为14.8GPa。
对比例2
称取Si3N4粉体89g,与2.06g Al2O3粉体、3.94g La2O3粉体和5克LiF粉体混合,配制成固含量为60wt%的浆料,250g Si3N4球为球磨介质,在200rpm下球磨6h,然后放入120℃恒温箱中烘3h,研磨,过200目筛;将所得粉体在50MPa压力下干压预成型后装入石墨热压模具中,将样品放置到碳管炉中,充入N2作为保护气,在1300℃,60MPa压力下烧结180分钟,得到的Si3N4陶瓷的致密度为98.4%,维氏硬度为14.9GPa。
对比例3
本对比例3中高硬度Si3N4陶瓷的制备过程基本参见实施例12,区别在于:B4C为25g。所得Si3N4陶瓷的致密度为96.1%,维氏硬度为17.5GPa。
对比例4
本对比例4中高硬度Si3N4陶瓷的制备过程基本参见实施例12,区别在于:稀土氧化物为Lu2O3。得Si3N4陶瓷的致密度为97.3%,维氏硬度为18.2GPa。
表1为本发明实施例制备的氮化硅陶瓷的组分及性能参数:
从上述实施案例可以看出,本发明选用Al2O3和La2O3为烧结助剂,Li2O或/和LiF为低温烧结助剂,SiC、TiC、ZrC、B4C或金刚石中的一种或多种为提高硬度的第二相,采用热压烧结的方式,可以获得高硬度的Si3N4陶瓷,并实现其可调节性。
图1为实施例2中所得Si3N4陶瓷的物相分析图,从图中可知陶瓷中主相为α-Si3N4,第二相为TiC,没有发现明显的β-Si3N4衍射峰,说明由于烧结温度较低,在烧结过程中没有发生α-Si3N4到β-Si3N4的相转变,α-Si3N4完好保留,有助于硬度的提高。
图2为实施例3中所得Si3N4陶瓷的物相分析图,从图中可知陶瓷中主相为α-Si3N4,第二相为ZrC,没有发现明显的β-Si3N4衍射峰,说明由于烧结温度较低,在烧结过程中没有发生α-Si3N4到β-Si3N4的相转变,α-Si3N4完好保留,有助于硬度的提高。
图3为实施例10中所得Si3N4陶瓷的抛光面形貌图,从图中可知TiC晶粒较大,较为均匀地分布于Si3N4基体中。Si3N4晶粒基本为等轴状,证明在烧结过程中确实没有发生明显的相转变。Si3N4晶粒尺寸较小,约为几十纳米,说明TiC的加入有效抑制了晶粒生长。以纳米级α-Si3N4晶粒为主的微结构有效提高了氮化硅陶瓷的硬度。
图4为实施例3所得Si3N4陶瓷的抛光面形貌图,从图中可知ZrC晶粒较大,较为均匀地分布于Si3N4基体中。Si3N4晶粒基本为等轴状,证明在烧结过程中确实没有发生明显的相转变。Si3N4晶粒尺寸较小,约为几十纳米,说明ZrC的加入有效抑制了晶粒生长。以纳米级α-Si3N4晶粒为主的微结构有效提高了氮化硅陶瓷的硬度。
最后有必要说明的是:以上实施例只用于对本发明的技术方案作进一步详细说明,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。
Claims (10)
1.一种高硬度氮化硅陶瓷,其特征在于,以Si3N4作为主相,以SiC、TiC、ZrC、B4C和金刚石中的至少一种作为第二相,以Al2O3和稀土氧化物作为烧结助剂,以Li2O或/和LiF作为低温烧结助剂,经烧结后得到所述高硬度氮化硅陶瓷。
2.根据权利要求1所述的高硬度氮化硅陶瓷,其特征在于,所述稀土氧化物为La2O3、Sm2O3、Nd2O3和CeO2中的至少一种。
3.根据权利要求1或2所述的高硬度氮化硅陶瓷,其特征在于,所述主相、第二相、烧结助剂和低温烧结助剂的质量比为(69~90):(5~20):(4~6):(1~5)。
4.根据权利要求3所述的高硬度氮化硅陶瓷,其特征在于,所述烧结助剂中Al2O3和稀土氧化物的摩尔比(1~4):1,优选为5:3。
5.根据权利要求1-4中任一项所述的高硬度氮化硅陶瓷,其特征在于,所述高硬度Si3N4陶瓷的维氏硬度为15.8~22.3 GPa。
6.一种如权利要求1-5中任一项高硬度氮化硅陶瓷的制备方法,其特征在于,包括:
将α-Si3N4粉体、Al2O3粉体、稀土氧化物粉体、第二相和低温烧结助剂按照质量比称量并混合,再经压制成型例,得到素坯;
将所得素坯置于石墨热压模具中并放入碳管炉中,经过烧结,得到所述高硬度氮化硅陶瓷。
7.根据权利要求6所述的制备方法,其特征在于,所述α-Si3N4粉体的粒径为0.3~0.8μm;所述Al2O3粉体的粒径为0.1~0.4μm;所述稀土氧化物粉体的粒径为0.5~2μm;所述低温烧结助剂的粒径为0.5~1μm;所述第二相的粒径为0.5~3μm。
8.根据权利要求6或7所述的制备方法,其特征在于,所述混合的方式为球磨混合;所述压制成型的方式为干压预成型;
优选地,所述球磨混合的转数为200~400 rpm,球磨时间为4~6小时,所述干压预成型的压力为20~50 MPa。
9.根据权利要求6-8中任一项所述的制备方法,其特征在于,所述烧结的方式为热压烧结;所述热压烧结的温度为1300~1450℃,保温时间为60~180分钟,烧结压力为30~60MPa。
10.一种权利要求1-5中任一项所述的高硬度氮化硅陶瓷在制备骨科植入物中的应用。
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