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CN109970454A - 一种过渡金属氧化物抑制氮化硅相变的方法及其制得的氮化硅陶瓷 - Google Patents

一种过渡金属氧化物抑制氮化硅相变的方法及其制得的氮化硅陶瓷 Download PDF

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CN109970454A
CN109970454A CN201910213957.7A CN201910213957A CN109970454A CN 109970454 A CN109970454 A CN 109970454A CN 201910213957 A CN201910213957 A CN 201910213957A CN 109970454 A CN109970454 A CN 109970454A
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silicon nitride
powder
mgo
metal oxide
transition metal
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于俊杰
魏万鑫
郭伟明
林华泰
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Guangdong University of Technology
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Abstract

本发明提供了一种过渡金属氧化物抑制氮化硅相变的方法及其制得的氮化硅陶瓷。该方法通过向α‑Si3N4粉中引入过渡金属氧化物MO(ZrO2、TiO2、HfO2、Ta2O5或Cr2O3)和烧结助剂MgO‑Re2O3经混料，干燥后得到α‑Si3N4‑MO‑MgO‑Re2O3的混合粉体，将混合粉体经冷等静压成型后，在1atm的氩气气氛下，升温至1450～1550℃并保温，经无压烧结或热压烧结后得到氮化硅陶瓷。本发明通过向α‑Si3N4粉中引入MO，抑制了α‑Si3N4在高温下向β‑Si3N4的相变。与现有技术相比，本发明通过抑制α‑Si3N4到β‑Si3N4的相变，实现氮化硅相变的可控性。

Description

一种过渡金属氧化物抑制氮化硅相变的方法及其制得的氮化 硅陶瓷
技术领域
本发明属于非氧化物基材料技术领域，更具体地，涉及一种过渡金属氧化物抑制氮化硅相变的方法及其制得的氮化硅陶瓷。
背景技术
Si3N4是一种强共价键化合物，很难通过固相烧结达到致密，一般采用液相烧结实现致密化。在液相烧结过程中通常伴随α→β-Si3N4的相变，α-Si3N4属低温稳定晶型，具有等轴状晶体形貌，硬度较高，但韧性低；β-Si3N4属高温稳定晶型，具有长棒状或针状晶体形貌，抗弯强度和断裂韧性较高，但硬度低。目前，有关氮化硅相变的研究主要集中在促进相变方面，如提高烧结温度、引入β-Si3N4晶种或低温烧结助剂Li2O-Y2O3等来实现[Lei Fan,MengZhou,Hongjie Wang,Zhongqi Shi,Xuefeng Lu,Chao Wang,Low-TemperaturePreparation ofβ-Si3N4Porous Ceramics with a Small Amount ofLi2O–Y2O3,J.Am.Ceram.Soc.97(2014)1371–1374.]。而有关控制/抑制氮化硅相变的研究较少且主要集中在降低烧结温度、引入低含量烧结助剂或纳米颗粒、采用放电等离子烧结(SPS)或其他场辅助烧结技术。如，Yu等通过SPS烧结技术获得α-Si3N4含量为75.5wt％的Si3N4陶瓷[J.J.Yu,W.M.Guo,W.X.Wei,H.T.Lin,C.Y.Wang,Fabrication and wear behaviors ofgraded Si3N4ceramics by the combination of two-step sintering and β-Si3N4seeds,J.Eur.Ceram.Soc.38(2018)3457–3462.]。基于此，若能控制Si3N4在高温烧结过程中的相变，即可制备出高α-Si3N4相的氮化硅陶瓷，从而提高其硬度。
发明内容
为了解决上述现有技术中存在的不足和缺点，本发明的首要目的在于提供一种过渡金属氧化物抑制氮化硅相变的方法。该方法通过引入MO粉(ZrO2、TiO2、HfO2、Ta2O5或Cr2O5)实现氮化硅相变的可控性。
本发明的另一目的在于提供上述方法制得的氮化硅陶瓷。
本发明的再一目的在于提供上述氮化硅陶瓷的应用。
本发明的目的通过下述技术方案来实现：
一种过渡金属氧化物抑制氮化硅相变的方法，包括如下具体步骤：
S1.将α-Si3N4、MO、MgO和Re2O3经混料，干燥后得到Si3N4-MO-MgO-Re2O3的混合粉体，所述MO为ZrO2、TiO2、HfO2、Ta2O5或Cr2O3；
S2.将Si3N4-MO-MgO-Re2O3混合粉体经冷等静压成型后，在1atm的氩气气氛下，升温Ⅰ至1100～1200℃，然后再升温Ⅱ至1450～1550℃并保温，经无压烧结或压力为30MPa的热压烧结后得到氮化硅陶瓷，所述氮化硅陶瓷中α-Si3N4相的质量分数为80～95％。
优选地，步骤S1中所述α-Si3N4：MO：MgO-Re2O3的体积比为(97～89)：(1～5)：(2～6)；所述MgO-Re2O3中MgO：Re2O3的体积比为(1～99)：(1～99)。
更为优选地，所述α-Si3N4：MO：MgO-Re2O3的体积比为37：1：2，所述MgO-Re2O3中MgO：Re2O3的体积比为3：2。
优选地，步骤S1中所述Re2O3中Re为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu。
优选地，所述α-Si3N4粉的纯度为98～100wt％，α-Si3N4粉的粒径为0.3～1μm；所述MO粉的纯度为99～99.99wt％，MO粉的粒径为20～100nm；所述MgO粉的纯度为99.8～99.99wt％，MgO粉的粒径为50～100nm；所述Re2O3粉的纯度为99.9～99.99wt％，Re2O3粉的粒径为50～100nm。
优选地，步骤S2中所述冷等静压成型的直径为10～50mm，厚度为3～6mm，成型压力为50～200MPa。
优选地，步骤S2中所述升温Ⅰ的速率为10～25℃/min，所述升温Ⅱ的速率为8～12℃/min，所述保温的时间为0.5～4h。
一种氮化硅陶瓷，所述陶瓷是所述的方法制得。
优选地，所述氮化硅陶瓷中α-Si3N4相的质量分数为80～95％。
所述的氮化硅陶瓷在高速切削刀具领域中的应用。
与现有技术相比，本发明具有以下有益效果：
1.本发明通过在α-Si3N4粉中引入的MO粉，其中，MO为ZrO2、TiO2、HfO2、Ta2O5或Cr2O5，可抑制α-Si3N4到β-Si3N4的相变；
2.本发明中得到的氮化硅陶瓷中α-Si3N4相含量较高，可实现高硬度。
附图说明
图1为实施例1氮化硅陶瓷的XRD图谱。
图2为对比例1氮化硅陶瓷的XRD图谱。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
实施例1
1.制备：
(1)以α-Si3N4粉为基体原料，以ZrO2粉、MgO粉和Yb2O3粉为烧结助剂，按照Si3N4：ZrO2：MgO：Yb2O3的体积比为90：2.5：3：2经混料、干燥后得到混合均匀的Si3N4-ZrO2-MgO-Yb2O3粉体。
(2)将Si3N4-ZrO2-MgO-Yb2O3混合粉体经50MPa的冷等静压成型后置于直径为50mm热压炉模具中，在1atm的氩气下，以15℃/min的速率升温至1200℃，然后以10℃/min的速率升温至1500℃，并保温1h，经压力为30MPa的热压烧结后得到氮化硅陶瓷。
2.性能测试：本实施例所得的Si3N4陶瓷中α-Si3N4相的质量分数为89％。对比例1
1.与实施例1不同在于：在步骤(1)中未加ZrO2粉，且Si3N4：MgO：Yb2O3的体积比为95：3：2。
2.性能测试：本对比例所得的Si3N4陶瓷中α-Si3N4相的质量分数为78％。
与对比例1相比，实施例1中α-Si3N4相的质量分数较高，ZrO2粉的添加可抑制α-Si3N4到β-Si3N4的相变。图1为实施例1氮化硅陶瓷的XRD图谱。从图1中可知，该氮化硅陶瓷以α-Si3N4为主相，β-Si3N4相峰强较低。图2为对比例1氮化硅陶瓷的XRD图谱。从图2中可知，该氮化硅陶瓷也以α-Si3N4为主相，但β-Si3N4相所对应的峰强较实施例1强，特别是在对比例1(图2)中β-Si3N4相的[110]、[200]和[210]峰强度较高。结合实施例1与对比例1中α-Si3N4相的质量分数也可明显看出，在实施例1中通过引入微量的ZrO2粉抑制了α-Si3N4到β-Si3N4的相变。
实施例2
1.制备：按照α-Si3N4粉体积分数为91.5％、TiO2粉的体积分数为2.5％、MgO体积分数为3％、Yb2O3体积分数为2％进行配料，按照实施例1的方法升温，冷等静压成型压力为200MPa、坯体直径为30mm，经无压烧结后得到氮化硅陶瓷。
2.性能测试：本实施例制得的Si3N4陶瓷中α-Si3N4相的质量分数为90％。
实施例3
1.制备：按照α-Si3N4粉体积分数为93.5％、HfO2粉的体积分数为2.5％、MgO体积分数为2％、Gd2O3体积分数为2％进行配料，按照实施例1方法制备Si3N4陶瓷。
2.性能测试：本实施例制得的Si3N4陶瓷中α-Si3N4相的质量分数为87％。
实施例4
1.制备：按照α-Si3N4粉体积分数为92.5％、Ta2O5粉的体积分数为2.5％、MgO体积分数为3％、La2O3体积分数为2％进行配料，按照实施例2方法制备Si3N4陶瓷。
2.性能测试：本实施例制得的Si3N4陶瓷中α-Si3N4相的质量分数为92％。
实施例5
1.制备：按照α-Si3N4粉体积分数为96％、Cr2O3粉的体积分数为1％、MgO体积分数为2％、Y2O3体积分数为2％进行配料，按照实施例1方法制备Si3N4陶瓷。
2.性能测试：本实施例制得的Si3N4陶瓷中α-Si3N4相的质量分数为86％。
实施例6
1.制备：按照Si3N4粉体积分数为90％、ZrO2粉的体积分数为2％、Al2O3体积分数为3％、CeO2体积分数为2％进行配料，按照实施例2方法制备Si3N4陶瓷。
2.性能测试：本实施例制得的Si3N4陶瓷中α-Si3N4相的质量分数为84％。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

1.一种过渡金属氧化物抑制氮化硅相变的方法，其特征在于，包括如下具体步骤：
S1.将α-Si3N4、MO、MgO和Re2O3经混料，干燥后得到Si3N4-MO-MgO-Re2O3的混合粉体，所述MO为ZrO2、TiO2、HfO2、Ta2O5或Cr2O3；
S2.将Si3N4-MO-MgO-Re2O3混合粉体经冷等静压成型后，在1atm的氩气气氛下，升温Ⅰ至1100～1200℃，然后再升温Ⅱ至1450～1550℃并保温，经无压烧结或压力为30MPa的热压烧结后得到氮化硅陶瓷，所述氮化硅陶瓷中α-Si3N4相的质量分数为80～95％。
2.根据权利要求1所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，步骤S1中所述α-Si3N4：MO：MgO-Re2O3的体积比为(97～89)：(1～5)：(2～6)；所述MgO-Re2O3中MgO：Re2O3的体积比为(1～99)：(1～99)。
3.根据权利要求2所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，所述α-Si3N4：MO：MgO-Re2O3的体积比为37：1：2，所述MgO-Re2O3中MgO：Re2O3的体积比为3：2。
4.根据权利要求1所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，步骤S1中所述Re2O3中Re为Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb或Lu。
5.根据权利要求1所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，所述α-Si3N4粉的纯度为98～100wt％，α-Si3N4粉的粒径为0.3～1μm；所述MO粉的纯度为99～99.99wt％，MO粉的粒径为20～100nm；所述MgO粉的纯度为99.8～99.99wt％，MgO粉的粒径为50～100nm；所述Re2O3粉的纯度为99.9～99.99wt％，Re2O3粉的粒径为50～100nm。
6.根据权利要求1所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，步骤S2中所述冷等静压成型的直径为10～50mm，厚度为3～6mm，成型压力为50～200MPa。
7.根据权利要求1所述的过渡金属氧化物抑制氮化硅相变的方法，其特征在于，步骤S2中所述升温Ⅰ的速率为10～25℃/min，所述升温Ⅱ的速率为8～12℃/min，所述保温的时间为0.5～4h。
8.一种氮化硅陶瓷，其特征在于，所述氮化硅陶瓷是根据权利要求1～7任一项所述的方法制得。
9.根据权利要求8所述氮化硅陶瓷，其特征在于，所述氮化硅陶瓷中α-Si3N4相的质量分数为80～95％。
10.权利要求8或9所述的氮化硅陶瓷在高速切削刀具领域中的应用。
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110818428A (zh) * 2019-12-03 2020-02-21 清华大学 一种共晶增强增韧氮化硅陶瓷的制备方法
CN111995403A (zh) * 2020-09-04 2020-11-27 中材高新氮化物陶瓷有限公司 一种耐腐蚀氮化硅陶瓷及其制备方法
TWI839896B (zh) * 2021-11-15 2024-04-21 日商黑崎播磨股份有限公司 氮化矽複合材料及探頭導引零件

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5021372A (en) * 1988-01-27 1991-06-04 The Dow Chemical Company Method of preparing a self-reinforced silicon nitride ceramic of high fracture toughness
JP2002293638A (ja) * 2001-03-28 2002-10-09 Ngk Spark Plug Co Ltd 窒化珪素焼結体
WO2003010113A1 (fr) * 2001-07-24 2003-02-06 Kabushiki Kaisha Toshiba Article en nitrure de silicium resistant a l'usure et procede de fabrication de cet article
CN103833391A (zh) * 2014-01-06 2014-06-04 宜兴市钰玺窑业有限公司 一种氮化硅复相结合碳化硅砖及其制备方法
CN104909765A (zh) * 2015-06-01 2015-09-16 广东工业大学 一种低成本、快速制备高性能Si3N4陶瓷球的方法
CN108046808A (zh) * 2018-01-05 2018-05-18 广东工业大学 一种Si3N4梯度材料及其制备方法
CN108383532A (zh) * 2018-05-28 2018-08-10 江苏东浦精细陶瓷科技股份有限公司 一种致密化氮化硅陶瓷材料及其制备方法
CN108863395A (zh) * 2017-05-12 2018-11-23 中国科学院上海硅酸盐研究所 一种高热导率、高强度氮化硅陶瓷材料及其制备方法
CN109206141A (zh) * 2018-08-27 2019-01-15 广东工业大学 一种高硬高韧氮化硅陶瓷及其制备方法和应用
CN109369193A (zh) * 2018-09-30 2019-02-22 广东工业大学 一种具有高硬、高韧性能的氮化硅陶瓷及其制备方法和应用

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5021372A (en) * 1988-01-27 1991-06-04 The Dow Chemical Company Method of preparing a self-reinforced silicon nitride ceramic of high fracture toughness
JP2002293638A (ja) * 2001-03-28 2002-10-09 Ngk Spark Plug Co Ltd 窒化珪素焼結体
WO2003010113A1 (fr) * 2001-07-24 2003-02-06 Kabushiki Kaisha Toshiba Article en nitrure de silicium resistant a l'usure et procede de fabrication de cet article
CN103833391A (zh) * 2014-01-06 2014-06-04 宜兴市钰玺窑业有限公司 一种氮化硅复相结合碳化硅砖及其制备方法
CN104909765A (zh) * 2015-06-01 2015-09-16 广东工业大学 一种低成本、快速制备高性能Si3N4陶瓷球的方法
CN108863395A (zh) * 2017-05-12 2018-11-23 中国科学院上海硅酸盐研究所 一种高热导率、高强度氮化硅陶瓷材料及其制备方法
CN108046808A (zh) * 2018-01-05 2018-05-18 广东工业大学 一种Si3N4梯度材料及其制备方法
CN108383532A (zh) * 2018-05-28 2018-08-10 江苏东浦精细陶瓷科技股份有限公司 一种致密化氮化硅陶瓷材料及其制备方法
CN109206141A (zh) * 2018-08-27 2019-01-15 广东工业大学 一种高硬高韧氮化硅陶瓷及其制备方法和应用
CN109369193A (zh) * 2018-09-30 2019-02-22 广东工业大学 一种具有高硬、高韧性能的氮化硅陶瓷及其制备方法和应用

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110818428A (zh) * 2019-12-03 2020-02-21 清华大学 一种共晶增强增韧氮化硅陶瓷的制备方法
CN110818428B (zh) * 2019-12-03 2020-12-04 清华大学 一种共晶增强增韧氮化硅陶瓷的制备方法
CN111995403A (zh) * 2020-09-04 2020-11-27 中材高新氮化物陶瓷有限公司 一种耐腐蚀氮化硅陶瓷及其制备方法
TWI839896B (zh) * 2021-11-15 2024-04-21 日商黑崎播磨股份有限公司 氮化矽複合材料及探頭導引零件

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