CN107814576B - 一种原位反应制备mb2-mc-bn超高温陶瓷基复合材料的方法 - Google Patents
一种原位反应制备mb2-mc-bn超高温陶瓷基复合材料的方法 Download PDFInfo
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 26
- 239000000463 material Substances 0.000 title claims abstract description 21
- 239000011216 ultra-high temperature ceramic matrix composite Substances 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000007731 hot pressing Methods 0.000 claims abstract description 11
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 239000011153 ceramic matrix composite Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010297 mechanical methods and process Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 238000007873 sieving Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000011812 mixed powder Substances 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000002490 spark plasma sintering Methods 0.000 claims 2
- 238000007580 dry-mixing Methods 0.000 claims 1
- 239000011215 ultra-high-temperature ceramic Substances 0.000 abstract description 6
- 239000007787 solid Substances 0.000 abstract description 4
- 239000002245 particle Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 8
- 229910052580 B4C Inorganic materials 0.000 description 6
- 229910052582 BN Inorganic materials 0.000 description 6
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 230000035939 shock Effects 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910007948 ZrB2 Inorganic materials 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- JEUVAEBWTRCMTB-UHFFFAOYSA-N boron;tantalum Chemical compound B#[Ta]#B JEUVAEBWTRCMTB-UHFFFAOYSA-N 0.000 description 2
- VWZIXVXBCBBRGP-UHFFFAOYSA-N boron;zirconium Chemical compound B#[Zr]#B VWZIXVXBCBBRGP-UHFFFAOYSA-N 0.000 description 2
- NFFIWVVINABMKP-UHFFFAOYSA-N methylidynetantalum Chemical compound [Ta]#C NFFIWVVINABMKP-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910003468 tantalcarbide Inorganic materials 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- MELCCCHYSRGEEL-UHFFFAOYSA-N hafnium diboride Chemical compound [Hf]1B=B1 MELCCCHYSRGEEL-UHFFFAOYSA-N 0.000 description 1
- -1 hafnium nitride Chemical class 0.000 description 1
- WHJFNYXPKGDKBB-UHFFFAOYSA-N hafnium;methane Chemical compound C.[Hf] WHJFNYXPKGDKBB-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 238000005498 polishing Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明属于超高温陶瓷领域，具体为一种原位反应制备MB2‑MC‑BN超高温陶瓷基复合材料的方法。原料由MN粉(M＝Ti,Zr,Hf或Ta)和B4C粉混合而成，在热压炉内进行原位反应热压烧结或在放电等离子体烧结炉内进行反应烧结。在保护气氛下，升温速率为10～100℃/分钟，烧结温度为1900℃～2100℃，烧结时间为10分钟～2小时，烧结压强为20MPa～40MPa，最终得到MB2‑MC‑BN复合材料(M＝Ti,Zr,Hf或Ta)，该复合材料可作为固体火箭发动机的喷管喉衬或超高速飞行器的鼻锥、翼前缘等耐高温结构元件的候选材料。
Description
技术领域
本发明属于超高温陶瓷领域，具体为一种原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法。
背景技术
超高温陶瓷一般是指可以在1800℃以上反应气氛中使用，并具有优良的高温抗氧化性能和力学性能的过渡金属硼化物和碳化物材料。在这些材料中，MB2 (M＝Ti,Zr,Hf或Ta)和MC(M＝Ti,Zr,Hf或Ta)具有高的熔点、好的化学稳定性、高的弹性模量、高的硬度、良好的导热性等优异的性能，适合于作为固体火箭发动机的喷管喉衬、燃气舵、以及超高速飞行器的鼻锥、端头、翼前缘等耐高温结构元件的候选材料。
然而，较差的抗热震性能(文献1，International Journal of RefractoryMetals and Hard Materials,2010,28(2):187-190)，极大地限制了这些材料在超高温领域的应用。文献2(Materials&Design,2011,32(1):401-405)报道，通过添加BN可以有效地提高ZrB2基材料的抗热震性能，然而当直接添加BN时，由于BN特殊的片层状结构，非常容易形成卡片房式结构，易引起团聚。因此，迫切需要发展一种方法，可以将BN相引入MB2或MC体系中，来提高它们的抗热震性能，同时又可以避免BN相的团聚。
发明内容
本发明的目的在于提供一种原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，通过原位反应的方法可以将BN相均匀的引入超高温陶瓷基体中，从而可以在提高超高温陶瓷抗热震性能的同时，又避免了BN的团聚。
本发明的技术方案是：
一种原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，具体步骤如下：
(1)原料组成及成分范围：
原料由MN粉和B4C粉组成，MN：B4C的摩尔比为2：1，M＝Ti,Zr,Hf或 Ta；
(2)制备工艺：
首先将MN粉和B4C粉按配比称重，经物理机械方法混合8～24小时，烘干过筛；然后将混合好的粉体装入石墨模具中冷压成型，施加的压强为10MPa～ 20MPa，在保护气氛下原位烧结，升温速率为10～100℃/分钟，烧结温度为 1900℃～2100℃，烧结时间为10分钟～2小时，烧结压强为20MPa～40MPa。
所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，原位烧结发生的化学反应为：
2MN+B4C→MB2+MC+2BN。
所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，MN粉的粒度范围为1～10微米，B4C粉粒度范围为200～400目。
所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，原位烧结方式为在热压炉内进行热压烧结，或在放电等离子体烧结炉内进行放电等离子体烧结。
所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，原位烧结的保护气氛为氩气或氦气。
所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，物理机械方法混合采用在聚氨酯罐或陶瓷罐中干混，或在酒精介质中球磨。
本发明的优点及有益效果是：
1、工艺简单，成本低。本发明通过简单的一步反应热压方法，就可以获得含MB2，MC和BN相的多组分超高温陶瓷基复合材料。
2、采用本发明获得MB2-MC-BN超高温陶瓷基复合材料，其各相分布均匀，可以在提高超高温陶瓷抗热震性能的同时，又避免了BN的团聚。
3、采用本发明获得MB2-MC-BN超高温陶瓷基复合材料，致密度高，合成产物除了目标产物，不存在其他杂质相，保证了合成的材料具有较好的高温力学性能
总之，本发明方法操作简单、工艺条件容易控制、成本低，同时制备出的材料具有高纯度、高致密度等特点，适合于作固体火箭发动机的喷管喉衬或超高速飞行器的鼻锥、端头、翼前缘等耐高温结构元件等。
附图说明
图1为原位烧结反应得到的ZrB2-ZrC-BN复合材料的X-射线衍射图谱。
图2为原位烧结反应得到的ZrB2-ZrC-BN复合材料表面抛光后的扫描电镜照片。
具体实施方式
在具体实施过程中，本发明是原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，原料由MN粉(M＝Ti,Zr,Hf或Ta)和B4C粉混合而成，MN：B4C 的摩尔比为2：1，在热压炉内进行原位反应热压烧结或在放电等离子体烧结炉内进行反应烧结。在保护气氛下，升温速率为10～100℃/分钟，烧结温度为1900 ℃～2100℃，烧结时间为10分钟～2小时，烧结压强为20MPa～40MPa，最终得到MB2-MC-BN复合材料(M＝Ti,Zr,Hf或Ta)。复合材料中，MB2占35～50wt％， MC占30～45wt％，BN占10～30wt％，复合材料的相对致密度在95％以上。该复合材料可作为固体火箭发动机的喷管喉衬或超高速飞行器的鼻锥、翼前缘等耐高温结构元件的候选材料。
下面，通过实施例和附图进一步详述本发明。
实施例1
本实施例中，首先将粒度为1微米的氮化钛(TiN)粉69.15克和粒度为200 目的碳化硼(B4C)粉30.85克，在球磨罐中球磨8小时，烘干后过筛。然后装入石墨模具中冷压成型，施加的压强为20MPa，冷压10分钟后，放入热压炉中热压烧结。升温速率为20℃/分钟，升温的同时压力逐渐加到40MPa，加热到2000℃保温2小时。整个烧结过程都是在氩气保护下进行。本实施例中，制备的复合材料主要由二硼化钛、碳化钛、氮化硼组成，二硼化钛占38.8wt％，碳化钛占33.5wt％，氮化硼占27.7wt％。另外，复合材料的相对致密度为97.3％。
实施例2
本实施例中，首先将粒度为10微米的氮化铪(HfN)粉87.45克和粒度为 300目的碳化硼(B4C)粉12.55克、在球磨罐中球磨24小时，烘干后过筛。然后装入石墨模具中冷压成型，施加的压强为15MPa，冷压10分钟后，放入放电等离子体烧结炉内烧结。升温速率为100℃/分钟，升温的同时压力逐渐加到 30MPa，加热到1900℃保温10分钟。整个烧结过程都是在氩气保护下进行。本实施例中，制备的复合材料主要由二硼化铪、碳化铪、氮化硼组成，二硼化铪占 45.4wt％，碳化铪占43.3wt％，氮化硼占11.3wt％，。另外，复合材料的相对致密度为98.6％。
实施例3
本实施例中，首先将粒度为5微米的氮化锆(ZrN)粉79.21克和粒度为400 目的碳化硼(B4C)粉20.79克，在球磨罐中球磨16小时，烘干后过筛。然后装入石墨模具中冷压成型，施加的压强为20MPa，冷压10分钟后，放入热压炉中热压烧结。升温速率为20℃/分钟，升温的同时压力逐渐加到40MPa，加热到 2100℃保温1小时。整个烧结过程都是在氩气保护下进行。将获得的反应产物进行XRD分析(见图1)，可以发现制备的复合材料由二硼化锆、碳化锆及氮化硼组成，在制备的复合材料中各相实现了均匀的分布(见图2)。本实施例制备的复合材料中，二硼化锆占42.5wt％，碳化锆占38.8wt％，氮化硼占18.7wt％。相对致密度为99.1％，杨氏模量约为200GPa，维氏硬度约为5.7GPa，三点弯曲强度约为342MPa，断裂韧性约为3.4MPa·m1/2，临界抗热震温度约为1300℃。
实施例4
本实施例中，首先将粒度为10微米的氮化钽(TaN)粉87.59克和粒度为200 目的碳化硼(B4C)粉12.41克，在球磨罐中球磨8小时，烘干后过筛。然后装入石墨模具中冷压成型，施加的压强为20MPa，冷压10分钟后，放入放电等离子体烧结炉内烧结。升温速率为50℃/分钟，升温的同时压力逐渐加到40MPa，加热到1900℃保温20分钟。整个烧结过程都是在氦气保护下进行。本实施例中，制备的复合材料由二硼化钽、碳化钽、氮化硼组成，二硼化钽占45.5wt％，碳化钽占43.3wt％，氮化硼占11.2wt％。另外，复合材料的相对致密度为95.1％。
Claims (4)
1.一种原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，其特征在于，具体步骤如下：
(1)原料组成及成分范围：
原料由MN粉和B4C粉组成，MN：B4C的摩尔比为2：1，M＝Ti,Zr,Hf或Ta；
(2)制备工艺：
首先将MN粉和B4C粉按配比称重，经物理机械方法混合8～24小时，烘干过筛；然后将混合好的粉体装入石墨模具中冷压成型，施加的压强为10MPa～20MPa，在保护气氛下原位烧结，升温速率为10～100℃/分钟，烧结温度为1900℃～2100℃，烧结时间为10分钟～2小时，烧结压强为20MPa～40MPa；
原位烧结发生的化学反应为：
2MN+B4C→MB2+MC+2BN；
MN粉的粒度范围为1～10微米，B4C粉粒度范围为200～400目；
复合材料中，MB2占35～50wt％，MC占30～45wt％，BN占10～30wt％，复合材料的相对致密度在95％以上。
2.按照权利要求1所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，其特征在于，原位烧结方式为在热压炉内进行热压烧结，或在放电等离子体烧结炉内进行放电等离子体烧结。
3.按照权利要求1所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，其特征在于，原位烧结的保护气氛为氩气或氦气。
4.按照权利要求1所述的原位反应制备MB2-MC-BN超高温陶瓷基复合材料的方法，其特征在于，物理机械方法混合采用在聚氨酯罐或陶瓷罐中干混，或在酒精介质中球磨。
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