CN107285771A - 一种三元稀土二硼二碳陶瓷材料的制备方法 - Google Patents
一种三元稀土二硼二碳陶瓷材料的制备方法 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 26
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- 229910052580 B4C Inorganic materials 0.000 claims abstract description 12
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
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- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
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- 239000011358 absorbing material Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及结构陶瓷领域，具体为一种三元稀土二硼二碳(ReB2C2)陶瓷材料的制备方法。采用稀土金属粉、碳化硼粉和石墨粉为原料，采用合适的计量比机械混合后，在加热炉内反应，升温速率为10～100℃/分钟，反应温度为1600～2100℃，施加的压强为0～40MPa，反应时间为10分钟～2小时。采用本发明方法能够实现原位合成高纯三元稀土二硼二碳陶瓷粉末及块体材料，通过该方法制备的该类材料具有典型的片层结构，优异的损伤容限及可加工性能，同时具有优异的高温刚性，以YB2C2为例，其在1500℃仍能维持室温模量。本发明工艺简单，可重复性好，适合进行规模生产，获得的ReB2C2陶瓷在航空航天、核工业、超高温结构件等高新技术领域有着广泛的应用前景。
Description
技术领域
本发明涉及结构陶瓷领域，具体为一种三元稀土二硼二碳(ReB2C2)陶瓷材料的制备方法。
背景技术
三元稀土二硼二碳陶瓷材料即ReB2C2(Re包括但不限于Sc,Y,La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu)，是三元稀土硼碳化合物庞大家族中的一大类别。其晶体结构可以描述为Re片层与B2C2在c轴方向上交替堆垛而成(文献1,J.Bauer等，Coordin.Chem.Rev.178(1998)723-753)。这一点与目前广泛研究的MAX相陶瓷极为相似，因此这类材料极有可能具有一些和MAX相陶瓷非常相似的性能，如：抗损伤，抗热震，可加工等(文献2,M.W.Barsoum,Prog.Solid StateChem.28(2000)201-81)。另外，文献3(A.Goldstein等J.Euro.Ceram.Soc.27(2007)695-700)报道ReB2C2中的一员YB2C2在2180℃热处理条件下仍然可以稳定存在，说明这类材料有可能具有很好的耐超高温性能。因此，ReB2C2在航空航天、核材料、燃料电池、电子信息、超高温结构件等高新技术领域都有着广泛的应用前景。
然而，目前关于此类材料合成及性能的报道非常少见，可能是由于其制备较为困难。目前制备此类材料的方法主要为电弧熔炼，以LaB2C2为例(文献4,J.BAUER等，Acta Cryst.(1980).B36,1540-154.)采用镧粉、硼粉和石墨粉为原料，需要经过多次电弧熔炼，而后在2000℃保温24h，成本昂贵、耗时而且难以制备大尺寸、高纯度、高致密、均匀的块体材料，极大地限制了对此类材料的研究与应用。因此，发展一种简单高效制备高纯度三元稀土二硼二碳陶瓷的方法，对研究其性能及推广其应用具有重要的意义。
发明内容
本发明的目的在于提供一种三元稀土二硼二碳陶瓷材料的制备方法，能够实现原位、简单、高效地合成高纯三元稀土二硼二碳陶瓷。
本发明的技术方案是：
一种三元稀土二硼二碳陶瓷材料的制备方法，采用稀土金属粉、碳化硼粉和石墨粉为原料，大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料；原料粉经物理机械方法混合8～24小时，过筛，装入石墨模具中冷压成型，施加的压强为5～20MPa；在通有惰性气体保护气氛的加热炉内原位反应，施加的压强为0～40MPa，升温速率为10～100℃/分钟，反应温度为1600～2100℃，反应时间为10分钟～2小时，合成的陶瓷材料为接近单相的ReB2C2相和少量杂质相。
所述的三元稀土二硼二碳陶瓷材料的制备方法，三元稀土二硼二碳陶瓷材料是粉体或块体陶瓷。
所述的三元稀土二硼二碳陶瓷材料制备方法，原料粉原位发生的化学反应为：
2Re+B4C+3C→2ReB2C2 (1)。
所述的三元稀土二硼二碳陶瓷材料的制备方法，Re为稀土元素，包括但不限于周期表中原子序数从57到71号的稀土金属元素La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb或Lu，或者，采用原子序数分别为21和39的稀土金属元素Sc和Y中的一种。
所述的三元稀土二硼二碳陶瓷材料的制备方法，大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料是指，称取原料时，严格按照化学计量比称取原料，或者考虑到反应实际情况对某种或某些原料进行适当调整，即相对于其化学计量比增加或减少称取量。
所述的三元稀土二硼二碳陶瓷材料的制备方法，稀土金属粉的粒度范围为200～400目，碳化硼粉的粒度范围为200～400目，石墨粉的粒度范围为200～400目。
所述的三元稀土二硼二碳陶瓷材料的制备方法，原位反应为无压反应或热压烧结反应或放电等离子体烧结反应。
所述的三元稀土二硼二碳陶瓷材料的制备方法，惰性气体为氩气或氦气。
所述的三元稀土二硼二碳陶瓷材料的制备方法，物理机械方法混合为在聚氨酯球磨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、本发明方法以稀土金属粉，碳化硼粉和石墨粉为原料，合成了三元稀土二硼二碳陶瓷，工艺简单、效率高、成本相对较低，并且可重复性好，适合进行规模生产。
2、采用本发明方法获得的三元稀土二硼二碳陶瓷具有较高的纯度，采用本发明方法获得的三元稀土二硼二碳陶瓷块体是一种潜在的超高温结构材料或中子吸收材料。
附图说明
图1为合成的YB2C2材料的X射线衍射谱。
图2为合成的YB2C2材料的抛光表面扫描电镜照片。
图3为合成的YB2C2材料的断口扫描电镜照片。
图4为合成的YB2C2材料经普通硬质合金转头加工后的光学照片。
具体实施方式
在具体实施过程中，本发明三元稀土二硼二碳陶瓷材料的制备方法，采用稀土金属粉、碳化硼粉和石墨粉为原料，大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料；原料粉经物理机械方法混合8～24小时，过筛，装入石墨模具中冷压成型，施加的压强为5～20MPa；冷压5～20分钟后，在通有惰性气体保护气氛的加热炉内原位反应，施加的压强为0～40MPa，升温速率为10～100℃/分钟，反应温度为1600～2100℃，反应时间为10分钟～2小时，合成的陶瓷材料为接近单相的ReB2C2相和少量杂质相(杂质相含量在3at％以下)。其中，原位反应为无压反应或热压烧结反应或放电等离子体烧结反应。大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料是指，称取原料时，严格按照化学计量比称取原料，或者考虑到反应实际情况对某种或某些原料进行适当调整，即相对于其化学计量比增加或减少称取量。例如，对于在反应阶段易挥发的原料，适当增加其称取量。
下面，通过实施例和附图进一步详述本发明。
实施例1
将粒度为400目的镧粉37.64克、300目的碳化硼粉4.48克和粒度为200目的石墨粉4.88克在玛瑙球磨罐中球磨24小时，之后装入石墨模具中冷压成型，施加的压强为5MPa；冷压10分钟后，将石墨模具放入以石墨为发热体的电阻炉中，升温速率为20℃/分钟，加热到1600℃保温2小时进行烧结。整个烧结过程都是在氩气保护下进行。对本实施例中得到的材料进行研磨，可以得到含少量六硼化镧相杂质的LaB2C2陶瓷粉体，粉体的粒度为1～10微米，LaB6杂质相含量为2.1at％。
实施例2
将粒度为200目的钇粉33.05克、400目的碳化硼粉10.26克和粒度为400目的石墨粉6.69克在聚氨酯球磨罐中球磨16小时，之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，将石墨模具放入以石墨为发热体的真空热压烧结炉中，升温速率为10℃/分钟，加热到2000℃保温1小时进行烧结，升温的同时施加的压力逐步增加到40MPa。整个烧结过程都是在氩气保护下进行。本实施例中，将获得的反应产物进行XRD分析(见图1)，可以发现制备的材料由YB2C2陶瓷及少量YB4相组成，YB4杂质相含量为1.6at％。其扫描电镜照片如图2所示，可以发现制备的样品非常致密，少量YB4杂质相(黑色)分布在YB2C2基体内。从断口形貌可以发现(见图3)，其具有典型的片层结构。使用本实施例方法制备的材料的维氏硬度约为4.2GPa，弯曲强度约为460MPa，弹性模量约为207GPa。该材料具有优异的高温刚性，在1500℃仍能维持其室温模量。同时该材料具有优异的损伤容限及可加工性，可以非常容易的使用普通硬质合金钻头对其加工(见图4)。
实施例3
将粒度为300目的钆粉38.76克、200目的铝粉6.81克和粒度为300目的石墨粉4.43克在玛瑙磨罐中球磨8小时，之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，将石墨模具放入放电等离子体烧结炉中，升温速率为100℃/分钟，加热到1700℃保温10分钟进行烧结，升温的同时施加的压力逐步增加到40MPa。整个烧结过程都是在氦气保护下进行。本实施例中，制备的材料由GdB2C2陶瓷及少量GdB4组成，GdB4杂质相含量为2.5at％。使用本实施例方法制备的材料具有优异的损伤容限及可加工性，可以非常容易的使用普通转头对其加工。
实施例4
将粒度为300目的镥粉39.67克、200目的碳化硼粉6.25克和粒度为300目的石墨粉4.08克在玛瑙磨罐中球磨8小时，之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，之后装入石墨模具中冷压成型，施加的压强为5MPa；冷压10分钟后，将石墨模具放入以石墨为发热体的电阻炉中，升温速率为20℃/分钟，加热到2100℃保温2小时进行烧结。整个烧结过程都是在氩气保护下进行。对本实施例中得到的材料进行研磨，可以得到含少量四硼化镥相杂质的LuB2C2陶瓷粉体，粉体的粒度为1～10微米，LuB4杂质相含量为2at％。
实施例结果表明，采用本发明方法能够实现原位合成各种三元稀土二硼二碳陶瓷材料。采用本发明方法制备的材料具有高的纯度，同时制备的块体材料具有良好的力学性能，优异的损伤容限及加工性能，同时还具有优异的高温刚性。因此，该类材料在航空航天、核工业、超高温结构件等高新技术领域有着广泛的应用前景。
Claims (9)
1.一种三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：采用稀土金属粉、碳化硼粉和石墨粉为原料，大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料；原料粉经物理机械方法混合8～24小时，过筛，装入石墨模具中冷压成型，施加的压强为5～20MPa；在通有惰性气体保护气氛的加热炉内原位反应，施加的压强为0～40MPa，升温速率为10～100℃/分钟，反应温度为1600～2100℃，反应时间为10分钟～2小时，合成的陶瓷材料为接近单相的ReB2C2相和少量杂质相。
2.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：三元稀土二硼二碳陶瓷材料是粉体或块体陶瓷。
3.按照权利要求1所述的三元稀土二硼二碳陶瓷材料制备方法，其特征在于：原料粉原位发生的化学反应为：
2Re+B4C+3C→2ReB2C2 (1)。
4.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：Re为稀土元素，包括但不限于周期表中原子序数从57到71号的稀土金属元素La,Ce,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb或Lu，或者，采用原子序数分别为21和39的稀土金属元素Sc和Y中的一种。
5.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：大体按照ReB2C2相陶瓷材料化学式中各元素的化学计量比称取原料是指，称取原料时，严格按照化学计量比称取原料，或者考虑到反应实际情况对某种或某些原料进行适当调整，即相对于其化学计量比增加或减少称取量。
6.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：稀土金属粉的粒度范围为200～400目，碳化硼粉的粒度范围为200～400目，石墨粉的粒度范围为200～400目。
7.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：原位反应为无压反应或热压烧结反应或放电等离子体烧结反应。
8.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：惰性气体为氩气或氦气。
9.按照权利要求1所述的三元稀土二硼二碳陶瓷材料的制备方法，其特征在于：物理机械方法混合为在聚氨酯球磨罐中干混或在酒精介质中球磨。
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| CN113213960A (zh) * | 2021-05-24 | 2021-08-06 | 苏长全 | 一种高韧性、高硬度耐磨陶瓷及其制备方法 |
| CN113213960B (zh) * | 2021-05-24 | 2021-11-23 | 潮州新动力净化器有限公司 | 一种高韧性、高硬度耐磨陶瓷及其制备方法 |
| CN114560699A (zh) * | 2022-03-14 | 2022-05-31 | 宁波杭州湾新材料研究院 | 一种中高熵陶瓷材料及其制备方法与应用 |
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